KR20120031086A - Photosensitive resin composition, photosensitive resin laminate, and method for forming resist pattern - Google Patents

Abstract

{식 중, R₁ 은 탄소수 1?9 의 알킬기, 탄소수 1?9 의 알콕실기, 탄소수 1?16 의 알킬티오기, 메르캅토기, 아미노기, 및 탄소수 1?9 의 알킬아미노기로 이루어지는 군에서 선택되는 1 개의 기를 나타낸다} 로 나타내는 메르캅토티아디아졸 화합물 0.01?5 질량% 를 함유하는 감광성 수지 조성물을 제공한다.The contrast just after exposure provides the favorable photosensitive resin composition. Ethylenic unsaturated containing (a) 20-80 mass% of alkali-soluble polymers which contain a carboxylic acid, acid equivalent is 100-600, and a weight average molecular weight is 5,000-500,000, and (b) the compound which has an acryl group. 5 to 60 mass% of addition polymerizable monomer, (c) 0.1 to 20 mass% of photopolymerization initiator containing N-aryl-α-amino acid compound, (d) 0.1 to 10 mass% of leuco dye, and (e) the following general formula (I):

{In formula, R <_1> is chosen from the group which consists of a C1-C9 alkyl group, a C1-C9 alkoxyl group, a C1-C16 alkylthio group, a mercapto group, an amino group, and a C1-C9 alkylamino group. The photosensitive resin composition containing 0.01-5 mass% of mercaptothiadiazole compounds represented by} is shown.

Description

Photosensitive resin composition, photosensitive resin laminated body and resist pattern formation method {PHOTOSENSITIVE RESIN COMPOSITION, PHOTOSENSITIVE RESIN LAMINATE, AND METHOD FOR FORMING RESIST PATTERN}

MEANS TO SOLVE THE PROBLEM This invention uses the photosensitive resin composition which can be developed by alkaline aqueous solution, the photosensitive resin laminated body formed by laminating | stacking the photosensitive resin composition on a support body, the method of forming a resist pattern on a board | substrate using this photosensitive resin laminated body, and its It relates to the use of a resist pattern. More specifically, manufacturing a printed wiring board, manufacturing a flexible printed wiring board, manufacturing a lead frame for mounting an IC chip (hereinafter referred to as a lead frame), metal foil precision processing represented by metal mask manufacturing, BGA (ball grid array) and Manufacture of semiconductor package represented by CSP (chip size package), manufacture of tape substrate represented by TAB (Tape Automated Bonding) and COF (Chip on Film mounted on micro wiring board on film), semiconductor bump Providing a resist pattern which is desirable in the manufacture of a substrate, the manufacture of a partition member represented by an ITO electrode, an address electrode, and an electromagnetic shield in the flat panel display field, and the manufacture of a protective mask member when processing a substrate by a sand blasting method. It relates to the photosensitive resin composition.

Conventionally, printed wiring boards are manufactured by the photolithography method. In the photolithography method, for example, in the case of a negative type, a photosensitive resin composition is applied onto a substrate, subjected to pattern exposure to polymerize and harden the exposed portion of the photosensitive resin composition, and the unexposed portion is removed with a developer to form a resist pattern on the substrate. The method of forming a conductor pattern on a board | substrate is mentioned after forming and carrying out an etching or plating process and forming a conductor pattern, and peeling and removing the resist pattern from the board | substrate.

In the said photolithography method, in apply | coating a photosensitive resin composition on a board | substrate, the method of apply | coating a photosensitive resin composition solution to a board | substrate as a photoresist solution and drying, or the layer which consists of a support body and the photosensitive resin composition (" Any of the methods of laminating | stacking a photosensitive resin layer "and the photosensitive resin laminated body (henceforth a" dry film resist ") which laminated | stacked the protective layer one by one according to necessity is used. And in manufacture of a printed wiring board, the latter dry film resist is used in many cases.

The method of manufacturing a printed wiring board using the said dry film resist is briefly described below.

First, when a dry film resist has a protective layer, for example, a polyethylene film, it peels this from the photosensitive resin layer. Subsequently, the photosensitive resin layer and the support body are laminated | stacked on the board | substrate (for example, copper clad laminated board) so that it may become the order of the board | substrate, the photosensitive resin layer, and a support body (for example, polyethylene terephthalate). Next, an exposure part is polymerized and hardened | cured by exposing the photosensitive resin layer to ultraviolet rays, such as i line | wire (wavelength 365nm) from which ultra-high pressure mercury lamp emits, through the photomask which has a wiring pattern. The support is then peeled off. Subsequently, the unexposed part of the photosensitive resin layer is melt | dissolved or disperse | dissolved by the developing solution, for example, the aqueous solution which has weak alkali property, and a resist pattern is formed on a board | substrate.

The method of manufacturing a metal conductor pattern using the resist pattern on the board | substrate formed in this way is divided into two methods, The method of removing the metal part which is not covered by a resist by etching, and attaching a metal by plating is performed. There is a way. In particular, the former method is used a lot in recent years in the simplicity of the process.

In the method of removing a metal part by etching, the metal in a hole is not etched normally by covering the through-hole (through hole) of a board | substrate and the via hole for interlayer connection with a hardening resist film. This method is called tenting method. In the etching process, for example, a ferric chloride solution, a ferric chloride solution, or a copper ammonia complex solution is used.

In recent years, with the increase of the output of a printed wiring board, the high sensitivity dry film resist corresponding to high production is calculated | required. There is also a tendency to improve productivity by introducing a tester after exposure and detecting defects caused by foreign matter at an early stage of the production line, for example. Since the determination by the defect inspection machine after exposure is generally performed by identifying an unexposed part and an exposure part, it is a present situation that the photosensitive resin layer immediately after exposure has a very favorable contrast immediately after exposure.

On the other hand, in the technology of manufacturing a printed wiring board, the direct drawing by a laser, in other words, the maskless exposure which eliminates the need for a photomask has shown rapid expansion in recent years. As a light source of maskless exposure, the light of wavelength 350-410 nm, especially i line | wire or h line | wire (wavelength 405 nm) is used in many cases. In maskless exposure, an alignment mark is required for alignment of the substrate during exposure. This alignment mark is manufactured by exposing only the alignment mark in advance before pattern exposure. For this reason, when the photosensitive resin layer does not have the contrast immediately after favorable exposure immediately after exposure, the tact time until pattern exposure will become long and the yield per hour will worsen. Therefore, it is a present situation that the photosensitive resin layer immediately after exposure is required to have contrast very immediately after exposure.

