Curable resin, resin containing haloethyl group, method for producing curable resin, curable composition, cured object, prepreg, circuit board, build-up film, semiconductor-sealing material, and semiconductor device

Abstract

Provided is a curable resin capable of giving a cured object having satisfactory heat resistance. The curable resin is obtained by subjecting a product of reaction between a haloethylbenzene represented by formula (2A) and a vinylbenzyl halide represented by formula (3A) to a dehydrohalogenation reaction.

Description

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.

[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.

[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 speed and frequency in various electronic devices, there has been a demand for resin compositions in which the cured product exhibits excellent dielectric properties (low dielectric constant and low dielectric loss tangent).

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

[0004] Japanese Patent Publication No. 2024-154968, Japanese Patent Publication No. 2024-135478, Japanese Patent Publication No. 2024-154969, Japanese Patent Publication No. 2024-139796, Japanese Patent Publication No. 2023-69669, International Publication No. 2021 / 100658

[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 warping of substrates. The hydrocarbon materials described in Patent Documents 1 to 6 have room for improvement in terms of heat resistance.

[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. (wherein, X １ is a hydrogen atom, X ２ is a halogen atom, or X １ is a halogen atom, X ２ is a hydrogen atom, and R ３ are each independently an alkyl group, an aryl group, an alkoxy group, an aryloxy group or a halogen atom, and m １ is an integer of 0 to 3.) (wherein, Y is a halogen atom, and R ４ are each independently an alkyl group, an aryl group, an alkoxy group, an aryloxy group or a halogen atom, and m ２ is an integer of 0 to 4.) [2] A curable resin containing the compound represented by formula (1). (wherein, R １ is a hydrogen atom, R ２ is a methyl group, or R １ is a methyl group, R ２ is a hydrogen atom, and R ３ are each independently an alkyl group, an aryl group, an alkoxy group, an aryloxy group or a halogen atom, and R ４ are each independently an alkyl group, an aryl group, an alkoxy group, an aryloxy group or a halogen atom, and m １ are each independently an integer of 0 to 3, and m ２ is an integer of 0 to 4, and n is an integer of 1 to 20.) [3] In the curable resin, the curable resin according to [2], represented by the following formula (1-1). (wherein, R １ , R ２ and n are as defined in formula (1).) [4] A haloethyl group-containing resin containing the compound represented by formula (1'). (wherein, R １ is a hydrogen atom, R ２ is a methyl group, or R １ is a methyl group, R ２ is a hydrogen atom, and R ３Each of these is independently an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a halogen atom, and R ４ Each of these is independently an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a halogen atom, and X １ X is a hydrogen atom, ２ is a halogen atom, or X １ X is a halogen atom, ２ is a hydrogen atom, m １ Each of these is an integer between 0 and 3, and m ２ (where n is an integer from 0 to 4, and n is an integer from 1 to 20.) [5] A method for producing a curable resin comprising the following steps (i) and (ii). Step (i): A step of reacting a haloethylbenzene represented by the following formula (2A) with a 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. (In the formula, X １ X is a hydrogen atom, ２ is a halogen atom, or X １ X is a halogen atom, ２ R is a hydrogen atom. ３ Each of these is independently an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a halogen atom, m １ (This is an integer between 0 and 3.) (In the formula, Y is a halogen atom, and R ４ Each of these is independently an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a halogen atom, m ２(wherein is an integer from 0 to 4.) [6] A curable composition comprising a curable resin according to any one of [1] to [3] and one or both of a curing agent and a curing catalyst. [7] A cured product of the curable composition according to [6]. [8] A prepreg having a reinforcing substrate and a semi-cured product of the curable composition according to [6] impregnated into the reinforcing substrate. [9] A circuit board having a laminate of the prepreg according to [8] and copper foil.

[10] A build-up film containing the curable composition according to [6].

[11] A semiconductor encapsulant containing the curable composition according to [6].

[12] A semiconductor device containing a cured product of the semiconductor encapsulant according to [7].

