Curable resin, curable resin composition, and, cured product

Abstract

The purpose is to provide a curable resin composition and a cured product thereof that can be made to have excellent solvent solubility, heat resistance (high glass transition temperature), and dielectric properties (low dielectric properties). Specifically, a curable resin composition is provided that comprises a repeating unit represented by the following general formula (1) and one or more reactive groups selected from the group consisting of (meth)acryloyloxy groups, vinylbenzyl ether groups, and acrylate ether groups as terminal structures, and a curable compound (B) represented by the following general formula (2). (The details of the substituents and the number of substituents indicated in the above general formula (1) are as described in the text.) (The details of the substituents and the number of substituents indicated in the above general formula (2) are as described in the text.)

Description

Technology Field

[0001] The present invention relates to a curable resin having a specific structure, a curable resin composition containing a curable compound, and a cured product obtained from said curable resin composition. Background Technology

[0002] With the recent increase in information and communication volume, information and communication in the high-frequency band has become active, and in order to achieve better electrical characteristics, and in particular, to reduce transmission loss in the high-frequency band, there has been a demand for electrical insulating materials having low dielectric constant and low dielectric loss tangent.

[0003] In addition, printed circuit boards or electronic components in which such electrical insulating materials are used are exposed to high-temperature solder reflow during mounting, so materials with excellent heat resistance and a high glass transition temperature are required. In particular, recently, as lead-free solder with a high melting point is used from the perspective of environmental issues, there is an increasing demand for electrical insulating materials with higher heat resistance.

[0004] In response to these requirements, various vinyl group-containing curable resins having different chemical structures have been proposed in the past. As such curable resins, for example, bisphenol divinylbenzyl ether or novolac polyvinylbenzyl ether has been proposed (see, for example, Patent Documents 1 and 2). However, these vinylbenzyl ethers cannot impart a cured product with sufficiently low dielectric properties, so the resulting cured product is problematic for stable use in the high-frequency range, and furthermore, bisphenol divinylbenzyl ether cannot be said to have sufficiently high heat resistance.

[0005] Regarding vinylbenzyl ethers with improved properties as described above, several polyvinylbenzyl ethers of specific structures have been proposed to improve dielectric properties, etc. (e.g., see Patent Documents 3 to 5). However, although attempts have been made to suppress dielectric loss tangents and improve heat resistance, these improvements in properties are not yet sufficient, and further improvement in properties is desired.

[0006] As such, conventional vinyl group-containing curable resins including polyvinylbenzyl ethers did not provide a cured product that combined the low dielectric loss tangent required for electrical insulation materials, particularly for high-frequency applications, with the heat resistance capable of withstanding lead-free soldering. Furthermore, the solvent solubility, which contributes to the moldability of the cured product, was also insufficient. Prior art literature

[0007] Japanese Patent Publication No. 63-68537, Japanese Patent Publication No. 64-65110, Japanese Patent Publication No. 1-503238, Japanese Patent Publication No. 9-31006, Japanese Patent Publication No. 2005-314556 The problem to be solved

[0008] Accordingly, the problem to be solved by the present invention is to improve the solvent solubility of the curable resin composition and to provide a cured product having excellent heat resistance (high glass transition temperature) and dielectric properties (low dielectric properties) by using a curable resin composition containing a curable resin having a specific structure and a curable compound. means of solving the problem

[0009] Therefore, the inventors, in order to solve the above problem, carefully examined the matter and discovered that a curable resin composition characterized by containing a curable resin of a specific structure and a curable compound has excellent solvent solubility, and furthermore, a cured product using said curable resin composition has excellent heat resistance and dielectric properties, thereby completing the present invention.

[0010] That is, the present invention relates to a curable resin composition characterized by comprising a repeating unit represented by the following general formula (1), a curable resin (A) having one or more reactive groups selected from the group consisting of (meth)acryloyloxy groups, vinylbenzyl ether groups, and acrylate ether groups as terminal structures, and a curable compound (B) represented by the following general formula (2).

[0011]

[0012] (In the food, Ra 1 , Rb 1 Each is independently an alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, or a cycloalkyl group, and k 1 is an integer from 0 to 3, X is a single bond or a hydrocarbon group, and Y represents any one of the following general formulas (3) to (5)

[0013]

[0014] (In the formula, Z represents a hydrocarbon group)

[0015]

[0016] (In the food, Ra 2 , Rb 2 Each is independently an alkyl group, aryl group, aralkyl group, or cycloalkyl group having 1 to 12 carbon atoms, and k 2 is an integer from 0 to 3, X is a single bond or hydrocarbon group, and V represents a (meth)acryloyloxy group, vinylbenzyl ether group, or acrylate ether group)

[0017] The present invention relates to a cured product obtained by curing the above-mentioned curable resin composition. Effects of the invention

[0018] The curable resin composition of the present invention is useful because it contributes to solvent solubility, thereby providing excellent moldability of the cured product, and furthermore, because it contributes to reactivity, heat resistance, and low dielectric properties, the resulting cured product has excellent heat resistance and low dielectric properties. Brief explanation of the drawing

[0019] [Fig. 1] This is a GPC chart of the curable resin (A1) obtained in Synthesis Example 1. [Fig. 2] This is a GPC chart of the curable resin (A2) obtained in Synthesis Example 2. Specific details for implementing the invention

[0020] The present invention will be described in detail below.

[0021] <Curing Resin (A)>

[0022] The curable resin composition of the present invention is characterized by containing a curable resin (A) having a repeating unit represented by the following general formula (1) and one or more reactive groups selected from the group consisting of (meth)acryloyloxy groups, vinylbenzyl ether groups, and acrylate ether groups as terminal structures.

[0023]

[0024] Among the above general formula (1), Ra 1 , Rb 1 Each is independently an alkyl group, aryl group, aralkyl group, or cycloalkyl group having 1 to 12 carbon atoms, and k 1 0 is an integer from 0 to 3, X is a single bond or a hydrocarbon group, and Y represents any one of the following general formulas (3) to (5).

[0025]

[0026] In the above general formulas (3) to (5), Z represents a hydrocarbon group.

[0027] The above-mentioned curable resin (A) has a repeating unit represented by the above-mentioned general formula (1) and one or more reactive groups selected from the group consisting of (meth)acryloyloxy groups, vinylbenzyl ether groups, and acrylate ether groups as terminal structures, so that the ester bonds, carbonate bonds, or ether bonds included in the above-mentioned curable resin (A) have low molecular mobility and low dielectric properties (especially low dielectric loss tangent), and additionally, at a location adjacent to the reactive group, a substituent Ra 1 Ina Rb 1 (Especially, Ra 1 Due to the presence of ), the polarity derived from the reactive group is Ra 1 It is desirable to obtain a cured product with a lower dielectric loss tangent by being restrained by steric hindrance. In addition, by having reactive groups in the curable resin, the cured product obtained has excellent heat resistance, and by having ester bonds, carbonate bonds, or ether bonds with low molecular mobility, a cured product having not only low dielectric properties but also a high glass transition temperature can be obtained.

[0028] Among the above general formula (1), Ra 1 and Rb 1 Each independently represents an alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, or a cycloalkyl group, and preferably, an alkyl group having 1 to 4 carbon atoms, an aryl group, or a cycloalkyl group. By being an alkyl group having 1 to 12 carbon atoms, etc., the planarity near any of the benzene ring, naphthalene ring, and anthracene ring described later is reduced, and as a result of the reduction in crystallinity, solvent solubility is improved and the melting point is lowered, which is a desirable embodiment.

