KR20170102789A - Photosensitive resin composition, dry film, cured product, and printed wiring board using same - Google Patents

Abstract

Provided are a photosensitive resin composition which makes solder heat resistance consist with dielectric characteristics and can obtain cured products having excellent development and adhesion, a dry film having a resin layer obtained from the composition, cured products of the composition or the resin layer of the dry film and a printed wiring board having the cured products. The photosensitive resin composition comprises: (A) an alkali soluble resin having three or more aromatic rings in a repeating unit and an unsaturated double bond; (B) a ring-shaped ether compound; and (C) a photopolymerization initiator.

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive resin composition, a dry film, a cured product, and a printed circuit board using the same. BACKGROUND OF THE INVENTION [0002]

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

Generally, as a solder resist, a composition including a thermosetting epoxy resin and a carboxyl group-containing resin for the purpose of developing alkali developability is widely used in printed wiring boards. This carboxyl group-containing resin is synthesized by adding an acid anhydride to a hydroxyl group formed by adding acrylic acid to a cresol novolak type epoxy resin (for example, Patent Document 1). As the solder resist, a resin composition containing a photosensitive resin or the like synthesized by copolymerization of an acrylate compound is also used (for example, Patent Document 2).

In recent years, the operating speed of information devices tends to increase. Among information appliances, radio equipment becomes high frequency and enters the area of microwave and millimeter wave. BACKGROUND ART [0002] In the field of printed wiring boards to cope with high frequency, development of low-loss dielectric substrate materials in high frequency bands has been actively conducted. Polytetrafluoroethylene, cycloolefin polymer, and liquid crystal polymer are used as low-loss materials in high-speed and high-frequency substrate materials, but they are difficult to be widely used because of lowering of handling as a substrate material including workability and raw material costing . On the other hand, when a solder resist is used for a high-speed, high-frequency substrate, dielectric properties and electrical characteristics are required in addition to solder heat resistance, gold plating resistance, and resolution, which are required characteristics of a solder resist used in conventional substrates.

Japanese Patent Application Laid-Open No. 61-243869 Japanese Patent Application Laid-Open No. 10-20493 Japanese Patent No. 4444060

In order to meet such a demand, it is required to realize a solder resist composition which is excellent in solder heat resistance and dielectric property, but it has not yet been realized that satisfying all of these characteristics.

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

Accordingly, an object of the present invention is to provide a photosensitive resin composition which can achieve a cured product which is highly compatible with solder heat resistance and dielectric properties, and which is also excellent in developability and adhesion, a dry film having a resin layer obtained from the composition, A cured product of a resin layer of a film and a printed wiring board having the cured product.

As a result of intensive studies in view of the above, the present inventors have found out that the above problems can be solved by using a photosensitive resin composition comprising a predetermined alkali-soluble resin, a cyclic ether compound and a photopolymerization initiator, It came to the following.

That is, the photosensitive resin composition of the present invention contains (A) an alkali-soluble resin having at least three aromatic rings and an unsaturated double bond, (B) a cyclic ether compound, and (C) a photopolymerization initiator .

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

In the photosensitive resin composition of the present invention, the alkali-soluble resin having at least three aromatic rings in the repeating unit (A) and having an unsaturated double bond preferably has at least one selected from a fluorene skeleton and a biphenyl skeleton Do.

In the photosensitive resin composition of the present invention, it is preferable that the photopolymerization initiator (C) is at least one selected from an oxime ester photopolymerization initiator, an? -Amino acetophenone photopolymerization initiator, and a titanocene photopolymerization initiator.

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

The photosensitive resin composition of the present invention is preferably used for forming at least one of an overcoat 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 including the photosensitive resin composition or the resin layer of the dry film.

The printed wiring board of the present invention is characterized by having the cured product.

According to the present invention, there is provided a photosensitive resin composition which can achieve a cured product which is highly compatible with solder heat resistance and dielectric properties and which is also excellent in developing property and adhesion property, a dry film having a resin layer obtained from the composition, A printed wiring board having a cured product of the resin layer and the cured product can be provided.

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 (hereinafter, simply referred to as "(A) alkali- A cyclic ether compound, and (C) a photopolymerization initiator. In the present invention, by blending (A) an alkali-soluble resin, solder heat resistance and dielectric properties can be highly compatible, and good developability and adhesion can be obtained.

