TW201917169A - Unsaturated polyester resin composition - Google Patents

Abstract

The purpose of the present invention is to provide an unsaturated polyester resin composition which has excellent impact resistance. The present invention provides an unsaturated polyester resin composition which contains an unsaturated polyester (A), an allyl polymer (B) that is obtained by polymerizing an allyl compound represented by formula (1), and a polyfunctional monomer (C) that has two or more (meth)acryloyl groups or two or more allyl groups, and which has excellent impact resistance. X-(COOCH2CH=CH2)n (1) (In the formula, n represents an integer of 2-4; and X represents an n-valent alicyclic hydrocarbon group which may have an alkyl group).

Description

Unsaturated polyester resin composition

The present invention relates to an unsaturated polyester resin composition excellent in impact resistance.

Thermosetting resin molding materials with excellent reliability or heat resistance are used in electronic parts such as capacitors, coils, and resistors. Although the required performance differs depending on the shape or size of electronic parts, physical properties include moisture resistance, low stress, high thermal conductivity, and impact resistance. As a resin satisfying this performance, a thermosetting resin such as diallyl phthalate resin or unsaturated polyester resin can be used.

However, with the recent increase in the functionality and miniaturization of electronic information equipment, the performance requirements for molded parts using thermosetting resins have become increasingly stringent. In particular, as the wall thickness is reduced along with the miniaturization, further improvement in impact resistance is sought.

As a method of improving impact resistance, Patent Documents 1 to 3 disclose acrylic resins made of rubbery polymers or having a specific average particle diameter (for example, an average particle diameter of about 0.05 to 100 μm, Patent Document 3). A method of dispersing fine particles composed of thermoplastic resin in an unsaturated polyester resin composition. However, in order to uniformly disperse fine particles of about several tens of micrometers in the composition, a high-level kneading technique is required, and in the case of insufficient dispersion, there is a concern that the physical properties may deviate. Prior art literature Patent literature

Patent Document 1: Japanese Patent Application Publication No. 2003-327845 Patent Document 2: Japanese Patent Application Publication No. 2004-123897 Patent Document 3: Japanese Patent Application Publication No. 2004-269761

[Problems to be solved by the invention]

An object of the present invention is to provide an unsaturated polyester resin composition excellent in impact resistance. [Technical means to solve the problem]

The present inventors have made intensive studies and found that by using an unsaturated polyester resin composition, a resin composition with improved impact resistance can be obtained, thereby completing the present invention, wherein the unsaturated polyester resin composition contains : Unsaturated polyester (A); allyl polymer (B) obtained by polymerizing the allyl compound represented by formula (1) [Wherein, n represents any integer from 2 to 4, X is an alicyclic hydrocarbon group which may have an n-valence of an alkyl group]; and 2 or more (meth) acryl acetyl groups, or 2 or more alkenes Propyl multifunctional monomer (C).

Item 1. An unsaturated polyester resin composition containing: an unsaturated polyester (A); an allyl polymer (B) obtained by polymerizing an allyl compound represented by formula (1) [Wherein, n represents any integer from 2 to 4, X is an alicyclic hydrocarbon group which may have an n-valence of an alkyl group]; and 2 or more (meth) acryl acetyl groups, or 2 or more alkenes Propyl multifunctional monomer (C). Item 2. The unsaturated polyester resin composition according to Item 1, wherein the allyl compound represented by the above formula (1) is any one of the compounds represented by the following formulas (4) to (11) By [Wherein, n represents any integer from 2 to 4]. Item 3. The resin composition according to Item 1 or 2, wherein the polyfunctional monomer (C) having two or more (meth) acryloyl groups or two or more allyl groups is represented by the formula ( 2) The allyl compound represented by or the (meth) acrylate compound represented by formula (3) [Wherein, n represents any integer from 2 to 4, Y is a bonding part, an n-valent aliphatic chain hydrocarbon group, an n-valent alicyclic hydrocarbon group which may have an alkyl group, or an n-valent aromatic hydrocarbon group , When Y is the bonding part, n is 2, 2 -COOCH ₂ CH = CH ₂ direct bonding], or [In the formula, n represents any integer from 2 to 4, R ₁ represents H or CH ₃ , and Z is an n-valent aliphatic chain hydrocarbon group having 2 to 10 carbon atoms]. Item 4. The composition according to any one of Items 1 to 3, which further contains a polymerization initiator (D). Item 5. The composition according to any one of Items 1 to 4, which further contains an inorganic filler (E). Item 6. A cured product obtained by thermally curing the unsaturated polyester resin composition according to any one of Items 1 to 5. Item 7. A molded product formed by molding the unsaturated polyester resin composition according to any one of Items 1 to 6.

The present invention has been completed based on the above findings and provides an unsaturated polyester resin composition excellent in impact resistance. [Effect of invention]

According to the present invention, an unsaturated polyester resin composition can be obtained that maintains heat resistance and insulation while having excellent impact resistance and is effective for miniaturization and thinning of electronic parts.

Hereinafter, the present invention will be described in detail. [Unsaturated polyester resin composition] The present invention is an unsaturated polyester resin composition comprising: an unsaturated polyester (A); an allyl group obtained by polymerizing an allyl compound represented by formula (1) Polymer (B) [Wherein, n represents any integer from 2 to 4, X is an alicyclic hydrocarbon group which may have an n-valence of an alkyl group]; and 2 or more (meth) acryl acetyl groups, or 2 or more alkenes Propyl multifunctional monomer (C).

According to the present invention, heat resistance and insulation can be maintained while achieving excellent impact resistance. Although the reason why such an effect is obtained is not necessarily known, it is presumed as follows. By blending the allyl polymer (B) with the unsaturated polyester (A), although the heat resistance of the resulting hardened product is improved, the unsaturated polyester resin composition tends to become brittle and the impact resistance is not full. Furthermore, by blending the multifunctional monomer (C) with the unsaturated polyester (A), although the impact resistance of the resulting hardened product is improved, the heat resistance of the unsaturated polyester resin composition tends to decrease . In this regard, in the present invention, by blending the polyfunctional monomer (C) and the allyl polymer (B) together with the unsaturated polyester (A), it is maintained that the allyl polymer is blended separately In the case of (B), the heat resistance is improved, and at the same time, the tendency of the heat resistance to decrease when the polyfunctional monomer (C) is blended alone is eliminated. It is presumed that the polyfunctional monomer (C) crosslinks the unsaturated polyester (A) and the allyl polymer (B), thereby achieving the above-mentioned effects.

[Unsaturated polyester (A)] The unsaturated polyester (A) used in the present invention is not particularly limited, and those known in the technical field can be used. The unsaturated polyester is generally a compound obtained by polycondensation (esterification) of a polyhydric alcohol and a polybasic acid (unsaturated polybasic acid or saturated polybasic acid), and can be appropriately selected and used according to the required characteristics.

