JP2017156590A - Photosensitive resin composition, dry film, cured product and printed wiring board prepared therewith - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition that can give a cured product that has both solder heat resistance and dielectric properties at high levels, and also shows excellent developability and adhesion, a dry film having a resin layer obtained from the composition, a cured product of the resin layer of the composition or the dry film, and a printed wiring board having the cured product.SOLUTION: A photosensitive resin composition comprises an alkali-soluble resin (A) that includes three or more aromatic rings in a repeating unit and has an unsaturated double bond, (B) a cyclic ether compound, and (C) a photopolymerization initiator.SELECTED DRAWING: None

Description

  The present invention relates to a photosensitive resin composition, a dry film, a cured product, and a printed wiring board using the same.

  In general, in a printed wiring board, a composition containing a thermosetting epoxy resin and a carboxyl group-containing resin for the purpose of developing alkali developability is widely used as a solder resist. This carboxyl group-containing resin is synthesized by adding an acid anhydride to a hydroxyl group generated by adding acrylic acid to a cresol novolac type epoxy resin (for example, Patent Document 1). Moreover, the resin composition containing the photosensitive resin etc. which were synthesize | combined by copolymerization of the acrylate compound as a soldering resist is also used (for example, patent document 2).

  In recent years, the operating speed of information equipment tends to increase. Among information devices, wireless devices have become higher in frequency and are in the microwave / millimeter wave region. In order to cope with higher frequencies, in the field of printed wiring boards, development of low-loss dielectric substrate materials in the high frequency band has been actively conducted. In high-speed and high-frequency substrate materials, polytetrafluoroethylene, cycloolefin polymer, and liquid crystal polymer are used as low-loss materials, but the handling of substrate materials such as processability is reduced and the cost of raw materials is increased. It is difficult to use widely. On the other hand, when using a solder resist for high-speed and high-frequency substrates, in addition to the required solder resist properties, soldering resistance, gold plating resistance, resolution, etc., used for conventional substrates, dielectric properties and electrical properties Is required.

JP-A 61-243869 Japanese Patent Laid-Open No. 10-20493 Japanese Patent No. 4444460

  In response to such demands, there is a demand for the realization of a solder resist composition that is excellent in dielectric properties in addition to solder heat resistance, but in reality the one that satisfies all these properties has not yet been realized. is there.

  Furthermore, Patent Document 3 proposes a composition using a resin having a fluorene skeleton in order to obtain high resolution, but the resolution due to heat resistance and developability is insufficient. There was a problem.

  Therefore, an object of the present invention is to provide a photosensitive resin composition capable of obtaining a cured product that has both high solder heat resistance and dielectric properties and is excellent in developability and adhesion, and a resin obtained from the composition. An object of the present invention is to provide a dry film having a layer, a cured product of the resin layer of the composition or the dry film, and a printed wiring board having the cured product.

  As a result of intensive studies in view of the above, the present inventors can solve the above problems by using a photosensitive resin composition containing a predetermined alkali-soluble resin, a cyclic ether compound, and a photopolymerization initiator. As a result, the present invention has been completed.

  That is, the photosensitive resin composition of the present invention comprises (A) an alkali-soluble resin having three or more aromatic rings in the repeating unit and having an unsaturated double bond, (B) a cyclic ether compound, and (C And a photopolymerization initiator.

  In the photosensitive resin composition of the present invention, the (B) cyclic ether compound preferably has at least one selected from a fluorene skeleton, a naphthalene skeleton, a biphenyl skeleton, and a dicyclopentadiene skeleton.

  The photosensitive resin composition of the present invention has at least one of (A) the alkali-soluble resin having three or more aromatic rings in the repeating unit and having an unsaturated double bond selected from a fluorene skeleton and a biphenyl skeleton. It is preferable to have.

  In the photosensitive resin composition of the present invention, the (C) photopolymerization initiator is at least one selected from oxime ester photopolymerization initiators, α-aminoacetophenone photopolymerization initiators, and titanocene photopolymerization initiators. It is preferable that

  The photosensitive resin composition of the present invention preferably further contains (D) a compound having an ethylenically unsaturated group.

  The photosensitive resin composition of the present invention is preferably used for forming at least one of an overcoat agent and a solder resist.

  The dry film of the present invention is characterized by having a resin layer obtained by applying and drying the photosensitive resin composition on a film.

  The cured product of the present invention is characterized by comprising the photosensitive resin composition or the resin layer of the dry film.

  The printed wiring board of this invention has the said hardened | cured material, It is characterized by the above-mentioned.

  ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin composition which can obtain the hardened | cured material which is highly compatible with solder heat resistance and a dielectric characteristic, and is excellent also in developability and adhesiveness, The resin layer obtained from this composition It is possible to provide a dry film having a cured product, a cured product of the composition or a resin layer of the dry film, and a printed wiring board having the cured product.

The photosensitive resin composition of the present invention is (A) an alkali-soluble resin having three or more aromatic rings in a repeating unit and having an unsaturated double bond (hereinafter, also simply referred to as “(A) alkali-soluble resin”). ), (B) a cyclic ether compound, and (C) a photopolymerization initiator. In the present invention, by blending (A) an alkali-soluble resin, both solder heat resistance and dielectric properties can be made highly compatible, and good developability and adhesion can be obtained.
Further, by using the photosensitive resin composition of the present invention, not only as a two-component photosensitive resin composition, but also as a one-component photosensitive resin composition or a dry film, the storage stability and sensitivity are good. It becomes.

