TWI491979B - A photosensitive resin composition, a photosensitive resin laminate, and a photoresist pattern - Google Patents

Description

Photosensitive resin composition, photosensitive resin laminate, and method for forming photoresist pattern

The present invention relates to a photosensitive resin composition which can be developed with an aqueous alkaline solution, a photosensitive resin laminate formed by laminating the photosensitive resin composition on a support, and formed on the substrate using the photosensitive resin laminate. A method of a photoresist pattern and the use of the photoresist pattern. More specifically, it relates to a photosensitive resin composition which can provide a preferable photoresist pattern in the following production: manufacture of a printed wiring board, manufacture of a flexible printed wiring board, and lead frame for IC wafer mounting (hereinafter referred to as Manufacture of a lead frame, fabrication of a metal foil represented by a metal mask, and fabrication of a semiconductor package represented by a BGA (Ball Grid Array) and a CSP (Chip Size Package) Manufacture of a tape substrate, such as TAB (Tape Automated Bonding) and COF (Chip on Film, film-on-film: a semiconductor IC mounted on a film-shaped micro-board) Manufacturing, partitioning member members represented by ITO (Indium Tin Oxide) electrodes, address electrodes, and electromagnetic wave masks in the field of flat panel display, and processing of substrates by a sandblasting method The manufacture of the protective mask member.

Previously, printed wiring boards were manufactured by a photolithography method. The photolithography method is, for example, a method in which a photosensitive resin composition is applied onto a substrate in a negative form, and pattern exposure is performed to thermally cure and expose the exposed portion of the photosensitive resin composition. A photoresist pattern is formed on the substrate by removing the unexposed portion from the developer, and etching or plating is performed to form a conductor pattern, and then the photoresist pattern is peeled off from the substrate to form a conductor pattern on the substrate.

In the photolithography method, any of the following methods may be used: when the photosensitive resin composition is applied onto a substrate, the photosensitive resin composition solution is applied as a photoresist solution to the substrate and dried. Or a photosensitive resin laminate in which a support, a layer containing a photosensitive resin composition (hereinafter also referred to as "photosensitive resin layer"), and an optional protective layer are sequentially laminated (hereinafter also A method called "dry film photoresist") laminated on a substrate. Moreover, in the manufacture of printed wiring boards, the dry film photoresist of the latter is often used.

Hereinafter, a method of manufacturing a printed wiring board using the above dry film photoresist will be briefly described.

First, when the dry film photoresist has a protective layer such as a polyethylene film, it is peeled off from the photosensitive resin layer. Then, a photosensitive resin layer and a support are laminated on the substrate (for example, a copper foil laminate) using a bonding machine in the order of the substrate, the photosensitive resin layer, and the support (for example, polyethylene terephthalate). Then, the photosensitive resin layer is exposed by ultraviolet rays such as i-rays (wavelength: 365 nm) emitted from an ultrahigh pressure mercury lamp through a mask having a line pattern, whereby the exposed portion is polymerized and cured. The support is then peeled off. Then, the unexposed portion of the photosensitive resin layer is dissolved or dispersed by a developing solution, for example, an aqueous solution having a weak alkalinity, to form a photoresist pattern on the substrate.

A method of forming a metal conductor pattern using a photoresist pattern on a substrate formed in the above manner is roughly classified into two methods, a method of removing a metal portion which is not photoresist-coated by etching, and a plating method. And the method of laying metal. Especially recently, in terms of the simplicity of the steps, the former method is mostly used.

In the method of removing a metal portion by etching, a through hole of a substrate and a via hole for interlayer connection are usually covered with a cured photoresist film, so that the metal in the hole is not etched. This method is called the cover hole method. In the etching step, for example, a copper chloride solution, a ferric chloride solution or a copper ammonia complex solution can be used.

Recently, as the production of printed wiring boards has increased, it has been demanded to cope with high-sensitivity dry film photoresists. Further, there is a tendency to introduce a detecting machine after exposure and to find defects such as foreign matter in an early stage of the production line, thereby improving productivity. The determination of the defect detecting machine after the exposure is usually performed by identifying the unexposed portion and the exposed portion. Therefore, it is required that the photosensitive resin layer immediately after exposure has an extremely good contrast immediately after exposure.

Moreover, on the other hand, in the manufacturing technology of printed wiring boards, it can be seen that direct writing by laser, that is, maskless exposure without a mask, has been rapidly spread in recent years. As a light source for the exposure of the mask, in most cases, light having a wavelength of 350 to 410 nm, particularly i-rays or h-rays (wavelength 405 nm), is used. In the reticle exposure, an alignment mark is required to align the substrate during exposure. The alignment mark is produced by exposing only the alignment mark in advance before pattern exposure. Therefore, if the photosensitive resin layer does not have a good contrast immediately after exposure immediately after exposure, the takt time until the pattern exposure becomes long, and the throughput per unit time is deteriorated. Therefore, the current state of the art requires that the photosensitive resin layer immediately after exposure has an extremely good contrast immediately after exposure.

A large number of documents relating to a photosensitive resin composition and a photosensitive resin laminate have been disclosed, and a large number of documents for improving the contrast immediately after exposure have been disclosed (see Patent Documents 1 to 3).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2000-241971

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2002-053621

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2001-209177

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2008-287227

However, the current situation is that even with the technique proposed in the above documents, the contrast immediately after exposure is insufficient. An object of the present invention is to provide a photosensitive resin composition which can overcome the above-mentioned problems, has excellent contrast, excellent resolution and sensitivity after exposure, and can suppress a decrease in residual film property in peeling in a specific aspect; A method of forming a photosensitive resin laminate and a photoresist pattern.

As a result of intensive research to solve the above problems, it has been found that the above problems can be solved by using a specific thiadiazole compound as a component of the photosensitive resin composition, and the present invention has been completed. That is, the present invention is as follows.

