WO2023032534A1 - Allyl ether compound, resin composition, and cured product thereof - Google Patents

Abstract

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

Description

Allyl ether compound, resin composition and cured product thereof

The present invention provides an allyl ether compound that provides a cured product excellent in low dielectric properties, high heat resistance, etc., a resin composition containing the allyl ether compound as an essential component, and a cured product and encapsulant obtained from this resin composition. , to circuit board materials, prepregs or laminates.

Thermosetting resins such as epoxy resins and phenolic resins are excellent in adhesiveness, flexibility, heat resistance, chemical resistance, insulation, and curing reactivity. It is used in a wide variety of materials. In particular, it is widely used for printed wiring boards, which is one of electrical and electronic materials, by imparting flame retardancy to epoxy resins.

With the dramatic increase in the amount of information in recent years, mobile devices, which are one of the applications of printed wiring boards, and infrastructure devices such as base stations that connect them, are always in demand for higher functionality. In particular, as the communication standard changes from 4G to 5G, it is expected that the amount of information will further increase, requiring high-frequency signal transmission. For this reason, materials with a lower dielectric loss tangent are required for printed wiring boards in order to suppress attenuation of signals due to high frequencies. In addition, in order to cope with the thinning and multi-layering of printed wiring boards, the matrix resin is required to have properties such as high adhesive strength and high heat resistance. Matrix resins using conventional epoxy resins are not sufficient to satisfy these requirements, and thermosetting resins with higher functionality are required.

Regarding the reduction of the dielectric constant of epoxy resins that have been used as matrix resins for printed wiring boards, as raw material epoxy resins, compounds obtained by glycidylating dihydric phenols such as bisphenol A, tris(glycidyloxyphenyl)alkanes and amino A compound obtained by glycidylating phenol or the like and a compound obtained by glycidylating novolaks such as phenol novolac are disclosed (Patent Document 1).
Patent Documents 2 and 3 disclose a method of using an imide group-containing phenolic resin to improve heat resistance and mechanical properties more than epoxy resins, and the imide group improves heat resistance. Further, as a resin suitable for a matrix resin that improves adhesion to a substrate, a compound obtained by epoxidizing an imide group-containing phenolic resin is disclosed (Patent Document 4).
In addition, Patent Document 5 discloses a composition in which the heat resistance and flame retardancy of a substrate is improved by using a maleimide compound, an epoxy resin, and a phenol curing agent with a specific structure. It is disclosed that a composition having excellent adhesive strength and dielectric properties can be provided by using a maleimide compound having
Patent Document 8 discloses that a curable resin composition having low dielectric properties and high heat resistance can be obtained by using a maleimide compound and an allyl ether compound. Patent Document 9 discloses that a composition having excellent curability and heat resistance can be obtained by using a thermosetting resin composition containing a maleimide compound having a specific structure and a compound having an allyl group or a methallyl group. disclosed.
However, none of the curable resin compositions disclosed in any of the documents sufficiently satisfies the requirements for dielectric properties based on recent advances in functionality, and does not satisfy all physical properties at the same time.

JP-A-5-43655 JP-A-7-33858 JP-A-7-10970 JP 2010-235823 A WO2011/126070 WO2016/208667 WO2020/054526 JP 2020-111744 A WO2017/170844

Therefore, the problem to be solved by the present invention is to provide a resin composition and a cured product thereof that have excellent performance satisfying both low dielectric properties and high heat resistance and are useful for applications such as lamination, molding, and adhesion. It is something to do.

In order to solve the above problems, the present inventors conducted extensive studies and found that a resin composition containing an allyl ether compound represented by the following formula (1) has unprecedented low dielectric properties and a high glass transition temperature (Tg). The present invention has been completed by finding that the following are satisfied at the same time.

That is, the present invention is an allyl ether compound characterized by being represented by the following general formula (1).

Here, R ¹ is independently a hydrocarbon group having 1 to 8 carbon atoms, R ² is independently a hydrogen atom or a dicyclopentenyl group, one or more is a dicyclopentenyl group, and R ³ is independently It represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, n indicates the number of repetitions, and the average value is 1 to 5.

The present invention also provides a resin composition characterized by containing the allyl ether compound and the maleimide compound.

The present invention also provides a cured product obtained by curing the above resin composition, and a circuit board material, encapsulating material, prepreg, or laminate using the above resin composition.

The resin composition of the present invention provides a cured product with a high glass transition temperature, excellent dielectric properties, and exhibits good properties in laminates and electronic circuit boards that require a low dielectric constant and a low dielectric loss tangent. .

1 is a GPC chart of an allyl ether resin obtained in Example 1. FIG. 1 is an IR chart of the allyl ether resin obtained in Example 1. FIG.

The present invention will be described in detail below.
The allyl ether compound of the present invention is an allyl ether compound represented by the above general formula (1). Here, since it is a mixture of repetition numbers n=0, 1, 2, . . . , it is also called an allyl ether resin.

In each formula of this specification, common symbols have the same meaning in principle.

In general formula (1), R ¹ independently represents a hydrocarbon group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 8 carbon atoms, an aralkyl group having 7 to 8 carbon atoms. , or allyl groups are preferred. The alkyl group having 1 to 8 carbon atoms may be linear, branched or cyclic, and examples thereof include methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl and hexyl. groups, cyclohexyl groups, methylcyclohexyl groups, and the like, but are not limited to these. Examples of aryl groups having 6 to 8 carbon atoms include, but are not limited to, phenyl, tolyl, xylyl, and ethylphenyl groups. The aralkyl group having 7 to 8 carbon atoms includes, but is not limited to, benzyl group, α-methylbenzyl group and the like. Among these substituents, a phenyl group and an alkyl group having 1 to 3 carbon atoms are preferable, and a methyl group is particularly preferable, from the viewpoints of availability and reactivity when a cured product is obtained.

R ² independently represents a hydrogen atom or a dicyclopentenyl group, and at least one is a dicyclopentenyl group. Preferably, R ² in one molecule has an average of 0.1 to 1 dicyclopentenyl groups per phenol ring.
A dicyclopentenyl group is a group derived from dicyclopentadiene and represented by the following formula (1a) or formula (1b).

R ³ independently represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms. Examples of alkyl groups having 1 to 4 carbon atoms include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, and t-butyl groups. Among these substituents, a hydrogen atom or a methyl group is preferable, and a hydrogen atom is particularly preferable, from the viewpoints of availability and reactivity when a cured product is obtained.

n is the number of repetitions and represents a number of 0 or 1 or more, the average value (number average) is 1 to 5, preferably 1.1 to 3, more preferably 1.5 to 2.5, 1.6 to 2 are more preferred. The content by GPC is preferably in the range of 10 area % or less for n=0, 50 to 80 area % for n=1, and 15 to 30 area % for n=2.

