JP3095658B2 - Cyanoguanidine derivative and thermosetting or photocurable thermosetting resin composition using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel cyanoguanidine derivative, and more particularly to a novel 2-cyanoguanidyl-4,6-diamino derivative which can be advantageously used in various applications such as curing agents for epoxy resins. -S-triazine. The present invention also relates to a cyanoguanidine-type epoxy resin curing agent that can be advantageously used for curing an epoxy resin, and a thermosetting resin composition or a photocurable thermosetting resin composition using the same.

[0002]

2. Description of the Related Art In a soldering process performed when a surface of an electronic component is mounted on a printed wiring board or the like, in order to protect the unnecessary portion from solder adhesion and to protect a circuit from an external environment. What is used is a solder mask. As the solder mask, a photocurable thermosetting resin composition of an alkali development type is generally used due to the problem of high density of the printed wiring board and environmental pollution. As the alkali-curable photocurable thermosetting resin composition, for example, Japanese Patent Publication No. 1-54390 discloses a saturated or unsaturated polybasic acid anhydride formed by reacting a novolak epoxy compound with an unsaturated monocarboxylic acid. And JP-A-3-289656 discloses a photocurable thermosetting resin composition containing a photosensitive resin obtained by reacting an alkyl (meth) acrylate and a glycidyl (meth) acrylate. A liquid photo solder resist capable of alkali development using a photosensitive resin obtained by reacting a copolymer with acrylic acid and further reacting with a polybasic acid anhydride is disclosed. However, in general, an alkali-developing photocurable thermosetting resin composition is liable to thicken or gel over time, and has a disadvantage of lacking storage stability. Therefore, usually, a main agent mainly composed of a photosensitive resin is used. And a curing agent mainly composed of a thermosetting component, which is commercially available as a two-pack type. When used, these main components and the curing agent are mixed and used.

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

Various compounds are known as curing agents for epoxy resins. One of them is cyanoguanidine (also referred to as dicyandiamide). However, when cyanoguanidine is used together with the epoxy resin in the above-described alkali-developable photocurable thermosetting resin composition, the storage stability after mixing the main agent and the curing agent is lacking, so-called usable time (pot life). ) Is short. In addition, it has been found that substituted cyanoguanidine is also useful as a curing agent for epoxy resins.
No. 92/01726 (Patent Application Publication, Hei 5-50867)
No. 8). The invention described in W092 / 01726 proposes to introduce a specific substituent in order to improve the solubility of cyanoguanidine, that is, to provide a substituted cyanoguanidine compound soluble in various organic solvents. It is intended to be. However,
Substituted cyanoguanidine compounds having solubility in various organic solvents generally have solubility in a liquid epoxy resin or a solution of an epoxy resin, and thus easily react with the epoxy resin at room temperature. As a result, thermosetting resin compositions and photocurable thermosetting resin compositions containing this together with an epoxy resin are stable at low temperatures around room temperature but harden in a short time at high temperatures, so-called latent curing. In addition, storage stability (shelf life, pot life) deteriorates.

[0005] US Patent No. 2,455,807 discloses that
Substituted 3- with aliphatic, aromatic and heterocyclic substituents
Although cyanoguanidines are disclosed, these include pharmaceuticals, dyes, pesticides, antioxidants, vulcanization accelerators, plasticizers,
Although taught to be useful in the preparation of resin modifiers, ion exchange resins, and leather, paper, and textile treatment agents,
There is no mention of use as a curing agent for epoxy resins. Further, regarding compounds similar to the cyanoguanidine derivative of the present invention, Journal of the
Chemical Society (J. Chem. Soc.) 1
956, pp. 4422-4425 and JP-A-64-7
No. 1846. In particular, JP-A-64-71
No. 846 discloses bis-biguanidine and polybiguanidine used as a disinfectant or a pesticide, and 1,6-diene, a useful intermediate for producing chlorhexidine useful as an antibacterial agent and a preservative. (N ³ - cyano -N ¹ - guanidino) hexane is disclosed. However, these publications do not describe the novel cyanoguanidine derivative to be provided by the present invention, nor do they describe the use of the cyanoguanidine derivative as a curing agent for epoxy resins.

[0006]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a novel cyanoguanidine derivative which is useful as a curing agent for epoxy resins and can be used as an intermediate of other useful compounds. is there. Further, an object of the present invention is to provide an epoxy resin having a so-called heat latent reactivity, which is hardly soluble in various organic solvents and does not react with an epoxy compound at a low temperature near ordinary temperature, but reacts quickly by applying heat. To provide a curing agent for use. Another object of the present invention is to provide a thermosetting resin composition having excellent latent curability and storage stability.

Still another object of the present invention is to provide an alkali-developable photocurable thermosetting resin composition which is excellent in photocurability, alkali developability and the like, and is excellent in latent curability and storage stability. It is in. A more specific object of the present invention is to contain a curing agent for an epoxy resin having the above-described thermal latent reactivity, and thus have excellent storage stability, and furthermore have excellent adhesion, heat resistance, chemical resistance, hardness, and electrical properties. An object of the present invention is to provide an alkali-developable photocurable thermosetting resin composition that can provide a cured coating film having excellent resistance to electroless gold plating, in addition to various properties required for a solder resist such as insulating properties.