(1) A photosensitive resin composition comprising: (a) an alkali-soluble polymer containing a carboxylic acid having an acid equivalent of 100 to 600 and a weight average molecular weight of 5,000 to 500,000: 20 to 80% by mass; (b) containing Ethylenically unsaturated addition polymerizable monomer of at least one compound having an acrylonitrile group: 5 to 60% by mass; (c) Photopolymerization initiator containing N-aryl-α-amino acid compound: 0.1 ~20% by mass; (d) leuco dye: 0.1 to 10% by mass; and (e) a mercaptothiadiazole compound represented by the following formula (I): 0.01 to 5% by mass:

[Chemical 1]

In the formula, R ₁ represents an alkyl group selected from the group consisting of an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 9 carbon atoms, an alkylthio group having 1 to 16 carbon atoms, an anthracenyl group, an amine group, and an alkyl group having 1 to 9 carbon atoms. One of the groups consisting of a group of amino groups}.

(2) The photosensitive resin composition according to the above (1), wherein the (b) ethylenically unsaturated addition polymerizable monomer having at least one compound having an acrylonitrile group has a propylene group; a compound represented by the following formula (II):

[Chemical 2]

Wherein R ₂ , R ₃ , R ₄ and R ₅ represent H, and X and Y each independently represent an alkylene group having 2 to 4 carbon atoms, and X and Y are different from each other, 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 the total of p ¹ , p ² , p ³ , p ⁴ , p ⁵ , p ⁶ , p ⁷ and p ⁸ is 0~ An integer of 20}.

(3) The photosensitive resin composition according to the above (1) or (2), wherein the (e) mercaptothiadiazole compound is selected from the group consisting of 5-methylthio-2-mercapto-1,3,4-thiadi Azole, 2-amino-5-mercapto-1,3,4-thiadiazole, 5-methylamino-2-mercapto-1,3,4-thiadiazole and 2,5-dimercapto-1 And at least one compound of the group consisting of 3,4-thiadiazole.

(4) The photosensitive resin composition according to any one of the above (1), wherein the (N) photopolymerization initiator contains the N-aryl-α-amino acid compound as N -Phenylglycine.

(5) The photosensitive resin composition according to any one of the above (1), wherein the (b) ethylenically unsaturated addition polymerizable monomer containing at least one compound having an acrylonitrile group contains At least one of the photopolymerizable unsaturated compounds represented by the following formula (III) is selected:

[Chemical 3]

In the formula, R ₆ and R ₇ each independently represent H or CH ₃ , A represents C ₂ H ₄ , B represents C ₃ H ₆ , n1+n2 is an integer of 2 to 30, and n3+n4 is an integer of 0 to 30. , n1 and n2 are independently integers from 1 to 29, n3 and n4 are each independently an integer from 0 to 30, and the arrangement of repeating units of -(AO)- and -(BO)- can be either random or Block}.

(6) A photosensitive resin laminate in which a photosensitive resin layer containing the photosensitive resin composition according to any one of the above (1) to (5) is laminated on a support comprising a base film.

(7) A method of forming a photoresist pattern, comprising the steps of: laminating a layer of a photosensitive resin layer as described in (6) above; and exposing the photosensitive resin in the photosensitive resin layered body The layer is exposed; and the developing step is performed to remove the unexposed portion of the photosensitive resin layer.

(8) The method of forming a photoresist pattern according to (7) above, wherein the exposing step is performed by direct writing of the writing pattern.

According to the present invention, there is provided a photosensitive resin composition which is excellent in contrast, resolution and sensitivity immediately after exposure, and which can suppress a decrease in residual film property in peeling in a specific aspect; and a photosensitive resin layer using the same A method of forming a body and a photoresist pattern.

Hereinafter, the present invention will be specifically described.

<Photosensitive Resin Composition>

The present invention provides a photosensitive resin composition comprising: (a) an alkali-soluble polymer containing a carboxylic acid, an acid equivalent of 100 to 600, and a weight average molecular weight of 5,000 to 500,000 (referred to as (a) a base in the present specification. Soluble polymer): 20 to 80% by mass; (b) an ethylenically unsaturated addition polymerizable monomer containing at least one compound having an acrylonitrile group (referred to as (b) ethylenically unsaturated in the present specification a polymerizable monomer): 5 to 60% by mass; (c) a photopolymerization initiator containing an N-aryl-α-amino acid compound (referred to as (c) photopolymerization initiator in the present specification) : 0.1 to 20% by mass; (d) leuco dye: 0.1 to 10% by mass; and (e) a mercaptothiadiazole compound represented by the following formula (I) (referred to as (e) mercapto group in the present specification Thiadiazole compound): 0.01 to 5% by mass:

[Chemical 4]

In the formula, R ₁ represents an alkyl group selected from a carbon number of 1 to 9, an alkoxy group having 1 to 9 carbon atoms, an alkylthio group having 1 to 16 carbon atoms, an anthracenyl group, an amine group, and a carbon number of 1 to 9. One of the groups consisting of alkylamino groups}.

(a) alkali soluble polymer

In the photosensitive resin composition of the present invention, the (a) alkali-soluble polymer contains 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.

In order to make the photosensitive resin composition developable and releasable to the developing solution and the peeling liquid containing an alkaline aqueous solution, (a) the carboxyl group of the alkali-soluble polymer is required. (a) The alkali-soluble polymer has an acid equivalent of from 100 to 600, preferably from 250 to 450. From the viewpoint of ensuring compatibility with the solvent or other components in the photosensitive resin composition, particularly the ethylenically unsaturated addition polymerizable monomer containing at least one compound having an acrylonitrile group (b) described later. The acid equivalent is 100 or more, and is 600 or less from the viewpoint of maintaining developability and peelability. The acid equivalent here means the mass (gram) of the alkali-soluble polymer having one equivalent of a carboxyl group. Further, the acid equivalent was measured by a potentiometric titration method using a Hiranuma Reporting Titrator (COM-555) using a 0.1 mol/L NaOH aqueous solution.

(a) The alkali-soluble polymer has a weight average molecular weight of 5,000 to 500,000. From the viewpoint of maintaining the thickness of the photosensitive resin layer uniformly and obtaining the resistance to the developer, it is 5,000 or more, and is 500,000 or less from the viewpoint of maintaining developability. More preferably, the weight average molecular weight is from 20,000 to 100,000. In the present specification, the weight average molecular weight refers to a calibration curve using polystyrene (for example, Shodex STANDARD SM-105 manufactured by Showa Denko Co., Ltd.) by gel permeation chromatography (GPC, Gel Permeation Chromatography). The weight average molecular weight determined. The weight average molecular weight is more typically measured by a gel permeation chromatography instrument manufactured by JASCO Corporation, under the following conditions.