The allyl ether compound (resin) preferably has a weight average molecular weight (Mw) of 500 to 2,000 and a number average molecular weight (Mn) of 450 to 1,000.
The hydroxyl equivalent (g/eq) is preferably 5,000 or more, more preferably 10,000 or more. The softening point is preferably (room temperature semi-solid) to 100° C., more preferably 45 to 80° C., and the melt viscosity at 150° C. is preferably 1.0 Pa·s or less, more preferably 0.50 Pa·s. s or less, more preferably 0.20 Pa·s or less. The total chlorine content is preferably 1,000 ppm or less, more preferably 500 ppm or less.

The allyl ether compound (resin) represented by the general formula (1) of the present invention can be obtained, for example, from a polyhydric hydroxy resin represented by the following general formula (2).

Here, R ¹ , R ² and n have the same definitions as in the general formula (1).

The polyhydric hydroxy resin represented by the general formula (2) is obtained by combining a 2,6-disubstituted phenol represented by the following general formula (3) and dicyclopentadiene with a boron trifluoride/ether catalyst or the like. It can be obtained by reacting in the presence of a Lewis acid.

Here, R ¹ has the same definition as in the general formula (1).

Examples of the 2,6-disubstituted phenols include 2,6-dimethylphenol, 2,6-diethylphenol, 2,6-dipropylphenol, 2,6-diisopropylphenol, 2,6-di(n-butyl ) phenol, 2,6-di(t-butyl)phenol, 2,6-dihexylphenol, 2,6-dicyclohexylphenol, 2,6-diphenylphenol, 2,6-ditolylphenol, 2,6-dibenzyl Phenol, 2,6-bis(α-methylbenzyl)phenol, 2-ethyl-6-methylphenol, 2-allyl-6-methylphenol, 2-tolyl-6-phenylphenol and the like are easily available. 2,6-diphenylphenol and 2,6-dimethylphenol are preferred, and 2,6-dimethylphenol is particularly preferred, from the viewpoints of properties and reactivity when used as a cured product.

The catalyst used in the above reaction is a Lewis acid, specifically boron trifluoride, boron trifluoride/phenol complex, boron trifluoride/ether complex, aluminum chloride, tin chloride, zinc chloride, iron chloride, and the like. Among them, boron trifluoride-ether complex is preferable because of ease of handling. In the case of boron trifluoride-ether complex, the amount of the catalyst used is 0.001 to 20 parts by mass, preferably 0.5 to 10 parts by mass, per 100 parts by mass of dicyclopentadiene.

The reaction method for introducing the dicyclopentenyl group into the 2,6-disubstituted compounds is a method of reacting dicyclopentadiene with a predetermined ratio of 2,6-disubstituted phenols, Dicyclopentadiene may be added continuously and allowed to react, or may be added in several steps (sequential addition in two or more divisions) and allowed to react intermittently. The ratio is 0.25 to 2 moles of dicyclopentadiene per 1 mole of 2,6-disubstituted phenols.
When dicyclopentadiene is continuously added and reacted, the ratio of dicyclopentadiene to 1 mol of 2,6-disubstituted phenols is 0.25 to 1 mol, and 0.28 to 1 mol. is preferred, and 0.3 to 0.5 times the molar amount is more preferred. When dicyclopentadiene is added in portions and successively for reaction, the total amount is preferably 0.8 to 2 mol, more preferably 0.9 to 1.7 mol. The ratio of dicyclopentadiene used in each stage is preferably 0.1 to 1 mol. In addition, unreacted 2,6-disubstituted phenols may be recovered during the reaction. Preferable is two or more divided sequential additions to introduce the dicyclopentadiene as the main chain and then the dicyclopentadienyl group as the side chain ^R2 .
In this reaction, not only isomers with different substitution positions but also structures in which a dicyclopentadiene structure and a phenolic hydroxyl group are bonded may be included.

As a method for confirming that a dicyclopentenyl group has been introduced into the polyvalent hydroxy resin represented by the general formula (2), mass spectrometry (MS) and Fourier transform infrared spectrophotometer (FT- IR) measurements can be used.

When using a mass spectrometry method, electrospray mass spectrometry (ESI-MS), field desorption method (FD-MS), etc. can be used. The introduction of a dicyclopentenyl group can be confirmed by subjecting a sample obtained by separating components having different numbers of nuclei by GPC or the like to mass spectrometry.

When using the FT-IR measurement method, a sample dissolved in an organic solvent such as THF is applied on the KRS-5 cell, and the organic solvent is dried to obtain a sample thin film-attached cell, which is measured by FT-IR. A peak derived from C—O stretching vibration in the phenol nucleus appears at around 1210 cm ⁻¹ , and a peak derived from C—H stretching vibration of the olefin site of the dicyclopentadiene skeleton appears at 3040 cm only when a dicyclopentenyl group is introduced. It appears around ^-1 . Since the dicyclopentadiene incorporated into the main chain loses its olefinic site, it is not detected, and only the olefin of the dicyclopentenyl group introduced as the side chain ^R2 can be measured. When the beginning and end of the target peak are linearly connected as the baseline, and the length from the top of the peak to the baseline is the peak height, the peak (A ₃₀₄₀ ) near 3040 cm ⁻¹ and 1210 cm ⁻¹ The introduction amount of the dicyclopentenyl group can be quantified by the ratio (A ₃₀₄₀ /A ₁₂₁₀ ) of the nearby peak (A ₁₂₁₀ ). It has been confirmed that the larger the ratio _, the better the physical property value _. 0.10 to 0.30.

The hydroxyl group equivalent weight of the polyfunctional hydroxy resin is preferably 150-500, more preferably 200-350. As for the average molecular weight, the weight average molecular weight (Mw) is preferably 400 to 2,000, more preferably 500 to 2,000, and the number average molecular weight (Mn) is preferably 350 to 1,000, more preferably 400-800. The softening point is preferably 70-150°C, more preferably 80-120°C.

For this reaction, a method of charging a 2,6-disubstituted phenol and a catalyst into a reactor and adding dicyclopentadiene dropwise over 1 to 10 hours is preferable.

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

After the reaction is completed, an alkali such as sodium hydroxide, potassium hydroxide, or calcium hydroxide is added to deactivate the catalyst. Thereafter, solvents such as aromatic hydrocarbons such as toluene and xylene, and ketones such as methyl ethyl ketone and methyl isobutyl ketone are added to dissolve and washed with water. hydroxy resins can be obtained. It is preferable to react the whole amount of dicyclopentadiene as much as possible, leave a part of the 2,6-disubstituted phenol unreacted, preferably 10% or less, and recover it under reduced pressure.

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

The allyl ether compound represented by the general formula (1) of the present invention can be obtained by allyl-etherifying the hydroxyl groups of the polyhydric hydroxy resin represented by the general formula (2).

