TWI431049B - Active energy ray curable resin composition using flame--retardant reactive compound and cured object thereof - Google Patents

Description

Active energy ray-curable resin composition using a flame retardant reactive compound and a cured product thereof

The present invention relates to an active energy ray-curable resin composition using a phosphine oxide which is a reactive compound which can be polymerized in various polymer materials for the purpose of making the polymer material difficult to ignite. The use of the active energy ray-curable resin composition is, for example, a material for forming a film, a solder resist for producing a printed circuit (wiring circuit) substrate, another resist material for alkali development, and an adhesive. , lenses, displays, optical fibers, optical waveguides, holograms, and the like.

Attempts to make flame-retardant materials such as molded articles and film forming materials have been widely practiced. In the past, although flame retardant materials using a halogen compound represented by bromide have been widely used, in recent years, such materials have been avoided due to increasingly serious environmental problems. The use of phosphorus-based compounds to replace flame retardant materials of such halogen compounds is under investigation.

Since a phosphorus compound is generally used alone in a resin composition or the like, it may be bleed out when the resin composition or the like is hardened or as time passes, so that a uniform flame retarding effect cannot be obtained. It may lower the thermal, electrical, mechanical properties, etc. of the hardened material. Therefore, development of a flame retardant capable of charging a phosphorus-based compound in a skeleton of a resin or the like and having reactivity has been expected to solve such problems.

Among them, a phosphoric acid type compound represented by the following general formula (2) is known as a phosphorus-containing polymerizable (meth)acrylic monomer (Patent Document 1):

(wherein R' ₁ , R' ₂ represents a linear or branched alkyl group having 1 to 10 carbon atoms, and R ₃ and R ₄ represent a hydrogen atom or a methyl group. R' ₁ and R' ₂ may be The same person can also be a different person).

When the phosphoric acid type structure represented by the above formula (2) is present, the adverse effect caused by the acidic group can be seen. For example, since the acidic group promotes hydrolysis or promotes corrosion of a substrate such as a metal, the durability of the cured product after long-term use is problematic. In particular, when it is used in a permanent resist for a circuit board or the like, since it is used for long-term protection of the circuit, the presence of such an acidic group causes a great problem.

Further, in the use of a solder resist or the like to be developed, an epoxy compound or the like is generally used as a curing agent, and the two components are mixed in the resin composition and used. At this time, when a large amount of an acidic group is contained in the composition, the storage stability after the two liquids are mixed or the step of developing to the development may cause a problem that the development of the curing agent may cause development.

Further, the phosphoric acid type compound which has been crosslinked with the epoxy resin is a substance which is hydrolyzed under high humidity and heat conditions, and is therefore inferior in reliability tests such as electrical characteristics.

On the other hand, a technique for interposing an epoxy group and introducing an ethylenically unsaturated group into a phosphine oxide having a hydroxyl group which is excellent in heat resistance and moisture resistance has been described. (Patent Document 2)

However, when it is hardened by the active energy ray, there is a problem that it flows out from the resin composition in addition to the sensitivity.

In order to impart flame retardancy to the resist material, although the so-called blending of the flame retardant and the inorganic extender pigment is a well-known general technique, a reactive flame retardant is not a general technique.

Further, in the resist material used for the flexible circuit board, since high flexibility is required, a large amount of the extender pigment is added, and it is difficult to impart flame retardancy.

In addition, in Patent Document 3, although a curable resin composition using the reactive compound (A) is described, it is not described that other reactive compound (B) is contained, and there is no description about when it is a cured product. Flame retardant heat resistance, moisture resistance or electrical insulation.

[Previous Technical Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2000-38398

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2004-143286

[Patent Document 3] Japanese Patent No. 3454544

In the photosensitive resin composition in which the epoxy resin has been prepared, it is required that the above-mentioned photosensitive phosphine oxide compound has heat stability which can be sufficiently alkali-developed even if it is heated and dried before exposure.

In addition, it is desirable that the phosphoric acid type compound which has been crosslinked with the epoxy resin is a compound which is not hydrolyzed under high-humidity heat conditions and which is excellent in heat resistance and moisture resistance in the reliability test such as electrical properties. Further, it is desirable to obtain a flame retardant which exhibits a flame retardant effect without requiring a large amount of addition.

The present invention has no such problems, and can be cured by an active energy ray such as ultraviolet rays, and has thermal stability, excellent heat resistance and moisture resistance, good electrical insulating properties, and exhibits a flame retardant effect even when added in a small amount. .

In view of the foregoing, the inventors of the present invention conducted intensive studies on a novel phosphine oxide compound having a photosensitive group and a photosensitive resin composition using the same, and as a result, found an unsaturated group-containing compound having a specific structure and a composition thereof. The present invention can be solved by solving the aforementioned problems. That is, the present invention relates to the following (1) to (13).

(1) An active energy ray-curable resin composition comprising a phosphine oxide compound (A) represented by the following formula (1) and having reactivity of two or more active energy ray-reactive functional groups in one molecule Compound (B), and photopolymerization initiator (C)

(wherein R represents a hydrogen atom or a methyl group).

(2) The active energy ray-curable resin composition according to (1), wherein the reactive functional group of the reactive compound (B) is a (meth) acrylate.

(3) The active energy ray-curable resin composition according to (1), wherein the reactive compound (B) is a (meth) acrylate having an acid value of 30 to 150 mg ‧ KOH/g.

(4) The active energy ray-curable resin composition according to (1), wherein the reactive compound (B) is an epoxy group-containing (meth) acrylate.

(5) The active energy ray-curable resin composition according to (4), wherein the reactive compound (B) is an acid modified biphenol type epoxy group (meth) acrylate.

(6) The active energy ray-curable resin composition according to any one of (1) to (5), which further comprises an epoxy resin as a curing agent.

(7) The active energy ray-curable resin composition according to (6), wherein the curing agent is a bisphenol type epoxy resin.

(8) The active energy ray-curable resin composition according to any one of (1) to (6), which is a material for molding.

(9) The active energy ray-curable resin composition according to any one of (1) to (6), which is a material for forming a film.

(10) The active energy ray-curable resin composition according to any one of (1) to (6), which is an electrically insulating material composition.

(11) The active energy ray-curable resin composition according to (10), wherein the electrically insulating material composition is a developable photosensitive solder resist composition.

(12) A method for producing a cured product, which is an active energy ray-curable resin composition according to any one of the above items (1) to (7).

(13) A multilayer material comprising: a layer of a cured product obtained by irradiating an active energy ray-curable resin composition according to any one of the above items (1) to (7).

The cured product obtained from the active energy ray-curable resin composition of the present invention can sufficiently satisfy the adhesion to the metal and the flame retardancy of the resin, and is excellent in heat resistance and moisture resistance, and is excellent in electrical insulating properties. A material with excellent reliability over a long period of time. Therefore, the photosensitive resin composition can be suitably used as a material for forming a film, a solder resist for manufacturing a printed circuit (wiring circuit) substrate, an alkali developable resist material, an adhesive, a lens, a display, an optical fiber, and an optical waveguide. The composition of the whole photo.

