JP5056088B2 - Photosensitive resin composition, photosensitive element using the same, resist pattern forming method, and printed wiring board manufacturing method - Google Patents

Description

  The present invention relates to a photosensitive resin composition, a photosensitive element using the same, a resist pattern forming method, and a printed wiring board manufacturing method.

  Conventionally, solder resist has been used in the production of printed wiring boards, but in recent years it has also been used in new LSI packages such as BGA (ball grid array), PGA (pin grid array), and CSP (chip size package). It has become like this. The solder resist is an indispensable material as a protective film or a permanent mask that prevents the solder from adhering to unnecessary portions in the soldering process.

  As a method for forming a solder resist, for example, there is a method of printing a thermosetting resin composition by a screen printing method. However, in recent years, with the increase in wiring density, the screen printing method has a limit in terms of resolution, and a photo solder resist that forms a pattern by a photographic method has been actively used. In particular, alkali-developable photosensitive resin compositions that can be developed with a weak alkaline solution such as a sodium carbonate solution have become mainstream from the viewpoints of work environment conservation, global environment conservation, and the like (for example, Patent Documents 1 and 2 below). reference).

  However, a solder resist formed using an alkali development type photosensitive resin composition has a problem that it is still insufficient in terms of durability. That is, chemical resistance, water resistance, heat resistance and the like tend to be inferior to a solder resist formed using a conventional thermosetting resin composition or a solvent development type photosensitive resin composition. The alkali-developable photosensitive resin composition is mainly composed of a resin having a hydrophilic group so that alkali development is possible. Therefore, the formed solder resist is infiltrated with chemicals, water, water vapor, and the like. Cheap. As a result, it is considered that the adhesion between the resist film and copper is lowered. In particular, in semiconductor packages such as BGA and CSP, the solder resist is particularly required to have resistance to PCT (pressure cooker resistance) and electric corrosion resistance, which is also referred to as heat and moisture resistance, but sufficient performance has not yet been obtained. is the current situation.

  Furthermore, since the mounting method changes from insertion mounting to surface mounting, the temperature applied to the package during mounting tends to increase. Specifically, in the case of surface mounting, cream solder is printed in advance on necessary parts, the whole is heated with infrared rays, and the solder is reflowed and fixed, so that the temperature reached inside and outside of the package is remarkably high at 220 to 280 ° C. . Therefore, in a solder resist formed using a conventional liquid photosensitive resin composition, cracking occurs due to thermal shock or peeling from the substrate or sealing material, so-called reflow resistance degradation and thermal shock resistance. There is a problem, and the improvement thereof has been studied (for example, see Patent Document 3 below).

  In recent years, a film-like printed wiring board called a flexible printed circuit (hereinafter referred to as “FPC”) has been used as a kind of printed wiring board, particularly in small devices such as cameras, magnetic heads, and mobile phones. It is used. This is because the FPC can maintain its function even when it is bent, and is optimal as a printed wiring board to be accommodated in a small device as described above. Particularly in recent years, there has been an increasing demand for further miniaturization and weight reduction of various electronic devices. By adopting FPC for wiring such devices, the size and weight of the small devices are reduced, and the product cost is reduced. Reduction, simplification of design, and the like have been realized.

  The solder resist used in this FPC is required to have the same characteristics as the solder resist used in a normal rigid printed wiring board, but in addition, it is required to be flexible so that it is not destroyed when the FPC is bent. Is done.

JP-A 61-243869 JP-A-1-141904 JP 10-329330 A

  However, conventional solder resists are not always sufficiently flexible and are difficult to apply to FPC. In particular, a solder resist that satisfies all of the flexibility, developability, adhesion, PCT resistance, electric corrosion resistance and thermal shock resistance at a high level has not been obtained.

  The present invention has been made in view of the above-mentioned problems of the prior art, and in addition to the flexibility required for flexible printed wiring boards (FPC), developability, adhesion, PCT resistance, electric corrosion resistance and heat resistance. An object of the present invention is to provide a photosensitive resin composition that can form a cured film having excellent impact properties and is suitably used in the production of printed wiring boards and semiconductor packages. In addition, the present invention includes a layer composed of the photosensitive resin composition, and can form a cured film excellent in flexibility, developability, adhesion, PCT resistance, electric corrosion resistance, and thermal shock resistance. It is an object to provide a photosensitive element that can be used. Furthermore, an object of this invention is to provide the formation method of a resist pattern using the said photosensitive resin composition, and the manufacturing method of a printed wiring board.

In order to achieve the above object, the present invention provides (A) an esterified product of (a) an epoxy compound having at least two epoxy groups in the molecule and (b) an unsaturated group-containing monocarboxylic acid, and (c) An acid-modified vinyl group-containing epoxy resin which is an addition reaction product obtained by adding a saturated or unsaturated group-containing polybasic acid anhydride, (B) a photopolymerization initiator, (C) a diluent, and (D) a curing agent. And (E) a urethane compound having at least two (meth) acryloyl groups in the molecule , the (E) urethane compound obtained from a bifunctional five-membered carbonate and an alkyldiamine or aralkyldiamine. Provided is a photosensitive resin composition comprising a hydroxyurethane compound obtained by treating the terminal of a polyhydroxyurethane with a methacryloylating agent .

  According to such a photosensitive resin composition, a cured film that satisfies all of the flexibility, developability, adhesion, PCT resistance, electric corrosion resistance, and thermal shock resistance at a high level is formed by having the above configuration. be able to. Therefore, the said photosensitive resin composition can be used suitably for manufacture of a printed wiring board etc.

In the photosensitive resin composition of this invention, since the electrical property of the cured film obtained can be improved more, it is preferable that the said (a) epoxy compound is a compound represented by the following general formula (I).


[Wherein, R ¹ represents a hydrogen atom or a glycidyl group, and R ² represents a hydrogen atom or a methyl group. A plurality of R ¹ and R ² may be the same or different. ]

  Moreover, it is preferable that the photosensitive resin composition of this invention further contains (F) elastomer. When the photosensitive resin composition contains the elastomer (F), the thermal shock resistance of the obtained cured film can be further improved.

  Moreover, it is preferable that the photosensitive resin composition of this invention further contains (G) phenoxy resin. When the photosensitive resin composition contains the (G) phenoxy resin, the heat resistance of the obtained cured film can be further improved.

  Furthermore, it is preferable that the photosensitive resin composition of the present invention further contains (H) a blocked isocyanate. When the photosensitive resin composition contains (H) blocked isocyanate, the heat resistance of the obtained cured film can be further improved.

  The present invention also provides a photosensitive element comprising a support and a photosensitive resin composition layer comprising the above-described photosensitive resin composition of the present invention formed on the support.

  According to such a photosensitive element, by providing the photosensitive resin composition layer comprising the photosensitive resin composition of the present invention, flexibility, developability, adhesion, PCT resistance, electric corrosion resistance, and thermal shock resistance are achieved. An excellent cured film can be formed. Therefore, the said photosensitive element can be used suitably for manufacture of a printed wiring board etc.

  The present invention also includes a step of laminating a photosensitive resin composition layer comprising the photosensitive resin composition of the present invention on a substrate, and irradiating the photosensitive resin composition layer with an actinic ray in an image form to illuminate an exposed portion. There is provided a method for forming a resist pattern, which is cured, and then an unexposed portion is removed by development.

  The present invention further provides a method for producing a printed wiring board, wherein a permanent mask is formed on a substrate by the method for forming a resist pattern of the present invention.

  According to the method for forming a resist pattern and the method for producing a printed wiring board, since the photosensitive resin composition of the present invention is used, flexibility, developability, adhesion, PCT resistance, electric corrosion resistance, and A cured film such as a permanent mask (solder resist) excellent in thermal shock resistance can be efficiently formed.

