JP5260745B2 - Photosensitive resin composition, photosensitive resin laminate, and resist pattern forming method - Google Patents

Description

  The present invention relates to a photosensitive resin composition that can be developed with an alkaline aqueous solution, a photosensitive resin laminate formed by laminating the photosensitive resin composition on a support, and a substrate using the photosensitive resin laminate. The present invention relates to a method for forming a resist pattern and a use of the resist pattern. More specifically, the manufacture of printed wiring boards, the manufacture of flexible printed wiring boards, the manufacture of lead frames for mounting IC chips (hereinafter referred to as lead frames), metal foil precision processing represented by metal mask manufacturing, BGA (ball grid array) ) And CSP (chip size package), and TAB (Tape Automated Bonding) and COF (Chip on Film: a semiconductor IC mounted on a film-like fine wiring board). In the manufacture of substrates, the production of semiconductor bumps, the manufacture of barrier ribs represented by ITO electrodes, address electrodes and electromagnetic wave shields in the field of flat panel displays, and the manufacture of protective mask members when processing substrates by sandblasting It relates to a photosensitive resin composition which gives a proper resist pattern.

  Conventionally, printed wiring boards are manufactured by a photolithography method. As a photolithography method, for example, in the case of a negative type, a photosensitive resin composition is applied on a substrate, pattern exposure is performed to polymerize and cure an exposed portion of the photosensitive resin composition, and an unexposed portion is removed with a developer. Then, a resist pattern is formed on the substrate, a conductor pattern is formed by etching or plating, and then the resist pattern is peeled off from the substrate to form a conductor pattern on the substrate. It is done.

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

  A method for producing a printed wiring board using the dry film resist will be briefly described below.

  First, when the dry film resist has a protective layer, for example, a polyethylene film, it is peeled off from the photosensitive resin layer. Next, using a laminator, the photosensitive resin layer and the support are laminated on the substrate (for example, copper-clad laminate) in the order of the substrate, the photosensitive resin layer, and the support (for example, polyethylene terephthalate). . Next, the exposed portion is polymerized and cured by exposing the photosensitive resin layer to ultraviolet rays such as i rays (wavelength 365 nm) emitted from an ultrahigh pressure mercury lamp through a photomask having a wiring pattern. Next, the support is peeled off. Next, an unexposed portion of the photosensitive resin layer is dissolved or dispersed and removed with a developer, for example, an aqueous solution having weak alkalinity, to form a resist pattern on the substrate.

  There are roughly two methods for producing a metal conductor pattern using a resist pattern on a substrate formed in this way. There are a method for removing a metal portion not covered with a resist by etching and a method for metal by plating. There is a way to turn on. In particular, the former method is frequently used recently because of the simplicity of the process.

  In the method of removing a metal part by etching, the through hole (through hole) of the substrate and the via hole for interlayer connection are usually covered with a cured resist film so that the metal in the hole is not etched. This construction method is called a tenting method. In the etching process, for example, a cupric chloride solution, a ferric chloride solution, or a copper ammonia complex solution is used.

  Recently, with the increase in the production volume of printed wiring boards, a high-sensitivity dry film resist corresponding to high production is required. In addition, there is a tendency to improve productivity by introducing an inspection machine after exposure and finding defects due to foreign matters at an early stage of the production line. Judgment by a defect inspection machine after exposure is generally performed by discriminating between an unexposed part and an exposed part. Therefore, it is required that the photosensitive resin layer immediately after the exposure has a very good contrast immediately after the exposure. This is the current situation.

  On the other hand, in the printed wiring board manufacturing technology, direct drawing with a laser, that is, maskless exposure that does not require a photomask, has shown a rapid spread in recent years. As a light source for maskless exposure, light having a wavelength of 350 to 410 nm, particularly i-line or h-line (wavelength 405 nm) is often used. In maskless exposure, alignment marks are required for alignment of the substrate during exposure. This alignment mark is produced by exposing only the alignment mark in advance before pattern exposure. For this reason, if the photosensitive resin layer does not have a good contrast immediately after the exposure immediately after the exposure, the tact time until the pattern exposure becomes longer, and the production amount per time becomes worse. Therefore, the present condition is that the photosensitive resin layer immediately after exposure is required to have a very good contrast immediately after exposure.

  So far, a large number of documents relating to a photosensitive resin composition and a photosensitive resin laminate have been disclosed, and there are also many documents relating to contrast enhancement immediately after exposure (see Patent Documents 1 to 3).

JP 2000-241971 A JP 2002-053621 A JP 2001-209177 A JP 2008-287227 A

  However, even with the technique proposed by the above document, the current contrast is still insufficient after exposure. The object of the present invention is to overcome the above-mentioned problems, have a very good contrast immediately after exposure, excellent in resolution and sensitivity, and in a specific aspect, can suppress a decrease in residual film properties at the time of peeling. It aims at providing the photosensitive resin composition, the photosensitive resin laminated body using the same, and the resist pattern formation method.

  As a result of intensive studies 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.

