JP2005309442A - Photosensitive resin composition, photosensitive element using same, method for manufacturing resist pattern, and method for manufacturing printed-wiring board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition for laser scanning exposure that excels in long time storage property, processibility, resolution after a long time storage, laser exposure performance, particularly ultraviolet laser exposure performance, and color change stability, a photosensitive element using this, a method for manufacturing a resist pattern, and a method for manufacturing a printed-wiring board. <P>SOLUTION: The photosensitive resin composition for laser scanning exposure comprises (A) a binder polymer, (B) a photopolymerizable compound having at least one polymerizable ethylenically unsaturated group in a molecule, and (C) a photopolymerization initiator, wherein the (C) component comprises a hexaaryl bisimidazol compound, an aryl glycine based compound, and a benzophenone compound having an alkyl amino group or a coumarin compound, and satisfies the formula (1). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a photosensitive resin composition, a photosensitive element using the same, a method for producing a resist pattern, and a method for producing a printed wiring board.

  Conventionally, in the field of manufacturing printed wiring boards, as a resist material used for etching, plating, etc., a photosensitive resin composition and a photosensitive element obtained by using a support and a protective film are widely used.

  A printed wiring board is formed by laminating a photosensitive element on a copper substrate, pattern exposure, removing the cured portion with a developer, etching or plating, forming a pattern, and then curing the cured portion on the substrate. It is manufactured by a method of peeling off from above.

  With the recent increase in the density of printed wiring boards, photosensitive elements are increasingly required to have higher resolution and higher adhesion than conventional photosensitive elements.

  At the same time, there is an increasing demand for higher resist sensitivity in terms of throughput.

  On the other hand, with the rapid change of generation of electronic devices such as mobile phones, there is a concern that the cost of a mask for a single substrate increases in a conventional resist pattern forming method using a phototool (photomask). ing. Therefore, a method (laser direct imaging) in which a circuit created by CAD is directly drawn with a laser beam without using a mask has been reviewed.

  As mentioned above, LDI can efficiently produce a small variety of products, and since it does not use a photomask, the alignment process can be omitted and scaling can be easily corrected. It is characterized by having many advantages such as no need for management.

  Conventional lasers using visible light have to be handled in a dark room or under a red light. Therefore, the inventors of the present application have found a laser exposure method capable of working under yellow light as in normal exposure by using a laser using ultraviolet rays. However, since the photosensitive resin composition for ultraviolet laser has high sensitivity, there is a problem in that the photosensitive characteristics fluctuate due to light such as safety light such as yellow light accompanying the work, heat, and the workability is limited. .

  On the other hand, the throughput depends on the scanning speed of the laser, but since the throughput is still inadequate, the spread is delayed compared to the expectation, and the current problem is not a mechanical one but a photosensitive resin composition. It was found that the scanning speed could not be increased because the sensitivity of the object was insufficient.

  In addition, in order to cope with UV (ultraviolet) laser scanning exposure, a resist with very high sensitivity and excellent resolution is required, and the current resist cannot cope with it.

  The present invention eliminates the above-mentioned problems, and the exposure amount under specific conditions after long-term storage is small. Therefore, the long-term storage and workability are excellent, and the resolution and laser after long-term storage are improved. The present invention provides a photosensitive resin composition for laser scanning exposure which has excellent exposure properties, particularly ultraviolet laser exposure properties and color change stability.

  The present invention is also excellent in sensitivity, resolution, developability, and mechanical strength, and is effective for increasing density of printed wiring boards and laser exposure, and particularly effective for ultraviolet laser exposure. A manufacturing method and a manufacturing method of a printed wiring board are provided.

  The present invention is further excellent in sensitivity, resolution, productivity and workability, is effective for increasing the density of printed wiring boards, can be operated under a yellow light, and can be operated in a conventional clean room. The present invention provides a method for producing a resist pattern.

In the present invention, when the photosensitive resin composition is irradiated with actinic rays at all wavelengths of a high-pressure mercury lamp, the density range is 0.00 to 2.00, the density step is 0.05, the tablet size is 20 mm × 187 mm, and the size of each step. The exposure amount of the 41-step tablet having a density of 1.00 of 21 steps, which is 3 mm × 12 mm, is set to E ₀ mJ / cm ² , and the photosensitive resin composition is used for 2 hours under a 40 W non-ultraviolet white lamp. When the exposure amount of the photosensitive resin composition after being allowed to stand to cure 21 stages of the 41-step tablet by irradiation with actinic rays at all wavelengths of the high-pressure mercury lamp is E ₁ mJ / cm ² , the following formula (1):

It is related with the photosensitive resin composition for laser scanning exposure characterized by satisfying these.

  The present invention also includes (A) a binder polymer, (B) a photopolymerizable compound having at least one polymerizable ethylenically unsaturated group in the molecule, and (C) a photosensitivity comprising a photopolymerization initiator. In the resin composition, the component (C) relates to a photosensitive resin composition having (C1) hexaarylbisimidazole compound, (C2) arylglycine compound and (C3) onium salt compound as essential components.

  Moreover, this invention relates to the said photosensitive resin composition in which the aryl group of (C1) hexaarylbisimidazole compound has a C1-C6 alkoxy group.

  Moreover, this invention relates to the said photosensitive resin composition whose number of C1-C6 alkoxy groups in a molecule | numerator of the (C1) hexaarylbisimidazole compound is four.

  In the present invention, the component (C1) is represented by the general formula (I).

In the formula, each of four R independently represents an alkyl group having 1 to 6 carbon atoms,
It is related with the said photosensitive resin composition which is a compound shown by these.

  In the present invention, the component (C2) is represented by the general formula (II).

In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
It is related with the said photosensitive resin composition which is a compound shown by these.

  Moreover, this invention relates to the said photosensitive resin composition whose (C3) onium salt compound is an ammonium salt compound, an iodonium salt compound, or a sulfonium salt compound.

  Moreover, this invention relates to the said photosensitive resin composition whose (C3) onium salt compound is an onium boron salt compound.

  The present invention also relates to the photosensitive resin composition further comprising (C4) an organic halogen compound.

  Moreover, this invention relates to the said photosensitive resin composition containing the benzophenone compound or coumarin compound which further has (C5) alkylamino group.

  Moreover, this invention relates to the said photosensitive resin composition whose (B) component has a bisphenol A type (meth) acrylate compound as an essential component.

  Moreover, this invention relates to the said photosensitive resin composition whose (A) binder polymer uses styrene or a styrene derivative as an essential copolymerization component.

