TWI516869B - An alkali developing type photosensitive resin composition, a dry film thereof and a cured product thereof, and a printed circuit board formed using one another - Google Patents

Description

Alkali development type photosensitive resin composition, dry film thereof and cured product thereof, and printed circuit board formed using the same

The present invention relates to an alkali-developable photosensitive resin composition which is suitable as a solder resist composition for a printed circuit board, a dry film thereof and a cured product thereof, and a printed circuit board formed using the same, particularly regarding the alkali development When the photosensitive resin composition is exposed to ultraviolet light and developed with a dilute aqueous alkali solution, an image can be formed, and in particular, the alkali-developing photosensitive resin composition has blast resistance, cavitation resistance, and through holes (through holes). The copper in the TH) is excellent in adhesion and crack resistance.

From the viewpoint of high precision and high density, in some solder resists for consumer printed circuit boards and almost all industrial printed circuit boards, ultraviolet light is used for post-exposure development to form images, and to transmit heat and light. A fully developed (main curing) liquid developing type solder resist composition was carried out. Further, from the viewpoint of environmental concerns, an alkali-developing type liquid solder resist composition using a dilute aqueous alkali solution as a developing solution has become mainstream. An alkali-developing type solder resist composition using a dilute alkali aqueous solution, for example, an active energy ray-curable resin described in Patent Document 1 (which is a novolac type ring) A liquid solder resist composition comprising a photopolymerization initiator, a diluent, and an epoxy compound, which is obtained by adding a polybasic acid anhydride to a reaction product of an oxygen compound and an unsaturated monocarboxylic acid, is widely used.

However, in the case of using an existing liquid solder resist composition, for example, in a method of directly filling a circuit board having TH, the formed solder resist film has the following problem: at the time of solder leveling (TH) There is a phenomenon of floating around (hereinafter referred to as "vacuum"); or when post-curing and soldering are leveled, the coating film filled in TH may overflow (hereinafter referred to as "burst").

Particularly in the Asian region headed by China, it is necessary to use a liquid solder resist composition to fill all the through-holes on the copper TH circuit board, and it is necessary to develop a solder resist composition that addresses the problems of the voids and the blast holes. For example, Patent Document 2 or Patent Document 3 discloses a liquid solder resist composition obtained by using a bisphenol type resin having a photosensitivity and alkali developability, a cresol novolak type resin, and a copolymer resin.

On the other hand, printed circuit boards use printed circuit boards that are thinner and younger and have a variety of apertures. In the case where the solder resist composition having the cavitation resistance and the blast resistance is used in a printed circuit board having a hole diameter of Φ500 or more, the adhesion between the copper and the solder resist composition interface in the TH may be insufficient. A bad condition that causes cracks. Figure 1 shows the shape of this inconvenience. Such a problem may lead to the following new problems: the flux easily enters the TH when the flux is applied, and the flux reflows to the opposite side of the flux coated surface, contaminating the surface of the substrate, and the residual flux in the TH is post-treated. It will swell when leveling, so it is expected to develop a resistance A solder resist composition excellent in blasthole property, cavitation resistance, and adhesion to copper in TH and crack resistance.

Patent Document 1: Japanese Patent Laid-Open No. 61-243869

Patent Document 2: JP-A-2008-116813

Patent Document 3: International Publication No. 2003-059975

Patent Document 4: 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 blast resistance, cavitation resistance, adhesion to copper in TH, and crack resistance, and which can provide a cured coating film, and a cured product thereof. A printed circuit board. A main object of the present invention is to provide an alkali-developable photosensitive resin composition which is excellent in adhesion to copper in TH and excellent in crack resistance and is suitable as a solder resist composition for a printed circuit board.

More specifically, it is an object of the present invention to provide not only excellent resistance to blasthole resistance and cavitation resistance required for a solder resist composition but also insufficient adhesion in the prior art to copper in TH in the present invention. An alkali-developable photosensitive resin composition excellent in crack resistance.

The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, have found that the alkali-developing photosensitive resin composition as described below can solve the above-mentioned problems. In the present invention, the alkali-developable photosensitive resin composition is characterized by comprising (A) a carboxyl group-containing resin, (B) a photopolymerization initiator, (C) a diluent solvent, and (D) a molecule. a compound having two or more ethylenically unsaturated groups and (E) talc as (A) a carboxyl group-containing resin containing at least one bisphenol type epoxy compound (a) and an unsaturated carboxylic acid (b) The esterification reaction is carried out to form an esterified product having an epoxy group, followed by a carboxyl group-containing resin (A-1) obtained by reacting with a saturated or unsaturated polybasic acid anhydride (c), and (E) the content of talc is The total amount is 10% by mass or more and 60% by mass or less.

In other words, the alkali-developable photosensitive resin composition of the present invention contains (A) a carboxyl group-containing resin, (B) a photopolymerization initiator, (C) a diluent solvent, and (D) two in one molecule. The above ethylenically unsaturated group-containing compound and (E) talc, as (A) carboxyl group-containing resin, esterification reaction of at least one bisphenol epoxy compound (a) with an unsaturated carboxylic acid (b) a carboxyl group-containing resin (A-1) obtained by reacting an esterified product having an epoxy group with a saturated or unsaturated polybasic acid anhydride (c), and (E) a talc content of 10 parts by mass % or more and 60% by mass or less.

Further, preferably, it is used to fill TH.

Further, preferably, it contains (F) a filler other than (E) talc.

Further, preferably, it contains (G) a thermosetting component.

