TW200846353A - Phosphorus-containg flame retardant and curable flame retardancy resin composition containing the same - Google Patents

Abstract

The objection of the present invention is providing a non-halogen phosphorus-containing flame retardant and a curable flame retardancy resin composition which contains the said phosphorus-containing flame retardant and is curable by means of radical polymerization, by which a curing article having excellent curability as well as excellent flame retardancy, curability and softness is obtained. The solution is reacting (meth)acryloyl of multifunctional (meth)acrylate compound having specific structure with phosphorus compound having P-H bond, and a phosphorus-containing flame retardant is obtained, and then blend the said phosphorus-containing flame retardant, alkali-soluble resin, (meth)acrylate compound, epoxy resin, photo-polymerization initiator and optional filler to form the curable flame retardancy resin composition.

Description

200846353 IX. Description of the Invention: [Technical Field] The present invention relates to a phosphorus-containing flame retardant containing a halogen-free compound, and a phosphorus-containing flame retardant containing the same and capable of being hardened by radical polymerization. The electronic substrate and the electronic component are particularly suitable for a curable flame retardant resin composition such as a flexible solder resist material. [Prior Art] From the viewpoint of safety such as prevention of fire, resins used for electrical equipment, electronic components, and the like are expected to be flame retardant. Heretofore, a curable flame retardant resin composition has been used, which is based on bromide. The main organic halogen-containing compound is formed as a flame retardant. The curable flame retardant resin composition containing a compound containing an organic halogen has excellent flame retardancy, but the curable flame retardant resin composition may cause harmful compounds such as rotten hydrogen halide during combustion. The possibility of having an impact on the environment. Therefore, it is proposed to replace the organic halogen-containing compound with a phosphate ester compound such as a trialkyl phosphate or a triaryl phosphate and a curable flame retardant resin composition obtained by blending red phosphorus with a curable resin. Burning agent. However, when the above-mentioned phosphate ester-based compound is blended in a curable resin, the obtained curable flame-retardant resin composition is likely to generate free phosphate ions by hydrolysis, and the curable flame retardant resin composition is used. The hardened electrical properties deteriorate. Therefore, it is proposed to use an aromatic condensed phosphate as a flame retardant for preventing such hydrolysis (for example, Patent Documents 1 and 2). However, when the amount of the aromatic condensed phosphate ester is increased, the aromatic condensed phosphate ester bleeds out from the cured product (b 1 e e d 0 u t ) in 200846353, and thus the amount of use thereof is limited. As a countermeasure against this, it is proposed to embed a reactive phosphorus compound in a hardened resin matrix and use a phosphorus-containing epoxy resin (Patent Document 3, Patent Document 4, and Patent Document 5). However, when such a reactive phosphorus compound or a phosphorus-containing epoxy resin is used alone to generate sufficient flame retardancy, the cured product becomes hard and brittle, and cannot be used, for example, in a flexible substrate. Soft solder resist material. Further, Patent Document 6 proposes a phosphorus-containing propionate compound obtained by reacting a (meth) acrylate compound with a reactive phosphorus compound, but lacks a balance between sensitivity and softness of a cured product. It is a low-adaptability material for a solder resist material used for a flexible substrate. Patent Document 1: Japanese Laid-Open Patent Publication No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. 5 - 2 7 7 3 4 No. 4 Patent Publication No. 4 - 1 1 6 6 No. 2 Patent Document 4: Special Japanese Patent Laid-Open Publication No. JP-A No. 2000-309623 No. JP-A No. 2000-309623 No. JP-A No. 2000-309623 The object of the present invention is to provide a phosphorus-containing flame retardant containing no halogen compound and a hardenable flame retardant resin composition containing the phosphorus-containing flame retardant and capable of being hardened by radical polymerization. Further, a cured product which is excellent in hardenability, excellent in flame retardancy, hardenability, and flexibility is obtained. In order to solve the above problems, the inventors of the present invention have repeatedly discussed the problem. As a result, it has been found that a phosphorus-containing flame retardant obtained by reacting a (meth)acryl fluorenyl group having a polyfunctional (meth) acrylate compound having a specific structure with a phosphorus compound having a P - fluorene bond is preferably a phosphorus-containing flame retardant obtained by reacting a (meth)acrylonitrile group with a phosphorus compound having a ruthenium-iridium bond, and a curable flame retardant resin composition containing the phosphorus-containing flame retardant, and capable of The above problem has been solved, and the present invention has been completed based on the findings. That is, the present invention is: φ ( 1 ) A phosphorus-containing flame retardant which is a (meth) acrylonitrile group having a polyfunctional (meth) acrylate compound represented by the following formula (1) and having P _ Η 之 phosphorus compound is obtained by reacting, formula (1)

(2) The phosphorus-containing flame retardant of (i) above, wherein n + m + l + 0 + p + q in the formula (丨) is an integer of 3 to 12; '200846353 (3) The phosphorus-containing flame retardant according to the above (1) or (2), wherein the compound having a P - Η bond of Mohr is reacted with a relative olefin group; the system is 0 · 3 5~〇. 7 & 1 (a) The phosphorus compound of the phosphorus-containing hardening-ruthenium bond according to any one of the above (1) to (3) is the following formula (2) or formula (1), formula (2) a flammable agent having a phosphine oxide as shown

(wherein R2 and R3 each independently represent a hydrogen atom, an aliphatic group having a carbon number of 1 to 10, or an aromatic group having 6 to 10 carbon atoms; and r and s each represent an integer of 1 to 4; r and When s is plural, 'each & 2 and R3 can be the same or different, % (3)