  In the present invention, the blending amount of the component (A), the component (B) and the component (C) is such that the component (A) is 40 to 40 parts by weight with respect to 100 parts by weight of the total amount of the component (A) and the component (B). 80 parts by weight, 20-60 parts by weight of component (B) and 0.01-20 parts by weight of component (C), and the blending amounts of component (C1), component (C2) and component (C3) are ( The total amount of the component (A) and the component (B) is 100 parts by weight, the component (C1) is 1 to 10 parts by weight, the component (C2) is 0.01 to 3 parts by weight, and the component (C3) is 0.01 to It is related with the said photosensitive resin composition which is 5 weight part.

  The present invention also relates to a photosensitivity comprising (A) a binder polymer, (B) a photopolymerizable compound having at least one polymerizable ethylenically unsaturated group in the molecule, and (C) a photopolymerization initiator. In the resin composition, the component (C) relates to a photosensitive resin composition containing (C1) a hexaarylbisimidazole compound and (C4) an organic halogen compound as essential components.

  Moreover, this invention relates to the said photosensitive resin composition in which (C4) organic halogen compound has a bromine atom in a molecule | numerator as a halogen atom.

  Moreover, this invention relates to the photosensitive element formed by apply | coating the said photosensitive resin composition on a support body, and drying.

  In the present invention, the photosensitive element is laminated on a circuit-forming substrate so that the photosensitive resin composition layer is in close contact, irradiated with actinic rays in the form of an image, and the exposed portion is photocured. The present invention relates to a method for producing a resist pattern, wherein an exposed portion is removed by development.

  The present invention also relates to a method for manufacturing a printed wiring board, wherein the circuit forming substrate on which the resist pattern is manufactured is etched or plated by the method for manufacturing a resist pattern.

  In the present invention, the photosensitive resin composition layer is laminated on the circuit forming substrate, and is exposed to scanning with a UV (ultraviolet) laser, the exposed portion is photocured, and the unexposed portion is developed. The present invention relates to a method for producing a resist pattern, which is characterized by being removed.

  Hereinafter, the present invention will be described in detail.

  In the present invention, (meth) acrylic acid means acrylic acid and methacrylic acid corresponding thereto, (meth) acrylate means acrylate and corresponding methacrylate, (meth) acryloyl group means acryloyl group and The corresponding methacryloyl group is meant.

  The photosensitive resin composition of the present invention has three independent characteristics.

The first feature of the photosensitive resin composition for laser scanning exposure of the present invention is that the photosensitive resin composition is irradiated with actinic rays at all wavelengths of a high-pressure mercury lamp, in a concentration range of 0.00 to 2.00, concentration step 0. 05, the exposure amount at which 21 steps of density 1.00 of a 41 step tablet having a tablet size of 20 mm × 187 mm and a step size of 3 mm × 12 mm is cured is E ₀ mJ / cm ^2. Of the photosensitive resin composition after leaving the photosensitive resin composition for 2 hours under a 40 W non-ultraviolet white lamp, the exposure amount at which 21 stages of the 41-step tablet are cured by irradiation with actinic rays at all wavelengths of the high-pressure mercury lamp is E _{When 1} mJ / cm ² , the following formula (1):

Is to satisfy.

  Examples of the photosensitive resin composition for laser scanning exposure satisfying such requirements include the photosensitive resin composition having the second feature of the present invention described below and the third feature of the present invention. Examples thereof include a photosensitive resin composition.

  The second feature of the photosensitive resin composition of the present invention is that (A) a binder polymer, (B) a photopolymerizable compound having at least one polymerizable ethylenically unsaturated group in the molecule, and (C) photopolymerization. An initiator is included, and the component (C) includes (C1) hexaarylbisimidazole compound, (C2) arylglycine compound and (C3) onium salt compound as essential components.

  The third feature of the photosensitive resin composition of the present invention is that (A) a binder polymer, (B) a photopolymerizable compound having at least one polymerizable ethylenically unsaturated group in the molecule, and (C). In the photosensitive resin composition containing a photopolymerization initiator, the component (C) includes (C1) a hexaarylbisimidazole compound and (C4) an organic halogen compound as essential components.

In the formula (1), {(E ₁ −E ₀ ) / E ₀ } × 100 needs to satisfy −25 ≦ {(E ₁ −E ₀ ) / E ₀ } × 100 ≦ 25, It is preferable that 0 ≦ {(E ₁ −E ₀ ) / E ₀ } × 100 ≦ 25, and more preferably 0 ≦ {(E ₁ −E ₀ ) / E ₀ } × 100 ≦ 20.

Examples of the photosensitive resin composition satisfying −25 ≦ {(E ₁ −E ₀ ) / E ₀ } × 100 ≦ 0 include, for example, photosensitivity containing a sensitizer having absorption at a long wavelength (visible light). Examples thereof include a resin composition.

In the formula (1), {(E ₁ −E ₀ ) / E ₀ } × 100 is less than −25, or exceeds 25, the photosensitive resin for laser scanning exposure after long-term storage of the photosensitive resin composition There is a tendency that it cannot be put to practical use as a composition.

  Examples of the (A) binder polymer include acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, and phenol resins. From the viewpoint of alkali developability, an acrylic resin is preferable. These can be used alone or in combination of two or more.

  The (A) binder polymer can be produced, for example, by radical polymerization of a polymerizable monomer.

  Examples of the polymerizable monomer include styrene, vinyltoluene, α-methylstyrene, p-methylstyrene, p-ethylstyrene, p-methoxystyrene, p-ethoxystyrene, p-chlorostyrene, and p-bromostyrene. Polymerizable styrene derivatives such as acrylamide, acrylamide such as diacetone acrylamide, esters of vinyl alcohol such as acrylonitrile, vinyl-n-butyl ether, (meth) acrylic acid alkyl ester, (meth) acrylic acid tetrahydrofurfuryl ester, (meta ) Acrylic acid dimethylaminoethyl ester, (meth) acrylic acid diethylaminoethyl ester, (meth) acrylic acid glycidyl ester, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl ( T) acrylate, (meth) acrylic acid, α-bromo (meth) acrylic acid, α-chloro (meth) acrylic acid, β-furyl (meth) acrylic acid, β-styryl (meth) acrylic acid, maleic acid, maleic Examples thereof include acid anhydrides, maleic acid monoesters such as monomethyl maleate, monoethyl maleate and monoisopropyl maleate, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid and propiolic acid.

  Examples of the (meth) acrylic acid alkyl ester include, for example, the general formula (III):

In the formula, R ² represents a hydrogen atom or a methyl group, R ³ represents an alkyl group having 1 to 12 carbon atoms,
And compounds in which a hydroxyl group, an epoxy group, a halogen group or the like is substituted on the alkyl group of these compounds.

