JP2011186208A - Photosensitive resin composition - Google Patents

Abstract

Photosensitive resin composition and photosensitivity capable of forming a resist pattern with excellent adhesion to a substrate, good image-forming properties, and little composition exudation and sublimation products even when used for a long time A resin laminate is provided.
SOLUTION: (A) Alkali-soluble resin having a weight average molecular weight of 400 to 500,000 30 to 70% by mass, (B) 20 to 60% by mass of a compound curable by light or heat, (C) Photopolymerization initiator 0 2 to 1% by mass, (C) the photopolymerization initiator contains a hexaarylbiimidazole compound in a proportion of 0.2 to 0.8% by mass with respect to the entire photosensitive resin composition, (A), The ratio which added (B) and (C) is 98.5 mass% or more of the whole photosensitive resin composition, The photosensitive resin composition characterized by the above-mentioned.
[Selection figure] None

Description

  The present invention relates to a photosensitive resin composition and a laminate, and relates to a method for producing a resist pattern that has excellent adhesion and generates less sublimates.

  As the electronic material or the display material, a fine structure material using a photosensitive resist pattern is widely used. For example, a resist pattern based on a resin such as polyamic acid, which is relatively excellent in forming a thick film, is used for a protective film or an interlayer insulating film of a semiconductor element (Patent Document 1). In addition, in a touch panel or the like, there is an example in which a photosensitive resist pattern is used as a spacer between two opposing electrodes (Patent Document 2). There is also an example in which a photosensitive resist pattern prepared by blending red, yellow, and blue pigments is used as a thick film black matrix (Patent Document 3).

  In general, when a photosensitive resist pattern is used as a permanent pattern for an electronic material or a display material, the adhesion between the resist pattern and the substrate is excellent, the image forming property is good, and even if used for a long time, from the resist pattern A resist pattern in which there is little exudation and sublimation of the composition is preferred. In addition, even when it does not remain in the electronic material or display material as a permanent pattern, for example, when a photosensitive resist pattern is used for gold plating, elution into the plating solution and generation of sublimates occur so that the plating solution does not change. Less is desirable. In addition, when the photosensitive resin layer is laminated on the substrate by laminating the photosensitive resin laminate, the unexposed photosensitive resin layer is heated by the lamination. If there are many sublimated substances, the apparatus or clean room may be contaminated. For example, hexaarylbiimidazole is used as the photopolymerization initiator of the photosensitive resin laminate (Patent Document 4), but there is no knowledge about the photopolymerization initiator exuding or sublimating.

JP 2008-197158 A JP 2008-233289 A JP 2008-304710 A Special table 2002-507004 gazette

  The object of the present invention is to provide a resist pattern that has excellent adhesion to a substrate, good image forming properties, little exudation of composition and sublimation products even when used for a long time, and good plating resistance and plating properties. It is providing the photosensitive resin composition and photosensitive resin laminated body which can be formed.

  By using a specific photosensitive resin composition, the inventor of the present application has excellent adhesion between a resist pattern and a substrate, good image formation, and exudation of the composition from the resist pattern even when used for a long time. It was also found that a resist pattern with less sublimation products can be formed. That is, the present invention is as follows.

  [1] (A) Alkali-soluble resin having a weight average molecular weight of 400 to 500,000 30 to 70 mass; (B) 20 to 60 mass% of a compound that is cured by light or heat; and (C) a photopolymerization initiator 0. A photosensitive resin composition containing 2 to 1% by mass, wherein (C) the photopolymerization initiator is in a ratio of 0.2 to 0.8% by mass with respect to the entire photosensitive resin composition. The total of (A) the alkali-soluble resin, (B) the compound that is cured with light or heat, and (C) the photopolymerization initiator is 98.5% by mass or more of the entire photosensitive resin composition. The photosensitive resin composition, characterized in that it is present.

  [2] The photosensitive resin composition according to [1], further including (D) a leuco dye in a proportion of 0.01 to 1% by mass with respect to the entire photosensitive resin composition.

  [3] The photosensitive resin composition according to [1] or [2], wherein (B) the compound that is cured by light or heat includes a compound having bisphenol A modified with alkylene oxide and having (meth) acryloyl groups at both ends. object.

  [4] Any of [1] to [3], wherein the compound (B) that is cured by light or heat contains a polyalkylene oxide di (meth) acrylate compound containing at least an ethylene oxide group and a propylene oxide group in the compound. The photosensitive resin composition as described in 2.

  [5] Any of [1] to [4], further comprising (E) a colorant having an absorption maximum at 550 to 700 nm in a proportion of 0.01 to 1% by mass relative to the whole photosensitive resin composition. The photosensitive resin composition as described in 2.

  [6] Any of [1] to [5], further comprising (F) a colorant having an absorption maximum at 400 to 550 nm in a ratio of 0.01 to 1% by mass with respect to the entire photosensitive resin composition. The photosensitive resin composition as described in 2.

（式中、Ｒ^１およびＲ^２は、各々独立に、直鎖もしくは分岐アルキル基、アルキル置換もしくは無置換フェニル基、シクロヘキシル基、カルボニル基、カルボニル基を介した直鎖もしくは分岐アルキル基、置換もしくは無置換フェニル基である。Ｒ^３およびＲ^４は、各々独立に、水素、水酸基、シクロヘキシル基、直鎖もしくは分岐アルキル基、置換もしくは無置換フェニル基、ＮＨ基を介して直鎖もしくは分岐アルキル基、アルキル置換もしくは無置換フェニル基、シクロヘキシル基、アミド基を介した直鎖もしくは分岐アルキル基、置換もしくは無置換フェニル基を表す。）
で表される構造である、［１］〜［６］のいずれかに記載の感光性樹脂組成物。 [7] (E) A colorant having an absorption maximum at 550 to 700 nm is represented by the following formula (I):

(Wherein R ¹ and R ² each independently represents a linear or branched alkyl group, an alkyl-substituted or unsubstituted phenyl group, a cyclohexyl group, a carbonyl group, a linear or branched alkyl group via a carbonyl group, a substituted or R ³ and R ⁴ are each independently hydrogen, a hydroxyl group, a cyclohexyl group, a linear or branched alkyl group, a substituted or unsubstituted phenyl group, and a linear or branched alkyl group via an NH group. Represents an alkyl-substituted or unsubstituted phenyl group, a cyclohexyl group, a linear or branched alkyl group via an amide group, or a substituted or unsubstituted phenyl group.)
The photosensitive resin composition in any one of [1]-[6] which is a structure represented by these.

（式中、Ｒ^５は水素または炭素数１〜４のアルキル基、Ｒ^６は水素、水酸基、カルボキシル基、ハロゲン基、炭素数１〜４のアルキル基、置換基を有してもよいアミノ基、置換基を有してもよいアミド基、ニトロ基、スルホニル基を表す。）
で表される基を有する、［１］〜［７］のいずれかに記載の感光性樹脂組成物。 [8] (F) A colorant having an absorption maximum at 400 to 550 nm is represented by the following formula (II):

(Wherein R ⁵ is hydrogen or an alkyl group having 1 to 4 carbon atoms, R ⁶ is hydrogen, a hydroxyl group, a carboxyl group, a halogen group, an alkyl group having 1 to 4 carbon atoms, or an amino group which may have a substituent. Represents an amide group, a nitro group or a sulfonyl group which may have a substituent.
The photosensitive resin composition in any one of [1]-[7] which has group represented by these.

  [9] The photopolymerization initiator according to any one of [1] to [8], wherein the (C) photopolymerization initiator further includes a pyrazoline derivative at a ratio of 0.01 to 1% by mass with respect to the entire photosensitive resin composition. Photosensitive resin composition.

  [10] A photosensitive resin laminate in which a photosensitive resin layer made of the photosensitive resin composition according to any one of [1] to [9] is laminated on at least a support layer.

  [11] A pattern forming method including a step of laminating the photosensitive resin laminate according to [10] to a substrate, an exposure step, and a development step.

  By using the photosensitive resin composition of the present invention, a resist pattern having excellent adhesion between a resist pattern and a substrate, good image forming properties, few sublimation products, and good plating resistance and plating properties is formed. it can.

  The present invention will be described in detail. In the present invention, (A) an alkali-soluble resin having an acid equivalent of 100 to 600 and a weight average molecular weight of 400 to 500,000 is 30 to 70% by mass; (B) a compound 20 to 60 that is cured by light or heat. And (C) a photosensitive resin composition containing 0.2 to 1% by mass of a photopolymerization initiator, wherein (C) the photopolymerization initiator is 70% of (C) the total photopolymerization initiator. The total of the photosensitive resin composition comprises a hexaarylbiimidazole compound in a proportion of mass% or more, and (A) an alkali-soluble resin, (B) a compound that is cured by light or heat, and (C) a photopolymerization initiator. It is the said photosensitive resin composition characterized by being 98.5 mass% or more.

First, (C) the photopolymerization initiator will be described.
In the present invention, (C) the photopolymerization initiator alone absorbs light having an exposure wavelength, cures the photosensitive resin composition, and makes it insoluble in the developer, and alone the photosensitive resin composition. However, the effect of the photopolymerization initiator is promoted by using it in combination with the photopolymerization initiator. However, in the present invention, (D) leuco dye is not included in (C) the photopolymerization initiator.

  (C) Photopolymerization initiators include quinones, aromatic ketones, acetophenones, acylphosphine oxides, benzoin or benzoin ethers, dialkyl ketals, thioxanthones, dialkylaminobenzoic acid esters, oxime esters , Acridines, hexaarylbiimidazole, pyrazoline derivatives, N-arylamino acids or ester compounds thereof, and halogen compounds.

  As quinones, 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2 , 3-dimethylanthraquinone, 3-chloro-2-methylanthraquinone and the like.

  Examples of aromatic ketones include benzophenone, Michler's ketone [4,4′-bis (dimethylamino) benzophenone], 4,4′-bis (diethylamino) benzophenone, and 4-methoxy-4′-dimethylaminobenzophenone. be able to.

