Allyl ether compound, resin composition thereof, cured product thereof, and method for producing allyl ether compound

Abstract

Provided are: an allyl ether compound that yields a cured product that is excellent in terms of low dielectric properties, high heat resistance, and the like; a resin composition thereof; and a cured product obtained from the resin composition.　The allyl ether compound is represented by general formula (1).　

Description

[Technical Field]

[0001] The present invention relates to an allyl ether compound that gives a cured product that is excellent in low dielectric properties, high heat resistance, etc.; a resin composition containing the allyl ether compound as an essential component; a cured product, encapsulant, circuit board material, prepreg, or laminate obtained from the resin composition; and a method for producing the allyl ether compound. [Background technology]

[0002] Thermosetting resins such as epoxy resins and phenolic resins are excellent in adhesiveness, flexibility, heat resistance, chemical resistance, insulation, and curing reactivity, and are therefore used in a wide range of applications, including paints, civil engineering adhesives, casting, electrical and electronic materials, film materials, etc. In particular, epoxy resins are widely used in printed wiring boards, one type of electrical and electronic material, by imparting flame retardancy to them.

[0003] Mobile devices, one of the applications for printed wiring boards, and the infrastructure equipment that connects them, such as base stations, are constantly being required to provide higher performance due to the dramatic increase in data traffic in recent years. In particular, the transition from 4G to 5G communication standards is expected to further increase data traffic, necessitating the transmission of high-frequency signals. Therefore, printed wiring boards require materials with lower dielectric loss tangents to suppress signal attenuation due to high frequencies. Furthermore, to accommodate the trend toward thinner wiring and higher multilayer counts in printed wiring boards, matrix resins must possess properties such as high adhesive strength and high heat resistance. To meet these requirements, conventional matrix resins using epoxy resins are insufficient, and more highly functional thermosetting resins are needed.

[0004] Regarding the reduction of the dielectric constant of epoxy resins that have been used as matrix resins for printed wiring boards, examples of raw material epoxy resins include compounds obtained by glycidylating dihydric phenols such as bisphenol A, compounds obtained by glycidylating tris(glycidyloxyphenyl)alkanes or aminophenols, and compounds obtained by glycidylating novolaks such as phenol novolak (Patent Document 1). Patent Documents 2 and 3 disclose methods of using imide group-containing phenolic resins to improve heat resistance and mechanical properties compared to epoxy resins, and the inclusion of imide groups improves heat resistance. Furthermore, Patent Document 4 cites compounds in which imide group-containing phenolic resins have been epoxidized as resins suitable for use as matrix resins that improve adhesion to substrates. Furthermore, Patent Document 5 describes a composition in which the heat resistance and flame retardancy of a substrate are improved by using a maleimide compound, an epoxy resin, and a phenolic curing agent with a specific structure, and Patent Documents 6 and 7 describe examples in which compositions with excellent adhesive strength and dielectric properties can be provided by using a maleimide compound with a specific structure. Patent Document 8 illustrates that by using a maleimide compound and an allyl ether compound, a curable resin composition having low dielectric properties and high heat resistance can be obtained. Patent Document 9 illustrates that a composition having excellent curability and heat resistance can be obtained by using a thermosetting resin composition containing a maleimide compound having a specific structure and a compound having an allyl group or a methallyl group. However, none of the curable resin compositions disclosed in any of the documents satisfies the dielectric property requirements required in recent years for high functionality, and none of them satisfies all of the physical properties simultaneously. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 5-43655 [Patent Document 2] Japanese Patent Application Publication No. 7-33858 [Patent Document 3] Japanese Patent Application Publication No. 7-10970 [Patent Document 4] Japanese Patent Application Laid-Open No. 2010-235823 [Patent Document 5] International Publication No. 2011 / 126070 [Patent Document 6] International Publication No. 2016 / 208667 [Patent Document 7] International Publication No. 2020 / 054526 [Patent Document 8] Japanese Patent Publication No. 2020-111744 [Patent Document 9] International Publication No. 2017 / 170844 Summary of the Invention

[0006] Therefore, the problem to be solved by the present invention is to provide a resin composition and a cured product thereof which have excellent properties such as low dielectric properties and high heat resistance, and are useful for applications such as lamination, molding, and adhesion.

[0007] In order to solve the above problems, the present inventors have conducted extensive research and have found that a resin composition containing an allyl ether compound (resin) represented by the following general formula (1) simultaneously satisfies unprecedented low dielectric properties and a high glass transition temperature (Tg), thereby completing the present invention.

[0008] That is, the present invention is an allyl ether compound (resin) characterized by being represented by the following general formula (1). [ka] where: R 1 each independently represents a hydrocarbon group having 1 to 8 carbon atoms, R 2 independently represent a hydrogen atom, a group represented by formula (2), or a group represented by formula (3), and at least one of them is formula (2) or formula (3). R 3 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, R 4 each independently represents a hydrogen atom or a group represented by formula (2), R 9 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. A is the two R 2 Residues other than R 2 are independently a hydrogen atom or a group represented by formula (2). Me represents a methyl group. i is an integer from 0 to 2. n and p1 each represent the number of repetitions, and the average value is a number from 0 to 5.

[0009] R 1 is preferably a methyl group or a phenyl group, and i is preferably 1 or 2.

[0010] The present invention also provides an allyl ether compound obtained by allyl-etherifying a polyhydric hydroxy resin represented by the following general formula (4). [ka] where: R 1 each independently represents a hydrocarbon group having 1 to 8 carbon atoms, R 2 Each ' independently represents a hydrogen atom, a group represented by formula (5), or a group represented by formula (6), and at least one of them is formula (5) or formula (6). R 3 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, R 4 each independently represents a hydrogen atom or a group represented by formula (5). A' is the sum of two R 2 A residue excluding R 2 ' are independently a hydrogen atom or a group represented by formula (5). Me represents a methyl group. i is an integer from 0 to 2. m and p2 each represent the number of repetitions, and the average value is a number from 0 to 5.

[0011] The present invention also provides a resin composition comprising the allyl ether compound and a maleimide compound.

[0012] The present invention also relates to a cured product obtained by curing the above-mentioned resin composition, and to a circuit board material, a sealing material, a prepreg, or a laminate, which uses the above-mentioned resin composition.

[0013] The present invention also provides a method for producing the allyl ether compound, which comprises allyl-etherifying the polyhydric hydroxy resin to obtain the allyl ether compound.

[0014] The allyl ether compound (resin) of the present invention, when used as a resin composition, provides a cured product with a high glass transition temperature. It also has excellent dielectric properties, and exhibits excellent properties in laminates and electronic circuit boards, which require low dielectric constants and low dielectric loss tangents. [Brief explanation of the drawings]

[0015] [Figure 1] 1 is a GPC chart of the allyl ether compound obtained in Example 1. [Figure 2] 1 is an IR chart of the allyl ether compound obtained in Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0016] The present invention will be described in detail below. The allyl ether compound of the present invention is an allyl ether compound represented by general formula (1). [ka] This allyl ether compound is advantageously obtained by allyl etherifying a polyhydric hydroxy compound (resin) represented by the above general formula (4), and is also called an allyl ether resin because it is a mixture of n=0 (monomer), n=1 (dimer), and n=2 or more (trimer or more). In the following formulas, common symbols have the same meaning.

[0017] In general formula (1), R 1 are independently a hydrocarbon group having 1 to 8 carbon atoms, and are preferably an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 8 carbon atoms, an aralkyl group having 7 to 8 carbon atoms, or an allyl group. The alkyl group may be linear, branched, or cyclic, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a t-butyl group, a hexyl group, a cyclohexyl group, and a methylcyclohexyl group. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, and an ethylphenyl group. Examples of the aralkyl group include a benzyl group and an α-methylbenzyl group. Of these substituents, from the viewpoints of availability and reactivity when a cured product is formed, a phenyl group and an alkyl group having 1 to 3 carbon atoms are preferred, and a methyl group is particularly preferred. R 1 The substitution position of may be any of the ortho, meta, and para positions relative to the allyl ether group, but the ortho position is preferred.

[0018] R 2 represents a hydrogen atom or a group represented by formula (2) or formula (3), and at least one of R is represented by formula (2) or formula (3). 2 is a substituent R 1 Unlike the above, it does not necessarily represent only a substituent, but also a hydrogen atom. [ka] The group represented by formula (2) is a group derived from an aromatic monovinyl compound represented by general formula (8a) described below among the aromatic vinyl compounds used as raw materials for the polyhydric hydroxy resin represented by general formula (4), and the group represented by formula (3) is a group derived from an aromatic divinyl compound represented by general formula (8b) described below among the aromatic vinyl compounds.