  Hereinafter, each component of the photosensitive resin composition of this invention is demonstrated.

[(A) Alkali-soluble resin having 3 or more aromatic rings in the repeating unit and having an unsaturated double bond]
The photosensitive resin composition of the present invention contains (A) an alkali-soluble resin having three or more aromatic rings in the repeating unit and having an unsaturated double bond. (A) The alkali-soluble resin preferably has at least one selected from a fluorene skeleton and a biphenyl skeleton. Among these, an alkali-soluble resin obtained by using a bifunctional epoxy resin having a fluorene skeleton is more preferable from the viewpoint of dielectric properties. (A) Alkali-soluble resin can be used individually by 1 type or in combination of 2 or more types.

  Examples of the (A) alkali-soluble resin include compounds listed below (any of oligomers and polymers).

  (1) Bifunctional epoxy having two or more aromatic rings such as bisphenol A type epoxy resin, bifunctional epoxy resin having a fluorene skeleton, biphenyl aralkyl bifunctional epoxy resin, and bifunctional epoxy resin having a naphthalene skeleton A resin obtained by polyaddition reaction of a tetrabasic acid dianhydride having an aromatic ring at a hydroxyl group produced by adding acrylic acid or methacrylic acid to a resin.

  (2) A resin obtained by adding an acid anhydride to a hydroxyl group produced by adding acrylic acid or methacrylic acid to a novolak epoxy resin having a biphenyl skeleton or a naphthalene skeleton.

  (3) A resin obtained by introducing an acid anhydride and acrylic acid or methacrylic acid into an alcoholic hydroxyl group produced by adding an alkylene oxide to a phenol novolac resin or cresol novolac resin having a biphenyl skeleton or a naphthalene skeleton. .

  The acid value of the alkali-soluble resin is desirably in the range of 20 to 200 mgKOH / g, and more preferably in the range of 40 to 180 mgKOH / g. When it is in the range of 20 to 200 mg KOH / g, adhesion of the coating film is obtained, alkali development is facilitated, dissolution of the exposed portion by the developer is suppressed, and the line does not fade more than necessary, and normal This is preferable because the resist pattern can be easily drawn.

  The weight average molecular weight of the alkali-soluble resin used in the present invention varies depending on the resin skeleton, but is preferably in the range of 2,000 to 150,000. Within this range, tack-free performance is good, the moisture resistance of the coated film after exposure is good, and film loss is less likely to occur during development. Further, when the weight average molecular weight is within the above range, the resolution is improved, the developability is good, and the storage stability is improved. More preferably, it is 5,000-100,000. The weight average molecular weight can be measured by gel permeation chromatography.

[(B) Cyclic ether compound]
The photosensitive resin composition of the present invention contains (B) a cyclic ether compound. Examples of the (B) cyclic ether compound include compounds having a plurality of 3, 4 or 5-membered cyclic ether groups in the molecule. For example, a compound having a plurality of epoxy groups in the molecule, that is, a polyfunctional epoxy compound, Examples thereof include compounds having a plurality of oxetanyl groups in the molecule, that is, polyfunctional oxetane compounds. Among these, from the viewpoint of dielectric properties, it is preferable to have at least one selected from a fluorene skeleton, a naphthalene skeleton, a biphenyl skeleton, and a dicyclopentadiene skeleton.

  Examples of the polyfunctional epoxy compound include a novolak type epoxy resin having a dicyclopentadiene skeleton, a biphenyl aralkyl type novolak resin, a biphenyl aralkyl bifunctional epoxy resin, an epoxy resin having a fluorene skeleton, a naphthalene type novolak resin, and a naphthalene type bifunctional epoxy. Examples thereof include resins.

  (B) As a compounding quantity of a cyclic ether compound, it is preferable that it is 5-60 mass parts with respect to 100 mass parts of said (A) alkali-soluble resin, and it is more preferable that it is 10-50 mass parts. When the blending amount of the cyclic ether compound is within the above range, the balance between the solder heat resistance required for the solder resist and the resolution resulting from the developability becomes good.

