JP2006243564A - Photosensitive composition and photosensitive film, and permanent pattern and method for forming the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive composition for forming an image by UV exposure, excellent in storage stability and exhibiting excellent chemical resistance, surface hardness, heat resistance, moisture resistance and insulation after development, a photosensitive film obtained by using the photosensitive composition, a high definition permanent pattern using the photosensitive film, excellent in heat history at the time of mounting and in thermal fatigue resistance in a temperature cycling test (TCT) even in the case of a thin layered permanent pattern (a protective film, an interlayer insulation film, a solder resist or the like), free from the occurrence of ion migration in a highly accelerated stress test (HAST) and excellent in moisture resistance, and a method for efficiently forming the permanent pattern. <P>SOLUTION: The photosensitive composition comprises an alkali-soluble photo-crosslinkable resin, a polymerizable compound, a photopolymerization initiator, a thermal crosslinking agent, an elastomer, an inorganic filler, a colorant, a heat curing accelerator and a solvent, wherein the photosensitive composition is subjected to ion adsorption treatment with an ion adsorbent. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a photosensitive composition, a photosensitive film using the same, and a high-definition permanent pattern (such as a protective film, an interlayer insulating film, and a solder resist), and particularly used for wiring boards and electronic component modules. Permanent pattern with excellent heat resistance during mounting, thermal fatigue in temperature cycle test (TCT) and moisture resistance to high acceleration test (HAST), excellent storage stability, chemical resistance, surface hardness, insulation, etc. It relates to an efficient forming method.

  In recent years, electronic devices have been reduced in size, thickness, and weight as represented by mobile communication devices, and high performance, high functionality, high quality, and high reliability have been required. Yes. Electronic component modules mounted on such electronic devices are also required to be smaller and higher in density. In response to such demands, in recent years, the surface of a ceramic wiring board made of ceramics such as an aluminum oxide sintered body, or an insulating board made of glass fiber and epoxy resin that can be made lighter and more dense. In addition, so-called printed wiring boards, 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, have been used for electronic component modules. This printed wiring board is changing to a build-up wiring board capable of achieving higher density wiring.

Such a build-up wiring board, for example, on the insulating substrate made of glass fiber and epoxy resin, after applying the photosensitive composition solution and drying to form an insulating layer, then exposure and development to this, After forming an opening or laminating a film made of a thermosetting resin and thermosetting to form an insulating layer, an opening is formed in the insulating layer with a laser, and then the surface of the insulating layer is chemically roughened. By depositing and forming a copper film using an electrolytic copper plating method and an electrolytic copper plating method, a conductor layer is formed in the opening and a wiring conductor layer is formed on the surface of the insulating layer. Furthermore, a multilayer build-up wiring board is produced by repeating the formation of the insulating layer and the wiring conductor layer.
Further, a solder having a thickness of 20 to 50 μm is provided on the surface of the printed wiring board in order to prevent oxidation and corrosion of the wiring conductor layer and to protect the insulating layer from heat when mounting electronic components on the printed wiring board. A resist layer (permanent pattern) is deposited. This solder resist layer is generally composed of an alkali-soluble photocrosslinkable resin having good adhesion to the wiring conductor layer and the insulating layer, and a flexible resin, and has a thermal expansion coefficient of the insulating layer or the wiring conductor. In order to match the thermal expansion coefficient of the layer, the inorganic filler is contained in an amount of 5 to 75% by mass.
Further, the printed circuit board forms an opening in the solder resist layer on the wiring conductor layer by exposure and development, and electrically connects the electronic component to the wiring conductor layer in the opening through a conductor bump made of solder or the like. Connected to an electronic component module such as a semiconductor device.
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 for the alkali-soluble photocrosslinkable resin contained to develop developability when an opening is formed in the solder resist layer by exposure and development. Yes. Therefore, the solder resist layer has a high water absorption rate, and gradually absorbs moisture in the air. This moisture reduces the insulation resistance of the solder resist layer to 10 ⁸ Ω or less, and the wiring conductor layers are short-circuited. And the electrical reliability of the printed wiring board is impaired, for example, the wiring conductor layer is corroded.

  Further, the photosensitive composition contained in the solder resist layer contains impurity ions composed of halogen ions such as chlorine ions and bromine ions, and alkali ions such as sodium ions, which cannot be removed during the purification process of the production. For example, when a high acceleration test (HAST) is performed in which a voltage of 5.5 V is applied for a long time in a high-temperature and high-humidity tank having a temperature of 130 ° C. and a relative humidity of 85%. There is a problem that the insulation resistance between the wiring conductor layers is abruptly lowered due to ion migration, causing dielectric breakdown, and as a result, the electronic component module is electrically short-circuited.

  In order to solve such problems, a photosensitive composition for a solder resist added with a fine particle ion adsorbent such as an inorganic ion exchanger that adsorbs the impurity ions in the photosensitive composition and prevents the occurrence of ion migration. (See Patent Document 1), a photosensitive solder resist layer (see Patent Document 2) to which a chelating polymer that traps impurity ions is added, and a method for removing metal ions from a polyamide compound by filtration using a filter medium (Patent Document) 3) is proposed.

  However, in the case of a proposal of a photosensitive composition to which a fine particle ion adsorbent such as an inorganic ion exchanger that prevents the occurrence of ion migration is proposed, the inorganic ion exchanger particles are likely to aggregate, such as a temperature cycle test (TCT). Cracks are likely to occur due to the stress concentration generated in the heat fatigue test. As a result, disconnection occurs in the wiring conductor layer, and there is a problem that reliability of electrical connection of the wiring board is lowered.

  In addition, in the case of the proposal of the photosensitive solder resist layer to which the chelate polymer that traps the impurity ions is added, since the trapped impurity ions remain in the solder resist layer, it is still insufficient for ensuring the reliability. is there. Moreover, in order to make a chelate polymer such as an imide diacetate styrene-methyl acrylate copolymer to act effectively, a large addition amount of 1 to 10% by mass is required, and the adverse effect on the cured film physical properties of the solder resist layer is small. There is a problem of being recognized.

  In addition, in the case of a proposal of a method for removing metal ions of a polyamide compound by filtration using the filter medium filter, the method of passing the polyamide compound used in the proposal is inferior in processing capacity per unit time, and is a photosensitive solder resist. There is a problem that it is not suitable for mass production.

JP 2000-159859 A JP 2002-31889 A JP 2003-238682 A

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, the present invention provides a photosensitive composition that can form an image by UV exposure, has excellent storage stability, and exhibits excellent chemical resistance, surface hardness, heat resistance, moisture resistance, insulation, and the like after development, and the like. The photosensitive film used and the permanent pattern (protective film, interlayer insulating film, solder resist, etc.) that is thinned using the photosensitive film, and the thermal history and temperature cycle test during mounting (TCT) It is an object of the present invention to provide a high-definition permanent pattern excellent in heat fatigue resistance and free from ion migration in a high acceleration test (HAST) and having excellent moisture resistance and an efficient formation method thereof.

Means for solving the problems are as follows. That is,
<1> Photosensitivity containing an alkali-soluble photocrosslinkable resin, a polymerizable compound, a photopolymerization initiator, a thermal crosslinker, an elastomer, an inorganic filler, a colorant, a thermosetting accelerator, and a solvent. A photosensitive composition, wherein the photosensitive composition is subjected to an ion adsorption treatment with an ion adsorbent.
In the photosensitive composition of <1>, when the photosensitive composition is subjected to an ion adsorption treatment, metal ions such as Na ions and K ions, chlorine ions and bromine contained in the photosensitive composition. Impurity ions consisting of halogen ions such as ions are captured and removed, the occurrence of ion migration is suppressed, and the wiring substrate having a permanent pattern (solder resist) formed using the photosensitive composition has an electron. Even if heat is applied by component mounting, decomposition due to the thermal history is prevented, and insulation is improved.
<2> The photosensitive composition according to <1>, wherein the ion adsorbent includes at least one of a metal ion adsorbent and an anion exchange resin.
In the photosensitive composition of <2>, since the ion adsorbent contains at least one of a metal ion adsorbent and an anion exchange resin, the impurity ions contained in the photosensitive composition are favorably adsorbed. The
<3> The photosensitive composition according to any one of <1> to <2>, wherein the metal ion adsorbent is any one of viscosity interlayer compounds.
In the photosensitive composition <3>, the metal ion adsorbent is any one of the viscosity interlayer compounds, and thus the metal ions contained in the photosensitive composition are favorably adsorbed.
<4> The ion adsorption treatment is performed before the photosensitive composition is applied, and the ions in the photosensitive composition are adsorbed by a batch method with an ion adsorbent and filtered to remove adsorbed ions. <1> to the photosensitive composition according to any one of <3>.
In the photosensitive composition according to <4>, when the ion adsorption treatment is performed before the photosensitive composition is applied, ions in the photosensitive composition are adsorbed, and ions to be adsorbed are filtered. Therefore, the impurity ions can be easily adsorbed and filtered under a low viscosity of the coating solution before a photosensitive film or the like is formed from the photosensitive composition.
<5> The solid content concentration of the photosensitive composition is 10 to 60% by mass, and the viscosity of the photosensitive composition is 5 to 60 cp at 25 ° C. It is a photosensitive composition of description.
In the photosensitive composition of <5>, since the solid content concentration of the photosensitive composition is 10 to 60% by mass, and the viscosity of the photosensitive composition is 5 to 60 cp at 25 ° C., Ions are easily adsorbed and filtered in a low-viscosity state, and are uniformly applied to a support or a substrate, thereby obtaining a high-definition permanent pattern.
<6> The content of the metal ion photosensitive composition in the solid content is 3 ppm or less, and the content of the anion in the solid content of the photosensitive composition is 1 ppm or less <1>. To <5>.
In the photosensitive composition of <6>, the content of metal ions in the solid content in the photosensitive composition is 3 ppm or less by the ion adsorption treatment, and the photosensitive composition of halogen ions is not more than 3 ppm. The content in the solid content is suppressed to 1 ppm or less, and the photosensitive composition is excellent in storage stability and excellent in chemical resistance, surface hardness, heat resistance, moisture resistance and insulation after development.
<7> The photosensitive composition according to any one of <1> to <6>, wherein the thermal crosslinking agent is any one of an epoxy resin and a polyfunctional oxetane compound.
In the photosensitive composition of <7>, when the thermal crosslinking agent is any one of an epoxy resin and a polyfunctional oxetane compound, chemical resistance, surface hardness, heat resistance, moisture resistance, and insulation are excellent. A photosensitive composition is obtained.
<8> The photosensitive composition according to any one of <1> to <7>, wherein the elastomer is any one of alkali-soluble urethane elastomers.
In the photosensitive composition of <8>, at least one of the alkali-soluble urethane elastomers is contained, and the alkali-soluble urethane elastomer is composed of a hard segment component and a soft segment component. As a result, heat resistance and strength are improved, and the latter has an effect of improving flexibility and toughness. Therefore, when the photosensitive composition contains an elastomer, the thermal stress when the electronic component is mounted on the wiring board or when the temperature cycle test (TCT) is performed is favorably absorbed by the elastomer. In addition, the occurrence of cracks in the permanent pattern (solder resist) after thermosetting is suppressed, and as a result, a permanent pattern with high electrical connection reliability without disconnecting the wiring conductor layer is obtained.
<9> 15 to 70% by mass of an alkali-soluble photocrosslinkable resin, 5 to 75% by mass of a polymerizable compound, 0.5 to 20% by mass of a photopolymerization initiator, 2 to 50% by mass of a thermal crosslinker, and an elastomer 2 to 30% by mass, inorganic filler 5 to 75% by mass, colorant 0.1 to 10% by mass, thermosetting accelerator 0.01 to 20% by mass and solvent <1> to <8 > It is a photosensitive composition in any one of.
<10> The photosensitive composition according to any one of <1> to <9>, wherein the polymerizable compound includes at least one selected from monomers having a (meth) acryl group.
<11> 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 <1> to <10> containing 1 type.

<12> A photosensitive film comprising: a support; and a photosensitive layer obtained by laminating the photosensitive composition according to any one of <1> to <11> on the support. It is.
<13> The photosensitive film according to <12>, having a protective film on the photosensitive layer.
<14> The photosensitive film according to any one of <12> to <13>, wherein the photosensitive layer has a thickness of 3 to 100 μm.
<15> The photosensitive film according to any one of <12> to <14>, wherein the support includes a synthetic resin and is transparent.
<16> The photosensitive film according to any one of <12> to <15>, wherein the support has a long shape.

  <17> A photosensitive composition laminate comprising: a substrate; and a photosensitive layer obtained by laminating the photosensitive composition according to any one of <1> to <11> on the substrate. Is the body.

<18> Either of the photosensitive layer in the photosensitive film according to any one of <12> to <16> and the photosensitive layer in the photosensitive composition laminate according to <17> above, on the surface of the substrate. After lamination, the photosensitive layer is exposed to light and developed, thereby forming a permanent pattern.
In the method for forming a permanent pattern according to <18>, the photosensitive film according to any one of <12> to <16> 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 described in <17> 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.
<19> The method for forming a permanent pattern according to <18>, wherein the base material is a printed wiring board on which wiring has been formed.
In the permanent pattern forming method according to <19>, 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 used. High-density mounting on a wiring board or the like is possible.
<20> The permanent pattern forming method according to any one of <18> to <19>, wherein the exposure is performed imagewise based on pattern information to be formed.
<21> The permanent pattern according to any one of <18> to <20>, 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.
<22> From <18> to <21, 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.
<23> 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 <22>, wherein modulation is performed according to a signal.
<24> The light modulation means has n picture element parts, and forms any less than n picture element parts continuously arranged from the n picture element parts. The permanent pattern forming method according to any one of <18> to <23>, which is controllable according to pattern information.
In the method for forming a permanent pattern according to <24>, 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.
<25> The permanent pattern forming method according to any one of <18> to <24>, wherein the light modulation unit is a spatial light modulation element.
<26> The method for forming a permanent pattern according to <25>, wherein the spatial light modulation element is a digital micromirror device (DMD).
<27> The permanent pattern forming method according to any one of <24> to <26>, wherein the pixel part is a micromirror.
<28> 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 modulator after the light is modulated by the light modulator. The method for forming a permanent pattern according to any one of <24> to <27>.
<29> The method for forming a permanent pattern according to <28>, wherein the aspherical surface is a toric surface.
In the method for forming a permanent pattern according to <29>, 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 photosensitive layer. Image distortion is efficiently suppressed. As a result, the photosensitive layer is exposed with high definition. Thereafter, the photosensitive layer is developed to form a high-definition permanent pattern.
<30> The method for forming a permanent pattern according to any one of <18> to <29>, wherein the exposure is performed through an aperture array.
In the method for forming a permanent pattern according to <30>, 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.
<31> The method for forming a permanent pattern according to any one of <18> to <30>, 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 <31>, exposure is performed at a high speed by performing exposure while relatively moving the modulated light and the photosensitive layer.
<32> The method for forming a permanent pattern according to any one of <18> to <31>, wherein the exposure is performed on a partial region of the photosensitive layer.
<33> The method for forming a permanent pattern according to any one of <18> to <32>, wherein the light irradiation unit can synthesize and irradiate two or more lights.
In the method for forming a permanent pattern described in <33>, the light irradiation unit 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.
<34> The above <18>, wherein the light irradiation means includes a plurality of lasers, a multimode optical fiber, and a collective optical system that condenses the laser beams emitted from the plurality of lasers and couples the laser beams to the multimode optical fiber. > To <33>.
In the method for forming a permanent pattern according to <34>, the light irradiation means allows the laser beams irradiated from the plurality of lasers to be condensed by the collective optical system and coupled to the multimode optical fiber. By doing so, 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.
<35> The permanent pattern forming method according to any one of <18> to <34>, wherein the exposure is performed using laser light having a wavelength of 395 to 415 nm.
<36> The method for forming a permanent pattern according to any one of <18> to <35>, wherein after the development, the photosensitive layer is cured.
In the permanent pattern forming method according to <36>, after the development, the curing treatment is performed on the photosensitive layer. As a result, the film strength of the cured region of the photosensitive layer is increased.
<37> The method for forming a permanent pattern according to <36>, 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 <37>, curing of the resin in the photosensitive composition is promoted in the overall 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.
<38> The method for forming a permanent pattern according to any one of <18> to <37>, wherein at least one of a protective film, an interlayer insulating film, and a solder resist pattern is formed.
In the method for forming a permanent pattern according to <38>, at least one of a protective film, an interlayer insulating film, and a solder resist pattern is formed. Protected from impact and bending.