[0019] In formula (1), R 9 are independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, preferably a hydrogen atom or an alkyl group.

[0020] i is the number of substitutions and is 0 to 2, preferably 1 or 2, and more preferably 2.

[0021] n is the number of repetitions and is a number of 0 or more, and its average value (number average) is 0 to 5, preferably 1.0 to 4.0, more preferably 1.1 to 3.0, and even more preferably 1.2 to 2.5.

[0022] In equation (2), R 3 represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms. Examples of the hydrocarbon group having 1 to 8 carbon atoms include R 1 Examples include the following: R 3 MoR 2 Similarly, the substituent R 1 Unlike the above, it does not necessarily represent only a substituent, but also a hydrogen atom. When an aromatic monovinyl compound represented by formula (8a) is used as a raw material for the polyhydric hydroxy resin represented by general formula (4), R 3 In terms of availability and heat resistance of the cured product, R is preferably a hydrogen atom, a methyl group, or an ethyl group, and more preferably a hydrogen atom or an ethyl group. When an aromatic divinyl compound represented by formula (8b) is used as a raw material, R 3 A vinyl group may be contained as R 3 The substitution position may be any of the ortho, meta and para positions, but the meta and para positions are preferred. Preferably, R 3 One of the groups is an ethyl group and the rest are hydrogen atoms.

[0023] In equation (3), A is the two R 2 Residues other than R 2 is a hydrogen atom or a group represented by formula (2). In other words, A is a divalent group having a structure similar to that of general formula (1), but is not a group represented by formula (3). R 3 is equivalent to equation (2). R 4 represents a hydrogen atom or a group represented by formula (2). 4 Also, R 2 or R 3 Similarly, the substituent R 1 Unlike the above, it does not necessarily represent only a substituent, but also a hydrogen atom. p1 is the number of repetitions and is a number of 0 or more, and the average value (number average) is 0 to 5, preferably 0.01 to 3, more preferably 0.1 to 2.0, still more preferably 0.2 to 1.0, and particularly preferably 0.3 to 0.8.

[0024] The weight average molecular weight (Mw) of the allyl ether compound (resin) of the present invention is preferably 400 to 5000, more preferably 500 to 4500, and even more preferably 600 to 4000. The number average molecular weight (Mn) is preferably 350 to 2000, more preferably 400 to 1500, and even more preferably 450 to 1000. The content by GPC is such that the molecular weight distribution of the polyhydric hydroxy resin, which is the raw material, is maintained almost unchanged, and in general formula (1), preferably, n=0 is 10 area% or less, n=1 is 30 to 90 area%, and n=2 or more is 0 to 70 area%. More preferably, n=0 is 1 to 10 area%, n=1 is 30 to 60 area%, and n=2 or more is 40 to 65 area%. The phenolic hydroxyl group equivalent (g / eq.) is preferably at least 5000, more preferably at least 10000. If it exceeds 10000, the amount of hydroxyl groups exceeds the amount that can be practically measured, indicating that the phenolic hydroxyl groups of the raw material polyhydric hydroxy resin have been almost completely allyl etherified. The softening point is preferably from 40 to 180°C, more preferably from 50 to 120°C.

[0025] The polyhydric hydroxy resin, which is the raw material for the allyl ether compound (resin) of the present invention, is represented by general formula (4). [ka]

[0026] In general formula (4), R 2 Each ' independently represents a hydrogen atom, a group represented by formula (5), or a group represented by formula (6), and at least one of them is formula (5) or formula (6). [ka] R4 each independently represents a hydrogen atom or a group represented by formula (5). A' is the sum of two R 2 A residue excluding R 2 ' are independently a hydrogen atom or a group represented by formula (5).

[0027] In general formula (4), R 1 and i are defined as in general formula (1). m is defined as n in general formula (1), but this is also almost the same in the case of the relationship between raw materials and products. R 2 R' represents a hydrogen atom or a group represented by formula (5) or formula (6), and at least one of R' represents formula (5) or formula (6). 2 ' is R in general formula (1) 2 Similarly, it does not necessarily represent only a substituent, but also a hydrogen atom.

[0028] In equation (5), R 3 is defined as in formula (2).

[0029] In equation (6), R 3 , R 4 , and Me are defined as in formula (3). p2 is defined as p1 in formula (3), but it is almost the same even in the case of the relationship between raw materials and products. A' is the two R 2’ Residues other than R 2’ is a hydrogen atom or a group represented by formula (5). In other words, A' is a divalent group having a structure similar to that of general formula (4), but is not a group represented by formula (6).

[0030] The weight average molecular weight (Mw) of the polyhydric hydroxy resin represented by general formula (4) is preferably 400 to 5000, more preferably 500 to 3000, and even more preferably 600 to 2000. The number average molecular weight (Mn) is preferably 350 to 2000, more preferably 400 to 1500, and even more preferably 450 to 1000. The phenolic hydroxyl group equivalent (g / eq.) is preferably 190-500, more preferably 220-400, and even more preferably 250-350. The softening point is preferably from 50 to 180°C, more preferably from 50 to 120°C.

[0031] The polyhydric hydroxy resin represented by general formula (4) can be obtained by reacting a dicyclopentadiene-type polyhydric hydroxy resin (a) represented by the following general formula (7) with an aromatic monovinyl compound represented by general formula (8a) and / or an aromatic divinyl compound represented by general formula (8b) in the presence of an acid catalyst. The aromatic monovinyl compound and aromatic divinyl compound are collectively referred to as aromatic vinyl compounds. Here, the polyhydric hydroxy resin (a) has a structure in which phenols are linked by dicyclopentadiene.

[0032] [ka]

[0033] [ka]

[0034] In general formula (7), R 1 and i have the same definition as in general formula (1), and s has the same definition as n in general formula (1), but this is also almost the same in the case of the relationship between raw materials and products.

[0035] In general formulas (8a) and (8b), R 3 is defined as in equation (2). 3 When is a substituent, the substitution position may be any of the ortho, meta, and para positions relative to the vinyl group, but the meta and para positions are preferred.

[0036] In the aromatic divinyl compound represented by general formula (8b), the substitution position of another vinyl group relative to a vinyl group may be any of the ortho, meta, and para positions, but the meta and para positions are preferred, and a mixture thereof may also be used.

[0037] The aromatic vinyl compound used as a raw material must be an aromatic monovinyl compound (a compound represented by general formula (8a)), and may also contain an aromatic divinyl compound (a compound represented by general formula (8b)). The greater the amount of aromatic divinyl compound, the greater the molecular weight of the polyhydroxy resin (A). Therefore, the amount of the polyhydroxy resin (a) can be adjusted to achieve the desired molecular weight, taking into account the molecular weight of the polyhydroxy resin (a). The aromatic monovinyl compound undergoes an addition reaction to become a substituent represented by formula (2), which reduces the dielectric properties.

[0038] Examples of aromatic monovinyl compounds include vinyl aromatic compounds such as styrene, vinylnaphthalene, vinylbiphenyl, and α-methylstyrene, nuclear alkyl-substituted vinyl aromatic compounds such as o-methylstyrene, m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, o-ethylvinylbenzene, m-ethylvinylbenzene, p-ethylvinylbenzene, ethylvinylbiphenyl, and ethylvinylnaphthalene, and cyclic vinyl aromatic compounds such as indene, acenaphthylene, benzothiophene, and coumarone. Styrene and ethylvinylbenzene are preferred. These may be used alone or in combination of two or more.

[0039] Examples of aromatic divinyl compounds include divinyl aromatic compounds such as divinylbenzene, divinylnaphthalene, and divinylbiphenyl. Divinylbenzene is preferred. These can be used alone or in combination of two or more.

[0040] The blending amounts of the aromatic monovinyl compound and aromatic divinyl compound are preferably 15 to 50 mass% of the aromatic monovinyl compound and 50 to 85 mass% of the aromatic divinyl compound relative to the total amount of the aromatic vinyl compounds. The aromatic monovinyl compound is preferably 15 to 50 mass%, more preferably 17 to 45 mass%. The aromatic divinyl compound is preferably 50 to 85 mass%, more preferably 55 to 83 mass%.

[0041] The phenolic hydroxyl group equivalent (g / eq.) of the polyhydric hydroxy resin (a) represented by the above general formula (7) is preferably 160-220, more preferably 165-210, and even more preferably 170-200. The content by GPC of s=0 is preferably 10% by area or less, s=1 is preferably 50 to 90% by area, and s=2 or more is preferably 0 to 50% by area.

