JP2007016184A - Elastomer, photosensitive composition, photosensitive film, and method for forming permanent pattern - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an alkali-soluble, photo-crosslinkable elastomer which can provide high-performance cured film excellent in heat resistance, moist-heat resistance, adhesiveness, mechanical properties, and electrical properties and is suitably used for producing a printed wiring board, a high-density multilayer board and a semiconductor package, and to provide a photosensitive composition and the like containing the elastomer. <P>SOLUTION: The elastomer is obtained by reacting a diisocyanate compound (A) with a diol compound (B) containing at least one carboxy group in a molecule, a diol compound (C) containing at least one unsaturated group in a molecule, and (D) a high-molecular-weight diol compound having a weight average molecular weight of 800 or more. The molar amount of the diisocyanate compound (A) is 1.0-2 times the total molar amount of all the diol compounds. The content of the high-molecular-weight diol compound (D) is 3-20 mol%. The photosensitive composition comprises the elastomer. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an alkali-soluble, photocrosslinkable elastomer suitably used for a solder resist and the like, a photosensitive composition using the elastomer, a photosensitive film using the photosensitive composition, and a high-definition The present invention relates to a method for efficiently forming a permanent pattern (such as a protective film, an interlayer insulating film, and a solder resist).

  In recent years, electronic devices have been required to have high performance, high functionality, high quality, and high reliability as well as small size, thinness, and light weight as represented by mobile communication devices. Electronic component modules mounted on devices are also required to be small and high in density. In response to such demands, in recent years, the surface of an insulating substrate made of a glass fiber and an epoxy resin that can be made lighter and densified from a ceramic wiring substrate made of ceramics such as an aluminum oxide sintered body. In addition, a so-called printed circuit board in which a wiring conductor layer is formed by a thin film forming method using copper, gold or the like which is a low resistance metal has been used for an electronic component module. In addition, this printed board is also changing to a build-up wiring board capable of higher density wiring.

For example, such a build-up wiring board is formed by laminating a film made of a thermosetting resin on an insulating board made of glass fiber and epoxy resin, and thermosetting the film to form an insulating layer. Opening, chemically roughening the surface of the insulating layer and depositing a copper film using electroless copper plating and electrolytic copper plating, thereby forming a conductor layer in the opening and forming a surface on the insulating layer. A wiring conductor layer is formed. Next, the insulating layer and the wiring conductor layer are formed repeatedly.
In addition, a solder resist layer having a thickness of 20 to 50 μm is deposited on the surface of the wiring board in order to prevent oxidation and corrosion of the wiring conductor layer and protect the insulating layer from heat when mounting electronic components on the wiring board. Is formed. This solder resist layer is generally composed of an alkali-soluble photocrosslinkable resin that has good adhesion to the wiring conductor layer and the insulating layer, and a flexible resin, and has a coefficient of thermal expansion that is the same as that of the insulating layer and the wiring conductor layer. In order to match the expansion coefficient, the inorganic filler is contained in an amount of 5 to 75% by mass.
Further, the wiring board is formed with an opening in the solder resist layer on the wiring conductor layer by exposure and development, and an electronic component is electrically connected to the wiring conductor layer in the opening via a conductor bump made of solder or the like. Thus, an electronic component module such as a semiconductor device is obtained.

Generally, the solder resist layer used for such an electronic component module has an insulation resistance of 10 ¹¹ to 10 ¹³ Ω in a dry state. However, this solder resist layer generally contains a hydroxyl group or a carboxyl group in order to develop developability when the alkali-soluble photocrosslinkable resin contained in the solder resist layer forms an opening by exposure and development. The water absorption rate is high and moisture in the air is gradually absorbed, and this moisture reduces the insulation resistance of the solder resist layer to 10 ⁸ Ω or less, thereby short-circuiting the wiring conductor layers. Further, the moisture corrodes the wiring conductor layer, and as a result, there is a problem that the electrical reliability of the wiring board is deteriorated. Also, in semiconductor package substrates such as BGA (ball grid array) and CSP (chip size package), cream solder is printed in advance on the necessary parts, the whole is heated with infrared rays, and the solder is reflowed and fixed. The external temperature reached is extremely high at 220-240 ° C, and there is a problem of so-called reflow resistance deterioration that the coating film cracks due to thermal shock or peels off from the substrate or the gunning material. It was sought after.
In addition, when applied to a flexible substrate, there is a problem that the surface is cracked or peeled off by a folding resistance test.

In order to solve such a problem, for example, it has been proposed to add an elastomer to a solder resist (see Patent Document 1). As the proposed elastomer, a polyester-based elastomer having a hydroxyl group is used, and a wide variety of other elastomers are exemplified. According to the addition of the elastomer, the necessary elastomer content needs to be included in an amount of 2 to 30 parts by mass with respect to 100 parts by mass of the acidic vinyl group-containing epoxy resin.
According to these elastomers, crack resistance can be improved, but developability of the unexposed portion of the solder resist is not sufficient.

  In addition, it is known to use an alkali-soluble butadiene copolymer as a binder for improving adhesion to a substrate. For example, styrene / butadiene / maleic acid amide copolymer, butadiene / methacrylic acid / divinylbenzene / methyl methacrylate copolymer, and the like have been proposed for application to solder resists (see Patent Documents 2 and 3).

  In addition, as a mixed binder that combines the reaction product of epoxy acrylate and polybasic acid anhydride with good alkali developability and hardness with other resins for the purpose of improving the adhesion of the photosensitive solder resist to the printed circuit board The use technique is also known. For example, as a crosslinkable binder combined with a reaction product of an epoxy acrylate and a polybasic acid anhydride, a reaction product of a carboxylic acid-added acrylonitrile butadiene rubber and an epoxy resin has been proposed (see Patent Document 4). However, even when this composition is applied as a solder resist, the adhesion to the substrate is sufficient, but it is insufficient in terms of alkali developability and heat resistance.

In addition, a solder resist containing carboxylic acid group-containing crosslinked elastomer fine particles has been proposed as one that improves substrate adhesion and reliability and further improves alkali developability (see Patent Document 5). According to this proposal, the reliability and developability are improved, but the dispersion stability of the carboxylic acid group-containing crosslinked elastomer fine particles is difficult. Therefore, when the content in the composition is increased to a necessary range, the solder resist There may be problems with the coatability of the layer.
Further, an alkali-soluble polyurethane resin having a polymer diol as a constituent element has been proposed as a polyurethane resin (see Patent Document 6). When the alkali-soluble polyurethane resin is added, it is sufficient to ensure the developability of the photosensitive solder resist, but the elastic modulus at high temperature of the cured film, which is the performance as an elastomer, cannot be lowered to a practical level. The crack prevention was not sufficient.

In general, it is known that a curable resin used in a photosensitive solder resist has a great influence on the properties of a cured film and alkali developability. Conventional alkaline light that can be used in a photosensitive permanent resist is known. The crosslinkable resin has the following drawbacks.
(1) Since the epoxy acrylate type has a small molecular weight, it is excellent in the concentration of the coating liquid and the flatness after coating. However, on the other hand, the uncured coating film has adhesiveness, which causes mask contamination during mask exposure. Further, when used as a photosensitive resist film, it has been a problem that defective peeling often occurs in the peeling step from the support after the laminate exposure. Moreover, since the film quality is brittle after post-baking after pattern formation, it is easy to cause cracks, and it is necessary to add an elastomer as a countermeasure. As the elastomer, an alkali-insoluble material is generally used, and often causes a development failure due to alkaline water. The use of a fine particle elastomer that is dispersible in an alkaline aqueous solution has also been proposed, but it is difficult to stabilize the dispersion with fine particles, and often agglomerates in the coating film, which may cause resist defects. Since these elastomer addition techniques are based on the principle of microphase separation in a cured film, the microstructure varies depending on factors such as curing conditions, and it has been difficult to always exhibit sufficient film strength.
(2) In the high molecular weight type system, the coating film has little surface stickiness, but on the other hand, the substrate adhesion is inferior, so that an additive that easily causes problems such as compatibility is required. Even if the adhesion is improved by the additive, it has been difficult to always exhibit sufficient film strength.

  Therefore, it is possible to obtain a high-performance cured film excellent in heat resistance, moist heat resistance, adhesion, mechanical properties, electrical properties, and folding resistance, and suitable for manufacturing printed wiring boards, high-density multilayer boards, semiconductor packages, and the like. The photosensitive composition used and its related technology have not been obtained yet, and it is desired to provide the photosensitive composition promptly.

Japanese Patent Laid-Open No. 11-240930 Japanese Patent Laid-Open No. 2-97502 JP-A-7-159998 JP-A-8-41167 Japanese Patent Laid-Open No. 2001-13679 JP-A-1-134354

An object of the present invention is to solve the conventional problems and achieve the following objects. That is, the present invention can obtain a high-performance cured film excellent in heat resistance, heat-and-moisture resistance, adhesion, mechanical properties, and electrical properties, and is suitable for manufacturing printed wiring boards, high-density multilayer boards, semiconductor packages, and the like. It is an object of the present invention to provide an alkali-soluble, photocrosslinkable elastomer used in the invention, and a photosensitive composition containing the elastomer.
The present invention also provides a photosensitive film obtained by laminating a layer of the photosensitive composition on a support to obtain a cured film having excellent heat resistance, moist heat resistance, adhesion, mechanical properties, and electrical insulation. The purpose is to provide.
Another object of the present invention is to provide a photosensitive film optimal for the blue-violet laser direct exposure method.
Furthermore, the present invention can provide a high-performance cured film excellent in heat resistance, heat-and-moisture resistance, adhesion, mechanical properties, and electrical properties, and is suitable not only for use in the photosensitive solder resist, but also in printing. Interlayer insulation film for substrates, color resists for color filters, photosensitive lithographic printing plates, various protective films, planarization films, photoresists for etching and plating, photosensitive pastes, holograms, microlenses, UV curable inks, UV curing An object of the present invention is to provide an alkali-soluble photocrosslinkable polymer that is also suitable for use in an adhesive paint.

Means for solving the problems are as follows. That is,
<1> (A) a diisocyanate compound, (B) a diol compound containing at least one carboxyl group in the molecule, (C) a diol compound containing at least one unsaturated group in the molecule, and (D) A high molecular weight diol compound having a weight average molecular weight of 800 or more, obtained by reacting the (A) diisocyanate compound in a molar amount of 1.0 to 2 times the total molar amount of all diol compounds;
The elastomer is characterized in that the content of the high molecular weight diol compound as the component (D) is 3 to 20 mol%.
<2> (A) a diisocyanate compound represented by the following general formula (I);
(B) at least one carboxylic acid group-containing diol compound represented by any one of the following general formulas (II-1) to (II-3), (C) the following general formulas (III-1) to (III- 2) at least one epoxy acrylate compound represented by any one of the above, and (D) at least one diol compound represented by any one of the following general formulas (IV-1) to (IV-5): The elastomer according to <1>, wherein the elastomer is a reaction product obtained by reacting.
However, in the general formula (I), R ¹ is a divalent aliphatic hydrocarbon group which may have a substituent and a divalent aromatic hydrocarbon group which may have a substituent. Represents either.
However, the general formula (II-1), (II -2), and in (II-3), ^{R 2} represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, or an alkoxy group and aryloxy group, These may be further substituted with a substituent. R ³ , R ⁴ , and R ⁵ may be the same as or different from each other, and each represents a single bond, an alkylene group, or an arylene group, and these are further substituted with a substituent. Alternatively, two or three of R ² , R ³ , R ⁴ , and R ⁵ may form a ring. Ar represents a trivalent aromatic hydrocarbon group which may have a substituent.
However, in the above general formula (III-1) and (III-2), ^{R 8} represents a hydrogen atom, or an optionally substituted alkyl group. R ^{9 to} R ¹⁶ may be the same as or different from each other, and each represents a hydrogen atom, a halogen atom, or an alkyl group that may have a substituent. R ^{17 to} R ³² may be the same as or different from each other, and each may have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, or a substituent. Represents a good alkoxy group.
However, in the general formulas (IV-1) to (IV-5), R ³³ , R ³⁴ , R ³⁵ , R ³⁶ and R ³⁷ may be the same as or different from each other. It represents either an alkylene group or an arylene group, which may be further substituted with a substituent. R ³⁸ represents a hydrogen atom, a cyano group, a halogen atom, an alkyl group, or an aryl group and aralkyl group, and these may be further substituted by substituents. R ³⁹ represents a cyano group or an aryl group which may have a substituent. m shows the integer of 2-4. n ₁ , n ₂ , n ₃ , n ₄ and n ₅ each represents an integer of 2 or more. n ₆ represents, represents 0 or an integer of 2 or more.
<3> The ratio of (A) component: (B) component: (C) component: (D) component is 33-50 mol%: 16-33 mol%: 7-40 mol%: 3-20 mol%, respectively. The ratio of the total number of moles of the component (A) to the total number of moles of the component (B), the component (C), and the component (D) is 1.0 to 2. The elastomer according to any one of <1> to <2>, which is 0.
<4> The elastomer according to any one of <1> to <3>, wherein the acid value is 20 to 70 mg KOH / g, and the bromine value is ₂ to 50 gBr 2/100 g.
<5> A photosensitive composition comprising the elastomer according to any one of <1> to <4>, a polymerizable compound, a photopolymerization initiator, a thermal crosslinking agent, and a colorant. It is a thing.
<6> The photosensitive composition according to <5>, wherein the thermal crosslinking agent is any one of an epoxy compound and a polyfunctional oxetane compound.
<7> The photosensitive composition according to any one of <5> to <6>, including an inorganic filler.
<8> Elastomer 15 to 70% by mass, polymerizable compound 5 to 75% by mass, photopolymerization initiator 0.5 to 20% by mass, thermal crosslinking agent 2 to 50% by mass, inorganic filler 5 to 75% by mass, coloring It is the photosensitive composition in any one of said <5> to <7> containing 0.1-10 mass% of agents, 0.01-20 mass% of thermosetting accelerators, and an organic solvent.

<9> The photosensitive composition according to any one of <5> to <8>, wherein the polymerizable compound includes at least one selected from monomers having a (meth) acryl group.
<10> The photopolymerization initiator is at least selected from halogenated hydrocarbon derivatives, phosphine oxides, hexaarylbiimidazoles, oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, and ketoxime ethers. It is the photosensitive composition in any one of said <5> to <9> containing 1 type.

<11> A photosensitive material comprising: a support; and a photosensitive layer formed by laminating the photosensitive solder resist composition according to any one of <5> to <10> on the support. It is a sex film.
<12> The photosensitive film according to <11>, having a protective film on the photosensitive layer.
<13> The photosensitive film according to any one of <11> to <12>, wherein the photosensitive layer has a thickness of 3 to 100 μm.
<14> The photosensitive film according to any one of <11> to <13>, wherein the support includes a synthetic resin and is transparent.
<15> The photosensitive film according to any one of <11> to <14>, wherein the support has a long shape.

  <16> A photosensitive material comprising: a substrate; and a photosensitive layer formed by coating the photosensitive composition according to any one of <5> to <10> on the substrate. It is a composition laminate.

<17> Either the photosensitive layer in the photosensitive film according to any one of <11> to <15> or the photosensitive layer in the photosensitive composition laminate according to <16> above, on the surface of the substrate. After laminating, the photosensitive layer is exposed to light and developed, thereby forming a permanent pattern.
In the method for forming a permanent pattern according to <17>, the photosensitive film according to any one of <11> to <15> is transferred to the surface of the substrate under at least one of heating and pressing. The photosensitive layer is laminated, or the photosensitive composition laminate according to <16> is applied to the surface of the substrate and dried to laminate the photosensitive layer. Any one of the photosensitive layers is exposed, and the exposed photosensitive layer is developed. As a result, the surface hardness is high, and a permanent pattern optimum for the protective film or insulating film is formed.
<18> The permanent pattern forming method according to <17>, wherein the base material is a printed wiring board on which wiring has been formed.
In the permanent pattern forming method according to <18>, since the base material is a printed wiring board on which wiring has been formed, by using the permanent pattern forming method, a multilayer wiring board or build-up of a semiconductor or a component can be performed. High-density mounting on a wiring board or the like is possible.
<19> The permanent pattern forming method according to any one of <17> to <18>, wherein the exposure is performed imagewise based on pattern information to be formed.
<20> The permanent pattern according to any one of <17> to <19>, wherein the exposure is performed using light that is generated based on pattern information to be formed and modulated in accordance with the control signal It is a forming method.
<21> From <17> to <20, wherein the exposure is performed using light irradiation means for irradiating light and light modulation means for modulating light emitted from the light irradiation means based on pattern information to be formed. The permanent pattern forming method according to any one of the above.
<22> The light modulation unit further includes a pattern signal generation unit that generates a control signal based on pattern information to be formed, and the pattern signal generation unit generates light emitted from the light irradiation unit. The method for forming a permanent pattern according to <21>, wherein modulation is performed according to a signal.
<23> The light modulation means includes n pixel parts, and forms any less than n pixel parts arranged continuously from the n pixel parts. The permanent pattern forming method according to any one of <17> to <22>, which is controllable according to pattern information.
In the method for forming a permanent pattern according to <23>, any less than n pixel parts arranged continuously from n pixel parts in the light modulation unit are controlled according to pattern information. By doing so, the light from the light irradiation means is modulated at high speed.
<24> The method for forming a permanent pattern according to any one of <17> to <23>, wherein the light modulator is a spatial light modulator.
<25> The method for forming a permanent pattern according to <24>, wherein the spatial light modulation element is a digital micromirror device (DMD).
<26> The permanent pattern forming method according to any one of <23> to <25>, wherein the picture element portion is a micromirror.
<27> Exposure is performed through a microlens array in which microlenses having aspherical surfaces capable of correcting aberrations due to distortion of the exit surface of the picture element portion in the light modulation means after the light is modulated by the light modulation means. The method for forming a permanent pattern according to any one of <23> to <26>.
<28> Exposure is performed through a microlens array in which microlenses having lens aperture shapes that do not allow light from the periphery of the picture element portion in the light modulation means to enter after the light is modulated by the light modulation means. The method for forming a permanent pattern according to any one of <23> to <27>. In the pattern forming method according to <28>, the light modulated by the light modulation unit passes through the microlens having a lens opening shape that does not allow the light from the peripheral part of the pixel part to enter, and thus distortion is large. The light reflected at the periphery of the image element, particularly at the four corners, is not collected, and distortion of the image formed on the photosensitive layer is suppressed. As a result, distortion of the image formed on the pattern forming material is suppressed, and exposure to the pattern forming material is performed with extremely high definition. For example, when the photosensitive layer is subsequently developed, an extremely fine pattern is formed.

<29> The method for forming a permanent pattern according to <28>, wherein the microlens has an aspherical surface capable of correcting an aberration due to distortion of the exit surface in the pixel portion.
<30> The permanent pattern forming method according to any one of <27> to <29>, wherein the aspherical surface is a toric surface. In the method for forming a permanent pattern according to <30>, since the aspherical surface is a toric surface, the aberration due to the distortion of the radiation surface in the pixel portion is efficiently corrected, and an image is formed on the pattern forming material. Image distortion is efficiently suppressed. As a result, the pattern forming material is exposed with extremely high definition. For example, when the photosensitive layer is subsequently developed, an extremely fine pattern is formed.
<31> The method for forming a permanent pattern according to any one of <27> to <30>, wherein the microlens has a circular lens opening shape.
<32> The pattern forming method according to any one of <27> to <31>, wherein the lens opening shape is defined by providing a light shielding portion on the lens surface.
<33> The permanent pattern forming method according to any one of <17> to <32>, wherein the exposure is performed through an aperture array.
In the method for forming a permanent pattern according to <33>, the extinction ratio is improved by performing exposure through the aperture array. As a result, the exposure is performed with extremely high definition. Thereafter, the photosensitive layer is developed to form a very fine permanent pattern.
<34> The permanent pattern forming method according to any one of <17> to <33>, wherein the exposure is performed while relatively moving the exposure light and the photosensitive layer.
In the method for forming a permanent pattern described in <34>, the exposure is performed at a high speed by performing exposure while relatively moving the modulated light and the photosensitive layer.
<35> The method for forming a permanent pattern according to any one of <17> to <34>, wherein the exposure is performed on a partial region of the photosensitive layer.
<36> The permanent pattern forming method according to any one of <17> to <35>, wherein the light irradiation unit can synthesize and irradiate two or more lights.
In the method for forming a permanent pattern according to <36>, the light irradiation means can synthesize and irradiate two or more lights, so that exposure is performed with exposure light having a deep focal depth. As a result, the exposure of the photosensitive layer is performed with extremely high definition. Thereafter, the photosensitive layer is developed to form a very fine permanent pattern.
<37> The light irradiation means includes a plurality of lasers, a multimode optical fiber, and a collective optical system that collects laser beams irradiated from the plurality of lasers and couples the laser beams to the multimode optical fiber The permanent pattern forming method according to any one of <17> to <36>.
In the method for forming a permanent pattern according to <37>, the laser light emitted from each of the plurality of lasers is condensed by the collective optical system by the light irradiation unit and can be coupled to the multimode optical fiber. Thus, exposure is performed with exposure light having a deep focal depth. As a result, the exposure of the photosensitive layer is performed with extremely high definition. Thereafter, the photosensitive layer is developed to form a very fine permanent pattern.
<38> The method for forming a permanent pattern according to any one of <17> to <37>, wherein the exposure is performed using a laser beam having a wavelength of 395 to 415 nm.
<39> The permanent pattern forming method according to any one of <17> to <38>, wherein the photosensitive layer is subjected to a curing treatment after development.
In the permanent pattern forming method according to <39>, after the development, the curing process is performed on the photosensitive layer. As a result, the film strength of the cured region of the photosensitive layer is increased.
<40> The method for forming a permanent pattern according to <39>, wherein the curing treatment is at least one of a whole surface exposure treatment and a whole surface heat treatment performed at 120 to 200 ° C.
In the permanent pattern forming method according to <40>, curing of the resin in the photosensitive solder resist composition is promoted in the entire surface exposure process. Moreover, the film | membrane intensity | strength of a cured film is raised in the whole surface heat processing performed on the said temperature conditions.
<41> The permanent pattern forming method according to any one of <17> to <40>, wherein at least one of a protective film, an interlayer insulating film, and a solder resist pattern is formed.
In the permanent pattern forming method according to <41>, since at least one of a protective film, an interlayer insulating film, and a solder resist pattern is formed, the wiring from the outside depends on the insulating property, heat resistance, and the like of the film. Protected from impact and bending.

<42> A permanent pattern formed by the method for forming a permanent pattern according to any one of <17> to <41>.
Since the permanent pattern described in <42> is formed by the permanent pattern forming method, it has excellent chemical resistance, surface hardness, heat resistance, and the like, and has high definition and multilayer wiring of semiconductors and components. This is useful for high-density mounting on boards and build-up wiring boards.
<43> The permanent pattern according to <42>, which is at least one of a protective film, an interlayer insulating film, and a solder resist pattern.
Since the permanent pattern according to <43> is at least one of a protective film, an interlayer insulating film, and a solder resist pattern, the wiring may be subjected to external impact, bending, etc. depending on the insulation and heat resistance of the film. Protected from.

According to the present invention, it is possible to provide a high-performance cured film excellent in heat resistance, heat and humidity resistance, adhesion, mechanical properties, and electrical properties, not only suitable for use in the photosensitive solder resist, Interlayer insulation film for printed circuit boards, color resists for color filters, photosensitive lithographic printing plates, various protective films, planarizing films, photoresists for etching and plating, photosensitive pastes, holograms, microlenses, UV curable inks, UV An alkali-soluble photocrosslinkable elastomer suitable for use in curable coatings and the like can be obtained, and by using the elastomer, it has excellent heat resistance, moist heat resistance, adhesion, mechanical properties, and electrical properties. Provided is a photosensitive composition that can obtain a high-performance cured film and is suitably used in the production of printed wiring boards, high-density multilayer boards, semiconductor packages, and the like.
Further, according to the present invention, a cured film having excellent heat resistance, moist heat resistance, adhesion, mechanical properties, and electrical insulation obtained by laminating the layer of the photosensitive composition on a support is obtained. Using the photosensitive film optimal for the blue-violet laser direct exposure method, and the photosensitive composition and photosensitive film, an efficient permanent pattern of a high-definition permanent pattern (protective film, interlayer insulating film, solder resist, etc.) A forming method can be provided.

(Elastomer)
The elastomer of the present invention is an alkali-soluble photocrosslinkable elastomer having at least an alkali-soluble group and a photocrosslinkable group.

The alkali-soluble refers to a property in which a photosensitive composition containing the same is dissolved by an alkaline solution. For example, the photosensitive composition should be soluble to the extent that the intended development processing is performed. That's fine. The alkaline developer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include alkali metal hydroxides such as sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, hydroxyethylamine, triethylamine Or an aqueous solution of a quaternary ammonium hydroxide such as tetramethylammonium hydroxide or a mixture thereof with a miscible organic solvent. pH is 8-14 and 0.01-10 mass% aqueous solution of these alkali agents is preferable. Among these alkaline developers, in the printed wiring board industry, 0.2 to 2 mass% sodium carbonate aqueous solution is generally used, and 1 mass% sodium carbonate aqueous solution is the most common.
The photocrosslinking property means a property of changing a linear polymer molecule into a network having a network three-dimensional structure by a photochemical reaction, and specifically, free radicals generated by photolysis of a photopolymerization initiator. This means a polymer that can be reticulated by polymerization reaction.

In the present invention, since the elastomer has an alkali-soluble and photocrosslinkable function, a stable microphase separation is obtained and it has excellent impact resistance. Therefore, heat resistance, moist heat resistance, adhesion, mechanical properties, electrical properties, Improved characteristics.
As the elastomer, (A) a diisocyanate compound, (B) a diol compound containing at least one carboxyl group in the molecule, (C) a diol compound containing at least one unsaturated group in the molecule, D) It is obtained by reacting a high molecular weight diol compound having a weight average molecular weight of 800 or more with a diisocyanate compound in a molar amount of 1.0 to 2 times the total molar amount of all diol compounds.
The content rate of the high molecular weight diol compound of the said (D) component is 3-20 mol%, and 5-15 mol% is preferable. When the content is less than 3 mol%, the cured resist film may have deteriorated PCT resistance, thermal shock resistance, folding resistance, and the like. When the content exceeds 20 mol%, the content of other components decreases. As a result, the performance balance may be lost, and for example, developability may be deteriorated.

Examples of the elastomer include (A) a diisocyanate compound represented by the following general formula (I);
(B) at least one carboxylic acid group-containing diol compound represented by any one of the following general formulas (II-1) to (II-3), (C) the following general formulas (III-1) to (III- 2) at least one epoxy acrylate compound represented by any one of the above, and (D) at least one diol compound represented by any one of the following general formulas (IV-1) to (IV-5): It is preferable that it is a reaction material of these.

<(A) Component Diisocyanate Compound>
There is no restriction | limiting in particular as a diisocyanate compound of the said (A) component, Although it can select suitably according to the objective, For example, the compound represented by the following general formula (I) is suitable.
However, in the general formula (I), R ¹ is a divalent aliphatic hydrocarbon group which may have a substituent and a divalent aromatic hydrocarbon group which may have a substituent. Represents either.

In the general formula (I), examples of the divalent aliphatic hydrocarbon group that R ¹ may have the substituent include an alkylene group and an aralkylene group. Examples of the divalent aromatic hydrocarbon group which may have a substituent include an arylene group.
Examples of the alkylene group include an ethylene group, a propylene group, and a butylene group.
Examples of the substituent include an alkyl group, an aralkyl group, an aryl group, an alkoxy group, and a halogen atom.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and the like. Examples of the aralkyl group include a benzyl group, a phenylethyl group, a phenylpropyl group, and the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a biphenylyl group, a naphthyl group, an anthryl group, a phenanthryl group, and the like.
R ¹ may have any other functional group that does not react with an isocyanate group, such as an ester group, a urethane group, an amide group, or a ureido group.

