TW202313772A - Allyl ether compound, resin composition and cured product thereof - Google Patents

Abstract

An object of the present invention is to provide an allyl ether compound capable of forming a cured product with excellent properties such as low dielectricity, high heat resistance, etc., a resin composition thereof, and a cured product obtained from the resin composition.

A solution to the above object is an allyl ether compound represented by the following general formula (1).

Description

Allyl ether compound, resin composition and hardened product thereof

The present invention relates to an allyl ether compound capable of forming 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 resin obtained from the resin composition Cured products, sealing materials, materials for circuit boards, prepregs, or laminates.

Thermosetting resins such as epoxy resins and phenol resins are widely used in coatings, civil engineering bonding, casting, electrical and electronic applications due to their excellent adhesiveness, flexibility, heat resistance, chemical resistance, insulation, and curing reactivity. Various fields such as materials and film materials. In particular, it is widely used for the application of printed wiring boards, which are one of electrical and electronic materials, because epoxy resins are imparted with flame retardancy.

Infrastructure devices such as portable devices and base stations connected to them, which are one of the uses of printed wiring boards, have been required to be highly functional as the amount of information has increased rapidly in recent years. In particular, due to the further increase in the amount of information due to the conversion of communication standards from 4G to 5G, it is predicted that signal transmission must be performed at high frequencies. Therefore, in order to suppress signal attenuation due to high frequencies when using a printed wiring board, a material with a lower dielectric loss tangent is desired. In addition, in order to cope with thinner lines and higher multilayers of printed wiring boards, properties such as high adhesive force and high heat resistance are required for matrix resins. In order to satisfy these demands, it is not sufficient to use conventional epoxy resin matrix resins, and thermosetting resins with higher functions are desired.

Regarding the lowering of the dielectric constant of epoxy resins conventionally used as matrix resins for printed wiring boards, epoxy resins used as raw materials include compounds obtained by glycidylating divalent phenols such as bisphenol A, tri( Glycidyloxyphenyl) alkanes, compounds obtained by glycidylating aminophenols, etc., and compounds obtained by glycidylating novolacs such as phenol novolaks are disclosed (Patent Document 1).

Patent Documents 2 and 3 disclose a method of using an imide group-containing phenol resin in order to improve heat resistance and mechanical properties compared to epoxy resins, and heat resistance is improved by containing an imide group. Also, Patent Document 4 discloses a compound obtained by epoxidizing an imide group-containing phenol resin as a resin suitable for a matrix resin for improving adhesion with a base material.

Also, 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 hardener with a specific structure, and Patent Documents 6 and 7 disclose that by using A composition with excellent adhesion and dielectric properties can be provided by using a maleimide compound with a specific structure.

Patent Document 8 discloses that by using a maleimide compound and an allyl ether compound, a curable resin composition with low dielectric characteristics and high heat resistance can be obtained. Patent Document 9 discloses that a composition with 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. thing.

However, none of the curable resin compositions disclosed in the literature can fully meet the specific requirements of the dielectric in response to recent high-performance, and cannot satisfy various physical properties at the same time.

[Prior Art Literature]

[Patent Document]

Patent Document 1: Japanese Patent Application Laid-Open No. 5-43655

Patent Document 2: Japanese Patent Application Laid-Open No. 7-33858

Patent Document 3: Japanese Patent Application Laid-Open No. 7-10970

Patent Document 4: Japanese Patent Laid-Open No. 2010-235823

Patent Document 5: International Publication No. 2011/126070

Patent Document 6: International Publication No. 2016/208667

Patent Document 7: International Publication No. 2020/054526

Patent Document 8: Japanese Patent Laid-Open No. 2020-111744

Patent Document 9: International Publication No. 2017/170844

Therefore, the problem to be solved by the present invention is to provide a resin composition and its cured product. The composition has excellent properties of low dielectric property and high heat resistance at the same time, and is useful for lamination, molding, bonding and other applications.

In order to solve the above-mentioned problems, the inventors of the present invention found, as a result of in-depth studies, that a resin composition containing an allyl ether compound represented by the following formula (1) can simultaneously satisfy an unprecedented low dielectric property and a high glass transition temperature ( Tg), and complete the present invention.

