JP5384149B2 - Active energy ray-curable resin composition using reactive compound having flame retardancy and cured product thereof - Google Patents

Description

 The present invention relates to an active energy ray-curable resin composition using a phosphine oxide compound, which is a reactive compound that can be polymerized to various polymer materials, for the purpose of making the polymer material flame-retardant. Examples of the application include film forming materials, solder resists in the production of printed (wiring circuit) substrates, other resist materials capable of alkali development, adhesives, lenses, displays, optical fibers, optical waveguides, holograms, and the like.

  Attempts to impart flame retardancy to molded articles, film-forming materials, etc. are widely performed. Conventionally, flame retardant materials using halogen compounds typified by bromine compounds have been widely used, but these have come to be avoided in recent years due to increasing environmental problems. As an alternative to these, studies are being made on flame retardant materials using phosphorus compounds.

  In general, phosphorus compounds are used by simply adding them to the resin composition, etc., so there is a possibility that a uniform flame retardant effect may not be obtained when the resin composition etc. is cured or bleed out over time. There is a risk that the thermal, electrical, mechanical properties, etc. of the object may deteriorate. Therefore, in order to solve these problems, development of a flame retardant having reactivity capable of incorporating a phosphorus compound into a skeleton such as a resin is required.

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

（式中、Ｒ’_１、Ｒ’_２は炭素数１〜１０の直鎖または分岐状のアルキレン基を表わし、Ｒ_３、Ｒ_４は水素原子又はメチル基を表わす。Ｒ’_１、Ｒ’_２は、互いに同一であっても、異なっていてもよい。）

(In the formula, R ′ ₁ and R ′ ₂ represent a linear or branched alkylene 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 as or different from each other.)

In the case of having a phosphoric acid type structure represented by the formula (2), an adverse effect due to this acidic group is observed. For example, acidic groups have been problematic in the long-term durability of cured products because they promote hydrolysis or promote corrosion of substrates such as metals. In particular, when it is used as a permanent resist for a circuit board, it is used for the purpose of protecting the circuit for a long period of time, so the presence of such acidic groups is a serious problem.
Furthermore, in applications such as solder resists that require development, an epoxy compound or the like is generally mixed in the resin composition as a curing agent. In this case, if the composition contains a lot of acidic groups, the storage stability after mixing the two liquids and the coating, the reaction of the curing agent is accelerated in the process until development, and development is impossible. There was a problem.
In addition, the phosphoric acid type compound cross-linked with the epoxy resin is hydrolyzed under high heat and humidity conditions, and there are problems in reliability tests such as electrical characteristics.

On the other hand, a technique is disclosed in which an ethylenically unsaturated group is introduced by interposing an epoxy group in a phosphine oxide having a hydroxyl group excellent in heat resistance and moisture resistance. (Patent Document 2)
However, when cured with active energy rays, there is a problem that the sensitivity does not appear and the resin composition bleeds out.

In order to impart flame retardancy to the resist material, it is a well-known general technique to add a so-called flame retardant and an inorganic extender pigment, but a reactive flame retardant is not common.
Furthermore, since a resist material for use in a flexible circuit board is required to have high flexibility, it is difficult to add flame retardant by adding more extender pigments.
Moreover, although it describes regarding the curable resin composition using the reactive compound (A) in patent document 3, it does not describe including the other reactive compound (B), and as cured | curing material There is no description about flame retardancy, heat resistance, moisture resistance and electrical insulation.

JP 2000-38398 A JP 2004-143286 A Japanese Patent No. 3454544

The photosensitive phosphine oxide compound is required to have a thermal stability that allows sufficient alkali development even in a photosensitive resin composition containing an epoxy resin, even if it is heated and dried before exposure.
In addition, a phosphoric acid type compound cross-linked with an epoxy resin is required to be a compound having excellent heat resistance and moisture resistance, which does not hydrolyze under high heat and humidity conditions and does not cause problems in reliability tests such as electrical characteristics. . Furthermore, there is a need for a flame retardant that can exhibit a flame retardant effect without being added in large amounts.
The present invention does not have these problems, is cured by active energy rays such as ultraviolet rays, has thermal stability, is excellent in heat resistance and moisture resistance, has good electrical insulation, and is flame retardant even when added in a small amount. An effect can be expressed.

In view of the above problems, the present inventors have conducted extensive research on a phosphine oxide compound having a novel photosensitive group and a photosensitive resin composition using the same, and as a result, an unsaturated group-containing compound having a specific structure and The present inventors have found that the composition solves the above problems and have completed the present invention. That is, the present invention relates to the following (1) to (13).

（式中、Ｒは水素原子又はメチル基を示す。）
で表わされるホスフィンオキサイド化合物（Ａ）、１分子内に２個以上の活性エネルギー線反応性官能基を有する反応性化合物（Ｂ）及び光重合開始剤（Ｃ）を含むことを特徴とする活性エネルギー線硬化型樹脂組成物。 (1) Following formula (1)

(In the formula, R represents a hydrogen atom or a methyl group.)
An active energy comprising a phosphine oxide compound (A) represented by the formula (A), a reactive compound (B) having two or more active energy ray-reactive functional groups in one molecule, and a photopolymerization initiator (C). A linear curable resin composition.

(2) The active energy ray-curable resin composition according to (1), wherein the reactive functional group of the reactive compound (B) is (meth) acrylates.
(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 a carboxyl group-containing epoxy (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 (meth) acrylate.
(6) The active energy ray-curable resin composition according to any one of (1) to (5), which further contains an epoxy resin as a curing agent.
(7) The active energy ray-curable resin composition according to (6), wherein the curing agent is a biphenol type epoxy resin.
(8) The active energy ray-curable resin composition according to any one of (1) to (6), which is a molding material.
(9) The active energy ray-curable resin composition according to any one of (1) to (6), which is a film forming material.
(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, wherein the active energy ray-curable resin composition according to any one of (1) to (7) is irradiated with active energy rays.
(13) A multilayer material having a cured product layer obtained by irradiating the active energy ray-curable resin composition according to any one of (1) to (7) with active energy rays.

  The cured product of the active energy ray-curable resin composition of the present invention sufficiently satisfies the adhesion to metal and the flame retardancy of the resin, is excellent in heat resistance and moisture resistance, has good electrical insulation, and lasts for a long time. It is a highly reliable material. Therefore, the photosensitive resin composition is used for film forming materials, solder resists for the production of printed (wiring circuit) substrates, resist materials capable of alkali development, adhesives, lenses, displays, optical fibers, optical waveguides, holograms, etc. Suitable as an ingredient.

  Details of the present invention will be described 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 formula (3) is obtained by reacting formaldehyde with a phosphorus-containing compound having at least one active hydrogen in the molecule as represented by formula (4). This compound can use a commercial item, for example, the brand name HCA by Sanko Co., Ltd. is mentioned.