Further, preferably, it is applied to copper and used.

Further, the dry film of the present invention is characterized in that it is coated on a carrier film The alkali-developable photosensitive resin composition is obtained by drying.

Further, the cured product of the present invention is obtained by photocuring a coating film obtained by applying the alkali-developing photosensitive resin composition onto copper and drying it. A film obtained by applying the alkali-developable photosensitive resin composition onto a carrier film, drying the film, and laminating the obtained photocurable dry film on copper.

Further, the printed wiring board of the present invention is obtained by photocuring a coating film obtained by applying the alkali developing type photosensitive resin composition onto a substrate, and then thermally curing the coating film. A coating film obtained by drying the coating film, or a coating film obtained by applying the alkali-developable photosensitive resin composition onto a carrier film, drying the film, and laminating the obtained photocurable dry film on a substrate.

The most important technical feature of the alkali-developable photosensitive resin composition of the present invention is that the (A) carboxyl group-containing resin contains at least one bisphenol epoxy compound (a) and an unsaturated carboxylic acid (b). a carboxyl group-containing resin (A-1) obtained by reacting an esterification product having an epoxy group, followed by reaction with a saturated or unsaturated polybasic acid anhydride (c), and (E) a total amount of talc 10% by mass or more and 60% by mass or less.

Based on the above-mentioned most important technical feature, the carboxyl group-containing resin (A-1) having flexibility is used as the (A) carboxyl group-containing resin, and the content of the (E) talc is 10% by mass or more based on the total amount. When the amount is 60% by mass or less, the hardness of the cured product can be made soft, and the cured product can be provided with the flexibility of the alkali-developable photosensitive resin composition used. The result can be slow And the curing shrinkage at the time of curing of the alkali-developing photosensitive resin composition at the time of post-curing, and the alkali-developing photosensitive resin composition can satisfactorily follow TH in the flexibility of the alkali-developing photosensitive resin composition The unevenness of the copper surface is cured, whereby cracks in the interface between the copper in the TH and the alkali-developable photosensitive resin composition can be prevented. Moreover, the fluidity of the alkali-developable photosensitive resin composition is improved, and the embeddingness in the TH is improved at the time of printing.

On the contrary, in the conventional solder resist composition having cavitation resistance, although the foam resistance is obtained, the adhesion to copper in TH cannot be sufficiently obtained. The reason is that the conventional solder resist composition contains the carboxyl group-containing resin (A-1) and (F) filler, but the (F) filler usually uses barium sulfate having a high Mohs hardness (Mohs hardness: 3). , cerium oxide (Mohs hardness: 7), and the hardness scale of Mohs hardness is an integer value of 1 to 10. The larger the number, the higher the hardness of the mineral. Since barium sulfate and cerium oxide having a high Mohs hardness are used, sufficient flexibility of the alkali-developable photosensitive resin composition cannot be imparted. As a result, the relaxation of the curing shrinkage at the time of post-curing is insufficient, and it is difficult to sufficiently cure the unevenness of the copper surface in the TH, and the adhesion to the copper in the TH cannot be sufficiently obtained.

As described above, the conventional alkali-developable photosensitive resin composition has insufficient flexibility, and it is difficult to impart adhesion between the alkali-developing type and copper in TH. Therefore, in the present invention, the aforementioned problem is improved by using (E) talc having a Mohs hardness of 1 and being one of the softest minerals in minerals.

As described above, according to the present invention, it is possible to provide an alkali-developable photosensitive resin composition which is excellent in adhesion to copper in TH, blasthole resistance, cavitation resistance, and crack resistance, and a cured product thereof.

1‧‧‧ ink

2‧‧‧ copper

3‧‧‧Substrate

Fig. 1A is a view showing an abnormality such as copper and a coating film of TH without peeling. b is a graph showing the peeling of the copper and the coating film of TH.

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

The alkali-developing photosensitive resin composition of the present invention is characterized in that (E) talc is contained as an essential component, and therefore (E) talc will be described first.

(E) Talc

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

As the (E) talc, the mother rock may be any of magnesium carbonate, serpentine, cerium oxide/cerium oxide-alumina, and magnesium deposit, and may be any of the so-called citrate minerals. It may be in the form of a block or a fine powder. Surface treatment may or may not be performed.

(E) The content of talc is 10% by mass or more and 60% by mass based on the total amount The following is appropriate. When the amount is less than 10% by mass, the adhesion to the copper in the TH and the crack resistance are not sufficiently obtained. When the amount is more than 60% by mass, the fluidity of the alkali-developable photosensitive resin composition is deteriorated, and the film is buried in the TH during printing. Into the sex is getting worse.

(A) carboxyl group-containing resin

First, as the carboxyl group-containing resin (A) of the present invention, esterification reaction of at least one bisphenol type epoxy compound (a) with an unsaturated carboxylic acid (b) to form an epoxy group is formed. The carboxyl group-containing resin (A-1) obtained by further reacting with a saturated or unsaturated polybasic acid anhydride (c) will be described.

In the production of the carboxyl group-containing resin (A-1), at least one bisphenol type epoxy compound (a) used is used on an alcoholic hydroxyl group of a bisphenol A type or a bisphenol F type with respect to an alcohol A compound obtained by adding an epihalohydrin such as epichlorohydrin to an equivalent amount of 1 equivalent or more of the hydroxyl group.

