JPH0882930A - Photosetting and thermosetting resin composition - Google Patents

Abstract

PURPOSE: To obtain a photosetting and thermosetting resin compsn. excellent in shelf stability, having a long shelf life as a one-pack compsn. and giving a cured coating film excellent in adhesion, heat and chemical resistances by using a specified cyanoguanidine deriv. as a curing agent for epoxy resin. CONSTITUTION: This photosetting and thermosetting resin compsn. contains a resin curable with active energy beams and having at least two ethylenically unsatd. double bonds and a carboxyl group in one molecule, a photopolymn. initiator, a diluent, epoxy resin and a curing agent for epoxy resin. The curing agent is a cyanoguanidine deriv. represented by formula I (where R is a substituent such as a substituent represented by formula II). The specified substituent is introduced into cyanoguanidine and the resultant cyanoguanidine deriv. is made slightly soluble and has improved latent reactivity.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photocurable thermosetting resin composition, and more particularly to a photocurable resin composition suitable for forming a solder mask and capable of being developed by a dilute alkaline aqueous solution having excellent storage stability. The present invention relates to a thermosetting resin composition.

[0002]

2. Description of the Related Art In order to protect a circuit from an external environment and to prevent solder from adhering to unnecessary parts in a soldering process performed when surface mounting electronic parts on a printed wiring board or the like. What is used is a solder mask. As the solder mask, an alkali-developing photocurable thermosetting resin composition is generally used due to the problem of environmental pollution as the printed wiring board becomes higher in density. As the alkali developing type photocurable thermosetting resin composition, for example, in Japanese Patent Publication No. 1-54390, a saturated or unsaturated polybasic acid anhydride is added to a reaction product of a novolac type epoxy compound and an unsaturated monocarboxylic acid. A photocurable thermosetting resin composition characterized by containing a photosensitive resin obtained by reacting a substance is disclosed, and JP-A-3-289656 discloses an alkyl (meth) acrylate. Disclosed is an alkali-developable liquid photosolder resist using a photosensitive resin obtained by reacting a copolymer composed of glycidyl (meth) acrylate with acrylic acid and further reacting it with a polybasic acid anhydride. There is. However, in general, the alkali developing type photocurable thermosetting resin composition easily thickens or gels with time,
There is a drawback of lacking storage stability, and therefore, it is usually marketed as a two-component type consisting of a main agent mainly composed of a photosensitive resin and a curing agent mainly composed of a thermosetting component, and when used, these main agents and curing agents are Used as a mixture.

By the way, in the solder resist,
The coating film formed from the photocurable thermosetting resin composition is exposed and developed to form a predetermined resist pattern, and then post-cured to heat cure. In the alkali-developable photocurable thermosetting resin composition as described above, an epoxy resin is generally used as a thermosetting component, and the side chain carboxyl group of the photosensitive resin and the epoxy resin are used during the post cure. It also causes a copolymerization reaction of the epoxy group to form a solder resist film having excellent adhesion, hardness, heat resistance, electric insulation and the like. Then, in order to accelerate the above reaction at the time of post-cure, a curing agent for epoxy resin is generally used together with the epoxy resin.

Various compounds are known as curing agents for epoxy resins, and one of them is cyanoguanidine (also called dicyandiamide). However, when cyanoguanidine is used together with an epoxy resin in the above-mentioned alkali-developing photocurable thermosetting resin composition, the storage stability after mixing the main agent and the curing agent is lacking, and the shelf life as one liquid is There is a problem of being short. Further, it is known that substituted cyanoguanidine is also useful as a curing agent for epoxy resins.
No. 726 (Japanese Patent Application Publication, No. 5-508678). Publication of this patent application, Hei 5-508678
The invention described in No. 1 proposes to introduce a specific substituent in order to improve the solubility of cyanoguanidine,
That is, it is an object to provide a substituted cyanoguanidine compound soluble in various organic solvents. However, a substituted cyanoguanidine compound having a solubility in various organic solvents generally has a solubility in a liquid epoxy resin or a solution of an epoxy resin, and thus easily reacts with an epoxy resin at room temperature. As a result, the photocurable thermosetting resin composition containing this together with the epoxy resin has a short so-called shelf life and cannot be used as a latent curing agent.

[0005]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is not only excellent in photocurability, alkali developability, etc., but stable at low temperatures near room temperature, but hard in a short time at high temperatures. Another object of the present invention is to provide an alkali developing type photocurable thermosetting resin composition having excellent curability and a long shelf life. A more specific object of the present invention is that it is sparingly soluble in various organic solvents, and does not react with epoxy resin at low temperatures near room temperature, but reacts quickly by applying heat, so-called thermal latent reactivity. It contains a specific curing agent for epoxy resin, and therefore has excellent storage stability, has a long shelf life as one solution, and is required as a solder resist with adhesion, heat resistance, chemical resistance, hardness, electrical insulation, etc. Another object of the present invention is to provide an alkali-developable photocurable thermosetting resin composition capable of obtaining a cured coating film having excellent properties.