  Examples of acetophenones include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, and 1- (4 -Dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenylketone, 2-benzyl- Mention may be made of 2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1. Examples of commercially available products include Irgacure 907, Irgacure 369, and Irgacure 379 manufactured by Ciba Specialty Chemicals.

  Examples of acylphosphine oxides include 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phosphine oxide, and bis (2,6-dimethoxybenzoyl) -2. , 4,4-trimethyl-pentyl phosphine oxide and the like. Commercially available products include Lucilin TPO manufactured by BASF and Irgacure 819 manufactured by Ciba Specialty Chemicals.

  Examples of benzoin or benzoin ethers include benzoin, benzoin ethyl ether, benzoin phenyl ether, methyl benzoin, and ethyl benzoin.

  Examples of dialkyl ketals include benzyl dimethyl ketal and benzyl diethyl ketal.

  Examples of thioxanthones include 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone.

  Examples of the dialkylaminobenzoates include ethyl dimethylaminobenzoate, ethyl diethylaminobenzoate, ethyl-p-dimethylaminobenzoate, 2-ethylhexyl-4- (dimethylamino) benzoate and the like.

  Examples of the oxime esters include 1-phenyl-1,2-propanedione-2-O-benzoyloxime and 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime. Commercially available products include CGI-325, Irgacure OXE01, and Irgacure OXE02 manufactured by Ciba Specialty Chemicals.

  Examples of acridines include 1,7-bis (9,9′-acridinyl) heptane, 9-phenylacridine, 9-methylacridine, 9-ethylacridine, 9-chloroethylacridine, 9-methoxyacridine, 9- Ethoxyacridine, 9- (4-methylphenyl) acridine, 9- (4-ethylphenyl) acridine, 9- (4-n-propylphenyl) acridine, 9- (4-n-butylphenyl) acridine, 9- ( 4-tert-butylphenyl) acridine, 9- (4-methoxyphenyl) acridine, 9- (4-ethoxyphenyl) acridine, 9- (4-acetylphenyl) acridine, 9- (4-dimethylaminophenyl) acridine, 9- (4-chlorophenyl) acridine, 9- (4-bromophenyl) acrylic Gin, 9- (3-methylphenyl) acridine, 9- (3-tert-butylphenyl) acridine, 9- (3-acetylphenyl) acridine, 9- (3-dimethylaminophenyl) acridine, 9- (3- Diethylaminophenyl) acridine, 9- (3-chlorophenyl) acridine, 9- (3-bromophenyl) acridine, 9- (2-pyridyl) acridine, 9- (3-pyridyl) acridine, 9- (4-pyridyl) acridine Can be mentioned.

  Examples of hexaarylbiimidazole include 2- (o-chlorophenyl) -4,5-diphenylbiimidazole, 2,2 ′, 5-tris- (o-chlorophenyl) -4- (3,4-dimethoxyphenyl) -4 ', 5'-diphenylbiimidazole, 2,4-bis- (o-chlorophenyl) -5- (3,4-dimethoxyphenyl) -diphenylbiimidazole, 2,4,5-tris- (o-chlorophenyl) ) -Diphenylbiimidazole, 2- (o-chlorophenyl) -bis-4,5- (3,4-dimethoxyphenyl) -biimidazole, 2,2′-bis- (2-fluorophenyl) -4,4 ′ , 5,5′-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2′-bis- (2,3-difluoromethylphenyl) -4,4 ′, 5 5'-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,4-difluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl)- Biimidazole, 2,2′-bis- (2,5-difluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2′-bis- (2 , 6-difluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2′-bis- (2,3,4-trifluorophenyl) -4, 4 ', 5,5'-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,3,5-trifluorophenyl) -4,4', 5,5'-tetrakis -(3-methoxyphenyl) Biimidazole, 2,2′-bis- (2,3,6-trifluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2′-bis -(2,4,5-trifluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,4,6-tri Fluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2′-bis- (2,3,4,5-tetrafluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,3,4,6-tetrafluorophenyl) -4,4', 5,5'- Tetrakis- (3-methoxyphenyl) -biimidazole And 2,2′-bis- (2,3,4,5,6-pentafluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -biimidazole and the like. .

  Examples of the pyrazoline derivative include 1- (4-tert-butyl-phenyl) -3-styryl-5-phenyl-pyrazoline, 1-phenyl-3- (4-tert-butyl-styryl) -5- (4- tert-butyl-phenyl) -pyrazoline, 1,5-bis- (4-tert-butyl-phenyl) -3- (4-tert-butyl-styryl) -pyrazoline, 1- (4-tert-octyl-phenyl) -3-styryl-5-phenyl-pyrazoline, 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-ethoxy-phenyl) -pyrazoline, 1-phenyl-3- (4-tert- Octyl-styryl) -5- (4-tert-octyl-phenyl) -pyrazoline, 1,5-bis- (4-tert-octyl-phenyl) -3 (4-tert-octyl-styryl) -pyrazoline, 1- (4-dodecyl-phenyl) -3-styryl-5-phenyl-pyrazoline, 1-phenyl-3- (4-dodecyl-styryl) -5- (4 -Dodecyl-phenyl) -pyrazoline, 1- (4-dodecyl-phenyl) -3- (4-dodecyl-stynyl) -5- (4-dodecyl-phenyl) -pyrazoline, 1- (4-tert-octyl-phenyl) ) -3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1- (4-tert-butyl-phenyl) -3- (4-tert-octyl-styryl) ) -5- (4-tert-octyl-phenyl) -pyrazoline, 1- (4-dodecyl-phenyl) -3- (4-tert-butyl-styryl) -5 (4-tert-butyl-phenyl) -pyrazoline, 1- (4-tert-butyl-phenyl) -3- (4-dodecyl-styryl) -5- (4-dodecyl-phenyl) -pyrazoline, 1- (4 -Dodecyl-phenyl) -3- (4-tert-octyl-styryl) -5- (4-tert-octyl-phenyl) -pyrazoline, 1- (4-tert-octyl-phenyl) -3- (4-dodecyl) -Styryl) -5- (4-dodecyl-phenyl) -pyrazoline, 1- (2,4-dibutyl-phenyl) -3- (4-dodecyl-styryl) -5- (4-dodecyl-phenyl) -pyrazoline, 1-phenyl-3- (3,5-di-tert-butyl-styryl) -5- (3,5-di-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (2 , 6-Di-tert-butyl-styryl) -5- (2,6-di-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (2,5-di-tert-butyl-styryl)- 5- (2,5-di-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (2,6-di-n-butyl-styryl) -5- (2,6-di-n-butyl) -Phenyl) -pyrazoline, 1- (3,4-di-tert-butyl-phenyl) -3-styryl-5-phenyl-pyrazoline, 1- (3,5-di-tert-butyl-phenyl) -3- Styryl-5-phenyl-pyrazoline, 1- (4-tert-butyl-phenyl) -3- (3,5-di-tert-butyl-phenyl) -5-phenyl-pyrazoline, 1- (3,5-di -Tert-butyl-phenyl -3- (3,5-di-tert-butyl-styryl) -5- (3,5-di-tert-butyl-phenyl) -pyrazoline, 1- (4- (5-tert-butyl-benzoxazole) 2-yl) phenyl) -3-styryl-5-phenyl-pyrazoline, 1- (4- (benzoxazol-2-yl) phenyl) -3- (4-tert-butyl-styryl) -5- (4- tert-butyl-phenyl) -pyrazoline, 1- (4- (4-tert-butyl-benzoxazol-2-yl) phenyl) -3- (4-tert-butyl-styryl) -5- (4-tert- Butyl-phenyl) -pyrazoline, 1- (4- (5-tert-octyl-benzoxazol-2-yl) phenyl) -3-styryl-5-phenyl-pyrazoline, 1- ( -(Benzoxazol-2-yl) phenyl) -3- (4-tert-octyl-styryl) -5- (4-tert-octyl-phenyl) -pyrazoline, 1- (4- (5-tert-octyl-) Benzoxazol-2-yl) phenyl) -3- (4-tert-octyl-styryl) -5- (4-tert-octyl-phenyl) -pyrazoline, 1- (4- (5-dodecyl-benzoxazole-2) -Yl) phenyl) -3-styryl-5-phenyl-pyrazoline, 1- (4- (benzoxazol-2-yl) phenyl) -3- (4-dodecyl-styryl) -5- (4-dodecyl-phenyl) ) -Pyrazoline, 1- (4- (5-dodecyl-benzoxazol-2-yl) phenyl) -3- (4-dodecyl-stynyl) -5- (4-do) Decyl-phenyl) -pyrazoline, 1- (4- (5-tert-octyl-benzoxazol-2-yl) phenyl) -3- (4-tert-butyl-styryl) -5- (4-tert-butyl- Phenyl) -pyrazolin, 1- (4- (5-tert-butyl-benzoxazol-2-yl) phenyl) -3- (4-tert-octyl-styryl) -5- (4-tert-octyl-phenyl) -Pyrazoline, 1- (4- (5-dodecyl-benzoxazol-2-yl) phenyl) -3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1 -(4- (5-tert-butyl-benzoxazol-2-yl) phenyl) -3- (4-dodecyl-styryl) -5- (4-dodecyl-fe L) -pyrazoline, 1- (4- (5-dodecyl-benzoxazol-2-yl) phenyl) -3- (4-tert-octyl-styryl) -5- (4-tert-octyl-phenyl) -pyrazoline 1- (4- (5-tert-octyl-benzooxazol-2-yl) phenyl) -3- (4-dodecyl-styryl) -5- (4-dodecyl-phenyl) -pyrazoline, 1- (4- (4,6-dibutyl-benzoxazol-2-yl) phenyl) -3- (4-dodecyl-styryl) -5- (4-dodecyl-phenyl) -pyrazoline, 1- (4- (benzoxazole-2- Yl) phenyl) -3- (3,5-di-tert-butylstyryl) -5- (3,5-di-tert-butyl-phenyl) -pyrazoline, 1- (4- (benzoo) Sazol-2-yl) phenyl) -3- (2,6-di-tert-butyl-styryl) -5- (2,6-di-tert-butyl-phenyl) -pyrazoline, 1- (4- (benzo Oxazol-2-yl) phenyl) -3- (2,5-di-tert-butyl-styryl) -5- (2,5-di-tert-butyl-phenyl) -pyrazoline, 1- (4- (benzo Oxazol-2-yl) phenyl) -3- (2,6-di-n-butyl-styryl) -5- (2,6-di-n-butyl-phenyl) -pyrazoline, 1- (4- (4 , 6-Di-tert-butyl-benzoxazol-2-yl) phenyl) -3-styryl-5-phenyl-pyrazoline, 1- (4- (5,7-di-tert-butyl-benzoxazol-2-yl) Yl) phenyl) -3-s Tyryl-5-phenyl-pyrazolin, 1- (4- (5-tert-butyl-benzoxazol-2-yl) phenyl) -3- (3,5-di-tert-butyl-styryl) -5-phenyl- Pyrazoline, 1- (4- (4,6-di-tert-butyl-benzoxazol-2-yl) phenyl) -3- (3,5-di-tert-butyl-styryl) -5- (3,5 -Di-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-amino-phenyl) -pyrazoline, 1-phenyl-3- (4-tert -Butyl-styryl) -5- (4-N-ethyl-phenyl) -pyrazoline and 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-N, N-diethyl-phenyl) - it includes the pyrazoline.

