KR101726114B1 - Alkali development type photosensitive resin composition, dry film and cured product thereof, and printed circuit board formed by using same - Google Patents

Abstract

The present invention provides a photosensitive resin composition which is excellent in spark plug resistance, fear resistance, and adhesiveness to copper in a through hole (hereinafter referred to as TH) and crack resistance. The photosensitive resin composition of the present invention is a photosensitive resin composition containing (A) a carboxyl group-containing resin, (B) a photopolymerization initiator, (C) a diluting solvent, (D) a compound having two or more ethylenically unsaturated groups in one molecule, (A) an esterification product of an epoxy group produced by an esterification reaction of at least one bisphenol-type epoxy compound (a) with an unsaturated carboxylic acid (b), and a saturated or unsaturated polybasic acid anhydride (c) (E) the content of talc is 10% by weight or more and 60% by weight or less based on the total amount of the resin (A-1).

Description

Technical Field [0001] The present invention relates to an alkali developing photosensitive resin composition, a dry film thereof, a cured product thereof, and a printed wiring board formed using the same. BACKGROUND ART [0002]

The present invention relates to an alkali-developable photosensitive resin composition and a cured product thereof suitable for forming a solder resist or the like of a printed wiring board. More particularly, the present invention relates to a photosensitive resin composition and a cured product thereof capable of forming an image by exposure to ultraviolet light and development with a dilute aqueous alkali solution, A cured product thereof, and a printed wiring board which are excellent in adhesion and resistance to copper in TH (through hole) and crack resistance, and which can obtain a cured coating film.

Currently, solder resists of some commercial printed wiring boards and most of industrial printed wiring boards thereof are subjected to ultraviolet exposure and development to form an image, from a viewpoint of high precision and high density, and to a liquid developing type Of solder resist is used. Further, in consideration of environmental problems, a liquid developer such as an alkaline developing type liquid solder resist using a dilute alkaline aqueous solution as a developer is the mainstream. As the alkali developing type solder resist using such a dilute alkaline aqueous solution, for example, there is known an alkaline developing type solder resist which has an active energy obtained by adding a polybasic acid anhydride to the reaction product of a novolak type epoxy compound and an unsaturated monocarboxylic acid A liquid solder resist composition containing a radiation curable resin, a photopolymerization initiator, a diluent, and an epoxy compound is widely used.

However, in the case of using the conventional liquid solder resist composition, for example, in a specification that directly charges a wiring board having TH, the solder resist film formed is a phenomenon (hereinafter simply referred to as " solder resist film " (Hereinafter simply referred to as " fogging "), or a phenomenon in which a coated film filled in the TH is discharged at the time of post-curing or solder leveling.

Especially in Asia including China, a wiring board having a specification in which the entirety of a through hole of a wiring board such as a copper TH wiring board is filled with a liquid solder resist composition is the mainstream, and a solder resist composition corresponding to the above problems of fear and spall has been demanded. For example, a liquid solder resist composition obtained by using a combination of a bisphenol-type resin having photosensitive and alkali developability, a cresol novolak-type resin and a copolymerizable type resin as described in Patent Document 2 or Patent Document 3 is widely known .

On the other hand, printed wiring boards have been made thin and light in weight each year, and printed wiring boards having various hole diameters have been used. In particular, when a solder resist composition having the above-described fear and spill resistance is used for a printed wiring board having a hole diameter of? 500 or more, cracks may occur due to insufficient adhesion between the copper in the TH and the interface of the solder resist composition . Figure 1 shows the shape of the problem. This problem is caused by the fact that the flux tends to be drawn into the TH at the time of flux application, the flux tends to flow to the opposite surface of the flux application surface, the contamination of the substrate surface and the residual flux in TH are expanded at the level of the post- There is a demand for a solder resist composition that is excellent in spark plug resistance, fear resistance, adhesion to copper in TH, and crack resistance.

Japanese Patent Application Laid-Open No. 61-243869 Japanese Patent Application Laid-Open No. 2008-116813 International Publication No. 2003-059975 Japanese Patent Laid-Open No. 2002-256060

An object of the present invention is to provide an alkali-developable photosensitive resin composition which is excellent in spark plug resistance, fear resistance, adhesion to copper and crack resistance in TH, and which can obtain a cured coating film, a cured product thereof, and a printed wiring board. And its main object is to provide an alkali developing type photosensitive resin composition suitable for a solder resist composition for a printed wiring board which is excellent in adhesion to copper and crack resistance in TH.

More specifically, it is an object of the present invention to provide a photosensitive resin composition which is excellent in the spark plug resistance and fear resistance required for a solder resist, as well as in adhesiveness to copper in TH which is insufficient in the prior art, and which is excellent in crack resistance.

