TWI695225B - Method for forming photosensitive resin composition, photosensitive element, resist pattern, and method for manufacturing printed wiring board - Google Patents

Abstract

A photosensitive resin composition comprising: (A) component: binder polymer, (B) component: photopolymerizable compound, (C) component: containing a dimer selected from 2,4,5-triarylimidazole At least one photopolymerization initiator in the group consisting of the derivatives thereof and (D) component: a nitroxide radical compound, and the (D) component contains 2,2,6,6-tetra Methylpiperidine-1-oxy compound.

Description

Method for forming photosensitive resin composition, photosensitive element, resist pattern, and method for manufacturing printed wiring board

The present disclosure relates to a method of forming a photosensitive resin composition, a photosensitive element, a resist pattern, and a method of manufacturing a printed wiring board.

In the field of manufacturing printed wiring boards, photosensitive resin compositions are widely used as resist materials used in etching processes or plating processes. The photosensitive resin composition is often used as a photosensitive element (laminate), the photosensitive element having a support and a layer formed using the photosensitive resin composition on the support (hereinafter also referred to as "photosensitive resin composition" Object layer").

The printed wiring board is manufactured as follows, for example. First, a photosensitive element having a support and a photosensitive resin composition layer is prepared, and the photosensitive resin composition layer of the photosensitive element is formed on a substrate for circuit formation (photosensitive layer formation step). Next, after peeling off the support, the predetermined part of the photosensitive resin composition layer is irradiated with actinic rays to harden the exposed portion (exposure step). Then, by removing (developing) the unexposed portion from the substrate, a resist pattern (developing as a resist hardened material) as a photosensitive resin composition (hereinafter referred to as “resist cured material”) is formed on the substrate step). Then, the substrate on which the resist pattern is formed is subjected to etching treatment or plating After processing and forming a circuit on the substrate (circuit formation step), the resist is finally stripped and removed to manufacture a printed wiring board (stripping step).

As a method of exposure, a method of exposing via a photomask using a mercury lamp as a light source has previously been used. In addition, in recent years, a direct drawing exposure method called Digital Light Processing (DLP) or Laser Direct Imaging (LDI) has been proposed. The direct drawing exposure method is based on digital data of a pattern. Draw directly on the photosensitive resin composition layer without going through the mask. Compared with the exposure method through a photomask, the direct drawing exposure method has good alignment accuracy and can obtain high-definition patterns. Therefore, it is continuously introduced to produce high-density package substrates.

Usually in the exposure step, in order to improve production efficiency, it is desirable to shorten the exposure time. However, in the direct drawing exposure method described above, in addition to using monochromatic light such as laser for the light source, actinic rays are irradiated while scanning the substrate. Therefore, compared with the previous exposure method through a photomask, there is a need for a large number of The tendency of exposure time. Therefore, in order to shorten the exposure time and increase the production efficiency, it is necessary to increase the sensitivity of the photosensitive resin composition as compared with the past.

On the other hand, with the recent increase in the density of printed wiring boards, the demand for a photosensitive resin composition that can form a resist pattern excellent in resolution (resolution) and adhesion has increased. In particular, a photosensitive resin composition capable of forming a resist pattern with an L/S (line width/space width) of 10/10 (unit: μm) or less when manufacturing a package substrate is particularly required. Therefore, even in the unit of 1 μm, there is a strong demand for improvement in resolution and adhesion.

In addition, various photosensitive resin compositions have been studied previously. Patent Literature 1 There is disclosed a photosensitive resin composition containing a phenol-based compound as a polymerization inhibitor. In addition, for example, several photosensitive resin compositions using stable radicals typified by spin traps or oxynitride compounds have been proposed (for example, refer to Patent Document 2 to Patent Document 5).

[Prior Art Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. 2000-162767

Patent Document 2: Japanese Patent Laid-Open No. 2003-140329

Patent Document 3: Japanese Patent Laid-Open No. 2003-215790

Patent Document 4: Japanese Patent Laid-Open No. 2006-11397

Patent Document 5: Japanese Patent Laid-Open No. 2007-133398

However, the photosensitive resin composition described in Patent Document 1 improves the resolution by containing a polymerization inhibitor. On the other hand, radical polymerization may be delayed and sufficient sensitivity may not be obtained. When the photosensitive resin composition described in Patent Document 2 to Patent Document 5 is used as a resist for printed wiring boards, it may not be said that the sensitivity, resolution, and adhesiveness can be sufficiently satisfied. That is, in the conventional photosensitive resin composition, while maintaining the sensitivity when forming the resist pattern, there is still room for improvement in terms of improving resolution and adhesion.

In addition, the photosensitive resin composition layer used to form the resist pattern is also required to reduce the residue on the bottom of the resist (also called "resist foot" or "fold" side"). The residue at the bottom of the resist (resist footing) is generated by the following: during the development step, the bottom of the resist expands due to swelling and does not peel off from the substrate due to drying. In the case of performing a plating process, if the amount of generation of resist feet is too large, the contact area between the plating and the substrate becomes small, and this causes a decrease in the mechanical strength of the formed circuit. The influence of the resist footing becomes larger as the circuit formation of the printed wiring board becomes finer, especially when forming a circuit with an L/S of 10/10 (unit: μm) or less. If the amount of footing is large, it may be difficult to form the circuit after plating itself. In addition, in the case of performing an etching process, if the amount of generation of resist feet is large, the area of contact between the etching solution and the substrate becomes small, so it is difficult to form a conductor pattern as designed. In addition, when the etching process is performed, if the amount of generation of resist feet is large, the width deviation of the conductor pattern may become large, which may affect the yield. Therefore, a photosensitive resin composition capable of forming a resist pattern with a smaller generation amount of resist feet is required.

An object of the present disclosure is to provide a photosensitive resin composition capable of forming a resist pattern with excellent sensitivity and excellent resolution and adhesion, and with reduced generation of resist feet, and a photosensitive resin composition using the photosensitive resin composition Method of forming a resistive element, a resist pattern, and a method of manufacturing a printed wiring board.

In order to solve the above-mentioned problems, diligent research was conducted, and as a result, it was found that by combining a binder polymer, a photopolymerizable compound, 2,4,5-triarylimidazole dimer or its derivative, and a specific nitroxide radical compound Combined, it is possible to obtain an anti-resistance that can form an excellent sensitivity with excellent resolution and adhesion, and the amount of generation of resist feet is reduced A photosensitive resin composition of an etchant pattern.

That is, one embodiment of the present disclosure provides a photosensitive resin composition comprising: (A) component: binder polymer, (B) component: photopolymerizable compound, (C) component: containing , 5-triarylimidazole dimer and its derivatives at least one photopolymerization initiator, and (D) component: nitroxide radical compound, and the (D) component contains 2,2,6,6-Tetramethylpiperidine-1-oxy compound.

The 2,4,5-triarylimidazole dimer and its derivatives may contain a compound represented by the following general formula (1).

[In formula (1), Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each independently represent an aryl group which may be substituted with at least one substituent selected from the group consisting of alkyl, alkenyl and alkoxy , X ¹ and X ² each independently represent a halogen atom, an alkyl group, an alkenyl group, or an alkoxy group, and p and q each independently represent an integer of 1 to 5; where, when p is 2 or more, there are multiple X ¹ may be the same or different, and when q is 2 or more, there are multiple X ² may be the same or different]

The (A) component may have a structural unit derived from (meth)acrylic acid and a structural unit derived from alkyl (meth)acrylate.

The photosensitive resin composition of one embodiment of the present disclosure may further contain (E) component: a phenol compound.

In addition, the photosensitive resin composition according to an embodiment of the present disclosure may further contain (F) component: a sensitizer, and the (F) component contains a pyrazoline compound.

In addition, another embodiment of the present disclosure provides a photosensitive element including a support and a photosensitive resin composition layer formed using the photosensitive resin composition provided on the support. By using such a photosensitive element, in particular, a resist pattern having excellent resolution and good adhesion and having a reduced amount of generation of resist feet can be efficiently formed.

In addition, another embodiment of the present disclosure provides a method for forming a resist pattern, which includes a photosensitive layer forming step of forming the photosensitive resin composition using the photosensitive resin composition or the photosensitive element on a substrate Layer; an exposure step, irradiating at least a part of the photosensitive resin composition layer with actinic rays to photoharden the area to form a hardened area; and a developing step, the photosensitive resin is removed from the substrate A region other than the hardened material region of the composition layer is removed to form a resist pattern as the hardened material region on the substrate. According to this forming method, it is possible to efficiently form a resist pattern having excellent resolution and excellent adhesion and reduced generation of resist feet.

In the method of forming the resist pattern, the wavelength of the actinic rays irradiated may be in the range of 340 nm to 430 nm. With this, it is possible to form a resist pattern with better sensitivity and more efficient and with better resolution and adhesion, and the amount of generation of resist feet is further reduced.

In addition, another embodiment of the present disclosure provides a method for manufacturing a printed wiring board, which includes the steps of performing etching or plating on a substrate on which a resist pattern is formed by the method for forming the resist pattern . According to this manufacturing method, a printed wiring board having high-density wiring such as a high-density packaging substrate can be efficiently manufactured with excellent accuracy and good productivity.

According to the present disclosure, it is possible to provide a photosensitive resin composition capable of forming a resist pattern with excellent sensitivity and excellent resolution and adhesion, and with reduced generation of resist feet, and a photosensitive element using the same Method for forming etchant pattern and method for manufacturing printed wiring board.

1: photosensitive element

2: Support

3. 32: photosensitive resin composition layer

4: protective layer

10: Conductor layer

15: Insulation

20: Mask

30: resist pattern

40: Conductor pattern

42: plating layer

50: Actinic rays

FIG. 1 is a schematic cross-sectional view showing an embodiment of the photosensitive element of the present disclosure.

