Curable resin, haloethyl group-containing resin, method for producing curable resin, curable composition, cured product, prepreg, circuit board, build-up film, semiconductor encapsulant and semiconductor device.

Abstract

The present invention provides a curable resin that can yield a cured product with good heat resistance. The curable resin is obtained by subjecting the reaction product of haloethylbenzene represented by formula (2A) and vinyl benzyl halide represented by formula (3A) to a dehalogenation reaction. [Case 1] TIFF0007861937000035.tif65165

Description

[Technical Field]

[0001] The present invention relates to a curable resin, a haloethyl group-containing resin, a method for producing a curable resin, a curable composition, a cured product, a prepreg, a circuit board, a build-up film, a semiconductor encapsulant, and a semiconductor device. [Background technology]

[0002] As circuit board materials for electronic devices, prepregs obtained by impregnating glass cloth with thermosetting resins such as epoxy resins or BT (bismaleimide-triazine) resins and then heat-drying them, laminates obtained by heat-curing the prepregs, and multilayer boards obtained by combining the laminates and the prepregs and then heat-curing them are widely used. In recent years, against the backdrop of increasing signal speeds and frequencies in various electronic devices, there has been a demand for resin compositions that exhibit excellent dielectric properties (low dielectric constant and low dielectric loss tangent) when cured.

[0003] To meet this requirement, Patent Documents 1 to 6 propose the use of hydrocarbon materials having highly reactive terminal double bonds. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2024-154968 [Patent Document 2] Japanese Patent Publication No. 2024-135478 [Patent Document 3] Japanese Patent Publication No. 2024-154969 [Patent Document 4] Japanese Patent Publication No. 2024-139796 [Patent Document 5] Japanese Patent Publication No. 2023-69669 [Patent Document 6] International Publication No. 2021 / 100658 [Overview of the project] [Problems that the invention aims to solve]

[0005] However, as electronic devices become more high-performance and finer, resin compositions are required to have even higher heat resistance to prevent cracking and substrate warping. The hydrocarbon materials described in Patent Documents 1 to 6 have room for improvement in terms of heat resistance. [Means for solving the problem]

[0006] The inventors of this invention have diligently conducted research to solve the above-mentioned problems, and as a result, have completed this invention.

[0007] The gist of this invention is as follows:

[0008] [1] A curable resin obtained by subjecting the reaction product of haloethylbenzene represented by formula (2A) and vinyl benzyl halide represented by formula (3A) to a dehalogenation reaction. [ka] (In the formula, X1 is a hydrogen atom and X2 is a halogen atom, or X1 is a halogen atom and X2 is a hydrogen atom. R3 is independently an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a halogen atom. m1 is an integer between 0 and 3. [ka] (In the formula, Y is a halogen atom, R4 is independently an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a halogen atom. m2 is an integer between 0 and 4. [2] A curable resin comprising a compound represented by formula (1). [ka] (In the formula, R1 is a hydrogen atom, R2 is a methyl group, or R1 is a methyl group and R2 is a hydrogen atom. R3s are each independently an alkyl group, an aryl group, an alkoxy group, an aryloxy group or a halogen atom. R4s are each independently an alkyl group, an aryl group, an alkoxy group, an aryloxy group or a halogen atom. m1s are each independently an integer from 0 to 3. m2 is an integer from 0 to 4. n is an integer from 1 to 20.) [3] The curable resin according to [2], which is represented by the following formula (1-1).

Chemical formula

Chemical formula

[10] [6] A build-up film containing the curable composition described in [6].

[11] [6] A semiconductor encapsulant containing the curable composition described in [6].

[12] [7] A semiconductor device comprising a cured product of the semiconductor encapsulant described above. [Effects of the Invention]

[0009] The curable resin of the present invention can produce a cured product with good heat resistance. [Brief explanation of the drawing]

[0010] [Figure 1] This shows the GPC measurement results for the 2-bromoethyl group-containing resin obtained in Example 1. [Figure 2] This shows the 13C-NMR measurement results of the 2-bromoethyl group-containing resin obtained in Example 1. [Figure 3] This shows the FD-MS measurement results of the 2-bromoethyl group-containing resin obtained in Example 1. [Figure 4] This shows the 1H-NMR measurement results of the 2-bromoethyl group-containing resin obtained in Example 1. [Figure 5] This shows the GPC measurement results for the curable resin obtained in Example 2. [Figure 6] This shows the 13C-NMR measurement results of the curable resin obtained in Example 2. [Figure 7] These are the FD-MS measurement results for the curable resin obtained in Example 2. [Figure 8] This shows the 1H-NMR measurement results of the curable resin obtained in Example 2. [Modes for carrying out the invention]

[0011] The following describes in detail the embodiments for carrying out the invention, but the present invention is not limited to the following description and can be implemented in various modifications within the scope of its gist.

[0012] [term] In this specification, "reaction raw material" refers to a compound used to obtain a target compound through a chemical reaction such as combination or decomposition, and which partially constitutes the chemical structure of the target compound. Substances that act as aids to chemical reactions, such as solvents and catalysts, are excluded. In particular, in this specification, "reaction raw material" refers to a precursor for obtaining a target intermediate through a chemical reaction. In this specification, "structural unit" refers to a (repeating) unit of chemical structure formed during a reaction or polymerization. In other words, in a compound formed by a reaction or polymerization, it refers to a substructure other than the chemical bond structure involved in the reaction or polymerization, and is commonly known as a residue. In this specification, "intermediate" specifically refers to the reaction products produced in each elementary reaction when the chemical reaction of the reaction raw materials is a multi-step reaction; in other words, it refers to precursors of the target final product that are produced at an intermediate stage in the manufacturing process.