｛式中、Ｒ₁は、炭素数１〜９のアルキル基、炭素数１〜９のアルコキシル基、炭素数１〜１６のアルキルチオ基、メルカプト基、アミノ基、及び炭素数１〜９のアルキルアミノ基からなる群より選ばれる１つの基を表す。｝で表されるメルカプトチアジアゾール化合物：０．０１〜５質量％を含有する、感光性樹脂組成物。
（２）前記（ｂ）アクリル基を有する化合物を少なくとも１種含有するエチレン性不飽和付加重合性モノマー中の、アクリル基を有する化合物が、下記一般式（ＩＩ）：

｛式中、Ｒ₂、Ｒ₃、Ｒ₄、及びＲ₅は、Ｈを表し、Ｘ及びＹは、各々独立に炭素数２〜４のアルキレン基を表し、Ｘ及びＹは互いに相異なり、ｐ¹、ｐ²、ｐ³、ｐ⁴、ｐ⁵、ｐ⁶、ｐ⁷及びｐ⁸は、各々独立に０又は正の整数であり、ｐ¹、ｐ²、ｐ³、ｐ⁴、ｐ⁵、ｐ⁶、ｐ⁷及びｐ⁸の合計は０〜２０の整数である。｝で表される化合物である、上記（１）に記載の感光性樹脂組成物。
（３）上記（ｅ）メルカプトチアジアゾール化合物が、５−メチルチオ−２−メルカプト−１，３，４−チアジアゾール、２−アミノ−５−メルカプト−１，３，４−チアジアゾール、５−メチルアミノ−２−メルカプト−１，３，４−チアジアゾール及び２，５−ジメルカプト−１，３，４−チアジアゾールからなる群より選ばれる少なくとも１種の化合物である、上記（１）又は（２）に記載の感光性樹脂組成物。
（４）上記（ｃ）光重合開始剤が含有する上記Ｎ−アリール−α−アミノ酸化合物がＮ−フェニルグリシンである、上記（１）〜（３）のいずれかに記載の感光性樹脂組成物。
（５）上記（ｂ）アクリル基を有する化合物を少なくとも１種含有するエチレン性不飽和付加重合性モノマーが、下記一般式（ＩＩＩ）：

｛式中、Ｒ₆及びＲ₇は、各々独立にＨ又はＣＨ₃を表し、ＡはＣ₂Ｈ₄を表し、ＢはＣ₃Ｈ₆を表し、ｎ１＋ｎ２は２〜３０の整数であり、ｎ３＋ｎ４は０〜３０の整数であり、ｎ１及びｎ２は各々独立に１〜２９の整数であり、ｎ３及びｎ４は各々独立に０〜３０の整数であり、そして−（Ａ−Ｏ）−及び−（Ｂ−Ｏ）−の繰り返し単位の配列は、ランダムであってもブロックであってもよい。｝で表される光重合可能な不飽和化合物から選ばれる少なくとも１種を含有する、上記（１）〜（４）のいずれかに記載の感光性樹脂組成物。
（６）基材フィルムからなる支持体上に、上記（１）〜（５）のいずれかに記載の感光性樹脂組成物からなる感光性樹脂層を積層してなる、感光性樹脂積層体。
（７）上記（６）に記載の感光性樹脂積層体を基板上に積層する積層工程、
感光性樹脂積層体における感光性樹脂層を露光する露光工程、及び
感光性樹脂層の未露光部を現像除去する現像工程
を含む、レジストパターン形成方法。
（８）上記露光工程を、描画パターンの直接描画により行う、上記（７）に記載のレジストパターン形成方法。(1) 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) Acrylic group Ethylenically unsaturated addition-polymerizable monomer containing at least one compound having the following: 5 to 60% by mass, (c) photopolymerization initiator containing N-aryl-α-amino acid compound: 0.1 to 20% by mass (D) leuco dye: 0.1 to 10% by mass, and (e) the following general formula (I):

{In the formula, R ₁ represents an alkyl group having 1 to 9 carbon atoms, an alkoxyl group having 1 to 9 carbon atoms, an alkylthio group having 1 to 16 carbon atoms, a mercapto group, an amino group, and an alkylamino group having 1 to 9 carbon atoms. It represents one group selected from the group consisting of groups. } The mercapto thiadiazole compound represented by these: The photosensitive resin composition containing 0.01-5 mass%.
(2) The compound having an acrylic group in the ethylenically unsaturated addition polymerizable monomer containing at least one compound having the acrylic group (b) is represented by the following general formula (II):

{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, 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 , The sum of p ⁶ , p ⁷ and p ⁸ is an integer of 0-20. } The photosensitive resin composition as described in said (1) which is a compound represented by these.
(3) The (e) mercaptothiadiazole compound is selected from the group consisting of 5-methylthio-2-mercapto-1,3,4-thiadiazole, 2-amino-5-mercapto-1,3,4-thiadiazole, and 5-methylamino-2. -Photosensitivity as described in (1) or (2) above, which is at least one compound selected from the group consisting of mercapto-1,3,4-thiadiazole and 2,5-dimercapto-1,3,4-thiadiazole. Resin composition.
(4) The photosensitive resin composition according to any one of (1) to (3), wherein the N-aryl-α-amino acid compound contained in the photopolymerization initiator (c) is N-phenylglycine. .
(5) An ethylenically unsaturated addition polymerizable monomer containing at least one compound having the above-mentioned (b) acrylic group is represented by the following general formula (III):

{Wherein 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, 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-(A-O)-and-( The sequence of the repeating unit (B-O)-may be random or block. } The photosensitive resin composition in any one of said (1)-(4) containing at least 1 sort (s) chosen from the photopolymerizable unsaturated compound represented by these.
(6) The photosensitive resin laminated body formed by laminating | stacking the photosensitive resin layer which consists of the photosensitive resin composition in any one of said (1)-(5) on the support body which consists of a base film.
(7) A laminating step of laminating the photosensitive resin laminate according to (6) above on a substrate,
A resist pattern forming method comprising an exposure step of exposing a photosensitive resin layer in a photosensitive resin laminate, and a development step of developing and removing an unexposed portion of the photosensitive resin layer.
(8) The resist pattern forming method according to (7), wherein the exposure step is performed by direct drawing of a drawing pattern.