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

Here, ^R1 independently represents a hydrocarbon group having 1 to 8 carbon atoms, ^R2 independently represents a hydrogen atom or a dicyclopentenyl group, and one or more of them are dicyclopentenyl groups, and ^R3 independently represents a hydrogen atom or a dicyclopentenyl group. In the hydrocarbon group with 1 to 4 carbons, n represents the number of repetitions, and the average value is a number of 1 to 5.

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

Also, the present invention relates to a cured product obtained by curing the above resin composition, and a circuit board material, sealing material, prepreg, or laminate characterized by using the above resin composition.

The resin composition of the present invention can obtain a hardened product with a high glass transition temperature, and has excellent dielectric properties. It can exhibit good properties in laminates and electronic circuit boards that require low dielectric coefficient and low dielectric loss tangent.

Fig. 1 is the GPC figure of the allyl ether resin that embodiment 1 gains.

Fig. 2 is the IR figure of the allyl ether resin obtained in embodiment 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, since it is a mixture of repetition number n=0, 1, 2..., it is also called an allyl ether resin.

In each formula in this specification, the common symbol has the same meaning in principle.

In the general formula (1), R independently represents a hydrocarbon group with 1 to 8 carbons, preferably ^an alkyl group with 1 to 8 carbons, an aryl group with 6 to 8 carbons, an aralkyl group with 7 to 8 carbons , or allyl. The alkyl group with 1 to 8 carbons can be straight chain, branched chain, or cyclic, such as methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl , hexyl, cyclohexyl, methylcyclohexyl, etc., but not limited thereto. The aryl group having 6 to 8 carbon atoms includes, for example, phenyl, tolyl, xylyl, ethylphenyl, etc., but is not limited thereto. Examples of the aralkyl group having 7 to 8 carbon atoms include benzyl and α-methylbenzyl, but are not limited thereto. Among these substituents, a phenyl group and an alkyl group having 1 to 3 carbon atoms are preferred, and a methyl group is particularly preferred from the viewpoint of ease of availability and reactivity when it is made into a cured product.

R ² independently represent a hydrogen atom or a dicyclopentenyl group, and one or more of them are dicyclopentenyl groups. Preferably, ^R2 in one molecule has an average of 0.1 to 1 dicyclopentenyl group with respect to one phenol ring.

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

R ³ independently represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbons, preferably an alkyl group having 1 to 4 carbons. Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, etc., but are not limited thereto. Among these substituents, a hydrogen atom or a methyl group is preferred, and a hydrogen atom is particularly preferred, from the viewpoint of ease of acquisition and reactivity when it is made into a cured product.

n is the number of repetitions, representing a number of 0 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 more preferably 1.6 to 2. The content obtained by GPC is preferably within the range of 10 area % or less for the n=0 body, 50 to 80 area % for the n=1 body, and 15 to 30 area % for the 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 hydrogen equivalent (g/eq) is preferably above 5,000, more preferably above 10,000, the softening point is preferably (semi-solid at room temperature) to 100°C, more preferably 45 to 80°C, and the melt viscosity at 150°C is higher than The best is 1.0Pa. s or less, more preferably 0.50Pa. s or less, more preferably 0.20Pa. below s. The total chlorine content is preferably at most 1000 ppm, more preferably at most 500 ppm.

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

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

The polyhydric hydroxyl resin represented by the general formula (2) can be obtained by contacting 2,6-disubstituted phenols represented by the following general formula (3) with dicyclopentadiene in boron trifluoride-ether Medium and other Lewis acid in the presence of the reaction derived.

Here, ^R1 has the same meaning as defined in the above general formula (1).