2(a) to 2(f) are perspective views schematically showing an example of a manufacturing process of a printed wiring board using a semi-additive process.

Hereinafter, the form for implementing the present disclosure will be described in detail. However, this The disclosure is not limited to the following embodiments. In the present invention, (meth)acrylic acid means acrylic acid or methacrylic acid, and (meth)acrylic acid ester means acrylate or methacrylate. The term "(poly)oxyethylidene" refers to at least one of oxyethylidene (sometimes referred to as "EO (oxyethylene) group") or at least two polyoxyethylene groups formed by ether linkage. One kind. The term "(poly)oxypropylene" refers to at least one of oxypropylene (sometimes referred to as "PO (oxypropylene) group") or polyoxypropylene in which two or more propylene groups are connected by an ether bond. One kind. Furthermore, the so-called "ethylene oxide (EO) modification" refers to a compound having (poly)oxyethylene, and the so-called "propylene oxide (PO) modification" refers to having (poly) The oxypropylene compound, so-called "EO.PO modified" refers to a compound having both (poly)oxypropylene and (poly)oxypropylene.

In addition, in this specification, the term "step" includes not only an independent step, but even if it cannot be clearly distinguished from other steps, as long as the desired function of the step is achieved, it is also included in the term. In addition, in this specification, the numerical range shown using "~" means the range containing the numerical value described before and after "~" as a minimum value and a maximum value, respectively. In addition, in the numerical range described in stages in this specification, the upper limit value or the lower limit value of the numerical range of a certain stage may be replaced with the upper limit value or the lower limit value of the numerical range of another stage. In addition, in the numerical range described in this specification, the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples. In addition, in this specification, the term “layer” includes a structure formed in a part of the shape in addition to a structure formed in the entire surface when viewed from above.

Furthermore, in this specification, when there are multiple substances corresponding to each component in the composition, unless otherwise specified, the content of each component in the composition refers to the total of the multiple substances present in the composition the amount.

<Photosensitive resin composition>

The photosensitive resin composition of this embodiment includes: (A) component: binder polymer, (B) component: photopolymerizable compound, (C) component: contains dimers selected from 2,4,5-triarylimidazole At least one photopolymerization initiator in the group consisting of substances and their derivatives, and (D) component: a nitroxide radical compound, and the (D) component contains 2,2,6,6- The compound of tetramethylpiperidine-1-oxy structure. The photosensitive resin composition may further contain other components as needed. In addition, in this specification, these components may only be referred to as (A) component, (B) component, (C) component, (D) component, and the like.

By using the following photosensitive resin composition, the sensitivity and formation of L/S (line width/space width) of 10/10 (unit: μm) or less can be formed with excellent sensitivity and excellent adhesion and the generation of resist feet The amount of the resist pattern is reduced. The photosensitive resin composition includes: a binder polymer, a photopolymerizable compound, and a composition selected from the group consisting of 2,4,5-triarylimidazole dimer and derivatives thereof. At least one photopolymerization initiator in the group, a nitroxide radical compound containing a compound having a 2,2,6,6-tetramethylpiperidine-1-oxy structure. Here, the reason why excellent adhesion is obtained and the amount of generation of the resist foot is reduced is presumed to be: by using the photosensitive resin composition, the hardening rate of the bottom of the resist pattern is improved and the resist The swelling of the agent pattern is suppressed.

((A) component: adhesive polymer)

Examples of component (A) include acrylic resin, styrene resin, epoxy resin, amide resin, amide epoxy resin, alkyd resin, phenol resin, ester resin, and urethane resin. Epoxy acrylate resin obtained by reaction of epoxy resin and (meth)acrylic acid, acid-modified epoxy acrylate resin obtained by reaction of epoxy acrylate resin and acid anhydride, etc. These resins may be used alone or in combination of two or more. From the viewpoint of more excellent alkali developability and film formability, it is preferable to use acrylic resin, and it is more preferable to use (a1) (meth)acrylic acid (hereinafter also referred to as (a1) component) among acrylic resins And acrylic resin derived from the structural unit of (a2) alkyl (meth)acrylate (hereinafter also referred to as (a2) component). Here, the "acrylic resin" refers to a polymer mainly containing a monomer unit derived from a polymerizable monomer having a (meth)acryloyl group.

The acrylic resin can be obtained, for example, by polymerizing (meth)acrylic acid, a (meth)acrylic acid alkyl ester as a polymerizable monomer (monomer), and other polymers used as needed by a common method Sexual monomers undergo free radical polymerization.

From the viewpoint of more effectively developing developability and peeling characteristics, based on the total mass (100% by mass, the same applies hereinafter) of the structural units derived from the polymerizable monomer constituting the binder polymer, derived from (a1 ) The content rate of the structural unit of (meth)acrylic acid may be 1% by mass to 99% by mass, 5% by mass to 80% by mass, 10% by mass to 60% by mass, or 15% by mass to 50% by mass.

The (a2) alkyl (meth)acrylate is preferably an alkyl (meth)acrylate having an alkyl group having 1 to 12 carbon atoms, and more preferably an alkyl group having 1 to 8 carbon atoms. Alkyl (meth)acrylate. Examples of alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, (meth) Amyl acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, (meth) Group) decyl acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate. These may be used alone or in combination of two or more.

In terms of more excellent releasability, it is derived from (a2) alkyl (meth)acrylate based on the total mass (100% by mass) of the structural units derived from the polymerizable monomer constituting the binder polymer. The content of the structural unit of the ester may be 1% by mass or more or 2% by mass or more. In addition, in terms of more excellent resolution and adhesion, the content may be 30% by mass or less, 20% by mass or less, or 10% by mass or less.

The acrylic resin may further contain other monomers copolymerizable with the (a1) component and/or (a2) component as structural units.

The other monomer copolymerizable with the (a1) component and/or (a2) component is not particularly limited. Examples of the other monomers include benzyl (meth)acrylate, cycloalkyl (meth)acrylate, benzyl (meth)acrylate derivatives, furfuryl (meth)acrylate, Tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, dicyclopentyl (meth)acrylate, dimethyl (meth)acrylate Aminoethyl, diethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, (meth)acrylic acid- 2,2,3,3-tetrafluoropropyl ester, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentyloxyethyl (meth)acrylate, isobornyl (meth)acrylate Oxyethyl, (methyl) Cyclohexyloxyethyl acrylate, adamantyloxyethyl (meth)acrylate, dicyclopentenyloxypropyloxyethyl (meth)acrylate, dicyclopentyloxy (meth)acrylate (Meth)acrylates such as propylpropyloxyethyl, dicyclopentenyloxypropyloxyethyl (meth)acrylate, adamantyloxypropyloxyethyl (meth)acrylate ; (Meth)acrylic acid derivatives such as α-bromoacrylic acid, α-chloroacrylic acid, (meth)acrylic acid-β-furanyl ester, (meth)acrylic acid-β-styryl ester; styrene, vinyl toluene 、Α-Methylstyrene is equal to the substituted polymerizable styrene derivative in the α-position or aromatic ring; diacetone acrylamide and other acrylamide; acrylonitrile; vinyl-n-butyl ether and other vinyl alcohol Ether compounds; maleic acid; maleic anhydride; maleic acid monomethyl ester, maleic acid monoethyl ester, maleic acid monoisopropyl ester and other maleic acid monoester ; Unsaturated carboxylic acid derivatives such as fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, propionic acid, etc.; These may be used alone or in combination of two or more.

In addition, from the viewpoint that the resist footing can be further reduced, the acrylic resin may further have a structural unit derived from styrene or a derivative thereof or a structural unit derived from benzyl (meth)acrylate. From the viewpoint of improving the resolution, it may further have a structural unit derived from benzyl (meth)acrylate.

In terms of more excellent resolution, based on the total mass (100% by mass, the same applies hereinafter) of the structural units derived from the polymerizable monomer constituting the binder polymer, the The content rate of the structural unit of benzyl methacrylate may be 3 mass% or more, 5 mass% or more, or 10 mass% or more. In addition, in terms of more excellent releasability and adhesion, the content may be 85% by mass or less, 75% by mass or less, 70% by mass or less, or 50% by mass or less.

In terms of further shortening the development time, the acid value of the component (A) may be 90 mgKOH/g or more, 100 mgKOH/g or more, 120 mgKOH/g or more, or 130 mgKOH/g or more. In addition, in terms of further improving the adhesion of the cured product of the photosensitive resin composition, the acid value may be 250 mgKOH/g or less, 240 mgKOH/g or less, 235 mgKOH/g or less, or 230 mgKOH/g or less.

(A) The acid value of the component can be measured as follows. That is, first, 1 g of the binder polymer to be measured as the acid value is accurately weighed. 30g of acetone was added to the precisely weighed binder polymer to dissolve it uniformly. Then, an appropriate amount of phenolphthalein as an indicator was added to the solution, and titration was performed using a 0.1N potassium hydroxide (KOH) aqueous solution. The acid value is obtained by calculating the mg number of KOH required to neutralize the binder polymer to be measured as an acetone solution. In the case where a solution obtained by mixing a binder polymer with a synthetic solvent, a dilution solvent, or the like is the measurement target, the acid value is calculated by the following formula.

Acid value=0.1×Vf×56.1/(Wp×I/100)

In the formula, Vf represents the titration amount (mL) of the KOH aqueous solution, Wp represents the mass (g) of the solution containing the measured binder polymer, and I represents the nonvolatile content of the solution containing the measured binder polymer Proportion (% by mass).

In addition, when the binder polymer is mixed with volatile components such as a synthetic solvent, a dilution solvent and the like, it may be pre-measured at a temperature higher than the boiling point of the volatile component by 10°C or more before accurate weighing Heating for 1 hour to 4 hours, will After removing the volatile components, the acid value was measured.