  According to the present invention, a cured film excellent in flexibility, developability, adhesion, PCT resistance, electric corrosion resistance, and thermal shock resistance can be formed, which is suitable for manufacturing printed wiring boards, semiconductor packages, and the like. The photosensitive resin composition used can be provided. Further, according to the present invention, a cured film excellent in flexibility, developability, adhesion, PCT resistance, electric corrosion resistance, and thermal shock resistance can be formed, and it can be used for manufacturing printed wiring boards and semiconductor packages. The photosensitive element used suitably can be provided. Furthermore, according to this invention, the formation method of the resist pattern using the photosensitive resin composition of the said invention and the manufacturing method of a printed wiring board can be provided.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as the case may be. In the drawings, the same or corresponding parts are denoted by the same reference numerals, and redundant description is omitted. Moreover, the (meth) acrylate in this invention means an acrylate and its corresponding methacrylate, and a (meth) acryloyl group means an acryloyl group and its corresponding methacryloyl group.

(Photosensitive resin composition)
The photosensitive resin composition of the present invention comprises (A) (a) an epoxy compound having at least two epoxy groups in the molecule (hereinafter sometimes referred to as “component (a)”), and (b) an unsaturated group-containing monoester. Further, (c) a saturated or unsaturated group-containing polybasic acid anhydride (hereinafter sometimes referred to as “component (c)”) is added to an esterified product with a carboxylic acid (hereinafter sometimes referred to as “component (b)”). An acid-modified vinyl group-containing epoxy resin (hereinafter sometimes referred to as “component (A)”) as an addition reaction product and (B) a photopolymerization initiator (hereinafter sometimes referred to as “component (B)”). (C) a diluent (hereinafter sometimes referred to as “component (C)”), (D) a curing agent (hereinafter sometimes referred to as “component (D)”), and (E) at least 2 in the molecule. Urethane compounds having two (meth) acryloyl groups Hereinafter, cases are those containing, as referred to as "component (E)").

  (A) As an epoxy compound having at least two epoxy groups in the molecule, for example, phenol novolac type epoxy resin, cresol novolac type epoxy resin, salicylaldehyde type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, Examples thereof include bisphenol A type phenol novolac type epoxy resins and bisphenol F type phenol novolac type epoxy resins.

  Among these, bisphenol A type phenol novolac type epoxy resins and bisphenol F type phenol novolac type epoxy resins represented by the above general formula (I) are preferable from the viewpoint of electrical characteristics.

  Examples of the bisphenol A type phenol novolac type epoxy resin include EPONSU8 series manufactured by Japan Epoxy Resin Co., Ltd. Although the manufacturing method in particular is not restrict | limited, It can obtain by making epichlorohydrin react with bisphenol A type resin by a well-known method. Examples of the bisphenol F-type phenol novolak-type epoxy resin include EXA-7376 series manufactured by Dainippon Ink & Chemicals, Inc. Although the manufacturing method in particular is not restrict | limited, It can obtain by making epichlorohydrin react with a bisphenol F-type resin by a well-known method.

  (B) Examples of unsaturated group-containing monocarboxylic acids include acrylic acid, dimer of acrylic acid, methacrylic acid, β-furfurylacrylic acid, β-styrylacrylic acid, cinnamic acid, crotonic acid, α-cyano. Cinnamic acid, a reaction product of a hydroxyl group-containing acrylate and a saturated or unsaturated dibasic acid anhydride, a half-ester compound, a reaction product of an unsaturated group-containing monoglycidyl ether and a saturated or unsaturated dibasic acid anhydride A certain half ester compound etc. are mentioned. These half ester compounds are obtained by reacting a hydroxyl group-containing acrylate or unsaturated group-containing monoglycidyl ether with a saturated or unsaturated dibasic acid anhydride in an equimolar ratio. These (b) unsaturated group containing monocarboxylic acids can be used individually by 1 type or in combination of 2 or more types.

  (B) Examples of the hydroxyl group-containing acrylate and unsaturated group-containing monoglycidyl ether used in the synthesis of the half ester compound as an example of the unsaturated group-containing monocarboxylic acid include hydroxyethyl acrylate, hydroxyethyl methacrylate, and hydroxypropyl acrylate. , Hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate , Pentaerythritol pentamethacrylate , Glycidyl acrylate and glycidyl methacrylate and the like.

  Examples of the saturated or unsaturated dibasic acid anhydride used for the synthesis of the half ester compound include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydro Examples thereof include phthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, itaconic anhydride and the like.

  In the reaction of (a) an epoxy compound having at least two epoxy groups in the molecule and (b) an unsaturated group-containing monocarboxylic acid in the present invention, (b) ) The unsaturated group-containing monocarboxylic acid is preferably reacted at a ratio of 0.8 to 1.10 equivalents, more preferably at a ratio of 0.9 to 1.0 equivalents.

  The (a) epoxy compound and (b) the unsaturated group-containing monocarboxylic acid can be dissolved and reacted in an organic solvent. Examples of the organic solvent include ketones such as ethyl methyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene, methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, Glycol ethers such as dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether and triethylene glycol monoethyl ether, esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate and carbitol acetate, aliphatic carbonization such as octane and decane Examples thereof include petroleum solvents such as hydrogen, petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha.

  Furthermore, it is preferable to use a catalyst in order to promote the reaction between the component (a) and the component (b). Examples of the catalyst used include triethylamine, benzylmethylamine, methyltriethylammonium chloride, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, and triphenylphosphine. It is preferable that the usage-amount of a catalyst is 0.1-10 mass parts with respect to a total of 100 mass parts of (a) component and (b) component.

  Moreover, it is preferable to use a polymerization inhibitor for the purpose of preventing polymerization during the reaction. Examples of the polymerization inhibitor include hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol and the like. It is preferable that the usage-amount of a polymerization inhibitor is 0.01-1 mass part with respect to a total of 100 mass parts of (a) component and (b) component.

  Moreover, it is preferable that the reaction temperature at the time of making (a) component and (b) component react is 60-150 degreeC, and it is more preferable that it is 80-120 degreeC.

  Furthermore, (b) the unsaturated group-containing monocarboxylic acid may be added with a polybasic acid anhydride such as trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, biphenyltetracarboxylic anhydride, if necessary. Can be used together.

  (C) Saturated or unsaturated group-containing polybasic acid anhydrides include, for example, succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydroanhydride Examples include phthalic acid, methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, itaconic anhydride and the like.

  In the reaction between the reaction product (A ′) of the component (a) and the component (b) and the component (c), the component (c) is added to 1 equivalent of the hydroxyl group in the reaction product (A ′). By making 0.1-1.0 equivalent reaction, the acid value of the (A) acid-modified vinyl group containing epoxy resin obtained can be adjusted.

  In addition, it is preferable that the acid value of (A) acid-modified vinyl group containing epoxy resin is 30-150 mgKOH / g, and it is more preferable that it is 50-120 mgKOH / g. If the acid value is less than 30 mg KOH / g, the solubility of the photosensitive resin composition in a dilute alkali solution tends to be reduced, and if it exceeds 150 mg KOH / g, the electric properties of the cured film tend to be reduced. The reaction temperature between the reaction product (A ′) and the component (c) is preferably 60 to 120 ° C.

  Moreover, as needed, as a (a) epoxy resin, hydrogenated bisphenol A type epoxy resin can also be used together partially, for example. Further, (A) acid-modified vinyl group-containing epoxy resin, styrene-maleic anhydride copolymer modified with hydroxyethyl acrylate or styrene-maleic anhydride copolymer modified with styrene-maleic anhydride A part of the acid resin may be used in combination.

  In the photosensitive resin composition, the content of the component (A) is preferably 20 to 60% by mass based on the total solid content of the photosensitive resin composition. When the content of the component (A) is within the above range, a coating film that is superior in heat resistance, electrical properties, and chemical resistance tends to be obtained.