By using the photosensitive resin composition of the present invention, not only the two-component photosensitive resin composition but also the one-component photosensitive resin composition or the dry film has good storage stability and sensitivity.

 Each component of the photosensitive resin composition of the present invention will be described below.

 [(A) an alkali-soluble resin having three or more aromatic rings in a repeating unit and having an unsaturated double bond]

The photosensitive resin composition of the present invention contains an alkali-soluble resin having three or more aromatic rings in the repeating unit (A) and having an unsaturated double bond. As the alkali-soluble resin (A), it is preferable to have at least one selected from a fluorene skeleton and a biphenyl skeleton. Among them, an alkali-soluble resin obtained by using a bifunctional epoxy resin having a fluorene skeleton is more preferable from the viewpoint of dielectric properties. The alkali-soluble resin (A) may be used alone or in combination of two or more.

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

(1) a bifunctional epoxy resin having two or more aromatic rings such as a bisphenol A type epoxy resin, a bifunctional epoxy resin having a fluorene skeleton, a biphenylaralkyl bifunctional epoxy resin, and a bifunctional epoxy resin having a naphthalene skeleton A resin obtained by subjecting a tetrabasic acid dianhydride having an aromatic ring to a hydroxyl group, which is formed by adding acrylic acid or methacrylic acid to a epoxy resin, by a heavy reaction.

(2) A resin obtained by adding an acid anhydride to a hydroxyl group formed by adding acrylic acid or methacrylic acid to a novolak type 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 formed by adding an alkylene oxide to a phenol novolak type resin having a biphenyl skeleton or a naphthalene skeleton or a cresol novolak type resin.

The acid value of the alkali-soluble resin is preferably in the range of 20 to 200 mg KOH / g, and more preferably in the range of 40 to 180 mg KOH / g. When the concentration is in the range of 20 to 200 mgKOH / g, adhesion of the coating film is obtained, alkali development is facilitated, dissolution of the exposed portion by the developer is suppressed, the line is not thinned more than necessary, .

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, the tack-and-dry performance is good, the moisture resistance of the coated film after exposure is good, and the film is hardly reduced at the time of development. When the weight average molecular weight is in the above range, the resolution is improved, the developing property is good, and the storage stability is improved. More preferably, it is from 5,000 to 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 cyclic ether compound (B) include compounds having a plurality of cyclic ether groups of 3, 4, or 5-membered rings in the molecule, and examples thereof include compounds having a plurality of epoxy groups in the molecule, i.e., polyfunctional epoxy compounds, A compound having an oxetanyl group, that is, a polyfunctional oxetane compound, and the like. Among them, 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 novolak type epoxy resins having a dicyclopentadiene skeleton, biphenylaralkyl type novolak resins, biphenylaralkyl bifunctional epoxy resins, fluorene skeletal epoxy resins, naphthalene type novolacs, Resin, naphthalene type bifunctional epoxy resin, and the like.

The blending amount of the cyclic ether compound (B) is preferably 5 to 60 parts by mass, more preferably 10 to 50 parts by mass with respect to 100 parts by mass of the alkali-soluble resin (A). If the blending amount of the cyclic ether compound is within the above range, balance between solder heat resistance required for the solder resist and resolution due to developability is improved.

[(C) Photopolymerization initiator]

The photosensitive resin composition of the present invention contains (C) a photopolymerization initiator. (C) an oxime ester-based photopolymerization initiator having a group represented by the following general formula (I), an? -Aminoacetophenone-based photopolymerization initiator having a group represented by the following general formula (II) An acylphosphine oxide-based photopolymerization initiator having a group to be displayed, and a titanocene-series photopolymerization initiator may be suitably used.