[0042] The polyhydric hydroxy resin (a) represented by the general formula (7) can be obtained by reacting a phenol represented by the following general formula (9) with dicyclopentadiene in the presence of a Lewis acid. [ka] where R 1 and i are defined as in general formula (1). 1 The substitution position may be any of the ortho, meta, and para positions, but the ortho position is preferred. The structural formula of dicyclopentadiene is: [ka]

[0043] Examples of phenols represented by general formula (9) include phenol, cresol, ethylphenol, propylphenol, isopropylphenol, n-butylphenol, t-butylphenol, hexylphenol, cyclohexylphenol, phenylphenol, tolylphenol, benzylphenol, α-methylbenzylphenol, allylphenol, dimethylphenol, diethylphenol, dipropylphenol, diisopropylphenol, di(n-butyl)phenol, di(t-butyl)phenol, dihexylphenol, dicyclohexylphenol, diphenylphenol, ditolylphenol, dibenzylphenol, bis(α-methylbenzyl)phenol, methylethylphenol, methylpropylphenol, methylisopropylphenol, methylbutylphenol, methyl-t-butylphenol, methylallylphenol, tolylphenylphenol, etc. From the viewpoints of availability and reactivity when formed into a cured product, phenol, cresol, phenylphenol, dimethylphenol, or diphenylphenol is preferred, and cresol and dimethylphenol are particularly preferred.

[0044] The catalyst used in the above reaction is a Lewis acid, specifically boron trifluoride, boron trifluoride phenol complex, boron trifluoride ether complex, aluminum chloride, tin chloride, zinc chloride, iron chloride, etc. Among these, boron trifluoride ether complex is preferred due to its ease of handling. In the case of boron trifluoride ether complex, the amount of catalyst used is 0.001 to 20 parts by mass, preferably 0.5 to 10 parts by mass, per 100 parts by mass of dicyclopentadiene.

[0045] The amount of dicyclopentadiene used is 0.08 to 0.80 mol, preferably 0.09 to 0.60 mol, more preferably 0.10 to 0.50 mol, still more preferably 0.10 to 0.40 mol, and particularly preferably 0.10 to 0.20 mol, per mol of the phenol.

[0046] This reaction is preferably carried out by charging a phenol and a catalyst into a reactor and then adding dicyclopentadiene dropwise over a period of 0.1 to 10 hours, preferably 0.5 to 8 hours, and more preferably 1 to 6 hours.

[0047] The reaction temperature is preferably 50 to 200° C., more preferably 100 to 180° C., and even more preferably 120 to 160° C. The reaction time is preferably 1 to 10 hours, more preferably 3 to 10 hours, and even more preferably 4 to 8 hours.

[0048] After the reaction is complete, an alkali such as sodium hydroxide, potassium hydroxide, or calcium hydroxide is added to deactivate the catalyst. The resulting product is then dissolved in a solvent such as an aromatic hydrocarbon (e.g., toluene or xylene) or a ketone (e.g., methyl ethyl ketone or methyl isobutyl ketone), washed with water, and the solvent is recovered under reduced pressure to obtain the desired polyhydroxy resin represented by general formula (7). It is preferable to react as much of the dicyclopentadiene as possible and recover the unreacted raw material phenols under reduced pressure.

[0049] In the reaction, if necessary, a solvent may be used, such as aromatic hydrocarbons such as benzene, toluene, and xylene; ketones such as methyl ethyl ketone and methyl isobutyl ketone; halogenated hydrocarbons such as chlorobenzene and dichlorobenzene; and ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether.

[0050] A reaction method for introducing the aromatic skeleton structure of formula (5) or (6) into polyhydroxy resin (a) is a method in which polyhydroxy resin (a) is reacted with an aromatic vinyl compound at a predetermined ratio. The reaction ratio is 0.05 to 2.0 moles, more preferably 0.1 to 1.0 moles, and particularly preferably 0.15 to 0.95 moles, of the aromatic vinyl compound per mole of phenolic hydroxyl group in polyhydroxy resin (a).

[0051] The catalyst used in the reaction is an acid catalyst, and specific examples include mineral acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; organic acids such as formic acid, oxalic acid, trifluoroacetic acid, and p-toluenesulfonic acid; Lewis acids such as zinc chloride, aluminum chloride, iron chloride, and boron trifluoride; and solid acids such as activated clay, silica-alumina, and zeolite. Among these, p-toluenesulfonic acid is preferred because of its ease of handling. In the case of p-toluenesulfonic acid, the amount of the catalyst used is 0.001 to 20 parts by mass, and preferably 0.5 to 10 parts by mass, per 100 parts by mass of the polyhydric hydroxy resin (a).

[0052] This reaction is preferably carried out by charging the polyhydric hydroxy resin (a), the catalyst, and the solvent into a reactor, dissolving them, and then adding the aromatic vinyl compound dropwise over 0.1 to 10 hours, preferably 0.5 to 8 hours, and more preferably 0.5 to 5 hours.

[0053] The reaction temperature is preferably 50 to 200° C., more preferably 100 to 180° C., and even more preferably 120 to 160° C. The reaction time is preferably 1 to 10 hours, more preferably 3 to 10 hours, and even more preferably 4 to 8 hours.

[0054] After the reaction is complete, an alkali such as sodium hydroxide, potassium hydroxide, or calcium hydroxide is added to deactivate the catalyst, and the resulting product is dissolved in a solvent such as an aromatic hydrocarbon such as toluene or xylene, or a ketone such as methyl ethyl ketone or methyl isobutyl ketone. After washing with water, the solvent is recovered under reduced pressure to obtain the desired polyhydric hydroxy resin.

[0055] Examples of the solvent used in the reaction include aromatic hydrocarbons such as benzene, toluene, xylene, etc., ketones such as methyl ethyl ketone, methyl isobutyl ketone, etc., halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, etc., ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, etc. These solvents may be used alone or in combination of two or more.

[0056] As the polyvalent hydroxy compound (resin) represented by the above general formula (4), it is preferable to use the polyvalent hydroxy resin obtained by the above reaction, but it is not limited thereto.

[0057] The allyl etherification method is an excellent method for obtaining the allyl ether compound (resin) of general formula (1). One example of this method is to react a polyhydric hydroxy resin represented by general formula (4) with an allyl halide compound in a solvent in the presence of an alkali compound (allyl etherification reaction). In this case, it is preferable to dissolve the polyhydric hydroxy resin in a solvent in advance, and then add the allyl halide compound and the alkali compound to cause the reaction. This allyl etherification reaction is preferably carried out by charging the polyhydric hydroxy resin and the solvent into a reactor, dissolving the resin, and then adding the allyl halide compound solution and the alkali compound solution dropwise.

[0058] Examples of halogenated allyl compounds used in the production of allyl ether compounds include allyl chloride, allyl bromide, methallyl chloride, and methallyl bromide. Among these, allyl bromide or allyl chloride is preferred from the viewpoint of reactivity with polyhydroxy resins. Furthermore, allyl chloride tends to polymerize with itself to form a polymer (polyallyl chloride), and it is preferable to use allyl chloride with a low polyallyl chloride content for the production. A high polyallyl chloride content in the allyl chloride used not only increases the total chlorine content of the resulting allyl ether compound, but also contributes to an increase in the molecular weight of the allyl ether compound, potentially resulting in the generation of trace amounts of gelled material in the cured product. Furthermore, reducing the chlorine content requires the addition of a significant amount of basic substance, which is industrially undesirable. The polyallyl chloride content can be easily confirmed by gas chromatography or the like. The polyallyl chloride content is preferably 1 area % or less, more preferably 0.5 area % or less, and even more preferably 0.2 area % or less, relative to the allyl chloride monomer. The amount of the halogenated allyl compound used is usually 1.0 to 2.0 mol, preferably 1.0 to 1.5 mol, more preferably 1.0 to 1.25 mol, and even more preferably 1.0 to 1.2 mol, per mol of hydroxyl group of the polyhydric hydroxy resin.

[0059] The alkali compound used in the production of the allyl ether compound is preferably an alkali metal hydroxide or carbonate, and specific examples thereof include sodium hydroxide, potassium hydroxide, potassium carbonate, and sodium carbonate, with sodium hydroxide and potassium hydroxide being preferred. Such alkali metal hydroxides may be used in the form of a solid or a solution thereof. The amount of the alkali compound used is usually 1.0 to 2.0 mol, preferably 1.0 to 1.8 mol, more preferably 1.0 to 1.5 mol, still more preferably 1.0 to 1.3 mol, and particularly preferably 1.0 to 1.1 mol, per mol of hydroxyl groups in the polyhydric hydroxy resin.