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

[0010] This is the GPC measurement result of the 2-bromoethyl group-containing resin obtained in Example 1. １３ This is the 13C-NMR measurement result. This is the FD-MS measurement result of the 2-bromoethyl group-containing resin obtained in Example 1. １ This is the H-NMR measurement result. This is the GPC measurement result of the curable resin obtained in Example 2. １３ This is the 13C-NMR measurement result. This is the FD-MS measurement result of the curable resin obtained in Example 2. １ This is the result of the H-NMR measurement.

[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 essence.

[0012] [Terminology] 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 this specification, "reaction raw material" specifically refers to a precursor for obtaining a target intermediate through a chemical reaction. In this specification, "structural unit" refers to a (repeating) unit of a chemical structure formed during a reaction or polymerization. In other words, it refers to a substructure other than the chemical bond structure involved in the reaction or polymerization in the resulting compound formed by the reaction or polymerization, and is a so-called residue. In this specification, "intermediate" specifically refers to the reaction product produced in each elementary reaction when the chemical reaction of the reaction raw material is a multi-step reaction. In other words, it refers to a precursor of the target final product that is 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, more preferably 1 to 6. In this specification, "aryl group" is, for example, phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, mesityl group, o-biphenyl group, m-biphenyl group, p-biphenyl group, 1-naphthyl group, 2-naphthyl group, 2-fluorenyl group, 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 above-described definition of alkyl groups applies to alkyl groups. 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 above-described definition applies to aryl groups. Examples of aryloxy groups include phenoxy, o-tolyloxy, m-tolyloxy, p-tolyloxy, mesityloxy, o-biphenyloxy, m-biphenyloxy, p-biphenyloxy, 1-naphthyloxy, 2-naphthyloxy, 2-fluorenyloxy, and phenanthryloxy groups. 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 resin] The curable resin of the present invention uses haloethylbenzene represented by formula (2A) and vinyl benzyl halide represented by formula (3A) as reaction materials. For example, when vinyl benzyl halide is used with bromoethylbenzene, a curable resin with higher heat resistance can be obtained compared to when the resin is produced by reacting it with α,α'-paraxylenedichloride.

[0016] <Haloethylbenzene represented by formula (2A)> (In the formula, X １ X is a hydrogen atom, ２ is a halogen atom, or X １ X is a halogen atom, ２ R is a hydrogen atom. ３ Each of these is independently an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a halogen atom, m １ (This 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. (In the formula, Hal is a halogen atom, and R ３ and m １ This is equivalent to equation (2A).

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

[0019] I understand １Examples of haloethylbenzenes in formula (2A) where 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] I understand １ It can also be 1 to 3, in which case R ３ A alkyl group or aryl group is preferred. １ If there are 2 or 3, multiple R ３ They may be the same or they may be different.

[0021] I understand １ Examples of haloethylbenzenes of formula (2A) in 1 to 3 include (2-bromoethyl)benzene, (1-bromoethyl)benzene, and the like.

[0022] X １ and X ２ Regarding this, a bromine atom is preferred as the halogen atom.

[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 by one or more in any ratio.

[0025] <Vinyl benzyl halide represented by formula (3A)> (In the formula, R ４ Each of these is independently an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a halogen atom, and Y is a halogen atom, m ２ (This is an integer between 0 and 4.)

[0026] The vinyl group and -CH in vinyl benzyl halide of formula (3A) ２ - The bond position with the Y group 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), m ２ It is preferable that m is 0, in which case it can be expressed by the following formula (3A-1). Here, m ２ If it is 0, in other words, in the benzene ring of formula (3A), the vinyl group and -CH ２ This corresponds to the case where carbon atoms other than those bonded to the -Y group are unsubstituted and hydrogen atoms are bonded to them. (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] I understand ２ can also be 1 to 4, in which case R ４ Preferably, the element is an alkyl group, an aryl group, or a halogen atom. ２ If the number is 2 to 4, multiple R ４ They may be the same or they may be different.