The invention is described in detail below. The phosphine oxide compound (A) of the present invention is obtained by reacting an alcohol compound of the formula (3) with a monocarboxylic acid compound having an ethylenically unsaturated group in the molecule.

The alcohol compound represented by the formula (3) is obtained by reacting a phosphorus-containing compound having at least one active hydrogen in the molecule of the formula (4) with formaldehyde. As the compound, a commercially available product such as a product manufactured by Sanko Co., Ltd.: trade name HCA can be used.

The monocarboxylic acid compound having an ethylenically unsaturated group in the molecule used in the production of the phosphine oxide compound (A) of the present invention is a compound for imparting reactivity with an active energy ray to cause it to react. Specifically, for example, acrylic acid or methacrylic acid can be mentioned.

When the phosphine oxide compound (A) of the present invention is produced, it can be produced by a method in which an alcohol compound of the formula (3) and a monocarboxylic acid compound having an ethylenically unsaturated group in the molecule are subjected to dehydration condensation in the presence of an acid catalyst. .

The acid catalyst to be used may be arbitrarily selected from well-known acids such as sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid, etc., and is used in an amount of 0.1 to 10 mol% relative to (meth)acrylic acid, and is 1 to 5% of the mole is better.

The water formed in the reaction can be distilled off using an azeotropic solvent. In this case, the term "azeotropic solvent" means a solvent having a boiling point of 60 to 130 ° C and easily separated from water, and it is particularly preferable to use an aliphatic hydrocarbon such as n-hexane or n-heptane; or an aromatic hydrocarbon such as benzene or toluene; An alicyclic hydrocarbon such as cyclohexane. Although it may be used arbitrarily, it is preferably from 10 to 70% by weight based on the reaction mixture.

The reaction temperature may be in the range of 60 to 130 ° C, but it is preferably carried out at 70 to 120 ° C in terms of shortening the reaction time and preventing polymerization.

When a commercially available (meth)acrylic acid or the like is used as a raw material, a polymerization inhibitor such as p-methoxyphenol is usually added, but a polymerization inhibitor may be added at the time of the reaction. Examples of such polymerization inhibitors are hydroquinone, p-methoxyphenol, 2,4-dimethyl-6-tert-butylphenol, 3-hydroxythiophene, p-benzoquinone, 2,5. - Dihydroxy-p-benzoquinone, phenothiazine, etc. are preferred. It is used in an amount of from 0.01 to 1% by weight based on the reaction raw material mixture.

The reactive compound (B) having two or more active energy ray-reactive functional groups in one molecule used in the present invention can be obtained by using in combination with the phosphine oxide compound (A) used in the present invention. A flame retardant and tough hardened product. Since it has two or more active energy ray reactive functional groups in one molecule, it can form a strong crosslinked structure when combined with the monofunctional phosphine oxide compound (A), and can inhibit hydrolysis of the phosphine oxide compound (A). Action or outflow, achieving long-term stability of flame retardancy and reliability.

The active energy ray-reactive functional group shown in the present invention means a functional group which can cause a reaction by an active energy ray and constitute a cross-linking bond. For example, a functional group which is reacted by a radical generated by irradiation with an active energy ray may, for example, be a polymerizable unsaturated bond such as a (meth) acrylonitrile group, a vinyl group or a vinyl ether group. Further, examples thereof include an epoxy group such as an epoxy group which is reacted by irradiation with an active energy ray, a cyclic ether group such as an oxetane group, and an unsaturated ether group such as a vinyl ether group.

Examples of the reactive compound (B) having two or more (meth) acrylonitrile groups include butanediol di(meth)acrylate, hexanediol di(meth)acrylate, and neopentyl glycol. Di(meth)acrylate, decanediol di(meth)acrylate, glycol di(meth)acrylate, di-ethylidene di(meth)acrylate, poly Ethylene glycol di(meth)acrylate, tris(meth)acryloxyethyl isocyanurate, polypropylene glycol di(meth)acrylate, adipic acid epoxy di(meth)acrylic acid Ester, bisphenol ethylene oxide di(meth)acrylate, hydrogenated bisphenol ethylene oxide di(meth)acrylate, bisphenol di(meth)acrylate, ε-caprolactone modified hydroxyl Valentic acid neopentyl glycol di(meth)acrylate, ε-caprolactone modified dipentaerythritol hexa(meth) acrylate, ε-caprolactone modified dipentaerythritol poly(meth) acrylate, dipentaerythritol Poly(meth)acrylate, trimethylolpropane tri(meth)acrylate, trishydroxyethylpropane tri(meth)acrylate, and its ethylene oxide adduct, pentaerythritol tri(methyl) acrylic acid A (meth) acrylate such as an ester, an ethylene oxide adduct thereof, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, or an ethylene oxide adduct thereof.

Other examples include peptide ester (meth) acrylates having a plurality of (meth) acrylonitrile groups and urethane bonds in the same molecule, and also having several in the same molecule (A a polyester (meth) acrylate having an acryloyl group and an ester bond, an epoxy (meth) acrylate derived from an epoxy resin and having a plurality of (meth) acrylonitrile groups, and a composite use thereof A reactive oligomer such as a bond.

Further, as will be described later, a reactive compound (B) having two or more active energy ray functional groups imparting an acid value may be similarly mentioned.

The amine ester (meth) acrylate represented by the present invention means a reaction product of a hydroxyl group-containing (meth) acrylate and a polyisocyanate and other alcohols used in combination. For example, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxyalkyl (meth)acrylate such as hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, glycerin Sugar alcohols such as glycerol (meth) acrylate such as di(meth) acrylate, pentaerythritol di(meth) acrylate, pentaerythritol tri(meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. Acrylates, with toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, xylene diisocyanate, hydrogenated xylene diisocyanate, The dicyclohexane methylene diisocyanate and the polyisocyanate such as the isocyanurate or the biuret reactant are reacted to form an amine ester (meth) acrylate.

The epoxy group (meth) acrylate represented by the present invention means a compound having an epoxy group and a carboxylic acid ester compound of (meth)acrylic acid. For example, phenol novolac type epoxy (meth) acrylate, cresol novolac type epoxy (meth) acrylate, trihydroxy phenyl methane type epoxy (meth) acrylate, Dicyclopentadiene phenol type epoxy (meth) acrylate, bisphenol A type epoxy (meth) acrylate, bisphenol F type epoxy (meth) acrylate, biphenol type epoxy Base (meth) acrylate, bisphenol A phenolic epoxy (meth) acrylate, epoxy group (meth) acrylate containing naphthalene skeleton, glyoxal type epoxy (meth) acrylate And a heterocyclic epoxy group (meth) acrylate or the like, and an acid anhydride-modified epoxy acrylate such as these.