(wherein R4 and R5 each independently represent a hydrogen atom, an aliphatic group having 1 to 1 carbon atoms or an aromatic group having 6 to 10 carbon atoms; and t and u are integers of 1 to 200846353 5; t and When u is a plural number, each of R 4 and R 5 may be the same or different); (5) a curable flame retardant resin composition containing an alkali-soluble resin, a (meth) acrylate compound, An epoxy resin, a photopolymerization initiator, and a phosphorus-containing flame retardant according to any one of the above (1) to (4); (6) The curable flame retardant resin composition according to (5) above, wherein It is made by mixing 20 to 70% by mass of an alkali-soluble resin, 5 to 30% by mass of a (meth) acrylate compound, 5 to 50% by mass of an epoxy resin, and 1 to 10% by mass of light. The polymerization initiator and 5 to 40% by mass of the phosphorus-containing flame retardant according to any one of the above (1) to (4). According to the present invention, it is possible to provide a phosphorus-containing flame retardant containing no halogen compound and a curable flame retardant resin composition containing the phosphorus-containing flame retardant and capable of being hardened by radical polymerization. A cured product which is excellent in flame retardancy, hardenability, and flexibility, and has excellent hardenability. [Embodiment] The best shape for carrying out the invention The present invention will be described in detail below. The present invention is a phosphorus-containing flame retardant obtained by reacting a (meth)acrylonyl group of a (meth)acrylic acid compound represented by the above formula (1) with a phosphorus compound having a P - fluorene bond. It is preferable to obtain a phosphorus-containing flame retardant which is obtained by reacting a phosphorus compound having a P-fluorene bond with a molar amount of 0.35 to 0.7 mol with respect to 1 mol of the (meth) acrylonitrile group, and hardening property containing the same Flammable resin composition. 200846353 The above compound represented by η is a compound obtained by dehydration condensation reaction of a hydroxyl group of dipentaerythritol with (meth)acrylic acid (n + m + 1 + 〇 + p + q 020, such as dipentaerythritol hexa(methyl) (Acrylate) or after the addition of caprolactone to the hydroxyl group of dipentaerythritol, the resulting hydroxyl group is further subjected to a dehydration condensation reaction with (meth)acrylic acid. As a specific product of the latter, a limited amount of Nippon Chemical Co., Ltd. can be exemplified. KAYARAD (registered trademark) DPCA-30 manufactured by the company (in the above formula (1), R1 is a hydrogen atom, n + m + o + p + q + r = 3), and DPCA-60 (in the above formula (1), R1 is • hydrogen atom, n + m + o + p + q + r^G), DPCA-12 0 (in the above formula (1), R1 is a hydrogen atom, n + m + o + p + q + r= 12) When dipentaerythritol hexa(meth) acrylate is used, since the softening property is lost if the amount of the phosphorus compound having a P - fluorene bond is small, it is preferably relative to (meth) acrylonitrile. The base 1 molar, the phosphorus compound having a P-fluorene bond reacts within a range of 0.5 to 0.7 mol. Further, n + m + o + p + q + r = When it is 3 to 12, the compound of the above formula (1) has six (meth)acryl fluorenyl groups in one molecule, and has excellent hardenability and flexibility by a caprolactone residue. A phosphorus atom can be introduced by adding a compound having a P - fluorene bond to a (meth) acrylonitrile group of the compound of the formula (1). From the viewpoint of flame retardancy and stability of the compound, it is preferable to have Ρ-Η. Examples of the compound of the bond include compounds represented by the above formulas (2) and (3). Specific examples of R2, R3, R4 and R5 in the above formulas (2) and (3) are as carbon numbers 1 to 10. Examples of the aliphatic group include a methyl group, an ethyl group, a n-propyl group, a n-butyl group, a hexyl group, and a 2-ethylhexyl group; and examples of the aromatic group having a carbon number of 6 to 10 include a phenyl group and a tolyl group. , xylyl, naphthyl, etc. The phosphorus compound of Tejia-10 - 200846353 is a compound of the formula (4) wherein R2, R3, R4 and R5 are all hydrogen atoms (9,10-dihydrogen) -9-噚-10-phosphaphenanthrene-10-oxide, Sanguang Co., Ltd., trade name HCA), diphenylphosphine oxide represented by formula (5), double (2) represented by formula (6) Methylbenzene Phosphine oxide, bis(2,5-dimethylphenyl)phosphine oxide represented by formula (7), bis(2,4,6-trimethylphenyl)phosphine oxide represented by formula (8) Equation (4)

H3C 200846353 (7)

Formula (8)

For the compound of the formula (1), the amount of addition of the bond is preferably in the range of 0.35 to 0.7 mol, preferably in the range of 1 mol to 1 mol of the (meth) acrylonitrile group. 0.35~0.5 m. If the amount of addition is in this range, sufficient flame retardancy can be obtained, and heat resistance does not decrease. Further, as described above, & n + m + l + o + p + q = 0, for the purpose of obtaining flexibility, &

The shell U is preferably 〇.5 〇. 7 摩尔 with respect to 1 mol of the (meth) acrylonitrile group. The reaction of the (meth)acrylic compound represented by the above formula (1) with the phosphorus-containing compound having a p bond is carried out by, for example, a reaction formula of the following formula (9), whereby a phosphorus-containing flame retardant can be obtained. In the reaction vessel, the mixture is stirred and heated, and it is heated. The catalyst is not particularly required. The reaction system is blown with dry air at a temperature of 50 to 180 ° C, preferably 1 〇 〇 to 1 3 〇 -12 to 200846353 ° C, and the reaction time is 〇 5 to 50 hours. When the temperature is too low, the reaction proceeds slowly and wastes time. When the temperature is too high, the polymerization reaction of the (methyl) ampoule forms a gel. The reaction may be carried out without using a solvent, and the inert solvent in the reaction may be selected depending on the solubility of the raw material and the reaction temperature. Formula (9)