Examples of the unsaturated carboxylic acid (b) to be added to the epoxy group of the bisphenol epoxy compound include dimers of acrylic acid and acrylic acid, methacrylic acid, and hydroxyethyl (meth)acrylate. Hydroxypropyl acrylate (meth) acrylate, hydroxybutyl (meth) acrylate, phenyl glycidyl (meth) acrylate, caprolactone (meth) acrylate adduct, etc. Amino acid anhydride adducts and the like, among which acrylic acid and methacrylic acid are particularly preferred. These unsaturated group-containing monocarboxylic acids may be used singly or in combination.

And as the bisphenol type epoxy compound and the unsaturated carboxylic acid The saturated or unsaturated polybasic acid anhydride (c) which reacts with an alcoholic hydroxyl group in the esterified product formed by the esterification reaction may, for example, be methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride or hexahydroorthophenylene. An aliphatic or aromatic dibasic acid anhydride such as dicarboxylic anhydride, methylhexahydrophthalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride or itaconic anhydride.

Further, such a saturated or unsaturated polybasic acid anhydride is preferably added in such a range that the acid value of the obtained carboxyl group-containing resin (A-1) is from 45 to 120 mgKOH/g.

Next, as a specific example of the other carboxyl group-containing resin (A), a compound (which may be any of an oligomer and a polymer) which is exemplified below is preferable.

(1) a carboxyl group-containing copolymer resin obtained by copolymerizing an unsaturated carboxylic acid such as (meth)acrylic acid with one or more compounds having an unsaturated double bond, and (2) in (meth)acrylic acid In the copolymer of an unsaturated carboxylic acid and one or more compounds having an unsaturated double bond other than the above, a glycidyl (meth)acrylate or a 3,4-epoxycyclohexylmethyl (meth)acrylate is used. a compound having an epoxy group and an unsaturated double bond, an ethylenically unsaturated group such as a (meth)acrylic acid chloride or the like as a side chain, thereby obtaining a photosensitive carboxyl group-containing copolymer resin, and (3) Copolymers of a compound having an epoxy group and an unsaturated double bond, such as glycidyl acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, and a compound having an unsaturated double bond other than , Reaction of an unsaturated carboxylic acid such as (meth)acrylic acid, a photosensitive carboxyl group-containing copolymer resin obtained by reacting a secondary hydroxyl group with a polybasic acid anhydride, and (4) an unsaturated double bond such as maleic anhydride a photosensitive carboxyl group-containing copolymer resin obtained by reacting a copolymer of an acid anhydride with a compound having an unsaturated double bond and a compound having a hydroxyl group and an unsaturated double bond such as 2-hydroxyethyl (meth)acrylate, (5) a carboxyl group-containing photosensitive resin obtained by reacting a polyfunctional epoxy compound with an unsaturated monocarboxylic acid to react a generated hydroxyl group with a saturated or unsaturated polybasic acid anhydride, and (6) a polyvinyl alcohol derivative or the like a hydroxyl group- and carboxyl group-containing photosensitive resin obtained by reacting a hydroxy polymer with a saturated or unsaturated polybasic acid anhydride, and reacting the produced carboxylic acid with a compound having an epoxy group and an unsaturated double bond in one molecule, (7) a reaction product of a polyfunctional epoxy compound, an unsaturated monocarboxylic acid, and a compound having at least one alcoholic hydroxyl group and a reactive group other than an alcoholic hydroxyl group which reacts with an epoxy group in one molecule a carboxyl group-containing photosensitive resin obtained by reacting an unsaturated polybasic acid anhydride, and (8) reacting a polyfunctional oxonium compound having at least two oxetane rings in one molecule with an unsaturated monocarboxylic acid to cause a change a carboxyl group-containing photosensitive resin obtained by reacting a primary hydroxyl group with a saturated or unsaturated polybasic acid anhydride in an oxygen oxime resin, and (9) reacting a polyfunctional epoxy resin with an unsaturated monocarboxylic acid to cause a reaction a carboxyl group-containing resin obtained by reacting a polybasic acid anhydride, and then further with a molecule A carboxyl group-containing photosensitive resin obtained by reacting a compound having one oxirane ring and one or more ethylenically unsaturated groups, but is not limited to the above.

Particularly preferred are the carboxyl group-containing resins of the above (2), (5), (7) and (9).

It should be noted that in the present specification, (meth) acrylate is a term collectively referred to as acrylate, methacrylate, and a mixture thereof, and the same applies to other similar expressions.

Since the carboxyl group-containing resin (A) has a plurality of free carboxyl groups in the side chain of the main chain polymer, it can be developed with a dilute aqueous alkali solution.

Further, the acid value of the carboxyl group-containing resin (A) is preferably in the range of 40 to 200 mgKOH/g, more preferably in the range of 45 to 120 mgKOH/g. When the acid value of the carboxyl group-containing resin is less than 40 mgKOH/g, it is difficult to develop alkali. On the other hand, when it exceeds 200 mgKOH/g, the dissolution of the developer to the exposed portion is promoted, and therefore, the wire becomes finer than necessary. Sometimes, the exposed portion and the unexposed portion are dissolved and peeled off by the developer without distinction, and it is difficult to draw a normal resist pattern.

Further, the weight average molecular weight of the carboxyl group-containing resin (A) varies depending on the resin skeleton, and is usually preferably from 2,000 to 150,000, and more preferably from 5,000 to 100,000. When the weight average molecular weight is less than 2,000, the non-sticking property after application to the substrate and subsequent drying may be deteriorated, and the moisture resistance of the coating film after exposure may be deteriorated, and the film generated during development may be reduced, and the resolution may be Greatly worse. On the other hand, the weight average molecule When the amount exceeds 150,000, the developability is remarkably deteriorated, and the storage stability may be deteriorated.