  The monocarboxylic acid compound having an ethylenically unsaturated group in the molecule for producing the phosphine oxide compound (A) of the present invention is reacted in order to impart reactivity to active energy rays. Specific examples include acrylic acid and methacrylic acid.

The phosphine oxide compound (A) of the present invention can be produced by a method of dehydrating and condensing an alcohol compound of the formula (3) and a monocarboxylic acid compound having an ethylenically unsaturated group in the molecule in the presence of an acid catalyst.
The acid catalyst used can be arbitrarily selected from known ones such as sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid, and the amount used is 0.1 to 10 mol%, preferably (meth) acrylic acid. Is 1 to 5 mol%.

  An azeotropic solvent can be used to distill off the water produced by the reaction. The azeotropic solvent here has a boiling point of 60 to 130 ° C. and can be easily separated from water, and in particular, aliphatic hydrocarbons such as n-hexane and n-heptane, and aromatics such as benzene and toluene. The use of alicyclic hydrocarbons such as aromatic hydrocarbons and cyclohexane is preferred. The amount used is arbitrary, but is preferably 10 to 70% by weight based on the reaction mixture.

  The reaction temperature may be in the range of 60 to 130 ° C, but is preferably 75 to 120 ° C from the viewpoint of shortening the reaction time and preventing polymerization.

  A commercially available (meth) acrylic acid or the like used as a raw material is usually already added with a polymerization inhibitor such as p-methoxyphenol, but a polymerization inhibitor may be added again during the reaction. Examples of such polymerization inhibitors include hydroquinone, p-methoxyphenol, 2,4-dimethyl-6-t-butylphenol, 3-hydroxythiophenol, p-benzoquinone, 2,5-dihydroxy-p-benzoquinone, Phenothiazine and the like are preferable. The amount used is 0.01 to 1% by weight based on the reaction raw material mixture.

  By using the reactive compound (B) having two or more active energy ray reactive functional groups in one molecule that can be used in the present invention in combination with the phosphine oxide compound (A) used in the present invention, A tough cured product can be obtained while having flame retardancy. By having two or more active energy ray reactive functional groups in one molecule, in combination with the monofunctional phosphine oxide compound (A), a strong cross-linked structure is formed, and the phosphine oxide compound (A) Suppresses the hydrolysis behavior and bleed-out, and can bring out stable flame retardancy and reliability in the long term.

  The active energy ray-reactive functional group shown in the present invention refers to a functional group that can react with active energy rays to form a cross-linked bond. For example, as a functional group that reacts with radicals generated by irradiation with active energy rays, polymerizable unsaturated bonds such as a (meth) acryl group, a vinyl group, and a vinyl ether group can be given. Moreover, unsaturated ether groups, such as cyclic ether groups, such as an epoxy group and an oxetane group, a vinyl ether group, etc. which react with the cation produced by active energy ray irradiation are mentioned.

  Examples of the reactive compound (B) having two or more (meth) acryl groups include butanediol di (meth) acrylate, hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and nonanediol di (meth). ) Acrylate, glycol di (meth) acrylate, diethylene di (meth) acrylate, polyethylene glycol di (meth) acrylate, tris (meth) acryloyloxyethyl isocyanurate, polypropylene glycol di (meth) acrylate, adipic acid epoxy di (meth) acrylate, Bisphenol ethylene oxide di (meth) acrylate, hydrogenated bisphenol ethylene oxide (meth) acrylate, bisphenol di (meth) acrylate, ε-caprolactone modified hydride Xipivalic acid neopent 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, triethylolpropane tri (meth) acrylate and its ethylene oxide adduct, pentaerythritol tri (meth) acrylate and its ethylene oxide adduct, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) ) And (meth) acrylic acid esters such as ethylene oxide adducts thereof.

In addition to this, urethane (meth) acrylates having a plurality of (meth) acrylic groups and urethane bonds in the same molecule, as well as polyester (meth) having a plurality of (meth) acrylic groups and ester bonds in the same molecule. Examples thereof include epoxy (meth) acrylates derived from acrylates and epoxy resins and having a plurality of (meth) acryl groups, and reactive oligomers in which these bonds are used in combination.
Furthermore, as will be described later, a reactive compound (B) having two or more active energy ray-reactive functional groups imparted with an acid value is also included.

  The urethane (meth) acrylates shown in the present invention are a reaction product of a hydroxyl group-containing (meth) acrylate, a polyisocyanate, and other alcohols used as necessary. For example, hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, glycerin (meta) such as glycerin mono (meth) acrylate and glycerin di (meth) acrylate ) Sugars (meth) acrylates such as acrylates, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate , Isophorone diisocyanate, norbornene diisocyanate, xylene diisocyanate, hydrogenated xylene diisocyanate , Dicyclohexane diisocyanate, and their isocyanurate, by reacting polyisocyanates such as buret reactants, the urethane (meth) acrylates.

  The epoxy (meth) acrylates shown in the present invention are carboxylate compounds of a compound having an epoxy group and (meth) acrylic acid. For example, phenol novolac type epoxy (meth) acrylate, cresol novolac type epoxy (meth) acrylate, trishydroxyphenylmethane type epoxy (meth) acrylate, dicyclopentadienephenol type epoxy (meth) acrylate, bisphenol-A type epoxy (meth) Acrylate, bisphenol-F type epoxy (meth) acrylate, biphenol type epoxy (meth) acrylate, bisphenol-A novolac type epoxy (meth) acrylate, naphthalene skeleton-containing epoxy (meth) acrylate, glyoxal type epoxy (meth) acrylate, heterocyclic ring Examples thereof include epoxy (meth) acrylates and the like, and anhydride-modified epoxy acrylates thereof.

  Examples of the compound (B) having a vinyl group include vinyl ethers such as ethylene glycol divinyl ether. Examples of styrenes include divinylbenzene. Other vinyl compounds include triallyl isocyanurate and trimethallyl isocyanurate.

  The compound having a cyclic ether group is not particularly limited as long as it is generally a compound having an epoxy group or an oxetane group. For example, alkyl diglycidyl ethers such as butyl diglycidyl ether, bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (“Syracure UVR-6110” manufactured by Union Carbide, etc.) ), 3,4-epoxycyclohexylethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide (such as “ELR-4206” manufactured by Union Carbide), limonene dioxide (“Celoxide 3000” manufactured by Daicel Chemical Industries, Ltd.) Etc.), allyl cyclohexylene dioxide, 3,4, -epoxy-4-methylcyclohexyl-2-propylene oxide, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy ) Cyclohexane-m-dioxane, bis (3,4-epoxycyclohexyl) adipate (such as “Syracure UVR-6128” manufactured by Union Carbide), bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4 And epoxy (cyclohexyl) ether, bis (3,4-epoxycyclohexylmethyl) ether, bis (3,4-epoxycyclohexyl) diethylsiloxane, and the like.