[0029] Among the above general formula (1), k 1 represents an integer from 0 to 3, and preferably is an integer from 0 to 1. k 1By being within the above range, the planarity near the benzene ring in the above general formula (1) is reduced, and due to the reduction in crystallinity, solvent solubility is improved and the melting point is lowered, which is a desirable form. Also, k 1 If this is not 0, that is, if the substituent Rb 1 If this exists and is located near the reactive group, the polarity derived from the reactive group is Rb 1 It is desirable to obtain a hardened product with a low dielectric loss tangent by being constrained by steric hindrance.

[0030] In the above general formula (1), X may be a single bond or a hydrocarbon group, but for ease of obtaining industrial raw materials, it is preferable to have a biphenyl structure or a structure of the following general formulas (4) to (6), and in particular, a structure of the following general formula (4) is more preferable because it has a good balance of heat resistance and low dielectric properties.

[0031]

[0032] In the above general formulas (4) to (7), R1 and R2 are each independently represented as a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, or a cycloalkyl group, or R1 and R2 may form a cyclic framework in which they are integrated. n represents an integer from 0 to 2, preferably an integer from 0 to 1. By having n within the above range, high heat resistance is achieved, which is a desirable aspect.

[0033] In the above general formula (1), Y is represented by any of the above general formulas (3) to (5), and in terms of heat resistance, preferably, it is the above general formula (3).

[0034] In the above general formula (4) or (5), Z represents a hydrocarbon group, and in terms of heat resistance, preferably is a hydrocyclic group, an aromatic group, or a heterocyclic group, and more preferably is a structure represented by the following general formulas (7) to (11), and in particular, the structure of the following general formula (7) is more preferable in terms of cost and heat resistance.

[0035]

[0036] The curable resin (A) of the present invention has one or more reactive groups selected from the group consisting of (meth)acryloyloxy groups, vinylbenzyl ether groups, and acrylate ether groups as terminal structures, and preferably, the methacryloyloxy group as the terminal structure is more preferable in that the resulting cured product has a low dielectric loss tangent. While the methacryloyloxy group forms an ester bond, the vinylbenzyl ether group and the allyl ether group form an ether bond, so the molecular mobility is high and the dielectric loss tangent tends to be high.

[0037] <Curing compound (B)>

[0038] The curable resin composition of the present invention is characterized by containing a curable compound (B) represented by the following general formula (2).

[0039]

[0040] Among the above general formula (2), Ra 2 and Rb 2 Each independently represents an alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, or a cycloalkyl group, preferably an alkyl group having 1 to 4 carbon atoms, an aryl group, or a cycloalkyl group.

[0041] Among the above general formula (2), k 2 represents an integer from 0 to 3.

[0042] In the above general formula (2), X represents a single bond or a hydrocarbon group.

[0043] In the above general formula (2), V represents any one of a (meth)acryloyloxy group, a vinylbenzyl ether group, or an allyl ether group.

[0044] Also, Ra 2 , Rb 2 , and k 2 is Ra in the above general formula (1). 1 , Rb 1 , and k 1 It may be the same or different. In terms of the curability of the resulting cured product, it is desirable that it be the same.

[0045] By including a curable compound (B) represented by the above general formula (2), the low molecular weight component becomes the starting point, and the solvent solubility is increased, thereby suppressing the precipitation rate of the curable resin (A) and increasing the storage stability of the curable resin composition, which is desirable.

[0046] The curable resin composition of the present invention contains a curable compound (B) in an area % calculated by gel permeation chromatography (hereinafter GPC) measurement, in a range of 0.5 to 30.0 area % when the total area % of the curable resin (A) and the curable compound (B) is 100 area %, preferably 1.0 to 20.0 area %, and more preferably 1.5 to 15.0%. Within the above range, it is preferred because the solvent solubility as a curable resin composition is excellent, and the heat resistance and dielectric properties are excellent when the cured product is formed.

[0047] The curable resin composition is manufactured by the method described below, but it is preferable to separately add a curable compound (B) so that the content of the curable compound (B) in the resin composition can be easily adjusted. Depending on the characteristics required for the cured product, the combination of the curable resin (A) and the curable compound (B) may also be appropriately adjusted.

[0048] The curable resin composition of the present invention preferably comprises a curable resin (A) having repeating units represented by the following general formula (1A), wherein the general formula (1) is used.

[0049]

[0050] In the above general formula (1A), Rc represents an alkyl group, an aryl group, an aralkyl group, or a cycloalkyl group, preferably a methyl group, an ethyl group, an isopropyl group, or a benzyl group. Also, in the above general formula (1A), Ra 1 , Rb 1 , and Y are the same as in the case of the above general formula (1).

[0051] The curable resin composition of the present invention preferably comprises a curable resin (A) having a weight average molecular weight (Mw) of 500 to 50,000, more preferably 1,000 to 10,000, and more preferably 1,500 to 5,000. Within the above range, solvent solubility is improved and processability is good, which is desirable.

[0052] Method for manufacturing a curable resin composition

[0053] The curable resin composition of the present invention may preferably contain a curable resin (A) and a curable compound (B), and may be prepared by a method of separately preparing the curable resin (A) and the curable compound (B) and mixing them, or by a method of simultaneously preparing the curable resin (A) and the curable compound (B) in a reaction system.

[0054] <Method for manufacturing curable resin (A)>

[0055] As a method for manufacturing the curable resin (A) of the present invention, methods such as reacting in an organic solvent such as interfacial polymerization, or reacting in a molten state such as solvent polymerization, may be used (reaction process).

[0056] Interfacial Polymerization

[0057] As an example of the above interfacial polymerization method, a solution (organic phase) in which a divalent carboxylic acid halide and a reactive group introducing agent used for introducing a reactive group having a terminal structure are dissolved in an organic solvent that is incompatible with water is mixed with an alkaline aqueous solution (aqueous phase) containing a divalent phenol, a polymerization catalyst, and an antioxidant, and a polymerization reaction is carried out while stirring at a temperature of 50°C or lower for 1 to 8 hours.

[0058] In addition, as a separate interfacial polymerization method, examples include a method in which a solution (organic phase) in which a reactive group-introducing agent used for introducing a reactive group at the end structure is dissolved in an organic solvent that is incompatible with water is mixed with an alkaline aqueous solution (aqueous phase) containing divalent phenol, a polymerization catalyst, and an antioxidant, and phosgene is blown into the mixture, and a polymerization reaction is carried out while stirring at a temperature of 50°C or lower for 1 to 8 hours.

[0059] As an organic solvent used in the organic phase, a solvent that is incompatible with water and dissolves polyarylate is preferred. Examples of such solvents include chlorine-based solvents such as methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride, chlorobenzene, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, o-,m-,p-dichlorobenzene, aromatic hydrocarbons such as toluene, benzene, and xylene, or tetrahydrofuran, and methylene chloride is preferred in that it is easy to use in manufacturing.

[0060] Examples of alkaline aqueous solutions used in aqueous solutions include aqueous solutions of sodium hydroxide and potassium hydroxide.

[0061] Antioxidants are used to prevent the oxidation of divalent phenolic components. Examples of antioxidants include sodium hydrosulfite, L-ascorbic acid, erythorbic acid, catechin, tocopherol, and butylhydroxyanisole. Among these, sodium hydrosulfite is preferred due to its excellent water solubility.

[0062] Examples of polymerization catalysts include quaternary ammonium salts such as tri-n-butylbenzylammonium halide, tetra-n-butylammonium halide, trimethylbenzylammonium halide, and triethylbenzylammonium halide; and quaternary phosphonium salts such as tri-n-butylbenzylphosphonium halide, tetra-n-butylphosphonium halide, trimethylbenzylphosphonium halide, and triethylbenzylphosphonium halide. Among these, tri-n-butylbenzylammonium halide, trimethylbenzylammonium halide, tetra-n-butylammonium halide, tri-n-butylbenzylphosphonium halide, and tetra-n-butylphosphonium halide are preferred in that they allow obtaining a polymer with a high molecular weight and a low acid value.