  According to the present invention, a photosensitive resin composition that has a very good contrast immediately after exposure, is excellent in resolution and sensitivity, and in a specific embodiment can suppress a decrease in residual film properties at the time of peeling, and A photosensitive resin laminate and a resist pattern forming method using the same are provided.

  Hereinafter, the present invention will be specifically described.

<Photosensitive resin composition>
The present invention provides an alkali-soluble polymer (a) containing a carboxylic acid, having an acid equivalent of 100 to 600, and a weight average molecular weight of 5,000 to 500,000 (in this specification, (a) alkali-soluble (Also referred to as a polymer): 20 to 80% by mass, (b) an ethylenically unsaturated addition polymerizable monomer containing at least one compound having an acrylic group (in this specification, (b) ethylenically unsaturated addition polymerization) 5-60 mass%, (c) a photopolymerization initiator containing an N-aryl-α-amino acid compound (also referred to as (c) photopolymerization initiator in this specification): 0 0.1 to 20% by mass, (d) leuco dye: 0.1 to 10% by mass, and (e) the following general formula (I):

{In the formula, R ₁ represents an alkyl group having 1 to 9 carbon atoms, an alkoxyl group having 1 to 9 carbon atoms, an alkylthio group having 1 to 16 carbon atoms, a mercapto group, an amino group, and an alkylamino group having 1 to 9 carbon atoms. It represents one group selected from the group consisting of groups. } The photosensitive resin composition containing 0.01-5 mass% (in this specification, it is also called (e) mercapto thiadiazole compound) represented by this.

(A) Alkali-soluble polymer (a) The alkali-soluble polymer in the photosensitive resin composition of the present invention contains a carboxylic acid, has an acid equivalent of 100 to 600, and a weight average molecular weight of 5,000 to 500, 000 alkali-soluble polymer.

  (A) The carboxyl group of the alkali-soluble polymer is necessary for the photosensitive resin composition to have developability and peelability with respect to the developer and stripper made of an aqueous alkali solution. (A) The acid equivalent of the alkali-soluble polymer is 100 to 600, preferably 250 to 450. The acid equivalent ensures compatibility with the solvent or other component in the photosensitive resin composition, particularly with an ethylenically unsaturated addition polymerizable monomer containing at least one compound (b) having an acrylic group described later. From the viewpoint of maintaining the developing property and the peelability. Here, the acid equivalent means the mass (gram) of the alkali-soluble polymer having 1 equivalent of a carboxyl group therein. The acid equivalent is measured by potentiometric titration with 0.1 mol / L NaOH aqueous solution using Hiranuma Reporting Titrator (COM-555).

(A) The weight average molecular weight of the alkali-soluble polymer is 5,000 to 500,000. It is 5,000 or more from the viewpoint of maintaining the thickness of the photosensitive resin layer uniform and obtaining resistance to the developing solution, and 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 this specification, the weight average molecular weight means a weight average molecular weight measured by gel permeation chromatography (GPC) using a calibration curve of polystyrene (for example, Shodex STANDARD SM-105 manufactured by Showa Denko KK). More typically, the weight average molecular weight can be measured using gel permeation chromatography manufactured by JASCO Corporation under the following conditions.
Differential refractometer: RI-1530
Pump: PU-1580
Degasser: DG-9-80-50
Column oven: CO-1560
Column: KF-802.5, KF-806M × 2, KF-807 in order
Eluent: THF

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

  The first monomer is a carboxylic acid or carboxylic anhydride having one polymerizable unsaturated group in the molecule. Examples include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, and maleic acid half ester. Among these, (meth) acrylic acid is particularly preferable.

  The second monomer 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, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl ( (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, vinyl alcohol esters such as vinyl acetate, (meth) Examples include acrylonitrile, styrene, and polymerizable styrene derivatives. Of these, methyl (meth) acrylate, n-butyl (meth) acrylate, styrene, and benzyl (meth) acrylate are particularly preferable.

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

  (A) The content rate of the alkali-soluble polymer in the photosensitive resin composition is in the range of 20 to 80% by mass, and preferably in the range of 30 to 70% by mass. From the viewpoint that the resist pattern formed by exposure and development has sufficient resist properties, such as tenting, etching, and various plating processes, the content is 20% by mass or more and 80% by mass or less. .

(B) Ethylenically unsaturated addition polymerizable monomer containing at least one compound having an acrylic group (b) Ethylenically unsaturated addition containing at least one compound having an acrylic group in the photosensitive resin composition of the present invention The polymerizable monomer is a monomer having one or more ethylenically unsaturated bonds. By containing at least one compound having an acrylic group, the effect of improving contrast immediately after exposure is imparted. Examples of the compound having an acrylic group include 1,6-hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, polypropylene glycol diacrylate, polyethylene glycol diacrylate, and 2-di (p-hydroxyphenyl) propanediene. Acrylate, glycerol triacrylate, trimethylolpropane triacrylate, polyoxypropyltrimethylolpropane triacrylate, polyoxyethyltrimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, Trimethylolpropane triglycidyl ether triacrylate, bisphenol A diglycidyl ether diacrylate, β-hydroxypropyl-β ′-(a Liloyloxy) propyl phthalate, phenoxy polyethylene glycol acrylate, nonyl phenoxy polyethylene glycol acrylate, nonyl phenoxy polyalkylene glycol acrylate, polypropylene glycol monoacrylate, alkylene oxide adduct of bisphenol A (for example, an average of 5 moles of ethylene oxide added at both ends) Polypropylene glycol with addition of diacrylate, triethylene glycol dodecapropylene glycol, propylene oxide), an adduct formed by adding propylene oxide with an average of 2 moles at both ends and an average of 15 moles of ethylene oxide at both ends. Ethylene oxide was further added to both ends (polyethylene oxide with an average of 12 moles of propylene oxide added). An average of 3 moles of ethylene oxide is added to both ends of propylene glycol, respectively) and polyalkylene glycol diacrylates. Among these, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, bisphenol A diglycidyl ether diacrylate, and diacrylate of bisphenol A alkylene oxide adduct are preferable.