Although the weight average molecular weight (Mw) of the unsaturated polyester (A) in the present invention is not particularly limited, it is preferably 5,000 to 20,000. In addition, in this specification, "weight-average molecular weight" refers to measurement using gel permeation chromatography (Shodex GPC-101 manufactured by Showa Denko Co., Ltd.) at normal temperature (25 ° C), using standard polystyrene calibration curve Find the value.

The polyol used for synthesizing the unsaturated polyester (A) of the present invention is not particularly limited, and known ones can be used. Examples of polyols include ethylene glycol, propylene glycol, neopentyl glycol, butylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, pentanediol, hexanediol, and hydrogenated bisphenol A. Bisphenol A, glycerin, etc. Among these, from the viewpoint of heat resistance, mechanical strength, and formability, propylene glycol, neopentyl glycol, and bisphenol A or hydrogenated bisphenol A are preferred. These polyols can be used alone or in combination.

The unsaturated polybasic acid used to synthesize the unsaturated polyester (A) of the present invention is not particularly limited, and known ones can be used. Examples of unsaturated polybasic acids include maleic anhydride, fumaric acid, citraconic acid, and itaconic acid. These can be used individually or in combination.

The saturated polybasic acid used to synthesize the unsaturated polyester is not particularly limited, and known ones can be used. Examples of saturated polybasic acids include phthalic anhydride, isophthalic acid, terephthalic acid, chlorobridge acid, succinic acid, adipic acid, sebacic acid, tetrachlorophthalic anhydride, Tetrabromophthalic anhydride, internal methylenetetrahydrophthalic anhydride, etc. These can be used individually or in combination.

Among the above-mentioned polybasic acids, from the viewpoint of heat resistance, mechanical strength, and moldability, unsaturated polybasic acids are preferred, and maleic anhydride and fumaric acid are more preferred. On the other hand, from the viewpoint that the effect of the present invention can be more suitably obtained, it is preferably a saturated polybasic acid, more preferably phthalic anhydride, isophthalic acid, terephthalic acid, tetrachlorophthalic acid Formic anhydride, tetrabromophthalic anhydride, internal methylenetetrahydrophthalic anhydride, further preferably phthalic anhydride, isophthalic acid, terephthalic acid, particularly isophthalic acid .

The unsaturated polyester (A) is not particularly limited, and may be used alone or in combination of two or more kinds, but for the reason that the effect of the present invention can be more suitably obtained, it is preferably a saturated polybasic acid-based unsaturated polyester It uses a saturated polybasic acid as the polybasic acid for the synthesis of unsaturated polyesters, more preferably an isophthalic acid-based unsaturated polyester, and it uses isophthalic acid as the polybasic acid for the synthesis of unsaturated polyesters.

The unsaturated polyester (A) of the present invention can be synthesized using the above-mentioned raw materials by a known method. Various conditions for this synthesis need to be appropriately set according to the raw materials used or their amounts, but generally speaking, in an inert gas stream such as nitrogen, the esterification can be performed under pressure or reduced pressure at a temperature of 140 to 230 ° C . In this esterification reaction, an esterification catalyst may be used if necessary. Examples of the catalyst include known catalysts such as manganese acetate, dibutyltin oxide, stannous oxalate, zinc acetate, and cobalt acetate. These can be used individually or in combination.

The content of the unsaturated polyester (A) of the present invention may be in the range of 5 to 95% by weight relative to the total amount of the unsaturated polyester resin composition, preferably in the range of 10 to 90% by weight, more preferably 10 to 70% by weight. The upper limit is particularly preferably 50% by weight, and most preferably 30% by weight. Within the above range, the effects of the present invention can be sufficiently obtained.

[Allyl polymer (B)] If the allyl polymer (B) of the present invention is an allyl compound represented by the polymerization formula (1) [In the formula, n represents any integer from 2 to 4, and X is an n-valent alicyclic hydrocarbon group which may have an alkyl group] The polymer obtained can be used without particular limitation. Furthermore, the n-valence refers to the amount of -COOCH ₂ CH = CH ₂ bonded to X in formula (1) based on the amount of COOH bonded to X. Similarly, the expression "an alicyclic hydrocarbon group which may have an n-valence of an alkyl group" does not exclude a state in which a substituent other than an alkyl group is bonded to an alicyclic hydrocarbon group, but may not have a substituent other than an alkyl group .

The weight average molecular weight (Mw) of the allyl polymer (B) is preferably 2,000 to 150,000, and more preferably 5,000 to 140,000. In particular, the weight average molecular weight of the allyl polymer (B) when n is 2 and X is an alicyclic hydrocarbon group having 4 to 10 carbon atoms forming the ring structure of the alicyclic hydrocarbon group is more preferably 8,000 or more, Furthermore, it is preferably 10,000 or more, particularly preferably 25,000 or more, more preferably 120,000 or less, and still more preferably 100,000 or less. In addition, in the specification, "weight average molecular weight" can be measured using gel permeation chromatography (GPC system manufactured by Shimadzu Corporation) at room temperature (25 ° C) and obtained using a standard polystyrene calibration curve.

The content of the monomer unit of the allyl compound represented by the above formula (1) is preferably 20% by weight or more, and more preferably 50% by weight or more in 100% by weight of the allyl polymer (B) Furthermore, it is preferably 80% by weight or more, particularly preferably 98% by weight or more, or 100% by weight. The allyl polymer (B) may be two or more different compounds among the allyl compounds represented by the above formula (1), that is, among the alicyclic allyl compounds and the aromatic allyl compounds More than 2 copolymers. In addition, the allyl polymer (B) may be a compound other than the allyl compound represented by the above formula (1) and the allyl compound represented by the formula (1), for example, a compound such as styrene monomer Copolymers of heterogeneous monomers with C = C double bonds. Particularly preferred is a homopolymer in which one of the allyl compounds represented by formula (1) is separately polymerized.

The content of the allyl polymer (B) in the present invention may be 5 to 900 parts by weight relative to 100 parts by weight of the unsaturated polyester (A), preferably 10 to 800 parts by weight, more preferably 10 to 300 parts by weight, more preferably 10 to 200 parts by weight. The upper limit is further preferably 150 parts by weight, particularly preferably 100 parts by weight, most preferably 70 parts by weight, and still more preferably 50 parts by weight. Within the above range, the effects of the present invention can be sufficiently obtained.

X in the above formula (1) is an n-valent alicyclic hydrocarbon group which may have an alkyl group from the viewpoint of further improving impact resistance.