[0063] As for the amount of the polymerization catalyst added, 0.01 to 5.0 mol% is preferred with respect to the molar amount of divalent phenol used for polymerization, and 0.1 to 1.0 mol% is more preferred. If the amount of the polymerization catalyst added is less than 0.01 mol%, the effect of the polymerization catalyst is not obtained, and the molecular weight of the polyarylate resin tends to decrease, so this is not desirable. On the other hand, if it exceeds 5.0 mol%, the hydrolysis reaction of the divalent aromatic carboxylic acid halide accelerates, and this also tends to decrease the molecular weight of the polyarylate resin, so this is not desirable.

[0064] As divalent phenols, for example, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,6-dimethylphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5,6-trimethylphenyl)propane, 2,2-bis(4-hydroxy-2,3,6-trimethylphenyl)propane, bis(4-hydroxy-3,5-dimethylphenyl)methane, bis(4-hydroxy-3,6-dimethylphenyl)methane, bis(4-hydroxy-3-methylphenyl)methane, bis(4-hydroxy-3,5,6-trimethylphenyl)methane, bis(4-hydroxy-2,3,6-trimethylphenyl)methane, bis(4-hydroxy-2,3,6-trimethylphenyl)methane, 1,1-Bis(4-hydroxy-3,5-dimethylphenyl)-1-phenylethane, 2,2-Bis(4-hydroxy-3,5-dimethylphenyl)butane, Bis(4-hydroxy-3,5-dimethylphenyl)diphenylmethane, 2,2-Bis(4-hydroxy-3-isopropylphenyl)propane, 1,1-Bis(4-hydroxy-3,5-dimethylphenyl)ethane, 1,3-Bis(2-(4-hydroxy-3,5-dimethylphenyl)-2-propyl)benzene, 1,4-Bis(2-(4-hydroxy-3,5-dimethylphenyl)-2-propyl)benzene, 1,1-Bis(4-hydroxy-3,5-dimethylphenyl)-3,3,5-trimethylcyclohexane, Examples include 1,1-bis(4-hydroxy-3,5-dimethylphenyl)cyclohexane, 2,2-bis(2-hydroxy-5-biphenylyl)propane, 2,2-bis(4-hydroxy-3-cyclohexyl-6-methylphenyl)propane, etc.

[0065] As divalent carboxylic acid halides, for example, terephthalic acid halide, isophthalic acid halide, orthophthalic acid halide, diphenic acid halide, biphenyl-4,4'-dicarboxylic acid halide, 1,4-naphthalenedicarboxylic acid halide, 2,3-naphthalenedicarboxylic acid halide, 2,6-naphthalenedicarboxylic acid halide, 2,7-naphthalenedicarboxylic acid halide, 1,8-naphthalenedicarboxylic acid halide, 1,5-naphthalenedicarboxylic acid halide, diphenyl ether-2,2'-dicarboxylic acid halide, diphenyl ether-2,3'-dicarboxylic acid halide, diphenyl ether-2,4'-dicarboxylic acid halide, diphenyl ether-3,3'-dicarboxylic acid halide, Examples include diphenyl ether-3,4'-dicarboxylic acid halide, diphenyl ether-4,4'-dicarboxylic acid halide, 1,4-cyclohexanedicarboxylic acid halide, 1,3-cyclohexanedicarboxylic acid halide, etc.

[0066] As a terminal structure of the above-mentioned curable resin, at least one reactive group selected from the group consisting of (meth)acryloyloxy groups, vinylbenzyl ether groups, and allyl ether groups may be used to introduce these reactive groups, and a reactive group introducing agent may be used. As the reactive group introducing agent, for example, (meth)acrylic anhydride, (meth)acrylic acid chloride, chloromethylstyrene, chlorostyrene, allyl chloride, and allyl bromide may be reacted. In particular, it is more preferable to use (meth)acrylic anhydride or (meth)acrylic acid chloride, as the curable product obtained by introducing a methacryloyloxy group as a terminal structure has a low dielectric loss tangent. By reacting these, reactive groups can be introduced into the curable resin, and furthermore, thermosetting properties such as low dielectric constant and low dielectric loss tangent are obtained, which is a desirable embodiment.

[0067] Examples of the above (meth)acrylic acid include acrylic anhydride and methacrylic anhydride. Examples of the above (meth)acrylic acid chloride include methacrylic acid chloride and acrylic acid chloride. In addition, examples of chloromethylstyrene include p-chloromethylstyrene and m-chloromethylstyrene, and examples of chlorostyrene include p-chlorostyrene and m-chlorostyrene. In addition, examples of allyl chloride include 3-chloro-1-propene, and examples of allyl bromide include 3-bromo-1-propene. These may be used individually or in combination. Among these, it is particularly preferable to use methacrylic anhydride or methacrylic acid chloride, which yield a cured product with a lower dielectric loss tangent.

[0068] <Melting Polymerization Method>

[0069] Examples of the above melt polymerization method include a method of acetylating the divalent phenol of the raw material and then deacetylating the acetylated divalent phenol with a divalent carboxylic acid, or a method of transesterifying the divalent phenol with a carbonate ester.

[0070] In the acetylation reaction, an aromatic dicarboxylic acid component, a divalent phenol component, and acetic anhydride are introduced into a reaction vessel. Then, nitrogen purging is performed, and the mixture is stirred under an inert atmosphere at a temperature of 100 to 240°C, preferably 120 to 180°C, for 5 minutes to 8 hours, preferably 30 minutes to 5 hours, under atmospheric pressure or pressurization. It is preferable that the molar ratio of acetic anhydride to the hydroxyl group of the divalent phenol component be 1.00 to 1.20.

[0071] Deacetic acid polymerization is a reaction in which acetylated divalent phenol reacts with a divalent carboxylic acid to perform polycondensation. In the deacetic acid polymerization reaction, the reaction is maintained for at least 30 minutes at a temperature of 240°C or higher, preferably 260°C or higher, more preferably 280°C or higher, and at a reduced pressure of 500 Pa or lower, preferably 260 Pa or lower, more preferably 130 Pa or lower, while stirring. If the temperature is below 240°C, if the reduced pressure exceeds 500 Pa, or if the maintenance time is less than 30 minutes, the deacetic acid reaction becomes insufficient, which may result in a higher amount of acetic acid in the obtained polyarylate resin, a longer overall polymerization time, or a deterioration in the polymer color tone.

[0072] In the acetylation reaction and deacetic acid polymerization reaction, it is preferable to use a catalyst as needed. Examples of catalysts include organic titanate compounds such as tetrabutyl titanate; alkali metal salts such as zinc acetate; alkali earth metal salts such as potassium acetate; antimony trioxide; organic tin compounds such as hydroxybutyltin oxide and tin octylate; and heterocyclic compounds such as N-methylimidazole. The amount of catalyst added is typically 1.0 mol% or less, more preferably 0.5 mol% or less, and even more preferably 0.2 mol% or less, relative to the total monomer components of the polyarylate resin obtained.

[0073] In the ester exchange reaction, the reaction is carried out at a temperature of 120 to 260°C, preferably 160 to 200°C, for 0.1 to 5 hours, preferably 0.5 to 6 hours, at a pressure of atmospheric pressure to 1 Torr.