[0008]

In order to achieve the above object, according to one aspect of the present invention, the following formula (1)
A novel cyanoguanidine derivative represented by the formula:
-Cyanoguanidyl-4,6-diamino-S-triazine is provided.

Embedded image According to another aspect of the present invention, 2 represented by the above formula (1)
A curing agent for an epoxy resin comprising -cyanoguanidyl-4,6-diamino-S-triazine; According to another aspect of the present invention, a thermosetting resin containing an epoxy resin and 2-cyanoguanidyl-4,6-diamino-S-triazine represented by the above formula (1) as a curing agent for the epoxy resin. A resin composition is provided. According to another aspect of 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) an epoxy resin curing agent, wherein the epoxy resin curing agent (E)
Is 2-cyanoguanidyl-4 represented by the above formula (1),
A photocurable thermosetting resin composition that is 6-diamino-S-triazine is provided.

[0009]

Operation and Mode of the Invention As described above, WO92 / 0
The invention described in 1726 proposes to introduce a specific substituent to improve the solubility of cyanoguanidine. The present invention is completely different from such a conventional approach, and rather makes the resulting cyanoguanidine derivative hardly soluble in an organic solvent by introducing a specific substituent to cyanoguanidine, thereby improving thermal latent reactivity. At the same time, it is intended to develop the properties of a specific substituent (triazine ring). The cyanoguanidine derivative according to the present invention represented by the formula (1), that is, 2-cyanoguanidyl-4,6-diamino-S-triazine,
It has one cyanoguanidyl group and therefore has seven active hydrogens, three bonded to the nitrogen atom of the cyanoguanidyl group and four amino groups on the triazine ring. As a result, it can theoretically react with seven epoxy groups, and is highly reactive with the epoxy compound. Nevertheless, the cyanoguanidine derivative of the present invention is sparingly soluble in various organic solvents or liquid epoxy compounds or solutions of epoxy compounds, and does not react with epoxy groups at low temperatures around room temperature. It can be particularly advantageously used as a so-called heat latent reactive epoxy resin curing agent having the property of reacting with epoxy resin.

Therefore, a thermosetting resin composition having excellent latent curability and storage stability can be obtained by composing the cyanoguanidine derivative of the present invention having such properties together with an epoxy resin. According to the study of the present inventors, the use of a cyanoguanidine derivative represented by the above formula (1) as a curing agent for an epoxy resin added to a photocurable thermosetting resin composition of an alkali development type enables storage stability. It has been found that in addition to the properties required for a solder resist such as excellent adhesion, heat resistance, chemical resistance, hardness, and electrical insulation, a cured coating film with excellent electroless gold plating resistance can be obtained. Was.

The cyanoguanidine derivative according to the present invention comprises:
Rose (FL Rose) and Swain (G. Swa)
in) (supra J. Chem. Soc., 1956).
Pp. 4422-4425) and JP-A-64-7184.
It can be advantageously produced using the method described in No. 6. That is, an alkali dicyanamide such as sodium dicyanamide is reacted with a salt of 2,4,6-triamino-S-triazine, preferably a hydrochloride thereof, in a suitable solvent while heating under reflux. When sodium dicyanamide is reacted with 2,4,6-triamino-S-triazine monohydrochloride, the desired 2-cyanoguanidyl-4,6-diamino- is obtained according to the following reaction formula (2).
S-triazine is formed.

Embedded image

Each reactant may be added to the solvent in a substantially stoichiometric ratio. As the reaction solvent, water, an alcohol having 1 to 6 carbon atoms, preferably 3 to 5 carbon atoms, such as butanol, propanol, and ethanol, particularly preferably n-butanol, or a mixture of these with water can be used. . Further, a neutral solvent such as dimethylformamide and sulfolane can also be used. When water is used as the solvent, the reaction can be promoted by the presence of a catalytic amount of a base. As the base, an aliphatic or cyclic aliphatic amine, an N-heterocyclic base and the like, for example, triethylamine, N-methylmorpholine, pyridine and the like can be used. The pH of the reaction mixture at the start of the reaction is preferably adjusted to an alkaline side, preferably 8 to 10 from the viewpoint of yield. This pH adjustment can be performed by the amount of base added to 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, generally with stirring, for 3 to 16 hours, preferably 6 to 1 hour, depending on the heating temperature.
Perform for 0 hours. After completion of the reaction, the solvent is distilled off, if necessary, and then water or a water / acetone mixture 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 a vacuum.