[(I) n-valent alicyclic hydrocarbon group which may have an alkyl group] In the case where X in the above formula (1) is an n-valent alicyclic hydrocarbon group which may have an alkyl group, a ring of an alicyclic hydrocarbon group is formed The carbon number of the structure is preferably 3-18, more preferably 4-12, still more preferably 4-10, and particularly preferably 5-7. The n-valent alicyclic hydrocarbon group may be a saturated n-valent alicyclic hydrocarbon group, or a part of it may have an unsaturated bond, but it is preferably a saturated n-valent alicyclic hydrocarbon group. That is, the number of unsaturated bonds is preferably 2 or less, more preferably 1 or less, and particularly preferably 0. In addition, in the present invention, the alicyclic type refers to a hydrocarbon group having a non-aromatic cyclic structure. In addition, the number of rings is preferably one or two, particularly preferably one, but it may be three or more. When the number of rings is two or more, it may be a condensed ring type, a bridged ring, or a structure of both a condensed ring and a bridged ring, but preferably a bridged ring. X in formula (1) is preferably an aliphatic chain hydrocarbon group of n valence, and n is preferably 2 or 3, more preferably 2.

In addition, the n-valent alicyclic hydrocarbon group may or may not have an alkyl group. The alkyl group may be a straight chain or branched chain having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, and more preferably a methyl group or an ethyl group. The alkyl group may exist in one or more than two positions at which the alicyclic hydrocarbon group may be substituted. Furthermore, the n-valent alicyclic hydrocarbon group may or may not have a substituent other than the alkyl group.

As specific allyl compounds when X in the above formula (1) is an n-valent alicyclic hydrocarbon group, the following general formulas (4) to (11) (particularly, formula (6) to formula ( 9)) The compound.

[Wherein, n represents any integer from 2 to 4. ]

In the formulas (4) to (11), crosslinking can be carried out in the ring structure. Examples of the crosslinking in the ring structure include adamantane and norbornane.

The substitution position of the COOCH ₂ CH = CH ₂ group on the ring of formulas (4) to (11) may be any combination, or a mixture of these. In particular, when two COOCH ₂ CH = CH ₂ groups are bonded to a 6-membered ring, the two COOCH ₂ CH = CH ₂ groups can be orientated (substituted by 2 of 2) or meta-oriented (1 , 3 position 2 substitution), or para orientation (1, 4 position 2 substitution), but preferably adjacent position (1, 2 position 2 substitution), or para orientation (1 , Replaced by 2 of 4).

Specific allyl compounds when X in the above formula (1) is an n-valent alicyclic hydrocarbon group include diallyl cyclobutane dicarboxylate and diallyl cyclopentane dicarboxylate , Diallyl cyclohexanedicarboxylate (diallyl hexahydrophthalate, more specifically, diallyl hexahydro-1,2-phthalate, hexahydro-1, 3-diallyl 3-isophthalate, diallyl hexahydro-1,4-terephthalate), diallyl norbornane dicarboxylate, diallyl cyclobutene dicarboxylate, Diallyl cyclopentene dicarboxylate, diallyl cyclohexene dicarboxylate (diallyl tetrahydrophthalate) and diallyl norbornene dicarboxylate, 3-methyl- Hexahydro-1,2-diallyl phthalate, 4-methyl-hexahydro-1,2-diallyl phthalate, 3-methyl-1,2,3,6- Tetrahydro-1,2-diallyl phthalate, 4-methyl-1,2,3,6-tetrahydro-1,2-diallyl phthalate, 3,6-in Methylene-3-methyl-hexahydro-1,2-phthalic acid diallyl ester, 3,6-endomethylene-4-methyl-hexahydro-1,2-phthalic acid Diallyl, 3,6-endomethylene-3-methyl-1,2,3,6-tetrahydro-1,2-phthalic acid Allyl ester, 3,6-endomethylene-4-methyl-1,2,3,6-tetrahydro-1,2-phthalic acid diallyl ester, 4-cyclohexene-1, Diallyl 2-dicarboxylate, diallyl 2-cyclohexene-1,2-dicarboxylate, etc. X is more preferably a cyclic structure having no unsaturated bond, preferably having a carbon number of 4 to 7, further preferably having a carbon number of 5 or 6, and most preferably having a carbon number of 6. Among them, preferred are diallyl 1,2-cyclohexanedicarboxylate, diallyl 1,3-cyclohexanedicarboxylate, diallyl 1,4-cyclohexanedicarboxylate, The diallyl dibenzyl dicarboxylate is more preferably diallyl 1,2-cyclohexane dicarboxylic acid.

Hereinafter, an allyl compound in which X is an alicyclic hydrocarbon group which may have an n-valence of an alkyl group is sometimes referred to as an "alicyclic allyl compound".

[(Ii) Production method of allyl compound] The allyl compound of the present invention can be purchased and used commercially, or in the presence of acidic substances, basic substances, catalysts, solvents, etc. that can be used as necessary It is produced by reacting a carboxylic acid compound represented by the following formula (12) or an acid anhydride thereof with allyl halide or allyl alcohol. The carboxylic acid compound represented by the general formula (12) can be obtained as a test drug or an industrial-grade drug. [In formula (12), n and W have the same meaning as n and X in the above formula (1). ]

Examples of the allyl halide include allyl chloride, allyl bromide, and allyl iodide. Although the usage amount of allyl halide is not particularly limited, it is usually preferably in the range of 2 to 20 equivalents relative to the carboxylic acid compound represented by the general formula (12), from the viewpoint of reaction rate and volumetric efficiency , More preferably in the range of 2.3 to 10 equivalents. These halogenated allyl compounds can be obtained as reagents or industrial grade drugs.

Allyl alcohol can be obtained as a test drug or industrial-grade drugs. Although the usage amount of allyl alcohol is not particularly limited, it is usually preferably in the range of 2 to 10 molar equivalents, more preferably 2 to 5 molar equivalents relative to the carboxylic acid compound represented by the general formula (12) Within.

Examples of the acidic substance include dodecylbenzenesulfonic acid and sulfuric acid. The amount of the acidic substance used is preferably within the range of 0.001 to 0.1 equivalents based on the carboxylic acid compound represented by the general formula (12), more preferably It is in the range of 0.005 to 0.05 equivalent.

As an alkaline substance, for example, in general, hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide; hydrides of alkali metals such as sodium hydride and potassium hydride; carbonates such as sodium carbonate and potassium carbonate; sodium bicarbonate , Potassium bicarbonate and other hydrogen carbonates, alcoholates, etc., but also alkaline earth metal hydroxides, hydrides, carbonates, hydrogen carbonates, or organics such as quaternary ammonium compounds or aliphatic or aromatic amines Bases. The amount of the alkaline substance used is preferably in the range of 0.5 to 30 equivalents, and more preferably in the range of 2 to 15 equivalents, relative to the carboxylic acid compound represented by the general formula (12).