As an allyl etherification method for obtaining the allyl ether compound of general formula (1), a polyhydric hydroxy resin represented by general formula (2) is reacted with an allyl halide compound in a solvent in the presence of an alkali compound. (allyl etherification reaction). In this case, it is preferable to dissolve the polyhydric hydroxy resin in advance in a solvent, and then add the allyl halide compound solution and the alkali compound solution to react. This allyl etherification reaction is preferably carried out by charging a polyhydric hydroxy resin and a solvent into a reactor, dissolving them, and then adding dropwise an allyl halide compound solution and an alkali compound solution.

Examples of allyl halide compounds include allyl chloride, allyl bromide, methallyl chloride, methallyl bromide and the like. Among these, allyl bromide or allyl chloride is preferable from the viewpoint of reactivity with the polyhydric hydroxy resin.
Allyl chloride tends to polymerize with each other to form a polymer (polyallyl chloride), but it is preferable to use allyl chloride containing a small amount of polyallyl chloride for production. If the content of polyallyl chloride in the allyl chloride used is high, not only will the total amount of chlorine in the allyl ether compound to be obtained increase, but also the molecular weight of the allyl ether compound will increase, resulting in a small amount of gelled matter in the cured product. may occur. In order to reduce the total chlorine content, there is a concern that a considerable amount of basic substance will need to be added. The content ratio of polyallyl chloride in allyl chloride can be easily confirmed by gas chromatography (GC) or the like. The following is preferable, 0.5 area % or less is more preferable, and 0.2 area % or less is even more preferable.
The amount of the allyl halide compound to be used is generally 1.0 to 2.0 mol, preferably 1.0 to 1.5 mol, more preferably 1.0 mol, per 1 mol of the hydroxyl group of the polyhydric hydroxy resin. It is up to 1.25 mol, more preferably 1.0 to 1.2 mol.

As the alkali compound used for producing the allyl ether compound, alkali metal hydroxides, carbonates, and the like are preferable, and specific examples include sodium hydroxide, potassium hydroxide, potassium carbonate, and sodium carbonate. Sodium and potassium hydroxide are preferred. Such an alkali metal hydroxide may be used in the form of a solid or in the form of an aqueous solution thereof.
The amount of the alkali compound to be used is generally 1.0 to 2.0 mol, preferably 1.0 to 1.8 mol, more preferably 1.0 to 1 mol, per 1 mol of hydroxyl group of the polyhydroxy resin. 0.5 mol, more preferably 1.0 to 1.3 mol, particularly preferably 1.0 to 1.1 mol.

The solvent used for the production of the allyl ether compound is not particularly limited. Ethers such as tetrahydrofuran, dioxane, and diglyme, aprotic polar solvents such as dimethylacetamide, dimethylformamide, and dimethylsulfoxide, and the like, and one or more organic solvents selected from these can be used. Also, water can be used by mixing with the above organic solvent.
The amount of the organic solvent used is preferably 20 to 300 parts by mass, more preferably 25 to 250 parts by mass, and particularly preferably 25 to 200 parts by mass, based on 100 parts by mass of the polyhydric hydroxy resin. Aprotic polar solvents such as dimethyl sulfoxide are not useful for purification such as washing with water, and have a high boiling point and are difficult to remove. It is not preferable to be overweight.
In addition to the above water and organic solvent, an organic solvent such as toluene (other organic solvent) may be included, and the amount of the other organic solvent used is preferably 100 parts by mass or less relative to the amount of the solvent used. , more preferably 0.5 to 50 parts by mass.

The reaction temperature for the allyl etherification reaction of the polyhydric hydroxy resin is generally 30 to 90°C, preferably 35 to 80°C. In order to obtain an allyl ether compound of higher purity, it is preferable to raise the reaction temperature in two or more steps, for example, 35 to 50°C in the first step and 45 to 100°C in the second step. is particularly preferred.
The reaction time for the allyl etherification reaction of the polyhydric hydroxy resin is usually 0.5 to 10 hours, preferably 1 to 8 hours, particularly preferably 1 to 5 hours. When the reaction time is 0.5 hours or longer, the reaction proceeds sufficiently, and when the reaction time is 10 hours or shorter, it becomes possible to suppress the amount of by-products produced.

After completion of the reaction, the solvent is distilled off under heating under reduced pressure, or without being distilled off, a ketone compound having 4 to 7 carbon atoms (eg, methyl isobutyl ketone, methyl ethyl ketone, cyclopentanone, cyclohexanone, etc.), It is dissolved in an organic solvent such as toluene, heated to 40 to 90° C., more preferably 50 to 80° C., and washed with water until the pH of the aqueous layer reaches 5 to 8 to remove by-produced salts.

Incidentally, the allyl etherification reaction of the polyhydric hydroxy resin is usually carried out while blowing an inert gas such as nitrogen into the system (in the air or in the liquid). By carrying out the reaction while blowing an inert gas into the system, it is possible to prevent the resulting product from being colored.
The amount of inert gas to be blown per unit time varies depending on the volume of the kettle used for the reaction. is preferably adjusted.

The maleimide compound contained in the resin composition of the present invention is not particularly limited, but examples include N-phenylmaleimide, N-hydroxyphenylmaleimide, 4,4'-diphenylmethanebismaleimide, and polyphenylmethanemaleimide. , m-phenylenebismaleimide, p-phenylenebismaleimide, 2,2′-[4-(4-maleimidophenoxy)phenyl]propane, 3,3′-dimethyl-5,5′-diethyl-4,4′- Diphenylmethanebismaleimide, bis(3,5-dimethyl-4-maleimidophenyl)methane, bis-(3-ethyl-5-methyl-4-maleimidophenyl)methane, bis(3,5-diethyl-4-maleimidophenyl) Methane, 4-methyl-1,3-phenylenebismaleimide, 4,4'-diphenyletherbismaleimide, 4,4'-diphenylsulfonebismaleimide, 1,3-bis(3-maleimidophenoxy)benzene, 1,3- Bis(4-maleimidophenoxy)benzene, N,N'-ethylenedimaleimide, N,N'-hexamethylenedimaleimide, a maleimide compound (resin) represented by the following general formula (4), and preforms of these maleimide compounds Examples thereof include polymers, prepolymers of maleimide compounds and amine compounds, and the like.

here,
R ⁴ independently represents an alkyl group having 1 to 5 carbon atoms or an aromatic group.
^R5 independently represents a hydrogen atom or a methyl group.
a represents 0 to 4, preferably 0 to 2;
b represents 0 to 3, preferably 0 to 2;
r and q are 0 or 1;
m is the number of repetitions, and the average value is 1-10, preferably 1-5.