In the case of measuring by gel permeation chromatography (Gel Permeation Chromatography, GPC) (converted by using a calibration curve of standard polystyrene), in terms of more excellent developability, component (A) The weight average molecular weight (Mw) may be 200,000 or less, 100,000 or less, 80,000 or less, or 60,000 or less. In terms of more excellent adhesion, the weight average molecular weight may be 10,000 or more, 15,000 or more, 20,000 or more, or 23,000 or more.

In terms of more excellent resolution and adhesion, the dispersion degree (weight average molecular weight/number average molecular weight) of the component (A) may be 3.0 or less, 2.8 or less, or 2.5 or less.

(A) The component may also have a characteristic group in its molecule as needed, and the characteristic group is sensitive to light having a wavelength in the range of 340 nm to 430 nm. Examples of the characteristic group include a group formed by removing at least one hydrogen atom from a sensitizer described later.

In terms of further improving the formability of the film (photosensitive resin composition layer), the content of the (A) component may be 30 parts by mass or more in 100 parts by mass of the total amount of the (A) component and (B) component , More than 35 parts by mass or more than 40 parts by mass. In terms of further improving sensitivity and resolution, the content may be 70 parts by mass or less, 65 parts by mass or less, or 60 parts by mass or less.

((B) component: photopolymerizable compound)

As the component (B), a photopolymerizable compound having an ethylenically unsaturated group can be used.

Examples of the compound having an ethylenically unsaturated group include compounds having one ethylenically unsaturated group in the molecule, compounds having two ethylenically unsaturated groups in the molecule, and three or more compounds in the molecule. Compounds of ethylenically unsaturated groups, etc.

The component (B) is preferably at least one compound containing two ethylenically unsaturated groups in the molecule. In the case of containing a compound having two ethylenically unsaturated groups in the molecule, the compound having two ethylenically unsaturated groups in the molecule in 100 parts by mass of the total amount of the (A) component and (B) component The content of can be 5 parts by mass to 70 parts by mass, 5 parts by mass to 65 parts by mass, or 10 parts by mass to 60 parts by mass.

Examples of the compound having two ethylenically unsaturated groups in the molecule include bisphenol di(meth)acrylate, hydrogenated bisphenol A di(meth)acrylate, and amino group in the molecule. Ester bond di(meth)acrylate, EO. PO modified polyalkylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, etc.

From the viewpoint of further improving the resolution and peeling characteristics, the component (B) preferably contains a member selected from the group consisting of bisphenol di(meth)acrylate, hydrogenated bisphenol A di(meth)acrylate and EO . At least one compound having two ethylenically unsaturated groups in the molecule in the group of PO modified polyalkylene glycol di(meth)acrylates, more preferably containing bisphenol type di(meth) Group) at least one acrylate compound, and more preferably at least one bisphenol di(meth)acrylate compound having an EO group.

As the bisphenol di(meth)acrylate, a compound represented by the following general formula (4) can be used.

In the general formula (4), R ² and R ³ each independently represent a hydrogen atom or a methyl group. XO and YO independently represent an EO group or a PO group. (XO) _r1 , (XO) _r2 , (YO) _s1 and (YO) _s2 represent (poly)oxyethylidene or (poly)oxypropylene respectively. r1, r2, s1 and s2 independently represent 0~40. r1, r2, s1, and s2 represent the number of structural units of the structural unit. Therefore, in the case of a single molecule, it represents an integer value, and in the case of an aggregate of multiple molecules, it represents a rational number as an average value. Hereinafter, the number of structural units of the structural units is the same.

In the case where the compound represented by the general formula (4) has a PO group, the total number of structural units of the PO group in the compound may be 2 as far as the resolution of the resist is more excellent Above or above 3. In addition, from the viewpoint of more excellent developability, the total number of PO-based structural units may be 5 or less.

In the case where the compound represented by the general formula (4) has an EO group, in terms of more excellent developability, the total number of structural units of the EO group in the compound may be 4 or more and 6 or more Or more than 8. In addition, from the viewpoint of more excellent resolution, the total number of structural units of the EO group may be 16 or less or 14 or less.

Among the compounds represented by the general formula (4), 2,2-bis(4-(methacryloxydodecethoxytetrapropoxy)phenyl)propane can be converted into FA-3200MY (Hitachi ( Stocks)) in the form of commercial acquisition, 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane can be obtained commercially in the form of FA-324M (Hitachi Chemicals (shares)), 2,2-bis(4-(methacryloxypentethoxy)phenyl)propane can be in the form of BPE-500 (Sinakamura Chemical Industry Co., Ltd.) or FA-321M (Hitachi Chemical Co., Ltd.) Commercially available, 2,2-bis(4-(methacryloxypentadecyloxy)phenyl)propane can be commercially obtained in the form of BPE-1300 (Sinakamura Chemical Industry Co., Ltd.). These may be used alone or in combination of two or more.

When the photosensitive resin composition contains bisphenol-type di(meth)acrylate, it is regarded as bisphenol-type bis(methyl) in 100 parts by mass of the total amount of (A) component and (B) component The content of acrylate may be 1 part by mass to 65 parts by mass, 5 parts by mass to 60 parts by mass, or 10 parts by mass to 55 parts by mass.

Examples of hydrogenated bisphenol A type di(meth)acrylates include 2,2-bis(4-(methacryloxypentethoxy)cyclohexyl)propane. When the photosensitive resin composition contains hydrogenated bisphenol A di(meth)acrylate, the hydrogenated bisphenol A type di is contained in 100 parts by mass of the total amount of the (A) component and (B) component The content of (meth)acrylate can be 1 part by mass to 50 parts by mass or 5 parts by mass to 40 parts by mass Copies.

In EO. In the PO modified polyalkylene glycol di(meth)acrylate, the (poly)oxyethylidene and (poly)oxypropylene in their molecules can be connected separately and exist in blocks, or without Regularly exists. In addition, in the (poly)oxypropylene group, the secondary carbon of the isopropyl group may be bonded to an oxygen atom, and the primary carbon may also be bonded to an oxygen atom.

As EO. Commercially available suppliers of PO-modified polyalkylene glycol di(meth)acrylates include, for example, polyalkylene groups having EO groups: 6 (average) and PO groups: 12 (average) Glycol di(meth)acrylate (Hitachi Chemicals Co., Ltd., "FA-023M"), polyalkylene glycol di(dimethacrylate) having EO group: 6 (average value) and PO group: 12 (average value) Meth)acrylate (Hitachi Chemical Co., Ltd., "FA-024M"), etc.

The photosensitive resin composition contains EO. In the case of PO-modified polyalkylene glycol di(meth)acrylate, from the viewpoint of improved resolution, it is regarded as EO in 100 parts by mass of the total amount of (A) component and (B) component . The content of PO-modified polyalkylene glycol di(meth)acrylate can be 5 to 30 parts by mass or 10 to 20 parts by mass.

The component (B) may contain at least one photopolymerizable compound having three or more ethylenic unsaturated groups in the molecule.

Examples of the compound having three or more ethylenic unsaturated groups include trimethylolpropane tri(meth)acrylate, EO modified trimethylolpropane tri(meth)acrylate (oxyethylene) The number of structural units of the group is 1~5), PO modified trimethylolpropane tri(meth)acrylate, EO. PO modified trimethylolpropane tri(methyl) Acrylate, tetramethylolmethane tri(meth)acrylate and tetramethylolmethane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, EO modified pentaerythritol tetraacrylate or dipentaerythritol hexa( Meth)acrylate. These can be used alone or in combination of two or more.

Tetramethylol methane triacrylate is commercially available in the form of A-TMM-3 (Xinzhongcun Chemical Industry Co., Ltd.), and EO-modified trimethylolpropane trimethacrylate can be TMPT21E and TMPT30E (Hitachi Chemical ( Shares)) in the form of commercial acquisition, pentaerythritol triacrylate can be commercially obtained in the form of SR444 (Sartomer (Sartomer) (share)), dipentaerythritol hexaacrylate can be A-DPH (Xinzhongcun Chemical Industry (share)) EO modified pentaerythritol tetraacrylate can be obtained commercially in the form of ATM-35E (Xinzhongcun Chemical Industry Co., Ltd.).

In the case of containing a photopolymerizable compound having three or more ethylenic unsaturated groups in the molecule, from the viewpoint of further improving the resolution, adhesion, resist shape, and peeling characteristics after curing in a well-balanced manner In the total amount of (A) component and (B) component 100 parts by mass, the content of the photopolymerizable compound having three or more ethylenic unsaturated groups in the molecule can be 3 parts by mass to 30 parts by mass, 5 Mass parts ~ 25 parts by mass or 5 parts by mass ~ 20 parts by mass.

In terms of further improving the resolution, adhesion, resist shape, and peeling characteristics after curing in a well-balanced manner or in terms of further suppressing the generation of scum, the component (B) may contain one ethylene in the molecule Photo-polymerizable compounds with unsaturated groups.

As a photopolymerizable compound with an ethylenically unsaturated group in the molecule Examples thereof include nonylphenoxy polyoxyethylene acrylate, phthalic acid compounds, and alkyl (meth)acrylate. Among the above compounds, from the viewpoint of further improving the resolution, adhesion, resist shape, and peeling characteristics after curing, it is preferable to contain nonylphenoxy polyoxyethylene acrylate or o-phthalic acid Formic acid compounds.

In the case of containing a photopolymerizable compound having one ethylenically unsaturated group in the molecule, of 100 parts by mass of the total amount of (A) component and (B) component, one having an ethylenically unsaturated group in the molecule The content of the photopolymerizable compound may be 1 part by mass to 20 parts by mass, 3 parts by mass to 15 parts by mass, or 5 parts by mass to 12 parts by mass.