  Further, for example, 1-phenyl-3- (4-biphenyl) -5- (4-n-butyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-tert-butyl) -Phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-isobutyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-n-pentyl) -Phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-isopentyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-neopentyl-phenyl) ) -Pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-hexyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-hept Ru-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-n-octyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4- tert-octyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-nonyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4- Decyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-undecyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-dodecyl- Phenyl) -pyrazoline.

  Among them, from the viewpoint of adhesion and rectangularity of the resist pattern, 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (4-Biphenyl) -5- (4-tert-butyl-phenyl) -pyrazoline and 1-phenyl-3- (4-biphenyl) -5- (4-tert-octyl-phenyl) -pyrazoline are preferred.

  It is preferable that a pyrazoline derivative is 0.01-1 mass% with respect to 100 mass% of solid content of the photosensitive resin composition. 0.01 mass% or more is preferable from the viewpoint of sensitivity, and 1 mass% or less is preferable from the viewpoint of adhesion. More preferably, it is 0.01-0.3 mass%, More preferably, it is 0.01-0.2 mass%.

  Examples of N-aryl amino acids or ester compounds thereof include N-phenylglycine, methyl ester of N-phenylglycine, ethyl ester of N-phenylglycine, n-propyl ester of N-phenylglycine, and isopropyl of N-phenylglycine. Ester, 1-butyl ester of N-phenylglycine, 2-butyl ester of N-phenylglycine, tert-butyl ester of N-phenylglycine, pentyl ester of N-phenylglycine, hexyl ester of N-phenylglycine, N-phenyl Examples include pentyl ester of glycine and octyl ester of N-phenylglycine. In particular, N-phenylglycine is preferable because of its high sensitizing effect. As for N-aryl amino acid or its ester compound, 0.001-0.1 mass% is preferable with respect to 100 mass% of solid content of the photosensitive resin composition. More preferably, it is 0.01-0.08 mass%.

  Examples of the halogen compound include 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, chlorinated triazine compounds, diallyl iodonium compounds, and the like. It is done.

  (C) 0.2-1 mass% of photoinitiators are contained with respect to 100 mass% of solid content of the photosensitive resin composition. It is 0.2% by mass or more from the viewpoint of practical photosensitivity and adhesion of the resist pattern, and 1% by mass or less from the viewpoint of sublimation from the resist pattern. 0.4-0.8 mass% is more preferable, and 0.5-0.8 mass% is further more preferable.

  (C) A photoinitiator contains a hexaaryl biimidazole compound in the ratio of 0.2-0.8 mass% with respect to 100 mass% of total solid content of the photosensitive resin composition. The amount is preferably 0.2% by mass or more from the viewpoint of the adhesion of the resist pattern and the rectangularity of the resist pattern, and is 0.8% by mass or less from the viewpoint of generation of sublimates from the resist pattern. More preferably, it is 0.2-0.6 mass%, More preferably, it is 0.2-0.4 mass%. Furthermore, the ratio of the hexaarylbiimidazole compound is preferably 60% by mass or more of the total amount of the (C) photopolymerization initiator. 60 mass% or more is preferable from a viewpoint of resolution, the relative amount of a sublimate, plating resistance, and plating property. The ratio of the hexaarylbiimidazole compound is more preferably 70% by mass or more. More preferably 75% by mass or more. Since the photopolymerization initiator is easily one-electron-oxidized and reduced, if bleeding and sublimation occur, the electronic material or other members in the display material may be reduced and oxidized, which is not preferable. One of the objects of the present invention is to provide a resist pattern that is suitably used for an electronic material or a display material by defining the total amount of the photopolymerization initiator at a specific ratio and further including the specific photopolymerization initiator at a specific ratio. It is to make it possible to produce. Among the hexaarylbiimidazole compounds, 2- (o-chlorophenyl) -4,5-diphenylbiimidazole is preferable.

Next, (A) the alkali-soluble resin will be described.
(A) The alkali-soluble resin having a weight average molecular weight of 400 to 500,000 refers to a resin having a weight average molecular weight of 400 to 500,000 that is dispersed or soluble in an alkaline aqueous solution. So long as it is dispersible or soluble in an alkaline aqueous solution, it may be soluble in other liquids. Vinyl resin containing carboxyl group, polyvinyl alcohol and derivatives thereof, polyvinyl ether, polyhydroxystyrene and derivatives thereof, polyamic acid resin and derivatives thereof, novolac resin and derivatives thereof, cellulose and derivatives thereof, ethylene oxide of bisphenol A, propylene oxide C4 or more alkylene oxide modified compounds and esters thereof, ether compounds, bisphenol A ethylene oxide and propylene oxide modified compounds, bisphenol S, F derivatives, phthalates such as diethyl phthalate, citric acid derivatives, polyethylene glycol and the like Esters, ether compounds, polypropylene glycol and its esters, ether compounds, polypropylene glycol and poly Block copolymers and random copolymers of ethylene glycol, may be mentioned polyalkylene glycols and esters thereof which are polymers having 4 or more alkylene glycol atoms, ether compounds, sorbitan ester derivatives, and the like. Among these, from the viewpoints of solubility in an organic solvent, film-forming properties in the case of a photosensitive resin laminate, and laminating properties, a vinyl resin containing a carboxyl group is preferable. For example, it is a copolymer such as (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylonitrile, (meth) acrylamide, and styrene.

  (A) The alkali-soluble resin preferably contains a carboxyl group, and the acid equivalent is preferably from 100 to 600. The acid equivalent means the mass of an alkali-soluble resin having 1 equivalent of a carboxyl group therein. The acid equivalent is more preferably 250 or more and 450 or less. The acid equivalent is 100 or more from the viewpoint of improving development resistance and improving resolution and adhesion, and is 600 or less from the viewpoint of improving developability and peelability. The acid equivalent is measured by a potentiometric titration method using Hiranuma automatic titrator (COM-555) manufactured by Hiranuma Sangyo Co., Ltd. and 0.1 mol / L sodium hydroxide.

  (A) The weight average molecular weight of the alkali-soluble resin is preferably 1,000 or more and 500,000 or less. The weight average molecular weight of the alkali-soluble resin is 500,000 or less from the viewpoint of improving the developability, and the properties of the development aggregate, the unfused film such as the edge fuse property and the cut chip property when the photosensitive resin laminate is used. It is 400 or more from the viewpoint of the property. The edge fuse property refers to a phenomenon in which the photosensitive resin composition layer protrudes from the end surface of the roll when the photosensitive resin laminate is wound into a roll. The cut chip property is the phenomenon that the chip flies when the unexposed film is cut with a cutter. If the chip adheres to the top surface of the photosensitive resin laminate, it is transferred to the mask during the subsequent exposure process, etc. It becomes. The weight average molecular weight is 400 or more from the viewpoint of suppressing the phenomenon that the alkali-soluble resin exudes from the protective layer. The weight average molecular weight of the alkali-soluble resin is more preferably 1,000 or more and 300,000 or less, more preferably 5,000 or more and 200,000 or less, and still more preferably 20,000 or more and 100,000 or less. Most preferably, it is 40,000 or more and 70,000 or less. The weight average molecular weight was measured by Gel Permeation Chromatography (GPC) manufactured by JASCO Corporation (pump: Gulliver, PU-1580 type, column: Shodex (registered trademark) manufactured by Showa Denko KK (KF-807, KF-806M). , KF-806M, KF-802.5) in series, moving bed solvent: tetrahydrofuran, polystyrene standard sample (use of calibration curve by Shodex STANDARD SM-105 manufactured by Showa Denko KK) as polystyrene conversion.

  The alkali-soluble resin is preferably a copolymer composed of at least one of the first monomers described below and at least one of the second monomers described below.

  The first monomer is a carboxylic acid or acid anhydride having one polymerizable unsaturated group in the molecule. Examples include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, and maleic acid half ester. Particularly preferred is (meth) acrylic acid. Here, (meth) acryl refers to acryl and / or methacryl. The same applies hereinafter.

  The second monomer is a non-acidic monomer having at least one polymerizable unsaturated group in the molecule. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl ( (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, vinyl alcohol esters such as vinyl acetate, (meth) Examples include acrylonitrile, styrene, and styrene derivatives. Among these, methyl (meth) acrylate, n-butyl (meth) acrylate, styrene, 2-ethylhexyl (meth) acrylate, and benzyl (meth) acrylate are preferable. From the viewpoint of adhesion of the resist pattern, benzyl (meth) acrylate is preferred.