As a result of diligent studies to solve the above problems, the present inventors have found that (A) a resin containing a carboxyl group, (B) a photopolymerization initiator, (C) a diluting solvent, (D) a compound having two or more ethylenically unsaturated groups in one molecule, (A) an esterified product of an epoxy group formed by an esterification reaction of at least one bisphenol-type epoxy compound (a) with an unsaturated carboxylic acid (b), and a saturated Containing resin (A-1) obtained by reacting an unsaturated polybasic acid anhydride (c) or an unsaturated polybasic acid anhydride (c) in an amount of 10 wt% or more and not more than 60 wt% It has been found that the resin composition can solve the above problems, and the present invention has been accomplished.

That is, the alkali-developable photosensitive resin composition of the present invention comprises (A) a carboxyl-containing resin, (B) a photopolymerization initiator, (C) a diluting solvent, (D) a compound having two or more ethylenically unsaturated groups in one molecule, and (A) an esterified product of an epoxy group formed by an esterification reaction of at least one bisphenol-type epoxy compound (a) with an unsaturated carboxylic acid (b), and a saturated or unsaturated (A) comprises a carboxyl group-containing resin (A-1) obtained by reacting a polybasic acid anhydride (c), and the content of talc (E) is 10 wt% or more and 60 wt% or less of the whole amount.

It is also preferable to use TH charging.

Further, it is preferable to contain (F) a filler other than (E) talc.

Further, it is preferable to contain a thermosetting component (G).

Further, it is preferable to be used by coating on copper.

Further, the dry film of the present invention is characterized by being obtained by applying the alkali-developable photosensitive resin composition to a carrier film and drying the same.

The cured product of the present invention can be obtained by coating the above-mentioned alkali-developable photosensitive resin composition on copper and drying it, or by applying the photosensitive resin composition to a carrier film and drying the obtained photocurable dry film on copper Which is obtained by laminating a coating film obtained by photo-curing.

The printed wiring board of the present invention is a printed wiring board obtained by applying the above alkali-developable photosensitive resin composition onto a base material and drying it, or a photocurable dry film obtained by applying the photosensitive resin composition to a carrier film and drying the base material, Curing the coating film obtained by laminating and then thermally curing the coating film.

The photosensitive resin composition of the present invention is a photosensitive resin composition containing as a carboxyl group-containing resin (A) at least one esterified product of an epoxy group produced by an esterification reaction of at least one bisphenol type epoxy compound (a) and an unsaturated carboxylic acid (b) Containing resin (A-1) obtained by reacting an unsaturated polybasic acid anhydride (c) with an unsaturated polybasic acid anhydride (c), and the content of talc (E) is 10 wt% or more and 60 wt% or less.

According to the characterizing feature of the present invention, the content of the talc (E) is 10% by weight or more and 60% by weight or less, Or less, the hardness of the cured product is softened, and flexibility is imparted to the photosensitive resin composition. As a result, the curing shrinkage when the photosensitive resin composition is cured at the time of post-curing is relieved and the photosensitive resin composition can be surely followed and cured by the flexibility of the photosensitive resin composition in the TH surface of the copper, It is possible to prevent cracks at the interface between the copper and the photosensitive resin composition in the photosensitive resin composition. Further, the flowability of the alkali-developable photosensitive resin composition is improved, and the filling property in TH is improved at the time of printing.

On the other hand, in the conventional solder resist composition having fear resistance, fear resistance can not be obtained, but sufficient adhesion with copper in TH can not be obtained. The reason for this is that although the conventional solder resist composition contains the carboxyl group-containing resin (A-1) and the filler (F), the filler (F) contains barium sulfate (moss) having a high Mohs hardness Hardness 3) or silica (Mohs hardness 7) is generally used. As a measure of the hardness of the Mohs hardness, an integer value from 1 to 10 is used, and the larger the number, the higher the hardness of the mineral. By using barium sulfate or silica having a high Moh hardness, sufficient flexibility is not imparted to the photosensitive resin composition. As a result, the relaxation of the curing shrinkage at the time of post-curing is not sufficient, and it is difficult to sufficiently follow the irregularities of the copper surface in the TH to harden, and sufficient adhesion with copper in TH can not be obtained sufficiently.

As described above, the conventional photosensitive resin composition described above is insufficient in flexibility, and it is difficult to impart adhesiveness to copper in TH. Therefore, in the present invention, the above-mentioned improvement is achieved by using (E) talc, which is one of the softest minerals in the mineral having a Mohs hardness of 1.

From the above, it is possible to provide a photosensitive resin composition and a cured product thereof excellent in adhesiveness to copper, spark resistance, fear resistance and crack resistance in TH.

Fig. 1 (a) is a view showing that there is no abnormality such as peeling in copper and coating film of TH, and b is a view showing that there is peeling in copper and coating film of TH.

Hereinafter, each component in the alkali-developable photosensitive resin composition of the present invention will be described.

The alkali-developable photosensitive resin composition of the present invention is characterized in that (E) talc is contained as an essential component. First, (E) talc is described.

(E) Talc

(E) Talc used in the alkali-developable photosensitive resin composition of the present invention is used for enhancing adhesion and crack resistance to copper in TH.