The resin composition of the present invention contains the allyl ether compound (resin) represented by the general formula (1) and the maleimide compound (resin) of the present invention as essential components. The content of the allyl ether compound is preferably 5 to 900 parts by mass, more preferably 10 to 300 parts by mass, still more preferably 50 to 200 parts by mass, and particularly preferably 100 to 200 parts by mass with respect to 100 parts by mass of the maleimide compound. Department.
As the allyl ether compound used to obtain the resin composition of the present invention, in addition to the allyl ether compound represented by the general formula (1) of the present invention, if necessary, one or more of various allyl ether compounds You may use two or more types together. Preferably, at least 30% by mass of the allyl ether compound is the allyl ether compound of the present invention, more preferably 50% by mass or more. If it is less than this, the dielectric properties may deteriorate.

Examples of allyl ether compounds that can be used in combination with the allyl ether compound (resin) of the present invention include bisphenol A, bisphenol F, bisphenol C, bisphenol K, bisphenol Z, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, Allyl ether compounds obtained by allyl etherifying bisphenols such as tetramethylbisphenol S, tetramethylbisphenol Z, dihydroxydiphenyl sulfide, 4,4'-thiobis(3-methyl-6-t-butylphenol), catechol, resorcin, methyl Allyl ether compounds, dihydroxynaphthalene, dihydroxymethylnaphthalene, dihydroxymethyl Allyl ether compounds obtained by allyl-etherifying hydroxynaphthalenes such as naphthalene and trihydroxynaphthalene, phenol novolac resins such as Shounol BRG-555 (manufactured by Aica Kogyo Co., Ltd.), DC-5 (manufactured by Nippon Steel Chemical & Materials Co., Ltd. ) and other cresol novolak resins, aromatic modified phenol novolak resins, bisphenol A novolak resins, trishydroxyphenylmethane type novolak resins such as Resitop TPM-100 (manufactured by Gunei Chemical Industry Co., Ltd.), phenols such as naphthol novolak resins, Condensates of naphthols and/or bisphenols and aldehydes, phenols such as SN-160, SN-395, SN-485 (manufactured by Nippon Steel Chemical & Materials Co., Ltd.), naphthols and/or bisphenols and xyloxy Condensates with lenglycol, condensates of phenols and/or naphthols with isopropenylacetophenone, reaction products of phenols, naphthols and/or bisphenols with dicyclopentadiene, phenols, naphthols and/or Examples include allyl ether compounds and triallyl isocyanurates obtained by allyl-etherifying polyhydric hydroxy resins such as so-called novolac phenol resins such as condensates of bisphenols and biphenyl-based cross-linking agents. From the viewpoint of reactivity and availability, allyl ether compounds obtained by allyl-etherifying bisphenols such as bisphenol A and bisphenol F are preferable.

A curing accelerator can be added to the resin composition of the present invention as necessary. When a curing accelerator is used, the compound capable of cross-linking reaction with maleimide group undergoes an addition reaction with maleimide group to cross-link, so that the cured product exhibits good physical properties.

Examples of curing accelerators include amines, imidazoles, organic phosphines, Lewis acids, organic peroxides, etc. Specifically, 1,8-diazabicyclo(5,4,0)undecene-7 , triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tertiary amines such as tris(dimethylaminomethyl)phenol, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2- imidazoles such as phenyl-4-methylimidazole and 2-heptadecylimidazole; organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine and phenylphosphine; addition of organic phosphines and quinone compounds; reactant, tetrasubstituted phosphonium/tetrasubstituted borate such as tetraphenylphosphonium/tetraphenylborate, tetraphenylphosphonium/ethyltriphenylborate, tetrabutylphosphonium/tetrabutylborate, 2-ethyl-4-methylimidazole/tetraphenylborate, Tetraphenylboron salts such as N-methylmorpholine and tetraphenylborate, organic peroxides such as ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxydicarbonates, and peroxyesters There is a kind. The amount to be added is in the range of 0.2 to 5 parts by mass with respect to 100 parts by mass of the resin composition.

If necessary, the resin composition of the present invention can be blended with other various curable resins and thermoplastic resins.

Examples of curable resins include epoxy resins, unsaturated polyester resins, curable maleimide resins, polycyanate resins, phenolic resins, and one or more vinyl compounds having one or more polymerizable unsaturated hydrocarbon groups in the molecule. etc. From the viewpoint of low dielectric constant and low dielectric loss tangent, one or more vinyl compounds having one or more polymerizable unsaturated hydrocarbon groups in the molecule are preferable.

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

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

Furthermore, when blending an epoxy resin, a curing accelerator can be used as necessary. Examples include amines, imidazoles, organic phosphines, and Lewis acids. The amount to be added is usually in the range of 0.2 to 5 parts by mass with respect to 100 parts by mass of the epoxy resin.

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

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

Vinyl compounds include, for example, triallyl isocyanurate (TAIC) and other trialkenyl isocyanurate compounds, modified polyphenylene ethers (PPE) whose terminals are modified with (meth)acryloyl groups or styryl groups, and (meth) Polyfunctional (meth)acrylate compounds having two or more acryloyl groups, vinyl compounds having two or more vinyl groups in the molecule such as polybutadiene (polyfunctional vinyl compounds), and vinylbenzyls such as styrene and divinylbenzene compounds and the like. Among these, those having two or more carbon-carbon double bonds in the molecule are preferable, and specifically, TAIC, polyfunctional (meth)acrylate compounds, modified PPE resins, polyfunctional vinyl compounds, and divinylbenzene compounds. etc. It is believed that the use of these compounds will result in more favorable formation of crosslinks through the curing reaction, and the heat resistance of the cured product of the resin composition can be further enhanced. Moreover, these may be used independently and may be used in combination of 2 or more type. A compound having one carbon-carbon unsaturated double bond in the molecule may also be used in combination. Compounds having one carbon-carbon unsaturated double bond in the molecule include compounds having one vinyl group in the molecule (monovinyl compounds).

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

If necessary, the resin composition of the present invention may contain other additives such as fillers, silane coupling agents, antioxidants, release agents, antifoaming agents, emulsifiers, thixotropic agents, smoothing agents, flame retardants, pigments, and the like. agents and the like can be contained.

Specific examples of fillers include fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide, boehmite, magnesium hydroxide, talc, mica, calcium carbonate, calcium silicate, calcium hydroxide, magnesium carbonate, carbonate Barium, barium sulfate, boron nitride, carbon, carbon fiber, glass fiber, alumina fiber, silica alumina fiber, silicon carbide fiber, polyester fiber, cellulose fiber, aramid fiber, ceramic fiber, fine particle rubber, thermoplastic elastomer and the like. One of the reasons for using a filler is the effect of improving the impact resistance. Moreover, when metal hydroxides such as aluminum hydroxide, boehmite, and magnesium hydroxide are used, they act as flame retardant aids and have the effect of improving flame retardancy. Among these, silica, mica, and talc are preferred, and spherical silica is more preferred. Moreover, these 1 type may be used independently and may be used in combination of 2 or more type.