(Wherein R ⁶ represents a hydrogen atom, a phenyl group (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 (which may be substituted with at least one hydroxyl group, A cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, or a benzoyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group), and R ⁷ (Which may be substituted with an alkyl group having from 1 to 6 carbon atoms, a phenyl group or a halogen atom), an alkyl group having from 1 to 20 carbon atoms (which may be substituted with at least one hydroxyl group or at least one oxygen atom 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 a benzoyl group (substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group) And R ¹⁰ and R ¹¹ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 2 to 6 carbon atoms, or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms; R ⁸ and R ⁹ each independently represent an alkyl group or an arylalkyl group having 1 to 12 carbon atoms; R ¹² and R ¹³ each independently represent a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclohexyl group, a cyclopentyl group, an aryl group, or a halogen atom, an alkyl group, or an alkoxy group Provided that one of R ¹² and R ¹³ may represent an RC (= O) - group (wherein R represents a hydrocarbon group having 1 to 20 carbon atoms)

As the oxime ester-based photopolymerization initiator, CGI-325, Irgacure OXE01, Irgacure OXE02 manufactured by BASF Japan Ltd., N-1919, NCI-831 manufactured by ADEKA, manufactured by Changzhou High Power Co., TR-PBG-304, and TR-PBG-305. Further, a photopolymerization initiator system having two oxime ester groups in the molecule can be suitably used, and specifically, an oxime ester photopolymerization initiator having a carbazole structure is preferable. These oxime ester-based photopolymerization initiators may be used alone or in combination of two or more.

The blending amount of the oxime ester-based photopolymerization initiator is preferably 0.01 to 20 parts by mass, more preferably 0.01 to 5 parts by mass based on 100 parts by mass of the alkali-soluble resin (A).

Specific examples of the? -aminoacetophenone-based photopolymerization initiator include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone- (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, bis (2,6- 2, 4, 4-trimethyl-pentylphosphine oxide, and the like. Commercially available products include lucylline TPO manufactured by BASF, Irgacure 819 manufactured by BASF Japan, and the like.

Specific examples of the titanocene photopolymerization initiator include bis (cyclopentadienyl) -di-phenyl-titanium, bis (cyclopentadienyl) -diochloro-titanium, bis (cyclopentadienyl) (Cyclopentadienyl) -bis (2,6-difluoro-3- (pyrrol-1-yl) phenyl) titanium, and the like. Commercially available products include Irgacure 784 manufactured by BASF Japan.

The blending amount of the (C) photopolymerization initiator is 0.01 to 30 parts by mass, preferably 0.5 to 15 parts by mass based on 100 parts by mass of the (A) alkali-soluble resin. By blending the photopolymerization initiator (C) in this range, the photocurability on copper becomes satisfactory, the curability of the coating film becomes good, the coating film properties such as chemical resistance are improved, and the deep curability is also improved.

The photopolymerization initiator (C) may be used alone or in combination of two or more.

Examples of the photopolymerization initiator, photoinitiator and sensitizer 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, benzophenone compounds, and 3 Secondary amine compounds and the like.

Concrete examples of the benzoin compound are, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.

Concrete examples of the acetophenone compound are, for example, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone and 1,1-dichloroacetophenone.

Concrete examples of the anthraquinone compound are, for example, 2-methyl anthraquinone, 2-ethyl anthraquinone, 2-t-butyl anthraquinone and 1-chloro anthraquinone.

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

Concrete examples of the ketal compound include, for example, acetophenone dimethyl ketal and benzyl dimethyl ketal.

Specific examples of the benzophenone compound include benzophenone, 4-benzoyldiphenylsulfide, 4-benzoyl-4'-methyldiphenylsulfide, 4-benzoyl- -Benzoyl-4'-propyldiphenylsulfide.

Specific examples of the tertiary amine compound include, for example, an ethanolamine compound, a compound having a dialkylaminobenzene structure such as 4,4'-dimethylaminobenzophenone (Nissokyura MABP manufactured by Nippon Soda Co., Ltd.), 4,4 (Diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- ( Dimethylaminobenzoate (Kayacure EPA manufactured by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (manufactured by International Bio-Synthesis, Inc., Quantacure, DMB), 4-dimethylaminobenzoic acid (n-butoxy) ethyl (Quantacure BEA manufactured by International Bio-Synthics Co.), p-dimethylaminobenzoic acid isoamylethyl ester (Kayacure DMBI manufactured by Nippon Kayaku Co., 2-ethylhexyl aminobenzoate (Esolol 507, Van Dyk), 4,4'-diethylamino A benzophenone (a product of Hodogaya Chemical Co., EAB).