Differential refractometer: RI-1530

Pump: PU-1580

Deaerator: DG-9-80-50

Column oven: CO-1560

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

Dissolution: THF

(a) The alkali-soluble polymer is preferably a copolymer of one or more of the first monomers described later and one or more of the second monomers described later.

A carboxylic acid or a carboxylic acid anhydride having one polymerizable unsaturated group in the first single system molecule. For example, (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, and maleic acid half ester are mentioned. Among them, (meth)acrylic acid is particularly preferred.

The second single system is a monomer which is non-acidic and has at least one polymerizable unsaturated group in the molecule. For example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, (methyl) ) isobutyl acrylate, tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, Benzyl (meth)acrylate, an ester of vinyl alcohol, such as vinyl acetate, (meth)acrylonitrile, styrene, and a styrene derivative capable of polymerization. Among them, methyl (meth)acrylate, n-butyl (meth)acrylate, styrene, and benzyl (meth)acrylate are particularly preferred.

In the present specification, the term "(meth)acryl fluorenyl) means an acryl fluorenyl group and/or a methacryl fluorenyl group.

(a) The content of the alkali-soluble polymer in the photosensitive resin composition is in the range of 20 to 80% by mass, preferably 30 to 70% by mass. The resist pattern formed by exposure and development has a characteristic as a photoresist, for example, a cap hole, etching, and sufficient resistance in various plating steps, and 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 acrylonitrile group

In the photosensitive resin composition of the present invention, (b) an ethylenically unsaturated addition polymerizable single system containing at least one compound having an acrylonitrile group has one or more ethylenically unsaturated bonds. By containing at least one compound having an acrylonitrile group, the contrast-improving effect immediately after exposure can be imparted. Examples of the compound having an acrylonitrile group include 1,6-hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, polypropylene glycol diacrylate, polyethylene glycol diacrylate, and 2- Di(p-hydroxyphenyl)propane diacrylate, glycerol triacrylate, trimethylolpropane triacrylate, polyoxypropyl trimethylolpropane triacrylate, polyoxyethyl trimethylolpropane triacrylate Ester, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, trimethylolpropane triglycidyl ether triacrylate, bisphenol A diglycidyl ether diacrylate, β-hydroxypropyl-β'-(propylene oxide Propyl phthalate, phenoxy polyethylene glycol acrylate, nonyl phenoxy polyethylene glycol acrylate, nonyl phenoxy polyalkylene glycol acrylate, polypropylene glycol monoacrylate An alkylene oxide adduct of bisphenol A (for example, an adduct obtained by adding an average of 5 moles of ethylene oxide at both ends, and an average of 2 moles of propylene oxide at both ends and An acrylate or triethylene compound obtained by adding an average of 15 moles of ethylene oxide at both ends Twelve propylene glycol, polypropylene glycol added to propylene oxide and further added ethylene oxide at both ends (addition of 12 mil propylene oxide to the two ends of the addition of polypropylene glycol An average of 3 moles of ethylene oxide) derived from a dialkyl diol diacrylate. Among them, preferred are pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, bisphenol A diglycidyl ether diacrylate, and diacrylate of bisphenol A alkylene oxide adduct.

In particular, from the viewpoint of achieving good contrast, sensitivity, resolution, and residual film ratio immediately after exposure, the compound having an acrylonitrile group is preferably a compound represented by the following formula (II):

[Chemical 5]

Wherein R ₂ , R ₃ , R ₄ and R ₅ represent H, and X and Y each independently represent an alkylene group having 2 to 4 carbon atoms, and X and Y are different from each other, 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 the total of p ¹ , p ² , p ³ , p ⁴ , p ⁵ , p ⁶ , p ⁷ and p ⁸ is 0~ An integer of 20}.

The content ratio of the compound having an acrylonitrile group in the photosensitive resin composition of the present invention is preferably from 1 to 45% by mass, more preferably from 1 to 30% by mass, even more preferably from 5 to 20% by mass. The content ratio is preferably 1% by mass or more, and more preferably 5% by mass or more, from the viewpoint of having good contrast properties immediately after exposure. Moreover, from the viewpoint of suppressing a decrease in residual film property at the time of peeling, it is preferably 45 mass% or less, and more preferably 30 mass% or less.

(b) The ethylenically unsaturated addition polymerizable monomer containing at least one compound having an acrylonitrile group preferably contains a photopolymerizable group selected from the following formula (III) in terms of resolution. At least one of the unsaturated compounds:

[Chemical 6]

In the formula, R ₆ and R ₇ each independently represent H or CH ₃ , A represents C ₂ H ₄ , B represents C ₃ H ₆ , n1+n2 is an integer of 2 to 30, and n3+n4 is an integer of 0 to 30. , n1 and n2 are independently integers from 1 to 29, n3 and n4 are each independently an integer from 0 to 30, and the arrangement of repeating units of -(AO)- and -(BO)- can be either random or Block}.

Examples of the compound represented by the above formula (III) include 2,2-bis{(4-propenyloxypolyethyloxy)phenyl}propane and 2,2-bis{(4-methyl). Acryloxypolyethyloxy)phenyl}propane or the like. The polyethylidene group which the compound represented by the above formula (III) has is preferably one selected from the group consisting of a monoethyloxy group and a diethylidene group. , tri-ethyloxy, tetra-ethyloxy, penta-ethyloxy, hexaethyloxy, heptaethyloxy, octaethyloxy, hexaethyloxy, X-epiethyloxy, eleven-ethyloxy, dodecylethyloxy, thirteen-extended ethyloxy, tetradecylethyloxy, and pentadecylethyloxy.