（式中、Ｒ^６は、水素原子、フェニル基（炭素数１〜６のアルキル基、フェニル基、若しくはハロゲン原子で置換されていてもよい）、炭素数１〜２０のアルキル基（１個以上の水酸基で置換されていてもよく、アルキル鎖の中間に１個以上の酸素原子を有していてもよい）、炭素数５〜８のシクロアルキル基、炭素数２〜２０のアルカノイル基又はベンゾイル基（炭素数が１〜６のアルキル基若しくはフェニル基で置換されていてもよい）を表し、Ｒ^７は、フェニル基（炭素数１〜６のアルキル基、フェニル基若しくはハロゲン原子で置換されていてもよい）、炭素数１〜２０のアルキル基（１個以上の水酸基で置換されていてもよく、アルキル鎖の中間に１個以上の酸素原子を有していてもよい）、炭素数５〜８のシクロアルキル基、炭素数２〜２０のアルカノイル基又はベンゾイル基（炭素数が１〜６のアルキル基若しくはフェニル基で置換されていてもよい）を表し、Ｒ^８及びＲ^９は、それぞれ独立に、炭素数１〜１２のアルキル基又はアリールアルキル基を表し、Ｒ^１０及びＲ^１１は、それぞれ独立に、水素原子、炭素数１〜６のアルキル基、又は２つが結合した環状アルキルエーテル基を表し、Ｒ^１２及びＲ^１３は、それぞれ独立に、炭素数１〜１０の直鎖状又は分岐状のアルキル基、シクロヘキシル基、シクロペンチル基、アリール基、又はハロゲン原子、アルキル基若しくはアルコキシ基で置換されたアリール基を表し、但し、Ｒ^１２及びＲ^１３の一方は、Ｒ−Ｃ（＝Ｏ）−基（ここでＲは、炭素数１〜２０の炭化水素基）を表してもよい。） [(C) Photopolymerization initiator]
The photosensitive resin composition of the present invention contains (C) a photopolymerization initiator. (C) As a photopolymerization initiator, an oxime ester photopolymerization initiator having a group represented by the following general formula (I), an α-aminoacetophenone-based light having a group represented by the following general formula (II) One or more photoinitiators selected from the group consisting of a polymerization initiator, an acylphosphine oxide photopolymerization initiator having a group represented by the following formula (III), and a titanocene photopolymerization initiator are preferably used. can do.

(In the formula, R ⁶ represents a hydrogen atom, a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a halogen atom), an alkyl group having 1 to 20 carbon atoms (one or more). Or may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, or benzoyl. Represents a group (which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group), and R ⁷ is a phenyl group (substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom). Or an alkyl group having 1 to 20 carbon atoms (which may be substituted with one or more hydroxyl groups, and may have one or more oxygen atoms in the middle of the alkyl chain), carbon number 5 ˜8 cycloalkyl groups, Represents an alkanoyl group or a benzoyl group prime 2-20 (carbon atoms may be substituted with 1-6 alkyl or phenyl group), R ⁸ and R ⁹ are each independently, a carbon number 1 to 12 R ¹⁰ and R ¹¹ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a cyclic alkyl ether group in which two are bonded, and R ¹² and R ^13. Each independently represents a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclohexyl group, a cyclopentyl group, an aryl group, or an aryl group substituted with a halogen atom, an alkyl group or an alkoxy group, provided that , R ¹² and R ¹³ may represent an R—C (═O) — group (where R represents a hydrocarbon group having 1 to 20 carbon atoms).

As the oxime ester photopolymerization initiator, commercially available products include CGI-325, Irgacure OXE01, Irgacure OXE02, ADEKA N-1919, NCI-831, and TR-PBG- 304, TR-PBG-305, and the like. In addition, a photopolymerization initiator having two oxime ester groups in the molecule can be suitably used. Specifically, an oxime ester photopolymerization initiator having a carbazole structure is preferable. These oxime ester photopolymerization initiators can be used alone or in combination of two or more.
The blending amount of the oxime ester photopolymerization initiator is preferably 0.01 to 20 parts by mass, more preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the (A) alkali-soluble resin.

  As the α-aminoacetophenone photopolymerization initiator, specifically, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, N , N-dimethylaminoacetophenone and the like. Examples of commercially available products include Irgacure 907, Irgacure 369, and Irgacure 379 manufactured by BASF Japan.

  Specific examples of the acylphosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and bis (2,6-dimethoxy). And benzoyl) -2,4,4-trimethyl-pentylphosphine oxide. Examples of commercially available products include Lucilin TPO manufactured by BASF and Irgacure 819 manufactured by BASF Japan.

  Specific examples of titanocene photopolymerization initiators include bis (cyclopentadienyl) -di-phenyl-titanium, bis (cyclopentadienyl) -di-chloro-titanium, and bis (cyclopentadienyl)-. Bis (2,3,4,5,6pentafluorophenyl) titanium, bis (cyclopentadienyl) -bis (2,6-difluoro-3- (pyrrol-1-yl) phenyl) titanium, and the like can be given. Examples of commercially available products include Irgacure 784 manufactured by BASF Japan.

The compounding quantity of such (C) photoinitiator is 0.01-30 mass parts with respect to 100 mass parts of said (A) alkali-soluble resin, Preferably it is 0.5-15 mass parts. (C) By blending the photopolymerization initiator in this range, the photocurability on copper becomes sufficient, the curability of the coating film is improved, the coating properties such as chemical resistance are improved, Deep part curability is also improved.
(C) A photoinitiator can be used individually or in combination of 2 or more types.

  Other photopolymerization initiators, photoinitiator assistants and sensitizers that can be suitably used in the photosensitive resin composition of the present invention include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, and benzophenone compounds. And tertiary amine compounds.

  Specific examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.

  Specific examples of the acetophenone compound include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, and 1,1-dichloroacetophenone.

  Specific examples of the anthraquinone compound include 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone.

  Specific examples of the thioxanthone compound include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone.

  Specific examples of the ketal compound include acetophenone dimethyl ketal and benzyl dimethyl ketal.

  Specific examples of the benzophenone compound include, for example, benzophenone, 4-benzoyldiphenyl sulfide, 4-benzoyl-4′-methyldiphenyl sulfide, 4-benzoyl-4′-ethyldiphenyl sulfide, 4-benzoyl-4′-propyldiphenyl. Sulfide.