The literature regarding many photosensitive resin compositions and photosensitive resin laminated bodies is disclosed until now, and there exist many documents regarding contrast improvement immediately after exposure (refer patent documents 1-3).

Japanese Laid-Open Patent Publication 2000-241971 Japanese Laid-Open Patent Publication 2002-053621 Japanese Laid-Open Patent Publication 2001-209177 Japanese Unexamined Patent Publication No. 2008-287227

However, even with the technique proposed by the above document, the current situation is still insufficient in contrast just after exposure. An object of the present invention is to provide a photosensitive resin composition which overcomes the above-mentioned problems, has very good contrast immediately after exposure, is excellent in resolution and sensitivity, and can suppress the deterioration of residual film upon peeling in certain embodiments. It aims at providing the used photosensitive resin laminated body and the resist pattern formation method.

As a result of earnestly examining in order to solve the said subject, it discovered that the said subject can be solved by using a specific thiadiazole compound as a component of the photosensitive resin composition, and came to complete this invention. That is, this invention is as follows.

(1) Alkali-soluble polymer which contains (a) carboxylic acid, acid equivalent is 100-600, and a weight average molecular weight is 5,000-500,000: 20-80 mass%, (b) At least 1 type of compound which has an acryl group Ethylenic unsaturated addition polymerizable monomer containing: 5-60 mass%, (c) Photoinitiator containing N-aryl- (alpha)-amino acid compound: 0.1-20 mass%, (d) leuco dye: 0.1-10 mass% And (e) the following general formula (I):

[Formula 1]

{In formula, R <_1> is chosen from the group which consists of a C1-C9 alkyl group, a C1-C9 alkoxyl group, a C1-C16 alkylthio group, a mercapto group, an amino group, and a C1-C9 alkylamino group. Mercaptothiadiazole compound represented by}} which represents one group to become: The photosensitive resin composition containing 0.01-5 mass%.

(2) The compound which has an acryl group in the ethylenically unsaturated addition polymerizable monomer containing at least 1 sort (s) of said (b) compound which has an acryl group has the following general formula (II):

[Formula 2]

{Wherein, R ₂ , R ₃ , R ₄ , and R ₅ represent H, X and Y each independently represent an alkylene group having 2 to 4 carbon atoms, X and Y are different from each other, and p ¹ , p ² , p ³ , p ⁴ , p ⁵ , p ⁶ , p ⁷ and p ⁸ are each independently 0 or a positive integer, and p ¹ , p ² , p ³ , p ⁴ , p ⁵ , p ⁶ , p ⁷ and The sum total of p <^8> is an integer of 0-20} The photosensitive resin composition as described in said (1) which is a compound represented by.

(3) The mercaptothiadiazole compound (e) is 5-methylthio-2-mercapto-1,3,4-thiadiazole, 2-amino-5-mercapto-1,3,4-thia At least one compound selected from the group consisting of diazoles, 5-methylamino-2-mercapto-1,3,4-thiadiazole and 2,5-dimercapto-1,3,4-thiadiazole The photosensitive resin composition as described in said (1) or (2) which is phosphorus.

(4) The photosensitive resin composition in any one of said (1)-(3) whose said N-aryl-alpha-amino acid compound which the said (c) photoinitiator contains is N-phenylglycine.

(5) The ethylenically unsaturated addition polymerizable monomer containing at least 1 type of said compound (b) which has an acryl group is the following general formula (III):

(3)

{Wherein, R ₆ and R ₇ represents H or CH _3, each independently, A denotes a C ₂ H _4, B is a represents a C ₃ H _6, n1 + n2 is 2? 30 integer, n3 + n4 is an integer from 0 to 30, n1 and n2 are each independently an integer from 1 to 29, n3 and n4 are each independently an integer from 0 to 30, and-(AO)-and-(BO)- The arrangement of the repeating units may be random or may be a block.

(6) The photosensitive resin laminated body formed by laminating | stacking the photosensitive resin layer which consists of a photosensitive resin composition in any one of said (1)-(5) on the support body which consists of a base film.

(7) a lamination step of laminating the photosensitive resin laminate according to (6) on a substrate,

An exposure step of exposing the photosensitive resin layer in the photosensitive resin laminate, and

The resist pattern formation method containing the image development process of image development removal of the unexposed part of the photosensitive resin layer.

(8) The resist pattern formation method as described in said (7) which performs the said exposure process by direct drawing of a drawing pattern.

According to this invention, the photosensitive resin composition which has very favorable contrast immediately after exposure, is excellent in a resolution and a sensitivity, and can suppress the fall of residual film at the time of peeling in a specific aspect, and the photosensitive resin laminated body using the same, and A resist pattern forming method is provided.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated concretely.

<Photosensitive resin composition>

The present invention contains (a) an alkali-soluble polymer having a carboxylic acid, an acid equivalent of 100 to 600, and a weight average molecular weight of 5,000 to 500,000 (also referred to herein as (a) an alkali-soluble polymer): 20? Ethylene unsaturated addition polymerizable monomer containing 80 mass%, (b) at least 1 sort (s) of the compound which has an acryl group (In this specification, it is also called (b) ethylenically unsaturated addition polymerizable monomer): 5-60 mass%, (c) Photoinitiator containing N-aryl- (alpha)-amino acid compound (In this specification, it is also called (c) photoinitiator): 0.1-20 mass%, (d) leuco dye: 0.1-10 mass%, and (e) the following general formula (I):

[Formula 4]

{In formula, R <_1> is chosen from the group which consists of a C1-C9 alkyl group, a C1-C9 alkoxyl group, a C1-C16 alkylthio group, a mercapto group, an amino group, and a C1-C9 alkylamino group. A mercaptothiadiazole compound represented by the present invention} (also called (e) mercaptothiadiazole compound in this specification): Photosensitive resin composition containing 0.01-5 mass% is provided.

(a) alkali-soluble polymers

The (a) alkali-soluble polymer in the photosensitive resin composition of this invention is an alkali-soluble polymer which contains a carboxylic acid, an acid equivalent is 100-600 and a weight average molecular weight is 5,000-500,000.