[0006]

To achieve the above object, according to the present invention, (A) an active energy ray-curable resin having at least two ethylenically unsaturated bonds and a carboxyl group in one molecule, (B) a photopolymerization initiator,
(C) a diluent, (D) an epoxy resin, and (E) a curing agent for an epoxy resin, wherein the curing agent for an epoxy resin (E) is represented by the following general formula (1) cyanoguanidine Provided is a photocurable thermosetting resin composition, which is a derivative.

[Chemical 3]

In the general formula (1), R is the following chemical formula 4
Is a substituent selected from the group consisting of the substituents (1) to (34) represented by:

[Chemical 4]

[0008]

The present inventors have found that the cyanoguanidine derivative represented by the general formula (1) is used as a curing agent for an epoxy resin added to an alkali-developable photocurable thermosetting resin composition. , Excellent in storage stability,
It has been found that a cured coating film having a long shelf life as one liquid and excellent in various properties required as a solder resist such as adhesion, heat resistance, chemical resistance, hardness, and electric insulation can be obtained. Has been completed. As mentioned above, the patent application publication, Hei 5-50867
The invention described in No. 8 proposes to introduce specific substituents in order to improve the solubility of cyanoguanidine. The present invention is completely different from such a conventional approach, and rather, by introducing a specific substituent into cyanoguanidine, the resulting cyanoguanidine derivative is made poorly soluble, the latent reactivity is improved, and the specific substitution is performed. The photocurable thermosetting resin composition containing the cyanoguanidine derivative has excellent storage stability and shelf life as one liquid. It also becomes longer, and it becomes possible to impart desired physical properties based on the characteristics of the specific substituent.

Among the cyanoguanidine derivatives represented by the general formula (1), the compounds having the substituents R (1) to (20) are biscyanoguanidine type derivatives, and have two cyanoguanidyl groups at both ends. Have, and thus have 6 active hydrogens attached to the nitrogen atom of the cyanoguanidyl group. As a result, it can theoretically react with 6 epoxy groups. Further, the substituent R is (21) to (3
The compound 4) is a cyanoguanidine derivative having an amine-based substituent introduced therein, has extremely high basicity, and is highly reactive with an epoxy compound. Nevertheless, these cyanoguanidine derivatives are generally sparingly soluble in various organic solvents, liquid epoxy resins or solutions of epoxy resins, and do not react with epoxy groups at room temperature, but react with epoxy groups by applying heat. It has properties and therefore can be used particularly advantageously as a thermal latent curing agent for epoxy resins.

By composing a cyanoguanidine derivative having such characteristics with an epoxy resin, it is stable at low temperatures around room temperature, but it cures in a short time at high temperatures, and is excellent in so-called latent curability. A photocurable thermosetting resin composition having a long shelf life can be obtained. Moreover, the photocurable thermosetting resin composition can produce a desired cured product from a relatively soft cured product to a hard cured product depending on the substituent introduced with the cyanoguanidine derivative.

The constituent components of the photocurable thermosetting resin composition of the present invention will be described below. First, the (A) 1
Examples of the active energy ray-curable resin having at least two ethylenically unsaturated bonds and a carboxyl group in the molecule include (1) an ester of an epoxy group of a polyfunctional novolac type epoxy compound and a carboxyl group of an unsaturated monocarboxylic acid. (2) a copolymer of alkyl (meth) acrylate and glycidyl (meth) acrylate, and (meth) acrylic acid To a copolymer of saturated or unsaturated polybasic acid anhydride, and (3) a copolymer of hydroxyalkyl (meth) acrylate, alkyl (meth) acrylate and glycidyl (meth) acrylate. After reacting (meth) acrylic acid, a saturated or unsaturated polybasic acid anhydride was further reacted. Can be used (4) alkyl (meth) acrylate and (meth) obtained by reacting a glycidyl (meth) acrylate copolymers of acrylic acid, and the like.

Since the above active energy ray-curable resin has a large number of free carboxyl groups added to the side chains of the backbone polymer, it can be developed with a dilute aqueous alkali solution and, at the same time, the coating film is developed after development. By post-heating, a copolymerization reaction occurs between the epoxy groups of the epoxy resin added separately as a thermosetting compounding component and the free carboxyl groups of the side chains, heat resistance of the coating film, solvent resistance, A solder resist film excellent in various properties such as acid resistance, adhesiveness, electrical properties, and hardness can be obtained. The acid value of the active energy ray-curable resin (A) is 40 to 160 m.
It is necessary to be in the range of gKOH / g, and the preferable range is 50 to 140 mg in the resin of (1) above.
KOH / g, 5 in the resins of (2) and (4) above
0 to 150 mgKOH / g, and in the resin of (3) above, it is 40 to 120 mgKOH / g. If the acid value is less than 40, the alkali solubility will be poor and conversely 160
If it is too large, it becomes a factor of deteriorating the properties of the cured film as a resist such as alkali resistance and electric properties.