[0013] In this specification, "alkyl group" may be linear or branched, and may have 1 to 20 carbon atoms. Examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, sec-pentyl group, tert-pentyl group, neopentyl group, amyl group, hexyl group, heptyl group, octyl group, cumyl group, nonyl group, decyl group, dodecyl group, undecyl group, dodecyl, etc. The number of carbon atoms is preferably 1 to 10, and more preferably 1 to 6. In this specification, "aryl group" refers to, for example, a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a mesityl group, an o-biphenyl group, an m-biphenyl group, a p-biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 2-fluorenyl group, a phenanthryl group, etc. The number of carbon atoms can be 6 to 20, preferably 6 to 10. In this specification, "alkoxy group" has an alkyl-O- structure, and the definition of alkyl group described above applies to the alkyl group. Examples of alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, and tert-butoxy groups. The number of carbon atoms can be 1 to 20, preferably 1 to 10, and more preferably 1 to 6. In this specification, "aryloxy group" has an aryl-O- structure, and the definition described above applies to aryl groups. Examples of aryloxy groups include phenoxy group, o-tolyloxy group, m-tolyloxy group, p-tolyloxy group, mesityloxy group, o-biphenyloxy group, m-biphenyloxy group, p-biphenyloxy group, 1-naphthyloxy group, 2-naphthyloxy group, 2-fluorenyloxy group, phenanthryloxy group, etc. The number of carbon atoms can be 6 to 20, preferably 6 to 10. In this specification, "halogen atom" refers to fluorine, chlorine, bromine, and iodine.

[0014] In this specification, the number-average molecular weight (Mn) and weight-average molecular weight (Mw) are values ​​measured using gel permeation chromatography (hereinafter also referred to as "GPC") under the measurement conditions described in the examples below.

[0015] [Reaction materials for curable resins] The curable resin of the present invention uses haloethylbenzene represented by formula (2A) and vinyl benzyl halide represented by formula (3A) as reaction raw materials. For example, when using vinyl benzyl halide with bromoethylbenzene, a curable resin with higher heat resistance can be obtained compared to when resin is produced by reacting it with α,α'-paraxylenedichloride.

[0016] <Haloethylbenzene represented by formula (2A)> [ka] (In the formula, X1 is a hydrogen atom and X2 is a halogen atom, or X1 is a halogen atom and X2 is a hydrogen atom. R3 is independently an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a halogen atom. m1 is an integer between 0 and 3.

[0017] As the haloethylbenzene of formula (2A), either the haloethylbenzene of formula (2A-1) or the haloethylbenzene of formula (2A-2) can be used. [ka] (In the formula, Hal is a halogen atom, R3 and m1 are equivalent to those in equation (2A).

[0018] In the compound of formula (2A), m1 is preferably 0, and either the haloethylbenzene of formula (2A-1-1) or the haloethylbenzene of formula (2A-2-1) can be used. Here, when m1 is 0, in other words, it corresponds to the case in the benzene ring of formula (2A) where the carbon atoms other than the position to which the haloethyl group is attached are unsubstituted and hydrogen atoms are attached. [ka] (In the formula, Hal represents a halogen atom.)

[0019] Examples of haloethylbenzenes in formula (2A) where m1 is 0 include (1-fluoroethyl)benzene, (2-fluoroethyl)benzene, (1-chloroethyl)benzene, (2-chloroethyl)benzene, (1-bromoethyl)benzene, (2-bromoethyl)benzene, (1-iodoethyl)benzene, and (2-iodoethyl)benzene.

[0020] m1 can be 1 to 3, in which case R3 is preferably an alkyl group or an aryl group. If m1 is 2 or 3, multiple R3s may be the same or different.

[0021] Examples of haloethylbenzenes in formula (2A) where m1 is 1 to 3 include (2-bromoethyl)benzene and (1-bromoethyl)benzene.

[0022] With respect to X1 and X2, bromine atoms are preferred as halogen atoms.

[0023] Among the haloethylbenzenes of formula (2A), (1-bromoethyl)benzene or (2-bromoethyl)benzene are preferred.

[0024] The haloethylbenzene in formula (2A) can be used as one or more in any ratio.

[0025] <Vinyl benzyl halide represented by formula (3A)> [ka] (In the formula, R4 is independently an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a halogen atom. Y is a halogen atom, m2 is an integer between 0 and 4.

[0026] The bond position between the vinyl group and the -CH2-Y group in the vinyl benzyl halide of formula (3A) may be ortho, meta, or para, but is preferably meta or para, and more preferably para.

[0027] In the vinyl benzyl halide of formula (3A), m2 is preferably 0, in which case it can be represented by the following formula (3A-1). Here, when m2 is 0, in other words, it corresponds to the case in the benzene ring of formula (3A) where carbon atoms other than those to which the vinyl group and the -CH2-Y group are bonded are unsubstituted and hydrogen atoms are bonded. [ka] (In the equation, Y is equivalent to equation (3A).)

[0028] Examples of vinyl benzyl halides of formula (3A) include 2-(fluoromethyl)styrene, 3-(fluoromethyl)styrene, 4-(fluoromethyl)styrene, 2-(chloromethyl)styrene, 3-(chloromethyl)styrene, 4-(chloromethyl)styrene, 2-(bromomethyl)styrene, 3-(bromomethyl)styrene, 4-(bromomethyl)styrene, 2-(iodomethyl)styrene, 3-(iodomethyl)styrene, and 4-(iodomethyl)styrene.

[0029] m2 can be 1 to 4, in which case R4 is preferably an alkyl group, an aryl group, or a halogen atom. When m2 is 2 to 4, the multiple R4s may be the same or different.