The carboxyl group of the (a) alkali-soluble polymer is necessary in order for the photosensitive resin composition to have developability and peelability with respect to the developing solution and peeling solution which consist of aqueous alkali solution. (a) The acid equivalent of alkali-soluble polymer is 100-600, Preferably it is 250-450. The said acid equivalent is 100 or more from a viewpoint of ensuring compatibility with the ethylenic unsaturated addition polymerizable monomer containing at least 1 sort (s) of a solvent or other component in the photosensitive resin composition, especially the compound which has the (b) acryl group mentioned later, Moreover, it is 600 or less from a viewpoint of maintaining developability and peelability. An acid equivalent means the mass (gram) of alkali-soluble polymer which has 1 equivalent of carboxyl group in it here. The acid equivalent is measured by potentiometric titration with a 0.1 mol / l NaOH aqueous solution using a hiranuma reporting titrator (COM-555).

(a) The weight average molecular weight of alkali-soluble polymer is 5,000-500,000. It is 5,000 or more from a viewpoint of maintaining the thickness of the photosensitive resin layer uniformly, and obtaining tolerance to a developing solution, and 500,000 or less from a viewpoint of maintaining developability. More preferably, the weight average molecular weight is 20,000 to 100,000. In this specification, a weight average molecular weight means the weight average molecular weight measured using the calibration curve of polystyrene (for example, Shodex STANDARD SM-105 by Showa Electric Co., Ltd.) by gel permeation chromatography (GPC). do. The weight average molecular weight can be measured on the following conditions more typically using Nippon Spectroscopy Co., Ltd. gel permeation chromatography.

Differential Refractometer: RI-1530

Pump: PU-1580

Degatsa: DG-9-80-50

Column Oven: CO-1560

Column: KF-802.5, KF-806M × 2, KF-807 in order

Eluent: THF

(a) It is preferable that alkali-soluble polymer is 1 or more types of copolymers of the 1st monomer mentioned later and the 2nd monomer mentioned later.

The first monomer is a carboxylic acid or carboxylic anhydride having one polymerizable unsaturated group in the molecule. For example, (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, and maleic acid half ester are mentioned. Especially, (meth) acrylic acid is preferable.

The second monomer is non-acidic and is a 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) acrylic Ester, ester of vinyl alcohol, For example, vinyl acetate, (meth) acrylonitrile, styrene, and the styrene derivative which can superpose | polymerize are mentioned. Especially, methyl (meth) acrylate, n-butyl (meth) acrylate, styrene, and benzyl (meth) acrylate are especially preferable.

In addition, in this specification, (meth) acryl means an acryl and / or methacryl.

The content rate of the (a) alkali-soluble polymer in the photosensitive resin composition is 20-80 mass%, Preferably it is 30-70 mass%. From the viewpoint that the resist pattern formed by exposure and development has sufficient resistance as a resist, for example, in tenting, etching and various plating processes, the content ratio is 20% by mass or more and 80% by mass or less.

(b) an ethylenically unsaturated addition polymerizable monomer containing at least one compound having an acryl group

The ethylenically unsaturated addition polymerizable monomer containing at least 1 sort (s) of the compound which has an acryl group in the photosensitive resin composition of this invention is a monomer which has one or more ethylenically unsaturated bonds. By containing at least 1 type of compound which has an acryl group, the contrast improvement effect immediately after exposure is provided. Examples of the compound having an acryl group include 1,6-hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, polypropylene glycol diacrylate, polyethylene glycol diacrylate, and 2-di (p-hydroxyphenyl Propanediacrylate, glycerol triacrylate, trimethylolpropanetriacrylate, polyoxypropyltrimethylolpropanetriacrylate, polyoxyethyltrimethylolpropanetriacrylate, pentaerythritol tetraacrylate, dipentaerythritol penta Acrylate, trimethylol propane triglycidyl ether triacrylate, bisphenol A diglycidyl ether diacrylate, β-hydroxypropyl-β '-(acryloyloxy) propyl phthalate, phenoxy polyethylene glycol acrylate, Nonylphenoxypolyethylene glycol acrylate, nonylphenoxy polyalkylene glycol acrylate , Polypropylene glycol monoacrylate, alkylene oxide adduct of bisphenol A (e.g., an adduct obtained by adding an average of 5 moles of ethylene oxide at both ends, an average of 2 moles of propylene oxide at both ends, and an average of 15 moles at both ends Addition product of both ends of ethylene oxide added to the polyacrylate glycol to which diacrylate, triethylene glycol dodecapropylene glycol, and propylene oxide were added (average of 12 mol of propylene oxide) Ethylene oxide is added on average at both ends of the polypropylene glycol) diacrylate of polyalkylene glycol. Especially, the diacrylate of pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, bisphenol A diglycidyl ether diacrylate, and the alkylene oxide adduct of bisphenol A is preferable.

In particular, the compound which has an acryl group has the following general formula (II):

[Chemical Formula 5]

{Wherein, R ₂ , R ₃ , R ₄ , and R ₅ represent H, X and Y each independently represent an alkylene group having 2 to 4 carbon atoms, X and Y are different from each other, and p ¹ , p ² , p ³ , p ⁴ , p ⁵ , p ⁶ , p ⁷ and p ⁸ are each independently 0 or a positive integer, and p ¹ , p ² , p ³ , p ⁴ , p ⁵ , p ⁶ , p ⁷ and The sum of p ⁸ is an integer of 0 to 20}. It is most preferable from the viewpoint of achieving a good balance of contrast property, sensitivity, resolution and residual film ratio immediately after exposure.

It is preferable that the content rate of the compound which has an acryl group in the photosensitive resin composition of this invention is 1-45 mass%, More preferably, it is 1-30 mass%, More preferably, it is 5-20 mass%. It is preferable that it is 1 mass% or more from a viewpoint that the said content ratio has favorable contrast immediately after exposure, and 5 mass% or more is more preferable. Moreover, it is preferable that it is 45 mass% or less from a viewpoint of suppressing the fall of the residual film property at the time of peeling, and 30 mass% or less is more preferable.

(b) The ethylenically unsaturated addition polymerizable monomer containing at least 1 sort (s) of the compound which has an acryl group is the following general formula (III):

[Formula 6]

{Wherein, R ₆ and R ₇ represents H or CH _3, each independently, A denotes a C ₂ H _4, B is a represents a C ₃ H _6, n1 + n2 is 2? 30 integer, n3 + n4 is an integer from 0 to 30, n1 and n2 are each independently an integer from 1 to 29, n3 and n4 are each independently an integer from 0 to 30, and-(AO)-and-(BO)- The arrangement of the repeating units may be random or may be a block}, preferably containing at least one selected from the photopolymerizable unsaturated compounds represented by the viewpoint of the resolution.