As the catalyst, for example, transition metals or transition metal salts such as copper, iron, cobalt, nickel, chromium, and vanadium can be used, but copper compounds are more suitable. The copper compound is not particularly limited, and most of the copper compounds can be used, but copper halide such as cuprous chloride, cupric chloride, cuprous bromide, copper bromide, cuprous iodide, cuprous oxide, etc. are preferred , Copper cyanide, cuprous sulfate, copper sulfate, copper phosphate, cuprous nitrate, copper nitrate and other inorganic acid copper salts, copper hydroxide, copper carbonate, cuprous acetate, copper acetate, etc. Among them, in particular, cuprous chloride, cupric chloride, cuprous bromide, cuprous bromide, cuprous iodide, copper sulfate, and copper acetate are more suitable in terms of being easily available and inexpensive.

The reaction can be carried out in the presence or absence of a solvent. The solvent is not particularly limited unless it adversely affects the reaction, but examples include aromatic hydrocarbons such as benzene, toluene, and xylene; hexane, heptane, octane, cyclohexane, and methylcyclohexane. Saturated aliphatic hydrocarbons; diethyl ether, diethylene glycol dimethyl ether, 1,4-dioxane, tetrahydrofuran and other ethers; ethyl acetate, butyl acetate and other esters; dichloromethane, chloroform, carbon tetrachloride Halogenated hydrocarbons; dimethylformamide, N-methylpyrrolidone, cyclazone, etc. These can be used alone or in combination of two or more. In the case of using a solvent, the amount of use is not particularly limited, but it is usually preferably in the range of 0.01 to 20 times the weight of the carboxylic acid compound represented by the general formula (12), more preferably 0.1 to Within 10 times the weight. In the case of this reaction, even if a solvent is not used especially, an allyl compound can be manufactured efficiently.

In particular, when an alkaline substance is used as an aqueous solution in the reaction, in order to promote the reaction, it is preferable to use a phase transfer catalyst. The phase transfer catalyst is not particularly limited, but examples include: quaternary ammonium salts such as trioctylmethylammonium chloride, tetrabutylammonium chloride, and tetrabutylammonium bromide; phosphonium such as tetrabutylphosphonium chloride Salt; crown ethers such as 15-crown-5, 18-crown-6, etc. In the case of using a phase transfer catalyst, the amount used is generally within the range of 0.001 to 1 equivalent, and more preferably within the range of 0.01 to 0.4 equivalent to the carboxylic acid compound represented by the general formula (12) Inside.

The reaction temperature is usually in the range of -30 to 150 ° C, and more preferably in the range of -10 to 130 ° C, in the sense of obtaining a sufficient reaction rate and effectively suppressing side reactions to obtain a high yield. In addition, the reaction time is preferably in the range of 10 minutes to 15 hours, and from the viewpoint of suppressing side reactions, it is more preferably in the range of 10 minutes to 10 hours.

The reaction is preferably carried out in an inert gas environment such as nitrogen or argon. In addition, the reaction may be carried out under atmospheric pressure or under pressure, but from the viewpoint of manufacturing equipment, it is preferably carried out under atmospheric pressure. The reaction can be carried out, for example, by adding the raw materials to the stirring-type reaction device at once or separately, and reacting for a predetermined time at the predetermined temperature described in the above paragraph [0043].

After the reaction is completed, after neutralizing the obtained reaction mixture, it is washed with water, saturated saline, etc. as necessary, and then concentrated, and further purification is carried out for purification of organic compounds such as distillation and column chromatography, etc. By operation, allyl compounds with higher purity can be obtained.

[(Iii) Production method of allyl polymer (B)] The polymerization method of the allyl compound is not particularly limited, and a general polymerization reaction can be used. In addition, in the polymerization reaction, a polymerization initiator may be appropriately added as necessary. By using a polymerization initiator, a higher molecular weight polymer can be obtained in a short time.

Examples of the polymerization initiator used in the polymerization reaction of allyl compounds include azo-based polymerization initiators such as azobisisobutyronitrile and dimethyl 2,2′-azobisisobutyrate. Peroxide-based polymerization initiators such as ketone oxide, peroxyketal, hydrogen peroxide, dialkyl peroxide, diacyl peroxide, peroxydicarbonate, peroxyester, benzoyl peroxide, etc., 2 -Methyl-1- [4- (methylthio) phenyl] -2-N-portalolinylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone and other acetophenone-based photopolymerization initiators , Benzoin, benzoin ether and other benzoin-based photopolymerization initiators, benzophenone and other benzophenone-based photopolymerization initiators, phosphine oxide and other phosphorus-based photopolymerization initiators. The above-mentioned photopolymerization initiator can be used in combination with a sensitizer such as a sulfur-based compound such as 9-oxothiokou Yamaguchi, a benzyl-based compound such as acetophenone and 9,10-phenanthrenequinone.

The amount of the polymerization initiator added is preferably 5.0 parts by weight or less relative to 100 parts by weight of the allyl compound, more preferably 3.0 parts by weight or less, and still more preferably 0.001 to 3.0 parts by weight. The reaction temperature during polymerization is preferably 60 to 240 ° C, more preferably 80 to 220 ° C. The reaction time is preferably 0.1 to 100 hours, and more preferably 1 to 30 hours.

The allyl compound represented by the above formula (1) is polymerized by the above method, etc., whereby an allyl polymer (B) having a monomer unit based on the allyl compound represented by the above formula (1) . Hereinafter, the allyl polymer obtained by polymerizing an "alicyclic allyl compound" is sometimes referred to as an "alicyclic allyl polymer."

[Multifunctional monomer (C)] As the multifunctional monomer (C) used in the present invention, as long as it has 2 or more (meth) acryloyl groups or 2 or more allyl groups The functional monomer is not particularly limited. Here, (meth) acryloyl refers to one or both of acryloyl and methacryloyl. The number of functional groups ((meth) acryloyl group or allyl group) possessed by the multifunctional monomer (C) is preferably 2 to 4 for the reason that the effect of the present invention can be more suitably obtained , More preferably 2 to 3, and still more preferably 2. Examples of the multifunctional monomer (C) include an allyl compound represented by formula (2) or a (meth) acrylate compound represented by formula (3). The polyfunctional monomer (C) is preferably a polyfunctional monomer having two or more (meth) acryloyl groups, and more preferably a (meth) acrylate compound represented by formula (3) . Further, it is preferably an n-valent aliphatic chain hydrocarbon group, or an n-valent alicyclic hydrocarbon group which may have an alkyl group, and a polyfunctional monomer having two or more allyl groups, and more preferably Y is n An allyl compound represented by the formula (2) of a valent aliphatic chain hydrocarbon group or an n-valent alicyclic hydrocarbon group which may have an alkyl group. [Wherein, n represents any integer from 2 to 4, Y is a bonding part, an n-valent aliphatic chain hydrocarbon group, an n-valent alicyclic hydrocarbon group which may have an alkyl group, or an n-valent aromatic hydrocarbon group , When Y is the bonding part, n is 2, 2 -COOCH ₂ CH = CH ₂ direct bonding], or [In the formula, n represents any integer from 2 to 4, R ₁ represents H or CH ₃ , and Z is an n-valent aliphatic chain hydrocarbon group having 2 to 10 carbon atoms].