The content of the carboxyl group-containing resin (A) is desirably 20 to 60% by mass, preferably 30 to 50% by mass based on the total composition. When the content of the carboxyl group-containing resin (A) is less than the above range, the coating film strength is lowered. On the other hand, in the case of more than the above range, the viscosity of the composition becomes high, or the coatability and the like are lowered.

(B) Photopolymerization initiator

The photopolymerization initiator (B) which can be suitably used in the alkali-developable photosensitive resin composition of the present invention includes benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin. Benzoin and benzoin alkyl ethers such as isopropyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenyl Acetophenone, 1,1-dichloroacetophenone, 1-[4-(4-benzylidenephenylsulfonyl)-2-methyl-2-(4-methylphenylsulfonyl) )] acetophenones such as propan-1-one; 2-methyl-1-[4-(methylthio)phenyl]-2-N- Morpholinoacetone-1, 2-benzyl-2-dimethylamino-1-(4-N- Amino acetophenones such as phenylphenyl)-butanone-1; 2-methylindole, 2-ethylhydrazine, 2-(tributyl)anthracene, 1-chloroindole, etc. Terpenoids; 2,4-dimethyl 9-oxosulfur (thioxanthone), 2,4-diethyl 9-oxosulfur 2-chloro 9-oxosulfur 2,4-diisopropyl 9-oxosulfur 9-oxosulfur a ketal such as acetophenone dimethyl ketal or 2,2-dimethoxy-2-phenyl acetophenone; a benzophenone such as benzophenone or ketone( Ketone (xanthone) class; bis(2,6-dimethoxybenzylidene) (2,4,4-trimethylpentyl)phosphine oxide, bis(2,4,6-trimethylbenzene Mercapto)-phenylphosphine oxide, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, 2,4,6-trimethylbenzimidylphenylphosphonic acid ethyl ester, etc. The phosphine oxides, various peroxides, and the like may be used alone or in combination of two or more of these conventionally known photopolymerization initiators.

As the (B) photopolymerization initiator, 2-methyl-1-[4-(methylthio)phenyl]-2-N- is preferably used. Morpholinoacetone-1, which is a commercially available product, is exemplified by IRGACURE 907 manufactured by Ciba-Geigy Company.

The content of the photopolymerization initiator (B) is preferably 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). When the amount of the photopolymerization initiator used is less than the above range, the photocurability of the composition is deteriorated. On the other hand, when the amount is too large, the properties as a solder resist are lowered.

(C) organic solvent

The organic solvent (C) used in the alkali-developable photosensitive resin composition of the present invention is used to synthesize the carboxyl group-containing resin (A) and to prepare a combination thereof. An organic solvent may be used, or in order to adjust the viscosity so as to be coated on the substrate and the carrier film.

Examples of the organic solvent include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, and petroleum solvents. More specifically, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellosolve, methyl stilbene, and butyl siroliol; Glycol ethers such as carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate Esters such as ester, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol diethyl ether acetate, propylene glycol butyl ether acetate; alcohols such as ethanol, propanol, ethylene glycol, propylene glycol; octane, An aliphatic hydrocarbon such as decane; a petroleum solvent such as petroleum ether, naphtha, hydrogenated naphtha or solvent naphtha. The above organic solvents may be used singly or in the form of a mixture of two or more.

(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 photocured by irradiation with an active energy ray to form the carboxyl group-containing resin (A). It is insoluble in an aqueous alkali solution or a compound which contributes to the insoluble of the aforementioned carboxyl group-containing resin in an aqueous alkali solution. Specific examples of such a compound include hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; Monoacrylate or diacrylate of diols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, propylene glycol; N,N-dimethyl decylamine, N-methylol acrylamide Acrylamides such as N,N-dimethylaminopropyl acrylamide; aminoalkyl acrylates such as N,N-dimethylaminoethyl acrylate and N,N-dimethylaminopropyl acrylate Polyols such as hexylene glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, trishydroxyethyl isocyanurate or the like, or an ethylene oxide adduct thereof or a propylene oxide adduct Class; phenoxy acrylate, bisphenol A diacrylate, and acrylates such as ethylene oxide adducts or propylene oxide adducts of these phenols; glycerol diglycidyl ether, glycerol triglycidyl ether And an acrylate of a glycidyl ether such as trimethylolpropane triglycidyl ether or triglycidyl isocyanurate; and at least one of melamine acrylate and each methacrylate corresponding to the above acrylate One kind.

Further, an epoxy acrylate resin obtained by reacting a polyfunctional epoxy resin such as a cresol novolak epoxy resin with acrylic acid, and a hydroxyl group of the epoxy acrylate resin and pentaerythritol triacrylate may be used. An epoxy urethane acrylate compound obtained by reacting a hydroxy acrylate with a half urethane compound of a diisocyanate such as isophorone diisocyanate.

The content of the compound (D) having two or more ethylenically unsaturated groups in such a molecule with respect to 100 parts by mass of the above carboxyl group-containing resin (A) The amount is desirably 5 to 100 parts by mass, more preferably 10 to 70 parts by mass. When the content is less than 5 parts by mass based on 100 parts by mass of the carboxyl group-containing resin (A), the photocurability of the obtained alkali-developable photosensitive resin composition is lowered, and it is difficult to pass the active energy ray irradiation. The alkali develops to form a pattern. On the other hand, when it exceeds 100 parts by mass, the solubility in an aqueous alkali solution is lowered, and the cured coating film becomes brittle.