According to another aspect of the present invention, there is provided a thermosetting resin containing an epoxy resin and 2-cyanoguanidyl-4,6-diamino-S-triazine represented by the formula (1) as a curing agent for the epoxy resin. A curable resin composition is provided.
In the thermosetting resin composition of the present invention, as the epoxy resin contained together with the cyanoguanidine derivative,
At least one epoxy group per molecule, preferably 2
A known epoxy resin having an epoxy group or more (including an epoxy oligomer) can be used. A typical example is a glycidyl ether type epoxy resin, for example, bisphenol A obtained by reacting bisphenol A with epichlorohydrin in the presence of an alkali.
Epoxy resin, epoxy resin of bisphenol A and formalin condensed and reacted, brominated bisphenol A instead of bisphenol A,
A novolak resin is reacted with epichlorohydrin, and a glycidyl-etherified novolak epoxy resin, for example, an epoxy resin such as a phenol novolak type, an orthocresol novolak type, a pt-butylphenol novolak type, or a bisphenol F or bisphenol S is used to form epichlorohydrin. There are bisphenol F-type epoxy resins and bisphenol S-type epoxy resins obtained by the reaction. Further, a cyclohexene oxide group,
Cycloaliphatic epoxy resin having tricyclodecene oxide group and cyclopentene oxide group; diglycidyl phthalate, diglycidyl tetrahydrophthalate, diglycidyl hexahydrophthalate, diglycidyl-p-oxybenzoic acid, glycidyl dimer acid Glycidyl ester resins such as esters; glycidyl amine resins such as tetraglycidyl diaminodiphenylmethane, triglycidyl p-aminophenol, diglycidyl aniline, diglycidyl toluidine, tetraglycidyl meta-xylylenediamine, diglycidyl tribromoaniline, and tetraglycidyl bisaminomethylcyclohexane Resin; Hydantoin type epoxy resin in which hydantoin ring is glycidylated; Triglycidyl isocyanate having triazine ring Rate; there are epoxy resins such bixylenol type or biphenol type. The epoxy resins can be used alone or in combination of two or more.

The mixing ratio of the cyanoguanidine derivative to the epoxy resin can be set as appropriate. However,
From the viewpoint of the properties of the cured film, it is desirable that the ratio of the cyanoguanidine derivative be such that the hydrogen of the amino group is in the range of 0.05 to 1.0 mol per 1 mol of the epoxy group of the epoxy resin.

In the thermosetting resin composition of the present invention, an organic solvent can be used if necessary. Examples of the organic solvent include, but not particularly limited to, ketones such as methyl ethyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene, and ipsol # 150 (manufactured by Idemitsu Petrochemical Co., Ltd.), cellosolve, butyl cellosolve, and carbitol. , Butyl carbitol, propylene glycol monomethyl ether, glycol ethers such as dipropylene glycol monomethyl ether, ethyl acetate,
Examples thereof include acetates such as butyl acetate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, and dipropylene glycol monomethyl ether acetate. These can be used alone or in combination of two or more.

The curing reaction of the thermosetting resin composition according to the present invention occurs at about 100 to 250 ° C., and the liquid or molten epoxy resin is converted into an insoluble or infusible solid three-dimensional crosslinked product. In general, a cured product having a sheet-like structure such as a film, a film, or an adhesive layer is obtained, but if molded simultaneously, a molded product such as a cast product, a press molded product, or a laminated product can be obtained. Curing can also be carried out, if desired, in a two-stage process in which the reaction is temporarily stopped during the curing reaction, whereby a fusible and soluble curable precondensate (so-called B-stage) is still obtained. Such a precondensate can be stored for a longer period of time, and can be used for the production of, for example, a prepreg, a compression molding composition, a powder for sintering, and the like.

Further, the thermosetting resin composition according to the present invention can be advantageously used in various technical fields such as surface protection technology and lamination technology, and various industrial fields such as electric industry and building industry. For example, adhesives, protective coatings for printed wiring boards and the like, insulating resin varnishes, paints, lacquers, compression molding resin compositions, casting resin compositions, injection molding compounds, impregnation resin compositions, laminating resins It can be used as a composition, a sealing and filling resin composition, a floor finishing resin composition, and the like.

According to another aspect of the present invention, there is provided (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 (E) for the epoxy resin is represented by the formula (1). A photocurable thermosetting resin composition is provided, which is a cyanoguanidine derivative represented, namely, 2-cyanoguanidyl-4,6-diamino-S-triazine. Since the photocurable thermosetting resin composition of the present invention contains the specific cyanoguanidine derivative described above as a curing agent for an epoxy resin, it has excellent storage stability, and as a result, the solder resist film preparation work Flexibility is increased, and since a specific substituent (triazine ring) is introduced into the derivative, resistance to electroless gold plating is improved.

The active energy ray-curable resin (A) having at least two ethylenically unsaturated bonds and a carboxyl group in one molecule includes (1) an epoxy group of a polyfunctional novolak type epoxy compound and an unsaturated group. The carboxyl group of a monocarboxylic acid is subjected to an esterification reaction, and the generated hydroxyl group is further reacted with a saturated or unsaturated polybasic anhydride, and (2) a copolymer comprising an alkyl (meth) acrylate and glycidyl (meth) acrylate (3) Hydroxyalkyl (meth) acrylate and alkyl (meth) obtained by reacting a polymer with (meth) acrylic acid and then with a saturated or unsaturated polybasic anhydride.
After reacting a copolymer of acrylate and glycidyl (meth) acrylate with (meth) acrylic acid, further reacting a saturated or unsaturated polybasic anhydride,
(4) A product obtained by partially reacting glycidyl (meth) acrylate with a copolymer of alkyl (meth) acrylate and (meth) acrylic acid can be used.

Since the active energy ray-curable resin has a large number of free carboxyl groups added to the side chain of the backbone polymer, a composition containing such a resin can be developed with a dilute aqueous alkali solution. At the same time as possible, after exposure and development, the coating film is post-heated to cause a copolymerization reaction between the epoxy group of the epoxy resin added separately as a thermosetting compound and 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 are improved.
Further, the acid value of the active energy ray-curable resin (A) needs to be in the range of 40 to 160 mgKOH / g, and the preferable range is 50 to 140 mgKOH / g in the resin of (1). (2) and (4) above
The resin of (3) is 50 to 150 mgKOH / g, and the resin of (3) is 40 to 120 mgKOH / g. When the acid value is less than 40 mgKOH / g, the alkali solubility is deteriorated. On the other hand, when the acid value is more than 160 mgKOH / g, the cured film becomes a cause of deteriorating the resist properties such as alkali resistance and electric properties. Is also not preferred.