The above-mentioned 2,6-disubstituted phenols can be, for example, 2,6-dimethylphenol, 2,6-diethylphenol, 2,6-dipropylphenol, 2,6-diisopropylphenol, 2 ,6-di(n-butyl)phenol, 2,6-di(tert-butyl)phenol, 2,6-dihexylphenol, 2,6-dicyclohexylphenol, 2,6-diphenylphenol, 2,6-xylylphenol, 2,6-dibenzylphenol, 2,6-bis(α-methylbenzyl)phenol, 2-ethyl-6-methylphenol, 2-allyl -6-methylphenol, 2-tolyl-6-phenylphenol, etc. From the viewpoint of ease of acquisition and reactivity when it is made into a hardened product, 2,6-diphenylphenol, 2,6- - Dimethylphenol, particularly preferably 2,6-dimethylphenol.

The catalyst or Lewis acid used in the above reaction is specifically composed of boron trifluoride, boron trifluoride. Phenol complexes, boron trifluoride-ether complexes, aluminum chloride, tin chloride, zinc chloride, ferric chloride, etc. Among them, boron trifluoride-ether complexes are preferred in consideration of ease of operation. The amount of catalyst used is three In the case of boron fluoride-ether complex, it is 0.001-20 mass parts with respect to 100 mass parts of dicyclopentadiene, Preferably it is 0.5-10 mass parts.

The method for introducing the above-mentioned dicyclopentenyl group into 2,6-substituted phenols is the same as the method of reacting 2,6-disubstituted phenols with dicyclopentadiene at a predetermined ratio, and the dicyclopentadiene can be added continuously The reaction of pentadiene may be performed in several stages (addition of two or more batches), or the reaction may be performed intermittently. The ratio is 0.25 to 2 times mole of dicyclopentadiene relative to 1 mole of 2,6-disubstituted phenol.

The ratio when dicyclopentadiene is continuously added and reacted is 0.25 to 1 mole, preferably 0.28 to 1 mole, of dicyclopentadiene relative to 1 mole of 2,6-disubstituted phenols mole, more preferably 0.3 to 0.5 times mole. When dicyclopentadiene is added in batches to react, the whole is preferably 0.8 to 2 times mole, more preferably 0.9 to 1.7 times mole. Also, the usage ratio of dicyclopentadiene in each stage is preferably 0.1 to 1 mole. Also, unreacted 2,6-disubstituted phenols can be recovered during the reaction. It is preferable to introduce dicyclopentadiene as the main chain, and then, to introduce the dicyclopentadienyl group as the side chain R ² , add two or more batches successively.

In this reaction, not only isomers with different substitution positions but also dicyclopentadiene structures and structures bonded to hydroxyl groups in phenol are included.

In the polyhydric hydroxyl resin represented by the above general formula (2), the method of confirming that the dicyclopentenyl group has been introduced can use mass spectrometry (MS) and Fourier transform infrared spectrometer (FT-IR) measurement.

When using mass spectrometry, electrospray ionization mass spectrometry (ESI-MS) or field desorption (FD-MS) can be used. The introduction of the dicyclopentenyl group can be confirmed by performing mass spectrometry on a sample whose nucleosome numbers have been separated into distinct components by GPC or the like.

When the FT-IR measurement method is used, the sample dissolved in an organic solvent such as THF is applied to the KRS-5 tank, and the organic solvent is dried to obtain a film tank with a sample. After measuring the film tank with a sample by IR, A peak originating from the stretching and stretching of CO in the phenol core appears around 1210cm ^-1 , and a peak originating from the stretching and stretching of CH at the olefin part of the dicyclopentadiene skeleton appears around 3040cm ^-1 when only dicyclopentenyl groups are introduced. The dicyclopentadiene bonded to the main chain was not detected because the olefin part disappeared, and only the olefin of the dicyclopentenyl group introduced as chain measuring ^R2 could be measured. The beginning and end of the target peak are connected by a straight line as the reference line, and when the peak height is taken as the peak height from the peak apex to the reference line, according to the peak near 3040cm ^-1 (A ₃₀₄₀ ) and the peak near 1210cm ^-1 (A ₁₂₁₀ ) ratio (A ₃₀₄₀ /A ₁₂₁₀ ), the amount of dicyclopentenyl introduced can be quantified. It has been confirmed that the larger the ratio, the better the physical properties. The preferred ratio (A ₃₀₄₀ /A ₁₂₁₀ ) for satisfying the target physical properties is 0.05 or more, more preferably 0.10 or more, and most preferably 0.10 to 0.30.