  Examples of the (B) photopolymerization initiator used in the present invention include benzoins such as benzoin, benzoin methyl ether, and benzoin isopropyl ether, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, and 2,2-diethoxy. 2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2,2-di Acetophenones such as ethoxyacetophenone and N, N-dimethylaminoacetophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, 2-aminoanthraquino Anthraquinones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, thioxanthones such as 2,4-diisopropylthioxanthone, ketones such as acetophenone dimethyl ketal and benzyl dimethyl ketal, benzophenone, methyl Benzophenones such as benzophenone, 4,4′-dichlorobenzophenone, 4,4′-bis (diethylamino) benzophenone, Michler's ketone, 4-benzoyl-4′-methyldiphenyl sulfide, 2- (o-chlorophenyl) -4,5- Diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4-di (p-methoxyphenyl) 2,4,5-triarylimidazole dimer such as -5-phenylimidazole dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimer, 9-phenylacridine, 1 , 7-bis (9,9′-acridinyl) heptane and the like, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide. These are used singly or in combination of two or more.

  Further, (B) photopolymerization initiation assistants include N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, dimethylethanolamine, triethylamine, There may be mentioned tertiary amines such as ethanolamine. These are used individually by 1 type or in combination of 2 or more types.

  In the photosensitive resin composition, the content of the (B) photopolymerization initiator is preferably 0.5 to 20% by mass, and 1 to 15% by mass based on the total solid content of the photosensitive resin composition. It is more preferable that it is 2-10 mass%. If this content is less than 0.5% by mass, the photosensitivity tends to decrease, and if it exceeds 20% by mass, the heat resistance of the cured film tends to decrease.

  As the diluent (C) used in the present invention, for example, an organic solvent and / or a photopolymerizable monomer can be used. Examples of the organic solvent include ketones such as ethyl methyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene, methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, Glycol ethers such as dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether and triethylene glycol monoethyl ether, esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate and carbitol acetate, aliphatic carbonization such as octane and decane Examples thereof include petroleum solvents such as hydrogen, petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha.

  Examples of the photopolymerizable monomer include 2-hydroxyethyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, N, N-dimethyl ( (Meth) acrylate, N-methylol (meth) acrylamide, polyethylene glycol, polypropylene glycol, polyethylene glycol or propylene glycol of bisphenol A, mono- or polyfunctional (meth) acrylates of tris (2-hydroxyethyl) isocyanuric acid, triglycidyl isocyanate Photopolymerizable monomers such as (meth) acrylates of glycidyl ether such as nurate and diallyl phthalate can be used. These can be used individually by 1 type or in mixture of 2 or more types.

  (C) When using a photopolymerizable monomer as a diluent, the content is preferably 0.5 to 30% by mass based on the total solid content of the photosensitive resin composition, and preferably 1 to 10% by mass. It is more preferable that If this content is less than 0.5% by mass, the photosensitivity tends to be low and the exposed area tends to be eluted during development, and if it exceeds 30% by mass, the heat resistance of the cured film tends to be reduced.

  As the (D) curing agent used in the present invention, (A) an acid-modified vinyl group-containing epoxy resin that is a compound that itself cures with heat, ultraviolet light, or the like, or a photocurable resin component in a photosensitive resin composition A compound that cures by reacting with a carboxyl group or a hydroxyl group with heat or ultraviolet rays is preferred. By using this (D) curing agent, the heat resistance, adhesion, chemical resistance, etc. of the finally obtained cured film can be improved.

  (D) As a hardening | curing agent, an epoxy compound, a melamine compound, a urea compound, an oxazoline compound etc. can be mentioned as a thermosetting compound, for example. Examples of the epoxy compound include bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, novolac type epoxy resin, bisphenol S type epoxy resin, and biphenyl type epoxy resin. Or heterocyclic epoxy resins such as triglycidyl isocyanurate, and bixylenol type epoxy resins. Examples of the melamine compound include triaminotriazine, hexamethoxymelamine, hexabutoxylated melamine and the like. Examples of the urea compound include dimethylol urea. These (D) curing agents are used singly or in combination of two or more.

  In the photosensitive resin composition, the content of the (D) curing agent is preferably 2 to 50% by mass, and preferably 10 to 40% by mass, based on the total solid content of the photosensitive resin composition. More preferred. If this content is less than 2% by mass, the heat resistance of the resulting cured film tends to decrease, and if it exceeds 50% by mass, the developability tends to decrease.

  The photosensitive resin composition of the present invention preferably contains an epoxy resin curing agent for the purpose of further improving various properties such as heat resistance, adhesion and chemical resistance of the cured film.

  Specific examples of such an epoxy resin curing agent include, for example, 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methyl. Imidazole derivatives such as -5-hydroxymethylimidazole; guanamines such as acetoguanamine and benzoguanamine; diaminodiphenylmethane, m-phenylenediamine, m-xylenediamine, diaminodiphenylsulfone, dicyandiamide, urea, urea derivatives, melamine, polybasic hydrazide, etc. These organic acid salts and / or epoxy adducts; amine complexes of boron trifluoride; ethyldiamino-S-triazine, 2,4-diamino-S-triazine, 2,4-diamino-6-xylyl- S Triazine derivatives such as triazine; trimethylamine, triethanolamine, N, N-dimethyloctylamine, N-benzyldimethylamine, pyridine, N-methylmorpholine, hexa (N-methyl) melamine, 2,4,6-tris ( Tertiary amines such as dimethylaminophenol), tetramethylguanidine, m-aminophenol; polyphenols such as polyvinylphenol, polyvinylphenol bromide, phenol novolac, alkylphenol novolac; tributylphosphine, triphenylphosphine, tris-2-cyanoethyl Organic phosphines such as phosphine; phosphonium salts such as tri-n-butyl (2,5-dihydroxyphenyl) phosphonium bromide and hexadecyltributylphosnium chloride Quaternary ammonium salts such as benzyltrimethylammonium chloride and phenyltributylammonium chloride; the above polybasic acid anhydrides; diphenyliodonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, 2,4,6-triphenylthiopyrylium Examples include hexafluorophosphate.

  These epoxy resin curing agents are used singly or in combination of two or more. When using an epoxy resin hardening | curing agent, it is preferable that the content is 0.01-20 mass% on the basis of the solid content whole quantity of the photosensitive resin composition, and it may be 0.1-10 mass%. More preferred.

  Moreover, a part of said epoxy resin hardening | curing agent can be substituted to another epoxy resin hardening | curing agent. Examples of the other epoxy resin curing agent include (a) an epoxy compound which is a starting material for (A) an acid-modified vinyl group-containing epoxy resin. Specific examples include novolak-type epoxy resins, bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, salicylaldehyde-type epoxy resins, epoxy group-containing polyamide resins, and epoxy group-containing polyamideimide resins. In addition, for example, biphenyl type epoxy resins such as YX4000 manufactured by Yuka Shell Epoxy Co., Ltd., dicyclo type epoxy resins such as Epicron HP7200 manufactured by Dainippon Ink and Chemicals, Ltd., manufactured by Dainippon Ink and Chemicals, Inc. Glycidylamine type epoxy resins such as Epicron 430 and Sumitomo Chemical Co., Ltd. ELM100, 120, 434, etc., glycidyl ester type epoxy resins such as Denacol EX-721 manufactured by Nagase Chemical Industries, Ltd., Dainippon Ink and Chemicals ( Naphthalene type epoxy resin such as Epiklon HP-4032 manufactured by Co., Ltd., heterocyclic type epoxy resin such as Tris (2,3-epoxypropyl) isocyanurate (Nissan Chemical Industry Co., Ltd.), manufactured by Toto Kasei Co., Ltd. Modified bisfees such as EBPS-300 and EXA-4004 manufactured by Dainippon Ink & Chemicals, Inc. Such Lumpur S type epoxy resins. These can be used individually by 1 type or in combination of 2 or more types.