  In particular, the compound having an acrylic group is represented by the following general formula (II):

{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, 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 , The sum of p ⁶ , p ⁷ and p ⁸ is an integer of 0-20. } Is most preferable from the viewpoint of achieving a good balance between the contrast immediately after exposure, the sensitivity, the resolution, and the remaining film ratio.

  It is preferable that the content rate of the compound which has an acrylic 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%. . The content is preferably 1% by mass or more, more preferably 5% by mass or more from the viewpoint of having good contrast immediately after exposure. Moreover, it is preferable that it is 45 mass% or less from a viewpoint of suppressing the fall of the remaining 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 one compound having an acrylic group is represented by the following general formula (III):

{Wherein 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, 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-(A-O)-and-( The sequence of the repeating unit (B-O)-may be random or block. } It is preferable from the point of resolution to contain at least 1 sort (s) chosen from the photopolymerizable unsaturated compound represented by these.

  Examples of the compound represented by the general formula (III) include 2,2-bis {(4-acryloxypolyethyleneoxy) phenyl} propane and 2,2-bis {(4-methacryloxypolyethyleneoxy) phenyl} propane. Is mentioned. The polyethyleneoxy group of the compound represented by the general formula (III) is monoethyleneoxy group, diethyleneoxy group, triethyleneoxy group, tetraethyleneoxy group, pentaethyleneoxy group, hexaethyleneoxy group, heptaethyleneoxy group. Group, octaethyleneoxy group, nonaethyleneoxy group, decaethyleneoxy group, undecaethyleneoxy group, dodecaethyleneoxy group, tridecaethyleneoxy group, tetradecaethyleneoxy group, and pentadecaethyleneoxy group It is preferably any group selected.

  Examples of the compound represented by the general formula (III) include 2,2-bis {(4-acryloxypolyalkyleneoxy) phenyl} propane and 2,2-bis {(4-methacryloxypolyalkyleneoxy). Phenyl} propane and the like are also included. Examples of the polyalkyleneoxy group possessed by the compound represented by the general formula (III) include a mixture of an ethyleneoxy group and a propyleneoxy group, and an adduct having a block structure of an octaethyleneoxy group and a dipropyleneoxy group. Or an adduct of random structure, an adduct of block structure of tetraethyleneoxy group and tetrapropyleneoxy group or an adduct of random structure, an adduct of block structure of pentadecaethyleneoxy group and dipropyleneoxy group or random Structure additions are preferred. Among these, 2,2-bis {(4-methacryloxypentaethyleneoxy) phenyl} propane is most preferable.

  (B) When the ethylenically unsaturated addition polymerizable monomer contains the compound represented by the general formula (III), the compound represented by the general formula (III) in the photosensitive resin composition of the present invention It is preferable that a content rate is 1-40 mass%, More preferably, it is 5-30 mass%. The content is preferably 1% by mass or more from the viewpoint of having good contrast immediately after exposure, and is preferably 40% by mass or less from the viewpoint of suppressing a decrease in resolution and adhesion. .

  (B) As the ethylenically unsaturated addition polymerizable monomer, for example, the following photopolymerization is possible in combination with or in place of the above-mentioned compound having an acrylic group and the compound represented by the general formula (III) Unsaturated compounds can be used. 1,6-hexanediol dimethacrylate, 1,4-cyclohexanediol dimethacrylate, polypropylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 2-di (p-hydroxyphenyl) propane dimethacrylate, glycerol trimethacrylate , Trimethylolpropane trimethacrylate, polyoxypropyltrimethylolpropane trimethacrylate, polyoxyethyltrimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentamethacrylate, trimethylolpropane triglycidyl Ether trimethacrylate, bisphenol A diglycidyl ether dimethacrylate, β-hydroxypropyl-β ′-( (Methacryloyloxy) propyl phthalate, phenoxypolyethylene glycol methacrylate, nonylphenoxypolyethylene glycol methacrylate, nonylphenoxypolyalkylene glycol methacrylate, polypropylene glycol monomethacrylate, alkylene oxide adduct of bisphenol A (for example, an average of 5 moles of ethylene oxide at both ends) Addition product of dimethacrylate, triethylene glycol dodecapropylene glycol, and propylene oxide (addition product of addition of 2 mol of propylene oxide on average at both ends and 15 mol of ethylene oxide on average at both ends) Further, ethylene oxide was added at both ends to the prepared polypropylene glycol (average 12 mol of propylene oxide). Polypropylene was added glycolate - addition le of both ends of ethylene oxide to each average 3 moles each) dimethacrylate polyalkylene glycol.