[0074] As a catalyst for the transesterification reaction, salts of zinc, tin, zirconium, and lead are preferably used, and these can be used alone or in combination. Specifically, as a transesterification catalyst, zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, tin chloride (II), tin chloride (IV), tin acetate (II), tin acetate (IV), dibutyltin dilaurate, dibutyltin oxide, dibutyltin dimethoxide, zirconium acetylacetonate, zirconium oxyacetate, zirconium tetrabutoxide, lead acetate (II), lead acetate (IV), etc. are used. These catalysts are used in a ratio of 0.000001 to 0.1 mol%, preferably 0.00001 to 0.01 mol%, per 1 mol of total divalent phenol.

[0075] As for the divalent phenol, the divalent phenol from the interfacial polymerization method described above can be used in the same way.

[0076] As divalent carboxylic acids, for example, terephthalic acid, isophthalic acid, orthophthalic acid, diphenic acid, biphenyl-4,4'-dicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, diphenyl ether-2,2'-dicarboxylic acid, diphenyl ether-2,3'-dicarboxylic acid, diphenyl ether-2,4'-dicarboxylic acid, diphenyl ether-3,3'-dicarboxylic acid, diphenyl ether-3,4'-dicarboxylic acid, diphenyl ether-4,4'-dicarboxylic acid, Examples include 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, etc.

[0077] Examples of carbonate esters include diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl)carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis(diphenyl)carbonate, diethyl carbonate, dimethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, etc.

[0078] As a terminal structure of the above-mentioned curable resin, at least one reactive group selected from the group consisting of (meth)acryloyloxy groups, vinylbenzyl ether groups, and allyl ether groups may be used to introduce these reactive groups, and as the reactive group introducing agent, the reactive group introducing agent in the interfacial polymerization method described above may be used in the same way.

[0079] After the above reaction process, the obtained polymer is washed (washing process). The washing process consists of solvent washing and water washing. For solvent washing, ketone-based solvents, ester-based solvents, ether-based solvents, amide-based solvents, alcohols, and mixtures thereof may be used. The washing process may be performed multiple times, or multiple times with different types of washing solutions. After washing, the polymer is dried (drying process).

[0080] Methods for simultaneously producing a curable resin (A) and a curable compound (B) include adjusting the reaction process or adjusting the purification process. Methods for adjusting the reaction process include, for example, adjusting the reaction temperature, reaction time, and the amount of polymerization catalyst added to suppress the increase in the overall high molecular weight of the resin. By doing so, it becomes possible to retain unreacted monomers (curable compound (B)) within the curable resin (A). Additionally, methods for adjusting the purification process include pure washing of the polymer or vacuum distillation.

[0081] <Curing compound (B)>

[0082] The method for manufacturing the curable compound (B) of the present invention is not particularly limited and can be manufactured by appropriately using conventionally known methods. As an example of one embodiment, a method may be used in which a solution (organic phase) in which a reactive group-introducing agent is dissolved in an organic solvent that is incompatible with water is mixed with an alkaline aqueous solution (aqueous phase) containing a divalent phenol and an antioxidant, and a reaction is carried out while stirring at a temperature of 50°C or lower for 1 to 8 hours.

[0083] As for the divalent phenol, the divalent phenol in the method for manufacturing the curable resin (A) described above can be used in the same way.

[0084] As the reactive group of the curable compound (B), a (meth)acryloyloxy group, a vinylbenzyl ether group, or an allyl ether group may be represented, but a reactive group introducing agent may be used to introduce these reactive groups, and as the reactive group introducing agent, the reactive group introducing agent in the method for manufacturing the curable resin (A) described above may be used in the same way. Furthermore, the reactive group introduced into the curable compound (B) is preferably the same as that of the curable resin (A) in terms of the curability of the cured product.

[0085] As an antioxidant, the antioxidant from the interfacial polymerization method described above can be used in the same way.

[0086] Other Suzy etc.

[0087] In the curable resin composition of the present invention, in addition to the curable resin (A) and the curable compound (B), other resins, curing agents, curing accelerators, etc. may be used without particular limitation within a range that does not impair the purpose of the present invention. As will be described later, the curable resin composition may be used to obtain a cured product by heating, etc. without incorporating a curing agent, but, for example, when incorporating other resins, etc., a curing agent or a curing accelerator may be incorporated.

[0088] In addition, the curable resin composition of the present invention includes the curable resin (A), but when an allyl ether group is introduced as a reactive group of the terminal structure in the curable resin (A), unlike a (meth)acryloyloxy group or a vinylbenzyl ether group, the reactive group cannot undergo homopolymerization (crosslinking / self-curing) (a cured product cannot be obtained alone), so in the case of the allyl ether group, it is necessary to use a curing agent or a curing accelerator.

[0089] <Guitar Suzy>

[0090] As other resins mentioned above, examples include styrene-butadiene resin, styrene-butadiene-styrene block resin, styrene-isoprene-styrene resin, styrene-maleic anhydride resin, acrylonitrile-butadiene resin, polybutadiene resin or their hydrogenated resins, acrylic resin, and silicone resin. By using the above thermoplastic resin, properties attributable to the resin can be imparted to the cured product, which is a preferred embodiment. For example, performance that can be imparted may include moldability, high-frequency characteristics, conductor adhesion, solder heat resistance, adjustment of glass transition temperature, coefficient of thermal expansion, and smear removal properties.

[0091] Hardener

[0092] Examples of the above-mentioned curing agents include amine compounds, amide compounds, acid anhydride compounds, phenol compounds, cyanate ester compounds, etc. These curing agents may be used alone or in combination of two or more types.

[0093] Hardening Accelerator

[0094] Various types of curing accelerators may be used, but examples include phosphorus-based compounds, tertiary amines, imidazoles, metal salts of organic acids, Lewis acids, and amine complexes. In particular, when used as a semiconductor encapsulation material, phosphorus-based compounds such as triphenylphosphine or imidazoles are preferred due to their excellent curability, heat resistance, electrical properties, and moisture resistance reliability. These curing accelerators may be used alone or in combination of two or more types.

[0095] Flame retardant

[0096] In the curable resin composition of the present invention, a flame retardant may be added as needed to provide flame retardancy, and among these, it is preferable to add a non-halogen flame retardant that substantially does not contain halogen atoms. Examples of the non-halogen flame retardants include phosphorus-based flame retardants, nitrogen-based flame retardants, silicone-based flame retardants, inorganic flame retardants, organometallic salt-based flame retardants, etc., and these flame retardants may be used alone or in combination of two or more types.

[0097] Filler

[0098] In the curable resin composition of the present invention, an inorganic filler may be incorporated as needed. Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide, etc. When the amount of the inorganic filler incorporated is particularly large, it is preferable to use fused silica. The fused silica may be used in either a crushed or spherical form, but in order to increase the amount of fused silica incorporated and to suppress the increase in the melt viscosity of the molding material, it is preferable to mainly use spherical silica. To further increase the amount of spherical silica incorporated, it is preferable to appropriately adjust the particle size distribution of the spherical silica. In addition, when the curable resin composition is used for applications such as conductive pastes described below, conductive fillers such as silver powder or copper powder may be used.

[0099] Other Mixtures

[0100] The curable resin composition of the present invention may, if necessary, add various compounding agents such as silane coupling agents, release agents, pigments, and emulsifiers.

[0101] <hardened material>

[0102] The present invention relates to a cured product obtained by curing a curable resin composition. The curable resin composition of the present invention is obtained by uniformly mixing each component, such as the flame retardant described above, depending on the purpose, and can be easily made into a cured product by a method similar to conventionally known methods. Examples of the cured products include laminates, molds, adhesive layers, coatings, films, etc.