  The copolymerization ratio of the first monomer and the second monomer is preferably 10 to 60% by mass of the first monomer and 40 to 90% by mass of the second monomer. More preferably, the first monomer is 15 to 35% by mass, and the second monomer is 65 to 85% by mass.

  Preferred combinations of the first monomer and the second monomer include the following combinations. That is, butyl acrylate, methyl methacrylate, methacrylic acid copolymer, styrene, methyl methacrylate, methacrylic acid copolymer, styrene, benzyl methacrylate, methacrylic acid copolymer, benzyl methacrylate, methacrylic acid A copolymer, a benzyl methacrylate, 2-ethylhexyl acrylate, a copolymer of methacrylic acid, etc. can be mentioned. A combination of benzyl methacrylate, 2-ethylhexyl acrylate, and a copolymer of methacrylic acid is preferable from the viewpoint of imparting appropriate flexibility to the resist pattern and obtaining adhesion.

  (A) The compounding quantity of alkali-soluble resin is the range of 30-70 mass% with respect to 100 mass% of total solids of the photosensitive resin composition, Preferably it is 40-60 mass%. From the viewpoint of development time, it is 70% by mass or less, and from the viewpoint of edge fuse property, it is 30% by mass or more.

Next, (B) a compound that is cured by light or heat will be described.
(B) As a compound curable by light or heat, a compound having an ethylenically unsaturated double bond, a compound having a conjugated diene moiety, a compound having a maleimide moiety, a thiol compound curable by an ene-thiol reaction, an epoxy compound, an acid Examples thereof include compounds having a group that crosslinks by action.

  Examples of the compound having a conjugated diene moiety include compounds in which a substituent is introduced into butadiene, isoprene, etc. to make it non-volatile, polyacetylene and its derivatives, polyphenylacetylene, and the like. Examples of the compound having a maleimide moiety include a polymer compound having a maleimide group in the side chain, a compound having two or more maleimide groups in the molecule, and a compound having a (meth) acryloyl group and a maleimide group in the molecule. it can. Examples of thiol compounds that cure by the ene-thiol reaction include pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakis (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3, Examples thereof include compounds having an aliphatic thiol group such as 5-triazine-2,4,6 (1H, 3H, 5H) -trione. Examples of the epoxy compound include an epoxy-modified novolak resin, an epoxy-modified cresol novolak resin, an epoxy-modified bisphenol A, and an epoxy-modified bisphenol A modified with ethylene oxide or propylene oxide. be able to.

As the compound having a group capable of crosslinking by the action of an acid, an amino compound such as a melamine resin, a urea resin, a guanamine resin, a glycoluril-formaldehyde resin, a succinylamide-formaldehyde resin, or an ethyleneurea-formaldehyde resin can be used. In particular, alkoxymethylated amino resins such as alkoxymethylated melamine resins and alkoxymethylated urea resins can be suitably used. The alkoxymethylated amino resin, for example, reacts a condensate obtained by reacting melamine or urea with formalin in a boiling aqueous solution with lower alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, and isopropyl alcohol. To form an ether, and then the reaction solution is cooled and precipitated. Specific examples of the alkoxymethylated amino resin include methoxymethylated melamine resin, ethoxymethylated melamine resin, propoxymethylated melamine resin, butoxymethylated melamine resin, methoxymethylated urea resin, ethoxymethylated urea resin, and propoxymethyl. And urea-oxygenated resin, butoxymethylated urea resin, and the like. The said alkoxymethylated amino resin can be used individually or in combination of 2 or more types. Methoxymethylated melamine resins, ethoxymethylated melamine resins, propoxymethylated melamine resins or butoxymethylated melamine resins are preferred.
Examples of the alkoxymethylated melamine resin include Nicarax MX-750, Nicarak MX-706, Nicarak MX-101, Nicarak MX-032, Nicarax MX-708, Nicarac MX-40, Nicarac MX-31, Nicarac MS-11, Nicarac MW. -22, Nicarak MW-30, MW-30HM, MW-100LM, Nicarac MW-390 (all manufactured by Sanwa Chemical Co., Ltd.) and the like. These may be used alone or in combination of two or more species. MX-290 (manufactured by Sanwa Chemical Co., Ltd.) is exemplified as the alkoxymethylated urea resin.

  It is preferable that the compound which has an ethylenically unsaturated double bond is included from a sclerosing | hardenable viewpoint. It is more preferable to include a compound having an acryloyl group in the molecule from the viewpoint of curability and compatibility with the alkali-soluble resin.

  For example, a compound in which (meth) acrylic acid is added to one end of polyalkylene oxide or a compound in which (meth) acrylic acid is added to one end and the other end is converted to an alkyl ether or allyl ether Can do.

  As such a compound, phenoxyhexaethylene glycol mono (meth) acrylate, which is a (meth) acrylate of a compound obtained by adding polyethylene glycol to a phenyl group, or polypropylene glycol added with an average of 2 mol of propylene oxide and an average of 7 mol of 4-Normal nonylphenoxyheptaethylene glycol dipropylene glycol (meth) acrylate, which is a (meth) acrylate of a compound obtained by adding polyethylene glycol with addition of ethylene oxide to nonylphenol, average of 5 with polypropylene glycol with addition of 1 mol of propylene oxide on average 4-normal nonyl which is a (meth) acrylate of a compound obtained by adding polyethylene glycol added with moles of ethylene oxide to nonylphenol E Bruno carboxymethyl pentaethylene glycol monopropylene glycol (meth) acrylate. Examples also include 4-normal nonylphenoxyoctaethylene glycol (meth) acrylate (manufactured by Toagosei Co., Ltd., M-114), which is an acrylate of a compound obtained by adding polyethylene glycol with an average of 8 moles of ethylene oxide added to nonylphenol.

  For example, a compound having a (meth) acryloyl group at both ends of an alkylene oxide chain or a compound having a (meth) acryloyl group at both ends of an alkylene oxide chain in which an ethylene oxide chain and a propylene oxide chain are bonded randomly or in blocks. be able to.

  Examples of such compounds include tetraethylene glycol di (meth) acrylate, pentaethylene glycol di (meth) acrylate, hexaethylene glycol di (meth) acrylate, heptaethylene glycol di (meth) acrylate, and octaethylene glycol di (meth). Examples thereof include acrylates, nonaethylene glycol di (meth) acrylate, decaethylene glycol di (meth) acrylate, and compounds having (meth) acryloyl groups at both ends of 12 moles of ethylene oxide chain. Furthermore, a polyalkylene oxide di (meth) acrylate compound containing at least an ethylene oxide group and a propylene oxide group in the compound is preferable from the viewpoints of resolution, flexibility, and plating resistance. From the same viewpoint, the molecular weight is preferably 600-1500. More preferably, it is 900-1300, More preferably, it is 1000-1200. As a polyalkylene oxide di (meth) acrylate compound containing at least an ethylene oxide group and a propylene oxide group in the compound, for example, an average of 3 moles of ethylene oxide was added to both ends of polypropylene glycol added with an average of 12 moles of propylene oxide. Examples include glycol dimethacrylate and glycol dimethacrylate obtained by adding an average of 15 moles of ethylene oxide to both ends of polypropylene glycol with an average of 18 moles of propylene oxide added.

  A compound in which bisphenol A is modified with alkylene oxide and has (meth) acryloyl groups at both ends is preferred from the viewpoints of adhesion and plating resistance. Examples of the alkylene oxide modification include ethylene oxide modification, propylene oxide modification, butylene oxide modification, pentylene oxide modification, and hexylene oxide modification. A compound having bisphenol A modified with ethylene oxide and having (meth) acryloyl groups at both ends is preferred. As such a compound, for example, 2,2-bis (4-((meth) acryloxydiethoxy) phenyl) propane (NK ester BPE-200 manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis (4-((meth) acryloxytriethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetraethoxy) phenyl) propane, 2,2-bis (4-((meth) acrylic) Roxypentaethoxy) phenyl) propane (NK ester BPE-500 manufactured by Shin-Nakamura Chemical Co., Ltd.), 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) acryloxynonaethoxy) 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 2,2-bis (4-((meth) acryloxypolyether) such as 2-bis (4-((meth) acryloxyhexadecaethoxy) phenyl) propane ) Phenyl) propane and the like.

  Furthermore, di (meth) acrylate of polyalkylene glycol obtained by adding an average of 2 mol of propylene oxide and an average of 6 mol of ethylene oxide to both ends of bisphenol A, or an average of 2 mol of propylene oxide and an average of 15 respectively at both ends of bisphenol A Preference is also given to compounds modified with ethylene oxide and propylene oxide, such as di (meth) acrylates of polyalkylene glycols to which a molar amount of ethylene oxide has been added. The number of moles of ethylene oxide in the compound having a (meth) acryloyl group at both ends modified with alkylene oxide of bisphenol A is preferably 10 to 30 moles from the viewpoint of adhesion, plating resistance and flexibility. 20 mol or less is more preferable.

  For example, a compound having more than two (meth) acryloyl groups in one molecule has 3 moles or more of a group capable of adding an alkylene oxide group in the molecule as a central skeleton, and includes an ethylene oxide group and a propylene oxide group. Alternatively, alcohol obtained by adding an alkylene oxide group such as butylene oxide can be obtained as (meth) acrylate. Examples of compounds that can be a central skeleton include glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, and isocyanurate rings.