[Allyl-based compound] As the allyl-based compound of the present invention, if it is an allyl-based compound represented by formula (2), it can be used without particular limitation. [In the formula, n represents any integer from 2 to 4 (preferably 2 to 3, more preferably 2), Y is a bonding part, an n-valent aliphatic chain hydrocarbon group, and may have an n-valence of an alkyl group The alicyclic hydrocarbon group or n-valent aromatic hydrocarbon group, when Y is a bonding part, n is 2, and two -COOCH ₂ Ch = CH _{2 are} directly bonded. ] Furthermore, the n-valence refers to the amount of -COOCH ₂ CH = CH ₂ bonded to Y in formula (2) based on the amount of COOH bonded to Y. In addition, the expression "n-valent aliphatic chain hydrocarbon group" means that the bonding of other substituents is not excluded, and it is not excluded that other substituents are bonded to the aliphatic chain hydrocarbon group. Similarly, the expression "an alicyclic hydrocarbon group which may have an n-valence of an alkyl group" does not exclude that a substituent other than an alkyl group is bonded to an alicyclic hydrocarbon group, but it may not have a substituent other than an alkyl group. In addition, the expression "n-valent aromatic hydrocarbon group" does not exclude the bonding of other substituents.

Y in the above formula (2) is a bonding portion, an n-valent aliphatic chain hydrocarbon group, an n-valent alicyclic hydrocarbon group which may have an alkyl group, an n-valent Aromatic hydrocarbon group. Among them, for the reason that the effect of the present invention can be more suitably obtained, n-valent aliphatic chain hydrocarbon groups and n-valent alicyclic hydrocarbon groups which may have alkyl groups are preferred. It is presumed that it is due to the higher compatibility between the aliphatic chain hydrocarbon group or the alicyclic hydrocarbon group and the alicyclic hydrocarbon group possessed by the allyl polymer (B).

[(I) Bonding part or n-valent aliphatic chain hydrocarbon group] When Y is a bonding part or an aliphatic chain hydrocarbon group, the allyl compound represented by the above formula (2) is an aliphatic carboxyl group Allyl acid. In the case where Y in the above formula (2) is an n-valent aliphatic chain hydrocarbon group, the carbon number may be 1 to 18, preferably 2 to 12, more preferably 2 to 8, and most preferably 2 to 6. In addition, the aliphatic chain hydrocarbon may be linear or branched, and preferably linear. In addition, the aliphatic chain hydrocarbon group may be a saturated n-valent aliphatic chain hydrocarbon group, or may have a part of unsaturated bonds, but it is preferably saturated. When Y in the above formula (2) is an n-valent aliphatic chain hydrocarbon group, n is preferably 2 or 3, and n is more preferably 2. That is, it is further preferred that Y has a carbon number of 2 to 8, and n is 2 or 3, and particularly an aliphatic chain hydrocarbon group in which n is 2.

Examples of the specific allyl compound when Y in the above formula (2) is a bonding part or an n-valent aliphatic chain hydrocarbon group include: Y is diallyl oxalate at the bonding part; and Y is saturated Compounds having an aliphatic linear hydrocarbon group and n = 2 include: diallyl malonate, diallyl succinate, diallyl glutarate, diallyl adipate, heptane Diallyl acid, diallyl suberate, diallyl azelate, diallyl sebacate; as the compound where Y is an unsaturated aliphatic linear hydrocarbon group and n = 2, there can be exemplified : Diallyl fumarate, diallyl maleate; as a compound wherein Y is a saturated aliphatic linear hydrocarbon group having a hydroxyl group and n = 2, there may be cited: diallyl malate 1, diallyl tartrate; as the compound wherein Y is a saturated aliphatic chain hydrocarbon group having a hydroxyl group and n = 3, mention may be made of triallyl citrate; as the compound having a hydrocarbon group containing an unsaturated bond, there may be given: Diallyl Iconate; and as n = 4 compounds, 1,2,3,4-butane tetracarboxylic acid tetraallyl ester can be cited. Among them, diallyl fumarate and diallyl maleate are preferred, and diallyl maleate is more preferred. Hereinafter, an allyl compound in which Y is a bonding part or an n-valent aliphatic chain hydrocarbon group may be referred to as an "aliphatic allyl compound".

[(Ii) N-valent alicyclic hydrocarbon group which may have an alkyl group] In the case where Y in the above formula (2) is an n-valent alicyclic hydrocarbon group which may have an alkyl group, a ring of an alicyclic hydrocarbon group is formed The carbon number of the structure is preferably 3-18, more preferably 4-12, still more preferably 4-10, and particularly preferably 5-7. The n-valent alicyclic hydrocarbon group may be a saturated n-valent alicyclic hydrocarbon group, or a part of it may have an unsaturated bond, but it is preferably a saturated n-valent alicyclic hydrocarbon group. That is, the number of unsaturated bonds is preferably 2 or less, more preferably 1 or less, and particularly preferably 0. In addition, in the present invention, the alicyclic type refers to a hydrocarbon group having a non-aromatic cyclic structure. In addition, the number of rings is preferably one or two, particularly preferably one, or more than three. When the number of rings is two or more, it may be a condensed ring type, a bridged ring, or a structure of both a condensed ring and a bridged ring, but preferably a bridged ring. When Y in formula (2) is an n-valent aliphatic chain hydrocarbon group, n is preferably 2 or 3, more preferably 2.

In addition, the n-valent alicyclic hydrocarbon group may or may not have an alkyl group. The alkyl group may be a straight chain or branched chain having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, and more preferably a methyl group or an ethyl group. The alkyl group may exist in one or more than two positions at which the alicyclic hydrocarbon group may be substituted. Furthermore, the n-valent alicyclic hydrocarbon group may or may not have a substituent other than the alkyl group.

As specific allyl compounds when Y in the formula (2) is an n-valent alicyclic hydrocarbon group, the following general formulas (13) to (20) (particularly, formula (15) to formula ( 18)) The compound.

[Wherein, n represents any integer from 2 to 4. ]

In the formulas (13) to (20), crosslinking can be performed within the ring structure. Examples of those performing crosslinking within the ring structure include adamantane and norbornane.