  Reactive compound (B) having two or more active energy ray-reactive functional groups in one molecule even when both radical and cationic functional groups such as glycidyl (meth) acrylate are contained in one molecule. Are treated as

  Of these, the reactive compound (B) is most preferably a compound having a (meth) acrylic group which is a radical curable type. In the case of the cation type, since the epoxy reacts with a slight acid derived from the phosphine oxide compound (A), it is necessary to use a two-component mixed type.

  Next, an acid value can also be imparted to the reactive compound (B) having two or more active energy ray reactive functional groups shown in the present invention. Thus, the reactive compound (B) having an acid value is used in applications where the curable resin composition is subjected to photo-patterning, that is, a patterning is performed on the exposed and non-exposed areas by a developing method using a crosslinking reaction by light. By using this, the non-exposed part can be eluted with an alkaline aqueous solution.

  In this case, the acid value of the reactive compound (B) is preferably 30 to 150 mg · KOH / g, and more preferably 60 to 110 mg · KOH / g. When the acid value at this time is less than 30 mg · KOH / g, more preferably less than 60 mg · KOH / g, the developability in the aqueous alkaline solution of the active energy ray-curable resin composition of the present invention is remarkably lowered. There is a risk that it will not be possible. On the other hand, when the acid value exceeds 150 mg · KOH / g, more preferably 110 mg · KOH / g, the developability becomes too high and patterning becomes difficult.

  The reactive compound (B) imparted with an acid value is a compound having both an acidic group such as a carboxyl group and a phenol group. Examples thereof include so-called acid-modified epoxy (meth) acrylate and acid-modified urethane (meth) acrylate. These include those obtained by adding an acid anhydride to the reactive compound (B) having a hydroxyl group and introducing an acid group (acid anhydride addition reaction type), monomers having an acid group, such as (meta ) A polymer obtained by (co) polymerizing acrylic acid, vinylphenol or the like with another compound having an active energy ray-reactive functional group (copolymer type).

  Specific examples of the acid anhydride addition reaction type compound having a carboxyl group include pentaerythritol triacrylate modified acid, acid modified phenol novolac type epoxy (meth) acrylate, acid modified cresol novolac type epoxy (meth). Acrylate, acid-modified trishydroxyphenylmethane type epoxy (meth) acrylate, acid-modified dicyclopentadienephenol type epoxy (meth) acrylate, acid-modified bisphenol-A type epoxy (meth) acrylate, acid-modified bisphenol-F type epoxy (meth) Acrylate, acid-modified biphenol type epoxy (meth) acrylate, acid-modified bisphenol-A novolak type epoxy (meth) acrylate, acid-modified naphthalene skeleton-containing epoxy (meth) acrylate, acid-modified glio Sar-type epoxy (meth) acrylate, acid-modified heterocyclic epoxy (meth) acrylate.

  The acid anhydride used here is not particularly limited, and any compound having an acid anhydride structure in the molecule can be used, but it is excellent in alkaline aqueous solution developability, heat resistance, hydrolysis resistance, and the like. Succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, itaconic anhydride, 3-methyl-tetrahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, trimellitic anhydride or maleic anhydride Particularly preferred.

Specific examples of the copolymer type include (meth) acrylic acid containing carboxylic acid and vinylphenol having a phenol group alone or (co) polymerized with other monomers. Examples of the polymer include those obtained by graft reaction using, for example, glycidyl (meth) acrylate or isocyanatoethyl (meth) acrylate to introduce an active energy ray-reactive functional group.

The acid anhydride addition type and the copolymer type are appropriately used depending on the application and development form, respectively, but in any case, the acid value is imparted to the resin to exhibit the developability with alkaline water, For this purpose, both can be used equally.
Especially for applications that require hardness and long-term reliability such as electrical insulation materials, the acid anhydride addition type with a high degree of freedom in the resin structure prior to acid anhydride addition is suitable, and flexibility, film-forming properties, and cost are reduced. If desired, a copolymer type is preferred.

  Among these, as the functional group for imparting an acid value, a carboxyl group is most preferably used rather than a phenol group. This is because the availability, good developability, and stability of the cured product are well balanced.

Further, when used as the electrical insulating material composition shown in the present invention, the reactive compound (B) is an epoxy (meth) derived from an epoxy resin and having a functional group capable of acting on active energy rays in the same molecule. Acrylates and acid-modified products thereof are preferably used.
This is because they are excellent in hardness, insulation and heat resistance, which are required as an electrical insulating material.

In the present invention, in particular, when an acid-modified biphenol type epoxy (meth) acrylate is used as the reactive compound (B), higher flame retardancy is exhibited by using it together with the phosphine oxide compound (A) of the present invention. be able to.
The biphenol type epoxy (meth) acrylate refers to an epoxy (meth) acrylate derived from an epoxy resin having a biphenyl skeleton.

  The active energy ray-curable resin composition of the present invention 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. In the present invention, a photopolymerization initiator (C) is usually added.

Examples of the photopolymerization initiator (C) include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2- Diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- ( Acetophenones such as methylthio) phenyl] -2-morpholino-propan-1-one; anthrax such as 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, 2-amylanthraquinone Thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 4 Benzophenones such as 2,4'-bismethylaminobenzophenone; phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide A radical type photoinitiator is mentioned.
In addition, an azo initiator such as azobisisobutyronitrile, a peroxide radical initiator sensitive to heat such as benzoyl peroxide, and the like may be used in combination. One type of initiator can be used alone, or two or more types can be used in combination.

  The active energy ray-curable resin composition of the present invention contains 1 to 75% by weight of the phosphine oxide compound (A) in the composition, preferably 5 to 70% by weight, 10 to 85% by weight of the reactive compound (B), and Preferably, it can be added as appropriate in the range of 3 to 80% by weight, photopolymerization initiator (C) 0.5 to 10% by weight, preferably 1 to 7% by weight.

Furthermore, in this invention, it is preferable to add a hardening | curing agent according to a use suitably. This curing agent is used in order to obtain a stronger cured film by reacting the contained acidic group, particularly in a material intended for electrical insulation.
Examples of the curing agent include epoxy compounds having two or more glycidyl groups in the molecule. Specifically, phenol novolac type epoxy resin, cresol novolac type epoxy resin, trishydroxyphenylmethane type epoxy resin, dicyclopentadiene phenol type epoxy resin, bisphenol-A type epoxy resin, bisphenol-F type epoxy resin, biphenol type epoxy Examples thereof include resins, bisphenol-A novolac type epoxy resins, naphthalene skeleton-containing epoxy resins, glyoxal type epoxy resins, and heterocyclic epoxy resins.

  Examples of the phenol novolac type epoxy resin include Epicron N-770 (manufactured by Dainippon Ink & Chemicals, Inc.), D.I. E. N438 (made by Dow Chemical Company), Epicoat 154 (made by Yuka Shell Epoxy Co., Ltd.), EPPN-201, RE-306 (made by Nippon Kayaku Co., Ltd.), etc. are mentioned. Examples of the cresol novolac type epoxy resin include Epicron N-695 (manufactured by Dainippon Ink & Chemicals, Inc.), EOCN-102S, EOCN-103S, EOCN-104S (manufactured by Nippon Kayaku Co., Ltd.), UVR-6650 ( Union Carbide), ESCN-195 (Sumitomo Chemical Co., Ltd.) and the like.