[0060] The solvent used in producing the allyl ether compound is not particularly limited, but examples thereof include alcohols such as methanol, ethanol, n-propanol, isopropanol, and n-butanol; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ethers such as tetrahydrofuran, dioxane, and diglyme; and aprotic polar solvents such as dimethylacetamide, dimethylformamide, and dimethyl sulfoxide. One or more of these solvents can be used. Water can also be mixed with the above solvents. The amount of the solvent used is preferably 20 to 300% by mass, more preferably 25 to 250% by mass, and particularly preferably 25 to 200% by mass, based on the total mass of the polyhydroxy resin. In particular, aprotic polar solvents are not useful for purification such as washing with water, and have high boiling points that make them difficult to remove, so it is not preferable for their amount to exceed 300% by mass based on the total mass of the polyhydroxy resin. In addition to the water and solvents described above, other solvents such as toluene (other organic solvents) may be contained, and the amount of other organic solvents used is preferably 100% by mass or less, more preferably 0.5 to 50% by mass, based on the amount of the solvent used.

[0061] The reaction temperature for the allyl etherification reaction of the polyhydric hydroxy resin is usually 30 to 90° C., and preferably 35 to 80° C. In order to obtain an allyl ether compound with higher purity, it is preferable to increase the reaction temperature in two or more stages. For example, it is particularly preferable to increase the reaction temperature to 35 to 50° C. in the first stage and 45 to 70° C. in the second stage. The reaction time for the allyl etherification reaction of the polyhydric hydroxy resin is usually 0.5 to 10 hours, preferably 1 to 8 hours, and particularly preferably 1 to 5 hours. A reaction time of 0.5 hours or more allows the reaction to proceed sufficiently, while a reaction time of 10 hours or less makes it possible to keep the amount of by-products produced low.

[0062] After the reaction is complete, the solvent is distilled off under reduced pressure with heating, or the residue is dissolved directly in a solvent such as a ketone solvent having 4 to 7 carbon atoms (for example, methyl isobutyl ketone, methyl ethyl ketone, cyclopentanone, cyclohexanone, etc.) or toluene, and the solution is heated to 40 to 90°C, more preferably 50 to 80°C, and washed with water until the aqueous layer reaches a pH of 5 to 8, thereby removing by-produced salts.

[0063] The allyl etherification reaction of the polyhydric hydroxy resin is usually carried out while blowing an inert gas such as nitrogen into the system (in air or in liquid). By blowing an inert gas into the system, coloration of the resulting product can be prevented. The amount of inert gas blown in per unit time varies depending on the volume of the vessel used in the reaction, and it is preferable to adjust the amount of inert gas blown in per unit time so that the volume of the vessel can be replaced in, for example, 0.5 to 20 hours.

[0064] The maleimide compound contained in the resin composition of the present invention is not particularly limited as long as it is a compound having one or more maleimide groups in one molecule, and examples thereof include N-phenylmaleimide, phenylmethanemaleimide, N-hydroxyphenylmaleimide, 4,4'-diphenylmethane bismaleimide, 4,4-diphenylether bismaleimide, polyphenylmethanemaleimide, m-phenylenebismaleimide, p-phenylenebismaleimide, 2,2'-[4-(4-maleimidophenoxy)phenyl]propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, bis(3,5-dimethyl-4-maleimidophenyl) Examples of suitable maleimide compounds include bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, bis(3,5-diethyl-4-maleimidophenyl)methane, 4-methyl-1,3-phenylene bismaleimide, 4,4'-diphenyl ether bismaleimide, 4,4'-diphenylsulfone bismaleimide, 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene, N,N'-ethylene dimaleimide, N,N'-hexamethylene dimaleimide, maleimide compounds represented by the following general formula (10), prepolymers of these maleimide compounds, and prepolymers of maleimide compounds and amine compounds. These maleimide compounds can be used alone or in combination. Among these, the maleimide compound (resin) represented by the following general formula (10) is preferred.

[0065] [ka] where: R 4 each independently represents an alkyl group having 1 to 5 carbon atoms or an aromatic group. R 5 each independently represents a hydrogen atom or a methyl group. a represents 0 to 4, and is preferably 0 or 1. b represents 0 to 3, and 0 or 1 is preferred. r and q are 0 or 1. m is the number of repetitions, and its average value is 1 to 10, preferably 1 to 7, and more preferably 1 to 5.

[0066] The resin composition of the present invention essentially comprises the allyl ether compound (resin) of the present invention and a maleimide compound (resin). The content of the allyl ether compound is preferably 5 to 900 parts by mass, more preferably 10 to 500 parts by mass, and even more preferably 20 to 200 parts by mass, relative to 100 parts by mass of the maleimide compound. The allyl ether compound used to obtain the resin composition of the present invention may be the allyl ether compound of the present invention, and one or more of various allyl ether compounds may be used in combination, as needed. Preferably, at least 30% by mass of the allyl ether compound is the allyl ether compound of the present invention, and more preferably 50% by mass or more. If the content is less than this, the dielectric properties may be deteriorated.

[0067] Examples of allyl ether compounds that can be used in combination with the allyl ether compound (resin) of the present invention include allyl ether compounds obtained by allyl etherifying bisphenols such as bisphenol A, bisphenol F, bisphenol C, bisphenol K, bisphenol Z, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol S, tetramethylbisphenol Z, dihydroxydiphenyl sulfide, and 4,4'-thiobis(3-methyl-6-t-butylphenol); allyl ether compounds obtained by allyl etherifying dihydroxybenzenes such as catechol, resorcinol, methylresorcinol, hydroquinone, monomethylhydroquinone, dimethylhydroquinone, trimethylhydroquinone, mono-t-butylhydroquinone, and di-t-butylhydroquinone; allyl ether compounds obtained by allyl etherifying hydroxynaphthalenes such as dihydroxynaphthalene, dihydroxymethylnaphthalene, dihydroxymethylnaphthalene, and trihydroxynaphthalene; and Shounol BRG-555 (Aica Chemical Co., Ltd.). phenol novolac resins such as DC-5 (manufactured by Nippon Steel Chemical & Material Co., Ltd.), cresol novolac resins such as DC-5 (manufactured by Nippon Steel Chemical & Material Co., Ltd.), aromatic modified phenol novolac resins, bisphenol A novolac resins, trishydroxyphenylmethane novolac resins such as Resitop TPM-100 (manufactured by Gunei Chemical Industry Co., Ltd.), naphthol novolac resins and other condensates of phenols, naphthols and / or bisphenols with aldehydes, phenols such as SN-160, SN-395, SN-485 (manufactured by Nippon Steel Chemical & Material Co., Ltd.), Examples of such compounds include allyl ether compounds obtained by allylic etherifying polyhydric hydroxy resins known as novolak phenolic resins, such as condensates of phenols, naphthols and / or bisphenols with xylylene glycol, condensates of phenols and / or naphthols with isopropenylacetophenone, reaction products of phenols, naphthols and / or bisphenols with dicyclopentadiene, and condensates of phenols, naphthols and / or bisphenols with a biphenyl-based crosslinking agent; and triallyl isocyanurate.From the viewpoints of reactivity and availability, allyl ether compounds obtained by allylic etherifying bisphenols such as bisphenol A and bisphenol F are preferred.

[0068] The resin composition of the present invention may contain a curing accelerator as needed. When a curing accelerator is used, a compound capable of crosslinking with imide groups undergoes an addition reaction with the imide groups to crosslink, thereby resulting in a cured product with good physical properties.

[0069] Examples of the curing accelerator include amines, imidazoles, organic phosphines, Lewis acids, organic peroxides, etc. Specific examples include tertiary amines such as 1,8-diazabicyclo(5,4,0)undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol; imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, and 2-heptadecylimidazole; organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, and phenylphosphine; and quinones of organic phosphines. Examples of suitable curing accelerators include addition reaction products with tetraphenylphosphonium compounds, tetra-substituted phosphonium tetra-substituted borates such as tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium ethyltriphenylborate, and tetrabutylphosphonium tetrabutylborate, tetraphenylboron salts such as 2-ethyl-4-methylimidazole tetraphenylborate and N-methylmorpholine tetraphenylborate, and organic peroxides such as ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxydicarbonates, and peroxyesters. The amount of curing accelerator added is in the range of 0.2 to 5 parts by mass per 100 parts by mass of the resin composition. These curing accelerators may be used alone or in combination.