[0030] Examples of vinyl benzyl halides of formula (3A) where m2 is 1 to 4 include p-chloromethylstyrene, m-chloromethylstyrene, o-chloromethylstyrene, and the like.

[0031] A chlorine atom is preferred as the halogen atom in Y.

[0032] Among the vinyl benzyl halides of formula (3A), 3-(chloromethyl)styrene and 4-(chloromethyl)styrene are preferred.

[0033] The vinyl benzyl halide of formula (3A) can be used by one or more in any ratio.

[0034] [Method for manufacturing curable resin] The curable resin of the present invention is obtained by subjecting the reaction product of the above-mentioned reaction raw materials to a dehydrohalogenation reaction. Specifically, it can be produced by a manufacturing method comprising the steps of (i) synthesizing an intermediate by an aromatic electrophilic substitution reaction and (ii) subjecting the intermediate to a dehydrohalogenation reaction. Step (i): A step of reacting haloethylbenzene represented by formula (2A) with vinyl benzyl halide represented by formula (3A); Step (ii): A step in which the reaction product obtained in step (i) is subjected to a dehalogenation reaction to obtain a curable resin.

[0035] <Process (i)> In step (i), the haloethylbenzene of formula (2A) is reacted with the vinyl benzyl halide of formula (3A). The reaction is an aromatic electrophilic substitution reaction.

[0036] The amount of haloethylbenzene of formula (2A) used can be 1 mole or more, preferably 1.5 moles or more, and can be 10 moles or less, preferably 9 moles or less, per mole of vinyl benzyl halide of formula (3A).

[0037] The reaction is preferably carried out in the presence of an acid catalyst. Examples of acid catalysts include acetates of nickel, cobalt, sodium, calcium, iron, lithium, and manganese; inorganic salts such as chlorides, bromides, sulfates, and nitrates; inorganic acids such as phosphoric acid, hydrochloric acid, and sulfuric acid; organic acids such as oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid, fluoromethanesulfonic acid, trifluoroacetic acid, and trifluoromethanesulfonic acid; solid acids such as activated clay, acid clay, silica alumina, zeolite, and strongly acidic ion exchange resins; and heteropolyhydrochloric acid. Among these, organic acids such as methanesulfonic acid and fluoromethanesulfonic acid are preferred. Acid catalysts can be used individually or in any ratio of two or more types.

[0038] The amount of acid catalyst used is preferably 0.1 to 30 parts by mass per 100 parts by mass of the total amount of reaction raw materials (haloethylbenzene of formula (2A) and vinyl benzyl halide of formula (3A)), and more preferably 0.5 to 20 parts by mass from the viewpoint of handling and economic efficiency.

[0039] It is preferable to react at least a portion of the haloethylbenzene of formula (2A) with an acid catalyst and mix it with the remaining reaction raw materials.

[0040] The reaction may be carried out without an organic solvent, or it may be carried out with an organic solvent.

[0041] Examples of organic solvents include ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, cyclohexanone, 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. When using organic solvents, one or more organic solvents can be used in any ratio.

[0042] When using an organic solvent, the amount of organic solvent used is not particularly limited as long as it is more than 0 parts by mass per 100 parts by mass of the total amount of reaction raw materials (haloethylbenzene of formula (2A) and vinyl benzyl halide of formula (3A)), but it is preferably 1000 parts by mass or less, and more preferably 900 parts by mass or less.

[0043] The reaction temperature can be between 0 and 200°C, and may even be carried out at room temperature. The reaction time is preferably 0.5 to 72 hours, and more preferably 1 to 70 hours, in order to allow the reaction to proceed sufficiently and to suppress side reactions.

[0044] After the reaction is complete, water or other liquids may be added as needed to separate the aqueous layer from the organic layer, and the aqueous layer may be removed to obtain the reaction product (organic layer). If necessary, an insoluble salt may be dissolved before removing the aqueous layer. The aqueous layer may be acidic, neutralized by neutralization, or basic. Examples of neutralizing agents include sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, triethylamine, and pyridine. These bases can be used individually or in any ratio of two or more. The resulting organic layer can be subjected to the reaction of step (ii).

[0045] <Intermediate> The intermediate is a reaction product of haloethylbenzene of formula (2A) and vinylbenzyl halide of formula (3A), and is a haloethyl group-containing resin containing haloethyl groups.

[0046] The intermediate may contain structural units represented by the following formulas (2') and (3). Formula (2') is the haloethylbenzene residue of formula (2), and formula (3) is the benzyl halide residue of formula (3A). [ka] (In the formula, R3, R4, m1, m2, X1, and X2 are synonymous with formulas (2A) and (3A), and the same applies to the preferred examples. * indicates a coupling.

[0047] The intermediate is usually a mixture of several compounds, and the above structural units may be present in any of the compounds in the mixture, but the intermediate as a whole shall have the structural units of formula (2') and formula (3). Preferably, the intermediate has a compound containing both the structural units of formula (2') and formula (3).

[0048] The intermediate preferably contains a compound in which the structural unit of formula (2') forms the terminal, in which case the terminal structural unit can be represented by formula (2'-1). [ka] (In the formula, R3, m1, X1, and X2 are equivalent to those in formula (2A), and the same applies to the preferred examples. * indicates a coupling.

[0049] The intermediate preferably contains a compound represented by formula (1'). [ka] (In the formula, R1 is a hydrogen atom and R2 is a methyl group, or R1 is a methyl group and R2 is a hydrogen atom. R3 is independently an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a halogen atom. R4 is independently an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a halogen atom. X1 is a hydrogen atom and X2 is a halogen atom, or X1 is a halogen atom and X2 is a hydrogen atom. Each m1 is an independent integer between 0 and 3. m2 is an integer between 0 and 4. n is an integer between 1 and 20.