The total content of the (B) component in the photosensitive resin composition may be 30 parts by mass to 70 parts by mass, 35 parts by mass to 65 parts by mass with respect to 100 parts by mass of the total of the components (A) and (B). Parts or 35 parts by mass to 60 parts by mass. If the content is 30 parts by mass or more, the sensitivity and resolution tend to be further improved. If the content is 70 parts by mass or less, a film (photosensitive resin composition layer) tends to be easily formed, and a good resist shape tends to be easily obtained.

((C) component: photopolymerization initiator)

The photosensitive composition contains, as the (C) component, a photopolymerization initiator containing at least one selected from the group consisting of 2,4,5-triarylimidazole dimer and derivatives thereof. In terms of further improving sensitivity and adhesion and further reducing the amount of resist footing, the 2,4,5-triarylimidazole dimer and its derivatives may contain the general formula (1) The compound represented.

In the general formula (1), it is preferred that at least one of X ¹ and X ² is a chlorine atom. When Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are each independently an aryl group having at least one substituent selected from the group consisting of alkyl, alkenyl and alkoxy, the substituent The number is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1. In addition, in the case where Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are each independently an aryl group having the substituent, the substitution position is not particularly limited, and it is preferably ortho or para. p and q are each independently an integer of 1 to 5, more preferably an integer of 1 to 3, and even more preferably 1.

Examples of the compound represented by the general formula (1) include 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5 -Di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5- Diphenylimidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer. Furthermore, the substituents of the aryl groups of two 2,4,5-triarylimidazoles may be the same to provide a symmetric compound, or may be different to provide an asymmetric compound. These can be used alone or in combination of two or more.

As the component (C), in addition to the 2,4,5-triarylimidazole dimer or its derivative, other photopolymerization initiators generally used may be contained. Examples of other photopolymerization initiators include benzophenone, N,N,N',N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone)), N,N,N',N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1, 2-methyl-1-[4-(methylthio)phenyl]-2 -Aromatic ketones such as morpholinyl-acetone-1; 2-ethylanthraquinone, phenanthrenequinone, 2-third butylanthraquinone, octamethylanthraquinone, 1,2-benzoanthraquinone, 2,3 -Benzoanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthrenequinone, 2-methyl-1,4-naphthoquinone, 2 Quinones such as ,3-dimethylanthraquinone; benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether; benzoin compounds such as benzoin, methyl benzoin, ethyl benzoin; 1,2-octane Alcohol-1-[4-(phenylthio)phenyl]-2-(O-benzyl oxime), 1-[9-ethyl-6-(2-methylbenzyl)-9H -Carbazol-3-yl] ethyl ketone-1-(O-acetyl oxime) and other oxime ester compounds; benzoyl derivatives such as benzoyl dimethyl ketal; 9-phenylacridine, 1, 7-bis(9,9'-acridinyl) heptane and other acridine derivatives; N-phenylglycine, N-phenylglycine derivatives and so on.

The content of the (C) component may be 0.1 to 10 parts by mass, 1 to 7 parts by mass, 2 to 6 parts by mass, or 100 parts by mass relative to the total amount of the (A) component and (B) component or 3 parts by mass to 5 parts by mass. If the content of the (C) component is 0.1 parts by mass or more, there is a tendency that it is easier to obtain better sensitivity, resolution, or adhesion, and the amount of generation of resist feet can be further reduced. If it is 10 parts by mass or less, then There is a tendency to easily obtain a better resist shape.

((D) component: nitroxide radical compound)

The nitroxide compound refers to a compound having a nitryl group. The nitryl group can also be referred to as a group represented by the following structural formula (5).

(D) The component contains a compound having a 2,2,6,6-tetramethylpiperidine-1-oxy structure as a nitroxide radical compound. By using a compound having the above structure in combination with at least one selected from the group consisting of 2,4,5-triarylimidazole dimer and derivatives thereof, the following photosensitive resin composition can be obtained, The photosensitive resin composition can form a resist pattern with excellent sensitivity and excellent resolution and adhesion, and the amount of generation of resist feet is reduced.

The compound having a 2,2,6,6-tetramethylpiperidine-1-oxy structure may be a compound represented by the following general formula (2). By containing the compound represented by the following general formula (2), the photosensitive resin composition can have good sensitivity and further improve the resolution and adhesion of the formed resist pattern, and can further reduce the resist base The amount of foot production.

[In formula (2), R ¹ represents a hydroxyl group, a C 1-5 alkyl group, an acetamido group, an amine group, a chloroacetamide group, a cyano group, a benzoyloxy group, or the following general formula (3 ) Represents the base]

[Chem 5]

[In formula (3), n1 represents an integer of 1 to 12]

In addition, in the photosensitive resin composition, the compound represented by the general formula (2) may exist in a state where the free radical site is bonded to other compounds, organic groups, or the like.

In the general formula (2), R ^{1 is} preferably a hydroxyl group, an acetamido group or a benzoyloxy group. If R ¹ is a hydroxyl group, the amount of resist footing can be further reduced. If R ¹ is an acetamide group or a benzoyloxy group, the sensitivity can be further improved.

Examples of the compound represented by the general formula (2) include 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxy radical, 4-hydroxy-2,2,6, 6-tetramethylpiperidine-1-oxybenzoate free radical, 4-acetamido-2,2,6,6-tetramethylpiperidine-1-oxy free radical, 4-amine Yl-2,2,6,6-tetramethylpiperidin-1-oxy free radical, 4-(2-chloroacetamido)-2,2,6,6-tetramethylpiperidine-1 -Oxy radical, 4-cyano-2,2,6,6-tetramethylpiperidine-1-oxy radical and 4-methoxy-2,2,6,6-tetramethylpiper Pyridine-1-oxy radical. These may be used alone or in combination of two or more.

Examples of other compounds having a 2,2,6,6-tetramethylpiperidine-1-oxy structure include 2,2,6,6-tetramethylpiperidine-1-oxy radical. This compound can be used in combination with the compound represented by the general formula (2), but it is difficult to use it alone because of its high volatility.

As component (D), it may contain in addition to 2,2,6,6-tetramethylpiperidine-1- Nitroxyl radical compounds other than oxy-structured compounds.

The content of the component (D) may be 0.005 to 10 parts by mass, 0.01 to 8 parts by mass, or 0.01 to 5 parts by mass relative to 100 parts by mass of the total component (A). When the content is 0.005 parts by mass or more, the resolution and adhesion tend to be more excellent, and if it is 10 parts by mass or less, the sensitivity tends to be more excellent. The content of the component (D) may be 0.005 to 20 parts by mass, 0.01 to 5 parts by mass, or 0.02 to 1 part by mass relative to 100 parts by mass of the total of the components (A) and (B). When the content is 0.005 parts by mass or more, there is a tendency that the resolution and the suppression of the generation amount of the resist foot are more excellent, and when it is 20 parts by mass or less, the sensitivity tends to be more excellent.

((E) component: phenol compound)

From the viewpoint of further improving the resolution, it is more preferable that the photosensitive resin composition contains at least one phenol compound used in combination with the components (A) to (D). Examples of the component (E) include 2,2-methylene-bis(4-methyl-6-tert-butylphenol), catechol, picric acid, 4-tert-butyl-o-benzene Diphenol, 2,6-di-tert-butyl-p-cresol, 4,4'-thiobis[ethylidene(oxy)(carbonyl)(ethylidene)]bis[2,6-bis( 1,1-dimethylethyl)phenol] etc.

The content of the (E) component may be 0.0001 to 1 part by mass, 0.001 to 0.1 part by mass, or 0.005 to 0.01 part by mass relative to 100 parts by mass of the total component (A). If the content is 0.0001 parts by mass or more, there is a tendency that the resolution and adhesion are more excellent, and if it is 1 part by mass or less, there is a tendency that the sensitivity is more excellent.

The photosensitive resin composition according to an embodiment of the present disclosure preferably contains (F) component: sensitizer and/or (G) component: hydrogen donor in addition to the above-mentioned components (A) to (E).

((F) component: sensitizer)

The photosensitive resin composition preferably contains at least one sensitizer. The sensitizer can effectively use the absorption wavelength of actinic rays used in exposure, and it is preferably a compound having a maximum absorption wavelength of 340 nm to 420 nm.

Examples of the component (F) include pyrazoline compounds, anthracene compounds, acridone compounds, coumarin compounds, xanthone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, and benzothiazole Compounds, triazole compounds, stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, etc. In particular, from the viewpoint of further improving resolution, adhesion, and sensitivity, the component (F) preferably contains a pyrazoline compound or an anthracene compound, and more preferably contains a pyrazoline compound. As the sensitizer (F) component, one kind may be used alone or two or more kinds may be used in combination.

From the viewpoint of improving the sensitivity and resolution in a well-balanced manner, the pyrazoline compound may be a compound represented by the following general formula (6).

[化6]

In the general formula (6), R represents an alkoxy group having 1 to 10 carbon atoms or an alkyl group having 1 to 12 carbon atoms, a, b, and c each independently represent an integer of 0 to 5, and the sum of a, b, and c It is 1~6. When the sum of a, b, and c is 2 to 6, multiple R in the same molecule may be the same or different.

The R may be linear or branched. Examples of R include methoxy, isopropyl, n-butyl, tertiary butyl, tertiary octyl, and dodecyl, but are not limited thereto. In addition, the sum of a, b, and c in the general formula (6) is 1 to 6, more preferably 1 to 4, and particularly preferably 1 or 2.

From the viewpoint of further improving sensitivity and solubility, the compound represented by the general formula (6) is preferably a pyrazoline compound in which R is an alkoxy group having 1 to 10 carbon atoms or an alkyl group having 1 to 3 carbon atoms. Among them, from the viewpoint of improving ease of synthesis and sensitivity, particularly preferred is 1-phenyl-3-(4-methoxystyryl)-5-(4-methoxyphenyl)pyrazoline , From the viewpoint of improving the ease of synthesis and solubility in the solvent, particularly preferably 1-phenyl-3-(4-isopropylstyryl)-5-(4-isopropylphenyl ) Pyrazoline.