The compound (B) having a vinyl group may, for example, be a vinyl ether such as ethylene glycol divinyl ether. Examples of the styrenes include divinylbenzene and the like. Other vinyl compounds include, for example, triallyl isocyanurate, trimethallyl isocyanurate, and the like.

Further, the compound having a cyclic ether group is not particularly limited as long as it is a compound having an epoxy group or an oxypropylene group. For example, alkyl diglycidyl ethers such as butyl diglycidyl ether, bisphenol A diglycidyl ether, and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylic acid Ester ("CYRACURE UVR-6110", manufactured by Union Carbide Co., Ltd.), 3,4-epoxycyclohexylethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexene oxide (Union) "ELR-4206" manufactured by Carbide Co., Ltd.), limonene dioxide (Celloxide 3000, etc.), propylene diallyl propylene, 3,4-epoxy 4-methylcyclohexyl-2-epoxypropane, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-inter-di Alkane, bis(3,4-epoxycyclohexyl) adipate ("CYRACURE UVR-6128", manufactured by Union Carbide Co., Ltd.), bis(3,4-epoxycyclohexylmethyl) adipate , bis(3,4-epoxycyclohexyl)ether, bis(3,4-epoxycyclohexylmethyl)ether, bis(3,4-epoxycyclohexyl)diethylcyclohexane, etc. .

For example, when glycidyl (meth)acrylate contains one type of one radical or one type of functional group in one molecule, it can also be regarded as having two or more active energy ray-reactive functionalities in one molecule. Base reactive compound (B).

Among these, the reactive compound (B) is preferably a compound having a radically curable (meth) acrylonitrile group. In the case of a cationic type, since a small amount of acid derived from the phosphine oxide (A) causes an epoxy group to react, it is necessary to form a two-liquid mixing type.

Next, the acid value of the reactive compound (B) having two or more active energy ray-reactive functional groups represented by the present invention may be imparted. Therefore, in the use of optical patterning of the curable resin composition by photo-crosslinking reaction, the exposed portion and the unexposed portion can be patterned by the development method, and the reactivity with acid value can be used. The compound (B) can be eluted by an aqueous alkaline solution to dissolve the unexposed portion.

At this time, the acid value of the reactive compound (B) is preferably from 30 to 150 mg ‧ KOH / g, and more preferably from 60 to 110 mg ‧ KOH / g When the acid value in this case is less than 30 mg ‧ KOH / g (preferably less than 60 mg ‧ KOH / g), the developability of the alkaline aqueous solution of the active energy ray-curable resin composition of the present invention is remarkably lowered, and the worst The situation is that there is no way to develop. Further, if the acid value exceeds 150 mg ‧ KOH / g (preferably, more than 110 mg ‧ KOH / g), the developability becomes too high, which makes drawing difficult.

The reactive compound (B) to which an acid value has been added is a compound having an acidic group such as a carboxyl group or a phenol group. For example, an acid-modified epoxy (meth) acrylate, an acid modified amine (meth) acrylate, etc. are mentioned. Examples of such a compound include an acid anhydride group obtained by an addition reaction of an acid anhydride or the like with a reactive compound (B) having a hydroxyl group, and an acid group (an acid anhydride addition reaction type); or a monomer having an acidic group (for an acid group) For example, a polymer obtained by (co)polymerization of (meth)acrylic acid or a vinyl phenol or the like, which is obtained by subjecting another compound having an active energy ray-reactive functional group to a graft reaction (copolymer type).

An acid anhydride addition reaction type compound having a carboxyl group, and specific examples thereof include pentaerythritol triacrylate acid modified product, acid modified phenol novolac type epoxy (meth) acrylate, and acid modified cresol novolac type epoxy. Base (meth) acrylate, acid modified trihydroxyphenylmethane epoxy (meth) acrylate, acid modified dicyclopentadiene phenol type epoxy (meth) acrylate, acid modified double Phenol A type epoxy (meth) acrylate, acid modified bisphenol F type epoxy (meth) acrylate, acid modified phenol type epoxy (meth) acrylate, acid modified double Phenol A phenolic epoxy (meth) acrylate, acid modified epoxy group (meth) acrylate containing naphthalene skeleton, acid modified glyoxal type epoxy (meth) acrylate, acid modification A heterocyclic epoxy group (meth) acrylate or the like.

The acid anhydride to be used herein is not particularly limited as long as it is a compound having an acid anhydride structure in the molecule, but is preferably succinic anhydride, phthalic anhydride, or tetrahydrogen which is excellent in alkaline aqueous solution developability, heat resistance, and hydrolysis resistance. Indane anhydride, hexahydrophthalic anhydride, itaconic anhydride, 3-methyl-tetrahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, trimellitic anhydride, or maleic anhydride are particularly preferred.

Specific examples of the copolymer type include, for example, a (co)polymer obtained by (co)polymerizing (meth)acrylic acid containing a carboxylic acid or a vinylphenol having a phenol group alone or in combination with another monomer. A glycidyl (meth)acrylate or an isocyanatoethyl (meth)acrylate is grafted to introduce an active energy ray-reactive functional group.

The acid anhydride addition molding and the copolymer type may be suitably used depending on the application or the development form. However, since the acidity is imparted to the resin and the developability is exhibited by the alkaline aqueous solution, the purpose of the present invention is In terms of these, they can be used equally.

In particular, in applications requiring hardness and long-term reliability of an electrical insulating material, it is preferable to add an acid anhydride having a high degree of freedom in resin structure before acid anhydride addition, and further, flexibility, film forming property or price is required. It is preferred to use a copolymer type.

Among them, the functional group imparting an acid value is more preferably a carboxyl group using a phenol group. This is because the phenol group is easily obtained, and a good balance between good developability and hardener stability can be sufficiently obtained.

Further, when the electrically insulating material composition shown in the present invention is used, the reactive compound (B) is a functional group derived from an epoxy resin and having both active energy ray-reactive reactions in the same molecule. Epoxy (meth) acrylates and their acid modifications are suitable.

Therefore, such a compound has excellent hardness, insulation, and heat resistance which are required as an electrical insulating material.

In the present invention, in particular, when an acid-modified bisphenol type epoxy (meth) acrylate is used as the reactive compound (B), it can be used in combination with the phosphine oxide (A) of the present invention. High flame retardancy.

The biphenol-type epoxy (meth) acrylate means an epoxy (meth) acrylate which can be derived from an epoxy resin having a biphenyl skeleton.

The active energy ray-curable resin composition of the present invention can be obtained by mixing the phosphine oxide compound (A) of the present invention with a reactive compound (B) having two or more active energy ray-reactive functional groups in one molecule. However, in the present invention, a photopolymerization initiator (C) is usually further added.