[0050] Preferred examples of R3, R4, X1, X2, m1, and m2 in formula (1') are the same as those in formulas (2A) and (3A). In equation (1'), n is preferably an integer between 1 and 10, and more preferably between 1 and 5.

[0051] In the compound of formula (1'), m1 and m2 are preferably 0, in which case it can be represented by the following formula (1'-1). [ka] (In the formula, R1, R2, X1, X2, and n are equivalent to those in formula (1'), and the preferred examples are also equivalent.)

[0052] In the compound of formula (1'-1), n ​​is preferably 1 to 10, and more preferably 1 to 5. When n is 1, R1 is a methyl group, and R2 is a hydrogen atom, it can be represented by the following formula (1'-1-1). [ka] (In the formula, X1 and X2 are equivalent to those in formula (1'), and the same applies to the preferred example.)

[0053] The intermediate may include the following structural units in addition to the structural units of formulas (2') and (3). [ka] (In the formula, * represents a coupling.)

[0054] Examples of compounds other than the compound of formula (1') that the intermediate may contain include the following: [ka]

[0055] The number-average molecular weight (Mn) of the intermediate can be in the range of 200 to 10,000, preferably in the range of 300 to 9,000. The weight-average molecular weight (Mw) of the intermediate can be in the range of 200 to 50,000, preferably in the range of 300 to 40,000.

[0056] <Process (ii)> In step (ii), the intermediate obtained in step (i) is subjected to a dehydrohalogenation reaction to obtain a curable resin. In this reaction, the haloethyl groups in the intermediate are converted to vinyl groups. Because the curable resin has vinyl groups, it exhibits high reactivity.

[0057] The reaction can be carried out in the presence of a base catalyst. Examples of base catalysts include potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, tert-butoxypotassium, tert-butoxysodium, and triethylamine. Aqueous solutions of these base catalysts may also be used. From the viewpoint of reactivity, potassium hydroxide or sodium hydroxide is preferred, and aqueous solutions of these are also preferred. The base catalyst can be used as one or more types in any ratio.

[0058] The amount of base catalyst used can be 40 to 1000 parts by mass per 100 parts by mass of intermediate. From the viewpoint of reactivity, it is preferably 50 to 900 parts by mass.

[0059] The reaction can be carried out in an organic solvent. Examples of organic solvents include aromatic solvents such as toluene and xylene, aliphatic solvents such as cyclohexane and n-hexane, ethers such as diethyl ether and diisopropyl ether, esters such as ethyl acetate and butyl acetate, ketones such as methyl isobutyl ketone and cyclopentanone, dimethyl sulfone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, and N-methylpyrrolidone. The use of aprotic polar solvents in combination is preferable because it can increase the progress of the dehalogenation reaction. Organic solvents can be used individually or in any ratio of two or more.

[0060] The amount of organic solvent used is not particularly limited, but it can be 50 to 1000 parts by mass per 100 parts by mass of the intermediate.

[0061] The reaction temperature can be 25 to 130°C, and is preferably 30 to 120°C from the viewpoint of promoting the reaction. The reaction time can be 0.5 to 72 hours, and is preferably 1 to 70 hours, from the viewpoint of allowing the reaction to proceed sufficiently and suppressing side reactions.

[0062] The reaction is preferably carried out in an organic solvent, with the base catalyst added dropwise to the intermediate. The dropwise addition can be carried out over, for example, 0.5 to 72 hours. After the reaction is complete, water is added to wash the organic layer, and after removing the aqueous layer, the base catalyst and organic solvent can be added again to carry out the reaction.

[0063] After the reaction is complete, water or other liquids may be added as needed to separate the aqueous layer from the organic layer, and the aqueous layer may be removed to obtain the reaction product. If necessary, an insoluble salt may be dissolved before removing the aqueous layer. The aqueous layer may be basic, neutralized by neutralization, or acidic. Examples of neutralizing agents used for neutralization include organic acids such as oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid, fluoromethanesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, and ammonium chloride; inorganic acids such as phosphoric acid, monosodium phosphate, disodium phosphate, trisodium phosphate, hydrochloric acid, sulfuric acid, and nitric acid; and solid acids such as activated clay, acid clay, silica alumina, zeolite, and strong acid ion exchange resin. One or more of these acids may be used in any ratio.

[0064] After the reaction is complete, a polymerization inhibitor can be added to the reaction product from step (ii). Examples of polymerization inhibitors include 2,6-di-tert-butyl-p-cresol (BHT), t-butylcatechol, methoxyphenol, hydroquinone, and BASF's Irganox and Irgafos series. From the viewpoint of inhibiting polymerization, 2,6-di-tert-butyl-p-cresol, methoxyphenol, or hydroquinone are preferred. These polymerization inhibitors can be used individually or in any ratio of two or more.

[0065] The amount of polymerization inhibitor used can be 0.0001 to 5 parts by mass per 100 parts by mass of curable resin. Preferably, it is 0.0001 to 3 parts by mass, from the viewpoint of inhibiting polymerization.

[0066] <Curable resin> The curable resin is a dehalogenated hydrogenated product of the intermediate (the reaction product of haloethylbenzene represented by formula (2A) and vinylbenzyl halide represented by formula (3A)). The haloethyl groups contained in the intermediate are converted to vinyl groups.

[0067] Structural units that can be contained in curable resins include the structural unit represented by formula (2) and the structural unit represented by formula (3). Formula (2) is a structural unit in which a hydrogen halide is removed from the haloethyl group in formula (2') to form a vinyl group. [ka] (In the formula, R3, R4, m1, and m2 are synonymous with formulas (2A) and (3A), and the same applies to the preferred examples. * indicates a coupling.