<39> A permanent pattern formed by the method for forming a permanent pattern according to any one of <18> to <38>.
Since the permanent pattern according to <39> 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 parts. This is useful for high-density mounting on boards and build-up wiring boards.
<40> The permanent pattern according to <39>, wherein the amount of sodium ions in the permanent pattern is 3 ppm or less and the amount of halogen ions is 1 ppm or less.
<41> The permanent pattern according to any one of <39> to <40>, which is at least one of a protective film, an interlayer insulating film, and a solder resist pattern.
Since the permanent pattern according to <41> is at least one of a protective film, an interlayer insulating film, and a solder resist pattern, the wiring has an impact or bending from the outside due to the insulating property, heat resistance, etc. of the film. Protected from.

  According to the present invention, a photosensitive composition that can form an image by UV exposure, has excellent storage stability, and exhibits excellent chemical resistance, surface hardness, heat resistance, moisture resistance, insulation, and the like after development, and The photosensitive film used and the permanent pattern (protective film, interlayer insulating film, solder resist, etc.) that is thinned using the photosensitive film, and the thermal history and temperature cycle test during mounting (TCT) ) With excellent thermal fatigue resistance, no occurrence of ion migration in the high acceleration test (HAST), and a high-definition permanent pattern excellent in moisture resistance and an efficient formation method thereof.

(Photosensitive composition)
The photosensitive composition of the present invention comprises an alkali-soluble photocrosslinkable resin, a polymerizable compound, a photopolymerization initiator, a thermal crosslinker, an elastomer, an inorganic filler, a colorant, and a thermosetting accelerator. And a solvent and other components appropriately selected as necessary. The photosensitive composition is a photosensitive composition that has been subjected to ion adsorption treatment with an ion adsorbent.

  In the photosensitive composition, metal ions such as Na ion and K ion, and halogen ions such as chlorine ion and bromine ion are mixed in several hundred ppm, and these ions are formed from the photosensitive composition. It remains in the photosensitive film and the permanent pattern and causes a decrease in the insulation resistance (Ω) as impurity ions, which causes the product reliability to be impaired.

  Causes of the impurity ions to be mixed into the photosensitive composition include (1) contamination of the catalyst and side reaction products during the production of the photosensitive composition, and (2) contamination of salts when the compound is crystallized. Can be mentioned. As a specific example of said (1), reaction of epichlorohydrin and a phenol compound is normally used at the time of epoxy resin manufacture, and salt may be produced | generated and mixed as a side reaction product. Further, a quaternary ammonium salt is added as a catalyst to the reaction between the epoxy group and the carboxylic acid group used in the production of the alkali-soluble photocrosslinkable resin. If halogen ions such as chlorine ions and bromine ions are contained in the catalyst, the halogen ions may be mixed in the alkali-soluble photocrosslinkable resin. As a specific example of the above (2), there is a possibility that salts are mixed when crystallization with sodium chloride is carried out during the production of the color pigment.

<Ion adsorption treatment>
The ion adsorption treatment is a treatment in which the impurity ions are adsorbed with an ion adsorbent and filtered to remove the ions to be adsorbed from the photosensitive composition.

-Ion adsorbent-
There is no restriction | limiting in particular as said ion adsorption agent, According to the objective, it can select suitably, For example, a metal ion adsorption agent, an anion exchange resin, etc. are mentioned. These may be used alone or in combination of two or more.

The metal ion adsorbent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include clay intercalation compounds, other clay intercalation compounds, activated carbon, graphite, and other adsorbents.
The clay intercalation compound is not particularly limited and can be appropriately selected according to the purpose.For example, borofluorite, hakuryu stone, borosoda stone, faujasite stone, rhyolite, dehydrated calcium rheolite, gmelin fluorite, Sorter fluorite, menteite, scholes fluorite, Thomson fluorite, Edinton fluorite, Konald fluorite, sardine feldspar, kaiju sardite, dysmond fluorite, morden fluorite, dachial fluorite, kifluorite, clinoptilolite, habbahite Natural zeolites such as Brewster fluorite, duck fluorite, Nigawara fluorite, Ryokuchu stone, Kinsey stone, Mirror stone, Osumi stone, Kasumi stone, Kankuri stone, zeolite A type, zeolite NA type, zeolite X type, zeolite Y Type, Zeora Synthetic zeolite such as HS type, zeolite ZK-5 type, zeolite B type, zeolite Ω type, zeolite R type, zeolite G type, zeolite D type, zeolite lower type, zeolite L type, zeolite W type, zeolite C type, etc. Many structures with unknown structures have been synthesized (described in Kodansha, "Zeolite" (1988), Gihodo "Zeolite and its use" (1985), etc.). These synthetic zeolites are commercialized by, for example, Union Carbide and Mizusawa Chemical Industry Co., Ltd. under the trade names of Molecular Sieves or Mizugas Sieves, respectively.

Examples of the other clay intercalation compounds include kaolinite, antigolite, decaitite, chrysotile, nacrite, pyrosite, pyrophyllite, montmorillonite, talc, vermiculite, muscovite, phlogopite, margarite, xanthophyllite, chlorite. Among them, montmorillonite, magnesia montmorillonite, tetsu montmorillonite, tectum magnesia montmorillonite, hydelite, aluminian beidelite, nontronite, aluminian nontronite, support stone, aluminian Smectite group minerals (acid clay) such as sapphire, hectorite, sauconite, and borgon scoreite. In addition, this acidic clay is treated with a known technique disclosed in DE305352, for example, a mineral acid such as hydrochloric acid and sulfuric acid to elute a part of basic components such as aluminum, magnesium and iron. By doing so, it is possible to use so-called “active clay” which has increased the specific surface area significantly and further improved the adsorption capacity inherently several times, and furthermore, water molecules coordinate like montmorillonite. However, when dried, water molecules evaporate and pores are formed, increasing the adsorption capacity. Therefore, heat treatment or the like may be performed.
As described in “Development and application of intercalation compounds” (P13-P14 (1985) issued by CMC), mascobite, illite, montmorillonite, nontronite, saponite, kaolinite are used as cation exchangers. Allophane, kaolin mineral, chlorite, vermulite, and gibbsite can also be used as the anion exchanger.
The specific adsorption of these clay intercalation compounds is thought to occur by physical adsorption (van der Waalska) and chemical adsorption (adsorption caused by metal cations present in the crystal), and impurity ions in the composition component solution In order to adsorb efficiently, it is preferable to select and use the adsorbent type and shape as appropriate.

There is no restriction | limiting in particular as said activated carbon, According to the objective, it can select suitably, For example, "activated carbon" (1960) Kyoritsu publishing, J.T. Phys. Chem. 39 P35 (1935), and the like. These activated carbons are known to adsorb various inorganic substances, organic acids and the like, and can also adsorb impure metal components in the photosensitive composition solution very efficiently.
The activator is commercially available, for example, from Kuraray Chemical Co., Ltd., Mitsubishi Kasei Co., Ltd., etc., and any of commercially available products such as powdered activated carbon or granulated activated carbon may be used. It is preferable to use it after removing the adhering foreign substances, and the foreign substances are usually removed by washing with water, washing with acid, high temperature heating, washing with alkali, washing with an organic solvent, or the like.

  The graphite is not particularly limited and may be appropriately selected depending on the intended purpose. For example, natural graphite or artificial graphite may be used, which is commercially available from Mitsui Metal Mining Co., Ltd. or Tokai Carbon. Graphite can be used. The graphite can form an intercalation compound with an alkali metal or a metal halide (“synthetic metal” P131 to P135 (1980) chemical coterie), and when applied to a photosensitive composition solution, impure metal ion components are extremely efficient. It can be reduced well. However, like activated carbon, it is preferable to perform washing, drying, etc. sufficiently before use.

  There is no restriction | limiting in particular as said other adsorption agent, According to the objective, it can select suitably, For example, a silica gel, an alumina gel, an alumino silica gel etc. are mentioned. The silica gel is commercially available from, for example, Shinagawa Kasei Co., Ltd., and has been conventionally known as a dehydrating agent, a desiccant, and an adsorbent for chromatography. When the impurity ions were reduced by applying to the photosensitive composition solution, it was found that the impure metal ion component can be reduced extremely efficiently.

  The anion exchange resin is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include strongly basic anion exchange resins such as quaternary ammonium salt type styrene-divinylbenzene copolymer, aromatic And weakly basic anion exchange resins such as group amine type resins, polyethylene amine type resins, and primary amine type resins. Specific examples include Diaion SA, Diaion PA, Diaion HPA, Diaion WA, Organo Amberlite IRA, Amberlyst A-21, Amberlyst A-27, etc. manufactured by Mitsubishi Kasei.

―Ion adsorption treatment method―
There is no restriction | limiting in particular as said ion adsorption processing method, According to the objective, it can select suitably, For example, a batch method, a column method, etc. are mentioned.
In the batch method, at least one adsorbent selected from the clay intercalation compound, activated carbon, graphite, silica gel, and alumina gel is placed in a solution of the photosensitive composition containing the impurity ions, and the mixture is stirred for a predetermined time. It is the method of removing by.
In the column method, at least one adsorbent selected from the clay intercalation compound, activated carbon, graphite, silica gel, alumina gel, and alumino silica gel is packed in a column, and the photosensitive composition containing the impurity ions in the column is used. In this method, the solution comprising the adsorbent is dropped and purified.
Among these, a batch method that can remove impurity ions more preferably is preferable. In the batch method, after stirring for a predetermined time, the solution of the photosensitive composition and the ions to be adsorbed can be separated and removed. As the separation method, techniques such as filtration with a filter and centrifugation are generally performed.
As for the solution of the photosensitive composition used for the said batch method, the density | concentration of the solid part of this photosensitive composition has preferable 10-60 mass%. When the concentration is less than 10% by mass or more than 60% by mass, it is difficult to uniformly apply a suitable thickness (generally 5 to 50 μm) of the photosensitive layer made of the photosensitive composition, which is not preferable.

  In the present invention, the mixture of the metal ion adsorbent and the anion exchange resin is dropped onto the photosensitive composition by a batch method, and after stirring for a predetermined time, the adsorbed ions are extracted from the solution of the photosensitive composition. Separated and removed by the separation method. By this ion adsorption treatment, the content of metal ions in the solid content of the photosensitive composition is reduced to 3 ppm or less, and the content of anions in the solid content of the photosensitive composition is reduced to 1 ppm or less. Can do.

<Alkali-soluble photocrosslinkable resin>
There is no restriction | limiting in particular as said alkali-soluble photocrosslinkable resin, According to the objective, it can select suitably, For example, (A) vinyl polymer type photocrosslinkable resin and (B) epoxy resin ester type photocrosslinkable property Examples thereof include resins.

<(A) Vinyl polymer photocrosslinkable resin>
The (A) vinyl polymer type (high molecular weight) photocrosslinkable resin is selected from at least one of the following types I to III compounds.
Type I is a photocrosslinkable resin obtained by a reaction between (a) a carboxyl group-containing copolymer resin and (b) an epoxy group-containing unsaturated compound.
The type II is obtained by addition reaction of (c) an epoxy group-containing copolymer resin and (d) a carboxyl group-containing unsaturated compound, and (e) an addition reaction of a polybasic acid anhydride to a hydroxyl group of a product obtained. It is a photocrosslinkable resin obtained.
The type III is photocrosslinkable obtained 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. Resin.

  In the present specification, the term “(meth) acrylate” is a general term for acrylate, methacrylate, and a mixture thereof, and the same applies to other similar expressions.

<Type I>
Type I is a photocrosslinkable resin obtained by a reaction between (a) a carboxyl group-containing copolymer resin and (b) an epoxy group-containing unsaturated compound.

-(A) carboxyl group-containing copolymer resin-
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, any of (meth) acrylic acid esters and styrenes. Obtained by copolymerization.
The compound (a) having one unsaturated group and at least one carboxyl group or acid anhydride group in one molecule having the carboxyl group-containing copolymer resin as a structural unit is not particularly limited, Can be appropriately selected depending on the case, and examples thereof include (meth) acrylic acid, and 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 etc. which are the reaction products of hydroxyl group containing (meth) acrylate and a saturated or unsaturated dibasic acid anhydride are 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 include di (meth) acrylate, pendaerythritol tri (meth) acrylate, and diventaerythritol penta (meth) acrylate. 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 can be mentioned as a preferable specific example.
These compounds having one unsaturated group and at least one carboxyl group or acid anhydride group in one molecule can be used alone or in combination of two or more.

  There is no restriction | limiting in particular as (meth) acrylic acid ester used as the structural unit of said (a) carboxyl group-containing copolymer resin, According to the objective, it can select suitably, For example, methyl (meth) acrylate, ethyl ( (Meth) acrylate, n-propyl (meth) acrylate, 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, fe (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, poly Tylene glycol monoethyl ether (meth) acrylate, β-phenoxyethoxyethyl acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) ) Acrylate, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, tribromophenyl (meth) acrylate, tribromophenyloxyethyl (meth) acrylate, and the like.

  Further, the styrenes as the structural unit of the (a) carboxyl group-containing copolymer resin are not particularly limited and may be appropriately selected according to the purpose. For example, styrene, methylstyrene, dimethylstyrene, trimethylstyrene , Ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene, bromo styrene, chloromethyl styrene, groups deprotectable by acidic substances (for example, t-Boc, etc. ) Protected hydroxystyrene, methyl vinylbenzoate, α-methylstyrene and the like.

The (a) carboxyl group-containing copolymer resin comprises 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 is obtained by copolymerizing with any of the above by a usual copolymerization method, for example, a solution polymerization method.
In addition, (a) maleic acid monoester / styrene copolymers, maleic acid monoamide / styrene copolymers, itaconic acid monoester / styrene copolymers, and itacon included in the carboxyl group-containing copolymer resin. In the case of acid monoamide / styrene copolymers, obtain by polymer reaction of maleic anhydride / styrene copolymers or itaconic anhydride / styrene copolymers with alcohols or primary or secondary amines, respectively. Can do.

  Alcohols suitable for use in the polymer reaction with the maleic anhydride are not particularly limited and may be appropriately selected depending on the intended purpose. For example, methanol, ethanol, n-propanol, isopropanol N-butanol, sec-butanol, t-butanol, pentanol, hexanol, cyclohexanol, methoxyethanol, ethoxyethanol, methoxypropanol, ethoxypropanol and the like.

  Suitable primary amines are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include benzylamine, phenethylamine, 3-phenyl-1-propylamine, 4-phenyl-1-butylamine, 5-phenyl-1-pentylamine, 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-chloroph Enyl) ethylamine, 2- (3-chlorophenyl) ethylamine, 2- (4-chlorophenyl) ethylamine, 2- (2-fluorophenyl) ethylamine, 2- (3-fluorophenyl) ethylamine, 2- (4-fluorophenyl) Ethylamine, 4-fluoro-α, α-dimethylphenethylamine, 2-methoxybenzylamine, 3-methoxybenzylamine, 4-methoxybenzylamine, 2-ethoxybenzylamine, 2-methoxyphenethylamine, 3-methoxyphenethylamine, 4-methoxy Phenethylamine, methylamine, ethylamine, isopropylamine, n-propylamine, n-butylamine, t-butylamine, sec-butylamine, pentylamine, hexylamine, cyclohexylamine, heptylamine, o Cutylamine, laurylamine, phenylamine, 1-naphthylamine, methoxymethylamine, 2-methoxyethylamine, 2-ethoxyethylamine, 3-methoxypropylamine, 2-butoxyethylamine, 2-cyclohexyloxyethylamine, 3-ethoxypropylamine , 3-propoxypropylamine, 3-isopropoxypropylamine and the like.