Further, examples of the compound represented by the above formula (III) include 2,2-bis{(4-propenyloxypolyalkyloxy)phenyl}propane and 2,2-dual {(4). -Methyl propylene oxime-polyalkyloxy)phenyl}propane or the like. The polyalkyleneoxy group which the compound represented by the above formula (III) has may be exemplified by a mixture of an ethyloxy group and a propyloxy group, preferably an octaethyloxy group and a di-extension propyl group. An adduct of a block structure of a oxy group or an adduct of a random structure, and an adduct of a block structure of a tetraethyl ethoxy group and a tetrapropyl propyloxy group or an adduct of a random structure An adduct of a block structure of a penta-extension ethyloxy group and a di-propyloxy group or an adduct of a random structure. Among these, 2,2-bis{(4-methylpropenyloxypentaethyloxy)phenyl}propane is most preferred.

When the (b) ethylenically unsaturated addition polymerizable monomer contains the compound represented by the above formula (III), the content ratio of the compound represented by the above formula (III) in the photosensitive resin composition of the invention It is preferably from 1 to 40% by mass, more preferably from 5 to 30% by mass. The content of the above-mentioned content is preferably 1% by mass or more, and is preferably 40% by mass or less from the viewpoint of suppressing the resolution and the adhesion.

As the (b) ethylenically unsaturated addition polymerizable monomer, for example, a photopolymerizable unsaturated compound shown below can be used in combination with the above compound having an acrylonitrile group and a compound represented by the formula (III). Or in place of the above compound having an acrylonitrile group and a compound represented by the formula (III). That is, 1,6-hexanediol dimethacrylate, 1,4-cyclohexanediol dimethacrylate, polypropylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 2-bis(p-hydroxyphenyl)propane dimethacrylate, glycerol trimethacrylate, trimethylolpropane trimethacrylate, polyoxypropyl trimethylolpropane trimethacrylate, poly Oxyethyl trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentamethyl acrylate, trimethylolpropane triglycidyl ether trimethacrylate, bisphenol A diglycidyl Ether dimethacrylate, β-hydroxypropyl-β'-(methacryloxy)propyl phthalate, phenoxy polyethylene glycol methacrylate, mercaptophenoxy Polyethylene glycol methacrylate, nonylphenoxy polyalkylene glycol methacrylate, polypropylene glycol monomethacrylate, bisphenol A alkylene oxide adduct (for example, average addition at both ends) Addition of 5 moles of ethylene oxide, adding 2 moles of propylene oxide at both ends and adding them to both ends 15 moles of ethylene oxide adduct) dimethacrylate, triethylene glycol dodecanol, on the addition of propylene oxide to polypropylene glycol and then add epoxy at both ends Ethane (dimethacrylate of polyalkylene glycol) obtained by adding an average of 3 moles of ethylene oxide to each end of the polypropylene glycol obtained by adding an average of 12 moles of propylene oxide.

Further, examples of the (b) ethylenically unsaturated addition polymerizable monomer include an amine ester compound. Examples of the amine ester compound include hexamethylene diisocyanate, toluene diisocyanate, and diisocyanate compounds, for example, 2,2,4-trimethylhexamethylene diisocyanate and a hydroxyl group and (methyl group) in one molecule. A compound of an acrylonitrile group, for example, an amine ester compound of 2-hydroxypropyl acrylate or oligomeric propylene glycol monomethacrylate. Specifically, there is a reaction product of hexamethylene diisocyanate and oligomeric polypropylene glycol monomethacrylate (manufactured by Nippon Oil & Fat Co., Ltd., Blemmer PP1000). The amine ester compound may be used singly or in combination of two or more.

The content of the (b) ethylenically unsaturated addition polymerizable monomer used in the present invention in the photosensitive resin composition is in the range of 5 to 60% by mass, preferably 10 to 50% by mass. In view of the improvement of the sensitivity, the resolution, and the adhesion, the content ratio is 5% by mass or more, and is 60% by mass or less from the viewpoint of suppressing edge fuse.

(c) Photopolymerization initiator

The (c) photopolymerization initiator in the photosensitive resin composition of the present invention contains an N-aryl-α-amino acid compound as an essential component. Good sensitivity is ensured by the N-aryl-α-amino acid compound. Among them, in terms of sensitivity, a particularly preferred N-aryl-α-amino acid compound is N-phenylglycine.

As the (c) photopolymerization initiator used in the present invention, a combination of an N-aryl-α-amino acid compound and an acridine derivative is preferably used in combination. As the acridine derivative, 9-phenyl acridine, 9-pyridyl acridine, and 9-pyridyl are exemplified. Acridine, 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 Kasei Kogyo Co., Ltd.) , N-1717), 1,8-bis(9-acridinyl)octane, 1,9-bis(9-acridinyl)decane, 1,10-bis(9-acridinyl)decane 1,11-bis(9-acridinyl)undecane, 1,12-bis(9-acridinyl)dodecane.

As the (c) photopolymerization initiator, in addition to the above-mentioned compounds, other photopolymerization initiators may be used in combination. The photopolymerization initiator herein refers to a compound which is activated by various active light rays such as ultraviolet rays to initiate polymerization.

As the other photopolymerization initiator, pyrroline, for example, 1-phenyl-3-(4-t-butyl-styryl)-5-(4-t-butyl-phenyl) can be mentioned. Pyrroline, anthraquinones such as 2-ethylhydrazine and 2-tert-butylfluorene, aromatic ketones such as benzophenone and benzoin, benzoin ethers such as benzoin methyl ether and benzoin ethyl ether, hydrazine Pyridine compounds, for example, 9-phenyl acridine, benzoin ketals, such as benzoin dimethyl ketal and benzoin diethyl ketal.

Further, as the other photopolymerization initiator, 9-oxosulfuric acid may be used in combination. Star class, such as 9-oxosulfur 2,4-diethyl-9-oxosulfur Or 2-chloro-9-oxosulfur With a graded amine compound, for example an alkyl dimethylaminobenzoate compound.

Further, examples of the other photopolymerization initiator include oxime esters such as 1-phenyl-1,2-propanedione-2-O-benzimidoxime and 1-phenyl-1. 2-propanedione-2-(O-ethoxycarbonyl)indole.

(c) The content ratio of the photopolymerization initiator in the photosensitive resin composition is in the range of 0.1% by mass to 20% by mass. If the above content ratio is less than 0.1% by mass, sufficient sensitivity cannot be obtained. In addition, when the content ratio exceeds 20% by mass, fogging due to diffraction of light passing through the mask is likely to occur during exposure, and as a result, the resolution is deteriorated. The content ratio is more preferably in the range of 0.1 to 15% by mass, still more preferably in the range of 0.1 to 10% by mass.