[0068] Curable resins are typically mixtures of multiple compounds, and the above-mentioned structural units may be present in any of the compounds in the mixture, but the curable resin as a whole shall have the structural units of formula (2) and formula (3). Preferably, the curable resin contains compounds having both the structural units of formula (2) and formula (3).

[0069] The curable resin preferably contains a compound in which the structural unit of formula (2) forms the terminal, in which case the terminal structural unit can be represented by formula (2-1). [ka] (In the formula, R3 and m1 are equivalent to those in formula (2), and the same applies to the preferred example. * indicates a coupling.

[0070] The curable resin of the present invention contains a compound represented by formula (1). [ka] (In the formula, R1 is a hydrogen atom and R2 is a methyl group, or R1 is a methyl group and R2 is a hydrogen atom. R3 is independently an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a halogen atom. R4 is independently an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a halogen atom. Each m1 is an independent integer between 0 and 3. m2 is an integer between 0 and 4. n is an integer between 1 and 20. Preferred examples of R3, R4, m1, m2, and n in formula (1) are the same as in formula (1').

[0071] In the compound of formula (1), m1 and m2 are preferably 0, in which case it can be represented by the following formula (1-1). [ka] (In the formula, R1, R2, and n are equivalent to those in formula (1).)

[0072] In the compound of formula (1-1), n ​​is preferably 1 to 10, and more preferably 1 to 5. When n is 1, R1 is a methyl group, and R2 is a hydrogen atom, it can be represented by the following formula (1-1-1). [ka]

[0073] In addition to the structural units of formulas (2) and (3), the curable resin may contain the following structural units. [ka] (In the formula, * represents a coupling.)

[0074] Examples of compounds other than the compound of formula (1) that the curable resin may contain include the following: [ka]

[0075] The number-average molecular weight (Mn) of the curable resin can be in the range of 200 to 10,000, preferably in the range of 250 to 9,000. The weight-average molecular weight (Mw) of the curable resin can be in the range of 200 to 50,000, preferably in the range of 250 to 40,000.

[0076] Regarding the structural units that constitute the intermediate and curable resin, 1 H-NMR, 13 It can be identified by analysis such as 13C-NMR, FD-MS, and GPC.

[0077] [Curable composition] The curable composition of the present invention comprises one or both of the curable resin, curing agent, and curing catalyst of the present invention. By using the curable resin of the present invention, the cured product obtained from the curable composition can be provided with excellent heat resistance.

[0078] The curing agent is not particularly limited as long as it is a compound that can react with the curable resin of the present invention. Examples include resin components such as epoxy resins, phenolic resins, activated ester resins, maleimide resins, cyanate resins, unsaturated polyester resins, and polybutadiene resins, as well as compounds such as styrene, divinylbenzene, triallyl isocyanurate, triallyl cyanurate, diallyl phthalate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, and polyphenylene ether (polyphenylene ether having an ethylenically unsaturated double bond). The hardening agent can be used in any ratio of one or more types.

[0079] The ratio of the curable resin of the present invention to the total amount of the curable resin and curing agent of the present invention is adjusted as appropriate according to the desired cured product performance, but is preferably 5% by mass or more, and more preferably 10% by mass or more.

[0080] The curing catalyst is not particularly limited and includes, for example, organic peroxides (e.g., benzoyl peroxide, cumene hydroperoxide, dicumyl peroxide, lauroyl peroxide, di-t-butyl peroxide, t-butyl hydroperoxide, methyl ethyl ketone peroxide, t-butyl perbenzoate, etc.), azo compounds (e.g., azobisisobutyronitrile), and free radicals (e.g., azobisisobutyronitrile, garbinoxyl, etc.).

[0081] The curable composition may contain various additives such as curing accelerators, silane coupling agents, mold release agents, pigments, emulsifiers, non-halogenated flame retardants, inorganic fillers, flame retardants (e.g., inorganic phosphorus-based flame retardants, organophosphorus-based flame retardants, halogenated flame retardants), and solvents.

[0082] A curable composition can be obtained by uniformly mixing the curable resin of the present invention with one or both of the curing agent and the curing catalyst, and any other component (e.g., curing catalyst, compounding agent, etc.).

[0083] [Cured product] The cured product of the present invention can be obtained by curing the curable composition of the present invention. The curing method is not particularly limited, and known methods can be employed. The cured product can take the form of a laminate, a cast product, an adhesive layer, a coating, a film, or the like.

[0084] [Semiconductor encapsulant] The semiconductor encapsulant of the present invention may contain the curable composition of the present invention. Since the curable composition of the present invention contains the curable resin of the present invention, it can exhibit excellent heat resistance in the semiconductor encapsulant.

[0085] For semiconductor encapsulants, a curable composition of the present invention containing an inorganic filler can be used. The inorganic filler is not particularly limited and can include, for example, barium sulfate, barium titanate, amorphous silica, crystalline silica, Neuburg silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, silicon nitride, aluminum nitride, and the like. The amount of inorganic filler can be 0.5 to 1200 parts by mass per 100 parts by mass of the curable composition.

[0086] The semiconductor encapsulant may contain various compounding agents, including those described in relation to curable compositions.

[0087] The semiconductor encapsulant can be obtained by mixing the curable composition of the present invention with compounding agents as needed, for example, by thoroughly melting and mixing until uniform using an extruder, kneader, roll, etc.

[0088] [Semiconductor device] The semiconductor device of the present invention may include a cured product of the semiconductor encapsulant of the present invention. The semiconductor encapsulant used in the semiconductor device of the present invention contains a curable composition containing the curable resin of the present invention. Because the semiconductor device of the present invention includes a cured product of the semiconductor encapsulant, it has excellent heat resistance.