  Further, suitable secondary amines are not particularly limited and may be appropriately selected depending on the purpose. For example, dimethylamine, diethylamine, methylethylamine, methylpropylamine, diethylamine, ethylpropylamine, dipropylamine , Dibutylamine, N, N-methylbenzylamine and the like.

-(B) Epoxy group-containing unsaturated compound-
The (b) epoxy group-containing unsaturated compound is used in the production of the type I high molecular weight photocrosslinkable resin. There is no restriction | limiting in particular as said (b) epoxy-group-containing unsaturated compound, According to the objective, it can select suitably, For example, one radical polymerizable unsaturated group and epoxy group are contained in 1 molecule. Any compound may be used, and examples thereof include compounds represented by the following structural formulas (1) to (14). These may be used alone or in combination of two or more.

In Structural Formulas (1) to (14), R ¹ is a hydrogen atom or a methyl group, R ² is an alkylene group having 1 to 10 carbon atoms, R ³ is a hydrocarbon group having 1 to 10 carbon atoms, and k is 0. Or the integer of 1-10 is represented.

  The (b) epoxy group-containing unsaturated compound is not particularly limited and may be appropriately selected depending on the intended purpose. For example, glycidyl (meth) acrylate, 2-methyl-2,3-epoxypropyl (meth) Examples thereof include acrylate and 2-ethyl-2,3-epoxypropyl (meth) acrylate. These may be used alone or in admixture of two or more. Among these, glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth) acrylate are preferable.

<Type II>
The type II is obtained by addition reaction of (c) an epoxy group-containing copolymer resin and (d) a carboxyl group-containing unsaturated compound, and (e) an addition reaction of a polybasic acid anhydride to a hydroxyl group of a product obtained. It is a photocrosslinkable resin obtained.

-(C) Epoxy group-containing copolymer resin-
The (c) epoxy group-containing copolymer resin is obtained by copolymerization of an epoxy group-containing monomer and any other (meth) acrylic ester non-reactive with epoxy groups and styrenes.
There is no restriction | limiting in particular as said epoxy group containing monomer, According to the objective, it can select suitably, For example, the compound as stated above is used suitably in description of type I photocrosslinkable resin.

  Any of the (meth) acrylic acid esters and styrenes that are non-reactive with the epoxy group is a carboxyl group, an alcoholic hydroxyl group, a phenolic hydroxyl group, an amino acid among those already described in the type I photocrosslinkable resin. Those not containing a group are preferably used.

  There is no restriction | limiting in particular as a manufacturing method of the (meth) acrylic acid ester and styrenes which are non-reactive with the said epoxy group, According to the objective, it can select suitably, For example, an epoxy-group containing monomer and other epoxy It is obtained by copolymerizing a group and a non-reactive (meth) acrylic acid ester or styrene by a solution polymerization method or the like.

The molar ratio between the epoxy group-containing monomer and any other non-reactive (meth) acrylic ester and styrene is preferably 60:40 to 20:80.
If the amount of the epoxy group-containing monomer is too small and the molar ratio is greater 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-
The (d) carboxyl group-containing unsaturated compound is a compound having one unsaturated group and at least one carboxyl group or acid anhydride group in one molecule in the description of the type I photocrosslinkable resin. Each of the aforementioned compounds can be preferably used.

-(E) Polybasic acid anhydride-
There is no restriction | limiting in particular as said (e) polybasic acid anhydride, According to the objective, it can select suitably, For example, maleic acid anhydride, succinic acid anhydride, hexahydrophthalic acid anhydride, 3-methyl Hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 3-ethylhexahydrophthalic anhydride, 4-ethylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride 4-methyltetrahydrophthalic acid anhydride, 3-ethyltetrahydrophthalic acid anhydride, 4-ethyltetrahydrophthalic acid anhydride, phthalic acid anhydride, etc., saturated with one acid anhydride group in the molecule or Unsaturated aliphatic, alicyclic or aromatic compounds are preferred. Among these, tetrahydrophthalic anhydride is particularly preferable.

The reaction between the (c) epoxy group-containing copolymer, the (d) carboxyl group-containing unsaturated compound, and the subsequent (e) polybasic acid anhydride is preferably carried out as follows.
That is, after addition reaction of 0.8 to 1.2 mol of unsaturated carboxylic acid per one epoxy group equivalent of the copolymer to the copolymer of the epoxy group-containing monomer, the resulting hydroxyl group of the product A polybasic acid anhydride is added to the group.

<Type III>
The type III is photocrosslinkable obtained 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. Resin.

-(F) Acid anhydride group-containing copolymer resin-
The (f) acid anhydride group-containing resin is obtained by copolymerization of maleic anhydride and styrene or copolymerization of itaconic anhydride and styrene. As the styrene as the copolymer component, those described above in the description of the type I photocrosslinkable resin are preferably used.
The maleic anhydride or the itaconic anhydride and the styrene have a copolymer composition ratio of preferably 90:10 to 10:90, more preferably 80:20 to 20:80, and 70:30 to 30:70. Is particularly preferred. When it is 90:10 or more, the development resistance of the cured portion is inferior, and when it is 10:90 or less, the developability is inferior.

  A copolymer having a mass average molecular weight of about 1,000 to 5,000 obtained by copolymerizing the styrene at a ratio of 1 to 3 moles with respect to 1 mole of the maleic anhydride is particularly preferable. For example, ARCO Chemical The SMA ranges 1000, 2000, 3000, etc. manufactured by the company are preferred.

-(G) Compound having one hydroxyl group and at least one (meth) acryloyl group in the molecule-
The compound (g) having one hydroxyl group and at least one (meth) acryloyl group in the molecule is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 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, pender erythritol tri (Meth) acrylate, trimethylolpropane di (meth) acrylate, neopentyl glycol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, mono (2- (meth) acryloyloxyethyl) Cyd phosphate, di (2- (meth) acryloyloxyethyl) acid phosphate, glycerol di (meth) acrylate.

  The ring-opening addition reaction between the acid anhydride copolymer, one hydroxyl group in the molecule, and a monomer having at least one (meth) acryloyl group is performed in an organic solvent containing no active hydrogen. It can be produced by a known method.

  There is no restriction | limiting in particular as said solvent, According to the objective, it can select suitably, For example, ethyl acetate, methoxypropyl acetate, methyl ethyl ketone, etc. are preferable. 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 carried out at 50 ° C. to 200 ° C., but preferably about 80 ° C. to 150 ° C. in order to prevent formation of diester and gelation. As reaction accelerators, tertiary amines such as triethylamine, triethanolamine, morpholine, and pentamethyldiethylenetriamine, or quaternary ammonium salts can be used. On the other hand, a known polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, t-butylhydroquinone, t-butylcatechol, benzoquinone, phenothiazine and the like can be added and used to prevent the formation of a polymer during the reaction.

  As described above, the obtained type I, II and III (A) vinyl polymer type (high molecular weight) photocrosslinkable resin needs to have an acid value in the range of 50 to 250 mgKOH / g. . The acid value is more preferably from 70 to 200 mgKOH / g, particularly preferably from 90 to 180 mgKOH / g. When the acid value is less than 50 mgKOH / g, it is difficult to remove the unexposed area with a developer that is a weakly alkaline aqueous solution. There are harmful effects. The (A) vinyl polymer type (high molecular weight) preferably has a mass average molecular weight in the range of 5,000 to 200,000, more preferably 10,000 to 100,000, and 30,000 to 80,000. 000 is particularly preferred. When the mass average molecular weight is less than 5,000, the dryness to touch is remarkably inferior, and the peelability from the support is inferior. On the other hand, if the mass average molecular weight exceeds 200,000, it is not preferable because it causes adverse effects such as removability of unexposed areas by an alkaline developer and storage stability.

<(B) Epoxy resin ester type photocrosslinkable resin>
There is no restriction | limiting in particular as said (B) epoxy resin ester type (low molecular weight) photocrosslinkable resin, According to the objective, it can select suitably, For example, (h) epoxy resin and one piece in 1 molecule It is formed by further reacting (j) a polybasic acid anhydride with an esterification reaction product of an unsaturated group and at least one compound having (i) a carboxyl group or an acid anhydride group.

  There is no restriction | limiting in particular as said (h) epoxy resin, According to the objective, it can select suitably, For example, Toto Kasei Co., Ltd. product YDCN-701, YDCN-704; Dainippon Ink and Chemicals Co., Ltd. product N-665, N-680, N-695; Nippon Kayaku Co., Ltd. EOCN-102, EOCN-104; Asahi Kasei Kogyo Co., Ltd. ECN-265, ECN-293, ECN-285, ECN-299, etc. Cresol novolac epoxy resin, YDPN-638, YDPN-602 manufactured by Toto Kasei Co., Ltd .; DEN-431, DEN-438, DEN-439 manufactured by Dow Chemical Japan Co., Ltd .; manufactured by Ciba Specialty Chemicals Co., Ltd. EPN-1138, EPN-1235, EPN-1299; Dai-Nippon Ink Chemical Co., Ltd. N-730, N-770, etc. Such as Nord-novolak type epoxy resins.

  Further, as a part of the novolac type epoxy resin, 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 tetraphenylethane type epoxy resin, alicyclic epoxy resin, salicylaldehyde type epoxy resin can also be used advantageously.

  Next, (i) a compound having one unsaturated group and at least one carboxyl group or acid anhydride group in one molecule is the compound described above in the description of the type I photocrosslinkable resin. Can be suitably used. In addition, as the (j) polybasic acid anhydride, the above-described compounds can be used as the component (e) in the description of the type II photocrosslinkable resin.

-(B) Production method of epoxy ester type photocrosslinkable resin-
There is no restriction | limiting in particular as a manufacturing method of said (B) epoxy ester type photocrosslinkable resin, According to the objective, it can select suitably, For example, (h) epoxy resin and (i) 1 piece in 1 molecule In the reaction of a compound having at least one carboxyl group or acid anhydride group with (i) one unsaturated group in one molecule per one equivalent of the epoxy group of the epoxy resin. And a compound having at least one carboxyl group or acid anhydride group can be reacted at a ratio of 0.8 to 1.05 equivalent, and the compound is more preferably 0.9 to 1.0 equivalent. .
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.

  The organic solvent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof 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, glycol ethers such as propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, butyl cellosolve acetate , Esters such as carbitol acetate, aliphatic hydrocarbons such as octane and decane, petroleum ethers such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha Agents and the like.

  Furthermore, a catalyst can be suitably used to promote the reaction. The catalyst is not particularly limited and may be appropriately selected depending on the intended purpose. For example, triethylamine, benzylmethylamine, methyltriethylammonium chlorite, benzyltrimethylammonium chlorite, benzyltrimethylammonium bromide, benzyltrimethylmethylammonium Examples include iodotide and triphenylphosphine. There is no restriction | limiting in particular as the usage-amount of the said catalyst, According to the objective, it can select suitably, For example, is with respect to a total of 100 mass parts of (h) epoxy resin and (b) vinyl group containing monocarboxylic acid. And 0.1-10 mass parts is preferable.

  In addition, a polymerization inhibitor can be preferably used because it prevents the polymerization during the reaction. There is no restriction | limiting in particular as said polymerization inhibitor, According to the objective, it can select suitably, For example, hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol etc. are mentioned, The usage-amount is (a). 0.01-1 mass part is preferable with respect to a total of 100 mass parts of an epoxy resin and (b) vinyl group containing monocarboxylic acid. There is no restriction | limiting in particular as reaction temperature, According to the objective, it can select suitably, For example, 60-150 degreeC is preferable and 80-120 degreeC is more preferable.

The (B) epoxy ester photocrosslinkable resin is obtained by reacting the reaction product thus obtained with (j) a polybasic acid anhydride. There is no restriction | limiting in particular as reaction temperature of the said reaction product and (c) polybasic acid anhydride, According to the objective, it can select suitably, For example, 60-120 degreeC is preferable.
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 value of the (B) epoxy ester type photocrosslinkable resin Can be adjusted. There is no restriction | limiting in particular as an acid value of the said (B) epoxy ester type photocrosslinkable resin, According to the objective, it can select suitably, For example, 30-150 mgKOH / g is preferable, and it is 50-120 mgKOH / g. More preferred. When the acid value is less than 30 mgKOH / g, the solubility of the photocurable resin composition in a dilute alkali solution is lowered, and when it exceeds 150 mgKOH / g, the electric properties of the cured film tend to be lowered.

  There is no restriction | limiting in particular as a mass average molecular weight of the said (B) epoxy ester type photocrosslinkable resin, According to the objective, it can select suitably, For example, 500-5,000 are preferable, 1,000-4, 000 is more preferable, and 1,500 to 3,500 is particularly preferable. If it is 500 or less, the adhesiveness is too high to make it difficult to peel off the protective film, and the resin exceeding 5,000 is difficult to produce.

The said alkali-soluble photocrosslinkable resin may be used individually by 1 type, and may use 2 or more types together. The solid content of the alkali-soluble photocrosslinkable resin in the total solid content of the permanent pattern is preferably 15 to 70% by mass. If it is less than 15% by mass, the toughness of the cured layer is inferior, and if it exceeds 70% by mass, the performance balance such as a decrease in reliability is deteriorated.
In particular, any one selected from the types I to III of the (A) vinyl polymer type photocrosslinkable resin and any one mixture selected from the (B) epoxy ester type photocrosslinkable resin are: It is preferable because balanced performance can be imparted. In this case, the mixing ratio is preferably 10/90 to 90/10 by mass, 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 intended 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 suitably used in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, and 2-acetoxy. Iminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2- ON, and 2-ethoxycarbonyloxyimino-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.

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.

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 capable of supporting laser light having a wavelength of 405 nm in the exposure described later. 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.

<Thermal crosslinking agent>
There is no restriction | limiting in particular as said heat-crosslinking agent, According to the objective, it can select suitably, For example, an epoxy resin, a polyfunctional oxetane compound, etc. are mentioned suitably.
The epoxy resin and the polyfunctional oxetane compound are not particularly limited and may be appropriately selected depending on the intended purpose. For example, the film strength after curing of the photosensitive layer formed using the photosensitive composition is improved. Therefore, an epoxy resin compound having at least two oxirane groups in one molecule, an oxetane compound having at least two oxetanyl groups in one molecule, and the like can be used within a range that does not adversely affect developability and the like. .

  There is no restriction | limiting in particular as said epoxy resin, According to the objective, it can select suitably, For example, a bixylenol type or a biphenol type epoxy resin ("YX4000; Japan Epoxy Resin Co., Ltd." etc.) or mixtures thereof, isocyania Heterocyclic epoxy resins having a nurate skeleton ("TEPIC; manufactured by Nissan Chemical Industries", "Araldite PT810; manufactured by Ciba Specialty Chemicals"), bisphenol A type epoxy resin, novolak type epoxy resin, bisphenol F type Epoxy resin, hydrogenated bisphenol A type epoxy resin, glycidylamine type epoxy resin, hydantoin type epoxy resin, alicyclic epoxy resin, trihydroxyphenylmethane type epoxy resin, bisphenol S type epoxy resin, bisphenol A Borac type epoxy resin, tetraphenylolethane type epoxy resin, glycidyl phthalate resin, tetraglycidyl xylenoyl ethane resin, naphthalene group-containing epoxy resin (“ESN-190, ESN-360; manufactured by Nippon Steel Chemical Co., Ltd.”, “HP-4032” , EXA-4750, EXA-4700; manufactured by Dainippon Ink & Chemicals, Inc.), epoxy resins having a dicyclopentadiene skeleton (“HP-7200, HP-7200H; manufactured by Dainippon Ink & Chemicals, Inc.”), glycidyl Examples thereof include a methacrylate copolymer epoxy resin (“CP-50S, CP-50M; manufactured by NOF Corporation”), a copolymer epoxy resin of cyclohexylmaleimide and glycidyl methacrylate, and the like. These epoxy resins may be used individually by 1 type, and may use 2 or more types together.