As such (E) talc, the parent rock may be any one of magnesium carbonate, serpentinite, silica / silica-alumina and magnesium sediments, or one so-called silicate mineral, and the shape may be massive or differential. There may or may not be surface treatment.

The blending ratio of these (E) talc is suitably 10% by weight or more and 60% by weight or less of the total amount. When the amount is less than 10% by weight, adhesion and crack resistance to copper in the TH can not be sufficiently obtained. If the amount is more than 60% by weight, the flowability of the alkali-developable photosensitive resin composition is deteriorated, not.

(A) a carboxyl group-containing resin

First, an esterification product of an epoxy group produced by the esterification reaction of at least one bisphenol-type epoxy compound (a) with an unsaturated carboxylic acid (b), which is the carboxyl group-containing resin (A) of the present invention, and a saturated or unsaturated polybasic acid The carboxyl group-containing resin (A-1) obtained by reacting the anhydride (c) is described.

As the at least one bisphenol-type epoxy compound (a) used in the production of the carboxyl group-containing resin (A-1), epihalohydrins such as epichlorohydrin and the like may be added to the alcoholic hydroxyl group of bisphenol A type or bisphenol F type Is used in an amount of 1 equivalent or more based on 1 equivalent of an alcoholic hydroxyl group.

Examples of the unsaturated carboxylic acid (b) added to the epoxy group of the bisphenol type epoxy compound include acrylic acid, dimer of acrylic acid, methacrylic acid, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, Unsaturated dibasic acid anhydride adducts of hydroxyl group-containing acrylates such as butyl (meth) acrylate, phenyl glycidyl (meth) acrylate, and (meth) acrylic acid caprolactone adduct. Particularly preferred here are acrylic acid and methacrylic acid. These unsaturated group-containing monocarboxylic acids may be used alone or in combination.

Examples of the saturated or unsaturated polybasic acid anhydride (c) which reacts with the alcoholic hydroxyl group in the esterified product produced by the esterification reaction of the bisphenol-type epoxy compound with the unsaturated carboxylic acid include methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, Aliphatic or aromatic dibasic acid anhydrides such as phthalic anhydride, methylhexahydrophthalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride and itaconic anhydride.

The amount of the saturated or unsaturated polybasic acid anhydride to be used is preferably added within a range that the acid value of the carboxyl group-containing resin (A-1) to be obtained is 45 to 120 mgKOH / g.

As specific examples of the other carboxyl-containing resin (A), the following compounds (which may be any of an oligomer and a polymer) are preferable.

(1) a carboxyl group-containing copolymer resin obtained by copolymerizing at least one unsaturated carboxylic acid such as (meth) acrylic acid with a compound having another unsaturated double bond,

(2) at least one copolymer of an unsaturated carboxylic acid such as (meth) acrylic acid or the like and a compound having an unsaturated double bond other than the above, with glycidyl (meth) acrylate or 3,4-epoxycyclohexylmethyl ) Acrylate, or a compound having an unsaturated double bond, or a (meth) acrylic acid chloride or the like, as a pendant, a photosensitive carboxyl group-containing copolymer resin obtained by adding an ethylenically unsaturated group as a pendant,

(3) To a copolymer of a compound having an unsaturated double bond with an epoxy group such as glycidyl (meth) acrylate or 3,4-epoxycyclohexylmethyl (meth) acrylate and a compound having an unsaturated double bond other than the above , (Meth) acrylic acid and the like, and reacting the produced secondary hydroxyl group with a polybasic acid anhydride, to obtain a photosensitive resin composition containing a carboxyl group,

(4) a copolymer of an unsaturated double bond-containing acid anhydride having an unsaturated double bond such as maleic anhydride with a compound having an unsaturated double bond with a hydroxyl group such as 2-hydroxyethyl (meth) acrylate A photosensitive carboxyl group-containing copolymer resin obtained by reacting a compound,

(5) a carboxyl group-containing photosensitive resin obtained by reacting a polyfunctional epoxy compound with an unsaturated monocarboxylic acid and reacting the resulting hydroxyl group with a saturated or unsaturated polybasic acid anhydride,

(6) a method of reacting a saturated or unsaturated polybasic acid anhydride with a hydroxyl group-containing polymer such as a polyvinyl alcohol derivative and then reacting the resultant carboxylic acid with a compound having an epoxy group and an unsaturated double bond in one molecule, Sensitive resin,

(7) A process for producing a reaction product of a polyfunctional epoxy compound, an unsaturated monocarboxylic acid, at least one alcoholic hydroxyl group in one molecule and a compound having one reactive group other than an alcoholic hydroxyl group reacting with an epoxy group, A carboxyl group-containing photosensitive resin obtained by reacting a polybasic acid anhydride,

(8) a carboxyl group obtained by reacting an unsaturated monocarboxylic acid with a polyfunctional oxetane compound having at least two oxetane rings in one molecule, and reacting a saturated or unsaturated polybasic acid anhydride with the primary hydroxyl group in the obtained modified oxetane resin Containing photosensitive resin and

(9) A polyfunctional epoxy resin obtained by reacting a polyfunctional epoxy resin with an unsaturated monocarboxylic acid and then reacting the polyfunctional epoxy resin with a polybasic acid anhydride to obtain a compound having one oxirane ring and at least one ethylenic unsaturated group in the molecule The carboxyl group-containing photosensitive resin

, But the present invention is not limited thereto.