By containing the pyrazoline compound as the (F) component, the photosensitive resin composition can further improve the following effects: the 2,4,5-triarylimidazole dimer or its derivative has 2,2,6, The combination of compounds with 6-tetramethylpiperidine-1-oxy structure brings The effect of improving the sensitivity, resolution and adhesion, and the effect of reducing the amount of resist footing. In other words, by means of 2,4,5-triarylimidazole dimer or its derivative, a compound having a 2,2,6,6-tetramethylpiperidine-1-oxy structure, and a pyrazoline compound The combination of components can achieve extremely good sensitivity, resolution, and adhesion, and can greatly reduce the amount of resist footing produced.

When the photosensitive resin composition contains the (F) component, the content of the (F) component may be 0.01 to 10 parts by mass relative to 100 parts by mass of the total amount of the (A) component and (B) component, 0.05 Mass parts ~ 5 parts by mass or 0.1 parts by mass ~ 3 parts by mass. If the content is 0.01 parts by mass or more, there is a tendency that the sensitivity and resolution are more excellent and the generation amount of the resist footing can be further reduced, and if it is 10 parts by mass or less, there is a tendency to obtain a better resist shape Propensity.

((G) component: hydrogen donor)

From the viewpoint of making the contrast between the exposed portion and the unexposed portion better (also referred to as "imageability"), the photosensitive resin composition may contain at least one hydrogen donor. The hydrogen donor is not particularly limited as long as it can supply hydrogen to the photopolymerization initiator during the reaction in the exposed portion, and examples include bis[4-(dimethylamino)phenyl]methane, Bis[4-(diethylamino)phenyl]methane, leuco crystal violet, etc. These can be used alone or in combination of two or more.

When the (G) component is included, the content of the (G) component may be 0.01 parts by mass to 10 parts by mass, 0.05 parts by mass to 5 parts by mass with respect to the total of 100 parts by mass of the components (A) and (B). Parts or 0.1 parts by mass to 2 parts by mass. If the content is 0.01 parts by mass or more, there is a tendency that a better sensitivity is easily obtained. If If the content is 10 parts by mass or less, there is a tendency that the excessive (G) component is suppressed from being precipitated as a foreign substance after film formation.

(Other ingredients)

The photosensitive resin composition of the present embodiment may optionally include a photopolymerizable compound (oxetane compound, etc.) having at least one cyclic ether group capable of cationic polymerization in the molecule; a cationic polymerization initiator; Malachite green, victoria pure blue, brilliant green, methyl violet and other dyes; tribromophenylbenzene, diphenylamine, benzylamine, triphenylbenzene Light coloring agents such as base amine, diethylaniline, 2-chloroaniline, etc.; heat-resistant coloring agents; plasticizers such as 4-toluenesulfonamide; pigments; fillers; defoamers; flame retardants; stabilizers; Adhesion-imparting agent; leveling agent; peeling accelerator; antioxidant; perfume; imaging agent; thermal cross-linking agent, etc. These can be used alone or in combination of two or more. When the photosensitive resin composition contains other components, the content of the other components is preferably about 0.01 to 20 parts by mass relative to 100 parts by mass of the total amount of the components (A) and (B).

[Solution of photosensitive resin composition]

In order to adjust the viscosity, the photosensitive resin composition of this embodiment may further contain at least one organic solvent as needed. Examples of organic solvents include alcohol solvents such as methanol and ethanol; ketone solvents such as acetone and methyl ethyl ketone; glycol ether solvents such as methyl cellosolve, ethyl cellosolve and propylene glycol monomethyl ether; and aromatics such as toluene Group hydrocarbon solvents; aprotic polar solvents such as N,N-dimethylformamide, etc. These may be used alone or in combination of two or more. Content of organic solvent contained in photosensitive resin composition It can be appropriately selected according to the purpose and the like. For example, the photosensitive resin composition can be used in the form of a solution having a solid content of about 30% by mass to 60% by mass. Hereinafter, the photosensitive resin composition containing an organic solvent is also called "coating liquid".

The photosensitive resin composition layer can be formed using a photosensitive resin composition by applying (for example, coating) the coating liquid on the surface of a support, a metal plate, etc. described later and drying. The metal plate is not particularly limited, and can be appropriately selected according to the purpose and the like. Examples of the metal plate include metal plates of iron-containing alloys such as copper, copper-containing alloys, nickel, chromium, iron, and stainless steel. The metal plate is preferably a metal plate that includes copper, a copper-containing alloy, an iron-containing alloy, or the like.

The thickness of the formed photosensitive resin composition layer is not particularly limited, and can be appropriately selected according to its use. The thickness of the photosensitive resin composition layer can be, for example, 1 μm to 100 μm after drying. In the case where the photosensitive resin composition layer is formed on the metal plate, the surface of the photosensitive resin composition layer on the side opposite to the metal plate may be covered with a protective layer. Examples of the protective layer include polymer films such as polyethylene and polypropylene.

The photosensitive resin composition can be applied to the formation of the photosensitive resin composition layer of the photosensitive element described later. That is, another embodiment of the present disclosure is the application of a photosensitive resin composition to a photosensitive element, the photosensitive resin composition comprising: (A) component: binder polymer, (B) component: photopolymerizable Compound, (C) component: a photopolymerization initiator containing at least one selected from the group consisting of 2,4,5-triarylimidazole dimer and derivatives thereof, (D) component: nitrogen and oxygen free Compound, and the (D) component contains a compound having a 2,2,6,6-tetramethylpiperidine-1-oxy structure Thing.

In addition, the photosensitive resin composition of this embodiment can be used for a method of forming a resist pattern described later. That is, another embodiment of the present disclosure is the application of a photosensitive resin composition in a method for forming a resist pattern, the photosensitive resin composition comprising: (A) component: binder polymer, (B) component : Photopolymerizable compound, (C) component: A photopolymerization initiator containing at least one selected from the group consisting of 2,4,5-triarylimidazole dimer and its derivatives, and (D) Ingredients: nitroxide radical compounds, and the (D) ingredient contains a compound having a 2,2,6,6-tetramethylpiperidine-1-oxy structure.

<Photosensitive element>

The photosensitive element according to an embodiment of the present disclosure includes a support and a photosensitive resin composition layer formed of the photosensitive resin composition provided on the support. Furthermore, the photosensitive resin composition layer may be a coating film. The coating film described in this specification is a film in which the photosensitive resin composition is in an uncured state. The photosensitive element may have other layers such as a protective layer as needed.

FIG. 1 shows an embodiment of a photosensitive element. In the photosensitive element 1 shown in FIG. 1, a support 2, a photosensitive resin composition layer 3 formed of a photosensitive resin composition, and a protective layer 4 are sequentially stacked. The photosensitive element 1 can be obtained as follows, for example. A coating liquid (that is, a photosensitive resin composition containing an organic solvent) is coated on the support 2 to form a coating layer and dried, thereby forming a photosensitive resin composition layer 3. Then, the surface of the photosensitive resin composition layer 3 on the opposite side to the support 2 is covered with the protective layer 4, thereby obtaining the photosensitive element 1 of the present embodiment. The sexual element 1 includes a support 2, a photosensitive resin composition layer 3 formed on the support 2, and a protective layer 4 laminated on the photosensitive resin composition layer 3. The photosensitive element 1 may not necessarily include the protective layer 4.

As the support, a polymer film containing polymers having heat resistance and solvent resistance such as polyesters such as polyethylene terephthalate, polyolefins such as polypropylene and polyethylene, and the like can be used.

The thickness of the support (polymer film) may be 1 μm to 100 μm, 5 μm to 50 μm, and 5 μm to 30 μm. When the thickness of the support is 1 μm or more, the support can be suppressed from being broken when the support 2 is peeled off. In addition, when the thickness of the support is 100 μm or less, a decrease in resolution can be suppressed.

As the protective layer, it is preferable that the adhesive force to the photosensitive resin composition layer is smaller than the adhesion force of the support to the photosensitive resin composition layer. In addition, a low fisheye film is preferred. Here, the "fish eye" refers to the foreign material, undissolved material, oxidative degradation material, etc. mixed in the material when the material is thermally melted and the film is produced by kneading, extrusion, biaxial stretching, casting method, etc. Made in the film. That is, the term "low fisheye" means that there are few foreign substances in the film.

Specifically, as the protective layer, a polymer film containing a polymer having heat resistance and solvent resistance such as polyester such as polyethylene terephthalate, polyolefin such as polypropylene, and polyethylene can be used. As a marketer, there may be mentioned: Alfan MA-410, E-200 of Oji Paper (share), polypropylene films such as Shin-Etsu Film (share), PS-25 such as Teijin (share) PS series Polyethylene terephthalate film. Furthermore, the protective layer 4 may be the same as the support 2.

The thickness of the protective layer may be 1 μm to 100 μm, 5 μm to 50 μm, 5 μm to 30 μm, or 15 μm to 30 μm. When the thickness of the protective layer is 1 μm or more, when the photosensitive resin composition layer and the support are laminated on the base material while peeling off the protective layer, cracking of the protective layer can be suppressed. If the thickness of the protective layer is 100 μm or less, it is excellent in handleability and low cost.

Specifically, the photosensitive element of this embodiment can be manufactured as follows, for example. It can be manufactured by a manufacturing method including the following steps: a step of preparing a coating liquid which is composed of (A) component: binder polymer, (B) component: photopolymerizable compound, (C) component: Contains at least one photopolymerization initiator selected from the group consisting of 2,4,5-triarylimidazole dimer and its derivatives, and (D) component: Contains 2,2,6,6 -The oxynitride compound of the tetramethylpiperidine-1-oxy structure compound is dissolved in an organic solvent; the coating liquid is applied (for example, coated) on a support to form a coating layer Step; and the step of drying the coating layer to form a photosensitive resin composition layer.