[0103] Examples of the above curing reactions include thermal curing and UV curing reactions. Among these, thermal curing reactions can be easily carried out even without a catalyst, but if you want to accelerate the reaction, it is effective to add polymerization initiators such as organic peroxides and azo compounds, or basic catalysts such as phosphine-based compounds and tertiary amines. Examples include benzoyl peroxide, dicumyl peroxide, azobisisobutyronitrile, triphenylphosphine, triethylamine, imidazoles, etc.

[0104] <Uses>

[0105] The cured product obtained by the curable resin composition of the present invention is suitable for use in heat-resistant materials or electronic materials due to its excellent heat resistance and low dielectric properties. In particular, it is suitable for use in prepregs, circuit boards, semiconductor encapsulants, semiconductor devices, build-up films, build-up substrates, adhesives, and resist materials. Furthermore, it is suitable for use in matrix resins of fiber-reinforced resins, making it particularly suitable as a high-heat-resistant prepreg. The curable resin composition of the present invention can be made into a paint due to its excellent solubility in various solvents. The heat-resistant materials or electronic materials obtained in this way can be suitable for various applications, and examples include industrial machine parts, general machine parts, parts for automobiles, railways, vehicles, etc., aerospace-related parts, electronic and electrical components, building materials, containers and packaging materials, household goods, sports and leisure goods, and casing materials for wind power generation, but are not limited thereto.

[0106] Hereinafter, a representative product manufactured using the curable resin composition of the present invention is described as an example.

[0107] Varnish

[0108] The present invention relates to a varnish obtained by diluting the above-mentioned curable resin composition with an organic solvent. As a method for preparing the above-mentioned varnish, a known method may be used, and the above-mentioned curable resin composition may be dissolved (diluted) in an organic solvent to form a resin varnish. The curable resin composition of the present invention has high solvent solubility and can be used appropriately.

[0109] As a solvent, preferably at least one solvent selected from ketone-based solvents, ester-based solvents, ether-based solvents, amide-based solvents, and alcohols, more preferably selected from toluene, methyl ethyl ketone, and cyclohexanone.

[0110] Prepreg

[0111] The present invention relates to a prepreg having a reinforcing substrate and a semi-cured varnish impregnated in the reinforcing substrate. A prepreg can be formed by impregnating the reinforcing substrate with the varnish (resin varnish) and heat-treating the reinforcing substrate to semi-cure (or uncure) the curable resin composition. The conditions for the heat treatment are appropriately selected depending on the type and amount of organic solvent, catalyst, and various additives used, but are typically carried out under conditions such as 3 minutes to 30 minutes at a temperature of 80 to 220°C.

[0112] As the above organic solvent, for example, among toluene, xylene, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, methyl ethyl ketone (MEK), methyl isobutyl ketone, dioxane, tetrahydrofuran, etc., it may be used alone or as a mixture of two or more solvents.

[0113] As a reinforcing material impregnated with the above varnish (resin varnish), it may be a woven or nonwoven fabric made of inorganic fibers such as glass fibers, polyester fibers, and polyamide fibers, or organic fibers, or a mat, paper, etc., and these may be used alone or in combination. The mass ratio of the curable resin composition and the reinforcing material is not particularly limited, but it is generally preferable to prepare the curable resin composition (the resin content therein) in the prepreg to be 20 to 60 mass%.

[0114] Laminated structure

[0115] As a laminate, it is preferable to include a cured product obtained by curing the above-mentioned curable resin composition. The laminate formed by a substrate and a layer (cured product layer) containing the above-mentioned cured product is preferred because it has a low dielectric constant, a low dielectric loss tangent, and high heat resistance, and can therefore be used in high-frequency compatible printed circuit boards, etc.

[0116] As a substrate used in the above laminate, inorganic materials such as metal or glass, or organic materials such as plastic or wood, may be appropriately used depending on the application, for example, glass fiber: E glass, D glass, S glass, Q glass, spherical glass, NE glass, L glass, T glass, inorganic fiber; quartz, fully aromatic polyamide; Examples include polyparaphenylene terephthalamide (Kevlar (trademark), manufactured by DuPont, Ltd.), copolyparaphenylene·3,4'oxydiphenylene·terephthalamide (Technora (registered trademark), manufactured by Teijin Techno Products Co., Ltd.), polyester: 2,6-hydroxynaphthoic acid·parahydroxybenzoic acid (Vectran (registered trademark), manufactured by Kuraray Co., Ltd.), Zexion (registered trademark, manufactured by KB Seiren), organic fiber: polyparaphenylenebenzoxazole (Xylon (registered trademark), manufactured by Toyobo Seki Co., Ltd.), polyimide, etc.

[0117] The shape of the above laminate may be flat, sheet-like, or have a three-dimensional structure, or be a solid shape. It may be any shape according to the purpose, such as having curvature on the entire surface or in part. In addition, there are no restrictions on the hardness, thickness, etc. of the substrate. Furthermore, the above cured material may be used as a substrate, and the cured material may be further laminated.

[0118] When the above laminate is used on a circuit board or a semiconductor package substrate, it is preferable to laminate a metal foil, and examples of metal foils include copper foil, aluminum foil, gold foil, silver foil, etc., and it is preferable to use copper foil because of its good processability.

[0119] In the above laminate, the layer containing the cured material (cured material layer) may be formed by direct coating or molding on the substrate, or it may be laminated from a pre-molded layer. In the case of direct coating, there are no particular limitations on the coating method, and examples include spray method, spin coating method, dipping method, roll coating method, blade coating method, doctor roll method, doctor blade method, curtain coating method, slit coating method, screen printing method, inkjet method, etc. In the case of direct molding, examples include in-mold molding, insert molding, vacuum forming, extrusion laminate molding, press molding, etc.

[0120] In addition, regarding the above-mentioned cured material, it may be laminated by coating and curing a precursor that can serve as the substrate, or it may be cured after bonding the precursor that can serve as the substrate or the curable resin composition of the present invention in an uncured or semi-cured state. There are no particular limitations on the precursor that can serve as the substrate, and various curable resin compositions may be used.

[0121] Circuit board

[0122] The present invention relates to a circuit board containing the prepreg. Specifically, a method for obtaining a circuit board from the curable resin composition of the present invention may include a method of laminating the prepreg according to a conventional method, stacking a copper foil, and heat-pressing molding at 170 to 300°C for 10 minutes to 3 hours under a pressure of 1 to 10 MPa.

[0123] Semiconductor packaging materials

[0124] As a semiconductor encapsulant, it is preferable to contain the above-mentioned curable resin composition. Specifically, as a method for obtaining a semiconductor encapsulant from the curable resin composition of the present invention, a method may be used in which a compounding agent, such as an optional component, a curing accelerator, and an inorganic filler, is additionally added to the above-mentioned curable resin composition and sufficiently melt-mixed until uniform using an extruder, kneader, roll, etc. At that time, fused silica is typically used as the inorganic filler; however, when used as a high thermal conductivity semiconductor encapsulant for power transistors or power ICs, it is preferable to use a highly filled material such as crystalline silica, alumina, or silicon nitride, which has a higher thermal conductivity than fused silica, or fused silica, crystalline silica, alumina, silicon nitride, etc. The filler content is preferably used in the range of 30 to 95 parts by mass per 100 parts by mass of the curable resin composition, and among these, in order to improve flame retardancy, moisture resistance, and solder crack resistance and to reduce the coefficient of linear expansion, 70 parts by mass or more is more preferable, and 80 parts by mass or more is more preferable.

[0125] Semiconductor Device

[0126] As a semiconductor device, it is preferable to include a cured product obtained by heat-curing the semiconductor encapsulant. Specifically, as a semiconductor package molding method for obtaining a semiconductor device from the curable resin composition of the present invention, the semiconductor encapsulant may be molded using a mold, a transfer molding machine, an injection molding machine, etc., and heat-cured at 50 to 250°C for 2 to 10 hours.