Examples of the alkyl group having 1 to 12 carbon atoms represented by R ³ in the general formula (III) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, Nonyl group, decyl group, undecyl group, dodecyl group and structural isomers thereof may be mentioned.

  Examples of the monomer represented by the general formula (III) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and (meth) acrylic. Examples include pentyl acid, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. These can be used alone or in combination of two or more.

  The binder polymer (A) preferably contains a carboxyl group from the viewpoint of alkali developability, and is produced, for example, by radical polymerization of a polymerizable monomer having a carboxyl group and other polymerizable monomers. can do. As the polymerizable monomer having a carboxyl group, methacrylic acid is preferable. Further, the (A) binder polymer preferably contains styrene or a styrene derivative as a polymerizable monomer from the viewpoint of flexibility.

  In order to improve both the adhesiveness and the release properties using the styrene or styrene derivative as a copolymerization component, it is preferably included in an amount of 0.1 to 30% by weight, more preferably 1 to 28% by weight, It is particularly preferred to contain ~ 27% by weight.

  If this content is less than 0.1% by weight, the adhesion tends to be inferior, and if it exceeds 30% by weight, the peel piece tends to be large and the peel time tends to be long.

  Moreover, the said binder polymer may have a photosensitive group as needed.

  These binder polymers are used alone or in combination of two or more. As a binder polymer in the case of using two or more types in combination, for example, two or more types of binder polymers comprising different copolymerization components, two or more types of binder polymers having different weight average molecular weights, and two or more types of binder polymers having different degrees of dispersion are used. Examples thereof include a binder polymer. In addition, a polymer having a multimode molecular weight distribution described in JP-A-11-327137 can also be used.

  The acid value of the component (A) is preferably 30 to 200 mgKOH / g, and more preferably 45 to 150 mgKOH / g. When the acid value is less than 30 mg KOH / g, the development time tends to be long, and when it exceeds 200 mg KOH / g, the developer resistance of the photocured resist tends to be lowered.

  The weight average molecular weight of the component (A) (measured by gel permeation chromatography (GPC) and converted by a calibration curve using standard polystyrene) is preferably 20,000 to 300,000, preferably 25,000. More preferably, it is ˜150,000. When the weight average molecular weight is less than 20,000, the developer resistance tends to decrease, and when it exceeds 300,000, the development time tends to be long.

  Examples of the photopolymerizable compound (B) having at least one polymerizable ethylenically unsaturated group in the molecule include compounds obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid, 2 , 2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolypropoxy) phenyl) propane, 2,2-bis (4- ( (Meth) acryloxypolybutoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane and other bisphenol A-based (meth) acrylate compounds, glycidyl group-containing compounds Urethane mono compounds such as compounds obtained by reacting α, β-unsaturated carboxylic acids and (meth) acrylate compounds having urethane bonds -Nonylphenoxypolyethyleneoxy (meth) acrylate, γ-chloro-β-hydroxypropyl-β '-(meth) acryloyloxyethyl-o-phthalate, β-hydroxyalkyl-β'-(meth) acryloyloxyalkyl-o -Phthalic acid compounds such as phthalates, (meth) acrylic acid alkyl esters and the like can be mentioned, but a bisphenol A (meth) acrylate compound or a (meth) acrylate compound having a urethane bond is preferably an essential component. These may be used alone or in combination of two or more.

  Examples of the compound obtained by reacting the polyhydric alcohol with an α, β-unsaturated carboxylic acid include, for example, polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups and 2 to 2 propylene groups. Polypropylene glycol di (meth) acrylate which is 14, polyethylene polypropylene glycol glycol di (meth) acrylate having 2 to 14 ethylene groups and 2 to 14 propylene groups, trimethylolpropane di (meth) acrylate , Trimethylolpropane tri (meth) acrylate, EO modified trimethylolpropane tri (meth) acrylate, PO modified trimethylolpropane tri (meth) acrylate, EO, PO modified trimethylolpropane tri (meth) acrylate, tetramethylolmethane Examples include tri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.

  Examples of the 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydiethoxy) phenyl) propane, 2,2 -Bis (4-((meth) acryloxytriethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetraethoxy) phenyl) propane, 2,2-bis (4-((meta ) Acryloxypentaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyheptaethoxy) phenyl) Propane, 2,2-bis (4-((meth) acryloxyoctaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxynonane) Xyl) phenyl) propane, 2,2-bis (4-((meth) acryloxydecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyundecaethoxy) phenyl) propane, 2 , 2-bis (4-((meth) acryloxydodecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytridecaethoxy) phenyl) propane, 2,2-bis (4- ((Meth) acryloxytetradecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentadecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxy) Hexadecaethoxy) phenyl) propane and the like, and 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane is BPE- 00 (made by Shin-Nakamura Chemical Co., Ltd., product name) and 2,2-bis (4- (methacryloxypentadecaethoxy) phenyl) propane is BPE-1300 (Shin-Nakamura Chemical) It is commercially available as a product name manufactured by Kogyo Co., Ltd. These may be used alone or in combination of two or more.

  Examples of the 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydiethoxyoctapropoxy) phenyl) propane. 2,2-bis (4-((meth) acryloxytetraethoxytetrapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexaethoxyhexapropoxy) phenyl) propane and the like. . These may be used alone or in combination of two or more.

  Examples of the urethane monomer include a (meth) acryl monomer having an OH group at the β-position and a diisocyanate compound such as isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, and 1,6-hexamethylene diisocyanate. Addition reaction product, tris ((meth) acryloxytetraethylene glycol isocyanate) hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate, EO, PO-modified urethane di (meth) acrylate, and the like. Examples of the EO-modified urethane di (meth) acrylate include Shin-Nakamura Chemical Co., Ltd., product name UA-11, and the like. Examples of EO and PO-modified urethane di (meth) acrylates include product name UA-13 manufactured by Shin-Nakamura Chemical Co., Ltd.

  Note that EO represents ethylene oxide, and the EO-modified compound has a block structure of an ethylene oxide group. PO represents propylene oxide, and the PO-modified compound has a block structure of propylene oxide groups.

  Examples of the nonylphenoxypolyethyleneoxy (meth) acrylate include nonylphenoxytetraethyleneoxy (meth) acrylate, nonylphenoxypentaethyleneoxy (meth) acrylate, nonylphenoxyhexaethyleneoxy (meth) acrylate, nonylphenoxyheptaethyleneoxy ( Examples include (meth) acrylate, nonylphenoxyoctaethyleneoxy (meth) acrylate, nonylphenoxynonaethyleneoxy (meth) acrylate, nonylphenoxydecaethyleneoxy (meth) acrylate, and nonylphenoxyundecaethyleneoxy (meth) acrylate.