(R2, R3, r and s are the same meanings as described above, and X represents a hydrocarbon group.) The phosphorus-containing flame retardant thus obtained preferably has a phosphorus content of 1 to 9% by mass, more preferably 2 to 8 . 5 mass%. When the phosphorus content is in the range of 1 to 9% by mass, the appearance of flame retardancy is also sufficient, the compatibility with other resin components is lowered, and the curability is not lowered. Since the phosphorus-containing flame retardant of the present invention forms a P · C bond which is hydrolytically stable, it has high hydrolysis resistance and contains the phosphorus-containing flame retardant as compared with a general flame retardant phosphate-based flame retardant. The cured product of the curable flame retardant resin composition is also flexible, and is suitable for use in insulating materials such as printed wiring boards and electronic components, and is suitable for use in suitable applications, and is particularly suitable for use in soldering for flexible substrates. Photoresist use. Next, the curable flame retardant resin composition will be described. -13- 200846353 The curable flame retardant resin composition of the present invention contains various resin components, tanning materials, fiber reinforced materials, additives, and the like depending on the application. For example, in the case of solder resist use, in addition to the phosphorus-containing flame retardant of the present invention, the following components are generally used as a main component: (1) an alkali-soluble resin, (2) a (meth) acrylate compound, (3) Epoxy resin, (4) photopolymerization initiator, (5) if necessary, etc. U) alkali-soluble resin alkali-soluble resin has a carboxyl group in the molecule, so that the alkali developer φ is dissolved and light can be imparted It is used for the purpose of the basic physical properties such as heat resistance, hardness, and flexibility of the barrier film. The alkali-soluble resin may, for example, be an epoxy group acrylate resin having a carboxyl group, which is a hydroxyl group of an epoxy group (meth) acrylate resin formed by adding an epoxy resin and (meth)acrylic acid shown below. It is obtained by reacting an acid anhydride such as succinic anhydride, tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride or hexahydrophthalic anhydride. Examples of the epoxy resin which can be used herein include bisphenol A epoxy resin, bisphenol F epoxy resin φ grease, tetramethyl bisphenol F epoxy resin, and phenol novolac epoxy resin. A cresol novolac type epoxy resin, a cyclopentadiene type epoxy resin, a biphenyl aralkyl type epoxy resin, a naphthol aralkyl type epoxy resin, a naphthol novolac type epoxy resin, or the like. Further, a (meth)acrylic acid urethane resin having a hydroxyl group as described in JP-A-2002-202-9201 can be exemplified. Further, a carboxylic acid having an ethylenically unsaturated group such as (meth)acrylic acid or an acrylic acid dimer, and a monomer having another ethylenically unsaturated group, for example, styrene, methylstyrene, or vinyl acetate, may be exemplified. , (meth)acrylic acid-14- 200846353 methyl ester, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, (a Tertiary butyl acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, (meth) acrylate Borneol ester, tetrahydrofuran methyl (meth)acrylate, (meth)acrylonitrile, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, N-vinylpyrrolidine a resin obtained by copolymerizing a compound having an ethylenically unsaturated group such as a ketone, N-vinyl caprolactam or N-(methyl)propenylmorpholine, and a hydroxy group of the resin Part with glycidyl (meth)acrylate, (meth) propyl Oleic acid-3,4-epoxycyclohexylmethyl ester, 4-(2,3-epoxypropyl)butyl (meth) acrylate, allyl glycidyl ether, etc. having an epoxy group A resin derived from a compound. Similarly, it can also be exemplified by having glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, and 4-(2,3-epoxypropyl)(meth)acrylate. a resin obtained by copolymerization of a compound having an epoxy group such as butyl ester and allyl glycidyl ether with an ethylenically unsaturated group, and a compound having a protonated ethylenically unsaturated group; and exemplified in the resin After adding a hydroxyl group of a carboxylic acid having an ethylenically unsaturated group such as (meth)acrylic acid or an acrylic acid dimer to an epoxy group, the resulting hydroxyl group is succinic anhydride, tetrahydrophthalic anhydride, and methylhexahydrobenzene. A resin obtained by reacting an acid anhydride such as dicarboxylic anhydride or hexahydrophthalic anhydride. The blending amount of the alkali-soluble resin is preferably from 20 to 70% by mass, more preferably from 30 to 60% by mass, based on the curable flame-retardant resin composition. (2) (Meth) acrylate compound -15- 200846353 The (meth) acrylate compound is used for the purpose of imparting high photocurability to a solder resist material. Specific examples thereof include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and tetraethylidene di(methyl). Acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, anthracene, 4-butadiene Alcohol di(meth)acrylate, anthracene, 3-butanediol di(meth)acrylate, neopentyl di(meth)acrylate, 1,6-hexanediol di(meth)acrylic acid Φ Di(meth) acrylate such as ester, bisglycidyl (meth) acrylate, dimethylolpropane di(meth) acrylate, pentaerythritol tri(meth) acrylate, represented by formula (1) Polyacrylates such as compounds, ethylene oxide 4 molar addition diacrylate of bisphenol 8, epoxy bisphenol 4 mil addition diacrylate, fatty acid modified pentaerythritol diacrylate, trimethyl丙 兀 兀 兀 我 我 我 ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; Alkyl of 6 mole propylene oxide adduct triacrylate modified polyol polyacrylate. The blending amount of the (meth) acrylate compound is preferably from 5 to 30% by mass, more preferably from 5% to 25 % by mass in the curable flame retardant resin composition. (3) Epoxy resin The oxy-resin is used for the purpose of imparting heat resistance and toughness to the photoresist film. Examples of the epoxy resin include bisphenol A epoxy resin, bisphenol F epoxy resin, tetramethyldicarboxylic acid F epoxy resin, benzene round epoxy resin, and toluic acid furfural ring. Oxygen resin, dicyclopentadiene type epoxy: fat, biphenyl aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, -16- 200846353 naphthol novolac type epoxy resin, triphenyl Methane type epoxy resin, N-glycidyl type epoxy resin, and the like. Further, various phosphorus-containing epoxy resins obtained by reacting the above various epoxy resins with a reactive phosphor compound to bond phosphorus atoms may be partially used. The reactive phosphorus compound may, for example, be a reaction of 9,10-dihydro-9-oxo-1 0-phosphaphenanthrene-1-oxide or diphenylphosphine oxide with benzoquinone or naphthoquinone. The product (the following formula a to d) and the like. Formula a