[0127] <Build-up Board>

[0128] A method for obtaining a build-up substrate from the curable resin composition of the present invention may be a method that passes through steps 1 to 3. In step 1, first, the curable resin composition, which is appropriately mixed with rubber, filler, etc., is applied to a circuit board having a circuit formed thereon using a spray coating method, a curtain coating method, etc., and then cured. In step 2, if necessary, holes such as predetermined through-holes are made in the circuit board coated with the curable resin composition, then treated with a harmonizing agent, and the surface is washed with hot water to form irregularities on the substrate, and then a metal such as copper is plated. In step 3, the operations of steps 1 and 2 are repeated sequentially as desired, and a resin insulating layer and a conductor layer of a predetermined circuit pattern are alternately built up to form a build-up substrate. Furthermore, in the above process, the making of through-holes may be performed after the formation of the outermost resin insulating layer. In addition, the build-up substrate of the present invention can be manufactured by forming a harmonized surface by heat-pressing a resin-attached copper foil, in which the resin composition is semi-cured on a copper foil, onto a wiring board having a circuit formed thereon at 170 to 300°C, thereby omitting the plating process.

[0129] Build-up Film

[0130] As a build-up film, it is preferable to contain the above-mentioned curable resin compound. As a method for obtaining a build-up film from the curable resin composition of the present invention, for example, a method of applying the curable resin composition onto a support film and then drying it to form a resin composition layer on the support film may be cited. When the curable resin composition of the present invention is used in a build-up film, it is important that the film softens under the temperature conditions of lamination in the vacuum lamination method (typically 70 to 140°C) and exhibits fluidity (resin flow) that allows for resin filling within via holes or through holes present in the circuit board simultaneously with lamination of the circuit board, and it is preferable to formulate each of the above components to exhibit such characteristics.

[0131] Here, the diameter of the through-hole of the circuit board is typically 0.1 to 0.5 mm and the depth is typically 0.1 to 1.2 mm, and it is generally desirable to enable resin filling within this range. In addition, when laminating both sides of the circuit board, it is desirable to fill about half of the through-hole.

[0132] A specific method for manufacturing the above-mentioned build-up film may be to prepare a resin composition that has been varnished by mixing an organic solvent, apply the varnished resin composition to the surface of a support film (Y), and further dry the organic solvent by heating or hot air spraying to form a resin composition layer (X).

[0133] As for the organic solvent used here, it is preferable to use, for example, ketones such as acetone, methyl ethyl ketone, and cyclohexanone; acetic acid esters 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, and N-methylpyrrolidone; and it is also preferable to use them in a ratio such that the non-volatile content is 30 to 60 mass%.

[0134] In addition, the thickness of the resin composition layer (X) formed needs to be greater than or equal to the thickness of the conductor layer. Since the thickness of the conductor layer of a circuit board is typically in the range of 5 to 70 μm, it is preferable that the thickness of the resin composition layer (X) be 10 to 100 μm. Furthermore, the resin composition layer (X) in the present invention may be protected by a protective film described later. By protecting it with a protective film, the adhesion of foreign substances or scratches to the surface of the resin composition layer can be prevented.

[0135] Examples of the above support film and protective film include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride; polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate; polycarbonates; polyimides; and also metal foils such as release paper, copper foil, and aluminum foil. In addition, the above support film and protective film may undergo a release treatment in addition to matte treatment and corona treatment. The thickness of the support film is not particularly limited, but is typically 10 to 150 μm, and preferably used in the range of 25 to 50 μm. In addition, it is preferable that the thickness of the protective film be 1 to 40 μm.

[0136] The above support film (Y) is peeled off after being laminated to a circuit board or after forming an insulating layer by heat curing. If the support film (Y) is peeled off after the resin composition layer constituting the build-up film has been heat-cured, the adhesion of foreign substances during the curing process can be prevented. When peeling off after curing, the support film is typically subjected to a release treatment in advance.

[0137] In addition, a multilayer printed circuit board can be manufactured from the build-up film obtained as described above. For example, if the resin composition layer (X) is protected by a protective film, the film is peeled off, and then the layer (X) of the resin composition is laminated onto one or both sides of the circuit board, for example, by a vacuum lamination method, so that it comes into direct contact with the circuit board. The lamination method may be a batch method or a continuous method using rolls. Additionally, if necessary, the build-up film and the circuit board may be preheated before lamination. Regarding the lamination conditions, it is preferable to set the compression temperature (lamination temperature) to 70 to 140°C and the compression pressure to 1 to 11 kgf / ㎠ (9.8 × 10⁻⁶). 4 ~107.9×10 4 It is preferable to use N / m² and to laminate under reduced pressure of 20 mmHg (26.7 hPa) or less.

[0138] Challenge Paste

[0139] As a method for obtaining a conductive paste from the curable resin composition of the present invention, for example, a method of dispersing conductive particles in said composition may be used. Depending on the type of conductive particles used, the conductive paste may be a paste resin composition for circuit connection or an anisotropic conductive adhesive.

[0140] [Example]

[0141] The present invention will be specifically explained below through examples and comparative examples, where "parts" and "%" are based on mass unless otherwise noted. Additionally, a curable resin, a curable compound, and a cured product obtained using these were prepared under the conditions shown below, and further, the obtained cured product was measured and evaluated under the following conditions.

[0142] <GPC 측정(경화성 수지의 중량 평균 분자량(Mw)의 평가)>

[0143] Measurements were taken using the following measuring device and measurement conditions, and the weight average molecular weight (Mw) and area % of the curable resin obtained by the synthesis method shown below were calculated.

[0144] Measuring device: "HLC-8320 GPC" manufactured by Doso Kabushiki Kaisha

[0145] Column: Toso Kabushiki Kaisha Guard Column "HXL-L" + Toso Kabushiki Kaisha "TSK-GEL G2000HXL" + Toso Kabushiki Kaisha "TSK-GEL G2000HXL" + Toso Kabushiki Kaisha "TSK-GEL G3000HXL" + Toso Kabushiki Kaisha "TSK-GEL G4000HXL"

[0146] Detector: RI (Refractor)

[0147] Data processing: "GPC Workstation EcoSEC-WorkStation" manufactured by Doso Kabushiki Kaisha

[0148] Measurement conditions: Column temperature 40℃

[0149] Developing solvent tetrahydrofuran

[0150] Flow rate 1.0 ml / min

[0151] Standard: In accordance with the measurement manual of the above "GPC Workstation EcoSEC-WorkStation," the following monodisperse polystyrene with a known molecular weight was used.

[0152] (Polystyrene used)

[0153] "A-500" manufactured by Toso Kabushiki Kaisha

[0154] "A-1000" manufactured by Doso Kabushiki Kaisha

[0155] "A-2500" manufactured by Dosokabushiki Kaisha

[0156] "A-5000" manufactured by Toso Kabushiki Kaisha

[0157] "F-1" manufactured by Doso Kabushiki Kaisha

[0158] "F-2" manufactured by Doso Kabushiki Kaisha

[0159] "F-4" manufactured by Doso Kabushiki Kaisha

[0160] "F-10" manufactured by Doso Kabushiki Kaisha

[0161] "F-20" manufactured by Toso Kabushiki Kaisha

[0162] "F-40" manufactured by Toso Kabushiki Kaisha

[0163] "F-80" manufactured by Toso Kabushiki Kaisha

[0164] "F-128" manufactured by Toso Kabushiki Kaisha

[0165] Sample: A tetrahydrofuran solution of 1.0 mass% in terms of solid content of the curable resin obtained in the examples and comparative examples, filtered through a microfilter (50 μl).