[0070] The resin composition of the present invention may contain various other curable resins and thermoplastic resins, if necessary.

[0071] Examples of the curable resin include epoxy resin, unsaturated polyester resin, curable maleimide resin, polycyanate resin, phenol resin, one or more vinyl compounds having one or more polymerizable unsaturated hydrocarbon groups in the molecule, etc. From the viewpoint of low dielectric constant and low dielectric loss tangent, one or more vinyl compounds having one or more polymerizable unsaturated hydrocarbon groups in the molecule are preferred.

[0072] When the curable resin is an epoxy resin, it is preferably one or more epoxy resins selected from epoxy resins having two or more epoxy groups in one molecule. Examples of such epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, tetramethylbisphenol F type epoxy resins, biphenol type epoxy resins, hydroquinone type epoxy resins, bisphenol fluorene type epoxy resins, naphthalenediol type epoxy resins, bisphenol S type epoxy resins, diphenyl sulfide type epoxy resins, diphenyl ether type epoxy resins, resorcinol type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, alkyl novolac type epoxy resins, styrenated phenol novolac type epoxy resins, bisphenol novolac type epoxy resins, naphthol novolac type epoxy resins, β-naphthol aralkyl type epoxy resins, naphthalenediol aralkyl type epoxy resins, α-naphthol aralkyl type epoxy resins, biphenyl aralkyl type epoxy resins, trihydroxyphenylmethane type epoxy resins, tetrahydroxyphenylethane type epoxy resins, dicyclopentadiene type epoxy resins, alkylene glycol type epoxy resins, and aliphatic cyclic epoxy resins. These epoxy resins may be used alone, or two or more types of epoxy resins of the same type may be used in combination, or epoxy resins of different types may be used in combination.

[0073] Furthermore, when an epoxy resin is contained, a curing agent may be used in addition to the epoxy resin. The curing agent is not particularly limited, and examples thereof include phenol-based curing agents, amine-based compounds, amide-based compounds, acid anhydride-based compounds, naphthol-based curing agents, active ester-based curing agents, benzoxazine-based curing agents, and cyanate ester-based curing agents. These may be used alone, or two or more of the same type may be used in combination, or different types may be used in combination.

[0074] Furthermore, when an epoxy resin is blended, a curing accelerator can be used as needed. Examples include amines, imidazoles, organic phosphines, Lewis acids, etc. The amount added is usually in the range of 0.2 to 5 parts by mass per 100 parts by mass of the epoxy resin.

[0075] When the curable resin is one or more vinyl compounds having one or more polymerizable unsaturated hydrocarbon groups in the molecule (hereinafter also referred to as vinyl compounds), the type thereof is not particularly limited. That is, the vinyl compounds may be any compounds that can be crosslinked and cured by reacting with the vinyl compound of the present invention. More preferably, the polymerizable unsaturated hydrocarbon group is a carbon-carbon unsaturated double bond, and more preferably, a compound having two or more carbon-carbon unsaturated double bonds in the molecule.

[0076] The average number of carbon-carbon unsaturated double bonds (the number of vinyl groups (including substituted vinyl groups); also referred to as the number of terminal double bonds) per molecule of vinyl compounds serving as curable resins varies depending on the Mw of the vinyl compounds, but is preferably, for example, 1 to 20, and more preferably 2 to 18. If the number of terminal double bonds is too small, it tends to be difficult to obtain a cured product with sufficient heat resistance. On the other hand, if the number of terminal double bonds is too large, the reactivity becomes too high, which may result in problems such as reduced storage stability or reduced fluidity of the composition.

[0077] Examples of vinyl compounds include trialkenyl isocyanurate compounds such as triallyl isocyanurate (TAIC), modified polyphenylene ethers (PPE) whose terminals are modified with (meth)acryloyl or styryl groups, polyfunctional (meth)acrylate compounds having two or more (meth)acryloyl groups in the molecule, vinyl compounds (polyfunctional vinyl compounds) having two or more vinyl groups in the molecule such as polybutadiene, and vinylbenzyl compounds such as styrene and divinylbenzene. Among these, compounds having two or more carbon-carbon double bonds in the molecule are preferred, specifically TAIC, polyfunctional (meth)acrylate compounds, modified PPE resins, polyfunctional vinyl compounds, and divinylbenzene compounds. The use of these compounds is believed to more effectively form crosslinks during the curing reaction, thereby improving the heat resistance of the cured resin composition. These compounds may be used alone or in combination. A compound having one carbon-carbon unsaturated double bond in the molecule may also be used in combination. Examples of compounds having one carbon-carbon unsaturated double bond in the molecule include compounds having one vinyl group in the molecule (monovinyl compounds).

[0078] Examples of thermoplastic resins include phenoxy resin, polyurethane resin, polyester resin, polyethylene resin, polypropylene resin, polystyrene resin, ABS resin, AS resin, vinyl chloride resin, polyvinyl acetate resin, polymethyl methacrylate resin, polycarbonate resin, polyacetal resin, cyclic polyolefin resin, polyamide resin, thermoplastic polyimide resin, polyamideimide resin, polytetrafluoroethylene resin, polyetherimide resin, polyphenylene ether resin, modified polyphenylene ether resin, polyethersulfone resin, polysulfone resin, polyetheretherketone resin, polyphenylene sulfide resin, polyvinyl formal resin, etc., as well as known thermoplastic elastomers (e.g., styrene-ethylene-propylene copolymer, styrene-ethylene-butylene copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, hydrogenated styrene-butadiene copolymer, hydrogenated styrene-isoprene copolymer, etc.), and rubbers (e.g., polybutadiene, polyisoprene). Polyphenylene ether resin (unmodified), hydrogenated styrene-butadiene copolymer, etc. are preferred.

[0079] The resin composition of the present invention may contain other additives such as a filler, a silane coupling agent, an antioxidant, a release agent, an antifoaming agent, an emulsifier, a thixotropy-imparting agent, a smoothing agent, a flame retardant, and a pigment, as necessary.

[0080] Specific examples of fillers include fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide, boehmite, magnesium hydroxide, talc, mica, calcium carbonate, calcium silicate, calcium hydroxide, magnesium carbonate, barium carbonate, barium sulfate, boron nitride, carbon, carbon fiber, glass fiber, alumina fiber, silica-alumina fiber, silicon carbide fiber, polyester fiber, cellulose fiber, aramid fiber, ceramic fiber, fine rubber particles, thermoplastic elastomer, and pigment. The filler is used to improve impact resistance. These fillers may be used alone or in combination of two or more. Metal hydroxides such as aluminum hydroxide, boehmite, and magnesium hydroxide act as flame retardant aids, improving flame retardancy. Among these, silica, mica, and talc are preferred, and spherical silica is more preferred. These fillers may be used alone or in combination of two or more.

[0081] The filler may be used as is, or may be surface-treated with a silane coupling agent such as an epoxysilane or aminosilane type. Preferred silane coupling agents include vinylsilane, methacryloxysilane, acryloxysilane, and styrylsilane types. This enhances the adhesive strength with the metal foil and the interlayer adhesive strength between resins. Instead of surface-treating the filler in advance, the silane coupling agent may be added by integral blending.

[0082] When the resin composition is used to form a plate-shaped substrate or the like, a fibrous filler is preferred in terms of dimensional stability, bending strength, etc. A more preferred example is a glass fiber substrate using a filler made of a fibrous base material woven from glass fibers in a mesh pattern.

[0083] The amount of filler to be added is preferably 1 to 200 parts by mass, more preferably 10 to 150 parts by mass, and even more preferably 30 to 70 parts by mass, per 100 parts by mass of the resin composition (solid content). If the amount is too high, the cured product may become brittle, and sufficient mechanical properties may not be obtained. If the amount is too low, the effects of adding the filler, such as improving the impact resistance of the cured product, may not be achieved. The amount of the other additives to be added is preferably in the range of 0.01 to 20 parts by mass relative to 100 parts by mass of the resin composition (solid content).

[0084] A cured product can be obtained by heat-curing the resin composition of the present invention. Suitable methods for obtaining a cured product include casting, compression molding, transfer molding, and laminating resin sheets, resin-coated copper foils, prepregs, and the like, followed by heat-pressure curing to form a laminate. The temperature during this process is typically in the range of 150 to 300°C, and the curing time is typically about 10 minutes to 5 hours.

[0085] The resin composition of the present invention can be obtained by uniformly mixing the above-mentioned components. The resin composition can be easily cured by a method similar to that known in the art. Examples of the cured product include laminates, cast products, molded products, adhesive layers, insulating layers, films, and other molded cured products.