The resin (1) is a reaction product of a novolac type epoxy compound and an unsaturated monocarboxylic acid as described below, a dibasic acid anhydride such as phthalic anhydride, trimellitic anhydride, or pyromellitic anhydride. It is obtained by reacting with an aromatic polycarboxylic acid anhydride such as an acid. In this case, a resin obtained by reacting 0.15 mol or more of a polybasic acid anhydride per one hydroxyl group contained in the reaction product of the novolac type epoxy compound and the unsaturated monocarboxylic acid is suitable. When the number of ethylenically unsaturated bonds present in one molecule of the epoxy compound is low, photocurability is slow, so it is desirable to use a novolac type epoxy compound as the raw material, but for the purpose of reducing the viscosity of the ink, bisphenol A type Epoxy compounds can also be used.

Typical novolac type epoxy compounds include phenol novolac type epoxy resin, cresol novolac type epoxy resin, and bisphenol A.
There are novolac type epoxy resin, etc.
A compound obtained by reacting each novolak resin with epichlorohydrin can be used.
Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, cinnamic acid, saturated or unsaturated dibasic acid anhydrides and 1
There are reaction products with (meth) acrylates having one hydroxyl group in the molecule, and these can be used alone or in combination of two or more, but from the viewpoint of photocurability, acrylic acid or methacrylic acid, especially Acrylic acid is preferred.

The polybasic acid anhydrides are typified by maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydro. Phthalic anhydride, Endomethylene tetrahydrophthalic anhydride, Methyl endomethylene tetrahydrophthalic anhydride,
Dibasic acid anhydrides such as chlorendic anhydride and methyltetrahydrophthalic anhydride; aromatic polyvalent carboxylic acid anhydrides such as trimellitic anhydride, pyromellitic dianhydride, benzophenonetetracarboxylic dianhydride; etc. For example, a polyvalent carboxylic acid anhydride derivative such as 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride can be used.

On the other hand, the copolymer, which is the base polymer of the resins of (2) and (3) above, is an alkyl (meth) acrylate and glycidyl (meth) acrylate as a monomer as described above, or further a hydroxyalkyl (meth). It can be obtained by using an acrylate and copolymerizing them by a known method such as a solution polymerization method. The alkyl (meth) acrylate is an alkyl ester of acrylic acid or methacrylic acid,
Here, the alkyl group is an aliphatic hydrocarbon group having 1 to 6 carbon atoms. Examples of the alkyl (meth) acrylate include, but are not limited to, esters of acrylic acid or methacrylic acid such as methyl, ethyl, propyl, isopropyl, butyl, and hexyl.

The hydroxyalkyl (meth) acrylate is a hydroxyalkyl ester of acrylic acid or methacrylic acid, and the hydroxyalkyl group is preferably an aliphatic hydrocarbon group having a primary hydroxyl group and having 1 to 6 carbon atoms. . This is a hydroxyalkyl (meth) acrylate having a primary hydroxyl group in terms of easiness of reaction when further reacting the copolymer with (meth) acrylic acid and then reacting with a polybasic acid anhydride. It is desirable to select and use as one of the monomers of the copolymer. Representative examples of such a hydroxyalkyl (meth) acrylate having a primary hydroxyl group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl acrylate, but are not limited thereto. is not.

In the copolymer (2) as the base of the resin, the molar ratio of alkyl (meth) acrylate and glycidyl (meth) acrylate is 40:60 to.
80:20 is preferred. On the other hand, in the copolymer as the base of the resin of (3), the ratio of hydroxy (meth) acrylate, alkyl (meth) acrylate and glycidyl (meth) acrylate is 10 to 50: molar ratio.
10 to 70:20 to 60, preferably 15 to 30:30
˜50: 30 to 50. If the proportion of glycidyl (meth) acrylate in the copolymer is lower than the above range, it is not preferable because the photocurability is lowered. On the other hand, if it exceeds the above range, the synthesis reaction of the photosensitive resin becomes smooth. It is not desirable because it is not necessary The degree of polymerization of the copolymer obtained by copolymerizing each of the above-mentioned monomers is preferably in the range of 10,000 to 70,000, preferably 20,000 to 60,000 as a weight average molecular weight.
When the weight average molecular weight is less than 10,000, the dryness to the touch is deteriorated, while when it exceeds 70,000, the developability is easily deteriorated, which is not preferable. In the present invention,
In addition to the above-mentioned monomers, vinyl compounds such as styrene and methylstyrene can also be used within a range that does not affect the characteristics.