  Examples of the trishydroxyphenylmethane type epoxy resin include, for example, EPPN-503, EPPN-502H, EPPN-501H (manufactured by Nippon Kayaku Co., Ltd.), TACTIX-742 (manufactured by Dow Chemical Co., Ltd.), Epicoat E1032H60 (oilized shell epoxy) Etc.). Examples of the dicyclopentadiene phenol type epoxy resin include Epicron EXA-7200 (manufactured by Dainippon Ink & Chemicals, Inc.) and TACTIX-556 (manufactured by Dow Chemical Co., Ltd.).

  Examples of bisphenol type epoxy resins include Epicoat 828, Epicoat 1001 (manufactured by Yuka Shell Epoxy Co., Ltd.), UVR-6410 (manufactured by Union Carbide), D.I. E. Bisphenol-A type epoxy resin such as R-331 (manufactured by Dow Chemical Co., Ltd.), YD-8125 (manufactured by Tohto Kasei Co., Ltd.), NER-1202, NER-1302 (manufactured by Nippon Kayaku Co., Ltd.) Bisphenol-F type epoxy resins such as Union Carbide), YDF-8170 (Toto Kasei), NER-7403, NER-7604 (Nippon Kayaku Co., Ltd.), and the like.

  Examples of the biphenol type epoxy resin include biphenol type epoxy resins such as NC-3000 and NC-3000-H (Nippon Kayaku Co., Ltd.), and bixylenol of YX-4000 (manufactured by Yuka Shell Epoxy Co., Ltd.). Type epoxy resin, YL-6121 (manufactured by Yuka Shell Epoxy Co., Ltd.) and the like. Examples of the bisphenol A novolak type epoxy resin include Epicron N-880 (manufactured by Dainippon Ink & Chemicals, Inc.) and Epicoat E157S75 (manufactured by Yuka Shell Epoxy Co., Ltd.).

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

Among these, in terms of flame retardancy, biphenol type epoxy resins are particularly effective, and biphenol type epoxy resins such as NC-3000 and NC-3000-H (Nippon Kayaku Co., Ltd.) are most preferable.
In this invention composition, when it contains a hardening | curing agent, it is 5 to 70 weight% in an active energy ray hardening-type resin composition, Preferably it is the range of about 10 to 60 weight%.

  The active energy ray-curable resin composition of the present invention is easily cured by active energy rays. Specific examples of the active energy rays include electromagnetic waves such as ultraviolet rays, visible rays, infrared rays, X rays, gamma rays and laser rays, particle rays such as alpha rays, beta rays and electron rays. Of these, ultraviolet rays, laser beams, visible rays, or electron beams are preferred in view of suitable applications of the present invention.

  In the present invention, the molding material refers to an uncured composition put into a mold, or a mold is pressed to form an object, and then a curing reaction is caused by active energy rays to form, or an uncured composition. It refers to a material used for applications in which a focused light such as a laser is irradiated to cause a curing reaction to be molded.

  Specific applications include a sheet formed into a flat shape, a sealing material for protecting the element, a so-called nanoimprint material that performs fine molding by pressing a "mold" that has been micro-processed into an uncured composition, Furthermore, sealing materials and the like for the purpose of electrical insulation, which are required to have flame retardancy and high reliability and are repelled from halogen compounds, are mentioned as suitable applications.

  In the present invention, the film forming material is used for the purpose of coating the surface of a substrate. Specific applications include gravure inks, flexo inks, silk screen inks, offset inks and other ink materials, hard coats, top coats, overprint varnishes, clear coats and other coating materials, laminating, optical disk and other various adhesives. Such materials include adhesive materials such as adhesives and adhesives, resist materials such as solder resists, etching resists, and resists for micromachines. Furthermore, after the film forming material is temporarily applied to the peelable substrate and formed into a film, it is bonded to the original target substrate to form a film, so-called dry film also corresponds to the film forming material. .

Generally, an insulating material composition forms a film layer of the composition on a base material, and in an electronic circuit or a component thereof, an electric current is large even when a voltage is applied between two target locations. It refers to an active energy ray-curable resin composition that does not flow. Specific applications include overcoat materials for flexible wiring boards and interlayer insulation films for multilayer substrates, molding materials for insulation films and passivation films for solid elements in the semiconductor industry, and interlayers for semiconductor integrated circuits and multilayer printed wiring boards. It is also preferably used for an insulating material, a solder resist used for protecting the substrate, and the like. It is particularly suitable for flexible substrates that are particularly required to have high flame resistance.
That is, not only can high flame retardancy be imparted, but also long-term insulation stability can be exhibited.

In the present invention, the insulating material has a portion requiring insulation and a portion requiring conduction on the substrate, and each of these must be patterned as necessary. At that time, a pattern may be formed by a printing method, but fine patterning is difficult and is not suitable for producing a high-density substrate.
A film layer of the composition is formed on a substrate, and then an active energy ray such as ultraviolet rays is partially irradiated, and an active energy ray intended to be drawn using a physical difference between an irradiated portion and an unirradiated portion In the case of a sensitive composition, unreacted sites are washed away with a solvent or the like. In the case of a so-called solvent development type, it can be used without using a reactive compound (B) having an acid value. However, it is also difficult to adjust the difference in solubility, and it is difficult to make a high-density substrate.
For this reason, the method of developing with alkaline water by using the reactive compound (B) imparted with an acid value is common, and it is easy to make a fine pattern. Therefore, it is preferable to use a reactive compound (B) having an acid value for this purpose because a high-density substrate can be produced.

In addition to this, the active energy ray-curable resin composition of the present invention can be applied to printed wiring boards, electrical / electronic / optical substrates such as optoelectronic substrates and optical substrates as optical waveguides that are similarly required to have high flame resistance. Is also used.
As a particularly suitable application, it is preferable as an insulating material that requires patterning, such as a permanent resist application such as a solder resist, taking advantage of the characteristics that can provide flame retardancy and high reliability.
Furthermore, since the phosphine oxide compound (A) and the reactive compound (B) of the present invention react as a resist material for use in a flexible circuit board in the resist material, they also have an effect as a crosslinking agent. Therefore, both high flame retardancy and flexibility can be achieved without adding many extender pigments.

The active energy ray-curable resin composition of the present invention does not contain a halogen-based flame retardant, and has flame retardancy even though the halogen compound content is 10000 ppm or less, more preferably 5000 ppm or less.
There are no particular restrictions on the method for forming the film, but an intaglio printing method such as gravure, a relief printing method such as flexo, a stencil printing method such as silk screen, a lithographic printing method such as offset, a roll coater, a knife coater, a die coater, Various coating methods such as curtain coater, spin coater, spray coater, etc. can be arbitrarily adopted.