[0166] (Synthesized Example 1)

[0167] In a reaction vessel equipped with a stirring device, 113.8 parts by mass of 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 64.0 parts by mass of sodium hydroxide, 0.25 parts by mass of tri-n-butylbenzylammonium chloride, and 2,000 parts by mass of pure water were added and dissolved to prepare an aqueous phase. In 1,500 parts by mass of methylene chloride, 30.5 parts by mass of terephthalic acid dichloride, 30.5 parts by mass of isophthalic acid dichloride, and 20.9 parts by mass of methacrylic acid chloride were dissolved to prepare an organic phase.

[0168] The aqueous phase was stirred in advance, the organic phase was added to the aqueous phase under strong stirring, and the reaction was carried out at 20°C for 5 hours. Afterward, stirring was stopped, the aqueous phase and the organic phase were separated, and the organic phase was washed 10 times with pure water. Afterward, methylene chloride was distilled from the organic phase under reduced pressure using an evaporator, and the polymer obtained by the reaction was dried. The solid was washed twice with a mixture of 1 L of methanol and 200 ml of tetrahydrofuran, then washed twice with 1 L of hot water, and then dried under reduced pressure at 80°C to obtain a curable resin (A1) having the following repeating unit, a methacryloyloxy group at the end, a weight average molecular weight of 3300, and 0 area% of 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propanedimethacrylate.

[0169]

[0170] (Synthesized Example 2)

[0171] In a reaction vessel equipped with a stirring device, 113.8 parts by mass of 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 64.0 parts by mass of sodium hydroxide, 0.25 parts by mass of tri-n-butylbenzylammonium chloride, and 2,000 parts by mass of pure water were added and dissolved to prepare an aqueous phase. In 1,500 parts by mass of methylene chloride, 30.5 parts by mass of terephthalic acid dichloride, 30.5 parts by mass of isophthalic acid dichloride, and 20.9 parts by mass of methacrylic acid chloride were dissolved to prepare an organic phase.

[0172] The aqueous phase was stirred in advance, the organic phase was added to the aqueous phase under strong stirring, and the reaction was carried out at 20°C for 5 hours. Afterward, stirring was stopped, the aqueous phase and the organic phase were separated, and the organic phase was washed 10 times with pure water. Afterward, methylene chloride was distilled from the organic phase under reduced pressure using an evaporator, and the polymer obtained by the reaction was dried. The obtained polymer was dried under reduced pressure to obtain a curable resin (A2) having the following repeating units, a methacryloyloxy group at the end, a weight average molecular weight of 3100, and 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propanedimethacrylate of 7 area%.

[0173]

[0174] (Synthesized Example 3)

[0175] Synthesis was carried out by the same method as in Synthesis Example 2, except that the 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane in Synthesis Example 2 was changed to 157.0 parts by mass of 2,2-bis(4-hydroxy-3-cyclohexyl-6-methylphenyl)propane, and a curable resin (A3) having the following repeating unit, a methacryloyloxy group at the end, a weight average molecular weight of 3200, and 7 area% of 2,2-bis(4-hydroxy-3-cyclohexyl-6-methylphenyl)propane dimethacrylate was obtained.

[0176]

[0177] (Synthesized Example 4)

[0178] Synthesis was carried out by the same method as in Synthesis Example 2, except that the terephthalic acid dichloride and isophthalic acid dichloride in Synthesis Example 2 were changed to 62.7 parts by mass of 1,4-cyclohexanedicarboxylic acid dichloride, and a curable resin (A4) having the following repeating unit, a methacryloyloxy group at the end, a weight average molecular weight of 3100, and 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propanedimethacrylate 8 area% was obtained.

[0179]

[0180] (Synthesized Example 5)

[0181] Synthesis was carried out by the same method as in Synthesis Example 2, except that the 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane in Example 2 above was changed to 91.3 parts by mass of 2,2-bis(4-hydroxyphenyl)propane, and a curable resin (A5) having the following repeating unit, a methacryloyloxy group at the end, a weight average molecular weight of 3000, and 9 area% of 2,2-bis(4-hydroxyphenyl)propane dimethacrylate was obtained.

[0182]

[0183] (Synthesized Example 6)

[0184] Synthesis was carried out by the same method as in Synthesis Example 2, except that the chloride methacrylate in Synthesis Example 2 was changed to 30.5 parts by mass of chloromethylstyrene, and a curable resin (A6) having the following repeating unit, a vinylbenzyl ether group at the end, a weight average molecular weight of 3100, and 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propanedimethacrylate of 8 area% was obtained.

[0185]

[0186] (Synthesized Example 7)

[0187] Synthesis was carried out by the same method as in Synthesis Example 2, except that the chloride of methacrylate in Synthesis Example 2 was changed to 15.3 parts by mass of allyl chloride, and a curable resin (A7) having the following repeating unit, having an allyl ether group at the end, a weight average molecular weight of 3100, and 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propanedimethacrylate of 8 area% was obtained.

[0188]

[0189] (Synthesized Example 8)

[0190] 113.8 parts by weight of 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 64.2 parts by weight of diphenyl carbonate, and 0.01 parts by weight of tetramethylammonium hydroxide were added to a reaction vessel equipped with a stirring device, a distillation column, and a vacuum device. After purging with nitrogen, the mixture was dissolved at 140°C. After stirring for 30 minutes, the internal temperature was raised to 180°C and the reaction was carried out for 30 minutes at an internal pressure of 100 mmHg, while the resulting phenol was removed by distillation. Subsequently, the internal temperature was raised to 200°C while the vacuum was gradually reduced, and the reaction was carried out for 30 minutes at 50 mmHg while removing the phenol by distillation. Additionally, the temperature was gradually raised to 220°C and the vacuum was reduced to 1 mmHg, and the reaction was carried out for 30 minutes under the same temperature and pressure conditions. The obtained solid was washed with methanol and dried under vacuum to obtain an intermediate compound.

[0191] 20 g of toluene and 22 g of the intermediate compound were mixed in a 200 mL flask equipped with a thermometer, a condenser, and a stirrer, and heated to about 85°C. 0.19 g of dimethylaminopyridine was added. When it was thought that all the solid had dissolved, 30.6 g of methacrylic anhydride was slowly added. The resulting solution was maintained at 85°C for 3 hours while continuously mixing. Next, the solution was cooled to room temperature and dropped into methanol in a 1 L beaker, which was vigorously stirred with a magnetic stirrer. The precipitate was washed twice with a mixture of 1 L of methanol and 200 ml of tetrahydrofuran, then washed twice with 1 L of hot water, and then dried under reduced pressure at 80°C to obtain a curable resin (A8) having the following repeating unit, a methacryloyloxy group at the end, a weight average molecular weight of 2700, and 0 area% of 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propanedimethacrylate.

[0192]

[0193] (Synthesized Example 9)

[0194] 113.8 parts by mass of 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 66.7 parts by mass of 48% sodium hydroxide, and 200 parts by mass of xylene were added to a reaction vessel equipped with a Dean-Stark trap, a condenser, a nitrogen inlet, a stirrer, and a thermometer, and heated to 140°C to collect an azeotropic mixture of water and xylene. After 4 hours, when it was completely dehydrated, the temperature of the reaction mixture was raised to 200°C, and the xylene was removed by distillation. Subsequently, 200 parts by mass of N-methyl-2-pyrrolidone, 70.8 parts by mass of 1,4-dibromobenzene, and 0.396 parts by mass of copper(I) chloride were added, and the mixture was stirred at 200°C for 20 hours. The reaction mixture was cooled to 60°C, 100 parts by mass of N-methyl-2-pyrrolidone, 20.2 parts by mass of triethylamine, and 20.9 parts by mass of chloride of methacrylate were added, and the mixture was stirred at 60°C for 10 hours. Next, the reaction mixture was gradually injected into a mixture of 2 L of methanol and 100 ml of acetic acid stirred at high speed to obtain a precipitate. The precipitate was washed twice with a mixture of 1 L of methanol and 200 ml of tetrahydrofuran, then washed twice with 1 L of hot water, and then dried under reduced pressure at 80°C to obtain a curable resin (A9) having the following repeating units, a methacryloyloxy group at the end, a weight average molecular weight of 2700, and 0 area% of 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propanedimethacrylate.

