Curable resin composition, cured product, prepreg, circuit board, build-up film, semiconductor sealing material, and semiconductor device

Abstract

The present invention relates to a curable resin composition, a cured product, a prepreg, a circuit board, a build-up film, a semiconductor sealing material, and a semiconductor device. Provided are: a cured product having excellent heat resistance (high glass transition temperature) and dielectric properties (low dielectric properties); a prepreg, a circuit board, a build-up film, a semiconductor sealing material, and a semiconductor device, each of which combines these properties; the curable resin composition is characterized by containing a vinyl benzyl compound having an indane bisphenol skeleton represented by general formula (1), the curable resin composition further containing a polymerization inhibitor, the content of the polymerization inhibitor being 50-5000 ppm with respect to the vinyl benzyl compound, and the total chlorine content being 100-5000 ppm with respect to the total amount of the vinyl benzyl compound and the polymerization inhibitor. Also provided are a cured product of the curable resin composition, a prepreg using the curable resin composition, a circuit board, a laminate film, a semiconductor sealing material, and a semiconductor device.

Description

Technical Field

[0001] The present invention relates to a curable resin composition containing a vinylbenzyl compound having an indane bisphenol skeleton, and a cured product, a prepreg, a circuit board, a build-up film, a semiconductor sealing material, and a semiconductor device obtained from the curable resin composition. Background Art

[0002] With the increase in the amount of information communication in recent years, information communication in high-frequency bands has been gradually actively carried out. In order to achieve better electrical properties, especially to reduce transmission loss in high-frequency bands, electrical insulating materials with low dielectric constant and low dielectric loss tangent are sought.

[0003] Furthermore, printed circuit boards or electronic components using these electrical insulating materials are exposed to high-temperature reflow soldering during installation, and therefore, materials with excellent heat resistance and a high glass transition temperature are sought. In particular, recently, from the perspective of environmental issues, the demand for electrical insulating materials with higher heat resistance has gradually increased due to the use of lead-free solders with high melting points.

[0004] In view of these requirements, curable resins containing vinyl groups with various chemical structures have been proposed. As such curable resins, curable resins such as divinyl benzyl ether of bisphenol or polyvinyl benzyl ether of novolac have been proposed (for example, with reference to patent documents 1 and 2). However, these vinyl benzyl ethers cannot provide solidified materials with sufficiently small dielectric properties, and the obtained solidified materials have problems in stable use in high frequency bands, and further, the divinyl benzyl ether of bisphenol cannot be said to be sufficiently high in terms of heat resistance.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Laid-Open No. 63-68537

[0008] Patent Document 2: Japanese Patent Application Laid-Open No. 64-65110 Summary of the invention

[0009] Problem that the invention aims to solve

[0010] Therefore, the problem to be solved by the present invention is to provide: a cured product having excellent heat resistance (high glass transition temperature) and dielectric properties (low dielectric properties), a prepreg, a circuit board, a laminated film, a semiconductor sealing material and a semiconductor device having these properties.

[0011] Solutions for solving problems

[0012] The present invention relates to a curable resin composition, characterized in that it contains a vinylbenzyl compound having an indane bisphenol skeleton represented by the following general formula (1), and the curable resin composition further contains a polymerization inhibitor, the content of the polymerization inhibitor is 50 to 5000 ppm relative to the vinylbenzyl compound, and the total chlorine content is 100 to 5000 ppm relative to the total amount of the vinylbenzyl compound and the polymerization inhibitor.

[0013]

[0014] [In formula (1), X represents a vinylbenzyloxy group. Ra each independently represents an alkyl group, an alkyloxy group, an alkylthio group, an aralkyl group, an aryl group, an aryloxy group, an arylthio group, a cycloalkyl group, a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group or a mercapto group having 1 to 15 carbon atoms, and q represents an integer value of 0 to 4. When q is 2 to 4, Ra can be the same or different in the same ring. Rb each independently represents an alkyl group, an alkyloxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, a cycloalkyl group, a hydrogen atom, a halogen atom, a hydroxyl group or a mercapto group having 1 to 15 carbon atoms, and r represents an integer value of 0 to 3. When r is 2 to 3, Rb can be the same or different in the same ring. n is the average number of repeating units, and represents a value of 0.2 to 20.]

[0015] The present invention also provides a cured product of the curable resin composition, and a prepreg, a circuit board, a build-up film, a semiconductor sealing material, and a semiconductor device using the curable resin composition.

[0016] Effects of the Invention

[0017] The cured product obtained from the curable resin composition of the present invention is excellent in heat resistance and low dielectric properties. DETAILED DESCRIPTION

[0018] Hereinafter, the present invention will be described in detail.

[0019] The present invention contains a vinylbenzyl compound having an indane bisphenol skeleton represented by the following general formula (1), a specific amount of a polymerization inhibitor, and a specific total chlorine content.

[0020]

[0021] In formula (1), X represents a vinylbenzyloxy group. Ra each independently represents an alkyl group, an alkyloxy group, an alkylthio group, an aralkyl group, an aryl group, an aryloxy group, an arylthio group, a cycloalkyl group, a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group or a mercapto group having 1 to 15 carbon atoms, and q represents an integer value of 0 to 4. When q is 2 to 4, Ra can be the same or different in the same ring. Rb each independently represents an alkyl group, an alkyloxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, a cycloalkyl group, a hydrogen atom, a halogen atom, a hydroxyl group or a mercapto group having 1 to 15 carbon atoms, and r represents an integer value of 0 to 3. When r is 2 to 3, Rb can be the same or different in the same ring. n is the average number of repeating units, and represents a value of 0.2 to 20.

[0022] The vinylbenzyl compound has an indane skeleton, so that the proportion of polar functional groups in the structure of the vinylbenzyl compound is small, and therefore, the dielectric properties of the cured product produced using the vinylbenzyl compound are excellent. In addition, the vinylbenzyl compound has an indane skeleton, so that the flexibility and softness are excellent, and the improvement of brittleness resistance is also expected.

[0023] As Ra in the aforementioned general formula (1), it is preferably any one of an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms. By using the aforementioned alkyl group having 1 to 4 carbon atoms, the planarity and crystallinity in the vicinity of the bisphenol group are reduced, thereby becoming a preferred embodiment in which the solvent solubility is improved and the reactivity of the bisphenol group is not impaired, thereby obtaining a cured product.

[0024] In the general formula (1), q is preferably 1 to 3, more preferably 2. When q is 2, the influence of steric hindrance is small, which is a more preferred embodiment in the production (synthesis) of a vinylbenzyl compound having an indane bisphenol skeleton.

[0025] Preferably, in the general formula (1), r is 0 and Rb is a hydrogen atom. Also, preferably, r is 1 to 3 and Rb is at least one selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms and an aryl group having 6 to 10 carbon atoms. In particular, when the indane skeleton of the vinylbenzyl compound having an indane bisphenol skeleton is formed by r being 0 and Rb being a hydrogen atom, steric hindrance is reduced, which is advantageous for the production (synthesis) of the vinylbenzyl compound having an indane bisphenol skeleton and thus becomes a preferred embodiment.

[0026] In the general formula (1), the presence of a vinylbenzyl group enables high radical polymerizability, and not only the curability alone but also the ability to be mixed with various curing agents, thereby achieving the effect of enabling compounding in accordance with various required properties.

[0027] The vinylbenzyl compound having an indane bisphenol skeleton is preferably a structure represented by the following general formula (2).

[0028]

[0029] In the above formula (2), X represents a vinylbenzyloxy group. R1 and R2 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group or a cycloalkyl group, and R1 and R2 are not both hydrogen atoms at the same time. n represents the average number of repeating units and represents a value of 0.2 to 20.