-17- 200846353 (c)

(d) HO The blending amount of the epoxy resin is in the curable flame retardant resin composition, and is preferably 5 to 50% by mass, more preferably 10 to 40% by mass. (4) Photopolymerization initiator The photopolymerization initiator is used for the purpose of imparting photocurability to a solder resist and forming a pattern by a compound capable of generating a radical by light, particularly in the ultraviolet field. Specifically, the compounds exemplified below are preferably used. For example, benzoin isobutyl ether, benzoin isopropyl ether, benzoin ethyl ether, benzyl dimethyl ketal and other benzoin compounds, diethoxyacetophenone, 2-hydroxyl -2-methyl-1-phenylpropane·1-ketone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone , 2-methyl·1-[4-(methylthio)phenyl]-2-morpholinylacetone-1,2-benzyl-2-dimethylamino-1-(4-) Polinylphenyl)-butanone-1 -18- '200846353

Acetophenone-based compound, butyral acid such as methylphenyl butyral, benzophenone, benzamidine benzoic acid methyl, hydroxydi-4-phenylbenzophenone, acrylated diphenyl a mercapto compound such as benzophenone or the like, a fluorenyl compound such as 2,4,6-trimethylbenzhydryldiphenylphosphine oxide, or bis(2,6-dimethoxybenzhydryl bromide 2,4, 4-triphosphine oxide, bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide phosphine oxide compound, etc. Further, as a sensitizer, 倂2,4-diethylthio Thioxanone such as ketone or 2-isopropylthioxanthone is 4,4'-bis(N,N-dimethylamino)benzophenone, 4,4,-diethylamino)di Use benzophenone or the like. The blending amount of the photopolymerization initiator is in the case of hardenability and flame retardancy, and is preferably from 1 to 10% by mass, more preferably from 2 to 8% by mass. (5) The tanning material is blended as needed to improve the viscosity characteristics, for example, calcium carbonate, barium sulfate, alumina, talc, vermiculite, and the amount of the mixture is relative to the alkali-soluble resin, (E acid ester compound, epoxy resin, photopolymerization initiator, and a total of 100 parts by mass of the fuel of the present invention, preferably 10 to 10%, more preferably 2 to 80 parts by mass. (6) Other additives As other additives, benzyldimethylamine, (N,N-dimethylaminomethyl)phenol, 1,8-diindole bicyclic (monocarbene-1, 2) -ethyl-4-methylimidazole, 2-phenylimidazole, imidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethylgimidazole, 1-cyanoethyl-2 -10 Examples of the mono-fluorenyl group such as a monocarbylimidazole, a 1-cyano group, an ester-based benzophenone, a ketone-based phosphine oxide-based methylpentyl group, and the like, (N, N-divalent composition, Etc. I base) propylene has a phosphorus content of more than 2,4,6 gins. 5 · 4 . 0 ) dec 2 - undecene S - 2 -phenylethyl _ 2 - methyl -19 - 200846353 11 hardened by epoxy resin such as trimellitate , 3-glycidoxypropyltrimethoxydecane, β-(3,4丨-epoxycyclohexyl)ethyltrimethoxydecane, 3-(methacryloxypropyl)trimethoxy a decane coupling agent such as a decane or a 3-aminopropyltriethoxy decane, a leveling agent, an antifoaming agent, a dispersing agent, an antioxidant, a polymerization inhibiting agent, a dye, a pigment, etc. Further, triphenyl phosphate, Tricresol phosphate, resorcinol biphenyl phosphate, resorcinol bis-xylyl phosphate, hydroxypropyl triphosphonium dichloride, phenoxy triphosphorus dichloride, etc. A phosphorus-based flame retardant can be added in a small amount without overflowing from the hardened material (b 1 eed • ut ut ). Also, an inorganic flame retardant such as aluminum hydroxide or magnesium hydroxide can also be used without physical properties. The phosphorus-containing flame retardant of the present invention has properties of flame retardancy, flexibility, and high photocurability, and therefore the curable flame retardant resin composition containing the same can be used for softness. Uses, for example, coating materials for plastic films, impregnating resins for fiber reinforced plastics, and polyphthalamides An adhesive for an amine and a copper foil, etc. Further, it can be suitably used for a solder resist, in particular, a solder resist for a flexible substrate. φ In addition to the above compounds, any one of them can be blended in order to improve various characteristics. The present invention is more specifically described by the examples, but the present invention is not limited to the examples, and the examples in the examples and the comparative examples are not particularly limited. <Synthesis Example of Phosphorus-Containing Flame Retardant> Example 1 -20- 200846353 In a reaction vessel equipped with a stirring device, a thermometer, and a condenser, KAYARAD DPCA30 at 9 2 1 g (1 mol) In the trade name, in the formula U), R1 is a hydrogen atom, n + m + l + o + p + q = 3, manufactured by Nippon Kayaku Co., Ltd., adding 3 8 8 · 8 g (1,8 mol) HCA (trade name, 9,10-dihydro- 9-oxo-1 0-phosphaphenanthrene-1 0-oxide, manufactured by Sanko Co., Ltd.), 3 2 7 g of propylene glycol methyl ether acetate An ester, 1.3 g of hydroquinone monomethyl ether (metoquinone), which is reacted at 110 ° C for 13 hours while blowing air. The compound 1 was obtained in a concentration of 80% by mass of a nonvolatile component and 4.3% by mass of a phosphorus in a nonvolatile component. Example 2 In a reaction vessel equipped with a stirring device, a thermometer, and a condenser, in a 2, 1 1 g (1 mol) KAYARAD DPCA 30 (trade name, manufactured by Nippon Kayaku Co., Ltd.), 6 4 8 g ( 3 · 0 Mo) HCA (trade name, manufactured by Erguang Co., Ltd.), 392 g of propylene glycol methyl ether acetate, 1.5 g of hydroquinone monomethyl ether, while blowing air at 11 ° ° C The reaction was carried out for 13 hours to obtain a compound 2 having a nonvolatile content of 80% by mass and a phosphorus content in the nonvolatile component of 5.9 mass%. Example 3 In a reaction vessel equipped with a stirring device, a thermometer, and a condenser, in 1 2 6 3 g (1 mol) of KAYARAD DPCA60 (trade name, formula (!), R1 is a hydrogen atom, n + m + l + o + p + q = 6, manufactured by Nippon Kayaku Co., Ltd.) 'Add 6 4 8 g (3 mol) of HCA (trade name, manufactured by Sanko Co., Ltd.), 478 g of propylene glycol A Ethyl ether acetate, 1.9 g of hydroquinone monomethyl ether, while reacting at 110 ° C while blowing air at 13 °-21 - 200846353, a non-volatile content of 80% by mass, non-volatile content The compound 3 having a scaly ratio of 4.9 mass%. Example 4 In a reaction vessel equipped with a stirring device, a thermometer, and a condenser, 607 g (3 mol) was added to KAYARAD DPCA60 (trade name, manufactured by Nippon Kayaku Co., Ltd.) of 1 2 6 3 g (1 mol). Diphenylphosphine oxide, 468 g of propylene glycol methyl ether acetate, 1.9 g of hydroquinone monomethyl ether, and reacted at 110 ° C for 13 hours while blowing air. Compound 4 having a non-volatile component concentration of 80% by mass and a non-volatile component having a phosphorus content of 5.1% by mass was obtained. Example 5 In a reaction vessel equipped with a stirring device, a thermometer, and a condenser, 7 7 5 g was added to KAYARAD DPCA 60 (trade name, manufactured by Nippon Kayaku Co., Ltd.) of 1 2 6 3 g (1 mol). (3 moles) of bis(2,5-dimethylphenyl)phosphine oxide, 510 g of propylene glycol methyl ether acetate, 2.Og of hydroquinone monomethyl ether, while blowing air at 110 ° The C reaction was carried out for 13 hours to obtain a compound 5 having a nonvolatile content of 80% by mass and a phosphorus content of 4.6% by mass in the nonvolatile component. Example 6 In a reaction vessel equipped with a stirring device, a thermometer, and a condenser, KAYARAD DPHA (trade name, dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.) was used in a 5 7 8 g (1 mol). 