  The polyfunctional oxetane compound is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether and 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) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate or oligomers thereof or In addition to polyfunctional oxetanes such as copolymers, oxetane groups and Novo And ether compounds with hydroxyl groups such as poly (p-hydroxystyrene), cardo-type bisphenols, calixarenes, calixresorcinarenes, silsesquioxanes, etc., and oxetane A copolymer of an unsaturated monomer having a ring and an alkyl (meth) acrylate is also included.

  There is no restriction | limiting in particular as solid content in solid content of the said photosensitive composition solution of the said epoxy resin or a polyfunctional oxetane compound, According to the objective, it can select suitably, For example, 2-50 mass% Is preferable, and 3-30 mass% is more preferable. If the solid content is less than 2% by mass, the hygroscopicity of the cured film is increased, resulting in deterioration of insulation, or solder heat resistance, electroless plating resistance, etc. may be reduced. If it exceeds 50% by mass, the developability may deteriorate and the exposure sensitivity may decrease, which is not preferable.

―Other thermal crosslinking agents―
The other thermal crosslinking agent can be added separately from the epoxy resin and the polyfunctional oxetane compound. The thermal crosslinking agent is not particularly limited and can be appropriately selected depending on the purpose. For example, a polyisocyanate compound described in JP-A-5-9407 can be used. As the polyisocyanate compound, It may be derived from an aliphatic, cycloaliphatic or aromatic group-substituted aliphatic compound containing at least two isocyanate groups.
Specifically, 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 .; bifunctional isocyanate; A polyfunctional alcohol; an alkylene oxide adduct of the polyfunctional alcohol and an adduct of the bifunctional isocyanate; hexamethylene diisocyanate, hexamethylene-1,6-diisocyanate Over preparative and cyclic trimer of such derivatives, and the like.

Furthermore, for the purpose of improving the preservability of the photosensitive composition or the photosensitive film, a compound obtained by reacting an isocyanate group of the polyisocyanate and its derivative with a blocking agent may be used.
There is no restriction | limiting in particular as said isocyanate group blocking agent, According to the objective, it can select suitably, For example, isopropanol, tert. Alcohols such as butanol; lactams such as ε-caprolactam; phenol, cresol, p-tert. -Butylphenol, p-sec. -Butylphenol, p-sec. Phenols such as amylphenol, p-octylphenol and p-nonylphenol; heterocyclic hydroxyl compounds such as 3-hydroxypyridine and 8-hydroxyquinoline; dialkylmalonate, methylethylketoxime, acetylacetone, alkylacetoacetate oxime, acetoxime, Active methylene compounds such as cyclohexanone oxime; and the like. 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, an aldehyde condensation product, a resin precursor, etc. can be used. Specifically, N, N′-dimethylolurea, N, N′-dimethylolmalonamide, N, N′-dimethylolsuccinimide, trimethylolmelamine, tetramethylolmelamine, hexamethylolmelamine, 1,3-N, N'-dimethylol terephthalamide, 2,4,6-trimethylolphenol, 2,6-dimethylol-4-methyliloanisole, 1,3-dimethylol-4,6-diisopropylbenzene and the like can be mentioned. Instead of these methylol compounds, the corresponding ethyl or butyl ether, or acetic acid or propionic acid ester may be used. Moreover, you may use the hexamethylated methylol melamine which consists of a formaldehyde condensation product of a melamine and urea, the butyl ether of a melamine and a formaldehyde condensation product, etc.

<Elastomer>
The elastomer is composed of a hard segment component and a soft segment component, and generally has a function in which the former contributes to heat resistance and strength and the latter contributes to flexibility and toughness.
By containing an elastomer in the photosensitive composition, the elastomer absorbs heat stress well when mounting electronic components on a wiring board or performing a temperature cycle test (TCT), and light and thermosetting. A crack is not generated in the subsequent permanent pattern (solder resist), and as a result, a permanent pattern excellent in electrical connection reliability without disconnection of the wiring conductor layer can be obtained.

  There is no restriction | limiting in particular as said elastomer, According to the objective, it can select suitably, For example, a styrene-type elastomer, an olefin-type elastomer, a urethane-type elastomer, a polyester-type elastomer, a polyamide-type elastomer, an acrylic elastomer, and a silicone-type elastomer Etc. Further, crosslinked elastomer fine particles, carboxyl group-containing crosslinked elastomer fine particles, and core-shell fine particles can also be suitably used.

  There is no restriction | limiting in particular as said styrene-type elastomer, According to the objective, it can select suitably, For example, a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, a styrene-ethylene-butylene-styrene block copolymer And styrene-ethylene-propylene-styrene block copolymer. In addition to styrene which is a component constituting the styrene-based elastomer, styrene derivatives such as α-methylstyrene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene and the like can be used. Specifically, Tufprene, Solprene T, Asaprene T, Taptec (made by Asahi Kasei Kogyo Co., Ltd.), Elastomer AR (made by Aron Kasei), Clayton G, Super Reflex (made by Gel Japan), JSR-TR , TSR-SIS, Dynalon (manufactured by Nippon Synthetic Rubber Co., Ltd.), Denka STR (manufactured by Denki Kagaku Kogyo Co., Ltd.), Quintac (manufactured by Nippon Zeon), TPE-SB series (manufactured by Sumitomo Chemical Industries, Ltd.) ), Rapalon (Mitsubishi Chemical Co., Ltd.), Cefton, Hybler (above, Kuraray Co., Ltd.), Sumiplex (Sumitomo Bakelite Co., Ltd.), Rheostomer, Actimer (above, Riken Vinyl Industries) .

  There is no restriction | limiting in particular as said olefin type elastomer, According to the objective, it can select suitably, For example, C2-C20, such as ethylene, propylene, 1-butyne, 1-hexene, 4-methyl-pentyne, etc. α-olefin copolymers, such as ethylene-propylene copolymer (EPR) and ethylene-propylene-diene copolymer (EPDM), and dicyclopentadiene, 1,4-hexadiene, cyclohexane Examples thereof include non-conjugated dienes having 2 to 20 carbon atoms such as octadiene, methylene norbornene, ethylidene norbornene, butadiene, and isoprene, and α-olefin copolymers. Furthermore, carboxy-modified NBR obtained by copolymerizing methacrylic acid with a butadiene-acrylonitrile copolymer can be used. Specifically, ethylene / α-olefin copolymer rubber, ethylene / α-olefin / non-conjugated diene copolymer rubber, propylene / α-olefin copolymer rubber, butyne / α-olefin copolymer rubber, etc. Can be mentioned. More specifically, Miralastoma (manufactured by Mitsui Petrochemical), EXACT (manufactured by Exxon Chemical), ENGAGE (manufactured by Dow Chemical), hydrogenated styrene-butadiene rubber “DYNABONHSBR” (manufactured by Nippon Synthetic Rubber Co., Ltd.), butadiene- Acrylonitrile copolymer “NBR series” (manufactured by Nippon Synthetic Rubber Co., Ltd.) or “XER series” of both terminal carboxyl group-modified butadiene-acrylonitrile copolymers having a crosslinking point (manufactured by Nippon Synthetic Rubber Co., Ltd.) Can be mentioned.

  The urethane elastomer is not particularly limited and can be appropriately selected according to the purpose. For example, a hard segment composed of low molecular weight glycol and diisocyanate and a soft segment composed of high molecular (long chain) diol and diisocyanate. It consists of structural units, and as a polymer (long chain) diol, polypropylene glycol, polytetramethylene oxide, poly (1,4-butylene adipate), poly (ethylene-1,4-butylene adipate), polycaprolactone, poly (1, 6-hexylene carbonate), poly (1,6-hexylene neopentylene adipate) and the like. The number average molecular weight of the polymer (long chain) diol is preferably 500 to 10,000. In addition to the ethylene glycol, short chain diols such as propylene glycol, 1,4-butanediol, and bisphenol A can be used, and the number average molecular weight of the short chain diol is preferably 48 to 500. Specific examples of the urethane elastomer include PANDEXT-2185, T-2983N (manufactured by Dainippon Ink), sylactolan E790, and the like.

  There is no restriction | limiting in particular as said polyester-type elastomer, According to the objective, it can select suitably, For example, what is obtained by polycondensing dicarboxylic acid or its derivative (s) and a diol compound or its derivative (s) is mentioned. Specific examples of the dicarboxylic acid include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid, and aromatic dicarboxylic acids in which hydrogen atoms of these aromatic nuclei are substituted with methyl groups, ethyl groups, phenyl groups, Examples thereof include aliphatic dicarboxylic acids having 2 to 20 carbon atoms such as adipic acid, sebacic acid and dodecanedicarboxylic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. These compounds can be used alone or in combination of two or more.

  Specific examples of the diol compound include aliphatic groups such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, and 1,4-cyclohexanediol. Examples include diols and alicyclic diols, or dihydric phenols. Specific examples thereof include bisphenol A, bis- (4-hydroxydiphenyl) methane, bis- (4-hydroxy-3-methylphenyl) propane, and resorcin. These compounds can be used alone or in combination of two or more. In addition, a multiblock copolymer having an aromatic polyester (for example, polybutylene terephthalate) portion as a hard segment component and an aliphatic polyester (for example, polytetramethylene glycol) portion as a soft segment component can be used. There are various grades depending on the kind, ratio, and molecular weight of the hard segment and the soft segment. Specific examples include Hytrel (manufactured by DuPont-Bundle Co., Ltd.), Perprene (manufactured by Toyobo Co., Ltd.), Espel (manufactured by Hitachi Chemical Co., Ltd.), and the like.

  There is no restriction | limiting in particular as said polyamide-type elastomer, According to the objective, it can select suitably, For example, the polyether block amide type | mold and polyether ester which used polyamide for the hard phase, and used polyether and polyester for the soft phase. As the polyamide, polyamide-6, 11, 12 or the like is used as the polyamide, and as the polyether, polyoxyethylene, polyoxypropylene, polytetramethylene glycol or the like is used. Specifically, UBE polyamide elastomer (manufactured by Ube Industries Co., Ltd.), Daiamide (manufactured by Daicel Huls Co., Ltd.), PEBAX (manufactured by Toray Industries, Inc.), Grilon ELY (manufactured by MMS Japan Corporation), Nopamid ( Mitsubishi Chemical Co., Ltd.), and Glais (Dainippon Ink Co., Ltd.).

  The acrylic elastomer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, ethyl acrylate, butyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, and the like are used mainly containing an acrylic ester. As the crosslinking point monomer, glycidyl methacrylate, allyl glycidyl ether, or the like is used. Furthermore, acrylonitrile and ethylene can be copolymerized. Specific examples include acrylonitrile-butyl acrylate copolymer, acrylonitrile-butyl acrylate-ethyl acrylate copolymer, acrylonitrile-butyl acrylate-glycidyl methacrylate copolymer, and the like.

  The silicone elastomer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the silicone elastomer is mainly composed of organopolysiloxane, such as polydimethylsiloxane, polymethylphenylsiloxane, and boridiphenylsiloxane. Divided into systems. Some are modified with vinyl groups, alkoxy groups, and the like. Specific examples include the KE series (manufactured by Shin-Etsu Chemical Co., Ltd.), the SE series, the CY series, and the SH series (above, manufactured by Toray Dow Corning Silicone Co., Ltd.). In addition to the above thermoplastic elastomer, a rubber-modified epoxy resin can be used.

  The rubber-modified epoxy resin is not particularly limited and may be appropriately selected depending on the purpose. For example, the bisphenol F type epoxy resin, bisphenol A type epoxy resin, salicylaldehyde type epoxy resin, phenol novolac type epoxy The resin or the cresol novolac type epoxy resin part or all of the epoxy groups can be modified with a carboxylic acid-modified butadiene-acrylonitrile rubber or a terminal amino-modified silicone rubber. Among these elastomers, in terms of shear adhesion, both end carboxyl group-modified butadiene-acrylonitrile copolymer and Espel (Espel 1612.1620, manufactured by Hitachi Chemical Co., Ltd.), which is a polyester elastomer having a hydroxyl group, are used. preferable.

The crosslinked elastomer fine particles are not particularly limited and may be appropriately selected depending on the purpose. For example, styrene / butadiene rubber (SBR), butadiene rubber (BR), butyl rubber, and these rubbers in the structural formula A copolymer having the following structure can be used.
Here, when the particle diameter of the crosslinked elastomer fine particles exceeds 1.0 μm, the dispersibility of the crosslinked elastomer fine particles in the photosensitive composition and the cured product thereof is lowered, and it becomes difficult to obtain uniform plasticity. Accordingly, the particle diameter of the crosslinked elastomer fine particles is preferably finer, and particularly preferably 0.5 μm or less. However, in order to effectively impart plasticity, the particle diameter of the crosslinked elastomer fine particles is preferably 0.02 μm or more.
If the content of the crosslinked elastomer fine particles having a particle diameter of 1.0 μm or less in the photosensitive composition is 3% by mass or more based on the total amount of the thermal crosslinking agent component, sufficient flexibility can be imparted. Can be obtained. However, if the content is less than 3% by mass, the effect of imparting flexibility is reduced. Moreover, when the said content rate shall be 15 mass% or less with respect to the total amount of a thermal crosslinking agent component, while being able to obtain appropriate flexibility, the fall of the glass transition temperature (Tg) after hardening can further be suppressed. If the content exceeds 15% by mass, the strength of the cured product may be reduced.

  The carboxyl group-containing crosslinked elastomer fine particles include a crosslinked acrylic rubber having a carboxyl group, a crosslinked NBR (acrylonitrile-butadiene copolymer rubber) having a carboxyl group, and a crosslinked MBS (butadiene styrene methyl methacrylate terpolymer) resin having a carboxyl group. Etc. Among these, a crosslinked acrylic rubber having a carboxyl group that dissolves in an alkaline solution and a crosslinked NBR having a carboxyl group are easy to obtain and are preferable because they contribute to an improvement in the adhesion between the solder resist and the copper foil. Moreover, since the photosensitive composition of this invention makes the insulating property at the time of hardening, and the alkali solubility at the time of non-hardening favorable, crosslinked acrylic rubber is more preferable.

The average particle diameter of the carboxyl group-containing crosslinked elastomer fine particles is preferably less than 1.0 μm as a value based on a volume standard method. When the average particle diameter exceeds 1.0 μm, the dispersibility of the fine particle component is deteriorated in the photosensitive composition of the present invention. Therefore, the average particle diameter is preferably 0.1 μm or less.
The content of the carboxyl group-containing crosslinked elastomer fine particles is in the range of 5 to 40% by mass of the entire photosensitive composition of the present invention in order for the cured product of the photosensitive composition of the present invention to obtain sufficient impact resistance. It is preferable that it exists in. When the amount exceeds 40% by mass, there is no harmful effect in terms of impact resistance, but when the photosensitive composition of the present invention is applied and dried on a substrate or a support, uneven coating and bubbles are likely to occur.

  The core-shell fine particles are used as fine particles for stress relaxation of the core-shell structure. Such a particulate stress relaxation agent is not particularly limited and may be appropriately selected depending on the intended purpose. For example, polybutadiene, polystyrene butadiene, polyacrylonitrile-butadiene, polyacrylic ester, polyacryl silicone, or poly Polymer components such as siloxane, or a flexible resin having a glass transition temperature of room temperature or lower obtained by crosslinking these polymer components with a polyfunctional vinyl compound is used as a core, and polymethyl methacrylate or the like or these polyfunctional vinyls. Examples thereof include a resin having a glass transition temperature cross-linked with a compound or the like as a shell.