(d) leuco dye

The (d) leuco dye in the photosensitive resin composition of the present invention may, for example, be a leuco crystal violet or a fluoran dye. Among them, when leuco crystal violet is used, the contrast immediately after exposure is good and preferable. Examples of the fluoran dye include 3-diethylamino-6-methyl-7-anilinofluoran, 3-dibutylamino-6-methyl-7-anilinofluoran, and 2 -(2-chloroanilino)-6-dibutylamino fluoran, 2-bromo-3-methyl-6-dibutylaminofluoran, 2-N,N-dibenzylamino- 6-Diethylaminofluoran, 3-diethylamino-7-chloroaminofluoran, 3,6-dimethoxyfluoran, 3-diethylamino-6-methoxy -7-Amino fluoran and the like.

(d) The content of the leuco dye in the photosensitive resin composition is in the range of 0.1 to 10% by mass, preferably in the range of 0.1 to 5% by mass, and more preferably in the range of 0.5 to 3% by mass. The content ratio is 0.1% by mass or more, and is 10% by mass or less from the viewpoint of maintaining storage stability from the viewpoint of the contrast after the exposure.

(e) mercaptothiadiazole compounds

The (e) mercaptothiadiazole compound in the photosensitive resin composition of the present invention is a compound represented by the following formula (I):

[Chemistry 7]

In the formula, R ₁ represents an alkyl group selected from a carbon number of 1 to 9, an alkoxy group having 1 to 9 carbon atoms, an alkylthio group having 1 to 16 carbon atoms, an anthracenyl group, an amine group, and a carbon number of 1 to 9. One of the groups consisting of alkylamino groups}.

As the (e) mercaptothiadiazole compound, for example, 5-methyl-2-mercapto-1,3,4-thiadiazole, 5-ethyl-2-mercapto-1,3,4-thiadi Oxazole, 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-propoxy-2-indolyl-1,3,4-thiazide Diazole, 5-isopropoxy-2-mercapto-1,3,4-thiadiazole, 5-methylthio-2-mercapto-1,3,4-thiadiazole, 5-ethylthio- 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- The mercapto-1,3,4-thiadiazole and 2,5-dimercapto-1,3,4-thiadiazole are preferably used because of their high sensitivity, adhesion, and contrast performance immediately after exposure. These may be used alone or in combination of two or more.

(e) The content of the mercaptothiadiazole compound in the photosensitive resin composition is in the range of 0.01 to 5% by mass, preferably 0.05 to 3% by mass, and most preferably 0.1 to 2% by mass. The content ratio is 0.01% by mass or more, and the storage stability is 5% by mass or less from the viewpoint of obtaining sufficient sensitivity, adhesion, and contrast. Further, since the (e) mercaptothiadiazole compound is a powder at normal temperature, the above content ratio is typically a solid content ratio.

In the present invention, it is preferred to contain a halide in the photosensitive resin composition. In this case, by using (d) a leuco dye in combination with a halide, the adhesion and the contrast immediately after exposure can be made better.

Examples of the halide include bromopentane, bromoisopentane, bromoisobutane, 1,2-dibromoethane, bromodiphenylmethane, dibromotoluene, dibromomethane, and tribromomethylphenyl. Bismuth, carbon tetrabromide, tris(2,3-dibromopropyl) phosphate, trichloroacetamide, iodopentane, iodoisobutane, 1,1,1-trichloro-2,2-double (p-chlorophenyl)ethane, hexachloroethane, halogenated three Compounds, etc.

When a halide is used in the present invention, the content of the halide in the photosensitive resin composition is preferably from 0.01 to 5% by mass, more preferably from 0.05 to 3% by mass.

In the present invention, in order to improve the handleability of the photosensitive resin composition, in addition to the above (d) leuco dye, the photosensitive resin composition may contain a coloring matter. Examples of the coloring matter include fuchsin, phthalocyanine green, auramine base, paramagenta, crystal violet, methyl orange, and Nile. Nile blue-2B, Victoria blue, malachite green (eg AIZEN (registered trademark) MALACHITE GREEN by Hodogaya Chemical Co., Ltd.), basic blue (basic blue) -20, diamond green (for example, AIZEN (registered trademark) DIAMOND GREEN GH manufactured by Hodogaya Chemical Co., Ltd.).

When the coloring matter is used, the content of the coloring matter in the photosensitive resin composition is preferably 0.001 to 1% by mass, more preferably 0.01 to 0.1% by mass. When the content ratio is 0.001% by mass or more, the effect of improving workability is good, and when it is 1% by mass or less, the effect of maintaining storage stability is good.

Moreover, in order to improve the thermal stability and storage stability of the photosensitive resin composition in the present invention, a stabilizer may be contained in the photosensitive resin composition. Examples of the stabilizer include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, t-butyl catechol, cuprous chloride, and 2,6-di-third. Base-p-cresol, 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-third Phenol), N-nitrosodiphenylamine, and the like. Further, benzotriazole, carboxybenzotriazole, 1-(2-dialkylamino)carboxybenzotriazole, pentaerythritol-3,5-di-t-butyl-4-hydroxyl Phenylpropionate tetraester and the like.

When the stabilizer is used, the content of the stabilizer in the photosensitive resin composition is preferably from 0.01 to 3% by mass, more preferably from 0.05 to 1% by mass. When the content ratio is 0.01% by mass or more, the effect of imparting storage stability to the photosensitive resin composition is good, and when it is 3% by mass or less, the effect of maintaining sensitivity is good.

Furthermore, the photosensitive resin composition of this invention may contain a plasticizer as needed. Examples of the plasticizer include phthalic acid esters such as diethyl phthalate, o-toluenesulfonamide, p-toluenesulfonamide, tributyl citrate, triethyl citrate, and ethyl hydrazine. Triethyl citrate, tri-n-propyl ethyl citrate, tri-n-butyl acetyl citrate, polypropylene glycol, polyethylene glycol, polyethylene glycol alkyl ether, polypropylene glycol alkyl ether, and the like. When the plasticizer is contained, the content of the plasticizer in the photosensitive resin composition is preferably from 5 to 50% by mass, more preferably from 5 to 30% by mass. When the content ratio is 50% by mass or less, the effect of suppressing the delay of the development time and imparting flexibility to the cured film is good, and when it is 5% by mass or more, the effect of suppressing insufficient hardening or cold flow is good.