  The (C1) hexaarylbisimidazole compound is not particularly limited, and the aryl group preferably has an alkoxy group having 1 to 6 carbon atoms, and the number of alkoxy groups having 1 to 6 carbon atoms in the molecule is four. Preferably there is. Examples of these include, for example, compounds represented by the general formula (I).

  Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a pentoxy group, and structural isomers thereof, and is preferably a methoxy group. . These may be used alone or in combination of two or more.

In the general formula (I), the four R's are each independently an alkyl group having 1 to 6 carbon atoms, such as those described above for R ³ in the general formula (III), and a methyl group. preferable.

  Moreover, the phenyl group in the said general formula (I) can have a substituent, As those examples, a halogen atom, a C1-C20 alkyl group, a C3-C10 cycloalkyl is mentioned, for example. Group, aryl group having 6 to 18 carbon atoms, phenacyl group, amino group, alkylamino group having 1 to 10 carbon atoms, dialkylamino group having 2 to 20 carbon atoms, nitro group, cyano group, carbonyl group, mercapto group, carbon A C1-C10 alkyl mercapto group, an allyl group, a hydroxyl group, a C1-C20 hydroxyalkyl group, a carboxyl group, a C1-C10 carboxyalkyl group, and a C1-C10 alkyl group. An acyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, an alkylcarbonyl group having 2 to 10 carbon atoms, and an alkyl group having 2 to 10 carbon atoms. Alkenyl group, N- alkylcarbamoyl group having 2 to 10 carbon atoms, a group containing a heterocyclic, aryl groups substituted with these substituents. When the number of the substituents is two or more, the two or more substituents may be the same or different.

  Examples of the (C1) hexaarylbisimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbisimidazole, 2,2′-bis (2, 4-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbisimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4', 5,5'-tetraphenylbisimidazole, 2 , 2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (3-methoxyphenyl) bisimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4', 5,5'-tetrakis (3-methoxyphenyl) bisimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetrakis (3-methoxyphenyl) Bis) imidazole, 2,2'-bis (2,6-dichlorophenyl) -4,4 ', 5,5'-tetrakis (3-methoxyphenyl) bisimidazole, 2,2'-bis (2-fluorophenyl) ) -4,4 ', 5,5'-tetraphenylbisimidazole, 2,2'-bis (2,4-difluorophenyl) -4,4', 5,5'-tetraphenylbisimidazole, 2,2 '-Bis (2,3-difluorophenyl) -4,4', 5,5'-tetraphenylbisimidazole, 2,2'-bis (2-fluorophenyl) -4,4 ', 5,5'- Tetrakis (3-methoxyphenyl) bisimidazole, 2,2'-bis (2,3-difluorophenyl) -4,4 ', 5,5'-tetrakis (3-methoxyphenyl) bisimidazole, 2,2' Bis (2,4-difluorophenyl) -4,4 ', 5,5'-tetrakis (3-methoxyphenyl) bisimidazole, 2,2'-bis (2,6-difluorophenyl) -4,4', 5,5′-tetrakis (3-methoxyphenyl) bisimidazole, 2,2′-bis (2-bromophenyl) -4,4 ′, 5,5′-tetraphenylbisimidazole, 2,2′-bis ( 2,4-dibromophenyl) -4,4 ', 5,5'-tetraphenylbisimidazole, 2,2'-bis (2,3-dibromophenyl) -4,4', 5,5'-tetraphenyl Bisimidazole etc. are mentioned. These may be used alone or in combination of two or more.

  Examples of the (C2) arylglycine compound include compounds represented by the general formula (II).

  In said general formula (II), a hydrogen atom or a C1-C6 alkyl group etc. are mentioned. Moreover, the phenyl group in the said general formula (II) may have a substituent, and the substituent mentioned above etc. are mentioned as those examples. When the number of the substituents is two or more, the two or more substituents may be the same or different.

  Examples of the (C2) arylglycine compound include N-phenylglycine (NPG), N- (p-chlorophenyl) glycine, N- (p-bromophenyl) glycine, N- (p-cyanophenyl) glycine, N- (p-methylphenyl) glycine, N-butyl-N-phenylglycine, N-ethyl-N-phenylglycine, N-propyl-N-phenylglycine, N-methyl-N-phenylglycine, N- (p -Bromophenyl) -N-methylglycine, N- (p-chlorophenyl) -N-ethylglycine and the like. These may be used alone or in combination of two or more.

  Examples of (C3) onium salt compounds include iodonium salt compounds, sulfonium salt compounds, ammonium salt compounds, phosphonium salt compounds, arsonium salt compounds, stibonium salt compounds, oxonium salt compounds, selenonium salt compounds, and stannonium salt compounds. An ammonium salt compound, an iodonium salt compound or a sulfonium salt compound is preferable. These may be used alone or in combination of two or more.

  As the iodonium salt compound, a diaryl iodonium salt compound is preferable, and examples thereof include a compound represented by the general formula (IV).

In the formula, R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, X- represents a counter anion,
And the like.

  Examples of X- in the general formula (IV) include halogen ions such as Cl- and Br-, HSO4-, BF4-, PF6-, AsF6-, ClO4-, FSO3-, F2PO2-, SbF6-, CF3SO3. -, C4F9SO3-, B (C6F5) 4-, CH3SO3-, C8F17SO3-,

And counter anions. These may be used alone or in combination of two or more.

  Examples of the iodonium salt compound include diphenyliodonium salt, ditolyliodonium salt, phenyl (p-methoxyphenyl) iodonium salt, bis (p-tert-butylphenyl) iodonium salt, bis (p-cyanophenyl) iodonium salt, Chloride such as 4-isopropyl-4'-methyldiphenyliodonium salt, bromide, triflate, boron tetrafluoride, phosphorus hexafluoride, arsenic hexafluoride, antimony hexafluoride, benzenesulfonate, p -Chloride, bromide, triflate, 4-boron fluoride salt, 6-fluorine phosphorus salt, 6-arsenic fluoride salt, 6-antimony fluoride, such as toluenesulfonate, tetrakis (pentafluorophenyl) boron salt Salt, benzenesulfonate, p-toluenesulfonate, te Such Rakisu (pentafluorophenyl) boric Motoshio the like.

  Preferable examples of these onium salt compounds include substances having the following structural formula.