Such core-shell structured microparticles are easy to handle because their surfaces are hard and the particles are unlikely to block each other. When the fine particles are dispersed in the curable composition, the internal soft component acts as a stress relaxation agent and has an effect of improving impact resistance, and is used as an additive for various engineering plastics such as vinyl chloride. Moreover, if the surface is hard and the central part is flexible, it can be used effectively for the above-mentioned applications, and the boundary between the core and the shell does not necessarily have to be clear.
In the core-shell fine particles, it is preferable that both constituent parts of the core and the shell are cross-linked because the solvent resistance becomes high. As specific examples, core-shell fine particles whose core is a butadiene styrene-based elastomer and whose shell is a crosslinked polymethyl methacrylate (for example, Kureha Chemical Industry Co., Ltd., Kureha BTA751, Kureha BTA731; Mitsubishi Rayon Co., Ltd. Metabrene C102; Kaneace B52 manufactured by Kaneka Chemical Co., Ltd.), core-shell fine particles having an acrylic elastomer core and a crosslinked polymethyl methacrylate shell (for example, Kureha KM334 manufactured by Kureha Chemical Industry Co., Ltd .; Metabrene manufactured by Mitsubishi Rayon Co., Ltd.) W-300A etc.), and core-shell fine particles (for example, Metabrene S-2001 manufactured by Mitsubishi Rayon Co., Ltd.) whose core is a silicone elastomer and whose shell is cross-linked polymethyl methacrylate.

Moreover, what contains functional groups, such as an epoxy group and a carboxyl group, can also be used in a shell part. If the shell part contains an epoxy group (for example, Kureha Paraloid EXL2314 manufactured by Kureha Chemical Industry Co., Ltd.), the interface between the fine particles and the curable resin is chemically bonded. can get. In addition, when a shell group containing a carboxyl group (for example, Staphyloid AC3871 manufactured by Takeda Pharmaceutical Co., Ltd.) is used as a solder resist, the resolution increases when developed with an alkaline developer.
There is no restriction | limiting in particular as content rate of the said core-shell fine particle, According to the objective, it can select suitably, For example, the range used as 5-50 mass% with respect to the total amount of composition solid content is preferable. When the content is less than 5% by mass, the effect of preventing the occurrence of cracks in the cured product is not sufficient, and when it exceeds 50% by mass, the applicability of the curable composition is deteriorated and the pattern developability is deteriorated. It becomes easy to cause.

  For use in the photosensitive composition, a diisocyanate represented by structural formula (A), at least one selected from diols represented by structural formulas (B) and (C), and a structure Alkali-soluble urethane elastomers obtained by reaction with at least one selected from diols represented by formula (D) are preferred.

In the structural formulas (A), (B) and (C), R ¹ represents a divalent aliphatic or aromatic hydrocarbon which may have a substituent. If necessary, R ¹ may have another functional group that does not react with an isocyanate group, for example, an ester, urethane, amide, or ureido group.
R ² represents a hydrogen atom, an optionally substituted alkyl, aralkyl, aryl, alkoxy, aryloxy group, a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 15 carbon atoms. To express. R ³ , R ⁴ and R ⁵ may be the same or different, each may have a single bond or a substituent, and represent a divalent aliphatic or aromatic hydrocarbon chain. The alkylene group is preferably an alkylene group having 20 to 20 alkylene atoms and 6 to 15 carbon atoms, and more preferably an alkylene group having 1 to 8 carbon atoms. If necessary, R ³ , R ⁴ , and R ⁵ may have other functional groups that do not react with isocyanate groups, such as esters, urethanes, amides, ureidos, and ester groups.
In addition, a ring may be formed by two or three of R ² , R ³ , R ⁴ and R ⁵ . Ar may have a substituent and represents a trivalent aromatic hydrocarbon, preferably an aromatic group having 6 to 15 carbon atoms.

In the structural formula (D), l, m, and n may be the same or different, and are positive integers up to 0 or 50.

  Specific examples of the alkali-soluble urethane elastomer include those shown below as the diisocyanate compound represented by the structural formula (A). That is, 2,4-tolylene diisocyanate, dimer of 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-xylylene diisocyanate, metaxylylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 1 , 5-naphthylene diisocyanate, 3,3′-dimethyl-biphenyl-4,4′-diisocyanate, etc .: aromatic diisocyanate compounds: hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisosoanate, dimer acid diisocyanate, etc. Aliphatic diisocyanate compounds such as: isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4 (or 2.6) -diisocyanate Aliphatic diisocyanate compounds such as 1,3- (isocyanatomethyl) cyclohexane: diisocyanate compounds that are a reaction product of diol and diisocyanate such as an adduct of 1 mol of 1,3-butylene glycol and 2 mol of tolylene diisocyanate Is mentioned.

  Specific examples of the diol compound having a carboxyl group represented by the structural formula (B) or (C) include those shown below. 3,5-dihydroxybenzoic acid, 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (hydroxyethyl) propionic acid, 2,2-bis (3-hydroxypropyl) propionic acid, Examples include 2-bis (hydroxymethyl) acetic acid, bis- (4-hydroxydiphenyl) acetic acid, 4,4-bis- (4-hydroxyphenyl) pentanoic acid, and tartaric acid.

  The urethane elastomer may be formed from two or more diol compounds having a diisocyanate compound represented by the structural formula (A) and a carboxyl group represented by the structure (B) or (C). Further, it may have a substituent that does not have a carboxyl group and does not react with other isocyanates. The diol compound can also be used in combination so as not to lower the alkali developability.

  Specific examples of the diol compound include those shown below. That is, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, neopentyl glycol, 1,3-butylene glycol, 1,6-hexanodiol, 2-butene -1,4-diol, 2,2,4-trimethyl-1,3-pentanediol, 1,4-bis-β-hydroxyethoxycyclohexane, cyclohexanedimethanol, tricyclodecane dimethanol, hydrogenated bisphenol A, water Bisphenol F, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, ethylene oxide adduct of bisphenol F, propylene oxide of bisphenol F Adduct, ethylene oxide adduct of hydrogenated bisphenol A, propylene oxide adduct of hydrogenated bisphenol A, 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-xylylenecarbamate, bis- (2-hydroxyethylphthalate), etc. may be used. it can.

  There is no restriction | limiting in particular as a compound of the said structure (D), According to the objective, it can select suitably, For example, polyethyleneglycol (1 = 10-50, m = n = 0), polypropylene glycol (m = 10) ~ 50, l = n = 0), polyoxytetramethylene glycol (n = 10-50, l = m = 0), polyethylene glycol / polypropylene glycol copolymer (l = 1-50, m = 1-50, n = 0), polyethylene glycol / polyoxytetramethylene glycol copolymer (l = 1-50, n = 1-50, m = 0), polypropylene glycol / polyoxytetramethylene glycol copolymer (m = 1-1) 50, n = 1 to 50, l = 0), polyethylene glycol / polypropylene glycol / polyoxytetramethylene glycol copolymer Body (l = 1~50, m = 1~50, n = 1~50) can be cited, among these, polyoxytetramethylene glycol.

  There is no restriction | limiting in particular as said alkali-soluble urethane elastomer, According to the objective, it can select suitably, For example, the said diisocyanate compound and the said diol compound are known in the activity according to each reactivity in an aprotic solvent. It is synthesized by adding a suitable catalyst and heating. The molar ratio of the diisocyanate and diol compound to be used is preferably 0.8: 1 to 1.2: 1. When an isocyanate group remains at the end of the polymer, it is finally treated with an alcohol or an amine. Synthesized with no isocyanate groups remaining.

  The ratio of the molar amount of the compound of the structural formula (B) and the structural formula (C) to the molar amount of the compound of the structural formula (D) can be selected in the range of 10/90 to 90/10. 15/85 to 85/15 are preferable, and 20/80 to 80/20 are more preferable. If this ratio is less than 10/90, the alkali developability is inferior, and if it exceeds 90/10, the thermosetting film is too high and cracks are liable to occur.

  There is no restriction | limiting in particular as molecular weight of the said alkali-soluble urethane elastomer, According to the objective, it can select suitably, For example, it is 1000 or more by weight average, and it is preferable that it is 5,000-100,000.

  The photosensitive composition exhibits excellent alkali developability and has sufficient flexibility because the urethane elastomer used contains many carboxylic acid groups in the molecule. . The acid value in the urethane elastomer is preferably 10 to 100 mgKOH / g, more preferably 20 to 90 mgKOH / g, and particularly preferably 30 to 80 mgKOH / g. If it is less than 10 mgKOH / g, the alkali developability is inferior, and if it exceeds 100 mgKOH / g, development is too fast.

  2-30 mass parts is preferable with respect to 100 mass parts of solid content of the said photosensitive composition, and, as for the compounding quantity of the said elastomer, 4-20 mass parts is more preferable. If it is less than 2 parts by mass, the elastic modulus in the high temperature region of the cured film tends not to be low, and if it exceeds 50 parts by mass, the unexposed part tends not to be eluted with the developer.

  In the photosensitive composition, another resin can be mixed in an amount of 50% by mass or less based on the polymer. There is no restriction | limiting in particular as said resin mixed, According to the objective, it can select suitably, For example, a polyamide resin, an epoxy resin, a poly resin cetal resin, an acrylic resin, a methacrylic resin, a polystyrene resin, a novolak type phenol Based resins.

<Inorganic filler>
The inorganic filler has the functions of improving the surface hardness of the permanent pattern, keeping the coefficient of linear expansion low, and keeping the dielectric constant and dielectric loss tangent of the cured layer itself low.
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, gas phase method 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. When the average particle diameter is 3 μm or more, resolution may be deteriorated 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 10-65 mass% is especially preferable. When the addition amount is less than 5% by mass, the linear expansion coefficient may not be sufficiently reduced. When the addition amount exceeds 90% 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 diameter 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.

  Since the inorganic filler contains particles having an average particle diameter of 0.1 to 2 μm, even if the permanent pattern is thinned to a thickness of 5 to 20 μm along with the thinning of the printed wiring board, The inorganic filler particles do not cross-link the front and back surfaces of the permanent pattern, and as a result, no ion migration occurs even in the high acceleration test (HAST), and a permanent pattern excellent in heat resistance and moisture resistance can be obtained. .

<Colorant>
There is no restriction | limiting in particular as said coloring agent, According to the objective, it can select suitably, For example, dyes, such as a coloring pigment suitably selected from well-known dyes, can be used.

―Coloring pigment―
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 in the solid content of the photosensitive composition solution of the color pigment can be determined in consideration of exposure sensitivity of the photosensitive layer at the time of permanent pattern formation, resolution, etc. Although it varies depending on the type, generally 0.1 to 10% by mass is preferable, and 0.5 to 8% by mass is more preferable.

<Thermosetting accelerator>
The thermosetting accelerator has a function of accelerating the thermosetting of the epoxy resin compound or the polyfunctional oxetane compound, and is preferably added to the photosensitive resin.
The thermosetting accelerator is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy. Amine compounds such as -N, N-dimethylbenzylamine and 4-methyl-N, N-dimethylbenzylamine; quaternary ammonium salt compounds such as triethylbenzylammonium chloride; blocked isocyanate compounds such as dimethylamine; imidazole and 2-methyl Imidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methyl Imidazole Any imidazole derivatives 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, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine isocyanuric acid S-triazine derivatives such as adducts, boron trifluoride-amine complex, organic hydrazide cumulative, phthalic anhydride, trimellitic anhydride, ethylene glycol bis (anhydro trimellitate), glycerol tris (anhydro trimellitate) , Benzo Aromatic acid anhydrides such as phenonetetracarboxylic anhydride, aliphatic acid anhydrides such as maleic anhydride and tetrahydrophthalic anhydride, polyphenols such as polyvinylphenol, polyvinylphenol bromide, phenol novolac and alkylphenol novolac Etc. can be used. These may be used alone or in combination of two or more. The epoxy resin compound or the polyfunctional oxetane compound is 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 the above. May be used.
The solid content in the solid content of the photosensitive composition solution of the epoxy resin, the polyfunctional oxetane compound, and a compound capable of accelerating thermal curing between these and the carboxylic acid is usually 0.01 to 20% by mass. It is.

<Solvent of photosensitive composition>
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, and the like; 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; 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.

<Other ingredients>
The other component is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include an adhesion promoter, a thermal polymerization inhibitor, a plasticizer, and other additives. Adhesion promoters and other auxiliaries (for example, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, perfumes, surface tension modifiers, chain transfer agents, etc. ) May be used in combination. By appropriately containing these components, it is possible to adjust properties such as the stability, photographic properties, and film properties of the intended photosensitive composition or photosensitive film.

―Adhesion promoter―
The adhesion promoter has a function of improving adhesion between layers, adhesion between the photosensitive layer and the substrate, and electrolytic corrosion.
The adhesion promoter is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include melamine, acetoguanamine, benzoguatemine, melamine-phenol formalin resin, ethyldiamino-S-triazine, 2,4-diamino. And triazine compounds such as -S-triazine and 2,4-diamino-6-xylyl-S-triazine. 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 the adhesion to the copper circuit, improve the PCT resistance, and have an effect on electrolytic corrosion. These can be used alone or in combination of two or more. 0.1-40 mass% is preferable with respect to the photosensitive composition solid content, and, as for the compounding quantity of an adhesion promoter, 0.1-20 mass% is more preferable.

-Thermal polymerization inhibitor-
The thermal polymerization inhibitor is preferably added to prevent thermal polymerization or temporal polymerization of the polymerizable compound and improve storage stability.
The thermal polymerization inhibitor is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 4-methoxyphenol, hydroquinone, hydroquinone monomethyl ether, alkyl or aryl-substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine, chloranil, naphthylamine, β-naphthol, 2,6-di-t-butyl-4-cresol, 2,2′-methylenebis ( 4-methyl-6-tert-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-toluidine, methylene blue, copper and organic chelating agent reactant, methyl salicylate, and phenothiazine, nitroso compound, nitroso compound Such chelates and Al.

  As content of the said thermal-polymerization inhibitor, 0.001-5 mass% is preferable with respect to the said polymeric compound, 0.005-2 mass% is more preferable, 0.01-1 mass% is especially preferable. When the content is less than 0.001% by mass, stability during storage may be lowered, and when it exceeds 5% by mass, sensitivity to active energy rays may be lowered.

―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)
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 are provided in this order on the support, On the support, the PC layer, the photosensitive layer, and the protective film are arranged in this order. On the support, the cushion layer, the PC layer, the photosensitive layer, and the protective film are arranged in this order. The form which has is 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 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 length 10m-20000m is mentioned.

(Photosensitive layer)
The photosensitive 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, According to the objective, it can select suitably, For example, 3-100 micrometers is preferable and 5-70 micrometers is more preferable.

  The photosensitive layer is formed by preparing the photosensitive composition solution by dissolving, emulsifying or dispersing the photosensitive composition of the present invention in water or the solvent on the support. The method of laminating | stacking by apply | coating directly and drying is mentioned.

The application method is not particularly limited and may be appropriately selected depending on the intended purpose. For example, using a spin coater, slit spin coater, roll coater, die coater, curtain coater, etc. 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, and 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.
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 discharge irradiation treatment, active plasma irradiation treatment, and laser beam irradiation treatment.

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, and when it exceeds 1.4, it is difficult to wind into a good roll. 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 having a thickness of about 1.5 μm formed mainly of polyvinyl alcohol.
The photosensitive film of the present invention has a photosensitive layer on which a photosensitive composition that exhibits excellent storage stability and exhibits excellent chemical resistance, surface hardness, heat resistance and the like after development is 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 photosensitive film of the present invention has a uniform thickness, even when the permanent pattern (protective film, interlayer insulating film, solder resist, etc.) is thinned during the formation of the permanent pattern, a high acceleration test is performed. In (HAST), there is no occurrence of ion migration, and a high-definition permanent pattern excellent in heat resistance and moisture resistance can be obtained.