The substitution position of the COOCH ₂ CH = CH ₂ group on the ring of formulas (13) to (20) may be any combination, or a mixture of these. In particular, when two COOCH ₂ CH = CH ₂ groups are bonded to a 6-membered ring, the two COOCH ₂ CH = CH ₂ groups can be orientated (substituted by 2 of 2) or meta-oriented (1 , 3 position 2 substitution), or para orientation (1, 4 position 2 substitution), but preferably adjacent position (1, 2 position 2 substitution), or para orientation (1 , Replaced by 2 of 4).

Specific allyl compounds when Y in the above formula (2) is an n-valent alicyclic hydrocarbon group include diallyl cyclobutanedicarboxylate and diallyl cyclopentanedicarboxylate Ester, diallyl cyclohexanedicarboxylate (diallyl hexahydrophthalate, more specifically, diallyl hexahydro-1,2-phthalate, hexahydro-1 , Diallyl 3-isophthalate, diallyl hexahydro-1,4-terephthalate), diallyl norbornane dicarboxylate, diallyl cyclobutene dicarboxylate , Diallyl cyclopentene dicarboxylate, diallyl cyclohexene dicarboxylate (diallyl tetrahydrophthalate) and diallyl norbornene dicarboxylate, 3-methyl -Hexahydro-1,2-diallyl phthalate, 4-methyl-hexahydro-1,2-diallyl phthalate, 3-methyl-1,2,3,6 -Tetrahydro-1,2-diallyl phthalate, 4-methyl-1,2,3,6-tetrahydro-1,2-diallyl phthalate, 3,6- Endmethylene-3-methyl-hexahydro-1,2-phthalic acid diallyl, 3,6-endmethylene-4-methyl-hexahydro-1,2-phthalate Diallyl formate, 3,6-endomethylene-3-methyl-1,2,3,6-tetrahydro-1,2-phthalate Diallyl ester, 3,6-endomethylene-4-methyl-1,2,3,6-tetrahydro-1,2-phthalate diallyl ester, 4-cyclohexene-1 , Diallyl 2-dicarboxylate, diallyl 2-cyclohexene-1,2-dicarboxylate, etc. Y is more preferably a cyclic structure having no unsaturated bond, preferably having a carbon number of 4 to 7, further preferably having a carbon number of 5 or 6, and most preferably having a carbon number of 6. Among them, preferred are diallyl hexahydro-1,2-phthalate, 3-methyl-hexahydro-1,2-diallyl phthalate, 4-methyl-hexahydro- 1,2-diallyl phthalate, more preferably diallyl hexahydro-1,2-phthalate.

Hereinafter, the allyl compound in which Y is an alicyclic hydrocarbon group which may have an n-valent alkyl group is sometimes referred to as an "alicyclic allyl compound".

[(Iii) n-valent aromatic hydrocarbon group] In the case where Y in the above formula (2) is an n-valent aromatic hydrocarbon group, it is preferably any one of 6 to 20 aromatic hydrocarbon groups It is more preferably any one of aromatic hydrocarbon groups having 6 to 12 carbon atoms. When Y in the above formula (2) is an n-valent aromatic hydrocarbon group, n is preferably 2 or 3, more preferably 2.

In the case where Y in the above formula (2) is an n-valent aromatic hydrocarbon group, the substitution position of the allyl ester (COOCH ₂ CH = CH ₂ ) group on the ring may be any combination, or it may be the Wait for the mixture. In particular, when two COOCH ₂ CH = CH ₂ groups are bonded to a 6-membered ring, the two COOCH ₂ CH = CH ₂ groups may be either orientated or meta-oriented or para-oriented, preferably Orientation for adjacent or meta orientation.

Specific allylic compounds when Y in the above formula (2) is an n-valent aromatic hydrocarbon group include diallyl phthalate, diallyl isophthalate, terephthalic acid Diallyl ester and the like are preferably diallyl phthalate and diallyl isophthalate.

Hereinafter, the allyl-based compound in which Y is an n-valent aromatic hydrocarbon group is sometimes referred to as an "aromatic allyl compound".

The allyl compound represented by the above formula (2) can be purchased and used commercially, or can be synthesized in the synthesis method described in [0035] to [0045].

[(Meth) acrylate-based compound] As the (meth) acrylate-based compound of the present invention, if it is a (meth) acrylate-based compound represented by formula (3), it can be used without particular limitation. It is speculated that the compound represented by formula (3) has an aliphatic chain hydrocarbon group and has high compatibility with the alicyclic hydrocarbon group possessed by the allyl polymer (B), so that the effect of the present invention can be more suitably obtained. [In the formula, n represents any integer from 2 to 4, R ₁ represents H or CH ₃ , and Z is an n-valent aliphatic chain hydrocarbon group having 2 to 10 carbon atoms] Furthermore, n-valent refers to bonding with Z the OCOCR ₁ = CH ₂ of the number, in the formula (3) and bonded to the -OCOCR Z ₁ = CH ₂ number of. In addition, the expression "n-valent aliphatic chain hydrocarbon group" means that the bonding of other substituents is not excluded, and it is not excluded that other substituents are bonded to the aliphatic chain hydrocarbon group.

In the case where Z in the above formula (3) is an n-valent aliphatic chain hydrocarbon group, the carbon number may be 2-10, preferably 2-9, and more preferably 6-9. In addition, the aliphatic chain hydrocarbon may be linear or branched, and preferably linear. In addition, the aliphatic chain hydrocarbon group may be a saturated n-valent aliphatic chain hydrocarbon group, or may have a part of unsaturated bonds, but it is preferably saturated. When Z in the above formula (3) is an n-valent aliphatic chain hydrocarbon group, n is preferably 2 or 3, and n is more preferably 2. That is, it is further preferred that Z has a carbon number of 2 to 9, and n is 2 or 3, and particularly an aliphatic chain hydrocarbon group in which n is 2.

R ₁ in the above formula (3) is H or CH ₃ , preferably CH ₃ .

The (meth) acrylate-based compound represented by the above formula (3) is not particularly limited, and a commercially available one can be used for purchase or a synthesizer can be used. Specific examples include ethylene glycol di (meth) acrylate, propylene glycol 1,3-di (meth) acrylate, butylene glycol 1,4-di (meth) acrylate, 1,5- Pentylene glycol di (meth) acrylate, Hexanediol 1,6-di (meth) acrylate, Heptanediol 1,7-di (meth) acrylate, 1,8-Di (methyl) Octanediol acrylate, nonanediol 1,9-di (meth) acrylate, decanediol 1,10-di (meth) acrylate. Among them, preferred is hexylene glycol 1,6-di (meth) acrylate, heptanediol 1,7-di (meth) acrylate, octanediol 1,8-di (meth) acrylate, 1,9-Dinonyl (meth) acrylate. In addition, as the (meth) acrylate compound used in the present invention, in addition to the above, trimethylolpropane triacrylate, neopentyl tetraol tetraacrylate, tricyclodecane dimethanol diacrylic acid can also be used Ester etc.