The filler may be used as it is, or may be surface-treated with a silane coupling agent such as epoxysilane type or aminosilane type. As the silane coupling agent, vinylsilane type, methacryloxysilane type, acryloxysilane type, and styrylsilane type silane coupling agents are preferable. As a result, the adhesive strength with the metal foil and the interlayer adhesive strength between resins are increased. In addition, a silane coupling agent may be added by an integral blend method instead of the method of surface-treating the filler in advance.

When the resin composition is used as a plate-like substrate or the like, fibrous fillers are preferred in terms of dimensional stability, bending strength, and the like. A more preferred example is a glass fiber substrate using a fibrous base material filler in which glass fibers are woven into a mesh.

The amount of the filler compounded is preferably 1 to 150 parts by mass, more preferably 10 to 70 parts by mass, per 100 parts by mass of the resin composition (solid content). If the compounding amount is too large, the cured product becomes brittle, and there is a possibility that sufficient mechanical properties cannot be obtained. On the other hand, if the blending amount is too small, there is a fear that the blending effect of the filler, such as improvement of the impact resistance of the cured product, may not be achieved.
The blending amount of other additives is preferably in the range of 0.01 to 20 parts by mass with respect to 100 parts by mass of the resin composition (solid content).

A cured product can be obtained by heat-curing the resin composition of the present invention. Methods for obtaining a cured product include cast molding, compression molding, transfer molding, etc., and methods such as laminating in the form of resin sheets, resin-coated copper foils, prepregs, etc., and curing them under heat and pressure to form laminates. is preferably used. The temperature at this time is usually in the range of 150 to 300° C., and the curing time is usually about 10 minutes to 5 hours.

The resin composition of the present invention is obtained by uniformly mixing the above components. The resin composition can be easily cured by a conventionally known method. Examples of cured products include molded cured products such as laminates, cast products, molded products, adhesive layers, insulating layers, and films.

Applications in which the resin composition is used include printed wiring board materials, resin compositions for flexible wiring boards, insulating materials for circuit boards such as interlayer insulating materials for build-up boards, semiconductor sealing materials, conductive pastes, conductive films, Adhesive films for build-up, resin casting materials, adhesives, and the like. Among these various applications, printed wiring board materials, insulating materials for circuit boards, and adhesive film applications for build-up are so-called substrates for embedding electronic components, in which passive components such as capacitors and active components such as IC chips are embedded in the substrate. can be used as an insulating material for Among these, due to their properties such as high flame retardancy, high heat resistance, low dielectric properties, and solvent solubility, they can be used as printed wiring board materials, resin compositions for flexible wiring boards, and circuit boards such as interlayer insulation materials for build-up boards ( It is preferably used as a material for laminates) and a semiconductor encapsulating material.

Sealing materials obtained using the resin composition of the present invention include tape-shaped semiconductor chips, potting-type liquid sealing, underfill, semiconductor interlayer insulating films, etc., and are preferably used for these. be able to. In order to prepare the resin composition for use as a semiconductor encapsulating material, additives such as inorganic fillers, coupling agents, and mold release agents, which are blended as necessary in the resin composition, are premixed, and then extruded. , a kneader, a roll, or the like, to sufficiently melt and mix until uniform. In this case, silica is usually used as the inorganic filler, and it is preferable to blend 70 to 95% by mass of the inorganic filler in the resin composition.

When using the resin composition obtained in this way as a semiconductor package, the resin composition is cast, or molded using a transfer molding machine, an injection molding machine, etc., and further 0.5 at 180 to 250 ° C. A method of obtaining a molded article by heat curing for ˜5 hours may be mentioned.
When used as a tape-shaped sealing material, this is heated to prepare a semi-cured sheet to form a sealing material tape, and then this sealing material tape is placed on a semiconductor chip and heated to 100 to 150 ° C. A method of softening and molding with heat and curing completely at 180 to 250°C can be mentioned. When used as a potting-type liquid encapsulant, the resulting resin composition may be dissolved in a solvent, if necessary, applied to a semiconductor chip or electronic component, and cured directly.

The resin composition of the present invention can be dissolved in an organic solvent to prepare a varnish. Organic solvents that can be used include alcohol solvents such as methanol and ethanol, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, ether solvents such as tetrahydrofuran, and nitrogen solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. Atom-containing solvents, sulfur atom-containing solvents such as dimethylsulfoxide, and the like can be mentioned, and one or a mixture of two or more thereof can be used. Although it is not particularly limited as long as it is an industrially available organic solvent, methyl ethyl ketone and dimethylformamide are preferred in terms of solubility and handling.

The resin composition of the present invention is dissolved in an organic solvent to form a composition varnish, impregnated with a fibrous material such as a glass cloth, an aramid nonwoven fabric, a polyester nonwoven fabric such as a liquid crystal polymer, etc., and then the solvent is removed to form a prepreg. be able to. Alternatively, an adhesive sheet can be obtained by applying the composition varnish onto a sheet-like material such as copper foil, stainless steel foil, polyimide film, polyester film, and the like, followed by drying.

When forming a laminate using the prepreg, one or more prepregs are laminated, a metal foil is arranged on one side or both sides to form a laminate, and the laminate is pressurized and heated. A laminate can be obtained by curing and integrating the prepreg. Here, as the metal foil, copper, aluminum, brass, nickel, or the like can be used alone, as an alloy, or as a composite metal foil. The conditions for heating and pressurizing the laminate may be appropriately adjusted so that the resin composition is cured. It is desirable to apply pressure under conditions that satisfy moldability. The heating temperature is preferably 160 to 250°C, more preferably 170 to 220°C. The applied pressure is preferably 0.5 to 10 MPa, more preferably 1 to 5 MPa. The heating and pressing time is preferably 10 minutes to 4 hours, more preferably 40 minutes to 3 hours. Furthermore, a multi-layer board can be produced by using the single-layer laminate board thus obtained as an inner layer material. In this case, first, a circuit is formed on the laminate by an additive method, a subtractive method, or the like, and the surface of the formed circuit is subjected to a blackening treatment to obtain an inner layer material. An insulating layer is formed on one or both sides of the inner layer material with a prepreg or an adhesive sheet, and a conductor layer is formed on the surface of the insulating layer to form a multilayer board.

The present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to these. Unless otherwise specified, "parts" represent parts by mass, "%" represents mass %, and "ppm" represents mass ppm. Moreover, the measurement method was each measured by the following methods.

・Hydroxyl equivalent:
The measurement was performed according to the JIS K0070 standard, and the unit was expressed as "g/eq.". Incidentally, unless otherwise specified, the hydroxyl group equivalent of the polyhydric hydroxy resin means the phenolic hydroxyl group equivalent.

