KR20240051917A - Allyl ether compounds, resin compositions and cured products thereof - Google Patents

Abstract

An allyl ether compound providing a cured product with excellent low dielectric properties, high heat resistance, etc., a resin composition thereof, and a cured product obtained from the resin composition are provided. An allyl ether compound represented by the following general formula (1).

Description

Allyl ether compounds, resin compositions and cured products thereof

The present invention relates to an allyl ether compound that provides a cured product with excellent low dielectric properties and high heat resistance, a resin composition containing the allyl ether compound as an essential component, and a cured product, sealant, and circuit board material obtained from the resin composition, It relates to prepreg, or laminate.

Thermosetting resins such as epoxy resins and phenolic resins have excellent adhesion, flexibility, heat resistance, chemical resistance, insulation, and curing reactivity, so they are used in a variety of fields, including paints, civil engineering adhesives, molds, electrical and electronic materials, and film materials. In particular, epoxy resin is widely used in printed wiring boards, which are one of the electrical and electronic materials, by imparting flame retardancy to epoxy resin.

Portable devices, which are one of the uses of printed wiring boards, and infrastructure devices such as base stations that connect them are always in demand for higher functionality due to the recent rapid increase in the amount of information. In particular, as communication standards change from 4G to 5G, the amount of information is expected to increase further, and transmission of signals using high frequencies is expected to become necessary. Therefore, in order to suppress signal decay due to high frequencies in printed wiring boards, materials with lower dielectric loss tangents are required. Additionally, in order to cope with thinner lines and higher multi-layering of printed wiring boards, the matrix resin is required to have characteristics such as high adhesive strength and high heat resistance. In order to meet these needs, matrix resins using conventional epoxy resins are not sufficient, and more highly functional thermosetting resins are required.

Regarding lowering the dielectric constant of epoxy resins that have been used as matrix resins for printed wiring boards, raw material epoxy resins include glycidylated compounds of dihydric phenols such as bisphenol A, tris(glycidyloxyphenyl)alkanes, aminophenols, etc. There are disclosures of compounds obtained by glycidylating and compounds obtained by glycidylating novolaks such as phenol novolak (Patent Document 1).

Patent Documents 2 and 3 disclose a method of using a phenol resin containing an imide group to improve heat resistance and mechanical properties over an epoxy resin, and the heat resistance is improved by containing an imide group. Additionally, as a resin suitable for a matrix resin that improves adhesion to a substrate, a compound obtained by epoxidizing an imide group-containing phenol resin is disclosed (Patent Document 4).

In addition, Patent Document 5 discloses a composition that improves the heat resistance and flame retardancy of the substrate by using a maleimide compound, an epoxy resin, and a phenol curing agent with a specific structure, and Patent Documents 6 and 7 disclose a composition that improves the heat resistance and flame retardancy of the substrate by using a maleimide compound with a specific structure. It is disclosed that a composition having excellent adhesion and dielectric properties can be provided.

Patent Document 8 discloses that a curable resin composition with 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 excellent in curability and heat resistance can be obtained by using a thermosetting resin composition containing a maleimide compound of a specific structure and a compound having an allyl group or a methallyl group.

However, none of the curable resin compositions disclosed in any literature sufficiently satisfies the requirements for dielectric properties based on recent high functionality, nor does it simultaneously satisfy each physical property.

Japanese Patent Publication No. 5-43655 Japanese Patent Publication No. 7-33858 Japanese Patent Publication No. 7-10970 Japanese Patent Publication No. 2010-235823 International Publication No. 2011/126070 International Publication No. 2016/208667 International Publication No. 2020/054526 Japanese Patent Publication No. 2020-111744 International Publication No. 2017/170844

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 that simultaneously satisfies low dielectric properties and high heat resistance and are useful for applications such as lamination, molding, and adhesion.

In order to solve the above problem, the present inventor has carefully studied and found that a resin composition containing an allyl ether compound represented by the following formula (1) satisfies both low dielectric properties and a high glass transition temperature (Tg), which are unprecedented in the past. discovered this and completed the present invention.

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

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

Additionally, the present invention is a resin composition characterized by containing the above allyl ether compound and a maleimide compound.

Furthermore, the present invention is a cured product obtained by curing the above resin composition, and is a material, sealant, prepreg, or laminate for a circuit board, characterized by using the above resin composition.

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

Figure 1 is a GPC chart of the allyl ether resin obtained in Example 1.
Figure 2 is an IR chart of the allyl ether resin obtained in Example 1.

Hereinafter, the present invention will be described in detail.

The allyl ether compound of the present invention is an allyl ether compound represented by the above general formula (1). Here, the number of repetitions n=0, 1, 2... Because it is a mixture of , it is also called allyl ether resin.

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

In general formula (1), R ¹ independently represents a hydrocarbon group with 1 to 8 carbon atoms, and is preferably an alkyl group with 1 to 8 carbon atoms, an aryl group with 6 to 8 carbon atoms, an aralkyl group with 7 to 8 carbon atoms, or an allyl group. . The alkyl group having 1 to 8 carbon atoms may be linear, branched, or cyclic, and examples include methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, hexyl, and cyclohexyl. Examples include, but are not limited to, methylcyclohexyl groups and methylcyclohexyl groups. Examples of the aryl group having 6 to 8 carbon atoms include phenyl group, tolyl group, xylyl group, and ethylphenyl group, but are not limited to these. Examples of aralkyl groups having 7 to 8 carbon atoms include benzyl group and α-methylbenzyl group, but are not limited to these. 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 viewpoint of ease of availability and reactivity when used as a cured product.

R ² independently represents a hydrogen atom or a dicyclopentenyl group, and at least one represents a dicyclopentenyl group. Preferably, R ² in one molecule has an average of 0.1 to 1 dicyclopentenyl group per phenol ring.

The dicyclopentenyl group is a group derived from dicyclopentadiene and is represented by the following formula (1a) or formula (1b).

R ³ independently represents a hydrogen atom or a hydrocarbon group with 1 to 4 carbon atoms, and an alkyl group with 1 to 4 carbon atoms is preferable. 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 viewpoint of ease of availability and reactivity when used as a cured product.

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

The molecular weight of the allyl ether compound (resin) is preferably in the range of 500 to 2000 for weight average molecular weight (Mw) and 450 to 1000 for number average molecular weight (Mn).

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. or less, more preferably 0.20 Pa·s or less. The total amount of chlorine 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 polyvalent hydroxy resin represented by the following general formula (2).

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

The polyhydric hydroxy resin represented by the general formula (2) is reacted with a 2,6-disubstituted phenol represented by the following general formula (3) and dicyclopentadiene in the presence of a Lewis acid such as a boron trifluoride/ether catalyst. You can get it by doing this.