[0030] I understand ２ Examples of vinyl benzyl halides of formula (3A) 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 producing curable resin] The curable resin of the present invention is obtained by subjecting the reaction product of the above reaction raw materials to a dehalogenation reaction. Specifically, it can be produced by a production method including a step (i) of synthesizing an intermediate by an aromatic electrophilic substitution reaction, and a step (ii) of subjecting the intermediate to a dehalogenation reaction. Step (i): A step of reacting haloethylbenzene represented by formula (2A) with vinyl benzyl halide represented by formula (3A); Step (ii): A step of subjecting the reaction product obtained in step (i) to a dehalogenation reaction to obtain a curable resin.

[0035] <Step (i)> In step (i), haloethylbenzene of formula (2A) is reacted with 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 also 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. One or more acid catalysts can be used in any ratio.

[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 economy.

[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 0 to 200°C, and may 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 used for neutralization include bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, triethylamine, and pyridine. One or more of these bases may be used in any ratio. The obtained 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 vinyl benzyl 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). (In the formula, R ３ , R ４ , m １ , m ２ , X １ and X ２ This is synonymous with formulas (2A) and (3A), and the preferred examples are similar; * 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). (In the formula, R ３ , m １ , X １ and X２ is synonymous with formula (2A), and the preferred examples are the same. * represents a bond.)

[0049] The intermediate preferably contains a compound represented by formula (1'). (In the formula, R １ is a hydrogen atom, R ２ is a methyl group, or R １ is a methyl group, R ２ is a hydrogen atom, R ３ are each independently an alkyl group, an aryl group, an alkoxy group, an aryloxy group or a halogen atom, R ４ are each independently an alkyl group, an aryl group, an alkoxy group, an aryloxy group or a halogen atom, X １ is a hydrogen atom, X ２ is a halogen atom, or X １ is a halogen atom, X ２ is a hydrogen atom, m １ are each independently an integer from 0 to 3, m ２ is an integer from 0 to 4, n is an integer from 1 to 20.)

[0050] In formula (1'), the preferred examples of R ３ , R ４ , X １ , X ２ , m １ and m ２ are the same as those in formula (2A) and formula (3A). In formula (1'), n is preferably an integer from 1 to 10, more preferably 1 to 5.

[0051] In the compound of formula (1'), it is preferable that m １ and m ２ are 0, and in this case, it can be represented by the following formula (1'-1). (In the formula, R １ [[ID=�6]]], R ２ , X １ , X ２ and n are synonymous with formula (1'), and the preferred examples are also the same.)

[0052] In the compound of formula (1'-1), n ​​is preferably 1 to 10, and more preferably 1 to 5. When n is 1, R １ is a methyl group, R ２ When is a hydrogen atom, it can be represented by the following equation (1'-1-1). (In the formula, X １ and X ２ This is equivalent to formula (1'), and the preferred example is similar.

[0053] The intermediate may include the following structural units in addition to the structural units of formulas (2') and (3). (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:

[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] <Step (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 contained 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. One or more base catalysts can be used 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 an aprotic polar solvent in combination is preferable because it can increase the progress of the dehalogenation reaction. One or more organic solvents can be used in any ratio.

[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 of step (ii). Examples of polymerization inhibitors include 2,6-di-tert-butyl-p-cresol (BHT), t-butylcatechol, methoxyphenol, hydroquinone, BASF's Irganox series, Irgafos series, etc. From the viewpoint of inhibiting polymerization, 2,6-di-tert-butyl-p-cresol, methoxyphenol, or hydroquinone are preferred. These polymerization inhibitors can be used one or more in any ratio.

[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 vinyl benzyl 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. (In the formula, R ３ , R ４ , m １ and m ２ This is synonymous with formulas (2A) and (3A), and the preferred examples are similar; * 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 end, in which case the terminal structural unit can be represented by formula (2-1). (In the formula, R ３ and m １ This is equivalent to formula (2), and the preferred example is similar; * indicates a coupling.