  Specific examples of the diisocyanate compound represented by the general formula (I) include those shown below. That is, 2,4-tolylene diisocyanate, dimer of 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, 4,4′-diphenylmethane diisocyanate, Aromatic diisocyanate compounds such as 1,5-naphthylene diisocyanate and 3,3′-dimethylhyphenyl-4,4′-diisocyanate; aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate and dimer acid diisocyanate Compound: isophorone diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4- (or 2,6) diisocyanate, 1,3- (isocyanate) Tomechiru) alicyclic diisocyanate compounds such as cyclohexane; 1,3-butylene glycol 1 mol of a diisocyanate compound which is a reaction product of a diol and a diisocyanate, an adduct of tolylene diisocyanate 2 mol, and the like.

<(B) Component Carboxylic Acid Group-Containing Diol Compound>
There is no restriction | limiting in particular as a diol compound which contains at least 1 carboxyl group in the molecule | numerator of the said (B) component, Although it can select suitably according to the objective, For example, from following General formula (II-1) At least one compound selected from carboxylic acid group-containing diol compounds represented by any one of (II-3) is preferred.

In the general formulas (II-1), (II-2) and (II-3), R ² represents a hydrogen atom, an alkyl group which may have a substituent, an aralkyl group, an aryl group, an alkoxy group, And an aryloxy group. An alkyl group having 1 to 3 carbon atoms and an aryl group having 6 to 15 carbon atoms are preferable.
Examples of the substituent include a cyano group, a ditro group, a halogen atom (—F, —Cl, —Br, —I), —CONH ₂ , —COOR ⁶ , —OR ⁶ , —NHCONHR ⁶ , —NHCOOR ^6. , -NHCOR ⁶ , -OCONHR ⁶ , -CONHR ⁶ (wherein R ⁶ represents an alkyl group having 1 to 10 carbon atoms or an aralkyl group having 7 to 15 carbon atoms), and the like. ).

R ³ , R ⁴ , and R ⁵ may be the same as or different from each other, a single bond, an alkylene group having 1 to 20 carbon atoms that may have a substituent, and a carbon number It represents any of 6 to 15 arylene groups, and 2 or 3 of R ² , R ³ , R ⁴ , and R ⁵ may form a ring.
Examples of the substituent include an alkyl group, an aralkyl group, an aryl group, an alkoxy group, and a halogen atom, and the same substituents as those described above can be used.
Further, if necessary, in R ³ , R ⁴ , and R ⁵ , any other functional group that does not react with the isocyanate group, such as a carbonyl group, an ester group, a urethane group, an amide group, a ureido group, or an ether group. You may have. In addition, you may form a ring by 2 or 3 of R < ² >, R < ³ >, R < ⁴ > and R < ⁵ >.

  Ar represents a trivalent aromatic hydrocarbon which may have a substituent, and an aromatic group having 6 to 15 carbon atoms is preferable.

  The diol compound having a carboxyl group represented by the general formulas (II-1) to (II-3) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 3,5-dihydroxy Benzoic acid, 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (2-hydroxyethyl) propionic acid, 2,2-bis (3-hydroxypropyl) propionic acid, bis (hydroxymethyl) acetic acid, Bis (4-hydroxydiphenyl) acetic acid, 4,4-bis (4-hydroxydiphenyl) pentanoic acid, tartaric acid, N, N-dihydroxyethylglycine, N, N-bis (2-hydroxyethyl) -3-carboxy-propion Amide, and the like.

<Epoxy acrylate compound of component (C)>
There is no restriction | limiting in particular as a diol compound which contains at least 1 unsaturated group in the molecule | numerator of the said (C) component, Although it can select suitably according to the objective, For example, following General formula (III-1) To at least one compound selected from epoxy acrylate compounds represented by any one of (III-2) is preferred.

In the general formulas (III-1) and (III-2), R ⁸ represents a hydrogen atom or an alkyl group which may have a substituent. R ^{9 to} R ¹⁶ may be the same as or different from each other, and each represents a hydrogen atom, a halogen atom, or an alkyl group that may have a substituent.
R ^{17 to} R ³² may be the same as or different from each other, and each may have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, or a substituent. Represents a good alkoxy group.
The alkyl group usually has about 1 to 20 carbon atoms. For example, methyl group, ethyl group, propyl group, i-propyl group, butyl group, i-butyl group, t-butyl group, pentyl group, hexyl group. Group, cyclohexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, 3,7-dimethyloctyl group, lauryl group, and the like.
Examples of the alkoxy group include methoxy group, ethoxy group, propyloxy group, i-propyloxy group, butoxy group, i-butoxy group, t-butoxy group, pentyloxy group, hexyloxy group, cyclohexyloxy group, heptyl. Examples thereof include an oxy group, an octyloxy group, a 2-ethylhexyloxy group, a nonyloxy group, a decyloxy group, a 3,7-dimethyloctyloxy group, and a lauryloxy group.

  The epoxy acrylate compound represented by any one of the general formulas (III-1) to (III-2) is a bifunctional epoxy compound and an unsaturated group-containing carboxylic acid such as (meth) acrylic acid or acrylic acid dimer. Obtained by addition reaction.

Examples of the unsaturated group-containing carboxylic acid further include those containing two or more carboxyl groups in the molecule, such as maleic acid and itaconic acid. Also included are maleic acid, itaconic acid monoesters, or monoamides. Moreover, the half ester compound which is a reaction product of a hydroxyl group containing (meth) acrylate and a saturated or unsaturated dibasic acid anhydride is mentioned.
The half ester compound can be obtained by reacting a hydroxyl group-containing (meth) acrylate with a saturated or unsaturated dibasic acid anhydride in an equimolar ratio. In this specification, (meth) acrylic acid, acrylic acid, methacrylic acid and mixtures thereof are generic terms, and the same applies to (meth) acrylate and the like.

  The bifunctional epoxy compound that is a raw material component of the epoxy acrylate is preferably an epoxy compound having an epoxy equivalent of 100 to 900 g / equivalent. When the epoxy equivalent is less than 100, the resulting alkali-soluble photocrosslinkable polyurethane resin has a small molecular weight, and film formation may be difficult, or flexibility may not be obtained sufficiently. The rate of introduction of C may be lowered, and the photosensitivity may be lowered.

  Here, the epoxy equivalent means the mass of the epoxy compound with respect to one epoxy group of the epoxy compound, and is expressed in units of g / equivalent, and is usually measured by the method described in JIS K7236.

  There is no restriction | limiting in particular as said bifunctional epoxy compound, According to the objective, it can select suitably, For example, bisphenol A type, bisphenol F type, bisphenol S type, other bisphenol type, biphenyl type, and aromatic diphenol Type epoxy resin.

  As the bisphenol A type epoxy resin, commercially available products include, for example, Epicoat 828, Epicoat 1001, Epicoat 1002, Epicoat 1003, Epicoat 1004 (all manufactured by Japan Epoxy Resin Co., Ltd.), Epomic R-140, Epomic R-301, and Epomic. R-304 (both manufactured by Mitsui Chemicals), D.I. E. R-331, D.I. E. R-332, D.I. E. R-324 (all manufactured by Dow Chemical), Epicron 840, Epicron 850 (all manufactured by Dainippon Ink), UVR-6410 (Union Carbide), YD-8125 (manufactured by Tohto Kasei), etc. Can be mentioned.

Examples of the bisphenol F type epoxy resin include commercially available products such as Epicoat 806 and Epicoat 4004P (all manufactured by Japan Epoxy Resin Co., Ltd.).
As the bisphenol S type epoxy resin, commercially available products such as Epicron EXA1514 (manufactured by Dainippon Ink & Chemicals), EBPS-200 (manufactured by Nippon Kayaku Co., Ltd.), EPX-30 (manufactured by Asahi Denka Co., Ltd.), 2, 2'-dimethyl-5,5-di-tert-butyl-4,4'-dihydroxydiphenylthioether diglycidyl ether (XSLV-120TE: manufactured by Toto Chemical Co., Ltd.), and the like.

Examples of the other bisphenol-type epoxy resins include methylene bisphenol-type 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxydiphenylmethane described in JP-A-10-97072. Diglycidyl ether (YSLV-80XY, manufactured by Tohto Kasei Co., Ltd. and ESLV80XY, manufactured by Nippon Steel Chemical Co., Ltd.), 2,2 ′, 3,3 ′, 5,5′-hexamethyl-4,4′-dihydroxydiphenylmethane diglycidyl And ether, 2,2′-dimethyl-5,5′-di-tert-butyl-4,4′-dihydroxydiphenylmethane diglycidyl ether, and the like.
Specific examples of other alkylene bis (phenol) type epoxy resins include 4,4 ′-[1,4-phenylenebis (isopropylidene)] bis (phenol), 4,4 ′-[1,4. -Phenylenebis (isopropylidene)] bis (2-methylphenol), 4,4 '-[1,4-phenylenebis (isopropylidene) bis (2,6-dimethylphenol), 4,4'-[1, 3-phenylenebis (isopropylidene)] bis (phenol), 4,4 '-[1,3-phenylenebis (isopropylidene)] bis (2-methylphenol), 4,4'-[1,3-phenylene Bis (isopropylidene) bis (2,6-dimethylphenol), 4,4 ′-[1,4-phenylenebis (ethylidene)] bis (phenol), 4,4 ′-[1,4-pheny Bis (ethylidene)] bis (2-methylphenol), 4,4 ′-[1,4-phenylenebis (ethylidene) bis (2,6-dimethyl) phenol, 4,4 ′-[1,3-phenylenebis] (Ethylidene)] bis (phenol), 4,4 ′-[1,3-phenylenebis (ethylidene)] bis (2-methylphenol), 4,4 ′-[1,3-phenylenebis (ethylidene) bis ( 2,6-dimethylphenol), 4,4 '-(1,4-xylylene) bis (phenol), 4,4'-(1,4-xylylene) bis (2-methylphenol), 4,4'- (1,4-xylylene) bis (2,6-dimethylphenol), 4,4 ′-(1,3-xylylene) bis (phenol), 4,4 ′-(1,3-xylylene) bis (2- Methylphenol), 4,4 '-( , 3-xylylene) bis (2,6-dimethylphenol) and the like, and among these, 4,4 ′-[1,4-phenylenebis (isopropylidene) bis (2,6-dimethyl). Phenolic diglycidyl ether is commercially available as Nippon Steel Chemical Co., Ltd. ESLV90CR.
In addition, dicyclopentadiene phenol polyaddition epoxy resin is included, and specific examples thereof include Epicron EXA-7200 manufactured by Dainippon Ink.

As the biphenyl type epoxy resin, for example, Epicoat YX4000 (produced by Japan Epoxy Resinshi Co., Ltd., a product, which is 4,4′-bis (2,3-epoxypropoxy) -3,3 ′, 5,5′-tetramethylbiphenyl) Name), 4,4′-bis (2,3-epoxypropoxy) -biphenyl.
Examples of the aromatic diphenol type epoxy compound include hydroquinone epoxy resin (manufactured by Nanya Plastic Co., Ltd.) and YDC-1312 (manufactured by Toto Chemical Co., Ltd.) which is 2,6-di-tert-butylhydroquinone diglycidyl ether. Can be mentioned. Specific examples of epoxy resins containing other condensed polycyclic aromatic skeletons include 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 2,3- , 2,6-, 2,7-dihydroxynaphthalene and epihalohydrin can be mentioned as dihydroxynaphthalenediglycidyl ether.

As a charge ratio of the raw material in the addition reaction of the bifunctional epoxy compound and the unsaturated group-containing carboxylic acid compound, the unsaturated group-containing carboxylic acid compound is 0.8 to 1 with respect to 1 equivalent of the epoxy group of the bifunctional epoxy compound. .2 equivalents are preferred. When deviating from this range, gelation may occur during the subsequent urethanization reaction, and the thermal stability of the finally obtained alkali-soluble photocrosslinkable polyurethane resin may be lowered.
In the reaction of the epoxy compound with the unsaturated group-containing carboxylic acid, a catalyst is preferably used to promote the reaction, and the amount of the catalyst used is preferably 0.1 to 10% by mass with respect to the reaction product.
Examples of the catalyst include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octoate, zirconium octoate and the like. Is mentioned.
The reaction temperature is preferably 60 to 150 ° C. Moreover, the said reaction time can be suitably selected by monitoring of the acid value mentioned later, and 5 to 60 hours are preferable.

Moreover, it is preferable to use hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, diphenylpicrylhydrazine, diphenylamine, 2,6-di-tert-butyl-p-cresol, etc. as the thermal polymerization inhibitor.
In the reaction, the acid value of the reaction solution is preferably 1 mgKOH / g or less, and the end point is set to 0.5 mgKOH / g or less.

<High molecular weight diol compound of component (D)>
The high molecular weight diol of the component (D) has a weight average molecular weight of 800 or more, preferably 800 to 3,000, more preferably 800 to 2,800, and particularly preferably 900 to 2,500. When the weight average molecular weight is less than 800, the resulting polyurethane resin may not exhibit sufficient elastomeric properties, and when it exceeds 2500, developability with an alkaline aqueous solution may be inferior.
There is no restriction | limiting in particular as high molecular weight diol of the said (D) component, Although it can select suitably according to the objective, For example, the high molecular weight diol compound of the following general formula (IV-1) to (IV-5) At least one compound selected from is preferred.

In the general formulas (IV-1) to (IV-5), R ³³ , R ³⁴ , R ³⁵ , R ³⁶ and R ³⁷ may be the same as or different from each other, and are each an alkylene group. , And an arylene group, which may be further substituted with a substituent. Preferably, R ³³ , R ³⁴ , R ³⁵ , R ³⁶ and R ³⁷ each represent an alkylene group having 2 to 20 carbon atoms or an arylene group having 6 to 15 carbon atoms, more preferably 2 to 2 carbon atoms. 10 represents an alkylene group or an arylene group having 6 to 10 carbon atoms, and R ³⁴ represents an alkylene group having 1 to 20 carbon atoms or an arylene group having 6 to 15 carbon atoms, more preferably a carbon number. An alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 10 carbon atoms is shown.
Examples of the substituent include an alkyl group, an aralkyl group, an aryl group, an alkoxy group, and a halogen atom.
There is no restriction | limiting in particular as said aralkyl group, According to the objective, it can select suitably, For example, a benzyl group, a phenylethyl group, a phenylpropyl group, etc. are mentioned.
Examples of the alkoxy group include methoxy group, ethoxy group, propyloxy group, i-propyloxy group, butoxy group, i-butoxy group, t-butoxy group, pentyloxy group, hexyloxy group, cyclohexyloxy group, heptyl. Examples thereof include an oxy group, an octyloxy group, a 2-ethylhexyloxy group, a nonyloxy group, a decyloxy group, a 3,7-dimethyloctyloxy group, and a lauryloxy group.
Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a biphenylyl group, a naphthyl group, an anthryl group, a phenanthryl group, and the like.
In R ³³ , R ³⁴ , R ³⁵ , R ³⁶ and R ³⁷ , any other functional group that does not react with the isocyanate group, such as a carbonyl group, an ester group, a urethane group, an amide group, a ureido group, or an ether group. You may have.

R ³⁸ represents a hydrogen atom, a cyano group, a halogen atom, an alkyl group, or an aryl group and aralkyl group, and these may be further substituted by substituents. Preferably, it represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, an aralkyl group having 7 to 15 carbon atoms, a cyano group or a halogen atom, more preferably a hydrogen atom, An alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms is shown. R ³⁸ may have another functional group that does not react with the isocyanate group, for example, an alkoxy group, a carbonyl group, an olefin, an ester group, or a halogen atom.
R ³⁹ represents a cyano group or an aryl group which may have a substituent. An aryl group or cyano group having 6 to 10 carbon atoms is preferred.
m shows the integer of 2-4. n ₁ , n ₂ , n ₃ , n ₄ and n ₅ each represent an integer of 2 or more, preferably an integer of 2 to 100. n ₆ represents, represents 0 or an integer of 2 or more, preferably an integer of 0 or 2 to 100.

Specific examples of the high molecular weight diol compounds represented by the general formulas (IV-1) to (IV-5) include compounds represented by the following chemical formulas of No1 to No27.

  However, in the specific example compounds, m and n may be the same or different and each represents an integer of 2 or more. Among these, compound no. 7, Compound No. 4, Compound No. 2 is particularly preferred.

  Further, the elastomer of the present invention may further be copolymerized with a low molecular weight diol containing no carboxylic acid group. Examples of the low molecular weight diol include ethylene glycol, 1,2-propylene glycol, 1,3- Propylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, 1,4-butanediol, 2,2'-dimethyl-1,3-propanediol, diethylene glycol, triethylene glycol, 1,5-pentamethylene Glycol, dipropylene glycol, neopentyl glycol, 1,6-hexamethylene glycol, cyclohexane-1,4-diol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, 2-butene-1,4 -Diol, 2,2,4-trimethyl-1,3- Nthanediol, xylylene glycol, 1,4-bis-β-hydroxyethoxycyclohexane, tridiclodecane dimethanol, hydrogenated bisphenol A, hydrogenated bisphenol F, bisphenol A, bisphenol S, hydroquinone dihydroxyethyl ether, p-xylylene Glycol, dihydroxyethyl sulfone, bis (2-hydroxyethyl) -2,4-tolylene dicarbamate, 2,4-tolylene-bis (2-hydroxyethylcarbamide), bis (2-hydroxyethyl) -m-xylylene dicarbamate Among these, 1,4-bis (2-hydroxyethyl) isophthalate, 1,4-bis (β-hydroxyethoxy) benzene, bis (β-hydroxyethyl) terephthalate, or a mixture thereof, among others, 1,4- Butanji All is particularly preferred.

  The copolymerization amount of the carboxylic acid group-free diol is preferably 95 mol% or less, more preferably 80% or less, and particularly preferably 50% or less in the low molecular weight diol. When the copolymerization amount exceeds 95 mol%, a urethane resin having good developability may not be obtained.

The acid value of the elastomer is the mass (g) of potassium hydroxide necessary to neutralize the acidity of the carboxylic acid in 1 g of the elastomer, and is measured by a normal neutralization titration method according to JIS K0070. .
The acid value is preferably 20 to 70 mgKOH / g. If the acid value is less than 20 mg KOH / g, the developability may be insufficient, and if it exceeds 70 mg KOH / g, the development speed may be too high, and development control may be difficult.

The bromine number of the elastomer is the mass (g) of bromine necessary for the bromine number of the unsaturated group in 100 g of the elastomer, and is measured by a usual electro titration method according to JIS K2605. Examples of the bromine number, preferably 2~50gBr ₂ / 100g, more preferably _{2~25gBr 2 / 100g, 3~20gBr 2 /} 100g being particularly preferred. Reducing the bromine number _is less than 2gBr 2 / 100g, the heat resistance of the cured resist film, there is the hardness, etc. solvent resistance is _{deteriorated,} when it exceeds 50gBr 2 / 100g, the other component content is Therefore, the performance balance is lost, and for example, developability and folding resistance may deteriorate.
The weight average molecular weight of the elastomer is preferably 3,000 or more, and more preferably 5,000 to 200,000. If the weight average molecular weight is less than 3,000, a sufficiently low elastic modulus at a high temperature of the cured film may not be obtained, and if it exceeds 200,000, developability may be deteriorated.

  These polymer compounds may be used alone or in combination of two or more in the photosensitive composition described below. As content of the said elastomer contained in total solid content, such as a photosensitive composition, 2-30 mass% is preferable and 5-25 mass% is more preferable. When the content is less than 2% by mass, a sufficiently low elastic modulus at a high temperature of the cured film may not be obtained, and when it exceeds 30% by mass, the developability may deteriorate and the toughness of the cured film may decrease. .

<Synthesis method of elastomer>
As a method for synthesizing the alkali-soluble photocrosslinkable polyurethane resin elastomer of the present invention, the diisocyanate compound of component (A) and the diol compound (mixture of component B, component C and component D) are mixed in an aprotic solvent. It is synthesized by adding a known catalyst having an activity corresponding to the reactivity and heating. The molar ratio of the diisocyanate and diol compound used is preferably 1: 1 to 2: 1. Each component is selected at least one type, but each component may be two or more types.
In the polyurethane production reaction, component A is gradually added to the mixed solution of component B, component C, and component D to react. Even without a catalyst, it is preferable to use a catalyst to promote the reaction, and the amount of the catalyst used is preferably 0.1 to 10% by mass with respect to the reaction product. Examples of the catalyst used include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octoate, and zirconium octoate. And tin-based catalysts such as dibutyltin dilaurate.

From the viewpoint of the electrical characteristics of the cured product obtained by irradiating the photosensitive composition of the present invention with active energy rays, this reaction is preferably carried out without using an organometallic catalyst. The reaction temperature is preferably 40 to 120 ° C., and the reaction time is appropriately determined by monitoring the infrared absorption spectrum described later, but is preferably 5 to 60 hours. In this case, a thermal polymerization inhibitor may be used.
Examples of the thermal polymerization inhibitor include hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, diphenylpicrylhydrazine, diphenylamine, and 2,6-di-tert-butyl-p-cresol.
In the urethanization reaction, the end point is the time when the absorption based on the isocyanate group in the vicinity of 2250 cm ⁻¹ in the infrared absorption spectrum of the reaction solution disappears.
Carboxylic acid group-containing diol (component B) is preferably added so that the solid content acid value of the alkali-soluble photocrosslinkable polyurethane resin of the present invention is 20 to 70 mgKOH / g. . If the solid content acid value is less than 20 mgKOH / g, the solubility in an alkaline aqueous solution is insufficient, and if patterning is performed, there is a possibility that the residue will remain as a residue or, in the worst case, patterning may not be possible. On the other hand, when the solid content acid value exceeds 70 mgKOH / g, the solubility in an alkaline aqueous solution becomes too high, and the development latitude of a photocured pattern may become too narrow, which is not preferable.

  In the urethanization reaction, the diisocyanate (component A) is in a mixture of a carboxylic acid group-containing diol (component B), an epoxy acrylate compound (component C), and a polymer diol (component D) with respect to the isocyanate group of the diisocyanate (component A). The ratio of the equivalents of hydroxyl groups, ie, the ratio of (number of moles of component B + number of moles of component C + number of moles of component D) / (number of moles of component A) is in the range of 1.0 to 2.0. It is preferable to charge as follows. If the ratio value is less than 1.0, isocyanate will remain at the end of the alkali-soluble photocrosslinkable polyurethane elastomer of the present invention, and the thermal stability is low, which may cause gelation during storage. Absent. On the other hand, when this value exceeds 2, the molecular weight of the alkali-soluble photocrosslinkable polyurethane resin is lowered, which may cause a problem of tackiness of the cured product and a problem of low sensitivity to active energy rays during curing. is there.

When the obtained alkali-soluble photocrosslinkable polyurethane resin of the present invention is produced using a solvent, it may be isolated and used by removing it by an appropriate method, but as a photosensitive permanent resist composition You may use as a liquid agent, without removing a solvent.
The alkali-soluble photocrosslinkable polyurethane elastomer used in the present invention is naturally soluble in an alkaline aqueous solution, but is also soluble in an organic solvent that can be used in the production described above, and is used as a solder resist, a plating resist, or the like. It is also possible to develop with a solvent.

  The elastomer of the present invention can provide a high-performance cured film excellent in heat resistance, heat and humidity resistance, adhesion, mechanical properties, and electrical properties. Photosensitive solder resist, interlayer insulating film for printed circuit boards, color resist for color filters Also suitable for use in photosensitive lithographic printing plates, various protective films, planarizing films, photoresists for etching and plating, photosensitive pastes, holograms, microlenses, UV curable inks, UV curable paints, etc. .

(Photosensitive composition)
The photosensitive composition of the present invention contains the alkali-soluble photocrosslinkable elastomer of the present invention, a polymerizable compound, a photopolymerization initiator, a thermal crosslinking agent, a colorant, and a thermosetting accelerator. It contains an inorganic filler and other components appropriately selected as necessary.

The thermal crosslinking agent is preferably one of an epoxy resin and a polyfunctional oxetane compound.
The thermosetting accelerator is preferably an epoxy thermosetting accelerator or an oxetane thermosetting accelerator.
Moreover, as a preferable composition of the photosensitive composition of this invention, (1) 15-70 mass% of said alkali-soluble photocrosslinkable polyurethane elastomers of this invention, and (2) polymeric compound 5-75 in a total solid. Mass%, (3) photopolymerization initiator 0.5 to 20 mass%, (4) epoxy resin and / or polyfunctional oxetane compound 2 to 50 mass%, (5) inorganic filler 5 to 75 mass%, (6 ) Colorant 0.1 to 10% by mass, (7) Epoxy or oxetane thermosetting accelerator 0.01 to 20% by mass, and (8) Organic solvent so that the total solids concentration is 10 to 90% by mass. The thing containing these can be mentioned suitably.

  According to the photosensitive composition of the present invention, it is possible to obtain a solder resist having excellent aqueous alkali developability, good adhesion to the wiring conductor layer and the insulating layer, and excellent reliability.

<Alkali-soluble photocrosslinkable resin>
In the photosensitive composition of the present invention, other alkali-soluble photocrosslinkable resins known in the art can be mixed and used together with the alkali-soluble photocrosslinkable polyurethane elastomer of the present invention.
The other alkali-soluble photocrosslinkable resin is a resin soluble in a 1% sodium carbonate aqueous solution (pH = 10) containing an alkali-soluble group and a crosslinkable group involved in photopolymerization in the molecule.

The other alkali-soluble photocrosslinkable resins are roughly classified into (A) vinyl polymer type and (B) epoxy resin ester type, and (A) is further divided into types (A-1) to (A-3). Can be classified.
(A) Vinyl polymer type photocrosslinkable resin (A) Vinyl polymer type photocrosslinkable resin used for this invention is chosen from the group of the following types (A-1)-(A-3).
Type (A-1): produced by reaction of (a) a carboxyl group-containing copolymer resin and (b) an epoxy group-containing unsaturated compound.
Type (A-2): (c) An epoxy group-containing copolymer resin and (d) a carboxyl group-containing unsaturated compound are subjected to an addition reaction, and (e) a polybasic acid anhydride is converted into a hydroxyl group of the resulting product. Produced by addition reaction.
Type (A-3): produced by addition reaction of (f) an acid anhydride group-containing copolymer resin and (g) a compound having one hydroxyl group and at least one (meth) acryloyl group in the molecule. The
In the present specification, (meth) acrylate is a generic term for acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.

<Type (A-1)>
-(A) carboxyl group-containing copolymer resin-
The (a) carboxyl group-containing copolymer resin used for the production of the vinyl polymer type photocrosslinkable resin of the type (A-1) is one unsaturated group and at least one carboxyl group in one molecule or It is obtained by copolymerizing a compound having an acid anhydride group and at least one of (meth) acrylic acid ester and styrenes.

  The compound (a) having one unsaturated group and at least one carboxyl group or acid anhydride group in one molecule constituting the carboxyl group-containing copolymer resin is (meth) acrylic acid, Include those containing two or more carboxyl groups in the molecule, such as maleic acid and itaconic acid. Also included are maleic acid, itaconic acid monoesters, or monoamides. Moreover, the half ester compound which is a reaction product of a hydroxyl group containing (meth) acrylate and a saturated or unsaturated dibasic acid anhydride is mentioned. These half ester compounds can be obtained by reacting a hydroxyl group-containing (meth) acrylate with a saturated or unsaturated dibasic acid anhydride in an equimolar ratio.

  Examples of the hydroxyl group-containing acrylate used in the synthesis of the half ester compound include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, and trimethylolpropane. Examples thereof include di (meth) acrylate, pendaerythritol tri (meth) acrylate, diventaerythritol penta (meth) acrylate, and the like.