[0030] <Method for producing indan bisphenol compound>

[0031] Next, a method for producing the indan bisphenol compound as a raw material of the vinyl benzyl compound will be described.

[0032] A compound, wherein in the following general formula (3), Rc each independently represents a monovalent functional group selected from the group consisting of the following general formulae (4) and (5), the ortho position of at least one of the two Rc's is a hydrogen atom, and Rb and r represent the same as above.

[0033]

[0034] In the following general formula (6), x is preferably 1 or 2, and x is more preferably 1. By having a hydroxyl group (phenolic hydroxyl group), a phenolic hydroxyl group can be introduced into the terminal, which is a preferred embodiment. It should be noted that Ra and q respectively represent phenol or its derivatives as described above, and by reacting the compound of the above general formula (3) with the compound of the following general formula (6) in the presence of an acid catalyst, an indane bisphenol compound represented by the following general formula (7) can be obtained. It should be noted that Ra, Rb, q, r, x and n in the following general formula (7) represent the same as described above.

[0035]

[0036]

[0037] The average number of repeating units n in the indane skeleton (see the general formula (8)) which is a characteristic of the indane bisphenol compound is 0.2 to 20, preferably 0.5 to 10, and more preferably 1.0 to 8.0 in terms of the average number of repeating units n (average value) in order to obtain a compound having a low melting point (low softening point), a low melt viscosity, and excellent handleability. The indane bisphenol compound has an indane skeleton in its structure, and thus has excellent solvent solubility. It should be noted that if the above n is less than 0.2, the content ratio of the high melting point substance in the structure of the indane bisphenol compound becomes high, the solvent solubility is poor, and further, the ratio of the high molecular weight component contributing to flexibility becomes low. Therefore, the brittleness resistance of the cured product obtained by using the indane bisphenol type epoxy resin using the indane bisphenol compound as a raw material is reduced, and further, there is a concern that the flexibility and softness are also reduced, which is not preferred. If n exceeds 20, the viscosity becomes high when dissolved in a solvent, and the heat resistance of the obtained cured product may be poor. Furthermore, the high molecular weight component becomes excessively large, and the fluidity decreases when formed into a cured product, and the handleability may be poor, which is not preferred.

[0038] The compound represented by the general formula (3) used in the present invention (hereinafter, "compound (a)") is not particularly limited, and typically p- and m-diisopropenylbenzene, p- and m-bis(α-hydroxyisopropyl)benzene, p- and m-bis(α-chloroisopropyl)benzene, 1-(α-hydroxyisopropyl)-2-isopropenylbenzene, 1-(α-hydroxyisopropyl)-3-isopropenylbenzene, 1-(α-hydroxyisopropyl)-4-isopropenylbenzene or a mixture thereof are used. In addition, core alkyl substituted products of these compounds, such as diisopropenyltoluene and bis(α-hydroxyisopropyl)toluene, etc., can also be used, and core halogen substituted products, such as chlorodiisopropenylbenzene and chlorobis(α-hydroxyisopropyl)benzene, etc. can also be used.

[0039] Examples of the compound (a) include 2-chloro-1,4-diisopropenylbenzene, 2-chloro-1,4-bis(α-hydroxyisopropyl)benzene, 2-bromo-1,4-diisopropenylbenzene, 2-bromo-1,4-bis(α-hydroxyisopropyl)benzene, 2-bromo-1,3-diisopropenylbenzene, 2-bromo-1,3-bis(α-hydroxyisopropyl)benzene, 4-bromo-1,3-diisopropylbenzene, 4-bromo-1,3-bis(α-hydroxyisopropyl)benzene, 5-bromo-1,3-diisopropenylbenzene, Propylenebenzene, 5-bromo-1,3-bis(α-hydroxyisopropyl)benzene, 2-methoxy-1,4-diisopropenylbenzene, 2-methoxy-1,4-bis(α-hydroxyisopropyl)benzene, 5-ethoxy-1,3-diisopropenylbenzene, 5-ethoxy-1,3-bis(α-hydroxyisopropyl)benzene, 2-phenoxy-1,4-diisopropenylbenzene, 2-phenoxy-1,4-bis(α-hydroxyisopropyl)benzene, 2,4-diisopropenylbenzenethiol, 2,4-bis(α-hydroxyisopropyl)benzene thiol, 2,5-diisopropenylbenzenethiol, 2,5-bis(α-hydroxyisopropyl)benzenethiol, 2-methylthio-1,4-diisopropenylbenzene, 2-methylthio-1,4-bis(α-hydroxyisopropyl)benzene, 2-phenylthio-1,3-diisopropenylbenzene, 2-phenylthio-1,3-bis(α-hydroxyisopropyl)benzene, 2-phenyl-1,4-diisopropenylbenzene, 2-phenyl-1,4-bis(α-hydroxyisopropyl)benzene, 2-cyclopentyl-1,4-diisopropenylbenzene, 2-cyclopentyl-1,4-diisopropenylbenzene, Pentyl-1,4-bis(α-hydroxyisopropyl)benzene, 5-naphthyl-1,3-diisopropenylbenzene, 5-naphthyl-1,3-bis(α-hydroxyisopropyl)benzene, 2-methyl-1,4-diisopropenylbenzene, 2-methyl-1,4-bis(α-hydroxyisopropyl)benzene, 5-butyl-1,3-diisopropenylbenzene, 5-butyl-1,3-bis(α-hydroxyisopropyl)benzene, 5-cyclohexyl-1,3-bis(α-hydroxyisopropyl)benzene, etc.

[0040] It should be noted that the substituent contained in the aforementioned compound (a) is not particularly limited, and the compounds exemplified above can be used. However, in the case of a substituent with large steric hindrance, compared with a substituent with small steric hindrance, it is less likely that the obtained indane bisphenol compounds will be stacked with each other, and it is less likely that the indane bisphenol compounds will be crystallized with each other, that is, the solvent solubility of the indane bisphenol compound is improved, which is a preferred embodiment.

[0041] In addition, the compound represented by the general formula (6) (hereinafter, "compound (b)") is a phenol or a derivative thereof, but is not particularly limited. Typical examples include: cresols such as o-cresol, m-cresol, and p-cresol; phenol; xylenols such as 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, and 3,5-xylenol; ethylphenols such as o-ethylphenol, m-ethylphenol, and p-ethylphenol; butylphenols such as isopropylphenol, butylphenol, and p-tert-butylphenol; p-amylphenol; Phenol, alkylphenols such as p-octylphenol, p-nonylphenol, and p-cumylphenol; halogenated phenols such as fluorophenol, chlorophenol, bromophenol, and iodinephenol; monosubstituted phenols such as p-phenylphenol, aminophenol, nitrophenol, dinitrophenol, and trinitrophenol; condensed polycyclic phenols such as 1-naphthol and 2-naphthol; polyphenols such as resorcinol, alkylresorcinol, pyrogallol, catechol, alkylpyrocatechol, hydroquinone, alkylhydroquinone, and phloroglucinol; catechol, isobutylphenol, sec-butylphenol, tert-butylphenol, tert-aminophenol, methyl tert-butylphenol, dibutylphenol, etc. Various o-, m-, and p-isomers of alkylphenols represented by tert-butylphenol and di-tert-amylphenol; various o-, m-, and p-isomers of alkenyl or alkynylphenols represented by vinylphenol, allylphenol, propenylphenol, ethynylphenol, etc.; various o-, m-, and p-isomers of alkoxy, alkenyloxy, or alkynyloxyphenols represented by methoxyphenol, ethoxyphenol, allyloxyphenol, propargyloxyphenol, etc.; cycloalkylphenols represented by cyclopentylphenol, cyclohexylphenol, cyclohexylcresol, etc.; halogen-substituted phenols represented by dichlorophenol and dibromophenol substituted phenols; other substituted phenols such as cyanophenol, arylphenol, and aralkylphenol; alkylhydroquinone, alkenylresorcinol, alkenylhydroquinone, alkoxyresorcinol, alkoxyhydroquinone, halogenatedresorcinol, hydroquinone and other resorcinols, various substituted hydroquinones, 2-tert-butyl-5-methylphenol, 2-tert-butyl-4-methylphenol, 2,4-di(tert-butyl)phenol, 2,4-di(tert-amyl)phenol, 2-cyclohexyl-5-methylphenol, 2-tert-butylphenol, 2-sec-butylphenol, 2-(tert-amyl)phenol, 2-cyclohexylphenol, etc. These phenols or their derivatives can be used alone or in combination of two or more. Among them, it is more preferred to use compounds such as 2,6-xylenol and o-cresol in which one or more of the ortho positions of the phenolic hydroxyl groups are substituted with alkyl groups. However, if the steric hindrance is too large, there is a concern that the reactivity during synthesis of the indane bisphenol compound may be inhibited. Therefore, for example, it is preferred to use a compound (b) having an alkyl group having 1 to 4 carbon atoms.