  Specific examples of the tertiary amine compound include, for example, an ethanolamine compound, a compound having a dialkylaminobenzene structure, such as 4,4′-dimethylaminobenzophenone (Nisso Cure MABP manufactured by Nippon Soda Co., Ltd.), 4,4′-diethylamino. Dialkylamino benzophenone such as benzophenone (EAB manufactured by Hodogaya Chemical Co.), and dialkylamino groups such as 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- (diethylamino) -4-methylcoumarin) Containing coumarin compound, ethyl 4-dimethylaminobenzoate (Kayacure EPA manufactured by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (Quantacure DMB manufactured by International Bio-Synthetics), 4-dimethylaminobenzoic acid ( -Butoxy) ethyl (Quantacure BEA, manufactured by International Bio-Synthetics), p-dimethylaminobenzoic acid isoamyl ethyl ester (Kayacure DMBI, manufactured by Nippon Kayaku Co., Ltd.), 2-ethylhexyl 4-dimethylaminobenzoate (manufactured by Van Dyk) Esolol 507), 4,4′-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.).

Among the above compounds, thioxanthone compounds and tertiary amine compounds are preferable. The composition of the present invention preferably contains a thioxanthone compound from the viewpoint of deep curable properties. Among them, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone A thioxanthone compound such as
The amount of such a thioxanthone compound is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, with respect to 100 parts by mass of the (A) alkali-soluble resin. If the amount of the thioxanthone compound is too large, the thick film curability is lowered and the cost of the product is increased, which is not preferable.

  As the tertiary amine compound, a compound having a dialkylaminobenzene structure is preferable, and among them, a dialkylaminobenzophenone compound and a dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 410 nm are particularly preferable. As the dialkylaminobenzophenone compound, 4,4'-diethylaminobenzophenone is preferable because of its low toxicity. The dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 410 nm has a maximum absorption wavelength in the ultraviolet region, so that it is less colored and uses a colored pigment as well as a colorless and transparent photosensitive composition. A colored solder resist film reflecting the color can be provided. In particular, 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferable because it exhibits an excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm.

  The amount of such a tertiary amine compound is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the (A) alkali-soluble resin. is there. When the amount of the tertiary amine compound is less than 0.1 parts by mass, a sufficient sensitizing effect tends not to be obtained. On the other hand, when the amount exceeds 20 parts by mass, light absorption on the surface of the dry solder resist coating film by the tertiary amine compound becomes intense, and the deep curability tends to decrease.

These photopolymerization initiators, photoinitiator assistants, and sensitizers can be used alone or as a mixture of two or more.
The total amount of such photopolymerization initiator, photoinitiator assistant, and sensitizer is preferably in the range of 35 parts by mass or less with respect to 100 parts by mass of the (A) alkali-soluble resin. When it exceeds 35 parts by mass, the deep curability tends to decrease due to light absorption.

((D) Compound having an ethylenically unsaturated group)
The photosensitive resin composition of the present invention can contain (D) a compound having an ethylenically unsaturated group. (D) The compound having an ethylenically unsaturated group is a compound having one or more ethylenically unsaturated groups in the molecule. The above compounds assist the polymerization reaction of ethylenically unsaturated groups by irradiation with active energy rays. As the ethylenically unsaturated group, those derived from (meth) acrylate are preferable.

Examples of the compound having an ethylenically unsaturated group include conventionally known polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, and epoxy (meth) acrylate. It is done. Specifically, hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; N, N-dimethylacrylamide Acrylamides such as N-methylol acrylamide and N, N-dimethylaminopropyl acrylamide; aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate and N, N-dimethylaminopropyl acrylate; hexanediol, trimethylolpropane, Polyhydric alcohols such as pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate or the like Polyvalent acrylates such as a tylene oxide adduct, a propylene oxide adduct, or an ε-caprolactone adduct; a polyvalent acrylate such as phenoxy acrylate, bisphenol A diacrylate, and ethylene oxide adduct or propylene oxide adduct of these phenols Acrylates; glyceryl diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyglycerides of glycidyl ether such as triglycidyl isocyanurate; acrylates having a dicyclopentadiene skeleton, acrylates having a fluorene skeleton; Not limited to polyether polyol, polycarbonate diol, hydroxyl-terminated polybutadiene, polyester polyol, etc. Examples include acrylates and melamine acrylates obtained by directly acrylated polyol or urethane acrylated via diisocyanate, and at least one of each methacrylate corresponding to the acrylate.
In the present specification, (meth) acrylate is a term that collectively refers to acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.

  Furthermore, you may use the epoxy acrylate resin etc. which made acrylic acid react with polyfunctional epoxy resins, such as a cresol novolak-type epoxy resin, as a compound which has an ethylenically unsaturated group. Such an epoxy acrylate resin can improve photocurability without deteriorating the touch drying property.

  The compounding amount of the compound having the (D) ethylenically unsaturated group is 5 to 30 parts by mass, more preferably 10 to 30 parts by mass with respect to 100 parts by mass of the (A) alkali-soluble resin. . When the blending amount is in the range of 5 to 30 parts by mass, photocurability and tackiness can be improved.