Examples of the saturated or unsaturated dibasic acid anhydride used in the synthesis of the half ester compound include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyl nadrahydrophthalic anhydride, ethyl tetrahydro Examples thereof include phthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, itaconic anhydride, and the like. Among these, (meth) acrylic acid is preferable.
These compounds having one unsaturated group and at least one carboxyl group or acid anhydride group in one molecule may be used alone or in combination of two or more.

  Examples of the (meth) acrylic acid ester that constitutes the structural unit of the carboxyl group-containing copolymer resin include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and isopropyl (meth). Acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) Acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, benzyl (meth) ) Acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, diethylene glycol monophenyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, Polyethylene glycol monomethyl ether (meth) acrylate, polyethylene glycol monoethyl ether (meth) acrylate , Β-phenoxyethoxyethyl acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, trifluoroethyl (meth) Examples include acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, tribromophenyl (meth) acrylate, and tribromophenyloxyethyl (meth) acrylate.

Examples of the styrenes constituting the structural unit of the carboxyl group-containing copolymer resin (a) include, for example, styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, hydroxystyrene, methoxystyrene, Butoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethylstyrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (for example, t-Boc, etc.), methyl vinylbenzoate, α-methyl Examples include styrene.
The (a) carboxyl group-containing copolymer resin is a compound having one unsaturated group and at least one carboxyl group or acid anhydride group in one molecule, a (meth) acrylic acid ester monomer, and styrenes. It can be obtained by copolymerization with at least one of the above by a usual copolymerization method, for example, solution polymerization method.
(A) Maleic acid monoester / styrene copolymers, maleic acid monoamide / styrene copolymers, itaconic acid monoester / styrene copolymers, and itaconic acid monoamide, which are included in the (a) carboxyl group-containing copolymer resin / Styrene copolymers can be obtained by polymer reaction of maleic anhydride / styrene copolymers or itaconic anhydride / styrene copolymers with alcohols or primary or secondary amines, respectively. .
Examples of the alcohols used for the polymer reaction with the maleic anhydride include methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, t-butanol, pentanol, hexanol, cyclohexanol, and methoxy. Preferable examples include ethanol, ethoxyethanol, methoxypropanol, and ethoxypropanol.
Examples of the primary amines include benzylamine, phenethylamine, 3-phenyl-1-propylamine, 4-phenyl-1-butylamine, 5-phenyl-1-pentylamine, and 6-phenyl-1-hexylamine. , Α-methylbenzylamine, 2-methylbenzylamine, 3-methylbenzylamine, 4-methylbenzylamine, 2- (p-tolyl) ethylamine, β-methylphenethylamine, 1-methyl-3-phenylpropylamine, 2- Chlorobenzylamine, 3-chlorobenzylamine, 4-chlorobenzylamine, 2-fluorobenzylamine, 3-fluorobenzylamine, 4-fluorobenzylamine, 4-bromophenethylamine, 2- (2-chlorophenyl) ethylamine, 2- (3-Chlorophenyl) ethyl Amine, 2- (4-chlorophenyl) ethylamine, 2- (2-fluorophenyl) ethylamine, 2- (3-fluorophenyl) ethylamine, 2- (4-fluorophenyl) ethylamine, 4-fluoro-α, α-dimethyl Phenethylamine, 2-methoxybenzylamine, 3-methoxybenzylamine, 4-methoxybenzylamine, 2-ethoxybenzylamine, 2-methoxyphenethylamine, 3-methoxyphenethylamine, 4-methoxyphenethylamine, methylamine, ethylamine, isopropylamine, n -Propylamine, n-butylamine, t-butylamine, sec-butylamine, pentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, laurylamine, phenylamine, 1-naphth Tylamine, methoxymethylamine, 2-methoxyethylamine, 2-ethoxyethylamine, 3-methoxypropylamine, 2-butoxyethylamine, 2-cyclohexyloxyethylamine, 3-ethoxypropylamine, 3-propoxypropylamine, 3-iso Propoxypropylamine and the like are preferred.
Further, examples of the secondary amines preferably include dimethylamine, diethylamine, methylethylamine, methylpropylamine, diethylamine, ethylpropylamine, dipropylamine, dibutylamine, N, N-methylbenzylamine and the like. Can do.

-(B) Epoxy group-containing unsaturated compound-
The (b) epoxy group-containing unsaturated compound used for the production of the vinyl polymer type photocrosslinkable resin of the type (A-1) includes one radical polymerizable unsaturated group and an epoxy group in one molecule. And glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth) acrylate are preferable.

<Type (A-2)>
-(C) Epoxy group-containing copolymer resin-
The (c) epoxy group-containing copolymer resin used for the production of the photocrosslinkable resin of the type (A-2) is an epoxy group-containing monomer and a non-reactive (meth) acrylic ester with an epoxy group. It can be obtained by copolymerization with at least one of styrenes.
As the epoxy group-containing monomer, the compounds described above in the description of the vinyl polymer type photocrosslinkable resin of the type (A-1) are preferably used.
At least one of the epoxy group and non-reactive (meth) acrylic acid ester and styrene is a carboxyl group or an alcoholic hydroxyl group among those already described in the type A-1 vinyl polymer photocrosslinkable resin. In addition, those which do not contain a phenolic hydroxyl group or amino group are preferably used.
The production method is obtained by copolymerizing an epoxy group-containing monomer, a non-reactive (meth) acrylic acid ester and styrenes with a conventional method such as a solution polymerization method.
Here, the molar ratio between the epoxy group-containing monomer and at least one of (meth) acrylic ester and styrenes that are non-reactive with other epoxy groups is preferably 60:40 to 20:80. If the amount of the epoxy group-containing monomer is too small and the molar ratio is larger than 20:80, the amount of addition of the next unsaturated carboxylic acid and polybasic acid anhydride to the copolymer is reduced. If the molar ratio is less than 60:40, the softening point tends to be too low.

-(D) Carboxyl group-containing unsaturated compound-
In the description of the vinyl polymer type photocrosslinkable resin of type (A-1), the above (d) carboxyl group-containing unsaturated compound is one unsaturated group and at least one carboxyl group or acid anhydride in one molecule. Each compound described above can be suitably used as the compound having a physical group.
-(E) Polybasic acid anhydride-
(E) As the polybasic acid anhydride, maleic anhydride, succinic anhydride, hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 3-ethylhexahydrophthalic anhydride, 4-ethylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, 3-ethyltetrahydrophthalic acid Saturated or unsaturated aliphatic, alicyclic or aromatic compounds having one acid anhydride group in the molecule, such as anhydride, 4-ethyltetrahydrophthalic anhydride, phthalic anhydride, etc. are preferably used It is done. Among these, tetrahydrophthalic anhydride is particularly preferably used.
The reaction of the epoxy group-containing copolymer, the carboxyl group-containing unsaturated compound and the subsequent polybasic acid anhydride is preferably carried out as follows. After addition reaction of 0.8 to 1.2 mol of unsaturated carboxylic acid per one epoxy group equivalent of the copolymer to the epoxy group-containing monomer copolymer, Polybasic acid anhydride is subjected to addition reaction.

<Type (A-3)>
-(F) Acid anhydride group-containing resin-
The (f) acid anhydride group-containing resin used for the production of the vinyl polymer type photocrosslinkable resin of the type (A-3) is a copolymer of maleic anhydride and styrene or itaconic anhydride and styrene. Can be obtained by copolymerization.
As the styrene as the copolymer component, those described above in the description of the vinyl polymer type photocrosslinkable resin of type (A-1) are preferably used. The copolymer composition ratio of maleic anhydride or itaconic anhydride and styrene is preferably 90:10 to 10:90, more preferably 80:20 to 20:80, and particularly preferably 70:30 to 30:70. preferable. When the composition ratio is 90:10 or more, the development resistance of the cured portion may be inferior, and when it is 10:90 or less, the developability may be inferior.
A copolymer having a weight average molecular weight of about 1,000 to 5,000 obtained by copolymerizing styrene at a ratio of 1 to 3 moles with respect to 1 mole of maleic anhydride is particularly preferable. For example, ARCO Chemical Examples thereof include SMA ranges 1000, 2000, 3000 manufactured by the company.

-(G) Compound having one hydroxyl group and at least one (meth) acryloyl group in the molecule-
Examples of the compound (g) having one hydroxyl group and at least one (meth) acryloyl group in the molecule include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2- Hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polycaprolactone mono (meth) acrylate, pendaerythritol tri (meth) acrylate, trimethylolpropane di (meth) acrylate, neopentyl Glycol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, mono (2- (meth) acryloyloxyethyl) acid phosphate, di (2- (meth) acryloyloxyethyl) acid phosphate, glycero Di (meth) acrylate.

The ring-opening addition reaction of the acid anhydride copolymer and a monomer having one hydroxyl group and at least one (meth) acryloyl group in the molecule is carried out in an organic solvent containing no active hydrogen. It can be manufactured by the method. Preferred examples of the organic solvent include ethyl acetate, methoxypropyl acetate, and methyl ethyl ketone. In this case, the molar ratio of hydroxyl group in the monomer / acid anhydride group in the copolymer is preferably 0.8 to 1.2.
The ring-opening addition reaction is usually performed at 50 to 200 ° C., but it is preferably performed at about 80 to 150 ° C. from the viewpoint of preventing formation of diester and gelation. As reaction accelerators, tertiary amines such as triethylamine, triethanolamine, morpholine, pentamethyldiethylenetriamine, or quaternary ammonium salts can be used. On the other hand, from the viewpoint of preventing formation of a polymer during the reaction, a known polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, t-butylhydroquinone, t-butylcatechol, benzoquinone, and phenothiazine can be added and used. .

The vinyl polymer photocrosslinkable resin comprising at least one of types (A-1), (A-2) and (A-3) obtained as described above has an acid value of 50 to 250 mgKOH / It must be in the range of g.
As said acid value, 70-200 mgKOH / g is more preferable, and 90-180 mgKOH / g is especially preferable. When the acid value is less than 50 mgKOH / g, it may be difficult to remove the unexposed portion with a developer that is a weakly alkaline aqueous solution. On the other hand, when the acid value exceeds 250 mgKOH / g, May cause problems such as inferiority.
Moreover, as a weight average molecular weight of (A) vinyl polymer type photocrosslinkable resin, what exists in the range of 5,000-200,000 is preferable. The weight average molecular weight is more preferably 10,000 to 100,000, and particularly preferably 30,000 to 80,000. When the weight average molecular weight is less than 5,000, the dryness to touch is remarkably inferior, and the peelability from the support may be inferior. On the other hand, if the weight average molecular weight exceeds 200,000, problems such as removability of unexposed areas by an alkaline developer and storage stability may be caused.

(B) Epoxy resin ester-type photocrosslinkable resin (B) Epoxy resin ester-type photocrosslinkable resin of the present invention is not particularly limited and may be appropriately selected depending on the purpose. For example, (h) epoxy (J) A polybasic acid anhydride is further reacted with an esterification reaction product of a resin and (i) a compound having one unsaturated group and at least one carboxyl group or acid anhydride group in one molecule. To generate.
-(H) Epoxy resin-
Examples of the (h) epoxy resin include YDCN-701, YDCN-704 manufactured by Toto Kasei Co., Ltd .; N-665, N-680, N-695 manufactured by Dainippon Ink & Chemicals, Inc .; Nippon Kayaku Co., Ltd. EOCN-102, EOCN-104 manufactured by Asahi Kasei Kogyo Co., Ltd. ECN-265, ECN-293, ECN-285, ECN-299 and other cresol novolac type epoxy resins, Toto Kasei Co., Ltd. YDPN-638, YDPN -602; Dow Chemical Japan Co., Ltd. DEN-431, DEN-438, DEN-439; Ciba Specialty Chemicals Co., Ltd. EPN-1138, EPN-1235, EPN-1299; Dainippon Ink & Chemicals, Inc. Phenol novolac type epoxy resins such as N-730 and N-770 manufactured by the company may be mentioned. In addition, a part of the novolac type epoxy resin is, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, bixylenol type epoxy resin, trishydroxyphenylmethane type epoxy resin, Epoxy resins such as a tetraphenylethane type epoxy resin, an alicyclic epoxy resin, and a salicylaldehyde type epoxy resin can also be advantageously used.

-(I) Compound having one unsaturated group and at least one carboxyl group or acid anhydride group in one molecule-
Next, as the compound (i) having one unsaturated group and at least one carboxyl group or acid anhydride group in one molecule, the vinyl polymer photocrosslinkable resin of the type (A-1) is used. In the explanation of, each of the compounds described above can be preferably used.
-(J) Polybasic acid anhydride-
As the above-mentioned (j) polybasic acid anhydride, the aforementioned compounds can be used as the component (e) in the description of the vinyl polymer type photocrosslinkable resin of the type (A-2).

<(B) Production method of epoxy resin ester type photocrosslinkable resin>
There is no restriction | limiting in particular as a manufacturing method of said (B) epoxy resin ester type photocrosslinkable resin, According to the objective, it can select suitably, For example, (h) epoxy resin at the time of manufacture, (i) In the reaction of a compound having one unsaturated group and at least one carboxyl group or acid anhydride group in one molecule, (i) for one equivalent of epoxy group of epoxy resin, (i) in one molecule Preferably, the compound having one unsaturated group and at least one carboxyl group or acid anhydride group is reacted at a ratio of 0.8 to 1.05 equivalent, 0.9 to 1.0 equivalent. Is more preferable.
The (h) epoxy resin and (i) a compound having one unsaturated group and at least one carboxyl group or acid anhydride group in one molecule are dissolved in an organic solvent and reacted. Examples of the organic solvent include ketones such as ethyl methyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene, methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, and propylene glycol monomethyl ether. , Glycol ethers such as dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether and triethylene glycol monoethyl ether, esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate and carbitol acetate, aliphatics such as octane and decane Examples include hydrocarbons, petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and petroleum solvents such as solvent naphtha.

Furthermore, it is preferable to use a catalyst to accelerate the reaction. Examples of the catalyst used include triethylamine, benzylmethylamine, methyltriethylammonium chlorite, benzyltrimethylammonium chlorite, benzyltrimethylammonium bromide, benzyltrimethylmethylammonium iodide, triphenylphosphine, and the like. As the usage-amount of the said catalyst, 0.1-10 mass parts is preferable with respect to a total of 100 mass parts of (h) epoxy resin and (j) vinyl group containing monocarboxylic acid.
Further, it is preferable to use a polymerization inhibitor for preventing polymerization during the reaction. Examples of the polymerization inhibitor include hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, and the amount used thereof is the sum of (h) epoxy resin and (j) vinyl group-containing monocarboxylic acid. 0.01-1 mass part is preferable with respect to 100 mass parts. As reaction temperature, 60-150 degreeC is preferable and 80-120 degreeC is more preferable.

  The (B) epoxy resin ester-type photocrosslinkable resin is obtained by reacting the thus obtained reaction product with (j) a polybasic acid anhydride. The reaction temperature between the reaction product and (j) polybasic acid anhydride is preferably 60 to 120 ° C.

By reacting 0.1 to 1.0 equivalent of (j) polybasic acid anhydride with respect to 1 equivalent of hydroxyl group in the reaction product, the acid of the (B) epoxy resin ester type photocrosslinkable resin is obtained. The price can be adjusted. (B) As an acid value of an epoxy resin ester type photocrosslinkable resin, it is preferable that it is 30-150 mgKOH / g, and it is more preferable that it is 50-120 mgKOH / g. When the acid value is less than 30 mg KOH / g, the solubility of the photosensitive composition in a dilute alkali solution may be reduced, and when it exceeds 150 mg KOH / g, the electrical properties of the cured film may be reduced.
The weight average molecular weight of the (B) epoxy resin ester type photocrosslinkable resin is preferably 500 to 5,000, more preferably 1,000 to 4,000, and particularly preferably 1,500 to 3,500. When the weight average molecular weight is less than 500, the tackiness is too high and it may be difficult to peel off the protective film, and when it exceeds 5,000, the production of the resin may be difficult.

The said alkali-soluble photocrosslinkable resin may be used individually by 1 type, and may use 2 or more types together.
The preferable solid content of the alkali-soluble photocrosslinkable resin in the total solid content of the photosensitive composition is preferably 15 to 70% by mass, and if it is less than 15% by mass, the toughness of the cured film is inferior. If it exceeds 70% by mass, the performance balance may deteriorate, such as a decrease in reliability.
In particular, one type from the types (A-1) to (A-3) and one type from the type B are preferable because balanced performance can be imparted. In this case, the mixing ratio is preferably 10/90 to 90/10 in terms of mass ratio (A / B), more preferably 20/80 to 80/20, and particularly preferably 30/70 to 70/30.

<Polymerizable compound>
The polymerizable compound is not particularly limited and may be appropriately selected depending on the purpose. The compound has at least one addition-polymerizable group in the molecule and has a boiling point of 100 ° C. or higher at normal pressure. For example, at least one selected from monomers having a (meth) acryl group is preferable.

  There is no restriction | limiting in particular as a monomer which has the said (meth) acryl group, According to the objective, it can select suitably, For example, polyethyleneglycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) ) Monofunctional acrylates and monofunctional methacrylates such as acrylates; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, trimethylolpropane diacrylate, neopentylglycol di (Meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hex (Meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, Polyfunctional alcohols such as glycerin tri (meth) acrylate, trimethylolpropane, glycerin, bisphenol, and the like, and (meth) acrylated after addition reaction of ethylene oxide or propylene oxide, Japanese Patent Publication No. 48-41708, Japanese Patent Publication Urethane acrylates described in publications such as JP 50-6034 and JP 51-37193; JP 48-64183, JP 49-4319 Polyester acrylates described in various publications such as JP, JP 30-30490, and polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of an epoxy resin and (meth) acrylic acid. It is done. Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are particularly preferable.

  5-75 mass% is preferable and, as for solid content in the said photosensitive composition solid content of the said polymeric compound, 10-40 mass% is more preferable. If the solid content is less than 5% by mass, problems such as deterioration in developability and reduction in exposure sensitivity may occur, and if it exceeds 75% by mass, the adhesiveness of the photosensitive layer may become too strong. Yes, not preferred.

<Photopolymerization initiator>
The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators, for example, visible from the ultraviolet region. Those having photosensitivity to light are preferable, and may be an activator that generates an active radical by causing some action with a photoexcited sensitizer, and initiates cationic polymerization according to the type of monomer. It may be an initiator.
The photopolymerization initiator preferably contains at least one component having a molecular extinction coefficient of at least about 50 within a range of about 300 to 800 nm (more preferably 330 to 500 nm).

  Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, those having an oxadiazole skeleton), phosphine oxide, hexaarylbiimidazole, Examples include oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, and ketoxime ethers.

  Examples of the halogenated hydrocarbon compound having a triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent 1388492, a compound described in JP-A-53-133428, a compound described in German Patent 3337024, F.I. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), compounds described in JP-A-62-258241, compounds described in JP-A-5-281728, compounds described in JP-A-5-34920, US Pat. No. 4,221,976 And the compounds described in the book.

  Wakabayashi et al., Bull. Chem. Soc. As a compound described in Japan, 42, 2924 (1969), for example, 2-phenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-chlorophenyl) -4,6 -Bis (trichloromethyl) -1,3,5-triazine, 2- (4-tolyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxyphenyl)- 4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (2,4-dichlorophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2, 4,6-tris (trichloromethyl) -1,3,5-triazine, 2-methyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2-n-nonyl-4,6- Bis (trichloromethyl) 1,3,5-triazine, and 2-(alpha, alpha, beta-trichloroethyl) -4,6-bis (trichloromethyl) -1,3,5-triazine.

Examples of the compound described in the British Patent 1388492 include 2-styryl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methylstyryl) -4,6- Bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxystyryl)- 4-amino-6-trichloromethyl-1,3,5-triazine and the like can be mentioned.
Examples of the compounds described in JP-A-53-133428 include 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2 -(4-Ethoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl]- 4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -1,3,5- Examples include triazine and 2- (acenaphtho-5-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine.

  Examples of the compound described in the specification of German Patent 3333724 include 2- (4-styrylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- (4 -Methoxystyryl) phenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (1-naphthylvinylenephenyl) -4,6-bis (trichloromethyl) -1,3,5 -Triazine, 2-chlorostyrylphenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-thiophen-2-vinylenephenyl) -4,6-bis (trichloromethyl)- 1,3,5-triazine, 2- (4-thiophene-3-vinylenephenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-furan-2 Vinylenephenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, and 2- (4-benzofuran-2-vinylenephenyl) -4,6-bis (trichloromethyl) -1,3 5-triazine etc. are mentioned.

  F. above. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964) include, for example, 2-methyl-4,6-bis (tribromomethyl) -1,3,5-triazine, 2,4,6-tris (tribromomethyl); -1,3,5-triazine, 2,4,6-tris (dibromomethyl) -1,3,5-triazine, 2-amino-4-methyl-6-tri (bromomethyl) -1,3,5- Examples include triazine and 2-methoxy-4-methyl-6-trichloromethyl-1,3,5-triazine.

  Examples of the compounds described in JP-A-62-258241 include 2- (4-phenylethynylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- Naphthyl-1-ethynylphenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- (4-tolylethynyl) phenyl) -4,6-bis (trichloromethyl) -1 , 3,5-triazine, 2- (4- (4-methoxyphenyl) ethynylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- (4-isopropylphenyl) Ethynyl) phenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- (4-ethylphenylethynyl) phenyl) -4,6-bis (trichloromethyl) Le) -1,3,5-triazine.

  Examples of the compound described in JP-A-5-281728 include 2- (4-trifluoromethylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (2, 6-difluorophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (2,6-dichlorophenyl) -4,6-bis (trichloromethyl) -1,3,5- Examples include triazine, 2- (2,6-dibromophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine.

  Examples of the compound described in JP-A-5-34920 include 2,4-bis (trichloromethyl) -6- [4- (N, N-diethoxycarbonylmethylamino) -3-bromophenyl] -1, 3,5-triazine, trihalomethyl-s-triazine compounds described in US Pat. No. 4,239,850, 2,4,6-tris (trichloromethyl) -s-triazine, 2- (4-chlorophenyl) Examples include -4,6-bis (tribromomethyl) -s-triazine.

  Examples of the compound described in US Pat. No. 4,221,976 include compounds having an oxadiazole skeleton (for example, 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2- Trichloromethyl-5- (4-chlorophenyl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1,3,4-oxadiazole, 2-trichloromethyl-5 -(2-naphthyl) -1,3,4-oxadiazole, 2-tribromomethyl-5-phenyl-1,3,4-oxadiazole, 2-tribromomethyl-5- (2-naphthyl) -1,3,4-oxadiazole; 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (4-chlorostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (4-methoxystyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1, 3,4-oxadiazole, 2-trichloromethyl-5- (4-n-butoxystyryl) -1,3,4-oxadiazole, 2-tripromomethyl-5-styryl-1,3,4 Oxadiazole, etc.).

  Examples of the oxime derivative include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutan-2-one, and 2-acetoxyiminopentane-3-one. 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one, and 2-ethoxy And carbonyloxyimino-1-phenylpropan-1-one.

  In addition, as photopolymerization initiators other than those described above, polyhalogen compounds (for example, 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane, etc.), N-phenylglycine (for example, Carbon tetrabromide, phenyl tribromomethyl sulfone, phenyl trichloromethyl ketone, etc.), coumarins (for example, 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) -7- (1-pyrrolidinyl) ) Coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3′-carbonylbis (5 , 7-di-n-propoxycoumarin), 3,3′-carbo Rubis (7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin, 7-methoxy-3 -(3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, 7-benzotriazol-2-ylcoumarin, JP-A-5-19475, JP-A-7-271028, JP JP-A 2002-363206, JP-A 2002-363207, JP-A 2002-363208, JP-A 2002-363209, and the like, and amines (for example, ethyl 4-dimethylaminobenzoate). 4-dimethylaminobenzoic acid n-butyl, 4-di Phenethyl of dimethylaminobenzoate, phenethyl of 4-dimethylaminobenzoate, 2-methacryloyloxyethyl 4-dimethylaminobenzoate, 2-methacryloyloxyethyl 4-dimethylaminobenzoate, pentadimethylbis (4-dimethylaminobenzoate), pentamethylene Ester, 4-dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, 4-dimethylaminobenzyl alcohol, ethyl (4-dimethylaminobenzoyl) acetate, 4-piperidinoacetophenone, 4-dimethylaminobenzoin, N, N-dimethyl-4-toluidine, N, N-diethyl-3-phenetidine, tribenzylamine, dibenzylphenylamine, N-methyl-N-phenylbenzylamine, 4-bromo-N, N-di Methylaniline, tridodecylamine, aminofluoranes (ODB, ODBII, etc.), crystal violet lactone, leuco crystal violet, etc., acylphosphine oxides (eg bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide) Bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphenylphosphine oxide, Lucirin TPO, etc.), metallocenes (for example, bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, η5-cyclopentadienyl-η6-cumenyl-iron (1 +)-hexafluorophosphate (1-), etc.), special 53-133428 JP, Sho 57-1819, JP-the 57-6096 and JP, US Patent compounds described in the 3,615,455 Patent specification mentioned.

  Examples of the ketone compound include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzolphenone, benzophenonetetracarboxylic acid or tetramethyl ester thereof, 4,4′-bis (dialkylamino) benzophenone (for example, 4,4′-bis (dimethylamino) benzophenone, 4,4′- Bisdicyclohexylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (dihydroxyethylamino) benzophenone, 4-methoxy-4′-dimethylamino Nzophenone, 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, benzyl, anthraquinone, 2-t-butylanthraquinone, 2-methylanthraquinone, phenanthraquinone, xanthone, thioxanthone, 2-chloro -Thioxanthone, 2,4-diethylthioxanthone, fluorenone, 2-benzyl-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino -1-propanone, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer, benzoin, benzoin ethers (for example, benzoin methyl ether, benzoin ethyl ether, In propyl ether, benzoin isopropyl ether, benzoin phenyl ether, benzyl dimethyl ketal), acridone, chloro acridone, N- methyl acridone, N- butyl acridone, N- butyl - such as chloro acrylic pyrrolidone.

  Examples of the hexaarylbiimidazole compound include 2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2′-bisimidazole and 2,2′-bis. (2-Chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) biimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2′- Bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) biimidazole, 2,2′-bis (2, , 6-trichlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) biimidazole, 2,2′-bis (2-cyanophenyl) -4,4 ′, 5.5′-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2′-bis (2-cyanophenyl) -4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) biimidazole, 2,2′-bis (2-methylphenyl) -4,4 ', 5,5'-tetrakis (4-methoxycarbonylphenyl) biimidazole, 2,2'-bis (2-methylphenyl) -4,4', 5,5'-tetrakis 4-ethoxycarbonylphenyl) biimidazole, 2,2′-bis (2-methylphenyl) -4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) biimidazole, 2,2′-bis ( 2-ethylphenyl) -4,4 ′, 5,5′-tetrakis (4-methoxycarbonylphenyl) biimidazole, 2,2′-bis (2-ethylphenyl) -4,4 ′, 5,5′- Tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2′-bis (2-ethylphenyl) -4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) biimidazole, 2,2′- Bis (2-phenylphenyl) -4,4 ′, 5,5′-tetrakis (4-methoxycarbonylphenyl) biimidazole, 2,2′-bis (2-phenyl) Enylphenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2′-bis (2-phenylphenyl) -4,4 ′, 5,5′-tetrakis ( 4-phenoxycarbonylphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4-dichlorophenyl)- 4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2 '-Bis (2-bromophenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,4-dibromophenyl) -4,4 ', 5,5'- Tetrafeni Biimidazole, 2,2′-bis (2,4,6-tribromophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-cyanophenyl) -4 , 4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4-dicyanophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4,6-tricyanophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-methylphenyl) -4,4 ′, 5,5′- Tetraphenylbiimidazole, 2,2′-bis (2,4-dimethylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4,6-trimethylphenyl) ) -4,4 ', 5,5'-tetraphenyl Imidazole, 2,2′-bis (2-ethylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4-diethylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4,6-triethylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2 -Phenylphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,4-diphenylphenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2′-bis (2,4,6-triphenylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole may be mentioned.