Among these examples, preferred are the carboxyl group-containing resins (2), (5), (7) and (9).

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

Since the carboxyl group-containing resin (A) has a large number of free carboxyl groups in the side chain of the backbone polymer, development with a dilute aqueous alkali solution becomes possible.

The acid value of the carboxyl group-containing resin (A) is preferably in the range of 40 to 200 mgKOH / g, more preferably 45 to 120 mgKOH / g. When the acid value of the carboxyl group-containing resin is less than 40 mgKOH / g, the alkali development becomes difficult. On the other hand, when the acid value exceeds 200 mgKOH / g, dissolution of the exposed portion by the developer proceeds, Is dissolved and peeled off as a developing solution without distinction between the exposed portion and the unexposed portion, which makes it difficult to draw a normal resist pattern.

The weight average molecular weight of the carboxyl group-containing resin (A) varies depending on the resin skeleton, but is generally in the range of 2,000 to 150,000, more preferably 5,000 to 100,000. If the weight average molecular weight is less than 2,000, the tack free performance after coating and drying on the substrate may be lowered, the moisture resistance of the coated film after exposure may deteriorate, the film may decrease during development, and the resolution may be significantly lowered . On the other hand, if the weight average molecular weight exceeds 150,000, the developability may be markedly deteriorated and the storage stability may be deteriorated.

The blending amount of the carboxyl group-containing resin (A) is preferably 20 to 60 mass%, more preferably 30 to 50 mass%, of the total composition. When the amount of the carboxyl group-containing resin (A) is less than the above range, the strength of the coating film is lowered, which is not preferable. On the other hand, if it is more than the above range, the viscosity of the composition tends to be high, and the coatability and the like decrease, which is not preferable.

(B) a photopolymerization initiator

As the photopolymerization initiator (B) suitably used in the alkali-developable photosensitive resin composition of the present invention,

Benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether;

Diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1- [4- (4-benzoylphenylsulfanyl) Methyl-2- (4-methylphenylsulfanyl) propan-1-one;

2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 Aminoacetophenones such as < RTI ID = 0.0 >

Anthraquinones such as 2-methyl anthraquinone, 2-ethyl anthraquinone, 2-tert-butyl anthraquinone, and 1-chloro anthraquinone;

Thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone;

Ketal such as acetophenone dimethyl ketal and benzyl dimethyl ketal;

Benzophenones such as benzophenone or xanthones;

Bis (2,6-dimethoxybenzoyl) (2,4,4-trimethylpentyl) phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldi Acylphosphine oxides such as phenylphosphine oxide and ethyl-2,4,6-trimethylbenzoyl phenylphosphinate;

Various peroxides

. These photopolymerization initiators for known purpose can be used singly or in combination of two or more kinds.

Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1 is used as a preferable form of the photopolymerization initiator (B), and commercially available products include Irgacure 907 .

The mixing ratio of these photopolymerization initiators (B) is 0.01 to 30 parts by mass, preferably 5 to 25 parts by mass, per 100 parts by mass of the carboxyl group-containing resin (A). If the amount of the photopolymerization initiator used is less than the above range, the photocurability of the composition becomes poor, and if too large, the properties of the solder resist deteriorate, which is not preferable.

(C) Organic solvents

The organic solvent (C) used in the alkali-developable photosensitive resin composition of the present invention is preferably an organic solvent (C) for the synthesis of the carboxyl group-containing resin (A) or for the preparation of the composition or for viscosity adjustment for application to a substrate or a carrier film A solvent may be used.

Examples of such organic solvents include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents and the like. More specifically, 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, triethylene glycol monoethyl ether And the like; Esters such as ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate and propylene glycol butyl ether acetate; Alcohols such as ethanol, propanol, ethylene glycol and propylene glycol; Aliphatic hydrocarbons such as octane and decane; Petroleum ether such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha. These organic solvents are used alone or as a mixture of two or more kinds.

(D) a compound having two or more ethylenically unsaturated groups in the molecule

The compound (D) having two or more ethylenically unsaturated groups in the molecule used in the alkali-developable photosensitive resin composition of the present invention is photo-cured by irradiation with active energy rays to insolubilize the carboxyl-containing resin (A) It is to help with anger or insolubility. As specific examples of such compounds,

Hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate;

Mono or 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, or polyhydric acrylates such as ethylene oxide adducts or propylene oxide adducts thereof;

Acrylates such as phenoxy acrylate, bisphenol A diacrylate and ethylene oxide adducts or propylene oxide adducts of these phenols;

Acrylates of glycidyl ethers such as glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylol propane triglycidyl ether and triglycidyl isocyanurate;

And at least one of melamine acrylate and each methacrylate corresponding to the acrylate.