[0086] Examples of applications for the resin composition include printed wiring board materials, resin compositions for flexible wiring boards, insulating materials for circuit boards such as interlayer insulating materials for build-up boards, semiconductor encapsulation materials, conductive pastes, conductive films, adhesive films for build-up boards, resin casting materials, adhesives, etc. Among these various applications, the resin composition can be used as an insulating material for so-called electronic component-embedded substrates, in which passive components such as capacitors and active components such as IC chips are embedded in the substrate. Among these, the resin composition is preferably used for printed wiring board materials, resin compositions for flexible wiring boards, circuit board (laminate) materials such as interlayer insulating materials for build-up boards, and semiconductor encapsulation materials, due to its properties such as high flame retardancy, high heat resistance, low dielectric properties, and solvent solubility.

[0087] The resin composition of the present invention can be used to produce encapsulants suitable for tape-type semiconductor chips, potting-type liquid encapsulation, underfill, and semiconductor interlayer insulating film applications. To prepare a resin composition for use as a semiconductor encapsulant, additives such as inorganic fillers, coupling agents, and release agents, which are optionally incorporated into the resin composition, can be premixed, followed by thorough melt mixing using an extruder, kneader, rolls, or the like until homogeneous. Silica is typically used as the inorganic filler, and the inorganic filler is preferably incorporated into the resin composition in an amount of 70 to 95% by mass.

[0088] When the resin composition thus obtained is used as a semiconductor package, for example, the obtained resin composition is molded using a casting machine, transfer molding machine, injection molding machine, or the like, and further heat-cured at 180 to 250°C for 0.5 to 5 hours to obtain a molded product. When used as a tape-shaped encapsulant, for example, the obtained resin composition is heated to prepare a semi-cured sheet to form an encapsulant tape, and this encapsulant tape is then placed on a semiconductor chip, heated to 100 to 150°C to soften and mold, and then completely cured at 180 to 250°C. When used as a potting-type liquid encapsulant, for example, the obtained resin composition may be dissolved in a solvent as needed, applied to a semiconductor chip or electronic component, and directly cured.

[0089] The resin composition of the present invention can be prepared into a varnish by dissolving it in an organic solvent. Usable organic solvents include alcoholic solvents such as methanol and ethanol, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, ether solvents such as tetrahydrofuran, nitrogen-containing solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone, and sulfur-containing solvents such as dimethyl sulfoxide. These solvents can be used alone or in combination. While any commercially available organic solvent can be used, methyl ethyl ketone and dimethylformamide are preferred from the viewpoints of solubility and ease of handling.

[0090] The resin composition of the present invention can be dissolved in an organic solvent to form a composition varnish, which can then be impregnated into a fibrous material such as glass cloth, aramid nonwoven fabric, or polyester nonwoven fabric made of liquid crystal polymer or the like, followed by removing the solvent to form a prepreg. Alternatively, the composition varnish can be applied to a sheet-like material such as copper foil, stainless steel foil, polyimide film, or polyester film, followed by drying to form an adhesive sheet.

[0091] When forming a laminate using the prepreg, one or more prepregs are laminated, and metal foil is placed on one or both sides to form a laminate. This laminate is then pressurized and heated to cure and integrate the prepregs, resulting in a laminate. The metal foil can be a single, alloy, or composite metal foil of copper, aluminum, brass, nickel, or the like. The conditions for heating and pressing the laminate can be appropriately adjusted to cure the resin composition. However, if the pressure is too low, air bubbles may remain inside the resulting laminate, resulting in reduced electrical properties. Therefore, it is desirable to pressurize the laminate under conditions that satisfy moldability. The heating temperature is preferably 160 to 250°C, more preferably 170 to 220°C. The pressure is preferably 0.5 to 10 MPa, more preferably 1 to 5 MPa. The heating and pressing time is preferably 10 minutes to 4 hours, more preferably 40 minutes to 3 hours. Furthermore, a multilayer board can be produced using the single-layer laminate thus obtained as an inner layer material. In this case, a circuit is first formed on the laminate by an additive or subtractive method, and the surface of the formed circuit is then blackened to obtain an inner layer material. An insulating layer is formed on one or both circuit-formed surfaces of this inner layer material using a prepreg or adhesive sheet, and a conductor layer is formed on the surface of the insulating layer to form a multilayer board. [Example]

[0092] The present invention will be specifically explained using examples and comparative examples, but the present invention is not limited to these. Unless otherwise specified, "parts" means parts by mass, "%" means % by mass, and "ppm" means ppm by mass. The measurements were performed using the following methods. The number of allyl groups in the allyl ether compound was considered to be the same as the number of hydroxyl groups in the raw material polyhydric hydroxy resins.

[0093] (1) Hydroxyl equivalent: Measurements were carried out in accordance with JIS K0070 and the unit was "g / eq." Unless otherwise specified, the hydroxyl group equivalent of the polyhydric hydroxy resin means the phenolic hydroxyl group equivalent.

[0094] (2) Softening point: The softening point was measured in accordance with the JIS K7234 standard, the ring and ball method, using an automatic softening point apparatus (ASP-MG4, manufactured by Meitec Corporation).

[0095] (3) Dielectric constant and dielectric loss tangent: The dielectric constant and dielectric loss tangent at a frequency of 1 GHz were evaluated by the capacitance method using a material analyzer (manufactured by Agilent Technologies) in accordance with IPC-TM-650 2.5.5.9.

[0096] (4) Glass transition temperature (Tg): Measurement was carried out in accordance with JIS C6481 standard, and was expressed as the peak top of tan δ when measurement was carried out using a dynamic viscoelasticity measuring device (Hitachi High-Tech Science Corporation, EXSTAR DMS6100) at a temperature increase rate of 5°C / min.

[0097] (5) GPC (gel permeation chromatography) measurement: The main unit (Tosoh Corporation, HLC-8220GPC) was equipped with columns (Tosoh Corporation, TSKgel G4000HXL, TSKgel G3000HXL, TSKgel G2000HXL) in series, and the column temperature was set to 40°C. Tetrahydrofuran (THF) was used as the eluent at a flow rate of 1 mL / min, and a refractive index detector was used. 50 μL of the sample was prepared by dissolving 0.1 g of sample in 10 mL of THF and filtering through a microfilter. Mw and Mn were calculated from a calibration curve obtained from standard polystyrene (Tosoh Corporation, PStQuick Kit-H). Data processing was performed using a Tosoh Corporation GPC-8020 Model II version 6.00.

[0098] (6)IR: A Fourier transform infrared spectrophotometer (Perkin Elmer Precisely, Spectrum One FT-IR Spectrometer 1760X) was used, and a KRS-5 cell was used. The sample dissolved in THF was applied to the cell, dried, and then measured at a wavenumber of 450 to 4000 cm. -1 The absorbance was measured.

[0099] (7) ESI-MS: Mass spectrometry was performed using a mass spectrometer (Shimadzu Corporation, LCMS-2020) with acetonitrile and water as the mobile phase, by measuring a sample dissolved in acetonitrile.

[0100] The abbreviations used in the examples and comparative examples are as follows.

[0101] [Allyl ether compounds (resins)] R1: Allyl ether compound obtained in Example 1 R2: Allyl ether compound obtained in Example 2 S1: Allyl ether compound obtained in Reference Example 1 S2: Allyl ether compound obtained in Reference Example 2 S3: 4,4'-(1-methylethylidene)bis(2-allylphenol) (Fujifilm Wako Pure Chemical Industries, Ltd., allyl group equivalent: 154)

[0102] [Polyhydroxy resin] P1: Polyhydric hydroxy resin obtained in Synthesis Example 2 P2: Polyhydric hydroxy resin obtained in Synthesis Example 3 P3: Polyhydric hydroxy resin obtained in Synthesis Example 4 MEH: Biphenyl aralkyl polyhydroxy resin (MEH-7851, manufactured by Meiwa Kasei Co., Ltd., hydroxyl equivalent weight 210, softening point 75°C) PN: Phenol novolac resin (manufactured by Aica Kogyo Co., Ltd., Shounol BRG-557, hydroxyl group equivalent 105, softening point 85°C)

[0103] [Maleimide compound (resin)] M1: Phenylmethanemaleimide (manufactured by Daiwa Chemical Industry Co., Ltd., BMI-2300) M2: Maleimide compound obtained in Synthesis Example 5

[0104] [Epoxy resin] E1: Biphenyl aralkyl epoxy resin (manufactured by Nippon Kayaku Co., Ltd., NC-3000, epoxy equivalent 274, softening point 60°C)

