JP2013117581A - Photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition excellent in peeling characteristics, hue stability and exposure contrast.SOLUTION: The photosensitive resin composition comprises (a) an alkali-soluble polymer, (b) an addition polymerizable monomer, (c) a photopolymerization initiator, and (d) leuco crystal violet. The photosensitive resin composition contains an acridine compound as the (c) photopolymerization initiator. The content of the (d) leuco crystal violet in the photosensitive resin composition is 0.6 mass% to 1.6 mass% with respect to the whole amount of the solid content in the resin composition.

Description

  The present invention relates to a photosensitive resin composition and the like.

  Conventionally, a printed wiring board is generally manufactured by a photolithography method. The photolithographic method is a method in which a photosensitive resin composition is applied onto a substrate, pattern exposure is performed, and an exposed portion of the photosensitive resin composition is polymerized and cured (in the case of a negative type) or solubilized in a developer (positive). Mold) and unexposed areas (in the case of negative molds) or exposed areas (in the case of positive molds) are removed with a developer to form a resist pattern on the substrate, and etching or plating is performed to form a conductor pattern. After forming, the resist pattern is peeled off from the substrate to form a conductor pattern on the substrate.

  In the photolithography method, usually, when a photosensitive resin composition is applied onto a substrate, the photosensitive resin composition solution is applied to the substrate and dried, or a support or a photosensitive resin composition is used. Any method of laminating a photosensitive resin laminate (hereinafter also referred to as “dry film resist”) in which a layer (hereinafter also referred to as “photosensitive resin layer”) and, if necessary, a protective layer are sequentially laminated, on a substrate. Is used. In the production of printed wiring boards, the latter dry film resist is often used.

  Here, with the recent miniaturization of the wiring interval in the printed wiring board, various characteristics are being required for the dry film resist. Patent Document 1 discloses a photosensitive resin composition containing leuco crystal violet in a photosensitive resin composition.

  Patent Document 2 discloses a photosensitive resin composition in which a pigment or dye containing leuco crystal violet is blended together with a binder component and a monomer component.

JP-A-5-333542 JP-A-10-111567

However, all of the photosensitive resin compositions described in Patent Documents 1 and 2 are from the viewpoint of sufficiently shortening the time until the resist is completely peeled from the substrate (hereinafter also referred to as “peeling time”). However, there was still room for improvement.
Accordingly, an object of the present invention is to provide a photosensitive resin composition that is excellent in peeling properties, hue stability, and exposure contrast.

  As a result of intensive studies to solve the above problems, the present inventor has found that the above problems can be solved by the following technical means.

  [1] A photosensitive resin composition comprising (a) an alkali-soluble polymer, (b) an addition polymerizable monomer, (c) a photopolymerization initiator, and (d) leuco crystal violet, wherein the photosensitive resin composition The product (c) contains an acridine compound as a photopolymerization initiator, and the content of (d) leuco crystal violet in the photosensitive resin composition is based on the total solid content of the photosensitive resin composition. The said photosensitive resin composition which is 0.6 mass%-1.6 mass%.

  [2] The photosensitive resin composition according to [1], wherein the (b) addition polymerizable monomer has a weight average molecular weight of 700 to 1,200.

  [3] The photosensitive resin composition according to [1] or [2], wherein the acridine compound is 9-phenylacridine.

  [4] The photosensitive resin composition according to any one of [1] to [3], further including Basic Green 1.

｛式中：
Ｒ^３及びＲ^４は、各々独立にＨ又はＣＨ_３であり；
Ａは、Ｃ_２Ｈ_４であり、Ｂは、Ｃ_３Ｈ_６であり、−（Ａ−Ｏ）−及び−（Ｂ−Ｏ）−の繰り返し単位の配列はランダムであってもブロックであってもよく、ブロックの場合には、−（Ａ−Ｏ）−及び−（Ｂ−Ｏ）−のいずれがビスフェノールＡ基側でもよく；
ｒ及びｓは、各々独立に１〜２９の整数であり、かつｒ＋ｓは２〜４０の整数であり；そして
ｘ及びｙは、各々独立に０〜２９の整数であり、かつｘ＋ｙは０〜３０の整数である。｝
で表される化合物を含む、［１］〜［４］のいずれか１項に記載の感光性樹脂組成物。 [5] As the (b) addition polymerizable monomer, the following general formula (I):

{In the formula:
R ³ and R ⁴ are each independently H or CH ₃ ;
A is C ₂ H ₄ , B is C ₃ H ₆ , and the sequence of repeating units of-(AO)-and-(B-O)-is a block even if it is random. In the case of a block, either-(A-O)-or-(B-O)-may be on the bisphenol A group side;
r and s are each independently an integer from 1 to 29, and r + s is an integer from 2 to 40; and x and y are each independently an integer from 0 to 29, and x + y is from 0 to 30. Is an integer. }
The photosensitive resin composition of any one of [1]-[4] containing the compound represented by these.

  [6] A photosensitive resin laminate comprising a support and a photosensitive resin layer comprising the photosensitive resin composition according to any one of [1] to [5].

  [7] A pattern forming method comprising the steps of laminating the photosensitive resin laminate according to [6] on a substrate, exposing and developing.

  [8] A method for forming a circuit board, comprising: laminating the photosensitive resin laminate according to [6] on a base material, exposing, developing, and etching.

  ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin composition which is excellent in peeling characteristics, is excellent also in hue stability, and exposure contrast is provided.

  Hereinafter, the best mode for carrying out the present invention (hereinafter abbreviated as “the present embodiment”) will be specifically described.

<Photosensitive resin composition>
In this embodiment, the photosensitive resin composition includes (a) an alkali-soluble polymer, (b) an addition polymerizable monomer, (c) a photopolymerization initiator, and a dye. c) An acridine compound is included as a photopolymerization initiator, and 0.6 to 1.6% by mass of (d) leuco crystal violet is included as a dye with respect to the total solid content of the photosensitive resin composition.

(A) Alkali-soluble polymer (a) The alkali-soluble polymer typically contains a carboxyl group-containing monomer as a copolymerization component, and has a weight average molecular weight of 5,000 to 500,000. It is a coalescence.