864 g (4 mol) of HCA, 618 g of diethylene glycol ethyl ether acetate, 1.44 g of hydroquinone monomethyl ether were added, and the reaction was carried out at 110 ° C -22 - 200846353 for 13 hours while blowing air. A compound having a nonvolatile content of 70% by mass and a phosphorus content of 8.6% by mass in a nonvolatile matter was obtained. Example 7 In a reaction vessel equipped with a stirring device, a thermometer, and a condenser, at 5 7 8 g (1) In KAYARAD DPHA of Moer), 809g (4 moles) of diphenylphosphine oxide, 595g of diethylene glycol ethyl ether acetate, 1.44g of chlorine chlorinated monomethyl The reaction was carried out at 110 ° C for 3 hours while blowing air, and a compound 7 having a nonvolatile content concentration of 7 〇 mass% and a phosphorus content of 8.9% by mass in the nonvolatile matter was obtained. 0Comparative Example 1 In a reaction vessel equipped with a stirring device, a thermometer, and a condenser, in a KAYARAD DPHA of 5 7 8 g (1 mol), a HCA (trade name) of 432 g (2. Mohr) was introduced. 353g of propylene glycol methyl ether acetate, hydrazine monomethyl ether of 丨.〇2, reacted at 1 10 C for 13 hours while blowing air, and obtained a non-volatile concentration of 80. % by mass and compound 8 in a non-volatile component having a phosphorus content of ό·1% by mass. ® Comparative Example 2 In a reaction vessel equipped with a stirring device, a thermometer, and a condenser, 216 g (1.0 mol) of HCA (trade name, three light) was added to 282 g (l mol) of trimethylolpropane triacrylate. Manufactured by Co., Ltd., 125 g of propylene glycol methyl ether acetate, and 5 g of hydroquinone monomethyl ether, and reacted at 1 1 ° C for 13 hours while blowing air to obtain a non-volatile concentration of 80. % by mass and compound 9 in a non-volatile content having a phosphorus content of 6 J mass%. -23- 200846353 <Synthesis of alkali-soluble resin> As the alkali-soluble resin, a urethane acrylate resin (U A - 1 ) having a hydroxyl group is synthesized as follows. In a reaction vessel equipped with a stirring device, a thermometer, and a condenser, 850 g (1 mol) of polytetramethylene glycol (PTG-850SN manufactured by Hodogaya Chemical Industry Co., Ltd., molecular weight 850) and 938 g (7 mol) were charged. Dihydroxymethylpropionic acid, 1998 g (9 mol) of isophorone diisocyanate, 1006 g of propylene glycol methyl ether acetate. While stirring, the mixture was stopped until it was heated to $60 °C, and 1.4 g of dibutyltin dilaurate was added. When the temperature in the reaction vessel was initially lowered, it was again heated to 80 ° C, and stirred at 7 5 to 8 5 ° C for 8 hours to synthesize a urethane oligomer. Then, each of 0. 9 g of P-methoxyphenol and di-tert-butyl-hydroxytoluene was introduced into the reaction vessel, and then 2 3 8 g (2·5 5 mol) of 2-hydroxyethyl acrylate was added. , start the reaction again. When the absorption spectrum of the isocyanate group (2,2 0 0 c π Τ 1 ) disappeared by the infrared absorption spectrum, the reaction was terminated to obtain a viscous liquid urethane acrylate compound. The obtained urethane acrylate (UA-1) had an average molecular weight of 1,600, a solid content of 90 mgKOH/g, and a nonvolatile content of 80% by mass. <Preparation of Curable Flame Retardant Resin Composition> Examples 8 to 14 and Comparative Examples 3 and 4 The blending ratio (parts by mass) shown in Table 1-1 and Table 1-2 described later, blended and mixed A phosphorus-containing flame retardant, an alkali-soluble resin (UA-1), a (meth) acrylate compound, an epoxy resin, a photopolymerization initiator, a dip, a thermal polymerization catalyst, to prepare a hardenability and flame retardancy Resin composition. Here, the main agent and the hardener of each of the examples and the comparative examples were passed through three times and kneaded by three roll type honing machines -24-200846353 (formed by RIII-1RM-2, Ltd.). The flame retardant resin composition is prepared. Phosphorus-containing epoxy resin ZX-1548-4 (trade name, phosphorus content: 4% by mass, dissolved in diethylene glycol ethyl ether acetate manufactured by Dongdu Chemical Co., Ltd., prepared to have a solid concentration of 70% by mass) A cresol novolac type epoxy resin EPICON, N680 (manufactured by Dainippon Ink and Chemicals Co., Ltd., dissolved in diethylene glycol ethyl ether acetate to prepare a solid concentration of 80% by mass) was used as an epoxy resin. Irgacure 907 (product name, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylacetone-1, manufactured by Ciba Specialty Industries, Inc.) ), Lucirin TPO (trade name, 2,4,6-trimethylbenzimidylphenylphosphine oxide, manufactured by BASF), EAB-F (trade name, 4,4 '-bis(diethylamino) ) benzophenone, manufactured by Hodogaya Chemical Industry Co., Ltd.) as a photopolymerization initiator. Melamine P C - 1 (trade name, manufactured by Nissan Chemical Industry Co., Ltd.) was used as an epoxy resin hardening accelerator. The aluminum hydroxide of the inorganic flame retardant is Η I G I L I T E Η 4 2 I S T E (trade name, 0 manufactured by Showa Denko Co., Ltd.). The talc Hi-F i 1 1 e r # 5 0 0 0 P (trade name, manufactured by Matsumura Industrial Co., Ltd.) was used as the inorganic tanning material. <Production and Evaluation of Test Piece> (1) Sensitivity A printed circuit board formed by laminating a copper foil having a thickness of 35//m on one side of a polyimide film having a thickness of 50 μm (Ube Industries Co., Ltd.) Manufactured by the company, UPISEL (registered trademark) N is washed with a 1% by mass aqueous solution of sulfuric acid, and washed with water after washing with water.) Warmed to 60. -25-200846353 The curable flame-retardant resin composition obtained in Examples 8 to 14 and Comparative Examples 3 and 4 was applied to the substrate by a 150-mesh polyester plate by a screen printing method. The thickness is 20~25//m. The substrate was dried at 80 ° C for 30 minutes, and then passed through a 2 1 step ladder plate (ste ρ tab 1 ets by an exposure machine having a metal halide lamp [〇RC (share)] MW MW - 6 8 0 GW (Manufactured by Hitachi Chemical Co., Ltd., 〇D値Ο. Ο 5~ 3.05 > A(deita)D-0. 15) 21-segment ladder (made by Hitachi Chemical Co., Ltd.) to 5000 m 〗 / cm 2 for exposure. Next, at 30 ° C, the unexposed portion was removed by spraying a 1% by mass aqueous sodium carbonate solution for 60 seconds to develop, and the number of completely hardened portions was read as the sensitivity of the composition. (2) Flexibility The curable flame-retardant resin compositions obtained in Examples 8 to 14 and Comparative Examples 3 and 4 were obtained by a screen printing method at a thickness of 25 Rm and 70 mm x 50 mm in a 150-mesh polyester plate. The polyimide film (made by Toray Dupont Co., Ltd., Kapton 100H) was coated on one surface with a thickness of 20 to 25 μm, and dried at 80 ° C for 30 minutes. The pre-exposure machine is exposed at 5000 m J / cm 2 . Then, after heat hardening at 1 50 °c x 60 minutes, the coated surface was bent 180 ° on the outside to visually judge whether or not whitening of the cured film occurred. The criterion is as follows: 〇: There is no whitening of the cured film, and X: the cured film is whitened or cracked. (3) Flammability The flammability test piece was formed into a polyimide film having a thickness of 25 μm, 200 mm >< 50 mm by the following method (Toray -26-200846353)