The cured product of the active energy ray-curable resin composition of the present invention refers to a product obtained by irradiating and curing the active energy ray-curable resin composition of the present invention with active energy rays.
The multilayer material of the present invention refers to a material having at least two layers that can be obtained by forming and curing a film of the active energy ray-curable resin composition shown in the present invention on a substrate.
In addition, for the purpose of adapting the active energy ray-curable resin composition of the present invention to various uses, “other components” may be added up to 70% by weight. Examples of other components include additives, coloring materials, and pigment materials. Examples of other components that can be used are shown below.

Examples of additives include thermosetting catalysts such as melamine, thixotropic agents such as aerosil, silicone leveling agents, fluorine leveling agents and antifoaming agents, hydroquinone, hydroquinone monomethyl ether and other polymerization inhibitors, stabilizers and antioxidants. Etc. can be used.
Examples of the color pigment include organic pigments such as phthalocyanine, azo, and quinacridone, carbon black, and inorganic pigments such as titanium oxide.
Further, as the pigment material, for example, a material not intended for coloring, so-called extender pigment can be used. Examples include talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, silica, clay and the like.

Other resins that are not reactive with active energy rays (so-called inert polymers), such as other epoxy resins, phenol resins, urethane resins, polyester resins, ketone formaldehyde resins, cresol resins, xylene resins, diallyl phthalate resins, styrene Resins, guanamine resins, natural and synthetic rubbers, acrylic resins, polyolefin resins, and modified products thereof can also be used. These are preferably used in the range of up to 40% by weight.
Further, depending on the purpose of use, a volatile solvent may be added in the range of 50% by weight, more preferably up to 35% by weight for the purpose of adjusting the viscosity.

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to these Examples. In the examples, “parts” represents parts by weight and “%” represents percent by weight unless otherwise specified.

（式中、Ｒは水素原子又はメチル基を示す。）
で表わされるホスフィンオキサイド化合物（Ａ）は以下の合成例１、２の方法に従って合成した。 Following formula (1)

(In the formula, R represents a hydrogen atom or a methyl group.)
A phosphine oxide compound (A) represented by the formula was synthesized according to the methods of Synthesis Examples 1 and 2 below.

Synthesis Example 1-1: Synthesis of Phosphine Oxide Compound (A-1) In a 2 L reactor equipped with a stirrer, a thermometer, and a condenser, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide ( Sanka Co., Ltd. HCA) was charged with 216.2 g (1.0 mol) and 246.2 g of toluene, and dissolved at a temperature of 80 to 90 ° C. Next, under stirring, 30.0 g (1.0 mol) of paraformaldehyde was gradually added and reacted at a reaction temperature of 80 ° C. to 90 ° C. for 3 hours, to obtain 246.2 g of white crystals.
Next, 246.2 g (1.0 mol) of the obtained crystal product, 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. The dehydration condensation reaction was carried out at 105 to 110 ° C. for 13 hours, and the resulting reaction solution was washed twice with 10% aqueous sodium carbonate solution and once with 20% brine, and then toluene was distilled under reduced pressure to obtain a pale yellow liquid phosphine. 267.9g (yield 89.2%) of oxide compounds (A-1) were obtained.

This phosphine oxide compound (A-1) exhibits the following physical properties.
Viscosity (40 ℃) 6300 CPS
Refractive index (20 ° C) 1.6145
H-NMR
4.80 ppm = 2H, 5.60 ppm = 1H, 6.16 ppm = 1H, 6.45 ppm = 1H, 7.24-7.93 ppm = 8H

Synthesis Example 1-2: Synthesis of Phosphine Oxide Compound (A-2) 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (into a 2 L reactor equipped with a stirrer, a thermometer, and a condenser ( Sanka Co., Ltd. HCA) was charged with 216.2 g (1.0 mol) and 246.2 g of toluene, and dissolved at a temperature of 80 to 90 ° C. Next, under stirring, 30.0 g (1.0 mol) of paraformaldehyde was gradually added and reacted at a reaction temperature of 80 ° C. to 90 ° C. for 3 hours, to obtain 246.2 g of white crystals.
Next, 246.2 g (1.0 mol) of the obtained crystal product, 172 g (2.0 mol) of methacrylic acid, 500 g of toluene, 1.7 g of methoquinone, and 17 g of p-toluenesulfonic acid monohydrate were charged at 105 to 110 ° C. The resulting reaction solution was washed twice with 10% aqueous sodium carbonate and once with 20% brine, and then toluene was distilled off under reduced pressure to obtain a pale yellow liquid phosphine oxide compound (A -2) (262 g, yield 83.4%) was obtained.

This phosphine oxide compound (A-2) exhibits the following physical properties.
Viscosity (40 ℃) 5200 CPS
Refractive index (20 ° C.) 1.6078
H-NMR
1.96 ppm = 3H, 4.80 ppm = 2H, 5.60 ppm = 1H, 6.16 ppm = 1H, 7.24-7.93 ppm = 8H

Comparative Synthesis Example: Compound described in JP 2000-38398 A 1000 mL four-necked flask equipped with a stirrer, thermometer, dropping funnel and condenser was charged with sodium hypophosphite · monohydrate 106.0 g (1.0 mol). A solution of 3.50 g of radical initiator tert-butylperoxy-2-ethylhexanate in 58.1 g (1.0 mol) of allyl alcohol was added over about 4 hours. The reaction was dropped under ethanol reflux. After completion of dropping, the mixture was aged at the same temperature for 2 hours and cooled to room temperature. When (1 + 1) hydrochloric acid aqueous solution was added to the reaction solution until the pH became acidic, sodium chloride was precipitated. The liquid amount was concentrated to 1/2, and the produced sodium chloride was removed by filtration and concentrated with an evaporator to obtain 128.6 g of a colorless and transparent liquid. The analysis results were as follows, and the product was 3-hydroxypropylphosphinic acid. The yield was 97.1%. 105.9 g (0.8 mol) of the obtained 3-hydroxypropylphosphinic acid was charged into a 500 mL four-necked flask and heated to 100 ° C. under a nitrogen stream. Next, a solution prepared by dissolving 3.17 g of the radical initiator di-tert-butyl peroxide charged in the dropping funnel in 55.7 g (0.96 mol) of allyl alcohol was dropped over about 4 hours. After completion of dropping, the mixture was aged at the same temperature for 2 hours. After cooling, the excess allyl alcohol was completely distilled off with a vacuum pump to obtain 147.0 g of a slightly yellow viscous liquid. As a result of analysis, the product was bis (3-hydroxypropyl) phosphinic acid, and the yield was 97.7%.
In a reactor equipped with a reflux condenser, a stirrer, a thermometer, a temperature control device, and a water separator, 182.2 g (1.0 mol) of bis (3-hydroxypropyl) phosphinic acid as an alcohol compound, ethylenic in the molecule As monocarboxylic acid compound (b) having an unsaturated group, 172.9 g (2.4 mol) of acrylic acid, 3.46 g of p-toluenesulfonic acid monohydrate as an acid catalyst, 1.31 g of hydroquinone as a thermal polymerization inhibitor, As a reaction solvent, 124.3 g of toluene and 53.3 g of cyclohexane were charged, and the reaction was carried out while azeotropically distilling the produced water with the solvent at a reaction temperature of 95 to 105 ° C. The reaction was terminated when the produced water reached 25.3 ml. . To the reaction mixture, 430.0 g of toluene and 181.2 g of cyclohexane were added, neutralized with 25% aqueous sodium hydroxide solution, and then washed 3 times with 100 g of 15% brine. The solvent was distilled off under reduced pressure to obtain 220.7 g (yield: 70.2%) of bis (3-acryloyloxypropyl) phosphinic acid (Comparative Compound 1).