  The weight average molecular weight of the thermoplastic copolymer is preferably 5,000 to 500,000. The weight average molecular weight of the thermoplastic copolymer is preferably 5,000 or more from the viewpoint of maintaining the thickness of the dry film resist uniformly and obtaining resistance to the developer, while being 500 from the viewpoint of maintaining developability. 1,000 or less is preferable. More preferably, the thermoplastic copolymer has a weight average molecular weight of 20,000 to 100,000.

  The thermoplastic copolymer is preferably obtained by copolymerizing a copolymer component composed of one or more first monomers described later and one or more second monomers described later.

  The first monomer is a monomer containing a carboxyl group in the molecule. Examples of the first monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, and maleic acid half ester. Among these, (meth) acrylic acid is particularly preferable. Here, (meth) acryl indicates acryl or methacryl. The same applies hereinafter.

  The second monomer is a monomer that is non-acidic and has at least one polymerizable unsaturated group in the molecule. Examples of the second monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. , Tert-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, vinyl acetate, etc. And esters of vinyl alcohol; (meth) acrylonitrile, styrene, and polymerizable styrene derivatives. Among these, methyl (meth) acrylate, n-butyl (meth) acrylate, styrene, and benzyl (meth) acrylate are preferable.

  In the present embodiment, the content of (a) alkali-soluble polymer in the photosensitive resin composition (however, based on the total solid content of the photosensitive resin composition. Unless otherwise specified, And the same in each component.) Is preferably in the range of 20% by mass to 80% by mass, more preferably in the range of 25% by mass to 70% by mass, and still more preferably in the range of 40% by mass to 60%. It is the range of mass%. This content is preferably 20% by mass or more from the viewpoint of maintaining alkali developability, while 80% by mass from the viewpoint that the resist pattern formed by exposure sufficiently exhibits the performance as a resist. The following is preferable.

(B) Addition polymerizable monomer (b) An addition polymerizable monomer is a monomer which has addition polymerization property by having an ethylenically unsaturated group, for example.

  In this embodiment, it is preferable that the weight average molecular weight of (b) addition polymerizable monomer is 700-1,200. When a plurality of (b) addition polymerizable monomers are contained in the photosensitive resin composition, the weight average molecular weight of (b) addition polymerizable monomer is [(b) addition polymerizable monomer The total value of each weight average molecular weight × the proportion of the corresponding monomer to all monomers]. (B) It is preferable to adjust the weight average molecular weight of the addition polymerizable monomer in the range of 700 to 1,200 from the viewpoint of improving tenting property, resolution, and exposure contrast. (B) The weight average molecular weight of the addition polymerizable monomer is more preferably 900 to 1,200.

｛式中：
Ｒ^３及びＲ^４は、各々独立にＨ又はＣＨ_３であり；
Ａは、Ｃ_２Ｈ_４であり、Ｂは、Ｃ_３Ｈ_６であり、−（Ａ−Ｏ）−及び−（Ｂ−Ｏ）−の繰り返し単位の配列はランダムであってもブロックであってもよく、ブロックの場合には、−（Ａ−Ｏ）−及び−（Ｂ−Ｏ）−のいずれがビスフェノールＡ基側でもよく；
ｒ及びｓは、各々独立に１〜２９の整数であり、かつｒ＋ｓは２〜４０の整数であり；そして
ｘ及びｙは、各々独立に０〜２９の整数であり、かつｘ＋ｙは０〜３０の整数である。｝
で表される少なくとも１種の光重合可能な不飽和化合物を含むことが好ましい。 In the present embodiment, from the viewpoint of h-ray sensitivity, high resolution and / or edge fuse resistance, the photosensitive resin composition is represented by the following general formula (I) as (b) addition polymerizable monomer:

{In the formula:
R ³ and R ⁴ are each independently H or CH ₃ ;
A is C ₂ H ₄ , B is C ₃ H ₆ , and the sequence of repeating units of-(AO)-and-(B-O)-is a block even if it is random. In the case of a block, either-(A-O)-or-(B-O)-may be on the bisphenol A group side;
r and s are each independently an integer from 1 to 29, and r + s is an integer from 2 to 40; and x and y are each independently an integer from 0 to 29, and x + y is from 0 to 30. Is an integer. }
It is preferable to include at least one photopolymerizable unsaturated compound represented by:

  In the general formula (I), r and s are each preferably 1 or more from the viewpoints of flexibility and tenting properties of the cured film, and are each preferably 29 or less from the viewpoint of resolution. Further, r + s is preferably 2 or more from the viewpoint of flexibility and tenting properties of the cured film, and is preferably 40 or less from the viewpoint of resolution. Furthermore, x and y are each preferably 29 or less from the viewpoint of resolution, and x + y is preferably 30 or less from the viewpoint of resolution. As a more preferable range of r, s, x and y, r and s are each 2 or more and 18 or less, and x and y are each 18 or less.

  In the compound represented by the general formula (I), r + s + x + y is preferably 2 or more from the viewpoint of flexibility and tenting properties of the cured film, and preferably 40 or less from the viewpoint of resolution.

  Specific examples of the photopolymerizable unsaturated compound represented by the general formula (I) include polyethylene glycol dimethacrylate (for example, Shin-Nakamura Chemical Co., Ltd.) having an average of 2 moles of ethylene oxide added to both ends of bisphenol A. NK ester BPE-200), polyethylene glycol dimethacrylate (for example, NK ester BPE-500 manufactured by Shin-Nakamura Chemical Co., Ltd.) and bisphenol A Polyalkylene glycol dimethacrylate with an average of 6 moles of ethylene oxide and 2 moles of propylene oxide added to each end, and an average of 2 moles of propylene oxide and 15 moles of ethylene oxide on each side of bisphenol A Include dimethacrylate of polyalkylene glycol. From the viewpoint of tent properties, polyalkylene glycol dimethacrylate in which an average of 2 mol of propylene oxide and an average of 15 mol of ethylene oxide are added to both sides of bisphenol A is preferable.

  The content of the photopolymerizable unsaturated compound represented by the general formula (I) in the photosensitive resin composition is preferably 3% by mass or more from the viewpoint of sensitivity, and on the other hand, from the viewpoint of edge fuse resistance. To 70% by mass or less is preferable. This content is more preferably 3% by mass to 35% by mass, and further preferably 3% by mass to 30% by mass.