(F) filler

In order to improve the adhesion between the heat resistance and the copper in the TH, the (F) filler can be used for the alkali-developable photosensitive resin composition of the present invention.

Examples of the (F) filler include barium sulfate, barium titanate, barium oxide powder, spherical ceria, clay, magnesium carbonate, calcium carbonate, alumina, aluminum hydroxide, glass fiber, carbon fiber, mica powder, and the like. Commonly used inorganic or organic fillers are known. (F) The filler may or may not be surface treated.

The content of the filler (F) is preferably 0.01% by mass or more and 50% by mass or less based on the total amount. When the amount is less than 0.01% by mass, the adhesion to the copper in the TH and the heat resistance are not sufficiently obtained. When the content is more than 50% by mass, the fluidity of the alkali-developable photosensitive resin composition is deteriorated, and it is buried in the TH during printing. Into the sex is getting worse.

(G) thermosetting component

The alkali-developable photosensitive resin composition used in the present invention has two or more reactive groups in a mixed molecule in order to impart heat resistance and crack resistance. A thermosetting component (G) of at least one of a cyclic ether group and a cyclic thioether group (hereinafter simply referred to as a cyclic (thio)ether group).

The thermosetting component (G) is any one or two or more kinds of a cyclic ether group or a cyclic thioether group having a three-membered ring, a four-membered ring or a five-membered ring in the molecule, for example, The polyfunctional epoxy compound (G-1) which is a compound having at least two or more epoxy groups in the molecule, and a compound having at least two or more oxon groups in the molecule, that is, a polyfunctional oxonium compound (G-2) A compound having at least two or more thioether groups in the molecule, that is, an episulfide resin (G-3) or the like.

Examples of the polyfunctional epoxy compound (G-1) include EPICOAT828, EPICOAT834, EPICOAT1001, EPICOAT1004 manufactured by Mitsubishi Chemical Corporation, Epiclon 840, Epiclon 850, Epiclon 1050, and Epiclon 2055 manufactured by DIC, manufactured by Tohto Kasei Co., Ltd. Epotote YD-011, YD-013, YD-127, YD-128, DER317, DER331, DER661, DER664 manufactured by Dow Chemical Company, Sumiepoxy ESA-011, ESA-014, ELA manufactured by Sumitomo Chemical Industries -115, ELA-128, AER330, AER331, AER661, AER664, etc. (all trade names) bisphenol A epoxy resin manufactured by Asahi Kasei Industrial Co., Ltd.; EPICOAT YL903 manufactured by Mitsubishi Chemical Corporation, Epiclon152 manufactured by DIC, Epiclon 165, Epotote YDB-400 manufactured by Dongdu Chemical Co., Ltd., YDB-500, DER542 manufactured by Dow Chemical Company, Sumiepoxy ESB-400 manufactured by Sumitomo Chemical Industries, Ltd., ESB-700, AER711 manufactured by Asahi Kasei Industrial Co., Ltd. AER714 (both trade names) brominated epoxy resin; EPICOAT152, EPICOAT154 manufactured by Mitsubishi Chemical Corporation, DEN431, DEN438 manufactured by Dow Chemical Company, Epiclon N-730, Epiclon N-770, Epiclon N-865 manufactured by DIC Epotote YDCN-701, YDCN-704 manufactured by Dongdu Chemical Co., Ltd., EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306 manufactured by Nippon Kayaku Co., Ltd., Sumiepoxy ESCN manufactured by Sumitomo Chemical Industries, Ltd. 195X, ESCN-220, AERECN-235, ECN-299, etc. (all trade names) manufactured by Asahi Kasei Kogyo Co., Ltd. (all are brand name) novolac type epoxy resin; Epiclon 830 manufactured by DIC, EPICOAT807 manufactured by Mitsubishi Chemical Corporation, manufactured by Dongdu Chemical Co., Ltd. Epotote YDF-170, YDF-175, YDF-2004 (all are trade names) bisphenol F-type epoxy resin; Epotote ST-2004, ST-2007, ST-3000 (trade name) manufactured by Dongdu Chemical Co., Ltd. Bisphenol A type epoxy resin; EPICOAT604 manufactured by Mitsubishi Chemical Corporation, Epotote YH-434 manufactured by Dongdu Chemical Co., Ltd., Sumiepoxy ELM-120 manufactured by Sumitomo Chemical Industries Co., Ltd. (all trade names) glycidylamine type epoxy tree ; 乙 醯 醯 环氧树脂 环氧树脂 ; ; DA DA DA DA DA DA DA DA DA DA DA DA DA DA DA DA DA DA DA DA DA DA DA DA DA DA DA DA DA DA DA DA DA DA DA DA DA DA DA DA DA DA DA DA DA DA DA EPPN-501, EPPN-502 (all are trade names), trihydroxyphenylmethane type epoxy resin; YL-6056, YX-4000, YL-6121 (all trade names) manufactured by Mitsubishi Chemical Corporation A phenolic or bisphenol type epoxy resin or a mixture thereof; EBPS-200 manufactured by PharmaTech, EPX-30 manufactured by Asahi Chemical Industry Co., Ltd., bisphenol S-type epoxy resin such as EXA-1514 (trade name) manufactured by DIC, and EPICOAT157S (trade name) manufactured by Mitsubishi Chemical Corporation Phenol A novolac type epoxy resin; EPICOAT YL-931 (all are trade names) manufactured by Mitsubishi Chemical Corporation, tetraphenylolethane type epoxy resin; TEPIC manufactured by Nissan Chemical Industries Co., Ltd. (all are trade names) a heterocyclic epoxy resin; a diglycidyl phthalate resin such as Blemmer DGT manufactured by Nippon Oil & Fats Co., Ltd.; a tetraglycidyl xylenoyl ethane resin such as ZX-1063 manufactured by Dongdu Chemical Co., Ltd. ESN-190, ESN-360 manufactured by Nippon Steel Chemical Co., Ltd., HP-4032, EXA-4750, EXA-4700 and other naphthalene-containing epoxy resins manufactured by DIC; HP-7200 and HP-7200H manufactured by DIC have Epoxy resin of dicyclopentadiene skeleton; glycidyl methacrylate copolymer epoxy resin such as CP-50S and CP-50M manufactured by Nippon Oil & Fats Co., Ltd.; and cyclohexylmaleimide and glycidol methacrylate Ester copolymer epoxy resin; epoxy modified poly Butadiene rubber derivative (for example, PB-3600 manufactured by DAICEL CHEMICAL INDUSTRIES, LTD.), CTBN modified epoxy resin (for example, YR-102, YR-450, etc. manufactured by Tosho Kasei Co., Ltd.), etc., but not limited thereto . These epoxy resins may be used alone or in combination of two or more. Among them, particularly preferred are bisphenol A type epoxy resins or a mixture thereof.