[0042] In the method for producing the indane bisphenol compound represented by the general formula (7) used in the present invention, the compound (a) and the compound (b) are added so that the molar ratio of the compound (b) to the compound (a) (compound (b) / compound (a)) is preferably 0.1 to 10, more preferably 0.2 to 8.0, and the reaction is carried out in the presence of an acid catalyst, thereby obtaining an indane bisphenol compound having an indane skeleton.

[0043] The acid catalyst used in the above-mentioned reaction includes, for example, inorganic acids such as phosphoric acid, hydrochloric acid and sulfuric acid, organic acids such as oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid and fluoromethanesulfonic acid, activated clay, acid clay, silica alumina, zeolite, solid acids such as strongly acidic ion exchange resins, and heteropoly acids. After the reaction, it is preferred to use oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid and fluoromethanesulfonic acid (particularly p-toluenesulfonic acid) which are homogeneous catalysts that can be easily removed by neutralization with an alkali and washing with water.

[0044] The amount of the acid catalyst is 0.001 to 40 parts by mass based on 100 parts by mass of the total amount of the compound (a) and the compound (b) initially charged as raw materials, and is preferably 0.001 to 5 parts by mass from the viewpoint of economic efficiency.

[0045] The reaction temperature may generally be in the range of 50 to 300°C, and is preferably 80 to 200°C in order to suppress the formation of isomeric structures, avoid side reactions such as thermal decomposition, and obtain a high-purity indan bisphenol compound.

[0046] The reaction time is generally in the range of 0.5 to 24 hours, preferably 0.5 to 12 hours, under the reaction temperature conditions, because the reaction does not proceed completely in a short time and side reactions such as thermal decomposition of the product may occur if the reaction is set to a long time.

[0047] In the above-mentioned method for producing an indane bisphenol compound, phenol or its derivative also serves as a solvent, and therefore, other solvents may not necessarily be used, but solvents may be used. For example, in the case of a reaction system that also has a dehydration reaction, specifically, when a compound having an α-hydroxypropyl group is reacted as a raw material, the following method may be adopted: a solvent capable of azeotropic dehydration such as toluene, xylene, or chlorobenzene is used, and after the dehydration reaction is completed, the solvent is distilled off and the reaction is carried out within the above-mentioned reaction temperature range.

[0048] Examples of the organic solvent used for synthesizing the indan bisphenol compound include ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, cyclohexanone, cyclopentanone, and acetophenone; aprotic solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, acetonitrile, and sulfolane; cyclic ethers such as dioxane and tetrahydrofuran; esters such as ethyl acetate and butyl acetate; and aromatic solvents such as benzene, toluene, and xylene. These solvents may be used alone or in combination.

[0049] The hydroxyl equivalent of the indan bisphenol compound is preferably 100 to 1000 g / eq, more preferably 150 to 800 g / eq, from the viewpoint of heat resistance. The hydroxyl equivalent of the indan bisphenol compound is calculated by titration, which refers to a neutralization titration method in accordance with JIS K 0070.

[0050] <Method for producing a vinylbenzyl compound having an indan bisphenol skeleton>

[0051] Next, the introduction of a vinyl benzyl ether group into the indan bisphenol compound will be described below.

[0052] The vinylbenzyl compound having an indane bisphenol skeleton can be obtained by the following known method: in the presence of a basic compound, the indane bisphenol compound is reacted with chloromethylstyrene, bromomethylstyrene, or iodinated methylstyrene to obtain the vinylbenzyl compound. By reacting the indane bisphenol compound, free radical polymerizability can be introduced into the indane bisphenol compound, and the indane bisphenol compound can be crosslinked with various crosslinking agents having low dielectric properties. In addition, since the indane bisphenol compound is a low polar substituent, the cured product of the obtained resin exhibits a low dielectric constant and a low dielectric loss tangent.

[0053] Examples of the chloromethylstyrene include p-chloromethylstyrene, m-chloromethylstyrene, and o-chloromethylstyrene. Examples of the bromomethylstyrene include p-bromomethylstyrene, m-bromomethylstyrene, and o-bromomethylstyrene, and these may be used alone or in combination. Among these, chloromethylstyrene is preferably used, which is a cheaper raw material and can produce a cured product with a low dielectric loss tangent.

[0054] Specific examples of the basic compound include nitrogen-containing compounds such as triethylamine, tributylamine, and dimethylaminopyridine, alkaline earth metal hydroxides, alkali metal carbonates, and alkali metal hydroxides, etc. Alkali metal hydroxides are particularly excellent in terms of high activity and low cost.

[0055] The reaction of the intermediate phenol compound with the chloromethylstyrene or chlorostyrene may be carried out by adding 1 to 10 moles of the chloromethylstyrene or chlorostyrene to 1 mole of the hydroxyl group contained in the intermediate phenol compound, and reacting at a temperature of 30 to 150° C. for 1 to 40 hours while adding 1 to 10 moles of a basic compound all at once or slowly. At this time, a phase transfer catalyst such as an alkylammonium salt may be used in an amount of 0.1 to 20 parts by weight relative to 100 parts by weight of the produced resin in order to increase the reaction rate.

[0056] In addition, when reacting with the above-mentioned chloromethylstyrene (introducing a crosslinking group), the reaction rate in the synthesis of the above-mentioned vinylbenzyl compound having an indane bisphenol skeleton can be increased by using an organic solvent in combination. Such an organic solvent is not particularly limited, and examples thereof include ketones such as acetone and methyl ethyl ketone, alcohols such as methanol, ethanol, 1-propanol, isopropanol, 1-butanol, sec-butanol, and tert-butanol, cellosolves such as methyl cellosolve and ethyl cellosolve, ethers such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxane, and diethoxyethane, aprotic polar solvents such as acetonitrile, dimethyl sulfoxide, and dimethylformamide, toluene, and xylene. These organic solvents can be used alone, or two or more can be used in combination to adjust the polarity.

[0057] After the reaction with the above-mentioned chloromethylstyrene (introduction of cross-linking groups) is completed, water may be added for liquid separation in order to remove the alkali metal salts and catalyst residues generated by the reaction, and these by-products may be removed as the water layer. These alkali metal salts and catalyst residues deteriorate the dielectric properties, so it is preferred to fully wash and remove them. Furthermore, after the reaction product is reprecipitated in a poor solvent, the precipitate is stirred in a poor solvent at a temperature of 20 to 100° C. for 0.1 to 5 hours, and after vacuum filtration, the precipitate is dried at a temperature of 40 to 80° C. for 1 to 10 hours, thereby achieving a higher purification. As described above, the target vinylbenzyl compound having an indane bisphenol skeleton (hereinafter sometimes referred to as a curable resin) can be obtained. As poor solvents, hexane and the like can be cited.