  The (C3) onium salt compound is preferably an onium boron salt compound, and examples thereof include tetramethylammonium butyltriphenylborate, tetraethylammonium butyltriphenylborate, and tetrabutylammonium butyltriphenyl. Borate, tetramethylammonium tris (2-fluorophenyl) butyl borate, tetramethylammonium tris (3-fluorophenyl) butyl borate, tetramethylammonium tris (4-fluorophenyl) butyl borate, tetraethylammonium tris (2-fluorophenyl) Butyl borate, tetraethylammonium tris (3-fluorophenyl) butyl borate, tetraethylammonium tris (4-fluorophenyl) ) Butyl borate, tetramethylammonium tris (2-fluorophenyl) hexyl borate, tetramethylammonium tris (3-fluorophenyl) hexyl borate, tetramethylammonium tris (4-fluorophenyl) hexyl borate, tetraethylammonium tris (2-fluoro) Phenyl) hexyl borate, tetraethylammonium tris (3-fluorophenyl) hexyl borate, tetraethylammonium tris (4-fluorophenyl) hexyl borate, tetrabutylammonium tris (2-fluorophenyl) hexyl borate, tetrabutylammonium tris (3-fluoro) Phenyl) hexyl borate, tetrabutylammonium tris (4-fluorophenyl) hexyl borate And the like, wherein the iodonium salt compound is preferably combined with a sulfonium salt compound. These may be used alone or in combination of two or more.

  The (C4) organic halogen compound is not particularly limited as long as it is an organic compound having a halogen atom in the molecule. Although there is no restriction | limiting in particular as said halogen atom, It is preferable that it is a bromine atom, and it is more preferable to have a tribromomethyl group in a molecule | numerator. Examples of these include tribromomethylphenylsulfone (trade name TPS manufactured by Sumitomo Seika Co., Ltd.), 2-tribromomethylsulfonylpyridine (trade name BSP manufactured by Sumitomo Seika Co., Ltd.), tribromoacetophenone, bis (tri Bromomethyl) sulfone and the like. These may be used alone or in combination of two or more.

  Examples of the benzophenone compound having an alkylamino group include N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N′-tetraethyl-4,4′-diaminobenzophenone, and the like. . These may be used alone or in combination of two or more.

  Examples of the coumarin compound include 7-amino-4-methylcoumarin, 7-dimethylamino-4-methylcoumarin, 7-diethylamino-4-methylcoumarin, 7-methylamino-4-methylcoumarin, and 7-ethylamino. -4-methylcoumarin, 7-dimethylaminocyclopenta [c] coumarin, 7-aminocyclopenta [c] coumarin, 7-diethylaminocyclopenta [c] coumarin, 4,6-dimethyl-7-ethylaminocoumarin, 4 , 6-Diethyl-7-ethylaminocoumarin, 4,6-dimethyl-7-diethylaminocoumarin, 4,6-dimethyl-7-dimethylaminocoumarin, 4,6-diethyl-7-diethylaminocoumarin, 4,6-diethyl -7-dimethylaminocoumarin, 4,6-dimethyl-7-ethylaminocoumarin Etc. The. These may be used alone or in combination of two or more.

  In addition, the photosensitive resin composition of the present invention starts photopolymerization other than the components (C1), (C2), (C3), (C4) and (C5) as long as the effects of the present invention are not impaired. An agent may be used in combination.

  The blending amount of the component (A) is preferably 40 to 80 parts by weight, and more preferably 40 to 70 parts by weight with respect to 100 parts by weight of the total amount of the components (A) and (B). . If the blending amount is less than 40 parts by weight, the photocured product tends to be brittle, and when used as a photosensitive element, the coating property tends to be inferior, and if it exceeds 80 parts by weight, the sensitivity tends to be insufficient.

  The blending amount of the component (B) is preferably 20 to 60 parts by weight, and preferably 30 to 60 parts by weight with respect to 100 parts by weight of the total amount of the components (A) and (B). If the amount is less than 20 parts by weight, the sensitivity tends to be insufficient, and if it exceeds 60 parts by weight, the photocured product tends to be brittle.

  The compounding amount of the component (C1) is preferably 1 to 10 parts by weight and more preferably 3 to 6 parts by weight with respect to 100 parts by weight of the total amount of the components (A) and (B). Is preferable. If the blending amount is less than 1 part by weight, the sensitivity tends to be insufficient, and if it exceeds 10 parts by weight, the resolution tends to decrease.

  The blending amount of the (C2) composition is preferably 0.01 to 3 parts by weight, and 0.1 to 1 part by weight with respect to 100 parts by weight of the total amount of the component (A) and the component (B). More preferably. If the blending amount is less than 0.01 parts by weight, the sensitivity tends to be insufficient, and if it exceeds 3 parts by weight, the resolution tends to decrease.

  The blending amount of the (C3) composition is preferably 0.01 to 5 parts by weight, and 0.1 to 1 part by weight with respect to 100 parts by weight of the total amount of the components (A) and (B). More preferably. If the blending amount is less than 0.01 parts by weight, the sensitivity and resolution tend to decrease, and if it exceeds 5 parts by weight, the resolution tends to decrease.

  The blending amount of the (C4) composition is preferably 0.01 to 5 parts by weight, and 0.1 to 1 part by weight with respect to 100 parts by weight of the total amount of the components (A) and (B). More preferably. If the blending amount is less than 0.01 parts by weight, the sensitivity and resolution tend to decrease, and if it exceeds 5 parts by weight, the resolution tends to decrease.

  The amount of the (C5) composition is preferably 0.01 to 5 parts by weight, preferably 0.1 to 1 part by weight, based on 100 parts by weight of the total amount of the components (A) and (B). More preferably. If the blending amount is less than 0.01 parts by weight, the sensitivity and resolution tend to decrease, and if it exceeds 5 parts by weight, the resolution tends to decrease.

  By blending the component (C2) and the component (C3) to about the same part by weight, a better effect can be obtained.

  In the photosensitive resin composition, if necessary, a photopolymerizable compound having a cyclic ether group capable of at least one cationic polymerization in the molecule, a cationic polymerization initiator, a dye such as malachite green, leuco crystal violet, etc. Photochromic agent, thermochromic inhibitor, plasticizer such as p-toluenesulfonamide, pigment, filler, antifoaming agent, flame retardant, stabilizer, adhesion imparting agent, leveling agent, peeling accelerator, antioxidant, A fragrance | flavor, an imaging agent, a thermal crosslinking agent, etc. can be contained about 0.01-20 weight part each with respect to 100 weight part of total amounts of (A) component and (B) component. These may be used alone or in combination of two or more.

  The photosensitive resin composition is dissolved in a solvent such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether or a mixed solvent thereof as necessary. Then, it can be applied as a solution having a solid content of about 30 to 60% by weight.