[0105] [Curing accelerator] C1: Dicumyl peroxide (Percumyl D, manufactured by Nippon Oil & Fats Co., Ltd.) C2: 2-ethyl-4-methylimidazole (Curesol 2E4MZ, manufactured by Shikoku Chemicals Corporation)

[0106] Synthesis Example 1 2,6-xylenol (structural formula below) was added to a reaction apparatus consisting of a separable glass flask equipped with a stirrer, a thermometer, a nitrogen inlet, a dropping funnel, and a condenser. [ka] 500 parts of ethanol and 7.3 parts of 47% BF3 ether complex were added and heated to 100°C with stirring. While maintaining the temperature, dicyclopentadiene (structural formula below) [ka] 67.6 parts (0.12 times the moles of 2,6-xylenol) of 2,6-xylenol were added dropwise over 1 hour. The reaction was continued for another 4 hours at 115-125°C, and then 11 parts of calcium hydroxide were added. 19 parts of a 10% aqueous oxalic acid solution were then added. The mixture was then heated to 160°C for dehydration, and then heated to 200°C under a reduced pressure of 5 mmHg to remove unreacted raw materials by evaporation. 1,320 parts of methyl isobutyl ketone (MIBK) were added to dissolve the product, and 400 parts of 80°C hot water was added for water washing, and the lower layer of water was separated and removed. The mixture was then heated to 160°C under a reduced pressure of 5 mmHg to remove the MIBK by evaporation, yielding 164 parts of a reddish-brown polyhydric hydroxy resin (PH1). The resulting polyhydric hydroxy resin (PH1) had a hydroxyl equivalent of 195 and a softening point of 73° C. The polyhydric hydroxy resin represented by formula (7), R 1 is a methyl group, i is 2, and GPC showed that Mw was 470, Mn was 440, the content of s=0 isomer was 2.8 area%, the content of s=1 isomer was 86.2 area%, and the content of s=2 or more isomers was 11.0 area%.

[0107] Synthesis Example 2 In a reaction apparatus similar to that used in Synthesis Example 1, 250 parts of the polyhydric hydroxy resin (PH1) obtained in Synthesis Example 1, 2.5 parts of paratoluenesulfonic acid monohydrate, and 62.5 parts of MIBK were charged and heated to 120°C with stirring. While maintaining the temperature, divinylbenzene (manufactured by Aldrich, 80% divinylbenzene, 20% ethylvinylbenzene) (structural formula shown below) was added. [ka] 150 parts (0.90 times the moles of PH1) were added dropwise over 1 hour. The reaction was continued for another 4 hours at a temperature of 120-130°C. 540 parts of MIBK were added to dissolve the product, which was then neutralized with 3.3 parts of sodium bicarbonate. 180 parts of 80°C hot water was added for washing, and the lower layer of water was separated and removed. The mixture was then heated to 180°C under a reduced pressure of 5 mmHg to evaporate and remove the MIBK, yielding 381 parts of a reddish-brown polyhydric hydroxy resin (P1). The resulting polyhydric hydroxy resin (P1) had a hydroxyl equivalent of 308 and a softening point of 81° C. The polyhydric hydroxy resin represented by formula (4), R 1 is a methyl group, i is 2, and GPC results show that Mw is 1750, Mn is 640, the content of m=0 isomer is 3.8 area %, the content of m=1 isomer is 41.1 area %, and the content of m=2 or more isomers is 55.1 area %. In formula (4), R 2 ' is a group (R 3 one of which is an ethyl group) and a group derived from divinylbenzene represented by formula (6) (R 3 are all hydrogen atoms) are mixed in approximately the same ratio. Mass spectrometry by ESI-MS (negative) confirmed M-=375, 507, 629, 639, 761.

[0108] Synthesis Example 3 A reactor similar to that used in Synthesis Example 1 was charged with 100 parts of the polyhydric hydroxy resin (PH1) obtained in Synthesis Example 1, 1.0 part of paratoluenesulfonic acid monohydrate, and 25 parts of MIBK, and the mixture was heated to 120°C with stirring. While maintaining the same temperature, 45 parts (0.67 times the molar ratio of PH1) of divinylbenzene (manufactured by Aldrich, 55% divinylbenzene, 45% ethylvinylbenzene) was added dropwise over 1 hour. The reaction was continued for another 4 hours at 120-130°C. 310 parts of MIBK was added to dissolve the product, which was then neutralized with 1.3 parts of sodium bicarbonate. The product was washed with 100 parts of 80°C hot water, and the lower layer of water was separated and removed. The mixture was then heated to 180°C under a reduced pressure of 5 mmHg, and the MIBK was evaporated to yield 139 parts of a reddish-brown polyhydric hydroxy resin (P2). The resulting polyhydric hydroxy resin (P2) had a hydroxyl equivalent of 276 and a softening point of 71° C. The polyhydric hydroxy resin represented by formula (4), R 1 is a methyl group, i is 2, and GPC showed that Mw was 730, Mn was 540, the content of m=0 isomer was 6.5 area %, the content of m=1 isomer was 45.7 area %, and the content of m=2 or more isomers was 47.9 area %. In formula (4), R 2 ' is a group (R 3 one of which is an ethyl group) and a group derived from divinylbenzene represented by formula (6) (R 3 are all hydrogen atoms) are mixed in approximately the same ratio. Mass spectrometry by ESI-MS (negative) confirmed M-=375, 507, 629, 639, 761.

[0109] Synthesis Example 4 In a reaction apparatus similar to that in Synthesis Example 1, phenol (structural formula below) [ka] 1507 parts of 47% BF3 ether complex and 22.7 parts of 47% BF3 ether complex were charged and heated to 100°C with stirring. While maintaining the temperature, dicyclopentadiene [ka] 211.7 parts (0.10 times the molar ratio of phenol) of phenol was added dropwise over 1 hour. The reaction was continued for another 4 hours at 115-125°C, and then 36 parts of calcium hydroxide was added. 60 parts of a 10% aqueous oxalic acid solution were then added. The mixture was then heated to 160°C for dehydration, and then heated to 200°C under a reduced pressure of 5 mmHg to remove unreacted raw materials by evaporation. 1720 parts of MIBK was added to dissolve the product, and 550 parts of 80°C hot water was added for water washing, and the lower aqueous layer was separated and removed. The mixture was then heated to 160°C under a reduced pressure of 5 mmHg to remove the MIBK by evaporation, yielding 480 parts of a reddish-brown polyhydric hydroxy resin (P3). The resulting polyhydric hydroxy resin (P3) had a hydroxyl equivalent of 175 and a softening point of 90° C. The polyhydric hydroxy resin (P3) was not a polyhydric hydroxy resin represented by formula (4), but R1 and R 2 ' is a hydrogen atom, i is 0, and GPC showed that Mw was 470, Mn was 410, the content of s=0 isomer was 1.0 area%, the content of s=1 isomer was 68.7 area%, and the content of s=2 or more isomers was 30.3 area%.

[0110] Synthesis Example 5 A flask equipped with a thermometer, condenser, Dean-Stark azeotropic distillation trap, and stirrer was charged with 100 parts of aniline and 50 parts of toluene, and 39.2 parts of 35% hydrochloric acid was added dropwise at room temperature over 1 hour. After the dropwise addition, the mixture was heated to cool and separate the azeotropic water and toluene. The organic layer (toluene) was then returned to the system for dehydration. Next, 33.6 parts of 4,4'-bis(chloromethyl)biphenyl were added over 1 hour while maintaining the temperature at 60-70°C, and the reaction was continued for another 2 hours at the same temperature. After the reaction was completed, the toluene was distilled off while the temperature was raised to 195-200°C, and the reaction was continued at this temperature for 15 hours. Subsequently, 86 parts of 30% aqueous sodium hydroxide solution was slowly added dropwise while cooling, avoiding vigorous reflux. The toluene that had distilled off during the temperature increase was returned to the system at below 80°C, and the system was allowed to stand at 70-80°C. The separated lower aqueous layer was removed, and the reaction mixture was repeatedly washed with water until the washings became neutral. Next, the excess aniline and toluene were distilled off from the oil layer using a rotary evaporator under heating and reduced pressure (200°C, 0.6 KPa) to obtain 47 parts of an aromatic amine resin. Next, 75 parts of maleic anhydride and 150 parts of toluene were charged into the flask and heated. The resulting azeotropic water and toluene were cooled and separated, and the organic layer (toluene) was returned to the system for dehydration. Next, a resin solution prepared by dissolving 100 parts of the aromatic amine resin in 100 parts of N-methyl-2-pyrrolidone was added dropwise over 1 hour while maintaining the system at 80-85°C. After the dropwise addition, the reaction was continued at the same temperature for 2 hours, 1.5 parts of p-toluenesulfonic acid was added, and the azeotropic condensed water and toluene were cooled and separated under reflux conditions. The organic layer (toluene) was then returned to the system for dehydration for 20 hours. After the reaction was completed, 100 parts of toluene was added, and the p-toluenesulfonic acid and excess maleic anhydride were removed by repeated water washing. The system was then heated to remove water from the system by azeotropy. The reaction solution was then concentrated to obtain 133 parts of maleimide compound (M2).