[0089] The semiconductor device can be obtained by heat curing the semiconductor encapsulant of the present invention. Examples include casting, molding using a transfer molding machine, injection molding machine, etc., and then heat curing it in a temperature range of room temperature (20°C) to 250°C.

[0090] [Prepreg] The prepreg of the present invention may have a reinforcing substrate and a semi-cured product of the curable composition of the present invention impregnated into the reinforcing substrate. The method for obtaining a prepreg from a curable composition is not particularly limited, and one method involves impregnating a reinforcing substrate (e.g., paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, glass roving cloth, etc.) with a varnished curable composition containing an organic solvent described later, and then heating it at a heating temperature (preferably 50 to 170°C) according to the type of solvent used to partially cure (or leave uncured) the curable composition. The mass ratio of the curable composition to the reinforcing substrate used is not particularly limited, but it is preferable to prepare it so that the resin content in the prepreg is 20 to 60% by mass.

[0091] A semi-cured product of a curable composition can be obtained by adjusting the heating temperature and heating time to stop the curing reaction before it is completed. The degree of curing of the semi-cured product can be, for example, 5 to 85%. Here, the cured product may have a higher degree of curing than the semi-cured product. The degree of hardening of a semi-cured product can be calculated using the following formula by measuring the heat generated during curing of the curable composition and the heat generated during curing of the semi-cured product using DSC. Degree of curing (%) = [1 - (heat generated during curing of the semi-cured material / heat generated during curing of the curable composition)] × 100

[0092] Examples of organic solvents used in the production of prepregs include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, and propylene glycol monomethyl ether acetate. The selection and amount of organic solvent can be appropriately chosen depending on the application. For example, when manufacturing circuit boards from prepregs, polar solvents with a boiling point of 160°C or lower, such as methyl ethyl ketone, acetone, and dimethylformamide, are preferred, and the amount used is preferably such that the non-volatile content is 40 to 80% by mass.

[0093] [Circuit board] The circuit board of the present invention consists of a laminate of the prepreg of the present invention and copper foil. The method for obtaining the circuit board is not particularly limited, and for example, one method is to laminate the prepreg of the present invention as needed, overlap the copper foil, and heat-press it at 170 to 300°C for 10 minutes to 3 hours under pressure of 1 to 10 MPa.

[0094] [Build-up film] The build-up film of the present invention may contain the curable composition of the present invention. The method for producing the build-up film is not particularly limited, and one example is to apply the curable composition of the present invention onto a support film to form a curable composition layer and use it as an adhesive film for multilayer printed circuit boards.

[0095] Since the build-up film is required to soften at the lamination temperature conditions (usually 70-140°C) in the vacuum lamination method and exhibit fluidity (resin flow) that allows for resin filling into via holes or through holes present in the circuit board simultaneously with lamination of the circuit board, it is preferable that the curable composition be formulated to exhibit these properties.

[0096] Here, the diameter of the through-holes in a multilayer printed circuit board is typically 0.1 to 0.5 mm, and the depth is typically 0.1 to 1.2 mm. It is generally preferable to be able to fill the holes with resin within this range. When laminating both sides of the circuit board, it is desirable to fill about half of the through-holes.

[0097] The adhesive film described above can be manufactured by first preparing a varnish-like curable composition, then applying this varnish-like composition to the surface of a support film (B), and finally drying the organic solvent by heating or blowing hot air to form a composition layer (A) made of the curable composition.

[0098] The thickness of the formed composition layer (A) is usually preferably greater than or equal to the thickness of the conductor layer. Since the thickness of the conductor layer of a circuit board is usually in the range of 5 to 70 μm, the thickness of the resin composition layer is preferably 10 to 100 μm.

[0099] The composition layer (A) may also be protected by a protective film, as described later. Protecting it with a protective film prevents dirt and other debris from adhering to the surface of the resin composition layer and prevents scratches.

[0100] The support film (B) and protective film mentioned above can be made of polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate, polycarbonate, polyimide, and also release paper, copper foil, aluminum foil, and other metal foils. The support film and protective film may be treated with a mat treatment, corona treatment, or release treatment.

[0101] The thickness of the support film is not particularly limited, but is usually 10 to 150 μm, and preferably in the range of 25 to 50 μm. The thickness of the protective film is preferably 1 to 40 μm.

[0102] The support film (B) described above is peeled off after lamination to the circuit board or after an insulating layer is formed by heat curing. Peeling off the support film (B) after heat curing the adhesive film prevents the adhesion of dust and other contaminants during the curing process. When peeling off after curing, the support film is usually treated with a release agent beforehand.

[0103] [Application] The cured product obtained from the curable composition containing the curable resin of the present invention exhibits excellent heat resistance and can therefore be suitably used in heat-resistant components or electronic components. In particular, it can be suitably used in prepregs, circuit boards, semiconductor encapsulants, semiconductor devices, build-up films, build-up substrates, adhesives and resist materials using conductive pastes, etc. It can also be suitably used as a matrix resin for fiber-reinforced resins and is particularly suitable as a high-heat-resistant prepreg. Furthermore, the curable resin contained in the curable composition exhibits excellent solubility in various solvents and can be made into a paint. The heat-resistant components and electronic components thus obtained can be suitably used in a variety of applications, including, but are not limited to, industrial machine parts, general machine parts, automobile, railway, and vehicle parts, aerospace-related parts, electronic and electrical components, building materials, containers and packaging materials, household goods, sports and leisure goods, wind power generation housing components, etc. [Examples]

[0104] The present invention will be specifically described by examples and comparative examples, but the present invention is not limited to the following description and can be implemented in various modifications within the scope of its gist. In the following, "parts" and "%" are based on mass unless otherwise specified.

[0105] The physical properties of the curable resin were evaluated as follows.