  The photosensitive resin composition is not particularly limited, but is coated as a liquid resist on a metal surface such as copper, a copper-based alloy, iron, and an iron-based alloy, dried, and then covered with a protective film as necessary. Or used in the form of a photosensitive element.

  Moreover, although the thickness of the photosensitive resin composition layer changes with uses, it is preferable that it is about 1-100 micrometers by the thickness after drying. In the case of using a liquid resist coated with a protective film, examples of the protective film include polymer films such as polyethylene and polypropylene.

  The photosensitive element can be obtained, for example, by applying and drying a photosensitive resin composition on a polymer film such as polyethylene terephthalate, polypropylene, polyethylene, or polyester as a support.

  The application can be performed by a known method such as a roll coater, a comma coater, a gravure coater, an air knife coater, a die coater, or a bar coater. Moreover, drying can be performed at 70-150 degreeC and about 5 to 30 minutes. Further, the amount of the remaining organic solvent in the photosensitive resin composition layer is preferably 2% by weight or less from the viewpoint of preventing the organic solvent from diffusing in the subsequent step.

  The thickness of these polymer films is preferably 1 to 100 μm. One of these polymer films may be laminated on both sides of the photosensitive resin composition layer as a support for the photosensitive resin composition layer, and the other as a protective film for the photosensitive resin composition. As the protective film, those having a smaller adhesive strength between the photosensitive resin composition layer and the protective film than the adhesive strength between the photosensitive resin composition layer and the support are preferable, and a film having a low fish eye is preferable.

  In addition to the photosensitive resin composition layer, the support and the protective film, the photosensitive element may have an intermediate layer or protective layer such as a cushion layer, an adhesive layer, a light absorption layer, or a gas barrier layer. .

  The photosensitive element is stored, for example, as it is or after a protective film is further laminated on the other surface of the photosensitive resin composition layer and wound around a cylindrical core. In addition, it is preferable to wind up so that a support body may become the 1st outer side at this time. An end face separator is preferably installed on the end face of the roll-shaped photosensitive element roll from the viewpoint of end face protection, and a moisture-proof end face separator is preferably installed from the viewpoint of edge fusion resistance. Moreover, as a packing method, it is preferable to wrap and package in a black sheet with low moisture permeability.

  Examples of the winding core include plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, and ABS resin (acrylonitrile-butadiene-styrene copolymer).

In producing a resist pattern using the photosensitive element, if the protective film is present, the protective film is removed and then the photosensitive resin composition layer is heated to about 70 to 130 ° C. Examples of the method include laminating by pressure bonding to a circuit forming substrate at a pressure of about 0.1 to 1 MPa (about 1 to 10 kgf / cm ² ), and lamination is preferably performed under reduced pressure. The surface to be laminated is usually a metal surface, but is not particularly limited.

  The photosensitive resin composition layer thus laminated is irradiated with actinic rays in an image form through a negative or positive mask pattern. As the light source of the actinic light, a known light source, for example, a light source that effectively emits ultraviolet light, visible light, or the like, such as a carbon arc lamp, a mercury vapor arc lamp, a high-pressure mercury lamp, or a xenon lamp is used. The photosensitive resin composition of the present invention is effective for laser scanning exposure, and can be suitably used particularly for UV (ultraviolet) laser scanning exposure.

  The UV laser is preferably an argon laser having a dominant wavelength of 300 to 400 nm, more preferably an argon laser of 330 to 385 nm, particularly preferably an argon laser of 340 to 375 nm, and 350 to 365 nm. It is very preferable to use an argon laser. Although there is no restriction | limiting in particular as an output, About 0.01-5W is preferable. Examples of the laser exposure apparatus include trade name DP-100 manufactured by Orbotech.

  Next, after exposure, when a support is present on the photosensitive resin composition layer, the support is removed, and then wet development or dry development with a developer such as an alkaline aqueous solution, an aqueous developer, or an organic solvent. The resist pattern can be manufactured by removing the unexposed portion with development or the like and developing.

  Examples of the alkaline aqueous solution include a dilute solution of 0.1 to 5 wt% sodium carbonate, a dilute solution of 0.1 to 5 wt% potassium carbonate, a dilute solution of 0.1 to 5 wt% sodium hydroxide, and the like. It is done. The pH of the alkaline aqueous solution is preferably in the range of 9 to 11, and the temperature is adjusted according to the developability of the photosensitive resin composition layer. Further, a surfactant, an antifoaming agent, an organic solvent, or the like may be mixed in the alkaline aqueous solution. Examples of the development method include a dip method, a spray method, brushing, and slapping.

  The 41-step tablet in the present invention has a density region of 0.00 to 2.00, a density step of 0.05, a tablet size of 20 mm × 187 mm, and a size of each step of 3 mm × 12 mm. For example, Fuji Photo Film Co., Ltd. ) Product name Hitachi 41-step tablet is available.

In the present invention, the photosensitive resin composition is a 41-step tablet (density region 0.00 to 2.00, density step 0.05, tablet size 20 mm × 187 mm, each step size 3 mm × 12 mm). 21 stages (concentration 1.00) are cured.
(1) When a 1 wt% aqueous sodium carbonate solution is sprayed onto the entire surface of the layer of the photosensitive resin composition laminated on the copper clad laminate at a pressure of 0.15 MPa, the layer of the photosensitive resin composition is When the removal time is set as the minimum development time,
(2) A photosensitive resin composition layer laminated on another copper-clad laminate is a 41 step tablet (concentration region 0.00 to 2.00, concentration step 0.05, tablet size 20 mm × 187 mm). , Irradiated with actinic rays (full wavelength of high pressure mercury lamp) through E (mJ / cm ² ) through each step (3 mm × 12 mm) and sprayed with 1 wt% sodium carbonate aqueous solution over the entire layer at a pressure of 0.15 MPa (minimum) The remaining area of the resist corresponding to 21 steps (concentration 1.00) on the substrate (with respect to the step size of 3 mm × 12 mm) is 90% or more when the development time is twice.

As the treatment after development, the resist pattern may be further cured and used by performing heating at about 60 to 250 ° C. or exposure at about 0.2 to 10 mJ / cm ² as necessary.

  For the etching of the metal surface performed after development, for example, a cupric chloride solution, a ferric chloride solution, an alkaline etching solution, or the like can be used.

  When a printed wiring board is produced using the photosensitive element of the present invention, the surface of the circuit forming substrate is treated by a known method such as etching or plating using the developed resist pattern as a mask. Examples of the plating method include copper plating, solder plating, nickel plating, and gold plating.