[0058] <Polymerization inhibitor>

[0059] The curable resin composition of the present invention must contain a specific amount of polymerization inhibitor. Generally, when a polymerization inhibitor is added to a curable resin having an indane bisphenol skeleton, it is believed that the polymerization inhibitor has a high polarity substituent such as a phenolic hydroxyl group, so the dielectric loss tangent and the like are significantly reduced. In addition, it is a low molecular weight component and has a high effect of hindering polymerization, so it becomes a result that also impairs heat resistance. However, it is found that in the present invention, according to the aspect of introducing a vinyl benzyl group into the curable resin and the aspect of using a specific amount of polymerization inhibitor, it is possible to take into account both excellent heat resistance and low dielectric properties.

[0060] As the above-mentioned polymerization inhibitor, a known polymerization inhibitor can be used. As the above-mentioned polymerization inhibitor, for example, a hindered phenol-based polymerization inhibitor (for example, pyrogallol, benzoquinone, hydroquinone, methylene blue, tert-butylcatechol, monobenzyl ether, methyl hydroquinone, amyl quinone, amyloxy hydroquinone, n-butylphenol, phenol, hydroquinone monopropyl ether, 4,4'-(1-methylethylidene)bis(2-methylphenol), 4,4'-(1-methylethylidene)bis(2,6-dimethylphenol), 4,4'-[1-[4-(1-(4-hydroxyphenyl)-1-methylethyl)phenyl]ethylidene]bisphenol , 4,4',4"-ethylenetris(2-methylphenol), 4,4',4"-ethylenetrisphenol, 1,1,3-tris(2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane, 2,6-di-tert-butyl-4-methylphenol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 4,4'-butylenebis(3-methyl-6-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 3,9-bis[2-(3-(3-tert-butyl-4-hydroxyphenyl)- [-5-methylphenyl)-propionyloxy)-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro(5,5)undecane, triethylene glycol-bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, n-octyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name IRGANOX 1010, manufactured by BASF Corporation), tris(3,5-di-tert-butylhydroxybenzyl ) isocyanurate, diethylene bis(3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate), etc.); other phenolic polymerization inhibitors other than hindered phenols (such as 4-methoxyphenol, 2,5-di-tert-butyl-4-methylphenol, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol) and 4-methoxynaphthol, etc.) (the above are summarized as phenolic polymerization inhibitors); hydroquinone polymerization inhibitors (such as hydroquinone and 2,6-di-tert-butylhydroquinone, etc.).

[0061] From the perspective of providing a cured product described later with more excellent heat resistance and dielectric properties, the polymerization inhibitor is preferably hydroquinone, trimethylhydroquinone, 4-tert-butylcatechol, tert-butylhydroquinone, o-methylhydroquinone (toluhydroquinone), p-benzoquinone, 4-methoxyphenol, and 2,6-di-tert-butyl-4-methylphenol, and more preferably 4-tert-butylcatechol, p-benzoquinone, 4-methoxyphenol, and 2,6-di-tert-butyl-4-methylphenol.

[0062] The polymerization inhibitor may be used alone or in combination of two or more. However, it is preferred to contain two or more polymerization inhibitors (two or more polymerization inhibitors are used in combination). There is no particular limitation on the combination of polymerization inhibitors when two or more polymerization inhibitors are used in combination. In terms of obtaining a more excellent effect of the present invention, hindered phenol-based polymerization inhibitors and / or the aforementioned other phenol-based polymerization inhibitors are preferred, and 4-methoxyphenol and / or 2,6-di-tert-butyl-4-methylphenol are more preferred.

[0063] In addition, as a mixing ratio when containing two types of said polymerization inhibitors, it is 5:95-95:5, for example.

[0064] The content of the polymerization inhibitor must be 50 to 5000 ppm relative to the vinyl benzyl compound in order to obtain the effects of the present invention, and is preferably 100 to 5000 ppm in order to better exert the effects and further improve the heat resistance and dielectric properties after curing. In other words, it is 0.005 to 0.5 parts by mass, preferably 0.01 to 0.5 parts by mass, relative to 100 parts by mass of the vinyl benzyl compound.

[0065] <Curable resin composition>

[0066] The curable resin composition of the present invention contains the aforementioned vinylbenzyl compound and a polymerization inhibitor, and further contains a specific total chlorine content. The aforementioned total chlorine content is 100 to 10000 ppm, preferably 100 to 5000 ppm, relative to the total amount of the aforementioned vinylbenzyl compound and the aforementioned polymerization inhibitor. It should be noted that the aforementioned total chlorine content represents the total content of chlorine atoms, and the raw materials derived from the aforementioned vinylbenzyl compound, for example, chloromethylstyrene, which is a raw material when vinylbenzylation is performed, and impurities contained therein, etc. can be cited as the generation source.

[0067] [Other resins, etc.]

[0068] In the curable resin composition of the present invention, in addition to the above-mentioned substances, other resins, curing agents, curing accelerators, etc. can be used without particular limitation within the scope not impairing the purpose of the present invention. As described later, the above-mentioned curable resin can obtain a cured product by heating or the like without mixing a curing agent, but when mixed with other resins or the like, for example, a curing agent, a curing accelerator, etc. can be mixed and used.

[0069] [Other resins]

[0070] As the aforementioned other resins, for example, alkenyl-containing compounds such as bismaleimides, allyl ether compounds, allylamine compounds, triallyl isocyanurate, alkenylphenol compounds, vinyl-containing polyolefin compounds, etc. can also be added. In addition, other thermosetting resins such as thermosetting polyimide resins, epoxy resins, phenolic resins, active ester resins, benzoxazine resins, cyanate resins, etc. can also be appropriately blended according to the purpose.

[0071] [Curing agent]

[0072] Examples of the curing agent include amine compounds, amide compounds, acid anhydride compounds, phenol compounds, cyanate compounds, active ester resins, etc. These curing agents may be used alone or in combination of two or more.

[0073] [Curing accelerator]

[0074] As the aforementioned curing accelerator, various substances can be used, for example, phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, amine complex salts, etc. can be cited. In the case of using as semiconductor sealing material purposes, phosphorus compounds or imidazoles such as triphenylphosphine are preferred from the aspects of excellent curability, heat resistance, electrical properties, moisture resistance reliability, etc. These curing accelerators can be used alone or in combination of two or more.

[0075] [Flame retardant]

[0076] In the curable resin composition of the present invention, a flame retardant may be blended as needed to exert flame retardancy, wherein a non-halogen flame retardant substantially containing no halogen atoms is preferably blended. Examples of the non-halogen flame retardant include phosphorus flame retardants, nitrogen flame retardants, silicone flame retardants, inorganic flame retardants, and organic metal salt flame retardants, and these flame retardants may be used alone or in combination of two or more.

[0077] [Bulking Agent]

[0078] In the curable resin composition of the present invention, an inorganic filler can be mixed as needed. As the aforementioned inorganic filler, for example, fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide, etc. can be listed. In the case of significantly increasing the compounding amount of the aforementioned inorganic filler, fused silica is preferably used. The aforementioned fused silica can be used in any shape of a crushed shape or a spherical shape. In order to increase the compounding amount of the fused silica and suppress the rise in the melt viscosity of the molding material, it is preferred to mainly use a spherical substance. Furthermore, in order to increase the compounding amount of spherical silica, it is preferred to appropriately adjust the particle size distribution of the spherical silica. In addition, when the aforementioned curable resin composition is used for the purposes of the conductive paste described in detail below, conductive fillers such as silver powder and copper powder can be used.