[0106] (1) GPC measurement The number-average molecular weight (Mn), weight-average molecular weight (Mw), and molecular weight distribution (Mw / Mn) were calculated for the haloethyl group-containing resin and curable resin obtained in the examples and comparative examples using the following measuring equipment and conditions. Measurement device: Tosoh Corporation "HLC-8320 GPC" Column: Guard column "HXL-L" manufactured by Tosoh Corporation + "TSK-GEL G2000HXL" manufactured by Tosoh Corporation + "TSK-GEL G2000HXL" manufactured by Tosoh Corporation + "TSK-GEL G3000HXL" manufactured by Tosoh Corporation + "TSK-GEL G4000HXL" manufactured by Tosoh Corporation Detector: RI (Differential Refractometer) Data processing: Tosoh Corporation's "GPC Workstation EcoSEC-WorkStation" Measurement conditions: Column temperature 40℃ Developing solvent: tetrahydrofuran Flow rate 1.0ml / min Standard: In accordance with the measurement manual for the aforementioned "GPC Workstation EcoSEC-WorkStation," the following monodisperse polystyrenes with known molecular weights were used. (Uses polystyrene) "A-500" manufactured by Tosoh Corporation "A-1000" manufactured by Tosoh Corporation "A-2500" manufactured by Tosoh Corporation "A-5000" manufactured by Tosoh Corporation "F-1" manufactured by Tosoh Corporation "F-2" manufactured by Tosoh Corporation "F-4" manufactured by Tosoh Corporation Tosoh Corporation's "F-10" F-20 manufactured by Tosoh Corporation Tosoh Corporation's "F-40" Tosoh Corporation's "F-80" Tosoh Corporation's "F-128" Sample: 50 μl of a tetrahydrofuran solution containing 1.0% by mass (based on resin solids content) filtered through a microfilter.

[0107] (2) FD-MS measurement The FD-MS spectra of the haloethyl group-containing resin and curable resin obtained in the examples were measured using the following measuring apparatus and conditions. Measuring device: JMS-T100GC AccuTOF Measurement conditions Measurement range: m / z = 4.00~2000.00 Rate of change: 51.2 mA / min Final current value: 45mA Cathode voltage: -10kV Recording interval: 0.07 seconds

[0108] (3) 13 C-NMR measurement The haloethyl group-containing resin and curable resin obtained in the examples 13 The 1C-NMR spectrum was measured using the following measuring instrument and conditions. 13 1C-NMR: JEOL JNM-ECA500 SuperCOOL probe Resonance frequency: 100MHz Total number of times: 2000 Solvent: Chloroform-d Sample concentration: 34% by mass Relaxation agent: Chromium(III) acetylacetonate

[0109] (4) 1 H-NMR measurement The haloethyl group-containing resin and curable resin obtained in the examples 1 The 1H-NMR spectra were measured under the following measurement apparatus and measurement conditions. 1 1H-NMR: JNM-ECA500 SuperCOOL probe manufactured by JEOL Resonance frequency: 500 MHz Number of integrations: 16 times Solvent: chloroform-d Sample concentration: 12% by mass

[0110] <Synthesis of Haloethyl Group-Containing Resin in Example 1> Under a nitrogen atmosphere, 647.7 parts by mass of 2-bromoethylbenzene and 39.1 parts by mass of methanesulfonic acid were charged into a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating column, and a stirrer, and the temperature was raised to 130 °C. Subsequently, 133.5 parts by mass of chloromethylstyrene (a 1:1 mixture of meta- and para-isomers. CMS-P, manufactured by AGC Seimi Chemical Co., Ltd.) was dropped into the dropping funnel, and the reaction was carried out at the same temperature for 6 hours from the end of dropping. Hydrogen chloride generated during the reaction was reacted while being trapped by a base trap.

[0111] Subsequently, 150.0 parts by mass of toluene and 899.2 parts by mass of methylcyclohexane were charged and neutralized with 33.2 parts by mass of a 49% aqueous sodium hydroxide solution. Subsequently, the organic layer was washed with 150.0 parts by mass of water, and the same operation was carried out 3 times. After washing, the solvent and 2-bromoethylbenzene were distilled off under heating and reduced pressure at 150 °C to obtain the target 2-bromoethyl group-containing resin (Mn 440, Mw is 672). It was confirmed that the intermediate compound represented by the formula (1'-1) was contained in the resin. The GPC chart of the obtained 2-bromoethyl group-containing resin is shown in Fig. 1, 13 the 13C-NMR chart in Fig. 2, the FD-MS chart in Fig. 3, 1 and the 1H-NMR chart in Fig. 4.

[0112] <Synthesis of Curable Resin in Example 2> Under a nitrogen atmosphere, 200 parts by mass of the 2-bromoethyl group-containing resin obtained in Example 1, 111.3 parts by mass of toluene, and 417.3 parts by mass of dimethyl sulfoxide (hereinafter abbreviated as DMSO) were charged into a flask equipped with a thermometer, dropping funnel, condenser, fractionation column, and stirrer, and the temperature was raised to 50°C. Subsequently, 163.6 parts by mass of 48% potassium hydroxide were added dropwise, taking care to avoid exothermic reactions, and the mixture was reacted at the same temperature for 6 hours from the end of the dropwise addition. Next, 150.5 parts by mass of water was added to wash the organic layer, and the aqueous layer was removed. 417.3 parts by mass of DMSO and 9.1 parts by mass of 48% potassium hydroxide were added to the organic layer, and the mixture was reacted at 50°C for 2 hours. After the reaction was complete, the mixture was washed with 139.1 parts by mass of water, and the same procedure was repeated 5 times. After washing, 0.07 parts by mass of 2,6-di-tert-butyl-p-cresol was added, and a curable resin solution with a non-volatile content of 52.3% by mass (Mn: 374, Mw: 750) was obtained by vacuum distillation using a rotary evaporator at 40°C. The presence of the compound represented by formula (1-1) in the resin was confirmed. The GPC chart of the obtained curable resin is shown in Figure 5. 13 Figure 6 shows the C-NMR chart, and Figure 7 shows the FD-MS chart. 1 The 1H-NMR chart is shown in Figure 8.