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

Examples of the 2,6-disubstituted phenols include 2,6-dimethylphenol, 2,6-diethylphenol, 2,6-dipropylphenol, 2,6-diisopropylphenol, and 2,6-di(n-butyl). ) Phenol, 2,6-di(t-butyl)phenol, 2,6-dihexylphenol, 2,6-dicyclohexylphenol, 2,6-diphenylphenol, 2,6-ditrilphenol, 2, Examples include 6-dibenzylphenol, 2,6-bis(α-methylbenzyl)phenol, 2-ethyl-6-methylphenol, 2-allyl-6-methylphenol, and 2-tryl-6-phenylphenol. , from the viewpoint of ease of availability and reactivity when used as a cured product, 2,6-diphenylphenol and 2,6-dimethylphenol are preferable, and 2,6-dimethylphenol is especially preferable.

The catalyst used in the above reaction is a Lewis acid, and specifically, it is boron trifluoride, boron trifluoride/phenol complex, boron trifluoride/ether complex, aluminum chloride, tin chloride, zinc chloride, iron chloride, etc., but among them, it is easy to handle. In this case, boron trifluoride-ether complex is preferred. In the case of a 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.

A reaction method for introducing the dicyclopentenyl group into 2,6-disubstituted phenols is a method of reacting dicyclopentadiene with 2,6-disubstituted phenols at a predetermined ratio, and dicyclopentadiene is continuously added to 2,6-disubstituted phenols. You may add it and react it, or you may add it in several steps (two or more divided successive additions) and react it intermittently. The ratio is 0.25 to 2 times the mole of dicyclopentadiene per mole of 2,6-disubstituted phenol.

When reacting by continuously adding dicyclopentadiene, the ratio is 0.25 to 1 mole of dicyclopentadiene per mole of 2,6-disubstituted phenol, preferably 0.28 to 1 mole, and 0.3 to 0.5 mole. Mole is more preferred. When dicyclopentadiene is added successively in divisions to cause the reaction, 0.8 to 2 times the mole as a whole is preferable, and 0.9 to 1.7 times the mole is more preferable. In addition, the ratio of dicyclopentadiene used in each step is preferably 0.1 to 1 times the mole. Additionally, unreacted 2,6-disubstituted phenols may be recovered during the reaction. Preferably, the sequential addition is done in two or more divisions to introduce dicyclopentadiene as the main chain and then introduce dicyclopentadienyl group as the side chain R ² .

In this reaction, not only isomers with different substitution positions but also structures in which the dicyclopentadiene structure and the hydroxyl group of phenol are bonded may be included.

Mass spectrometry (MS) and Fourier transform infrared spectrophotometry (FT-IR) measurement methods can be used to confirm that a dicyclopentenyl group has been introduced into the polyvalent hydroxy resin represented by the general formula (2).

When using a mass spectrometry method, electrospray mass spectrometry (ESI-MS) or desorption mass spectrometry (FD-MS) can be used. By subjecting samples separated into components with different nucleoid numbers by GPC or the like to mass spectrometry, it is possible to confirm that a dicyclopentenyl group has been introduced.

When using the FT-IR measurement method, a sample dissolved in an organic solvent such as THF is applied on a KRS-5 cell, and the sample thin film attached cell obtained by drying the organic solvent is measured by FT-I. In the phenol nucleus, The peak derived from the CO stretching vibration appears around 1210 cm ^-1 , and only when a dicyclopentenyl group is introduced, the peak derived from the CH stretching vibration of the olefin portion of the dicyclopentadiene skeleton appears around 3040 cm ^-1 . appear. Dicyclopentadiene introduced into the main chain is not detected because the olefin portion is lost, and only the olefin of the dicyclopentenyl group introduced as the side chain R ² can be measured. When the baseline is the straight connection between the start and end of the target peak and the length from the peak peak to the baseline is the peak height, the peak around 3040 cm ^-1 (A ₃₀₄₀ ) and the peak around 1210 cm ^-1 The amount of dicyclopentenyl group introduced can be quantified by the ratio (A ₃₀₄₀ / A ₁₂₁₀ ) of the peak (A ₁₂₁₀ ). It can be seen that the larger the ratio, the better the physical properties, and the preferable ratio (A ₃₀₄₀ / A ₁₂₁₀ ) to satisfy the target physical properties is 0.05 or more, more preferably 0.10 or more, especially 0.10 to 0.30.

The hydroxyl equivalent weight of the polyfunctional hydroxy resin is preferably 150 to 500, more preferably 200 to 350. The 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 to 800. The softening point is preferably 70 to 150°C, more preferably 80 to 120°C.

This reaction is preferably performed by adding 2,6-disubstituted phenols and a catalyst into a reactor and adding dicyclopentadiene dropwise over 1 to 10 hours.

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

After completion of the reaction, 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 and dissolved, washed with water, and the solvent is recovered under reduced pressure to obtain the target polyvalent hydroxy resin. You can get it. In addition, it is preferable to react as much of the dicyclopentadiene as possible, leave a portion of the 2,6-disubstituted phenol unreacted, preferably 10% or less unreacted, and recover it under reduced pressure.

During 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, ethylene glycol dimethyl ether, and diethylene. You may use solvents such as ethers such as glycol dimethyl ether.

The allyl ether compound represented by general formula (1) of the present invention can be obtained by allyletherifying the hydroxyl group of a polyvalent hydroxy resin represented by general formula (2).

As an allyl etherification method to obtain an allyl ether compound of general formula (1), a polyvalent hydroxy resin represented by general formula (2) is reacted with a halogenated allyl compound in the presence of an alkali compound in a solvent (allyl etherification). reaction). In this case, it is better to dissolve the polyvalent hydroxy resin in a solvent in advance and then add the halogenated allyl compound solution and the alkaline compound solution to react. This allyl etherification reaction is preferably performed by dissolving the polyvalent hydroxy resin and the solvent in a reactor, and then adding the halogenated allyl compound solution and the alkaline compound solution dropwise.

Examples of halogenated allyl compounds include allyl chloride, allyl bromide, methallyl chloride, and methallyl bromide. Among these, allyl bromide or allyl chloride is preferred from the viewpoint of reactivity with the polyvalent hydroxy resin.