Examples of the polyfunctional oxonium compound (G-2) include bis[(3-methyl-3-oxomethoxymethyl)methyl]ether and bis[(3-ethyl-3-oxo). Mercaptomethoxy)methyl]ether, 1,4-bis[(3-methyl-3-oxomethoxymethyl)methyl] Benzene, 1,4-bis[(3-ethyl-3-oxomethoxymethyl)methyl]benzene, (3-methyl-3-oxomethyl)methyl acrylate, acrylic acid (3-ethyl 3-oxomethoxy)methyl ester, (3-methyl-3-oxomethyl)methyl methacrylate, (3-ethyl-3-oxomethyl)methyl methacrylate, their oligomerization Polyfunctional oxime such as a substance or a copolymer, and oxetane and novolac resin, poly(p-hydroxystyrene), cardo type bisphenol, calixarene, resorcinol calixarene ( An ether compound of a resin having a hydroxyl group such as calixresorcinarene or silsesquioxane. Further, a copolymer of an unsaturated monomer having an oxonium ring and an alkyl (meth)acrylate may, for example, be mentioned.

The compound (G-3) having two or more cyclic thioether groups in the molecule may, for example, be a bisphenol A type episulfide resin YL7000 manufactured by Mitsubishi Chemical Corporation. Further, an episulfide resin obtained by replacing the oxygen atom of the epoxy group of the novolac type epoxy resin with a sulfur atom by the same synthesis method may be used.

The content of the (G) thermosetting component having two or more cyclic (thio)ether groups in the molecule is preferably a ring with respect to 1 equivalent of the carboxyl group of the carboxyl group-containing resin (A). The (thio)ether group is in the range of 0.6 to 2.0 equivalents, more preferably in the range of 0.8 to 1.5 equivalents. When the content of the thermosetting component (G) having two or more cyclic (thio)ether groups in the molecule is less than 0.6 equivalent, the carboxyl group remains in the solder resist film, and heat resistance, alkali resistance, electrical insulation, and the like are lowered. . On the other hand, in the case of more than 2.0 equivalents, since a low-molecular-weight cyclic (thio)ether group remains in the dried coating film, the strength and the like of the coating film are lowered.

In the case of using the thermosetting component (G) having two or more cyclic (thio)ether groups in the molecule, the alkali-developable photosensitive resin composition preferably contains a thermosetting catalyst. Examples of the thermosetting catalyst include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, and 1-cyanoquinone. Imidazole derivatives such as ethyl-2-phenylimidazole and 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4-(dimethylamine) Amine compounds such as N-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine; adipic acid An antimony compound such as diterpene or azelaic acid dioxime; a phosphorus compound such as triphenylphosphine; and the like, and a thermosetting catalyst of a commercial product, for example, 2MZ-A manufactured by Shikoku Chemicals Co., Ltd., 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all trade names of imidazole-based compounds), U-CAT3503N and U-CAT3502T (trade names of blocked isocyanate compounds of dimethylamine) manufactured by SAN-APRO Co., Ltd., DBU, DBN, U-CATSA102, U-CAT5002 (both bicyclic hydrazine compounds and salts thereof) and the like are not particularly limited to these compounds. The thermosetting catalyst of the epoxy resin, the thermosetting catalyst of the oxonium compound, or the catalyst for promoting the reaction of at least one of the epoxy group and the oxon group with the carboxyl group may be used singly or in combination of two or more. In addition, guanamine, methyl decylamine, benzoguanamine, melamine, 2,4-diamino-6-methylpropenyloxyethyl-symmetric three can also be used. (sym-triazine), 2-vinyl-2,4-diamino-symmetric three 2-vinyl-4,6-diamino-symmetric three ‧Isocyanuric acid adduct, 2,4-diamino-6-methylpropenyloxyethyl-symmetric three ‧ Isocyanuric acid adducts and other symmetry three The derivative preferably uses a compound as an adhesion-imparting agent in combination with the above-mentioned thermosetting catalyst.