The hardening property of Examples 8 to 14 and Comparative Examples 3 and 4 was difficult to be obtained by the screen printing method on the single side of the substrate of Dupont Co., Ltd., Kapton 100H) using a 150-mesh polyester plate. The flammable resin composition was applied to a thickness of 20 to 25 μm, and subjected to solvent drying at 80 ° C for 30 minutes, and then thermally cured at 150 ° C for 60 minutes. Then, on the other surface, the curable flame retardant resin composition obtained in Examples 6 to 10 and Comparative Examples 3 and 4 was applied in the same manner by a screen printing method to a thickness of 2 〇 to 2 5 μm. Thereafter, solvent drying and heat hardening were carried out under the same conditions to prepare a sample. The combustion knows that the flame retardancy is evaluated according to the method of the flame retardancy test specification of the polymer material of Underwriters Laboratories I n c · (Insurer Laboratory, u L for short). Further, "VTM" and "NOT" in Table 1-1 and Table 1-2 are as follows. VTM-0 : Fully meets the following requirements. (1) The entire test piece was fired after more than 1 second after the flame was stopped. (2) A total of 1 接 of flames were applied to each of the 5 test pieces of each group, and the flame burning hours totaled no more than 50 seconds. (3) Flame or red heat combustion systems do not reach the 1 2 5 m m marking. (4) Degreased cotton does not catch fire due to flame dripping. (5) After the second flame is stopped, the flame and red heat of each sample are not more than 30 seconds. -27- 200846353 (6) When only one of the five test pieces in a group does not meet the requirements, or when the total flame time is in the range of 5 1 second to 55 seconds, 5 test pieces are tested. The above (1) to (5) are completely satisfied. V T Μ - 1 : The following requirements are fully met. (1) After the flame was stopped, the entire test piece did not undergo flaming combustion for more than 30 seconds. (2) A total of 10 flames were applied to each of the five test pieces of each group, and the total flame burning time was not more than 260 seconds. φ ( 3 ) Flame or red heat combustion system does not reach the 1 2 5 m m marking. (4) Degreased cotton does not catch fire due to flame dripping. (5) After the second flame is stopped, the flame and red heat of each sample are not more than 60 seconds. (6) When only one of the five test pieces of the group 1 does not meet the requirements, or when the total flame time is in the range of 2 5 1 second to 2 55 seconds, 5 test pieces are tested, which fully satisfy the above (1) to (5). VTM-2: Fully meets the following requirements. ^ (1) The test piece as a whole is not flaming after more than 30 seconds after each flame is stopped. (2) A total of 1 接 of flames was applied to each of the 5 test pieces of each group, and the total flame burning time was not more than 260 seconds. (3) Markings with a flame or red heat burning up to 1 2 5 m m. (4) Degreased cotton can catch fire due to flame dripping. (5) After the second flame is stopped, the flame and red heat of each sample are not more than 60 seconds. -28 - 200846353 (6) When only one of the five test pieces in the first group did not meet the requirements, or when the total flame time was in the range of 2 5 1 second to 2 55 seconds, 5 test pieces were tested. , completely satisfying the above (1) to (5). N〇T : None of the above grades were qualified.