  In the present invention, when these epoxy resin curing agents are used, the content thereof is preferably 1 to 50% by mass, and 5 to 30% by mass based on the total solid content of the photosensitive resin composition. Is more preferable. When this content is less than 1% by mass, curing tends to be insufficient, and when it exceeds 50% by mass, problems tend to occur in photosensitive characteristics.

  The urethane compound having at least two (meth) acryloyl groups in the molecule (E) used in the present invention is, for example, an addition reaction of a hydroxyl group-containing ethylenically unsaturated compound to a compound having at least two isocyanate groups in the molecule. Can be obtained. Such an addition reaction is preferably performed in the presence of, for example, p-methoxyphenol, di-t-butyl-hydroxy-toluene, etc. In addition, it is preferable to add dibutyltin dilaurate as a catalyst. The reaction temperature is preferably 60 to 90 ° C. If the reaction temperature is less than 60 ° C, the reaction tends not to proceed sufficiently. If the reaction temperature exceeds 90 ° C, gelation tends to occur due to rapid heat generation. The end point of the reaction may be, for example, the time when the isocyanate group disappears in the infrared absorption spectrum.

  (E) It is preferable that a urethane compound is a thing obtained by copolymerizing the component containing a carboxyl group from a viewpoint of improving developability.

  The (E) urethane compound includes at least one hydroxyl group and at least two (meta) in the molecule from the viewpoint of improving compatibility with the component (A) and / or the component (C) and improving developability. It is preferable to use a hydroxyurethane compound having an acryloyl group.

  As said hydroxy urethane compound used for this invention, what processed the terminal of the polyhydroxy urethane obtained from a bifunctional five-membered ring carbonate and alkyldiamine or aralkyldiamine with the methacryloylating agent is mentioned, for example. Examples of the bifunctional five-membered ring carbonate include bisphenol A di (1,3-dioxolan-2-one-4-ylmethyl) ether and bisphenol F di (1,3-dioxolan-2-one-4-ylmethyl). C2-C40 alkyl such as ether, ethylene glycol di (1,3-dioxolan-2-one-4-ylmethyl) ether, butanediol di (1,3-dioxolan-2-one-4-ylmethyl) ether And compounds having two five-membered ring carbonates via a group, an ether group or an aralkyl group. Examples of diamines include alkyl diamines having 2 to 20 carbon atoms and aralkyl diamines, and examples include butane diamine, hexane diamine, octane diamine, decane diamine, dodecane diamine, and xylylene diamine. Examples of the methacryloylating agent include 2-methacryloyloxyethyl isocyanate, glycidyl methacrylate, 1,3-dioxolan-2-one-4-ylmethyl methacrylate, anhydrous methacrylic acid, methacrylic acid chloride, methacrylic acid bromide, and methacrylic acid. .

  In the photosensitive resin composition, the content of the (E) urethane compound is preferably 0.5 to 20% by mass based on the total solid content of the photosensitive resin composition, and preferably 1 to 10% by mass. Is more preferable, and it is especially preferable that it is 2-8 mass%. If the content is less than 0.5% by mass, the adhesion, the electric corrosion resistance and the thermal shock resistance tend to be inferior, and if it exceeds 20% by mass, the developability tends to be inferior.

  It is preferable that the photosensitive resin composition of the present invention further contains (F) an elastomer. (F) By containing an elastomer, the adhesiveness with the conductor layer of the printed wiring board when the photosensitive resin composition is used for the solder resist can be further improved, and the heat resistance and thermal shock of the cured film are improved. , Flexibility and toughness can be further improved.

  Examples of (F) elastomers include styrene elastomers, olefin elastomers, urethane elastomers, polyester elastomers, polyamide elastomers, acrylic elastomers, and silicone elastomers. These (F) elastomers preferably have a glass transition temperature (Tg) of 20 ° C. or lower and are thermoplastic.

  Examples of the styrenic elastomer include styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-ethylene-butylene-styrene block copolymer, styrene-ethylene-propylene-styrene block copolymer, and the like. As a component constituting the styrene-based elastomer, styrene derivatives such as α-methylstyrene, 3-methylstyrene, 4-propylstyrene, and 4-cyclohexylstyrene can be used in addition to styrene. Specifically, Tufprene, Solprene T, Asaprene T, Tuftec (Asahi Kasei Kogyo Co., Ltd.), Elastomer AR (Aron Kasei Co., Ltd.), Clayton G, Super Reflex (October, Shell Japan Co., Ltd.), JSR- TR, TSR-SIS, Dynalon (manufactured by Nippon Synthetic Rubber Co., Ltd.), Denka STR (manufactured by Denki Kagaku Co., Ltd.), Quintac (manufactured by Nippon Zeon Co., Ltd.), TPE-SB series (manufactured by Sumitomo Chemical Co., Ltd.), Examples include Lavalon (manufactured by Mitsubishi Chemical Corporation), Septon, Hybler (manufactured by Kuraray Co., Ltd.), Sumiflex (manufactured by Sumitomo Bakelite Co., Ltd.), Rheostomer, Actimer (manufactured by Riken Vinyl Industry Co., Ltd.), and the like.

  The olefin elastomer is a copolymer of an α-olefin having 2 to 20 carbon atoms such as ethylene, propylene, 1-butene, 1-hexene, 4-methyl-pentene, for example, an ethylene-propylene copolymer (EPR). ), Ethylene-propylene-diene copolymer (EPDM) and the like. The olefin-based elastomer includes dicyclopentadiene, 1,4-hexadiene, cyclooctanediene, methylene norbornene, ethylidene norbornene, butadiene, isoprene, and the like. Examples include coalesced and epoxidized polybutadiene. Examples of the olefin-based elastomer include carboxy-modified NBR obtained by copolymerizing butadiene-acrylonitrile copolymer with methacrylic acid. Further, as the olefin elastomer, ethylene-α-olefin copolymer rubber, ethylene-α-olefin-nonconjugated diene copolymer rubber, propylene-α-olefin copolymer rubber, butene-α-olefin copolymer Rubber etc. are mentioned.

  Specific examples of olefin-based elastomers include milastoma (manufactured by Mitsui Petrochemical), EXACT (manufactured by Exxon Chemical), ENGAGE (manufactured by Dow Chemical), hydrogenated styrene-butadiene rubber “DYNABON HSBR” (Japanese synthetic rubber) ), Butadiene-acrylonitrile copolymer “NBR series” (manufactured by Nippon Synthetic Rubber Co., Ltd.), and “XER series” of both terminal carboxyl group-modified butadiene-acrylonitrile copolymers having a crosslinking point (manufactured by Nippon Synthetic Rubber Co., Ltd.) ) And the like.

  Urethane elastomers are composed of structural units of a hard segment composed of low molecular (short chain) diol and diisocyanate and a soft segment composed of high molecular (long chain) diol and diisocyanate. Examples of the polymer (long chain) diol include polypropylene glycol, polytetramethylene oxide, poly (1,4-butylene adipate), poly (ethylene-1,4-butylene adipate), polycaprolactone, and poly (1,6-hexene). Xylene carbonate), poly (1,6-hexylene-neopentylene adipate) and the like. The number average molecular weight of the polymer (long chain) diol is preferably 500 to 10,000. Examples of the low molecular (short chain) diol include ethylene glycol, propylene glycol, 1,4-butanediol, and bisphenol A. The number average molecular weight of the short-chain diol is preferably 48 to 500. Specific examples of the urethane elastomer include PANDEX T-2185, T-2983N (manufactured by Dainippon Ink & Chemicals, Inc.), sylactolan E790, and the like.