Examples of the compound represented by General Formula (III) include 2,2-bis {(4-acryloxypolyethyleneoxy) phenyl} propane and 2,2-bis {(4-methacryloxypolyethyleneoxy) phenyl} propane. Can be mentioned. The polyethyleneoxy group which the compound represented by the said General formula (III) has has a monoethyleneoxy group, a diethyleneoxy group, a triethyleneoxy group, a tetraethyleneoxy group, a pentaethyleneoxy group, a hexaethyleneoxy group, a heptaethyleneoxy group, and an octa Any selected from the group consisting of ethyleneoxy group, nonaethyleneoxy group, decaethyleneoxy group, undecaethyleneoxy group, dodecaethyleneoxy group, tridecaethyleneoxy group, tetradecaethyleneoxy group, and pentadecaethyleneoxy group It is preferable that it is a group.

Moreover, as a compound represented by the said General formula (III), 2, 2-bis {(4-acryloxy polyalkylene oxy) phenyl} propane and 2, 2-bis {(4-methacryloxy polyalkylene oxy) ) Phenyl} propane etc. are mentioned. As a polyalkyleneoxy group which the compound represented by the said General formula (III) has, the mixture of an ethyleneoxy group and a propyleneoxy group is mentioned, The addition of the block structure addition product or random structure of an octaethyleneoxy group and a dipropyleneoxy group is carried out. Water and the addition product of the block structure of a tetraethyleneoxy group and a tetrapropylene oxy group or the addition product of a random structure, the addition product of the block structure of a pentadecaethyleneoxy group and a dipropyleneoxy group, or the addition product of a random structure are preferable. Among them, 2,2-bis {(4-methacryloxypentaethyleneoxy) phenyl} propane is most preferred.

(b) When ethylenically unsaturated addition polymeric monomer contains the compound represented by the said General formula (III), the content rate of the compound represented by the said General formula (III) in the photosensitive resin composition of this invention is 1-40 mass%. It is preferable that it is, More preferably, it is 5-30 mass%. It is preferable that the said content ratio is 1 mass% or more from a viewpoint of having favorable contrast immediately after exposure, and 40 mass% or less from a viewpoint of suppressing the fall of resolution and adhesiveness.

(b) As an ethylenic unsaturated addition polymerizable monomer, the unsaturated compound which can be photopolymerized shown below can be used in combination with or instead of the compound which has the said acryl group, and the compound represented by General formula (III), for example. . Namely, 1,6-hexanediol dimethacrylate, 1,4-cyclohexanediol dimethacrylate, polypropylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 2-di (p-hydroxyphenyl) Propanedimethacrylate, glycerol trimethacrylate, trimethylolpropanetrimethacrylate, polyoxypropyltrimethylolpropanetrimethacrylate, polyoxyethyltrimethylolpropanetrimethacrylate, pentaerythritol tetramethacrylate, Dipentaerythritol pentamethacrylate, trimethylolpropanetriglycidyl ethertrimethacrylate, bisphenol A diglycidyl ether dimethacrylate, β-hydroxypropyl-β '-(methacryloyloxy) propyl Phthalates, phenoxypolyethylene glycol methacrylates, nonylphenoxypolyethylene glycol methacrylates, nonylphenoxypolyalkylene glycols Acrylate, polypropylene glycol monomethacrylate, alkylene oxide adduct of bisphenol A (e.g., an adduct obtained by adding an average of 5 moles of ethylene oxide at both ends, an average of 2 moles of propylene oxide at both ends and both ends Addition of ethylene oxide to both ends of dimethacrylate, triethylene glycol dodecapropylene glycol, and propylene oxide added (average of 12 moles) of dimethacrylate, triethylene glycol dodecapropylene glycol, Dimethacrylate of polyalkylene glycols may be added to both ends of the polypropylene glycol to which propylene oxide is added.

Moreover, a urethane compound is also mentioned as (b) ethylenic unsaturated addition polymerizable monomer. As a urethane compound, For example, hexamethylene diisocyanate, tolylene diisocyanate, and a diisocyanate compound, for example, 2,2,4-trimethylhexamethylene diisocyanate, and a hydroxyl group and a (meth) acryl group in 1 molecule The compound which has, for example, a urethane compound of 2-hydroxypropyl acrylate and oligopropylene glycol monomethacrylate is mentioned. Specifically, there is a reactant of hexamethylene diisocyanate and oligopropylene glycol monomethacrylate (manufactured by Nippon Oils & Fats, Inc., Brenma PP1000). A urethane compound may be used independently and may be used together two or more types.

The content rate in the photosensitive resin composition of the (b) ethylenically unsaturated addition polymeric monomer used for this invention is the range of 5-60 mass%, Preferably it is the range of 10-50 mass%. The said content ratio is 5 mass% or more from a viewpoint of the improvement of a sensitivity, a resolution, and adhesiveness, and 60 mass% or less from a viewpoint which an edge fuse is suppressed.

(c) photopolymerization initiator

The (c) photoinitiator in the photosensitive resin composition of this invention contains an N-aryl- (alpha)-amino acid compound as an essential component. Good sensitivity is ensured by the inclusion of the N-aryl-α-amino acid compound. Especially, it is especially preferable from a viewpoint of a sensitivity that N-aryl- (alpha)-amino acid compound is N-phenylglycine.

As a (c) photoinitiator used for this invention, the system which uses together an N-aryl- (alpha)-amino acid compound and an acridine derivative is preferable. Examples of the acridine derivative include 9-phenylacridine, 9-pyridylacridine, 9-pyrazinylacridine, 1,2-bis (9-acridinyl) ethane, 1,3-bis (9 -Acridinyl) propane, 1,4-bis (9-acridinyl) butane, 1,5-bis (9-acridinyl) pentane, 1,6-bis (9-acridinyl) hexane, 1 , 7-bis (9-acridinyl) heptane (manufactured by Asahi Telephone Co., Ltd., N-1717), 1,8-bis (9-acridinyl) octane, 1,9-bis (9-acridy Nil) nonane, 1,10-bis (9-acridinyl) decane, 1,11-bis (9-acridinyl) undecane, 1,12-bis (9-acridinyl) dodecane have.

(c) As a photoinitiator, in addition to the compound shown above, it is also possible to use another photoinitiator together. The photoinitiator here means a compound which is activated by various actinic rays, for example, ultraviolet rays, and initiates polymerization.

As said other photoinitiator, pyrazolines, for example, 1-phenyl- 3- (4-tert- butyl- styryl) -5- (4-tert- butyl- phenyl)-pyrazoline, quinones, for example For example 2-ethylanthraquinone and 2-tert-butylanthraquinone, aromatic ketones such as benzophenone and benzoin, benzoin ethers such as benzoin methyl ether and benzoin ethyl ether, acridine compounds For example, 9-phenylacrydine, benzyl ketals, such as benzyl dimethyl ketal and benzyl diethyl ketal, are mentioned.