[0070] The curable resin of the present invention contains a compound represented by formula (1). (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 R is a hydrogen atom. ３ Each of these is independently an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a halogen atom, and R ４ Each of these is independently an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a halogen atom, m １ Each of these is an integer between 0 and 3, and m ２ R is an integer from 0 to 4, and n is an integer from 1 to 20.) In equation (1), ３ , R ４ , m １ , m ２ Preferred examples of n are the same as those in formula (1').

[0071] In the compound of formula (1), m１ and m ２ It is preferable that this value is 0, in which case it can be expressed by the following formula (1-1). (In the formula, R １ , R ２ And n are equivalent to equation (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, R １ is a methyl group, R ２ When is a hydrogen atom, it can be represented by the following equation (1-1-1).

[0073] In addition to the structural units of formulas (2) and (3), the curable resin may contain the following structural units. (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:

[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 through analysis such as C-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). One or more curing agents can be used in any ratio.

[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, galbinoxyl, 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 used. The cured product can be in the form of a laminate, a cast product, an adhesive layer, a coating, a film, etc.

[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 examples include 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. For example, this can be done by 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 the curable composition is not particularly limited, and one method is to impregnate a reinforcing substrate (for example, paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, glass roving cloth, etc.) with a curable composition that has been varnished by incorporating an organic solvent, as described later, and then heat it at a heating temperature (preferably 50 to 170°C) according to the type of solvent used to semi-cure (or not cure) 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 the prepreg so that the resin content 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 curing of the semi-cured product can be calculated by measuring the heat of curing when the curable composition is heated and the heat of curing of the semi-cured product using DSC, and using the following formula: Degree of curing (%) = [1 - (heat of curing of semi-cured product / heat of curing of 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, place copper foil on top, 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 in the vacuum lamination method (usually 70 to 140°C) 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 polyethylene, polypropylene, polyvinyl chloride or other polyolefins, polyethylene terephthalate (hereinafter sometimes abbreviated as "PET"), polyethylene naphthalate or other polyesters, polycarbonate, polyimide, and also release paper, copper foil, aluminum foil or 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 debris during the curing process. When peeling off after curing, the support film is usually treated with a release agent beforehand.

[0103] [Applications] Cured products obtained from curable compositions containing the curable resin of the present invention exhibit excellent heat resistance and are therefore suitable for use in heat-resistant components or electronic components. In particular, they are suitable for use in prepregs, circuit boards, semiconductor encapsulants, semiconductor devices, build-up films, build-up substrates, adhesives and resist materials using conductive pastes, etc. They can also be suitable for use as matrix resins in fiber-reinforced resins and are especially suitable as high-heat-resistant prepregs. Furthermore, the curable resin contained in the curable composition exhibits excellent solubility in various solvents, making it possible to manufacture paints. 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.

[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) of the haloethyl group-containing resin and curable resin obtained in the examples and comparative examples were calculated using the following measuring equipment and measurement conditions. Measurement device: Tosoh Corporation "HLC-8320 GPC", Column: Tosoh Corporation Guard Column "HXL-L" + Tosoh Corporation "TSK-GEL G2000HXL" + Tosoh Corporation "TSK-GEL G2000HXL" + Tosoh Corporation "TSK-GEL G3000HXL" + Tosoh Corporation "TSK-GEL G4000HXL" Detector: RI (Differential Refractometer) Data processing: Tosoh Corporation "GPC Workstation EcoSEC-WorkStation" Measurement conditions: Column temperature 40°C Developing solvent tetrahydrofuran flow rate 1.0 ml / min Standard: In accordance with the measurement manual for the "GPC Workstation EcoSEC-WorkStation", the following monodisperse polystyrene with known molecular weight was used. (Polystyrene used) Tosoh Corporation "A-500" Tosoh Corporation "A-1000" Tosoh Corporation "A-2500" Tosoh Corporation "A-5000" Tosoh Corporation "F-1" Tosoh Corporation "F-2" Tosoh Corporation "F-4" Tosoh Corporation "F-10" Tosoh Corporation "F-20" Tosoh Corporation "F-40" Tosoh Corporation "F-80" Tosoh Corporation "F-128" Sample: 50 μl of a tetrahydrofuran solution containing 1.0% by mass in terms of resin solids content, filtered through a microfilter.