The coating of the solution of the photosensitive resin composition on the support can be performed by known methods such as roll coating, comma coat, gravure coating, air knife coating, die coating, and bar coating. .

The drying of the coating layer is not particularly limited as long as at least a part of the organic solvent can be removed from the coating layer. For example, it can be dried at 70°C to 150°C for 5 to 30 minutes. After drying, the amount of residual organic solvent in the photosensitive resin composition layer may be 2% by mass or less from the viewpoint of preventing the diffusion of the organic solvent in the subsequent step.

The thickness of the photosensitive resin composition layer in the photosensitive element can be Choose appropriately. The thickness of the photosensitive resin composition layer may be 1 μm to 100 μm, 1 μm to 50 μm, or 5 μm to 40 μm in terms of the thickness after drying. When the thickness of the photosensitive resin composition layer is 1 μm or more, industrial coating becomes easy. If it is 100 μm or less, the adhesion and resolution tend to be more excellent.

For ultraviolet rays having a wavelength in the range of 350 nm to 420 nm, the transmittance of the photosensitive resin composition layer to ultraviolet rays may be 5% to 75%, 10% to 65%, or 15% to 55%. If the transmittance is 5% or more, there is a tendency to obtain better adhesion. If it is 75% or less, it tends to be easier to obtain better resolution. Furthermore, the transmittance can be measured using an ultraviolet (Ultra Violet, UV) spectrometer. As a UV spectrometer, a 228A type W beam spectrophotometer from Hitachi, Ltd. can be cited.

The photosensitive element may further have intermediate layers such as a buffer layer, an adhesive layer, a light absorption layer, and a gas barrier layer. As these intermediate layers, for example, the intermediate layer described in Japanese Patent Laid-Open No. 2006-098982 can be applied to one embodiment of the present disclosure.

The photosensitive element of this embodiment can be suitably used in a method of forming a resist pattern described later, for example.

<Method of forming resist pattern>

A resist pattern can be formed using the photosensitive resin composition or the photosensitive element. The method for forming a resist pattern of this embodiment includes: (i) a step of forming a photosensitive resin composition layer using the photosensitive resin composition or the photosensitive element on the substrate (photosensitive layer formation step); ii) The photosensitive resin composition layer The step of irradiating at least a part of the area with actinic rays to photoharden the area to form a hardened area (exposure step); and (iii) the hardened body of the photosensitive resin composition layer from the substrate A step (development step) of removing the area other than the area and forming a resist pattern on the substrate as the hardened area. The method for forming the resist pattern may further include other steps as needed, and the photosensitive resin composition layer in the photosensitive layer forming step may be a coating film. In addition, the photosensitive resin composition and the photosensitive element can also be applied to a method of manufacturing a resist patterned substrate obtained by obtaining the resist patterned substrate by the resist pattern forming method in.

(i) photosensitive layer forming step

First, a photosensitive resin composition layer is formed on the substrate using the photosensitive resin composition or the photosensitive element. As the substrate, a substrate (circuit-forming substrate) including an insulating layer and a conductive layer formed on the insulating layer can be used.

For example, when the photosensitive element has the protective layer 4, the photosensitive resin composition layer is formed on the substrate by removing the protective layer while heating the photosensitive resin composition layer of the photosensitive element Pressing is performed on the substrate. When a photosensitive resin composition is used, the photosensitive resin composition layer can be formed by applying (for example, coating) the coating liquid on the surface of the substrate and drying. Thereby, a laminate in which the substrate, the photosensitive resin composition layer, and the support are sequentially stacked can be obtained.

From the viewpoint of adhesion and followability, the photosensitive layer forming step is preferably performed under reduced pressure. The heating of at least one of the photosensitive resin composition layer and the substrate at the time of pressure bonding is preferably performed at a temperature of 70° C. to 130° C., preferably about 0.1 MPa to 1.0 MPa (1 kgf/cm ² to 10kgf/cm ² pressure). These conditions are not particularly limited, and can be adjusted as needed. Furthermore, if the photosensitive resin composition layer is heated to 70° C. to 130° C., the substrate may not be pre-heat-treated in advance. By performing pre-heat treatment of the circuit forming substrate, the adhesion and followability can be further improved.

(ii) Exposure steps

In the exposure step, as described above, at least a portion of the photosensitive resin composition layer formed on the substrate is irradiated with actinic rays, whereby the exposed portion to which the actinic rays are irradiated is photohardened to form a latent image. At this time, when a support is present on the photosensitive resin composition layer, if the support is transparent to actinic rays, the actinic rays can be irradiated through the support. On the other hand, when the support shows light-shielding properties to actinic rays, after removing the support, the photosensitive resin composition layer is irradiated with actinic rays.

Examples of the exposure method include a method of irradiating actinic rays in an image form through a negative or positive mask pattern called an art work (mask exposure method). In addition, a method of directly irradiating actinic rays in an image form by a direct drawing exposure method such as a laser direct imaging (LDI) exposure method or a digital light processing (Digital Light Processing (DLP) exposure method) may also be used.

The light source for actinic rays is not particularly limited, and a known light source can be used. For example, gas lasers such as carbon arc lamps, mercury vapor arc lamps, high-pressure mercury lamps, xenon lamps, argon lasers, and yttrium aluminum garnet (YAG) can be used Light sources such as solid-state lasers such as lasers, semiconductor lasers, and blue-violet lasers such as gallium nitride effectively emit ultraviolet light and visible light.

From the viewpoint of more surely obtaining the effect of one embodiment of the present disclosure, the wavelength of the actinic rays (exposure wavelength) is preferably in the range of 340 nm to 430 nm, more preferably in the range of 350 nm to 420 nm .

(iii) Development steps

In the development step, the uncured portion of the photosensitive resin composition layer is removed from the circuit-forming substrate by development processing, and a resist pattern, which is a cured product formed by photo-curing the photosensitive resin composition layer on the substrate, is formed on the substrate . When there is a support on the photosensitive resin composition layer, the unexposed portion is removed (development) after the support is removed. There are wet development and dry development in the development process, but wet development is widely used.

In the case of wet development, development is performed by a known development method using a developer corresponding to the photosensitive resin composition. Examples of the development method include methods using an immersion method, a coating method, a spray method, brushing, slapping, scraping, shaking immersion, etc. From the viewpoint of improving resolution, the The best method is high-pressure spraying. These two or more methods can be combined for development.

The developer can be appropriately selected according to the structure of the photosensitive resin composition. Examples of the developer include alkaline aqueous solutions and organic solvent developers.

The alkaline aqueous solution is safe and stable when used as a developer, and has good operability. As the base of the alkaline aqueous solution, hydroxides of lithium, sodium, or potassium can be used Alkali hydroxide; carbonates such as lithium, sodium, potassium or ammonium carbonate or bicarbonate; alkali metal phosphates such as potassium phosphate and sodium phosphate; alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate; otherwise Can use borax (sodium tetraborate), sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl-1,3-propanediol, 1 , 3-diamine-2-propanol, morpholine, etc.

As the alkaline aqueous solution used in the development, a dilute solution of 0.1% by mass to 5% by mass of sodium carbonate, a dilute solution of 0.1% by mass to 5% by mass of potassium carbonate, and a solution of 0.1% by mass to 5% by mass of sodium hydroxide are preferred. Dilute solution, 0.1% to 5% by mass of sodium tetraborate dilute solution, etc. The pH of the alkaline aqueous solution is preferably in the range of 9 to 11. In addition, the temperature can be adjusted according to the alkali developability of the photosensitive resin composition layer. In the alkaline aqueous solution, a surfactant, defoamer, or a small amount of organic solvent used to promote development can be mixed.

The alkaline aqueous solution may contain more than one organic solvent. Examples of the organic solvent used include acetone, ethyl acetate, alkoxyethanol having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, and diethylene glycol. Monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, etc. These can be used alone or in combination of two or more. When the organic solvent is contained, the content of the organic solvent is preferably 2% to 90% by mass based on the total mass (100% by mass) of the alkaline aqueous solution. In addition, the temperature can be adjusted according to alkali developability. A small amount of surfactant, defoamer, etc. may be mixed in the alkaline aqueous solution used in development.

Examples of the organic solvent used in the organic solvent developer include 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, Methyl isobutyl ketone, γ-butyrolactone, etc. In order to prevent fire, it is preferable to add water to these organic solvents in the range of 1% by mass to 20% by mass to prepare an organic solvent developer.

The method of forming a resist pattern, may further comprise the steps of: in the unexposed portion is removed, optionally heated 60 ℃ ~ 250 ℃ or energy to ^{0.2J / cm 2 ~ 10J / cm} 2 was exposed, This further hardens the resist pattern.

<Manufacturing method of printed wiring board>

A method of manufacturing a printed wiring board according to an embodiment of the present disclosure includes the steps of: performing etching treatment or plating treatment on a substrate formed with the resist pattern by the method for forming the resist pattern, and then providing an insulating layer A conductor pattern (may also be referred to as a "circuit pattern") is formed on the conductor layer of the substrate (circuit-forming substrate) of the conductor layer formed on the insulating layer. The manufacturing method of the printed wiring board may include other steps such as a resist removal step as needed. The etching process or the plating process of the substrate is performed on the conductive layer of the substrate, etc., using the formed resist pattern as a mask.

In the etching process, the resist pattern (hardened resist) formed on the substrate is used as a mask, and the conductor layer of the circuit-forming substrate not covered with the hardened resist is etched away to form a conductor pattern. The etching treatment method can be appropriately selected according to the conductor layer to be removed. Examples of the etching solution include copper chloride aqueous solution, ferric chloride aqueous solution, alkaline etching solution, and hydrogen peroxide etching solution. Among these, in terms of good etching factor, an aqueous solution of ferric chloride can be used.