  (B) Examples other than the compound represented by the general formula (I) that can be used as an addition polymerizable monomer include known compounds having at least one terminal ethylenically unsaturated group.

  (B) More specific examples of addition polymerizable monomers include, for example, 4-nonylphenylheptaethylene glycol dipropylene glycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, phenoxyhexaethylene glycol acrylate, phthalic anhydride and 2 -Reaction product of a half ester compound with hydroxypropyl acrylate and propylene oxide (for example, Nippon Shokubai Chemical Co., Ltd., trade name OE-A 200), 4-normal octylphenoxypentapropylene glycol (meth) acrylate, 1,6-hexanediol Polyoxy, such as di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate Alkylene glycol di (meth) acrylate, 2-di (p-hydroxyphenyl) propane di (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol Hexa (meth) acrylate, trimethylolpropane triglycidyl ether tri (meth) acrylate, 2,2-bis (4-methacryloxypentaethoxyphenyl) propane, glycol tetraacrylate with an average of 4 moles of ethylene oxide added to pentaerythritol , Triacrylate obtained by adding an average of 3 moles of ethylene oxide to trimethylolpropane (Shin-Nakamura Chemical A-TMPT-3EO, product name), hexamethylene di Examples thereof include polyfunctional group (meth) acrylates containing urethane groups such as urethane products of isocyanate and nonapropylene glycol monomethacrylate, and polyfunctional (meth) acrylates of isocyanuric acid ester compounds. These may be used alone or in combination of two or more.

  The content of the (b) addition polymerizable monomer in the photosensitive resin composition of the present invention is preferably in the range of 5% by mass to 60% by mass. This content is preferably 5% by mass or more from the viewpoint of suppressing poor curing and delay in development time, while being 60% by mass or less from the viewpoint of suppressing cold flow and delayed peeling of the cured resist. It is preferable. Further, this content is more preferably in the range of 15% by mass to 60% by mass, and further preferably in the range of 30-50% by mass.

(C) Photopolymerization initiator (c) The photopolymerization initiator is a compound that polymerizes a monomer by light. In this embodiment, it is preferable that the photosensitive resin composition contains an acridine compound as a photopolymerization initiator (c) from the viewpoint of exhibiting good release characteristics. Moreover, in this embodiment, the photosensitive resin composition may contain compounds other than an acridine compound as (c) photoinitiator.

｛式中、Ｒは、水素原子、炭素数１〜２０のアルキル基、炭素数２〜２０のアルキレン基、フェニル基又はベンジル基であり、そしてｍは、１又は２の整数である。｝
で表される化合物が挙げられる。 As an acridine compound, the following general formula (II):

{In the formula, R is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkylene group having 2 to 20 carbon atoms, a phenyl group or a benzyl group, and m is an integer of 1 or 2. }
The compound represented by these is mentioned.

｛式中、Ｒは、水素原子、炭素数１〜２０のアルキル基、フェニル基又はベンジル基である。｝
で表される化合物であることが好ましい。本実施形態では、剥離特性及び／又はｈ線感度をさらに向上させるという観点から、一般式（ＩＩＩ）において、Ｒは、アクリジン骨格の９位に位置するアルキル基又はフェニル基であることが好ましい。また、本実施形態では、感光性樹脂組成物は、一般式（ＩＩ）又は（ＩＩＩ）で表される化合物以外のアクリジン化合物を含んでもよい。 In the present embodiment, the acridine compound is represented by the following general formula (III) from the viewpoint of improving peeling characteristics and / or h-ray sensitivity.

{In formula, R is a hydrogen atom, a C1-C20 alkyl group, a phenyl group, or a benzyl group. }
It is preferable that it is a compound represented by these. In the present embodiment, R is preferably an alkyl group or a phenyl group located at the 9-position of the acridine skeleton in the general formula (III) from the viewpoint of further improving the peeling characteristics and / or h-ray sensitivity. Moreover, in this embodiment, the photosensitive resin composition may contain acridine compounds other than the compound represented by general formula (II) or (III).

  (C) Preferred examples of the acridine compound used as a photopolymerization initiator include acridine, 9-phenylacridine, 1,6-bis (9-acridinyl) hexane, 1,7-bis (9-acridinyl) heptane, 1,8-bis (9-acridinyl) octane, 1,9-bis (9-acridinyl) nonane, 1,10-bis (9-acridinyl) decane, 1,11-bis (9-acridinyl) undecane, Examples include acridine derivatives such as 12-bis (9-acridinyl) dodecane. In particular, 9-phenylacridine is preferable from the viewpoint of improving h-ray sensitivity.

  In the present embodiment, the content of the acridine compound in the photosensitive resin composition is preferably in the range of 0.1% by mass to 2% by mass. It is preferable to adjust this content in the range of 0.1% by mass to 2% by mass from the viewpoint of obtaining good peeling characteristics. The content is preferably in the range of 0.4% by mass to 1.2% by mass, more preferably in the range of 0.5% by mass to 1.2% by mass, and 0.8% by mass. It is particularly preferable that the amount be in the range of% to 1.2% by mass.

  Examples of other photopolymerization initiators used in combination with the acridine compound include N-aryl amino acids, organic halogen compounds, hexaarylbisimidazole derivatives, and photosensitizers.

  Examples of N-aryl amino acids include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine and the like. Among these, N-phenylglycine is particularly preferable. The content of the N-aryl amino acid in the photosensitive resin composition is preferably 0.05% by mass to 5% by mass from the viewpoint of improving the peeling properties and / or sensitivity, and is 0.1-2% by mass. % Is more preferable.

  Examples of the organic halogen compound include, for example, amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, methylene bromide, tribromomethylphenyl sulfone, carbon tetrabromide, Tris (2,3-dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, and chlorinated triazine compounds. Of these, tribromomethylphenylsulfone is particularly preferably used. The content of the organic halogen compound in the photosensitive resin composition is preferably 0.05% by mass to 5% by mass, and preferably 0.1% by mass to 3% from the viewpoint of improving peeling characteristics and / or sensitivity. More preferably, it is mass%.