The hydroxyl equivalent weight of the polyfunctional hydroxyl resin is preferably 150-500, more preferably 200-350. The average molecular weight, the weight average molecular weight (Mw) is preferably 400-2000, more preferably 500-2000, and the number average molecular weight (Mn) is preferably 350-1000, more preferably 400-800. The softening point is preferably from 70 to 150°C, more preferably from 80 to 120°C.

This reaction can be carried out in the following manner, that is, the 2,6-disubstituted phenol and the catalyst are loaded into the reactor, and the dicyclopentadiene is dropped over 1 to 10 hours.

The reaction temperature is preferably from 50 to 200°C, more preferably from 100 to 180°C, and still more preferably from 120 to 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 finished, alkalis such as sodium hydroxide, potassium hydroxide, and calcium oxide are added to deactivate the catalyst. After that, add aromatic hydrocarbons such as toluene and xylene, or ketones such as methyl ethyl ketone and methyl isobutyl ketone to dissolve them, wash with water, and recover the solvent under reduced pressure to obtain the polyhydric hydroxyl group of the target product. resin. Moreover, it is preferable to react as much dicyclopentadiene as possible and to recover a part (preferably 10% or less) of 2,6-disubstituted phenols under reduced pressure without reacting.

During the reaction, 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; Solvents such as ethers such as methyl ether and diethylene glycol dimethyl ether.

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

The allyl etherification method used to obtain the allyl ether compound represented by the general formula (1) can be, for example, make the polyhydric hydroxyl resin represented by the general formula (2) in the presence of an alkali compound in a solvent Reaction with halogenated allyl compounds (allyl etherification). At this time, after dissolving the polyhydric hydroxyl resin in a solvent in advance, you may add and react a halogenated allyl compound solution and an alkali compound solution. The allyl etherification reaction can be carried out in the following manner, that is, the polyhydric hydroxyl resin and the solvent are filled in a reactor to be dissolved, and then the halogenated allyl compound solution and the alkali compound solution are dropped.

The halogenated allyl compound includes, for example, allyl chloride, allyl bromide, methallyl chloride, methallyl bromide, and the like. Among these, allyl chloride or allyl bromide is preferred from the viewpoint of reactivity with polyhydric hydroxy resins.

Allyl chloride tends to polymerize with each other to form a polymer (polyallyl chloride). Therefore, it is preferable to use a polyallyl chloride with a small content of the allyl chloride used in the production. . If the content ratio of polyallyl chloride in the allyl chloride used is high, it will become the main reason for the increase of the total chlorine content of the obtained allyl ether compound, and the molecular weight of the allyl ether compound will increase. There is a risk of a small amount of gelation in the medium. In order to reduce the total chlorine, it may be necessary to add a considerable amount of alkaline substances. The content ratio of polyallyl chloride in allyl chloride can be easily confirmed by gas chromatography (GC), etc. In terms of area ratio, polyallyl chloride relative to allyl chloride monomer The content ratio of the compound is preferably at most 1 area %, more preferably at most 0.5 area %, and still more preferably at most 0.2 area %.

The amount of the halogenated allyl compound is usually 1.0 to 2.0 moles, preferably 1.0 to 1.5 moles, more preferably 1.0 to 1.25 moles, and more preferably 1.0 moles relative to 1 mole of hydroxyl groups in the polyhydroxy resin. to 1.2 moles.

Alkali compounds used in the manufacture of allyl ether compounds are preferably alkali metal hydroxides. Specific examples can include sodium hydroxide, potassium hydroxide, potassium carbonate, and sodium carbonate, preferably sodium hydroxide, hydroxide potassium. Such an alkali metal hydroxide may be used in the state of a solid, or in the state of its aqueous solution.

Relative to 1 mole of hydroxyl groups in the polyhydroxy resin, the amount of the alkali compound used is usually 1.0 to 2.0 moles, preferably 1.0 to 1.8 moles, more preferably 1.0 to 1.5 moles, and more preferably 1.0 to 1.3 moles mol, preferably 1.0 to 1.1 mol.

