Allyl polymer, thermosetting resin composition, cured product, and molded article

Abstract

Provided are an allyl polymer that has excellent fluidity, a thermosetting resin composition that uses the allyl polymer, a cured product, and a molded article. The present invention relates to an allyl polymer that is obtained by polymerizing an allyl compound represented by formula (1) and an allyl compound represented by formula (2), the value of the amount (mol%) of constituent units based on the allyl compound represented by formula (1) / the amount (mol%) of constituent units based on the allyl compound represented by formula (2) being at least 0.5. (1) X-(COOCH2CH=CH2)n (in which n is an integer from 2 to 4, inclusive, and X is a n-valent aromatic hydrocarbon group that may include an alkyl group). (2) Y-(COOCH2CH=CH2)n (in which n is an integer from 2 to 4, inclusive, and Y is a n-valent alicyclic hydrocarbon group that may include an alkyl group).

Description

Allyl polymers, thermosetting resin compositions, cured products, molded articles

[0001] This invention relates to allyl polymers, thermosetting resin compositions, cured products, and molded articles.

[0002] Recently, encapsulating resins have come into use in electronic components such as capacitors, coils, and resistors to improve reliability and productivity. The required performance of encapsulating resins varies depending on the shape and size of the electronic component, but physical properties include moisture resistance, low stress resistance, high thermal conductivity, and impact resistance. Thermosetting resins such as diallyl phthalate resin and unsaturated polyester resin are used to satisfy these performance requirements.

[0003] For example, Patent Document 1 discloses a thermosetting resin composition using an unsaturated polyester resin, a diallyl 1,2-cyclohexanedicarboxylic acid homopolymer, and a diallyl phthalate homopolymer as resins.

[0004] International Publication No. 2019 / 039185

[0005] As a result of diligent research by the present inventors, it has been newly discovered that there is room for improvement in the fluidity of 1,2-cyclohexanedicarboxylic acid diallyl homopolymer and diallyl phthalate homopolymer. The object of the present invention is to provide an allyl polymer with excellent fluidity, a thermosetting resin composition using the allyl polymer, a cured product, and a molded article.

[0006] As a result of diligent research, the inventors of the present invention have found that an allyl polymer obtained by polymerizing an allyl compound represented by formula (1) and an allyl compound represented by formula (2), wherein the content of constituent units based on the allyl compound represented by formula (1) (mol%) / content of constituent units based on the allyl compound represented by formula (2) (mol%) is 0.5 or more, exhibits excellent fluidity, and thus completed the present invention. X-(COOCH ２ CH=CH ２ ) ｎ (1) [In formula (1), n ​​represents an integer from 2 to 4, and X is an n-valent aromatic hydrocarbon group which may have an alkyl group.] Y-(COOCH ２ CH=CH ２ ) ｎ(2) [In formula (2), n represents an integer of any one of 2 to 4, and Y is an n-valent alicyclic hydrocarbon group which may have an alkyl group.]

[0007] Item 1 An allyl polymer obtained by polymerizing an allyl compound represented by formula (1) and an allyl compound represented by formula (2), and the content (mol%) of the structural unit based on the allyl compound represented by formula (1) / the content (mol%) of the structural unit based on the allyl compound represented by formula (2) is 0.5 or more. X-(COOCH ２ CH=CH ２ ) ｎ (1) [In formula (1), n represents an integer of any one of 2 to 4, and X is an n-valent aromatic hydrocarbon group which may have an alkyl group.] Y-(COOCH ２ CH=CH ２ ) ｎ (2) [In formula (2), n represents an integer of any one of 2 to 4, and Y is an n-valent alicyclic hydrocarbon group which may have an alkyl group.] Item 2 A thermosetting resin composition containing the allyl polymer according to Item 1. Item 3 The thermosetting resin composition according to Item 2, further containing an initiator. Item 4 The thermosetting resin composition according to Item 2 or 3, further containing an inorganic filler. Item 5 A cured product obtained by thermally curing the thermosetting resin composition according to any one of Items 2 to 4. Item 6 A molded product characterized by being formed by molding the thermosetting resin composition according to any one of Items 2 to 4.

[0008] The allyl polymer of the present invention is an allyl polymer obtained by polymerizing the allyl compound represented by the above formula (1) and the allyl compound represented by the above formula (2), and the content (mol%) of the structural unit based on the allyl compound represented by the above formula (1) / the content (mol%) of the structural unit based on the allyl compound represented by the above formula (2) is 0.5 or more, so it has excellent fluidity.

[0009] The allyl polymer of the present invention is obtained by polymerizing an allyl compound represented by formula (1) and an allyl compound represented by formula (2), and is an allyl polymer in which the content of constituent units based on the allyl compound represented by formula (1) (mol%) / content of constituent units based on the allyl compound represented by formula (2) (mol%) is 0.5 or more, and therefore exhibits excellent fluidity. X-(COOCH ２ CH=CH ２ ) ｎ (1) [In formula (1), n ​​represents an integer from 2 to 4, and X is an n-valent aromatic hydrocarbon group which may have an alkyl group.] Y-(COOCH ２ CH=CH ２ ) ｎ (2) [In formula (2), n represents an integer from 2 to 4, and Y is an n-valent alicyclic hydrocarbon group which may have an alkyl group.]

[0010] The reason for obtaining the aforementioned effects is not entirely clear, but it is presumed to be due to the following mechanism. While there is room for improvement in the fluidity of homopolymers obtained by polymerizing the allyl compound represented by formula (1) and homopolymers obtained by polymerizing the allyl compound represented by formula (2), a copolymer in which the content of constituent units based on the allyl compound represented by formula (1) (mol%) / content of constituent units based on the allyl compound represented by formula (2) (mol%) is 0.5 or more surprisingly exhibits excellent fluidity. This is presumed to be because copolymerization improves the flexibility of the polymer and reduces its crystallinity.

[0011] The allyl polymer of the present invention not only exhibits excellent fluidity, but also provides good heat resistance, tracking resistance, and mechanical properties (e.g., flexural strength, flexural modulus, impact strength) while maintaining good fluidity.

[0012] (Allyl Polymer) The allyl polymer of the present invention is obtained by polymerizing an allyl compound represented by formula (1) and an allyl compound represented by formula (2), and is an allyl polymer in which the content of constituent units based on the allyl compound represented by formula (1) (mol%) / content of constituent units based on the allyl compound represented by formula (2) (mol%) is 0.5 or more. X-(COOCH ２CH=CH ２ ) ｎ (1) [In formula (1), n ​​represents an integer from 2 to 4, and X is an n-valent aromatic hydrocarbon group which may have an alkyl group.] Y-(COOCH ２ CH=CH ２ ) ｎ (2) [In formula (2), n represents an integer from 2 to 4, and Y is an n-valent alicyclic hydrocarbon group which may have an alkyl group.]

[0013] Note that the n-valence is based on the number of COOH groups that bond with X or Y, and in formula (1), the number of COOH groups that bond with X is -COOH. ２ CH=CH ２ It refers to the number of and combines with Y in equation (2) -COOCH ２ CH=CH ２ This refers to the number of substituents. Furthermore, as is clear from the fact that the bonding of other substituents is not excluded, the expression "n-valent aromatic hydrocarbon group which may have an alkyl group" does not exclude the configuration in which substituents other than alkyl groups are bonded to the aromatic hydrocarbon group, but it does not have to have substituents other than alkyl groups. Similarly, the expression "n-valent alicyclic hydrocarbon group which may have an alkyl group" does not exclude the configuration in which substituents other than alkyl groups are bonded to the alicyclic hydrocarbon group, but it does not have to have substituents other than alkyl groups.

[0014] <Allyl compounds represented by formula (1)> The allyl compounds represented by formula (1) will be explained below. The allyl compounds represented by formula (1) may be used alone or in combination of two or more. X-(COOCH) ２ CH=CH ２ ) ｎ (1) [In formula (1), n ​​represents an integer from 2 to 4, and X is an n-valent aromatic hydrocarbon group which may have an alkyl group.]

[0015] The n-valent aromatic hydrocarbon group is preferably any aromatic hydrocarbon group having 6 to 20 carbon atoms, and more preferably any aromatic hydrocarbon group having 6 to 12 carbon atoms. n is preferably 2 or 3, and more preferably 2.

[0016] The substitution positions of allyl ester (COOCH ２ CH=CH ２ ) groups on the ring can be any combination, or a mixture thereof. 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 in ortho orientation (1,2-disubstitution), meta orientation (1,3-disubstitution), or para orientation (1,4-disubstitution), but are preferably in ortho orientation (1,2-disubstitution) or meta orientation (1,3-disubstitution), and more preferably in meta orientation (1,3-disubstitution).

[0017] The n-valent aromatic 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 having 1 to 5 carbon atoms, more preferably a methyl group or an ethyl group. The alkyl group may be present at one or more substitutable positions of the aromatic hydrocarbon group. Furthermore, the n-valent aromatic hydrocarbon group may or may not have a substituent other than the alkyl group.

[0018] Specific allyl compounds represented by the above formula (1) include diallyl phthalate, diallyl isophthalate, diallyl terephthalate, etc., with diallyl phthalate and diallyl isophthalate being preferred, and diallyl isophthalate being more preferred.

[0019] Hereinafter, the allyl compound represented by the above formula (1) may be referred to as an "aromatic allyl compound".

[0020] The allyl compound represented by the above formula (1) may be purchased and used commercially available ones, or can also be synthesized by known synthetic methods (for example, the method described in International Publication No. 2019 / 039185).

[0021] <Allyl compound represented by formula (2)> The allyl compound represented by formula (2) will be described. The allyl compound represented by formula (2) may be used alone or in combination of two or more. Y-(COOCH ２ CH=CH ２ )ｎ (2) [In formula (2), n represents an integer of any one of 2 to 4, and Y is an n-valent alicyclic hydrocarbon group which may have an alkyl group.]

[0022] The number of carbon atoms forming the ring structure of the alicyclic hydrocarbon group is preferably 3 to 18, more preferably 4 to 12, even more preferably 4 to 10, and particularly preferably 5 to 7. The n-valent alicyclic hydrocarbon group may be a saturated n-valent alicyclic hydrocarbon group, and may have an unsaturated bond in part, but 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 the present invention, alicyclic means having a cyclic structure that does not have aromaticity, and an alicyclic hydrocarbon group means a hydrocarbon group having a cyclic structure that does not have aromaticity. Also, the number of rings is preferably 1 or 2, particularly preferably 1, but may be 3 or more. When the number of rings is 2 or more, it may be a condensed ring type, a bridged ring type, or may have both a condensed ring and a bridged ring structure, but those having a bridged ring are preferred. n is preferably 2 or 3, and more preferably 2.

[0023] Further, 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 having 1 to 5 carbon atoms, and more preferably a methyl group or an ethyl group. The alkyl group may be present at one or more substitutable positions of the alicyclic hydrocarbon group. Furthermore, the n-valent alicyclic hydrocarbon group may or may not have a substituent other than an alkyl group.

[0024] Specific allyl compounds represented by the above formula (2) can include compounds of the following general formulas (13) to (20) (particularly, formulas (15) to (18) are preferred).

[0025] [In the formula, n is an integer of any one of 2 to 4.]

[0026] In equations (13) to (20), the ring structure may be bridged, and examples of materials that are bridged within the ring structure include adamantane and norbornane.

[0027] COOCH on the ring ２ CH=CH ２ The substitution positions of the groups may be any combination, or a mixture thereof. In particular, two COOCH ２ CH=CH ２ When the group is bonded to a six-membered ring, two COOCH groups ２ CH=CH ２ The group may be ortho-oriented (disubstituted at positions 1 and 2), meta-oriented (disubstituted at positions 1 and 3), or para-oriented (disubstituted at positions 1 and 4), but ortho-oriented (disubstituted at positions 1 and 2) or para-oriented (disubstituted at positions 1 and 4) is preferred, and ortho-oriented (disubstituted at positions 1 and 2) is more preferred.

[0028] Specific allyl compounds represented by the above formula (2) include diallyl cyclobutanedicarboxylate, diallyl cyclopentanedicarboxylate, diallyl cyclohexanedicarboxylate (diallyl hexahydrophthalate, more specifically, 1,2-diallyl cyclohexanedicarboxylate, 1,3-diallyl cyclohexanedicarboxylate, 1,4-diallyl cyclohexanedicarboxylate), diallyl norbornanedicarboxylate, diallyl cyclobutenedicarboxylate, diallyl cyclopentenedicarboxylate, diallyl cyclohexenedicarboxylate (diallyl tetrahydrophthalate), and diallyl norbornenedicarboxylate, 3-methyl-hexahydro-1,2-diallylphthalate, 4-methyl-hexahydro- Examples include 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-endomethylene-3-methyl-hexahydro-1,2-diallyl phthalate, 3,6-endomethylene-4-methyl-hexahydro-1,2-diallyl phthalate, 3,6-endomethylene-3-methyl-1,2,3,6-tetrahydro-1,2-diallyl phthalate, 3,6-endomethylene-4-methyl-1,2,3,6-tetrahydro-1,2-diallyl phthalate, 4-cyclohexene-1,2-dicarboxylic acid diallyl, and 2-cyclohexene-1,2-dicarboxylic acid diallyl. Among these, 1,2-cyclohexanedicarboxylate diallyl, 3-methyl-hexahydro-1,2-diallyl phthalate, and 4-methyl-hexahydro-1,2-diallyl phthalate are preferred, with 1,2-cyclohexanedicarboxylate diallyl being more preferred.

[0029] Hereinafter, allyl compounds represented by the above formula (2) are sometimes referred to as "alicyclic allyl compounds."

[0030] The allyl compound represented by formula (2) above may be purchased commercially or synthesized using a known synthesis method (for example, the method described in International Publication No. 2019 / 039185).

[0031] <About Allyl Polymers> The method for synthesizing allyl polymers by polymerizing the allyl compound represented by formula (1) and the allyl compound represented by formula (2) is not particularly limited. For example, they can be synthesized by appropriately changing the monomers used in accordance with the method for synthesizing homopolymers described in International Publication No. 2019 / 039185.

[0032] In the allyl polymer of the present invention, the content (mol%) of constituent units based on the allyl compound represented by formula (1) / content (mol%) of constituent units based on the allyl compound represented by formula (2) is 0.5 or more, preferably 0.6 or more, more preferably 0.7 or more, even more preferably 0.8 or more, particularly preferably 0.9 or more, most preferably 1.1 or more, even more preferably 1.5 or more, even more preferably 1.8 or more, particularly most preferably 2.0 or more, particularly most preferably 2.5 or more, and most preferably 3.0 or more. There is no particular upper limit, but it is preferably 99 or less, more preferably 20 or less, even more preferably 15 or less, particularly preferably 10 or less, most preferably 5 or less, and even more preferably 3.5 or less. Within the above range, the effects of the present invention tend to be obtained more fully. In this specification, the content of constituent units in the polymer is measured by a nuclear magnetic resonance spectrometer.

[0033] The allyl polymer of the present invention may have structural units other than those based on the allyl compound represented by formula (1) and those based on the allyl compound represented by formula (2). However, the total content of structural units based on the allyl compound represented by formula (1) and those based on the allyl compound represented by formula (2) in 100 mol% of the allyl polymer of the present invention is preferably 50 mol% or more, more preferably 80 mol% or more, even more preferably 90 mol% or more, particularly preferably 95 mol% or more, most preferably 98 mol% or more, and may be 100 mol%. Within the above range, the effects of the present invention tend to be obtained more fully.

[0034] The weight-average molecular weight (Mw) of the allyl polymer of the present invention is preferably 2,000 to 150,000, more preferably 5,000 to 140,000, and even more preferably 10,000 to 100,000. Within the above range, the effects of the present invention tend to be more fully obtained. In this specification, "weight-average molecular weight" can be determined by measuring it at 40°C using gel permeation chromatography (GPC system, manufactured by Shimadzu Corporation) and using a standard polystyrene calibration curve.

[0035] (Thermosetting Resin Composition) The thermosetting resin composition of the present invention contains the allyl polymer of the present invention. The allyl polymer of the present invention may be used alone or in combination of two or more types. The content of the allyl polymer of the present invention in 100% by mass of the thermosetting resin composition of the present invention is preferably 15 to 75% by mass, more preferably 20 to 60% by mass, and even more preferably 25 to 45% by mass. Within the above range, the effects of the present invention tend to be obtained more fully.

[0036] In the thermosetting resin composition of the present invention, the content of the allyl polymer of the present invention in 100% by mass of the resin (polymer) is preferably 10% by mass or more, more preferably 50% by mass or more, even more preferably 80% by mass or more, particularly preferably 90% by mass or more, most preferably 95% by mass or more, and most preferably 98% by mass or more, and may be 100% by mass. Within the above range, the effects of the present invention tend to be obtained more fully.

[0037] <Crosslinking Agent> The thermosetting resin composition of the present invention preferably contains a crosslinking agent. The crosslinking agent is not particularly limited as long as it is a polyfunctional compound, and examples include a polyfunctional monomer having two or more (meth)acryloyl groups or two or more allyl groups. These may be used alone or two or more may be used in combination. Among these, a polyfunctional monomer having two or more allyl groups is preferred. Here, (meth)acryloyl group means either or both of an acryloyl group and a methacryloyl group. The number of functional groups ((meth)acryloyl groups or allyl groups) that the crosslinking agent has is preferably 2 to 4, more preferably 2 to 3, and even more preferably 2, for the reason that the effects of the present invention can be more favorably obtained.

[0038] Examples of polyfunctional monomers having two or more allyl groups include allyl compounds represented by formula (1) and allyl compounds represented by formula (2).

[0039] As polyfunctional monomers having two or more (meth)acryloyl groups, commercially available ones may be purchased and used, or synthesized ones may be used. Specific examples include ethylene glycol di(meth)acrylate, 1,3-propanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, tricyclodecanedimethanol diacrylate, and the like. In particular, 1,6-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, and 1,9-nonanediol di(meth)acrylate are preferred.

[0040] In the thermosetting resin composition of the present invention, the crosslinking agent content is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, even more preferably 1 part by mass or more, preferably 80 parts by mass or less, more preferably 50 parts by mass or less, and even more preferably 10 parts by mass or less, based on 100 parts by mass of the resin (polymer) (preferably the allyl polymer of the present invention) contained in the thermosetting resin composition of the present invention. Within the above range, the effects of the present invention tend to be obtained more fully.

[0041] <Initiators (Polymerization Initiators)> The thermosetting resin composition of the present invention preferably contains an initiator (polymerization initiator). Examples of polymerization initiators include dialkyl peroxides such as di-tert-butyl peroxide and dicumyl peroxide, diallyl peroxides, peroxyesters such as tert-butyl-peroxybenzoate, tert-butyl-peroxy-isopropyl carbonate peroxides, peroxyketals such as 1,1-di-tert-butyl-peroxycyclohexane, benzoyl peroxides, dialoyl peroxides such as 2,4-dichlorobenzoin peroxide, diacyl peroxides, hydroperoxides such as hydroperoxides, and azo compounds such as azobisisobutyronitrile. These may be used alone or in combination of two or more.

[0042] In the thermosetting resin composition of the present invention, the initiator content is preferably 0.1 to 20 parts by mass, and more preferably 1 to 10 parts by mass, per 100 parts by mass of the resin (polymer) (preferably the allyl polymer of the present invention) contained in the thermosetting resin composition of the present invention. Within the above range, the effects of the present invention tend to be obtained more fully.

[0043] <Inorganic Fillers> Inorganic fillers may be added to the thermosetting resin composition of the present invention as needed. Examples of inorganic fillers include hydrates of metals such as fused silica, crystalline silica, alumina, quartz glass, calcium carbonate, aluminum hydroxide, and calcium sulfate, glass powder, talc, and mica. These may be used alone or in combination of two or more. The particle size of the inorganic filler is 0.1 to 100 μm. Preferably, it is 0.5 to 60 μm. If the particle size is too small, the viscosity of the composition will be high, and the reinforcing fibers will not be sufficiently impregnated, making it easy for air to be mixed into the material and for molded products to be prone to voids. On the other hand, if the particle size is too large, the specific surface area of ​​the particles will be small, resulting in decreased fluidity.

[0044] In the thermosetting resin composition of the present invention, the inorganic filler content may be 10 to 1,000 parts by mass, and more preferably 30 to 800 parts by mass, per 100 parts by mass of the resin (polymer) (preferably the allyl polymer of the present invention) contained in the thermosetting resin composition of the present invention. Within the above range, the effects of the present invention tend to be obtained more fully.

[0045] In addition to the above components, the thermosetting resin composition of the present invention may contain components known in the art, such as fiber reinforcing agents, low-shrinkage agents, mold release agents, thickeners, pigments, viscosity reducers, and silane coupling agents, to the extent that they do not impair the effects of the present invention. These may be used individually or in combination of two or more.

[0046] The fiber reinforcing agent used in the present invention is not particularly limited, and any known in the art can be used. Examples of fiber reinforcing materials include various organic and inorganic fibers such as glass fibers, pulp fibers, Tetron® fibers, vinylon fibers, carbon fibers, aramid fibers, and wollastonite. Among these, it is preferable to use chopped strand glass cut to a fiber length of about 1.5 to 25 mm. These may be used alone or in combination of two or more types.

[0047] In the thermosetting resin composition of the present invention, the content of the fiber reinforcing agent may be 10 to 1,000 parts by mass, and more preferably 30 to 800 parts by mass, per 100 parts by mass of the resin (polymer) (preferably the allyl polymer of the present invention) contained in the thermosetting resin composition of the present invention. Within the above range, the effects of the present invention tend to be obtained more fully.

[0048] Examples of low-shrinkage agents used in the present invention include thermoplastic polymers commonly used as low-shrinkage agents, such as polystyrene, polymethyl methacrylate, polyvinyl acetate, saturated polyester, and styrene-butadiene rubber. These may be used individually or in combination of two or more.

[0049] Examples of release agents used in the present invention include stearic acid, zinc stearate, calcium stearate, aluminum stearate, magnesium stearate, and carnauba wax. These may be used individually or in combination of two or more.

[0050] Examples of thickening agents used in the present invention include metal oxides such as magnesium oxide, magnesium hydroxide, calcium hydroxide, and calcium oxide, as well as isocyanate compounds. These may be used individually or in combination of two or more.

[0051] The thermosetting resin composition of the present invention can be produced by methods commonly used in the art, such as kneading using a planetary mill or a kneader.

[0052] The thermosetting resin composition of the present invention can be used to produce molded products (cured products, molded articles) by molding it into a desired shape and curing it (thermosetting). The cured product of the present invention is obtained by thermosetting the thermosetting resin composition of the present invention. Furthermore, the molded article of the present invention is obtained by molding the thermosetting resin composition of the present invention. The molding and thermosetting methods are not particularly limited, and methods commonly used in the art, such as compression molding, transfer molding, injection molding, etc., can be used.

[0053] The present invention will be described in more detail below with reference to examples, but the present invention is not limited in any way by these examples.

[0054] The materials used in the examples and comparative examples described below are explained below.

[0055] DAPM: Diallyl phthalate (a compound represented by the following formula) DAIM: Diallyl isophthalate (a compound represented by the following formula) MDAC: 1,2-Cyclohexanedicarboxylate diallyl (a compound represented by the following formula) Silane coupling agent: KBM-503 manufactured by Shin-Etsu Silicone Co., Ltd. Glass fiber: CS 3E-227 manufactured by Nitto Boseki Co., Ltd. Calcium carbonate: MC Coat S-1 manufactured by Maruo Calcium Co., Ltd. Calcium stearate: SC-100 manufactured by Sakai Chemical Industry Co., Ltd. Dicumyl peroxide: Percumyl D manufactured by NOF Corporation

[0056] Comparative Example 1: Synthesis of DAIM=100 homopolymer 1200 g of diallyl isophthalate and 30 g of benzoyl peroxide were added to a 3 L separable flask and heated and stirred at 80°C for 2 hours. After cooling, methanol was added and the polymer was precipitated. The obtained polymer was dried under reduced pressure at 40°C for 16 hours (yield: 230 g, yield: 19%, Mw = 39,000, Mw / Mn = 4.1). The obtained polymer was used in the preparation of thermosetting resin compositions.

[0057] Example 1: Synthesis of DAIM / MDAC = 76 / 24 (molar basis) copolymer. 900 g of diallyl isophthalate, 300 g of diallyl 1,2-cyclohexanedicarboxylate, and 30 g of benzoyl peroxide were added to a 3 L separable flask. The mixture was heated and stirred at 80°C and reacted for 2 hours. After cooling, methanol was added to precipitate the polymer. The obtained polymer was dried under reduced pressure at 40°C for 16 hours (yield: 202 g, yield: 17%, Mw = 23,000, Mw / Mn = 2.3, copolymer composition ratio (molar basis, the same applies below): diallyl isophthalate / diallyl 1,2-cyclohexanedicarboxylate = 76 / 24). The obtained polymer is used in the preparation of thermosetting resin compositions.

[0058] Example 2: Synthesis of DAIM / MDAC = 68 / 32 (molar basis) copolymer 820 g of diallyl isophthalate, 380 g of diallyl 1,2-cyclohexanedicarboxylate, and 30 g of benzoyl peroxide were added to a 3 L separable flask and heated and stirred at 80°C for 2 hours. After cooling, methanol was added and the polymer was precipitated. The obtained polymer was dried under reduced pressure at 40°C for 16 hours (yield: 198 g, yield: 16%, Mw = 23,000, Mw / Mn = 2.2, copolymer composition ratio: diallyl isophthalate / diallyl 1,2-cyclohexanedicarboxylate = 68 / 32). The obtained polymer is used in the preparation of thermosetting resin compositions.

[0059] Example 3: Synthesis of DAIM / MDAC = 51 / 49 (molar basis) copolymer 600 g of diallyl isophthalate, 600 g of diallyl 1,2-cyclohexanedicarboxylate, and 30 g of benzoyl peroxide were added to a 3 L separable flask and heated and stirred at 80°C for 2.5 hours. After cooling, methanol was added and the polymer was precipitated. The obtained polymer was dried under reduced pressure at 40°C for 16 hours (yield: 198 g, yield: 17%, Mw = 27,000, Mw / Mn = 2.3, copolymer composition ratio: diallyl isophthalate / diallyl 1,2-cyclohexanedicarboxylate = 51 / 49). The obtained polymer is used in the preparation of thermosetting resin compositions.

[0060] Example 4: Synthesis of DAIM / MDAC = 42 / 58 (molar basis) copolymer. 480 g of diallyl isophthalate, 720 g of diallyl 1,2-cyclohexanedicarboxylate, and 30 g of benzoyl peroxide were added to a 3 L separable flask. The mixture was heated and stirred at 80°C and reacted for 2.5 hours. After cooling, methanol was added to precipitate the polymer. The obtained polymer was dried under reduced pressure at 40°C for 16 hours (yield: 209 g, yield: 17%, Mw = 31,000, Mw / Mn = 2.5, copolymer composition ratio: diallyl isophthalate / diallyl 1,2-cyclohexanedicarboxylate = 42 / 58). The obtained polymer is used in the preparation of thermosetting resin compositions.

[0061] Comparative Example 2: Synthesis of DAIM / MDAC = 30 / 70 (molar basis) copolymer 300 g of diallyl isophthalate, 900 g of diallyl 1,2-cyclohexanedicarboxylate, and 30 g of benzoyl peroxide were added to a 3 L separable flask and heated and stirred at 80°C for 3 hours. After cooling, methanol was added and the polymer was precipitated. The obtained polymer was dried under reduced pressure at 40°C for 16 hours (yield: 232 g, yield: 19%, Mw = 32,000, Mw / Mn = 2.5, copolymer composition ratio: diallyl isophthalate / diallyl 1,2-cyclohexanedicarboxylate = 30 / 70). The obtained polymer is used in the preparation of thermosetting resin compositions.

[0062] Preparation of Thermosetting Resin Compositions According to the compositions shown in Table 1, each material was pre-mixed, then melt-kneaded using a heated roll at 80-100°C, cooled, and then pulverized to prepare thermosetting resin compositions.

[0063] The numerical units for composition in the table are parts by mass.

[0064] The following evaluations were performed on each of the obtained polymers and thermosetting resin compositions. The results are shown in Table 2.

[0065] Fluidity (Spiral Flow) Measurement: For each thermosetting resin composition, the longest length of the cured spiral-shaped portion, resembling a thin spiral mosquito coil, was measured. This length was defined as fluidity, and its change over time was measured. The measurements were performed under the following conditions: Molding machine: 37-ton transfer molding machine (Shinto Metal Industries Co., Ltd. "Transfer Molding Machine TA37"); Measurement mold: EMMI Spiral Flow (manufactured in-house by Osaka Soda); Measurement temperature: 150°C (mold temperature); Injection pressure: 8.5 MPa; Sample amount: 15 g; Pressurization time: 300 sec.

[0066] Measurement of tracking resistance: Using each thermosetting resin composition, molded products with a diameter of 100 mm and a thickness of 3 mm were obtained by compression molding at a mold temperature of 160°C for a molding time of 3 minutes. In accordance with JIS C 2134, the tracking resistance was measured using a tracking resistance tester (Yamayo Testing Equipment Co., Ltd. YST-112H) with an upper limit of 1000 V for the test voltage.

[0067] Measurement of 5% Weight Loss Temperature: Using each thermosetting resin composition, molded products were obtained by transfer molding at a mold temperature of 160°C for a molding time of 4 minutes. The weight loss was measured in an air atmosphere in the range of 30°C to 500°C using a Hitachi High-Tech Science (TG / DTA STA7200RV) under a heating rate of 10°C / min. The mass before heating was set as 100%, and the temperature at which a 5% mass loss occurred from the mass before heating was defined as the 5% weight loss temperature.

[0068] Using thermosetting resin compositions with different bending strengths and flexural moduli, molded products measuring 80 mm × 10 mm × 4 mm were obtained by transfer molding at a mold temperature of 160°C for a molding time of 4 minutes. Measurements were performed using a STROGRAPH VG20F manufactured by Toyo Seiki Seisakusho Co., Ltd., in accordance with JIS-K6911 "General Test Methods for Thermosetting Plastics". The measurements were performed under the following conditions: Crosshead speed: 2 mm / min, distance between pivots: 65 mm

[0069] For the measurement of impact strength, molded products were obtained by compression molding using each thermosetting resin composition at a mold temperature of 160°C for a molding time of 5 minutes. The impact strength was measured using a Charpy impact tester manufactured by Toyo Seiki Seisakusho Co., Ltd. in accordance with JIS K6911 "General Test Methods for Thermosetting Plastics".

[0070] Using each thermosetting resin composition, molded products measuring 80 mm × 10 mm × 4 mm were obtained by transfer molding at a mold temperature of 160°C for a molding time of 4 minutes. From the obtained molded products, pieces measuring 10 mm in height, 4 mm in width, and 4 mm in thickness were cut out and post-cured at 220°C for 2 hours to obtain test specimens. The coefficient of linear expansion of the obtained test specimens was measured by thermomechanical analysis. Specifically, a Netsch (TMA 4000 SE) measuring device was used, and measurements were taken by compression in a nitrogen atmosphere, under a load of 10 g and a heating rate of 5°C / min, in the temperature range of 25 to 300°C. Analysis of the coefficient of linear expansion was performed in the temperature range of 100 to 200°C.

[0071]

[0072] (Criteria for each evaluation) Spiral flow (◎: 300 mm or more, ○: 200 mm or more and less than 300 mm, ×: less than 200 mm) Tracking resistance (○: 1000 V or more, ×: less than 1000 V) 5% weight loss temperature (○: 350 °C or more, ×: less than 350 °C) Bending strength (○: 130 MPa or more, ×: less than 130 MPa) Bending modulus (○: 14 GPa or more, ×: less than 14 GPa) Charpy impact strength (○: 4 kJ / m ２ Above, ×: 4kj / m ２ (Less than) Coefficient of linear expansion (◎: Less than 70 ppm / °C, ○: 70 ppm / °C or more and less than 100 ppm / °C, ×: 100 ppm / °C or more)

[0073] As shown in Table 2, the allyl polymers of the examples obtained by polymerizing the allyl compound represented by formula (1) and the allyl compound represented by formula (2), in which the content of constituent units based on the allyl compound represented by formula (1) (mol%) / content of constituent units based on the allyl compound represented by formula (2) (mol%) is 0.5 or more, were found to have a large spiral flow and excellent fluidity.

[0074] This invention relates to an allyl polymer and thermosetting resin composition having excellent fluidity. The allyl polymer and thermosetting resin composition of this invention, taking advantage of its excellent fluidity, can be used in electrical and electronic components such as small, thin-walled coil bobbins, switch cases, terminal boards, connectors, and magnetic switches.

Claims

1. An allyl polymer obtained by polymerizing an allyl compound represented by formula (1) and an allyl compound represented by formula (2), wherein the content of constituent units based on the allyl compound represented by formula (1) (mol%) / content of constituent units based on the allyl compound represented by formula (2) (mol%) is 0.5 or more. X-(COOCH ２ CH=CH ２ ) ｎ (1) [In formula (1), n ​​represents an integer from 2 to 4, and X is an n-valent aromatic hydrocarbon group which may have an alkyl group.] Y-(COOCH ２ CH=CH ２ ) ｎ (2) [In formula (2), n represents an integer from 2 to 4, and Y is an n-valent alicyclic hydrocarbon group which may have an alkyl group.] 2. A thermosetting resin composition comprising the allyl polymer described in claim 1.

3. The thermosetting resin composition according to claim 2, further comprising an initiator.

4. The thermosetting resin composition according to claim 2, further comprising an inorganic filler.

5. A cured product obtained by thermosetting the thermosetting resin composition according to any one of claims 2 to 4.

6. A molded article characterized by being formed by molding a thermosetting resin composition according to any one of claims 2 to 4.

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