The photopolymerization initiator (C) may, for example, be benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin or the like; acetophenone, 2,2-diethoxy-2- Phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, Acetophenones such as 2-methyl-1-[4-(methylthio)phenyl]-2-(N-morpholinyl)-propan-1-one; 2-ethylhydrazine, 2- Terpenes such as tert-butyl hydrazine, 2-chloroindole, 2-pentyl hydrazine, etc.; 2,4-diethylthioxanthone, 2-isopropylthioxanthone , thioxanthones such as 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; diphenyl ketone, 4-benzylidene-4'-A Diphenyl ketones such as diphenyl sulfide and 4,4'-bismethylaminodiphenyl ketone; 2,4,6-trimethylbenzimidyl diphenylphosphine oxide, double ( A generally known radical type photoreaction initiator such as a phosphine oxide such as 2,4,6-trimethylbenzylidene)-phenylphosphine oxide.

Further, it may be used in combination with a heat-sensitive peroxide radical initiator such as an azo initiator such as azobisisobutyronitrile or a benzoyl peroxide group. The initiator may be used alone or in combination of two or more.

The active energy ray-curable resin composition of the present invention preferably contains the phosphine oxide compound (A) in an amount of from 1 to 75% by weight, preferably from 5 to 70% by weight, and the reactive compound (B). It is preferably from 10 to 85% by weight, and preferably from 3 to 80% by weight, and the photoinitiator (C) is from 0.5 to 10% by weight, and preferably from 1 to 7% by weight.

Further, in the present invention, a curing agent may be added in combination with an appropriate use. In particular, in the material for electrical insulation, the curing agent is used to react the contained acidic groups to obtain a strong cured film.

The hardener may be an epoxy compound having two or more glycidyl groups in the molecule. Specific examples thereof include a phenol novolak type epoxy resin, a cresol novolac type epoxy resin, a trishydroxyphenylmethane type epoxy resin, a dicyclopentadiene phenol type epoxy resin, and a bisphenol A type epoxy resin. Bisphenol F type epoxy resin, biphenol type epoxy resin, bisphenol A type phenolic type epoxy resin, epoxy resin containing naphthalene skeleton, glyoxal type epoxy resin, heterocyclic epoxy resin, and the like.

Examples of the phenol novolak type epoxy resin include Epiclon N-770 (manufactured by Dainippon Ink and Chemicals Co., Ltd.), DEN 438 (manufactured by Dow Chemical Co., Ltd.), and Epicoat 154 (manufactured by Oiled Shell Epoxy Co., Ltd.). , EPPN-201, RE-306 (Nippon Chemical Co., Ltd.), etc. Examples of the cresol novolac type epoxy resin include Epiclon N-695 (manufactured by Dainippon Ink and Chemicals Co., Ltd., EOCN-102S, EOCN-103S, EOCN-104S (manufactured by Nippon Kayaku Co., Ltd.), UVR-6650 (manufactured by Union Carbide Co., Ltd.), ESCN-195 (manufactured by Sumitomo Chemical Co., Ltd.), and the like.

Examples of the trihydroxyphenylmethane type epoxy resin include EPPN-503, EPPN-502H, EPPN-501H (manufactured by Nippon Kayaku Co., Ltd.), TACTIX-742 (manufactured by Dow Chemical Co., Ltd.), and Epicoat E1032H60 (oiled). Shell Epoxy (share) system, etc. Examples of the dicyclopentadiene phenol type epoxy resin include Epiclon EXA-7200 (manufactured by Dainippon Ink and Chemicals Co., Ltd.), TACTIX-556 (manufactured by Dow Chemical Co., Ltd.), and the like.

Examples of the bisphenol type epoxy resin include Epicoat 828, Epicoat 1001 (manufactured by Oiled Shell Epoxy Co., Ltd.), UVR-6410 (manufactured by Union Carbide Co., Ltd.), DER-331 (manufactured by Dow Chemical Co., Ltd.), YD- 8125 (made by Toho Chemical Co., Ltd.), NER-1202, NER-1302 (made by Nippon Chemical Co., Ltd.), bisphenol A type epoxy resin, UVR-6490 (manufactured by Union Carbide Co., Ltd.), YDF-8170 (Dongdu Chemical Co., Ltd.) Bisphenol F type epoxy resin such as NER-7403 or NER-7604 (manufactured by Nippon Chemical Co., Ltd.).

Examples of the bisphenol type epoxy resin include a biphenol type epoxy resin such as NC-3000, NC-3000-H (manufactured by Nippon Kayaku Co., Ltd.), and YX-4000 (oiled Shell Epoxy). A bisphenol-based epoxy resin, YL-6121 (manufactured by Oiled Shell Epoxy Co., Ltd.), and the like. Examples of the bisphenol A phenolic epoxy resin include Epiclon N-880 (manufactured by Dainippon Ink and Chemicals Co., Ltd.) and Epicoat 157S75 (manufactured by Oiled Shell Epoxy Co., Ltd.).

Examples of the epoxy resin containing a naphthalene skeleton include, for example, NC-7000 (manufactured by Nippon Kayaku Co., Ltd.) and EXA-4750 (manufactured by Dainippon Ink Chemicals Co., Ltd.). The glyoxal type epoxy resin may, for example, be GTR-1800 (manufactured by Nippon Kayaku Co., Ltd.). The alicyclic epoxy resin may, for example, be EHPE-3150 (manufactured by Daicel Chemical Industry Co., Ltd.). Examples of the heterocyclic epoxy resin include TEPIC (manufactured by Nissan Chemical Industries Co., Ltd.).

Among them, from the viewpoint of flame retardancy, it is particularly effective as a biphenol type epoxy resin, for example, a biphenol type epoxy resin such as NC-3000 or NC-3000-H (manufactured by Nippon Kayaku Co., Ltd.). optimal.

When the composition of the present invention contains a hardener, the content thereof is from 5 to 70% by weight in the active energy ray-curable resin composition, and preferably from about 10 to 60% by weight.

The active energy ray-curable resin composition of the present invention can be easily cured by an active energy ray. Here, specific examples of the active energy ray include electromagnetic waves such as ultraviolet rays, visible rays, infrared rays, X-rays, γ-rays, and laser rays; and particle lines such as α-rays, β-rays, and electron beams. When considering the ideal use of the present invention, it is preferred to use ultraviolet light, laser light, visible light or electron beams.

The molding material in the present invention refers to a composition which is formed by putting an uncured composition into a mold or forming a molded object into an object and causing a hardening reaction by an active energy ray, or an unhardened composition. A material used in an application in which a material such as a laser is irradiated with a focus light such as a laser to cause a hardening reaction.

Specific applications include, for example, a sheet formed into a flat shape, a sealing material for a protective member, and a micro-formed "molded" which is subjected to microfabrication to be subjected to micro-forming. A nanoimprint material and a sealing material for the purpose of requiring flame retardancy and high reliability and avoiding electrical insulation of a halogen compound.