Moreover, as said other photoinitiator, thioxanthones, for example, thioxanthone, 2, 4- diethyl thioxanthone, or 2-chloro thioxanthone, a tertiary amine compound, for example, dimethylamino benzoate alkyl Combination of ester compounds is also possible.

Moreover, as said other photoinitiator, oxime ester, for example, 1-phenyl- 1, 2- propanedione- 2-O-benzoyl oxime and 1-phenyl- 1, 2- propanedione- 2- (O- Oxycarbonyl) oxime is also mentioned.

(c) The content rate of the photoinitiator in the photosensitive resin composition is the range of 0.1 mass%-20 mass%. If the said content ratio is less than 0.1 mass%, sufficient sensitivity will not be obtained. Moreover, when the said content rate exceeds 20 mass%, fogging by the diffraction of the light which passed the photomask at the time of exposure will generate | occur | produce easily, and as a result, resolution will deteriorate. The range of 0.1-15 mass% is more preferable, and, as for the said content rate, the range of 0.1-10 mass% is further more preferable.

(d) leuco dyes

As (d) leuco dye in the photosensitive resin composition of this invention, leuco crystal violet, a fluorane dye, etc. are mentioned. Especially, when leuco crystal violet is used, the contrast immediately after exposure is favorable and preferable. As a fluorane dye, for example, 3-diethylamino-6-methyl-7-anilinofluorane, 3-dibutylamino-6-methyl-7-anilinofluorane, 2- (2-chloroaniyl Lino) -6-dibutylaminofluoran, 2-bromo-3-methyl-6-dibutylaminofluoran, 2-N, N-dibenzylamino-6-diethylaminofluoran, 3-diethyl Amino-7-chloroamino fluorane, 3,6-dimethoxy fluorane, 3-diethylamino-6-methoxy-7-amino fluorane and the like.

(d) The content rate of the leuco dye in the photosensitive resin composition is 0.1-10 mass%, Preferably it is 0.1-5 mass%, More preferably, it is 0.5-3 mass%. The said content ratio is 0.1 mass% or more from a viewpoint of expressing contrast immediately after sufficient exposure, and is 10 mass% or less from a viewpoint of maintaining storage stability.

(e) mercaptothiadiazole compounds

The (e) mercaptothiadiazole compound in the photosensitive resin composition of this invention is following General formula (I):

[Formula 7]

{In formula, R <_1> is chosen from the group which consists of a C1-C9 alkyl group, a C1-C9 alkoxyl group, a C1-C16 alkylthio group, a mercapto group, an amino group, and a C1-C9 alkylamino group. It represents the one group which becomes}}.

(e) As a mercapto thiadiazole compound, for example, 5-methyl-2- mercapto-1,3,4- thiadiazole, 5-ethyl-2- mercapto-1,3,4-thia Diazole, 5-n-propyl-2-mercapto-1,3,4-thiadiazole, 5-isopropyl-2-mercapto-1,3,4-thiadiazole, 5-methoxy-2 Mercapto-1,3,4-thiadiazole, 5-ethoxy-2-mercapto-1,3,4-thiadiazole, 5-n-propyloxy-2-mercapto-1,3, 4-thiadiazole, 5-isopropyloxy-2-mercapto-1,3,4-thiadiazole, 5-methylthio-2-mercapto-1,3,4-thiadiazole, 5-ethyl Thio-2-mercapto-1,3,4-thiadiazole, 5-n-propylthio-2-mercapto-1,3,4-thiadiazole, 5-isopropylthio-2-mercapto- 1,3,4-thiadiazole, 2-amino-5-mercapto-1,3,4-thiadiazole, 5-methylamino-2-mercapto-1,3,4-thiadiazole, 2 , 5-dimercapto-1,3,4-thiadiazole and the like.

In particular, 5-methylthio-2-mercapto-1,3,4-thiadiazole, 2-amino-5-mercapto-1,3,4-thiadiazole, 5-methylamino-2-mercapto Since -1,3,4-thiadiazole and 2,5-dimercapto-1,3,4-thiadiazole are high in sensitivity, adhesiveness, and contrast performance immediately after exposure, they are used preferably. These can be used individually or in combination of 2 or more types.

(e) The content ratio of the mercaptothiadiazole compound in the photosensitive resin composition is 0.01-5 mass%, Preferably it is 0.05-3 mass%, Most preferably, it is 0.1-2 mass%. . The said content ratio is 0.01 mass% or more from a viewpoint of obtaining sufficient sensitivity, adhesiveness, and contrast, and is 5 mass% or less from a viewpoint of maintaining storage stability. In addition, since the (e) mercaptothiadiazole compound is powder at room temperature, the content ratio is typically a solid content ratio.

In this invention, it is preferable to contain a halogen compound in the photosensitive resin composition. In this case, (d) leuco dye and a halogen compound are used in combination, and the adhesiveness and contrast immediately after exposure become more favorable.

As a halogen compound, for example, amyl bromide, isoamyl bromide, isobutyl bromide, ethylene bromide, diphenyl methyl bromide, benzyl bromide, methylene bromide, tribromomethylphenyl sulfone, carbon tetrabromide, and tris (2,3- Dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, hexachloroethane, halogenated triazine compounds, etc. Can be mentioned.

When using a halogen compound in this invention, it is preferable that content of the halogen compound in the photosensitive resin composition is 0.01-5 mass%, More preferably, it is 0.05-3 mass%.

In this invention, in order to improve the handleability of the photosensitive resin composition, in addition to the above-mentioned (d) leuco dye, it is also possible to contain a coloring substance in the photosensitive resin composition. As the coloring substance, for example, fuchsin, phthalocyanine green, oramin base, paramagenta, crystal violet, methyl orange, nile blue 2B, victoria blue, malachite green (e.g., Hodogaya Chemical Co., Ltd. ) MALACHITE GREEN), basic blue 20, diamond green (For example, Hodogaya Chemical Co., Ltd. Eisen (registered trademark) DIAMOND GREEN GH), etc. are mentioned.

When using the said coloring substance, it is preferable that it is 0.001-1 mass%, and, as for the content rate of the coloring substance in the photosensitive resin composition, it is more preferable that it is 0.01-0.1 mass%. When the said content ratio is 0.001 mass% or more, the effect of a handleability improvement is favorable, and when it is 1 mass% or less, the effect of maintaining storage stability is favorable.