Examples 1-2 and Comparative Examples 1-3 (Preparation and evaluation of a 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 at the blending ratio shown in Table 1, and 3 as required. The active energy ray-curable resin composition of the present invention was obtained by kneading with a roll mill. This was applied to a copper circuit printed circuit board by a silk screen printing method so as to have a thickness of 25 microns, and the coating film was dried with a hot air drier at 80 ° C. for 60 minutes. After cooling to room temperature, absorbent cotton was adhered to the coating film, and tackiness was observed. Next, the mask film on which the pattern was drawn was brought into close contact, and irradiated with ultraviolet rays using an ultraviolet exposure device (USHIO: 500 W multilight). Next, spray development (spray pressure: 0.2 MPa) was performed for 60 seconds using a 1% aqueous sodium carbonate solution (temperature: 30 ° C.) as a developer. After washing with water, heat treatment was performed for 60 minutes in a hot air dryer at 150 ° C. to obtain a cured product of the present invention. As described later, tackiness, sensitivity, developability, curability, flame retardancy, HAST resistance, and flexibility were tested. The results are shown in Table 2. The test method and evaluation method are as follows.

(Sensitivity evaluation)
Sensitivity was determined by how many density portions remained in the exposed portion that passed through the step tablet during development. The higher the number of steps (value), the higher sensitivity is determined in the dark part of the tablet (unit: step). In addition, it was set as x about the thing which cannot develop and a sensitivity measurement is impossible.
(Developability evaluation)
The developability was evaluated based on the time until the pattern-shaped portion was completely developed, that is, the so-called break time when the exposed portion that passed through the pattern mask was developed (unit: second). In addition, regarding what did not break within 60 seconds, it was set as x.
(Curability evaluation)
The evaluation of curability was shown by the pencil hardness of the cured film after heating at 150 ° C.
The evaluation method was based on JIS K5600-5-4: 1999.

(Adhesion evaluation)
For the evaluation of adhesion, according to JIS K5400, 100 1-mm goblets were made on a test piece, and a peeling test was performed using a cello tape (registered trademark; R). The peeled state of the goblet was observed and evaluated according to the following criteria.
○ ································································································
Flame retardancy is non-halogen flame retardant substrate RO-67G (0.2mmt material) manufactured by Hitachi Chemical.
Each surface was coated with 15 μm on one side by silk screen printing, and UV-cured with 80 W / cm 3 high pressure mercury lamp. The test piece was measured for burning time according to the UL94 flammability test.
: Equivalent to UL V-0
(The total combustion time when 5 test pieces are ignited twice each is 50 seconds or less)
○: UL V-1 equivalent (total combustion time when 5 test pieces are ignited twice each, 50 to 250 seconds)
×: No self-extinguishing

(HAST resistance evaluation)
The FR-4 substrate on which comb-shaped electrodes (line / space = 50 microns / 50 microns) are formed is printed on the entire surface of the active energy ray-curable resin composition, exposed and developed, and then thermally cured to evaluate the substrate. It was created. This evaluation substrate was placed in a high-temperature and high-humidity tank in an atmosphere of 130 ° C. and 85% humidity, charged with a voltage of 5 V, and subjected to a HAST test for 168 hours. The electrical insulation after the HAST test was measured.
○: 1010Ω or more △: 1010 to 108Ω
X: 108Ω or less (flexibility evaluation) The cured film is bent and observed at 180 degrees. The following criteria were used:
○: No crack on the film surface ×: The film surface breaks

(Table 1) Mixing ratio of active energy ray-curable resin composition
Examples Comparative examples
1 2 1 2 3
Note Compound (A-1) 10.00 62.61
Compound (A-2) 10.00
Comparative compound 1 10.00
Reactive compound (B)
ZFR-1401H * 1 46.55 46.55 46.55 46.55
DPCA-60 * 2 6.06 6.06 6.06 16.06
Photopolymerization initiator (C)
Irg. 907 * 3 4.54 4.54 4.54 4.54 4.54
DETX-S * 4 0.91 0.91 0.91 0.91 0.91
Hardener
NC-3000H * 5 18.31 18.31 18.31 18.31 18.31
Thermosetting catalyst Melamine 1.00 1.00 1.00 1.00 1.00
Extender pigment
Barium sulfate 15.15 15.15 15.15 15.15 15.15
Phthalocyanine blue 0.61 0.61 0.61 0.61 0.61
Additive BYK-354 * 6 0.39 0.39 0.39 0.39 0.39
KS-66 * 7 0.69 0.69 0.69 0.69 0.69
Concentration adjusting solvent
CA * 8 4.54 4.54 4.54 4.54 4.54

(note)
* 1 ZFR-1401H Nippon Kayaku Co., Ltd. acrylate oligomer Acid-modified polyfunctional bisphenol F-type epoxy acrylate (average number of functional groups 5, solid content converted acid value 100 mg · KOH / g)
* 2 DPCA-60 Nippon Kayaku Co., Ltd. acrylate monomer ε-caprolactone modified dipentaerythritol hexaacrylate
* 3 Irg. 907 Photopolymerization initiator 2-methyl- (4- (methylthio) phenyl) -2-morpholino-1-propane manufactured by Ciba Specialty Chemicals
* 4 DETX-S Nippon Kayaku Co., Ltd. photopolymerization initiator 2,4-diethylthioxanthone
* 5 NC-3000H Nippon Kayaku Co., Ltd. Epoxy resin Biphenol type epoxy resin
* 6 Leveling agent manufactured by BYK-354 Big Chemie Japan
* 7 KS-66 Shin-Etsu Chemical defoamer
* 8 Carbitol acetate manufactured by CA Osaka Organic Chemical Industry Co., Ltd.