Representative examples of the photopolymerization initiator (B) described above include benzoin and its alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether; acetophenone, 2,2. -Dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1
-Acetophenones such as hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one;
Anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone and 2-amylanthraquinone; 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone,
Thioxanthones such as 2,4-diisopropylthioxanthone, ketals such as acetophenone dimethyl ketal, and benzyl dimethyl ketal; benzophenones such as benzophenone or xanthones.
The photopolymerization initiator (B) can be used in combination with one or more known photopolymerization accelerators such as benzoic acid-based or tertiary amine-based photopolymerization accelerators. A suitable range of the amount of the photopolymerization initiator (B) used is 0.1% by weight based on 100 parts by weight of the active energy ray-curable resin (A).
The proportion is 2 to 30 parts by weight, preferably 2 to 20 parts by weight. When the blending ratio of the photopolymerization initiator is less than 0.2 parts by weight, the photocurability is poor, while when it is more than 30 parts by weight, the properties of the cured coating film are poor and the storage stability is poor. It is not preferable because it worsens.

Further, as the (C) diluent, a photopolymerizable monomer and / or an organic solvent can be used. Typical examples of the photopolymerizable monomer are 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, N-vinylpyrrolidone, acryloylmorpholine, methoxytetraethylene glycol acrylate,
Methoxy polyethylene glycol acrylate, polyethylene glycol diacrylate, N, N-dimethyl acrylamide, N-methyl acrylamide, N, N-
Dimethylaminopropyl acrylamide, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminopropyl acrylate, melamine acrylate, diethylene glycol acrylate, triethylene glycol diacrylate, propylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate Acrylate, polypropylene glycol diacrylate, phenoxyethyl acrylate, tetrahydrofurfuryl acrylate, cyclohexyl acrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, glycerin diglycidyl ether diacrylate, glycerin triglycidyl ether triacrylate, pentaerythritol tria Relate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, isoborneolyl acrylate, cyclopentadiene mono- or di-acrylate, and each methacrylate corresponding to the above acrylate, polybasic acid and hydroxyalkyl ( Mono-, di-, tree or higher polyesters with (meth) acrylates.

On the other hand, as the organic solvent, ketones such as methyl ethyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene, Ipsol # 150 (manufactured by Idemitsu Petrochemical Co., Ltd.), cellosolves such as cellosolve and butyl cellosolve, carbitol. Carbitols such as butyl carbitol, propylene glycol monomethyl ether such as propylene glycol monomethyl ether, propylene glycol ethers such as dipropylene glycol monomethyl ether, ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol There are acetic acid esters such as monomethyl ether acetate and dipropylene glycol monomethyl ether acetate.

The above-mentioned diluent (C) is used alone or as a mixture of two or more kinds. A suitable range of the amount used is 30 to 300 parts by weight, preferably 50 to 200 parts by weight, based on 100 parts by weight of the active energy ray-curable resin (A).

Here, the purpose of using the monomer is to dilute the active energy ray-curable resin so that it can be easily applied and to impart photopolymerization property. It is 3 to 50 parts by weight with respect to 100 parts by weight of the organic resin (A). If it is less than 3 parts by weight, the photocurability is poor, while if it exceeds 50 parts by weight, the dryness to the touch is deteriorated, which is not preferable. Further, the purpose of using the organic solvent is to dissolve the active energy ray-curable resin (A), dilute it, apply it as a liquid thereby to form a film by drying and enable contact exposure. is there.

The (D) epoxy resin as the thermosetting component is a known epoxy resin (including epoxy oligomer) having at least one epoxy group, preferably two or more epoxy groups in one molecule. Can be used. Typical examples include glycidyl ether-based epoxy resins, for example, bisphenol A-based epoxy resins obtained by reacting bisphenol A and epichlorohydrin in the presence of an alkali, and epoxidized resins obtained by condensation reaction of bisphenol A and formalin. In some cases, brominated bisphenol A is used instead of bisphenol A. In addition, there are novolac type epoxy resins obtained by reacting novolac resins with epichlorohydrin to form glycidyl ethers, for example, phenol novolac type, orthocresol novolac type, pt-butylphenol novolac type epoxy resins, and the like. In addition, there are bisphenol F-based epoxy resin and bisphenol S-based epoxy resin obtained by reacting bisphenol F or bisphenol S with epichlorohydrin. Furthermore, cyclohexene oxide group, tricyclodecene oxide group, cycloaliphatic epoxy resin having a cyclopentene oxide group, diglycidyl phthalate ester,
Tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, diglycidyl-p
-Glycidyl ester resins such as oxybenzoic acid and glycidyl dimer acid, tetraglycidyl diaminodiphenylmethane, triglycidyl p-aminophenol, diglycidyl aniline, diglycidyl toluidine,
There are glycidyl amine resins such as tetraglycidyl metaxylylenediamine, diglycidyl tribromaniline, and tetraglycidyl bisaminomethylcyclohexane, hydantoin-type epoxy resins obtained by glycidylating a hydantoin ring, and triglycidyl isocyanurate having a triazine ring. These may be used alone or in combination of two or more. The blending amount of the epoxy resin as the thermosetting component is 5 to 100 parts by weight, preferably 15 to 60 parts by weight, based on 100 parts by weight of the active energy ray-curable resin (A).