Of these compounds, thioxanthone compounds and tertiary amine compounds are preferred. The composition of the present invention preferably contains a thioxanthone compound from the viewpoint of deep curability. Among them, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2- Thioxanthone compounds such as 2,4-diisopropylthioxanthone are preferable.

The blending amount of such a thioxanthone compound is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, based on 100 parts by mass of the alkali-soluble resin (A). If the blending amount of the thioxanthone compound is too large, the thick film curability is lowered, leading to an increase in the cost of the product, which is not preferable.

As the tertiary amine compound, a compound having a dialkylaminobenzene structure is preferable, and 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 it has low toxicity. Since a dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 410 nm has a maximum absorption wavelength in the ultraviolet ray region, the coloring is small and the color of the coloring pigment itself is reflected by using a coloring pigment as well as a colorless transparent photosensitive composition It becomes possible to provide a colored solder resist film. Particularly, 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferable because it exhibits an excellent increase / decrease 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 based on 100 parts by mass of the alkali-soluble resin (A). When the compounding amount of the tertiary amine compound is less than 0.1 part by mass, sufficient increase or decrease effect can not be obtained. On the other hand, when the amount exceeds 20 parts by mass, the light absorption at the surface of the dried solder resist coating film by the tertiary amine compound becomes severe, and the deep portion curing property tends to be lowered.

These photopolymerization initiators, photoinitiator and sensitizer may be used alone or as a mixture of two or more.

The total amount of the photopolymerization initiator, photoinitiator and sensitizer is preferably in the range of not more than 35 parts by mass based on 100 parts by mass of the alkali-soluble resin (A). When the amount exceeds 35 parts by mass, the deep curing property tends to be lowered due to the light absorption.

((D) a compound having an ethylenically unsaturated group)

The photosensitive resin composition of the present invention may contain (D) a compound having an ethylenic unsaturated group. (D) The compound having an ethylenically unsaturated group is a compound having at least one ethylenic unsaturated group in the molecule. The above-mentioned compound is to assist the polymerization of the ethylenically unsaturated group by irradiation with active energy rays. As the ethylenic unsaturated group, those derived from (meth) acrylate are preferable.

Examples of the compound having an ethylenic unsaturated group include polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, epoxy And the like. Specific examples thereof include 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; Acrylamides such as N, N-dimethyl acrylamide, N-methylol acrylamide and N, N-dimethylaminopropylacrylamide; Aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate and N, N-dimethylaminopropyl acrylate; Polyhydric alcohols such as hexanediol, trimethylol propane, pentaerythritol, dipentaerythritol, and tris-hydroxyethylisocyanurate; and ethylene oxide adducts, propylene oxide adducts, and? -Caprolactone adducts Polyfunctional acrylates; Polyfunctional acrylates such as phenoxy acrylate, bisphenol A diacrylate and ethylene oxide adducts or propylene oxide adducts of these phenols; Polyhydric acrylates of glycidyl ethers such as glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylol propane triglycidyl ether and triglycidyl isocyanurate; Acrylates having a dicyclopentadiene skeleton, acrylates having a fluorene skeleton; The present invention is not limited thereto. Examples of the polyol include polyhydric alcohols such as acrylates and melamine acrylates obtained by directly acrylating a polyol such as a polyether polyol, a polycarbonate diol, a hydroxyl-terminated polybutadiene or a polyester polyol, or a urethane acrylate through a diisocyanate; And at least one of the respective methacrylates corresponding to the acrylate.

In the present specification, (meth) acrylate is a generic term for acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.

An epoxy acrylate resin obtained by reacting a polyfunctional epoxy resin such as cresol novolak type epoxy resin with acrylic acid may be used as a compound having an ethylenic unsaturated group. Such an epoxy acrylate resin can improve photo-curability without deteriorating the touch-dry composition.

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

(Organic solvent)

In addition, the photosensitive resin composition of the present invention may contain an organic solvent for the purpose of preparing the composition and adjusting the viscosity upon application to a substrate or a carrier film. Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; Aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; Methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, diethylene glycol monomethyl ether Glycol ethers such as acetate and tripropylene glycol monomethyl ether; Esters such as ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate and propylene carbonate; Aliphatic hydrocarbons such as octane and decane; And petroleum solvents such as petroleum ether, petroleum naphtha and solvent naphtha. These organic solvents may be used alone or in combination of two or more.