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

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

[0109] (4) １ The haloethyl group-containing resin and curable resin obtained in the H-NMR measurement example １ The 1H-NMR spectrum was measured using the following measuring equipment and conditions. １ H-NMR: JEOL JNM-ECA500 SuperCOOL probe. Resonance frequency: 500 MHz. Number of integrations: 16. Solvent: Chloroform-d. Sample concentration: 12% by mass.

[0110] <Example 1: Synthesis of Haloethyl Group-Containing Resin> 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, dropping funnel, condenser, fractionation column, and 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 added dropwise to the dropping funnel, and the reaction was carried out at the same temperature for 6 hours from the end of the dropwise addition. Hydrogen chloride produced during the reaction was collected using a base trap.

[0111] Next, 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% sodium hydroxide aqueous solution. Subsequently, the organic layer was washed with 150.0 parts by mass of water, and this procedure was repeated three times. After washing, the solvent and 2-bromoethylbenzene were removed by distillation under reduced pressure at 150°C to obtain the target product, a 2-bromoethyl group-containing resin (Mn 440, Mw 672). It was confirmed that the resin contained an intermediate compound represented by formula (1'-1). The GPC chart of the obtained 2-bromoethyl group-containing resin is shown in Figure 1. １３Figure 2 shows the C-NMR chart, and Figure 3 shows the FD-MS chart. １ The H-NMR chart is shown in Figure 4.

[0112] <Example 2 Synthesis of Curable Resin> 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 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 H-NMR chart is shown in Figure 8.

[0113] <Comparative Example 1: Synthesis of Curable Resin> The curable resin of the comparative example was 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 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 maximum (tanδ was largest) was evaluated as the glass transition temperature (Tg). The results are shown in Table 1. The cut cured material was exposed to an environment of 121 °C and 100% humidity for 6 hours, and the glass transition temperature was measured in the same manner. The results are shown in Table 1.

[0115]

[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.

[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. (In the formula, X １ X is a hydrogen atom, ２ is a halogen atom, or X １ X is a halogen atom, ２ R is a hydrogen atom. ３ Each of these is independently an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a halogen atom, m １ (This is an integer between 0 and 3.) (In the formula, Y is a halogen atom, and R ４ Each of these is independently an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a halogen atom, m ２ (This is an integer between 0 and 4.) 2. A curable resin containing the compound represented by formula (1). (In the formula, １ R ２ is a hydrogen atom, R １ is a methyl group, or R ２ is a methyl group and R ３ is a hydrogen atom, and R ３ are each independently an alkyl group, an aryl group, an alkoxy group, an aryloxy group or a halogen atom, and R ４ are each independently an alkyl group, an aryl group, an alkoxy group, an aryloxy group or a halogen atom, m １ are each independently an integer of 0 to 3, m ２ is an integer of 0 to 4, and n is an integer of 1 to 20.) 3. The curable resin according to claim 2, wherein the curable resin is represented by the following formula (1-1). (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'). (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 R is a hydrogen atom. ３ Each of these is independently an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a halogen atom, and R ４ Each of these is independently an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a halogen atom, and X １ X is a hydrogen atom, ２ is a halogen atom, or X １ X is a halogen atom, ２ is a hydrogen atom, m １ Each of these is an integer between 0 and 3, and m ２ n is an integer between 0 and 4, and 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 a haloethylbenzene represented by the following formula (2A) with a 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. (In the formula, X １ X is a hydrogen atom, ２ is a halogen atom, or X １ X is a halogen atom, ２ R is a hydrogen atom. ３ Each of these is independently an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a halogen atom, m １ (This is an integer between 0 and 3.) (In the formula, Y is a halogen atom, and R ４ Each of these is independently an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a halogen atom, m ２ (This is an integer between 0 and 4.) 6. A curable composition comprising the curable resin according to any one of claims 1 to 3, and 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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