  Examples of hexaarylbisimidazole derivatives (hereinafter also referred to as dimers of triarylimidazolyl derivatives or triarylimidazolyl dimers) include, for example, 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer (Hereinafter also referred to as 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,1′-bisimidazole), 2,2 ′, 5-tris- (O-chlorophenyl) -4- (3,4-dimethoxyphenyl) -4 ′, 5′-diphenylimidazolyl dimer, 2,4-bis- (o-chlorophenyl) -5- (3,4-dimethoxyphenyl) ) -Diphenylimidazolyl dimer, 2,4,5-tris- (o-chlorophenyl) -diphenylimidazolyl dimer, 2- (o-chlorophenyl)- -4,5- (3,4-dimethoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2-fluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxy Phenyl) -imidazolyl dimer, 2,2′-bis- (2,3-difluoromethylphenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2, , 2′-bis- (2,4-difluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2,5 -Difluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2,6-difluorophenyl) -4,4', 5,5′-tetrakis- (3-methoxyph Nyl) -imidazolyl dimer, 2,2′-bis- (2,3,4-trifluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer 2,2′-bis- (2,3,5-trifluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis -(2,3,6-trifluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2,4,5 -Trifluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2,4,6-trifluorophenyl) -4 , 4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -Imidazolyl dimer, 2,2'-bis- (2,3,4,5-tetrafluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer 2,2′-bis- (2,3,4,6-tetrafluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, and 2,2 Examples include '-bis- (2,3,4,5,6-pentafluorophenyl) -4,4', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer. In particular, 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer is a photopolymerization initiator having a high effect on the resolution and the strength of the cured film, and is preferably used. The content of the hexaarylbisimidazole derivative in the photosensitive resin composition is preferably 0.05% by mass to 5% by mass from the viewpoint of improving the peeling characteristics and / or sensitivity, and 0.1% by mass. More preferably, it is -3 mass%.

  Examples of photosensitizers include, for example, 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone Quinones such as 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, and 3-chloro-2-methylanthraquinone, benzophenone, Michler's ketone [4,4′-bis (dimethylamino) benzophenone] and aromatic ketones such as 4,4′-bis (diethylamino) benzophenone, benzoin, benzoin ethyl ether, benzoin phenyl ether, methyl benzoin, ethyl benzoin and the like Nzoin ethers, benzyl dimethyl ketal, benzyl diethyl ketal, and 1-phenyl-1,2-propanedione-2-O-benzoin oxime, and 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) Examples include oxime esters such as oxime. The content of the photosensitizer in the photosensitive resin composition is preferably 0.05% by mass to 5% by mass from the viewpoint of improving the peeling characteristics and / or sensitivity, and 0.1% by mass to More preferably, it is 3% by mass.

  Moreover, in this embodiment, it is also preferable that the photosensitive resin composition contains a pyrazoline compound as a photosensitizer. Examples of the pyrazoline compound include 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1- (4- (benzoxazol-2-yl) phenyl) -3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-tert-butyl-phenyl) -Pyrazolin and 1-phenyl-3- (4-biphenyl) -5- (4-tert-octyl-phenyl) -pyrazoline are preferred.

  The content of the photopolymerization initiator (c) in the photosensitive resin composition is preferably 0.1% by mass to 20% by mass. This content is preferably 0.1% by mass or more from the viewpoint of sensitivity, and is preferably 20% by mass or less from the viewpoint of resolution. The content is more preferably 0.1% by mass to 10% by mass, and further preferably 0.1% by mass to 3% by mass. (C) As the photopolymerization initiator, one kind of the compounds listed above may be used alone, or two or more kinds may be used in combination.

で表される化合物（ＣＡＳ番号：６０３−４８−５）又はその誘導体であり、そして感光性樹脂組成物に着色性（すなわち、発色性）を付与するために使用される。また、本実施形態では、感光性樹脂組成物中にロイコクリスタルバイオレット及びアクリジン化合物を含有させることにより、良好な剥離特性を得ることができるため好ましい。 (D) Leuco Crystal Violet Generally, leuco crystal violet is represented by the following formula (IV):

(CAS number: 603-48-5) or a derivative thereof, and used for imparting colorability (that is, color developability) to the photosensitive resin composition. Further, in the present embodiment, it is preferable to include leuco crystal violet and an acridine compound in the photosensitive resin composition because good peeling characteristics can be obtained.

  In this embodiment, it is preferable that content of the leuco crystal violet in the photosensitive resin composition is 0.6 mass%-1.6 mass%. From the viewpoint of adjusting the content in the range of 0.6% by mass to 1.6% by mass, imparting good color developability to the photosensitive resin composition for easy recognition, and shortening the peeling time. To preferred. Moreover, this content is more preferably 0.8% by mass to 1.2% by mass from the viewpoint of further shortening the peeling time.

(Other ingredients)
The photosensitive resin composition of the present invention contains (a) an alkali-soluble polymer, (b) an addition polymerizable monomer, (c) a photopolymerization initiator, and (d) leuco crystal violet as essential components. Depending on the case, additives such as base dyes, plasticizers, antioxidants and stabilizers may be included.

  Examples of the base dye include Basic Green 1 [CAS number (hereinafter the same): 633-03-4] (for example, Aizen Diamond Green GH, trade name, manufactured by Hodogaya Chemical Co., Ltd.), Malachite Green Oxalate [2437 -29-8] (for example, Aizen Malachite Green, trade name, manufactured by Hodogaya Chemical Industry), brilliant green [633-03-4], fuchsin [632-99-5], methyl violet [603-47-4], Methyl violet 2B [8004-87-3], Crystal violet [548-62-9], Methyl green [82-94-0], Victoria blue B [2580-56-5], Basic blue 7 [2390-60- 5] (for example, Aizen Victoria Pu e Blue BOH, trade name, manufactured by Hodogaya Chemical), rhodamine B [81-88-9], rhodamine 6G [989-38-8], Basic Yellow 2 [2465-27-2], and the like. Of these, basic green 1, malachite green oxalate, and basic blue 7 are preferable, and basic green 1 is particularly preferable from the viewpoint of improving hue stability and exposure contrast.

  The content of the dye in the photosensitive resin composition is preferably in the range of 0.001% by mass to 3% by mass, more preferably in the range of 0.01% by mass to 2% by mass, and still more preferably, The range is 0.01% by mass to 1.2% by mass. The content is preferably 0.001% by mass or more from the viewpoint of obtaining good colorability, and is preferably 3% by mass or less from the viewpoint of maintaining sensitivity.