  Examples of the (b) ethylenically unsaturated addition polymerizable monomer also include urethane compounds. Examples of urethane compounds include hexamethylene diisocyanate, tolylene diisocyanate, and diisocyanate compounds such as 2,2,4-trimethylhexamethylene diisocyanate, and compounds having a hydroxyl group and a (meth) acryl group in one molecule, such as , 2-hydroxypropyl acrylate, and urethane compounds with oligopropylene glycol monomethacrylate. Specifically, there is a reaction product of hexamethylene diisocyanate and oligopropylene glycol monomethacrylate (Nippon Yushi Co., Ltd., Blenmer PP1000). Urethane compounds may be used alone or in combination of two or more.

  The content ratio in the photosensitive resin composition of the (b) ethylenically unsaturated addition polymerizable monomer used in the present invention is in the range of 5 to 60% by mass, and preferably in the range of 10 to 50% by mass. The said content rate is 5 mass% or more from a viewpoint which a sensitivity, a resolution, and adhesiveness improve, and it is 60 mass% or less from a viewpoint from which an edge fuse is suppressed.

(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. By including the N-aryl-α-amino acid compound, good sensitivity is ensured. Among these, N-aryl-α-amino acid compound is particularly preferably N-phenylglycine from the viewpoint of sensitivity.

  As the (c) photopolymerization initiator used in the present invention, a system in which an N-aryl-α-amino acid compound and an acridine derivative are used in combination is preferable. Examples of acridine derivatives 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 (Asahi Denka Kogyo Co., Ltd.) N-1717), 1,8-bis (9-acridinyl) octane, 1,9-bis (9-acridinyl) nonane, 1,10-bis (9-acridinyl) decane, 1,11-bis (9 -Acridinyl) undecane, 1,12-bis (9-acridinyl) dodecane.

  (C) In addition to the compounds shown above, other photopolymerization initiators can be used in combination as the photopolymerization initiator. Here, the photopolymerization initiator means a compound that is activated by various actinic rays, such as ultraviolet rays, and starts polymerization.

  Examples of the other photopolymerization initiator include pyrazolines such as 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, quinones such as 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 such as 9-phenylacridine, benzyl ketals Examples thereof include benzyldimethylketal and benzyldiethylketal.

  As other photopolymerization initiators, thioxanthones such as thioxanthone, 2,4-diethylthioxanthone or 2-chlorothioxanthone can be used in combination with a tertiary amine compound such as a dimethylaminobenzoic acid alkyl ester compound. It is.

  Examples of the other photopolymerization initiator include oxime esters such as 1-phenyl-1,2-propanedione-2-O-benzoyloxime and 1-phenyl-1,2-propanedione-2- (O -Ethoxycarbonyl) oxime is also mentioned.

  (C) The content rate in the photosensitive resin composition of a photoinitiator is the range of 0.1 mass%-20 mass%. If the content is less than 0.1% by mass, sufficient sensitivity cannot be obtained. On the other hand, when the content ratio exceeds 20% by mass, fog due to diffraction of light passing through the photomask at the time of exposure tends to occur, and as a result, resolution is deteriorated. The content ratio is more preferably in the range of 0.1 to 15% by mass, and still more preferably in the range of 0.1 to 10% by mass.

(D) Leuco dye Examples of (d) leuco dye in the photosensitive resin composition of the present invention include leuco crystal violet and fluoran dye. Among these, when leuco crystal violet is used, the contrast immediately after exposure is good, which is preferable. Examples of the fluorane dye include 3-diethylamino-6-methyl-7-anilinofluorane, 3-dibutylamino-6-methyl-7-anilinofluorane, and 2- (2-chloroanilino) -6-dibutylamino. Fluorane, 2-bromo-3-methyl-6-dibutylaminofluorane, 2-N, N-dibenzylamino-6-diethylaminofluorane, 3-diethylamino-7-chloroaminofluorane, 3,6-dimethoxy Fluorane, 3-diethylamino-6-methoxy-7-aminofluorane and the like can be mentioned.

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

(E) Mercaptothiadiazole Compound (e) Mercaptothiadiazole compound in the photosensitive resin composition of the present invention is represented by the following general formula (I):

{In the formula, R ₁ represents an alkyl group having 1 to 9 carbon atoms, an alkoxyl group having 1 to 9 carbon atoms, an alkylthio group having 1 to 16 carbon atoms, a mercapto group, an amino group, and an alkylamino group having 1 to 9 carbon atoms. It represents one group selected from the group consisting of groups. } It is a compound represented.

  (E) Examples of mercaptothiadiazole compounds include 5-methyl-2-mercapto-1,3,4-thiadiazole, 5-ethyl-2-mercapto-1,3,4-thiadiazole, and 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-ethylthio-2-mercapto-1,3,4-thiadiazole, 5- -Propylthio-2-mercapto-1,3,4-thiadiazole, 5-isopropylthio-2-mercapto-1,3,4-thiadiazole, 2-amino-5-mercapto-1,3,4-thiadiazole, 5- Examples include methylamino-2-mercapto-1,3,4-thiadiazole and 2,5-dimercapto-1,3,4-thiadiazole.

  In particular, 5-methylthio-2-mercapto-1,3,4-thiadiazole, 2-amino-5-mercapto-1,3,4-thiadiazole, 5-methylamino-2-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 can be used alone or in combination of two or more.