(Organic solvent)
The photosensitive resin composition of the present invention may contain an organic solvent for the purpose of preparing the composition and adjusting the viscosity when applied to a substrate or a carrier film. Examples of organic solvents include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether , Glycol ethers such as dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, diethylene glycol monomethyl ether acetate, tripropylene glycol monomethyl ether; ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butylcarby Tall acetate, propylene glycol monomethyl ether acetate, dip Propylene glycol monomethyl ether acetate, esters such as propylene carbonate; octane, aliphatic hydrocarbons decane; petroleum ether, petroleum naphtha, and petroleum solvents such as solvent naphtha, organic solvents conventionally known can be used. These organic solvents can be used alone or in combination of two or more.

  Furthermore, you may mix | blend the other well-known and usual additive in the field | area of an electronic material with the photosensitive resin composition of this invention. Other additives include curing catalysts, stabilizers (antioxidants, heat stabilizers, UV absorbers, anti-aging agents, etc.), thermal polymerization inhibitors, plasticizers, flame retardants, antistatic agents, antibacterial / antifungal agents Agents, surface treatment agents (antifoaming agents, leveling agents, thickeners, thixotropic agents, etc.), colorants, dispersants, dispersion aids, phosphors and the like.

  The photosensitive resin composition of the present invention may be used as a dry film or as a liquid. When used as a liquid, it may be one-component or two-component or more.

  The dry film of the present invention has a resin layer obtained by applying and drying the photosensitive resin composition of the present invention on a carrier film. When forming a dry film, first, the photosensitive resin composition of the present invention is diluted with the above organic solvent and adjusted to an appropriate viscosity, and then a comma coater, a blade coater, a lip coater, a rod coater, and a squeeze coater. Apply a uniform thickness on the carrier film using a reverse coater, transfer roll coater, gravure coater, spray coater or the like. Then, the resin layer can be formed by drying the applied composition at a temperature of 50 to 130 ° C. for 1 to 30 minutes. Although there is no restriction | limiting in particular about a coating film thickness, Generally, it is 10-150 micrometers by the film thickness after drying, Preferably it selects suitably in the range of 20-60 micrometers.

  As the carrier film, a plastic film is used. For example, a polyester film such as polyethylene terephthalate (PET), a polyimide film, a polyamideimide film, a polypropylene film, a polystyrene film, or the like can be used. Although there is no restriction | limiting in particular about the thickness of a carrier film, Generally, it selects suitably in the range of 10-150 micrometers.

  After the resin layer made of the photosensitive resin composition of the present invention is formed on the carrier film, a peelable cover film is further formed on the film surface for the purpose of preventing dust from adhering to the film surface. It is preferable to laminate. As the peelable cover film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, or the like can be used. As a cover film, what is necessary is just a thing smaller than the adhesive force of a resin layer and a carrier film when peeling a cover film.

  In the present invention, a resin layer may be formed by applying and drying the photosensitive resin composition of the present invention on the cover film and laminating a carrier film on the surface thereof. That is, as the film to which the photosensitive resin composition of the present invention is applied when producing a dry film in the present invention, either a carrier film or a cover film may be used.

  In addition, the exposed portion (light irradiated portion) is cured by applying exposure (light irradiation) to the resin layer obtained after applying the photosensitive resin composition of the present invention and evaporating and drying the solvent. . Specifically, exposure is selectively performed with an active energy ray through a photomask having a pattern formed by a contact method or a non-contact method, or direct pattern exposure is performed by a laser direct exposure machine, and an unexposed portion is diluted with a dilute alkaline aqueous solution ( For example, a resist pattern is formed by developing with a 0.3 to 3 mass% sodium carbonate aqueous solution. When the photosensitive resin composition of the present invention contains a thermosetting component, it is further heated to a temperature of about 100 to 180 ° C. and thermally cured (post-cure), whereby heat resistance, chemical resistance and moisture absorption resistance are obtained. A cured film (cured product) excellent in various properties such as property, adhesion, and electrical properties can be formed.

  In addition, the photosensitive resin composition of the present invention is adjusted to a viscosity suitable for the coating method using, for example, the organic solvent, and the dip coating method, flow coating method, roll coating method, bar coater on the substrate. After coating by a method such as a printing method, a screen printing method, or a curtain coating method, a tack-free resin layer is formed by volatile drying (temporary drying) of an organic solvent contained in the composition at a temperature of about 60 to 100 ° C. Can be formed. In the case of a dry film obtained by applying the above composition on a carrier film or a cover film and drying and winding it as a film, the layer of the composition of the present invention is brought into contact with the substrate by a laminator or the like. After bonding together, the resin layer can be formed by peeling off the carrier film.

  Examples of the base material include printed wiring boards and flexible printed wiring boards that have been previously formed with copper or the like, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / non-woven cloth epoxy, glass cloth / paper epoxy. It is made of materials such as copper-clad laminates for high-frequency circuits using synthetic fiber epoxy, fluororesin, polyethylene, polyphenylene ether, polyphenylene oxide, cyanate, etc., and copper-clad laminates of all grades (FR-4 etc.) Examples thereof include a plate, a metal substrate, a polyimide film, a PET film, a polyethylene naphthalate (PEN) film, a glass substrate, a ceramic substrate, and a wafer plate.