  Examples of the plasticizer include polyethylene glycol, polypropylene glycol, polyoxypropylene polyoxyethylene ether, polyoxyethylene monomethyl ether, polyoxypropylene monomethyl ether, polyoxyethylene polyoxypropylene monomethyl ether, polyoxyethylene monoethyl ether, polyoxyethylene monomethyl ether, Glycol esters such as oxypropylene monoethyl ether and polyoxyethylene polyoxypropylene monoethyl ether, phthalic acid esters such as diethyl phthalate, o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, citric acid Triethyl acid, triethyl acetyl citrate, tri-n-propyl acetyl citrate, and tri-n-butyl acetyl citrate Propylene glycol respectively by adding propylene oxide to both sides of the bisphenol A, and ethylene glycol, respectively adding ethylene oxide to both sides of the bisphenol A and the like.

  Content of the plasticizer in the photosensitive resin composition becomes like this. Preferably it is 0.1 mass%-50 mass%, More preferably, it is 1 mass%-20 mass%. This content is preferably 0.1% by mass or more from the viewpoint of suppressing delay in development time and imparting flexibility to the cured film, while being 50% from the viewpoint of suppressing insufficient curing and cold flow. % Or less is preferable.

  Examples of the antioxidant include triphenyl phosphite (for example, manufactured by Asahi Denka Kogyo Co., Ltd., trade name: TPP), tris (2,4-di-t-butylphenyl) phosphite (for example, manufactured by Asahi Denka Kogyo Co., Ltd., product) No. 2112), tris (monononylphenyl) phosphite (for example, manufactured by Asahi Denka Kogyo Co., Ltd., trade name: 1178), and bis (monononylphenyl) -dinonylphenyl phosphite (for example, manufactured by Asahi Denka Kogyo Co., Ltd., trade name: 329K).

  The content of the antioxidant in the photosensitive resin composition is preferably in the range of 0.01% by mass to 0.8% by mass, and more preferably in the range of 0.01% by mass to 0.3% by mass. It is. When this content is 0.01 mass% or more, the effect which is excellent in the hue stability of the photosensitive resin composition expresses favorably, and the sensitivity at the time of exposure of the photosensitive resin composition becomes favorable. On the other hand, when the content is 0.8% by mass or less, since color developability is suppressed, hue stability is improved and adhesion is also improved.

  The stabilizer is preferably used from the viewpoint of improving the thermal stability and / or storage stability of the photosensitive resin composition. Examples of the stabilizer include one or more compounds selected from the group consisting of radical polymerization inhibitors, benzotriazoles, carboxybenzotriazoles, and alkylene oxide compounds having a glycidyl group.

  Examples of the radical polymerization inhibitor include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, 2,2′-methylenebis. (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), nitrosophenylhydroxyamine aluminum salt, diphenylnitrosamine and the like.

  Examples of benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3-benzotriazole, Examples thereof include bis (N-2-ethylhexyl) aminomethylene-1,2,3-tolyltriazole and bis (N-2-hydroxyethyl) aminomethylene-1,2,3-benzotriazole.

  Examples of carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, and N- (N, N-di-2-ethylhexyl) aminomethylene. Examples thereof include carboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylenecarboxybenzotriazole, and N- (N, N-di-2-ethylhexyl) aminoethylenecarboxybenzotriazole.

  Examples of the alkylene oxide compound having a glycidyl group include neopentyl glycol diglycidyl ether (for example, Epolite 1500NP manufactured by Kyoeisha Chemical Co., Ltd.), nonaethylene glycol diglycidyl ether (for example, Epolite 400E manufactured by Kyoeisha Chemical Co., Ltd.), and bisphenol A. -Propylene oxide 2 mol adduct diglycidyl ether (for example, Epolite 3002 manufactured by Kyoeisha Chemical Co., Ltd.), 1,6-hexanediol diglycidyl ether (for example, Epolite 1600 manufactured by Kyoeisha Chemical Co., Ltd.) and the like.

  The total content of the radical polymerization inhibitor, benzotriazoles, carboxybenzotriazoles, and alkylene oxide compounds having a glycidyl group in the photosensitive resin composition is preferably 0.01% by mass to 3% by mass, More preferably, it is 0.05-1 mass%. This total content is preferably 0.01% by mass or more from the viewpoint of imparting good storage stability to the photosensitive resin composition, while 3% by mass from the viewpoint of maintaining good sensitivity. The following is preferable.

<Photosensitive resin composition preparation solution>
The photosensitive resin composition of the present invention may be used as a photosensitive resin composition preparation liquid formed by adding a solvent thereto. Suitable solvents include ketones represented by methyl ethyl ketone (MEK), and alcohols such as methanol, ethanol, and isopropyl alcohol. It is preferable to add a solvent to the photosensitive resin composition so that the viscosity of the photosensitive resin composition preparation liquid is 500 to 4000 mPa · sec at 25 ° C.

<Photosensitive resin laminate>
Another aspect of the present invention provides a photosensitive resin laminate having a support and a photosensitive resin layer made of the above-described photosensitive resin composition according to the present invention laminated on the support. The photosensitive resin laminate of the present invention has a protective layer on the surface of the photosensitive resin layer opposite to the support-forming side, if necessary, in addition to the photosensitive resin layer and the support that supports the layer. May be.

  The support is preferably a transparent one that transmits light emitted from the exposure light source. Examples of such a support include polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, polymethyl methacrylate copolymer film, polystyrene film. , A polyacrylonitrile film, a styrene copolymer film, a polyamide film, and a cellulose derivative film. As these films, those stretched as necessary can be used. The haze is preferably 5 or less. The thinner the film, the more advantageous in terms of image forming property and economic efficiency, but a film having a thickness of 10 to 30 μm is preferably used because the strength needs to be maintained.

  Further, an important characteristic of the protective layer used in the photosensitive resin laminate is that the protective layer is sufficiently smaller than the support and can be easily peeled with respect to the adhesion with the photosensitive resin layer. For example, a polyethylene film and a polypropylene film can be preferably used as the protective layer. Further, for example, a film having excellent peelability disclosed in JP-A-59-202457 can be used. The thickness of the protective layer is preferably 10 to 100 μm, and more preferably 10 to 50 μm.