[0079] [Other compounding agents]

[0080] To the curable resin composition of the present invention, various compounding agents such as a silane coupling agent, a release agent, a pigment, and an emulsifier may be added as necessary.

[0081] <Cured product>

[0082] The present invention relates to a cured product, characterized in that it is obtained by subjecting the aforementioned curable resin composition to a curing reaction. The aforementioned curable resin composition is obtained by mixing the aforementioned curable resin alone, or uniformly mixing the aforementioned curing agent and other components in addition to the aforementioned curable resin, and can be easily made into a cured product by the same method as the conventionally known method. Examples of the aforementioned cured product include laminated products, cast products, adhesive layers, coatings, films, and other shaped cured products.

[0083] Examples of the curing reaction include heat curing and ultraviolet curing reactions. Among them, heat curing reactions are easy to carry out even without a catalyst. However, if one wishes to accelerate the reaction, it is effective to add a polymerization initiator such as an organic peroxide or an azo compound, or a basic catalyst such as a phosphine compound or a tertiary amine. Examples include benzoyl peroxide, dicumyl peroxide, azobisisobutyronitrile, triphenylphosphine, triethylamine, and imidazoles.

[0084] <Application>

[0085] The cured product obtained by the curable resin composition of the present invention has excellent heat resistance and dielectric properties, therefore, can be suitably used for heat-resistant components, electronic components. Can be particularly suitably used for prepreg, circuit board, semiconductor sealing material, semiconductor device, laminated film, laminated substrate, adhesive, corrosion-resistant material etc. In addition, it can also be suitably used for the matrix resin of fiber-reinforced resin, and is particularly suitable as a prepreg of high heat resistance. In addition, the aforementioned curable resin contained in the aforementioned curable resin composition shows excellent solubility to various solvents, therefore, can be coated. The heat-resistant components and electronic components obtained by such operation can be suitably used for various purposes, and can list out for example industrial machinery parts, general machinery parts, parts such as automobile / railway / vehicle, aerospace / aviation related parts, electronic / electrical parts, building materials, container / packaging components, daily necessities, sports / leisure goods, housing components for wind power generation etc., but are not limited to these objects.

[0086] <Prepreg>

[0087] The prepreg of the present invention preferably comprises: a reinforcing substrate, and a semi-cured product of the curable resin composition impregnated in the reinforcing substrate. As a method for preparing the prepreg, a known method can be used, wherein a resin varnish in which the curable resin composition is dissolved (diluted) in an organic solvent is impregnated in the reinforcing substrate, and the reinforcing substrate impregnated with the resin varnish is heat-treated, thereby semi-curing (or uncuring) the curable resin composition, thereby forming a prepreg.

[0088] As the aforementioned organic solvent, for example, toluene, xylene, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, methyl ethyl ketone (MEK), methyl isobutyl ketone, dioxane, tetrahydrofuran, etc. can be used alone or in the form of a mixed solvent of two or more.

[0089] The reinforcing substrate to be impregnated with the resin varnish is a woven fabric, a nonwoven fabric, a mat, or paper made of inorganic fibers such as glass fibers, polyester fibers, and polyamide fibers, or organic fibers, and these may be used alone or in combination.

[0090] The mass ratio of the curable resin composition to the reinforcing base material in the prepreg is not particularly limited, but the prepreg is usually preferably prepared so that the curable resin composition (resin component therein) is 20 to 80 mass %.

[0091] The heat treatment conditions for the prepreg are appropriately selected depending on the types and amounts of the organic solvent, catalyst, and various additives used, and are generally performed at a temperature of 80 to 220° C. for 3 to 30 minutes.

[0092] <Heat-resistant materials and electronic materials>

[0093] The cured product obtained by the curable resin composition of the present invention has excellent heat resistance and dielectric properties, therefore, can be suitable for heat-resistant components, electronic components. Can be particularly suitable for circuit substrates, semiconductor sealing materials, semiconductor devices, laminated films, laminated substrates, adhesives, corrosion-resistant materials, etc. In addition, it can also be suitable for the matrix resin of fiber-reinforced resins, and is particularly suitable as a prepreg with high heat resistance. In addition, the aforementioned vinyl benzyl compound contained in the aforementioned curable resin composition shows excellent solubility to various solvents, therefore, can be coated. The heat-resistant components and electronic components thus obtained can be suitable for various purposes, for example, industrial machinery parts, general machinery parts, parts such as automobiles / railways / vehicles, aerospace / aviation related parts, electronic / electrical parts, building materials, containers / packaging components, daily necessities, sports / leisure goods, housing components for wind power generation, etc., but are not limited to these objects.

[0094] Hereinafter, typical products produced using the curable resin composition of the present invention will be described with reference to examples.

[0095] <Circuit board>

[0096] In the present invention, the circuit substrate is preferably obtained by laminating the prepreg and copper foil and performing heat compression molding. Specifically, as a method for obtaining a circuit substrate from the curable resin composition of the present invention, the following method can be cited: laminating the prepreg according to a conventional method, appropriately overlapping the copper foil, and performing heat compression molding at 170 to 300° C. under a pressure of 1 to 10 MPa for 10 minutes to 3 hours.

[0097] <Semiconductor sealing materials>

[0098] In the present invention, as a semiconductor sealing material, it is preferred to contain the aforementioned curable resin composition. Specifically, as a method for obtaining a semiconductor sealing material from the curable resin composition of the present invention, it can be cited that: using an extruder, a kneader, a roller, etc. as needed, further fully melt-mixing the curing accelerator and inorganic filler as optional components in the aforementioned curable resin composition until a uniform method is achieved. At this time, as an inorganic filler, fused silica is generally used. When used as a high thermal conductivity semiconductor sealing material for power transistors and power ICs, high filling of crystalline silica, alumina, silicon nitride, etc. with higher thermal conductivity than fused silica can be used, or fused silica, crystalline silica, alumina, silicon nitride, etc. Its filling rate is preferably used in the range of 30 to 95 parts by mass relative to 100 parts by mass of the curable resin composition. Among them, in order to achieve flame retardancy, moisture resistance, improvement of solder crack resistance, and reduction of linear expansion coefficient, it is more preferably 70 parts by mass or more, and more preferably 80 parts by mass or more.

[0099] <Semiconductor devices>

[0100] In the present invention, as a semiconductor device, it is preferred to include a cured product obtained by heat-curing the semiconductor sealing material. Specifically, as a semiconductor package molding of a semiconductor device obtained from the curable resin composition of the present invention, there can be cited a method in which the semiconductor sealing material is molded using a casting or transfer molding machine, an injection molding machine, etc., and then heat-cured at 50 to 250° C. for 2 to 10 hours.

[0101] <Laminated substrate>

[0102] As a method for obtaining a laminated substrate from the curable resin composition of the present invention, a method that goes through steps 1 to 3 can be cited. In step 1, first, the aforementioned curable resin composition appropriately mixed with rubber, filler, etc. is applied to a circuit substrate formed with a circuit using a spraying method, a curtain coating method, etc., and then cured. In step 2, after the circuit substrate coated with the curable resin composition is opened with a predetermined through-hole portion, etc. as needed, it is treated with a roughening agent, and its surface is washed with hot water, thereby forming a concave-convex surface on the aforementioned substrate, and a metal such as copper is plated. In step 3, the operations of steps 1 to 2 are repeated in sequence as desired, and the resin insulating layer and the conductor layer of the predetermined circuit pattern are alternately stacked to form a laminated substrate. It should be noted that in the aforementioned step, the opening of the through-hole portion can be performed after the outermost resin insulating layer is formed. In addition, the laminated substrate in the present invention can also be produced by heat-pressing the resin-coated copper foil obtained by semi-curing the aforementioned resin composition on the copper foil at 170 to 300° C. onto a wiring substrate formed with a circuit, thereby forming a roughened surface and omitting the plating process step to produce a laminated substrate.