  Examples of such compounds include trimethylolpropane EO3 mol-modified triacrylate, trimethylolpropane EO6 mol-modified triacrylate, trimethylolpropane EO9 mol-modified triacrylate, trimethylolpropane EO12 mol-modified triacrylate, and the like. Can do. Examples of such compounds include glycerol EO3 mol-modified triacrylate (A-GLY-3E manufactured by Shin-Nakamura Chemical Co., Ltd.), glycerol EO9 mol-modified triacrylate (Shin-Nakamura Chemical Industry Co., Ltd. A-GLY-). 9E), EO 6 mol PO6 mol modified triacrylate of glycerin (A-GLY-0606PE), EO 9 mol PO9 mol modified triacrylate of glycerin (A-GLY-0909PE). As such compounds, pentaerythritol 4EO-modified tetraacrylate (SR-494 manufactured by Sartomer Japan Co., Ltd.), pentaerythritol 35EO-modified tetraacrylate (NK Nakamura Chemical Co., Ltd. NK ester ATM-35E) ).

  In addition to the above compounds, the following compounds can be included as appropriate. For example, 1,6-hexanediol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, 2-di (p-hydroxyphenyl) propanedi (meth) acrylate, 2,2-bis [(4- (Meth) acryloxypolypropyleneoxy) phenyl] propane, 2,2-bis [(4- (meth) acryloxypolybutyleneoxy) phenyl] propane, glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, Polyoxypropyltrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane triglycidyl ether tri (meth) acrylate, β-hydroxypropyl-β '-(acryloyloxy) propyl Examples thereof include tartrate, nonylphenoxypolypropylene glycol (meth) acrylate, nonylphenoxypolybutylene glycol (meth) acrylate, and polypropylene glycol mono (meth) acrylate. Furthermore, the following urethane compounds are also mentioned. For example, hexamethylene diisocyanate, tolylene diisocyanate or diisocyanate compound (for example, 2,2,4-trimethylhexamethylene diisocyanate) and a compound having a hydroxyl group and a (meth) acryl group in one molecule, for example, 2-hydroxypropyl Examples thereof include urethane compounds with acrylates and oligopropylene glycol monomethacrylates. Specifically, there is a reaction product of hexamethylene diisocyanate and oligopropylene glycol monomethacrylate (Nippon Yushi Co., Ltd., Blenmer PP1000). In addition, diisocyanate or di (tri) acrylate of isocyanurate modified with polypropylene glycol or polycaprolactone is also included. Moreover, the urethane oligomer obtained by making the terminal of the urethane compound obtained as a polyaddition product of a diisocyanate and a polyol react with the compound which has an ethylenically unsaturated double bond and a hydroxyl group etc. can be mentioned, for example.

(B) The compounding quantity of the compound hardened | cured with light or a heat | fever is 20-60 mass% with respect to 100 mass% of total solid content of the photosensitive resin composition. (B) The compounding quantity of the compound hardened | cured with light or a heat | fever is 20 mass% or more from a viewpoint of a sensitivity, resolution, and adhesiveness, and is 60 mass% or less from a viewpoint of resolution and adhesiveness. Also from the viewpoint of film physical properties of an unexposed film when coated on a support film to form a dry film, it is 60% by mass or less, and more preferably 30 to 45% by mass.
A resin that is cured by light or heat and is dispersed or soluble in an alkaline aqueous solution is (A) an alkali-soluble resin when the weight average molecular weight is 5000 or more, and a resin having a weight average molecular weight of less than 5000 ( B) A compound that is cured by light or heat.

  The ratio of (A) the alkali-soluble resin, (B) the compound that is cured by light or heat, and (C) the photopolymerization initiator is 98.5% by mass or more of the entire photosensitive resin composition. From the viewpoint of the relative amount of the sublimate, plating resistance, and plating property, it is 98.5% by mass or more, and more preferably 98.8% by mass or more.

  The photosensitive resin composition of the present invention preferably further contains (D) a leuco dye. A leuco dye is a colorless intermediate of a triphenylmethane dye and is also called a leuco base (see Iwanami Shoten, “Iwanami Physical Dictionary, 5th Edition”, page 1505).

  Examples of the leuco dye include tris (4-dimethylaminophenyl) methane, tris (4-diethylaminophenyl) methane, bis (4-diethylaminophenyl)-(4-diethylamino-2-methylphenyl) methane, and bis (4- Diethylamino-2-methylphenyl)-(4-diethylaminophenyl) methane, bis (1-ethyl-2-methylindol-3-yl) -phenylmethane, (4-dimethylamino-2-methoxyphenyl) -bis (4 -Dimethylaminophenyl) methane, (4-dimethylamino-2-ethoxyphenyl) -bis (4-dimethylaminophenyl) methane, (4-dimethylamino-2-butoxyphenyl) -bis (4-dimethylaminophenyl) methane , (4-Dimethylamino-2-chlorophenyl) -bi (4-dimethylaminophenyl) methane, (4-dimethylamino-2-fluorophenyl) -bis (4-dimethylaminophenyl) methane, (4-diethylamino-2-methoxyphenyl) -bis (4-diethylaminophenyl) methane (4-diethylamino-2-ethoxyphenyl) -bis (4-diethylaminophenyl) methane, (4-diethylamino-2-isopropoxyphenyl) -bis (4-diethylaminophenyl) methane, (4-diethylamino-2-butoxy Phenyl) -bis (4-diethylaminophenyl) methane, (4-diethylamino-2-hexyloxyphenyl) -bis (4-diethylaminophenyl) methane, (4-diethylamino-2-octyloxyphenyl) -bis (4-diethylamino) Phenyl) Tan, (4-diethylamino-2-dodecyloxyphenyl) -bis (4-diethylaminophenyl) methane, (4-diethylamino-2-benzyloxyphenyl) -bis (4-diethylaminophenyl) methane, (4-diethylamino-2) -Chlorophenyl) -bis (4-diethylaminophenyl) methane, (4-diethylamino-2-fluorophenyl) -bis (4-diethylaminophenyl) methane, (4-dimethylamino-2-methoxyphenyl) -bis (4-diethylamino) Phenyl) methane, (4-dimethylamino-2-ethoxyphenyl) -bis (4-diethylaminophenyl) methane, (4-diethylamino-2-methoxyphenyl) -bis (4-dimethylaminophenyl) methane, (4-diethylamino) -2-Ethoxy Phenyl) -bis (4-dimethylaminophenyl) methane, (4-piperidylino-2-ethoxyphenyl) -bis (4-dimethylaminophenyl) methane,

[4- (1-pyrrolidinyl) -2-ethoxyphenyl] -bis (4-diethylaminophenyl) methane, (4-morpholino-2-ethoxyphenyl) -bis (4-dimethylaminophenyl) methane, (4-piperidylino- 2-ethoxyphenyl) -bis (4-dimethylaminophenyl) methane, [4- (1-pyrrolidinyl) -2-ethoxyphenyl] -bis (4-diethylaminophenyl) methane, (4-morpholino-2-ethoxyphenyl) -Bis (4-diethylaminophenyl) methane, (4-N-ethyl-Np-tolylamino-2-ethoxyphenyl) -bis (4-diethylaminophenyl) methane, (4-N-ethyl-N-phenylamino-) 2-ethoxyphenyl) -bis (4-diethylaminophenyl) methane, (4-diphenyl) Amino-2-ethoxyphenyl) - bis (4-diethylamino-phenyl) methane, (4-diethylamino-2-benzyloxyphenyl) - bis (4-dimethylaminophenyl) methane, and the like. Of these, tris (4-dimethylaminophenyl) methane is preferable from the viewpoints of sensitivity and mask line width reproducibility of the resist pattern. Tris (4-dimethylaminophenyl) methane is also called leuco crystal violet.

  (D) It is preferable that the compounding quantity of a leuco dye is 0.01-1 mass% with respect to 100 mass% of solid content of the photosensitive resin composition. 0.01 mass% or more is preferable from an adhesive viewpoint, and 1 mass% or less is preferable from a mask line width reproducibility viewpoint of a resist pattern. 0.05-0.8 mass% is more preferable, and 0.1-0.6 mass% is further more preferable.

The photosensitive resin composition of the present invention preferably contains (E) a colorant having an absorption maximum at 550 to 700 nm.
In the present invention, the absorption maximum is confirmed as follows.
In the present invention, (A) 60 parts of an alkali-soluble resin, (B) 40 parts of a compound that is cured by light or heat, and (E) 0.1 part of a colorant are uniformly mixed at a solid content of 50% by mass using methyl ethyl ketone as a solvent. . The obtained resin composition solution is uniformly applied to a PET film with a bar coater. The film thickness is adjusted to 50 um after drying. The transmittance of the obtained film is measured for each wavelength in the range of 400 to 700 nm, and the wavelength having the largest absorption is taken as the absorption maximum.

  (E) Examples of the colorant having an absorption maximum at 550 to 700 nm include a blue or green colorant. For example, α type copper phthalocyanine blue, α type monochloro copper phthalocyanine blue, β type copper phthalocyanine blue, ε type copper phthalocyanine blue, cobalt phthalocyanine blue, metal free phthalocyanine blue dye, Examples thereof include pigments, anthraquinone dyes or pigments such as aminoanthraquinone, and triphenylmethane dyes or pigments such as diamond green, Victoria pure blue, and malachite green.

The following can be cited by using the color index (CI; issued by The Society of Dyers and Colorists).
Pigment Blue 15, Pigment Blue 15: 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4, Pigment Blue 15: 6, Pigment Blue 16, Pigment Blue 60, as dye system Solvent Blue 35, Solvent Blue 63, Solvent Blue 68, Solvent Blue 70, Solvent Blue 83, Solvent Blue 87, Solvent Blue 94, Solvent Blue 97, Solvent Blue 122, Solvent Blue 136, Solvent Blue 67, Solvent Blue 70, etc. Can be used.

  In addition, Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28, etc. can be used as a green pigment or dye. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.

  The colorant having an absorption maximum at (E) 550 to 700 nm in the present invention is preferably nonionic from the viewpoint of sublimation and transmittance stability after baking.