  (E) The content ratio of the mercaptothiadiazole compound in the photosensitive resin composition is in the range of 0.01 to 5% by mass, preferably in the range of 0.05 to 3% by mass, most preferably 0.00. It is the range of 1-2 mass%. The content is 0.01% by mass or more from the viewpoint of obtaining sufficient sensitivity and adhesion, and contrast, and is 5% by mass or less from the viewpoint of maintaining storage stability. In addition, since the (e) mercaptothiadiazole compound is a powder at normal temperature, the above-mentioned content ratio is typically a solid content ratio.

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

  Examples of the halogen compound include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzal bromide, methylene bromide, tribromomethylphenyl sulfone, carbon tetrabromide, tris (2 , 3-dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, hexachloroethane, halogenated triazine compounds and the like. .

  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 the present invention, in order to improve the handleability of the photosensitive resin composition, in addition to the above-mentioned (d) leuco dye, a coloring substance can be contained in the photosensitive resin composition. Examples of the coloring substance include fuchsin, phthalocyanine green, olamine base, paramadienta, crystal violet, methyl orange, Nile Bull-2B, Victoria Bull, malachite green (for example, Eisen (registered trademark) manufactured by Hodogaya Chemical Co., Ltd.) ) MALACHITE GREEN), Basic Bull-20, and diamond green (for example, Eizen (registered trademark) DIAMOND GREEN GH manufactured by Hodogaya Chemical Co., Ltd.).

  When using the said coloring substance, it is preferable that the content rate of the coloring substance in the photosensitive resin composition is 0.001-1 mass%, and it is more preferable that it is 0.01-0.1 mass%. When the said content rate 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 the present invention, it is also possible to contain a stabilizer in the photosensitive resin composition. Examples of the stabilizer include 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), diphenylnitrosamine and the like. Also included are benzotriazole, carboxybenzotriazole, 1- (2-dialkylamino) carboxybenzotriazole, pentaerythritol-3,5-di-t-butyl-4-hydroxyphenylpropionic acid tetraester and the like.

  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 content 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. is there.

  Furthermore, the photosensitive resin composition of the present invention can contain a plasticizer as necessary. Plasticizers include phthalates such as diethyl phthalate, o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, acetyl triethyl citrate, acetyl citrate tri-n-propyl, Examples include tri-n-butyl acetyl citrate, 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 content ratio is 50% by mass or less, the effect of suppressing the delay of development time and imparting flexibility to the cured film is good, and when it is 5% by mass or more, insufficient curing and cold flow are suppressed. The effect of doing is good.

<Photosensitive resin laminate>
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 laminate of the present invention has a photosensitive resin layer and a support made of a base film that supports the photosensitive resin layer, and if necessary, a surface of the photosensitive resin layer opposite to the support. May have a protective layer.

  The base film is preferably a transparent film that transmits light emitted from the exposure light source. Examples of such a base film include 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, and a polymethyl methacrylate copolymer film. , Polystyrene film, polyacrylonitrile film, styrene copolymer film, polyamide film, cellulose derivative film and the like. These films can be stretched if necessary. The haze of the base film is preferably 5 or less. The thinner the film, the more advantageous in terms of image forming property and economic efficiency, but it is preferably 10 to 30 μm in order to maintain the strength.

  Further, an important characteristic of the protective layer used for the photosensitive resin laminate as necessary is that the protective layer is sufficiently smaller than the support in terms of adhesion to the photosensitive resin layer 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 having excellent peelability disclosed in JP-A-59-202457 can be used. The thickness of the protective layer is preferably 10 to 100 μm, and more preferably 10 to 50 μm.

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

  As a method for producing the photosensitive resin laminate of the present invention by sequentially laminating a support, a photosensitive resin layer, and if necessary, a protective layer, a conventionally known method can be employed. For example, the photosensitive resin composition used for the photosensitive resin layer is mixed with a solvent that dissolves the photosensitive resin composition to form a uniform solution. First, the solution is applied onto a support using a bar coater or a roll coater and dried. A photosensitive resin layer made of a photosensitive resin composition is laminated on the body. Next, if necessary, a photosensitive resin laminate can be produced by laminating a protective layer on the photosensitive resin layer.

  Examples of the solvent include ketones represented by methyl ethyl ketone (MEK), and alcohols represented by methanol, ethanol, and isopropanol. It is preferable to add a solvent to the photosensitive resin composition so that the viscosity of the solution of the photosensitive resin composition applied on the support is 500 to 4000 mPa · s at 25 ° C.

<Resist pattern formation method>
The above-described photosensitive resin composition and photosensitive resin laminate according to the present invention can be used for forming a negative resist pattern. The present invention includes a laminating step of laminating the above-described photosensitive resin laminate of the present invention on a substrate, an exposure step of exposing the photosensitive resin layer in the photosensitive resin laminate, and developing an unexposed portion of the photosensitive resin layer. There is also provided a resist pattern forming method including a developing step of removing. An example of a specific method is shown below.

  Examples of the substrate include a copper-clad laminate for the purpose of manufacturing a printed wiring board, and a glass substrate coated with a glass rib paste for the purpose of manufacturing an uneven substrate, for example, a substrate for a plasma display panel, a surface electrolytic display Examples include a substrate, an organic EL sealing cap substrate, a silicone wafer having a through hole, and a ceramic substrate. The plasma display substrate is a substrate in which an electrode is formed on glass, a dielectric layer is applied, a partition wall glass paste is then applied, and a partition wall glass paste portion is subjected to sandblasting to form a partition wall. What passed through the sandblasting process for these substrates becomes an uneven substrate.