The said photoinitiator may be used individually by 1 type, and may use 2 or more types together.
Particularly preferred examples of the photopolymerization initiator include halogenated carbonization having the phosphine oxides, the α-aminoalkyl ketones, and the triazine skeleton, which can handle laser light having a wavelength of 405 nm in the later-described exposure. Examples include a composite photoinitiator, a hexaarylbiimidazole compound, or titanocene, which is a combination of a hydrogen compound and an amine compound as a sensitizer described later.

  As content in the said photosensitive composition of the said photoinitiator, 0.5-20 mass% is preferable, 1-15 mass% is more preferable, 2-10 mass% is especially preferable.

In addition to the photopolymerization initiator, a sensitizer can be added for the purpose of adjusting the exposure sensitivity and the photosensitive wavelength in exposure to the photosensitive layer described later.
The sensitizer can be appropriately selected by a visible light, an ultraviolet laser, a visible light laser or the like as a light irradiation means described later.
The sensitizer is excited by active energy rays and interacts with other substances (eg, radical generator, acid generator, etc.) (eg, energy transfer, electron transfer, etc.) to thereby generate radicals, acids, etc. It is possible to generate a useful group of

  The sensitizer is not particularly limited and may be appropriately selected from known sensitizers. For example, known polynuclear aromatics (for example, pyrene, perylene, triphenylene), xanthenes (for example, Fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (eg, indocarbocyanine, thiacarbocyanine, oxacarbocyanine), merocyanines (eg, merocyanine, carbomerocyanine), thiazines (eg, thionine, methylene blue) , Toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squariums (eg, squalium), acridones (eg, acridone, chloroacrid) N-methylacridone, N-butylacridone, N-butyl-chloroacridone, etc.), coumarins (for example, 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) -7 -(1-pyrrolidinyl) coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3 ′ -Carbonylbis (5,7-di-n-propoxycoumarin), 3,3'-carbonylbis (7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl) -7-diethylamino Coumarin, 3- (4-Diethylaminocinnamoyl) -7-diethylaminocoumarin Examples thereof include 7-methoxy-3- (3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, and others, such as JP-A-5-19475, JP-A-7-271028, No. 2002-363206, JP-A 2002-363207, JP-A 2002-363208, JP-A 2002-363209, and the like.

  Examples of the combination of the photopolymerization initiator and the sensitizer include, for example, an electron transfer start system described in JP-A-2001-305734 [(1) an electron donating initiator and a sensitizing dye, (2) A combination of an electron-accepting initiator and a sensitizing dye, (3) an electron-donating initiator, a sensitizing dye and an electron-accepting initiator (ternary initiation system)], and the like.

  As content of the said sensitizer, 0.05-30 mass% is preferable with respect to all the components in the said photosensitive composition, 0.1-20 mass% is more preferable, 0.2-10 mass% Is particularly preferred. When the content is less than 0.05% by mass, the sensitivity to active energy rays is reduced, the exposure process takes time, and productivity may be reduced. The sensitizer may be precipitated from the photosensitive layer.

<Thermal crosslinking agent>
The thermal crosslinking agent is not particularly limited and may be appropriately selected depending on the purpose. In order to improve the film strength after curing of the photosensitive layer formed using the photosensitive composition, developability For example, an epoxy compound having at least two oxirane groups in one molecule and an oxetane compound having at least two oxetanyl groups in one molecule can be used.
Examples of the epoxy compound having at least two oxirane rings in one molecule include a bixylenol type or biphenol type epoxy resin (“YX4000, manufactured by Japan Epoxy Resin Co., Ltd.”) or a mixture thereof, an isocyanurate skeleton, and the like. Heterocyclic epoxy resins (“TEPIC; manufactured by Nissan Chemical Industries, Ltd.”, “Araldite PT810; manufactured by Ciba Specialty Chemicals”, etc.), bisphenol A type epoxy resin, novolak type epoxy resin, bisphenol F type epoxy resin, hydrogenated Bisphenol A type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, halogenated epoxy resin (for example, low brominated epoxy resin, high halogenated epoxy resin, Hydrogenated phenol novolac type epoxy resin, etc.), allyl group-containing bisphenol A type epoxy resin, trisphenol methane type epoxy resin, diphenyldimethanol type epoxy resin, phenol biphenylene type epoxy resin, dicyclopentadiene type epoxy resin ("HP-7200") , HP-7200H; manufactured by Dainippon Ink & Chemicals, Inc.), glycidylamine type epoxy resins (diaminodiphenylmethane type epoxy resins, diglycidylaniline, triglycidylaminophenol, etc.), glycidyl ester type epoxy resins (diglycidyl phthalate) Ester, adipic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, dimer acid diglycidyl ester, etc.) Hydantoin type epoxy resin, alicyclic epoxy resin (3,4) Epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, dicyclopentadiene diepoxide, “GT-300, GT-400, ZEHPE3150; manufactured by Daicel Chemical Industries”, etc. )), Imide type alicyclic epoxy resin, trihydroxyphenylmethane type epoxy resin, bisphenol A novolak type epoxy resin, tetraphenylolethane type epoxy resin, glycidyl phthalate resin, tetraglycidyl xylenoyl ethane resin, naphthalene group-containing epoxy Resin (naphthol aralkyl type epoxy resin, naphthol novolac type epoxy resin, tetrafunctional naphthalene type epoxy resin, commercially available products “ESN-190, ESN-360; manufactured by Nippon Steel Chemical Co., Ltd.”) "HP-4032, EXA-4750, EXA-4700; manufactured by Dainippon Ink & Chemicals, Inc."), polyphenol compounds obtained by addition reaction of phenol compounds with diolefin compounds such as divinylbenzene and dicyclopentadiene, and epichlorohydrin Reaction product of 4-vinylcyclohexene-1-oxide ring-opened polymer with peracetic acid or the like, epoxy resin having a linear phosphorus-containing structure, epoxy resin having a cyclic phosphorus-containing structure, α-methyl Stilbene liquid crystal epoxy resin, dibenzoyloxybenzene liquid crystal epoxy resin, azophenyl liquid crystal epoxy resin, azomethine phenyl liquid crystal epoxy resin, binaphthyl liquid crystal epoxy resin, azine epoxy resin, glycidyl methacrylate copolymer epoxy resin (“CP − 50S, CP-50M; manufactured by NOF Corporation, etc.), copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate, bis (glycidyloxyphenyl) fluorene type epoxy resin, bis (glycidyloxyphenyl) adamantane type epoxy resin, etc. Although it is mentioned, it is not restricted to these. These epoxy resins may be used individually by 1 type, and may use 2 or more types together.

In addition to the epoxy compound having at least two oxirane rings in one molecule, an epoxy compound containing at least two epoxy groups having an alkyl group at the β-position can be used, and the β-position is an alkyl group. Particularly preferred is a compound containing an epoxy group substituted with a (specifically, a β-alkyl-substituted glycidyl group or the like).
In the epoxy compound containing at least an epoxy group having an alkyl group at the β-position, all of two or more epoxy groups contained in one molecule may be a β-alkyl-substituted glycidyl group, and at least one epoxy group May be a β-alkyl-substituted glycidyl group.

From the viewpoint of storage stability at room temperature, the epoxy compound containing an epoxy group having an alkyl group at the β-position is substituted with β-alkyl in all epoxy groups in the total amount of the epoxy compound contained in the photosensitive composition. The proportion of glycidyl groups is preferably 30% or more, more preferably 40% or more, and particularly preferably 50% or more.
The β-alkyl-substituted glycidyl group is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include β-methylglycidyl group, β-ethylglycidyl group, β-propylglycidyl group, β-butylglycidyl group. Among these, a β-methylglycidyl group is preferred from the viewpoint of improving the storage stability of the photosensitive resin composition and the ease of synthesis.

  As the epoxy compound containing an epoxy group having an alkyl group at the β-position, for example, an epoxy compound derived from a polyhydric phenol compound and a β-alkylepihalohydrin is preferable.

  The β-alkylepihalohydrin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, β-methylepichlorohydrin, β-methylepibromohydrin, β-methylepifluorohydrin, etc. Β-methyl epihalohydrin, β-ethyl epichlorohydrin, β-ethyl epibromohydrin, β-ethyl epihalohydrin, such as β-ethyl epihalohydrin, β-propyl epichlorohydrin, β-propyl epibromohydrin Β-propyl epihalohydrin such as phosphorus and β-propyl epifluorohydrin; β-butyl epihalohydrin such as β-butyl epichlorohydrin, β-butyl epibromohydrin, β-butyl epifluorohydrin; . Among these, β-methylepihalohydrin is preferable from the viewpoint of reactivity with the polyhydric phenol and fluidity.

  The polyhydric phenol compound is not particularly limited as long as it is a compound containing two or more aromatic hydroxyl groups in one molecule, and can be appropriately selected according to the purpose. For example, bisphenol A, bisphenol F Bisphenol compounds such as bisphenol S, biphenol compounds such as biphenol and tetramethylbiphenol, naphthol compounds such as dihydroxynaphthalene and binaphthol, phenol novolac resins such as phenol-formaldehyde polycondensates, cresol-formaldehyde polycondensates 1 1-10 monoalkyl-substituted phenol-formaldehyde polycondensate, xylenol-formaldehyde polycondensate and the like, and C1-C10 dialkyl-substituted phenol-formaldehyde polycondensate, bisphenol A-formalde De polycondensates such bisphenol compounds of - formaldehyde polycondensates, phenol and copolycondensates of monoalkyl-substituted phenol and formaldehyde having 1 to 10 carbon atoms, and phenolic compounds and polyaddition products of divinylbenzene. Among these, when selecting for the purpose of improving fluidity | liquidity and storage stability, the said bisphenol compound is preferable, for example.

Examples of the epoxy compound containing an epoxy group having an alkyl group at the β-position include di-β-alkyl glycidyl ether of bisphenol A, di-β-alkyl glycidyl ether of bisphenol F, and di-β-alkyl glycidyl of bisphenol S. Di-β-alkyl glycidyl ethers of bisphenol compounds such as ethers; di-β-alkyl glycidyl ethers of biphenols such as di-β-alkyl glycidyl ethers of biphenols and di-β-alkyl glycidyl ethers of tetramethylbiphenol; Β-alkyl glycidyl ethers of naphthol compounds such as di-β-alkyl glycidyl ethers of binaphthol, di-β-alkyl glycidyl ethers of binaphthol; poly- of phenol-formaldehyde polycondensates β-alkyl glycidyl ether; poly-β-alkyl glycidyl ether of monoalkyl-substituted phenol-formaldehyde polycondensate having 1 to 10 carbon atoms such as poly-β-alkyl glycidyl ether of cresol-formaldehyde polycondensate; xylenol-formaldehyde C1-C10 dialkyl-substituted phenol-formaldehyde polycondensate poly-β-alkyl glycidyl ether such as poly-β-alkyl glycidyl ether of condensate; poly-β-alkyl glycidyl ether of bisphenol A-formaldehyde polycondensate Bisphenol compound-formaldehyde polycondensate poly-β-alkyl glycidyl ether; phenol compound-divinylbenzene polyaddition product poly-β-alkyl glycidyl ether; The
Among these, a bisphenol compound represented by the following structural formula (i), a β-alkyl glycidyl ether derived from a polymer obtained from the bisphenol compound and epichlorohydrin, and the following structural formula (ii) Poly-β-alkyl glycidyl ethers of phenol compound-formaldehyde polycondensates are preferred.
However, in said structural formula (i), R represents either a hydrogen atom or a C1-C6 alkyl group, and n represents the integer of 0-20.
In the Structural Formula (ii), R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R "represents either hydrogen atoms, and CH _3, n is 0 to 20 Represents an integer.

  These epoxy compounds containing an epoxy group having an alkyl group at the β-position may be used alone or in combination of two or more. It is also possible to use together an epoxy compound having at least two oxirane rings in one molecule and an epoxy compound containing an epoxy group having an alkyl group at the β-position.

  Examples of the oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3-methyl -3-Oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl) In addition to polyfunctional oxetanes such as methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate, oligomers or copolymers thereof, and compounds having an oxetane group , Novolac resin, poly (p-hydroxystyrene), potassium Bisphenols, calixarenes, calixresorcinarenes, ether compounds with hydroxyl group resins such as silsesquioxane, etc. In addition, unsaturated monomers having an oxetane ring and alkyl (meth) acrylates And a copolymer thereof.

Further, in order to promote the thermal curing of the epoxy compound or the oxetane compound, for example, an amine compound (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N , N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (eg, triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (eg, dimethylamine, etc.), imidazole derivatives Cyclic amidine compounds and salts thereof (for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenyl) Midazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, etc.), phosphorus compounds (eg triphenylphosphine etc.), guanamine compounds (eg melamine, guanamine, acetoguanamine, benzoguanamine etc.), S- Triazine derivatives (for example, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric An acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct, etc.) can be used. These may be used alone or in combination of two or more. In addition, there is no restriction | limiting in particular as long as it can accelerate | stimulate the reaction of the said epoxy compound and the said oxetane compound, or these and a carboxyl group, Use the compound which can accelerate | stimulate thermosetting other than the above. Also good.
Solid content in the said photosensitive composition solid content of the said epoxy compound, the said oxetane compound, and the compound which can accelerate | stimulate thermosetting with these and carboxylic acid is 0.01-15 mass% normally.

  Further, as the thermal crosslinking agent, a polyisocyanate compound described in JP-A-5-9407 can be used, and the polyisocyanate compound is aliphatic, cycloaliphatic or aromatic containing at least two isocyanate groups. It may be derived from a group-substituted aliphatic compound. Specifically, bifunctional isocyanate (for example, a mixture of 1,3-phenylene diisocyanate and 1,4-phenylene diisocyanate, 2,4- and 2,6-toluene diisocyanate, 1,3- and 1,4-xylylene). Diisocyanate, bis (4-isocyanate-phenyl) methane, bis (4-isocyanatocyclohexyl) methane, isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, etc.), the bifunctional isocyanate, trimethylolpropane, pentalithol tol Polyfunctional alcohols such as glycerin; alkylene oxide adducts of the polyfunctional alcohols and adducts of the bifunctional isocyanates; hexamethylene diisocyanate, hexamethylene-1,6-di Isocyanate and cyclic trimers thereof derivatives; and the like.

Furthermore, for the purpose of improving the storage stability of the photosensitive composition of the present invention, a compound obtained by reacting a blocking agent with the isocyanate group of the polyisocyanate and its derivative may be used.
Examples of the isocyanate group blocking agent include alcohols (eg, isopropanol, tert.-butanol, etc.), lactams (eg, ε-caprolactam, etc.), phenols (eg, phenol, cresol, p-tert.-butylphenol, p -Sec.-butylphenol, p-sec.-amylphenol, p-octylphenol, p-nonylphenol, etc.), heterocyclic hydroxyl compounds (eg, 3-hydroxypyridine, 8-hydroxyquinoline, etc.), active methylene compounds (eg, Dialkyl malonate, methyl ethyl ketoxime, acetylacetone, alkyl acetoacetate oxime, acetooxime, cyclohexanone oxime, etc.). In addition to these, compounds having at least one polymerizable double bond and at least one blocked isocyanate group in the molecule described in JP-A-6-295060 can be used.

  Moreover, a melamine derivative can be used as the thermal crosslinking agent. Examples of the melamine derivative include methylol melamine, alkylated methylol melamine (a compound obtained by etherifying a methylol group with methyl, ethyl, butyl, or the like). These may be used individually by 1 type and may use 2 or more types together. Among these, alkylated methylol melamine is preferable and hexamethylated methylol melamine is particularly preferable in that it has good storage stability and is effective in improving the surface hardness of the photosensitive layer or the film strength itself of the cured film.

  1-50 mass% is preferable and, as for solid content in the said photosensitive composition solid content of the said thermal crosslinking agent, 3-30 mass% is more preferable. When the solid content is less than 1% by mass, improvement in the film strength of the cured film is not recognized, and when it exceeds 50% by mass, developability and exposure sensitivity may be deteriorated.

<Epoxy or oxetane thermosetting accelerator>
Moreover, in order to accelerate | stimulate the thermosetting of the said epoxy compound or the said polyfunctional oxetane compound, it is preferable to add an epoxy or oxetane thermosetting accelerator. Examples of the epoxy or oxetane thermosetting accelerator include dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N. Amine compounds such as N, dimethylbenzylamine; quaternary ammonium salt compounds such as triethylbenzylammonium chloride; blocked isocyanate compounds such as dimethylamine; imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methyl Imidazole derivatives such as imidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, etc. Bicyclic amidine compounds And salts thereof; phosphorus compounds such as triphenylphosphine; guanamine compounds such as melamine, guanamine, acetoguanamine, benzoguanamine; 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino S-triazine derivatives such as -S-triazine, 2-vinyl-4,6-diamino-S-triazine / isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct Boron trifluoride-amine complex, organic hydrazide, phthalic anhydride, trimellitic anhydride, ethylene glycol bis (anhydrotrimellitate), glycerol tris (anhydrotrimellitate), benzophenone tetracarboxylic anhydride, etc. Aromatic acid anhydride, anhydrous Maleic acid, aliphatic acid anhydrides such as tetrahydrophthalic anhydride, polyvinyl phenol, polyvinyl phenol bromide, phenol novolak, or the like can be used polyphenols such as alkylphenol novolaks. These may be used alone or in combination of two or more. The epoxy compound or the polyfunctional oxetane compound may be a curing catalyst, or any compound capable of promoting the reaction of the carboxyl group with these, and any compound capable of promoting thermal curing other than those described above. It may be used.

  The solid content in the total solid content of the photosensitive composition of the epoxy compound and / or the compound capable of promoting the thermosetting reaction of the polyfunctional oxetane compound and carboxylic acid is usually 0.01 to 20% by mass. It is. If it is 0.01% by mass or less, the curing promoting ability is insufficient, and if it exceeds 20% by mass, the storage stability of the photosensitive composition is deteriorated.

<Inorganic filler>
The photosensitive composition of the present invention has the purpose of improving the surface hardness of the permanent pattern or keeping the coefficient of linear expansion low, or keeping the dielectric constant or dielectric loss tangent of the cured film low, as necessary. Inorganic fillers can be added.
The inorganic filler is not particularly limited and can be appropriately selected from known ones. For example, kaolin, barium sulfate, barium titanate, silicon oxide powder, finely divided silicon oxide, vapor-phase process silica, none Examples include regular silica, crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, and mica.
The average particle size of the inorganic filler is preferably less than 3 μm, more preferably 0.1 to 2 μm. If the average particle size is 3 μm or more, the resolution may deteriorate due to light scattering.
5-75 mass% is preferable, as for the addition amount of the said inorganic filler, 8-70 mass% is more preferable, and 10-60 mass% is especially preferable. If the addition amount is less than 5% by mass, the coefficient of linear expansion may not be sufficiently reduced. If the addition amount exceeds 75% by mass, when the cured film is formed on the surface of the photosensitive layer, The film quality becomes fragile, and when a wiring is formed using a permanent pattern, the function of the wiring as a protective film may be impaired.

Further, organic fine particles can be added as necessary. Suitable organic fine particles are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include melamine resin, benzoguanamine resin, and crosslinked polystyrene resin. Further, silica having an average particle size of 0.1 to ² μm and an oil absorption of about 100 to 200 m ² / g, spherical porous fine particles made of a crosslinked resin, and the like can be used.

<Colorant>
There is no restriction | limiting in particular as said coloring agent, The dye suitably selected from the coloring pigment and the well-known dye as needed can be used as needed.

  There is no restriction | limiting in particular as said coloring pigment, According to the objective, it can select suitably, For example, Victoria pure blue BO (CI. 42595), auramine (CI. 41000), fat black HB (CI. 26150), Monolite Yellow GT (CI Pigment Yellow 12), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow HR). Yellow 83), Permanent Carmine FBB (CI Pigment Red 146), Hoster Balm Red ESB (CI Pigment Violet 19), Permanent Ruby FBH (CI Pigment Red 11) Fastel Pink B Supra (CI Pigment Red 81) Monastral Fa Strike Blue (C.I. Pigment Blue 15), mono Light Fast Black B (C.I. Pigment Black 1), carbon, C. I. Pigment red 97, C.I. I. Pigment red 122, C.I. I. Pigment red 149, C.I. I. Pigment red 168, C.I. I. Pigment red 177, C.I. I. Pigment red 180, C.I. I. Pigment red 192, C.I. I. Pigment red 215, C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 22, C.I. I. Pigment blue 60, C.I. I. Pigment blue 64 and the like. These may be used alone or in combination of two or more.

  The solid content of the colored pigment in the total solid content of the photosensitive composition can be determined in consideration of the exposure sensitivity, resolution, etc. of the photosensitive layer during permanent pattern formation. Generally, 0.1 to 10% by mass is preferable, and 0.5 to 8% by mass is more preferable. When the content is less than 0.1% by mass, the degree of coloring may not be sufficient. When the content exceeds 10% by mass, the photosensitivity may be lowered and the defect inspection property of the cured film may be inferior.

<Adhesion promoter>
Examples of the adhesion promoter include melamine, acetoguanamine, benzoguanamine, melamine-phenol formalin resin, ethyldiamino-S-triazine, 2,4-diamino-S-triazine, 2,4-diamino-6-xylyl-S-triazine, etc. A triazine compound is mentioned. Commercially available triazine compounds include Shikoku Kasei Kogyo Co., Ltd. shown in the following structural formulas (E) to (G); 2MZ-AZINE (structural formula (E)), 2E4MZ-AZINE (structural formula (F)), CllZ -AZINE (Structural Formula (G)) and the like can be given.

  These compounds increase adhesion to copper wiring, improve PCT resistance, and are effective in resistance to electrolytic corrosion. These can be used alone or in combination of two or more. As a compounding quantity of an adhesion promoter, 0.1-40 mass% is preferable with respect to the total solid of a photosensitive composition, and 0.1-20 mass% is more preferable. If the blending amount is less than 0.1% by mass, the adhesion promoting function may not be exhibited, and if it exceeds 40% by mass, the developability may be adversely affected.

<Thermal polymerization inhibitor>
For the purpose of improving the storage stability of the photosensitive composition of the present invention, known polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, tert-butylcatechol, pyrogallol, and phenothiazine can be added.

<Other additives>
The other additive is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include thixotropic agents such as benton, montmorillonite, aerosol, amide wax, silicone-based, fluorine-based, and polymer-based. Additives such as antifoaming agents and leveling agents can be used.

(Photosensitive film)
Although the photosensitive composition of this invention can be used also as a liquid resist by apply | coating and drying on the board | substrate with which the conductor wiring was formed, it is especially useful for manufacture of the photosensitive film.
As shown in FIG. 1, the photosensitive film has at least a support 1 and a photosensitive layer 2, preferably a protective film 3, and, if necessary, a cushion layer, oxygen It has other layers such as a blocking layer (hereinafter abbreviated as PC layer).
The form of the photosensitive film is not particularly limited and can be appropriately selected according to the purpose. For example, the photosensitive layer and the protective film on the support in this order, The PC layer, the photosensitive layer, and the protective film are provided in this order on the support, and the cushion layer, the PC layer, the photosensitive layer, and the protective film are provided on the support. The form etc. which have in order are mentioned. The photosensitive layer may be a single layer or a plurality of layers.

-Support-
The support is not particularly limited and may be appropriately selected depending on the intended purpose. It is preferable that the photosensitive layer can be peeled off and has good light transmittance, and further has a smooth surface. It is more preferable that it is good.

The support is preferably made of a synthetic resin and transparent, for example, polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, poly (meth) acrylic acid alkyl ester, poly ( (Meth) acrylic acid ester copolymer, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide, polyimide, vinyl chloride / vinyl acetate copolymer, polytetrafluoroethylene, polytrifluoro Various plastic films such as ethylene, cellulose-based film, nylon film and the like can be mentioned, and among these, polyethylene terephthalate is particularly preferable. These may be used alone or in combination of two or more.
As the support, for example, the support described in JP-A-4-208940, JP-A-5-80503, JP-A-5-173320, JP-A-5-72724, or the like is used. You can also.

There is no restriction | limiting in particular as thickness of the said support body, According to the objective, it can select suitably, For example, 4-300 micrometers is preferable and 5-175 micrometers is more preferable.
There is no restriction | limiting in particular as a shape of the said support body, According to the objective, it can select suitably, A long shape is preferable. There is no restriction | limiting in particular as the length of the said elongate support body, For example, the thing of the length of 10m-20,000m is mentioned.

(Photosensitive layer)
The layer is formed by the photosensitive composition of the present invention.
There is no restriction | limiting in particular as a location provided in the said photosensitive film of the said photosensitive layer, Although it can select suitably according to the objective, Usually, it laminates | stacks on the said support body.
In the exposure process described later, the photosensitive layer modulates the light from the light irradiating means by means of a light modulating means having n picture element portions that receive and emit light from the light irradiating means, and then It is preferable that exposure is performed with light passing through a microlens array in which microlenses having aspherical surfaces capable of correcting aberration due to distortion of the exit surface at the portion are arranged.

  There is no restriction | limiting in particular as thickness of the said photosensitive layer, Although it can select suitably according to the objective, For example, 3-100 micrometers is preferable and 5-70 micrometers is more preferable.

As a method for forming the photosensitive layer, a photosensitive composition solution is prepared by dissolving, emulsifying or dispersing the photosensitive composition of the present invention in water or a solvent on the support, and the solution is directly applied to the photosensitive layer. The method of laminating | stacking by apply | coating and drying is mentioned.
There is no restriction | limiting in particular as a solvent of the said photosensitive composition solution, According to the objective, it can select suitably, For example, methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, n-hexanol Alcohols such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone, etc .; ethyl acetate, butyl acetate, n-amyl acetate, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate, and Esters such as methoxypropyl acetate; aromatic hydrocarbons such as toluene, xylene, benzene, ethylbenzene; carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, methylene chloride, monochlorobenzene Halogenated hydrocarbons of: ethers such as tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 1-methoxy-2-propanol; dimethylformamide, dimethylacetamide, dimethylsulfoxide, sulfolane, etc. . These may be used alone or in combination of two or more. Moreover, you may add a well-known surfactant. Particularly preferred solvents include methyl ethyl ketone, methoxypropyl acetate and mixed solvents thereof.
The solid concentration of the coating solution is preferably 10 to 90% by mass, and more preferably 15 to 50% by mass for producing a photosensitive layer for a photosensitive film having a thickness of 20 to 50 μm.

The coating method is not particularly limited and can be appropriately selected depending on the purpose. For example, using a spin coater, a slit spin coater, a roll coater, a die coater, a curtain coater, or the like, it is directly applied to the support. The method of apply | coating is mentioned.
The drying conditions vary depending on each component, the type of solvent, the use ratio, and the like, but are usually about 60 to 110 ° C. for about 30 seconds to 15 minutes.

〔Protective film〕
The protective film has a function of preventing and protecting the photosensitive layer from being stained and damaged.
There is no restriction | limiting in particular as a location provided in the said photosensitive film of the said protective film, Although it can select suitably according to the objective, Usually, it is provided on the said photosensitive layer.
Examples of the protective film include those used for the support, silicone paper, polyethylene, paper laminated with polypropylene, polyolefin or polytetrafluoroethylene sheet, etc. Among these, polyethylene film, Polypropylene film is preferred.
There is no restriction | limiting in particular as thickness of the said protective film, Although it can select suitably according to the objective, For example, 5-100 micrometers is preferable and 8-30 micrometers is more preferable.