  The volatile drying or thermal curing may be performed by a hot air circulation drying furnace, an IR furnace, a hot plate, a convection oven or the like (a method and nozzle in which hot air in a dryer is brought into countercurrent contact using a steam-heated type heat source. And a method of spraying on a support.

As an exposure machine used for the active energy ray irradiation, a high-pressure mercury lamp lamp, an ultra-high pressure mercury lamp lamp, a metal halide lamp, a mercury short arc lamp, and the like may be used as long as the apparatus irradiates ultraviolet rays in a range of 350 to 450 nm. Furthermore, a direct drawing apparatus (for example, a laser direct imaging apparatus that directly draws an image with a laser using CAD data from a computer) can also be used. The lamp light source or laser light source of the direct drawing machine may have a maximum wavelength in the range of 350 to 410 nm. The exposure amount for image formation varies depending on the film thickness and the like, but is generally 20 to 1000 mJ / cm ² , preferably 20 to 800 mJ / cm ² .

  The developing method can be a dipping method, a shower method, a spray method, a brush method, etc., and as a developing solution, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, Alkaline aqueous solutions such as ammonia and amines can be used.

  The photosensitive resin composition of the present invention is preferably used for forming a cured film on a printed wiring board, that is, for a printed wiring board, and more preferably used for forming a permanent insulating film, Specifically, it is used for forming an overcoat agent, a solder resist, an interlayer insulating layer or a coverlay. Particularly preferably, it is used for forming a solder resist, that is, as a solder resist composition. In addition, you may use the photosensitive resin composition of this invention in order to form a solder dam.

  Hereinafter, the present invention will be described in more detail with reference to examples.

[Synthesis Example 1 (alkali-soluble resin A-1, resin having a fluorene skeleton)]
With reference to Example 1 described in JP-A-2001-354735, 1,2,3,6-tetrahydrophthalic anhydride was reacted with a reaction product of bisphenolfluorene epoxy acrylate and benzophenone tetracarboxylic dianhydride. . This reaction product (reaction solution) was designated as a resin solution A-1. The obtained resin solution A-1 had a solid content of 54% by mass and an acid value of the solid content of 60 mgKOH / g.

[Synthesis Example 2 (alkali-soluble resin A-2, resin having a biphenylaralkyl skeleton)]
While stirring 205 parts by mass of phenol resin (Maywa Kasei Co., Ltd., trade name “MEH-7851”, OH equivalent: 205), 0.6 parts by mass of triphenylphosphine and 112 parts by mass of propylene carbonate, 150 The reaction was started by heating to ˜160 ° C., and then continued at 200 to 220 ° C. for about 2 hours. Since carbon dioxide gas was generated as the reaction progressed, it was removed from the system. Thereafter, the mixture was cooled to room temperature, and the hydroxyl group equivalent was 269 g / eq. A propylene carbonate reaction product of a phenol resin was obtained. This was equivalent to an average of 1.1 mol of propylene oxide added per equivalent of phenolic hydroxyl group.

  After the above reactant was dissolved in 150 parts by mass of toluene, 36.0 parts by mass of acrylic acid, 1.7 parts by mass of paratoluenesulfonic acid, and 0.04 parts by mass of methylhydroquinone were charged therein, and air was added at 10 ml / min. The mixture was allowed to react at 100 ± 10 ° C. for 7 hours with stirring. The water produced | generated by reaction distilled 9.6 mass parts water as an azeotrope with toluene. Then, it cooled to room temperature, the obtained reaction solution was washed with water, and toluene was distilled off, substituting with 150 mass parts of diethylene glycol monoethyl ether acetate, and the acrylate resin solution was obtained.

  Next, 442 parts by mass of the obtained acrylate resin solution and 1.1 parts by mass of triphenylphosphine were charged into a reactor equipped with a stirrer, a thermometer, and an air blowing tube, and air was blown at a rate of 10 ml / min. While stirring, 76.0 parts by mass of tetrahydrophthalic anhydride was gradually added and reacted at 95 to 105 ° C. for about 6 hours to obtain a resin solution A-2. The obtained resin solution A-2 had a solid content of 71.0% by mass and an acid value of the solid content of 79.0 mgKOH / g.

[Synthesis Example 3 (alkali-soluble resin A-3, novolac-type epoxy acrylate resin)]
Put 330 g of cresol novolac type epoxy resin (Epiclon N-695, manufactured by DIC, epoxy equivalent 220) into a flask equipped with a gas introduction tube, a stirrer, a cooling tube and a thermometer, add 340 g of carbitol acetate, and dissolve by heating. Then, hydroquinone 0.46 g and triphenylphosphine 1.38 g were added. This mixture was heated to 95 to 105 ° C., 108 g of acrylic acid was gradually added dropwise, and reacted for 16 hours. The reaction product was cooled to 80 to 90 ° C., 68 g of tetrahydrophthalic anhydride was added, reacted for 8 hours, and cooled. Let the obtained resin solution be resin solution A-3. The solid content of the resin solution A-3 was 60% by mass, and the acid value of the solid content was 50 mgKOH / g.