[Lamination process]
In the lamination step, for example, a photosensitive resin laminate is laminated on the substrate using a laminator or the like. 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 substrate surface with a laminator and laminated. In this case, the photosensitive resin layer may be laminated only on one side of the substrate surface or on both sides. The heating temperature at this time is generally 40 to 160 ° C. Moreover, adhesion and chemical resistance are improved by performing the thermocompression bonding twice or more. At this time, a two-stage laminator having two rolls may be used for pressure bonding, or the photosensitive resin laminate and the substrate may be repeatedly passed through the roll and pressure bonded.

[Exposure process]
Next, 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 exposed to active light through a photomask. The exposure amount is determined by the illuminance of the light source and the exposure time, and may be measured using a light meter. The exposure process may be performed by direct drawing of a drawing pattern. The direct drawing exposure method is a method in which exposure is performed by directly drawing on a substrate without using a photomask. As the light source, for example, a semiconductor laser having a wavelength of 350 to 410 nm or an ultrahigh pressure mercury lamp is used. The drawing pattern is controlled by a computer, and the exposure amount in this case is determined by the light source illuminance and the moving speed of the substrate.

[Development process]
In the development step, the unexposed portion of the photosensitive resin layer is developed and removed using a developing device. After exposure, when there is a support on the photosensitive resin layer, this is removed as necessary, and then the unexposed portion is developed and removed using a developer of an alkaline aqueous solution to obtain a resist pattern. As the alkaline aqueous solution, for example, an aqueous solution of Na ₂ CO ₃ or K ₂ CO ₃ is used. These are selected in accordance with the characteristics of the photosensitive resin layer, but an aqueous Na ₂ CO ₃ solution having a concentration of 0.2 to 2% by mass and 20 to 40 ° C. is common. In the alkaline aqueous solution, a surfactant, an antifoaming agent, a small amount of an organic solvent for accelerating development, and the like may be mixed.

  Although a resist pattern can be obtained by the above-described process, a heating process at 100 to 300 ° C. can be further performed in some cases. By carrying out this heating step, chemical resistance can be further improved. For the heating, a hot air, infrared or far-infrared heating furnace can be used.

<Conductor Pattern Manufacturing Method and Printed Wiring Board Manufacturing Method>
The present invention can be suitably applied to a conductor pattern manufacturing method and a printed wiring board manufacturing method. For example, a conductor pattern and a printed wiring board can be manufactured by using a copper-clad laminate or a flexible substrate as a substrate and performing the following steps following the resist pattern forming method described above.

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

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

<Lead frame manufacturing method>
The present invention can also be suitably applied to a lead frame manufacturing method. Specifically, a lead frame can be manufactured by using a metal plate, for example, a copper, copper alloy, or iron-based alloy plate as a substrate and following the above-described resist pattern forming method through the following steps.

  First, the substrate exposed by development in the resist pattern forming method is etched to form a conductor pattern. Thereafter, the resist pattern is peeled off by a method similar to the method for manufacturing a printed wiring board described above to obtain a desired lead frame.

<Semiconductor package manufacturing method>
The present invention can also be suitably applied to a semiconductor package manufacturing method. Specifically, a semiconductor package can be manufactured by using a wafer on which an LSI circuit has been formed as a substrate and performing the following steps following the resist pattern forming method described above.

  First, the opening exposed by the development in the resist pattern forming method is subjected to columnar plating with, for example, copper or solder to form a conductor pattern. Thereafter, the resist pattern is peeled off by the same method as the above-described printed wiring board manufacturing method, and a thin metal layer other than the columnar plating is removed by etching to obtain a desired semiconductor package.

<Manufacturing method of substrate having concave / convex pattern>
The present invention can also be suitably applied to a method for producing a substrate having an uneven pattern. When processing the substrate by the sandblasting method using the photosensitive resin laminate of the present invention as a dry film resist, a glass substrate coated with a glass rib paste is used as the substrate, and the same method as described above is used on the substrate. The photosensitive resin laminate is laminated by the method, and exposure and development are performed.
Furthermore, the substrate is subjected to a sand blasting process in which a blasting material is sprayed from the formed resist pattern and cut to a desired depth, and a resin part remaining on the substrate is removed from the substrate with an alkaline stripping solution. A fine concavo-convex pattern can be processed on top. As the blast material used in the sandblasting process used known ones, for _{example, SiO, SiO 2, Al 2} O 3, CaCO 3, ZrO, and a glass, or a stainless steel material, particle diameter of about 2~100μm Fine particles are used.

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

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

<Preparation of photosensitive resin laminate>
Prepare the compounds shown in Table 1, thoroughly stir and mix the photosensitive resin compositions in the composition ratios shown in Tables 2 and 3, and uniformly use a bar coater on the surface of a 19 μm-thick polyethylene terephthalate film as a support. This was applied and 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. Next, a 23 μm thick polyethylene film was laminated as a protective layer on the surface of the photosensitive resin layer on which the polyethylene terephthalate film was not laminated to obtain a photosensitive resin laminate. In Table 1, “P” corresponds to (a) an alkali-soluble polymer, and “M-1” and “M-2” are (b) photopolymerizable monomers in an ethylenically unsaturated addition polymerizable monomer. Corresponding to a saturated compound, “M-3” corresponds to (b) a compound having an acrylic group in an ethylenically unsaturated addition polymerizable monomer, and “I-1” corresponds to (c) an acridine derivative in a photopolymerization initiator. Correspondingly, “I-2” corresponds to (c) the N-aryl-α-amino acid compound in the photopolymerization initiator, and “I-3”, “I-4” and “I-5” are (e) Corresponding to the mercaptothiadiazole compound, “D-1” corresponds to (d) leuco dye. Moreover, the mass part of P in Tables 2 and 3 is a value including methyl ethyl ketone.