When the protective film is used, it is preferable that the adhesive force A between the photosensitive layer and the support and the adhesive force B between the photosensitive layer and the protective film satisfy the relationship of adhesive force A> adhesive force B.
When the protective film is used, it is preferable that the adhesive force A between the photosensitive layer and the support and the adhesive force B between the photosensitive layer and the protective film satisfy the relationship of adhesive force A> adhesive force B.
Examples of the combination of the support and the protective film (support / protective film) include polyethylene terephthalate / polypropylene, polyethylene terephthalate / polyethylene, polyvinyl chloride / cellophane, polyimide / polypropylene, polyethylene terephthalate / polyethylene terephthalate, and the like. . Moreover, the relationship of the above adhesive forces can be satisfy | filled by surface-treating at least any one of a support body and a protective film. The surface treatment of the support may be performed in order to increase the adhesive force with the photosensitive layer. For example, coating of a primer layer, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency irradiation treatment, glow treatment Examples thereof include a discharge irradiation process, an active plasma irradiation process, and a laser beam irradiation process.

Moreover, as a static friction coefficient of the said support body and the said protective film, 0.3-1.4 are preferable and 0.5-1.2 are more preferable.
When the coefficient of static friction is less than 0.3, slipping is excessive, so that winding deviation may occur when the roll is formed. Sometimes.

  The photosensitive film is preferably stored, for example, wound around a cylindrical core, wound in a long roll shape. There is no restriction | limiting in particular as the length of the said elongate photosensitive film, For example, it can select suitably from the range of 10m-20,000m. Further, slitting may be performed so that the user can easily use, and a long body in the range of 100 m to 1,000 m may be formed into a roll. In this case, it is preferable that the support is wound up so as to be the outermost side. Moreover, you may slit the said roll-shaped photosensitive film in a sheet form. When storing, from the viewpoint of protecting the end face and preventing edge fusion, it is preferable to install a separator (particularly moisture-proof and containing a desiccant) on the end face, and use a low moisture-permeable material for packaging. Is preferred.

The protective film may be surface-treated in order to adjust the adhesion between the protective film and the photosensitive layer. In the surface treatment, for example, an undercoat layer made of a polymer such as polyorganosiloxane, fluorinated polyolefin, polyfluoroethylene, or polyvinyl alcohol is formed on the surface of the protective film. The undercoat layer can be formed by applying the polymer coating solution to the surface of the protective film and then drying at 30 to 150 ° C. (especially 50 to 120 ° C.) for 1 to 30 minutes.
In addition to the photosensitive layer, the support, and the protective film, a cushion layer, an oxygen blocking layer (PC layer), a release layer, an adhesive layer, a light absorption layer, a surface protective layer, and the like may be included. .
The cushion layer is a layer that has no tackiness at room temperature and melts and flows when laminated under vacuum and heating conditions.
The PC layer is usually a film of about 1.5 μm formed mainly of polyvinyl alcohol.
The photosensitive film of the present invention has a small surface tack, good laminating and handling properties, excellent storage stability, and excellent chemical resistance, surface hardness, heat resistance and the like after development. It has a photosensitive layer on which objects are laminated. For this reason, it can be widely used for the formation of permanent patterns such as printed wiring boards, color filters, pillar materials, rib materials, spacers, partition walls, holograms, micromachines, proofs, and the like. It can be suitably used for the forming method.
In particular, since the thickness of the photosensitive film of the present invention is uniform, lamination to a substrate is performed more finely when forming a permanent pattern.

(Permanent pattern and permanent pattern forming method)
The permanent pattern of the present invention is obtained by the permanent pattern forming method of the present invention.
The permanent pattern is preferably at least one of a protective film, an interlayer insulating film, and a solder resist pattern.
In the method for forming a permanent pattern of the present invention, as a first embodiment, the photosensitive composition of the present invention is applied to the surface of a substrate, dried to form a photosensitive layer, and then exposed and developed.
In addition, in the method for forming a permanent pattern of the present invention, as a second aspect, the photosensitive film of the present invention is laminated on the surface of the substrate under at least one of heating and pressing, and then exposed and developed. .
Hereinafter, the details of the permanent pattern of the present invention will be clarified through the description of the method for forming a permanent pattern of the present invention.

〔Base material〕
The base material is not particularly limited, and can be appropriately selected from known materials having high surface smoothness to those having an uneven surface. A plate-shaped base material (substrate) is preferable, Specific examples include known printed wiring board forming substrates (for example, copper-clad laminates), glass plates (for example, soda glass plates), synthetic resin films, paper, metal plates, and the like. Among them, the printed wiring board forming substrate is preferable, and the printed wiring board forming substrate has already been formed in that it enables high-density mounting of a semiconductor or the like on a multilayer wiring board or a build-up wiring board. Is particularly preferred.

  The base material is a laminate in which a photosensitive layer made of the photosensitive composition is formed on the base material as the first aspect, or the photosensitive layer in the photosensitive film overlaps as the second aspect. Thus, a laminated body formed by being laminated can be formed and used. That is, by exposing the photosensitive layer in the laminated body to be described later, the exposed region can be cured, and a permanent pattern can be formed by development to be described later.

<Laminated body>
There is no restriction | limiting in particular as a formation method of the laminated body of the said 1st aspect, Although it can select suitably according to the objective, It formed by apply | coating and drying the said photosensitive composition on the said base material. It is preferable to laminate a photosensitive layer.
There is no restriction | limiting in particular as the method of the said application | coating and drying, According to the objective, it can select suitably, For example, application | coating of the said photosensitive composition solution performed when forming the photosensitive layer in the said photosensitive film. For example, a method of applying the photosensitive composition solution using a spin coater, a slit spin coater, a roll coater, a die coater, a curtain coater, or the like can be given.

There is no restriction | limiting in particular as a formation method of the laminated body of a said 2nd aspect, Although it can select suitably according to the objective, At least any one of a heating and pressurization of the said photosensitive film on the said base material is carried out. It is preferable to laminate while performing. In addition, when the said photosensitive film has the said protective film, it is preferable to peel this protective film and to laminate | stack so that the said photosensitive layer may overlap with the said base material.
There is no restriction | limiting in particular as said heating temperature, Although it can select suitably according to the objective, For example, 70-130 degreeC is preferable and 80-110 degreeC is more preferable.
There is no restriction | limiting in particular as a pressure of the said pressurization, Although it can select suitably according to the objective, For example, 0.01-1.0 MPa is preferable and 0.05-1.0 MPa is more preferable.

  There is no restriction | limiting in particular as an apparatus which performs at least any one of the said heating and pressurization, According to the objective, it can select suitably, For example, heat press, a heat roll laminator (For example, Taisei Laminator company make, VP-II). ), A vacuum laminator (for example, MVLP500, manufactured by Meiki Seisakusho Co., Ltd.) and the like can be cited as suitable devices.

[Exposure process]
The said exposure process is a process of exposing with respect to the photosensitive layer which consists of a photosensitive composition of this invention. The pattern forming material of the present invention is as described above.

  The subject of the exposure is not particularly limited as long as it is a photosensitive layer made of the photosensitive composition, and can be appropriately selected according to the purpose. For example, the photosensitive composition is used on a substrate. It is preferable to carry out with respect to the laminated body formed.

  The substrate is not particularly limited, and can be appropriately selected from known materials having high surface smoothness to those having an uneven surface. A plate-like substrate (substrate) is preferable, and Specifically, known printed wiring board forming substrates (for example, copper-clad laminates), glass plates (for example, soda glass plates, etc.), synthetic resin films, paper, metal plates, and the like can be mentioned. The copper-clad laminate is preferable in that it has excellent adhesion to a material containing copper.

The method for forming the laminate is not particularly limited and may be appropriately selected depending on the purpose. However, the pattern forming material may be laminated on the substrate while performing at least one of heating and pressing. preferable.
There is no restriction | limiting in particular as said heating temperature, Although it can select suitably according to the objective, For example, 15-180 degreeC is preferable and 60-140 degreeC is more preferable.
There is no restriction | limiting in particular as a pressure of the said pressurization, Although it can select suitably according to the objective, For example, 0.1-1.0 MPa is preferable and 0.2-0.8 MPa is more preferable.

  There is no restriction | limiting in particular as an apparatus which performs at least any one of the said heating and pressurization, According to the objective, it can select suitably, For example, a laminator (For example, Taisei Laminator company make, VP-II) vacuum laminator etc. Preferably mentioned.

  There is no restriction | limiting in particular as said exposure, According to the objective, it can select suitably, Digital exposure, analog exposure, etc. are mentioned, Among these, digital exposure is preferable.

  The digital exposure is not particularly limited and can be appropriately selected depending on the purpose.For example, a control signal is generated based on pattern formation information to be formed, and light modulated in accordance with the control signal is generated. It is preferable to use.

  The digital exposure means is not particularly limited and may be appropriately selected depending on the purpose. For example, the light irradiation means for irradiating light, and the light irradiation means for irradiating based on the pattern information to be formed. Examples thereof include light modulation means for modulating light.

<Light modulation means>
The light modulating means is not particularly limited as long as it can modulate light, and can be appropriately selected according to the purpose. For example, it preferably has n pixel portions.
The light modulation means having the n picture elements is not particularly limited and can be appropriately selected according to the purpose. For example, a spatial light modulation element is preferable.

  Examples of the spatial light modulator include a digital micromirror device (DMD), a MEMS (Micro Electro Mechanical Systems) type spatial light modulator (SLM), and modulates transmitted light by an electro-optic effect. An optical element (PLZT element), a liquid crystal optical shutter (FLC), etc. are mentioned, Among these, DMD is mentioned suitably.

Moreover, it is preferable that the said light modulation means has a pattern signal generation means which produces | generates a control signal based on the pattern information to form. In this case, the light modulation unit modulates light according to the control signal generated by the pattern signal generation unit.
There is no restriction | limiting in particular as said control signal, According to the objective, it can select suitably, For example, a digital signal is mentioned suitably.

Hereinafter, an example of the light modulation means will be described with reference to the drawings.
As shown in FIG. 1, in the DMD 50, a large number (for example, 1024 × 768) of micromirrors (micromirrors) 62, each constituting a pixel (pixel), are arranged in a lattice pattern on an SRAM cell (memory cell) 60. It is a mirror device arranged. In each pixel, a micromirror 62 supported by a support column is provided at the top, and a material having high reflectivity such as aluminum is deposited on the surface of the micromirror 62. In addition, the reflectance of the micromirror 62 is 90% or more, and the arrangement pitch is 13.7 μm as an example in both the vertical direction and the horizontal direction. A silicon gate CMOS SRAM cell 60 manufactured in a normal semiconductor memory manufacturing line is disposed directly below the micromirror 62 via a support including a hinge and a yoke. The entire structure is monolithic. ing.

  When a digital signal is written in the SRAM cell 60 of the DMD 50, the micromirror 62 supported by the support is tilted in a range of ± α degrees (for example, ± 12 degrees) with respect to the substrate side on which the DMD 50 is disposed with the diagonal line as the center. It is done. 2A shows a state where the micromirror 62 is tilted to + α degrees when the micromirror 62 is in the on state, and FIG. 2B shows a state where the micromirror 62 is tilted to −α degrees when the micromirror 62 is in the off state. Therefore, by controlling the inclination of the micro mirror 62 in each pixel of the DMD 50 as shown in FIG. 1 according to the pattern information, the laser light B incident on the DMD 50 is reflected in the inclination direction of each micro mirror 62. The

  FIG. 1 shows an example of a state in which a part of the DMD 50 is enlarged and the micromirror 62 is controlled to + α degrees or −α degrees. The on / off control of each micromirror 62 is performed by a controller 302 (see FIG. 12) connected to the DMD 50. Further, a light absorber (not shown) is arranged in the direction in which the laser beam B reflected by the off-state micromirror 62 travels.

  Further, it is preferable that the DMD 50 is arranged with a slight inclination so that the short side forms a predetermined angle θ (for example, 0.1 ° to 5 °) with the sub-scanning direction. 3A shows the scanning trajectory of the reflected light image (exposure beam) 53 by each micromirror when the DMD 50 is not tilted, and FIG. 3B shows the scanning trajectory of the exposure beam 53 when the DMD 50 is tilted. Show.

In the DMD 50, a number of micromirror arrays in which a large number (for example, 1024) of micromirrors are arranged in the longitudinal direction are arranged in a short direction (for example, 756 sets). as shown, by tilting the DMD 50, the pitch P ₂ of the scanning locus of the exposure beams 53 from each micromirror (scan line), it becomes narrower than the pitch P ₁ of the scanning line in the case of not tilting the DMD 50, significant resolution Can be improved. On the other hand, the inclination angle of the DMD 50 is small, the scanning width _{W 2} in the case of tilting the DMD 50, which is substantially equal to the scanning width _{W 1} when not inclined DMD 50.

Next, a method for increasing the modulation speed in the optical modulation means (hereinafter referred to as “high-speed modulation”) will be described.
It is preferable that the light modulation means can control any less than n pixel parts arranged continuously from the n picture elements according to pattern information. There is a limit to the data processing speed of the light modulation means, and the modulation speed per line is determined in proportion to the number of pixels to be used. By using, the modulation speed per line is increased.

Hereinafter, the high-speed modulation will be further described with reference to the drawings.
When the laser light B is irradiated from the fiber array light source 66 to the DMD 50, the laser light reflected when the micromirror of the DMD 50 is in the on state is imaged on the pattern forming material 150 by the lens systems 54 and 58. In this manner, the laser light emitted from the fiber array light source 66 is turned on / off for each pixel, and the pattern forming material 150 is exposed in approximately the same number of pixel units (exposure area 168) as the number of used pixel elements of the DMD 50. . Further, when the pattern forming material 150 is moved at a constant speed together with the stage 152, the pattern forming material 150 is sub-scanned in the direction opposite to the stage moving direction by the scanner 162, and a strip-shaped exposed region 170 is provided for each exposure head 166. Is formed.

  In this example, as shown in FIGS. 4A and 4B, the DMD 50 has 768 micromirror arrays in which 1024 micromirrors are arrayed in the main scanning direction. In this example, the controller 302 (see FIG. 12) performs control so that only a part of the micromirror rows (for example, 1024 × 256 rows) are driven.

  In this case, a micromirror array arranged at the center of the DMD 50 as shown in FIG. 4 (A) may be used, and a micromirror arranged at the end of the DMD 50 as shown in FIG. 4 (B). A column may be used. In addition, when a defect occurs in some of the micromirrors, the micromirror array to be used may be appropriately changed depending on the situation, such as using a micromirror array in which no defect has occurred.

  Since the data processing speed of the DMD 50 is limited and the modulation speed per line is determined in proportion to the number of pixels used, the modulation speed per line can be increased by using only a part of the micromirror array. Get faster. On the other hand, in the case of an exposure method in which the exposure head is continuously moved relative to the exposure surface, it is not necessary to use all the pixels in the sub-scanning direction.

  When the sub-scan of the pattern forming material 150 by the scanner 162 is finished and the rear end of the pattern forming material 150 is detected by the sensor 164, the stage 152 is moved upstream of the gate 160 along the guide 158 by the stage driving device 304. It returns to the origin on the side and is moved again along the guide 158 from the upstream side to the downstream side of the gate 160 at a constant speed.

  For example, in the case of using only 384 sets out of 768 sets of micromirror arrays, the modulation can be performed twice as fast per line as compared with the case of using all 768 sets. Also, when only 256 pairs are used in the 768 sets of micromirror arrays, modulation can be performed three times faster per line than when all 768 sets are used.

  As described above, according to the pattern forming method of the present invention, the micromirror array in which 1,024 micromirrors are arranged in the main scanning direction includes the DMD in which 768 sets are arranged in the subscanning direction. By controlling so that only a part of the micromirror rows are driven by the controller, the modulation rate per line becomes faster than when all the micromirror rows are driven.

  In addition, an example in which the DMD micromirror is partially driven has been described, but the length of the direction corresponding to the predetermined direction is reflected on the substrate longer than the length of the direction intersecting the predetermined direction according to the control signal. Even if a long and narrow DMD in which a large number of micromirrors capable of changing the surface angle are arranged in a two-dimensional manner is used, the number of micromirrors for controlling the angle of the reflecting surface is reduced. Can do.

  The exposure method is preferably performed while relatively moving the exposure light and the photosensitive layer, and in this case, it is preferable to use the high-speed modulation together. Thereby, high-speed exposure can be performed in a short time.

  In addition, as shown in FIG. 5, the entire surface of the pattern forming material 150 may be exposed by a single scan in the X direction by the scanner 162, and as shown in FIGS. 6A and 6B, the scanner 162. After the pattern forming material 150 is scanned in the X direction, the scanner 162 is moved one step in the Y direction, and scanning is performed in the X direction. Thus, the pattern forming material 150 is scanned a plurality of times. Alternatively, the entire surface may be exposed. In this example, the scanner 162 includes 18 exposure heads 166. Note that the exposure head includes at least the light irradiation unit and the light modulation unit.

  The exposure is performed on a partial area of the photosensitive layer to cure the partial area, and uncured areas other than the cured partial area are removed in a development step described later. A pattern is formed.

Next, an example of a pattern forming apparatus including the light modulation means will be described with reference to the drawings.
As shown in FIG. 7, the pattern forming apparatus including the light modulation means includes a flat plate stage 152 that holds a sheet-like pattern forming material 150 by adsorbing to the surface.
Two guides 158 extending along the stage moving direction are installed on the upper surface of the thick plate-like installation table 156 supported by the four legs 154. The stage 152 is arranged so that the longitudinal direction thereof faces the stage moving direction, and is supported by a guide 158 so as to be reciprocally movable. The pattern forming apparatus has a drive device (not shown) for driving the stage 152 along the guide 158.

  A U-shaped gate 160 is provided at the center of the installation table 156 so as to straddle the movement path of the stage 152. Each of the ends of the U-shaped gate 160 is fixed to both side surfaces of the installation table 156. A scanner 162 is provided on one side of the gate 160, and a plurality of (for example, two) detection sensors 164 for detecting the front and rear ends of the pattern forming material 150 are provided on the other side. . The scanner 162 and the detection sensor 164 are respectively attached to the gate 160 and fixedly arranged above the moving path of the stage 152. The scanner 162 and the detection sensor 164 are connected to a controller (not shown) that controls them.

As shown in FIGS. 8 and 9B, the scanner 162 includes a plurality of (for example, 14) exposure heads 166 arranged in a substantially matrix of m rows and n columns (for example, 3 rows and 5 columns). ing. In this example, four exposure heads 166 are arranged in the third row in relation to the width of the pattern forming material 150. In addition, when showing each exposure head arranged in the m-th row and the n-th column, it is expressed as an exposure head 166 _mn .

An exposure area 168 by the exposure head 166 has a rectangular shape with a short side in the sub-scanning direction. Accordingly, as the stage 152 moves, a strip-shaped exposed region 170 is formed in the pattern forming material 150 for each exposure head 166. In addition, when showing the exposure area by each exposure head arranged in the m-th row and the n-th column, it is expressed as an exposure area 168 _mn .

Further, as shown in FIGS. 9A and 9B, each of the exposure heads in each row arranged in a line so that the strip-shaped exposed regions 170 are arranged in the direction orthogonal to the sub-scanning direction without gaps. These are arranged with a predetermined interval (natural number times the long side of the exposure area, twice in this example) in the arrangement direction. Therefore, can not be exposed portion between the exposure area _{168 11} in the first row and the exposure area _{168 12,} it can be exposed by the second row of the exposure area _{168 21} and the exposure area _{168 31} in the third row.

As shown in FIGS. 10 and 11, each of the exposure heads 166 _{11 to} 166 _mn serves as the light modulation means (spatial light modulation element that modulates each pixel) according to the pattern information. A digital micromirror device (DMD) 50 manufactured by Texas Instruments, USA is provided. The DMD 50 is connected to the controller 302 (see FIG. 12) including a data processing unit and a mirror drive control unit. The data processing unit of the controller 302 generates a control signal for driving and controlling each micromirror in the region to be controlled by the DMD 50 for each exposure head 166 based on the input pattern information. The area to be controlled will be described later. The mirror drive control unit controls the angle of the reflection surface of each micromirror of the DMD 50 for each exposure head 166 based on the control signal generated by the pattern information processing unit. The control of the angle of the reflecting surface will be described later.

  On the light incident side of the DMD 50, a fiber array light source 66 including a laser emitting section in which emission ends (light emitting points) of an optical fiber are arranged in a line along a direction corresponding to the long side direction of the exposure area 168, a fiber A lens system 67 for correcting the laser light emitted from the array light source 66 and condensing it on the DMD, and a mirror 69 for reflecting the laser light transmitted through the lens system 67 toward the DMD 50 are arranged in this order. In FIG. 10, the lens system 67 is schematically shown.

  As shown in detail in FIG. 11, the lens system 67 is inserted into the optical path of the light passing through the condenser lens 71 and the condenser lens 71 that collects the laser light B as the illumination light emitted from the fiber array light source 66. A rod-shaped optical integrator (hereinafter referred to as a rod integrator) 72 and an imaging lens 74 disposed in front of the rod integrator 72, that is, on the mirror 69 side. The condensing lens 71, the rod integrator 72, and the imaging lens 74 cause the laser light emitted from the fiber array light source 66 to enter the DMD 50 as a light beam that is close to parallel light and has a uniform beam cross-sectional intensity. The shape and action of the rod integrator 72 will be described in detail later.

  The laser beam B emitted from the lens system 67 is reflected by the mirror 69 and irradiated to the DMD 50 via the TIR (total reflection) prism 70. In FIG. 10, the TIR prism 70 is omitted.

  An imaging optical system 51 that images the laser beam B reflected by the DMD 50 on the pattern forming material 150 is disposed on the light reflection side of the DMD 50. The imaging optical system 51 is schematically shown in FIG. 10, but as shown in detail in FIG. 11, the imaging optical system 51 includes a first imaging optical system including lens systems 52 and 54 and lens systems 57 and 58. The optical system includes a second imaging optical system, a microlens array 55 inserted between these imaging optical systems, and an aperture array 59.

The microlens array 55 is formed by two-dimensionally arranging a large number of microlenses 55a corresponding to the pixels of the DMD 50. In this example, as described later, only 1024 × 256 rows of the 1024 × 768 rows of micromirrors of the DMD 50 are driven, and accordingly, 1024 × 256 rows of microlenses 55a are arranged. The arrangement pitch of the micro lenses 55a is 41 μm in both the vertical and horizontal directions. As an example, the microlens 55a has a focal length of 0.19 mm, an NA (numerical aperture) of 0.11, and is formed from the optical glass BK7. The shape of the micro lens 55a will be described in detail later.
The beam diameter of the laser beam B at the position of each microlens 55a is 41 μm.

  The aperture array 59 is formed by forming a large number of apertures (openings) 59 a corresponding to the respective micro lenses 55 a of the micro lens array 55. The diameter of the aperture 59a is, for example, 10 μm.

  The first imaging optical system forms an image on the microlens array 55 by enlarging the image by the DMD 50 three times. The second imaging optical system enlarges the image that has passed through the microlens array 55 by 1.6 times, and forms and projects the image on the pattern forming material 150. Therefore, as a whole, the image formed by the DMD 50 is enlarged and enlarged by 4.8 times, and is imaged and projected on the pattern forming material 150.

  A prism pair 73 is disposed between the second imaging optical system and the pattern forming material 150. By moving the prism pair 73 in the vertical direction in FIG. 11, an image on the pattern forming material 150 is obtained. The focus can be adjusted. In the figure, the pattern forming material 150 is sub-scanned in the direction of arrow F.

The pixel portion is not particularly limited as long as it can receive and emit light from the light irradiation means, and can be appropriately selected according to the purpose. For example, the pattern forming method of the present invention When the pattern to be formed is an image pattern, it is a pixel, and when the light modulation means includes a DMD, it is a micromirror.
There is no restriction | limiting in particular as the number (the said n) of picture element parts which the said light modulation element has, It can select suitably according to the objective.
The arrangement of the picture element portions in the light modulation element is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is preferably arranged in a two-dimensional form, and arranged in a lattice form. More preferably.

<Light irradiation means>
The light irradiation means is not particularly limited and may be appropriately selected depending on the purpose. For example, (ultra) high pressure mercury lamp, xenon lamp, carbon arc lamp, halogen lamp, copier, fluorescent tube, LED, etc. , A known light source such as a semiconductor laser, or a means capable of synthesizing and irradiating two or more lights. Among these, a means capable of synthesizing and irradiating two or more lights is preferable.
The light emitted from the light irradiation means is, for example, an electromagnetic wave that passes through the support and activates the photopolymerization initiator and sensitizer used when the light is irradiated through the support. In particular, ultraviolet to visible light, electron beam, X-ray, laser beam, and the like can be mentioned. Of these, laser beam is preferable, and a laser combining two or more lights (hereinafter, referred to as “combined laser”). More preferred. Even when light irradiation is performed after the support is peeled off, the same light can be used.

As a wavelength of the ultraviolet to visible light, for example, 300 to 1500 nm is preferable, 320 to 800 nm is more preferable, and 330 nm to 650 nm is particularly preferable.
As a wavelength of the said laser beam, 200-1500 nm is preferable, for example, 300-800 nm is more preferable, 330 nm-500 nm is still more preferable, 400 nm-450 nm is especially preferable.

  Examples of means capable of irradiating the combined laser include, for example, a plurality of lasers, a multimode optical fiber, and collective optics for condensing and coupling the laser beams respectively emitted from the plurality of lasers to the multimode optical fiber. Means having a system are preferred.

  Hereinafter, means (fiber array light source) capable of irradiating the combined laser will be described with reference to the drawings.

  As shown in FIG. 27 a, the fiber array light source 66 includes a plurality of (for example, 14) laser modules 64, and one end of the multimode optical fiber 30 is coupled to each laser module 64. An optical fiber 31 having the same core diameter as that of the multimode optical fiber 30 and a smaller cladding diameter than the multimode optical fiber 30 is coupled to the other end of the multimode optical fiber 30. As shown in detail in FIG. 27b, seven end portions of the multimode optical fiber 31 opposite to the optical fiber 30 are arranged along the main scanning direction orthogonal to the sub-scanning direction, and they are arranged in two rows to form a laser. An emission unit 68 is configured.

  As shown in FIG. 27b, the laser emitting portion 68 configured by the end portion of the multimode optical fiber 31 is sandwiched and fixed between two support plates 65 having a flat surface. In addition, a transparent protective plate such as glass is preferably disposed on the light emitting end face of the multimode optical fiber 31 for protection. The light exit end face of the multimode optical fiber 31 has high light density and is likely to collect dust and easily deteriorate. However, the protective plate as described above prevents the dust from adhering to the end face and deteriorates. Can be delayed.

  In this example, in order to arrange the emission ends of the optical fibers 31 with a small cladding diameter in a line without any gaps, the multimode optical fiber 30 is placed between two adjacent multimode optical fibers 30 at a portion with a large cladding diameter. Two exit ends of the optical fiber 31 coupled to the two multimode optical fibers 30 adjacent to each other at the portion where the cladding diameter is large are the exit ends of the optical fiber 31 coupled to the stacked and stacked multimode optical fibers 30. Are arranged so as to be sandwiched between them.

  For example, as shown in FIG. 28, an optical fiber 31 having a length of 1 to 30 cm and having a small cladding diameter is coaxially connected to the tip portion of the multimode optical fiber 30 having a large cladding diameter on the laser light emission side. Can be obtained by linking them together. In the two optical fibers, the incident end face of the optical fiber 31 is fused and joined to the outgoing end face of the multimode optical fiber 30 so that the central axes of both optical fibers coincide. As described above, the diameter of the core 31 a of the optical fiber 31 is the same as the diameter of the core 30 a of the multimode optical fiber 30.

  In addition, a short optical fiber in which an optical fiber having a short cladding diameter and a large cladding diameter is fused to an optical fiber having a short cladding diameter and a large cladding diameter may be coupled to the output end of the multimode optical fiber 30 via a ferrule or an optical connector. Good. By detachably coupling using a connector or the like, the tip portion can be easily replaced when an optical fiber having a small cladding diameter is broken, and the cost required for exposure head maintenance can be reduced. Hereinafter, the optical fiber 31 may be referred to as an emission end portion of the multimode optical fiber 30.