・Softening point:
It was measured according to the JIS K7234 standard and the ring and ball method. Specifically, an automatic softening point apparatus (ASP-MG4 manufactured by Meitec Co., Ltd.) was used.

・Glass transition temperature (Tg):
It was measured according to JIS C6481 standard. It was expressed by tan δ peak top when measured with a dynamic viscoelasticity measuring device (manufactured by Hitachi High-Tech Science Co., Ltd., EXSTAR DMS6100) at a temperature rising condition of 5°C/min.

・Relative permittivity and dielectric loss tangent:
According to IPC-TM-650 2.5.5.9, using a material analyzer (manufactured by AGILENT Technologies), the dielectric constant and dielectric loss tangent at a frequency of 1 GHz were determined by the capacitance method for evaluation.

・GPC (gel permeation chromatography) measurement:
A column (TSKgelG4000HXL, TSKgelG3000HXL, TSKgelG2000HXL manufactured by Tosoh Corporation) in series with a main body (HLC-8220GPC manufactured by Tosoh Corporation) was used, and the column temperature was set to 40°C. Tetrahydrofuran (THF) was used as an eluent at a flow rate of 1 mL/min, and a differential refractive index detector was used as a detector. As a measurement sample, 0.1 g of the sample was dissolved in 10 mL of THF and filtered through a microfilter, and 50 μL of the solution was used. For data processing, GPC-8020 model II version 6.00 manufactured by Tosoh Corporation was used.

・ IR:
A Fourier transform infrared spectrophotometer (Perkin Elmer Precisely, Spectrum One FT-IR Spectrometer 1760X) was used, KRS-5 was used for the cell, and a sample dissolved in THF was applied on the cell and dried. After that, absorbance was measured at wavenumbers of 650 to 4000 cm ⁻¹ .

・ESI-MS:
Mass spectrometry was performed by using a mass spectrometer (Shimadzu Corporation, LCMS-2020), using acetonitrile and water as mobile phases, and measuring a sample dissolved in acetonitrile.

Abbreviations used in Examples and Comparative Examples are as follows.

[Allyl ether compound]
R1: Allyl ether compound (resin) obtained in Example 1
R2: allyl ether compound (resin) obtained in Example 2
R3: Allyl ether compound (resin) obtained in Example 3
S1: Allyl ether compound obtained in Comparative Example 1 S2: Allyl ether compound obtained in Comparative Example 2 S3: 4,4'-(1-methylethylidene) bis (2-allylphenol) (Fuji Film Wako Pure Chemical Co., Ltd., allyl group equivalent 154)

[Polyvalent hydroxy resin]
P1: Polyvalent hydroxy resin obtained in Synthesis Example 1 P2: Polyvalent hydroxy resin obtained in Synthesis Example 2 P3: Polyvalent hydroxy resin obtained in Synthesis Example 3 P4: Polyvalent hydroxy resin obtained in Synthesis Example 4 Hydroxy resin MEH: biphenyl aralkyl type polyhydric hydroxy resin (manufactured by Meiwa Kasei Co., Ltd., MEH-7851, hydroxyl equivalent 210, softening point 75 ° C.)
PN: phenol novolac resin (manufactured by Aica Kogyo Co., Ltd., Shaunol BRG-557, hydroxyl equivalent 105, softening point 85 ° C.)

[Maleimide compound]
M1: phenylmethane maleimide (manufactured by Daiwa Kasei Kogyo Co., Ltd., BMI-2300)
M2: Maleimide compound (resin) obtained in Synthesis Example 5

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

[Curing accelerator]
C1: dicumyl peroxide (manufactured by NOF Co., Ltd., Parkmil D)
C2: 2-ethyl-4-methylimidazole (manufactured by Shikoku Kasei Co., Ltd., Curesol 2E4MZ)

Synthesis example 1
500 parts of 2,6-xylenol (structural formula below) was added to a reaction apparatus consisting of a glass separable flask equipped with a stirrer, thermometer, nitrogen blowing tube, dropping funnel, and cooling tube.

7.3 parts of 47% BF ₃ ether complex (0.1 times moles relative to the initially added dicyclopentadiene) were charged and heated to 100° C. while stirring. While maintaining the same temperature, 67.6 parts of dicyclopentadiene (the following structural formula) (0.12 times moles relative to 2,6-xylenol)

was added dropwise in 1 hour. Furthermore, the reaction was carried out at a temperature of 115-125° C. for 4 hours. Thereafter, the mixture was heated to 200° C. under a reduced pressure of 5 mmHg to evaporate off unreacted raw materials, and 46.7 parts of MIBK was added to dissolve the product. After charging 3.3 parts of 47% BF ₃ ether complex, the temperature was raised to 100° C., and 74.7 parts of dicyclopentadiene was added dropwise over 1 hour while maintaining the same temperature. Furthermore, the reaction was carried out at 115-125° C. for 4 hours. 5 parts of calcium hydroxide are added. An additional 9 parts of 10% aqueous oxalic acid solution was added. 350 parts of MIBK was added to dissolve the product, and 120 parts of hot water at 80° C. was added to wash with water to separate and remove the lower aqueous layer. After heating to 120° C. for reflux dehydration and filtration, the reaction mixture was heated to 160° C. under reduced pressure of 5 mmHg to remove MIBK by evaporation to obtain 259 parts of a reddish brown polyhydric hydroxy resin (P1).
The obtained polyhydric hydroxy resin (P1) had a hydroxyl equivalent of 323, a softening point of 97° C., and an absorption ratio (A ₃₀₄₀ /A ₁₂₁₀ ) of 0.27. Mw in GPC is 740, Mn is 490, n = 0 body content is 6.6 area%, n = 1 body content is 70.1 area%, n = 2 or more body content is 23.3 area %Met. Mass spectrum measurement by ESI-MS (negative) confirmed M−=375, 507, 629, 639, 761.