  The polyester elastomer is obtained by polycondensation of a dicarboxylic acid or a derivative thereof and a diol compound or a derivative thereof. Specific examples of the dicarboxylic acid include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid, and aromatic dicarboxylic acids in which hydrogen atoms of these aromatic rings are substituted with a methyl group, an ethyl group, a phenyl group, and the like, Examples thereof include aliphatic dicarboxylic acids having 2 to 20 carbon atoms such as adipic acid, sebacic acid and dodecanedicarboxylic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. These compounds can be used alone or in combination of two or more. Specific examples of the diol compound include aliphatic diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, and 1,4-cyclohexanediol; Examples include alicyclic diol, bisphenol A, bis- (4-hydroxyphenyl) -methane, bis- (4-hydroxy-3-methylphenyl) -propane, resorcin and the like. These compounds can be used alone or in combination of two or more. In addition, a multiblock copolymer having an aromatic polyester (for example, polybutylene terephthalate) portion as a hard segment component and an aliphatic polyester (for example, polytetramethylene glycol) portion as a soft segment component can be used. Polyester elastomers are available in various grades depending on the types and ratios of hard segments and soft segments, and the difference in molecular weight. Specific examples of polyester elastomers include Hytrel (Du Pont-Toray), Perprene (Toyobo), Espel (Hitachi Chemical Industries), and the like.

  Polyamide elastomers are composed of hard segments made of polyamide and soft segments made of polyether or polyester, and are roughly divided into two types: polyether block amide type and polyether ester block amide type. The Examples of the polyamide include polyamide 6, polyamide 11, and polyamide 12. Examples of the polyether include polyoxyethylene, polyoxypropylene, polytetramethylene glycol and the like. Specific examples of polyamide-based elastomers include UBE polyamide elastomer (manufactured by Ube Industries), Daiamide (manufactured by Daicel Huls), PEBAX (manufactured by Toray Industries, Inc.), Grilon ELY (manufactured by MS Japan), Novamid (manufactured by Mitsubishi Chemical Corporation). ), Glase (Dainippon Ink Chemical Co., Ltd.) and the like.

  Acrylic elastomers are acrylic esters such as ethyl acrylate, butyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, monomers having an epoxy group such as glycidyl methacrylate, allyl glycidyl ether, and / or vinyls such as acrylonitrile and ethylene. It is obtained by copolymerizing with a monomer. Examples of the acrylic elastomer include acrylonitrile-butyl acrylate copolymer, acrylonitrile-butyl acrylate-ethyl acrylate copolymer, acrylonitrile-butyl acrylate-glycidyl methacrylate copolymer, and the like.

  Silicone elastomers are mainly composed of organopolysiloxane, and are classified into polydimethylsiloxane, polymethylphenylsiloxane, and polydiphenylsiloxane. Further, a part of organopolysiloxane modified with a vinyl group, an alkoxy group or the like may be used. Specific examples of the silicone elastomer include KE series (manufactured by Shin-Etsu Chemical Co., Ltd.), SE series, CY series, SH series (above, manufactured by Toray Dow Corning Silicone Co., Ltd.) and the like.

  In addition to the above-mentioned elastomer, a rubber-modified epoxy resin can be used. The rubber-modified epoxy resin is, for example, a part or all of the epoxy groups such as the above-mentioned bisphenol F type epoxy resin, bisphenol A type epoxy resin, salicylaldehyde type epoxy resin, phenol novolac type epoxy resin, or cresol novolak type epoxy resin. Is obtained by modification with carboxylic acid-modified butadiene-acrylonitrile rubber, terminal amino-modified silicone rubber or the like.

  As the (F) elastomer used in the photosensitive resin composition of the present invention, from the viewpoint of shear adhesion and thermal shock resistance, both terminal carboxyl group-modified butadiene-acrylonitrile copolymers and polyester-based elastomer Esper ( Espel 1612 and 1620, manufactured by Hitachi Chemical Co., Ltd.) are preferable.

  When (F) elastomer is contained in the photosensitive resin composition, the content thereof is preferably 0.1 to 20% by mass based on the total solid content of the photosensitive resin composition, and is preferably 0.5 to More preferably, it is 10 mass%, and it is especially preferable that it is 1-5 mass%.

  The photosensitive resin composition of the present invention preferably further contains (G) a phenoxy resin. (G) By including a phenoxy resin, not only can the adhesiveness with the conductor layer of the printed wiring board be used when the photosensitive resin composition is used for the solder resist, but also the flexibility of the cured film. And heat resistance can be improved.

  (G) As the phenoxy resin, for example, a phenoxy resin having a repeating unit represented by the following general formula (II) can be used.

In the formula, R ¹¹ represents a hydrogen atom or a methyl group, and m represents an integer of 30 or more. Phenoxy resins are those wherein R ¹¹ is hydrogen atom, any of those R ¹¹ structural units and R ¹¹ as or R ¹¹ is a methyl group is a hydrogen atom is present both a structural unit which is methyl There may be.

In the general formula (II), examples of the phenoxy resin in which R ¹¹ is a methyl group include YP-50, YP-50S, YP-55 (manufactured by Tohto Kasei Co., Ltd.), Epicoat 1256 (manufactured by Japan Epoxy Resin Co., Ltd.). ), PKHC, PKHH, PKHB (above, manufactured by InChem Corp.) and the like. These are used singly or in combination of two or more.

Examples of the phenoxy resin having both a structural unit in which R ¹¹ is a hydrogen atom and a structural unit in which R ¹¹ is a methyl group include YP-70, FX239 (above, manufactured by Tohto Kasei Co., Ltd.), Epicoat 4250, Epicoat 4275 (manufactured by Japan Epoxy Resin Co., Ltd.) and the like. These are used singly or in combination of two or more.

  The weight average molecular weight of these (G) phenoxy resins is preferably 20,000 to 100,000, and more preferably 30,000 to 80,000. When the weight average molecular weight is less than 20,000, the flexibility of the obtained cured film tends to be lowered, and when it exceeds 100,000, the developability tends to be lowered. In the present invention, the weight average molecular weight is a value measured by gel permeation chromatography (GPC) and converted by a calibration curve using standard polystyrene.

  When the photosensitive resin composition contains the (G) phenoxy resin, the content is preferably 0.1 to 20% by mass based on the total solid content of the photosensitive resin composition. More preferably, it is 10 mass%, It is especially preferable that it is 1-5 mass%.

  The photosensitive resin composition of the present invention preferably further contains (H) blocked isocyanate. (H) By containing block isocyanate, the sclerosis | hardenability of the photosensitive resin composition and the heat resistance of the cured film obtained can be improved more.

  (H) As the blocked isocyanate, an addition reaction product of a polyisocyanate compound and an isocyanate blocking agent is used. Examples of the polyisocyanate compound include tolylene diisocyanate, xylylene diisocyanate, phenylene diisocyanate, naphthylene diisocyanate, bis (isocyanate methyl) cyclohexane, tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, and isophorone diisocyanate. Polyisocyanate compounds, and adducts, burettes and isocyanurates of these.

  Examples of the isocyanate blocking agent include phenolic blocking agents such as phenol, cresol, xylenol, chlorophenol and ethylphenol; lactam blocking agents such as ε-caprolactam, δ-palerolactam, γ-butyrolactam and β-propiolactam; Active methylene blocking agents such as ethyl acetoacetate and acetylacetone; methanol, ethanol, propanol, butanol, amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl Ether, methyl glycolate, butyl glycolate, diacetone alcohol, lactic acid And alcohol blocking agents such as ethyl lactate; oxime blocking agents such as formaldehyde oxime, acetaldoxime, acetoxime, methylethyl ketoxime, diacetyl monooxime, cyclohexane oxime; butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, Mercaptan block agents such as methylthiophenol and ethylthiophenol; Acid amide block agents such as acetic acid amide and benzamide; Imide block agents such as succinimide and maleic imide; Amines such as xylidine, aniline, butylamine and dibutylamine Blocking agents; imidazole blocking agents such as imidazole and 2-ethylimidazole; imine blocking agents such as methyleneimine and propyleneimine It is.