(Table 2) Evaluation of resist
Examples Comparative examples
1 2 1 2 3
Evaluation item
Tackiness ○ ○ × × ○
Sensitivity 7 6 × × 7
Developability 21 17 × × 19
Curing 6H 6H 5H H 6H
Adhesion ○ ○ ○ × ○
Flame resistance ◎ ◎ ○ ◎ ×
HAST resistance ○ ○ × × ○
Flexibility ○ ○ ○ × ○

From the above results, the phosphoric acid type compound having an ethylenically unsaturated group as in Comparative Example 1 has poor tackiness and reacts with the epoxy compound in the resin composition, making development impossible. . Moreover, the phosphoric acid type compound cross-linked with the epoxy resin as in Comparative Example 1 is hydrolyzed under high humidity and heat conditions, which causes a problem in reliability tests such as HAST resistance. Moreover, when the reactive compound (A) as in Comparative Example 2 is cured alone, a tough cured coating film cannot be obtained. When the reactive compound (A) is not included as in Comparative Example 3, the coating film has no self-extinguishing property and flame retardancy cannot be obtained.
On the other hand, in Examples 1 and 2, since the reactive compounds (A) and (B) do not have an acidic group, the tackiness is good and the development is performed while having high flame retardancy. It became clear that it has the characteristic which was excellent in property and HAST tolerance.
Therefore, the active energy ray-curable resin composition of the present invention has high flame retardancy and excellent photosensitivity, and the cured film has developability, curability, adhesion, HAST resistance, flexibility and the like. It is sufficiently satisfactory and is particularly suitable for a photosensitive resin composition for flexible printed circuit boards.

Examples 3 to 5 (Improvement of flame retardancy by combination with biphenol type epoxy acrylate resin)
Following the above Examples 1 and 2, the improvement in flame retardancy was evaluated when a biphenol type epoxy acrylate was used as the reactive compound (B) and in combination with an epoxy resin used as a curing agent.
The flame retardant evaluation was changed to a polyimide film having a thickness of 25 microns from RO-67G in order to make comparison under more severe conditions than in the case of Examples 1 and 2 described above. Other than that, the same test was conducted. The criteria for determination are the same as those in the first and second embodiments. The number of seconds in parentheses after the sign indicates the time taken to extinguish the fire. Table 3 shows the blending ratio of the active energy ray-curable resin composition, and Table 4 shows the evaluation of flame retardancy. The reference values according to Example 1 are also shown.

(Table 3) Mixing ratio of active energy ray-curable resin composition
Example 1 Example 3 Example 4 Example 5
note
Compound (A-1) 10.0 10.0 10.0 10.0
Reactive compound (B)
ZFR-1401H * 1 46.55 46.55
ZCR-1361 * 9 46.55 46.55
DPCA-60 * 2 6.06 6.06 6.06 6.06
Photopolymerization initiator (C)
Irg. 907 * 3 4.54 4.54 4.54 4.54
DETX-S * 4 0.91 0.91 0.91 0.91
Hardener
NC-3000H * 5 18.31 18.31
EPPN-201 * 10 18.31 18.31
Thermosetting catalyst melamine 1.00 1.00 1.00 1.00
Extender pigment
Barium sulfate 15.15 15.15 15.15 15.15
Phthalocyanine blue 0.61 0.61 0.61 0.61
Additive BYK-354 * 6 0.39 0.39 0.39 0.39
KS-66 * 7 0.69 0.69 0.69 0.69
Concentration adjusting solvent CA * 8 4.54 4.54 4.54 4.54

(note)
* 1 ZFR-1401H Nippon Kayaku Co., Ltd. acrylate oligomer Acid-modified polyfunctional bisphenol F type epoxy acrylate (average number of functional groups 5, solid content converted acid value 100 mg · KOH / g)
* 2 DPCA-60 Nippon Kayaku Co., Ltd. acrylate monomer ε-caprolactone modified dipentaerythritol hexaacrylate
* 3 Irg. 907 Photopolymerization initiator 2-methyl- (4- (methylthio) phenyl) -2-morpholino-1-propane manufactured by Ciba Specialty Chemicals
* 4 DETX-S Nippon Kayaku Co., Ltd. photopolymerization initiator 2,4-diethylthioxanthone
* 5 NC-3000H Nippon Kayaku Co., Ltd. Epoxy resin Biphenol type epoxy resin
* 6 BYK-354 BYK-Chemie leveling agent
* 7 KS-66 Shin-Etsu Chemical defoamer
* 8 Carbitol acetate manufactured by CA Osaka Organic Industries, Ltd.
* 9 ZCR-1361 Nippon Kayaku Co., Ltd. acrylate oligomer Acid-modified polyfunctional biphenol-type epoxy acrylate (functional group average 4; solid content converted acid value 100 mg · KOH / g)
* 10 EPPN-201 Nippon Kayaku Co., Ltd. Epoxy resin Phenol novolac type epoxy resin

(Table 4) Flame retardancy evaluation of active energy ray-curable resin composition
Example 1 Example 3 Example 4 Example 5
Flame retardant evaluation ○ (85 seconds) ◎ (32 seconds) ○ (230 seconds) ○ (65 seconds)

 From the above results, it was found that a particularly excellent flame retardant effect can be exhibited by using a biphenol type epoxy acrylate as the reactive compound (B) and a biphenol type epoxy resin as the curing agent.

Examples 6 to 9 (Examination of difference in developability due to difference in acid value)
Following the examples described in Examples 1 and 2 above, the change in developability due to the difference in the acid value of the biphenol type epoxy acrylate as the reactive compound (B) was evaluated.
10 g of the phosphine oxide compound (A-1) prepared in Synthesis Example 1 and a reactive compound (B) having an acid value shown in the table as a biphenol acid-modified epoxy acrylate having each acid value (both from Japan) 47 g of Kazaku ZCR-series), 6 g of DPCA-60 as a reactive compound (B) without acid value, 2.5 g of Irgacure 907 (manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator, DETX -S (Nippon Kayaku) 1g, Biphenol-based epoxy resin NC-3000-H (Nippon Kayaku) 18g as a curing agent, 1g of melamine as a thermosetting catalyst, 15g of barium sulfate as an extender pigment in a three roll mill The solder resist composition was obtained by kneading.
This composition was coated on a copper foil-bonded polyimide film with a silk screen so as to have a film thickness of 25 microns when dried, and dried in an 80 ° C. oven for 30 minutes.
A mask film on which a pattern was drawn was brought into close contact with the obtained coating film, and irradiated with ultraviolet rays using an ultraviolet exposure device (USHIO: 500 W multilight). Next, spray development (spray pressure: 0.2 MPa) was performed for 60 seconds using a 1% aqueous sodium carbonate solution (temperature: 30 ° C.) as a developer. After washing with water, heat treatment was performed 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, resolution, flame retardancy, and HAST resistance were performed. The results are shown in Table 5 together with the blending ratio of the resin composition. In addition, the test method and evaluation method except a resolution were implemented according to the test method shown in the term of above-mentioned Example 1-2.
Evaluation of resolution: Evaluation was carried out with the development state of the drawing part having a line and space of 50 microns.