The resin (1) is a reaction product of a novolak-type epoxy resin and an unsaturated monocarboxylic acid, as described later, with a dibasic acid anhydride such as phthalic anhydride or trimellitic anhydride or pyromellitic anhydride. It is obtained by reacting with an aromatic polycarboxylic anhydride such as an acid. In this case, a resin obtained by reacting a polybasic acid anhydride in an amount of 0.15 mol or more per hydroxyl group contained in the reaction product of the novolak epoxy resin and the unsaturated monocarboxylic acid is suitable. When the number of ethylenically unsaturated bonds present in one resin molecule is small, photocurability is slow, so it is preferable to use a novolak type epoxy resin as a raw material. However, in order to reduce the viscosity of the ink, a bisphenol A type epoxy resin is used. Compounds can also be used.

Typical novolak type epoxy resins include phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, etc., and epichlorohydrin is reacted with each novolak resin by a conventional method. Resins that can be obtained at least can be used. Examples of the unsaturated monocarboxylic acid include a reaction product of acrylic acid, methacrylic acid, cinnamic acid, a saturated or unsaturated dibasic acid anhydride and a (meth) acrylate having one hydroxyl group in one molecule. These can be used alone or in combination of two or more, but acrylic acid or methacrylic acid, particularly acrylic acid is preferred from the viewpoint of photocurability.

The polybasic acid anhydrides include, for example, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylhexahydro anhydride. Phthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride,
Dibasic acid anhydrides such as chlorendic anhydride and methyltetrahydrophthalic anhydride; aromatic polycarboxylic anhydrides such as trimellitic anhydride, pyromellitic anhydride and benzophenonetetracarboxylic dianhydride; For example, a polycarboxylic anhydride derivative such as 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride can be used.

On the other hand, the copolymer which is a base polymer of the resins (2) and (3) is, as described above, alkyl (meth) acrylate and glycidyl (meth) acrylate as a monomer, or hydroxyalkyl (meth) acrylate. It is obtained by using acrylates and copolymerizing them by a known method, for example, 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, wherein the hydroxyalkyl group is preferably an aliphatic hydrocarbon group having a primary hydroxyl group and having 1 to 6 carbon atoms. . This is because, after reacting (meth) acrylic acid with the copolymer, a polyalkyl anhydride is reacted with a polybasic acid anhydride, so that a hydroxyalkyl (meth) acrylate having a primary hydroxyl group can be easily reacted. Is desirably selected and used as one of the monomers of the copolymer. Representative examples of such hydroxyalkyl (meth) acrylates having a primary hydroxyl group include, but are not limited to, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and 3-hydroxypropyl acrylate. is not.

In the copolymer serving as the base of the resin (2), the ratio of the alkyl (meth) acrylate to the glycidyl (meth) acrylate is from 40:60 in molar ratio.
80:20 is preferred. On the other hand, in the copolymer serving as the base of the resin (3), the molar ratio of hydroxyalkyl (meth) acrylate, alkyl (meth) acrylate and glycidyl (meth) acrylate is 10%.
The ratio is preferably from 50:10 to 70:20 to 60, and more preferably from 15 to 30:30 to 50:30 to 50. If the proportion of glycidyl (meth) acrylate in the copolymer is too low, the photocurability decreases, which is not preferable. On the other hand, if it exceeds the above range, the synthesis reaction of the photosensitive resin proceeds smoothly. It is not desirable because it does not go.
The degree of polymerization of the copolymer obtained by copolymerizing each of the monomers was 10,000 as a weight average molecular weight.
~ 70,000, preferably 20,000 ~ 60,000
A range of 0 is desirable. If the weight average molecular weight is less than 10,000, the dryness to the touch is reduced, while if it exceeds 70,000, the developability is apt to be reduced, which is not preferable. In the present invention, in addition to the above monomers, vinyl compounds such as styrene and methylstyrene can be used as long as the properties are not affected.

Typical examples of the photopolymerization initiator (B) include benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether and their alkyl ethers; acetophenone, 2,2 -Dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone,
-Hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl)- 1-
Acetophenones such as butanone; anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone and 2-amylanthraquinone; 2,4-dimethylthioxanthone and 2,4-diethylthioxanthone Thioxanthones, such as 2-chlorothioxanthone and 2,4-diisopropylthioxanthone; ketals, such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones, such as benzophenone, or xanthones. These photopolymerization initiators can be used alone or in combination of two or more. The photopolymerization initiator (B) can be used in combination with one or more publicly known and commonly used photopolymerization accelerators such as benzoic acid or tertiary amine.

The preferred range of the amount of the photopolymerization initiator (B) used is 0.2 to 30 parts by weight, preferably 2 to 30 parts by weight, based on 100 parts by weight of the active energy ray-curable resin (A). It is a ratio of ２０20 parts by weight. When the compounding ratio of the photopolymerization initiator is less than 0.2 parts by weight, the photocurability is deteriorated. It is not preferable because it becomes worse.