  The colorant having an absorption maximum at (E) 550 to 700 nm in the present invention is represented by the following formula (I) from the viewpoints of sublimation, colorability, and storage stability:

(Wherein R ¹ and R ² each independently represents a linear or branched alkyl group, an alkyl-substituted or unsubstituted phenyl group, a cyclohexyl group, a carbonyl group, a linear or branched alkyl group via a carbonyl group, a substituted or R ³ and R ⁴ are each independently hydrogen, a hydroxyl group, a cyclohexyl group, a linear or branched alkyl group, a substituted or unsubstituted phenyl group, and a linear or branched alkyl group via an NH group. And an anthraquinone dye described in (1) represents a linear or branched alkyl group or a substituted or unsubstituted phenyl group via an alkyl-substituted or unsubstituted phenyl group, a cyclohexyl group or an amide group.

R ¹ and R ² are preferably an alkyl-substituted or unsubstituted phenyl group, and more preferably an alkyl-substituted phenyl group, from the viewpoints of sublimation, colorability, and storage stability. R ³ and R ⁴ are preferably hydrogen or a hydroxyl group.

  (E) It is preferable that the compounding quantity of the coloring agent which has an absorption maximum in 550-700 nm is 0.01-1 mass% with respect to 100 mass% of solid content of the photosensitive resin composition. 0.01 mass% or more is preferable from a viewpoint of coloring property, and 1 mass% or less is preferable from a viewpoint of a sensitivity, sublimation property, and storage stability. 0.01-0.5 mass% is more preferable. 0.05-0.2 mass% is further more preferable.

  The photosensitive resin composition of the present invention preferably contains (F) a colorant having an absorption maximum at 400 to 550 nm. (F) Examples of the colorant having an absorption maximum at 400 to 550 nm include yellow, orange, and red colorants. Examples of yellow colorants include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, anthraquinone, and the like.

(Anthraquinone)
Solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 108, Pigment Yellow 193, Pigment Yellow 147, Pigment Yellow 199, Pigment Yellow 202
(Isoindolinone series)
Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185
(Condensed azo)
Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 180
(Benz imidazolone)
Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 181
(Monoazo)
PigmentYellow 1,2,3,4,5,6,9,10,12,61,62,62: 1,65,73,74,75,97,100,104,105,111,116,167,168,169,182,183,
(Disazo)
PigmentYellow12,13,14,16,17,55,63,81,83,87,126,127,152,170,172,174,176,188,198

Examples of red colorants include monoazo, disazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone. Specific examples include the following: It is done.
(Monoazo)
Pigment Red 1,2,3,4,5,6,8,9,12,14,15,16,17,21,22,23,31,32,112,114,146,147,151,170,184,187,188,193,210,245,253,258,266,267,268,269,
(Disazo series)
Pigment Red 37,38,41
(Monoazo lake)
Pigment Red 48: 1,48: 2,48: 3,48: 4,49: 1,49: 2,50: 1,52: 1,52: 2,53: 1,53: 2,57: 1, 58: 4,63: 1,63: 2,64: 1,68
(Benz imidazolone)
Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208
(Perylene)
Solvent Red 135, Solvent Red 179, Pigment Red 123, Pigment Red 149, Pigment Red 166, Pigment Red 178, Pigment Red 179, Pigment Red 190, Pigment Red 194, Pigment Red 224
(Diketopyrrolopyrrole)
Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, Pigment Red 272
(Condensed azo)
Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221 and Pigment Red 242
(Anthraquinone)
Pigment Red 168, Pigment Red 177, Pigment Red 216, Solvent Red 149, Solvent Red 150, Solvent Red 52, Solvent Red 207
(Quinacridone series)
Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209

  The following orange colorants are CI pigment orange 1, CI pigment orange 5, CI pigment orange 13, CI pigment orange 14, CI pigment orange 16, CI pigment orange 17, CI pigment orange 24 and CI pigment orange. 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, CI Pigment Orange 51, CI Pigment Orange 61, CI Pigment Orange 63, CI Pigment Orange 64, CI pigment orange 71, and CI pigment orange 73.

  In the present invention, (F) the colorant having an absorption maximum at 400 to 550 nm is preferably nonionic from the viewpoints of sublimation and transmittance stability after baking.

  Among these, the following formula (II):

(Wherein R ⁵ is hydrogen or an alkyl group having 1 to 4 carbon atoms, R ⁶ is hydrogen, a hydroxyl group, a carboxyl group, a halogen group, an alkyl group having 1 to 4 carbon atoms, or an amino group which may have a substituent. Represents an amide group, a nitro group or a sulfonyl group, which may have a substituent, and a compound having a group represented by:

Sensitivity, coloring property, from the viewpoint of storage stability, R ⁶ is hydroxyl, R ⁶ is preferably an alkyl group. From the viewpoint of sublimability, it is preferable that two or more groups represented by formula (II) are present in one molecule of (F) colorant. For example, examples of the colorant (F) having an absorption maximum at 400 to 550 nm include compounds represented by the following formulas (III), (IV), and (V).

(F) It is preferable that the compounding quantity of the coloring agent which has an absorption maximum in 400-550 nm is 0.01-1 mass% with respect to 100 mass% of solid content of the photosensitive resin composition. 0.01 mass% or more is preferable from a viewpoint of coloring property, and 1 mass% or less is preferable from a viewpoint of a sensitivity, sublimation property, and storage stability. 0.01-0.5 mass% is more preferable. 0.05-0.4 mass% is further more preferable.
From the viewpoint of colorability, the photosensitive resin composition preferably contains (E) a colorant having an absorption maximum at 550 to 700 nm and (F) a colorant having an absorption maximum at 400 to 550 nm.

  Further, in order to improve the thermal stability and storage stability of the photosensitive resin composition, the photosensitive resin composition is composed of radical polymerization inhibitors, benzotriazoles, carboxybenzotriazoles, and bisphenol A epoxy compounds. You may further contain the 1 or more types of compound chosen from the group which consists of.

  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. A nitrosophenylhydroxyamine aluminum salt is preferred from the viewpoint of not impairing sensitivity.

  Examples of benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3-benzotriazole, Bis (N-2-ethylhexyl) aminomethylene-1,2,3-tolyltriazole, bis (N-2-hydroxyethyl) aminomethylene-1,2,3-benzotriazole and the like can be mentioned.

  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, N- (N, N-di-2-ethylhexyl) aminoethylenecarboxybenzotriazole and the like.

  Examples of the bisphenol A epoxy compounds include compounds obtained by modifying bisphenol A with polypropylene glycol and epoxidizing the terminals.

  The total content of the radical polymerization inhibitor, benzotriazoles, carboxybenzotriazoles and epoxy compounds of bisphenol A is preferably 0.001 to 0.2% by mass with respect to the entire photosensitive resin composition, More preferably, it is 0.01-0.1 mass%. The content is preferably 0.001% by mass or more from the viewpoint of imparting storage stability to the photosensitive resin composition, and 0.1% by mass from the viewpoint of maintaining sensitivity and suppressing decolorization and color development of the dye. The following is more preferable.

  Another aspect of the present invention relates to a photosensitive resin laminate in which at least a support layer and a photosensitive resin layer made of the photosensitive resin composition are laminated.

  The photosensitive resin laminated body of this invention contains the photosensitive resin layer and support layer which consist of a photosensitive resin composition. If necessary, you may have a protective layer on the surface on the opposite side to the support layer side of the photosensitive resin layer. The support layer used here is preferably a transparent layer that transmits light emitted from the exposure light source. As such a support layer, for example, a polyethylene terephthalate film, a polyvinyl alcohol film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyvinylidene chloride film, a vinylidene chloride copolymer film, a polymethyl methacrylate copolymer film, Examples include polystyrene film, polyacrylonitrile film, styrene copolymer film, polyamide film, and cellulose derivative film. These films can be stretched if necessary. The haze is preferably 5 or less. More preferably, it is 1 or less, More preferably, it is 0.5 or less, Most preferably, it is 0.2 or less. The thinner the film, the more advantageous in terms of image formation and economy, but a film having a thickness of 10 to 30 μm is preferably used in order to maintain the strength.

  An important characteristic of the protective layer used for the photosensitive resin laminate is that the protective layer is sufficiently smaller than the support layer in terms of adhesion to the photosensitive resin layer and can be easily peeled off. For example, a polyethylene film or a polypropylene film can be preferably used as the protective layer. Also, 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 varies depending on the application, but is preferably 5 to 100 μm, more preferably 7 to 60 μm. The thinner the resolution is, the higher the film strength is. .

  When polyethylene is used for the protective layer, there is a gel called fish eye on the surface of the polyethylene film, which may be transferred to the photosensitive resin layer. When the fish eye is transferred to the photosensitive resin layer, air may be entrained during the lamination, resulting in voids, leading to a defect in the resist pattern. From the viewpoint of fisheye, the protective layer is preferably made of stretched polypropylene. A specific example is Alfane E-200A manufactured by Oji Paper Co., Ltd.

  A publicly known method can be adopted as a method for producing a photosensitive resin laminate by sequentially laminating a support layer, a photosensitive resin layer, and, if necessary, a protective layer. For example, the photosensitive resin composition used for the photosensitive resin layer is mixed with a solvent that dissolves the photosensitive resin composition to form a uniform solution, first applied onto the support layer using a bar coater or roll coater, and then dried to form a support film. A photosensitive resin layer made of a photosensitive resin composition can be laminated thereon.

  The thickness of the photosensitive resin layer after drying can be appropriately selected depending on the application. The thickness of the photosensitive resin layer after drying can be adjusted within a range of 10 to 200 μm when a die coater is used, and within a range of about 1 to 150 μm when a reverse roll coater is used. .

  The photosensitive resin laminate of the present invention can be produced by coating a photosensitive resin composition on a support layer and drying it, and then laminating a protective layer on the photosensitive resin layer.

  Examples of the solvent that dissolves the photosensitive resin composition include ketones typified by methyl ethyl ketone (MEK), alcohols typified by methanol, ethanol, and isopropanol. The solvent is appropriately selected and blended depending on the coating method and the desired film thickness. For example, when coating using a die coater, it is added to the photosensitive resin composition so that the viscosity of the solution of the photosensitive resin composition applied on the support layer is 500 to 4000 mPa · s at 25 ° C. It is preferable to do.