[0103] <Laminated Film>

[0104] The laminated film of the present invention preferably contains the aforementioned curable resin composition. As a method for obtaining a laminated film from the curable resin composition of the present invention, there can be cited a method in which, for example, a curable resin composition is applied to a support film and then dried to form a resin composition layer on the support film. When the curable resin composition of the present invention is used for a laminated film, it is important that the aforementioned film softens under the lamination temperature conditions (usually 70 to 140° C.) in a vacuum lamination method, and exhibits fluidity (resin flow) capable of filling the via hole or through hole present in the circuit substrate while being laminated with the circuit substrate, and the aforementioned components are preferably compounded in a manner that exhibits such characteristics.

[0105] Here, the diameter of the through hole of the circuit board is usually 0.1 to 0.5 mm, and the depth is usually 0.1 to 1.2 mm. Usually, it is preferable that the resin filling can be performed within this range.

[0106] As a specific method for producing the aforementioned laminated film, the following method can be listed: after preparing a varnished resin composition by mixing an organic solvent, the aforementioned varnished resin composition is applied to the surface of a supporting film (Y), and then the organic solvent is dried by heating or blowing hot air, etc., to form a resin composition layer (X).

[0107] As the organic solvent used here, it is preferred to use ketones such as acetone, methyl ethyl ketone, and cyclohexanone; acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc., and it is preferred to use them in a ratio of 30 to 60% by mass of non-volatile components.

[0108] It should be noted that the thickness of the resin composition layer (X) formed usually needs to be set to be greater than the thickness of the conductor layer. The thickness of the conductor layer of the circuit substrate is usually in the range of 5 to 70 μm, so the thickness of the resin composition layer (X) preferably has a thickness of 10 to 100 μm. It should be noted that the resin composition layer (X) in the present invention can be protected by a protective film described later. By protecting with a protective film, it is possible to prevent the adhesion and damage of dirt on the surface of the resin composition layer.

[0109] Examples of the supporting film and protective film include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride; polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate; polycarbonate, polyimide; and metal foils such as release paper, copper foil, and aluminum foil. It should be noted that in addition to matte treatment and corona treatment, the supporting film and protective film may also be subjected to release treatment. The thickness of the supporting film is not particularly limited, and is generally used in the range of 10 to 150 μm, preferably 25 to 50 μm. In addition, the thickness of the protective film is preferably set to 1 to 40 μm.

[0110] The supporting film (Y) is peeled off after being laminated on a circuit board or after being cured by heating to form an insulating layer. If the supporting film (Y) is peeled off after the resin composition layer constituting the laminated film is cured by heating, adhesion of dirt and the like during the curing process can be prevented. When peeling off after curing, the supporting film is usually subjected to a demolding treatment in advance.

[0111] It should be noted that a multilayer printed circuit board can be manufactured from the laminated film obtained by the above operation. For example, when the aforementioned resin composition layer (X) is protected by a protective film, after peeling them off, the layer (X) of the aforementioned resin composition is laminated on one or both sides of the circuit substrate in a manner of directly contacting the circuit substrate, for example, by a vacuum lamination method. The lamination method can be intermittent or continuous based on a roller. In addition, as needed, the laminated film and the circuit substrate can be heated (preheated) as needed before lamination. Regarding the lamination conditions, it is preferred to set the crimping temperature (lamination temperature) to 70 to 140°C, and the crimping pressure is preferably set to 1 to 11 kgf / cm 2 (9.8×104 ~107.9×10 4 N / m 2 ), preferably lamination is carried out under reduced pressure with an air pressure of 20 mmHg (26.7 hPa) or less.

[0112] <Conductive paste>

[0113] As a method of obtaining a conductive paste from the curable resin composition of the present invention, for example, a method of dispersing conductive particles in the composition can be mentioned. The conductive paste can be made into a circuit connection paste resin composition or an anisotropic conductive adhesive depending on the type of conductive particles used.

[0114] The following are examples of the present invention, but the present invention is not limited thereto. The present invention is specifically described based on the examples and comparative examples, and "parts" and "%" are based on mass unless otherwise specified. It should be noted that, under the conditions shown below, a curable resin and a cured product obtained by using a curable resin composition containing the curable resin are synthesized, and further, the obtained cured product is measured / evaluated under the following conditions.

[0115] <Method for determining the number of repeating units n>

[0116] The following measuring apparatus and measuring conditions are used to measure and obtain the GPC spectra of the vinylbenzyl compounds (B-1) to (B-3) having an indane bisphenol skeleton obtained in the synthesis examples shown below. Based on the results of the aforementioned GPC spectra, the average number of repeating units n contributing to the indane skeleton in the indane bisphenol compound is calculated based on the number average molecular weight (Mn) of the indane bisphenol compound. Specifically, for compounds where n is 0 to 4, the theoretical molecular weight and each measured molecular weight in GPC are plotted on a scatter plot, an approximate straight line is drawn, and the number average molecular weight (Mn) is determined from the points indicated by the measured value Mn (1) on the straight line to calculate n.

[0117] Measuring device: Tosoh Corporation "HLC-8320GPC"

[0118] Column: Guard column "HXL-L" made by Tosoh Co., Ltd. + "TSK-GEL G2000HXL" made by Tosoh Co., Ltd. + "TSK-GEL G2000HXL" made by Tosoh Co., Ltd. + "TSK-GEL G3000HXL" made by Tosoh Co., Ltd. + "TSK-GEL G4000HXL" made by Tosoh Co., Ltd.

[0119] Detector: RI (differential refractometer)

[0120] Data processing: Tosoh Corporation's "GPC Workstation EcoSEC-WorkStation"

[0121] Determination conditions: column temperature 40°C

[0122] Developing solvent: tetrahydrofuran

[0123] Flow rate 1.0ml / min

[0124] Standard: According to the measurement manual of the aforementioned "GPC Workstation EcoSEC-WorkStation", the following monodisperse polystyrene having a known molecular weight was used.

[0125] (Using polystyrene)

[0126] "A-500" manufactured by Tosoh Corporation

[0127] "A-1000" manufactured by Tosoh Corporation

[0128] "A-2500" manufactured by Tosoh Corporation

[0129] "A-5000" manufactured by Tosoh Corporation

[0130] "F-1" manufactured by Tosoh Corporation

[0131] "F-2" manufactured by Tosoh Corporation

[0132] "F-4" manufactured by Tosoh Corporation

[0133] "F-10" manufactured by Tosoh Corporation

[0134] "F-20" manufactured by Tosoh Corporation

[0135] "F-40" manufactured by Tosoh Corporation

[0136] "F-80" manufactured by Tosoh Corporation

[0137] "F-128" manufactured by Tosoh Corporation

[0138] Sample: A tetrahydrofuran solution containing 1.0% by mass of the vinylbenzyl compounds (B-1) to (B-3) having an indane bisphenol skeleton obtained in the following synthesis examples was filtered with a microfilter (50 μl).

[0139] <Measurement of Hydroxyl Concentration>

[0140] The hydroxyl value was measured by a method in accordance with JIS K 0070: 1992, and the hydroxyl equivalent (g / eq) was calculated based on the calculation formula of 1000×56.11 / hydroxyl value.