In the present invention, the cyanoguanidine derivative used as the curing agent (E) for the epoxy resin is rose (FL) or swain (G. Swain).
Method (J. Chem. Soc., 1956, 44th
22 to 4425) and the method described in JP-A No. 64-71846. That is, when an alkali dicyanamide, for example sodium dicyanamide, is reacted with a salt of an amine compound having a substituent R, preferably a hydrochloride thereof in a suitable solvent while heating under reflux, a reaction formula (5) According to 2), the desired cyanoguanidine derivative is produced.

[Chemical 5]

On the other hand, of the cyanoguanidine derivatives of the present invention represented by the general formula (1), the biscyanoguanidine type cyanoguanidine derivative having a substituent R (1) to (20) is preferably synthesized. Is performed according to the reaction formula (3) of the following chemical formula 6. That is, when an alkali dicyanamide such as sodium dicyanamide is reacted with a salt of a diamine compound having a substituent R ₁ , preferably its dihydrochloride in a suitable solvent while heating under reflux, the reaction formula (3) Then, the desired biscyanoguanidine-type derivative is produced.

[Chemical 6] In the reaction formula (3), the substituent R ₁ means a residue obtained by removing the cyanoguanidyl group from the substituent R.

In any of the above reactions, each reactant may be added to the solvent in a substantially stoichiometric ratio. As the reaction solvent, water, butanol, propanol, ethanol, or another alcohol having 1 to 6 carbon atoms, preferably 3 to 5 carbon atoms, particularly preferably n-butanol, or a mixed solution thereof with water can be used. . A neutral solvent such as dimethylformamide or sulfolane can also be used. When water is used as the solvent, the reaction can be accelerated by the presence of a catalytic amount of base. As the base, an aliphatic or cycloaliphatic amine, N-heterocyclic base, etc., such as triethylamine, N-methylmorpholine, pyridine, etc. can be used. The pH of the reaction mixture at the start of the reaction is on the alkaline side, preferably 8 to
It is desirable to adjust to 10 from the viewpoint of yield, and this pH adjustment can be performed by the addition amount of the base in the reaction mixture.

The reaction is carried out at a temperature of about 75 ° C. to 170 ° C., preferably about 90 ° C. to 160 ° C. under reflux with heating for 3 to 16 hours depending on the reaction temperature, preferably 6 to 1 depending on the reaction temperature.
Do it for 0 hours. After completion of the reaction, the solvent is distilled off if necessary, and then water or a water / alcohol mixed solution is added to wash the alkali salt (NaCl) and crystallize the product.
After filtering the reaction product from the salt-containing liquid phase, the solid is dried to obtain the final product. Drying is preferably performed by heating in vacuum.

The blending ratio of the cyanoguanidine derivative is preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the active energy ray-curable resin (A). If the amount is less than 0.5 part by weight, the thermosetting property cannot be expected to be exhibited, while 5.0
If it is blended in a large amount in excess of parts by weight, the shelf life of the photocurable thermosetting resin composition tends to be shortened when it is liquefied, and the electrical characteristics (insulation resistance value) of the formed solder resist film deteriorate. Is seen, which is not preferable.

In the photocurable thermosetting resin composition of the present invention, if necessary, a known / common epoxy curing accelerator may be used to accelerate the reaction between the cyanoguanidine derivative and the epoxy resin. Yes, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl ) -2-ethyl-4-methylimidazole and other imidazole derivatives, acetoguanamine, benzoguanamine and other guanamines, benzyldimethylamine, 4-
(Dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine,
Examples thereof include amine compounds such as 4-methyl-N, N-dimethylbenzylamine. Examples of commercially available products include 2MZ-A and 2MZ-OK manufactured by Shikoku Kasei.
2PHZ, 2P4BHZ, 2P4MHZ (both are trade names of imidazole compounds), San-Apro UC
AT3503X, U-CAT3502X (both are trade names of blocked isocyanate compounds of dimethylamine)
and so on. Since the reaction initiation temperature in post-cure becomes a high temperature of about 200 ° C. only with the above-mentioned cyanoguanidine derivative, it is preferable to blend the epoxy curing accelerator as described above to lower the reaction initiation temperature. The shelf life when the photocurable thermosetting resin composition is made into one liquid is shortened. Therefore,
The amount of the epoxy curing accelerator compounded is 0.1 to 100 parts by weight of the active energy ray-curable resin (A).
A ratio of 2.0 parts by weight is preferred.

Further, in the photocurable thermosetting resin composition of the present invention, barium sulfate, silicon oxide, and
Known / common fillers such as talc, clay, calcium carbonate, silica, bentonite, kaolin, glass fiber, carbon fiber, mica, asbestos, metal powder, phthalocyanine blue,
Known and commonly used coloring pigments such as phthalocyanine green, titanium oxide and carbon black, various additives such as defoaming agents, adhesion promoters or leveling agents, or hydroquinone, hydroquinone monomethyl ether, pyrogallol, t-butylcatechol, phenothiazine. Known or commonly used polymerization inhibitors such as the above may be added.