In the photosensitive resin composition of the present invention, other additives known in the field of electronic materials may be added. Examples of other additives include curing catalysts, stabilizers (antioxidants, heat stabilizers, ultraviolet absorbers, antioxidants, etc.), heat polymerization inhibitors, plasticizers, flame retardants, antistatic agents, antimicrobial and antifungal agents, surface treatment agents (antifoaming agents, leveling agents, A thixotropic agent, etc.), a colorant, a dispersant, a dispersion aid, and a fluorescent substance.

The photosensitive resin composition of the present invention may be used as a dry film or as a liquid phase. When used as a liquid phase, it may be one-liquid or two-liquid 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 the dry film is formed, the photosensitive resin composition of the present invention is first diluted with the above-mentioned organic solvent and adjusted to an appropriate viscosity. Thereafter, the photosensitive resin composition is applied to a substrate such as a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, A gravure coater, a spray coater or the like to a uniform thickness on the carrier film. Thereafter, the applied composition is dried at a temperature of usually 50 to 130 DEG C for 1 to 30 minutes to form a resin layer. The thickness of the coating film is not particularly limited, but is generally appropriately selected in the range of 10 to 150 占 퐉, preferably 20 to 60 占 퐉 in the film thickness after drying.

As the carrier film, a plastic film is used, and for example, a polyester film such as polyethylene terephthalate (PET), a polyimide film, a polyamideimide film, a polypropylene film, a polystyrene film and the like can be used. The thickness of the carrier film is not particularly limited, but is generally appropriately selected in the range of 10 to 150 mu m.

It is preferable to laminate a peelable cover film on the surface of the film for the purpose of preventing the adhesion of dust to the surface of the film after the resin layer containing the photosensitive resin composition of the present invention is formed on the carrier film Do. As the peelable cover film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper and the like can be used. The cover film may be one that is smaller than the adhesive force between the resin layer and the carrier film when the cover film is peeled off.

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 a carrier film may be laminated on the surface of the resin layer. That is, in the present invention, as the film to be coated with the photosensitive resin composition of the present invention when producing a dry film, either a carrier film or a cover film may be used.

Further, the exposed portion (light-irradiated portion) is cured by exposing (irradiating) the resin layer obtained by applying the photosensitive resin composition of the present invention and volatilizing and drying the solvent. Concretely, the photoresist is selectively exposed to an active energy beam through a photomask having a pattern formed thereon by a contact or noncontact method, or directly pattern-exposed by a laser direct exposure machine, and the unexposed portion is exposed to a dilute alkali solution For example, 0.3 to 3 mass% aqueous sodium carbonate solution) to form a resist pattern. When the photosensitive resin composition of the present invention contains a thermosetting component, the composition is heated to a temperature of about 100 to 180 DEG C to thermoset (postcure), whereby heat resistance, chemical resistance, moisture absorption resistance, (Cured product) excellent in various properties can be formed.

The photosensitive resin composition of the present invention may be coated on the substrate by a suitable coating method such as dip coating method, flow coating method, roll coating method, bar coater method, screen printing method The resin layer can be formed by volatilization and drying (drying) the organic solvent contained in the composition at a temperature of about 60 to 100 占 폚. Further, in the case of a dry film obtained by applying the above composition onto a carrier film or a cover film, drying the film, and winding the film as a film, the layer of the composition of the present invention is laminated on the substrate by a laminator or the like so as to be in contact with the substrate. By peeling, a resin layer can be formed.

As the base material, there may be used a resin such as a paper phenol, a paper epoxy, a glass cloth epoxy, a glass polyimide, a glass cloth / nonwoven epoxy, a glass cloth / paper epoxy, a synthetic fiber epoxy, · Copper-clad laminate for high-frequency circuits using polyethylene · polyphenylene ether, polyphenylene oxide · cyanate, etc., and it is possible to use copper clad laminate of all grades (FR-4 etc.), other metal substrate, polyimide film , A PET film, a polyethylene naphthalate (PEN) film, a glass substrate, a ceramic substrate, and a wafer plate.