-29- 200846353 Table 1 - 1 Blending Composition and Evaluation Results of Each Example and Comparative Example

Blending composition [mixing amount of non-volatile component in parts by mass] 1 Team Example 8 1 1 Example 9 Example 10 Example 11 Example 12 Resin component UA-1 (nonvolatile content concentration 80% by mass 50.0 (40.0) 50.0 (40.0) 50.0 (40.0) 50.0 (40.0) 50.0 (40.0) H HIGILITE H42ISTE 20.0 (20.0) 20.0 (20.0) 20.0 (20.0) 20.0 (20.0) 20.0 (20.0) Miscellaneous Hi-Filler #5000PJ 15.0 (15.0) 15.0 (15.0) 15.0 (15.0) 15.0 (15.0) 15.0 (15.0) Composition of epoxy-based hardening catalyst melamine PC - 1 0.5 (0.5) 0.5 (0.5) 0.5 (0.5) 0.5 (0.5) 0.5 (0.5) Main Irgacure 907 3.0 (3.0) 3.0 (3.0) 3.0 (3.0) 3.0 (3.0) 3.0 (3.0) : ft polymerization initiator L uciri η TP 0 (phosphorus content 8 · 9 mass%) 0.5 (0.5) 0.5 (0.5) 0.5 (0.5) 0.5 (0.5) 0.5 (0.5) EAB-F 0.5 (0.5) 0.5 (0.5) 0.5 (0.5) 0.5 (0.5) 0.5 (0.5) Solvent Diethylene Glycol Ethyl Acetate · 10.0 10.0 10.0 10.0 10.0 Epoxy resin N - 6 8 0 (non-volatile content concentration 80% by mass) 12.5 (10.0) 12.5 (10.0) 12.5 (10.0) 12.5 (10.0) 12.5 (10.0) ZX-1548-4 (Non- Volatile concentration 70% Amount % Non-volatile content of phosphorus content 4% by mass) 2 1.4 (15.0) 2 1.4 (15.0) 2 1.4 (15.0) 2 1.4 (15.0) 2 1.4 (15.0) Acrylate monomer pentaerythritol triacrylate 10.0 (10.0) 14.0 (14.0) 10.0 (10.0) 10.0 (10.0) 10.0 (10.0) Compound 1 (phosphorus content 4.3% by mass in non-volatile content) 25.0 (20.0) - - - - Blending compound 2 (Phosphorus content 5.9 mass in non-volatile content) %) - 20.0 (16.0) - - - Compound 3 (phosphorus content of non-volatile components 4.9% by mass) - - 25.0 (20.0) • - Compound 4 (Phosphorus content of non-volatile components 5.1% by mass) - - - 25.0 (20.0 ) - Hardener phosphorus-containing (meth)acrylic compound compound 5 (phosphorus content of non-volatile components: 4.6% by mass) - • - - 25.0 (20.0) 'Compound 6 (phosphorus content of non-volatile components: 8.5% by mass) - - - - - Compound 7 (Phosphorus content of non-volatile components is 8.9% by mass) - - - - - Compound 8 (Potas content of non-volatile components is 6.2% by mass) - - - - - Compound 9 (Plasma content of non-volatile components is 6.2% by mass) ) - - - - - + tone HIGILITE H421STE 20.0 (20.0) 20.0 (20,0) 2 0.0 (20.0 20,0 (20.0) 20.0 (20.0) Hi Hi-Filler #5 00 0PJ 15.0 (15.0) 15.0 (15.0) 15.0 (15.0) 15.0 (15.0) 15.0 (15.0) Solvent Diethylene Glycol Ethyl Acetate Ester 10.0 10.0 10.0 10.0 10.0 Solvent in organic matter other than phosphorus content (% by mass) 1.5 1 1.59 1.58 1.67 1.57 Sensitivity 6 6 5 5 5 BT top towel mouth and bending 〇〇〇〇〇 flame retardant (UL - 9 4 ) VT Μ - 0 V Τ Μ - 0 VTM-0 VTM -0 V Τ Μ - 0 -30- 200846353 Table 1 · 2 Blending composition and evaluation results of each example and comparative example