The photocurable thermosetting resin composition of the present invention comprises
If necessary, the viscosity is adjusted to be suitable for the coating method, and this is applied to a circuit-formed printed wiring board by a method such as a screen printing method, a curtain coating method, a spray coating method, or a roll coating method. A tack-free coating film can be formed by volatilizing and drying the organic solvent contained in the composition at a temperature of -100 ° C. After that, the resist pattern can be formed by selectively exposing the unexposed portion to an actinic ray through a patterned photomask and developing the unexposed portion with a dilute aqueous alkali solution.
By heating to a temperature of 40 to 200 ° C. and thermosetting, the heat resistance, solvent resistance, and acid resistance of the resist film obtained through polymerization promotion of the photocurable resin component and copolymerization with the thermosetting component are obtained. It is possible to improve various properties such as adhesion, electrical properties and hardness, and it is particularly useful as a solder resist.

As the alkaline aqueous solution used for the above-mentioned development, an alkaline aqueous solution of potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines or the like can be used. A low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp or a metal halide lamp is suitable as an irradiation light source for photocuring. In addition, a laser beam or the like can also be used as an active light beam for exposure.

[0034]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples. All “parts” are based on weight unless otherwise specified.

Synthesis Example 1 (3,9-bis (3-cyanoguanidinopropyl)-
Synthesis of 2,4,8,10-tetraoxaspiro [5.5] undecane) Sodium dicyanamide and 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5. 5] When reacted with undecane dihydrochloride, the desired 3,9-bis (3-cyanoguanidinopropyl) -2,
4,8,10-Tetraoxaspiro [5.5] undecane is produced.

[Chemical 7] Specifically, the synthesis was performed according to the following procedure.

Sodium dicyanamide 0.89 g in a 50 ml eggplant-shaped flask equipped with a Dimroth condenser.
(0.01 mol), 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5.
5] Undecane dihydrochloride (1.74 g, 0.005 mol) and n-butanol (10 ml) were added, and the mixture was reacted in an oil bath under heating and refluxing conditions for 8 hours while stirring with a magnetic stirrer. Immediately after completion of the reaction, the reaction solvent was distilled off under reduced pressure using an evaporator. Water on residue /
After adding methanol (mixing ratio 2.5 / 1.5) and stirring well, the mixture was filtered using a glass filter and the solid content was dried in a heating vacuum dryer at 80 ° C. for 8 hours to obtain 3,9-bis. (3-Cyanoguanidinopropyl) -2,4,8,1
0-Tetraoxaspiro [5.5] undecane (abbreviation A
1.99 g (yield 97.5%) of TU2CG was obtained.

Synthesis Example 2 (Synthesis of 1,1'-p-phenylene-bis-3,3'cyanoguanidine) When sodium dicyanamide and p-phenylenediamine dihydrochloride are reacted with each other, a reaction formula of the following chemical formula 8 is obtained. According to (5), the desired 1,1'-p-phenylene-bis-3,3'-cyanoguanidine is produced.

Embedded image Specifically, the synthesis was performed according to the following procedure.

Sodium dicyanamide 0.89 g in a 50 ml eggplant-shaped flask equipped with a Dimroth condenser.
(0.01 mol), 0.91 g (0.005 mol) of p-phenylenediamine dihydrochloride, and n-butanol 1
0 ml was added, and the mixture was reacted in an oil bath under heating and refluxing conditions for 8 hours while stirring with a magnetic stirrer. Immediately after completion of the reaction, the reaction solvent was distilled off under reduced pressure using an evaporator. Water / methanol (mixing ratio 2.5 /
1.5) was added, and the mixture was stirred well and then filtered using a glass filter, and the solid content was dried in a heating vacuum dryer at 80 ° C. for 8 hours. Light gray 1,1'-p-phenylene-
Bis-3,3'-cyanoguanidine (abbreviation Ph2CG)
0.98 g (yield 81.3%) was obtained.

Synthesis Example 3 (Methylene-bis (1,1'-p-phenylene-3,
Synthesis of 3'-cyanoguanidine) When sodium dicyanamide is reacted with 4,4'-diaminodiphenylmethane dihydrochloride, the desired methylene-bis (1,1'- p-phenylene-3,
3'-Cyanoguanidine) is produced.

[Chemical 9] Specifically, the synthesis was performed according to the following procedure.

0.89 g of sodium dicyanamide in a 50 ml eggplant-shaped flask equipped with a Dimroth condenser.
(0.01 mol), 4,4'-diaminodiphenylmethane dihydrochloride 1.37 g (0.005 mol), and 10 ml of n-butanol were added, while stirring with a magnetic stirrer under heating and refluxing conditions in an oil bath. Reacted for hours. Immediately after completion of the reaction, the reaction solvent was distilled off under reduced pressure using an evaporator. Water / methanol (mixing ratio 2.5 / 1.5) was added to the residue, and the mixture was thoroughly stirred and then filtered using a glass filter, and the solid content was dried in a heating vacuum dryer at 80 ° C. for 8 hours. 1.33 g of yellow methylene-bis (1,1'-p-phenylene-3,3'-cyanoguanidine) (abbreviation: DDM-2CG) (yield 8
0.1%) was obtained.