  The thickness of the photosensitive resin layer in the photosensitive resin laminate of the present invention is preferably 5 to 100 μm, more preferably 7 to 60 μm. As the thickness is thinner, the resolution is improved, and as the thickness is thicker, the film strength is improved.

  As a method for preparing the photosensitive resin laminate of the present invention by sequentially laminating the support, the photosensitive resin layer, and if necessary, the protective layer, a conventionally known method can be employed.

  For example, the photosensitive resin composition used for forming the photosensitive resin layer is made into the above-mentioned photosensitive resin composition preparation solution, and is first coated on a support using a bar coater or a roll coater and dried. Then, a photosensitive resin layer made of the photosensitive resin composition is laminated on the support. Then, if necessary, a photosensitive resin laminate can be produced by laminating a protective layer on the photosensitive resin layer.

<Resist pattern formation method>
The present invention includes a laminating step of forming a photosensitive resin layer on a substrate using the above-described photosensitive resin laminate of the present invention, an exposure step of exposing the photosensitive resin layer, and a photosensitive resin after the exposure There is also provided a resist pattern forming method that sequentially includes a developing step of forming a resist pattern by removing an unexposed portion in a layer with a developer. An example of a specific method for forming a resist pattern using the photosensitive resin laminate of this embodiment will be described.

  First, in a laminating process, a photosensitive resin layer is formed on a substrate using a laminator. Specifically, when the photosensitive resin laminate has a protective layer, the protective layer is peeled off, and then the photosensitive resin layer is heat-pressed and laminated on the substrate surface with a laminator. Examples of the material of the substrate include copper, stainless steel (SUS), glass, indium tin oxide (ITO), and the like. In this case, the photosensitive resin layer may be laminated on only one surface of the substrate surface, or may be laminated on both surfaces as necessary. The heating temperature at this time is generally 40 to 160 ° C. Moreover, the adhesiveness with respect to the board | substrate of the resist pattern obtained by performing this thermocompression bonding twice or more improves. At this time, a two-stage laminator provided with two rolls may be used for pressure bonding, or a laminate of the substrate and the photosensitive resin layer may be repeatedly passed through the roll and pressure bonded.

  Next, in the exposure step, the photosensitive resin composition is exposed to active light using an exposure machine. If necessary, the exposure can be performed after peeling off the support. In the case of exposure through a photomask, the exposure amount is determined by the light source illuminance and the exposure time, and may be measured using a light meter.

  In the exposure step, a maskless exposure method may be used. In maskless exposure, exposure is performed directly on the substrate by a drawing apparatus without using a photomask. As the light source, a semiconductor laser having a wavelength of 350 nm to 410 nm, an ultrahigh pressure mercury lamp, or the like is used. The drawing pattern is controlled by a computer, and the exposure amount in this case is determined by the illuminance of the exposure light source and the moving speed of the substrate.

Next, in the development step, unexposed portions in the exposed photosensitive resin layer are removed with a developer using a developing device. After exposure, if a support is present on the photosensitive resin layer, this is excluded. Subsequently, the unexposed portion is developed and removed using a developer composed of an alkaline aqueous solution to obtain a resist image. As the alkaline aqueous solution, an aqueous solution of Na ₂ CO ₃ or K ₂ CO ₃ is preferable. These are selected in accordance with the characteristics of the photosensitive resin layer, but an aqueous Na ₂ CO ₃ solution having a concentration of 0.2% by mass to 2% by mass is common. In the alkaline aqueous solution, a surfactant, an antifoaming agent, a small amount of an organic solvent for accelerating development, and the like may be mixed. In addition, it is preferable to maintain the temperature of the developing solution in a development process at a constant temperature in the range of 20 to 40 ° C.

  Although a resist pattern is obtained by the above-mentioned process, depending on the case, the heating process of 100 to 300 degreeC can also be performed further. By carrying out this heating step, chemical resistance can be further improved. For heating, a heating furnace such as hot air, infrared rays, or far infrared rays can be used.

<Conductor pattern manufacturing method>
The present invention includes a laminating step of forming a photosensitive resin layer on a substrate that is a metal plate or a metal film insulating plate using the above-described photosensitive resin laminate of the present invention, and exposure for exposing the photosensitive resin layer. A step of forming a resist pattern by removing a non-exposed portion of the photosensitive resin layer after the exposure with a developer, and a step of forming a conductor pattern for etching or plating the substrate on which the resist pattern is formed. A method for manufacturing a conductor pattern is also provided. That is, the method for producing a conductor pattern of the present embodiment is implemented by using a metal plate or a metal film insulating plate as a substrate, forming a resist pattern by the above-described resist pattern forming method, and then performing the following conductor pattern forming step. Is done. In the conductor pattern forming step, a conductor pattern is formed on a substrate surface (for example, a copper surface) exposed by development using a known etching method or plating method on a substrate on which a resist pattern is formed by the method described above.

  Furthermore, the present invention is suitably applied in the following applications, for example.

<Manufacture of printed wiring boards>
After the conductor pattern is produced according to the present invention, a printed wiring board having a desired wiring pattern can be obtained by further performing a peeling step of peeling the resist pattern from the substrate with an aqueous solution having alkalinity stronger than the developer. . In the production of a printed board, a copper-clad laminate or a flexible board is preferably used as the board. There is no particular limitation on the alkaline aqueous solution for stripping (hereinafter also referred to as “stripping solution”), but an aqueous solution of NaOH or KOH having a concentration of 2% by mass to 5% by mass is generally used. A small amount of a water-soluble solvent can be added to the stripping solution. The temperature of the stripping solution in the stripping step is preferably in the range of 40 ° C to 70 ° C.

<Manufacture of lead frames>
A lead frame can be manufactured by forming a resist pattern by the above-mentioned resist pattern forming method using a metal plate such as copper, a copper alloy, or an iron-based alloy as a substrate and then performing the following steps. First, a step of etching the substrate exposed by development to form a conductor pattern is performed. Then, the peeling process which peels a resist pattern with the method similar to the manufacturing method of the above-mentioned printed wiring board is performed, and a desired lead frame is obtained.