Other ingredients

The alkali-developable photosensitive resin composition of the present invention may further contain Phthalocyanine Blue, Phthalocyanine Green, Iodine green , disazo yellow, crystal violet, and titanium oxide as needed. , commonly known coloring agents such as carbon black, naphthalene black, etc., hydroquinone, hydroquinone monomethyl ether, tert-butyl catechol, 1,2,3-trihydroxybenzene (Pyrogallol), thiophene Commonly known thermal polymerization inhibitors such as (phenothiazine), known powder thickeners such as fine powder (particulate or powdery) cerium oxide, organic bentonite, montmorillonite, organic lanthanide, fluorine-based, polymer-based, etc. At least one of an antifoaming agent and a leveling agent is also a commonly known additive such as an imidazole imparting agent such as an imidazole-based, a thiazole-based or a triazole-based or a decane coupling agent.

When the alkali-developing photosensitive resin composition of the present invention is used as a solder resist for forming a printed circuit board, if necessary, the viscosity of the alkali-developable photosensitive resin composition of the present invention is adjusted to a viscosity suitable for the coating method. It is applied to, for example, a printed circuit board on which a circuit is formed by a screen printing method, a curtain printing method, a spray coating method, a roll coating method, or the like, and is dried, for example, at a temperature of about 60 to 100 ° C as needed. It can form a coating film that is not sticky. Then, the photomask formed with the predetermined exposure pattern is selectively exposed by the active light, and the unexposed portion is developed by the alkaline aqueous solution to form a resist pattern, and further, for example, by adding The heat is cured to a temperature of about 140 to 180 ° C, whereby the curing reaction of the thermosetting component and the polymerization of the photosensitive resin component can be promoted, and the heat resistance, solvent resistance, and acid resistance of the obtained resist film can be improved. Various properties such as properties, moisture absorption resistance, PCT resistance, adhesion, and electrical properties.

As the aqueous alkali solution used in the above development, an aqueous alkali solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium citrate, ammonia or an amine can be used. Further, as the irradiation light source for photocuring, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a semiconductor laser, a solid laser, a xenon lamp or a metal halide lamp or the like is suitable.

Example

The present invention will be described in more detail based on examples and comparative examples, but the scope of the invention and the embodiments thereof are not limited thereto. The "parts" or "%" in the examples and comparative examples are based on mass unless otherwise specified. The characteristic value test of the composition of the present example was carried out by the method described below.

Synthesis Example 1

86 parts by mass of 1,4-cyclohexanedicarboxylic acid (carboxylic acid equivalent: 86 g/eq.) was placed in a reaction vessel equipped with a gas introduction tube, a stirring device, a condenser, a thermometer, and a dropping funnel for continuous dropwise addition. 1,4-cyclohexanedicarboxylic acid) and 378 parts by mass of bisphenol A epoxy resin (manufactured by Mitsubishi Chemical Corporation, EPICOAT 828, epoxy equivalent 189 g/eq. of bisphenol A epoxy resin), It was dissolved at 110 ° C under stirring in a nitrogen atmosphere. Then, 0.3 parts by mass of triphenylphosphine was added, and the temperature in the reaction vessel was raised to 150 ° C, and the reaction was carried out for about 90 minutes while maintaining the temperature at 150 ° C to obtain an epoxy compound having an epoxy equivalent of 464 g / equivalent. Next, the temperature in the flask was cooled to 40 ° C, 390 parts by mass of carbitol acetate was added, dissolved by heating, and 0.46 parts by mass of methylhydroquinone and 1.38 parts by mass of triphenylphosphine were added and heated to 95 to 105 ° C. 72 parts by mass of acrylic acid was slowly added dropwise and allowed to react for 16 hours. The reaction product was cooled to 80 to 90 ° C, and 190 parts by mass of tetrahydrophthalic anhydride was added to carry out a reaction for 8 hours. The carboxyl group-containing photosensitive resin obtained in this manner had a nonvolatile content of 65%, and the solid content had an acid value of 100 mgKOH/g. Hereinafter, the resin solution is referred to as varnish A.

Synthesis Example 2

214 parts by mass of a cresol novolac type epoxy resin EPICLON N-695 (manufactured by DIC, epoxy equivalent = 214) was placed in a four-necked flask equipped with a stirrer and a reflux condenser, and 103 parts by mass of carbitol was added. The acetate and 103 parts by mass of a petroleum hydrocarbon solvent (manufactured by Japan Energy Corporation: Cactus Fines SF-01) were dissolved by heating. Next, 0.1 part by mass of hydroquinone as a polymerization inhibitor and 2.0 parts by mass of triphenylphosphine as a reaction catalyst were added. The mixture was heated to 95 to 105 ° C, and 72 parts by mass of acrylic acid was slowly added dropwise to carry out a reaction for 16 hours. The obtained reaction product was cooled to 80 to 90 ° C, and 91.2 parts by mass of tetrahydrophthalic anhydride was added thereto, and the mixture was reacted for 8 hours, and then taken out after cooling. The carboxyl group-containing photopolymerizable unsaturated compound thus obtained The nonvolatile content was 65%, and the acid value of the solid content was 87.5 mgKOH/g. Hereinafter, the solution of the reaction product is referred to as varnish B.