In addition, an epoxy acrylate resin obtained by reacting a polyfunctional epoxy resin such as cresol novolak type epoxy resin with acrylic acid, or an epoxy acrylate resin obtained by reacting a hydroxy acrylate such as pentaerythritol triacrylate with an isophorone di And an epoxy urethane acrylate compound obtained by further reacting a half urethane compound of a diisocyanate such as an isocyanate.

The amount of the compound (D) having two or more ethylenically unsaturated groups in the molecule is preferably 5 to 100 parts by mass, more preferably 10 to 70 parts by mass, per 100 parts by mass of the carboxyl-containing resin (A) Ratio. When the blending amount is less than 5 parts by mass based on 100 parts by mass of the carboxyl group-containing resin (A), the photocurability of the resulting alkali-developable photosensitive resin composition is lowered, and pattern formation becomes difficult due to the alkali development after irradiation with active energy rays , Which is undesirable. On the other hand, when it exceeds 100 parts by mass, the solubility in an alkali aqueous solution is lowered, or the cured coating film becomes brittle, which is not preferable.

(F) Filler

In the alkali-developable photosensitive resin composition of the present invention, a filler (F) may be used to improve heat resistance and adhesiveness to copper in TH.

Examples of the filler (F) include inorganic fillers such as barium sulfate, barium titanate, silicon oxide, spherical silica, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, glass fiber, carbon fiber, Organic fillers. These (F) fillers may or may not have a surface treatment.

The mixing ratio of these (F) fillers is suitably 0.01 wt% to 50 wt% of the total amount. When the amount is less than 0.01% by weight, the adhesiveness to the copper in TH and the heat resistance are not sufficiently obtained. When the amount exceeds 50% by weight, the flowability of the alkali developing photosensitive resin composition is deteriorated and the filling property in TH is poor during printing .

(G) Thermosetting component

The alkali-developable photosensitive resin composition for use in the present invention is a photosensitive resin composition containing two or more reactive groups (at least one of a cyclic ether group and a cyclic thioether group (hereinafter referred to as a cyclic (thio) ether group ) Is blended with the thermosetting component (G).

The thermosetting component (G) is a compound having two or more groups of one or two kinds of cyclic ether groups or cyclic thioether groups of 3, 4 or 5-membered rings in the molecule. For example, at least two epoxy groups (G-1), a compound having at least two oxetanyl groups in the molecule, that is, a polyfunctional oxetane compound (G-2), a compound having two or more thioether groups in the molecule , An episulfide resin (G-3), and the like.