The solvent used in the production of the allyl ether compound is not particularly limited, and examples include alcohols such as methanol, ethanol, n-propanol, isopropanol, and n-butanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. Ketones, tetrahydrofuran, dioxane, ethers such as diglyme, aprotic polar solvents such as dimethylacetamide, dimethylformamide, and dimethyloxide, etc. One or two or more of these organic solvents are used. Moreover, water and the said organic solvent can also be mixed and used.

The amount of the organic solvent used is preferably 20 to 300 parts by mass, more preferably 25 to 250 parts by mass, and most preferably 25 to 200 parts by mass relative to 100 parts by mass of the total mass of the polyvalent hydroxyl resin. Aprotic polar solvents such as dimethylsulfoxide are useless for purification such as washing with water and are difficult to remove due to their high boiling points. The amount used should not exceed 300 parts by mass relative to 100 parts by mass of the total mass of the polyhydroxy resin.

Also, in addition to the above-mentioned water and organic solvents, organic solvents such as toluene (other organic solvents) may also be contained, and the usage-amount of other organic solvents is preferably less than 100 parts by mass, more preferably 0.5 parts by mass, relative to the usage-amount of the aforementioned solvents. to 50 parts by mass.

The reaction temperature of the allyl etherification reaction of the polyhydroxy resin is usually 30 to 90°C, preferably 35 to 80°C. Also, in order to obtain an allyl ether compound of higher purity, it is preferable to raise the reaction temperature in two or more stages, for example, it is particularly preferable to set the temperature at 35 to 50°C in the first stage and 45 to 100°C in the second stage.

The reaction time of the allyl etherification reaction of the polyhydroxy resin is usually 0.5 to 10 hours, preferably 1 to 8 hours, and particularly preferably 1 to 5 hours. When the reaction time is 0.5 hours or more, the reaction can proceed sufficiently, and by being 10 hours or less, the amount of by-products produced can be kept low.

After the reaction is over, the solvent is distilled off under heat and reduced pressure, or not distilled off, but dissolved in a ketone compound with 4 to 7 carbons (such as methyl isobutyl ketone, methyl ethyl ketone, cyclopentanone, cyclohexane Ketones, etc.), or organic solvents such as toluene, and wash with water in a state heated to 40 to 90°C (preferably 50 to 80°C) to make the pH of the water layer 5 to 8 to remove by-product salts.

Also, the allyl etherification reaction of polyhydric hydroxyl resin is generally carried out by blowing inert gas such as nitrogen into the system (in gas or in liquid). By carrying out the reaction by blowing an inert gas into the system, coloration of the resulting product can be prevented.

The blowing amount of the inert gas per unit time varies depending on the volume of the reactor used for the reaction, but it is preferable to adjust the inactive gas so that the volume of the reactor can be replaced in 0.5 to 20 hours, for example. The amount of gas blown in per unit time.

The maleimide compound contained in the resin composition of the present invention is not particularly limited, and examples include N-phenylmaleimide, N-hydroxyphenylmaleimide, 4,4'- Diphenylmethane bismaleimide, polyphenylmethane maleimide, m-phenylene bismaleimide, p-phenylene bismaleimide, 2,2'-[4 -(4-maleimidephenoxy)phenyl]propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide Amine, bis(3,5-dimethyl-4-maleimidophenyl)methane, bis-(3-ethyl- 5-Methyl-4-maleimidephenyl)methane, bis(3,5-diethyl-4-maleimidephenyl)methane, 4-methyl-1,3-phenylene 1,3-bis(3-maleimide) iminophenoxy)benzene, N,N'-ethylene dimaleimide, N,N'-hexamethylene dimaleimide, horses represented by the following general formula (4) A maleimide compound (resin), or a prepolymer of the maleimide compound, or a prepolymer of a maleimide compound and an amine compound, etc.

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 0-4, preferably 0-2.

b represents 0-3, preferably 0-2.

r and q are 0 or 1.