<Photosensitive Resin Laminate>

The present invention also provides a photosensitive resin laminate in which a photosensitive resin layer containing the photosensitive resin composition of the present invention is laminated on a support comprising a substrate film. The photosensitive resin laminate of the present invention has a photosensitive resin layer and a support comprising a base film which supports the photosensitive resin layer, and may have a protective layer on the surface of the photosensitive resin layer opposite to the support, if necessary. .

As the base film, a transparent base film that transmits light emitted from the exposure light source is preferable. Examples of such a substrate film include a polyethylene terephthalate film, a polyvinyl alcohol film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyvinylidene chloride film, and a vinylidene chloride copolymer. A film, a polymethyl methacrylate copolymer film, a polystyrene film, a polyacrylonitrile film, a styrene copolymer film, a polyamide film, a cellulose derivative film, or the like. These films may also be used as extensions as needed. The haze of the base film is preferably 5 or less. Although the thickness of the film is thin, it is advantageous in terms of image formation property and economic efficiency, but it is preferably 10 to 30 μm because it is required to maintain strength.

Moreover, the important characteristic of the protective layer used as needed in the photosensitive resin laminated body is that the adhesive force of the protective layer and the photosensitive resin layer is sufficiently smaller than the support, and can be easily peeled off. For example, a polyethylene film and a polypropylene film can be preferably used as the protective layer. Further, for example, a film excellent in peelability disclosed in Japanese Laid-Open Patent Publication No. SHO 59-202457 can be used. The film thickness of the protective layer is preferably from 10 to 100 μm, more preferably from 10 to 50 μm.

The thickness of the photosensitive resin layer in the photosensitive resin laminate of the present invention varies depending on the application, and is preferably 5 to 100 μm, more preferably 7 to 60 μm. The thinner the resolution is, the thicker the film is. The strength is increased.

As a method of producing the photosensitive resin laminate of the present invention as a sequential buildup support, a photosensitive resin layer, and an optional protective layer, a previously known method can be employed. For example, a photosensitive resin composition used in a photosensitive resin layer is mixed with a solvent dissolved therein to prepare a uniform solution, and the solution is first applied onto a support by a bar coater or a roll coater and dried. A photosensitive resin layer containing a photosensitive resin composition is laminated on a support. Then, a protective layer is bonded to the photosensitive resin layer as needed, whereby a photosensitive resin laminate can be produced.

Examples of the solvent include ketones represented by methyl ethyl ketone (MEK), and alcohols represented by methanol, ethanol, and isopropyl alcohol. The solvent is added to the photosensitive resin composition so that the viscosity of the solution of the photosensitive resin composition coated on the support is 500 to 4000 mPa·s at 25°C.

<Method of Forming Photoresist Pattern>

The photosensitive resin composition and the photosensitive resin laminate of the present invention described above can be used to form a negative photoresist pattern. The present invention also provides a method for forming a photoresist pattern, comprising the steps of: laminating a layer of the photosensitive resin layer of the present invention on a substrate; and exposing the photosensitive resin layer in the photosensitive resin laminate The exposure is performed; and the developing step is performed to remove the unexposed portion of the photosensitive resin layer. An example of a specific method is shown below.

In the case of manufacturing a printed wiring board, a copper foil laminated board is used as a substrate, and a glass substrate coated with a glass rib slurry, for example, a plasma display, is used for the purpose of producing a textured base material. A panel substrate, a surface electrolytic display substrate, an organic EL sealing cover substrate, a tantalum wafer in which a through hole is formed, and a ceramic substrate. In the substrate for a plasma display, after forming an electrode on a glass, a dielectric layer is applied, and then a glass paste for a partition wall is applied, and a glass paste portion for a partition wall is subjected to sandblasting to form a substrate of a partition wall. The blasting step is performed on the substrates to form an uneven substrate.

[Lamination step]

In the lamination step, a photosensitive resin layer is laminated on the substrate using, for example, a laminator. When the photosensitive resin laminate has a protective layer, the protective layer is peeled off, and then the photosensitive resin layer is heated and pressure-bonded to the surface of the substrate by a bonding machine to be laminated. At this time, the photosensitive resin layer may be laminated only on one surface of the substrate surface, or may be laminated on both surfaces. The heating temperature at this time is usually 40 to 160 °C. Moreover, the adhesion and chemical resistance can be improved by performing the thermocompression bonding twice or more. In this case, a two-stage laminator having a double roll can be used for the pressure bonding, and the photosensitive resin laminate can be pressure-bonded by a roller several times over the substrate.

[Exposure step]

Then, in the exposure step, the photosensitive resin layer in the photosensitive resin laminate is exposed using an exposure machine. If necessary, the support is peeled off before exposure, and exposure is performed by active light through a photomask. The amount of exposure is determined by the illumination of the light source and the exposure time, and can be measured using a light meter. Moreover, the exposing step can also be performed by direct writing of the writing pattern. The direct writing exposure method is a method of directly writing and exposing on a substrate without using a photomask. As the light source, for example, a semiconductor laser or an ultrahigh pressure mercury lamp having a wavelength of 350 to 410 nm can be used. The writing pattern is controlled by a computer, and the exposure amount at this time is determined by the illumination of the light source and the moving speed of the substrate.

[Development Step]

In the developing step, the unexposed portion of the photosensitive resin layer is developed and removed using a developing device. After the exposure, when the support is provided on the photosensitive resin layer, it is removed as needed, and then the unexposed portion is developed and removed using a developing solution of an alkaline aqueous solution to obtain a photoresist pattern. As the alkaline aqueous solution, for example, an aqueous solution of Na ₂ CO ₃ or K ₂ CO ₃ can be used. These may be selected according to the characteristics of the photosensitive resin layer, and are usually a Na ₂ CO ₃ aqueous solution having a concentration of 0.2 to 2% by mass and a temperature of 20 to 40 °C. A surfactant, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like may be mixed in the alkaline aqueous solution.