<Resist pattern formation method>
The resist pattern using the photosensitive resin laminate can be formed by a process including a laminating process for laminating, an exposing process for exposing active light, and a developing process for removing unexposed portions. Further, in consideration of the strength of the resist pattern and generation of sublimation, a baking process for heating the pattern at a constant temperature can be added.

Hereinafter, a specific example of the resist pattern forming method will be described.
As a substrate, a copper-clad laminate, a glass substrate on which transparent electrodes such as ITO and IZO are sputtered or deposited, a similar film substrate, a glass substrate coated with a dielectric paste, a silicon wafer, a glass on which amorphous silicon is deposited A wafer, a silicon wafer on which a metal thin film such as copper, tantalum, or molybdenum is sputtered can be used.

  In order to laminate the photosensitive resin on the substrate, first, a laminating process is performed using a laminator. When the photosensitive resin laminate has a protective layer, the protective layer is peeled off, and the photosensitive resin layer is laminated on the substrate surface by thermocompression bonding with a laminator. In this case, the photosensitive resin layer may be laminated only on one side of the substrate surface, or may be laminated on both sides. The heating temperature at this time is generally about 40 to 160 ° C. In addition, adhesion and chemical resistance are improved by performing the thermocompression bonding twice or more. For thermocompression bonding, a two-stage laminator provided with two rolls may be used, or it may be repeatedly crimped through a roll several times.

  Next, an exposure process is performed using an exposure machine. If necessary, the support layer is peeled off and exposed to active light through a photomask. The exposure amount is determined by the light source illuminance and the exposure time. The exposure amount may be measured using a light meter. Examples of the exposure machine include a scattered light exposure machine using an ultra-high pressure mercury lamp as a light source, a parallel light exposure machine with the same degree of parallelism, and a proximity exposure machine with a gap between the mask and the workpiece. Furthermore, a projection type exposure machine having a mask to image size ratio of 1: 1, a reduction projection exposure machine called a high illuminance stepper (registered trademark), or an exposure machine using a concave mirror called a mirror projection aligner (registered trademark). be able to.

  In the exposure process, a direct drawing exposure method may be used. Direct drawing exposure is a method in which a pattern is directly drawn and exposed on a substrate without using a photomask. As the light source, for example, a semiconductor laser having a wavelength of 350 to 410 nm or an ultrahigh pressure mercury lamp is used.

Next, a developing process is performed using a developing device. After the exposure, if there is a support film on the photosensitive resin layer, this is removed if necessary, and then the unexposed portion is developed and removed using a developer 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 used. The alkaline aqueous solution is appropriately selected according to the characteristics of the photosensitive resin layer, but a Na ₂ CO ₃ aqueous solution having a concentration of about 0.2 to 2% by mass and about 20 to 40 ° C. is generally used. A surface active agent, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like may be mixed in the alkaline aqueous solution. An amine-based alkaline aqueous solution such as a tetraammonium hydroxide (TMAH) aqueous solution can also be used in consideration of the influence on the substrate. The density can be appropriately selected according to the developing speed.

  Although a resist pattern can be obtained through each of the above steps, a heating step at about 100 to 300 ° C. can be further performed in some cases. By performing this heating step, it is possible to react a compound that is cured by unreacted light or heat in the resist pattern, or to sublimate a sublimable component before incorporating the resist pattern as a member. Moreover, chemical resistance is also improved by this heating step. For heating, a hot-air, infrared, or far-infrared heating furnace can be used.

<Conductor Pattern Manufacturing Method and Printed Wiring Board Manufacturing Method>
The printed wiring board can be obtained through the following steps following the resist pattern forming method using a copper-clad laminate or a flexible substrate as a substrate.

  First, the copper surface of the substrate exposed by development is etched or plated to produce a conductor pattern.

  Thereafter, the resist pattern is peeled from the substrate with an aqueous solution having alkalinity stronger than that of the developer to obtain a desired printed wiring board. The alkaline aqueous solution for peeling (hereinafter also referred to as “peeling solution”) is not particularly limited, but an aqueous solution of NaOH and / or KOH having a concentration of about 2 to 5% by mass and a temperature of about 40 to 70 ° C. is generally used. . A small amount of a water-soluble solvent can also be added to the stripping solution.

<Lead frame manufacturing method>
The lead frame can be obtained through the following steps following the above-described resist pattern forming method using a metal plate, for example, copper, a copper alloy, or an iron-based alloy as a substrate.

  First, a conductive pattern is formed by etching the substrate exposed by development. Thereafter, the resist pattern is peeled off by a method similar to the method for manufacturing a printed wiring board described above to obtain a desired lead frame.

<Production method of ITO electrode>
The ITO electrode can be obtained through the following steps following the above-described resist pattern forming method using a glass substrate or a film substrate on which an ITO film is formed as a base material.

  First, the ITO film exposed by development is etched. Etching solutions include iron chloride-based, oxalic acid-based, and mixed acid-based ones, which can be appropriately selected according to the film quality of the ITO film. After the etching, the desired electrode pattern can be obtained by peeling off by the same method as the above-described printed wiring board manufacturing method.

<Black matrix production method>
The black matrix can be obtained through the following steps following the above-described resist pattern forming method using a glass substrate on which glass or ITO film is formed.

  First, the resist pattern is baked together with the substrate. It can be baked by heating with a hot air drying oven or an infrared heater. Depending on the purpose, baking can be performed in an atmosphere other than air, such as nitrogen. After baking at a baking temperature and time according to the purpose, a black matrix can be obtained.

<Semiconductor bump manufacturing method>
The semiconductor bump can be produced by the following method.
An insulating layer is provided on the silicon wafer substrate, and electrodes for connecting to the silicon wafer are formed on necessary portions. Next, a conductive film such as copper is formed by a method such as sputtering.

  When a liquid resist is used, the liquid resist is spin-coated on the substrate thus obtained. The solvent is removed by pre-baking and drying is performed to obtain a resist coating film. Next, a pattern is formed by exposure and development. In the case of using a dry film, the pattern is formed by the same method as the above <Method for forming resist pattern>.

  Thereafter, plating is performed in the pattern, and examples of the pretreatment include a method of immersing in water or a plating solution itself. When forming a solder bump, a nickel film called an under bump metal is formed by plating in order to ensure adhesion with the bump, and solder is plated thereon by a plating method to form a bump. When forming a copper post, copper plating is performed in the pattern, and then a solder bump is formed. Examples of the plating bath used for plating include the following. Examples of the nickel plating bath include a watt bath and a sulfamic acid bath. As the solder plating bath, a bath of high lead, eutectic, lead-free or the like is selected according to the properties of the solder. As the copper plating bath, an electrolytic copper plating bath such as copper sulfate is generally used.

  After plating, the resist is stripped with a stripping solution. The stripping solution is composed of an alkali component such as ethanolamine, tetramethylammonium hydroxide (TMAH) or the like, an alkali component combining one or more organic alkalis, a highly polar water-soluble organic solvent such as glycol and dimethyl sulfoxide, water An organic stripping solution in combination of the above can be used. Copper plating is generally a plating bath such as copper sulfate.

  After removing the resist, the conductive film is removed by etching. For the etching, a known method using copper chloride or the like can be used. After the etching, the solder portion is heated by a heating process called reflow to produce a solder ball to be a semiconductor bump.

Hereinafter, examples of embodiments of the present invention will be specifically described.
(Examples 1-12, Comparative Examples 1-5)
First, a method for producing samples for evaluation of Examples and Comparative Examples will be described, and then an evaluation method and evaluation results for the obtained samples will be shown.

1. Production of Evaluation Samples Evaluation samples in Examples and Comparative Examples were produced as follows.
<Preparation of photosensitive resin laminate>
A photosensitive resin composition mixed solution obtained by sufficiently stirring and mixing a photosensitive resin composition and a solvent having a composition shown in the following Table 1 (however, each component number indicates a blending amount (part by mass) as a solid content). And coated uniformly on the surface of a 16 μm thick polyethylene terephthalate film (GR-16, manufactured by Teijin Films Ltd.) as a support using a bar coater, and dried for 5 minutes in a dryer at 95 ° C. for photosensitivity. A resin layer was formed. The thickness of the photosensitive resin layer was 45 μm.

  Next, a 20 μm thick polyethylene film (manufactured by Tamapoly Co., Ltd., GF-18) 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.

  Table 1 shows the names of the material components in the photosensitive resin composition preparation liquid, and Tables 2 and 3 show the blending amounts and evaluation results in the photosensitive resin composition preparation liquid.

2. Adhesion evaluation <Board>
A transparent conductive film (Toyobo Co., Ltd., 300R (125Ω, 20 nm)) obtained by sputtering ITO on the PET surface was used.

<Laminate>
While peeling the polyethylene film of the photosensitive resin laminate, lamination was performed at a roll temperature of 105 ° C. with a hot roll laminator (AL-700, manufactured by Asahi Kasei Electronics Co., Ltd.). The air pressure was 0.35 MPa, and the laminating speed was 1.5 m / min. It was.

<Exposure>
Using a chrome glass photomask, the number of steps remaining in the film when exposed through a stouffer 21-step step tablet with a high-precision exposure machine (EXM-1066-H-01, ghi line, 23 mW) manufactured by Oak Co., Ltd. It exposed with the exposure amount which will be 7 steps | paragraphs.

  In addition, the cross-beam pattern mask with the ratio of the width | variety of an exposed part and an unexposed part 1:10 was used for the chromium glass photomask. The gap between the chromium glass photomask and the photosensitive resin laminate was 100 μm.