The material for forming a film in the present invention means a material which is used for the purpose of covering the surface of the substrate. Specific uses thereof include: gravure ink, flexo ink, sllk screen ink, lithographic ink, and the like; bar paint, top coat (top coat) ), overprint varnish, clear coat and other coating materials; laminates, other adhesives for adhesives, adhesives, etc.; solder resists, resists, micromachines, etc. Agent materials, etc. In addition, a film which is formed by temporarily applying a film forming material to a release substrate and forming a film, and then bonding it to the original target substrate to form a film, is a so-called dry film, which is also a film forming material. .

In general, the insulating material composition means that after forming a film layer of the composition on a substrate, in an electronic circuit or the like, the resistance between the two places is large enough to be applied even if voltage is applied. An active energy ray-curable resin composition in a state in which an electric current is passed. For specific applications, it can be applied to an overcoat material of a flexible circuit board or an interlayer insulating film of a multilayer substrate, an insulating film for a solid element or a forming material of a passive film in a semiconductor industry, and a semiconductor integrated circuit or An interlayer insulating material such as a multilayer printed circuit board, a solder resist for protecting a substrate, or the like. Especially suitable for flexible circuit boards that require a high degree of flame retardancy.

That is to say, this is because it can not only impart a high degree of flame retardancy, but also exhibits long-term insulation stability.

The insulating material of the present invention has a portion of the substrate that must be insulated and a portion that must be turned on. Therefore, it is necessary to draw these separately in accordance with the requirements. At this time, although there is a case where a pattern is formed by a printing method, it is difficult to perform fine drawing, and it is not suitable for producing a substrate having a high density.

After the film layer of the composition is formed on the substrate, the portion is irradiated with an active energy ray such as ultraviolet rays, and then, if the active energy ray-sensitive composition is drawn by the difference in physical properties between the irradiated portion and the unirradiated portion, The unreacted portion can be removed by a solvent or the like. In the case of the so-called solvent development type, it is also possible to use the reactive compound (B) to which the acid value is not used. However, these compositions are also difficult to produce a high-density substrate because it is difficult to adjust the difference in solubility.

Therefore, a method of developing an aqueous alkaline solution using a reactive compound (B) having an acid value is generally used, and it is easy to produce a fine pattern. Therefore, in the case where the reactive compound (B) having an acid value is used for this purpose, it is preferable to form a substrate having a high density.

In addition, the active energy ray-curable resin composition of the present invention can be used for an electric ‧ electronic ‧ optical substrate such as a printed circuit board, an optoelectronic substrate, or an optical substrate, as an optical waveguide which is required to have high flame retardancy.

In particular, it is preferable to use an insulating material that requires drawing, such as a solder resist or a permanent resist, which is required to be used for the purpose of obtaining flame retardancy and reliability.

Further, in the case of the resist material used on the flexible circuit board, the phosphine oxide compound (A) and the reactive compound (B) of the present invention have an effect as a crosslinking agent because they can react in the resist material. Therefore, even if the extender pigment is not added in a large amount, it is possible to have both high flame retardancy and flexibility.

The active energy ray-curable resin composition of the present invention does not contain a halogen-based flame retardant, and has a halogen compound content of 10,000 ppm or less, and has a flame retardancy even when it is 5,000 ppm or less.

The method of forming the film is not particularly limited, and a gravure printing method such as a gravure, a gravure printing method such as a relief printing, a stencil printing method such as a stencil, a lithography method such as a lithography, a roll coater, a knife coater, and a die can be used. Various coating methods such as a coater, a vertical coater, a spin coater, and a spray coater.

The cured product of the active energy ray-curable resin composition of the present invention is obtained by irradiating an active energy ray-curable resin composition of the present invention with an active energy ray and curing it.

The multilayer material of the present invention is a material formed by forming at least two or more layers obtained by forming a film of the active energy ray-curable resin composition shown in the present invention on a substrate and curing it.

Further, in order to make the active energy ray-curable resin composition of the present invention suitable for various uses, "other components" having an upper limit of 70% by weight may be added. The other component may, for example, be an additive, a coloring material, a pigment material or the like. The following are examples of other ingredients that can be used.

As the additive, for example, a thermosetting catalyst such as melamine, a thixotropy agent such as gas phase cerium oxide (Aerosil), a silicone type, and a fluorine leveling agent can be used. Or a defoaming agent, a polymerization inhibitor such as hydroquinone or hydroquinone monomethyl ether, a stabilizer, an antioxidant, or the like.

Examples of the coloring material include organic pigments such as phthalocyanines, azos, and quinacridones, and inorganic pigments such as carbon black and the like.

Further, the pigment material can also be used without the purpose of coloring, that is, a so-called body pigment. For example, talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, cerium oxide, clay, and the like.

Further, resins (so-called inert polymers) which do not exhibit reactivity to active energy rays, such as other epoxy resins, phenol resins, amine ester resins, polyester resins, ketone-formaldehyde resins, cresol resins, and the like, may also be used. Xylene resin, diallyl phthlate resin, styrene resin, quinamine resin, natural and synthetic rubber, acrylic resin, polyolefin resin, and modified products of these resins. These resins are preferably used in an amount of 40% by weight.

Further, when the viscosity is adjusted in accordance with the purpose of use, 50% by weight of a volatile solvent may be added, and it is preferably in the range of 35% by weight.

(Example)

Hereinafter, the present invention will be described in more detail by way of examples, but the scope of the invention is not limited to the examples. In the meantime, in the examples, "parts" means parts by weight, and "%" means weight%.

The phosphine oxide compound (A) represented by the following formula (1) was synthesized in accordance with the following Synthesis Examples 1 and 2.

(wherein R represents a hydrogen atom or a methyl group).

(Synthesis Example 1-1) Synthesis of Phosphine Oxygen Compound (A-1)

In a 2L reactor equipped with a stirrer, a thermometer, and a condenser, 216.2 g (1.0 mol) of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (three-light (share) HCA) and 246.2 g of toluene were dissolved at a temperature of 80 to 90 °C. Next, 30.0 g (1.0 mol) of p-formaldehyde was slowly added thereto under stirring, and after reacting for 3 hours at a reaction temperature of 80 to 90 ° C, 246.2 g of white crystals were obtained.

Next, the obtained 246.2 g (1.0 mol) of crystals, 144.7 g (2.0 mol) of acrylic acid, 400 g of toluene, 1.5 g of methoquinone, and 14.5 g of p-toluenesulfonic acid monohydrate were charged at 105 to 110 ° C. The dehydration condensation reaction was carried out for 13 hours, and the obtained reaction liquid was washed twice with 10% sodium carbonate aqueous solution and once with 20% saline solution, and then distilled under reduced pressure to obtain 267.9 g (yield 89.2%). Light yellow liquid phosphine oxide (A-1).