[0113] <Comparative Example 1: Synthesis of Curable Resin> The curable resins of the comparative examples were synthesized in the same manner as in Synthesis Examples 1 and 2 of Japanese Patent Application Publication No. 2024-154968.

[0114] The glass transition temperature of the cured product of the curable resin was measured as follows. The curable resin solution obtained in Example 2 and the resin solution obtained in Comparative Example 1 were each mixed homogeneously in toluene with 30 parts by mass of a terminally modified polyphenylene ether compound (SABIC, product name: SA-9000) in an amount that resulted in 70 parts by mass of curable resin in terms of solid content. The mixed solution was heated in a rotary evaporator at 80°C under reduced pressure for 30 minutes to remove the solvent and obtain a resin composition. Subsequently, the obtained resin composition was vacuum pressed at 2 MPa and 200°C for 2 hours to obtain a cured product. The obtained cured material was cut into pieces with a width of 5 mm, a length of 55 mm, and a thickness of 1.2 to 1.6 mm. Using a viscoelasticity analyzer (DMA: Rheometric RSAII solid viscoelasticity analyzer, rectangular tension method; frequency 1 Hz, heating rate 3 °C / min), the temperature at which the ratio of the change in elastic modulus to the change in viscoelasticity was maximized (tanδ was largest) was evaluated as the glass transition temperature (Tg). The results are shown in Table 1. The cut-out hardened material was exposed to an environment of 121°C and 100% humidity for 6 hours, and then the glass transition temperature was measured in the same manner. The results are shown in Table 1.

[0115] [Table 1]

[0116] From the results shown in Table 1 above, it can be seen that the cured product of the curable resin in Example 2 has higher heat resistance than the cured product of the curable resin in Comparative Example 1. Furthermore, the Tg of the cured product of the curable resin in Example 2 after moisture absorption did not change from the Tg before moisture absorption, indicating that it can maintain good heat resistance even after moisture absorption. [Industrial applicability]

[0117] According to the present invention, it is possible to provide a curable resin that can produce a cured product with good heat resistance.

Claims

1. A curable resin obtained by subjecting the reaction product of haloethylbenzene represented by formula (2A) and vinyl benzyl halide represented by formula (3A) to a dehalogenation reaction. 【Chemistry 1】 (In the formula, X １ X is a hydrogen atom, ２ is a halogen atom, or X １ X is a halogen atom, ２ It is a hydrogen atom, R ３ Each of these is independently an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a halogen atom. I understand １ (This is an integer between 0 and 3.) 【Chemistry 2】 (In the formula, Y is a halogen atom, R ４ Each of these is independently an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a halogen atom. I understand ２ (This is an integer between 0 and 4.)

2. A curable resin containing a compound represented by formula (1). 【Transformation 3】 (In the formula, R １ is a hydrogen atom, and R ２ is a methyl group, or R １ is a methyl group and R ２ is a hydrogen atom, R ３ Each of these is independently an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a halogen atom. R ４ Each of these is independently an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a halogen atom. I understand １ These are each an integer between 0 and 3, independently of each other. I understand ２ is an integer from 0 to 4, n is an integer between 1 and 20.

3. The curable resin according to claim 2, wherein the curable resin is represented by the following formula (1-1). 【Chemistry 4】 (In the formula, R １ , R ２ And n are equivalent to equation (1).

4. A haloethyl group-containing resin comprising a compound represented by formula (1'). 【Transformation 5】 (In the formula, R １ is a hydrogen atom, and R ２ is either a methyl group or R １ R is a methyl group, ２ It is a hydrogen atom, R ３ Each of these is independently an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a halogen atom. R ４ Each of these is independently an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a halogen atom. X １ X is a hydrogen atom, ２ is a halogen atom, or X １ X is a halogen atom, ２ It is a hydrogen atom, I understand １ These are each an integer between 0 and 3, independently of each other. I understand ２ is an integer from 0 to 4, n is an integer between 1 and 20.

5. A method for producing a curable resin, comprising the following steps (i) and (ii). Step (i): A step of reacting haloethylbenzene represented by the following formula (2A) with vinyl benzyl halide represented by the following formula (3A); Step (ii): A step of subjecting the reaction product obtained in step (i) to a dehalogenation reaction to obtain a curable resin. 【Transformation 6】 (In the formula, X １ X is a hydrogen atom, ２ is a halogen atom, or X １ X is a halogen atom, ２ It is a hydrogen atom, R ３ Each of these is independently an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a halogen atom. I understand １ (This is an integer between 0 and 3.) 【Transformation 7】 (In the formula, Y is a halogen atom, R ４ Each of these is independently an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a halogen atom. I understand ２ (This is an integer between 0 and 4.)

6. A curable resin according to any one of claims 1 to 3, and a curable composition comprising one or both of a curing agent and a curing catalyst.

7. A cured product of the curable composition according to claim 6.

8. A prepreg having a reinforcing substrate and a semi-cured product of the curable composition according to claim 6 impregnated into the reinforcing substrate.

9. A circuit board having a laminate of prepreg and copper foil as described in claim 8.

10. A build-up film containing the curable composition described in claim 6.

11. A semiconductor encapsulant containing the curable composition described in claim 6.

12. A semiconductor device comprising a cured product of the semiconductor encapsulant according to claim 11.

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