[0141] Synthesis Example 1 (Synthesis of Indan Bisphenol (A-1))

[0142] In a flask equipped with a stirrer, a Dean-Stark apparatus, a condenser and a nitrogen sealing port, 244 parts of 2,6-xylenol, 388 parts of m-bis(α-hydroxyisopropyl)benzene, 633 parts of toluene, and 19 parts of p-toluenesulfonic acid monohydrate were added while blowing nitrogen and heated. The water generated during the reaction was removed using a Dean-Stark apparatus, and the temperature was raised to 120°C and maintained for 10 hours. After the reaction solution was cooled, it was neutralized with a 49% aqueous sodium hydroxide solution until the pH became neutral. After removing the catalyst residue by washing with water, the volatile components were distilled off by heating and reducing pressure to obtain indane bisphenol (A-1). The hydroxyl equivalent of the obtained indane bisphenol (A-1) was 342 g / eq.

[0143] Synthesis Example 2 (Synthesis of Indan Bisphenol (A-2))

[0144] In a flask equipped with a stirrer, a Dean-Stark apparatus, a condenser and a nitrogen sealing port, 244 parts of 2,6-xylenol, 777 parts of m-bis(α-hydroxyisopropyl)benzene, 1022 parts of toluene and 31 parts of p-toluenesulfonic acid monohydrate were used while blowing nitrogen gas, and the same operation as in Synthesis Example 1 was carried out to obtain indane bisphenol (A-2). The hydroxyl equivalent of the obtained indane bisphenol (A-2) was 580 g / eq.

[0145] Synthesis Example 3 (Synthesis of Indan Bisphenol (A-3))

[0146] In a flask equipped with a stirrer, a Dean-Stark apparatus, a condenser and a nitrogen sealing port, 244 parts of 2,6-xylenol, 194 parts of m-bis(α-hydroxyisopropyl)benzene, 439 parts of toluene and 13 parts of p-toluenesulfonic acid monohydrate were used while blowing nitrogen gas, and the same operation as in Synthesis Example 1 was carried out to obtain indane bisphenol (A-3). The hydroxyl equivalent of the obtained indane bisphenol (A-3) was 299 g / eq.

[0147]

[0148] Synthesis Example 4 (Vinylbenzyl Modification of Indane Bisphenol (A-1))

[0149] In a flask equipped with a stirrer, a Dean-Stark apparatus and a condenser, 100 parts of indane bisphenol (A-1), 74 parts of isopropanol, 172 parts of toluene, 49 parts of chloromethylstyrene (product name CMS-P, manufactured by AGC SEIMI CHEMICAL CO., LTD.), and 0.8 parts of tetrabutylammonium bromide were added, and heated to 75°C while stirring to dissolve. 79 parts of a 49% aqueous sodium hydroxide solution were added dropwise over 30 minutes, and the reaction was continued for 5 hours. After removing salts and catalyst residues from the reaction solution by washing with water, the volatile components were adjusted by heating and reducing pressure to obtain a toluene solution of a vinylbenzyl compound (B-1) having an indane bisphenol skeleton. The number of repeating units n was 0.4.

[0150] Synthesis Example 5 (Vinylbenzyl Modification of Indane Bisphenol (A-2))

[0151] In a flask equipped with a stirrer, a Dean-Stark apparatus and a condenser, 100 parts of indane bisphenol (A-2), 64 parts of isopropanol, 149 parts of toluene, 29 parts of chloromethylstyrene (product name CMS-P, manufactured by AGC SEIMI CHEMICAL CO., LTD.), and 0.6 parts of tetrabutylammonium bromide were added, and the mixture was heated to 75°C and dissolved while stirring. 46 parts of a 49% aqueous sodium hydroxide solution were added dropwise over 30 minutes, and the reaction was continued for 5 hours. After removing salts and catalyst residues from the reaction solution by washing with water, the volatile components were adjusted by heating and reducing pressure to obtain a toluene solution of a vinylbenzyl compound (B-2) having an indane bisphenol skeleton. The number of repeating units n was 2.0.

[0152] Synthesis Example 6 (Vinylbenzyl Modification of Indane Bisphenol (A-3))

[0153] In a flask equipped with a stirrer, a Dean-Stark apparatus and a condenser, 100 parts of indane bisphenol (A-3), 77 parts of isopropanol, 180 parts of toluene, 56 parts of chloromethylstyrene (product name CMS-P, manufactured by AGC SEIMI CHEMICAL CO., LTD.), and 0.8 parts of tetrabutylammonium bromide were added, and heated to 75°C while stirring to dissolve. 90 parts of a 49% aqueous sodium hydroxide solution were added dropwise over 30 minutes, and the reaction was continued for 5 hours. After removing salts and catalyst residues from the reaction solution by washing with water, the volatile components were adjusted by heating and reducing pressure to obtain a toluene solution of a vinylbenzyl compound (B-3) having an indane bisphenol skeleton. The number of repeating units n was 0.2.

[0154]

[0155] Synthesis Example 7 (Vinylbenzyl Modification of Indane Bisphenol (A-2))

[0156] In a flask equipped with a stirrer and a condenser, 100 parts (0.172 equivalents) of indane bisphenol (A-2), 165 parts of dimethyl sulfoxide, 135 parts of tetrahydrofuran, 7.2 parts of powdered sodium hydroxide, and 0.17g of methylhydroquinone were added and stirred at 40°C for 1 hour. 27.3 parts of chloromethylstyrene (product name CMS-P, AGC SEIMI CHEMICAL CO., LTD.) were added dropwise over 1 hour, and the temperature was raised to 80°C for continuous reaction for 14 hours. The reaction solution was diluted with 300g of toluene, and after removing salts, catalyst residues, dimethyl sulfoxide and tetrahydrofuran from the reaction solution by washing with water, the volatile components were adjusted by heating and decompression to obtain a toluene solution of a vinylbenzyl compound (B-4) having an indane bisphenol skeleton. The number of repeating units n is 2.0.

[0157] Synthesis Example 8 (Purification of Vinylbenzyl Compound (B-2))

[0158] To 200 parts of a toluene solution (50% non-volatile matter) of a vinylbenzyl compound having an indane bisphenol skeleton obtained in the same manner as in Synthesis Example 5, 1000 parts of methanol were added at room temperature to precipitate a resin. The supernatant was removed by decantation to obtain a precipitate. The precipitate was dissolved again in 100 parts of toluene, and 1000 parts of methanol were added to precipitate the resin. The supernatant was removed by decantation to obtain a purified resin as a precipitate. After being dissolved again in toluene, the volatile matter was adjusted by heating and reducing pressure to obtain a toluene solution of a vinylbenzyl compound (B-5) having an indane bisphenol skeleton. The number of repeating units n is 3.0.

[0159] Synthesis Example 9 (Synthesis of Vinylbenzyl Compound (B-6))

[0160] In a 1L flask equipped with a thermometer, a condenser, a Dean-Stark water trap, and a stirrer, 48.9 g (0.4 mol) of 2,6-dimethylphenol, 272.0 g (1.4 mol) of α,α'-dihydroxy-1,3-diisopropylbenzene, 280 g of xylene, and 70 g of activated clay were added, and heated to 120°C while stirring. The distilled water was removed by a Dean-Stark tube, and the temperature was raised to 210°C, and the reaction was carried out for 3 hours. Thereafter, the mixture was cooled to 140°C, 146.6 g (1.2 mol) of 2,6-dimethylphenol was added, and the temperature was raised to 220°C, and the reaction was carried out for 3 hours. After the reaction, the mixture was air-cooled to 100°C, diluted with 300 g of toluene, the activated clay was removed by filtration, and low molecular weight substances such as the solvent and unreacted products were distilled off under reduced pressure to obtain 365.3 g of an intermediate phenol compound. The hydroxyl equivalent (phenol equivalent) of the obtained intermediate phenol compound was 299.