<Smoothing of copper-clad laminate>
Using a 0.4 mm thick copper clad laminate on which 35 μm rolled copper foil was laminated, the surface was polished with jet scrub (made by Ishii Corporation).

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

<Exposure: Direct drawing method>
A photosensitive resin laminate laminated on a copper-clad laminate is 20 mJ / with a direct drawing type exposure apparatus (manufactured by Hitachi Via Mechanics Co., Ltd., DI exposure machine DE-1AH, light source: GaN blue-violet diode, main wavelength 407 ± 3 nm). It exposed with the exposure amount of cm < ² >.

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

2. Evaluation Method (1) Contrast Evaluation Method Immediately after Exposure After 30 seconds and 1 minute after the exposure of the photosensitive resin layer, the colorimetric colorimeter ( The color difference ΔE was measured by Σ80) manufactured by Nippon Denshoku Co., Ltd. The contrasts after 30 seconds and 1 minute after exposure were ranked 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) Resolution Evaluation Method A line pattern having a ratio of 1: 1 between the exposed area and the unexposed area was drawn by direct exposure and developed. The minimum width at which the cured resist line was normally formed without chipping or peeling was defined as the resolution value. The resolution was ranked as follows.
AA: 35 μm or less A: Over 35 μm

(3) Sensitivity evaluation method Exposure and development were carried out using a 21-step tablet manufactured by Stofer, whose brightness was changed from transparent to black in 21 steps. The ranks were classified as follows according to the number of step tablet stages in which the resist film remained completely after development.
AA: The number of step tablet stages where the resist film remains completely is 5 or more A: The number of step tablet stages where the resist film completely remains is less than 5 stages

(4) Evaluation method of remaining film rate After exposing the photosensitive resin laminate from the polyethylene terephthalate film side, peeling the polyethylene terephthalate film and the polyethylene film from the exposed photosensitive resin laminate, and measuring the mass of the cured film The mixture was stirred in a 3 mass% NaOH solution at 50 ° C. for 3 hours. Next, the NaOH solution was filtered, the cured film remaining on the filter paper was dried, and the mass was measured. The ratio of the mass of the cured film remaining to the mass of the cured film before stirring was defined as the remaining film ratio.
AA: The remaining film rate is 25% or more A: The remaining film rate is less than 25%

3. Evaluation results Tables 2 and 3 show the evaluation results of Examples and Comparative Examples.

  The present invention includes, for example, production of printed wiring boards, production of lead frames for mounting IC chips, precision metal foil processing represented by metal mask production, production of packages represented by BGA and CSP, and representative of COF and TAB. It can be suitably used for the production of tape substrates, semiconductor bumps, flat panel display partitions represented by ITO electrodes, address electrodes and electromagnetic wave shields, and the production of substrates having uneven patterns by sandblasting. .

Claims (6)

Containing (a) a carboxylic acid, acid equivalent is 100 to 600, alkali-soluble polymer having a weight average molecular weight of 5,000 to 500,000: 20 to 80 wt%, (b) having an acrylic Roiruokishi group Ethylenically unsaturated addition polymerizable monomer containing at least one compound: 5 to 60% by mass, (c) Photopolymerization initiator containing N-aryl-α-amino acid compound: 0.1 to 20% by mass, ( d) Leuco dye: 0.1 to 10% by mass, and (e) the following general formula (I):

{In the formula, R ₁ represents an alkyl group having 1 to 9 carbon atoms, an alkoxyl group having 1 to 9 carbon atoms, an alkylthio group having 1 to 16 carbon atoms, a mercapto group, an amino group, and an alkylamino group having 1 to 9 carbon atoms. It represents one group selected from the group consisting of groups. } Mercaptothiadiazole compound represented by: 0.01 to 5% by mass,
Wherein a compound having an acrylate Roiruokishi group containing 5 wt% to 45 wt%,
A photosensitive resin composition for direct drawing of a drawing pattern, wherein the photopolymerization initiator contains an N-aryl-α-amino acid compound and 9-phenylacridine.   The (e) mercaptothiadiazole compound is 5-methylthio-2-mercapto-1,3,4-thiadiazole, 2-amino-5-mercapto-1,3,4-thiadiazole, 5-methylamino-2-mercapto- The photosensitive resin composition according to claim 1, which is at least one compound selected from the group consisting of 1,3,4-thiadiazole and 2,5-dimercapto-1,3,4-thiadiazole.   The photosensitive resin composition according to claim 1 or 2, wherein the N-aryl-α-amino acid compound contained in the (c) photopolymerization initiator is N-phenylglycine. Wherein (b) ethylenically unsaturated addition polymerizable monomer containing at least one compound having an acrylic Roiruokishi group is represented by the following general formula (III):

{Wherein 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, 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-(A-O)-and-( The sequence of the repeating unit (B-O)-may be random or block. } The photosensitive resin composition of Claim 1 or 2 containing the at least 1 sort (s) chosen from the photopolymerizable unsaturated compound represented by these.   The photosensitive resin laminated body formed by laminating | stacking the photosensitive resin layer which consists of the 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 5 on a substrate,
A resist pattern forming method, comprising: an exposure step of exposing a photosensitive resin layer in a photosensitive resin laminate by direct drawing of a drawing pattern; and a development step of developing and removing an unexposed portion of the photosensitive resin layer.