Moreover, in order to improve the thermal stability and storage stability of the photosensitive resin composition in this invention, it is also possible to contain a stabilizer in the photosensitive resin composition. As the stabilizer, for example, p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, 2, 2'-methylenebis (4-ethyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), diphenylnitrosoamine, etc. are mentioned. In addition, benzotriazole, carboxybenzotriazole, 1- (2-dialkylamino) carboxybenzotriazole, pentaerythritol-3,5-di-t-butyl-4-hydroxyphenylpropionic acid tetraester and the like can also be mentioned. have.

When it contains the said stabilizer, it is preferable that the content rate of the stabilizer in the photosensitive resin composition is 0.01-3 mass%, More preferably, it is 0.05-1 mass%. When the said content rate is 0.01 mass% or more, the effect of providing storage stability to the photosensitive resin composition is favorable, and when it is 3 mass% or less, the effect of maintaining a sensitivity is favorable.

Moreover, it is also possible to contain a plasticizer in the photosensitive resin composition of this invention as needed. As the plasticizer, phthalic acid esters such as diethyl phthalate, o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, triethyl citrate, acetyl citrate tri-n-propyl, acetyl citric acid Tri-n-butyl, polypropylene glycol, polyethylene glycol, polyethylene glycol alkyl ether, polypropylene glycol alkyl ether, and the like. When it contains the said plasticizer, it is preferable that the content rate of the plasticizer in the photosensitive resin composition is 5-50 mass%, More preferably, it is 5-30 mass%. When the said content rate is 50 mass% or less, the effect of suppressing delay of image development time and providing flexibility to a cured film is favorable, and when it is 5 mass% or more, the effect of suppressing hardening shortage or cold flow is favorable.

<Photosensitive resin laminated body>

This invention also provides the photosensitive resin laminated body formed by laminating | stacking the photosensitive resin layer which consists of the photosensitive resin composition of this invention mentioned above on the support body which consists of a base film. The photosensitive resin laminated body of this invention has a support body which consists of a photosensitive resin layer and the base film which supports this photosensitive resin layer, and if necessary, may have a protective layer on the surface on the opposite side to the support body of a photosensitive resin layer.

As a base film, the transparent thing which permeate | transmits the light radiated | emitted from an exposure light source is preferable. As such a base film, 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, for example , Polystyrene film, polyacrylonitrile film, styrene copolymer film, polyamide film, cellulose derivative film and the like. These films can also be stretched as needed. It is preferable that the haze of a base film is five or less. Although the thickness of the film is advantageous in terms of image formation and economical efficiency, it is preferable that the thickness is 10 to 30 µm in order to maintain the strength.

In addition, the important characteristic of the protective layer used as needed for a photosensitive resin laminated body is that a protective layer is small enough compared with a support body with respect to adhesive force with the photosensitive resin layer, and can be peeled easily. For example, a polyethylene film and a polypropylene film can be used suitably as a protective layer. Moreover, the film excellent in the peelability disclosed by Unexamined-Japanese-Patent No. 59-202457 can be used, for example. 10-100 micrometers is preferable and, as for the film thickness of a protective layer, 10-50 micrometers is more preferable.

Although the thickness of the photosensitive resin layer in the photosensitive resin laminated body of this invention differs according to a use, Preferably it is 5-100 micrometers, More preferably, it is 7-60 micrometers, The thinner, the resolution improves, and the thicker it is The film strength is improved.

As a method of laminating | stacking a support body, the photosensitive resin layer, and a protective layer sequentially as needed, and manufacturing the photosensitive resin laminated body of this invention, the method conventionally known can be employ | adopted. For example, the photosensitive resin composition used for the photosensitive resin layer is mixed with the solvent which melt | dissolves this, and it is made a uniform solution, First, apply | coat and apply the solution using a bar coater or a roll coater on a support body, and dry it, The photosensitive resin layer which consists of a photosensitive resin composition is laminated | stacked. Then, the photosensitive resin laminated body can be manufactured by laminating a protective layer on the photosensitive resin layer as needed.

As said solvent, ketones represented by methyl ethyl ketone (MEK) and alcohols represented by methanol, ethanol and isopropanol are mentioned. It is preferable to add a solvent to the photosensitive resin composition so that the viscosity of the solution of the photosensitive resin composition apply | coated on a support body may be 500-4000 mPa * s at 25 degreeC.

<Resist Pattern Forming Method>

The photosensitive resin composition and photosensitive resin laminated body which concern on this invention mentioned above can be used for formation of a negative resist pattern. This invention develops and removes the lamination process of laminating | stacking the photosensitive resin laminated body of this invention mentioned above on a board | substrate, the exposure process which exposes the photosensitive resin layer in the photosensitive resin laminated body, and the unexposed part of the photosensitive resin layer. There is also provided a resist pattern forming method including a developing step. An example of a specific method is shown below.

As a board | substrate, a copper clad laminated board is mentioned in the case of the manufacture of a printed wiring board, and the glass substrate which apply | coated the glass rib paste for the purpose of manufacture of an uneven | corrugated base material, for example, a substrate for plasma display panels, a surface electrolytic display board | substrate, organic EL sealing A cap substrate, the silicon wafer in which the through-hole was formed, and a ceramic substrate are mentioned. The substrate for plasma display is a substrate on which a dielectric layer is applied after forming an electrode on glass, then a glass paste for partition walls is applied, and sand blasting is performed on the glass paste portion for partition walls to form partition walls. These substrates are subjected to the sand blasting step to form the uneven substrate.

[Lamination process]

In a lamination process, a photosensitive resin laminated body is laminated | stacked on a board | substrate using a laminator etc., for example. When the photosensitive resin laminated body has a protective layer, after peeling a protective layer, a photosensitive resin layer is heat-compressed and laminated | stacked on a board | substrate surface 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 40-160 degreeC. In addition, the adhesion and chemical resistance are improved by performing the heat pressing twice or more. At this time, a two-stage laminator provided with two rolls may be used for crimping, and the photosensitive resin laminate and the substrate may be repeatedly passed through the roll several times to crimp.

Exposure process

Next, in an exposure process, the photosensitive resin layer in the photosensitive resin laminated body is exposed using an exposure machine. If necessary, the support is peeled off before the exposure, and exposed with actinic light through a photomask. An exposure amount is determined according to light source illumination intensity and exposure time, and you may measure using a photometer. Moreover, you may perform an exposure process by direct drawing of a drawing pattern. The direct drawing exposure method is a method of drawing and exposing directly on a substrate without using a photomask. As a light source, the semiconductor laser or ultrahigh pressure mercury lamp of wavelength 350-410 nm is used, for example. The drawing pattern is controlled by a computer, and the exposure amount in this case is determined according to the illuminance of the light source and the moving speed of the substrate.