Examples of the polyfunctional epoxy compound (G-1) include Epikote 828, Epikote 834, Epikote 1001, Epikote 1004 manufactured by Mitsubishi Chemical Corporation, Epiclon 840, Epiclon 850, Epiclon 1050 YD-013, YD-127, YD-128 manufactured by Dot Chemical Industries, Ltd., DER317, DER331, DER661, DER664 manufactured by Dow Chemical Co., Ltd., Sumitomo Chemical Co., Bisphenol A type epoxy resins such as SUMI-epoxy ESA-011, ESA-014, ELA-115, ELA-128, AER330, AER331, AER661 and AER664 manufactured by Asahi Kasei Corporation; Epotho YDB-400, YDB-500 manufactured by Toko Kasei Co., DER542 manufactured by Dow Chemical Co., Sumitomo Chemical Co., Ltd., Sumitomo Chemical Industries, Ltd., Epikote YL903 manufactured by Mitsubishi Kagaku Co., Epoxy ESB-400, ESB-700, AER711 manufactured by Asahi Kasei Kogyo Co., Ltd. and AER714 (all trade names); DEN431, DEN438 manufactured by Dow Chemical, Epiclon N-730 manufactured by DIC, Epiclon N-770, Epiclon N-865, manufactured by Toko Kasei Co., Epoxies ESCN-195X and ESCN-201X manufactured by Nippon Kayaku Co., Ltd., EOCN-1025, EOCN-1020, EOCN-104S and RE- 306 manufactured by Sumitomo Chemical Co., 220, AERECN-235 and ECN-299 (all trade names) manufactured by Asahi Kasei Corporation; Bisphenol F type epoxy resin of Epiclon 830 manufactured by DIC, Epikote 807 manufactured by Mitsubishi Kagaku Co., Ltd., Epototo YDF-170, YDF-175 and YDF-2004 manufactured by Tokto Kasei Co., Hydrogenated bisphenol A type epoxy resins such as Eptoto ST-2004, ST-2007 and ST-3000 (trade name) manufactured by Toko Kasei Kogyo; Epikote 604 manufactured by Mitsubishi Kagaku Co., Ltd., Epototo YH-434 manufactured by Toko Kasei Co., Ltd., Sumi-epoxy ELM-120 manufactured by Sumitomo Chemical Co., Ltd., glycidylamine type epoxy resin; Hidanto dolphin epoxy resin; Alicyclic epoxy resins such as Celloxide 2021 (all trade names) manufactured by Daicel Chemical Industries, Ltd.; A trihydroxyphenylmethane type epoxy resin such as YL-933 manufactured by Mitsubishi Chemical Corporation, T.E.N., EPPN-501, and EPPN-502 manufactured by Dow Chemical Co. (all trade names); Non-cisolene type or biphenol type epoxy resins such as YL-6056, YX-4000 and YL-6121 (all trade names) manufactured by Mitsubishi Chemical Corporation or a mixture thereof; Bisphenol S type epoxy resins such as EBPS-200 manufactured by Nippon Kayaku Co., EPX-30 manufactured by Asahi Denka Kogyo K.K. and EXA-1514 (trade name) manufactured by DIC; A bisphenol A novolak type epoxy resin such as Epikote 157S (trade name) manufactured by Mitsubishi Chemical Corporation; Tetraphenylol ethane type epoxy resin such as Epikote YL-931 (all trade names) manufactured by Mitsubishi Chemical Corporation; A heterocyclic epoxy resin of TEPIC manufactured by Nissan Kagaku Kogyo Co., Ltd. (all trade names); Diglycidyl phthalate resins such as Blemmer DGT manufactured by Nippon Yushi Co., Ltd.; Tetraglycidylcyloyl ethane resins such as ZX-1063 manufactured by Tohto Kasei Co., Ltd.; Naphthalene group-containing epoxy resins such as ESN-190, ESN-360, DIC HP-4032, EXA-4750 and EXA-4700 manufactured by Shin Nippon Sekisui Chemical Co., An epoxy resin having a dicyclopentadiene skeleton such as HP-7200, HP-7200H made by DIC; Glycidyl methacrylate copolymer-based epoxy resins such as CP-50S and CP-50M manufactured by Nippon Yushi; A copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; Epoxy-modified polybutadiene rubber derivatives (e.g., PB-3600 manufactured by Daicel Chemical Industries, Ltd.), CTBN-modified epoxy resins (e.g., YR-102 and YR-450 manufactured by Tokto Kasei Co., Ltd.) , But are not limited thereto. These epoxy resins may be used alone or in combination of two or more. Of these, bisphenol A type epoxy resins or mixtures thereof are particularly preferred.

Examples of the polyfunctional oxetane compound (G-2) include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [ (3-methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [ (3-ethyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl) methyl acrylate, In addition to polyfunctional oxetanes such as methyl methacrylate and oligomers or copolymers thereof, oxetane alcohol and novolak resins, poly (p-hydroxystyrene), cardo type bisphenols, calixarene, Isocyanuric acid, isophorone diisocyanate, isophorone diisocyanate, isophorone diisocyanate, isophorone diisocyanate, isophorone diisocyanate, Other examples include copolymers of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate.

Examples of the compound (G-3) having two or more cyclic thioether groups in the molecule include a bisphenol A type episulfide resin YL7000 manufactured by Mitsubishi Chemical Corporation. An episulfide resin in which the oxygen atom of the epoxy group of the novolak type epoxy resin is substituted with a sulfur atom can also be used by using the same synthesis method.

The amount of the thermosetting component (G) having two or more cyclic (thio) ether groups in the molecule is preferably 0.6 to 2.0 equivalents, more preferably 0.6 to 2.0 equivalents, relative to 1 equivalent of the carboxyl group of the carboxyl group- Preferably 0.8 to 1.5 equivalents. When the blending amount of the thermosetting component (G) having two or more cyclic (thio) ether groups in the molecule is less than 0.6, the carboxyl groups remain in the solder resist film and the heat resistance, alkali resistance, electrical insulation and the like are lowered. On the other hand, when the amount is more than 2.0 equivalents, a low molecular weight cyclic (thio) ether group remains in the dried coating film, and the strength or the like of the coating film is lowered.

When a thermosetting component (G) having two or more cyclic (thio) ether groups in the molecule is used, it is preferable to contain a thermosetting catalyst. Examples of such thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, Imidazole derivatives such as 1-cyanoethyl-2-phenylimidazole and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; Amines such as dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine and 4- Compounds, hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (trade names of all imidazole-based compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd., acid-phosphorus compounds such as triphenylphosphine, DBU, DBN, U-CATSA102 and U-CAT5002 (both bicyclic amidine compounds and salts thereof), U-CAT3503N and U-CAT3502T (all of the block isocyanate compounds of dimethylamine) But is not limited to these, and any resin may be used as long as it accelerates the reaction between a thermosetting catalyst of an epoxy resin or an oxetane compound or a carboxyl group with at least one of an epoxy group and an oxetanyl group, It can also be used. Further, it is also possible to use at least one selected from the group consisting of guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, Azine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine isocyanuric acid Triazine derivatives such as adducts may be used. Preferably, a compound that also functions as such an adhesion-imparting agent is used in combination with the above-mentioned thermosetting catalyst.