<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.
In the method for forming a permanent pattern of the present invention, as a first aspect, 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, Specifically, a known printed wiring board forming substrate (for example, a copper-clad laminate), a glass plate (for example, a soda glass plate), a synthetic resin film, paper, a metal plate, etc. may be mentioned. Among them, a printed wiring board forming substrate is preferable, and the printed wiring board forming substrate has already been formed with a wiring 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 a said 1st aspect, According to the objective, it can select suitably, The photosensitive composition formed by apply | coating and drying the said photosensitive composition on the said base material. It is preferable to laminate the layers.
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 the said 2nd aspect, According to the objective, it can select suitably, At least any one of heating and pressurizing the said photosensitive film on the said base material is performed. However, it is preferable to laminate them. 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, According to the objective, it can select suitably, 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, According to the objective, it can select suitably, 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) and the like are preferable.

<Exposure process>
The exposure step is a step of exposing the photosensitive layer.

  The subject of the exposure is not particularly limited as long as it is a material having a photosensitive layer, and can be appropriately selected according to the purpose. For example, the photosensitive composition or the photosensitive film is formed on a substrate. It is preferable to be performed on the laminated body.

  There is no restriction | limiting in particular as exposure to the said laminated body, According to the objective, it can select suitably, For example, you may expose the said photosensitive layer through the said support body, cushion layer, and PC layer, After peeling the support, the photosensitive layer may be exposed through the cushion layer and the PC layer. After peeling the support and cushion layer, the photosensitive layer is exposed through the PC layer. Alternatively, the photosensitive layer may be exposed after the support, the cushion layer and the PC layer are peeled off.

  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 used. Preferably.

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

<Light modulation means>
The light modulation 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.
There is no restriction | limiting in particular as a light modulation means which has the said n image drawing part, According to the objective, it can select suitably, 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.

The light modulation means preferably includes pattern signal generation means for generating a control signal based on pattern information to be formed. 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. 2, in the DMD 50, a large number (for example, 1024 × 768) of micromirrors (micromirrors) 62 constituting pixels (pixels) 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 reflectance such as aluminum is deposited on the surface of the micromirror 62. 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 and horizontal directions. 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 monolithically configured. 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. 3A shows a state in which the micromirror 62 is tilted to + α degrees when the micromirror 62 is in an on state, and FIG. 3B shows a state in which the micromirror 62 is tilted to −α degrees that is in an off state. Therefore, by controlling the tilt of the micromirror 62 in each pixel of the DMD 50 according to the pattern information as shown in FIG. 2, the laser light B incident on the DMD 50 is reflected in the tilt direction of each micromirror 62. The

  FIG. 2 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 the controller 302 (see FIG. 13) 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. 4A shows the scanning trajectory of the reflected light image (exposure beam) 53 by each micromirror when the DMD 50 is not tilted, and FIG. 4B 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 DMD 50 is irradiated with the laser beam B from the fiber array light source 66, the laser beam reflected when the micromirror of the DMD 50 is in an on state is imaged on the photosensitive layer 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 photosensitive layer 150 is exposed with pixel units (exposure area 168) of approximately the same number as the number of used pixels of the DMD 50. Further, when the photosensitive layer 150 is moved at a constant speed together with the stage 152, the photosensitive layer 150 is sub-scanned in the direction opposite to the stage moving direction by the scanner 162, and a strip-shaped exposed area 170 is formed for each exposure head 166. Is done.

  In this example, as shown in FIGS. 5A and 5B, in the DMD 50, 768 sets of micromirror arrays in which 1024 micromirrors are arranged in the main scanning direction are arranged in the subscanning direction. In this example, the controller 302 (see FIG. 13) controls 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. 5 (A) may be used, and a micromirror arranged at the end of the DMD 50 as shown in FIG. 5 (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 photosensitive layer 150 by the scanner 162 is finished and the rear end of the photosensitive layer 150 is detected by the sensor 164, the stage 152 is moved to the uppermost stream side of the gate 160 along the guide 158 by the stage driving device 304. It returns to a certain origin, and again moves along the guide 158 from the upstream side to the downstream side of the gate 160 at a constant speed.

  For example, when only 384 sets of 768 sets of micromirror arrays are used, 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. In this case, it is preferable to use the exposure light in combination with the high-speed modulation. Thereby, high-speed exposure can be performed in a short time.

  In addition, as shown in FIG. 6, the entire surface of the photosensitive layer 150 may be exposed by a single scan in the X direction by the scanner 162, and as shown in FIGS. 7A and 7B, After scanning the photosensitive layer 150 in the X direction, the scanner 162 is moved one step in the Y direction, and scanning in the X direction is repeated, so that the entire surface of the photosensitive layer 150 is scanned by a plurality of scans. You may make it expose. 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 permanent 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. 8, the pattern forming apparatus including the light modulation unit includes a flat stage 152 that holds the stacked body having the photosensitive layer 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-shaped 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 photosensitive layer 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. 9 and 10B, the scanner 162 includes a plurality of (for example, 14) exposure heads 166 arranged in an approximately 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 photosensitive layer 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. Therefore, as the stage 152 moves, a strip-shaped exposed region 170 is formed in the photosensitive layer 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. 10A and 10B, each of the exposure heads in each row arranged in a line so that the strip-shaped exposed regions 170 are arranged without gaps in the direction orthogonal to the sub-scanning direction. 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 FIG. 11 and FIG. 12, 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 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. 13) having 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 area 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. 11, the lens system 67 is schematically shown.

  As shown in detail in FIG. 12, 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. 11, the TIR prism 70 is omitted.

  Further, an imaging optical system 51 that images the laser beam B reflected by the DMD 50 on the photosensitive layer 150 is disposed on the light reflection side of the DMD 50. The imaging optical system 51 is schematically shown in FIG. 11, but as shown in detail in FIG. 12, the imaging optical system 51 includes a first imaging optical system including lens systems 52 and 54 and lens systems 57 and 58. A second imaging optical system, a microlens array 55 inserted between these imaging optical systems, and an aperture array 59 are included.

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 will be 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 enlarges the image by the DMD 50 three times and forms an image on the microlens array 55. 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 photosensitive layer 150. Therefore, as a whole, the image by the DMD 50 is magnified 4.8 times and is formed and projected on the photosensitive layer 150.

  A prism pair 73 is disposed between the second imaging optical system and the photosensitive layer 150, and the prism pair 73 is moved in the vertical direction in FIG. 12 to focus the image on the photosensitive layer 150. Can be adjusted. In the figure, the photosensitive layer 150 is sub-scanned in the direction of arrow F.

The pixel part 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, by the permanent pattern forming method of the present invention When the formed permanent pattern 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 can be appropriately selected according to the purpose. Is more preferable.

<Light irradiation means>
The light irradiation means is not particularly limited and can be appropriately selected depending on the purpose. , 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 laser beam obtained by combining two or more beams (hereinafter, referred to as “combined laser beam”). ) Is more preferable. 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, 395 nm-415 nm is especially preferable.

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

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

  As shown in FIG. 28 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. 28b, 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 these are arranged in two rows to form a laser. An emission unit 68 is configured.

  As shown in FIG. 28b, 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. Further, 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. 29, such an optical fiber is coaxial with an optical fiber 31 having a length of 1 to 30 cm and a small cladding diameter at the tip of the laser beam emission side of a multimode optical fiber 30 having a large cladding diameter. 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.

  Also, a short optical fiber in which an optical fiber having a short length and a large cladding diameter is fused to an optical fiber having a small 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 laser light in the infrared region, 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 clad 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. 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. 31 and 32, 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 through 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. 32, 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. 33 shows the front shape of the attachment part of the collimator lenses 11-17. Each of the collimator lenses 11 to 17 is formed in a shape obtained by cutting a region including the optical axis of a circular lens having an aspherical surface into a long and narrow 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 light emitting point arrangement direction so that the length direction is orthogonal to the light emitting point arrangement direction of the GaN-based semiconductor lasers LD1 to LD7 (the horizontal direction in FIG. 33).

  On the other hand, each of the GaN-based semiconductor lasers LD1 to LD7 includes an active layer having a light emission width of 2 μm, and each of the laser beams B1 in a state in which the divergence angles in a direction parallel to and perpendicular to the active layer are, for example 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. In addition, 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 formed by cutting a region including the optical axis of a circular lens having an aspheric surface into a long and narrow shape in parallel planes, and is long in the arrangement direction of the collimator lenses 11 to 17, that is, in a horizontal direction and short in a 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.

  Further, since the cladding diameter of the output end of the optical fiber is smaller than the cladding diameter of the incident 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 a light irradiation means having a plurality of light emitting points, for example, as shown in FIG. 34, 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. Further, a chip-shaped multicavity laser 110 in which a plurality of (for example, five) light emitting points 110a shown in FIG. 35A is arranged in a predetermined direction is known. Since the multicavity laser 110 can arrange the light emitting points with high positional accuracy as compared with 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, as the number of light emitting points increases, the multicavity laser 110 is likely to be bent at the time of laser manufacturing. Therefore, 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 as shown in FIG. 35 (B) has the same direction as the arrangement direction of the light emitting points 110a of each chip. A multi-cavity laser array arranged in the above 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. 22, 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 as the condenser lens 120, substantially the same as the core diameter of the multimode optical fiber 130. By using a convex lens having a new focal length and 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 is increased. be able to.

  As shown in FIG. 36, 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 equally spaced 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-capability laser 110, and a single lens arranged between the laser array 140 and the plurality of lens arrays 114. A rod 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 multi-capability 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 condensed in a predetermined direction by the rod lens 113 and then each microlens of the lens array 114. Is collimated. The collimated laser beam L is condensed by the condensing lens 120 and is incident on 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. 37A and 37B, 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 divergence angle of the laser beam 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 beam 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 beam to the incident end of the multimode optical fiber 130. Is arranged.

  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 disposed on the laser blocks 180 and 182 is collimated by the collimating lens array 184 and collected. The light is condensed by the optical 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 formed, which is particularly suitable as a fiber light source constituting the laser light source of the pattern forming apparatus.

  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 permanent 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. Since the area of the light emitting region is 0.62 mm ² (0.675 mm × 0.925 mm), the luminance at the laser emitting portion 68 is 1.6 × 10 ⁶ (W / m ² ) and one optical fiber is used. 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 the combined laser light, an output of about 1 W can be obtained with six multimode optical fibers, and the light emitting area of the laser emitting portion 68 can be obtained. Since the area 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. Can be planned. Further, the luminance per optical fiber is 90 × 10 ⁶ (W / m ² ), and the luminance can be increased by about 28 times compared with the conventional one.

  Here, with reference to FIGS. 38A and 38B, 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, the diameter of the light emitting region of the fiber array light source 66 in the sub-scanning direction is small, so that the light flux that passes through the lens system 67 and enters the DMD 50 , And 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. Note that DMD is a reflective spatial light modulator, but FIGS. 38A and 38B 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 photosensitive film 150 having the photosensitive layer 150 adsorbed on the surface thereof is moved at a constant speed along the guide 158 from the upstream side to the downstream side of the gate 160 by a driving device (not shown). When the leading edge of the photosensitive layer 150 is detected by the detection sensor 164 attached to the gate 160 when 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. 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 forms an image on the exposed surface 56 of the photosensitive layer 150 by the lens systems 54 and 58. Is done. In this manner, the laser light emitted from the fiber array light source 66 is turned on / off for each pixel, and the photosensitive layer 150 is exposed in approximately the same number of pixel units (exposure area 168) as the number of pixels used in the DMD 50. Further, when the photosensitive layer 150 is moved at a constant speed together with the stage 152, the photosensitive layer 150 is sub-scanned in the direction opposite to the stage moving direction by the scanner 162, and a strip-shaped exposed area 170 is formed for each exposure head 166. Is done.

<Microlens array>
The exposure is preferably performed through the microlens array with the modulated light, 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 depending on the purpose. For example, a microlens array having an aspherical surface capable of correcting aberration due to distortion of the exit surface in the pixel portion Are preferable.

  There is no restriction | limiting in particular as said aspherical surface, According to the objective, it can select suitably, 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. 14A shows DMD 50, light irradiation means 144 for irradiating DMD 50 with laser light, lens systems (imaging optical systems) 454, 458, DMD 50 for enlarging and imaging the laser light reflected by 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. 15 shows the result of measuring the flatness of the reflecting surface of the micromirror 62 constituting the DMD 50. In the figure, the same height position of the reflecting surface is 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. 16A and 16B 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. 15 and 16, there is distortion on the reflecting surface of the micromirror 62, and when attention is particularly paid 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 permanent 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. 17A and 17B 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 permanent pattern forming method of the present invention, as described above with reference to FIG. 5, the 1024 × 256 rows of micromirrors 62 of the DMD 50 are driven. A row of 1024 microlenses 55a arranged in the horizontal direction is arranged by arranging 256 rows 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.

  18A and 18B show the front shape and the side shape of one microlens 55a in the microlens array 55, respectively. In FIG. 9A, contour lines of the microlens 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. 19A and 19B, respectively. That is, when the cross section parallel to the x direction is compared with the cross section parallel to the y direction, the radius of curvature of the microlens 55a is smaller and the focal length is shorter in the latter cross section. .

  20A, 20B, 20C, and 20D show the results of simulating the beam diameter in the vicinity of the condensing position (focal position) of the microlens 55a when the microlens 55a has the above-described shape by a computer. For comparison, FIGS. 21A, 21B, 21C, and 21D 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.

  20A to 20D and FIGS. 21A to 21D, in the permanent pattern forming method of the present invention, the microlens 55a has a focal length in the cross section parallel to the y direction in the cross section parallel to the x direction. By using a toric lens that is smaller than the focal length, distortion of the beam shape in the vicinity of the condensing position is suppressed. If so, a higher-definition image without distortion can be exposed on the photosensitive layer 150. It can also be seen that the present embodiment shown in FIGS. 20a to 20d has a wider region with a smaller beam diameter, that is, a greater depth of focus.

  In addition, when the magnitude relation of the distortion of the central part in the x direction and the y direction of the micromirror 62 is opposite to the above, the focal length in the cross section parallel to the x direction is If the microlens is composed of a toric lens that is smaller than the focal length, similarly, a higher-definition image without distortion can be exposed on the photosensitive layer 150.

  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 permanent pattern forming method of the present invention, the microlens 55a may have a secondary aspherical shape or a higher order (4th, 6th,...) Aspherical shape. Good. By adopting the higher order aspherical shape, the beam shape can be further refined.

  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.

  24A and 24B 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 microlens 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, etc. The position changed with the pitch is shown. As shown in the figure, when the cross section parallel to the x direction and the cross section parallel to the y direction are compared, the ratio of the refractive index change of the microlens 155a is larger in the latter cross section, and the focal length is larger. It is shorter. 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. 18 and 19, 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.

  In the above embodiment, the aberration due to the distortion of the reflection surface of the micromirror 62 constituting the DMD 50 is corrected. However, in the permanent pattern forming method of the present invention using a spatial light modulation element other than the DMD, the spatial When there is distortion on the surface of the picture element portion of the light modulation element, the present invention can be applied to correct the aberration caused by 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 unit 144, the cross-sectional area of the light beam 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 expanded 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. 14B, 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. Thereby, as shown in FIG. 14C, 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 characteristic is 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 arranged 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 permanent 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 quantity 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 flux 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. 25A, 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. 25A, 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 light beam width is changed between the incident side and the exit side (FIGS. 25B and 25C).

  FIG. 25B 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. 25C shows a case where the entire light flux width H0 on the incident side is “enlarged” by the width Η3 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 permanent 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 part near the optical axis is larger than the light quantity in the peripheral part by reducing the core diameter of the multimode 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 aspherical data is represented by a coefficient in the following mathematical formula (A) representing the aspherical 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 subsequent numerical value is a “power index” with 10 as the base. The numerical value represented by the exponential function with the base of 10 is multiplied by the numerical value before “E”. For example, “1.0E-02” indicates “1.0 × 10 ⁻² ”.

  FIG. 27 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. 26 shows a light amount distribution (Gaussian distribution) of illumination light when correction is not performed. As can be seen from FIG. 26 and FIG. 27, a light amount distribution that is substantially uniform is obtained by performing correction using the light amount distribution correcting optical system 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.