  Next, the resist pattern can be peeled with a stronger alkaline aqueous solution than the alkaline aqueous solution used for development, for example. As said strong alkaline aqueous solution, 1-10 weight% sodium hydroxide aqueous solution, 1-10 weight% potassium hydroxide aqueous solution, etc. are used, for example. Examples of the peeling method include an immersion method and a spray method. The printed wiring board on which the resist pattern is formed may be a multilayer printed wiring board or may have a small diameter through hole.

  Hereinafter, the present invention will be described with reference to examples.

Examples 1-8 and Comparative Examples 1-3
(A) component shown in Table 1, (B) component, and another component were mix | blended and the solution was obtained.

  Subsequently, (C) component shown in Table 2, Table 3, and Table 4 was dissolved in the obtained solution, and the solution of the photosensitive resin composition was obtained.

The materials used in Table 2, Table 3 and Table 4 are shown below.
^* 1: 3-MeO-2,6F-HABI (2,2′-bis (2,6-fluorophenyl) -4,4 ′, 5,5′-tetrakis (3-methoxyphenyl) bisimidazole, black gold Sample name manufactured by Kasei Kogyo Co., Ltd.)
^* 2: BBI105 (4,4′-bis (tert-butyl) phenyliodonium triflate, trade name, manufactured by Midori Chemical Co., Ltd.)

  Next, the solution of the photosensitive resin composition was uniformly applied onto a 16 μm thick polyethylene polyethylene terephthalate film and dried for 10 minutes in a hot air convection dryer at 100 ° C. to obtain a photosensitive element. The film thickness of the photosensitive resin composition layer was 20 μm.

  On the other hand, a copper surface of a copper-clad laminate (product name: MCL-E-61, manufactured by Hitachi Chemical Co., Ltd.), which is a glass epoxy material in which copper foil (thickness 35 μm) is laminated on both sides, is a brush equivalent to # 600. Polishing is performed using a polishing machine (manufactured by Sankei Co., Ltd.), washed with water, dried by air flow, and the obtained copper-clad laminate is heated to 80 ° C. The conductive resin composition layer was laminated while heating to 110 ° C.

Next, by using an exposure machine (manufactured by Oak Co., Ltd.) 590 having a high pressure mercury lamp lamp, a 41-step stove step tablet as a negative was placed on the test piece and exposed at 5, 10 or 20 mJ / cm ² . Next, the polyethylene terephthalate film was peeled off, and a 1% by weight aqueous sodium carbonate solution was sprayed at 30 ° C. for 20 seconds (minimum development time: 10 seconds) to remove unexposed portions. Furthermore, by measuring the number of steps of the step tablet of the photocured film formed on the copper-clad laminate plate, the exposure amount E ₀ corresponding to the 21-step from the resulting step number was determined by exposure logarithmic regression calculation.

  Next, the developed pattern at the exposure amount in step 21 was observed with an optical microscope, and the resolution (μm) was obtained from the remaining line width (μm) as line and space.

  These results are shown in Table 5.

Next, the photosensitive elements used in Examples 3 to 5 and Comparative Examples 1 to 3 were similarly laminated on a copper-clad laminate, and negative using a direct imaging system (trade name DP-100M manufactured by Orbotech). A stove 41 step tablet was placed on the test piece, and laser scanning exposure (Dominant wavelength: 351 to 6441 nm, output: 0.27 to 4.0 W) was performed at 5, 10 or 20 mJ / cm ² . Thereafter, the polyethylene terephthalate film was removed, and a 1 wt% aqueous sodium carbonate solution was sprayed at 30 ° C. for 20 seconds to remove unexposed portions.

  Furthermore, the number of steps of the step tablet of the photocured film formed on the copper-clad laminate was measured, and the exposure amount corresponding to step 21 was obtained from the obtained step step number by exposure logarithmic regression calculation.

  Next, the developed pattern at the exposure amount in step 21 was observed with an optical microscope, and the resolution (μm) was obtained from the remaining line width (μm) as line and space. These results are shown in Table 6.

  As a result, it was found that the photosensitive elements used in Examples 3 to 5 were cured with a smaller amount of exposure with a UV laser than the photosensitive elements used in Comparative Examples 1 to 3, and the resolution was excellent.

Comparative Example 4
It mix | blends with the compounding quantity of (A) component shown in the said Table 1, (B) component, a pigment, and a solvent, a solution is obtained, and 2,2'-bis (2-chlorophenyl) -4,4 'is obtained in the obtained solution. Add 3.3 g of -5,5'-tetraphenylbisimidazole, 9-phenylacridine, 0.04 g of diethylaminobenzophenone, 0.11 g of N-phenylglycine and 1.6 g of leucocrystal violet, and add a solution of the photosensitive resin composition. Obtained.

  Next, the solution of the photosensitive resin composition was uniformly applied onto a 16 μm thick polyethylene polyethylene terephthalate film and dried for 10 minutes in a hot air convection dryer at 100 ° C. to obtain a photosensitive element. The film thickness of the photosensitive resin composition layer was 20 μm.

  On the other hand, a copper surface of a copper-clad laminate (product name: MCL-E-61, manufactured by Hitachi Chemical Co., Ltd.), which is a glass epoxy material in which copper foil (thickness 35 μm) is laminated on both sides, is a brush equivalent to # 600. Polishing is performed using a polishing machine (manufactured by Sankei Co., Ltd.), washed with water, dried by air flow, and the obtained copper-clad laminate is heated to 80 ° C. The conductive resin composition layer was laminated while heating to 110 ° C.

  The photosensitive resin composition layer was laminated while heating to 110 ° C.

Next, using an exposure machine (manufactured by Oak Co., Ltd.) 590 having a high-pressure mercury lamp, a 41-step stove step tablet as a negative was placed on the test piece and exposed to 5, 10, ²⁰ mJ / cm ² . Next, the polyethylene terephthalate film was peeled off, and a 1% by weight sodium carbonate aqueous solution was sprayed at 30 ° C. for 20 seconds to remove unexposed portions. Furthermore, by measuring the number of steps of the step tablet of the photocured film formed on the copper-clad laminate plate, the exposure amount E ₀ corresponding to the 21-step from the resulting step number was determined by exposure logarithmic regression calculation.

  Next, the developed pattern at the exposure amount in step 21 was observed with an optical microscope, and the resolution (μm) was obtained from the remaining line width (μm) as line and space.

The exposure amount E ₀ of Comparative Example 4 was 23 mJ / cm ² and the resolution was 30 μm.