The physical properties of this phosphine oxide compound (A-1) are shown below.

Viscosity (40 ° C) 6300CPS

Refractive index (20 ° C) 1.6145

H-NMR

4.80ppm=2H, 5.60ppm=1H, 6.16ppm=1H, 6.45ppm=1H, 7.24-7.93ppm=8H

(Synthesis Example 1-2) Synthesis of Phosphine Oxygen Compound (A-2)

In a 2L reactor equipped with a stirrer, a thermometer, and a condenser, 216.2 g (1.0 mol) of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (three-light (share) HCA) and 246.2 g of toluene were dissolved at a temperature of 80 to 90 °C. Next, 30.0 g (1.0 mol) of p-formaldehyde was slowly added thereto under stirring, and after reacting for 3 hours at a reaction temperature of 80 to 90 ° C, 246.2 g of white crystals were obtained.

Next, 246.2 g (1.0 mol) of the obtained crystals, 172 g (2.0 mol) of methacrylic acid, 500 g of toluene, 1.7 g of clofibrate, and 17 g of p-toluenesulfonic acid monohydrate were charged, and the mixture was subjected to 105 to 110 ° C for 13 hours. After the dehydration condensation reaction, the obtained reaction solution was washed twice with 10% aqueous sodium carbonate solution and once with 20% saline solution, and then distilled under reduced pressure to obtain 262 g (yield: 83.4%) of a pale yellow liquid phosphine. Oxygen compound (A-2).

The physical properties of this phosphine oxide compound (A-2) are shown below.

Viscosity (40 ° C) 5200CPS

Refractive index (20 ° C) 1.6078

H-NMR

1.96ppm=3H, 4.80ppm=2H, 5.60ppm=1H, 6.16ppm=1H, 7.24-7.93ppm=8H

(Comparative Synthesis Example) Compound of JP-A-2000-38398

In a 1,000-mL four-necked flask equipped with a stirrer, a thermometer, a dropping funnel, and a condenser, 106.0 g (1.0 mol) of sodium hypophosphite ‧ monohydrate salt and 30 mL of pure water, 300 mL of ethanol were charged, and 3.5 g of free was charged. A solution of the base initiator, tert-butylperoxy-2-hexanoic acid ethyl ester, dissolved in 58.1 g of allyl alcohol was allowed to react under reflux of ethanol for about 4 hours. After the completion of the dropwise addition, the mixture was aged at this temperature for 2 hours, and allowed to cool to room temperature. To the reaction liquid, a (1+1) aqueous hydrochloric acid solution was added until the pH became acidic, and sodium chloride was precipitated. After concentrating the liquid amount to 1/2, the formed sodium chloride was removed by filtration, and concentrated by an evaporator to obtain 128.6 g of a colorless transparent liquid. The analysis results are as follows: The product is 3-hydroxypropylphosphonic acid. The yield was 97.1%. 105.9 g (0.8 mol) of the obtained 3-hydroxypropylphosphonic acid was placed in a 500 mL four-necked flask, and the temperature was raised to 100 ° C under a nitrogen gas stream. Next, a solution obtained by dissolving 3.17 g of a radical initiator third butyl peroxide in a dropping funnel in 55.7 g (0.96 mol) of allyl alcohol was dropped over about 4 hours. After the completion of the dropwise addition, the mixture was aged at this temperature for 2 hours. After cooling, after the excess allyl alcohol was completely distilled off by a vacuum pump, 147.0 g of a yellowish viscous liquid was obtained. As a result of analysis, the product was bis(3-hydroxypropyl)phosphonic acid in a yield of 97.7%.

In a reactor equipped with a reflux condenser, a stirrer, a thermometer, a temperature regulator and a water separator, 182.2 g (1.0 mol) of bis(3-hydroxypropyl)phosphonic acid was charged as an alcohol compound, and 172.9 g (2.4 mol). Acrylic acid as a monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule, 3.46 g of p-toluenesulfonic acid monohydrate as an acid catalyst, 1.31 g of hydroquinone as a thermal polymerization inhibitor, 124.3 g of toluene and 53.3 g As a reaction solvent, cyclohexane is reacted at a reaction temperature of 95 to 105 ° C while azeotropically distilling the produced water and the solvent, and is a reaction end point when the produced water reaches 25.3 ml. 430.0 g of toluene and 181.2 g of cyclohexane were added to the reaction mixture, and after neutralizing with a 25% aqueous solution of caustic soda, it was washed three times with 100 g of 15% saline. After the solvent was distilled off under reduced pressure, 220.7 g (yield: 70.2%) of bis(3-propenyloxypropyl)phosphonic acid (Comparative Compound 1) was obtained.

(Examples 1 to 2, Comparative Examples 1 to 3) Modulation and evaluation of the composition for solder resist

The reactive compounds (A-1), (A-2) and (Comparative Compound 1) of the present invention obtained in the above Synthesis Examples and Comparative Synthesis Examples were mixed as shown in Table 1, and the requirements were combined with three After kneading by a three roll mill, the active energy ray-curable resin composition of the present invention is obtained. This composition was coated on a copper circuit printed substrate by screen printing to have a thickness of 25 μm, and the film was dried by a hot air dryer at 80 ° C for 60 minutes. After cooling to room temperature, the absorbent cotton was attached to the coating film, and the tackiness was observed. Next, after the mask film on which the pattern was drawn was adhered, ultraviolet rays were irradiated by an ultraviolet exposure apparatus (manufactured by USHIO: 500W Multilight). Next, a 1% sodium carbonate aqueous solution (temperature: 30 ° C) was used as a developing solution, and development was carried out by spraying (spraying pressure: 0.2 MPa) for 60 seconds. After washing with water, heat treatment was carried out for 60 minutes in a hot air dryer at 150 ° C to obtain a cured product of the present invention. As described later, tests for adhesion, sensitivity, developability, hardenability, flame retardancy, HAST resistance, and flexibility were performed. The results are shown in Table 2. The test methods and evaluation methods are as follows.

(sensitivity evaluation)

The sensitivity is the exposed portion of the step tablet that has been penetrated, and it is determined that the concentration portion until that step remains in development. If the order (value) is larger, it can be determined as high sensitivity (unit: order) depending on the concentration portion of the tablet. Meanwhile, for those who do not develop and cannot measure the sensitivity, they are indicated by ×.

(developability evaluation)

The developability is the time (i.e., seconds) at which the development of the pattern portion is developed until the pattern shape is completely developed, that is, the development time (unit: second) is evaluated. For those who do not develop within 60 seconds, they are indicated by ×.

(hardenability assessment)

The hardenability evaluation indicates the pencil hardness of the cured film after heating at 150 °C.

The evaluation method is based on JIS K5600-5-4:1999.