Other components

The alkali-developable photosensitive resin composition of the present invention may contain, if necessary, colorants such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black and naphthalene black, , Known thermoset polymerization inhibitors such as hydroquinone monomethyl ether, t-butyl catechol, pyrogallol and phenothiazine, water-soluble thickeners such as finely divided silica, organic bentonite and montmorillonite, silicone-based, fluorine-based and high- An antifoaming agent and a leveling agent, and an additive for known additives such as an imidazole-based, thiazole-based, triazole-based adhesion promoter and silane coupling agent can be further blended.

When the alkali-developable photosensitive resin composition of the present invention is used for forming a solder resist for a printed wiring board, the composition is adjusted to a viscosity suitable for the application method, if necessary, Coating by a coating method, a spray coating method, a roll coating method, and the like, and if necessary, drying treatment at a temperature of, for example, about 60 to 100 ° C, whereby a latent-image coat film can be formed. Thereafter, the resist pattern can be selectively formed through a photomask having a predetermined exposure pattern formed thereon, and the unexposed portion can be developed with an aqueous alkali solution to form a resist pattern. Further, for example, The polymerization of the photosensitive resin component is accelerated in addition to the curing reaction of the thermosetting component and the resulting resist film is heated to a temperature in the range of 40 to 60 ° C to obtain a resist film having various heat resistance, solvent resistance, acid resistance, hygroscopicity, PCT resistance, So that the characteristics can be improved.

As the alkali aqueous solution used for the above development, an aqueous alkali solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines and the like can be used. As the irradiation light source for light curing, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a semiconductor laser, a solid laser, a xenon lamp or a metal halide lamp are suitable.

[Example]

The present invention will be described in more detail based on Examples and Comparative Examples, but the technical scope of the present invention and its embodiments are not limited thereto. In the examples and comparative examples, " part " or "% " The property value test of the composition of this example was conducted by the method described below.

Synthesis Example 1

A reaction vessel equipped with a stirrer, a gas introducing tube, a stirrer, a thermometer and a dropping funnel for continuous loading was charged with 86 parts of 1,4-cyclohexanedicarboxylic acid having a carboxylic acid equivalent of 86 g / equivalent and bisphenol A type epoxy resin (Manufactured by Mitsubishi Chemical Corp., Epicote 828, epoxy equivalent: 189 g / eq.), And the mixture was melted at 110 DEG C under nitrogen atmosphere. Thereafter, 0.3 part of triphenylphosphine was added, the temperature in the reaction vessel was raised to 150 캜, and the reaction was carried out for about 90 minutes while maintaining the temperature at 150 캜 to obtain an epoxy compound having an epoxy equivalent of 464 g / equivalent. Next, the temperature in the flask was cooled to 40 占 폚, 390 parts of carbitol acetate was added, and the mixture was dissolved by heating. Then, 0.46 part of methylhydroquinone and 1.38 parts of triphenylphosphine were added and heated to 95 to 105 占 폚. Slowly added dropwise and reacted for 16 hours. The reaction product was cooled to 80 to 90 占 폚, and 190 parts of tetrahydrophthalic anhydride was added and reacted for 8 hours. The carboxyl group-containing photosensitive resin thus obtained had a nonvolatile content of 65% and an acid value of a solid content of 100 mgKOH / g. This resin solution is hereinafter referred to as a varnish A.

Synthesis Example 2

214 parts of Epiclon N-695 (epoxy equivalent = 214), which is a cresol novolak type epoxy resin, was placed in a four-necked flask equipped with a stirrer and a reflux condenser, and 103 parts of carbitol acetate, a petroleum hydrocarbon solvent Trade name: Cocktus Fine SF-01) was added and heated to dissolve. Then, 0.1 part of hydroquinone as a polymerization inhibitor and 2.0 parts of triphenylphosphine as a reaction catalyst were added. The mixture was heated to 95 to 105 DEG C, and 72 parts of acrylic acid was slowly added dropwise, followed by reaction for 16 hours. The obtained reaction product was cooled to 80 to 90 占 폚, and 91.2 parts of tetrahydrophthalic anhydride was added and reacted for 8 hours, cooled, and then taken out. The carboxyl group-containing photopolymerizable unsaturated compound thus obtained had a nonvolatile content of 65% and an acid value of a solid of 87.5 mgKOH / g. Hereinafter, the solution of this reaction product is referred to as a varnish B.