On the other hand, in the plating process, the resist pattern (hardened resist) formed on the substrate is used as a mask, and the conductor layer of the circuit-forming substrate not covered with the hardened resist is plated Copper, solder, etc. After the plating process, the resist is hardened After removing, the conductive layer covered with the hardened resist is further etched to form a conductive pattern. The method of plating treatment may be electrolytic plating treatment or electroless plating treatment. Examples of the plating treatment include copper plating such as copper sulfate plating and copper pyrophosphate plating, high-throw solder plating (high-throw solder plating) and other solder plating, and a Watt bath (nickel sulfate-chloride Nickel plating, nickel sulfamate and other nickel plating, hard gold plating, soft gold plating and other gold plating.

After the etching process and the plating process, the resist pattern on the substrate is removed (stripped). The removal of the resist pattern can be performed using, for example, an aqueous solution that is more alkaline than the alkaline aqueous solution used in the development step. As the strongly alkaline aqueous solution, a 1% by mass to 10% by mass sodium hydroxide aqueous solution, a 1% by mass to 10% by mass potassium hydroxide aqueous solution, or the like can be used. Among them, it is preferable to use an aqueous solution of 1% by mass to 10% by mass of sodium hydroxide or an aqueous solution of 1% by mass to 10% by mass of potassium hydroxide, more preferably to use an aqueous solution of 1% by mass to 5% by mass of sodium hydroxide or 1% by mass~ 5 mass% potassium hydroxide aqueous solution. Examples of the method for applying the strongly alkaline aqueous solution to the resist pattern include a dipping method and a spray method. These may be used alone or in combination of two or more.

When the resist pattern is removed after the plating process is performed, the conductor layer covered with the hardened resist is further removed by etching to form a conductor pattern, whereby a desired printed wiring board can be manufactured. The etching treatment method can be appropriately selected according to the conductor layer to be removed. For example, the etching solution can be applied.

The method for manufacturing a printed wiring board according to an embodiment of the present disclosure can be applied not only to manufacturing a single-layer printed wiring board, but also to manufacturing a multilayer printed wiring board, and can also be applied to manufacturing printed wiring having small-diameter through holes Board etc.

The photosensitive resin composition of this embodiment can be preferably used for manufacturing a wiring board. That is, one of the preferred embodiments of one embodiment of the present disclosure is the application of a photosensitive resin composition in the manufacture of a printed wiring board. The photosensitive resin composition includes: (A) a component: a binder polymer, (B) component: photopolymerizable compound, (C) component: a photopolymerization initiator containing at least one selected from the group consisting of 2,4,5-triarylimidazole dimer and its derivatives, And (D) component: a nitroxide radical compound, and the (D) component contains a compound having a 2,2,6,6-tetramethylpiperidine-1-oxy structure.

In addition, a more preferred embodiment is the application of the photosensitive resin composition in the manufacture of a high-density package substrate, and the application of the photosensitive resin composition in a semi-additive process. Hereinafter, an example of a manufacturing process of a wiring board using a semi-additive process will be described with reference to the drawings.

In FIG. 2(a), a substrate (substrate for circuit formation) in which the conductor layer 10 is formed on the insulating layer 15 is prepared. The conductor layer 10 is, for example, a metal copper layer. In FIG. 2(b), the photosensitive resin composition layer 32 is formed on the conductor layer 10 of the substrate by the photosensitive layer forming step. In FIG. 2(c), the mask 20 is arranged on the photosensitive resin composition layer 32, and by the above-mentioned exposure step, the photosensitive resin composition layer 32 is irradiated with actinic rays 50, and the region where the mask 20 is arranged An area other than the area is exposed to form a photo-hardened portion on the photosensitive resin composition layer 32. In FIG. 2(d), in the photosensitive resin composition layer 32, a region other than the photo-hardened portion is removed from the substrate by a development step, thereby forming a resist pattern 30 as a photo-hardened portion on the substrate . In FIG. 2(e), the plating process using the resist pattern 30 as a photo-hardened portion as a mask, The plating layer 42 is formed on the conductor layer 10. In FIG. 2(f), after the resist pattern 30 as the photo-hardened portion is peeled off with an aqueous solution of strong alkali, a part of the plating layer 42 and the resist pattern 30 are removed by flash etching The shielded conductive layer 10 is removed to form a conductive pattern 40. The material of the conductor layer 10 and the plating layer 42 may be the same or different. 2(a) to 2(f) illustrate the method of forming the resist pattern 30 using the mask 20. The resist pattern 30 may be formed by a direct drawing exposure method without using the mask 20.

[Example]

Hereinafter, an embodiment of the present disclosure will be described in more detail with reference to examples. However, the embodiments of the present disclosure are not limited to the following examples.

(Example 1 to Example 11 and Comparative Example 1 to Comparative Example 7)

(Preparation of solution of photosensitive resin composition)

The components (A) to (G) and (O) shown in Tables 2 to 4 are mixed with 9 g of acetone, 5 g of toluene, and 5 g of methanol at the blending amounts (g units) shown in the table. In this way, solutions of the photosensitive resin compositions of Examples 1 to 11 and Comparative Examples 1 to 7 were prepared, respectively. The compounding amount of the component (A) shown in Table 2 to Table 4 is the mass of the non-volatile component (amount of solid content). The details of each component shown in Table 2 to Table 4 are as follows. In addition, "-" means unprovisioned.

(A) Ingredient: adhesive polymer

[Synthesis of binder polymer (A-1)]

90g of methacrylic acid as a polymerizable monomer (monomer), 6g of methyl methacrylate, 150g of styrene, and 54g of benzyl methacrylate (mass ratio is 30/2/50/18) and 1.5 g of azobisisobutyronitrile were mixed, and the resulting solution was designated as "solution a".

0.5 g of azobisisobutyronitrile was dissolved in 100 g of a mixed solution (mass ratio of 3:2) of 60 g of methyl cellosolve and 40 g of toluene, and the resulting solution was referred to as "solution b".

Into a flask equipped with a stirrer, a reflux cooler, a thermometer, a dropping funnel, and a nitrogen introduction tube, 300 g of a mixed solution (mass ratio of 3:2) of 180 g of methyl cellosolve and 120 g of toluene was introduced, and nitrogen was blown into the flask , And heated while stirring, raising the temperature to 80 ℃.

In the mixed solution in the flask, the solution a was added dropwise while fixing the drop rate for 4 hours, and then stirred at 80°C for 2 hours. Then, the solution b was added dropwise to the solution in the flask for 10 minutes while fixing the drop rate, and the solution in the flask was stirred at 80° C. for 3 hours. Furthermore, the solution in the flask was heated to 90°C while stirring for 30 minutes. After stirring at 90°C for 2 hours, the solution was cooled to room temperature and the stirring was stopped to obtain a solution of binder polymer (A-1). In addition, the room temperature mentioned in this specification means 25 degreeC.

The non-volatile content (solid content) of the binder polymer (A-1) was 47.4% by mass, the weight average molecular weight was 44000, the acid value was 196 mgKOH/g, and the degree of dispersion was 1.6.

In addition, the weight average molecular weight (Mw) is derived by measuring by gel permeation chromatography (GPC) and converting using a calibration curve of standard polystyrene. The conditions of GPC are shown below.

[GPC condition]

Pump: Hitachi L-6000 type (Hitachi Manufacturing Co., Ltd.)

Pipe string: 3 pieces in total, specification of pipe string: 10.7mmΦ×300mm

Gelpack GL-R440

Gelpack GL-R450

Gelpack GL-R400M (above, Hitachi Chemical Co., Ltd.)

Dissolution solution: Tetrahydrofuran (Tetrahydrofuran, THF)

Sample concentration: Samples were prepared by taking 120 mg of a binder polymer solution with an NV (nonvolatile content concentration) of 47.4% by mass and dissolving in 5 mL of THF.

Measuring temperature: 40℃

Injection volume: 200μL

Pressure: 49Kgf/cm ² (4.8MPa)

Flow rate: 2.05mL/min

Detector: Hitachi L-3300 RI (Hitachi Manufacturing Co., Ltd.)

[Synthesis of binder polymer (A-2), binder polymer (A-3)]

Except for using the materials shown in Table 1 as the polymerizable unit mass (monomer) at the mass ratio shown in Table 1, a binder polymer was obtained in the same manner as the solution of the binder polymer (A-1) was obtained (A-2). Solution of binder polymer (A-3). The non-volatile components (solid content) of the binder polymer (A-2) and the binder polymer (A-3) were 47.4% by mass.

Regarding binder polymer (A-1) to binder polymer (A-3), the mass ratio (%), acid value, weight average molecular weight The degree of dispersion is shown in Table 1. In addition, "-" means no provisioning.

(B) Ingredients

. B-1: 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (Hitachi Chemical Co., Ltd., "FA-324M")

. B-2: 2,2-bis(4-(methacryloxydodecethoxytetrapropoxy)phenyl)propane (average of 12 mol of ethylene oxide and 4 mol of propylene oxide on average) Products) (Hitachi Chemical Co., Ltd., "FA-3200MY")

. B-3: Polyoxyalkylene glycol dimethacrylate (Hitachi Chemical Co., Ltd., "FA-023M", with (poly)oxyethylidene (average 6mol) and (poly)oxygen in the molecule Propyl (an average of 12mol) compounds of both)

(C) Ingredients (2,4,5-triarylimidazole dimer and its derivatives)

. C-1: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole[2-(2-chlorophenyl)-4,5-diphenyl Diimidazole] (Hampford, "B-CIM")

(Photopolymerization initiator other than 2,4,5-triarylimidazole dimer and its derivatives)

. C'-2: Diphenyl-2,4,6-trimethylbenzyl phosphine oxide (BASF) Company, "LUCIRIN TPO")

(D) Ingredients

. D-1: 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxy radical (Tokyo Chemical Industry Co., Ltd.)