[0195]

[0196] (Synthesized Example 10)

[0197] In a reaction vessel equipped with a stirring device, 113.8 parts by mass of 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 64.0 parts by mass of sodium hydroxide, 0.25 parts by mass of tri-n-butylbenzylammonium chloride, and 2,000 parts by mass of pure water were added and dissolved to prepare an aqueous phase. 125.6 parts by mass of chloride methacrylate were dissolved in 1,500 parts by mass of methylene chloride to prepare an organic phase.

[0198] The aqueous phase was stirred in advance, the organic phase was added to the aqueous phase under strong stirring, and the reaction was carried out at 20°C for 5 hours. Afterward, stirring was stopped, the aqueous phase and the organic phase were separated, and the organic phase was washed 10 times with pure water. Afterward, methylene chloride was distilled from the organic phase under reduced pressure using an evaporator, and the compound obtained by the reaction was dried. The obtained compound was dried under reduced pressure to obtain a curable compound (B1) having the following structure.

[0199]

[0200] <Preparation of Curable Resin Composition>

[0201] Using the curable resin or curable compound obtained in the above synthesis example, a curable resin composition with the formulation contents (raw materials, formulation amounts) described in Tables 1 and 2 below, and a sample for evaluation (resin film (cured product)) was prepared based on the conditions (temperature, time, etc.) shown below, and these were evaluated as examples and comparative examples.

[0202] Production of Resin Film (Curing Material)

[0203] The above curable resin composition was placed in a 5cm square mold, fitted with a stainless steel plate, and set with a vacuum press. It was pressurized to 1.5 MPa under atmospheric pressure and room temperature. Next, the pressure was reduced to 10 torr, and then heated over 30 minutes to a temperature 50°C higher than the heat curing temperature. After standing for 2 hours, it was slowly cooled to room temperature to obtain a uniform resin film (cured product) with an average film thickness of 100 μm.

[0204] <Evaluation of Genetic Traits>

[0205] Regarding the dielectric properties in the in-plane direction of the obtained resin film (cured product), the permittivity and dielectric loss tangent at a frequency of 10 GHz were measured using the split post dielectric resonance technique with Keysight Technologies' network analyzer N5247A.

[0206] As the above dielectric loss tangent, 10.0 × 10-3 If it is less than or equal to, there are no practical problems, and preferably, 3.0×10 -3 Less than, and more preferably 2.5×10 -3 It is as follows.

[0207] In addition, regarding the permittivity above, if it is 3 or less, there is no practical problem, preferably it is 2.7 or less, and more preferably 2.5 or less.

[0208] <Evaluation of Heat Resistance (Glass Transition Temperature)>

[0209] For the obtained resin film (cured product), after observing the exothermic peak temperature (thermal curing temperature) when measured from 30°C under a heating condition of 20°C / min using a PerkinElmer DSC device (Pyris Diamond), the temperature was maintained at a temperature 50°C higher than that for 30 minutes. Subsequently, the sample was cooled to 30°C under a cooling condition of 20°C / min, and then further heated again under a heating condition of 20°C / min to measure the glass transition point temperature (Tg) (°C) of the resin film (cured product).

[0210] As for the above glass transition point temperature (Tg), there is no practical problem if it is 100°C or higher, preferably 150°C or higher, more preferably 190°C or higher.

[0211] <Evaluation of Heat Resistance>

[0212] For the obtained resin film (cured product), the 5% weight loss temperature (Td5) was measured by using a TG-DTA device (TG-8120) manufactured by Kabushiki Kaisharigaku under a nitrogen air stream of 20 mL / min and a heating rate of 20℃ / min.

[0213] <Evaluation of Solvent Solubility>

[0214] The obtained curable resin composition was dissolved in toluene at a ratio of 50% non-volatile content (mass ratio), left to stand for one week, and solvent solubility was evaluated from the appearance of the solution. The evaluation criteria are shown below. In addition, if the evaluation result is “○” or “◎” according to the criteria below, there is no practical problem, and preferably it is “◎”.

[0215] ◎: Completely dissolved

[0216] ○: It is dissolved, but slightly cloudy.

[0217] △: Some remains unmelted

[0218] ×: Almost nothing melts, or most of it remains undissolved

[0219] [Table 1]

[0220]

[0221] [Table 2]

[0222] Industrial applicability

[0223] Since the curable resin composition of the present invention contributes to solvent solubility, the moldability of the cured product is excellent. Furthermore, since it contributes to reactivity, heat resistance, and low dielectric properties, the resulting cured product has excellent heat resistance and low dielectric properties, making it suitable for use in heat-resistant materials or electronic materials.

Claims

Claim 1 A curable resin composition comprising a curable resin (A) having a repeating unit represented by the following general formula (1) and one or more reactive groups selected from the group consisting of (meth)acryloyloxy groups, vinylbenzyl ether groups, and acrylate ether groups as terminal structures, and a curable compound (B) represented by the following general formula (2), wherein, when the total area % of the curable resin (A) and the curable compound (B) is set to 100 by gel permeation chromatography (GPC) measurement, the area % of the curable compound (B) is 0.5 to 30.0 area %. (In the food, Ra 1 , Rb 1 Each is independently an alkyl group, aryl group, aralkyl group, or cycloalkyl group having 1 to 12 carbon atoms, and k 1 is an integer from 0 to 3, X is a single bond or a hydrocarbon group, and Y represents any one of the following general formulas (3) to (5) (In the formula, Z represents a hydrocarbon group) (In the food, Ra 2 , Rb 2 Each is independently an alkyl group, aryl group, aralkyl group, or cycloalkyl group having 1 to 12 carbon atoms, and k 2 is an integer from 0 to 3, X is a single bond or hydrocarbon group, and V represents a (meth)acryloyloxy group, vinylbenzyl ether group, or acrylate ether group) Claim 2 A curable resin composition according to claim 1, wherein the above general formula (1) is represented by the following general formula (1A). (wherein Rc is an alkyl group, an aryl group, an aralkyl group, or a cycloalkyl group, and Ra 1 , Rb 1 , Y is the same as above) Claim 3 A curable resin composition according to claim 1 or 2, wherein Z is any one of a cycloid group, an aromatic group, or a complex circulating group. Claim 4 A curable resin composition according to claim 1 or 2, wherein the terminal structure is a methacryloyloxy group. Claim 5 A curable resin composition according to claim 1 or 2, wherein the weight average molecular weight of the curable resin (A) is 500 to 5000. Claim 6 A cured product obtained by curing the curable resin composition described in paragraph 1 or 2. Claim 7 A varnish obtained by diluting the curable resin composition described in paragraph 1 or 2 with an organic solvent. Claim 8 A prepreg having a reinforcing substrate and a semi-finished product of the varnish described in claim 7 impregnated in the reinforcing substrate. Claim 9 A circuit board obtained by laminating the prepreg described in claim 8 and copper foil and heat-pressing molding. Claim 10 delete

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