  The block isocyanate which consists of said polyisocyanate and blocking agent is used individually by 1 type or in combination of 2 or more types.

  When (H) blocked isocyanate is contained in the photosensitive resin composition, the content is preferably 0.5 to 20% by mass based on the total solid content of the photosensitive resin composition, and preferably 1 to 10%. It is more preferable that it is mass%, and it is especially preferable that it is 2-8 mass%.

  In the photosensitive resin composition of the present invention, if necessary, known colorants such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, kustal violet, titanium oxide, carbon black, naphthalene black, hydroquinone, Polymerization inhibitors such as methyl hydroquinone, hydroquinone monomethyl ether, catechol and pyrogallol, thickeners such as benton and montmorillonite, silicone, fluorine and vinyl resin antifoaming agents, silane coupling agents, and antimony trioxide Various known additives such as a flammable auxiliary agent can be used.

  Moreover, the thermosetting accelerator can be used for the photosensitive resin composition of this invention as needed. Examples of thermosetting accelerators include boron trifluoride-amine complex, dicyandiamide, organic acid hydrazide, diaminomaleonitrile, diaminodiphenylmethane, metaphenylenediamine, diaminodiphenylmethane, metaxylenediamine, diaminodiphenylsulfone, and “Hardener HT972” (Ciba Specialty).・ Aromatic amines such as Chemicals; phthalic anhydride, trimellitic anhydride, ethylene glycol bis (anhydrotrimellitate), glycerol tris (anhydrotrimellitate), benzophenone tetracarboxylic anhydride, etc. Aromatic acid anhydride; aliphatic acid anhydride such as maleic anhydride and tetrahydrophthalic anhydride; metal salt of acetylacetone such as zinc acetylacetonate; enamine, tin octylate, quaternary Tertiary phosphine such as phosphonium salt and triphenylphosphine; Phosphonium salt such as tri-n-butyl (2,5-dihydroxyphenyl) phosphonium bromide and hexadecyltributylphosphonium chloride; benzyltrimethylammonium chloride and phenyltributylammonium chloride Quaternary ammonium salts such as diphenyliodonium tetrafluoroporate; antimonates such as triphenylsulfonium hexafluoroantimonate; dimethylbenzylamine, 1,8-diazabicyclo [5,4,0] undecene, m -Tertiary amines such as aminophenol, 2,4,6-tris (dimethylaminophenol), tetramethylguanidine; 2-ethyl-4-methylimidazole , 2-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenyl imidazole, and 2-phenyl-4-methyl-5-hydroxymethyl imidazole imidazoles. These are used singly or in combination of two or more. Moreover, when these thermosetting accelerators are contained in the photosensitive resin composition, the content thereof is preferably 0.01 to 10% by mass based on the total solid content of the photosensitive resin composition.

  The photosensitive resin composition of the present invention can be obtained by uniformly kneading and mixing each of the above-described blending components with a roll mill, a bead mill or the like. According to such a photosensitive resin composition, a cured film that satisfies all of the flexibility, developability, adhesion, PCT resistance, electric corrosion resistance, and thermal shock resistance at a high level is formed by having the above configuration. be able to. Moreover, the cured film obtained is excellent also in a flame retardance, a mechanical characteristic, and electrical insulation. Therefore, the said photosensitive resin composition can be used suitably for manufacture of a printed wiring board etc.

(Photosensitive element)
FIG. 1 is a schematic cross-sectional view showing a preferred embodiment of the photosensitive element of the present invention. The photosensitive element 1 shown in FIG. 1 has a structure in which a photosensitive resin composition layer 14 is laminated on a support 10. The photosensitive resin composition layer 14 is a layer made of the above-described photosensitive resin composition of the present invention.

  As the support 10, for example, a metal plate such as copper, a copper-based alloy, iron, or an iron-based alloy, or a polymer film such as polyethylene terephthalate, polypropylene, polyethylene, or polyester can be used. The thickness of the support is preferably 1 μm to 100 μm.

  The photosensitive resin composition layer 14 can be formed by applying the photosensitive resin composition of the present invention on the support 10 as a liquid resist.

  Examples of the coating method include a roll coater, a comma coater, a gravure coater, an air knife coater, a die coater, and a bar coater. The solvent can be removed by heating, for example, and the heating temperature is preferably about 70 ° C. to 150 ° C., and the heating time is preferably about 5 minutes to about 30 minutes.

  The amount of the remaining organic solvent in the photosensitive resin composition layer 14 thus formed is preferably 2% by mass or less from the viewpoint of preventing the organic solvent from diffusing in the subsequent step.

  Moreover, although the thickness of the photosensitive resin composition layer 14 changes with uses, it is preferable that the thickness after removing a solvent is about 1 micrometer-100 micrometers.

  In the photosensitive element 1, you may coat | cover the surface F1 on the opposite side to the support body side of the photosensitive resin composition layer 14 with a protective film (not shown) as needed.

  Examples of the protective film include polymer films such as polyethylene and polypropylene. Further, the protective film is preferably a low fish eye film, and the adhesive force between the protective film and the photosensitive resin composition layer 14 is to make it easy to peel the protective film from the photosensitive resin composition layer 14. Furthermore, it is preferable that the adhesive strength between the photosensitive resin composition layer 14 and the support 10 is smaller.

  The photosensitive element 1 includes a cushion layer, an adhesive layer, a light absorption layer, between the support 10 and the photosensitive resin composition layer 14 and / or between the photosensitive resin composition layer 14 and the protective film. An intermediate layer such as a gas barrier layer or a protective layer may be further provided.

  The photosensitive element 1 is, for example, in the form of a flat plate as it is, or by laminating a protective film on one surface of the photosensitive resin composition layer (on the surface that is not protected and exposed) to form a cylindrical shape or the like. It can be wound around a core and stored in roll form. The core is not particularly limited as long as it is conventionally used. For example, plastic such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, ABS resin (acrylonitrile-butadiene-styrene copolymer), etc. Etc. At the time of storage, it is preferable that the support is wound up so as to be the outermost side. Moreover, it is preferable to install an end face separator from the viewpoint of protecting the end face on the end face of the photosensitive element (photosensitive element roll) wound up in a roll shape, and in addition, a moisture-proof end face separator is installed from the viewpoint of edge fusion resistance. It is preferable to do. Moreover, when packaging the photosensitive element 1, it is preferable to wrap it in a black sheet with low moisture permeability.

(Resist pattern forming method and printed wiring board manufacturing method)
The method for forming a resist pattern of the present invention comprises laminating a photosensitive resin composition layer comprising the above photosensitive resin composition of the present invention on a substrate, and irradiating the photosensitive resin composition layer with actinic rays in an image form. In this method, the exposed portion is photocured, and then the unexposed portion is removed by development. Here, a flexible printed wiring board etc. are mentioned as a board | substrate.

  Lamination of the photosensitive resin composition layer on the substrate is, for example, 10 to 200 μm of the photosensitive resin composition by a method such as a screen printing method, a spray method, a roll coating method, a curtain coating method, or an electrostatic coating method. It can apply by apply | coating on a board | substrate with a film thickness, and drying a coating film at 60-110 degreeC.

Moreover, you may laminate | stack the photosensitive resin composition layer on a board | substrate using the said photosensitive element 1. FIG. As a lamination method in that case, when the photosensitive element 1 includes a protective film, the protective film is removed, and then the photosensitive resin composition layer 14 is heated to about 70 ° C. to 130 ° C. while being heated to about 0.1 MPa on the substrate. a method in which bonding at a pressure of about ^{~1MPa (1kgf / cm 2 ~10kgf /} cm 2 or so) can be mentioned. Such a lamination process may be performed under reduced pressure. The surface of the substrate on which the photosensitive resin composition layer 14 is laminated is usually a metal surface, but is not particularly limited.