<Manufacture of a substrate having an uneven pattern>
The resist pattern formed by the resist pattern forming method of the present invention can be used as a protective mask member when processing a substrate by a sandblasting method. Examples of the substrate at this time include glass, a silicon wafer, amorphous silicon, polycrystalline silicon, ceramic, sapphire, and a metal material. A resist pattern is formed on these substrates by the same method as the above-described resist pattern forming method. Thereafter, the substrate is subjected to a sandblasting process in which a blast material is sprayed from the formed resist pattern and cut to a desired depth, and a resist pattern portion remaining on the substrate is removed from the substrate with an alkali stripping solution or the like. The base material which has a fine uneven | corrugated pattern on it can be manufactured. A known material can be used as the blasting material used in the above-mentioned sandblasting process. For example, fine particles having a particle size of about 2 μm to 100 μm, such as SiC, SiO ₂ , Al ₂ O ₃ , CaCO ₃ , ZrO, glass, and stainless steel, are used. It is done.

<Manufacture of semiconductor packages>
A semiconductor package can be manufactured by using a wafer on which a large-scale integrated circuit (LSI) has been formed as a substrate and forming a resist pattern on the wafer by the above-described resist pattern forming method, followed by the following steps. First, a step of forming a conductor pattern by performing columnar plating such as copper or solder on the opening exposed by development is performed. Thereafter, a peeling process for peeling the resist pattern by the same method as the above-described method for manufacturing a printed wiring board is performed, and further, a thin metal layer other than the columnar plating is removed by etching. A semiconductor package is obtained.

  In addition, the photosensitive resin composition of the present embodiment is used for the manufacture of printed wiring boards, the manufacture of lead frames for mounting IC chips, the manufacture of metal foils such as the manufacture of metal masks, ball grid arrays (BGA), or chip sizes.・ Manufacture of packages such as packages (CSP), manufacture of tape substrates such as chip-on-film (COF) or tape automated bonding (TAB), manufacture of semiconductor bumps, flats such as ITO electrodes or address electrodes, electromagnetic wave shields, etc. It can be used for manufacturing a partition wall of a panel display.

  Below, it shows about the preparation method of the sample for evaluation of Examples 1-14 and Comparative Examples 1-6, and the evaluation method and evaluation result about the obtained sample.

1. Production of Evaluation Sample The photosensitive resin laminates in Examples 1 to 14 and Comparative Examples 1 to 6 were produced as follows.

<Preparation of photosensitive resin laminate>
A photosensitive resin composition solution prepared by blending the compounds shown in Table 1 in the composition ratios shown in Tables 2 and 3 (units are parts by mass), and sufficiently stirring and mixing them, is a 16 μm thick polyethylene terephthalate as a support. The film was uniformly coated on the surface of the film using a bar coater and dried for 3 minutes in a dryer at 95 ° C. to form a photosensitive resin layer. The thickness of the photosensitive resin layer was 33 μm.

  In addition, in the composition shown to Table 2 and 3, the mass part of P-1 and P-2 is solid content.

  Next, a 22 μm thick polyethylene film was laminated as a protective layer on the surface of the photosensitive resin layer on which the polyethylene terephthalate film was not laminated to obtain a photosensitive resin laminate.

<Preparation of photosensitive resin laminate sample for hue stability evaluation>
After the photosensitive resin composition solution prepared by blending the compounds shown in Table 1 in the composition ratios (unit: parts by mass) shown in Tables 2 and 3 and sufficiently stirring and mixing them at a temperature of 40 ° C. for 3 days, Then, it was uniformly applied to the surface of a 16 μm-thick polyethylene terephthalate film as a support using a bar coater. This was dried in a dryer at 95 ° C. for 3 minutes to form a photosensitive resin layer. The thickness of the photosensitive resin layer was 33 μm.

  Next, a 22 μm thick polyethylene film was bonded as a protective layer on the surface of the photosensitive resin layer on which the polyethylene terephthalate film was not laminated to obtain a photosensitive resin laminate sample for evaluating hue stability.

<Board surface preparation>
As a substrate for evaluating peeling time, h-ray sensitivity, and hue stability, a 0.4 mm thick copper clad laminate on which 35 μm rolled copper foil was laminated, and this was roughened with a CPE-900 surface treatment solution. Processed.

<Laminate>
While peeling the polyethylene film of the photosensitive resin laminate, it was laminated at a roll temperature of 105 ° C. with a hot roll laminator (Asahi Kasei Co., Ltd., AL-70) on a copper clad laminate that had been leveled and preheated to 60 ° C. The air pressure was 0.35 MPa, and the laminating speed was 1.5 m / min.

<Exposure>
It exposed by the direct drawing type exposure method using the direct drawing type exposure apparatus (Nippon Orbotech Co., Ltd. make, Paragon9000, main wavelength 355nm).
Moreover, the direct drawing type exposure apparatus (Hitachi Via Co., Ltd. make, DE-1DH, main wavelength 405nm) was used for the exposure for evaluating h-line sensitivity.

<Development>
After the polyethylene terephthalate film is peeled off, a 1 mass% Na ₂ CO ₃ aqueous solution at 30 ° C. is sprayed for a predetermined time using an alkali developing machine (produced by Fuji Kiko Co., Ltd., a dry film developing machine), and an unexposed portion of the photosensitive resin layer Was removed by dissolution in a time twice as long as the minimum development time. At this time, the minimum time required for completely dissolving the photosensitive resin layer in the unexposed portion was defined as the minimum development time.

2. Evaluation Method 2.1 Weight Average Molecular Weight In this specification, the weight average molecular weight is measured by gel permeation chromatography (GPC) using a calibration curve of polystyrene (for example, Shodex STANDARD SM-105 manufactured by Showa Denko KK). Weight average molecular weight. A weight average molecular weight can be measured on condition of the following, for example using JASCO Corporation gel permeation chromatography.
Differential refractometer: RI-1530
Pump: PU-1580
Degasser: DG-980-50
Column oven: CO-1560
Column: KF-8025, KF-806M × 2, KF-807 in order
Eluent: THF

2.2 Evaluation of Peeling Time Using a substrate that has passed 15 minutes after the treatment described in <Laminate>, a rectangular pattern of 5 cm × 6 cm was formed by a direct drawing type exposure apparatus (Nippon Orbotech Co., Ltd., Paragon 9000, main wavelength 355 nm). It exposed and developed by the method demonstrated in said <development>. However, the exposure amount was set to such a value that the number of remaining film limit stages becomes 7 when exposed by the same exposure machine using a stove 21-step tablet as a mask and developed by the method described in <Development> above. The cured resist on the obtained substrate was immersed in 55 ° C. and 3% by mass of NaOH, and the time until the resist was completely peeled from the substrate was measured and defined as the peeling time.