[Developing process]

In the developing step, the unexposed part of the photosensitive resin layer is developed and removed using a developing device. After exposure, when a support body exists on the photosensitive resin layer, it removes as needed and then develops and removes an unexposed part using the developing solution of aqueous alkali solution, and obtains a resist pattern. With an aqueous alkali solution is, for example, an aqueous solution of Na ₂ CO ₃ or K ₂ CO _3. These are selected according to the characteristics of the photosensitive resin layer. A concentration of 0.2 to 2% by mass and an aqueous Na ₂ CO ₃ solution at 20 to 40 ° C are common. In the alkaline aqueous solution, a small amount of an organic solvent for promoting the surface active agent, an antifoaming agent, and the like may be mixed.

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

<Method for manufacturing conductor pattern and method for manufacturing printed wiring board>

This invention can be preferably applied to the manufacturing method of a conductor pattern, and the manufacturing method of a printed wiring board. For example, a conductor pattern and a printed wiring board can be manufactured by using a copper clad laminated board or a flexible substrate as a board | substrate, and going through the following processes following the resist pattern formation method mentioned above.

First, the copper surface of the board | substrate exposed by the image development in the resist formation method of this invention mentioned above is etched or plated by a conventionally well-known method, and a conductor pattern is formed.

Then, a resist pattern is peeled from a board | substrate with the aqueous solution which has stronger alkalinity than a developing solution, and a desired printed wiring board is obtained. There is no restriction | limiting in particular about the aqueous alkali solution for peeling (henceforth "a peeling liquid"), The aqueous solution of NaOH or KOH with a density | concentration of 2-5 mass% and a temperature of 40-70 degreeC is generally used. It is also possible to add a small amount of water-soluble solvents to the stripping solution.

<Production method of the lead frame>

The present invention can also be preferably applied to a method for producing a lead frame. Specifically, a lead frame can be manufactured by using a metal plate, for example, a plate of copper, a copper alloy, or an iron-based alloy, as the substrate, and then going through the following steps following the above-described resist pattern forming method.

First, the substrate exposed by the development in the resist pattern formation method is etched to form a conductor pattern. Thereafter, the resist pattern is peeled off in the same manner as the method for producing a printed wiring board described above to obtain a desired lead frame.

<Method of Manufacturing Semiconductor Package>

The present invention can also be preferably applied to a method for manufacturing a semiconductor package. Specifically, the semiconductor package can be manufactured by using the wafer in which the circuit formation as LSI is complete | finished as a board | substrate, and going through the following processes following the resist pattern formation method mentioned above.

First, plating of the columnar with copper or solder is performed in the opening exposed by the development in the resist pattern forming method to form a conductor pattern. Thereafter, the resist pattern is peeled off in the same manner as in the above-described method for producing a printed wiring board, and a desired semiconductor package is obtained by removing a thin metal layer in a portion other than columnar plating by etching.

<The manufacturing method of the base material which has an uneven pattern>

The present invention can also be preferably applied to a method for producing a substrate having an uneven pattern. When processing the board | substrate by the sandblasting method using the photosensitive resin laminated body of this invention as a dry film resist, using the glass substrate which apply | coated the glass rib paste as a board | substrate, on the board | substrate, In the same manner, the photosensitive resin laminate is laminated to perform exposure and development.

Further, a fine rugged pattern on the substrate is subjected to a sand blast treatment step of blowing out the blast material from the formed resist pattern and cutting it to a desired depth, and a peeling step of removing a resin portion remaining on the substrate with an alkali stripper. Can be processed. Blasting a material used in the sandblasting treatment process is known to use, for example, SiO, SiO _2, Al ₂ O _3, CaCO _3, ZrO, glass, or a stainless steel as a material, particle diameter of 2? Approximately 100 ㎛ Particulates are used.

Example

Hereinafter, the example of embodiment of this invention is described in detail by an Example.

1. Preparation of Samples for Evaluation

The photosensitive resin laminated body in an Example and a comparative example was manufactured as follows.

<Production of Photosensitive Resin Laminate>

The compound shown in Table 1 was prepared, the photosensitive resin composition of the composition ratio shown in Table 2 and 3 was stirred well, it mixed, it was apply | coated uniformly using the bar coater to the surface of the polyethylene terephthalate film of 19 micrometer thickness as a support body, And dried for 3 minutes in a 95 degreeC dryer to form the photosensitive resin layer. The thickness of the photosensitive resin layer was 30 micrometers. Subsequently, a 23 micrometer-thick polyethylene film was adhere | attached as a protective layer on the surface which does not laminate | stack the polyethylene terephthalate film of the photosensitive resin layer, and the photosensitive resin laminated body was obtained. In addition, in Table 1, "P" corresponds to (a) alkali-soluble polymer | macromolecule, and "M-1" and "M-2" refer to the photopolymerizable unsaturated compound in (b) ethylenic unsaturated addition polymerizable monomer. Correspondingly, "M-3" corresponds to the compound having an acryl group in the (b) ethylenically unsaturated addition polymerizable monomer, and "I-1" corresponds to the acridine derivative in (c) the photoinitiator. In addition, "I-2" corresponds to the (c) N-aryl- (alpha)-amino acid compound in a photoinitiator, "I-3", "I-4", and "I-5" are (e) mer It corresponds to a captothiadiazole compound, and "D-1" corresponds to (d) leuco dye. In addition, the mass part of P in Tables 2 and 3 is the value containing methyl ethyl ketone.

<Front of Copper Clad Laminate>

The 0.4 mm-thick copper clad laminated board which laminated | stacked the 35 micrometers rolled copper foil was used, and the surface was grind | polished with the jet scrub (Ishii Co., Ltd. make).

<Laminate>

While peeling the polyethylene film of the photosensitive resin laminated body, the photosensitive resin laminated body is carried out by the hot roll laminator (Asahi Kasei Co., Ltd. product, AL-70) at the roll temperature of 105 degreeC to the copper clad laminated board which preheated at 60 degreeC. Laminated. The air pressure was 0.35 MPa, and the lamination speed was 1.5 m / min.

<Exposure: Direct Drawing Method>

The photosensitive resin laminate laminated on the copper clad laminate was 20 mJ / using a direct drawing exposure apparatus (manufactured by Hitachi Via Mechanics Co., Ltd., DI exposure machine DE-1AH, light source: GaN celadon diode, dominant wavelength 407 ± 3 nm). It exposed at the exposure amount of cm <2>.