  The exposed portion is photocured by irradiating the photosensitive resin composition layer laminated on the substrate in this way with an actinic ray in an image form through a negative or positive mask pattern. At this time, when the photosensitive resin composition layer 14 is laminated using the photosensitive element 1, the support 10 exists on the photosensitive resin composition layer 14, but this support 10 is active. When the support 10 is transparent to the light beam, it can be irradiated with an actinic ray, and when the support 10 shows a light-shielding property against the active light, it is photosensitive after the support 10 is removed. The resin composition layer 14 is irradiated with actinic rays.

  As the active light source, a conventionally known light source, for example, a light source that effectively emits ultraviolet light, visible light, or the like, such as a carbon arc lamp, a mercury vapor arc lamp, a high-pressure mercury lamp, or a xenon lamp is used. Further, a laser direct drawing exposure method or the like can also be used.

  After formation of the exposed portion, the photosensitive resin composition layer (unexposed portion) other than the exposed portion is removed by development to form a resist pattern. As a method for removing such an unexposed portion, when the support 10 is present on the photosensitive resin composition layer 14, the support 10 is removed by an auto peeler or the like, and an alkaline aqueous solution, an aqueous developer, an organic solvent, or the like is used. Examples include a method in which an unexposed portion is removed and developed by wet development using a developer or dry development. Examples of the alkaline aqueous solution used for wet development include a dilute solution of 0.1% by mass to 5% by mass of sodium carbonate, a dilute solution of 0.1-5% by mass of potassium carbonate, and 0.1% by mass to 5% by mass of hydroxide. A dilute solution of sodium and the like can be mentioned. The pH of the alkaline aqueous solution is preferably in the range of 9 to 11, and the temperature is adjusted according to the developability of the photosensitive resin composition layer. Moreover, you may mix surfactant, an antifoamer, an organic solvent, etc. in alkaline aqueous solution. Examples of the development method include a dip method, a spray method, brushing, and slapping.

Next, as a treatment after development, the exposed portion is sufficiently cured by post-exposure (ultraviolet light exposure) and / or post-heating to obtain a cured film. The post-exposure is preferably performed with an exposure amount of 1 to 5 J / cm ² . Post-heating is preferably performed at 100 to 200 ° C. for 30 minutes to 12 hours.

  The manufacturing method of the printed wiring board of this invention is a method including the process of forming a permanent mask on a board | substrate with the formation method of the resist pattern of the said invention. The permanent mask formed in this way has sufficient flexibility required for flexible printed wiring boards, and is excellent in developability, adhesion, PCT resistance, electric corrosion resistance, and thermal shock resistance. Therefore, this permanent mask effectively functions as a solder resist, an interlayer insulating film or the like in the printed wiring board.

EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on a reference example, an Example, and a comparative example, this invention is not limited to a following example.

[Synthesis of Resin A]
In a flask equipped with a stirrer, a reflux condenser and a thermometer, 1052 parts by mass of (a) component, bisphenol A type epoxy resin (trade name: RE-310S, Nippon Kayaku Co., Ltd., epoxy equivalent: 185), (b ) 144 parts by mass of acrylic acid, 1 part by mass of methylhydroquinone, 850 parts by mass of carbitol acetate and 100 parts by mass of solvent naphtha were added as components, and the mixture was dissolved by heating and stirring at 70 ° C. Next, the obtained solution is cooled to 50 ° C., 2 parts by mass of triphenylphosphine and 75 parts by mass of solvent naphtha are added thereto and heated to 100 ° C., and the solid content acid value becomes 1 mgKOH / g or less. Reacted until. Next, the obtained solution was cooled to 50 ° C., and 745 parts by mass of tetrahydrophthalic anhydride, 75 parts by mass of carbitol acetate, and 75 parts by mass of solvent naphtha were added thereto as the component (c). Reacted for hours. As a result, an unsaturated group-containing polycarboxylic acid resin (resin A) having a solid acid value of 80 mgKOH / g and a solid content of 62% by mass was obtained as the component (A).

[Synthesis of Resin B]
In a flask equipped with a stirrer, a reflux condenser and a thermometer, 1052 parts by mass of (b) component as component (a), bisphenol F type epoxy resin (trade name: 806, manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent: 180) As above, 144 parts by mass of acrylic acid, 1 part by mass of methylhydroquinone, 850 parts by mass of carbitol acetate, and 100 parts by mass of solvent naphtha were charged and heated and stirred at 70 ° C. to dissolve the mixture. Next, the obtained solution is cooled to 50 ° C., 2 parts by mass of triphenylphosphine and 75 parts by mass of solvent naphtha are added thereto and heated to 100 ° C., and the solid content acid value becomes 1 mgKOH / g or less. Reacted until. Next, the obtained solution was cooled to 50 ° C., and 745 parts by mass of tetrahydrophthalic anhydride, 75 parts by mass of carbitol acetate, and 75 parts by mass of solvent naphtha were added thereto as the component (c). Reacted for hours. As a result, an unsaturated group-containing polycarboxylic acid resin (resin B) having a solid content acid value of 80 mgKOH / g and a solid content of 62% by mass as component (A) was obtained.

[Synthesis of urethane compound A (hydroxyurethane compound having at least two (meth) acryloyl groups in the molecule)]
Bisphenol A di (1,3-dioxolan-2-one-4-ylmethyl) ether (8.72 g, 20 mmol), p-xylylenediamine (3.04 g, 22 mmol), and N-methylpyrrolidinone (30 mL) were charged at 70 ° C. The mixture was stirred with heating until the carbonate groups were completely consumed. Next, the obtained solution was cooled to 30 ° C., and a toluene solution (2.52 g) of 16.25% by mass of 1,3-dioxolan-2-one-4-ylmethyl methacrylate was used until the amino group disappeared. added. Thereby, both terminal methacryloylated polyhydroxyurethane (urethane compound A) was obtained.

[Synthesis of urethane compound B (hydroxyurethane compound having at least two (meth) acryloyl groups in the molecule)]
Bisphenol A diglycidyl ether (17 g, 50 mmol), lithium bromide (0.13 g, 1.5 mmol) and N-methylpyrrolidinone (60 mL) were charged, and the mixture was heated and stirred at 80 ° C. for 1 day while blowing carbon dioxide. After releasing the system and sufficiently removing carbon dioxide while heating and stirring, 7.5 g (55 mmol) of p-xylylenediamine was added and stirred at 70 ° C. until the epoxy group was completely consumed. Next, the obtained solution was cooled to 30 ° C., and a toluene solution (11.4 g) of 16.25% by mass of 1,3-dioxolan-2-one-4-ylmethyl methacrylate was removed until the amino group disappeared. In addition, methacryloylated polyhydroxyurethane (urethane compound B) was obtained at both ends.

( Reference Examples 2, 4, Examples 1 , 3 and Comparative Examples 1-3)
According to the blending composition shown in Table 1, compositions A and B were blended separately and prepared by kneading with a three-roll mill. Next, 70 parts by mass of composition A and 30 parts by mass of composition B were mixed to obtain a photosensitive resin composition (resist ink composition).

The details of each material in Table 1 are as follows.
* 1: Irgacure 907 (trade name, manufactured by Ciba Specialty Chemicals),
* 2: Kayacure DETX-S (trade name, manufactured by Nippon Kayaku Co., Ltd.),
* 3: XER-91 (trade name, manufactured by Nippon Synthetic Rubber Co., Ltd., both terminal carboxyl group-modified butadiene-acrylonitrile copolymer),
* 4: YP-50 (trade name, manufactured by Toto Kasei Co., Ltd.),
* 5: BL3257 (trade name, manufactured by Sumitomo Bayern Urethane),
* 6: C11-A (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.)
* 7: ESLV-120TE (trade name, manufactured by Nippon Steel Chemical Co., Ltd.)
* 8: Kayalad DPHA (trade name, manufactured by Nippon Kayaku Co., Ltd.).