Further, as the diluent (C), a photopolymerizable monomer and / or an organic solvent can be used. Representative photopolymerizable monomers include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, N-vinylpyrrolidone, acryloylmorpholine, methoxytetraethylene glycol acrylate,
Methoxy polyethylene glycol acrylate, polyethylene glycol diacrylate, N, N-dimethylacrylamide, N-methylolacrylamide, N, N-
Dimethylaminopropyl acrylamide, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminopropyl acrylate, melamine acrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, propylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol Diacrylate, polypropylene glycol diacrylate, phenoxyethyl acrylate, tetrahydrofurfuryl acrylate, cyclohexyl acrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, glycerin diglycidyl ether diacrylate, glycerin triglycidyl ether triacrylate, pentaerythritol triacrylate Acrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, isoborneolyl acrylate, cyclopentadiene mono- or di-acrylate, and methacrylates corresponding to the above acrylates, polybasic acids and hydroxyalkyl ( Mono-, g-, tree or higher polyesters with (meth) acrylates. On the other hand, as the organic solvent, ketones, aromatic hydrocarbons, cellosolves, carbitols, glycol ethers, acetates, and the like as listed in relation to the thermosetting resin composition may be used. I can do it.

The diluent (C) as described above is used alone or as a mixture of two or more. A suitable range of the amount 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 use of the monomer is to dilute the active energy ray-curable resin so as to make it easy to apply and to give photopolymerizability. 3 to 50 parts by weight based on 100 parts by weight of the conductive resin (A). If the amount is less than 3 parts by weight, the photocurability is inferior, while if it exceeds 50 parts by weight, the dryness to the touch is reduced, which is not preferable. The purpose of using the organic solvent is to dissolve the active energy ray-curable resin (A), dilute it, apply it as a liquid, and then dry it to form a film, thereby enabling contact exposure. is there.

As the epoxy resin (D) as the thermosetting component, the epoxy resins listed in connection with the thermosetting resin composition can be used. Among these epoxy resins, powdery epoxy resins hardly soluble in organic solvents, for example, EBPS-200 manufactured by Nippon Kayaku Co., Ltd.
Bisphenol S such as EPX-30 manufactured by Asahi Denka Kogyo Co., Ltd. and Epicron EXA-1514 manufactured by Dainippon Ink and Chemicals, Inc.
Epoxy resin; diglycidyl terephthalate resin such as Blemmer DGT manufactured by NOF Corporation; TEP manufactured by Nissan Chemical Industries, Ltd.
Triglycidyl isocyanurate such as IC, TEPIC-H, Araldite PT810 manufactured by Ciba-Geigy;
Yuka Shell Epoxy YX-4000, YL-612
It is preferable to mainly use a bixylenol type or biphenol type epoxy resin such as 1. The epoxy resins may be used alone or in combination of two or more. The mixing amount of the epoxy resin as the thermosetting component is 5 to 1 with respect to 100 parts by weight of the active energy ray-curable resin (A).
00 parts by weight is suitable, preferably 15 to 60 parts by weight.

The mixing ratio of the cyanoguanidine derivative in the photocurable thermosetting resin composition of the present invention is 0.1 to 100 parts by weight of the active energy ray-curable resin (A).
5 to 5 parts by weight are preferred. If the amount is less than 0.5 part by weight, the development of thermosetting properties cannot be expected. On the other hand, if the amount is more than 5.0 parts by weight, the storage stability of the photocurable thermosetting resin composition tends to deteriorate, Also, the electrical characteristics (insulation resistance value) are deteriorated in the formed solder resist film, which is not preferable.

The thermosetting or light-curing thermosetting resin composition of the present invention may further comprise, if necessary, a known / curable resin for promoting the reaction between the cyanoguanidine derivative and the epoxy resin.
Conventional epoxy curing accelerators can be used, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2 -Phenylimidazole,
Imidazole derivatives such as 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, guanamines such as acetoguanamine and benzoguanamine, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine And amine compounds such as 4-methoxy-N, N-dimethylbenzylamine and 4-methyl-N, N-dimethylbenzylamine. As commercially available products, for example, 2MZ-A manufactured by Shikoku Chemicals, Inc.
2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ
(All are trade names of imidazole compounds), U-CAT3503X, U-CAT3502X manufactured by San Apro
(All are trade names of blocked isocyanate compounds of dimethylamine).

Since the reaction initiation temperature in post cure is as high as about 200 ° C. using only the above-mentioned cyanoguanidine derivative, it is preferable to lower the reaction initiation temperature by blending the epoxy curing accelerator as described above. When it is blended with the resin, the storage stability of the photocurable thermosetting resin composition is deteriorated. Therefore, the compounding amount of the epoxy curing accelerator depends on the amount of the active energy ray-curable resin (A).
The ratio is preferably 0.1 to 2.0 parts by weight based on 100 parts by weight.

The thermosetting or photocurable thermosetting resin composition of the present invention may further contain barium sulfate, silicon oxide, talc, clay, calcium carbonate, silica, kaolin, glass fiber, carbon fiber, etc., depending on the desired physical properties. Known fiber, mica, etc.
Conventional fillers, known and common coloring pigments such as phthalocyanine blue, phthalocyanine green, titanium oxide, and carbon black; thickeners such as bentonite, organobentonite, and finely divided silica; defoaming agents; adhesion-imparting agents or leveling agents. And various additives such as hydroquinone, hydroquinone monomethyl ether, pyrogallol, t-butylcatechol, and phenothiazine.
A conventional polymerization inhibitor may be added.