  Next, the photosensitive elements obtained in Examples 1 to 8 and Comparative Example 4 were subjected to a non-ultraviolet white lamp (manufactured by Hitachi, Ltd., Hitachi fading prevention lamp, removing light in a region of 400 nm or less, 40 W). It was left for 2 hours at a distance of 5 m.

  On the other hand, a copper surface of a copper-clad laminate (product name: MCL-E-61, manufactured by Hitachi Chemical Co., Ltd.), which is a glass epoxy material in which copper foil (thickness 35 μm) is laminated on both sides, is a brush equivalent to # 600. Polishing using a polishing machine (manufactured by Sankei Co., Ltd.), washing with water, drying with air flow, heating the obtained copper-clad laminate to 80 ° C, and leaving it on the copper surface The photosensitive resin composition layer of the photosensitive element was laminated while being heated to 110 ° C.

Next, using an exposure machine (manufactured by Oak Co., Ltd.) 590 having a high-pressure mercury lamp lamp, a 41-step stove tablet as a negative was placed on the test piece and exposed to 5, 10 or 20 mJ / cm ² . Next, the polyethylene terephthalate film was peeled off, and a 1% by weight sodium carbonate aqueous solution was sprayed at 30 ° C. for 20 seconds to remove unexposed portions. Furthermore, by measuring the number of steps of the step tablet of the photocured film formed on the copper-clad laminate plate, the exposure amount E ₁ corresponding to the 21-step from the resulting step number was determined by exposure logarithmic regression calculation.

  Next, the developed pattern at the exposure amount in step 21 was observed with an optical microscope, and the resolution (μm) was obtained from the remaining line width (μm) as line and space. These results are shown in Table 7.

  When the amount of color change of the photosensitive elements obtained in Examples 1 to 8 and Comparative Example 4 was measured under a non-ultraviolet white lamp for 2 hours, Examples 1 to 8 of the present invention were compared with Comparative Example 4. It was found that the color change after standing for 2 hours was small and the workability was excellent.

The photosensitive resin composition for laser scanning exposure of the present invention has little fluctuation in the exposure amount E ₀ and the exposure amount E ₁ after long-term storage, and therefore has excellent long-term storage and workability, and also has a resolution after long-term storage, Laser exposure, especially ultraviolet laser exposure and color change stability are excellent.

  The photosensitive resin composition of the present invention is excellent in sensitivity, resolution, developability and mechanical strength, and is effective for densification of printed wiring boards and laser exposure, particularly ultraviolet laser exposure.

  The photosensitive element of the present invention is excellent in sensitivity, resolution, developability, mechanical strength, productivity and workability, and is effective for increasing the density of printed wiring boards and laser exposure, particularly ultraviolet laser exposure.

  Furthermore, the method for producing a resist pattern of the present invention is excellent in sensitivity, resolution, developability, mechanical strength, productivity and workability, and is effective for increasing the density of printed wiring boards and laser exposure, particularly ultraviolet laser exposure.

  Furthermore, the method for producing a printed wiring board of the present invention is excellent in sensitivity, resolution, developability, mechanical strength, productivity and workability, and is effective for increasing the density of printed wiring boards and laser exposure, particularly ultraviolet laser exposure.

  Furthermore, the resist pattern manufacturing method of the present invention is excellent in sensitivity, resolution, productivity and workability, is effective for increasing the density of printed wiring boards, can be operated under a yellow light, and can be used in a conventional clean room. Work can be done.

Claims (13)

In the photosensitive resin composition comprising (A) a binder polymer, (B) a photopolymerizable compound having at least one polymerizable ethylenically unsaturated group in the molecule, and (C) a photopolymerization initiator,
(C) Component contains (C1) hexaarylbisimidazole compound, (C2) arylglycine compound, and (C5) benzophenone compound or coumarin compound having alkylamino group, Concentration 1 of a 41-step tablet having a density region of 0.00 to 2.00, a density step of 0.05, a tablet size of 20 mm × 187 mm, and a size of each step of 3 mm × 12 mm by irradiation with actinic light of a wavelength. The exposure amount for curing 21 steps of 0.00 was E ₀ mJ / cm ² , and the photosensitive resin composition was allowed to stand under a 40 W non-ultraviolet white lamp for 2 hours. formula when the 21-stage 41-step tablet by active ray irradiation has an exposure amount of curing with _E 1 mJ / cm ² (1 :

The photosensitive resin composition for laser scanning exposure characterized by satisfying these.   The photosensitive resin composition for laser scanning exposure according to claim 1, wherein the photosensitive resin composition contains an (C3) onium salt compound. The component (C2) is represented by the general formula (II)

In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
The photosensitive resin composition of Claim 1 or 2 which is a compound shown by these.   (C3) The photosensitive resin composition according to claim 2, wherein the onium salt compound is an ammonium salt compound, an iodonium salt compound or a sulfonium salt compound.   (C3) The photosensitive resin composition according to claim 2, wherein the onium salt compound is an onium boron salt compound.   The photosensitive resin composition according to claim 1 or 2, further comprising (C4) an organic halogen compound.   The photosensitive resin composition according to claim 1 or 2, wherein the component (B) comprises a bisphenol A-based (meth) acrylate compound as an essential component.   (A) The photosensitive resin composition of Claim 1 or 2 in which a binder polymer uses styrene or a styrene derivative as an essential copolymerization component.   Component (A), Component (B), and Component (C) are blended in amounts of 100 to parts by weight of Component (A) and Component (B), and the amount of Component (A) is 40 to 80 parts by weight. ) Component is 20 to 60 parts by weight and (C) component is 0.01 to 20 parts by weight, and the blending amounts of (C1) component, (C2) component and (C5) component are (A) component and (B The component (C1) is 1 to 10 parts by weight, the component (C2) is 0.01 to 3 parts by weight, and the component (C5) is 0.01 to 5 parts by weight with respect to 100 parts by weight of the total component) Item 3. The photosensitive resin composition according to Item 1 or 2.   The photosensitive element formed by apply | coating the photosensitive resin composition of Claim 1 or 2 on a support body, and drying.   The photosensitive element according to claim 10 is laminated on a circuit-forming substrate so that the photosensitive resin composition layer is in close contact, irradiated with an actinic ray in an image shape, and an exposed portion is photocured, and an unexposed portion A process for producing a resist pattern, characterized in that is removed by development.   A method for producing a printed wiring board, comprising etching or plating a circuit forming substrate on which a resist pattern has been produced by the method for producing a resist pattern according to claim 11.   It is characterized in that the photosensitive resin composition layer is laminated on a circuit-forming substrate, is exposed by scanning with a UV (ultraviolet) laser, the exposed portion is photocured, and the unexposed portion is removed by development. A method for producing a resist pattern.