[0161] In a 2L flask equipped with a thermometer, a condenser, and a stirrer, 365.3 g of the intermediate phenol compound obtained, 0.184 g (0.001 mol) of 2,4-dinitrophenol (2,4-DNP), 23.5 g (0.073 mol) of tetrabutylammonium bromide (TBAB), 209 g (1.37 mol) of chloromethylstyrene, and 400 g of methyl ethyl ketone were added, and the temperature was raised to 75°C while stirring. Then, 48%-NaOHaq was added dropwise in a reaction vessel maintained at 75°C for 20 minutes. After the addition was completed, stirring was continued at 75°C for 4 hours. After 4 hours, it was cooled to room temperature, 100 g of toluene was added, and 10% HCl was added for neutralization. After that, the aqueous phase was separated by liquid separation, and then the liquid separation and washing were performed 3 times with 300 ml of water. The obtained organic phase was distilled to concentrate it, and methanol was added to reprecipitate the product. The precipitate was filtered and dried to obtain a vinylbenzyl compound (B-6) having an indane bisphenol skeleton (average number of repeating units n=1.6).

[0162] <Determination of total chlorine content>

[0163] 0.3 g of the vinylbenzyl compound having an indane bisphenol skeleton obtained in the synthesis example was accurately weighed in a 200 ml Erlenmeyer flask with a stopper, 20 ml of 1-butanol was added, and the mixture was dissolved by reflux in an oil bath at 120° C. Further, 1 g of metallic sodium was added, and the mixture was refluxed in an oil bath for 1 hour. After natural cooling, 5 ml of pure water and 5 ml of nitric acid were added, and the solution was titrated with a 0.01 mol / L silver nitrate aqueous solution using a potentiometric titrator (“AT-310J” manufactured by Kyoto Electronics Industries) to obtain the generated NaCl.

[0164] <Production of Cured Product>

[0165] Using a 10MIL applicator, a curable resin composition containing a toluene solution of a vinylbenzyl compound having an indane bisphenol skeleton obtained in the synthesis example and 4-methoxyphenol (MQ) and 2,6-di-tert-butyl-4-methylphenol (BHT) as polymerization inhibitors in the amounts shown in Table 1 and Table 2 was applied to a PET film and dried at 120°C for 10 minutes. The obtained film was collected and filled into a mold frame, and then heated at 200°C for 2 hours while being pressed at 4.9 MPa using a vacuum hot press to obtain a cured product. This was cut out as a test piece.

[0166] <Evaluation of heat resistance (glass transition temperature Tg)>

[0167] The obtained cured product was cut into a size of 55 mm in length × 5 mm in width × 1.6 mm in thickness as a test piece. For the test piece, a viscoelasticity measuring device (DMA: solid viscoelasticity measuring device "DMS6100" manufactured by Hitachi High-Tech Corporation, deformation mode: bending with both ends clamped, measurement mode: sine wave vibration, frequency 1 Hz, heating rate 3 ° C / min) was used to evaluate the temperature at which the elastic modulus changes to the maximum as the glass transition temperature Tg. It should be noted that as a glass transition temperature (Tg), if it is above 100 ° C, there is no problem in practical use, preferably above 150 ° C.

[0168] <Evaluation of Dielectric Properties>

[0169] The dielectric constant and dielectric loss tangent at 10 GHz of the test piece stored in a room at 23°C and 50% humidity for 24 hours after drying were measured using a network analyzer "E8362C" manufactured by Agilent Technologies td. by the cavity resonance method in accordance with JIS-C-6481.

[0170] [Table 1]

[0171]

[0172] [Table 2]

[0173]

[0174] [Table 3]

[0175]

[0176] According to the evaluation results in Tables 1 to 3 above, it can be confirmed that in the examples, the cured products exhibit high heat resistance and low dielectric properties.

[0177] On the other hand, the evaluation results in Tables 1 to 3 above show that, in Comparative Examples 1 to 3, no polymerization inhibitor was used, and thus oxidation of the cured product could not be suppressed, so that the dielectric properties were higher than those of the Examples. Furthermore, even if a polymerization inhibitor was used, since the total chlorine content was 50 ppm or less in Comparative Example 4 and 5300 ppm in Comparative Example 5, both the heat resistance and the dielectric properties were inferior to those of the Examples. Comparative Example 6, in which no polymerization inhibitor was used and the total chlorine content was 50 ppm or less, both the heat resistance and the dielectric properties were inferior to those of the Examples.

[0178] The evaluation results in Table 3 above confirmed that in Comparative Example 7, since MQ and BHT were excessively blended, the dielectric properties were higher than those of Examples. This confirmed that it is important to blend an appropriate amount of a polymerization inhibitor.

[0179] Industrial Applicability

[0180] The cured product obtained by blending a polymerization inhibitor with the vinylbenzyl compound having an indane bisphenol skeleton of the present invention has excellent heat resistance and dielectric properties, and therefore can be suitably used in heat-resistant components and electronic components, and can be particularly suitably used in prepregs, semiconductor sealing materials, circuit boards, laminated films, laminated substrates, adhesives, and corrosion-resistant materials. In addition, it can also be suitably used in the matrix resin of fiber-reinforced resins, and is suitable as a highly heat-resistant prepreg.

Claims

1. A curable resin composition, characterized in that A vinylbenzyl compound having an indane bisphenol skeleton represented by the following general formula (1): The curable resin composition further comprises a polymerization inhibitor, wherein the content of the polymerization inhibitor is 50 to 5000 ppm relative to the vinyl benzyl compound. The total chlorine content is 100 to 5000 ppm relative to the total amount of the vinylbenzyl compound and the polymerization inhibitor. In the formula (1), X represents a vinylbenzyloxy group, Ra each independently represents an alkyl group having 1 to 15 carbon atoms, an alkyloxy group, an alkylthio group, an aralkyl group, an aryl group, an aryloxy group, an arylthio group, a cycloalkyl group, a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group or a mercapto group, q represents an integer value of 0 to 4, and when q is 2 to 4, Ra can be the same or different in the same ring, Rb each independently represents an alkyl group having 1 to 15 carbon atoms, an alkyloxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, a cycloalkyl group, a hydrogen atom, a halogen atom, a hydroxyl group or a mercapto group, r represents an integer value of 0 to 3, and when r is 2 to 3, Rb can be the same or different in the same ring, and n is the average number of repeating units and represents a value of 0.2 to 20.

2. The curable resin composition according to claim 1, wherein The vinylbenzyl compound is represented by the following general formula (2): In the formula (2), X represents a vinylbenzyloxy group, R1 and R2 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group or a cycloalkyl group, and R1 and R2 are not both hydrogen atoms at the same time, and n is the average number of repeating units, which represents a value of 0.2 to 20.

3. The curable resin composition according to claim 1, wherein The polymerization inhibitor is a phenolic polymerization inhibitor.

4. A solidified product, characterized in that: This is obtained by subjecting the curable resin composition according to claim 1 to a curing reaction.

5. A prepreg, characterized in that: A reinforcing substrate is provided, and the curable resin composition according to claim 1 is impregnated into the reinforcing substrate.

6. A circuit substrate, characterized in that: The prepreg according to claim 5 and copper foil are laminated and heat-pressed to form the laminate.

7. A laminated film, characterized in that: A curable resin composition comprising the curable resin composition according to claim 1.

8. A semiconductor sealing material, characterized in that: A curable resin composition comprising the curable resin composition according to claim 1.

9. A semiconductor device, characterized in that: The semiconductor sealing material according to claim 8 is cured by heating.

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