Although the photoresist pattern can be obtained by the above steps, a heating step of 100 to 300 ° C can be further performed depending on the case. By performing this heating step, chemical resistance can be further improved. A heating furnace in the form of hot air, infrared rays or far infrared rays can be used for heating.

<Method for Producing Conductor Pattern and Method for Manufacturing Printed Wiring Board>

The present invention can be preferably applied to a method of manufacturing a conductor pattern and a method of manufacturing a printed wiring board. For example, a copper foil laminate or a flexible substrate is used as the substrate, and the conductor pattern and the printed wiring board can be manufactured by the following steps following the method of forming the photoresist pattern.

First, a copper conductor of a substrate exposed by development in the above-described photoresist forming method of the present invention is etched or plated by a conventionally known method to form a conductor pattern.

Thereafter, the desired printed wiring board is obtained by peeling the photoresist pattern from the substrate with an aqueous solution having a stronger alkalinity than the developer. The alkaline aqueous solution for peeling (hereinafter also referred to as "peeling liquid") is not particularly limited, and an aqueous solution of NaOH or KOH having a concentration of 2 to 5% by mass and a temperature of 40 to 70 ° C is usually used. A small amount of a water-soluble solvent may also be added to the stripping solution.

<Method of manufacturing lead frame>

The present invention can also be preferably applied to a method of manufacturing a lead frame. Specifically, a metal plate, for example, a plate of copper, a copper alloy, or an iron-based alloy is used as a substrate, and after the method of forming the photoresist pattern, the lead frame is manufactured through the following steps.

First, a substrate which is exposed by development in a method of forming a photoresist pattern is etched to form a conductor pattern. Thereafter, the photoresist pattern is peeled off in the same manner as in the above-described method of manufacturing a printed wiring board to obtain a desired lead frame.

<Method of Manufacturing Semiconductor Package>

The present invention can also be preferably applied to a method of manufacturing a semiconductor package. Specifically, a wafer formed as a circuit of an LSI (large scale integrated circuit) is used as a substrate, and after the method of forming the photoresist pattern, the semiconductor package can be manufactured through the following steps.

First, a columnar plating such as copper or solder is applied to an opening exposed by development in a photoresist pattern forming method to form a conductor pattern. Thereafter, the photoresist pattern is removed in the same manner as in the above-described method of manufacturing a printed wiring board, and a thin metal layer other than the columnar plating is removed by etching, whereby a desired semiconductor package is obtained.

<Method of Manufacturing Substrate Having Concavo-Concave Pattern>

The present invention is also preferably applied to a method of producing a substrate having a concavo-convex pattern. When the substrate is processed by the blasting method using the photosensitive resin laminate of the present invention as a dry film resist, a glass substrate coated with a glass rib slurry is used as a substrate, and a layer is laminated on the substrate in the same manner as the above method. The photosensitive resin laminate is subjected to exposure and development.

Further, a blasting step of cutting the target material by blowing the blast material from the formed photoresist pattern, and a peeling step of removing the resin portion remaining on the substrate from the substrate by the alkaline stripping solution may be performed. A fine concavo-convex pattern is processed on the substrate. As the blasting material used in the blasting step, a known material can be used. For example, a particle size of 2 to 100 μm made of SiO, SiO ₂ , Al ₂ O ₃ , CaCO ₃ , ZrO, glass or stainless steel can be used. Left and right particles.

[Examples]

Hereinafter, examples of embodiments of the present invention will be described in detail by way of examples.

1. Production of samples for evaluation

The photosensitive resin laminates of the examples and the comparative examples were produced as follows.

<Production of Photosensitive Resin Laminate>

The compound shown in Table 1 was prepared, and the photosensitive resin composition of the composition ratio shown in Tables 2 and 3 was sufficiently stirred and mixed, and uniformly applied to a 19 μm-thick pair as a support by a bar coater. The surface of the ethylene phthalate film was dried in a dryer at 95 ° C for 3 minutes to form a photosensitive resin layer. The thickness of the photosensitive resin layer was 30 μm. Then, a polyethylene film having a thickness of 23 μm was bonded to the surface of the uncovered polyethylene terephthalate film of the photosensitive resin layer as a protective layer to obtain a photosensitive resin laminate. In addition, in Table 1, "P" corresponds to (a) an alkali-soluble polymer, and "M-1" and "M-2" correspond to (b) an optically unsaturated addition polymerizable monomer. The polymerized unsaturated compound, "M-3" corresponds to (b) a compound having an acrylonitrile group in the ethylenically unsaturated addition polymerizable monomer, and "I-1" corresponds to (c) a photopolymerization initiator In the acridine derivative, "I-2" corresponds to (c) the N-aryl-α-amino acid compound in the photopolymerization initiator, "I-3", "I-4" and "I" -5" corresponds to (e) a mercaptothiadiazole compound, and "D-1" corresponds to (d) a leuco dye. Further, the mass parts of P in Tables 2 and 3 contain the value of methyl ethyl ketone.

<The whole surface of the copper foil laminate>

The surface was ground by a jet scrubber (manufactured by Ishii Kee Co., Ltd.) using a 0.4 mm thick copper foil laminate laminated with a 35 μm rolled copper foil.

<layer>

The polyethylene film of the photosensitive resin laminate was peeled off on a copper foil laminate which was preheated to 60 ° C by a heating roll laminator (manufactured by Asahi Kasei Co., Ltd., AL-70). A photosensitive resin laminate was laminated at a temperature of 105 °C. The gas pressure was set to 0.35 MPa, and the stacking speed was set to 1.5 m/min.

<Exposure: Direct writing method>

Directly engraved exposure device (manufactured by Hitachi Via Mechanics Co., Ltd., DI exposure machine DE-1AH, light source: GaN blue-violet diode, dominant wavelength 407±3 nm), at 20 mJ/ The amount of exposure of cm ² was exposed to a photosensitive resin laminate laminated on a copper foil laminate.