[0111] Example 1 In a reaction vessel similar to that of Synthesis Example 1, 100 parts of the polyhydric hydroxy resin (P1) obtained in Synthesis Example 2 and 150 parts of diglyme were placed and heated to 100°C to form a homogeneous solution, which was then cooled to approximately 35°C. 29 parts of 50% sodium hydroxide solution (1.1 times the molar amount of the polyhydric hydroxy resin) was added to form a phenolate solution, which was then heated at 30 to 40°C to form a phenolate solution containing allyl bromide (structural formula: [ka] 47 parts (1.2 times the molar amount of the polyhydric hydroxy resin) of the mixture was added dropwise over 1 hour, and after the completion of the addition, the mixture was heated to 60°C and reacted at the same temperature for 3 hours. After the reaction was completed, 220 parts of MIBK was added, and 70 parts of warm water was added for washing, and the lower layer was separated and removed. Thereafter, the mixture was heated to 130°C under a reduced pressure of 5 mmHg to evaporate and remove the MIBK, yielding 109 parts of a brown allyl ether compound (R1). The obtained allyl ether compound (R1) had a softening point of 51°C, a hydroxyl equivalent of 12180, a melt viscosity at 150°C of 0.15 Pa s, and a total chlorine content of 77 ppm. 1is a methyl group, i is 2, and the Mw measured by GPC was 3200, Mn was 710, the content of n=0 isomer was 3.3 area %, the content of n=1 isomer was 38.2 area %, and the content of n=2 or more isomers was 58.5 area %. In formula (1), R 2 is a group (R 3 one of which is an ethyl group) and a group derived from divinylbenzene represented by formula (6) (R 3 are all hydrogen atoms) are mixed in approximately the same ratio. 9 is a hydrogen atom. Mass spectrometry by ESI-MS (negative) confirmed M-=455, 587, 719, 749. The GPC chart of the obtained allyl ether compound (R1) is shown in FIG. 1, and the IR chart is shown in FIG.

[0112] Example 2 A reaction vessel similar to that used in Synthesis Example 1 was charged with 100 parts of the polyhydric hydroxy resin (P2) obtained in Synthesis Example 3 and 150 parts of diglyme. The mixture was heated to 100°C to form a homogeneous solution, and then cooled to approximately 35°C. 33 parts of 50% sodium hydroxide solution (1.1 times the molar ratio relative to the polyhydric hydroxy resin) was added to form a phenolate solution, and 53 parts of allyl bromide (1.2 times the molar ratio relative to the polyhydric hydroxy resin) was added dropwise over 1 hour at 30-40°C. After completion of the dropwise addition, the mixture was heated to 60°C and allowed to react at the same temperature for 3 hours. After completion of the reaction, 230 parts of MIBK were added, and 70 parts of warm water were added for water washing, and the lower layer was separated and removed. The mixture was then heated to 130°C under a reduced pressure of 5 mmHg to evaporate and remove the MIBK, yielding 110 parts of a brown allyl ether compound (R2). The obtained allyl ether compound (R2) was semi-solid at room temperature, had a hydroxyl equivalent of 10200, a melt viscosity at 150°C of 0.03 Pa s, and a total chlorine content of 90 ppm. 1 is a methyl group, i is 2, and the Mw measured by GPC was 800, Mn was 530, the content of n=0 isomer was 6.2 area %, the content of n=1 isomer was 42.5 area %, and the content of n=2 or more isomers was 51.3 area %. In formula (1), R 2 is a group (R 3one of which is an ethyl group) and a group derived from divinylbenzene represented by formula (6) (R 3 are all hydrogen atoms) are mixed in approximately the same ratio. 9 is a hydrogen atom. Mass spectrometry by ESI-MS (negative) confirmed M-=455, 587, 719, 749.

[0113] Reference example 1 An allyl ether compound (S1) was obtained in the same manner as in Example 1, except that the polyhydric hydroxy resin was changed to P3.

[0114] Reference example 2 An allyl ether compound (S2) was obtained in the same manner as in Example 1, except that the polyhydric hydroxy resin was changed to MEH.

[0115] Example 3 100.0 parts of the maleimide compound (M1), 188.4 parts of the allyl ether compound (R1) obtained in Example 1, and 2.9 parts of the curing accelerator (C1) were mixed and dissolved in methyl ethyl ketone (MEK) to obtain a resin composition varnish with a resin concentration of 50%. The resulting resin composition varnish was impregnated into glass cloth (Nitto Boseki Co., Ltd., WEA 7628 XS13, 0.18 mm thick). The impregnated glass cloth was dried for 10 minutes in a hot air circulating oven at 150°C to obtain a prepreg. Eight of the resulting prepregs were stacked on top and bottom with copper foil (Mitsui Mining & Smelting Co., Ltd., 3EC-III, 35 μm thick), and vacuum pressed at 2 MPa under temperature conditions of 130°C x 15 minutes + 220°C x 120 minutes to obtain a 1.6 mm thick laminate. The Tg measurement results of the laminate are shown in Table 1.

[0116] The resulting prepreg was then loosened and sieved to form a powdered prepreg. The resulting prepreg powder was placed in a fluororesin mold and vacuum pressed at 2 MPa under the following temperature conditions: 130°C for 15 minutes and 220°C for 120 minutes, yielding a 50 mm square x 2 mm thick cured resin test piece. The dielectric constant and dielectric loss tangent of the test piece were measured and are shown in Table 1.

[0117] Examples 4 to 6, Comparative Examples 1 to 4 The components were blended in the amounts (parts) shown in Table 1, and a resin composition varnish was obtained using the same equipment and procedures as in Example 3, and a laminate and a cured resin test piece were also obtained. Tests similar to those in Example 3 were carried out, and the results are shown in Table 1.

[0118] [Table 1] [Industrial Applicability]

[0119] The allyl ether compound (resin) of the present invention is particularly useful in laminates and electronic circuit boards that require a low dielectric constant and a low dielectric loss tangent.

Claims

1. An allyl ether compound represented by the following general formula (1): 【Chemistry 1】 Here, R １ each independently represents a hydrocarbon group having 1 to 8 carbon atoms; R ２ R independently represent a hydrogen atom, a group represented by formula (2), or a group represented by formula (3), and at least one of R is formula (2) or formula (3). ３ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms; R ４ each independently represents a hydrogen atom or a group represented by formula (2), and R ９ A is a group consisting of two R ２ Residues other than R ２ are independently a hydrogen atom or a group represented by formula (2). Me represents a methyl group. i is an integer of 0 to 2. n and p1 each represent the number of repetitions, with the average value of n being 1.0 to 4.0 and the average value of p1 being a number of 0 to 5.

2. The R １ The allyl ether compound according to claim 1, wherein i is a methyl group or a phenyl group, and i is 1 or 2.

3. A resin composition comprising the allyl ether compound according to claim 1 and a maleimide compound.

4. A cured product obtained by curing the resin composition according to claim 3.

5. A sealing material comprising the resin composition according to claim 3.

6. A circuit board material, comprising the resin composition according to claim 3.

7. A prepreg using the resin composition according to claim 3.

8. A laminate comprising the resin composition according to claim 3.

9. 2. The method for producing the allyl ether compound according to claim 1, comprising allyl-etherifying a polyhydric hydroxy resin represented by the following general formula (4): 【Chemistry 2】 Here, R １ each independently represents a hydrocarbon group having 1 to 8 carbon atoms; R ２ R' independently represents a hydrogen atom, a group represented by formula (5), or a group represented by formula (6), and at least one of R' is formula (5) or formula (6). ３ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms; R ４ A' is a group selected from two R ２ A residue excluding R ２ Each ' is independently a hydrogen atom or a group represented by formula (5). Me represents a methyl group. i is an integer of 0 to 2. m and p2 each represent the number of repetitions, with the average value of m being 1.0 to 4.0 and the average value of p2 being a number of 0 to 5.

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