<Phenomena>

After peeling the polyethylene terephthalate film, an alkali developing device given a 1 mass% Na ₂ CO ₃ aqueous solution for 30 ℃ time spraying using (Fuji pore production, the dry film developing device for), and at least the unexposed portion of the photosensitive resin layer It dissolved and removed in 2 times of development time. At this time, the minimum time required for complete dissolution of the photosensitive resin layer of the unexposed part was made into the minimum developing time.

2. Evaluation method

(1) Contrast Evaluation Method Immediately After Exposure

30 seconds and 1 minute after exposure of the photosensitive resin layer, about the photosensitive resin layer of the unexposed part and the exposed part, color difference (DELTA) E was measured with the colorimetry colorimeter (Sigma 80 manufactured by Nippon Denshoku Corporation). Contrast 30 seconds after exposure and 1 minute after exposure were divided as follows, respectively.

AAA: ΔE is 2.5 or more

AA: ΔE is 1 or more and less than 2.5

B: ΔE is less than 1

(2) evaluation method of resolution

The line pattern whose width | variety of an exposure part and an unexposed part is a ratio of 1: 1 was drawn by direct exposure, and developed. The minimum width formed normally without the hardening resist line being missing or peeling off was made into the value of the resolution. The resolution is divided as follows.

AA: 35 μm or less

A: It exceeds 35 micrometers

(3) Evaluation method of sensitivity

It exposed and developed using the 21-step step tablet made by STOPPA which brightness has changed in 21 steps from transparent to black. The rankings were divided as follows by the number of step tablets in which the resist film remained completely after development.

AA: Step tablet number of stages in which the resist film remains completely 5 or more

A: The number of step tablet stages in which a resist film remains completely is less than 5 stages

(4) Evaluation method of residual film rate

After exposing to a photosensitive resin laminated body from the polyethylene terephthalate film side, peeling a polyethylene terephthalate film and a polyethylene film from the photosensitive resin laminated body after exposure, and after measuring the mass of a cured film, it is 3 in 50 mass% 3 NaOH solution. Stirred for time. Subsequently, NaOH solution was filtered, the cured film which remained on the filter paper was dried, and the mass was measured. The ratio of the mass of the cured film which remained to the mass of the cured film before stirring was made into the residual film ratio.

AA: Remaining rate is over 25%

A: Residual rate is less than 25%

3. Evaluation result

The evaluation result of an Example and a comparative example is shown to Tables 2 and 3.

Industrial availability

The present invention provides, for example, the production of printed wiring boards, production of IC chip mounting lead frames, metal foil precision machining represented by metal mask production, production of packages represented by BGA and CSP, tape substrates represented by COF and TAB. It can use suitably for manufacture, manufacture of a semiconductor bump, manufacture of the partition of a flat panel display represented by an ITO electrode, an address electrode, and an electromagnetic shield, and the manufacture of the base material which has an uneven | corrugated pattern by a sandblasting method.

Claims (8)

(a) Alkali-soluble polymer which contains a carboxylic acid, acid equivalent is 100-600, and a weight average molecular weight is 5,000-500,000: 20-80 mass%, (b) Ethylene containing at least 1 type of compound which has an acryl group Unsaturated unsaturated addition polymerizable monomer: 5 to 60 mass%, (c) photopolymerization initiator containing N-aryl-α-amino acid compound: 0.1 to 20 mass%, (d) leuco dye: 0.1 to 10 mass%, and ( e) the following general formula (I):
[Formula 1]

{In formula, R <_1> is chosen from the group which consists of a C1-C9 alkyl group, a C1-C9 alkoxyl group, a C1-C16 alkylthio group, a mercapto group, an amino group, and a C1-C9 alkylamino group. Mercaptothiadiazole compound represented by}} which represents one group to become: The photosensitive resin composition containing 0.01-5 mass%. The method of claim 1,
The compound which has an acryl group in the ethylenically unsaturated addition polymeric monomer containing at least 1 sort (s) of the compound which has the said (b) acryl group is following General formula (II):
(2)

{Wherein, R ₂ , R ₃ , R ₄ , and R ₅ represent H, X and Y each independently represent an alkylene group having 2 to 4 carbon atoms, X and Y are different from each other, and p ¹ , p ² , p ³ , p ⁴ , p ⁵ , p ⁶ , p ⁷ and p ⁸ are each independently 0 or a positive integer, and p ¹ , p ² , p ³ , p ⁴ , p ⁵ , p ⁶ , p ⁷ and the total of p ⁸ is an integer of 0 to 20}. The method according to claim 1 or 2,
The mercaptothiadiazole compound (e) is 5-methylthio-2-mercapto-1,3,4-thiadiazole, 2-amino-5-mercapto-1,3,4-thiadiazole, Photosensitive resin which is at least one compound selected from the group consisting of 5-methylamino-2-mercapto-1,3,4-thiadiazole and 2,5-dimercapto-1,3,4-thiadiazole Composition. The method according to claim 1 or 2,
The photosensitive resin composition whose said N-aryl- (alpha)-amino acid compound which the said (c) photoinitiator contains is N-phenylglycine. The method according to claim 1 or 2,
The ethylenically unsaturated addition polymerizable monomer containing at least 1 sort (s) of the compound which has the said (b) acryl group is following General formula (III):
(3)

{Wherein, R ₆ and R ₇ represents H or CH _3, each independently, A denotes a C ₂ H _4, B is a represents a C ₃ H _6, n1 + n2 is 2? 30 integer, n3 + n4 is an integer from 0 to 30, n1 and n2 are each independently an integer from 1 to 29, n3 and n4 are each independently an integer from 0 to 30, and-(AO)-and-(BO)- The photosensitive resin composition containing at least 1 sort (s) chosen from the unsaturated compound which can be polymerized by the repeating unit of may be random or a block may be}. The photosensitive resin laminated body formed by laminating | stacking the photosensitive resin layer which consists of a photosensitive resin composition of Claim 1 or 2 on the support body which consists of a base film. A lamination step of laminating the photosensitive resin laminate according to claim 6 on a substrate,
An exposure step of exposing the photosensitive resin layer in the photosensitive resin laminate, and
The resist pattern formation method containing the image development process of image development removal of the unexposed part of the photosensitive resin layer. The method of claim 7, wherein
The resist pattern formation method which performs the said exposure process by direct drawing of a drawing pattern.