. D-2: 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxybenzoate free radical (Tokyo Chemical Industry Co., Ltd.)

. D-3: 4-Acetylamino-2,2,6,6-tetramethylpiperidine-1-oxy radical (Tokyo Chemical Industry Co., Ltd.)

(E) Ingredient

. E-1: 4-Third-butyl catechol (DIC (DIC), "DIC-TBC")

(F) Ingredient

. F-1: 1-phenyl-3-(4-methoxystyryl)-5-(4-methoxyphenyl)pyrazoline (Japan Chemical Industry Corporation (share))

. F-2: 2,4-diethylthioxanthone (2,4-diethylthioxanthone) (Japanese chemical (share), "DETX-S")

. F-3: N-methylacridone (Tokyo Chemical Industry Co., Ltd.)

(G) ingredients

. G-1: leuco crystal violet (Yamada Chemical Industry Co., Ltd., "LCV")

Other ingredients (dye)

. O-1: Malachite Green (Osaka Organic Chemical Industry Co., Ltd., "MKG")

[Table 2]

<Manufacture of photosensitive element>

The solution of the obtained photosensitive resin composition was coated on a polyethylene terephthalate film (Toray (share), "FB-40") (support) with a thickness of 16 μm, respectively Then, a 70°C and 110°C hot air convection dryer was used for the drying process in order to form a photosensitive resin composition layer with a film thickness of 25 μm after drying. A polypropylene film (Oji Paper (share), "E-200K") (protective layer) is laminated on the photosensitive resin composition layer, and a support, a photosensitive resin composition layer and a protective layer are sequentially laminated Photosensitive element.

<Fabrication of laminated substrate>

A copper-clad laminate (Hitachi Chemical Co., Ltd., "MCL-E-679F") (hereinafter referred to as "substrate") including glass epoxy material and copper foil (thickness 16 μm) formed on both sides (hereinafter referred to as “substrate”) is heated and heated After the temperature was raised to 80° C., the photosensitive elements of Examples 1 to 11 and Comparative Examples 1 to 7 were laminated (laminated) on the copper surface of the substrate. While removing the protective layer, the photosensitive resin composition layer of each photosensitive element was adhered to the copper surface of the substrate at a temperature of 120° C. and a lamination pressure of 4 kgf/cm ² (0.4 MPa). laminated. Then, a laminated substrate in which a photosensitive resin composition layer and a support were laminated on the copper surface of the substrate was obtained by cooling to 23°C.

<evaluation of sensitivity>

A photo tool having a 41 step-shaped plate is closely adhered to the support of the obtained laminated substrate, the concentration area of the 41 step-shaped plate is 0.00 to 2.00, the concentration step is 0.05, the size of the plate It is 20 mm × 187 mm, and the size of each step is 3 mm × 12 mm. Use a direct-scan exposure machine (Hitachi Via Mechanics (share), "DE-1UH") using a blue-violet laser diode with a wavelength of 405 nm as the light source. The photosensitive resin composition layer is exposed.

After the exposure, the support was peeled from the build-up substrate to expose the photosensitive resin composition layer, and the unexposed portion was removed by spraying a 1% by mass sodium carbonate aqueous solution at 30°C for 60 seconds. In this way, a resist pattern containing the cured product of the photosensitive resin composition is formed on the copper surface of the substrate. The sensitivity of the photosensitive resin composition was evaluated by measuring the remaining order (step order) of the trapezoidal plate obtained as a resist pattern (cured film). The sensitivity is expressed by the energy (unit: mJ/cm ² ) of the step order of 14, and the lower the value, the better the sensitivity. If the value is 200 mJ/cm ² or less, it can be said to have sufficient sensitivity. The results are shown in Table 5 to Table 7.

<Evaluation of resolution and adhesion>

A drawing pattern with a line width (L)/space width (S) (hereinafter referred to as "L/S") of 3/3 to 30/30 (unit: μm) (for the resolution evaluation drawing pattern and the adhesion evaluation (Draw a pattern) Adhere to the support of the obtained laminated substrate. In addition, the drawing pattern for resolution evaluation is a drawing pattern in which a space (blank) is formed in the cured product of the photosensitive resin composition. Then, with the same direct drawing exposure machine as in the evaluation of sensitivity, the remaining steps of the 41 stepped plate become 14 steps of energy, and the photosensitive resin composition layer is exposed through the optical tool, the drawing pattern, and the support (draw). After exposure, the same development process as the above-mentioned evaluation of sensitivity was performed.

After development, the minimum value of the line width/space width in the resist pattern formed by removing the space portion (unexposed portion) and the line portion (exposed portion) without bending or defects is evaluated for analysis Degree (resolution) and adhesion. The resolution is evaluated by the minimum value of the space width, and the adhesion is evaluated by the minimum value of the line width. The smaller the value, the better the resolution and adhesion. The results are shown in Table 5 to Table 7.

<Evaluation of resist footing>

By observing the line portion of the line width of the resist pattern formed in the evaluation of the resolution and adhesiveness to be 12 μm, the resist foot (the amount of generation of the resist foot) was evaluated. Use Scanning Electron Microscope (SEM) (Hitachi High-technologies, "SU-1500") The resist shape was observed at an acceleration voltage of 15 kV, a magnification of 3,000 times, and an inclination angle of 60 degrees, and the resist footing was evaluated according to the following criteria. That is, if the maximum value of the length of the leg generated from the side surface of the resist and the bottom of the resist is 0 μm or more and less than 0.5 μm, it is evaluated as “A”, and if it is 0.5 μm or more, it is evaluated as “B”. In addition, when the undercut was observed at the bottom of the resist, it was evaluated as "C". The evaluation results are shown in Table 5 to Table 7.

※1：無法形成線寬為12μm的抗蝕劑圖案，因此無法評價。

※1: A resist pattern with a line width of 12 μm cannot be formed, and therefore cannot be evaluated.

It is clear from Tables 5 to 7: any of the sensitivity, resolution, adhesion, and reduction in resist footing of the resist pattern formed using the photosensitive resin compositions of Examples 1 to 11 Both are excellent, and the photosensitive resin composition includes: a binder polymer, a photopolymerizable compound, and contains at least one selected from the group consisting of 2,4,5-triarylimidazole dimer and derivatives thereof A photopolymerization initiator and a nitroxide radical compound containing a compound having a 2,2,6,6-tetramethylpiperidine-1-oxy structure. On the other hand, in Comparative Example 1 to Comparative Example 7, it is difficult to make the sensitivity, resolution, adhesiveness, and reduction in resist footing all good.

[Industry availability]

The photosensitive resin composition of one embodiment of the present disclosure can be suitably used as a material for forming a resist pattern for manufacturing a printed wiring board. In particular, the photosensitive resin composition has good sensitivity, resolution, adhesion, and reduction in resist footing. Therefore, it can also be preferably used to form a resist pattern. The resist pattern is It is used to manufacture printed wiring boards with high-density wiring such as high-density packaging substrates and silicon wafer rewiring with high accuracy and efficiency.

1‧‧‧Photosensitive element

2‧‧‧Support

3‧‧‧Photosensitive resin composition layer

4‧‧‧Protection layer

Claims (6)

A method of manufacturing a printed wiring board, which includes a step of etching or plating a substrate formed with a resist pattern using a resist pattern forming method, the resist pattern forming method including: photosensitive In the layer forming step, a photosensitive resin composition layer is formed on the substrate using a photosensitive resin composition or a photosensitive element; in the exposure step, at least a part of the area of the photosensitive resin composition layer is irradiated with actinic rays to make the area Photocuring to form a hardened material region; and a developing step of removing the area other than the hardened material region of the photosensitive resin composition layer from the substrate and forming the hardened material region on the substrate The resist pattern of the photosensitive resin composition includes: (A) component: adhesive polymer, (B) component: photopolymerizable compound, (C) component: containing selected from 2,4,5-triaryl At least one photopolymerization initiator in the group consisting of the imidazole dimer and its derivatives, and (D) component: a nitroxide radical compound, and the (D) component contains 2,2, A compound of 6,6-tetramethylpiperidine-1-oxy structure, the photosensitive element includes: a support, and the photosensitive resin group provided on the support The photosensitive resin composition layer formed by the product. The method for manufacturing a printed wiring board according to item 1 of the patent application scope, wherein the 2,4,5-triarylimidazole dimer and its derivatives contain a compound represented by the following general formula (1),

[In formula (1), Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each independently represent an aryl group which may be substituted with at least one substituent selected from the group consisting of alkyl, alkenyl and alkoxy , X ¹ and X ² each independently represent a halogen atom, an alkyl group, an alkenyl group, or an alkoxy group, and p and q each independently represent an integer of 1 to 5; wherein, when p is 2 or more, there are multiple X ¹ may be the same or different, and when q is 2 or more, there are a plurality of X ^{2 that} may be the same or different]. The method for manufacturing a printed wiring board according to item 1 or 2 of the patent application scope, wherein the component (A) has a structural unit derived from (meth)acrylic acid and an alkyl group derived from (meth)acrylic acid The structural unit of the ester. The manufacture of printed wiring boards as described in item 1 or item 2 of the scope of patent applications In the manufacturing method, the photosensitive resin composition further contains (E) component: a phenol compound. According to the method of manufacturing a printed wiring board as described in item 1 or 2 of the patent application scope, the photosensitive resin composition further contains (F) component: a sensitizer, and the (F) component contains pyrazoline Compound. The method for manufacturing a printed wiring board according to item 1 or 2 of the patent application range, wherein the wavelength of the actinic rays is in the range of 340 nm to 430 nm.

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