―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. For example, alkali metal or alkaline earth metal hydroxide or carbonate, hydrogen carbonate, aqueous ammonia, quaternary ammonium salt An aqueous solution of 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 permanent pattern forming method of the present invention preferably further includes a curing treatment step.
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, According to the objective, it can select suitably, 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. The entire surface exposure accelerates the curing of the resin in the photosensitive composition forming the photosensitive layer, 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, According to the objective, it can select suitably, 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. The entire surface heating increases the film strength of the surface of the permanent pattern.
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 photosensitive composition is decomposed, and the film quality is weak and brittle. Sometimes.
The heating time in the entire surface heating is preferably 10 to 120 minutes, and more preferably 15 to 60 minutes.
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 and an interlayer insulating film. When the permanent pattern formed by the permanent pattern forming method is the protective film or the interlayer insulating film, the wiring can be protected from external impact and bending, particularly when the interlayer insulating film is the interlayer insulating film. Is useful for high-density mounting of semiconductors and components on, for example, multilayer wiring boards and build-up wiring boards.

The permanent pattern forming method of the present invention can be widely used for forming various patterns because the pattern can be formed at a high speed, and can be particularly suitably used for forming a wiring pattern.
In addition, the permanent pattern formed by the method for forming a permanent pattern of the present invention has excellent surface hardness, insulation, heat resistance, moisture resistance, etc., and is suitably used as a protective film, interlayer insulation film, solder resist pattern, etc. can do.

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

  Alkali-soluble photocrosslinkable resins (P1) to (P4) (Synthesis Examples 1 to 4), metal ion adsorbent a (Synthesis Example 5), metal ion adsorbent b (Synthesis Example 6) contained in the photosensitive composition, An alkali-soluble urethane elastomer (Synthesis Example 7), a pigment, and an inorganic filler dispersion (Synthesis Example 8) were synthesized as follows.

(Synthesis Example 1)
-Synthesis of alkali-soluble photocrosslinkable resin (P1)-
YDCN704 (manufactured by Toto Kasei Co., Ltd., cresol novolac type epoxy resin (epoxy equivalent = 220), 220 parts by mass, 72 parts by mass of acrylic acid, 1.0 part by mass of hydroquinone, and 180 parts by mass of methoxypropyl acetate were charged at 90 ° C. The reaction mixture was dissolved by heating and stirring.
Next, the obtained reaction mixture was cooled to 60 ° C., charged with 1 part by mass of benzyltrimethylammonium chloride, heated to 100 ° C., and reacted until the solid content acid value reached 1 mgKOH / g. Furthermore, 152 parts by mass of tetrahydrophthalic anhydride and 100 parts by mass of methoxypropyl acetate were added, heated to 80 ° C., reacted for about 6 hours, cooled, and diluted with methoxypropyl acetate so that the solid content concentration became 60% by mass. Thus, an alkali-soluble photocrosslinkable resin (P1) was obtained. The obtained (P1) had a mass average molecular weight of 4.020 and a solid content acid value of 138 mgKOH / g.

(Synthesis Example 2)
-Synthesis of alkali-soluble photocrosslinkable resin (P2)-
145 parts by mass of methoxypropyl acetate was placed in a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, stirred while purging with nitrogen, and heated to 120 ° C.
Next, t-butyl hydroperoxide (Nippon Yushi Co., Ltd.) was added to a monomer mixture consisting of 10.4 parts by mass of styrene, 71 parts by mass of glycidyl methacrylate and 82 parts by mass of dicyclopentenyl acrylate (FA-511A manufactured by Hitachi Chemical Co., Ltd.). 7.6) perbutyl O) 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 to 6 ° C at 120 ° C. The reaction was continued for a while, and 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), 0.8 mass of triethylamine Part was added and reacted at 120 ° C. for 3.5 hours, and diluted with methoxypropyl acetate to a solid content concentration of 60% by mass to obtain an alkali-soluble photocrosslinkable resin (P2). The obtained (P2) had a mass average molecular weight of 12,000 and a solid content acid value of 84 mgKOH / g.

(Synthesis Example 3)
-Synthesis of alkali-soluble photocrosslinkable resin (P3)-
Mixing 60 parts by weight of methyl methacrylate and 57 parts by weight of glycidyl methacrylate, adding 70 parts by weight of methoxypropyl acetate as a solvent, and in the presence of 2 parts by weight of azobisisobutyronitrile as a catalyst in a nitrogen gas atmosphere, Solution polymerization was performed at 60 ° C. Thereafter, in the presence of 1 part by mass of benzyltrimethylammonium chloride in the air, 42 parts by mass of acrylic acid (corresponding to 1.05 mol per 1 epoxy equivalent in the copolymer) is reacted to make the acid value constant. After that, 48.6 parts by mass of tetrahydrophthalic anhydride (corresponding to 0.8 mol per 1 mol of epoxy group in the copolymer) is further reacted so that the solid content concentration becomes 60% by mass with methoxypropyl acetate. Dilution was performed to obtain an alkali-soluble photocrosslinkable resin (P3) having a softening point of 60 ° C. The obtained (P3) had a mass average molecular weight of 30,000 and a solid content acid value of 100 mgKOH / g.

(Synthesis Example 4)
-Synthesis of alkali-soluble photocrosslinkable resin (P4)-
200 parts by mass of styrene maleic anhydride copolymer (SMA resin 1000 manufactured by Arcochemical Co., copolymerization molar composition ratio of styrene maleic anhydride = 1/1) and 130 parts by mass of 2-hydroxyethyl methacrylate were mixed with 200 methoxypropyl acetate. It melt | dissolved in the mass part, it was made to react at 100 degreeC for 20 hours, it diluted so that solid content concentration might be 60 mass% with methoxypropyl acetate, and alkali-soluble photocrosslinkable resin (P4) which is a half-esterified compound was obtained. The obtained (P4) had a mass average molecular weight of 4,950 and a solid content acid value of 170 mgKOH / g.

(Synthesis Example 5)
-Synthesis of metal ion adsorbent a-
According to the synthesis method described in Japanese Patent Publication No. 42-8129, 100 g of Mizusawa Sieves Y-500 (synthetic zeolite) manufactured by Mizusawa Chemical Industry Co., Ltd. was placed in an aqueous solution in which 300 g of ammonium sulfate was dissolved in 1,500 g of ion-exchanged water. Treated at 30 ° C. with stirring for 30 minutes. After filtration with a solid (zeolite) Teflon (registered trademark) filter, similarly, 100 g of ammonium sulfate was treated with an aqueous solution in 1500 g of water. The solid (zeolite) was washed with water until there was no sulfate ion, and further heat-treated at 550 ° C. for 3 hours. Furthermore, 300 g of ammonium sulfate was treated with stirring in an aqueous solution obtained by dissolving 6,000 g of ion-exchanged water, and the zeolite was filtered off, followed by washing with water and heat treatment (550 ° C.) twice. Finally, after sufficiently washing with water, heat treatment was performed at 850 ° C. for 3 hours. The metal ion adsorbent a made of ultrastable zeolite was obtained by exchanging sodium ions contained in the zeolite with ammonium ions by the above treatment.

(Synthesis Example 6)
-Synthesis of metal ion adsorbent b-
Mizusawa Chemical Industry Co., Ltd. Mizuga Life P-1 (silica-magnesia clay intercalation compound) was previously washed several times with ion-exchanged water, washed twice with ethyl lactate, and then dried at 120 ° C. for 48 hours to obtain a metal ion adsorbent. b was obtained.

(Synthesis Example 7)
―Synthesis of alkali-soluble urethane elastomer―
In a 500 ml three-necked flask, 41.07 g of 4,4′-diphenylmethane diisocyanate, 48.49 g of polyoxytetramethylene glycol (molecular weight = 981) and 15.56 g of 2,2-bis (hydroxymethyl) propionic acid were added to 90 ml of dioxane. Dissolved. After adding 0.3 g of N, N-diethylaniline, the mixture was stirred for 6 hours under reflux of dioxane. 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 105 g of an alkali-soluble urethane elastomer. The acid value was 62 mgKOH / g. The molecular weight was measured with a gel permeation chromatograph (GPC) applying the principle that the elution rate of solute molecules depends on the shape, size and molecular weight in the solution, and the mass average (polystyrene standard) was 30,000. there were.

(Synthesis Example 8)
―Synthesis 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 60 parts by mass of a 60% by mass methoxypropyl acetate solution of each alkali-soluble photocrosslinkable resin. 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, is mixed and stirred in the green pigment dispersion, and the pigment and the inorganic filler co-dispersed with the green pigment (solid content concentration 35% by mass) are filled with inorganic filler. An agent dispersion was obtained.

Example 1
<Preparation of photosensitive composition coating solution>
The following components (see Table 3) were mixed to prepare a photosensitive composition coating solution.
――――――――――――――――――――――――――――――――――――――――
・ Alkali-soluble photocrosslinkable resin (P1) solution (solid content concentration 60 mass%) 40.3 mass parts ・ Dipentaerythritol hexaacrylate (Nippon Kayaku DPHA) 11 mass parts ・ Bisacylphosphine oxide (Ciba Specialty Chemicals) Irgacure 819) 7 parts by mass, dicyandiamide 2.8 parts by mass, bisphenol A type epoxy resin (Epicoat 1004 manufactured by Japan Epoxy Resin Co., Ltd.) 17 parts by mass, pigment and inorganic filler dispersion (synthesized in Synthesis Example 8) 81.4 parts by mass-Alkali-soluble urethane elastomer synthesized in Synthesis Example 6 9.5 parts by mass-Methoxypropyl acetate 12.8 parts by mass ------- ――――――――――――――――――――

―Ion adsorption treatment with metal ion adsorbent and anion exchange resin―
As shown in Table 4, 8.0 g of the zeolite adsorbent obtained in Synthesis Example 5 as a metal ion adsorbent and 182 g of the obtained photosensitive composition coating liquid (solid content concentration 55% by mass, viscosity 20 cp) Ion exchange resin (Rom & Haas "Amberlyst" A21) 8.0g was added, stirred for 24 hours, and then filtered to perform ion adsorption treatment with metal ion adsorbent and anion exchange resin. .

-Production of photosensitive film-
As shown in FIG. 1, 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 with a bar coater. Is coated in a hot-air circulating drier at 80 ° C. for 30 minutes, and then a 12 μm-thick polypropylene film is laminated as a protective film on the photosensitive layer. A conductive film was prepared.

<Formation of permanent pattern>
―Preparation of laminates―
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. A vacuum laminator (MVLP500, manufactured by Meiki Seisakusho Co., Ltd.) was used on the copper clad laminate while peeling off the protective film on the photosensitive film so that the photosensitive layer of the photosensitive film was in contact with the copper clad laminate. Lamination was performed to prepare a laminate in which the copper-clad laminate, 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. Then, spray development was performed at 30 ° C. for 60 seconds at a pressure of 1.8 kgf / cm ₂ to dissolve and remove unexposed areas. Thereafter, it was washed with water and dried to form a permanent pattern.

―Curing process―
The entire surface of the laminate on which the permanent pattern was formed was heat treated at 150 ° C. for 1 hour to cure the surface of the permanent pattern and increase the film strength.
According to the permanent pattern resist thus obtained, the insulation resistance after being left for 168 hours in an environment having the above composition and a temperature of 85 ° C. and a relative humidity of 85% is processed to be 10 ¹⁰ Ω or more. Therefore, even when used in a high temperature and high humidity atmosphere, the wiring conductor layers are not short-circuited, and the wiring conductor layers are not corroded, and are excellent in moisture resistance. Further, since the obtained printed wiring board is formed by depositing a wiring conductor layer on the surface of the insulating substrate and covering the part of the insulating substrate, the permanent pattern is deposited. However, it is possible to protect the insulating layer from heat when mounting electronic components on a printed wiring board, and to protect the wiring conductor layer from oxidation and corrosion due to moisture. As a result, the heat resistance and moisture resistance are excellent.

  With respect to the permanent pattern (solder resist), the insulation resistance (Ω) described later was measured. Moreover, about the said permanent pattern peeled from the printed wiring board (copper clad laminated board), the dynamic elastic modulus (storage elastic modulus) (MPa) was measured by the dynamic viscoelasticity measurement test. Table 5 shows the measurement results. The measurement and evaluation by the reliability test are as follows.

<Measurement and evaluation by reliability test>
―Measurement of insulation resistance―
As described in JIS C6481, first, circular electrodes were formed on the front and back surfaces of the film-like photosensitive layer A, and an evaluation substrate was prepared. This was an atmosphere having a temperature of 85 ° C. and a relative humidity of 85%. It was determined by measuring after standing for 168 hours and applying a voltage of 500 V for 1 minute between the circular electrodes on the front and back surfaces. The insulation resistance of the film-like photosensitive layer A at this time was 9 × 10 ¹¹ Ω.

―Measurement of impurity ion concentration―
Further, the impurity ion concentration of the film-like photosensitive layer A is determined after leaving the film-like photosensitive layer A with hot water at 100 ° C. after being left in an atmosphere having a temperature of 85 ° C. and a relative humidity of 85% for 96 hours. The extract was measured using ion chromatography. The impurity ion concentration of the photosensitive layer A was 0.5 ppm for chlorine ions and 0.1 ppm for sodium ions with respect to the solid content of the photosensitive layer A. Table 5 shows the measurement results.
Next, a photosensitive film having a photosensitive layer having a thickness of 10 μm was laminated on the insulating substrate and the wiring conductor layer using a vacuum laminator to form a photosensitive layer. Also, exposure is performed by irradiating a laser beam of 405 nm with an energy amount of 40 mJ / cm ₂ using a pattern forming apparatus by blue-violet laser exposure, and then developing with a 1% by mass sodium carbonate aqueous solution to open an opening having a diameter of 50 μm. The film was further irradiated with 405 nm laser light having an energy amount of 400 mJ / cm ₂ and cured by heating in an oven at 150 ° C. for 1 hour to form a permanent pattern.
Next, nickel and gold plating are sequentially applied to the openings of the permanent pattern, a conductor paste made of lead-tin is printed in the openings, and then a conductor bump is formed by passing through a reflow furnace, and a semiconductor element is formed on the conductor bump. An electronic component module A was produced by electrically connecting each electrode of the semiconductor element and the conductor bump through a reflow furnace, and finally injecting an underfill material into the gap between the semiconductor element and the permanent pattern.

As a reliability test, a temperature cycle test (TCT) and a high acceleration test (HAST) are performed. In TCT, appearance and resistance change rate (%) such as cracks and peeling, and in HAST, ion migration and insulation resistance (Ω) Evaluated. The evaluation results are shown in Table 5.
In TCT, using a gas-phase thermal test machine, the electronic component module is left in the gas phase at −55 ° C. and 125 ° C. for 30 minutes each, and this is performed under the conditions of 1,500 cycles as one cycle. The rate of change (%) was calculated by measuring the insulation resistance (Ω) before and after the test.
HAST uses a high-acceleration tester, and after applying voltage 5.5V for 200 hours in an atmosphere where the temperature of the electronic component module is 130 ° C. and the relative humidity is 85%, the ion migration and insulation resistance (Ω) of the conductor bumps are measured. It was measured. Ion migration was determined as follows.
No migration: ○
With migration: ×

-Measurement of dynamic modulus-
The dynamic elastic modulus (MPa) was measured using a solid analyzer RSAII (manufactured by Rheometrics) at a vibration frequency of 1 Hz (6.28 rad / sec).
Sample size is 22.5 x width 3.0 x thickness 0.06 mm, measurement temperature 40-250 ° C (temperature rise 5 ° C / min), strain 0.15%, mode static force tracking dynamic The initial static force was 15.0 g, and the dynamic elastic modulus (MPa) at 220 ° C. was measured. Table 5 shows the measurement results.

(Example 2)
Except for replacing 40.3 parts by mass of the alkali-soluble photocrosslinkable resin (P1) in the photosensitive composition of Example 1 with 40.3 parts by mass of the alkali-soluble photocrosslinkable resin (P2) (see Table 3), In the same manner as in Example 1, a photosensitive composition coating solution was prepared, and ion adsorption treatment with a metal ion adsorbent and an anion exchange resin was performed (see Table 4), a permanent pattern was formed, insulation resistance (Ω) and The dynamic elastic modulus (MPa) was measured and evaluated. The results are shown in Table 5.