2.3 Evaluation of hue stability (difference in transmittance at 600 nm)
The polyethylene film was peeled from the photosensitive resin laminate, and the light transmittance at a wavelength of 600 nm was measured using an ultraviolet-visible (UV-vis) spectrometer (manufactured by Shimadzu Corporation, UV-240).
Using the transmittance of a sample for hue stability evaluation of a photosensitive resin laminate produced using a photosensitive resin composition solution stored at a temperature of 40 ° C. for 3 days, and the photosensitive resin composition solution before storage The transmittance of the produced photosensitive resin laminate was compared.

2.4 Evaluation of h-ray sensitivity Using the substrate that has passed 15 minutes after the processing described in the above <laminate>, the direct drawing type exposure apparatus (DE-1DH, manufactured by Hitachi Via Co., Ltd.) using a stove 21-step tablet as a mask. It was exposed at an exposure amount of 10mJ ^/ cm ² ~35mJ ^/ cm 2 by using a dominant wavelength 405 nm). Thereafter, development was performed by the method described in the above <Development>, and the exposure amount at which the remaining film limit step number at that time was 6 was defined as sensitivity.

2.5 Evaluation of Tenting Property A 1.6 mm-thick double-sided copper-clad laminate with 1008 through-holes having a diameter of 6 mm was surface-treated with a jet scrubbing machine. Lamination was performed on both surfaces by the method described in <Lamination> above, and both surfaces were exposed on the entire surface with a direct drawing type exposure apparatus (Nippon Orbotech Co., Ltd., Paragon 9000, main wavelength 355 nm). The number of tent holes torn when developed by the method described in <Development> above was measured, and the tear rate for all tent holes was calculated.

2.6 Exposure contrast evaluation The photosensitive resin laminate sample was vacuum-adsorbed on the stage of a direct drawing type exposure apparatus (Nippon Orbotech Co., Ltd., Paragon 9000, main wavelength 355 nm) with the polyethylene terephthalate film laminated side up. Exposure was performed at 20 mJ / cm ² . The polyethylene film was peeled off from the photosensitive resin laminate after the exposure, and the transmittance of light having a wavelength of 600 nm was measured using a UV-vis spectrometer (manufactured by Shimadzu Corporation, UV-240). The difference between this value and the transmittance of light having a wavelength of 600 nm of the sample obtained by peeling the polyethylene film from the photosensitive resin laminate before exposure was calculated.

  The evaluation results of Examples 1 to 14 and Comparative Examples 1 to 6 are shown in Tables 2 and 3. In addition, Table 4 shows the evaluation criteria for each evaluation.

From the above results, the following contents can be read.
(1) This example, in which an acridine compound and a specific amount of leuco crystal violet are blended, is a photosensitive resin composition that is superior to the comparative example in terms of peeling time, hue stability, and exposure contrast.
(2) From the comparison between Examples 8 to 12 and Examples 13 to 14, when the weight average molecular weight of the addition polymerizable monomer is 700 to 1,200, a photosensitive resin composition having further excellent tent properties is realized. Is done.
(3) From the comparison between Example 3 and Example 7, when 9-phenylacridine is contained as an acridine compound, a photosensitive resin composition having further excellent h-line sensitivity is realized.
(4) From the comparison between Example 8 and Example 9, when basic green 1 is further included, a photosensitive resin composition having further excellent contrast or hue stability is realized.
(5) From the comparison between Examples 10, 11, 13 and Examples 12, 14, (b) As an addition polymerizable monomer, an average of 2 moles of propylene oxide and an average of 15 moles of ethylene oxide were added to both sides of bisphenol A, respectively. When the added polyalkylene glycol dimethacrylate is included, a photosensitive resin composition having excellent tent properties can be realized.

  The above-mentioned photosensitive resin composition, etc. are used for the manufacture of printed wiring boards, the manufacture of lead frames for mounting IC chips, the precision processing of metal foils such as the manufacture of metal masks, the manufacture of packages such as BGA or CSP, COF or TAB, etc. It can be used for the production of tape substrates, semiconductor bumps, ITO or address electrodes, and flat panel display partitions such as electromagnetic wave shields.

Claims (8)

  A photosensitive resin composition comprising (a) an alkali-soluble polymer, (b) an addition polymerizable monomer, (c) a photopolymerization initiator, and (d) leuco crystal violet, the photosensitive resin composition comprising: The (c) acridine compound is contained as a photopolymerization initiator, and the content of the (d) leuco crystal violet in the photosensitive resin composition is 0. 0 with respect to the total solid content of the photosensitive resin composition. The said photosensitive resin composition which is 6 mass%-1.6 mass%.   The photosensitive resin composition according to claim 1, wherein the (b) addition polymerizable monomer has a weight average molecular weight of 700 to 1,200.   The photosensitive resin composition according to claim 1, wherein the acridine compound is 9-phenylacridine.   The photosensitive resin composition according to claim 1, further comprising Basic Green 1. As the (b) addition polymerizable monomer, the following general formula (I):

{In the formula:
R ³ and R ⁴ are each independently H or CH ₃ ;
A is C ₂ H ₄ , B is C ₃ H ₆ , and the sequence of repeating units of-(AO)-and-(B-O)-is a block even if it is random. In the case of a block, either-(A-O)-or-(B-O)-may be on the bisphenol A group side;
r and s are each independently an integer from 1 to 29, and r + s is an integer from 2 to 40; and x and y are each independently an integer from 0 to 29, and x + y is from 0 to 30. Is an integer. }
The photosensitive resin composition of any one of Claims 1-4 containing the compound represented by these.   A photosensitive resin laminate comprising a photosensitive resin layer comprising the photosensitive resin composition according to any one of claims 1 to 5 laminated on a support.   A pattern forming method comprising the steps of laminating the photosensitive resin laminate according to claim 6 on a substrate, exposing and developing.   A method for forming a circuit board, comprising: laminating the photosensitive resin laminate according to claim 6 on a base material, exposing, developing, and etching.