(Table 5)
Example 6 Example 7 Example 8 Example 9
Compound (A-1) 10.0 10.0 10.0 10.0
Reactive compound (B)
ZCR-series ZCR-176X ZCR-1361 ZCR-157X ZCR-164X
Solid acid value (mgKOH / g) 135 100 50 25
DPCA-60 6.0 6.0 6.0 6.0
Photopolymerization initiator Irg. 907 2.5 2.5 2.5 2.5
DETX-S 1.0 1.0 1.0 1.0
Hardener
NC-3000H 18 18 18 18
Thermosetting catalyst melamine 1.0 1.0 1.0 1.0
Extender pigment
Barium sulfate 15.0 15.0 15.0 15.0

(Evaluation)
Developability (seconds) 7 20 40 58
Resolution Loss Good Good Line width Borderline development failure Flame resistance ○ ○ ○ ○
HAST resistance △ ○ ○ ○

If the acid value is higher than the preferred range, the fine pattern will be lost, resulting in difficulty in fine patterning. On the other hand, if the acid value is too low, the developability of the boundary portion deteriorates, and similarly, fine patterning becomes difficult.
From the above results, it was revealed that a suitable acid value range exists when the reactive compound (B) imparted with an acid value is used as a developable photosensitive composition.

Reference Examples 10 to 11 and Comparative Example 4 (Evaluation of copolymerization type acid value imparting reactive compound (B))
Following the examples described in Examples 1 and 2 above, the phosphine oxide compound (A-1) prepared in Synthesis Example 1 was used in the amount shown in the table, and the reactive compound (B) was methacrylic acid, methylmeta. Glycidyl methacrylate graft compound of acrylate copolymer (R-178X manufactured by Nippon Kayaku, weight average molecular weight 15,000, acid value 60 mg · KOH / g), or polyvinylphenol glycidyl methacrylate graft compound (R- manufactured by Nippon Kayaku) 777X, weight average molecular weight 5,000, acid value 90 mg · KOH / g) listed in the table, methyl isobutyl ketone 30 g as a solvent, Irgacure 907 (manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator, 1 g of DETX-S (manufactured by Nippon Kayaku) was mixed to obtain a resist composition.
This composition was coated on a copper foil-bonded polyimide film with a silk screen so as to have a film thickness of 25 microns when dried, and dried in an 80 ° C. oven for 30 minutes.
A mask film on which a pattern was drawn was brought into close contact with the obtained coating film, and irradiated with ultraviolet rays using an ultraviolet exposure device (USHIO: 500 W multilight). Next, spray development (spray pressure: 0.2 MPa) was performed for 60 seconds using a 1% aqueous sodium hydroxide solution (temperature: 30 ° C.) as a developer. After washing with water, heat treatment was performed for 60 minutes in a hot air dryer at 150 ° C. to obtain a cured product of the present invention. As described later, developability and flame retardancy tests were performed. The results are shown in Table 6 together with the blending ratio of the resin composition.

  From the above results, even when the copolymerization-type acid value-imparting reactive compound (B) is used, as with the acid-modified epoxy acrylates, the combination with the phosphine oxide compound (A-1) leads to good developability. It became clear that it showed flame retardancy.

Reference Examples 12-15, Comparative Example 5 (Preparation and Evaluation of Flame Retardant Coating Composition)
10 g of the phosphine oxide compound (A-1) prepared in Synthesis Example 1, 30 g of the compound described in the table as the reactive compound (B), 10 g of acrylic polymer as an inert resin, 10 g of Dainal BR-80 manufactured by Mitsubishi Rayon, 2 g of Irgacure 184 manufactured by Ciba Specialty Chemicals as a photopolymerization initiator, 10 g of methyl isobutyl ketone as a diluent solvent, and 0.5 g of KS-66 manufactured by Shin-Etsu Chemical Co., Ltd. as a surface tension adjusting agent were mixed and stirred well until uniform. The coating composition thus obtained was coated on a 25 micron polyethylene terephthalate film to a thickness of about 20 microns using a wire bar coater, and the solvent was evaporated in an oven at 80 ° C.
Then, the ultraviolet-ray of 600 mJ / square centimeter was irradiated, the coating film was hardened, and the two-layer material which consists of a polyethylene terephthalate and a coating composition was obtained.
Pencil hardness (according to JIS K5600-5-4: 1999) and flame retardancy (confirm the presence or absence of self-extinguishing properties, sample preparation method, evaluation conditions are in accordance with Examples 1-2) and After the weather test, the flame retardancy (the evaluation method is the same) was evaluated.
For the flame resistance of the weather resistance test, the coating surface obtained was sprayed with pure water for 96 hours, and the sample of the double-layer material after the weather resistance test was prepared in the same manner to evaluate the flame resistance. The results are shown in Table 7 together with the blending ratio of the resin composition.

R-684: Tricyclodecane structure diacrylate (bifunctional) manufactured by Nippon Kayaku
R-190: Nippon Kayaku bisphenol A type epoxy acrylate (bifunctional)
UX-5000: Nippon Kayaku polyfunctional urethane acrylate (hexafunctional)
DPCA-60: Nippon Kayaku caprolactone-modified dipentaerythritol hexaacrylate (hexafunctional)
R-128H: Nippon Kayaku glycerin monophenyl ether monoacrylate (monofunctional)

From the above results, it became clear that the flame resistance of the coating material obtained from R-128H having one reactive functional group in one molecule is lowered after the weather resistance test. It is considered that this is because the phosphine oxide compound (A-1) imparting flame retardance is washed away and the flame retardancy is lowered.

Claims (12)

Following formula (1)

(In the formula, R represents a hydrogen atom or a methyl group.)
As a phosphine oxide compound (A), a reactive compound (B) having two or more active energy ray-reactive functional groups in one molecule provided with an acid value , a photopolymerization initiator (C), and a curing agent An active energy ray-curable resin composition comprising an epoxy resin. The active energy ray-curable resin composition according to claim 1, wherein the reactive functional group of 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 a (meth) acrylate having an acid value of 30 to 150 mg · KOH / g. The active energy ray-curable resin composition according to claim 1, wherein the reactive compound (B) is a carboxyl group-containing epoxy (meth) acrylate. The active energy ray-curable resin composition according to claim 4, wherein the reactive compound (B) is an acid-modified biphenol type epoxy (meth) acrylate. The active energy ray-curable resin composition according to claim 1, wherein the curing agent is a biphenol type epoxy resin. The active energy ray-curable resin composition according to any one of claims 1 to 6, which is a molding material. The active energy ray-curable resin composition according to any one of claims 1 to 6, which is a film-forming material. The active energy ray-curable resin composition according to any one of claims 1 to 6, which is an electrically insulating material composition. The active energy ray-curable resin composition according to claim 9, wherein the electrically insulating material composition is a developable photosensitive solder resist composition. A method for producing a cured product, wherein the active energy ray-curable resin composition according to any one of claims 1 to 6 is irradiated with active energy rays. The multilayer material which has a layer of the hardened | cured material obtained by irradiating an active energy ray curable resin composition as described in any one of Claims 1-6 with an active energy ray.