<Development>
After peeling the polyethylene terephthalate film, a 0.4 mass% Na ₂ CO ₃ aqueous solution at 30 ° C. was sprayed and developed to dissolve and remove the unexposed portion of the photosensitive resin layer. At this time, the minimum time required for completely dissolving the photosensitive resin layer of the unexposed portion was measured as the minimum development time, and development was performed under the same conditions twice as long as the minimum development time to prepare a resist pattern. The minimum mask line width in which the resist pattern is normally formed is ranked as the adhesion value as follows.
A: Adhesion value is 20 μm or less.
○: Adhesion value exceeds 20 μm and 50 μm or less.
X: Adhesion value exceeds 50 μm.

3. Evaluation of Resolution A resist pattern was prepared in the same manner as in the evaluation of adhesion except that a striped pattern mask having a line / space ratio of 1/1 was used as the chromium glass photomask in the exposure.

The minimum mask line width in which the resist pattern is normally formed is ranked as the resolution value as follows.
A: The resolution value is 30 μm or less.
○: The resolution value exceeds 30 μm and is 40 μm or less.
(Triangle | delta): The value of resolution exceeds 40 micrometers and is 50 micrometers or less.
X: The value of resolution exceeds 50 μm.

4). Sublimation evaluation <Preparation of evaluation substrate>
The above 2. except that a chrome glass photomask is used. Similar to the adhesion evaluation, development was performed to prepare a solid pattern for evaluation. This was heat-treated in a hot air oven at 120 ° C./1 hour to produce an evaluation substrate.

<Sublimation evaluation>
The evaluation substrate was cut into 2 mm × 5 mm, heated with a pyrolyzer (made by FRONTIER LAB, DOUBLE SHOT PYROLYZER), and the generated sublimate was connected to gas chromatography (Agilent Technologies, 6890N Network GC System 30). And continuously monitored by a FID detector. The pyrolyzer condition was 100 ° C. to 10 ° C./min. The interface temperature was 300 ° C. The conditions for gas chromatography were detection of sublimates for 15 minutes at an injection temperature of 350 ° C. and a column oven temperature of 350 ° C. The temperature of the FID detector is 370 ° C., and the flow rate of the carrier gas (He) is 2.0 m / min. It was.

The detection time is output on the horizontal axis and the FID detection intensity is output on the vertical axis, and the integrated value of the detection intensity over the entire detection time is defined as the amount of generated sublimation. The sublimate generation amount of the composition used in Example 1 was set to 1, and the sublimate generation amount of each Example and Comparative Example was calculated as a relative amount, and the following determination was made based on the value.
(Double-circle): The value of a sublimate generation amount relative value is 1.5 or less.
○: The value of the sublimate generation amount relative value exceeds 1.5 and is 3 or less.
X: The value of the sublimate generation amount relative value exceeds 3.

5. Transmittance <Production of evaluation substrate>
The above 2. except that a chrome glass photomask is used. Similar to the adhesion evaluation, development was performed to prepare a solid pattern for evaluation. This was heat-treated at 200 ° C. for 1 hour using a hot air oven to produce an evaluation substrate.

<Colorability evaluation>
The absorbance of the evaluation substrate was measured with a spectrophotometer (manufactured by Hitachi High-Technologies Corporation, U3010), the difference from the base material was determined, and the value obtained by converting this to the transmittance was defined as the transmittance of the resist pattern. The transmittance at wavelengths of 400 nm to 700 nm was obtained every 1 nm, and the averaged value was defined as the transmittance average value, and the colorability was determined as follows.
A: The average transmittance value is 40% or less.
○: The transmittance average value exceeds 40% and is 60% or less.
Δ: The transmittance average value exceeds 60%.

6). Gold plating <Substrate>
A copper clad laminate having a copper thickness of 35 μm and a plate thickness of 1.2 mm was used.

<Laminate>
While peeling the polyethylene film of the photosensitive resin laminate, lamination was performed at a roll temperature of 105 ° C. with a hot roll laminator (AL-700, manufactured by Asahi Kasei Electronics Co., Ltd.). The air pressure was 0.35 MPa, and the laminating speed was 1.5 m / min. It was.

<Exposure>
Exposure amount such that the number of remaining films becomes 7 when exposed through a stouffer 21-step tablet with a high-precision exposure machine (HMW-201KB) manufactured by Oak Co., Ltd. using a film mask for electrode circuits. And exposed.

<Development>
After the polyethylene terephthalate film was peeled off, a 0.4 mass% Na ₂ CO ₃ aqueous solution at 30 ° C. was sprayed and developed for twice the minimum increase time to dissolve and remove unexposed portions of the photosensitive resin layer.

<Electrolytic gold plating>
Degreasing step: The evaluation substrate after development was immersed in a commercially available acid degreasing solution at 40 ° C. for 4 minutes.
Acid immersion step: Subsequently, the substrate was immersed in 10% sulfuric acid at room temperature for 1 minute.
Electrolytic nickel plating: plating was performed at 60 ° C. for 15 minutes using a Watt bath (pH 4.0). The plating film thickness was 5 μm.
Electrolytic gold plating: Plating was performed at 55 ° C. for 4 minutes using a gold-cobalt plating bath (manufactured by Kojima Chemical Co., Ltd., K-750, pH 4.2). The plating film thickness was 1 μm.
It was confirmed whether or not there was peeling of the resist pattern after plating. The same samples as those used in Examples 1 to 11 and Comparative Examples 1 to 6 were used as evaluation samples.

<Plating resistance evaluation>
○: No peeling of the resist pattern is observed after plating.
Δ: Partial peeling of the resist pattern was observed after plating.
X: Most of the resist pattern was peeled off after plating.

<Plating evaluation>
The cured resist Watts bath (pH 4.0) used in the electroless nickel plating was immersed so that 0.04 m ^2/500 ml, and heated at 80 ° C. 24 hours. Gold used in electroless gold plating - cobalt plating bath (Kojima Chemicals Co., Ltd., K-750, pH4.2) was immersed cured resist so that 0.04 m ^2/500 ml, and heated at 80 ° C. 24 hours . Plating was performed in the same manner as the plating resistance evaluation except that the electrolytic nickel plating bath and the electrolytic gold plating bath thus obtained were used.

The obtained plated substrates were observed and ranked as follows.
○: Gloss is seen on the entire plating. Uniform film thickness.
(Triangle | delta): Gloss is not seen in a part of plating. Uniform film thickness.
X: The film thickness is not uniform.

  The present invention is excellent in adhesion between the resist pattern and the substrate, and since there are few exudation and sublimation products of the composition from the resist pattern, it is suitable as a resist pattern for gold plating or a permanent pattern in an electronic material or display material. Used.

Claims (11)

  (A) Alkali-soluble resin having a weight average molecular weight of 400 to 500,000 30 to 70% by mass; (B) 20 to 60% by mass of a compound curable by light or heat; and (C) a photopolymerization initiator 0.2 to 0.2%. A photosensitive resin composition containing 1% by mass, wherein (C) the photopolymerization initiator is a hexaarylbiimidazole compound in a proportion of 0.2 to 0.8% by mass with respect to the entire photosensitive resin composition. And (A) the alkali-soluble resin, (B) the compound that is cured by light or heat, and (C) the photopolymerization initiator is 98.5% by mass or more of the entire photosensitive resin composition. The said photosensitive resin composition characterized by the above-mentioned.   The photosensitive resin composition of Claim 1 which further contains (D) leuco dye in the ratio of 0.01-1 mass% with respect to the said whole photosensitive resin composition.   (B) The photosensitive resin composition of Claim 1 or 2 in which the compound hardened | cured by light or a heat | fever contains the compound which modified | denatured bisphenol A by alkylene oxide and has a (meth) acryloyl group in the both terminal.   (B) The compound hardened | cured with light or a heat | fever contains the polyalkylene oxide di (meth) acrylate compound which contains an ethylene oxide group and a propylene oxide group at least in a compound, It is any one of Claims 1-3. Photosensitive resin composition.   The colorant which further has a colorant which has an absorption maximum in 550-700 nm in the ratio of 0.01-1 mass% with respect to the said whole photosensitive resin composition is described in any one of Claims 1-4. Photosensitive resin composition.   6. The composition according to claim 1, further comprising (F) a colorant having an absorption maximum at 400 to 550 nm at a ratio of 0.01 to 1% by mass with respect to the entire photosensitive resin composition. Photosensitive resin composition. (E) A colorant having an absorption maximum at 550 to 700 nm is represented by the following formula (I):

(Wherein R ¹ and R ² each independently represents a linear or branched alkyl group, an alkyl-substituted or unsubstituted phenyl group, a cyclohexyl group, a carbonyl group, a linear or branched alkyl group via a carbonyl group, a substituted or R ³ and R ⁴ are each independently hydrogen, a hydroxyl group, a cyclohexyl group, a linear or branched alkyl group, a substituted or unsubstituted phenyl group, and a linear or branched alkyl group via an NH group. Represents an alkyl-substituted or unsubstituted phenyl group, a cyclohexyl group, a linear or branched alkyl group via an amide group, or a substituted or unsubstituted phenyl group.)
The photosensitive resin composition as described in any one of Claims 1-6 which is a structure represented by these. (F) A colorant having an absorption maximum at 400 to 550 nm is represented by the following formula (II):

(Wherein R ⁵ is hydrogen or an alkyl group having 1 to 4 carbon atoms, R ⁶ is hydrogen, a hydroxyl group, a carboxyl group, a halogen group, an alkyl group having 1 to 4 carbon atoms, or an amino group which may have a substituent. Represents an amide group, a nitro group or a sulfonyl group which may have a substituent.
The photosensitive resin composition as described in any one of Claims 1-7 which has group represented by these.   (C) The photosensitive resin as described in any one of Claims 1-8 in which a photoinitiator further contains a pyrazoline derivative in the ratio of 0.01-1 mass% with respect to the said whole photosensitive resin composition. Composition.   The photosensitive resin laminated body by which the photosensitive resin layer which consists of the photosensitive resin composition as described in any one of Claims 1-9 was laminated | stacked on the support layer at least.   The pattern formation method including the process of laminating the photosensitive resin laminated body of Claim 10 to a base material, the process of exposing, and the process of developing.