The photocurable thermosetting resin composition of the present invention comprises:
If necessary, the viscosity is adjusted to a suitable coating method, and this is applied, for example, to a circuit-formed printed wiring board by a method such as a screen printing method, a curtain coating method, a spray coating method, a roll coating method and the like. By evaporating and drying the organic solvent contained in the composition at a temperature of １００100 ° C., a tack-free coating film can be formed. Thereafter, the resist pattern can be formed by selectively exposing with an actinic ray through a photomask on which a pattern is formed, and developing an unexposed portion with a dilute alkaline aqueous solution to form a resist pattern.
By heating to a temperature of 40 to 200 ° C. and thermosetting, in addition to the curing reaction of the thermosetting component, the polymerization of the photocurable resin component is promoted, and the heat resistance and solvent resistance of the obtained resist film In addition to various properties such as acid resistance, adhesion, electrical properties, and hardness, the resistance to electroless gold plating can be improved, and it is particularly useful as a solder resist.

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

[0040]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Synthesis Examples and Examples, but it goes without saying that the present invention is not limited to the following Synthesis Examples and Examples.
All parts are by weight unless otherwise specified.

Synthesis Example: (Synthesis of 2-cyanoguanidyl-4,6-diamino-S-triazine) 100 m equipped with a Dimroth condenser
8.9 g of sodium dicyanamide in an eggplant-shaped flask
(0.10 mol), 1.63 g (0.10 mol) of 2,4,6-triamino-S-triazine monohydrochloride, and n
-Butanol (20 ml) was added, and the mixture was reacted in an oil bath for 5 hours while stirring with a magnetic stirrer under heating and refluxing conditions. Immediately after completion of the reaction, the reaction solvent was distilled off under reduced pressure using an evaporator. Water / acetone (mixing ratio: 1.0 / 1.0) was added to the residue, and the mixture was mixed well, filtered off using a glass filter, and the solid content was dried at 80 ° C. for 8 hours in a heated vacuum dryer. 0.55 g of white 2-cyanoguanidyl-4,6-diamino-S-triazine
(28.5% yield).

The product obtained, 2-cyanoguanidyl-
Fourier transform infrared spectrophotometer FT-IR for 4,6-diamino-S-triazine (hereinafter abbreviated as MD)
FIG. 1 shows an IR spectrum measured by using. As is clear from the figure, C≡N of the cyanoguanidyl group of MD is
A peak due to stretching motion appears at a wave number of 2195 cm ^-1 . In addition, MD ¹ H-NMR spectrum (solvent DMSO (dimethyl sulfoxide), internal standard TMS
(Tetramethylsilane)) is shown in FIG. FIG. 2 also shows a curve indicating the proton integral ratio of each peak.

Example 1 The reactivity of MD to epoxy resin was measured using a differential scanning calorimeter (DSC). Epicoat 828 (epoxy equivalent: 190, manufactured by Yuka Shell Epoxy Co., Ltd.) was used as the epoxy resin, and the hydrogen of the amino group of MD was mixed as a curing catalyst to 1.0 mol with respect to 1 mol of the epoxy group. After mixing, about 10 mg was taken in an aluminum container for DSC and precisely weighed to obtain a sample. The apparatus used was an SSC5200 type differential scanning calorimeter manufactured by Seiko Denshi Kogyo KK, and the temperature was measured in air at a rate of 5 ° C./min.
As a result, a remarkable exothermic peak due to the curing reaction was confirmed at 216.1 ° C. Table 1 shows the results. Further, a brown cured product was obtained from inside the cell after heating.

[Table 1]

Example 2 The solubility of MD in various organic solvents (ethanol, methyl ethyl ketone (MEK), cyclohexane) and water was examined. Various solvents 1 in a 50 ml Erlenmeyer flask with a stopper
0 ml was taken, MD was added in a predetermined amount, the mixture was stirred at 25 ° C. for 30 minutes, and filtered. The solvent in the filtrate was evaporated and dried, and the weight was determined to calculate the solubility. Table 2 shows the results.

[Table 2] As is clear from Table 2, the cyanoguanidine derivative MD according to the present invention is poorly soluble in various organic solvents and water.

EXAMPLE 3 0.07 g of MD and 0.50 g of Epicoat 828 were mixed in a mortar and placed on a 8 mm thick copper plate (14 × 60 mm).
It was applied to a thickness of μm to obtain a sample. This was heated in a 210 ° C. oven for 66 minutes to cure. The characteristics of the obtained cured product were measured by using a rigid edge pendulum type viscoelasticity meter (Reo Vibron) DDV-OPAIII type manufactured by Orientec Co., Ltd., using a knife edge type pendulum (R = 0.3 mm), and using a heating rate of 3 mm.
The measurement was carried out by increasing the temperature from room temperature to 250 ° C. at 0 ° C./min.
Table 3 shows the physical properties of the obtained cured product.