(adhesion assessment)

The adhesion evaluation was carried out according to JIS K5400, and the cured film was made into 100 1 mm checkerboard sheets, and the peeling test was performed with a tape (R). After observing the peeling state of the checkerboard, the evaluation was performed on the basis of the following criteria.

○...will not be stripped

×...will be stripped

(flame retardancy assessment)

On a halogen-free flame-retardant substrate RO-67G (0.2 mmt material) manufactured by Hitachi Chemical Co., Ltd., a screen coating was used to perform total coating of 15 μm on each single side, and then ultraviolet curing was performed using a high-pressure mercury lamp of 80 W/cm three lamps. The burning time of this test piece was measured according to the UL94 flammability test, which is a flame retardancy evaluation.

◎: equivalent to UL V-0

(The total burning time when the five test pieces are each fired twice is 50 seconds or less)

○: Equivalent to UL V-1

(The total burning time of the five test pieces when they are fired twice is 50 to 250 seconds)

×: no self-digestibility

(HAST resistance)

On the FR-4 substrate on which the comb-shaped electrode (line/space = 50 μm / 50 μm) was formed, the active energy ray-curable resin composition was printed in its entirety, exposed to light, developed, and then thermally cured to prepare an evaluation substrate. . The evaluation substrate was placed in a high-temperature and high-humidity bath at a temperature of 130 ° C and 85% humidity, and subjected to a HAST test for 168 hours after passing a voltage of 5 V. The electrical insulation properties after the HAST test were measured.

○: 1010 Ω or more

△: 1010 to 108 Ω

×: below 108 Ω

(Softness) The cured film was bent to 180 degrees and observed. Use the following benchmarks.

○: no crack on the film surface

×: film surface rupture

Acid-modified polyfunctional bisphenol F-type epoxy acrylate (average number of functional groups 5, acid value of solid content 100mg ‧ KOH / g)

*2 DPCA-60 Nippon Chemical Co., Ltd. acrylate monomer

Ε-caprolactone modified dipentaerythritol hexaacrylate

*3 Irg. 907 Ciba Specialty Chemicals Co., Ltd. Photopolymerization initiator

2-methyl-(4-(methylthio)phenyl)-2-(N-morpholinyl)-1-propane

*4 DETEX-S Nippon Chemical Co., Ltd. Photopolymerization initiator

2,4-diethylthioxanthone

*5 NC-3000H Nippon Chemical Co., Ltd. Epoxy resin

Bisphenol type epoxy resin

*6 BYK-354 BYK Chemical Co., Ltd.

*7 KS-66 Shin-Etsu Chemicals Defoamer

*8 CA Osaka Organic Co., Ltd.

From the above results, it is understood that the phosphoric acid type compound having a vinyl unsaturated group as in Comparative Example 1 has poor adhesion and reacts with the epoxy compound in the resin composition, so that development is impossible. At the same time, the phosphoric acid type compound which was crosslinked with the epoxy resin in Comparative Example 1 was a compound which hydrolyzed under high heat and humidity conditions, and was therefore inferior in reliability tests such as HAST resistance. Further, when the reactive compound (A) was cured alone as in Comparative Example 2, a tough cured film could not be obtained. When the reactive compound (A) was not contained as in Comparative Example 3, since the coating film had no self-ignition property, flame retardancy could not be obtained.

In contrast, in Examples 1 and 2, since the reactive compounds (A) and (B) do not have an acidic group, they are clearly characterized in that they have good adhesion and are highly flame retardant. Developability or HAST resistance is also excellent.

Therefore, the active energy ray-curable resin composition of the present invention has high flame retardancy and is excellent in light sensitivity, and the cured film can sufficiently satisfy the developability, curability, adhesion, HAST resistance, flexibility, etc., and is particularly suitable. It is a photosensitive resin composition for a flexible printed circuit board.

(Examples 3 to 5) improve flame retardancy by combination with a bisphenol type epoxy acrylate resin

The use of the biphenol type epoxy acrylate as the reactive compound (B) and the case of improving the flame retardancy by the combination with the epoxy resin used as the hardener were evaluated along with the above Examples 1 to 2. .

When compared with the above Examples 1 to 2, since the evaluation of the flame retardancy was performed under more severe conditions, the coating substrate was changed from RO-67G to a polyimide film having a thickness of 25 μm. Others conduct the same test. The judgment criteria are the same as those of the above-described Embodiments 1 to 2. The number of seconds in the brackets behind the mark is the time taken until the fire is extinguished. The compounding ratio of the active energy ray-curable resin composition is shown, for example, in Table 3, and the evaluation of the flame retardancy is shown in Table 4. The reference value from Example 1 is also noted together.

2,4-diethylthioxanthone

*5 NC-3000H Nippon Chemical Co., Ltd. Epoxy resin

Bisphenol type epoxy resin

*6 BYK-354 BYK Chemical Co., Ltd.

*7 KS-66 Shin-Etsu Chemicals Defoamer

*8 CA Osaka Organic Co., Ltd.

*9 ZCR-1361 Nippon Chemical Co., Ltd. Acrylate oligomer acid modified polyfunctional phenolic epoxy acrylate (average number of functional groups 4, acid value of solid content 100mg ‧ KOH / g)

*10 EPPN-201 Nippon Chemical Co., Ltd. Epoxy Resin

Phenolic novolac epoxy resin

From the above results, it is understood that the biphenol-type epoxy acrylate is used as the reactive compound (B) and the phenol-based epoxy resin as a curing agent is used in combination, so that a particularly excellent flame retarding effect can be exhibited.

(Examples 6 to 9) Exploring the difference in developability due to the difference in acid value

The change in developability due to the difference in the acid value of the bisphenol type epoxy acrylate as the reactive compound (B) was evaluated along with the examples of the foregoing Examples 1 to 2.

10 g of the phosphine oxide compound (A-1) prepared in Synthesis Example 1 and 47 g of a biphenol-type epoxy acrylate having a respective acid value (all ZCR series manufactured by Nippon Kayaku Co., Ltd.) were used as Reactive compound (B) with an acid value in the table, 6 g of DPCA-60 as a reactive compound (B) not given an acid value, 2.5 g of Irgacure 907 (manufactured by Ciba Specialty Chemicals Co., Ltd.), 1 g of DETX -S (manufactured by Nippon Kayaku Co., Ltd.) as a photopolymerization initiator, 18 g of a biphenolic epoxy resin NC-3000-H (manufactured by Nippon Kayaku Co., Ltd.) as a curing agent, 1 g of melamine as a thermosetting catalyst, and 15 g of barium sulfate As a body pigment, after being kneaded by a three-roll mill, a solder resist composition is obtained.

This composition was applied to a polyimide film coated with a copper foil in a stencil, and dried at 80 ° C for 30 minutes in such a manner that the film thickness at the time of drying was 25 μm.