Allyl chloride tends to polymerize with each other to form a polymer (polyallyl chloride), but it is preferable to use allyl chloride used in production with a low content of polyallyl chloride. If the content of poly allyl chloride in the allyl chloride used is high, not only does this increase the total chlorine content of the resulting allyl ether compound, but also the molecular weight of the allyl ether compound increases, which may cause slight gelation in the cured product. . In order to reduce the total amount of chlorine, there is a risk that addition of a significant amount of basic material will be necessary. The content ratio of poly allyl chloride in allyl chloride can be easily confirmed by gas chromatography (GC), etc., and the content ratio of poly allyl chloride is preferably 1 area% or less relative to the allyl chloride monomer in terms of area ratio. , 0.5 area% or less is more preferable, and 0.2 area% or less is further preferable.

The amount of the halogenated allyl compound used is usually 1.0 to 2.0 mol, preferably 1.0 to 1.5 mol, more preferably 1.0 to 1.25 mol, and even more preferably 1.0 to 1.2 mol, based on 1 mole of hydroxyl group of the polyhydric hydroxy resin. am.

The alkaline compound used for producing the allyl ether compound is preferably an alkali metal hydroxide or carbonate. Specific examples include sodium hydroxide, potassium hydroxide, potassium carbonate, and sodium carbonate, and sodium hydroxide and potassium hydroxide are preferable. These alkali metal hydroxides may be used in the form of a solid substance or in the form of an aqueous solution.

The amount of the alkaline compound used is usually 1.0 to 2.0 mol, preferably 1.0 to 1.8 mol, more preferably 1.0 to 1.5 mol, and still more preferably 1.0 to 1.3 mol, based on 1 mol of hydroxyl group of the polyhydric hydroxy resin. , especially preferably 1.0 to 1.1 mol.

The solvent used in the production of the allyl ether compound is not particularly limited, but examples include alcohols such as methanol, ethanol, n-propanol, isopropanol, and n-butanol, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, Examples include ethers such as tetrahydrofuran, dioxane, diglyme, and aprotic polar solvents such as dimethylacetamide, dimethylformamide, and dimethyl sulfoxide. Among these, one or two or more types of organic solvents may be used. You can. Additionally, water may be mixed with the 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 total mass of the polyvalent hydroxy resin. Since aprotic polar solvents such as dimethyl sulfoxide are not useful for purification such as water washing and have a high boiling point and are difficult to remove, the amount used exceeds 300 parts by mass based on 100 parts by mass of the total mass of the polyhydric hydroxy resin. It is not desirable to be

Additionally, in addition to the water and organic solvents described above, an organic solvent such as toluene (another organic solvent) may be included. The amount of the other organic solvent used is preferably 100 parts by mass or less relative to the amount of the above-mentioned solvent, and is preferably 0.5 to 0.5 parts by mass. 50 parts by mass is more preferable.

The reaction temperature for the allyl etherification reaction of the polyvalent hydroxy resin is usually 30 to 90°C, preferably 35 to 80°C. In addition, in order to obtain a higher purity allyl ether compound, it is preferable to increase the reaction temperature in two or more steps. For example, it is particularly preferable to set the reaction temperature to 35 to 50°C in the first step and 45 to 100°C in the second step. do.

The reaction time for the allyl etherification reaction of the polyvalent hydroxy resin is usually 0.5 to 10 hours, preferably 1 to 8 hours, and particularly preferably 1 to 5 hours. Since the reaction time is 0.5 hours or more, the reaction proceeds sufficiently, and since it is 10 hours or less, it becomes possible to suppress the production amount of by-products to a low level.

After completion of the reaction, the solvent is distilled off under heating and reduced pressure, or without distillation, and a ketone compound having 4 to 7 carbon atoms (for example, 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 aqueous layer reaches pH 5 to 8 to remove by-produced salts.

Additionally, the allyl etherification reaction of the polyvalent hydroxy resin is usually performed 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, coloring of the resulting product can be prevented.

The amount of inert gas blown per unit time varies depending on the volume of the kiln used for the reaction. For example, the amount of inert gas blown per unit time is such that the volume of the kiln can be replaced in 0.5 to 20 hours. It is desirable to adjust .

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 polyphenylmethane. Maleimide, m-phenylenebismaleimide, p-phenylenebismaleimide, 2,2'-4-(4-maleimidephenoxy)phenyl]propane, 3,3'-dimethyl-5,5'- Diethyl-4,4'-diphenylmethanebismaleimide, bis(3,5-dimethyl-4-maleimidephenyl)methane, bis-(3-ethyl-5-methyl-4-maleimidephenyl)methane, Bis(3,5-diethyl-4-maleimidephenyl)methane, 4-methyl-1,3-phenylenebismaleimide, 4,4'-diphenyletherbismaleimide, 4,4'-diphenyl Sulfonbismaleimide, 1,3-bis(3-maleimidephenoxy)benzene, 1,3-bis(4-maleimidephenoxy)benzene, N,N'-ethylenedimaleimide, N,N'- Examples include hexamethylene dimaleimide, maleimide compounds (resins) represented by the following general formula (4), prepolymers of these maleimide compounds, or prepolymers of maleimide compounds and amine compounds.

From here,

R ⁴ independently represents an alkyl group or an aromatic group having 1 to 5 carbon atoms.

R ⁵ independently represents a hydrogen atom or a methyl group.

a represents 0 to 4, and 0 to 2 is preferable.

b represents 0 to 3, and 0 to 2 is preferable.

r and q are 0 or 1.

m is the number of repetitions, and the average value is 1 to 10, preferably 1 to 5.

The resin composition of the present invention contains as essential components an allyl ether compound (resin) and a maleimide compound (resin) represented by the general formula (1) of the present invention. The content of the allyl ether compound is preferably 5 to 900 parts by mass, more preferably 10 to 300 parts by mass, further preferably 50 to 200 parts by mass, especially preferably 100 to 100 parts by mass, based on 100 parts by mass of the maleimide compound. It is 200 parts by mass.