[Table 3]

The logarithmic decay rate (Δ) shown in the above Table 3 refers to a heat block in which a rigid pendulum 1 is placed on a substrate 3 coated with paint 2 and the substrate 3 is supported, as shown in FIGS. The vibration change of the pendulum 1 was measured while heating the pendulum 4, and based on the obtained vibration change of the pendulum as shown in FIG. 5, it was determined by the following formula (3). Pendulum 1
Of the tip 1a penetrates into the coating film 2 and reaches the substrate surface, and becomes a fulcrum of vibration.

Embedded image The larger the logarithmic decay rate, the softer the cured product. Incidentally, in the case of cyanoguanidine (abbreviation CG), which is conventionally generally used as a curing agent for epoxy resins, the glass transition point Tg is 166 ° C. and the logarithmic decay rate is 0.13.
It is. In the case of MD, a cured product having almost the same hardness as that of CG was obtained.

Example 4 One equivalent of a cresol novolak type epoxy resin having an epoxy equivalent of 220 and having an average of seven phenolic nuclei residues per molecule and an epoxy group, and 1.05 equivalent of acrylic acid To the reaction product obtained by reacting
0.67 equivalents of tetrahydrophthalic anhydride were reacted at normal pressure using carbitol acetate as a solvent. It contains 52 parts of carbitol acetate (solid resin 10
(Based on 0 parts) and contained an acid number of 63.4 mg KOH / g as a mixture. Hereinafter, this is abbreviated as resin A. Ingredient (a) Resin A 150.0 parts 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one 16.0 parts KS-66 (antifoaming agent, Shin-Etsu Chemical Co., Ltd.) 2.0 parts Fastogen Green S (colored pigment, manufactured by Dainippon Ink and Chemicals, Inc.) 5.0 parts Dipropylene glycol monomethyl ether 4.0 parts Ipsol # 150 (solvent manufactured by Idemitsu Petrochemical Industries, Ltd.) 3 0.0 parts Barium sulfate 30.0 parts Finely divided silica 30.0 parts Product MD of synthesis example 8.0 parts Total 248.0 parts The above compound was kneaded with a three-roll mill to prepare a main ingredient. Furthermore, the following epoxy resin composition was similarly kneaded with a three-roll mill as a crosslinking agent,
A curing agent was prepared. Ingredient (b) Dipropylene glycol monomethyl ether 12.0 parts Ipsol # 150 12.0 parts DPHA (photopolymerizable monomer, Nippon Kayaku Co., Ltd.) 24.0 parts Triglycidyl isocyanurate 26.0 parts YX-4000 26 0.0 parts Barium sulfate 50.0 parts Total 150.0 parts The base agent and the curing agent thus prepared were mixed at a ratio of 70:30 to obtain a solder resist ink.

Comparative Example 1 A main ingredient was prepared in the same manner as in Example 4 except that "8.0 parts of the product of Synthesis Example MD" was changed to "6.0 parts of melamine". The curing agent is the same as in Example 4.

Each of the ink compositions obtained in Example 4 and Comparative Example 1 was examined for electroless gold plating resistance as follows. Electroless gold plating resistance: Surface treatment of copper surface of patterned copper through-hole printed wiring board ((a) Jet scrub polishing using abrasive No. 270 manufactured by Ishii Notation Co., Ltd. or (b) Ishii No. 1 made by Notation Co., Ltd.
(200 buff polishing), washed with water and dried. Each of the ink compositions obtained in Example 4 and Comparative Example 1 was applied on the entire surface of the copper through-hole printed wiring board surface-treated by screen printing, and dried at 80 ° C. for 20 minutes. A negative film was brought into close contact with this substrate, and the solder resist pattern was exposed to 800 mJ / cm ^2.
The pattern was formed by developing with a wt% aqueous solution of sodium carbonate for 1 minute. This substrate was thermally cured at 150 ° C. for 50 minutes,
An evaluation substrate was manufactured. After performing electroless gold plating using the evaluation substrate as described below, a peel test using a cellophane adhesive tape was performed. The appearance change of the resist layer after the electroless gold plating and the peeling state of the resist layer after the peel test were evaluated according to the following criteria. ：: No change in appearance and no peeling of the resist layer. Δ: No change in appearance, but slight peeling of resist layer. ×: Floating resist was observed, plating dive was observed,
Large peeling of resist layer in peel test.

Electroless gold plating method: A substrate for evaluation was subjected to an acidic degreasing solution at 30 ° C. (Metex L- manufactured by Fuji Chemical Industry Co., Ltd.).
5B 20 Vol% aqueous solution) for 3 minutes to degrease,
Then, it was immersed in running water for 3 minutes and washed with water. Next, the evaluation substrate was immersed in a 14.3% by weight aqueous solution of ammonium persulfate at room temperature for 3 minutes, soft-etched, then immersed in running water for 3 minutes and washed with water, and then immersed in a 10% by volume aqueous solution of sulfuric acid at room temperature for 1 minute Then, it was immersed in running water for 30 seconds to 1 minute and washed with water. Next, the evaluation substrate was subjected to a catalyst solution of 30 ° C.
Meltex, metal plate activator 350
The sample was immersed in running water for 7 minutes to give a catalyst, and then immersed in running water for 3 minutes and washed with water. The evaluation substrate to which the catalyst was applied was plated with a nickel plating solution (85 ° C.)
20V of Melplate Ni-865M made by Meltex
ol% aqueous solution, pH 4.6) for 20 minutes to perform electroless nickel plating, immersion in a 10 vol% sulfuric acid aqueous solution for 1 minute at room temperature, and immersion in running water for 30 seconds to 1 minute to wash. Next, a gold plating solution of 95 ° C. (manufactured by Meltex Co., Ltd., Aurolectrores UP 1)
An aqueous solution of 5% by volume and 3% by volume of potassium gold cyanide,
After immersion in electroless gold plating by immersion in pH 6) for 10 minutes, it was immersed in running water for 3 minutes and washed with water, and further immersed in 60 ° C. warm water for 3 minutes and washed with hot water. After sufficient washing with water, the water was thoroughly removed, dried, and an evaluation board plated with electroless gold was obtained. Table 4 shows the results.