  The multimode optical fiber 30 and the optical fiber 31 may be any of a step index type optical fiber, a graded index type optical fiber, and a composite type optical fiber. For example, a step index type optical fiber manufactured by Mitsubishi Cable Industries, Ltd. can be used. In the present embodiment, the multimode optical fiber 30 and the optical fiber 31 are step index type optical fibers, and the multimode optical fiber 30 has a cladding diameter = 125 μm, a core diameter = 50 μm, NA = 0.2, an incident end face. The transmittance of the coat is 99.5% or more, and the optical fiber 31 has a cladding diameter = 60 μm, a core diameter = 50 μm, and NA = 0.2.

  In general, in the laser light in the infrared region, the propagation loss increases as the cladding diameter of the optical fiber is reduced. For this reason, a suitable cladding diameter is determined according to the wavelength band of the laser beam. However, the shorter the wavelength, the smaller the propagation loss. In the case of laser light having a wavelength of 405 nm emitted from a GaN-based semiconductor laser, the cladding thickness {(cladding diameter−core diameter) / 2} is set to an infrared light having a wavelength band of 800 nm. The propagation loss hardly increases even if it is about ½ of the case of propagating infrared light and about ¼ of the case of propagating infrared light in the 1.5 μm wavelength band for communication. Therefore, the cladding diameter can be reduced to 60 μm.

  However, the cladding diameter of the optical fiber 31 is not limited to 60 μm. The clad diameter of the optical fiber used in the conventional fiber array light source is 125 μm, but the depth of focus becomes deeper as the clad diameter becomes smaller. Therefore, the clad diameter of the multimode optical fiber is preferably 80 μm or less, preferably 60 μm or less. More preferably, it is 40 μm or less. On the other hand, since the core diameter needs to be at least 3 to 4 μm, the cladding diameter of the optical fiber 31 is preferably 10 μm or more.

  The laser module 64 includes a combined laser light source (fiber array light source) shown in FIG. This combined laser light source includes a plurality of (for example, seven) chip-like lateral multimode or single mode GaN-based semiconductor lasers LD1, LD2, LD3, LD4, LD5, LD6, arrayed and fixed on the heat block 10. And LD7, collimator lenses 11, 12, 13, 14, 15, 16, and 17 provided corresponding to each of the GaN-based semiconductor lasers LD1 to LD7, one condenser lens 20, and one multi-lens. Mode optical fiber 30. The number of semiconductor lasers is not limited to seven. For example, as many as 20 semiconductor laser beams can be incident on a multimode optical fiber having a cladding diameter = 60 μm, a core diameter = 50 μm, and NA = 0.2. In addition, the number of optical fibers can be further reduced.

  The GaN-based semiconductor lasers LD1 to LD7 all have the same oscillation wavelength (for example, 405 nm), and the maximum output is also all the same (for example, 100 mW for the multimode laser and 30 mW for the single mode laser). As the GaN-based semiconductor lasers LD1 to LD7, lasers having an oscillation wavelength other than the above 405 nm in a wavelength range of 350 nm to 450 nm may be used.

  As shown in FIGS. 30 and 31, the combined laser light source is housed in a box-shaped package 40 having an upper opening together with other optical elements. The package 40 includes a package lid 41 created so as to close the opening thereof. After the deaeration process, a sealing gas is introduced, and the package 40 and the package lid 41 are closed by closing the opening of the package 40 with the package lid 41. 41. The combined laser light source is hermetically sealed in a closed space (sealed space) formed by 41.

  A base plate 42 is fixed to the bottom surface of the package 40, and the heat block 10, a condensing lens holder 45 that holds the condensing lens 20, and the multimode optical fiber 30 are disposed on the top surface of the base plate 42. A fiber holder 46 that holds the incident end is attached. The exit end of the multimode optical fiber 30 is drawn out of the package from an opening formed in the wall surface of the package 40.

  Further, a collimator lens holder 44 is attached to the side surface of the heat block 10, and the collimator lenses 11 to 17 are held. An opening is formed in the lateral wall surface of the package 40, and wiring 47 for supplying a driving current to the GaN-based semiconductor lasers LD1 to LD7 is drawn out of the package through the opening.

  In FIG. 31, in order to avoid complication of the figure, only the GaN-based semiconductor laser LD7 among the plurality of GaN-based semiconductor lasers is numbered, and only the collimator lens 17 among the plurality of collimator lenses is numbered. is doing.

  FIG. 32 shows a front shape of a mounting portion of the collimator lenses 11 to 17. Each of the collimator lenses 11 to 17 is formed in a shape in which a region including the optical axis of a circular lens having an aspherical surface is cut out in a parallel plane. This elongated collimator lens can be formed, for example, by molding resin or optical glass. The collimator lenses 11 to 17 are closely arranged in the arrangement direction of the light emitting points so that the length direction is orthogonal to the arrangement direction of the light emitting points of the GaN-based semiconductor lasers LD1 to LD7 (left and right direction in FIG. 32).

  On the other hand, each of the GaN-based semiconductor lasers LD1 to LD7 includes an active layer having an emission width of 2 μm, and the laser beams B1 to A laser emitting B7 is used. These GaN-based semiconductor lasers LD1 to LD7 are arranged so that the light emitting points are arranged in a line in a direction parallel to the active layer.

Therefore, in the laser beams B1 to B7 emitted from the respective light emitting points, the direction in which the divergence angle is large coincides with the length direction and the divergence angle is small with respect to the elongated collimator lenses 11 to 17 as described above. Incident light is incident in a state where the direction coincides with the width direction (direction perpendicular to the length direction). That is, the collimator lenses 11 to 17 have a width of 1.1 mm and a length of 4.6 mm, and the horizontal and vertical beam diameters of the laser beams B1 to B7 incident thereon are 0.9 mm and 2. 6 mm. Each of the collimator lenses 11 to 17 has a focal length f ₁ = 3 mm, NA = 0.6, and a lens arrangement pitch = 1.25 mm.

The condensing lens 20 is obtained by cutting a region including the optical axis of a circular lens having an aspherical surface into a shape that is elongated in a parallel plane and is long in the arrangement direction of the collimator lenses 11 to 17, that is, in the horizontal direction and short in the direction perpendicular thereto. Is formed. This condenser lens 20 has a focal length f ₂ = 23 mm and NA = 0.2. This condensing lens 20 is also formed by molding resin or optical glass, for example.

  In addition, since the light emitting means for illuminating the DMD uses a high-intensity fiber array light source in which the output ends of the optical fibers of the combined laser light source are arranged in an array, it has a high output and a deep depth of focus. A pattern forming apparatus can be realized. Furthermore, since the output of each fiber array light source is increased, the number of fiber array light sources required to obtain a desired output is reduced, and the cost of the pattern forming apparatus can be reduced.

  In addition, since the cladding diameter at the exit end of the optical fiber is smaller than the cladding diameter at the entrance end, the diameter of the light emitting portion is further reduced, and the brightness of the fiber array light source can be increased. Thereby, a pattern forming apparatus having a deeper depth of focus can be realized. For example, even in the case of ultra-high resolution exposure with a beam diameter of 1 μm or less and a resolution of 0.1 μm or less, a deep depth of focus can be obtained, and high-speed and high-definition exposure is possible. Therefore, it is suitable for a thin film transistor (TFT) exposure process that requires high resolution.

  The light irradiating means is not limited to a fiber array light source including a plurality of the combined laser light sources, and for example, emits laser light incident from a single semiconductor laser having one light emitting point. A fiber array light source in which fiber light sources including optical fibers are arrayed can be used.

  Further, as the light irradiation means having a plurality of light emitting points, for example, as shown in FIG. 33, a laser in which a plurality of (for example, seven) chip-shaped semiconductor lasers LD1 to LD7 are arranged on the heat block 100. An array can be used. A chip-shaped multicavity laser 110 in which a plurality of (for example, five) light emitting points 110a shown in FIG. 34A is arranged in a predetermined direction is known. Since the multicavity laser 110 can arrange the light emitting points with higher positional accuracy than the case where the chip-shaped semiconductor lasers are arranged, it is easy to multiplex the laser beams emitted from the respective light emitting points. However, since the multicavity laser 110 is likely to be bent at the time of manufacturing the laser when the number of light emitting points increases, the number of light emitting points 110a is preferably 5 or less.

  As the light irradiation means, the multi-cavity laser 110 or a plurality of multi-cavity lasers 110 on the heat block 100 in the same direction as the arrangement direction of the light emitting points 110a of each chip as shown in FIG. An arrayed multi-cavity laser array can be used as a laser light source.

  The combined laser light source is not limited to one that combines laser beams emitted from a plurality of chip-shaped semiconductor lasers. For example, as shown in FIG. 21, a combined laser light source including a chip-shaped multicavity laser 110 having a plurality of (for example, three) light emitting points 110a can be used. This combined laser light source is configured to include a multi-cavity laser 110, one multi-mode optical fiber 130, and a condensing lens 120. The multi-cavity laser 110 can be composed of, for example, a GaN-based laser diode having an oscillation wavelength of 405 nm.

  In the above configuration, each of the laser beams B emitted from each of the plurality of light emitting points 110 a of the multicavity laser 110 is collected by the condenser lens 120 and enters the core 130 a of the multimode optical fiber 130. The laser light incident on the core 130a propagates in the optical fiber, is combined into one, and is emitted.

  A plurality of light emitting points 110 a of the multicavity laser 110 are arranged in parallel within a width substantially equal to the core diameter of the multimode optical fiber 130, and a focal point substantially equal to the core diameter of the multimode optical fiber 130 is formed as the condenser lens 120. By using a convex lens of a distance or a rod lens that collimates the outgoing beam from the multi-cavity laser 110 only in a plane perpendicular to the active layer, the coupling efficiency of the laser beam B to the multi-mode optical fiber 130 can be increased. it can.

  As shown in FIG. 35, a multi-cavity laser 110 having a plurality of (for example, three) emission points is used, and a plurality of (for example, nine) multi-cavity lasers 110 are equidistant from each other on the heat block 111. A combined laser light source including the laser array 140 arranged in (1) can be used. The plurality of multi-cavity lasers 110 are arranged and fixed in the same direction as the arrangement direction of the light emitting points 110a of each chip.

  This combined laser light source includes a laser array 140, a plurality of lens arrays 114 arranged corresponding to each multi-cavity laser 110, and a single rod arranged between the laser array 140 and the plurality of lens arrays 114. The lens 113, one multimode optical fiber 130, and a condenser lens 120 are provided. The lens array 114 includes a plurality of microlenses corresponding to the emission points of the multicavity laser 110.

  In the above configuration, each of the laser beams B emitted from each of the plurality of light emitting points 110a of the plurality of multi-cavity lasers 110 is collected in a predetermined direction by the rod lens 113, and then each microlens of the lens array 114. It becomes parallel light. The collimated laser beam L is condensed by the condensing lens 120 and enters the core 130a of the multimode optical fiber 130. The laser light incident on the core 130a propagates in the optical fiber, is combined into one, and is emitted.

  Still another example of the combined laser light source will be described. In this combined laser light source, as shown in FIGS. 36A and 36B, a heat block 182 having an L-shaped cross section in the optical axis direction is mounted on a substantially rectangular heat block 180, and two heats are provided. A storage space is formed between the blocks. On the upper surface of the L-shaped heat block 182, a plurality of (for example, two) multi-cavity lasers 110 in which a plurality of light emitting points (for example, five) are arranged in an array form the light emitting points 110a of each chip. It is arranged and fixed at equal intervals in the same direction as the arrangement direction.

  A concave portion is formed in the substantially rectangular heat block 180, and a plurality of (for example, two) light emitting points (for example, five) are arranged in an array on the upper surface of the space side of the heat block 180. The multi-cavity laser 110 is arranged such that its emission point is located on the same vertical plane as the emission point of the laser chip arranged on the upper surface of the heat block 182.

  On the laser beam emission side of the multi-cavity laser 110, a collimator lens array 184 in which collimator lenses are arranged corresponding to the light emission points 110a of the respective chips is arranged. In the collimating lens array 184, the length direction of each collimating lens coincides with the direction in which the laser beam divergence angle is large (fast axis direction), and the width direction of each collimating lens is in the direction in which the divergence angle is small (slow axis direction). They are arranged to match. Thus, by collimating and integrating the collimating lenses, the space utilization efficiency of the laser light can be improved, the output of the combined laser light source can be increased, and the number of parts can be reduced and the cost can be reduced. .

  Further, on the laser light emitting side of the collimating lens array 184, there is one multimode optical fiber 130 and a condensing lens 120 that condenses and couples the laser light to the incident end of the multimode optical fiber 130. Has been placed.

  In the above-described configuration, each of the laser beams B emitted from each of the plurality of light emitting points 110a of the plurality of multicavity lasers 110 arranged on the laser blocks 180 and 182 is collimated by the collimating lens array 184 and condensed. The light is condensed by the lens 120 and enters the core 130 a of the multimode optical fiber 130. The laser light incident on the core 130a propagates in the optical fiber, is combined into one, and is emitted.

  As described above, the combined laser light source can achieve particularly high output by the multistage arrangement of multicavity lasers and the array of collimating lenses. By using this combined laser light source, a higher-intensity fiber array light source or bundle fiber light source can be configured, so that it is particularly suitable as a fiber light source constituting the laser light source of the pattern forming apparatus of the present invention.

  It should be noted that a laser module in which each of the combined laser light sources is housed in a casing and the emission end of the multimode optical fiber 130 is pulled out from the casing can be configured.

  In addition, the other end of the multimode optical fiber of the combined laser light source is coupled with another optical fiber having the same core diameter as the multimode optical fiber and a cladding diameter smaller than the multimode optical fiber. However, for example, a multimode optical fiber having a cladding diameter of 125 μm, 80 μm, 60 μm or the like may be used without coupling another optical fiber to the emission end.

Here, the pattern forming method of the present invention will be further described.
In each exposure head 166 of the scanner 162, laser light B1, B2, B3, B4, B5, B6 emitted in a divergent light state from each of the GaN-based semiconductor lasers LD1 to LD7 constituting the combined laser light source of the fiber array light source 66. , And B7 are collimated by corresponding collimator lenses 11-17. The collimated laser beams B <b> 1 to B <b> 7 are collected by the condenser lens 20 and converge on the incident end face of the core 30 a of the multimode optical fiber 30.

  In this example, the collimator lenses 11 to 17 and the condenser lens 20 constitute a condensing optical system, and the condensing optical system and the multimode optical fiber 30 constitute a multiplexing optical system. That is, the laser beams B1 to B7 collected as described above by the condenser lens 20 enter the core 30a of the multimode optical fiber 30 and propagate through the optical fiber to be combined with one laser beam B. The light is emitted from the optical fiber 31 coupled to the output end of the multimode optical fiber 30.

  In each laser module, when the coupling efficiency of the laser beams B1 to B7 to the multimode optical fiber 30 is 0.85 and each output of the GaN-based semiconductor lasers LD1 to LD7 is 30 mW, the light arranged in an array For each of the fibers 31, a combined laser beam B with an output of 180 mW (= 30 mW × 0.85 × 7) can be obtained. Therefore, the output from the laser emitting unit 68 in which the six optical fibers 31 are arranged in an array is about 1 W (= 180 mW × 6).

  In the laser emitting portion 68 of the fiber array light source 66, light emission points with high luminance are arranged in a line along the main scanning direction as described above. A conventional fiber light source that couples laser light from a single semiconductor laser to a single optical fiber has a low output, so that a desired output cannot be obtained unless multiple rows are arranged. Since the laser light source has a high output, a desired output can be obtained even with a small number of columns, for example, one column.

For example, in a conventional fiber light source in which a semiconductor laser and an optical fiber are coupled on a one-to-one basis, a laser having an output of about 30 mW (milliwatt) is usually used as the semiconductor laser, and the core diameter is 50 μm and the cladding diameter is 125 μm. Since a multimode optical fiber having a numerical aperture (NA) of 0.2 is used, if an output of about 1 W (watt) is to be obtained, 48 multimode optical fibers (8 × 6) must be bundled. Narazu, the area of the light emitting region 0.62 mm ² because it is (0.675mm × 0.925mm), the luminance at laser emitting portion 68 is ^{1.6 × 10 6 (W / m} 2), 1 present optical fiber The luminance per hit is 3.2 × 10 ⁶ (W / m ² ).

On the other hand, when the light irradiating means is a means capable of irradiating a combined laser, an output of about 1 W can be obtained with six multimode optical fibers, and the area of the light emitting region at the laser emitting portion 68 can be obtained. Is 0.0081 mm ² (0.325 mm × 0.025 mm), the luminance at the laser emitting portion 68 is 123 × 10 ⁶ (W / m ² ), which is about 80 times higher than the conventional luminance. be able to. Further, the luminance per optical fiber is 90 × 10 ⁶ (W / m ² ), and the luminance can be increased by about 28 times compared to the conventional one.

  Here, with reference to FIGS. 37A and 37B, the difference in depth of focus between the conventional exposure head and the exposure head of the present embodiment will be described. The diameter of the light emission region of the bundled fiber light source of the conventional exposure head in the sub-scanning direction is 0.675 mm, and the diameter of the light emission region of the fiber array light source of the exposure head in the sub-scanning direction is 0.025 mm. As shown in FIG. 37A, in the conventional exposure head, since the light emitting area of the light irradiating means (bundle-shaped fiber light source) 1 is large, the angle of the light beam incident on the DMD 3 is increased, and as a result, the scanning surface 5 is moved. The angle of the incident light beam increases. For this reason, the beam diameter tends to increase with respect to the light condensing direction (shift in the focus direction).

  On the other hand, as shown in FIG. 37B, in the exposure head in the pattern forming apparatus of the present invention, the diameter of the light emitting region of the fiber array light source 66 in the sub-scanning direction is small, so that it passes through the lens system 67 and enters the DMD 50. As a result, the angle of the light beam incident on the scanning surface 56 is reduced. That is, the depth of focus becomes deep. In this example, the diameter of the light emitting region in the sub-scanning direction is about 30 times that of the conventional one, and a depth of focus substantially corresponding to the diffraction limit can be obtained. Therefore, it is suitable for exposure of a minute spot. This effect on the depth of focus is more prominent and effective as the required light quantity of the exposure head is larger. In this example, the size of one pixel projected on the exposure surface is 10 μm × 10 μm. The DMD is a reflective spatial light modulator, but FIGS. 37A and 37B are developed views for explaining the optical relationship.

  Pattern information corresponding to the exposure pattern is input to a controller (not shown) connected to the DMD 50 and temporarily stored in a frame memory in the controller. This pattern information is data representing the density of each pixel constituting the image as binary values (whether or not dots are recorded).

  The stage 152 having the pattern forming material 150 adsorbed on the surface thereof is moved at a constant speed from the upstream side to the downstream side of the gate 160 along the guide 158 by a driving device (not shown). When the leading edge of the pattern forming material 150 is detected by the detection sensor 164 attached to the gate 160 while the stage 152 passes under the gate 160, the pattern information stored in the frame memory is sequentially read out for a plurality of lines. Then, a control signal is generated for each exposure head 166 based on the pattern information read by the data processing unit. Then, each of the micromirrors of the DMD 50 is controlled on and off for each exposure head 166 based on the generated control signal by the mirror drive control unit.

  When the DMD 50 is irradiated with laser light from the fiber array light source 66, the laser light reflected when the micromirror of the DMD 50 is in the on state is coupled onto the exposed surface 56 of the pattern forming material 150 by the lens systems 54 and 58. Imaged. In this manner, the laser light emitted from the fiber array light source 66 is turned on / off for each pixel, and the pattern forming material 150 is exposed in the number of pixel units (exposure area 168) substantially equal to the number of used pixel elements of the DMD 50. . Further, when the pattern forming material 150 is moved at a constant speed together with the stage 152, the pattern forming material 150 is sub-scanned in the direction opposite to the stage moving direction by the scanner 162, and a strip-shaped exposed region 170 is provided for each exposure head 166. Is formed.

<Microlens array>
The exposure is preferably performed using the modulated light through a microlens array, and may be performed through an aperture array, an imaging optical system, or the like.

  The microlens array is not particularly limited and may be appropriately selected according to the purpose. For example, microlenses having an aspheric surface capable of correcting aberration due to distortion of the exit surface in the pixel portion are arranged. Preferably, a microlens having a lens aperture shape that does not allow the light from the peripheral portion of the picture element portion to enter is arranged.

  There is no restriction | limiting in particular as said aspherical surface, Although it can select suitably according to the objective, For example, a toric surface is preferable.

  Hereinafter, the microlens array, the aperture array, the imaging optical system, and the like will be described with reference to the drawings.

FIG. 13A shows each of DMD 50, light irradiation means 144 for irradiating the DMD 50 with laser light, lens systems (imaging optical systems) 454, 458, and DMD 50 for enlarging and imaging the laser light reflected by the DMD 50. A microlens array 472 in which a large number of microlenses 474 are arranged corresponding to the picture element portion, an aperture array 476 in which a large number of apertures 478 are provided corresponding to each microlens of the microlens array 472, and a laser that has passed through the aperture An exposure head composed of lens systems (imaging optical systems) 480 and 482 for forming an image of light on an exposed surface 56 is shown.
Here, FIG. 14 shows a result of measuring the flatness of the reflection surface of the micromirror 62 constituting the DMD 50. In the figure, the same height positions of the reflecting surfaces are shown connected by contour lines, and the pitch of the contour lines is 5 nm. Note that the x direction and the y direction shown in the figure are two diagonal directions of the micromirror 62, and the micromirror 62 rotates around the rotation axis extending in the y direction as described above. 15A and 15B show the height position displacement of the reflecting surface of the micromirror 62 along the x direction and the y direction, respectively.

  As shown in FIGS. 14 and 15, there is distortion on the reflection surface of the micromirror 62, and when attention is paid particularly to the center of the mirror, distortion in one diagonal direction (y direction) is different from that in the other diagonal line. It is larger than the distortion in the direction (x direction). For this reason, the problem that the shape in the condensing position of the laser beam B condensed with the micro lens 55a of the micro lens array 55 may be distorted may occur.

  In the pattern forming method of the present invention, in order to prevent the above problem, the microlens 55a of the microlens array 55 has a special shape different from the conventional one. Hereinafter, this point will be described in detail.

  FIGS. 16A and 16B respectively show the front and side shapes of the entire microlens array 55 in detail. These drawings also show the dimensions of each part of the microlens array 55, and the unit thereof is mm. In the pattern forming method of the present invention, as described above with reference to FIG. 4, the 1024 × 256 rows of micromirrors 62 of the DMD 50 are driven. A row of 1024 microlenses 55a arranged in the direction is arranged in parallel in the vertical direction. In FIG. 9A, the arrangement order of the microlens array 55 is indicated by j in the horizontal direction and k in the vertical direction.

  17A and 17B show the front shape and the side shape of one microlens 55a in the microlens array 55, respectively. In FIG. 9A, the contour lines of the micro lens 55a are also shown. The end surface of each microlens 55a on the light emitting side has an aspherical shape that corrects aberration due to distortion of the reflecting surface of the micromirror 62. More specifically, the micro lens 55a is a toric lens, and has a radius of curvature Rx = −0.125 mm in a direction optically corresponding to the x direction and a radius of curvature Ry = − in a direction corresponding to the y direction. 0.1 mm.

  Therefore, the condensing state of the laser beam B in the cross section parallel to the x direction and the y direction is roughly as shown in FIGS. 18A and 18B, respectively. That is, when comparing the parallel cross section in the x direction and the parallel cross section in the y direction, the radius of curvature of the microlens 55a is smaller and the focal length is shorter in the latter cross section.

  19A, 19B, 19D, and 19D show simulation results of the beam diameter in the vicinity of the condensing position (focal position) of the microlens 55a when the microlens 55a has the above shape. For comparison, FIGS. 20a, 20b, 20c, and 20d show the results of a similar simulation when the microlens 55a has a spherical shape with a radius of curvature Rx = Ry = −0.1 mm. In addition, the value of z in each figure has shown the evaluation position of the focus direction of the micro lens 55a with the distance from the beam emission surface of the micro lens 55a.

The surface shape of the microlens 55a used for the simulation is calculated by the following calculation formula.
In the above formula, Cx means the curvature in the x direction (= 1 / Rx), Cy means the curvature in the y direction (= 1 / Ry), and X is the lens optical axis in the x direction. The distance from O means Y, and Y means the distance from the lens optical axis O in the y direction.

  19A to 19D and FIGS. 20A to 20D, in the pattern forming method of the present invention, the microlens 55a has a focal length in the cross section parallel to the y direction that is greater than the focal distance in the cross section parallel to the x direction. Since the toric lens is also small, distortion of the beam shape in the vicinity of the condensing position is suppressed. If so, the pattern forming material 150 can be exposed to a higher-definition image without distortion. Moreover, it turns out that the area | region with a small beam diameter is wider, ie, the depth of focus is larger in this embodiment shown to FIG.

  In addition, when the magnitude relation of the distortion of the center part in the x direction and the y direction of the micromirror 62 is opposite to the above, the focal length in the parallel section in the x direction is the focal length in the parallel section in the y direction. If the microlens is formed of a smaller toric lens, the pattern forming material 150 can be similarly exposed to a higher-definition image without distortion.

  In addition, the aperture array 59 disposed in the vicinity of the condensing position of the microlens array 55 is disposed such that only light having passed through the corresponding microlens 55a is incident on each aperture 59a. That is, by providing this aperture array 59, it is possible to prevent light from adjacent microlenses 55a not corresponding to each aperture 59a from entering, and to increase the extinction ratio.

  Originally, if the diameter of the aperture 59a of the aperture array 59 installed for the above purpose is reduced to some extent, an effect of suppressing the distortion of the beam shape at the condensing position of the microlens 55a can be obtained. However, in such a case, the amount of light blocked by the aperture array 59 is increased, and the light use efficiency is reduced. On the other hand, when the microlens 55a has an aspherical shape, the light utilization efficiency is kept high because the light is not blocked.

  In the pattern forming method of the present invention, the micro lens 55a which is a toric lens having different curvatures in the x direction and the y direction optically corresponding to the two diagonal directions of the micro mirror 62 is applied. According to the distortion of 62, the xx direction and yy optically corresponding to the two side directions of the rectangular micromirror 62 are shown in FIGS. A microlens 55a ′ composed of toric lenses having different curvatures in directions may be applied.

  In the pattern forming method of the present invention, the microlens 55a may have a secondary aspherical shape or a higher order (4th, 6th,...) Aspherical shape. By adopting the higher order aspherical shape, the beam shape can be further refined. Furthermore, it is possible to adopt a lens shape in which the curvatures in the x direction and the y direction described above coincide with each other in accordance with the distortion of the reflection surface of the micromirror 62. Hereinafter, examples of such lens shapes will be described in detail.

39A and 39B, the microlens 55a ″ showing the front shape and the side shape with contour lines, respectively, has the same curvature in the x direction and the y direction, and the curvature is equal to the curvature Cy of the spherical lens. The spherical lens shape that is the basis of the lens shape of the microlens 55a ″ is, for example, the lens height (lens) according to the following formula (Equation 2). A curved surface in which the position in the optical axis direction) z is defined is adopted.
FIG. 40 is a graph showing the relationship between the lens height z and the distance h when the curvature Cy = (1 / 0.1 mm).

Then, the curvature Cy of the spherical lens shape is corrected according to the following formula (Equation 3) in accordance with the distance h from the lens center to obtain the lens shape of the microlens 55a ″.

Also in the calculation formula (Formula 3), the meaning of z is the same as the above-described calculation formula (Formula 2). Here, the curvature Cy is corrected using the fourth-order coefficient a and the sixth-order coefficient b. . The lens height z and the distance h when the curvature Cy = (1 / 0.1 mm), the fourth-order coefficient a = 1.2 × 10 ³ , and the sixth-order coefficient a = 5.5 × 10 ⁷ are described. The relationship is shown in a graph in FIG.