Using the carboxyl group-containing resin solution (varnish A, varnish B) of Synthesis Example 1-2, the components were mixed with the various components (parts by mass) shown in Table 1, preliminarily mixed in a stirrer, To thereby produce an alkali developing photosensitive resin composition. Here, the degree of dispersion of the obtained alkali-developable photosensitive resin composition was evaluated by particle size measurement by a grindmeter manufactured by Eric Sens, and it was 15 탆 or less.

Performance evaluation:

(1) Spill resistance

Each of the alkali-developable photosensitive resin compositions of Examples 1-4 and Comparative Examples 1-3 was filled in a substrate of? 0.5 and 0.8 mmt, and then a photocurable and thermosetting cured coating film was tested according to JIS C6481 Was immersed in a solder bath at 288 DEG C for 3 seconds 10 seconds using a rosin system and an aqueous flux. Thereafter, the state of the coating film of the TH part was visually observed. The evaluation criteria are as follows.

○: TH500 of φ500 No protrusion of coating film at all

△: TH500 hole of φ500 having less than 5 protrusions of coating film

X: TH500 holes of 500 mm or more with 5 or more projections of coating film

(2) fear tolerance

Each of the alkali-developable photosensitive resin compositions of Examples 1-4 and Comparative Examples 1-3 was filled in a substrate of? 0.5 and 0.8 mmt, and then a photocurable and thermosetting cured coating film was tested according to JIS C6481 Was immersed in a solder bath at 288 DEG C for 3 seconds 10 seconds using a rosin system and an aqueous flux. Thereafter, tape peeling was performed to confirm the peeling state around the TH. The evaluation criteria are as follows.

?: No occurrence of fear among TH500 holes of? 500

?: TH500 holes of? 500 have less than five occurrences of fear

X: TH500 of φ500 holes with five or more occurrences of fear

(3) Adhesion to copper in TH

Each of the alkali-developable photosensitive resin compositions of Examples 1-4 and Comparative Examples 1-3 was filled in a substrate of? 0.5 and 0.8 mmt, and then cured and thermally cured to form a cured coating film. Then, the cross-sectional state of the substrate was confirmed by an optical microscope. The evaluation criteria are as follows. A schematic view of the cross-sectional shape is shown in the figure.

○: No abnormality such as peeling in copper and coating film of TH

X: Thin copper and coating film peeled off

(4) Crack resistance

Each of the alkali-developable photosensitive resin compositions of Examples 1-4 and Comparative Examples 1-3 was filled in a substrate of? 0.5 and 0.8 mmt, followed by photocuring and thermosetting to form a cured coating film. Thereafter, the state of the coating film of the TH part was observed with an optical microscope. The evaluation criteria are as follows.

○: TH500 of φ500 No crack in hole

?: TH500 holes of? 500 have cracks less than 5

×: TH500 of φ500 having 5 or more cracks in holes

The results of the above tests are shown in Table 2.

From the above, it can be seen that by adjusting to the composition of Example 1-4, a photosensitive resin composition excellent in spark plug resistance, fear resistance, adhesion to copper in TH and crack resistance is obtained. On the other hand, in Comparative Example 1, the content of (E) talc was low, so that sufficient adhesiveness was not sufficient, and as a result, adhesiveness to copper in TH was not obtained. In Comparative Example 2, although the content of (E) talc was sufficient, the resin had insufficient flexibility because it did not contain the carboxyl group-containing resin (A-1), and as a result, the spark resistance and fear resistance were not obtained. Comparative Example 3 lacked sufficient adhesiveness and flexibility because it did not contain (E) talc. As a result, adhesion to copper and crack resistance in TH were not obtained.

1 ink
2 Copper
3 substrate

Claims (8)

(A) a carboxyl group-containing resin, (B) a photopolymerization initiator, (C) a diluting solvent, (D) a compound having at least two ethylenically unsaturated groups in one molecule, (E) talc and (F) (C) an esterification product of an epoxy group produced by an esterification reaction of at least one bisphenol-type epoxy compound (a) and an unsaturated carboxylic acid (b), and a saturated or unsaturated polybasic acid anhydride (c) (E) the content of talc is 10 wt% or more and 60 wt% or less of the whole amount, (F) the content of the filler other than talc is 0.01 wt% % Or more and 50 wt% or less based on the total weight of the solder resist composition. The solder resist composition according to claim 1, which contains (G) a thermosetting component. The solder resist composition according to claim 1, which is applied on copper. A photocurable dry film obtained by applying the solder resist composition according to any one of claims 1 to 3 to a carrier film and drying the solder resist composition. A photocurable dry film obtained by applying the solder resist composition according to any one of claims 1 to 3 onto copper and drying it, or applying the solder resist composition to a carrier film and drying the photocurable dry film, And a cured product obtained by photo-curing a coating film obtained by laminating. A coating film obtained by applying and drying the solder resist composition according to any one of claims 1 to 3 onto a substrate or a photocurable dry film obtained by applying the solder resist composition to a carrier film and drying the substrate, And a cured product obtained by photo-curing a coating film obtained by laminating and then thermally curing. delete delete

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