[Table 4]

[0051]

As described above, according to the present invention, a novel cyanoguanidine derivative, 2-cyanoguanidyl-4,
6-Diamino-S-triazine is provided. Although the cyanoguanidine derivative according to the present invention is rich in reactivity with an epoxy resin, it is hardly soluble in various organic solvents and liquid epoxy resins or solutions of epoxy resins, and does not react with epoxy groups at room temperature. It has the property of reacting with an epoxy group by the application of heat, and can therefore be used particularly advantageously as a curing agent for epoxy resin having thermal latent reactivity.

The thermosetting resin composition of the present invention comprising a cyanoguanidine derivative having such properties together with an epoxy resin is stable at a low temperature near normal temperature.
At a high temperature, there is obtained an advantage that it cures in a short time, that is, is excellent in so-called latent curability, and is also excellent in storage stability. Further, the photocurable thermosetting resin composition of the present invention,
Since it contains the specific cyanoguanidine derivative described above as a curing agent for an epoxy resin, it has excellent storage stability, and as a result, the flexibility of the solder resist film forming operation increases. In addition, the photocurable thermosetting resin composition of the present invention can be developed with a dilute alkaline aqueous solution, and after the exposure and development, the coating film is post-heated so that the heat resistance of the coating film required as a solder resist can be improved. A solder resist film excellent in electroless gold plating resistance in addition to various properties such as resistance, solvent resistance, acid resistance, adhesion, electrical properties, and hardness can be obtained.

[Brief description of the drawings]

FIG. 1 shows 2-cyanoguanidyl-4,
It is an IR spectrum figure of 6-diamino-S-triazine.

FIG. 2 shows 2-cyanoguanidyl-4,
FIG. 2 is a ¹ H-NMR spectrum of 6-diamino-S-triazine.

FIG. 3 is a schematic diagram illustrating a basic concept of logarithmic decay rate measurement in a third embodiment.

FIG. 4 is a partial cross-sectional view showing a state when a logarithmic decrement of a cured product is measured by the apparatus shown in FIG.

FIG. 5 is a schematic diagram showing a change in vibration of a pendulum when measuring a logarithmic decrement in Example 3.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Pendulum 1a Tip of pendulum 2 Coating film 3 Substrate 4 Heat block

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ identification code FI H05K 3/06 H05K 3/06 H (58) Field surveyed (Int.Cl. ⁷ , DB name) C07D 251/70 C08F 2 / 50 C08G 59/40 G03F 7/004 G03F 7/038 CA (STN) REGISTRY (STN)

Claims (10)

(57) [Claims] 1. A 2-cyanoguanidyl-4,6-diamino-S-triazine represented by the following formula (1). Embedded image 2. A curing agent for epoxy resin comprising 2-cyanoguanidyl-4,6-diamino-S-triazine represented by the following formula (1). Embedded image 3. A thermosetting resin composition containing an epoxy resin and 2-cyanoguanidyl-4,6-diamino-S-triazine represented by the following formula (1) as a curing agent for the epoxy resin. . Embedded image 4. 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, and (D) An epoxy resin, and (E) a curing agent for epoxy resin, wherein the curing agent for epoxy resin (E) is 2-cyanoguanidyl- represented by the following formula (1).
A photocurable thermosetting resin composition which is 4,6-diamino-S-triazine. Embedded image 5. The method according to claim 1, wherein the active energy ray-curable resin is added to a reactant of a polyfunctional novolak type epoxy compound and an unsaturated monocarboxylic acid in an amount of 0.15 mol or more per one hydroxyl group of the reactant. The composition according to claim 4, which is obtained by reacting an unsaturated polybasic acid anhydride. 6. The method according to claim 1, wherein the active energy ray-curable resin is 4
The composition according to claim 4 or 5, which has an acid value of 0 to 160 mgKOH / g. 7. The composition according to claim 4, wherein the photopolymerization initiator is contained in a ratio of 0.2 to 30 parts by weight based on 100 parts by weight of the active energy ray-curable resin. Stuff. 8. The diluent is at least one selected from an organic solvent and a photopolymerizable monomer, and is used in an amount of 30 to 300 parts by weight based on 100 parts by weight of the active energy ray-curable resin.
The composition according to any one of claims 4 to 7, which is contained in parts by weight. 9. The epoxy resin curing agent is added in an amount of from 0.5 to 100 parts by weight of the active energy ray-curable resin.
The composition according to any one of claims 4 to 8, wherein the composition is contained in a proportion of 5.0 parts by weight. 10. The active energy ray-curable resin 10
The composition according to any one of claims 4 to 9, further comprising 0.1 to 2.0 parts by weight of an epoxy curing accelerator with respect to 0 parts by weight.