As the allyl ether compound used to obtain the resin composition of the present invention, in addition to the allyl ether compound represented by general formula (1) of the present invention, various allyl ether compounds may be used one type or in combination of two or more types as needed. Preferably, at least 30% by mass of the allyl ether compound is the allyl ether compound of the present invention, and it is more preferable to contain 50% by mass or more. If it is less than this, there is a risk that the dielectric characteristics 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, tetramethyl bisphenol A, tetramethyl bisphenol F, Allyl ether compounds obtained by allyl ethering bisphenols such as tetramethyl bisphenol S, tetramethyl bisphenol Z, dihydroxydiphenyl sulfide, and 4,4'-thiobis(3-methyl-6-t-butylphenol). , dihydroxybenzenes such as catechol, resorcin, methylresorcin, hydroquinone, monomethylhydroquinone, dimethylhydroquinone, trimethylhydroquinone, mono-t-butylhydroquinone, and di-t-butylhydroquinone. Allyl ether compounds obtained by allyl ethering, allyl ether compounds obtained by allyl ethering hydroxynaphthalenes such as dihydroxynaphthalene, dihydroxymethyl naphthalene, dihydroxymethyl naphthalene, and trihydroxynaphthalene, or Shonol BRG-555 Phenol novolak resins such as (manufactured by Aica Kogyo Co., Ltd.), cresol novolac resins such as DC-5 (manufactured by Nippon Steel Chemical & Material Co., Ltd.), aromatic modified phenol novolak resins, bisphenol A Rockfish resin, trihydroxyphenyl methane type novolak resin such as RESITOP TPM-100 (manufactured by Gun Ei Chemical Industry Co., Ltd.), phenols such as naphthol novolac resin, naphthols and/or bisphenols and aldehydes. Condensates, phenols such as SN-160, SN-395, SN-485 (manufactured by NIPPON STEEL Chemical & Material Co., Ltd.), condensates of naphthols and/or bisphenols and xylylene glycol, phenols and/ or a condensate of naphthols and isopropenyl acetophenone, a reaction product of phenols, naphthols and/or bisphenols and dicyclopentadiene, a condensate of phenols, naphthols and/or bisphenols and a biphenyl-based crosslinking agent, etc. Examples include allyl ether compounds obtained by allyl etherifying polyvalent hydroxy resins, so-called novolac phenol resins, and triallyl isocyanurate. From the viewpoint of reactivity and ease of 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 needed. When a curing accelerator is used, the compound capable of crosslinking with the maleimide group undergoes an addition reaction with the maleimide group to crosslink, so the cured product exhibits good physical properties.

Curing accelerators include, for example, amines, imidazoles, organic phosphines, Lewis acids, organic peroxides, etc. Specifically, 1,8-diazabicyclo(5,4,0)undecene-7, tri Tertiary amines such as ethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylamino methyl)phenol, 2-methylimidazole, 2-phenylimidazole, and 2-ethyl-4-methylimida. Imidazoles such as sol, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole, tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine Organic phosphines such as organic phosphines, addition reactants of organic phosphines and quinone compounds, tetra-substituted phosphoniums such as tetraphenylphosphonium, tetraphenyl borate, tetraphenylphosphonium, ethyltriphenyl borate, tetrabutylphosphonium, tetrabutyl borate, etc. Tetra-substituted borate, 2-ethyl-4-methylimidazole, tetraphenyl borate, N-methylmorpholine, tetraphenyl boron salts such as tetraphenyl borate, ketone peroxide, peroxyketals, hydroperoxide, dialkyl There are organic peroxides such as peroxide, diacyl peroxide, peroxydicarbonate, and peroxy ester. The addition amount is in the range of 0.2 to 5 parts by mass with respect to 100 parts by mass of the resin composition.

The resin composition of the present invention can be blended with other various curable resins and thermoplastic resins as needed.

Examples of the curable resin include epoxy resin, unsaturated polyester resin, curable maleimide resin, polycyanate resin, phenol resin, and one or more vinyl compounds having one or more polymerizable unsaturated hydrocarbon groups in the molecule. . From the viewpoint of low dielectric constant and low dielectric loss tangent, it is preferably one or more vinyl compounds having one or more polymerizable unsaturated hydrocarbon groups in the molecule.

When the curable resin is an epoxy resin, it is preferably at least one type of epoxy resin selected from epoxy resins having two or more epoxy groups in one molecule. Such epoxy resins include, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, tetramethyl bisphenol F type epoxy resin, biphenol type epoxy resin, hydroquinone type epoxy resin, bisphenol fluorene type epoxy resin, and 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. Examples include kilphenol-type epoxy resin, trihydroxyphenylmethane-type epoxy resin, tetrahydroxyphenylethane-type epoxy resin, dicyclopentadiene-type epoxy resin, alkylene glycol-type epoxy resin, and aliphatic cyclic epoxy resin. These epoxy resins may be used individually, two or more types of epoxy resins of the same type may be used in combination, or epoxy resins of different types may be used in combination.

Additionally, when an epoxy resin is included, a curing agent other than the epoxy resin may be used. The curing agent is not particularly limited and includes, for example, phenol-based curing agents, amine-based compounds, amide-based compounds, acid anhydride-based compounds, naphthol-based curing agents, activated ester-based curing agents, benzoxazine-based curing agents, and cyanate ester-based curing agents. You can. These may be used alone, two or more types of the same type may be used in combination, or other types may be used in combination.

Additionally, when mixing an epoxy resin, a curing accelerator can be used as needed. For example, amines, imidazoles, organic phosphines, Lewis acids, etc. The addition amount is usually in the range of 0.2 to 5 parts by mass per 100 parts by mass of the epoxy resin.

If the curable resin is one or more vinyl compounds (hereinafter referred to as vinyl compounds) having one or more polymerizable unsaturated hydrocarbon groups in the molecule, the type is not particularly limited. In other words, the vinyl compounds may be any that can be cured by forming crosslinks by reacting with the vinyl compound of the present invention. It is more preferable that the polymerizable unsaturated hydrocarbon group is a carbon-carbon unsaturated double bond, and a compound having two or more carbon-carbon unsaturated double bonds in the molecule is more preferable.

The average number of carbon-carbon unsaturated double bonds (number of vinyl groups (including substituted vinyl groups), referred to as the number of terminal double bonds) per molecule of vinyl compounds as curable resins varies depending on the Mw of the vinyl compounds, For example, it is preferable that it is 1 to 20 pieces, and it is more preferable that it is 2 to 18 pieces. If the number of terminal double bonds is too small, it tends to be difficult to obtain sufficient heat resistance of the cured product. Additionally, if the number of terminal double bonds is too large, the reactivity becomes too high, and there is a risk that defects such as, for example, a decrease in the storage stability of the composition or a decrease in the fluidity of the composition may occur.

Examples of vinyl compounds include triallyl isocyanurate (TAIC) and other triallyl isocyanurate compounds, and modified polyphenylene ether (PPE) whose terminals are modified with (meth)acryloyl or styryl groups. , polyfunctional (meth)acrylate compounds having two or more (meth)acryloyl groups in the molecule, vinyl compounds (polyfunctional vinyl compounds) having two or more vinyl groups in the molecule such as polybutadiene, and styrene, di Vinyl benzyl compounds, such as vinyl benzene, etc. are mentioned. Among these, those having two or more carbon-carbon double bonds in the molecule are preferred, and specifically, TAIC, polyfunctional (meth)acrylate compounds, modified PPE resins, polyfunctional vinyl compounds, and divinylbenzene compounds. I can hear it. When these are used, it is believed that crosslinking is more easily formed through the curing reaction, and the heat resistance of the cured product of the resin composition can be further improved. Moreover, these may be used individually, or two or more types may be used in combination. Additionally, compounds having one carbon-carbon unsaturated double bond in the molecule may be used together. Examples of compounds having one carbon-carbon unsaturated double bond in the molecule include compounds having one vinyl group in the molecule (monovinyl compounds).