The volatile drying or thermosetting may be carried out by using a hot air circulating drying furnace, an IR, a hot plate, a convection oven or the like (a method in which hot air in a dryer is brought into countercurrent contact with a heat source using an air heating method by steam, As shown in FIG.

As the exposure device used for the irradiation of the active energy ray, any device that irradiates ultraviolet rays in a range of from 350 to 450 nm by mounting a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, Devices (e.g., laser direct imaging devices that draw images directly with a laser by CAD data from a computer) can also be used. As the lamp light source or the laser light source of the direct shot, the maximum wavelength may be in the range of 350 to 410 nm. The exposure dose for image formation varies depending on the film thickness and the like, but may be generally in the range of 20 to 1000 mJ / cm 2, preferably 20 to 800 mJ / cm 2.

Examples of the developing method include a dipping method, a shower method, a spraying method, a brushing method and the like. As the developing solution, an alkali aqueous solution of potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, Can be used.

The photosensitive resin composition of the present invention is suitably used for forming a cured film on a printed wiring board, that is, for a printed wiring board, and more preferably for forming a permanent insulating film. Specifically, the photosensitive resin composition is used as an overcoating agent, It is used to form an insulating layer or coverlay. Particularly preferably, it is used for forming a solder resist, that is, as a solder resist composition. Further, the photosensitive resin composition of the present invention may be used for forming a solder dam.

[Example]

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

[Synthesis Example 1 (alkali-soluble resin A-1, resin having fluorene skeleton)]

With reference to Example 1 described in Japanese Patent Application Laid-Open No. 2001-354735, 1,2,3,6-tetrahydrophthalic anhydride was reacted with a reaction product of bisphenol fluorene epoxy acrylate and benzophenone tetracarboxylic dianhydride . This reaction product (reaction solution) was referred to as Resin Solution A-1. The obtained resin solution A-1 had a solid content of 54% by mass and an acid value of solid content of 60 mgKOH / g.

[Synthesis Example 2 (alkali-soluble resin A-2, resin having biphenylaralkyl skeleton)]

, 205 parts by mass of phenol resin (MEH-7851, OH equivalent: 205, manufactured by Meiwa Chemical Industries, Ltd.), 0.6 part by mass of triphenylphosphine and 112 parts by mass of propylene carbonate were charged into a reaction kettle and stirred at 150 to 160 ° C , The reaction was initiated, and the reaction was continued at 200 to 220 ° C for about 2 hours. Carbon dioxide gas was generated along with the progress of the reaction, and thus the system was removed from the system. Thereafter, the mixture was cooled to room temperature to obtain a propylene carbonate reaction product of a phenol resin having a hydroxyl group equivalent of 269 g / eq. This was equivalent to an average of 1.1 moles of propylene oxide per equivalent of the phenolic hydroxyl group.

After dissolving the reaction product in 150 parts by mass of toluene, 36.0 parts by mass of acrylic acid, 1.7 parts by mass of para-toluenesulfonic acid and 0.04 parts by mass of methylhydroquinone were charged into the autoclave, air was blown thereinto at a rate of 10 ml / The reaction was carried out at 10 DEG C for 7 hours. Water produced by the reaction was an azeotropic mixture with toluene, and 9.6 parts by mass of water was distilled out. Thereafter, the reaction solution was cooled to room temperature, the reaction solution was washed with water, and toluene was distilled off by replacing toluene with 150 parts by mass of diethylene glycol monoethyl ether acetate with an evaporator to obtain an acrylate resin solution.

Next, 442 parts by mass of the obtained acrylate resin solution and 1.1 parts by mass of triphenylphosphine were placed in a reactor equipped with a stirrer, a thermometer and an air blowing tube, air was blown at a rate of 10 ml / min and, with stirring, tetrahydrophthalic acid And 76.0 parts by mass of an anhydride were gradually added and reacted at 95 to 105 DEG 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 a solid content of 79.0 mgKOH / g.