Blending composition [mixing amount of non-volatile components in parts by mass] 1 Team Example 13 Example 14 Comparative Example 3 Comparative Example 4 Resin component UA-1 (nonvolatile content concentration 80% by mass) 50.0 (40.0) 50.0 (40.0) 50.0 (40.0) 50.0 (40.0) Dip - HIGILITE H42ISTE 20.0 (20.0) 20.0 (20.0) 20.0 (20.0) 20.0 (20.0) Blending Hi-Filler #5 0 00 PJ 15.0 (15,0) 15.0 (15.0) 15.0 (15.0) 15.0 (15.0) Composition of epoxy-based hardening catalyst melamine PC-1 0.5 (0.5) 0.5 (0.5) 0.5 (0.5) 0.5 (0.5) Main Irgacure 907 3.0 (3.0) 3.0 (3.0) 3.0 (3.5) 3.0 (3.5) Xiangguang polymerization initiator L uciri η TP 0 (phosphorus content 8.9 mass%) 0.5 (0.5) 0.5 (0.5) 0.5 (0.5) 0.5 (0.5) E AB-F 0.5 (0.5) 0.5 (0.5) 0.5 (0.5) 0.5 (0.5) Solvent Diethylene glycol ethyl ether acetate 10.0 10.0 10.0 10.0 Epoxy resin N-680 (non-volatile content concentration 80% by mass) 12.5 (10.0) 12.5 (10.0 12.5 (10.0) 12.5 (10.0) ΖΧ· 1 5 4 8 -4 (non-volatile content 70% by mass phosphorus content 4% by mass in non-volatile components) 2 1.4 (15.0) 21.4 (15.0) 21.4 (15.0) 2 1.4 (15.0) C Ethyl ester monomer pentaerythritol triacrylate 10.0 (10.0) 10.0 (10.0) 14.0 (14.0) 14.0 (14.0) Compound 1 (phosphorus content in non-volatile components 4 · 3 mass %) - - - - Blending compound 2 (Non- Phosphorus content of volatile components: 5.9 mass%) - - - - Compound 3 (phosphorus content of non-volatile components 4.9% by mass) - - - - Composition of compound 4 (phosphorus content of non-volatile components 5.1% by mass) - - - - Hardener containing phosphorus (meth) acrylate compound 5 (phosphorus content of non-volatile components 4.6% by mass) - - - - Compound 6 (scale content of non-volatile components 8.5 mass%) _ 15.0 (10.5) - - - Compound 7 (Phosphorus content of non-volatile matter 8.9% by mass) - 15.0 (10.5) - - Compound 8 (Potas content of non-volatile components: 6.2% by mass) - - 20.0 (16.0) - Compound 9 (Phosphorus content in non-volatile components 6 . 2 mass % ) - - - 20.0 (16.0) HIGILITEH 421STE 2 0.0 (20.0) 2 0.0 (20.0) 20.0 (20.0) 2 0,0 (20.0) Hi Hi-Filler #5000PJ 15.0 (15.0) 15.0 (15.0) 15.0 (15.0) 15.0 (15.0) Solvent Diethylene Glycol Ethyl Acetate 10.0 10.0 10.0 10.0 Dissolved 1 , Phosphorus content in organic components (% by mass) 1.53 1.5 8 1.63 1 .64 c=7T\ ya® {τάζ FIELD Sensitivity 5 5 . 6 3 Evaluation of knots 'WWW '~ 〇〇X 〇 Flame retardant (UL - 9 4 ) VTM-0 VTM-0 VTM-0 VTM-0 200846353 As shown in Table 1-1 and Table i-2 'by using the phosphorus-containing flame retardant of the present invention, it is shown to be sufficiently flame retardant Sex, sensitivity 'softness. Therefore, the phosphorus-containing flame retardant of the present invention has, in particular, suitability for use in applications having both flexibility and flame retardancy. According to the present invention, it is possible to provide a phosphorus-containing flame retardant containing no halogen compound and a curable flame retardant resin composition which contains the phosphorus-containing flame retardant and can borrow Hardened by free radical polymerization, and obtained in hard

A hardened W material that is excellent in refractory properties, excellent in flame retardancy, hardenability, and softness. [Simple description of the schema] Sister. [Main component symbol description] y v\\

-32-

Claims (1)

200846353 X. Patent application scope: 1. A phosphorus-containing flame retardant which is a (meth) acrylonitrile group having a polyfunctional (meth) acrylate compound represented by the following formula (1) and having a P-? The phosphorus compound of the bond is obtained by reacting, formula (1) (wherein R1 represents a hydrogen atom or a methyl group, and further, n + m + 1 + o + p + q = 0 to 1 2 integer). 2. The phosphorus-containing flame retardant according to claim 1, wherein n + m + 1 + o + p + q in the formula (1) is an integer of from 3 to 12. 3 · If the phosphorus-containing flame retardant of claim 1 or 2 is applied, it is 0. 3 5~0. 7 moles of compound having P Η bond and relative to 1 mole of (meth) Acetylene thiol reaction derived. 4. The phosphorus-containing flame retardant according to any one of claims 1 to 3, wherein the phosphorus compound having a Ρ-Η bond is a phosphine oxide compound represented by the following formula (2) or (3), 33- 200846353 (2) (wherein R2 and R3 each independently represent a hydrogen atom, an aliphatic group having 1 to 1 carbon atoms or an aromatic group having 6 to 10 carbon atoms, and r and s each represent an integer of 1 to 4; r& When s is plural, each R2 and R3 system may be the same or different, and formula (3) h φ (wherein R 4 and R 5 each independently represent a hydrogen atom, an aliphatic group having 1 to 10 carbon atoms or an aromatic group having 6 to 10 carbon atoms; and t and U are integers of 1 to 5; When t and u are plural, each of R4 and R5 may be the same or different. 5 - a hardenable flame retardant resin composition comprising an alkali-soluble resin, a (meth) acrylate compound, an epoxy resin, a photopolymerization initiator, and any one of claims 1 to 4 The composition of the phosphorus-containing flame retardant. -34- 200846353 6. A sclerosing flame retardant resin composition according to claim 5, which comprises a mixture of 20 to 70% by mass of an alkali-soluble resin and 5 to 30% by mass of a (meth) acrylate. a compound, 5 to 50% by mass of an epoxy resin, 1 to 10% by mass of a photopolymerization initiator, and 5 to 40% by mass of a phosphorus-containing flame retardant according to any one of claims 1 to 4 of the patent application. Composition of the agent. -35- 200846353 VII. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: Μ 〇 8. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention.