Thermosetting resin composition, cured product, and molded article

Abstract

Provided are: a thermosetting resin composition with which it is possible to provide a cured product and a molded article having both good strength and toughness; and a cured product and a molded article having both good strength and toughness. The present invention pertains to a thermosetting resin composition comprising: an allyl polymer having a structural unit based on an allyl compound represented by formula (1); and at least two crosslinking agents selected from the group consisting of (A) polyfunctional allyl ester compounds, (B) polyfunctional allyl ether compounds, and (C) polyfunctional (meth)acrylate compounds. (1): X-(COOCH2CH=CH2)n [In formula (1), n represents an integer of 2-4, and X represents an n-valent aromatic hydrocarbon group optionally having an alkyl group or an n-valent alicyclic hydrocarbon group optionally having an alkyl group.]

Description

Thermosetting resin compositions, cured products, molded products

[0001] This invention relates to 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 achieving both good strength and toughness in the cured products and molded articles obtained by the composition described in Patent Document 1. The object of the present invention is to provide a thermosetting resin composition that can provide cured products and molded articles that achieve both good strength and toughness, and to provide cured products and molded articles that achieve both good strength and toughness.

[0006] As a result of diligent research, the inventors of this invention have found that while it is difficult to obtain cured products or molded articles with good strength and toughness when using a single crosslinking agent, as in the composition described in Patent Document 1, a thermosetting resin composition comprising an allyl polymer having a structural unit based on an allyl compound represented by formula (1) and at least two crosslinking agents selected from the group consisting of (A) a polyfunctional allyl ester compound, (B) a polyfunctional allyl ether compound, and (C) a polyfunctional (meth)acrylate compound can provide cured products or molded articles with good strength and toughness, thus completing the present invention. 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, or an n-valent alicyclic hydrocarbon group which may have an alkyl group.]

[0007] Item 1 A thermosetting resin composition comprising an allyl polymer having a structural unit based on an allyl compound represented by formula (1), and at least two crosslinking agents selected from the group consisting of (A) polyfunctional allyl ester compounds, (B) polyfunctional allyl ether compounds, and (C) polyfunctional (meth)acrylate compounds. X-(COOCH ２ CH=CH ２ ) ｎ(1) [In formula (1), n ​​represents an integer of any 2 to 4, and X is an n-valent aromatic hydrocarbon group which may have an alkyl group or an n-valent alicyclic hydrocarbon group which may have an alkyl group.] Item 2 The thermosetting resin composition according to Item 1, wherein X in formula (1) is an n-valent aromatic hydrocarbon group which may have an alkyl group. Item 3 The thermosetting resin composition according to Item 1, wherein X in formula (1) is a divalent or trivalent aromatic hydrocarbon group which may have an alkyl group. Item 4 The thermosetting resin composition according to any one of Items 1 to 3, wherein the (A) polyfunctional allyl ester compound is an allyl compound represented by formula (1). Item 5 The thermosetting resin composition according to any one of Items 1 to 4, wherein the (B) polyfunctional allyl ether compound is an aliphatic allyl ether compound. Item 6 The thermosetting resin composition according to any one of Items 1 to 4, wherein the (B) polyfunctional allyl ether compound is a branched aliphatic allyl ether compound. Item 7 A thermosetting resin composition according to any one of items 1 to 6, wherein the (C) polyfunctional (meth)acrylate compound is an aliphatic (meth)acrylate compound. Item 8 A thermosetting resin composition according to any one of items 1 to 6, wherein the (C) polyfunctional (meth)acrylate compound is a linear aliphatic (meth)acrylate compound. Item 9 A thermosetting resin composition according to any one of items 1 to 8, wherein at least one of (A) a polyfunctional allyl ester compound, (B) a polyfunctional allyl ether compound, and (C) a polyfunctional (meth)acrylate compound is an aliphatic compound. Item 10 A thermosetting resin composition according to any one of items 1 to 9, comprising (B) a polyfunctional allyl ether compound and at least one crosslinking agent selected from the group consisting of (A) a polyfunctional allyl ester compound and (C) a polyfunctional (meth)acrylate compound. Item 11 A thermosetting resin composition according to any one of items 1 to 10, further comprising an initiator. Item 12 A thermosetting resin composition according to any one of items 1 to 11, further comprising an inorganic filler. Item 13 A cured product obtained by thermosetting the thermosetting resin composition according to any one of items 1 to 12. Item 14 A molded article characterized by being formed by molding the thermosetting resin composition according to any one of items 1 to 12.

[0008] The thermosetting resin composition of the present invention is a thermosetting resin composition comprising an allyl polymer having a structural unit derived from an allyl compound represented by the above formula (1), and at least two crosslinking agents selected from the group consisting of (A) a polyfunctional allyl ester compound, (B) a polyfunctional allyl ether compound, and (C) a polyfunctional (meth)acrylate compound, and therefore can provide a cured product and a molded article that achieve both good strength and good toughness.

[0009] The thermosetting resin composition of the present invention is a thermosetting resin composition comprising an allyl polymer having a structural unit derived from an allyl compound represented by formula (1), and at least two crosslinking agents selected from the group consisting of (A) a polyfunctional allyl ester compound, (B) a polyfunctional allyl ether compound, and (C) a polyfunctional (meth)acrylate compound, and therefore can provide a cured product and a molded article that achieve both good strength (for example, flexural strength) and good toughness (for example, flexural modulus, bending fracture strain). 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 or an n-valent alicyclic hydrocarbon group which may have an alkyl group.]]

[0010] The reason why the aforementioned effects are obtained is not entirely clear, but it is presumed to be due to the following mechanism. (A) Polyfunctional allyl ester compounds, (B) Polyfunctional allyl ether compounds, and (C) Polyfunctional (meth)acrylate compounds are crosslinking agents having allyl ester groups, allyl ether groups, and (meth)acrylate groups as reaction sites, respectively. Crosslinking agents differ in reactivity depending on the reaction sites they possess. When (A) Polyfunctional allyl ester compounds, (B) Polyfunctional allyl ether compounds, and (C) Polyfunctional (meth)acrylate compounds are used individually, cured products or molded products with excellent strength or excellent toughness can be obtained, but it is often difficult to obtain cured products or molded products that have both good strength and toughness. On the other hand, by using an allyl polymer having a structural unit based on an allyl compound represented by formula (1), along with at least two crosslinking agents selected from the group consisting of (A) polyfunctional allyl ester compounds, (B) polyfunctional allyl ether compounds, and (C) polyfunctional (meth)acrylate compounds, it is possible to provide cured products and molded articles that have both good strength and toughness. This is presumed to be because by using multiple specific crosslinking agents with different reactivity together with an allyl polymer having a structural unit based on an allyl compound represented by formula (1), a better crosslinked structure is formed, and cured products and molded articles that have both good strength and toughness can be provided.

[0011] The thermosetting resin composition of the present invention not only achieves both good strength and toughness in the resulting cured products and molded articles, but also provides good expansion resistance and heat resistance while maintaining both good strength and toughness.

[0012] <Allyl Polymer> The thermosetting resin composition of the present invention contains an allyl polymer (also referred to as the allyl polymer of the present invention or allyl polymer) having a structural unit based on an allyl compound represented by formula (1). 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, or an n-valent alicyclic hydrocarbon group which may have an alkyl group.]

[0013] The allyl polymer of the present invention is obtained by polymerizing an allyl compound represented by formula (1). This yields an allyl polymer having a structural unit based on the allyl compound represented by formula (1). The n-valence is based on the number of COOH groups bonded to X, and in formula (1), the number of -COOH groups bonded to X is n. 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, or an n-valent alicyclic hydrocarbon group which may have an alkyl group.]

[0015] <<<When X is an n-valent aromatic hydrocarbon group which may have an alkyl group>>> 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] If X is an n-valent aromatic hydrocarbon group which may have an alkyl group, then the allyl ester (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=CH２ 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 meta-oriented (disubstituted at positions 1 and 3) is preferred, and meta-oriented (disubstituted at positions 1 and 3) is more preferred.

[0017] The n-valent aromatic hydrocarbon group may or may not have an alkyl group. The alkyl group may be a straight 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. One or more alkyl groups may be present at the substituted positions of the aromatic hydrocarbon group. Furthermore, the n-valent aromatic hydrocarbon group may or may not have substituents other than alkyl groups.

[0018] When X is an n-valent aromatic hydrocarbon group which may have an alkyl group, specific allyl compounds represented by the above formula (1) include diallyl phthalate, diallyl isophthalate, and diallyl terephthalate, with diallyl phthalate and diallyl isophthalate being preferred, and diallyl isophthalate being more preferred.

[0019] Hereinafter, when X is an n-valent aromatic hydrocarbon group which may have an alkyl group, the allyl compound represented by the above formula (1) may be referred to as an "aromatic allyl compound".

[0020] When X is an n-valent aromatic hydrocarbon group which may have an alkyl group, the allyl compound represented by formula (1) above may be purchased commercially or synthesized by known synthetic methods (for example, the method described in International Publication No. 2019 / 039185).

[0021] <<<When X is an n-valent alicyclic hydrocarbon group which may have an alkyl group>>> 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 unsaturated bonds in part, but it is preferable to be 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 this invention, alicyclic means having a cyclic structure which does not have an aroma, and alicyclic hydrocarbon group means a hydrocarbon group which has a cyclic structure which does not have an aroma. The number of rings is preferably 1 or 2, particularly preferably 1, but it may be 3 or more. When the number of rings is 2 or more, it may be a fused ring type, a bridging ring type, or it may have both a fused ring and a bridging ring structure, but it is preferable to have a bridging ring. n is preferably 2 or 3, and more preferably 2.

[0022] Furthermore, the n-valent alicyclic hydrocarbon group may or may not have an alkyl group. The alkyl group may be a straight 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. One or more alkyl groups may be present at the substituted positions of the alicyclic hydrocarbon group. Moreover, the n-valent alicyclic hydrocarbon group may or may not have substituents other than alkyl groups.

[0023] When X is an n-valent alicyclic hydrocarbon group which may have an alkyl group, specific examples of allyl compounds represented by the above formula (1) include the compounds of the following general formulas (13) to (20) (formulas (15) to (18) are particularly preferred).

[0024] [In the formula, n is an integer between 2 and 4.]

[0025] 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.

[0026] When X is an n-valent alicyclic hydrocarbon group which may have an alkyl group, COOCH on the ring ２ CH=CH ２ The substitution positions of the groups may be any combination, or may be 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 may be in any of ortho orientation (disubstituted at positions 1 and 2), meta orientation (disubstituted at positions 1 and 3), or para orientation (disubstituted at positions 1 and 4); ortho orientation (disubstituted at positions 1 and 2) or para orientation (disubstituted at positions 1 and 4) is preferred, and ortho orientation (disubstituted at positions 1 and 2) is more preferred.

[0027] When X is an n-valent alicyclic hydrocarbon group which may have an alkyl group, specific allyl compounds represented by the above formula (1) 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 Examples include 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-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.

[0028] Hereinafter, when X is an n-valent alicyclic hydrocarbon group which may have an alkyl group, the allyl compound represented by the above formula (1) may be referred to as an "alicyclic allyl compound".

[0029] When X is an n-valent alicyclic hydrocarbon group which may have an alkyl group, the allyl compound represented by the above formula (1) may be a commercially available product purchased for use, or may be synthesized by a known synthesis method (for example, the method described in International Publication No. 2019 / 039185).

[0030] <<<<Regarding Allyl Polymer>>>> The method for synthesizing an allyl polymer by polymerizing the allyl compound represented by formula (1) is not particularly limited, and for example, the allyl polymer can be synthesized by appropriately changing the monomer used in accordance with the method for synthesizing a homopolymer described in International Publication No. 2019 / 039185.

[0031] X is an n-valent aromatic hydrocarbon group which may have an alkyl group or an n-valent alicyclic hydrocarbon group which may have an alkyl group; X is preferably an n-valent aromatic hydrocarbon group which may have an alkyl group, and more preferably a divalent or trivalent aromatic hydrocarbon group which may have an alkyl group. This tends to provide better strength and toughness.

[0032] In the allyl polymer of the present invention, based on 100 mol% of the constitutional units derived from the allyl compound represented by formula (1), the content of constitutional units derived from the allyl compound represented by formula (1) wherein X is an n-valent aromatic hydrocarbon group which may have an alkyl group is preferably 50 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, particularly preferably 95 mol% or more, most preferably 98 mol% or more, and may be 100 mol%. When the content is within the above range, the effects of the present invention tend to be obtained more sufficiently. In the present specification, the content of constitutional units in a polymer is measured by a nuclear magnetic resonance apparatus.

[0033] The allyl polymer of the present invention may have structural units other than those based on the allyl compound represented by formula (1). However, the content of structural units based on the allyl compound represented by formula (1) 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] 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 may be in the range of 5 to 80% by mass, but the lower limit of the content of the allyl polymer of the present invention is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass or more. The upper limit of the content of the allyl polymer of the present invention is preferably 75% by mass or less, more preferably 60% by mass or less, and even more preferably 45% by mass or less. Preferred ranges for the content of the allyl polymer of the present invention include 5 to 75% by mass, 5 to 60% by mass, 5 to 45% by mass, 10 to 75% by mass, 10 to 60% by mass, 10 to 45% by mass, 20 to 75% by mass, 20 to 60% by mass, and 20 to 45% by mass. Within the above ranges, the effects of the present invention tend to be obtained more fully.

[0036] The thermosetting resin composition of the present invention may contain polymers (resins) other than the allyl polymer of the present invention. The polymers (resins) other than the allyl polymer of the present invention that can be used in the thermosetting resin composition of the present invention are not particularly limited, and examples include unsaturated polyester resins, epoxy resins, phenolic resins, melamine resins, and the like. These may be used individually or in combination of two or more.

[0037] In the thermosetting resin composition of the present invention, the content of the allyl polymer of the present invention is 80% by mass or more of 100% by mass of the resin (polymer), preferably 90% by mass or more, more preferably 95% by mass or more, and even more 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.

[0038] <Crosslinking Agents> The thermosetting resin composition of the present invention contains at least two crosslinking agents selected from the group consisting of (A) polyfunctional allyl ester compounds, (B) polyfunctional allyl ether compounds, and (C) polyfunctional (meth)acrylate compounds. (A) Polyfunctional allyl ester compounds may be used alone or in combination of two or more. Similarly, (B) Polyfunctional allyl ether compounds may be used alone or in combination of two or more. Similarly, (C) Polyfunctional (meth)acrylate compounds may be used alone or in combination of two or more.

[0039] In this specification, polyfunctional means that the crosslinking agent has two or more reaction sites. Therefore, in this specification, a polyfunctional allyl ester compound means a compound having two or more allyl ester groups, a polyfunctional allyl ether compound means a compound having two or more allyl ether groups, and a polyfunctional (meth)acrylate compound means a compound having two or more (meth)acrylate groups. In this specification, an allyl ester group means -COOCH ２ CH=CH ２ It means a group, and the allyl ether group is -OCH ２ CH=CH ２ It means a group, and a (meth)acrylate group is an acrylate group (-OCOCH=CH). ２ (CH group) and methacrylate group (-OCOC(CH)３ ) = CH ２ It means one or both of the base.

[0040] The number of functional groups (number of allyl ester groups, number of allyl ether groups, number of (meth)acrylate groups) in each of the (A) polyfunctional allyl ester compound, (B) polyfunctional allyl ether compound, and (C) polyfunctional (meth)acrylate compound is not particularly limited as long as each is 2 or more, but is preferably 2 to 6, more preferably 2 to 4, even more preferably 2 to 3, and particularly preferably 2.

[0041] It is preferable that at least one of (A) a polyfunctional allyl ester compound, (B) a polyfunctional allyl ether compound, and (C) a polyfunctional (meth)acrylate compound is an aliphatic compound. This allows for better flexibility through crosslinking, resulting in better toughness and a tendency to provide cured products and molded articles that have both better strength and toughness. It is preferable that at least one of (A) a polyfunctional allyl ester compound, (B) a polyfunctional allyl ether compound, and (C) a polyfunctional (meth)acrylate compound has a ring structure. This allows for better strength through crosslinking, and a tendency to provide cured products and molded articles that have both better strength and toughness. Therefore, it is preferable that the thermosetting resin composition of the present invention contains at least two crosslinking agents, at least one of which is an aliphatic compound and at least one which has a ring structure. This tends to provide cured products and molded articles that have both better strength and toughness.

[0042] In this specification, "aliphatic compound" means hydrocarbon, and (A) a polyfunctional allyl ester compound is an aliphatic compound if it is a hydrocarbon having two or more allyl ester groups (also referred to as an aliphatic allyl ester compound), (B) a polyfunctional allyl ether compound is an aliphatic compound if it is a hydrocarbon having two or more allyl ether groups (also referred to as an aliphatic allyl ether compound), and (C) a polyfunctional (meth)acrylate compound is an aliphatic compound if it is a hydrocarbon having two or more (meth)acrylate groups (also referred to as an aliphatic (meth)acrylate compound).

[0043] Hydrocarbons may be linear or branched. They may also have unsaturated bonds, or they may not, but it is preferable that they do not. The number of carbon atoms in the hydrocarbon is not particularly limited, but is preferably 2 to 20, more preferably 2 to 16, and even more preferably 2 to 10. This allows for better flexibility through crosslinking, resulting in better toughness and a tendency to provide cured or molded products with both better strength and toughness. Furthermore, in addition to allyl ester groups, allyl ether groups, and (meth)acrylate groups, hydrocarbons may also have hydroxyl groups, aldehyde groups, carboxyl groups, amino groups, halogen groups, ester bonds, and ether bonds.

[0044] Atoms that form a ring structure include carbon atoms. The ring structure may also contain heteroatoms other than carbon atoms (e.g., nitrogen atoms, sulfur atoms, oxygen atoms, etc.), or it may not contain heteroatoms, but it is preferable that it does not contain heteroatoms. In other words, it is preferable that the atoms forming the ring structure are only carbon atoms. The number of carbon atoms forming the ring structure is preferably 3 to 18, more preferably 4 to 12, even more preferably 4 to 10, and particularly preferably 5 to 7. The ring structure may or may not contain unsaturated bonds. The number of rings is preferably one or two, particularly preferably one, but it may also be three or more. When the number of rings is two or more, it may be a fused ring type, a bridging ring type, or it may have both fused and bridging ring structures, but it is preferable that it has a bridging ring.

[0045] <<(A) Polyfunctional Allyl Ester Compound>> The polyfunctional allyl ester compound (A) is not particularly limited as long as it is a compound having two or more allyl ester groups, but it is preferable that it has a ring structure, and more preferably that it is an allyl compound represented by formula (1). The allyl compound represented by formula (1) is as described above, including preferred embodiments. In the allyl compound represented by formula (1), when X is an n-valent aromatic hydrocarbon group which may have an alkyl group, it tends to have superior strength, and when X is an n-valent alicyclic hydrocarbon group which may have an alkyl group, it tends to have superior toughness.

[0046] (A) As for the polyfunctional allyl ester compound, commercially available products may be purchased and used, or synthesized products may be used. Specific examples, including preferred embodiments, are as described above for the allyl compound represented by formula (1).

[0047] <<(B) Polyfunctional Allyl Ether Compounds>> The polyfunctional allyl ether compound (B) is not particularly limited as long as it is a compound having two or more allyl ether groups, but it is preferably an aliphatic allyl ether compound, and more preferably a branched aliphatic allyl ether compound.

[0048] (B) As for the polyfunctional allyl ether compound, commercially available products may be purchased and used, or synthesized products may be used. Specific examples include ethylene glycol diallyl ether, 1,3-propylene glycol diallyl ether, 1,4-butanediol diallyl ether, 1,5-pentanediol diallyl ether, 1,6-hexanediol diallyl ether, 1,7-heptanediol diallyl ether, 1,8-octanediol diallyl ether, 1,9-nonanediol diallyl ether, 1,10-decanediol diallyl ether, trimethylolpropane diallyl ether, trimethylolpropane triallyl ether, pentaerythritol diallyl ether, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether, glycerin diallyl ether, glycerin triallyl ether, dimethylolcyclohexane diallyl ether, bisphenol A diallyl ether, bisphenol F diallyl ether, bisphenol S diallyl ether, and novolacphenol allyl ethers (excluding monoallyl ethers). Among these, trimethylolpropanediallyl ether, pentaerythritol triallyl ether, and pentaerythritol tetraallyl ether are preferred, and trimethylolpropanediallyl ether and pentaerythritol triallyl ether are more preferred.

[0049] <<(C) Polyfunctional (meth)acrylate compound>> The (C) polyfunctional (meth)acrylate compound is not particularly limited as long as it is a compound having two or more (meth)acrylate groups, but it is preferably an aliphatic (meth)acrylate compound, and more preferably a linear aliphatic (meth)acrylate compound.

[0050] (C) As for the polyfunctional (meth)acrylate compound, commercially available products may be purchased and used, or synthesized products 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, etc. Among these, 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, with 1,6-hexanediol di(meth)acrylate being more preferred.

[0051] <<Combination of Crosslinking Agents>> The thermosetting resin composition of the present invention contains at least two crosslinking agents selected from the group consisting of (A) polyfunctional allyl ester compounds, (B) polyfunctional allyl ether compounds, and (C) polyfunctional (meth)acrylate compounds. That is, the thermosetting resin composition of the present invention may contain at least two crosslinking agents from the three types (A) polyfunctional allyl ester compounds, (B) polyfunctional allyl ether compounds, and (C) polyfunctional (meth)acrylate compounds (for example, (A) polyfunctional allyl ester compound and (B) polyfunctional allyl ether compound).

[0052] The thermosetting resin composition of the present invention preferably comprises (A) a polyfunctional allyl ester compound and (C) a polyfunctional (meth)acrylate compound, and (B) a polyfunctional allyl ether compound. Furthermore, the thermosetting resin composition of the present invention may also preferably comprise (A) a polyfunctional allyl ester compound and (C) a polyfunctional (meth)acrylate compound. These combinations tend to provide cured products and molded articles with better strength and toughness.

[0053] In the thermosetting resin composition of the present invention, the crosslinking agent content (total content of (A) polyfunctional allyl ester compound, (B) polyfunctional allyl ether compound, and (C) polyfunctional (meth)acrylate compound) 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, particularly preferably 2 parts by mass or more, preferably 80 parts by mass or less, more preferably 50 parts by mass or less, even more preferably 10 parts by mass or less, particularly preferably 9 parts by mass or less, most preferably 8 parts by mass or less, and most preferably 7 parts by mass or less. Within the above range (especially in the case of small amounts such as 10 parts by mass or less), the effects of the present invention tend to be obtained more fully.

[0054] The thermosetting resin composition of the present invention may contain a crosslinking agent other than (A) a polyfunctional allyl ester compound, (B) a polyfunctional allyl ether compound, and (C) a polyfunctional (meth)acrylate compound (other crosslinking agents). Other crosslinking agents that can be used in the thermosetting resin composition of the present invention are not particularly limited and include, for example, polyfunctional vinyl compounds and polyfunctional thiol compounds. These may be used alone or in combination of two or more.

[0055] In the thermosetting resin composition of the present invention, the total content of (A) a polyfunctional allyl ester compound, (B) a polyfunctional allyl ether compound, and (C) a polyfunctional (meth)acrylate compound in 100% by mass of the crosslinking agent is preferably 80% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, 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.

[0056] <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.

[0057] 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.

[0058] <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.

[0059] 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.

[0060] 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.

[0061] 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.

[0062] 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.

[0063] 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.

[0064] 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.

[0065] 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.

[0066] 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.

[0067] 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.

[0068] 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.

[0069] The materials used in the examples and comparative examples described below are explained below.

[0070] Aromatic allyl polymer: Daiso Isodap (DAIM=100 homopolymer) manufactured by Osaka Soda Co., Ltd. Alicyclic allyl polymer: RADPAR AD-032 (MDAC=100 homopolymer) manufactured by Osaka Soda Co., Ltd. Diallyl phthalate (DAPM): Daiso Dap monomer (compound represented by the following formula) manufactured by Osaka Soda Co., Ltd. Diallyl isophthalate (DAIM): Daiso DAP 100 monomer manufactured by Osaka Soda (a compound represented by the following formula) 1,2-Diallyl cyclohexanedicarboxylate (MDAC, a compound represented by the following formula) Trimethylolpropanediallyl ether: Neoallyl T-20 manufactured by Osaka Soda Co., Ltd. 1,6-Hexanediol dimethacrylate: Light Ester 1.6HX manufactured by Kyoeisha Chemical Co., Ltd. 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

[0071] 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 pulverized to prepare the thermosetting resin composition.

[0072] The obtained thermosetting resin compositions were evaluated as follows. The results are shown in Table 1. In addition, we checked whether any problems occurred during mixing or molding. If a problem occurred, the details of the problem were recorded in the workability column of Table 1, and if no problems occurred, a circle (○) was indicated.

[0073] (Bending strength, bending modulus, bending fracture strain) Each thermosetting resin composition was subjected to transfer molding at a mold temperature of 160°C for 4 minutes to obtain molded products measuring 80 mm × 10 mm × 4 mm. Measurements were performed in accordance with JIS-K6911 "General Test Methods for Thermosetting Plastics" using a STROGRAPH VG20F manufactured by Toyo Seiki Seisakusho Co., Ltd. The measurements were performed under the following conditions: Crosshead speed: 2 mm / Distance between pivots: 65 mm

[0074] (Coefficient of linear expansion) Each thermosetting resin composition was subjected to transfer molding at a mold temperature of 160°C for a molding time of 4 minutes to obtain molded products measuring 80 mm × 10 mm × 4 mm. 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.

[0075] (5% weight loss temperature) Molded products were obtained from each thermosetting resin composition 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 from 30°C to 500°C using a Hitachi High-Tech Science Corporation (TG / DTA STA7200RV) under a heating rate of 10°C / min. The mass before heating was set to 100%, and the temperature at which a 5% mass loss occurred from the mass before heating was defined as the 5% weight loss temperature.

[0076] For bending strength, bending strain at fracture, and 5% weight loss temperature, higher values ​​indicate better performance. On the other hand, for bending modulus and coefficient of thermal expansion, lower values ​​indicate better performance. When an aromatic allyl polymer, in which X in formula (1) may have an alkyl group, is used as the resin, it was determined that good strength and toughness are achieved when the bending strength is 150 MPa or higher, the bending modulus is 14.5 GPa or lower, and the bending strain at fracture is 1.45% or higher. Furthermore, it was determined that good expansion resistance is obtained when the coefficient of thermal expansion is 60 ppm / K or lower. In addition, it was determined that good heat resistance is obtained when the 5% weight loss temperature is 320°C or higher. When an alicyclic allyl polymer in formula (1), where X is an n-valent alicyclic hydrocarbon group that may have an alkyl group, is used as the resin, it was determined that good strength and toughness are achieved when the flexural strength is 130 MPa or higher, the flexural modulus is 14.5 GPa or lower, and the flexural fracture strain is 1.45% or higher. Furthermore, it was determined that good expansion resistance is obtained when the coefficient of linear expansion is 90 ppm / K or lower. In addition, it was determined that good heat resistance is obtained when the 5% weight loss temperature is 320°C or higher.

[0077]

[0078] As shown in Table 1, the thermosetting resin composition of the example, comprising an allyl polymer having a structural unit based on the allyl compound represented by formula (1) and at least two crosslinking agents selected from the group consisting of (A) polyfunctional allyl ester compounds, (B) polyfunctional allyl ether compounds, and (C) polyfunctional (meth)acrylate compounds, was found to provide cured products and molded articles that exhibit both good strength and toughness.

[0079] The present invention relates to a thermosetting resin composition that can provide cured products and molded articles that have both good strength and toughness, and to cured products and molded articles that have both good strength and toughness. The thermosetting resin composition, cured products, and molded articles of the present invention can be used in electrical and electronic components such as small, thin-walled coil bobbins, switch cases, terminal boards, terminal blocks, connectors, magnetic switches, sockets, brush holders, capacitors, inductors, resistors, relays, stators, busbars, power modules, and semiconductors, taking advantage of their good strength and toughness.

Claims

1. A thermosetting resin composition comprising an allyl polymer having a structural unit based on an allyl compound represented by formula (1), and at least two crosslinking agents selected from the group consisting of (A) polyfunctional allyl ester compounds, (B) polyfunctional allyl ether compounds, and (C) polyfunctional (meth)acrylate compounds. 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, or an n-valent alicyclic hydrocarbon group which may have an alkyl group.] 2. The thermosetting resin composition according to claim 1, wherein X in formula (1) is an n-valent aromatic hydrocarbon group which may have an alkyl group.

3. The thermosetting resin composition according to claim 1, wherein X in formula (1) is a divalent or trivalent aromatic hydrocarbon group which may have an alkyl group.

4. The thermosetting resin composition according to claim 1, wherein the polyfunctional allyl ester compound (A) is an allyl compound represented by formula (1).

5. The thermosetting resin composition according to claim 1, wherein the (B) polyfunctional allyl ether compound is an aliphatic allyl ether compound.

6. The thermosetting resin composition according to claim 1, wherein the (B) polyfunctional allyl ether compound is a branched aliphatic allyl ether compound.

7. The thermosetting resin composition according to claim 1, wherein the (C) polyfunctional (meth)acrylate compound is an aliphatic (meth)acrylate compound.

8. The thermosetting resin composition according to claim 1, wherein the (C) polyfunctional (meth)acrylate compound is a linear aliphatic (meth)acrylate compound.

9. The thermosetting resin composition according to claim 1, wherein at least one of (A) a polyfunctional allyl ester compound, (B) a polyfunctional allyl ether compound, and (C) a polyfunctional (meth)acrylate compound is an aliphatic compound.

10. The thermosetting resin composition according to claim 1, comprising (B) a polyfunctional allyl ether compound and at least one crosslinking agent selected from the group consisting of (A) a polyfunctional allyl ester compound and (C) a polyfunctional (meth)acrylate compound.

11. The thermosetting resin composition according to claim 1, further comprising an initiator.

12. The thermosetting resin composition according to claim 1, further comprising an inorganic filler.

13. A cured product obtained by thermosetting the thermosetting resin composition according to any one of claims 1 to 12.

14. A molded article characterized by being formed by molding a thermosetting resin composition according to any one of claims 1 to 12.

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