  In the embodiment described above, the end surface on the light emission side of the micro lens 55a is an aspherical surface (toric surface). However, one of the two light passing end surfaces is a spherical surface and the other is a cylindrical surface. Thus, the microlens array can be configured to obtain the same effect as the above embodiment.

  Furthermore, in the embodiment described above, the microlens 55a of the microlens array 55 has an aspherical shape that corrects aberration due to distortion of the reflecting surface of the micromirror 62. Such an aspherical shape is adopted. Instead, the same effect can be obtained even if each microlens constituting the microlens array has a refractive index distribution that corrects aberration due to distortion of the reflection surface of the micromirror 62.

  An example of such a microlens 155a is shown in FIG. (A) and (B) of the same figure respectively show the front shape and side shape of the micro lens 155a, and the external shape of the micro lens 155a is a parallel plate shape as shown in the figure. The x and y directions in the figure are as described above.

  23A and 23B schematically show the condensing state of the laser beam B in the cross section parallel to the x direction and the y direction by the micro lens 155a. The microlens 155a has a refractive index distribution that gradually increases outward from the optical axis O. In the drawing, the broken line shown in the microlens 155a indicates that the refractive index is predetermined from the optical axis O. The position changed with the pitch is shown. As shown in the drawing, when the parallel cross section in the x direction is compared with the parallel cross section in the y direction, the ratio of the refractive index change of the microlens 155a is larger in the latter cross section, and the focal length is shorter. It has become. Even when a microlens array composed of such a gradient index lens is used, it is possible to obtain the same effect as when the microlens array 55 is used.

  In addition, in the microlens whose surface shape is aspherical like the microlens 55a previously shown in FIGS. 17 and 18, the refractive index distribution as described above is given together, and both by the surface shape and the refractive index distribution. The aberration due to the distortion of the reflection surface of the micromirror 62 may be corrected.

Next, another example of the microlens array will be described with reference to the drawings.
As shown in FIG. 42, the microlens array of this example is formed by arranging microlenses having a lens opening shape that does not allow light from the peripheral portion of the picture element portion to enter.

  As described above with reference to FIGS. 14 and 15, there is distortion on the reflection surface of the micromirror 62 of the DMD 50, but the amount of change in the distortion gradually increases from the center of the micromirror 62 toward the periphery. Has a trend. The amount of change in peripheral distortion in one diagonal direction (y direction) of the micromirror 62 is larger than the amount of change in peripheral distortion in another diagonal direction (x direction), and the above-described tendency is more remarkable. .

  The microlens array of this example is applied to cope with the above-described problem. In the microlens array 255, the microlenses 255a arranged in an array have a circular lens opening. Therefore, as described above, the laser light B reflected at the peripheral portion of the reflecting surface of the micromirror 62 having a large distortion, particularly at the four corners, is not condensed by the microlens 255a, and the condensing position of the condensed laser light B is reduced. Can be prevented from being distorted. Therefore, a higher-definition image without distortion can be exposed on the photosensitive layer 150.

  In the microlens array 255, as shown in FIG. 42, the back surface of the transparent member 255b holding the microlens 255a (which is usually formed integrally with the microlens 255a), that is, the microlens 255a. A light-shielding mask 255c is formed on the surface opposite to the surface on which the lens openings are formed so as to fill the outer regions of the lens openings of the plurality of microlenses 255a separated from each other. By providing such a mask 255c, the laser beam B reflected at the periphery of the reflecting surface of the micromirror 62, particularly at the four corners, is absorbed and blocked there, so the shape of the focused laser beam B Is more reliably prevented from being distorted.

  In the microlens array 255, the opening shape of the microlens is not limited to the circular shape described above. For example, as shown in FIG. 43, a microlens array in which a plurality of microlenses 455a having elliptical openings are arranged in parallel. As shown in FIG. 44, a microlens array 555 formed by arranging a plurality of microlenses 555a having polygonal (quadrangle in the illustrated example) openings can be used. Note that the microlenses 455a and 555a are formed by cutting out a part of a normal axisymmetric spherical lens into a circular shape or a polygonal shape, and have a light collecting function similar to that of a normal axisymmetric spherical lens.

  Furthermore, in the present invention, a microlens array as shown in FIGS. 45A, 45B, and 45C can be applied. The microlens array 655 shown in FIG. 5A is such that a plurality of microlenses 655a similar to the microlenses 55a, 455a, and 555a are in close contact with the surface of the transparent member 655b on the side where the laser beam B is emitted. A mask 655c similar to the mask 255c is formed on the surface on the side where the laser beam B is incident. Note that the mask 255c in FIG. 42 is formed in the outer portion of the lens opening, whereas the mask 655c is provided in the lens opening. In the microlens array 755 shown in FIG. 5B, a plurality of microlenses 755a are arranged in parallel with each other on the surface of the transparent member 455b on the side where the laser beam B is emitted, and the microlens 755a is disposed between the microlenses 755a. Then, a mask 755c is formed. In the microlens array 855 shown in FIG. 5C, a plurality of microlenses 855a are arranged in parallel with each other on the surface of the transparent member 855b on the side where the laser beam B is emitted, and the periphery of each microlens 855a is arranged. A mask 855c is formed on the portion.

  The masks 655c, 755c, and 855c all have a circular opening as in the above-described mask 255c, whereby the opening of the microlens is defined to be circular.

  FIG. 17 shows a configuration in which a lens opening shape that does not allow light from the periphery of the micromirror 62 of the DMD 50 to enter by providing a mask, such as the microlenses 255a, 455a, 555a, 655a, and 755a described above. An aspherical lens that corrects aberration due to the distortion of the surface of the micromirror 62 like the microlens 55a described above, or a lens having a refractive index distribution that corrects the aberration like the microlens 155a shown in FIG. It is also possible to employ them. By doing so, the effect of preventing the distortion of the exposure image due to the distortion of the reflection surface of the micromirror 62 is synergistically enhanced.

  In particular, as shown in FIG. 45C, in the configuration in which the mask 855c is formed on the lens surface of the microlens 855a in the microlens array 855, the microlens 855a has the above-described aspherical shape and refractive index distribution. When the imaging position of the first imaging optical system such as the lens systems 52 and 54 shown in FIG. 11 is set on the lens surface of the microlens 855a, The light utilization efficiency is increased, and the photosensitive layer 150 can be exposed with higher intensity light. That is, at that time, the first imaging optical system refracts the light so that stray light due to the distortion of the reflecting surface of the micromirror 62 is focused at one point at the imaging position of the optical system. If the mask 855c is formed, light other than stray light is not shielded, and light use efficiency is improved.

  In each of the above microlens array examples, the aberration due to the distortion of the reflection surface of the micromirror 62 constituting the DMD 50 is corrected. However, in the pattern forming method of the present invention using a spatial light modulation element other than the DMD. If there is distortion on the surface of the picture element portion of the spatial light modulator, the present invention can be applied to correct the aberration due to the distortion and prevent the beam shape from being distorted.

Next, the imaging optical system will be further described.
In the exposure head, when the laser beam is irradiated from the light irradiation means 144, the cross-sectional area of the beam line reflected in the ON direction by the DMD 50 is enlarged several times (for example, two times) by the lens systems 454 and 458. The The enlarged laser light is condensed by each microlens of the microlens array 472 so as to correspond to each pixel part of the DMD 50 and passes through the corresponding aperture of the aperture array 476. The laser light that has passed through the aperture is imaged on the exposed surface 56 by the lens systems 480 and 482.

  In this imaging optical system, the laser light reflected by the DMD 50 is magnified several times by the magnifying lenses 454 and 458 and projected onto the exposed surface 56, so that the entire image area is widened. At this time, if the microlens array 472 and the aperture array 476 are not arranged, as shown in FIG. 13B, one pixel size (spot size) of each beam spot BS projected onto the exposed surface 56 is set. MTF (Modulation Transfer Function) characteristics representing the sharpness of the exposure area 468 are reduced depending on the size of the exposure area 468.

  On the other hand, when the microlens array 472 and the aperture array 476 are arranged, the laser light reflected by the DMD 50 is condensed corresponding to each pixel part of the DMD 50 by each microlens of the microlens array 472. Accordingly, as shown in FIG. 13C, even when the exposure area is enlarged, the spot size of each beam spot BS can be reduced to a desired size (for example, 10 μm × 10 μm), and the MTF characteristics are obtained. It is possible to perform high-definition exposure while preventing a decrease in the image quality. The exposure area 468 is tilted because the DMD 50 is tilted and disposed in order to eliminate the gap between the pixels.

  In addition, the aperture array can shape the beam so that the spot size on the surface to be exposed 56 is constant even if the beam is thick due to the aberration of the micro lens. Thus, crosstalk between adjacent picture elements can be prevented by passing through the aperture array.

  Further, by using a high-intensity light source, which will be described later, as the light irradiating means 144, the angle of the light beam incident on each microlens of the microlens array 472 from the lens 458 becomes small. The incident can be prevented. That is, a high extinction ratio can be realized.

<Other optical systems>
In the pattern forming method of the present invention, it may be used in combination with other optical systems appropriately selected from known optical systems, for example, a light amount distribution correcting optical system composed of a pair of combination lenses.
The light amount distribution correcting optical system changes the light flux width at each exit position so that the ratio of the light flux width at the peripheral portion to the light flux width at the central portion close to the optical axis is smaller on the exit side than on the incident side. When the DMD is irradiated with the parallel light beam from the light irradiation means, the light amount distribution on the irradiated surface is corrected so as to be substantially uniform. Hereinafter, the light quantity distribution correcting optical system will be described with reference to the drawings.

  First, as shown in FIG. 24A, the case where the entire luminous flux widths (total luminous flux widths) H0 and H1 are the same for the incident luminous flux and the outgoing luminous flux will be described. In FIG. 24A, the portions denoted by reference numerals 51 and 52 virtually indicate the entrance surface and the exit surface in the light quantity distribution correction optical system.

  In the light quantity distribution correcting optical system, it is assumed that the light flux widths h0 and h1 of the light beam incident on the central portion near the optical axis Z1 and the light flux incident on the peripheral portion are the same (h0 = hl). The light quantity distribution correcting optical system expands the light flux width h0 of the incident light flux at the central portion with respect to the light having the same light flux width h0, h1 on the incident side, and conversely changes the incident light flux at the peripheral portion. On the other hand, the light beam width h1 is reduced. That is, the width h10 of the outgoing light beam at the center and the width h11 of the outgoing light beam at the periphery are set to satisfy h11 <h10. In terms of the ratio of the luminous flux width, the ratio “h11 / h10” of the luminous flux width in the peripheral portion to the luminous flux width in the central portion on the emission side is smaller than the ratio (h1 / h0 = 1) on the incident side ( (H11 / h10) <1).

  By changing the light flux width in this way, the light flux in the central part, which normally has a large light quantity distribution, can be utilized in the peripheral part where the light quantity is insufficient, and the overall light utilization efficiency is not reduced. In addition, the light quantity distribution on the irradiated surface is made substantially uniform. The degree of uniformity is, for example, such that the unevenness in the amount of light in the effective area is within 30%, preferably within 20%.

  The operations and effects of the light quantity distribution correcting optical system are the same when the entire luminous flux width is changed between the incident side and the exit side (FIGS. 24B and 24C).

  FIG. 24B shows a case where the entire light flux width H0 on the incident side is “reduced” to the width H2 and emitted (H0> H2). Even in such a case, the light quantity distribution correcting optical system has the same light beam width h0, h1 on the incident side, and the light beam width h10 in the central part is larger than that in the peripheral part on the emission side. Conversely, the luminous flux width h11 at the peripheral part is made smaller than that at the central part. Considering the reduction rate of the light beam, the reduction rate with respect to the incident light beam in the central part is made smaller than that in the peripheral part, and the reduction rate with respect to the incident light beam in the peripheral part is made larger than that in the central part. Also in this case, the ratio “H11 / H10” of the light flux width in the peripheral portion to the light flux width in the central portion is smaller than the ratio (h1 / h0 = 1) on the incident side ((h11 / h10) <1). .

  FIG. 24C shows a case where the entire light flux width H0 on the incident side is “enlarged” to the width H3 and emitted (H0 <H3). Even in such a case, the light quantity distribution correcting optical system has the same light beam width h0, h1 on the incident side, and the light beam width h10 in the central part is larger than that in the peripheral part on the emission side. Conversely, the luminous flux width h11 at the peripheral part is made smaller than that at the central part. Considering the expansion rate of the light beam, the expansion rate for the incident light beam in the central portion is made larger than that in the peripheral portion, and the expansion rate for the incident light beam in the peripheral portion is made smaller than that in the central portion. Also in this case, the ratio “h11 / h10” of the light flux width in the peripheral portion to the light flux width in the central portion is smaller than the ratio (h1 / h0 = 1) on the incident side ((h11 / h10) <1). .

  As described above, the light quantity distribution correcting optical system changes the light beam width at each emission position, and the ratio of the light beam width in the peripheral part to the light beam width in the central part near the optical axis Z1 is larger on the outgoing side than on the incident side. Since the light having the same luminous flux width on the incident side is larger on the outgoing side, the luminous flux width in the central portion is larger than that in the peripheral portion, and the luminous flux width in the peripheral portion is smaller than that in the central portion. Become smaller. As a result, it is possible to make use of the light beam at the center part to the peripheral part, and it is possible to form a light beam cross-section with a substantially uniform light amount distribution without reducing the light use efficiency of the entire optical system.

Next, an example of specific lens data of a pair of combination lenses used as the light quantity distribution correcting optical system will be shown. In this example, lens data in the case where the light amount distribution in the cross section of the emitted light beam is a Gaussian distribution as in the case where the light irradiation means is a laser array light source is shown. When one semiconductor laser is connected to the incident end of the single mode optical fiber, the light quantity distribution of the emitted light beam from the optical fiber becomes a Gaussian distribution. The pattern forming method of the present invention can be applied to such a case. Further, the present invention can be applied to a case where the light amount in the central portion near the optical axis is larger than the light amount in the peripheral portion, for example, by reducing the core diameter of the multi-mode optical fiber and approaching the configuration of the single mode optical fiber.
Table 1 below shows basic lens data.

  As can be seen from Table 1, the pair of combination lenses is composed of two rotationally symmetric aspherical lenses. If the light incident side surface of the first lens disposed on the light incident side is the first surface and the light exit side surface is the second surface, the first surface is aspherical. In addition, when the surface on the light incident side of the second lens disposed on the light emitting side is the third surface and the surface on the light emitting side is the fourth surface, the fourth surface is aspherical.

In Table 1, the surface number Si indicates the number of the i-th surface (i = 1 to 4), the curvature radius ri indicates the curvature radius of the i-th surface, and the surface interval di indicates the i-th surface and the i + 1-th surface. The distance between surfaces on the optical axis is shown. The unit of the surface interval di value is millimeter (mm). The refractive index Ni indicates the value of the refractive index with respect to the wavelength of 405 nm of the optical element having the i-th surface.
Table 2 below shows the aspheric data of the first surface and the fourth surface.

The aspheric data is expressed by a coefficient in the following formula (A) that represents the aspheric shape.

In the above formula (A), each coefficient is defined as follows.
Z: Length of a perpendicular line (mm) drawn from a point on the aspheric surface at a height ρ from the optical axis to the tangent plane (plane perpendicular to the optical axis) of the apex of the aspheric surface
ρ: Distance from optical axis (mm)
K: conic coefficient C: paraxial curvature (1 / r, r: paraxial radius of curvature)
ai: i-th order (i = 3 to 10) aspheric coefficient In the numerical values shown in Table 2, the symbol “E” indicates that the next numerical value is a “power exponent” with 10 as the base. The numerical value represented by the exponential function with the base 10 is multiplied by the numerical value before “E”. For example, “1.0E-02” indicates “1.0 × 10 ⁻² ”.

  FIG. 26 shows a light amount distribution of illumination light obtained by the pair of combination lenses shown in Tables 1 and 2. The horizontal axis indicates coordinates from the optical axis, and the vertical axis indicates the light amount ratio (%). For comparison, FIG. 25 shows a light amount distribution (Gaussian distribution) of illumination light when correction is not performed. As can be seen from FIG. 25 and FIG. 26, the light amount distribution correction optical system corrects the light amount distribution that is substantially uniform as compared with the case where correction is not performed. Thereby, it is possible to perform exposure with uniform laser light without reducing the use efficiency of light, without causing any unevenness.

[Other processes]
There is no restriction | limiting in particular as said other process, Although selecting suitably from the process in well-known pattern formation is mentioned, For example, a image development process, a hardening process process, etc. are mentioned. These may be used alone or in combination of two or more.

<Development process>
The developing step is a step of forming a permanent pattern by exposing the photosensitive layer by the exposing step, curing the exposed region of the photosensitive layer, and then developing by removing the uncured region.

  There is no restriction | limiting in particular as the removal method of the said unhardened area | region, According to the objective, it can select suitably, For example, the method etc. which remove using a developing solution are mentioned.

  The developer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include alkali metal or alkaline earth metal hydroxides or carbonates, bicarbonates, aqueous ammonia, and quaternary ammonium. A salt aqueous solution is preferred. Among these, an aqueous sodium carbonate solution is particularly preferable.

  The developer includes a surfactant, an antifoaming agent, an organic base (for example, benzylamine, ethylenediamine, ethanolamine, tetramethylammonium hydroxide, diethylenetriamine, triethylenepentamine, morpholine, triethanolamine, etc.) May be used in combination with an organic solvent (for example, alcohols, ketones, esters, ethers, amides, lactones, etc.). The developer may be an aqueous developer obtained by mixing water or an aqueous alkali solution and an organic solvent, or may be an organic solvent alone.

<Curing process>
The curing treatment step is a step of performing a curing treatment on the photosensitive layer in the formed permanent pattern after the development step is performed.

  There is no restriction | limiting in particular as said hardening process, Although it can select suitably according to the objective, For example, a whole surface exposure process, a whole surface heat processing, etc. are mentioned suitably.

Examples of the entire surface exposure processing method include a method of exposing the entire surface of the laminate on which the permanent pattern is formed after the developing step. By the entire surface exposure, curing of the resin in the pattern forming material for forming the photosensitive layer is accelerated, and the surface of the permanent pattern is cured.
There is no restriction | limiting in particular as an apparatus which performs the said whole surface exposure, Although it can select suitably according to the objective, For example, UV exposure machines, such as an ultrahigh pressure mercury lamp, are mentioned suitably.

Examples of the entire surface heat treatment method include a method of heating the entire surface of the laminate on which the permanent pattern is formed after the developing step. By heating the entire surface, the film strength of the surface of the permanent pattern is increased.
As heating temperature in the said whole surface heating, 120-250 degreeC is preferable and 120-200 degreeC is more preferable. When the heating temperature is less than 120 ° C., the film strength may not be improved by heat treatment. When the heating temperature exceeds 250 ° C., the resin in the pattern forming material is decomposed, and the film quality is weak and brittle. There is.
As heating time in the said whole surface heating, 10 to 120 minutes are preferable and 15 to 60 minutes are more preferable.
There is no restriction | limiting in particular as an apparatus which performs the said whole surface heating, According to the objective, it can select suitably from well-known apparatuses, For example, a dry oven, a hot plate, IR heater etc. are mentioned.

When the substrate is a printed wiring board such as a multilayer wiring board, the permanent pattern of the present invention can be formed on the printed wiring board, and further soldered as follows.
That is, the development step forms a hardened layer that is the permanent pattern, and the metal layer is exposed on the surface of the printed wiring board. Gold plating is performed on the portion of the metal layer exposed on the surface of the printed wiring board, and then soldering is performed. Then, a semiconductor or a component is mounted on the soldered portion. At this time, the permanent pattern by the hardened layer exhibits a function as a protective film or an insulating film (interlayer insulating film), and prevents external impact and conduction between adjacent electrodes.

  In the permanent pattern forming method of the present invention, it is preferable to form at least one of a protective film, an interlayer insulating film, and a solder resist pattern. When the permanent pattern formed by the permanent pattern forming method is the protective film, the interlayer insulating film, and the solder resist pattern, the wiring can be protected from external impact and bending, and in particular, the interlayer insulation In the case of a film, it is useful for high-density mounting of semiconductors and components on, for example, a multilayer wiring board or a build-up wiring board.

  Since the permanent pattern forming method of the present invention can form a permanent pattern with high definition and efficiency by suppressing distortion of an image formed on the photosensitive layer, high-definition exposure is required. In particular, it can be suitably used for forming high-definition permanent patterns.

  Examples of the present invention will be described below, but the present invention is not limited to the following examples.

(Synthesis Example 1)
-Synthesis of bisphenol-A epoxy acrylate-
In a 2 L flask equipped with a stirrer and a reflux tube, as a bisphenol-A type epoxy compound, 368.0 g of RE310S (bifunctional bisphenol-A type epoxy resin, epoxy equivalent: 184 g / equivalent) manufactured by Nippon Kayaku Co., Ltd. , 1427 g of acrylic acid (molecular weight: 72.06), 2.94 g of 2,6-di-tert-butyl-p-cresol as a thermal polymerization inhibitor, and 1.53 g of triphenylphosphine as a reaction catalyst, The reaction solution was reacted at a temperature of 0 ° C. until the acid value of the reaction solution became 0.5 mgKOH / g or less to synthesize bisphenol-A epoxy acrylate (theoretical molecular weight: 510.7).

(Synthesis Example 2)
-Synthesis of alkali-soluble photocrosslinkable polyurethane elastomer (U1)-
In a 500 mL three-necked flask, 50.1 g of 4,4′-diphenylmethane diisocyanate, 29.4 g of polyoxytetramethylene glycol (Compound Example No. 7, molecular weight = 981), 10.7 g of 2,2-bis (hydroxymethyl) propionic acid, And 46.0 g of bisphenol-A epoxy acrylate of Synthesis Example 1 were dissolved in 90 mL of dioxane. After adding 0.3 g of N, N-diethylaniline, the mixture was stirred for 6 hours under reflux of dioxane to obtain a polyurethane resin solution having a carboxyl group.
After completion of the reaction, add 3.84 g of glycidyl acrylate, 0.11 g of triphenylphosphine and 0.027 g of hydroquinone monomethyl ether under a mixed air flow of 7 vol% oxygen and 93 vol% nitrogen, and react at 100 ° C. for 10 hours. Thus, a photocrosslinkable resin solution was obtained.
After the reaction, it was added little by little to a solution of 1.3 L of water and 13 mL of acetic acid to precipitate a polymer. This solid was vacuum-dried to obtain 122 g of an alkali-soluble polyurethane elastomer (U1).
The obtained elastomer (U1) was dissolved in methoxypropylene glycol acetate to prepare a 60% by mass solution.
The resulting solid portion acid value of the alkali-soluble polyurethane elastomer (U1) is 60 mg KOH / g, solids bromine number was 3.9gBr ₂ / 100g. When the molecular weight was measured by GPC, the weight average molecular weight (polystyrene standard) was 50,000.
The acid value was measured according to JIS K0070. However, when the sample did not dissolve in water, dioxane or tetrahydrofuran was used as a solvent.
The bromine number was measured according to JIS K2605.
The said weight average molecular weight was measured using the high-speed GPC apparatus (The Toyo Soda Co., Ltd. make, HLC-802A). That is, 0.5% by mass of a THF solution was used as a sample solution, 62 columns of TSKgelGMH were used, 200 μl of a sample was injected, eluted with the THF solution, and measured at 25 ° C. with a refractive index detector. Subsequently, the weight average molecular weight was calculated | required from the molecular weight distribution curve calibrated with the standard polystyrene.

(Synthesis Example 3 to Synthesis Example 11)
-Synthesis of alkali-soluble photocrosslinkable polyurethane elastomers (U2) to (U10)-
In Synthesis Example 1, alkali-soluble photocrosslinkable polyurethane elastomers (U2) to (U10) were synthesized in the same manner as in Synthesis Example 1 except that the compositions shown in Tables 3 and 4 were changed.

(Synthesis Examples 12-15)
Except having changed into the composition shown in Table 3 and Table 4 in the synthesis example 1, it carried out similarly to the synthesis example 1, and synthesize | combined the alkali-soluble photocrosslinkable polyurethane elastomer (U11)-(U14) for comparative examples.

(Synthesis Example 16)
-Preparation of pigment and inorganic filler dispersion-
Pigment Blue 15: 3 is 0.80 part by mass, Pigment Yellow 180 is 0.7 part by mass, and 15 parts by mass of a 60% by mass methoxypropyl acetate solution of each alkali-soluble photocrosslinkable polyurethane elastomer is weighed to obtain zirconia beads. Dispersion was performed using a filled mill type disperser to obtain a green pigment dispersion.
Subsequently, 18 parts by mass of barium sulfate, which is an inorganic filler, was mixed and stirred in the green pigment dispersion to prepare 81.4 parts by mass (solid content concentration: 35% by mass) of a co-dispersion with a green pigment.

(Synthesis Example 17)
-Synthesis of alkali-soluble photocrosslinkable resin P1-
In a four-necked flask equipped with a stirrer and a reflux condenser, 220 parts by mass of cresol novolak type epoxy resin Epicron N-695 (Dainippon Ink Chemical Co., Ltd., epoxy equivalent = 220) was placed, and carbitol acetate 214 was added. A part by mass was added and dissolved by heating. Next, 0.1 part by mass of hydroquinone as a polymerization inhibitor and 2.0 parts by mass of dimethylbenzylamine as a reaction catalyst were added. This mixture was heated to 95 to 105 ° C., and 72 parts by mass of acrylic acid was gradually added dropwise to react for 16 hours. The reaction product was cooled to 80 to 90 ° C., 106 parts by mass of tetrahydrophthalic anhydride was added and reacted for 8 hours. After cooling, 52 parts by mass of carbitol acetate was added and taken out.
The resulting ethylenically unsaturated bond and a photosensitive resin having both a carboxyl group (P1) had a nonvolatile content of 60 wt%, an acid value 100 mg KOH / g of solids, in Bromine Number 39gBr ₂ / 100g, the weight average molecular weight 4,020.

(Synthesis Example 18)
-Synthesis of alkali-soluble photocrosslinkable resin P2-
In a 2 liter separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introduction tube, dipropylene glycol monomethyl ether (300 g of “MFDG” manufactured by Nippon Emulsifier Co., Ltd.) and t-butylperoxy After introducing 8.0 g of 2-ethylhexanoate (“Perbutyl O” manufactured by NOF Corporation) and raising the temperature to 95 ° C., 124 g of methacrylic acid, 196 g of methyl methacrylate, and 2,2′-azobis (2-methyl) Butyronitrile) (“ABN-E” manufactured by Nippon Hydrazine Kogyo Co., Ltd.) (6.4 g) and MFDG (45 g) were both added dropwise over 3 hours, and then aged for 4 hours to synthesize a backbone polymer having a carboxy group.
Next, 79 g of glycidyl methacrylate (“Blenmer G” manufactured by Mitsubishi Rayon Co., Ltd.) and 101 g of 3,4-epoxycyclohexylmethyl acrylate (“Cyclomer A200” manufactured by Daicel Chemical Industries, Ltd.) and 4 g of triphenylphosphine were added to the trunk polymer solution. Then, 1.0 g of methylhydroquinone was added and reacted at 100 ° C. for 10 hours. The reaction was carried out under a mixed atmosphere of air / nitrogen. Solid content concentration of the obtained copolymer (P2) solution was 60 mass%.
Solids acid value of the obtained P2 is 37 mg KOH / g, solids bromine number is 36gBr ₂ / 100g, the weight average molecular weight was 20,000.