Example 1 1 equivalent of a cresol novolac type epoxy resin having an epoxy capacity of 220 and having an average of 7 phenol nucleus residues in one molecule and further an epoxy group and 1. The reaction product obtained by reacting with 05 equivalents was reacted with 0.67 equivalents of tetrahydrophthalic anhydride under atmospheric pressure using carbitol acetate as a solvent.
This was a viscous liquid containing 52 parts of carbitol acetate (based on 100 parts of the solid resin) and showed an acid value of 63.4 mgKOH / g as a mixture. Hereinafter, this is abbreviated as resin A. Ingredient (a) Resin A 152.0 parts Irgacure 907 (manufactured by Ciba Geigy) 17.0 parts Modaflow (leveling agent, manufactured by Monsanto, USA) 3.0 parts KS-66 (antifoaming agent, manufactured by Shin-Etsu Chemical Co., Ltd.) 4.0 parts Fastgen Green S (pigment, manufactured by Dainippon Ink and Chemicals, Inc.) 1.5 parts Aerosil # 200 (silica, manufactured by Nippon Aerosil Co., Ltd.) 2.0 parts Barium sulfate 65.0 parts 2PHZ (Shikoku Chemicals Co., Ltd.) 0.5 parts) Product of Synthesis Example 1 3.2 parts Dipropylene glycol monomethyl ether 2.0 parts Ipsol # 150 (solvent manufactured by Idemitsu Petrochemical Industry Co., Ltd.) 2.0 parts 252.2 parts The above composition Was kneaded with a three-roll mill to prepare a main agent. Further, as a cross-linking agent for this, the following epoxy resin composition was similarly kneaded in a three-roll mill,
A curing agent was prepared. Ingredient (b) N695 (cresol novolac type epoxy resin, manufactured by Dainippon Ink and Chemicals, Inc.) 32.0 parts Triglycidyl isocyanurate 10.0 parts DPHA (photopolymerizable monomer, manufactured by Nippon Kayaku Co., Ltd.) 20.0 parts Dipropylene glycol monomethyl ether 5.0 parts Ipsol # 150 5.0 parts Barium sulphate 35.0 parts 107.0 parts The main agent and curing agent thus prepared were mixed in the following proportions to obtain a solder resist ink. . The mixing ratios of the main agent and the curing agent are the same in the following Examples 2 to 4 and Comparative Example 1. Main agent: Curing agent = 70:30

Example 2 "3.2 parts of the product of Synthesis Example 1" of Example 1 was used as "Synthesis Example 2".
The main component was prepared in the same manner as in Example 1 except that the amount of the product was changed to 1.9 parts. The curing agent is the same as in Example 1.

Example 3 "3.2 parts of the product of Synthesis Example 1" of Example 1 was used as "Synthesis Example 3".
The main component was prepared in the same manner as in Example 1 except that the amount of the product was changed to 2.6 parts. The curing agent is the same as in Example 1.

Example 4 A main agent was prepared in the same manner as in Example 1 except that "3.2 parts of the product of Synthesis Example 1" in Example 1 was changed to "2.0 parts of hexamethylene-bis-cyanoguanidine". did. The curing agent is the same as in Example 1.

Comparative Example 1 A main agent was prepared in the same manner as in Example 1 except that "3.2 parts of the product of Synthesis Example 1" in Example 1 was changed to "1.0 part of cyanoguanidine". The curing agent is the same as in Example 1.

Performance Evaluation Each of the obtained ink compositions was screen-printed on a patterned copper foil substrate and dried at 80 ° C. for 20 minutes. A negative film was brought into close contact with this substrate, the solder resist pattern was exposed, and the pattern was formed by developing with a 1 wt% sodium carbonate aqueous solution. This substrate, 15
It was heat-cured at 0 ° C. for 50 minutes to prepare an evaluation substrate, and the solder heat resistance, acid resistance, alkali resistance, pencil hardness, and electrical characteristics were examined. The developability and storage stability of the ink composition were evaluated by the methods described below.

Developability: Each ink composition thus obtained was screen-printed on a copper foil substrate having a pattern formed thereon and provisionally dried at 80 ° C. by changing the drying time at 10 minute intervals. Then, a negative film was brought into close contact with this substrate, the solder resist pattern was exposed, and the life (the longest dry time during which development was possible) when developed with a 1 wt% sodium carbonate aqueous solution was examined to evaluate the developability.