Using the carboxyl group-containing resin solution (varnish A and varnish B) of the synthesis example 1-2, the various components shown in Table 1 and the ratio (parts by mass) thereof were mixed, premixed with a stirrer, and then subjected to a 3-roll mill. The alkali-developable photosensitive resin composition was prepared by kneading. Here, the particle size measurement was performed by a particle size analyzer manufactured by ERICHSEN Co., Ltd., and the degree of dispersion of the obtained alkali-developable photosensitive resin composition was evaluated and found to be 15 μm or less.

Performance evaluation: (1) blast resistance

Each of the alkali-developable photosensitive resin compositions of the above Examples 1-4 and Comparative Examples 1-3 was filled in a substrate of Φ0.5 and 0.8 mmt, and then cured by photocuring and heat curing to obtain a cured coating film according to JIS. In the test method of C6481, the above coating film was immersed in a solder bath at 288 ° C for 3 seconds 3 times using a rosin-based and water-soluble flux. Then, the state of the coating film of the TH portion was visually observed. The evaluation criteria are as follows.

○: The coating film in the TH500 hole of Φ500 is completely absent.

△: less than 5 protrusions of the coating film in the TH500 hole of Φ500

×: The protrusion of the coating film in the TH500 hole of Φ500 is 5 or more

(2) Cavitation resistance

Each of the alkali-developable photosensitive resin compositions of the above Examples 1-4 and Comparative Examples 1-3 was filled in a substrate of Φ0.5 and 0.8 mmt, and then cured by photocuring and heat curing to obtain a cured coating film according to JIS. In the test method of C6481, the above coating film was immersed in a solder bath at 288 ° C for 3 seconds 3 times using a rosin-based and water-soluble flux. Then, the tape was peeled off, and the peeling state around TH was confirmed. The evaluation criteria are as follows.

○: No bubble is generated in the TH500 hole of Φ500

△: less than 5 vacuoles are produced in the TH500 hole of Φ500

×: More than 5 vacuoles are generated in the TH500 hole of Φ500

(3) Adhesion to copper in TH

Each of the alkali-developable photosensitive resin compositions of the above Examples 1-4 and Comparative Examples 1-3 was filled in a substrate of Φ0.5 and 0.8 mmt, and then photocured 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.

○: There is no abnormality such as peeling of copper and coating film of TH

×: TH is peeled off from the coating film

(4) Crack resistance

Filling the substrates of Φ0.5 and 0.8 mmt with the examples 1-4 and the ratio Each of the alkali-developable photosensitive resin compositions of Comparative Example 1-3 was subjected to photocuring and thermal curing to form a cured coating film. Then, the state of the coating film of the TH portion was observed with an optical microscope. The evaluation criteria are as follows.

○: There is no crack in the TH500 hole of Φ500.

△: less than 5 cracks in the TH500 hole of Φ500

×: More than 5 cracks are generated in the TH500 hole of Φ500

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

As described above, by adjusting the composition of Example 1-4, it is possible to obtain a photosensitive resin composition which is excellent in blast resistance, cavitation resistance, and adhesion to copper in TH and crack resistance. On the other hand, in Comparative Example 1, since the content of (E) talc was low, the adhesion was insufficient, and as a result, the adhesion to copper in TH could not be obtained. In Comparative Example 2, although the content of the (E) talc is sufficient, the carboxyl group-containing resin (A-1) is not contained, so that the flexibility is insufficient, and as a result, the blast resistance and the cavitation resistance are not obtained. In Comparative Example 3, since the (E) talc was not contained, the adhesion and the flexibility were insufficient, and as a result, the adhesion to the copper in the TH and the crack resistance could not be obtained.

1‧‧‧ ink

2‧‧‧ copper

3‧‧‧Substrate

Claims (7)

An alkali-developable photosensitive resin composition comprising (A) a carboxyl group-containing resin, (B) a photopolymerization initiator, (C) a diluent solvent, and (D) two or more ethyl groups in one molecule. a compound of an unsaturated group, (E) talc, and (F) a filler other than talc; and (A) a carboxyl group-containing resin containing at least one bisphenol type epoxy compound (a) and an unsaturated carboxylic acid (b) a carboxyl group-containing resin (A-1) obtained by an esterification reaction to form an esterification product having an epoxy group, followed by reaction with a saturated or unsaturated polybasic acid anhydride (c), and (E) a content of talc It is 10% by mass or more and 60% by mass or less of the total amount of the composition. The alkali-developable photosensitive resin composition according to the first aspect of the invention, which is used for filling a through hole (TH). The alkali-developable photosensitive resin composition according to the first aspect of the invention, wherein the (G) thermosetting component is contained. The alkali-developable photosensitive resin composition according to the first aspect of the invention, which is applied to copper and used. A photocurable dry film obtained by applying the alkali-developable photosensitive resin composition according to any one of claims 1 to 4 to a carrier film and drying it. A cured product obtained by photocuring a coating film obtained by coating an alkali developing type photosensitive resin composition according to any one of claims 1 to 4 a coating film obtained by drying on copper; or a base according to any one of claims 1 to 4; The development type photosensitive resin composition is coated on a carrier film and dried, and the obtained photocurable dry film is laminated on copper to obtain a coating film. A printed circuit board comprising: a cured product obtained by photocuring a coating film which is thermally cured, and the coating film is an alkali developed according to any one of claims 1 to 4. A coating film obtained by applying a photosensitive resin composition to a substrate and drying the film, or applying the alkali-developing photosensitive resin composition according to any one of claims 1 to 4 to a carrier film and drying A coating film obtained by laminating a obtained photocurable dry film on a substrate.