(Synthesis Example 19)
-Synthesis of alkali-soluble photocrosslinkable resin P3-
Into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 145 parts by mass of methoxypropyl acetate was taken, stirred while being purged with nitrogen, and heated to 120 ° C. Next, t-butyl hydroperoxide (Japan) was added to a monomer mixture composed of 10.4 parts by mass of styrene, 71 parts by mass of glycidyl methacrylate, and 82 parts by mass of dicyclopentenyl acrylate (manufactured by Hitachi Chemical Co., Ltd., FA-511A). 7.6 parts by mass of Perfume O, manufactured by Yushi Co., Ltd. was added. This mixed solution was dropped into the flask from the dropping funnel over 2 hours, and further stirred at 120 ° C. for 2 hours. Next, the inside of the flask was replaced with air, 0.9 parts by mass of trisdimethylaminomethylphenol and 0.145 parts by mass of hydroquinone were added to 34.2 parts by mass of acrylic acid, and the flask was heated at 120 ° C. The reaction was continued for 6 hours. When the solid content acid value was 0.8, the reaction was terminated. Further, 60.8 parts by mass of tetrahydrophthalic anhydride (84.2 mol% of the generated hydroxyl group), triethylamine 0 .8 parts by mass was added and reacted at 120 ° C. for 3.5 hours, diluted with methoxypropyl acetate to a solid content concentration of 60% by mass to synthesize an alkali-soluble photocrosslinkable resin (P3).
Obtained in P3 solids acid value = 84 mgKOH / g, a bromine number in 29gBr ₂ / 100g, the weight average molecular weight was 12,000.

(Synthesis Example 20)
-Synthesis of alkali-soluble photocrosslinkable resin P4-
200 g of styrene-maleic anhydride copolymer (manufactured by Arcochemical, SMA Resin 1000: equimolar copolymer of styrene / maleic anhydride) and 130 g of 2-hydroxyethyl methacrylate were dissolved in 220 g of butyl cellosolve acetate, and 100 ° C. For 20 hours to synthesize a half-esterified compound (P4) solution.
A solids concentration of 60 wt% of the resulting P4 solution, the acid value of the solid 170 mg KOH / g, Bromine Number 48gBr ₂ / 100g, the weight average molecular weight was 4,900.

Example 1
<Preparation of photosensitive composition coating solution>
The following components (specifically, the respective compositions shown in Table 5) were mixed to prepare a photosensitive composition coating solution.
-60 mass% solution of polyurethane resin (U1) synthesized in Synthesis Example 2 ... 56.1 parts by mass-Bisphenol A type epoxy resin (Japan Epoxy Resin, Epicoat 1004) ... 17 parts by mass-Dipentaerythritol Hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., DPHA): 11 parts by mass Bisacylphosphine oxide (manufactured by Ciba Specialty Chemicals, Irgacure 819): 7 parts by mass Pigment dispersion obtained in Synthesis Example 16・ 81.4 parts by mass ・ Dicyandiamide ・ ・ ・ 2.8 parts by mass

-Production of photosensitive film-
As shown in FIG. 46, 25 μm-thick polyethylene terephthalate film (PET) is used as the support 1, and the photosensitive composition coating liquid is dried on the support 1 using a bar coater. Was applied in a hot air circulating dryer at 80 ° C. for 30 minutes to prepare a photosensitive film.

<Formation of permanent pattern>
-Preparation of laminate-
Next, the substrate was prepared by subjecting the surface of a copper-clad laminate (printed wiring board having no through hole and a copper thickness of 12 μm) on which wiring had been formed to chemical polishing. On the copper-clad laminate, the photosensitive layer of the photosensitive film is in contact with the copper-clad laminate, and is laminated using a vacuum laminator (MVLP500, manufactured by Meiki Seisakusho). A laminate was prepared in which the photosensitive layer and the polyethylene terephthalate film (support) were laminated in this order. The pressure bonding conditions were a pressure bonding temperature of 90 ° C., a pressure bonding pressure of 0.4 MPa, and a laminating speed of 1 m / min.

-Exposure process-
A predetermined pattern can be obtained with a laser beam of 405 nm from the polyethylene terephthalate film (support) side using the pattern forming apparatus by blue-violet laser exposure having a predetermined pattern with respect to the photosensitive layer in the prepared laminate. In this way, an energy amount of 40 mJ / cm ² was irradiated for exposure, and a partial region of the photosensitive layer was cured.

-Development process-
After standing at room temperature for 10 minutes, the polyethylene terephthalate film (support) is peeled off from the laminate, and a 1% by mass aqueous sodium carbonate solution is used as an alkaline developer on the entire surface of the photosensitive layer on the copper clad laminate. Spray development was performed at 30 ° C. for 60 seconds at a pressure of 0.18 MPa (1.8 kgf / cm ² ) to dissolve and remove unexposed areas. Thereafter, it was washed with water and dried to form a permanent pattern. The developability and photosensitivity were evaluated using the obtained images.

-Curing process-
The entire surface of the laminate on which the permanent pattern was formed was subjected to heat treatment at 150 ° C. for 1 hour to cure the surface of the permanent pattern, increase the film strength, and prepare a test plate.

  With respect to the obtained test plate, an insulation resistance test (Ω) was measured as described in detail later. Moreover, about the coating film peeled from the board | substrate (copper clad laminated board), the dynamic elastic modulus (storage elastic modulus) (MPa) was measured by the dynamic viscoelasticity measurement test. Table 7 shows the measurement results. Details of measurement and evaluation by the reliability test are as described later.

<Applied surface>
The surface of the photosensitive composition coating solution after coating and drying was visually observed on a 25 μm thick polyethylene terephthalate support, and the surface smoothness was inspected.
〔Evaluation criteria〕
○: Smooth ×: Foreign matter or repellency

<Surface tackiness>
A photosensitive solution is applied and dried on a polyethylene terephthalate support having a thickness of 25 μm to form a photosensitive layer having a thickness of 10 μm, and a polypropylene cover film having a thickness of 12 μm is laminated at room temperature, and then allowed to stand overnight. After peeling from the layer, the peelability of the cover film was tested.
〔Evaluation criteria〕
○: Easy to peel ×: Power is required to peel off, and a peeling sound is produced

<Sensitivity>
Using a pattern forming apparatus by blue-violet laser exposure having a predetermined step wedge pattern (Δlog E = 0.15, 15 steps) from the polyethylene phthalate film side to an unexposed photosensitive layer having a thickness of 10 μm on the substrate, Laser irradiation was performed at 40 mJ / cm ² , spray development was performed at 30 ° C. for 60 seconds using a 1% by mass aqueous sodium carbonate solution, and the number of step wedge patterns obtained was evaluated.
〔Evaluation criteria〕
○: 8 steps or more △: 5 to 7 steps ×: 4 steps or less

<Developability>
An unexposed photosensitive layer having a thickness of 10 μm on the substrate was spray-developed at 30 ° C. using a 1% by mass aqueous sodium carbonate solution and evaluated by whether it could be removed in 10 to 60 seconds.
〔Evaluation criteria〕
○: Removed in 10 seconds to less than 60 seconds, no development residue ×: Removed in less than 10 seconds XX: Development residue even after 60 seconds

<Appearance of solder resist (back bake shape)>
After baking at 150 ° C. for 1 hour, the surface unevenness of the solder resist pattern was measured using a surface roughness measuring machine (Surfcom 1400D: manufactured by Tokyo Seimitsu Co., Ltd.) and evaluated based on the following criteria.
〔Evaluation criteria〕
○: Ra = less than 0.5 μm and excellent in surface shape ×: Ra = 0.5 μm or more, inferior in surface shape

<Adhesion>
In accordance with JISK5400, 100 1 mm grids were prepared on the cured test piece, and a peel test was performed using cellophane tape (registered trademark). The peeled state of the grid was observed and evaluated according to the following criteria.
〔Evaluation criteria〕
○: No peeling at 90/100 or more Δ: No peeling at 50/100 or more to less than 90/100 ×: No peeling at 0/100 to less than 50/100

<Solvent resistance>
The cured test piece was immersed in isopropyl alcohol at room temperature for 30 minutes, and after confirming that there was no abnormality in the appearance, a peel test was performed with a cellophane tape, and the following criteria were evaluated.
〔Evaluation criteria〕
○: No abnormality in the appearance of the coating film and no peeling ×: No abnormality in the appearance of the coating film or peeling

<Acid resistance>
After curing, the test piece was immersed in a 10% by mass hydrochloric acid aqueous solution at room temperature for 30 minutes, and after confirming that there was no abnormality in the appearance, a peel test was performed using a cellophane tape, and the following criteria were evaluated.
〔Evaluation criteria〕
○: No abnormality in the appearance of the coating film and no peeling ×: No abnormality in the appearance of the coating film or peeling

<Alkali resistance>
The test piece after curing was immersed in a 5% by mass aqueous sodium hydroxide solution at room temperature for 30 minutes, and after confirming that there was no abnormality in the appearance, a peel test was performed using a cellophane tape, and the following criteria were evaluated.
〔Evaluation criteria〕
○: There is no abnormality in the appearance of the coating film and there is no peeling ×: There is an abnormality in the appearance of the coating film or peeling

<Solder heat resistance>
A rosin-based flux or a water-soluble flux was applied to the test piece and immersed in a solder bath at 260 ° C. for 10 seconds. After repeating this for 6 cycles, the appearance of the coating film was visually observed and evaluated according to the following criteria.
〔Evaluation criteria〕
○: There is no abnormality (peeling, blistering) in the coating film appearance, and there is no solder peeling ×: There is an abnormality (peeling, blistering) in the coating film appearance, or there is solder peeling

<Gold resistance>
A test substrate on which a solder resist pattern was formed on a gold-resistant plating substrate was immersed in an acidic degreasing solution (manufactured by Nihon McDermitt, 20 vol% aqueous solution of Metex L-5B) for 3 minutes, and then washed with water. Next, the test substrate was immersed in a 14.4 mass% ammonium persulfate aqueous solution for 3 minutes at room temperature, then washed with water, and further, the test substrate was immersed in a 10 vol% sulfuric acid aqueous solution at room temperature for 1 minute and then washed with water. Next, this substrate was immersed in a 30 ° C. catalyst solution (Meltex, 10 vol% aqueous solution of metal plate activator 350) for 7 minutes, washed with water, and 85 ° C. nickel plating solution (Meltex, Melplate) After Ni-8, it was immersed in a 10 vol% sulfuric acid aqueous solution at room temperature for 1 minute and washed with water.The test substrate was then subjected to 95 ° C. gold plating solution (Meltex Co., Ouro-Retroless UP 15 vol% and potassium gold cyanide 3 vol%). It was immersed in an aqueous solution, pH 6) for 10 minutes, subjected to electroless gold plating, washed with water, further immersed in warm water at 60 ° C. for 3 minutes, washed with water, and dried, and the obtained electroless gold plating evaluation substrate was observed. Observation was made on the adhesion failure of the plating and the presence or absence of plating moggles, which were evaluated according to the following criteria.
〔Evaluation criteria〕
○: No abnormality at all ×: Plating adhesion failure or plating moguri observed

<Insulation resistance test>
Using IPC-B-25 comb-shaped test pattern B, applying a photomask for pattern B, exposing the entire surface with the laser device at 40 mJ / cm ² , 1 mass% sodium carbonate at 30 ° C. for 60 seconds Development with an aqueous solution, washing with water and drying were carried out, and a test substrate was prepared by post-heating treatment at 150 ° C. for 1 hour. About the obtained test board | substrate, the insulation resistance in a normal state was measured in accordance with the test method of IPC-SM-840B.
[Criteria]
○: Insulation resistance value is 10 ¹⁰ Ω or more ×: Insulation resistance value is less than 10 ¹⁰ Ω

<PCT (pressure cooker test) resistance>
The PCT resistance test substrate was allowed to stand in water at 121 ° C. and 2 atm for 96 hours, and after confirming that there was no abnormality in appearance, a peeling test using cello tape (registered trademark) was conducted, and evaluation was performed according to the following criteria.
〔Evaluation criteria〕
○: Appearance of the coating film is normal and there is no swelling or peeling ×: Coating film has swelling or peeling

<Heat shock resistance>
As a reliability test item, a temperature cycle test (TCT) was used to evaluate the appearance such as cracks and peeling and the resistance value change rate. TCT uses a gas-phase cold-heat test machine, and the solder resist-formed substrate is left on the comb-shaped electrode substrate in a gas phase at temperatures of −55 ° C. and 125 ° C. for 30 minutes each, and this is 1,000 for one cycle. The thermal shock resistance was evaluated according to the following criteria.
〔Evaluation criteria〕
○: No crack occurred △: Shallow crack occurred ×: Deep crack occurred

<Dynamic elasticity>
Using a solid analyzer RSAII (Rheometrics), dynamic elastic viscoelasticity was measured at a vibration frequency of 1 Hz (6.28 rad / sec). Sample size: length 22.5 x width 3.0 x thickness 0.06 mm, measurement temperature 40 to 250 ° C (temperature rise 5 ° C / min), tensile amount 0.15%, mode static force tracking dynamic force The initial static force was 15.0 g, and the dynamic elastic modulus at 220 ° C. was examined.

<Folding resistance>
Each photosensitive composition of Examples 1 to 13 and Comparative Examples 1 to 4 is applied to a bar coating method or a non-adhesive two-layer flexible substrate made of a rolled copper foil (thickness = 35 μm) on a polyimide substrate (thickness = 25 μm). A photosensitive layer was formed by coating by screen printing. Next, after exposure at 500 mJ / cm ² , a cured film (thickness = 35 μm) is formed by heating at 160 ° C. for 2 hours, and using VCM FLEX TEESTER (IPC-FC241C, JIS-C5016), temperature = room temperature, Evaluation was made based on the bending life (number of times) from when bending was performed to cracking of copper under the conditions of frequency = 25 Hz, stroke = 25 mm, and radius of curvature = 2 mm.
[Evaluation criteria]
○: Bending life 5000 times or more ×: Bending life less than 5000 times

(Example 2 to Example 13)
For Example 2 to Example 13, in Example 1, as shown in Table 5, except that the composition was changed, the photosensitive film of each Example was produced in the same manner as Example 1, A photosensitive layer was formed and evaluated for reliability. The results are shown in Table 7.

(Comparative Examples 1-9)
About Comparative Examples 1-9, as shown in Table 6 in Example 1, except having changed composition, the photosensitive film of each comparative example was produced like Example 1, and it continued, and photosensitive layer The reliability was evaluated. The results are shown in Table 8.

  From the results of Tables 7 and 8, in Examples 1 to 13, by including the elastomer of the present invention in the photosensitive composition, the developability is improved, and the adhesion to the substrate is not deteriorated. An excellent photosensitive composition capable of forming a highly sensitive photosensitive solder resist was obtained. In addition, by using the photosensitive composition, it is possible to obtain a solder resist pattern having a high-performance cured film that has excellent heat resistance, moist heat resistance, adhesion, mechanical properties, electrical properties, and sufficient film strength. did it.

The elastomer of the present invention can provide a high-performance cured film excellent in heat resistance, heat and humidity resistance, adhesion, mechanical properties, and electrical properties. Photosensitive solder resist, interlayer insulating film for printed circuit boards, color resist for color filters , Photosensitive lithographic printing plates, various protective films, flattening films, photoresists for etching and plating, photosensitive pastes, holograms, microlenses, UV curable inks, UV curable paints, etc. .
Further, the photosensitive composition of the present invention using the elastomer and the photosensitive film using the photosensitive composition are excellent in storage stability and exhibit excellent chemical resistance, surface hardness, heat resistance, etc. after development. To do. In addition, even if the permanent pattern (protective film, interlayer insulating film, solder resist, etc.) of the present invention is thinned, a high-definition permanent pattern excellent in surface hardness, insulation, heat resistance, and moisture resistance can be obtained. It can be suitably used as a protective film and interlayer insulating film, and can be used for printed wiring boards (multi-layer wiring boards, build-up wiring boards, etc.), color filters, pillar materials, rib materials, spacers, display members such as partition walls, holograms, It can be widely used for forming permanent patterns such as micromachines and proofs.

FIG. 1 is an example of a partially enlarged view showing a configuration of a digital micromirror device (DMD). 2A and 2B are examples of explanatory diagrams for explaining the operation of the DMD. FIGS. 3A and 3B are examples of plan views showing the arrangement of the exposure beam and the scanning line in a case where the DMD is not inclined and in a case where the DMD is inclined. 4A and 4B are examples of diagrams illustrating examples of DMD usage areas. FIG. 5 is an example of a plan view for explaining an exposure method in which the pattern forming material is exposed by one scanning by the scanner. 6A and 6B are examples of plan views for explaining an exposure method for exposing a pattern forming material by a plurality of scans by a scanner. FIG. 7 is an example of a schematic perspective view illustrating an appearance of an example of the pattern forming apparatus. FIG. 8 is an example of a schematic perspective view illustrating the configuration of the scanner of the pattern forming apparatus. FIG. 9A is an example of a plan view showing an exposed region formed in the pattern forming material, and FIG. 9B is an example of a diagram showing an array of exposure areas by each exposure head. FIG. 10 is an example of a perspective view showing a schematic configuration of an exposure head including light modulation means. FIG. 11 is an example of a sectional view in the sub-scanning direction along the optical axis showing the configuration of the exposure head shown in FIG. FIG. 12 is an example of a controller that controls DMD based on pattern information. FIG. 13A is an example of a cross-sectional view along the optical axis showing the configuration of another exposure head having a different coupling optical system, and FIG. 13B shows the exposure when a microlens array or the like is not used. FIG. 13C is an example of a plan view showing a light image projected on a surface to be exposed when a microlens array or the like is used. FIG. 14 is an example of a diagram showing the distortion of the reflection surface of the micromirror constituting the DMD with contour lines. FIGS. 15A and 15B are examples of graphs showing the distortion of the reflection surface of the micromirror in the two diagonal directions of the mirror. FIG. 16 is an example of a front view (A) and a side view (B) of a microlens array used in the pattern forming apparatus. FIG. 17 is an example of a front view (A) and a side view (B) of a microlens constituting a microlens array. FIG. 18 is an example of a schematic diagram illustrating a condensing state by a microlens in one cross section (A) and another cross section (B). FIG. 19a is an example of a diagram showing the result of simulating the beam diameter in the vicinity of the condensing position of the microlens of the present invention. FIG. 19B is an example of a diagram showing the same simulation result as that in FIG. 19A at another position. FIG. 19c is an example of a diagram showing the same simulation result as in FIG. 19a at another position. FIG. 19d is an example of a diagram showing the same simulation result as in FIG. 19a at another position. FIG. 20a is an example of a diagram showing the result of simulating the beam diameter in the vicinity of the condensing position of the microlens in the conventional pattern forming method. FIG. 20b is an example of a diagram showing the same simulation result as in FIG. 20a at another position. FIG. 20c is an example of a diagram showing the same simulation result as in FIG. 20a for another position. FIG. 20d is an example of a diagram illustrating simulation results similar to those in FIG. 20a at different positions. FIG. 21 is an example of a plan view showing another configuration of the combined laser light source. FIG. 22 shows an example of a front view (A) and an example of a side view (B) of the microlens constituting the microlens array. FIG. 23 is an example of a schematic diagram illustrating a light condensing state by the microlens of FIG. 22 in one cross section (A) and another cross section (B). 24A, 24B, and 24C are examples of explanatory diagrams about the concept of correction by the light amount distribution correction optical system. FIG. 25 is an example of a graph showing the light amount distribution when the light irradiation means has a Gaussian distribution and the light amount distribution is not corrected. FIG. 26 is an example of a graph showing the light amount distribution after correction by the light amount distribution correcting optical system. 27A (A) is a perspective view showing the configuration of the fiber array light source, FIG. 27A (B) is an example of a partially enlarged view of FIG. 27A, and FIGS. 27A (C) and (D) are lasers. It is an example of the top view which shows the arrangement | sequence of the light emission point in an emission part. FIG. 27 b is an example of a front view showing the arrangement of light emitting points in the laser emission part of the fiber array light source. FIG. 28 is an example of a diagram illustrating a configuration of a multimode optical fiber. FIG. 29 is an example of a plan view showing the configuration of the combined laser light source. FIG. 30 is an example of a plan view showing the configuration of the laser module. FIG. 31 is an example of a side view showing the configuration of the laser module shown in FIG. 32 is a partial side view showing the configuration of the laser module shown in FIG. FIG. 33 is an example of a perspective view showing a configuration of a laser array. FIG. 34A is an example of a perspective view showing a configuration of a multi-cavity laser, and FIG. 34B is a perspective view of a multi-cavity laser array in which the multi-cavity lasers shown in FIG. It is an example. FIG. 35 is an example of a plan view showing another configuration of the combined laser light source. FIG. 36A is an example of a plan view showing another configuration of the combined laser light source, and FIG. 36B is an example of a cross-sectional view along the optical axis of FIG. FIGS. 37A and 37B are examples of cross-sectional views along the optical axis showing the difference between the depth of focus in the conventional exposure apparatus and the depth of focus by the pattern forming method (pattern forming apparatus) of the present invention. FIG. 38 is a front view (A) and a side view (B) showing another example of the microlens constituting the macro array. FIG. 39 is an example of a front view (A) and a side view (B) of a microlens constituting a macro array. FIG. 40 is a graph showing a spherical lens shape example. FIG. 41 is a graph showing another lens surface shape example. FIG. 42 is a perspective view showing another example of the microlens array. FIG. 43 is a plan view showing another example of the microlens array. FIG. 44 is a plan view showing another example of the microlens array. 45A to 45C are longitudinal sectional views showing other examples of the microlens array. FIG. 46 is an explanatory view showing the layer structure of the photosensitive solder resist film.

Explanation of symbols

LD1-LD7 GaN-based semiconductor laser 10 Heat block 11-17 Collimator lens 20 Condensing lens 30-31 Multimode optical fiber 44 Collimator lens holder 45 Condensing lens holder 46 Fiber holder 50 Digital micromirror device (DMD)
52 Lens system 53 Reflected light image (exposure beam)
54 Lens of second imaging optical system 55 Micro lens array 55a Micro lens 55a 'Micro lens 55a "Micro lens 56 Surface to be exposed (scanning surface)
57 Lens of second imaging optical system 58 Lens of second imaging optical system 59 Aperture array 64 Laser module 66 Fiber array light source 67 Lens system 68 Laser emitting unit 69 Mirror 70 Prism 71 Condensing lens 72 Rod integrator 73 Combination lens 74 Imaging lens 100 Heat block 110 Multi cavity laser 111 Heat block 113 Rod lens 120 Condensing lens 130 Multimode optical fiber 130a Core 140 Laser array 144 Light irradiation means 150 Pattern forming material 152 Stage 155a Micro lens 156 Installation table 158 Guide 160 Gate 162 Scanner 164 Sensor 166 Exposure head 168 Exposure area 170 Exposed area 180 Heat block 184 Collimating lens Ray 255 Micro lens array 255a Micro lens 302 Controller 304 Stage drive device 355 Micro lens array 355a Micro lens 454 Lens system 455 Micro lens array 455a Micro lens 468 Exposure area 472 Micro lens array 474 Micro lens 476 Aperture array 478 Aperture 480 Lens system 555 Micro lens array 555a Micro lens 655 Micro lens array 655a Micro lens 755 Micro lens array 755a Micro lens 855 Micro lens array 855a Micro lens

Claims (16)

(A) a diisocyanate compound, (B) a diol compound containing at least one carboxyl group in the molecule, (C) a diol compound containing at least one unsaturated group in the molecule, and (D) a weight average molecular weight. Is obtained by reacting the diisocyanate compound (A) in a molar amount of 1.0 to 2 times the total molar amount of all diol compounds.
The elastomer characterized in that the content of the high molecular weight diol compound as the component (D) is 3 to 20 mol%. (A) a diisocyanate compound represented by the following general formula (I);
(B) at least one carboxylic acid group-containing diol compound represented by any one of the following general formulas (II-1) to (II-3), (C) the following general formulas (III-1) to (III- 2) at least one epoxy acrylate compound represented by any one of the above, and (D) at least one diol compound represented by any one of the following general formulas (IV-1) to (IV-5): The elastomer according to claim 1, which is a reaction product obtained by reacting.
However, in the general formula (I), R ¹ is a divalent aliphatic hydrocarbon group which may have a substituent and a divalent aromatic hydrocarbon group which may have a substituent. Represents either.
However, the general formula (II-1), (II -2), and in (II-3), ^{R 2} represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, or an alkoxy group and aryloxy group, These may be further substituted with a substituent. R ³ , R ⁴ , and R ⁵ may be the same as or different from each other, and each represents a single bond, an alkylene group, or an arylene group, and these are further substituted with a substituent. Alternatively, two or three of R ² , R ³ , R ⁴ , and R ⁵ may form a ring. Ar represents a trivalent aromatic hydrocarbon group which may have a substituent.
However, in the above general formula (III-1) and (III-2), ^{R 8} represents a hydrogen atom, or an optionally substituted alkyl group. R ^{9 to} R ¹⁶ may be the same as or different from each other, and each represents a hydrogen atom, a halogen atom, or an alkyl group that may have a substituent. R ^{17 to} R ³² may be the same as or different from each other, and each may have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, or a substituent. Represents a good alkoxy group.
However, in the general formulas (IV-1) to (IV-5), R ³³ , R ³⁴ , R ³⁵ , R ³⁶ and R ³⁷ may be the same as or different from each other. It represents either an alkylene group or an arylene group, which may be further substituted with a substituent. R ³⁸ represents a hydrogen atom, a cyano group, a halogen atom, an alkyl group, or an aryl group and aralkyl group, and these may be further substituted by substituents. R ³⁹ represents a cyano group or an aryl group which may have a substituent. m shows the integer of 2-4. n ₁ , n ₂ , n ₃ , n ₄ and n ₅ each represents an integer of 2 or more. n ₆ represents, represents 0 or an integer of 2 or more.   Component (A): Component (B): Component (C): Component (D) are copolymerized at a ratio of 33 to 50 mol%: 16 to 33 mol%: 7 to 40 mol%: 3 to 20 mol%, respectively. And the ratio of the total number of moles of the component (A) to the total number of moles of the component (B), the component (C), and the component (D) is 1.0 to 2.0. The elastomer according to claim 1. The elastomer according to any one of claims 1 to 3, which has an acid value of 20 to 70 mgKOH / g and a bromine value of ₂ to 50 gBr2 / 100 g.   A photosensitive composition comprising the elastomer according to any one of claims 1 to 4, a polymerizable compound, a photopolymerization initiator, a thermal crosslinking agent, and a colorant.   The photosensitive composition according to claim 5, wherein the thermal crosslinking agent is one of an epoxy compound and a polyfunctional oxetane compound.   The photosensitive composition in any one of Claim 5 to 6 containing an inorganic filler.   A photosensitive film comprising: a support; and a photosensitive layer obtained by laminating the photosensitive composition according to claim 5 on the support.   The method for forming a permanent pattern according to claim 8, wherein the photosensitive layer is transferred to the surface of the substrate, then exposed and developed.   A photosensitive composition according to any one of claims 5 to 7 is applied to the surface of a substrate, dried to laminate a photosensitive layer to form a laminate, and then exposed and developed. Permanent pattern forming method.   The exposure is performed through a microlens array in which microlenses having aspherical surfaces capable of correcting aberrations due to distortion of the exit surface of the picture element portion in the light modulation means after the light is modulated by the light modulation means. The permanent pattern formation method in any one of 9 to 10.   The exposure is performed through a microlens array in which microlenses having a lens opening shape in which light from a peripheral portion of a picture element portion in the light modulation unit is not incident after the light is modulated by the light modulation unit. To 10. The pattern forming method according to any one of 10 to 10.   The permanent pattern forming method according to claim 11, wherein the aspherical surface is a toric surface.   The permanent pattern forming method according to claim 9, wherein after the development, the photosensitive layer is cured.   The permanent pattern formation method according to claim 14, wherein the curing process is at least one of a whole surface exposure process and a whole surface heat treatment performed at 120 to 200 ° C. The permanent pattern forming method according to claim 9, wherein at least one of a protective film, an interlayer insulating film, and a solder resist pattern is formed.