Thermoplastic resins include, for example, phenoxy resin, polyurethane resin, polyester resin, polyethylene resin, polypropylene resin, polystyrene resin, ABS resin, AS resin, vinyl chloride resin, polyvinyl acetate resin, and polymethyl methacrylate resin. , polycarbonate resin, polyacetal resin, cyclic polyolefin resin, polyamide resin, thermoplastic polyimide resin, polyamideimide resin, polytetrafluoroethylene resin, polyetherimide resin, polyphenylene ether resin, modified polyphenylene ether. Resins, polyether sulfone resins, polysulfone resins, polyether ether ketone resins, polyphenylene sulfide resins, polyvinyl formal resins, etc., and known thermoplastic elastomers (for example, styrene-ethylene-propylene copolymer, styrene -Ethylene-butylene copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, hydrogenated styrene-butadiene copolymer, hydrogenated styrene-isoprene copolymer, etc.) or rubbers (e.g., polybutadiene, polyisoprene), etc. can be mentioned. Polyphenylene ether resin (unmodified), hydrogenated styrene-butadiene copolymer, etc. are preferred.

The resin composition of the present invention may, if necessary, contain other additives such as fillers, silane coupling agents, antioxidants, mold release agents, antifoaming agents, emulsifiers, thixotropy imparting agents, lubricants, flame retardants, pigments, etc.

As fillers, specifically, fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide, boehmite, magnesium hydroxide, talc, mica, calcium carbonate, calcium silicate, calcium hydroxide, magnesium carbonate, barium carbonate, barium sulfate, boron nitride, and carbon. , carbon fiber, glass fiber, alumina fiber, silica alumina fiber, silicon carbide fiber, polyester fiber, cellulose fiber, aramid fiber, ceramic fiber, particulate rubber, thermoplastic elastomer, etc. A reason for using a filler is the effect of improving impact resistance. Additionally, 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 circular silica is more preferred. Moreover, one type of these may be used individually, and two or more types may be used in combination.

The filler may be used as is, but one that has been surface treated with a silane coupling agent such as an epoxysilane type or aminosilane type may also be used. As this silane coupling agent, vinylsilane type, methacryloxysilane type, acryloxysilane type, and styrylsilane type silane coupling agent are preferable. This increases the adhesive strength with the metal foil and the interlayer adhesion strength between the resins. Additionally, instead of using a method of surface treating the filler in advance, a silane coupling agent may be added by an integral blend method.

When the resin composition is used as a plate-shaped substrate, a fibrous filler is preferred in terms of dimensional stability, bending strength, etc. More preferably, a glass fiber substrate using a filler of a fibrous base material made by knitting glass fibers into a network is included.

The mixing amount of the filler 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 mixing amount is large, there is a risk that the cured product may become brittle and sufficient mechanical properties may not be obtained. In addition, if the mixing amount is small, there is a risk that the mixing effect of the filler, such as improving the impact resistance of the cured product, will not be achieved.

The mixing amount of other additives is preferably in the range of 0.01 to 20 parts by mass based on 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 the cured product include casting, compression molding, transfer molding, etc., and methods such as laminating resin sheets, resin-attached copper foil, prepreg, etc., and heating and pressing to form a laminated board are 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 converted into a cured product by a method similar to a conventionally known method. Examples of the cured product include molded cured products such as laminates, molds, molded products, adhesive layers, insulating layers, and films.

Applications for 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-ups, and resins. Examples include molding materials and adhesives. Among these various applications, printed wiring board materials, insulating materials for circuit boards, and adhesive films for build-up are used to fill passive components such as condensers and active components such as IC chips within the board, so-called insulating materials for boards for embedding electronic components. It can be used as. Among these, materials for circuit boards (laminated boards) such as printed wiring board materials, resin compositions for flexible wiring boards, and interlayer insulating materials for build-up boards, and semiconductors due to the characteristics of high flame resistance, high heat resistance, low dielectric properties, and solvent solubility. It is preferred for use in sealing materials.

Sealing materials obtained by using the resin composition of the present invention include those for tape-like semiconductor chips, potting-type liquid seals, underfills, and interlayer insulating films of semiconductors, and can be suitably used for these. To prepare a resin composition for use as a semiconductor encapsulating material, additives such as inorganic fillers, coupling agents, and mold release agents that are mixed as needed in the resin composition are premixed, and then using an extruder, kneader, roll, etc. until uniform. A method of sufficiently melting and mixing may be used. At that time, silica is usually used as the inorganic filler, and it is preferable to mix 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 molded using a mold, transfer molding machine, injection molding machine, etc., and then heat-cured at 180 to 250 ° C. for 0.5 to 5 hours to obtain a molded product. can be mentioned.

When using it as a tape-shaped sealing material, this is heated to produce a semi-hardened sheet, used as a sealing material tape, and then this sealing material tape is placed on a semiconductor chip, heated to 100 to 150 ° C. to soften and molded, and then heated to 180 to 250 ° C. A method of completely curing at ℃ is included. In addition, when using it as a potting type liquid sealant, the obtained resin composition may be dissolved in a solvent as needed, then applied on a semiconductor chip or electronic component, and cured directly.

The resin composition of the present invention can be prepared in a varnish state by dissolving it in an organic solvent. Organic solvents that can be used include alcohol-based solvents such as methanol and ethanol, ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, ether-based solvents such as tetrahydrofuran, dimethylformamide, and dimethyl acetate. Solvents containing nitrogen atoms such as amide and N-methylpyrrolidone, and solvents containing sulfur atoms such as dimethyl sulfoxide can be mentioned, and they can be used one type or in a mixture of two or more types. There is no particular limitation as long as it is an industrially available organic solvent, but methyl ethyl ketone and dimethyl formamide are preferable in terms of solubility and handleability.

The resin composition of the present invention can be used as a prepreg by dissolving it in an organic solvent into a composition varnish, impregnating it with fibrous materials such as glass cloth, aramid nonwoven fabric, and polyester nonwoven fabric such as liquid crystal polymer, and then removing the solvent. Additionally, the composition varnish can be applied onto a sheet-like material such as copper foil, stainless steel foil, polyimide film, or polyester film, and then dried to form an adhesive sheet.