(Production of evaluation board)
The photosensitive resin compositions of Reference Examples 2, 4, Examples 1 and 3 and Comparative Examples 1 to 3 were screen-printed using a 120 mesh Tetron screen so that the thickness after drying was about 30 μm. Then, it was applied to a polyimide film having a thickness of 22 μm with copper wiring, and dried at 80 ° C. for 30 minutes by a hot air circulating dryer. Thereby, the evaluation board | substrate which has the photosensitive resin composition layer which consists of a polyimide film, copper wiring, and a photosensitive resin composition in this order was obtained.

  Each characteristic was evaluated by the method shown below using the obtained evaluation substrate. The results obtained are summarized in Table 2.

(Developability)
A mask with a via mask opening size of 100 μm is placed on the photosensitive resin composition layer of the evaluation substrate, and irradiated with ultraviolet rays with an integrated exposure amount of 500 mJ / cm ² using an ultraviolet exposure device, and then with a 1% aqueous sodium carbonate solution for 60 seconds. Spray development was performed at a pressure of 1.8 kgf / cm ² . Thereafter, the evaluation substrate was visually observed to confirm the presence or absence of the development residue, and evaluated according to the following criteria.
A: No development residue
B: Development remains.

(Adhesion)
The photosensitive resin composition layer of the evaluation substrate is irradiated with ultraviolet rays having an integrated exposure amount of 500 mJ / cm ² using an ultraviolet exposure device, and then sprayed with a 1% sodium carbonate aqueous solution for 60 seconds at a pressure of 1.8 kgf / cm ^2. Developed. Using this evaluation substrate, a peel test was performed by a method according to JIS K5400. That is, 100 1 mm grids were prepared on the photosensitive resin composition layer of the evaluation substrate, and a cellophane tape was applied to the grids and then peeled off. The peeled state after the peeling was observed, and the adhesion was evaluated according to the following criteria.
A: 90/100 or more of the grid pattern has no peeling,
B: 50/100 or more and less than 90/100 of the grid is not peeled,
C: Less than 50/100 of the grid is not peeled.

(Preparation of test plate)
A negative mask having a predetermined pattern was brought into close contact with the photosensitive resin composition layer of the evaluation substrate, and irradiated with 500 mJ / cm ² of ultraviolet rays using an ultraviolet exposure device. Thereafter, spray development was performed with a 1% aqueous sodium carbonate solution for 60 seconds at a pressure of 1.8 kgf / cm ² , and the unexposed area was dissolved and developed. Next, heating was performed at 150 ° C. for 1 hour to obtain a test plate. The following characteristics were evaluated using this test plate.

(Solder heat resistance)
After applying the rosin-based flux to the photosensitive resin composition layer of the test plate, it was immersed in a solder bath at 260 ° C. for 10 seconds. After repeating this for 6 cycles, the appearance of the photosensitive resin composition layer was visually observed, and solder heat resistance was evaluated according to the following criteria.
A: There is no abnormality (peeling, swelling) in the appearance of the photosensitive resin composition layer, and there is no solder peeling.
B: The appearance of the photosensitive resin composition layer is abnormal (peeling or blistering), or there is solder peeling.

(Electric corrosion resistance)
The test plate was allowed to stand for 1000 hours or 2000 hours under the conditions of 85 ° C., 85% RH, and 100 V, and then the insulation resistance value of the photosensitive resin composition layer was measured, and the electric corrosion resistance was evaluated according to the following criteria.
A: Insulation resistance value is 1 × 10 ¹² Ω or more,
B: The insulation resistance value is less than 1 × 10 ¹² Ω.

(Flexibility)
The state when the test plate was folded 180 ° with goby was visually observed, and the flexibility was evaluated according to the following criteria.
A: There is no crack in the photosensitive resin composition layer,
B: There is a crack in the photosensitive resin composition layer.

(Heat shock resistance)
The process of leaving the test plate at −55 ° C. for 30 minutes and then leaving it at 125 ° C. for 30 minutes was taken as one cycle, and the photosensitive resin composition layer after 1000 cycles of this was observed visually and with a microscope. The thermal shock resistance was evaluated according to the criteria.
A: No cracking occurred
B: Cracks are generated.

(PCT resistance)
The test plate was left standing at 121 ° C. under saturated water vapor at 2 atm for a predetermined time (PCT treatment), and then the appearance of the photosensitive resin composition layer was visually observed. Next, a peel test similar to the adhesion test was performed using the test plate after PCT treatment. The appearance of the photosensitive resin composition layer was evaluated according to the following criteria, and the adhesiveness was evaluated according to the same criteria as in the adhesion test, and the appearance and adhesion of the photosensitive resin composition layer after the PCT treatment were evaluated.
A: There is no abnormality (peeling, swelling) in the appearance of the photosensitive resin composition layer,
B: The appearance of the photosensitive resin composition layer is abnormal (peeling or swelling).

  The present invention provides a photosensitive resin composition useful in the fields of electrical and electronic materials such as printed wiring boards and semiconductor packages. More specifically, the present invention is useful for flexible printed wiring boards, high-density multilayer boards, tape carriers, etc., and is a solder resist excellent in flexibility, developability, adhesion, PCT resistance, electric corrosion resistance, and thermal shock resistance. A photosensitive resin composition capable of forming an interlayer insulating film (build-up material) or a plating resist, a photosensitive element using the same, a resist pattern forming method, and a printed wiring board manufacturing method are provided.

FIG. 1 is a schematic cross-sectional view showing a preferred embodiment of the photosensitive element of the present invention.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Photosensitive element, 10 ... Support body, 14 ... Photosensitive resin composition layer.

Claims (8)

(A) (a) esterified product of epoxy compound having at least two epoxy groups in the molecule and (b) unsaturated group-containing monocarboxylic acid; (c) saturated or unsaturated group-containing polybasic acid anhydride An acid-modified vinyl group-containing epoxy resin which is an addition reaction product obtained by adding
(B) a photopolymerization initiator;
(C) a diluent;
(D) a curing agent;
(E) a urethane compound having at least two (meth) acryloyl groups in the molecule;
Contain,
The said (E) urethane compound is a photosensitive resin composition containing the hydroxy urethane compound which processed the terminal of polyhydroxy urethane obtained from a bifunctional five-membered ring carbonate and alkyldiamine or aralkyldiamine with the methacryloylating agent . The photosensitive resin composition of Claim 1 whose said (a) epoxy compound is a compound represented by the following general formula (I).


[Wherein, R ¹ represents a hydrogen atom or a glycidyl group, and R ² represents a hydrogen atom or a methyl group. A plurality of R ¹ and R ² may be the same or different. ]   (F) The photosensitive resin composition of Claim 1 or 2 which further contains an elastomer.   (G) The photosensitive resin composition as described in any one of Claims 1-3 which further contains a phenoxy resin.   (H) The photosensitive resin composition as described in any one of Claims 1-4 which further contains block isocyanate.   A photosensitive element provided with a support body and the photosensitive resin composition layer which consists of the photosensitive resin composition as described in any one of Claims 1-5 formed on this support body.   A photosensitive resin composition layer comprising the photosensitive resin composition according to claim 1 is laminated on a substrate, and the photosensitive resin composition layer is irradiated with actinic rays in an image form. Then, the exposed portion is photocured, and then the unexposed portion is removed by development.   A method for manufacturing a printed wiring board, wherein a permanent mask is formed on a substrate by the method for forming a resist pattern according to claim 7.