[Synthesis Example 3 (alkali-soluble resin A-3, novolak type epoxy acrylate resin)]

330 g of cresol novolak type epoxy resin (Epiclon N-695, manufactured by DIC Corporation, epoxy equivalent 220) was placed in a flask equipped with a gas introduction tube, a stirring device, a cooling tube and a thermometer, and 340 g of carbitol acetate was added, After heating and dissolution, 0.46 g of hydroquinone and 1.38 g of triphenylphosphine were added. The mixture was heated to 95 to 105 占 폚, and 108 g of acrylic acid was gradually added dropwise and reacted for 16 hours. The reaction product was cooled to 80 to 90 占 폚, and 68 g of tetrahydrophthalic anhydride was added, followed by reaction for 8 hours and cooling. The obtained resin solution is referred to as resin solution A-3. The solids 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 DEG C, and 174.0 parts by mass of methacrylic acid, 竜 -caprolactone modified methacrylic acid 314), 77.0 parts by mass of methyl methacrylate, 222.0 parts by mass of dipropylene glycol monomethyl ether, and 12.0 parts by mass of t-butylperoxy 2-ethylhexanoate (manufactured by Nichi- The mixture was added dropwise over 3 hours and further stirred at 110 DEG C for 3 hours to inactivate the polymerization catalyst to obtain a resin solution. After cooling the resin solution, 289.0 parts by mass of Cychroma M100 manufactured by Daicel Chemical Industries, Ltd., 3.0 parts by mass of triphenylphosphine and 1.3 parts by mass of hydroquinone monomethyl ether were added, and the temperature was raised to 100 占 폚, 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 a solid content of 79.8 mgKOH / g.

Each component was compounded according to the formulation shown in the following Tables, premixed with a stirrer, dispersed with a three-roll mill, and kneaded to prepare a composition. The amounts in the tables represent parts by mass.

* 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, novolak-type epoxy acrylate resin

* 4: Synthesis Example 4, alkali-soluble resin A-4, copolymer resin

* 5: EG-200 manufactured by Osaka Gas Chemical Co., Ltd., epoxy resin having fluorene skeleton

* 6: HP-6000 manufactured by DIC Corporation, an epoxy resin having a naphthalene skeleton

* 7: NC-3000 manufactured by Nippon Kayaku Co., Ltd., epoxy resin having biphenylaralkyl skeleton

* 8: HP-7200 manufactured by DIC Corporation, epoxy resin having dicyclopentadiene skeleton

* 9: N-695 manufactured by DIC Corporation, cresol novolak type epoxy resin

* 10: OXE02 manufactured by BASF Japan, oxime ester-based photopolymerization initiator

* 11: Irgacure 369 manufactured by BASF Japan, alpha -amino acetophenone based photopolymerization initiator

* 12 Irgacure TPO manufactured by BASF Japan, acylphosphine oxide-based photopolymerization initiator

* 13 Irgacure 784 manufactured by BASF Japan, a titanocene photopolymerization initiator

* 14: A-DCP manufactured by Shin-Nakamura Chemical Co., Ltd., acrylate having dicyclopentadiene skeleton

* 15: A-BPEF manufactured by Shin-Nakamura Chemical Co., Ltd., acrylate having fluorene skeleton

* 16: Dipentaerythritol hexaacrylate

The resin compositions of each of the examples and comparative examples thus obtained were evaluated as follows. The results are shown in the table above.

≪ Preparation of evaluation substrate &

The compositions obtained in Examples 1 to 5 and Comparative Examples 1 to 3 shown in Table 1 were applied on the entire surface of the substrate so as to have a thickness of 20 mu m after being dried by screen printing and dried at 80 DEG C for 30 minutes, Lt; / RTI > This substrate was subjected to solid exposure at an optimum exposure dose using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp), and developed for 60 seconds under the condition of a 1 mass% sodium carbonate aqueous solution at 30 캜 and a spray pressure of 0.2 MPa. This substrate was irradiated with ultraviolet rays under the condition of an integrated exposure dose of 1000 mJ / cm 2 in a UV conveyer, and then cured by heating at 160 캜 for 60 minutes. The obtained evaluation substrate was evaluated as follows.

<Developability>

Each of the compositions of Examples and Comparative Examples was applied to the FR-4 material under the conditions for producing the evaluation substrate described above, and dried. Then, a 1 mass% sodium carbonate aqueous solution at 30 캜 was extruded at a pressure of 0.2 MPa And the time until the dry film was completely dissolved was measured. The results were evaluated based on the following criteria.