(Example 3)
Except for replacing 40.3 parts by mass of the alkali-soluble photocrosslinkable resin (P1) in the photosensitive composition of Example 1 with 40.3 parts by mass of the alkali-soluble photocrosslinkable resin (P3) (see Table 3), In the same manner as in Example 1, a photosensitive composition coating solution was prepared, and ion adsorption treatment with a metal ion adsorbent and an anion exchange resin was performed (see Table 4), a permanent pattern was formed, insulation resistance (Ω) and The dynamic elastic modulus (MPa) was measured and evaluated. The results are shown in Table 5.

Example 4
Except for replacing 40.3 parts by mass of the alkali-soluble photocrosslinkable resin (P1) in the photosensitive composition of Example 1 with 40.3 parts by mass of the alkali-soluble photocrosslinkable resin (P4) (see Table 3), In the same manner as in Example 1, a photosensitive composition coating solution was prepared, and ion adsorption treatment with a metal ion adsorbent and an anion exchange resin was performed (see Table 4), a permanent pattern was formed, insulation resistance (Ω) and The dynamic elastic modulus (MPa) was measured and evaluated. The results are shown in Table 5.

(Example 5)
40.3 parts by mass of the alkali-soluble photocrosslinkable resin (P1) in the photosensitive composition of Example 1, 20.2 parts by mass of the alkali-soluble photocrosslinkable resin (P1) and the alkali-soluble photocrosslinkable resin (P2) 20 Except for changing to 2 parts by mass (see Table 3), a photosensitive composition coating solution was prepared in the same manner as in Example 1, and ion adsorption treatment with a metal ion adsorbent and an anion exchange resin was performed (Table 4). A permanent pattern was formed, and insulation resistance (Ω) and dynamic elastic modulus (MPa) were measured and evaluated. The results are shown in Table 5.

(Example 6)
40.3 parts by mass of the elastomer alkali-soluble photocrosslinkable resin (P1) in the photosensitive composition of Example 1, 20.2 parts by mass of the alkali-soluble photocrosslinkable resin (P1) and the alkali-soluble photocrosslinkable resin (P2) Instead of 20.2 parts by mass (see Table 3), the metal ion adsorbent obtained in Synthesis Example 6 was replaced with the metal ion adsorbent a obtained in Synthesis Example 5 for the ion adsorption treatment with the metal ion adsorbent and the anion exchange resin. A photosensitive composition coating solution was prepared in the same manner as in Example 1 except that it was replaced with b (see Table 4), and a permanent pattern was formed. Insulation resistance (Ω) and dynamic elastic modulus (MPa) ) Was measured and evaluated. The results are shown in Table 5.

(Comparative Example 1)
9.5 parts by mass of the alkali-soluble urethane elastomer synthesized in Synthesis Example 6 in the photosensitive composition of Example 1 was replaced with 9.5 parts by mass of a styrene-ethylene-butylene-styrene-triblic polymer (see Table 3). As a result of not performing the ion adsorption treatment with the metal ion adsorbent and the anion exchange resin, the photosensitive composition coating solution contained impurity ions having a halogen ion concentration of 120 ppm and a sodium ion concentration of 50 ppm. A permanent pattern was formed in the same manner as in Example 1 using the adhesive composition coating solution, and insulation resistance (Ω) and dynamic elastic modulus (MPa) were measured and evaluated. The results are shown in Table 5.

(Comparative Example 2)
The 9.5 parts by mass of the alkali-soluble urethane elastomer synthesized in Synthesis Example 6 in the photosensitive composition of Example 1 was replaced with 9.5 parts by mass of a styrene-ethylene-butylene-styrene-triblic polymer, and further an ion adsorbent. Except that 5 parts by mass of an iminodiacetic acid-type styrene-methyl acrylate copolymer composed of a chelate polymer was added (see Table 3), and the ion adsorption treatment with a metal ion adsorbent and an anion exchange resin was not performed. Similar to Example 1, a permanent pattern was formed, and insulation resistance (Ω) and dynamic elastic modulus (MPa) were measured and evaluated. The results are shown in Table 5.

From the results of Table 5, in Comparative Example 1, since the ion adsorption treatment with the metal ion adsorbent and the anion exchange resin was not performed on the photosensitive composition, the impurity ion concentration was changed to the solid content of the photosensitive layer A. In contrast, with Cl ⁻ , 120 to 3 ppm Na ⁺ has a concentration of 50 to 0.5 ppm, and it was found that many ions causing harmful effects remain in the photosensitive composition. In contrast, in the photosensitive compositions of Examples 1 to 6, the impurity ion concentration was 0.8 ppm or less with respect to the solid content, and the effect of the ion adsorption treatment with the metal ion adsorbent and the anion exchange resin. Appears prominently. About Example 1-6 about the electronic component module A which formed the permanent pattern obtained from the photosensitive composition in which the removal process of the impurity ion was performed, in evaluation of 1000 cycles-1500 cycles in a temperature cycle test (TCT) The appearance of cracks is not observed. On the other hand, in Comparative Example 1, it was found that cracks occurred and the harmful effects of impurity ions appeared remarkably. The resistance value change rate (%) obtained from the insulation resistance (Ω) before and after the test is 2 to 5%, and the change is very small. However, in Comparative Example 1, it rises to 30% and the insulation resistance is lowered. I found out.
In the high acceleration test (HAST), the evaluation of the ion migration and insulation resistance (Ω) of the conductor bump after 200 hours application at a voltage of 5.5 V confirmed that there was no ion migration, and the insulation resistance (Ω) Was 1.1 or less, and it was confirmed that there was little deterioration. On the other hand, in Comparative Example 1, it was found that the insulation resistance (Ω) was extremely low, and the influence of impurity ions appeared remarkably. In Comparative Example 2, the resistance change rate (%) after the cycle test in the temperature cycle test (TCT) and the high acceleration test (HAST) is not different from that in each example by adding an ion adsorbent composed of a chelate polymer. The dynamic elastic modulus is 205 MPa, which is about 3 times higher than in each example, the dynamic elastic modulus of the photosensitive layer is increased, and the insulation resistance is slightly inferior to that in each example, which may cause cracks. I understood. From the above, in the photosensitive compositions of Examples 1 to 6, it was confirmed that the ion adsorption treatment with the metal ion adsorbent for removing impurity ions and the anion exchange resin has a remarkable effect on the permanent pattern. It was done.

  The photosensitive composition of the present invention and the photosensitive film using the photosensitive composition are excellent in storage stability and exhibit excellent chemical resistance, surface hardness, heat resistance and the like after development. In addition, even if the permanent pattern (protective film, interlayer insulating film, solder resist, etc.) of the present invention is thinned, no ion migration occurs in the high acceleration test (HAST), and surface hardness, insulation, heat resistance, moisture resistance High-definition permanent patterns with excellent properties can be obtained, so it can be suitably used as protective films and interlayer insulation films. Printed wiring boards (multi-layer wiring boards, build-up wiring boards, etc.), color filters and column materials, It can be widely used for forming a permanent pattern such as a rib member, a spacer, a display member such as a partition wall, a hologram, a micromachine, or a proof.

FIG. 1 is an explanatory view showing the layer structure of the photosensitive film. FIG. 2 is an example of a partially enlarged view showing a configuration of a digital micromirror device (DMD). 3A and 3B are examples of explanatory diagrams for explaining the operation of the DMD. FIGS. 4A and 4B are examples of plan views showing the arrangement of exposure beams and scanning lines in a case where the DMD is not inclined and in a case where the DMD is inclined. 5A and 5B are examples of diagrams illustrating examples of DMD usage areas. FIG. 6 is an example of a plan view for explaining an exposure method in which the photosensitive layer is exposed by one scanning by the scanner. FIGS. 7A and 7B are examples of plan views for explaining an exposure method in which the photosensitive layer is exposed by a plurality of scans by the scanner. FIG. 8 is an example of a schematic perspective view showing an appearance of an example of the pattern forming apparatus. FIG. 9 is an example of a schematic perspective view illustrating the configuration of the scanner of the pattern forming apparatus. FIG. 10A is an example of a plan view showing an exposed region formed on the photosensitive layer, and FIG. 10B is an example of a diagram showing an array of exposure areas by each exposure head. FIG. 11 is an example of a perspective view showing a schematic configuration of an exposure head including a light modulation unit. FIG. 12 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. 13 is an example of a controller that controls DMD based on pattern information. FIG. 14A 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. 14B shows an object to be exposed when a microlens array or the like is not used. FIG. 14C is an example of a plan view showing an optical image projected on an exposed surface when a microlens array or the like is used. FIG. 15 is an example of a diagram showing the distortion of the reflection surface of the micromirror constituting the DMD with contour lines. FIGS. 16A and 16B are examples of graphs showing the distortion of the reflection surface of the micromirror in the two diagonal directions of the mirror. FIG. 17 is an example of a front view (A) and a side view (B) of a microlens array used in the pattern forming apparatus. FIG. 18 is an example of a front view (A) and a side view (B) of a microlens constituting a microlens array. FIG. 19 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. 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 of the present invention. 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. 21a is an example of a diagram showing a result of simulating the beam diameter in the vicinity of the condensing position of the microlens in the conventional pattern forming method. FIG. 21 b is an example of a diagram showing the same simulation result as in FIG. 21 a for another position. FIG. 21c is an example of a diagram showing the same simulation result as in FIG. 21a at another position. FIG. 21d is an example of a diagram showing the same simulation result as in FIG. 21a at another position. FIG. 22 is an example of a plan view showing another configuration of the combined laser light source. FIG. 23 is an example of a front view (A) and an example of a side view (B) of a microlens constituting a microlens array. FIG. 24 is an example of a schematic diagram illustrating a light collection state by the microlens of FIG. 22 in one cross section (A) and another cross section (B). FIG. 25 is an example of an explanatory diagram about the concept of correction by the light amount distribution correction optical system. FIG. 26 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. 27 is an example of a graph showing the light amount distribution after correction by the light amount distribution correcting optical system. 28A (A) is a perspective view showing the configuration of the fiber array light source, FIG. 28A (B) is an example of a partially enlarged view of (A), and FIGS. 28A (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. 28 b is an example of a front view showing the arrangement of light emitting points in the laser emitting section of the fiber array light source. FIG. 29 is an example of a diagram illustrating a configuration of a multimode optical fiber. FIG. 30 is an example of a plan view showing the configuration of the combined laser light source. FIG. 31 is an example of a plan view showing the configuration of the laser module. FIG. 32 is an example of a side view illustrating the configuration of the laser module illustrated in FIG. 31. FIG. 33 is a partial side view showing the configuration of the laser module shown in FIG. FIG. 34 is an example of a perspective view showing a configuration of a laser array. FIG. 35A is an example of a perspective view showing a configuration of a multi-cavity laser, and FIG. 35B is a perspective view of a multi-cavity laser array in which the multi-cavity lasers shown in FIG. It is an example. FIG. 36 is an example of a plan view showing another configuration of the combined laser light source. FIG. 37A is an example of a plan view showing another configuration of the combined laser light source, and FIG. 37B is an example of a cross-sectional view taken along the optical axis of FIG. FIGS. 38A and 38B 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 permanent pattern formation method (pattern formation apparatus) of the present invention. .

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Support body 2 Photosensitive layer 3 Protective film LD1-LD7 GaN type 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 56 Surface to be exposed (scanning surface)
55a Micro lens 57 Lens of second image forming optical system 58 Lens of second image forming optical system 59 Aperture array 64 Laser module 66 Fiber array light source 67 Lens system 68 Laser emitting portion 69 Mirror 70 Prism 73 Combination lens 74 Imaging lens 100 Heat block 110 Multicapacity laser 111 Heat block 113 Rod lens 120 Condensing lens 130 Multimode optical fiber 130a Core 140 Laser array 144 Light irradiation means 150 Photosensitive layer 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 array 302 Controller 30 4 Stage Drive Device 454 Lens System 468 Exposure Area 472 Micro Lens Array 476 Aperture Array 478 Aperture 480 Lens System

Claims (24)

  Photosensitive composition comprising an alkali-soluble photocrosslinkable resin, a polymerizable compound, a photopolymerization initiator, a thermal crosslinker, an elastomer, an inorganic filler, a colorant, a thermosetting accelerator, and a solvent. A photosensitive composition, wherein the photosensitive composition is subjected to ion adsorption treatment with an ion adsorbent.   The photosensitive composition of Claim 1 in which an ion adsorbent contains at least any one of a metal ion adsorbent and an anion exchange resin.   The photosensitive composition according to claim 1, wherein the metal ion adsorbent is any one of clay intercalation compounds.   The ion adsorption treatment is performed before the photosensitive composition is applied, and ions in the photosensitive composition are adsorbed by a batch method with an ion adsorbent and filtered to remove adsorbed ions. 4. The photosensitive composition according to any one of 3.   The photosensitive composition according to any one of claims 1 to 4, wherein a solid content concentration of the photosensitive composition is 10 to 60% by mass, and a viscosity of the photosensitive composition is 5 to 60 cp at 25 ° C. .   The content in the solid content of the photosensitive composition of metal ions is 3 ppm or less, and the content of the anion in the solid content of the photosensitive composition is 1 ppm or less. A photosensitive composition according to claim 1.   The photosensitive composition according to any one of claims 1 to 6, wherein the thermal crosslinking agent is one of an epoxy resin and a polyfunctional oxetane compound.   The photosensitive composition according to any one of claims 1 to 7, wherein the elastomer is any one of alkali-soluble urethane elastomers.   15 to 70% by mass of the alkali-soluble photocrosslinkable resin, 5 to 75% by mass of the polymerizable compound, 0.5 to 20% by mass of the photopolymerization initiator, 2 to 50% by mass of the thermal crosslinking agent, and 2 to 2% of the elastomer. The composition according to any one of claims 1 to 8, comprising 30% by mass, 5 to 75% by mass of an inorganic filler, 0.1 to 10% by mass of a colorant, 0.01 to 20% by mass of a thermosetting accelerator, and a solvent. Photosensitive composition.   A photosensitive film comprising: a support; and a photosensitive layer obtained by laminating the photosensitive composition according to claim 1 on the support.   The photosensitive film according to claim 10, comprising a protective film on the photosensitive layer.   The photosensitive film according to claim 10, wherein the photosensitive layer has a thickness of 3 to 100 μm.   A method for forming a permanent pattern, comprising: laminating a photosensitive layer in the photosensitive film according to claim 10 on a surface of a base material; and exposing and developing the photosensitive layer.   The permanent pattern forming method according to claim 13, wherein the base material is a printed wiring board on which wiring has been formed.   A method for forming a permanent pattern, characterized in that 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 light modulation means further comprises a pattern signal generation means for generating a control signal based on the pattern information to be formed, and the light emitted from the light irradiation means corresponds to the control signal generated by the pattern signal generation means The method for forming a permanent pattern according to claim 15, wherein the permanent pattern is modulated.   The light modulation means has n picture element parts, and pattern information to form any less than n picture element parts continuously arranged from the n picture element parts. The permanent pattern forming method according to claim 15, wherein the permanent pattern forming method can be controlled accordingly.   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 forming method according to any one of 13 to 17.   The permanent pattern forming method according to claim 18, wherein the aspherical surface is a toric surface.   The permanent pattern forming method according to claim 13, wherein after the development, the photosensitive layer is subjected to a curing process.   The permanent pattern formation method according to claim 20, 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.   It forms with the permanent pattern formation method in any one of Claim 13 to 21, The permanent pattern characterized by the above-mentioned.   The permanent pattern according to claim 22, wherein the content of sodium ions in the permanent pattern is 3 ppm or less, and the content of halogen ions is 1 ppm or less. The permanent pattern according to any one of claims 22 to 23, which is at least one of a protective film, an interlayer insulating film, and a solder resist pattern.