The obtained coating film was adhered to a mask film on which a pattern was drawn, and ultraviolet rays were irradiated by an ultraviolet exposure apparatus (manufactured by USHIO: 500 W Multilight). Subsequently, a 1% sodium carbonate aqueous solution (30 ° C) was used as a developing solution, and development was carried out by spraying (spray pressure: 0.2 MPa) for 60 seconds. After washing with water, heat treatment was carried out for 60 minutes in a hot air dryer at 150 ° C to obtain a cured product of the present invention. Tests for developability, resolution, flame retardancy, and HAST resistance were carried out as described later. These results are shown together with the compounding ratio of the resin composition in Table 5. Meanwhile, in addition to understanding the image, other test methods and evaluation methods are in accordance with the test methods shown in Examples 1 to 2.

Resolution evaluation: Evaluation was performed in a developing state having a line-space drawing portion of 50 μm.

If the acid value is higher than the desired range, the fine pattern is lost and it is difficult to form a fine pattern. Further, when the acid value is too low, the developability of the boundary portion is deteriorated, and similarly, it is difficult to form a fine pattern.

From the above results, it is understood that when the reactive compound (B) having an acid is used as the developable photosensitive composition, a suitable acid value range exists.

(Examples 10 to 11, Comparative Example 4) Evaluation of Reactive Compound (B) Copolymerized with Acid

The phosphine oxide compound (A-1) prepared in the amounts of Synthesis Example 1 and the amount of methacrylic acid as the reactive compound (B) in the table were used in the examples of Examples 1 to 2 described above. Glycidyl methacrylate grafting compound of methyl methacrylate copolymer (R-178X, manufactured by Nippon Chemical Co., Ltd., weight average molecular weight: 15,000, acid value: 60 mgKOH/g) or grafted with polyvinylphenol glycidyl methacrylate Compound (manufactured by Nippon Chemical Co., Ltd., R-777X, weight average molecular weight: 5,000, acid value: 90 mgKOH/g), 30 g of methyl isobutyl ketone as a solvent, and 2.5 g of Irgacure 907 as a photopolymerization initiator (Ciba essence) The company's system), 1 g of DETX-S (manufactured by Nippon Kayaku Co., Ltd.) was mixed to obtain a resist composition.

This composition was applied on a copper foil-attached polyimide film in a stencil to be dried in an oven at 80 ° C for 30 minutes so that the film thickness at the time of drying became 25 μm.

The obtained coating film was adhered to a mask film on which a pattern was drawn, and ultraviolet rays were irradiated by an ultraviolet exposure apparatus (manufactured by USHIO: 500 W Multilight). Subsequently, a 1% sodium carbonate aqueous solution was used as a developing solution (30 ° C), and development was carried out by spraying (spraying pressure: 0.2 MPa) for 60 seconds. After washing with water, heat treatment was carried out for 60 minutes in a hot air dryer at 150 ° C to obtain a cured product of the present invention. As described later, tests for developability and flame retardancy were carried out. These results are shown in Table 6 together with the compounding ratio of the resin composition.

From the above results, it is understood that when a copolymerized acid-reactive compound (B) is used, it is also the same as the acid-modified epoxy acrylate, and is combined with the phosphine oxide (A-1). It shows good developability and flame retardancy.

(Examples 12 to 15, Comparative Example 5) Modulation and evaluation of flame retardant coating compositions

10 g of the phosphine oxide compound (A-1) prepared in Synthesis Example 1, 30 g of the compound in the table as the reactive compound (B), and 10 g of the acrylic polymer as an inert resin (Dianal BR-80 manufactured by Mitsubishi) 2 g of Irgacure 184 (manufactured by Ciba Specialty Chemicals Co., Ltd.) as a photopolymerization initiator, 10 g of methyl isobutyl ketone as a diluent solvent, and 0.5 g of Shin-Etsu Chemical Co., Ltd. as a surface tension adjuster were thoroughly stirred until well mixed.

The thus obtained coating composition was coated on a 25 μm polyethylene terephthalate film by a bar coater so as to be about 20 μm, and the solvent was volatilized in an oven at 80 °C.

Thereafter, the coating film was cured by irradiation with ultraviolet rays of 600 mJ/cm 2 to obtain a two-layer material composed of a polyethylene terephthalate film and a coating composition.

The pencil hardness (according to JIS K5600-5-4:1999) and flame retardancy of the obtained cured film were evaluated (confirmed whether or not self-extinguishing property was observed, the sample was evaluated and evaluated under the conditions of Examples 1 to 2) and the flame retardant after the weathering test. Sex (the same evaluation method).

The flame retardancy after the weathering test was performed by spraying 96 hours of pure water on the surface of the obtained coating layer, and similarly, the two-layer material after the weathering test was prepared to prepare a sample, and then the flame retardancy evaluation was performed. These results are shown together with the compounding ratio of the resin composition in Table 7.

(hexafunctional)

R-128H: Glycerol monophenyl ether monoacrylate (monofunctional) made from Nippon Kayaku

From the above results, it is understood that the coating material obtained from R-128H having one reactive functional group in one molecule has a low flame retardancy after the weather resistance test is carried out. It is presumed that this is due to the loss of the flame retardant phosphine oxide (A-1), which causes a decrease in flame retardancy.

Claims (12)

An active energy ray-curable resin composition characterized by comprising: a phosphine oxide compound (A) represented by the following formula (1), and an acid value of 30 to 150 mg. a reactive compound (B) having two or more (meth)acryl fluorenyl groups in one molecule of KOH/g, and a photopolymerization initiator (C); (wherein R represents a hydrogen atom or a methyl group). The active energy ray-curable resin composition according to claim 1, wherein the reactive compound (B) is a (meth) acrylate. The active energy ray-curable resin composition according to claim 1, wherein the reactive compound (B) is an epoxy group-containing (meth) acrylate. The active energy ray-curable resin composition of the first aspect of the invention, wherein the reactive compound (B) is an acid-modified phenol type epoxy (meth) acrylate. The active energy ray-curable resin composition according to any one of claims 1 to 4, which further comprises an epoxy resin as a curing agent. An active energy ray-curable resin composition according to claim 5, wherein the curing agent is a bisphenol type epoxy resin. Active energy ray hardening according to any one of claims 1 to 4 A resin composition which is a material for molding. The active energy ray-curable resin composition according to any one of claims 1 to 4, which is a material for forming a film. The active energy ray-curable resin composition according to any one of claims 1 to 4, which is an electrical insulating material composition. The active energy ray-curable resin composition of claim 9, wherein the electrically insulating material composition is a developable photosensitive solder resist composition. A method for producing a cured product, which is an active energy ray-curable resin composition according to any one of the first to sixth aspects of the invention. A multilayer material having a layer of a cured product obtained by irradiating an active energy ray-curable resin composition of any one of the above-mentioned claims 1 to 6 with an active energy ray.