When forming a laminate using the prepreg, one or more sheets of prepreg are stacked, metal foil is placed on one side or both sides to form a laminate, and the prepreg is cured by pressurizing and heating the laminate, By integrating them, a laminated board can be obtained. Here, as the metal foil, single, alloy, or composite metal foils such as copper, aluminum, brass, or nickel can be used. The conditions for heating and pressing the laminate may be adjusted appropriately to the conditions under which the resin composition is cured and then heated and pressed. However, if the pressurizing pressure is too low, air bubbles may remain inside the resulting laminate, which may deteriorate the electrical properties, thereby reducing the formability. It is desirable to pressurize under conditions that satisfy. The heating temperature is preferably 160 to 250°C, and more preferably 170 to 220°C. The pressurizing pressure is preferably 0.5 to 10 MPa, and more preferably 1 to 5 MPa. The heating and pressing time is preferably 10 minutes to 4 hours, and more preferably 40 minutes to 3 hours. Additionally, a multilayer board can be produced by using the single-layer laminated board obtained in this way as an inner layer material. In this case, first, a circuit is formed on a laminate by an additive method or a subtractive method, and the surface of the formed circuit is subjected to blackening treatment to obtain an inner layer material. An insulating layer is formed with prepreg or an adhesive sheet on one or both circuit formation surfaces of the inner layer material, and a conductor layer is formed on the surface of the insulating layer to form a multilayer plate.

(Example)

The present invention will be described in detail by way of Examples and Comparative Examples, but the present invention is not limited to these. Unless otherwise specified, “part” represents mass part, “%” represents mass%, and “ppm” represents mass ppm. In addition, the measurement method was each measured by the following method.

·Hydroxyl equivalent weight:

Measurements were made based on the JIS K0070 standard, and the unit was expressed as “g/eq.” Additionally, unless specifically mentioned, the hydroxyl equivalent of the polyhydric hydroxy resin refers to the phenolic hydroxyl equivalent.

·Softening point:

Measurements were made based on the JIS K7234 standard and the circle method. Specifically, an automatic softening point device (ASP-MG4, manufactured by Meitec Corporation) was used.

·Glass transition temperature (Tg):

Measurements were made based on JIS C6481 standards. It was expressed as the tan δ peak top when measurement was performed with a dynamic viscoelasticity measuring device (EXSTAR DMS6100, manufactured by Hitachi High-Tech Science) under temperature rising conditions of 5°C/min.

·Relative permittivity and dielectric loss tangent:

Evaluation was made by using a material analyzer (manufactured by Agilent Technologies) in accordance with IPC-TM-6502.5.5.9 and determining the relative permittivity and dielectric loss tangent at a frequency of 1 GHz using the capacitance method.

GPC (Gel Permeation Chromatography) measurement:

A main body (HLC-8220GPC, manufactured by Tosoh Corporation) equipped with columns (TSKgelG4000HXL, TSKgelG3000HXL, TSKgelG2000HXL, manufactured by Tosoh Corporation) in series was used, and the column temperature was set to 40°C. In addition, tetrahydrofuran (THF) was used as the eluent, the flow rate was 1 mL/min, and a differential refractive index detector was used as the detector. For the measurement sample, 50 μL of 0.1 g of the sample was dissolved in 10 mL of THF and filtered through a microfilter. For data processing, GPC-8020 Model II version 6.00 manufactured by Tosoh Corporation was used.

·IR:

A Fourier transform infrared spectrophotometer (Spectrum One FT-IR Spectrometer 1760X, manufactured by Perkin Elmer Precisely) was used, KRS-5 was used for the cell, and the sample dissolved in THF was applied on the cell, dried, and then measured at a wave number of 650. The absorbance of ∼4000 cm ^-1 was measured.

·ESI-MS:

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

The abbreviations used in the 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) (manufactured by FUJIFILM Wako Pure Chemical Corporation, allyl equivalent 154)

[Multi-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

MEH: Biphenyl aralkyl type polyvalent hydroxy resin (Meiwa Plastic Industrie, Ltd., MEH-7851, hydroxyl equivalent weight 210, softening point 75°C)

PN: Phenol novolak resin (manufactured by Aica Kogyo Company, Limited, Shonol BRG-557, hydroxyl equivalent weight 105, softening point 85°C)

[Maleimide compound]

M1: Phenylmethane maleimide (manufactured by Daiwa Kasei Industry 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 weight 274, softening point 60°C)

[Curing accelerator]

C1: Dicumyl peroxide (manufactured by Nippon Oil & Fats Co., Ltd., PERCUMYL D)

C2: 2-ethyl-4-methylimidazole (manufactured by Shikoku Kasei Holdings Corporation, CUREZOL 2E4MZ)

Synthesis Example 1

In a reaction apparatus consisting of a glass separable flask equipped with a stirrer, thermometer, nitrogen blowing tube, dropping lot, and cooling tube, 500 parts of 2,6-xylenol (structural formula below),

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

was added dropwise in 1 hour. The reaction was continued for 4 more hours at a temperature of 115-125°C. Afterwards, the reaction mixture was heated to 200°C under reduced pressure of 5 mmHg to remove unreacted raw materials by evaporation, and 46.7 parts of MIBK was added to dissolve the product. After adding 3.3 parts of 47% BF ₃ ether complex, it was heated to 100°C and maintained at the same temperature, while 74.7 parts of dicyclopentadiene was added dropwise in 1 hour. The reaction was continued at 115∼125℃ for another 4 hours. 5 parts of calcium hydroxide was added. An additional 9 parts of 10% aqueous oxalic acid solution were added. 350 parts of MIBK was added to dissolve the product, and 120 parts of 80°C hot water was added to wash with water, and the lower water layer was separated and removed. It was heated to 120°C, refluxed and dehydrated, filtered, and then heated to 160°C under reduced pressure of 5 mmHg to remove MIBK by evaporation, thereby obtaining 259 parts of red-brown polyvalent hydroxy resin (P1).

The obtained polyhydroxy resin (P1) was a resin with a hydroxyl equivalent weight of 323 and a softening point of 97°C, and the water absorption ratio (A ₃₀₄₀ /A ₁₂₁₀ ) was 0.27. In GPC, Mw was 740, Mn was 490, n = 0 body content was 6.6 area%, n = 1 body content was 70.1 area%, and n = 2 or more body content was 23.3 area%. When the mass spectrum was measured by ESI-MS (negative), M-=375, 507, 629, 639, 761 were confirmed.