Synthesis example 2
500 parts of 2,6-xylenol and 7.3 parts of 47% BF ₃ ether complex were placed in the same reactor as in Synthesis Example 1 and heated to 100° C. while stirring. While maintaining the same temperature, 67.6 parts of dicyclopentadiene (0.12-fold mol with respect to 2,6-xylenol) was added dropwise over 1 hour. Furthermore, the reaction was carried out at a temperature of 115-125° C. for 4 hours. Thereafter, the mixture was heated to 200° C. under a reduced pressure of 5 mmHg to evaporate off unreacted raw materials, and 46.7 parts of MIBK was added to dissolve the product. After charging 3.3 parts of 47% BF ₃ ether complex, the temperature was raised to 100° C., and 56.0 parts of dicyclopentadiene was added dropwise over 1 hour while maintaining the same temperature. Furthermore, the reaction was carried out at 115-125° C. for 4 hours. 5 parts of calcium hydroxide are added. An additional 9 parts of 10% aqueous oxalic acid solution was added. 320 parts of MIBK was added to dissolve the product, and 110 parts of hot water at 80° C. was added to wash with water to separate and remove the lower water tank. After heating to 120° C. for reflux dehydration and filtration, the reaction mixture was heated to 160° C. under reduced pressure of 5 mmHg to remove MIBK by evaporation to obtain 240 parts of a reddish brown polyhydric hydroxy resin (P2).
The obtained polyhydric hydroxy resin (P2) had a hydroxyl equivalent of 276, a softening point of 94° C., and an absorption ratio (A ₃₀₄₀ /A ₁₂₁₀ ) of 0.17. Mw in GPC is 670, Mn is 490, n = 0 body content is 6.6 area%, n = 1 body content is 70.3 area%, n = 2 or more body content is 23.1 area %Met. Mass spectrum measurement by ESI-MS (negative) confirmed M−=375, 507, 629, 639, 761.

Synthesis example 3
In the same reactor as in Synthesis Example 1, 500 parts of 2,6-xylenol and 7.3 parts of 47% BF ₃ ether complex (0.1 times the molar amount of dicyclopentadiene initially added) were charged and stirred. while heating to 100°C. While maintaining the same temperature, 67.6 parts of dicyclopentadiene (0.12-fold mol with respect to 2,6-xylenol) was added dropwise over 1 hour. Furthermore, the reaction was carried out at a temperature of 115-125° C. for 4 hours. Thereafter, the mixture was heated to 200° C. under a reduced pressure of 5 mmHg to evaporate off unreacted raw materials, and 46.7 parts of MIBK was added to dissolve the product. After charging 3.3 parts of 47% BF ₃ ether complex, the temperature was raised to 100° C., and 28.0 parts of dicyclopentadiene was added dropwise over 1 hour while maintaining the same temperature. After reacting at 115 to 125° C. for 4 hours, 5 parts of calcium hydroxide was added. An additional 9 parts of 10% aqueous oxalic acid solution was added. 280 parts of MIBK was added to dissolve the product, and 100 parts of hot water at 80° C. was added to wash with water to separate and remove the lower aqueous layer. After heating to 120° C. for reflux dehydration and filtration, the reaction mixture was heated to 160° C. under reduced pressure of 5 mmHg to remove MIBK by evaporation to obtain 213 parts of a reddish brown polyhydric hydroxy resin (P3).
The obtained polyhydric hydroxy resin (P3) had a hydroxyl equivalent of 234, a softening point of 86° C., and an absorption ratio (A ₃₀₄₀ /A ₁₂₁₀ ) of 0.11. Mw in GPC is 560, Mn is 470, n = 0 body content is 6.2 area%, n = 1 body content is 74.0 area%, n = 2 or more body content is 19.8 area %Met. Mass spectrum measurement by ESI-MS (negative) confirmed M−=375, 507, 629, 639, 761.

Synthesis example 4
1507 parts of phenol and 22.7 parts of 47% BF ₃ ether complex were charged into the same reactor as in Synthesis Example 1 and heated to 100° C. while stirring. While maintaining the same temperature, 211.7 parts of dicyclopentadiene (0.10 times the molar amount of phenol) was added dropwise over 1 hour. Further, the mixture was reacted at a temperature of 115 to 125° C. for 4 hours, and 36 parts of calcium hydroxide was added. An additional 60 parts of a 10% aqueous oxalic acid solution was added. Then, after heating to 160° C. for dehydration, the mixture was heated to 200° C. under a reduced pressure of 5 mmHg to evaporate and remove unreacted raw materials. 1720 parts of MIBK was added to dissolve the product, and 550 parts of hot water at 80° C. was added to wash with water to separate and remove the lower aqueous layer. After heating to 120° C. for reflux dehydration, filtering, heating to 160° C. under reduced pressure of 5 mmHg to evaporate and remove MIBK, a reddish brown polyhydric hydroxy resin represented by the following general formula (5). 480 parts of (P4) were obtained.
The resulting polyhydric hydroxy resin (P4) had a hydroxyl equivalent of 175 and a softening point of 90°C. Mw in GPC is 470, Mn is 410, s = 0 body content is 1.0 area%, s = 1 body content is 68.7 area%, s = 2 or more body content is 30.3 area %Met.

Synthesis example 5
A flask equipped with a thermometer, a condenser, a Dean-Stark azeotropic distillation trap and a stirrer was charged with 100 parts of aniline and 50 parts of toluene, and 39.2 parts of 35% hydrochloric acid was added dropwise at room temperature over 1 hour. After the dropwise addition was completed, the water and toluene that had been azeotroped by heating were cooled and separated, and then only the toluene, which was the organic layer, was returned to the system for dehydration. Then, 33.6 parts of 4,4'-bis(chloromethyl)biphenyl was added over 1 hour while maintaining the temperature at 60 to 70°C, and the reaction was further carried out at the same temperature for 2 hours. After completion of the reaction, toluene was distilled off while raising the temperature to raise the inside temperature to 195 to 200° C., and the reaction was carried out at this temperature for 15 hours. Thereafter, while cooling, 86 parts of a 30% aqueous sodium hydroxide solution is slowly added dropwise so as not to violently reflux the system, and the toluene distilled off when the temperature rises below 80°C is returned to the system and allowed to stand at 70 to 80°C. bottom. The separated lower aqueous layer was removed, and the reaction solution was washed with water repeatedly until the washing solution became neutral. Then, excess aniline and toluene were distilled off from the oil layer with a rotary evaporator under heating and reduced pressure (200° C., 0.6 KPa) to obtain 47 parts of an aromatic amine resin.
Next, 75 parts of maleic anhydride and 150 parts of toluene are charged into the flask, and the water and toluene that are azeotroped by heating are cooled and separated, and only the toluene, which is the organic layer, is returned to the system and dehydrated. did Next, a resin solution prepared by dissolving 100 parts of the above aromatic amine resin in 100 parts of N-methyl-2-pyrrolidone was added dropwise over 1 hour while the system was maintained at 80 to 85°C. After the completion of dropping, the reaction is carried out at the same temperature for 2 hours, 1.5 parts of p-toluenesulfonic acid is added, and the condensed water and toluene that are azeotropically distilled under reflux conditions are cooled and separated, and then the organic layer is obtained. The reaction was carried out for 20 hours while dehydration was carried out by returning only toluene to the system. After completion of the reaction, 100 parts of toluene was added, and the mixture was repeatedly washed with water to remove p-toluenesulfonic acid and excess maleic anhydride, followed by heating to azeotropically remove water from the system. Then, the reaction solution was concentrated to obtain 133 parts of maleimide compound (M2). Here, the maleimide compound (M2) has a = 0, b = 0, r = 1, q = 1 in formula (4), all R ⁵ are hydrogen atoms, and m is 1.3. .