○: 60 seconds or less

B: 60 seconds to less than 120 seconds

×: 120 seconds or more

&Lt; Soldering heat resistance &

Each composition of the examples and comparative examples was applied to a cured coating film obtained by coating, drying, exposure, development, and post-curing by applying the FR-4 material under the conditions of the evaluation substrate described above, and rosin- After immersing in the solder bath for 30 seconds was repeated three times, a cross-cut tape peeling test was carried out. The results were evaluated based on the following criteria.

○: No peeling

×: In peeling

&Lt; Adhesion (pencil hardness) >

The pencil hardness on the surface was measured using a cured coating film obtained by applying each of the compositions of Examples and Comparative Examples to FR-4 material under the conditions for producing the above evaluation substrate, drying, exposure, development, K 5600-5-4. And the hardness of the pencil peeling off the partition wall was measured. The results were evaluated based on the following criteria.

○: 5H or more

×: less than 5H

<Permittivity, dielectric tangent>

(Preparation of test piece)

Each of the compositions obtained in Examples 1 to 5 and Comparative Examples 1 to 3 was appropriately diluted with methyl ethyl ketone and then applied to a PET film (FB- 50: 16 占 퐉), and dried at 80 占 폚 for 30 minutes to obtain a dry film. Using the vacuum laminator (MVLP (registered trademark) -500 manufactured by Meiki Seisakusho Co., Ltd.) on the electrolytic copper foil (manufactured by Furukawa Denko Co., Ltd.) having a thickness of 9 탆, 70 ° C for 1 minute, and a degree of vacuum of 133.3 Pa. The dry film laminated on the copper foil was subjected to solid exposure at an optimum exposure dose using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp) to peel off the PET film. A dry film was again laminated on the exposed dry film, followed by solid exposure at an optimal exposure amount. The laminate and exposure were repeated 20 times to form a resin layer having a thickness of 400 mu m on the copper foil. The copper foil having the resin layer thus formed was irradiated with ultraviolet rays under the conditions of an integrated exposure dose of 1000 mJ / cm 2 with a UV conveyer, and then heated at 160 占 폚 for 60 minutes to cure the resin layer. Subsequently, the copper foil having the dry film layer was etched away using an etching solution having a composition of 340 g / l of cupric chloride and 51.3 g / l of free hydrochloric acid, A test piece including a cured resin layer of 탆 was prepared.

(Assessment Methods)

The thus prepared test piece was measured and evaluated for dielectric constant and dielectric tangent at 1 GHz using an RF impedance / material analyzer (Agilent E4991A, manufactured by Agilent Technologies). The evaluation criteria are as follows.

permittivity

?: Not more than 3.0

?: More than 3.0 and less than 3.5

×: 3.5 or more

Dielectric tangent

?: 0.010 or less

?: More than 0.010 and less than 0.015

X: 0.015 or more

Claims (9)

(A) an alkali-soluble resin having at least three aromatic rings in the repeating unit and having an unsaturated double bond, (B) a cyclic ether compound, and (C) a photopolymerization initiator. The photosensitive resin composition according to claim 1, wherein the cyclic ether compound (B) has at least one selected from a fluorene skeleton, a naphthalene skeleton, a biphenyl skeleton, and a dicyclopentadiene skeleton. The photosensitive resin composition according to claim 1 or 2, wherein the alkali-soluble resin having at least three aromatic rings in the repeating unit (A) and having an unsaturated double bond has at least one selected from a fluorene skeleton and a biphenyl skeleton Sensitive resin composition. The photosensitive resin composition according to any one of claims 1 to 3, wherein the photopolymerization initiator (C) is at least one selected from an oxime ester photopolymerization initiator, an? -Amino acetophenone photopolymerization initiator and a titanocene photopolymerization initiator . The photosensitive resin composition according to any one of claims 1 to 4, further comprising (D) a compound having an ethylenic unsaturated group. The photosensitive resin composition according to any one of claims 1 to 5, which is used for forming at least one of an overcoating agent and a solder resist. A dry film comprising a resin layer obtained by applying the photosensitive resin composition according to any one of claims 1 to 6 onto a film and drying the film. A cured product comprising the above resin layer of the photosensitive resin composition according to any one of claims 1 to 6 or the dry film according to claim 7. A printed wiring board having the cured product according to claim 8.