Synthesis Example 2

In the same reaction apparatus as in Synthesis Example 1, 500 parts of 2,6-xylenol and 7.3 parts of 47% BF ₃ ether complex were added and heated to 100°C while stirring. While maintaining the same temperature, 67.6 parts of dicyclopentadiene (0.12 times the mole relative to 2,6-xylenol) was added dropwise in 1 hour. The reaction was conducted at a temperature of 115 to 125°C for 4 hours. Afterwards, the reaction mixture was heated to 200°C under reduced pressure of 5 mmHg to remove unreacted raw materials by evaporation, and 46.7 parts of MIBK was added to dissolve the product. After adding 3.3 parts of 47% BF ₃ ether complex, it was heated to 100°C and maintained at the same temperature, while 56.0 parts of dicyclopentadiene was added dropwise in 1 hour. The reaction was continued at 115∼125℃ for another 4 hours. 5 parts of calcium hydroxide was added. An additional 9 parts of 10% aqueous oxalic acid solution were added. 320 parts of MIBK was added to dissolve the product, 110 parts of 80°C hot water was added, the solution was washed, and the lower water tank was separated and removed. It was heated to 120°C, refluxed and dehydrated, filtered, and then heated to 160°C under reduced pressure of 5 mmHg to remove MIBK by evaporation, and 240 parts of red-brown polyvalent hydroxy resin (P2) was obtained.

The obtained polyhydroxy resin (P2) was a resin with a hydroxyl equivalent weight of 276 and a softening point of 94°C, and the water absorption ratio (A ₃₀₄₀ /A ₁₂₁₀ ) was 0.17. In GPC, Mw was 670, Mn was 490, n = 0 body content was 6.6 area%, n = 1 body content was 70.3 area%, and n = 2 or more body content was 23.1 area%. When the mass spectrum was measured by ESI-MS (negative), M-=375, 507, 629, 639, 761 were confirmed.

Synthesis Example 3

In the same reaction apparatus 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 mole of dicyclopentadiene added initially) were added and stirred at 100°C. It was warm. While maintaining the same temperature, 67.6 parts of dicyclopentadiene (0.12 times the mole relative to 2,6-xylenol) was added dropwise in 1 hour. The reaction was continued for 4 more hours at a temperature of 115-125°C. Afterwards, the reaction mixture was heated to 200°C under reduced pressure of 5 mmHg to remove unreacted raw materials by evaporation, and 46.7 parts of MIBK was added to dissolve the product. After adding 3.3 parts of 47% BF ₃ ether complex, it was heated to 100°C and maintained at the same temperature, while 28.0 parts of dicyclopentadiene was added dropwise in 1 hour. The reaction was continued at 115 to 125°C for another 4 hours, and 5 parts of calcium hydroxide was added. An additional 9 parts of 10% aqueous oxalic acid solution were added. 280 parts of MIBK were added to dissolve the product, 100 parts of 80°C hot water was added, the solution was washed, and the lower water layer was separated and removed. It was heated to 120°C, refluxed and dehydrated, filtered, and then heated to 160°C under reduced pressure of 5 mmHg to remove MIBK by evaporation, thereby obtaining 213 parts of red-brown polyvalent hydroxy resin (P3).

The obtained polyhydroxy resin (P3) was a resin with a hydroxyl equivalent weight of 234 and a softening point of 86°C, and the water absorption ratio (A ₃₀₄₀ /A ₁₂₁₀ ) was 0.11. In GPC, Mw was 560, Mn was 470, n = 0 body content was 6.2 area%, n = 1 body content was 74.0 area%, and n = 2 or more body content was 19.8 area%. When the mass spectrum was measured by ESI-MS (negative), M-=375, 507, 629, 639, 761 were confirmed.

Synthesis Example 4

In the same reaction apparatus as in Synthesis Example 1, 1507 parts of phenol and 22.7 parts of 47% BF ₃ ether complex were added and heated to 100°C while stirring. While maintaining the same temperature, 211.7 parts of dicyclopentadiene (0.10 times the mole relative to phenol) was added dropwise in 1 hour. The reaction was continued for another 4 hours at a temperature of 115 to 125°C, and 36 parts of calcium hydroxide was added. An additional 60 parts of a 10% aqueous solution of oxalic acid was added. Afterwards, it was heated to 160°C and dehydrated, and then heated to 200°C under reduced pressure of 5 mmHg to remove unreacted raw materials by evaporation. 720 parts of MIBK1 were added to dissolve the product, and 550 parts of 80°C hot water were added to wash with water, and the lower water layer was separated and removed. After heating to 120°C, refluxing and dehydration, and filtering, MIBK was removed by evaporation by heating to 160°C under reduced pressure of 5 mmHg, and 480 parts of a reddish-brown polyvalent hydroxy resin (P4) represented by the following general formula (5) was added. got it

The obtained polyvalent hydroxy resin (P4) had a hydroxyl equivalent weight of 175 and a softening point of 90°C. In GPC, Mw was 470, Mn was 410, s = 0 body content was 1.0 area%, s = 1 body content was 68.7 area%, and s = 2 or more body content was 30.3 area%.

Synthesis Example 5

100 parts of aniline and 50 parts of toluene were added to a flask equipped with a thermometer, cooling tube, Dean-Stark azeotropic distillation trap, and stirrer, and 39.2 parts of 35% hydrochloric acid were added dropwise in 1 hour at room temperature. After the dropwise addition was completed, the water and toluene that had been heated and azeotroped were cooled and separated into liquids, and then only the toluene, which was the organic layer, was returned to the system and dehydrated. Next, 33.6 parts of 4,4'-bis(chloromethyl)biphenyl was added over 1 hour while maintaining the temperature at 60 to 70°C, and reaction was further conducted at the same temperature for 2 hours. After completion of the reaction, toluene was distilled off while the temperature was raised, the system temperature was adjusted to 195 to 200°C, and the reaction was carried out at this temperature for 15 hours. Afterwards, while cooling, 86 parts of a 30% aqueous solution of sodium hydroxide was added dropwise slowly to prevent the system from violently refluxing, and the toluene distilled off when the temperature was raised to 80°C or lower was returned to the system and allowed to stand at 70 to 80°C. The separated lower aqueous layer was removed, and the reaction solution was repeatedly washed with water until the washing solution became neutral. Next, excess aniline and toluene were distilled off from the oil layer under heating and reduced pressure (200°C, 0.6 kPa) using a rotary evaporator, thereby obtaining 47 parts of aromatic amine resin.