Solder heat resistance: A substrate coated with a rosin-based flux was immersed in a solder bath previously set at 260 ° C. for 30 seconds, washed with propylene glycol monomethyl ether acetate and ethanol, and then the resist layer was visually observed. Was evaluated for swelling and discoloration, and a peel test with a cellophane adhesive tape was performed to evaluate for peeling. The judgment criteria are as follows. ◯: No change was observed Δ: Slightly changed ×: Swelling, peeling, or discoloration of the coating film

Acid resistance: 10% by weight of the above substrate at room temperature
Was immersed in the sulfuric acid aqueous solution for 30 minutes, washed with water, and then subjected to a peel test with a cellophane adhesive tape to evaluate peeling of the resist layer and discoloration. The judgment criteria are as follows. ◯: No change was observed Δ: Slightly changed ×: Swelling, peeling, or discoloration of the coating film

Alkali resistance: The above substrate was subjected to 10
Immerse in a wt% sodium hydroxide aqueous solution for 30 minutes, wash with water, and then perform a peel test with cellophane adhesive tape.
The peeling and discoloration of the resist layer were evaluated. The judgment criteria are as follows. ◯: No change was observed Δ: Slightly changed ×: Swelling, peeling, or discoloration of the coating film

Pencil hardness: JIS K-5400 6.1
It measured based on 4.

Electrical characteristics: IPC SM-840B B-
Using 25 comb-type electrode B coupons, an evaluation substrate was prepared under the above conditions, a bias voltage of DC 500 V was applied to this comb-shaped electrode, and the initial insulation resistance value was measured. This substrate was processed at 121 ° C. and 100% R. H. The same applies to the substrate that has been humidified under 2 atmospheres for 12 hours (indicated as "after PCT" in Table 1) and the substrate to which DC100V is applied under the same conditions (indicated as "after PCBT" in Table 1). Similarly, the insulation resistance value was measured.

Storage stability: After mixing the main agent and the curing agent, each ink composition was allowed to stand in a constant temperature bath at 40 ° C. for 1 week, and the storage stability was evaluated from the change in viscosity. The judgment criteria are as follows. ◯: Viscosity change less than 1.5 times the initial value Δ: Viscosity change 1.5 times or more and less than 3.0 times the initial value X: Viscosity change 3.0 times or more of the initial value

Table 1 shows the results of the above performance evaluations.

[Table 1]

[0055]

As described above, since the photocurable thermosetting resin composition of the present invention contains the above-mentioned specific cyanoguanidine derivative as a curing agent for epoxy resin, it has excellent storage stability. As a result, the shelf life of one liquid becomes long, and as a result, the flexibility of the solder resist film production work increases. Further, the photocurable thermosetting resin composition of the present invention has, in addition to the effects peculiar to the present invention, the active energy ray-curable resin contained in the composition in the side chain of the backbone polymer. Since a large number of free carboxyl groups are added, development with a dilute alkaline aqueous solution is possible, and after development, by heating the coating film again, an epoxy resin added as a thermosetting compounding component is added. A copolymerization reaction occurs with the free carboxyl group of the side chain, and various properties such as heat resistance, solvent resistance, acid resistance, adhesion, electrical properties, and hardness of the coating film required as a solder resist are excellent. It also has a basic effect that a solder resist film can be obtained.

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Claims (7)

[Claims] 1. An active energy ray-curable resin having (A) at least two ethylenically unsaturated bonds and a carboxyl group in one molecule, (B) a photopolymerization initiator, (C) a diluent, and (D). An epoxy resin and (E) a curing agent for an epoxy resin, wherein the curing agent (E) for an epoxy resin is a cyanoguanidine derivative represented by the following general formula (1). Curable thermosetting resin composition. Embedded image (However, in the above formula (1), R is a substituent selected from the group represented by the following chemical formula 2.) 2. The active energy ray-curable resin comprises a reaction product of a novolac type epoxy compound and an unsaturated monocarboxylic acid, and a saturated or unsaturated polycarboxylic acid of 0.15 mol or more per hydroxyl group contained in the reaction product. The composition according to claim 1, which is obtained by reacting a basic acid anhydride. 3. The active energy ray-curable resin is 4
The composition according to claim 1 or 2, which has an acid value of 0 to 160 mgKOH / g. 4. The composition according to claim 1, wherein the photopolymerization initiator is contained in a proportion of 0.2 to 30 parts by weight with respect to 100 parts by weight of the active energy ray-curable resin. Stuff. 5. The diluent is a photopolymerizable monomer and / or an organic solvent, and is used alone or in combination at a ratio of 30 to 300 parts by weight with respect to 100 parts by weight of the active energy ray-curable resin. The composition according to any one of 1 to 4. 6. The curing agent for an epoxy resin is 0.5 to 100 parts by weight of the active energy ray-curable resin.
The composition according to any one of claims 1 to 5, which is contained in an amount of 5.0 parts by weight. 7. The active energy ray curable resin 100.
The composition according to claim 1, further comprising 0.1 to 2.0 parts by weight of an epoxy curing accelerator with respect to parts by weight.