[Synthesis Example 4 (alkali-soluble resin A-4, copolymer resin)]
In a flask equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser, 325.0 parts by mass of dipropylene glycol monomethyl ether as a solvent was heated to 110 ° C., 174.0 parts by mass of methacrylic acid, and ε-caprolactone modified Methacrylic acid (average molecular weight 314) 174.0 parts by mass, methyl methacrylate 77.0 parts by mass, dipropylene glycol monomethyl ether 222.0 parts by mass, and t-butylperoxy 2-ethylhexanoate as a polymerization catalyst A mixture of 12.0 parts by mass (manufactured by NOF Corporation, perbutyl O) was added dropwise over 3 hours, and further stirred at 110 ° C. for 3 hours to deactivate the polymerization catalyst to obtain a resin solution. After cooling this resin solution, 289.0 parts by mass of Daicel Cyclomer M100, 3.0 parts by mass of triphenylphosphine and 1.3 parts by mass of hydroquinone monomethyl ether are added, and the temperature is raised to 100 ° C. and stirred. Thus, an epoxy group ring-opening addition reaction was performed to obtain a resin solution A-4. The obtained resin solution A-4 had a solid content of 45.5% by mass and an acid value of the solid content of 79.8 mgKOH / g.

  In accordance with the composition shown in the following table, each component was blended, premixed with a stirrer, dispersed with a three-roll mill, and kneaded to prepare compositions. In addition, the compounding quantity in a table | surface shows a mass part.

＊１：合成例１、アルカリ可溶性樹脂Ａ−１、フルオレン骨格を有する樹脂
＊２：合成例２、アルカリ可溶性樹脂Ａ−２、ビフェニルアラルキル骨格を有する樹脂
＊３：合成例３、アルカリ可溶性樹脂Ａ−３、ノボラック型エポキシアクリレート樹脂
＊４：合成例４、アルカリ可溶性樹脂Ａ−４、共重合樹脂
＊５：大阪ガスケミカル社製ＥＧ−２００、フルオレン骨格を有するエポキシ樹脂
＊６：ＤＩＣ社製ＨＰ−６０００、ナフタレン骨格を有するエポキシ樹脂
＊７：日本化薬社製ＮＣ−３０００、ビフェニルアラルキル骨格を有するエポキシ樹脂
＊８：ＤＩＣ社製ＨＰ−７２００、ジシクロペンタジエン骨格を有するエポキシ樹脂
＊９：ＤＩＣ社製Ｎ−６９５、クレゾールノボラック型エポキシ樹脂
＊１０：ＢＡＳＦジャパン社製ＯＸＥ０２、オキシムエステル系光重合開始剤
＊１１：ＢＡＳＦジャパン社製イルガキュア３６９、α−アミノアセトフェノン系光重合開始剤
＊１２：ＢＡＳＦジャパン社製イルガキュアＴＰＯ、アシルホスフィンオキサイド系光重合開始剤
＊１３：ＢＡＳＦジャパン社製イルガキュア７８４、チタノセン系光重合開始剤
＊１４：新中村化学工業社製Ａ−ＤＣＰ、ジシクロペンタジエン骨格を有するアクリレート
＊１５：新中村化学工業社製Ａ−ＢＰＥＦ、フルオレン骨格を有するアクリレート
＊１６：ジペンタエリスリトールヘキサアクリレート

* 1: Synthesis example 1, alkali-soluble resin A-1, resin having fluorene skeleton * 2: Synthesis example 2, alkali-soluble resin A-2, resin having biphenylaralkyl skeleton * 3: Synthesis example 3, alkali-soluble resin A -3, novolac-type epoxy acrylate resin * 4: Synthesis example 4, alkali-soluble resin A-4, copolymer resin * 5: EG-200 manufactured by Osaka Gas Chemical Company, epoxy resin having a fluorene skeleton * 6: HP manufactured by DIC -6000, epoxy resin having naphthalene skeleton * 7: NC-3000 manufactured by Nippon Kayaku Co., Ltd., epoxy resin having biphenylaralkyl skeleton * 8: HP-7200 manufactured by DIC, epoxy resin having dicyclopentadiene skeleton * 9: DIC N-695, cresol novolac type epoxy resin * 10: OXE manufactured by BASF Japan 2. Oxime ester photopolymerization initiator * 11: BASF Japan Irgacure 369, α-aminoacetophenone photopolymerization initiator * 12: BASF Japan Irgacure TPO, acylphosphine oxide photopolymerization initiator * 13: BASF Japan Irgacure 784, titanocene photopolymerization initiator * 14: Shin-Nakamura Chemical Co., Ltd. A-DCP, dicyclopentadiene acrylate * 15: Shin-Nakamura Chemical Co., Ltd. A-BPEF, fluorene acrylate acrylate * 16: Dipentaerythritol hexaacrylate

  The obtained resin compositions of Examples and Comparative Examples were evaluated according to the following. The results are shown in the above table.

<Production of evaluation substrate>
The compositions obtained in Examples 1 to 5 and Comparative Examples 1 to 3 shown in Table 1 above were applied on the entire surface of the substrate so that the film thickness after drying by screen printing was 20 μm, and 30 minutes at 80 ° C. Dried and allowed to cool to room temperature. Using this exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp) on this substrate, solid exposure was performed at an optimum exposure amount, and development was performed for 60 seconds at 30 ° C. with a 1% by mass sodium carbonate aqueous solution under a spray pressure of 0.2 MPa. . This substrate was irradiated with ultraviolet rays under a condition of an integrated exposure amount of 1000 mJ / cm ^{2 in} a UV conveyor furnace, and then cured by heating at 160 ° C. for 60 minutes. The obtained evaluation substrate was evaluated as follows.