<development>

After peeling off the polyethylene terephthalate film, an alkali developing machine (manufactured by FUJI KIKO, a dry film developing machine) was used to spray a 1% by mass Na ₂ CO ₃ aqueous solution at 30 ° C for a specific time to minimize the development time. The unexposed portion of the photosensitive resin layer was dissolved and removed twice. At this time, the minimum time required to completely dissolve the photosensitive resin layer of the unexposed portion is taken as the minimum development time.

2. Evaluation method (1) Contrast evaluation method after exposure

After the exposure of the photosensitive resin layer for 30 seconds and 1 minute, the color difference ΔE was measured for the photosensitive resin layer of the unexposed portion and the exposed portion by a colorimetric color difference meter (Σ80 manufactured by Nippon Denshoku Co., Ltd.). The contrasts after 30 seconds and after 1 minute after exposure were respectively classified as follows.

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

A line pattern in which the width of the exposed portion and the unexposed portion is 1:1 is written by direct exposure, and development is performed. The minimum width normally formed by the hardened photoresist line not missing or peeled off is taken as the value of the resolution. The resolution is graded as follows.

AA: 35 μm or less

A: More than 35 μm

(3) Evaluation method of sensitivity

Exposure and development were carried out using a 21-stage stage exposure meter manufactured by Stouffer, which was changed from transparent to black, using a brightness stage of 21 stages. According to the number of staged exposure tables in which the photoresist film completely remains after development, it is classified as follows.

AA: The number of stage exposure tables in which the photoresist film completely remains is 5 or more

A: The number of stage exposure tables in which the photoresist film completely remains is less than 5

(4) Evaluation method of residual film rate

The photosensitive resin laminate is exposed from the polyethylene terephthalate film side, and the polyethylene terephthalate film and the polyethylene film are peeled off from the exposed photosensitive resin laminate, and the quality of the cured film is measured. Then, it was stirred for 3 hours in a 3 mass% NaOH solution at 50 °C. The NaOH solution was then filtered to dry the cured film remaining on the filter paper and the mass was measured. The ratio of the mass of the remaining cured film to the mass of the cured film before stirring was taken as the residual film ratio.

AA: residual film rate is 25% or more

A: The residual film rate is less than 25%.

3. Evaluation results

The evaluation results of the examples and comparative examples are shown in Tables 2 and 3.

[Industrial availability]

The present invention can be preferably used, for example, in the manufacture of a printed wiring board, the manufacture of a lead frame for mounting an IC chip, the precision processing of a metal foil represented by a metal mask manufacturing, and the manufacture of a package represented by BGA and CSP. COF and TAB are representative of the manufacture of the tape substrate, the manufacture of the semiconductor bump, the manufacture of the partition wall of the flat panel display represented by the ITO electrode, the address electrode and the electromagnetic wave mask, and the concave and convex pattern generated by the sand blasting method. Fabrication of substrates.

Claims (8)

A photosensitive resin composition comprising: (a) an alkali-soluble polymer containing a carboxylic acid, an acid equivalent of 100 to 600, a weight average molecular weight of 5,000 to 500,000: 20 to 80% by mass; (b) at least one kind Ethylene unsaturated addition polymerizable monomer having a propylene fluorenyl group: 5 to 60% by mass; (c) photopolymerization initiator containing an N-aryl-α-amino acid compound and an acridine derivative : 0.1 to 20% by mass; (d) leuco dye: 0.1 to 10% by mass; and (e) a mercaptothiadiazole compound represented by the following formula (I): 0.01 to 5% by mass: In the formula, R ₁ represents an alkyl group selected from the group consisting of an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 9 carbon atoms, an alkylthio group having 1 to 16 carbon atoms, an anthracenyl group, an amine group, and an alkyl group having 1 to 9 carbon atoms. One of the groups consisting of a group of amino groups, wherein the compound having an acryloyl group is contained in an amount of from 5% by mass to 45% by mass. The photosensitive resin composition of claim 1, wherein the (b) ethylenically unsaturated addition polymerizable monomer having at least one compound having an acrylonitrile group has a propylene fluorenyl group as a general formula Compounds shown in (II): Wherein R ₂ , R ₃ , R ₄ and R ₅ represent H, and X and Y each independently represent an alkylene group having 2 to 4 carbon atoms, and X and Y are different from each other, 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 the total of p ¹ , p ² , p ³ , p ⁴ , p ⁵ , p ⁶ , p ⁷ and p ⁸ is 0~ An integer of 20}. The photosensitive resin composition of claim 1 or 2, wherein the (e) mercaptothiadiazole compound is selected from the group consisting of 5-methylthio-2-mercapto-1,3,4-thiadiazole, 2-amino group -5-mercapto-1,3,4-thiadiazole, 5-methylamino-2-mercapto-1,3,4-thiadiazole and 2,5-dimercapto-1,3,4-thiazide At least one compound of the group consisting of oxazoles. The photosensitive resin composition of claim 1 or 2, wherein the above-mentioned N-aryl-α-amino acid compound contained in the above (c) photopolymerization initiator is N-phenylglycine. The photosensitive resin composition of claim 1 or 2, wherein the (b) ethylenically unsaturated addition polymerizable monomer containing at least one compound having an acrylonitrile group is selected from the group consisting of the following formula (III) At least one of the photopolymerizable unsaturated compounds is shown: In the formula, R ₆ and R ₇ each independently represent H or CH ₃ , A represents C ₂ H ₄ , B represents C ₃ H ₆ , n1+n2 is an integer of 2 to 30, and n3+n4 is an integer of 0 to 30. , n1 and n2 are independently integers from 1 to 29, n3 and n4 are each independently an integer from 0 to 30, and the arrangement of repeating units of -(AO)- and -(BO)- can be either random or Block}. A photosensitive resin laminate which is obtained by laminating a photosensitive resin layer containing the photosensitive resin composition of claim 1 or 2 on a support comprising a base film. A method for forming a photoresist pattern, comprising the steps of: laminating a layer of a photosensitive resin layer as claimed in claim 6 on a substrate; and exposing the photosensitive resin layer in the photosensitive resin laminate; And a developing step of developing and removing the unexposed portion of the photosensitive resin layer. A method of forming a photoresist pattern according to claim 7, wherein the exposing step is performed by direct drawing of the drawing pattern.