The content of the polyfunctional monomer (C) is preferably 0.1 parts by weight or more, more preferably 0.5 parts by weight or more, and still more preferably 1 part by weight or more relative to 100 parts by weight of the unsaturated polyester (A). It is preferably 80 parts by weight or less, more preferably 50 parts by weight or less, and further preferably 25 parts by weight or less. Within the above range, the effects of the present invention can be sufficiently obtained.

The ratio of the content of polyfunctional monomer (C) to the content of unsaturated polyester (A) (content of polyfunctional monomer (C) / content of unsaturated polyester (A)) is preferably 1/100 ~ 1 / 1.25, more preferably 1/50 to 1/2, and still more preferably 1/20 to 1/4. Within the above range, the effects of the present invention can be sufficiently obtained. The ratio of the content of allyl polymer (B) to the content of unsaturated polyester (A) (content of allyl polymer (B) / content of unsaturated polyester (A)) is preferably 1/100 ～ 1/1, more preferably 1/50 ～ 1/2, and still more preferably 1/20 ～ 1/2. The lower limit is particularly preferably 1/10, and the best is 1/5. Within the above range, the effects of the present invention can be sufficiently obtained.

[Polymerization initiator (D)] The polymerization initiator (D) used in the present invention can be exemplified by dialkyl peroxides such as di-tertiary butyl peroxide, dicumyl peroxide or Diallyl peroxides, such as peroxide esters of tertiary butyl peroxybenzoate, tertiary butyl peroxide peroxides, such as 1,1-tertiary butyl peroxide Cyclohexane-based peroxyketals, such as benzophenone peroxide, 2,4-dichlorobenzoyl peroxide, diaromatic peroxides or diacyl peroxide, such as hydroperoxide Hydroperoxides, such as azo compounds such as azobisisobutyronitrile.

The amount of the polymerization initiator (D) used in the present invention is preferably 0.1 to 20 parts by weight, and more preferably 3 to 10 parts by weight, relative to 100 parts by weight of the unsaturated polyester (A). In order to maintain the curing rate and improve the formability, it is desirable to be 3 parts by weight or more. In addition, in order to prevent a decrease in mechanical strength, it is desirably 10 parts by weight or less.

[Inorganic Filler (E)] An inorganic filler (E) may be added to the unsaturated polyester resin composition of the present invention if necessary. Examples of the inorganic filler (E) include hydrated metals such as fused silica, crystalline silica, alumina, quartz glass, calcium carbonate, aluminum hydroxide, and calcium sulfate, glass powder, talc, and mica. The particle size of the inorganic filler is 0.1-100 μm. It is preferably 0.5 to 60 μm. If the particle size is too small, the viscosity of the composition becomes large, and the fiber is not sufficiently impregnated into the reinforcing fiber, air is easily mixed into the material, and the molded product is likely to form pores. On the other hand, if the particle size is too large, the specific surface area of the particles becomes small, and the fluidity decreases. In addition, in this specification, the inorganic filler (E) does not contain the fiber reinforcement agent mentioned later.

The addition amount of the inorganic filler (E) of the present invention may be 10 to 1000 parts by weight relative to 100 parts by weight of the unsaturated polyester (A), more preferably 200 to 800 parts by weight. The upper limit is more preferably 600 parts by weight, further preferably 400 parts by weight, and particularly preferably 300 parts by weight. If the added amount is small, the operability of the material before forming is reduced. In addition, if the amount of addition is large, the viscosity is greatly increased, the fluidity during forming is reduced, and the impregnability of the reinforcing fiber is reduced. Air is easily mixed into the material, and the molded product is likely to form pores.

In addition to the above components, the unsaturated polyester resin composition of the present invention may include fiber reinforcement, low shrinkage agent, mold release agent, tackifier, pigment, viscosity reducer Silane coupling agent and other components known in this technical field.

The fiber reinforcing agent used in the present invention is not particularly limited, and those known in the technical field can be used. Examples of fiber-reinforced materials include various organic fibers and inorganic fibers such as glass fiber, pulp fiber, Tedlon (registered trademark) fiber, vinylon fiber, carbon fiber, aromatic polyamide fiber, and wollastonite. Among them, it is preferable to use glass fiber chopped strand cut to a fiber length of about 1.5 to 25 mm.

The amount of the fiber reinforcement added may be 10 to 1000 parts by weight relative to 100 parts by weight of the unsaturated polyester (A), more preferably 50 to 800 parts by weight. The upper limit is more preferably 600 parts by weight, and particularly preferably 400 parts by weight.

Examples of the low shrinkage agent used in the present invention include polystyrene, polymethyl methacrylate, polyvinyl acetate, saturated polyester, and styrene-butadiene rubber. polymer. These can be used alone or in combination of two or more.

Examples of the mold release agent used in the present invention include stearic acid, zinc stearate, calcium stearate, aluminum stearate, magnesium stearate, and carnauba wax. These can be used alone or in combination of two or more. Examples of the thickener used in the present invention include metal oxides such as magnesium oxide, magnesium hydroxide, calcium hydroxide, and calcium oxide, and isocyanate compounds. These can be used alone or in combination of two or more.

The unsaturated polyester resin composition of the present invention can be produced by kneading using a method generally performed in this technical field, such as a kneader.

The unsaturated polyester resin composition of the present invention can be formed into a desired shape by forming curing (thermosetting) into a desired shape (cured product, molded product). The molding and hardening method are not particularly limited, and methods generally performed in this technical field, such as compression molding, transfer molding, injection molding, etc., can be used.

[Examples] Hereinafter, examples will be given to explain the present invention more specifically, but the present invention is not limited to these examples.

[(Analysis method)] In the production examples described later, the analysis of the allyl polymer was performed using the method described below.

[1) Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of allyl polymer] The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) were measured using GPC. It is the value of weight average molecular weight converted from standard polystyrene. Column: ShodexKF-806L, KF-804, KF-803, KF-802, KF-801 in series Flow rate: 1.0 mL / min Temperature: 40 ° C Detection: RID-6A Sample: 20 mg of the sample is dissolved in tetrahydrofuran 8 mL to prepare a sample for measurement.