Next, 75 parts of maleic anhydride and 150 parts of toluene were added to the flask, and after heating and cooling and separating the azeotropic water and toluene, only the toluene, which was the organic layer, was returned to the system and dehydrated. Next, a resin solution in which 100 parts of the aromatic amine resin was dissolved in 100 parts of N-methyl-2-pyrrolidone was added dropwise over 1 hour while maintaining the temperature of the system at 80 to 85°C. After the dropwise addition was completed, the reaction was carried out at the same temperature for 2 hours, 1.5 parts of p-toluenesulfonic acid was added, and the azeotropic condensation water and toluene were cooled and separated under reflux conditions, and then only the toluene, which was the organic layer, was returned to the system and dehydrated. The reaction was carried out for 20 hours. After completion of the reaction, 100 parts of toluene was added, washing with water was repeated to remove p-toluenesulfonic acid and excess maleic anhydride, and water was removed from the system by azeotropy by heating. Next, 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), R ⁵ is all a hydrogen atom, and m is 1.3.

Example 1

In the same reaction apparatus as in Synthesis Example 1, 100 parts of the polyvalent hydroxy resin (P1) and 150 parts of diglyme obtained in Synthesis Example 1 were placed, heated to 100°C to form a uniform solution, and then cooled to about 35°C. 27 parts of a 50% sodium hydroxide solution (1.1 times the mole relative to the polyhydric hydroxy resin) was added to make a phenolate solution, and then 45 parts of allyl bromide (structural formula below) was added (relative to the polyhydric hydroxy resin) at a temperature of 30 to 40°C. 1.2 times mole)

was added dropwise over 1 hour, and after completion of the dropwise addition, the temperature was raised to 60°C and reaction was performed at the same temperature for 3 hours. After completion of the reaction, 220 parts of MIBK were added, 70 parts of warm water were added, the mixture was washed with water, and the lower layer was separated and removed. Thereafter, MIBK was removed by evaporation by heating to 130°C under reduced pressure of 5 mmHg, and 109 parts of brown allyl ether compound (R1) were obtained.

The obtained allyl ether compound (R1) had a softening point of 61°C, a hydroxyl equivalent weight of 12870, a melt viscosity of 0.14 Pa·s at 150°C, and a total chlorine content of 68 ppm. In GPC, Mw was 790, Mn was 510, n = 0 body content was 5.9 area%, n = 1 body content was 70.5 area%, and n = 2 or more body content was 23.6 area%. When the mass spectrum was measured by ESI-MS (negative), M-=455, 587, 719, 749 were confirmed. The GPC of the obtained allyl ether compound (R1) is shown in Figure 1, and the IR chart is shown in Figure 2.

Example 2

In the same reaction apparatus as in Synthesis Example 1, 100 parts of the polyvalent hydroxy resin (P2) and 150 parts of diglyme obtained in Synthesis Example 2 were placed, heated to 100°C to form a uniform solution, and then cooled to about 35°C. 32 parts of a 50% sodium hydroxide solution (1.1 times the mole relative to the polyhydric hydroxy resin) was added to make a phenolate solution, and then 52.5 parts of allyl bromide (1.2 times the mole relative to the polyhydric hydroxy resin) was added in the range of 30 to 40°C. It was added dropwise over 1 hour, and after completion of the dropwise addition, the temperature was raised to 60°C and reaction was performed at the same temperature for 3 hours. After completion of the reaction, 230 parts of MIBK were added, 70 parts of warm water were added, the mixture was washed with water, and the lower layer was separated and removed. After that, MIBK was removed by evaporation by heating to 130°C under reduced pressure of 5 mmHg, and 110 parts of brown allyl ether compound (R2) was obtained.

The obtained allyl ether compound (R2) had a softening point of 48°C, a hydroxyl equivalent weight of 20000, a melt viscosity of 0.07 Pa·s at 150°C, and a total chlorine content of 132 ppm. In GPC, Mw was 670, Mn was 490, n = 0 body content was 6.1 area%, n = 1 body content was 71.7 area%, and n = 2 or more body content was 22.1 area%. When the mass spectrum was measured by ESI-MS (negative), M-=455, 587, 719, 749 were confirmed.

Example 3

In the same reaction apparatus as in Synthesis Example 1, 100 parts of the polyvalent hydroxy resin (P3) and 150 parts of diglyme obtained in Synthesis Example 3 were placed, heated to 100°C to form a uniform solution, and then cooled to about 35°C. 38 parts of a 50% sodium hydroxide solution (1.1 times the mole relative to the polyhydric hydroxy resin) was added to make a phenolate solution, and then 62.2 parts of allyl bromide (1.2 times the mole relative to the polyhydric hydroxy resin) were added in the range of 30 to 40°C. It was added dropwise over 1 hour, and after completion of the dropwise addition, the temperature was raised to 60°C and reaction was performed at the same temperature for 3 hours. After completion of the reaction, 240 parts of MIBK were added, 70 parts of warm water were added and washed, and the lower layer was separated and removed. Thereafter, MIBK was evaporated and removed by heating to 130°C under reduced pressure of 5 mmHg, and a brown allyl ether compound (R3 ) obtained 114 copies.

The obtained allyl ether compound (R3) was a semi-solid resin at room temperature, had a hydroxyl equivalent weight of 69000, a melt viscosity at 150°C of 0.03 Pa·s, and a total chlorine content of 148 ppm. In GPC, Mw was 560, Mn was 460, n = 0 body content was 6.0 area%, n = 1 body content was 74.1 area%, and n = 2 or more body content was 20.0 area%. When the mass spectrum was measured by ESI-MS (negative), M-=455, 587, 719, 749 were confirmed.

Comparative Example 1

Allyl ether compound (S1) was obtained in the same manner as in Example 1, except that the polyvalent hydroxy resin was changed to the polyvalent hydroxy resin (P4) obtained in Synthesis Example 4.

Comparative Example 2

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 (1 times the mole of the maleimide compound), and 3.0 parts of the curing accelerator (C1) (1 phr based on the total amount of resin). The mixture was mixed and stirred on a hot plate at 140°C for 10 minutes.

The obtained resin composition was placed in a fluororesin mold and vacuum pressed at 2 MPa under the temperature conditions of 150°C x 30 min + 220°C x 100 min to obtain a cured resin test piece measuring 50 mm square x 2 mm thick. Table 1 shows the measurement results of Tg, relative permittivity, and dielectric loss tangent of the test piece.

Examples 5 to 9, Comparative Examples 3 to 6

It was mixed in the amount (part) of the prescription in Table 1, a resin composition was obtained through the same operation, and the same test as in Example 4 was performed, and the results are shown in Table 1.

The resin composition of the present invention can be used in a variety of fields such as paints, civil engineering adhesives, molds, 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)

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

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