<Developability>
Each composition of Examples and Comparative Examples was applied to FR-4 material under the above-mentioned evaluation substrate preparation conditions and dried, and a dry coating film (film thickness 20 μm) obtained at 30 ° C. with a 1% by mass sodium carbonate aqueous solution. The time until the dried coating film was completely dissolved was measured by spraying at a pressure of 0.2 MPa. The results were evaluated based on the following criteria.
○: 60 seconds or less Δ: Over 60 seconds and less than 120 seconds ×: 120 seconds or more

<Solder heat resistance>
The rosin-based flux was applied to the cured coating film obtained by applying each composition of Examples and Comparative Examples to the FR-4 material by curing, applying, drying, exposing, developing, and post-curing under the above-mentioned evaluation substrate production conditions. Was applied three times and immersed in a solder bath at 260 ° C. for 30 seconds, and then a cross-cut tape peel test was performed. The results were evaluated based on the following criteria.
○: No peeling ×: With peeling

<Adhesion (pencil hardness)>
Using the cured coating film obtained by curing each composition of Examples and Comparative Examples by applying, drying, exposing, developing, and post-curing the FR-4 material under the above-mentioned evaluation substrate production conditions, The pencil hardness was measured according to JIS K 5600-5-4. The hardness of a pencil that was pressurized to a load of 1 kg and peeled off the partition wall was measured. The results were evaluated based on the following criteria.
○: 5H or more ×: Less than 5H

<Dielectric constant, dielectric loss tangent>
(Preparation of test piece)
After appropriately diluting the compositions obtained in Examples 1 to 5 and Comparative Examples 1 to 3 with methyl ethyl ketone, respectively, using an applicator, a PET film (manufactured by Toray Industries Inc.) so that the film thickness after drying becomes 20 μm. FB-50: 16 μm) and dried at 80 ° C. for 30 minutes to obtain a dry film. The obtained dry film was applied on a 9 μm thick electrolytic copper foil (manufactured by Furukawa Electric Co., Ltd.) using a vacuum laminator (manufactured by Meiki Seisakusho, MVLP (registered trademark) -500). , 70 ° C., 1 minute, vacuum lamination: 133.3 Pa. The dry film laminated on the copper foil was subjected to solid exposure with an optimum exposure amount using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp), and the PET film was peeled off. The dry film was heat laminated again on the exposed dry film, and then solid exposure was performed with an optimum exposure amount. Lamination and exposure were repeated 20 times to form a 400 μm thick resin layer on the copper foil. The copper foil thus formed with the resin layer was irradiated with ultraviolet rays under a condition of an integrated exposure amount of 1000 mJ / cm ^{2 in} a UV conveyor furnace, and then heated at 160 ° C. for 60 minutes to cure the resin layer. Next, the copper foil is removed from the copper foil with a dry film layer using an etching solution having a composition of cupric chloride of 340 g / l and free hydrochloric acid concentration of 51.3 g / l, sufficiently washed with water and dried. A test piece made of a cured product of a resin layer having a thickness of 400 μm was prepared.

(Evaluation method)
The test piece thus prepared was evaluated by measuring the dielectric constant and dielectric loss tangent at 1 GHz using an RF impedance / material analyzer (Agilent Technology, Agilent E4991A). The evaluation criteria are as follows.
Dielectric constant ○: 3.0 or less Δ: More than 3.0 and less than 3.5 ×: 3.5 or more Dielectric loss tangent ○: 0.010 or less Δ: More than 0.010 and less than 0.015 ×: 0.015 or more

Claims (9)

  (A) It contains three or more aromatic rings in the repeating unit, an alkali-soluble resin having an unsaturated double bond, (B) a cyclic ether compound, and (C) a photopolymerization initiator. A photosensitive resin composition.   The photosensitive resin composition according to claim 1, wherein the (B) cyclic ether compound has at least one selected from a fluorene skeleton, a naphthalene skeleton, a biphenyl skeleton, and a dicyclopentadiene skeleton.   The photosensitive resin according to claim 1 or 2, wherein the alkali-soluble resin (A) having 3 or more aromatic rings in the repeating unit and having an unsaturated double bond has at least one selected from a fluorene skeleton and a biphenyl skeleton. Resin composition.   The (C) photopolymerization initiator is at least one selected from oxime ester photopolymerization initiators, α-aminoacetophenone photopolymerization initiators, and titanocene photopolymerization initiators. The photosensitive resin composition according to one item.   Furthermore, the photosensitive resin composition as described in any one of Claims 1-4 containing the compound which has (D) ethylenically unsaturated group.   The photosensitive resin composition as described in any one of Claims 1-5 used in order to form at least any one of an overcoat agent and a soldering resist.   It has a resin layer obtained by apply | coating and drying the photosensitive resin composition as described in any one of Claims 1-6 on a film, The dry film characterized by the above-mentioned.   Hardened | cured material which consists of the said resin layer of the photosensitive resin composition as described in any one of Claims 1-6, or the dry film of Claim 7. A printed wiring board comprising the cured product according to claim 8.