[Manufacturing Example 1: Synthesis of diallyl fumarate (diallyl fumarate)] Added 145.2 g (2.50 mol) of allyl alcohol, 137.5 g (1.49 mol) of toluene, and fumaric acid 116.1 g (1.00 mol) and dodecylbenzenesulfonic acid 6.53 g (0.02 mol) were stirred in a 500 mL flask with a magnetic stirrer and refluxed in an oil bath. After 24 hours, the heating was stopped and the flask was cooled. The obtained reaction liquid was neutralized and washed with water, the low boiling point component was distilled off with a rotary evaporator, and the obtained concentrated liquid was distilled under reduced pressure to obtain 74.0 g of the target diallyl fumarate. The diallyl fumarate obtained was used in Example 2.

[Production Example 2 Polymerization of diallyl hexahydro-1,2-phthalate polymer] Addition of diallyl hexahydro-1,2-phthalate (1,2-cyclohexanedicarboxyl Diallyl acid ester, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) 600 g in a 3 L separable flask, heated and stirred at 160 ° C, and reacted for 5 hours. Thereafter, after cooling to 60 ° C in an ice bath, 1.8 kg of methanol was added to the flask to precipitate the obtained polymer. After that, it was refluxed at a bath temperature of 60 ° C for 1 hour, and the monomer was extracted from the obtained polymer. The polymer obtained after monomer extraction was dried at 40 ° C under reduced pressure for 8 hours. (Yield: 120 g, yield: 20%). The obtained polymer (Mw = 61,000, Mw / Mn = 3.9) was used in each example.

[Examples 1 to 4, and Comparative Example 1] The materials shown in Table 1 were blended to obtain a composition. After the obtained composition is pre-mixed, it is melt-kneaded with a heating roller of 90 to 110 ° C, cooled and then pulverized to obtain each molding material.

[Table 1]

(Notes to Table 1) ※ 1 Unsaturated polyester resin: “Unsaturated polyester 8542” manufactured by Japan Upiqa Co., Ltd. ※ 2 Hexahydro-1,2-diallyl phthalate polymer: manufactured Example 2 Polymerized polymer ※ 3 Diallyl phthalate resin: “Daiso dap A” manufactured by Osaka Soda Co., Ltd. ※ 4 Diallyl fumarate: synthesized by Production Example 1 ※ 5 Hexahydro- 1,2-Diallyl Phthalate: Fuji Film Wako Pure Chemicals Co., Ltd. ※ 6 1,6-Hexanediol Dimethacrylate: "HD-N" manufactured by Shin Nakamura Chemical Industry Corporation ※ 7 Diallyl phthalate: "Daiso dap monomer" manufactured by OsakaSoda Co., Ltd. * 8 "Higilite H-32" manufactured by Showa Denko Co., Ltd. * 9 Glass fiber: manufactured by Owens Corning Japan Co., Ltd. "03IE830A" ※ 10 "Percumyl D" manufactured by Nippon Oil Co., Ltd. ※ 11 "Zinc stearate" manufactured by Sakai Chemical Industry Co., Ltd.

The physical properties of the molding materials obtained in Examples and Comparative Examples were measured under the following conditions. The measurement results are shown in Table 2.

[Measurement of impact strength] Each molded material was obtained by compression molding of a mold temperature of 160 degrees and a molding time of 5 minutes. Toyo Seiki Co., Ltd. was used according to JIS-K6911 "General Test Method for Thermosetting Plastics" The Charpy impact testing machine was used for measurement.

[Bending strength] Each molded material is obtained by transfer molding at a mold temperature of 160 degrees and a molding time of 4 minutes. According to JIS-K6911 "General Test Method for Thermosetting Plastics", manufactured by Toyo Seiki Co., Ltd. STROGRAPH W was measured.

[Volume resistivity] A molded product was obtained by transfer molding, and it was measured using 4329A HIGH RESISTANCE METER manufactured by HEWLETT PACKARD in accordance with JIS-K6911 "General Test Method for Thermosetting Plastics".

[Heat Distortion Temperature under Load] A molded product is obtained by compression molding at a mold temperature of 160 degrees and a molding time of 5 minutes. According to JIS-K6911 "General Test Method for Thermosetting Plastics", Heat Distortion Tester manufactured by Yasuda Seiki Co., Ltd. Perform the measurement.

[Table 2]

As shown in Table 2, all of Examples 1 to 4 showed no substantial difference in bending strength, volume resistivity, and heat deformation temperature under load, but the Charpy impact strength was improved and the impact resistance was improved. It can be seen that in general, heat resistance (heat deformation temperature under load) and impact resistance (Charpy impact strength) are opposite properties, so it is difficult to balance both, but by blending unsaturated polyester (A) and allyl The base polymer (B) and the multifunctional monomer (C) can have good heat resistance (heat deflection temperature under load), and at the same time improve the impact resistance (Charpy impact strength). [Industry availability]

The unsaturated polyester resin composition of the present invention is an unsaturated polyester resin molding material having very excellent impact resistance with substantially no loss of electrical characteristics, mechanical characteristics and heat resistance. The unsaturated polyester resin molding material of the present invention effectively utilizes excellent impact resistance, for example, it can be used in small, thin-walled bobbins, switch cases (switch cases), terminal boards, connectors, magnetic switches, etc. Parts, etc.

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Claims (7)

An unsaturated polyester resin composition comprising: an unsaturated polyester (A); an allyl polymer (B) obtained by polymerizing an allyl compound represented by formula (1) [Wherein, n represents any integer from 2 to 4, X is an alicyclic hydrocarbon group which may have an n-valence of an alkyl group]; and 2 or more (meth) acryl acetyl groups, or 2 or more alkenes Propyl multifunctional monomer (C). The unsaturated polyester resin composition according to claim 1, wherein the allyl compound represented by the above formula (1) is any one of the compounds represented by the following formulas (4) to (11) [Wherein, n represents any integer from 2 to 4]. The unsaturated polyester resin composition according to claim 1 or 2, wherein the polyfunctional monomer (C) having two or more (meth) acryloyl groups or two or more allyl groups is Allyl compound represented by formula (2), or (meth) acrylate compound represented by formula (3) [Wherein, n represents any integer from 2 to 4, Y is a bonding part, an n-valent aliphatic chain hydrocarbon group, an n-valent alicyclic hydrocarbon group which may have an alkyl group, or an n-valent aromatic hydrocarbon group , When Y is the bonding part, n is 2, 2 -COOCH ₂ CH = CH ₂ direct bonding], or [In the formula, n represents any integer from 2 to 4, R ₁ represents H or CH ₃ , and Z is an n-valent aliphatic chain hydrocarbon group having 2 to 10 carbon atoms]. The unsaturated polyester resin composition according to any one of claims 1 to 3, which further contains a polymerization initiator (D). The unsaturated polyester resin composition according to any one of claims 1 to 4, which further contains an inorganic filler (E). A cured product obtained by thermally curing the unsaturated polyester resin composition according to any one of claims 1 to 5. A molded product obtained by molding the unsaturated polyester resin composition described in any one of claims 1 to 6.