Example 1
100 parts of the polyhydric hydroxy resin (P1) obtained in Synthesis Example 1 and 150 parts of diglyme were placed in the same reactor as in Synthesis Example 1, heated to 100°C to form a uniform solution, and then heated to about 35°C. cooled to After adding 27 parts of a 50% sodium hydroxide solution (1.1 times mol with respect to the polyhydric hydroxy resin) to make a phenolate solution, 45 parts of allyl bromide (the following structural formula) (multiple 1.2 times mol with respect to the hydroxy resin)

was added dropwise over 1 hour, and after the completion of the dropwise addition, the temperature was raised to 60° C. and the reaction was allowed to proceed at the same temperature for 3 hours. After completion of the reaction, 220 parts of MIBK was added and 70 parts of hot water was added to wash with water to separate and remove the lower layer. Thereafter, the reaction mixture was heated to 130° C. under a reduced pressure of 5 mmHg to remove MIBK by evaporation to obtain 109 parts of brown allyl ether compound (R1).
The obtained allyl ether compound (R1) had a softening point of 61° C., a hydroxyl equivalent of 12870, a melt viscosity at 150° C. of 0.14 Pa·s, and a total chlorine content of 68 ppm. Mw in GPC is 790, Mn is 510, n = 0 body content is 5.9 area%, n = 1 body content is 70.5 area%, n = 2 or more body content is 23.6 area %Met. Mass spectrum measurement by ESI-MS (negative) confirmed M−=455, 587, 719 and 749. The GPC of the obtained allyl ether compound (R1) is shown in FIG. 1, and the IR chart is shown in FIG.

Example 2
100 parts of the polyhydric hydroxy resin (P2) obtained in Synthesis Example 2 and 150 parts of diglyme were placed in the same reactor as in Synthesis Example 1, heated to 100°C to form a uniform solution, and then heated to about 35°C. cooled to 32 parts of a 50% sodium hydroxide solution (1.1 times the molar amount of the polyhydric hydroxy resin) was added to make a phenolate solution, and then 52.5 parts of allyl bromide (polyhydric hydroxy resin 1.2 times mol) was added dropwise over 1 hour, and after the dropwise addition was completed, the temperature was raised to 60°C, and the reaction was carried out at the same temperature for 3 hours. After completion of the reaction, 230 parts of MIBK was added and 70 parts of hot water was added to wash with water to separate and remove the lower layer. Thereafter, the reaction mixture was heated to 130° C. under a reduced pressure of 5 mmHg to remove MIBK by evaporation to obtain 110 parts of brown allyl ether compound (R2).
The obtained allyl ether compound (R2) had a softening point of 48° C., a hydroxyl equivalent of 20000, a melt viscosity at 150° C. of 0.07 Pa·s, and a total chlorine content of 132 ppm. Mw in GPC is 670, Mn is 490, n = 0 body content is 6.1 area%, n = 1 body content is 71.7 area%, n = 2 or more body content is 22.1 area %Met. Mass spectrum measurement by ESI-MS (negative) confirmed M−=455, 587, 719 and 749.

Example 3
100 parts of the polyhydric hydroxy resin (P3) obtained in Synthesis Example 3 and 150 parts of diglyme were placed in the same reactor as in Synthesis Example 1, heated to 100°C to form a uniform solution, and then heated to about 35°C. cooled to 38 parts of a 50% sodium hydroxide solution (1.1 times the molar amount of the polyhydric hydroxy resin) was added to make a phenolate solution, and then 62.2 parts of allyl bromide (polyhydric hydroxy resin 1.2 times mol) was added dropwise over 1 hour, and after the dropwise addition was completed, the temperature was raised to 60°C, and the reaction was carried out at the same temperature for 3 hours. After completion of the reaction, 240 parts of MIBK was added and 70 parts of hot water was added to wash with water to separate and remove the lower layer. After that, the reaction mixture was heated to 130° C. under a reduced pressure of 5 mmHg to remove MIBK by evaporation to obtain 114 parts of brown allyl ether compound (R3).
The obtained allyl ether compound (R3) was a semi-solid resin at room temperature, and had a hydroxyl equivalent of 69,000, a melt viscosity at 150° C. of 0.03 Pa·s, and a total chlorine content of 148 ppm. Mw in GPC is 560, Mn is 460, n = 0 body content is 6.0 area%, n = 1 body content is 74.1 area%, n = 2 or more body content is 20.0 area %Met. Mass spectrum measurement by ESI-MS (negative) confirmed M−=455, 587, 719 and 749.

Comparative example 1
An allyl ether compound (S1) was obtained in the same manner as in Example 1, except that the polyhydroxy resin (P4) obtained in Synthesis Example 4 was used instead of the polyhydroxy resin.

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

Example 4
100.0 parts of the maleimide compound (M1), 196.1 parts of the allyl ether compound (R1) obtained in Example 1 (one-fold mole relative to the maleimide compound), and 3.0 parts of the curing accelerator (C1) (1 phr based on the total amount of resin) and stirred on a hot plate at 140° C. for 10 minutes.

The resulting resin composition was placed in a fluororesin mold and subjected to vacuum pressing at 2 MPa under temperature conditions of 150°C x 30 minutes + 220°C x 100 minutes to obtain a cured resin test piece of 50 mm square x 2 mm thickness. . Table 1 shows the measurement results of Tg, dielectric constant and dielectric loss tangent of the test piece.

Examples 5-9, Comparative Examples 3-6
A resin composition was prepared in the same manner as described in Table 1, and the same test as in Example 4 was performed. The results are shown in Table 1.

INDUSTRIAL APPLICABILITY The resin composition of the present invention can be used in a wide variety of applications such as coatings, civil engineering adhesives, cast molding, electrical and electronic materials, and film materials, and is particularly useful for laminates and electronic circuit boards that require low dielectric constant and low dielectric loss tangent. .

Claims (7)

1. An allyl ether compound characterized by being represented by the following general formula (1).
   

   

   Here, R ¹ is independently a hydrocarbon group having 1 to 8 carbon atoms, R ² is independently a hydrogen atom or a dicyclopentenyl group, one or more is a dicyclopentenyl group, and R ³ is independently It represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, n indicates the number of repetitions, and the average value is 1 to 5.
2. A resin composition comprising the allyl ether compound according to claim 1 and a maleimide compound.
3. A cured product obtained by curing the resin composition according to claim 2.
4. A sealing material characterized by using the resin composition according to claim 2.
5. A circuit board material characterized by using the resin composition according to claim 2.
6. A prepreg characterized by using the resin composition according to claim 2.
7. A laminate using the resin composition according to claim 2 .
   
   
   

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