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

The lipid composition of the present invention contains the allyl ether compound (resin) and the maleimide compound (resin) represented by the general formula (1) of the present invention as essential components. With respect to 100 parts by mass of the maleimide compound, the content of the allyl ether compound is preferably 5 to 900 parts by mass, more preferably 10 to 300 parts by mass, more preferably 50 to 200 parts by mass, particularly preferably 100 to 200 parts by mass.

In order to obtain the allyl ether compound used for the resin composition of the present invention, in addition to the allyl ether compound represented by the general formula (1) of the present invention, various allyl ether compounds can also be used in combination as required. One or more than two. Preferably, at least 30 mass % or more of the allyl ether compound is the allyl ether compound of this invention, More preferably, it contains 50 mass % or more. When it is less than this content, there exists a possibility that a dielectric characteristic may deteriorate.

In addition to the allyl ether compound (resin) of the present invention, the allyl ether compound that can be used in combination can be, for example, bisphenol A, bisphenol F, bisphenol C, bisphenol K, bisphenol Z, bisphenol S , tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol S, tetramethylbisphenol Z, dihydroxydiphenylsulfide, 4,4'-thiobis(3-methyl - Allyl ether compounds of bisphenols such as 6-tert-butylphenol after allyl etherification, so that catechol, resorcinol, methyl resorcinol, hydroquinone, monomethyl Allyl ether compounds of dihydroxyphenyl allyletherification such as dihydroquinone, dimethylhydroquinone, trimethylhydroquinone, mono-tert-butylhydroquinone, di-tert-butylhydroquinone, etc. , the allyl ether compound after allyl etherification of hydroxynaphthalene such as dihydroxynaphthalene, dihydroxymethylnaphthalene, dihydroxymethylnaphthalene, trihydroxynaphthalene, or Shonol BRG-555 (AICA Industry Co., Ltd. ) and other phenol novolac resins, DC-5 (Nippon Steel Chemical Materials Co., Ltd. Phenols such as trishydroxyphenylmethane-type novolac resins such as Naphthalene Novolac resins, naphthols and/or bisphenols and aldehydes condensates, SN-160, SN-395 Condensates of phenols, naphthols and/or bisphenols and diols, phenols and/or naphthols and isopropenyl acetophenone, etc. Condensates of phenols, naphthols and/or bisphenols and dicyclopentadiene, condensates of phenols, naphthols and/or bisphenols and biphenyl crosslinking agents, etc. Novolac resin is allyl ether compound after allyl etherification such as polyhydroxy resin, triallyl triisocyanate, etc. From the viewpoint of reactivity and ease of acquisition, it is preferable to use bisphenol A, bisphenol A, Allyl ether compound after allyl etherification of bisphenols such as phenol F.

A hardening accelerator may be formulated in the resin composition of the present invention as needed. If a hardening accelerator is used, a compound capable of cross-linking reaction with maleimide groups will undergo addition reaction with maleimide groups to cause cross-linking, so the cured product exhibits good physical properties.

Hardening accelerators include, for example, amines, imidazoles, organic phosphines, Lewis acids, organic or oxides, etc., specifically 1,8-diazabicyclo(5,4,0)undeca-7 Tertiary amines such as -ene, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol, 2-methylimidazole, 2-phenyl Imidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole and other imidazoles, tributylphosphine, methyldiphenylphosphine, triphenylphosphine , diphenylphosphine, phenylphosphine and other organic phosphines, addition reactants of organic phosphines and quinone compounds, tetraphenylphosphonium-tetraphenylborate, tetraphenylphosphonium-ethyltriphenylborate, Tetrabutylphosphonium-tetrabutyl borate and other tetrasubstituted phosphonium-tetrasubstituted borates, 2-ethyl-4-methylimidazole. Tetraphenylborate, N-methylmorpholine. Tetraphenyl boron salts such as tetraphenyl borate, copper peroxide, aldehyde peroxide, hydrogen peroxide, dialkyl peroxide, diacyl peroxide, peroxydicarbonate, peroxyester and other organic Peroxides, etc. The addition amount of the hardening accelerator is in the range of 0.2 to 5 parts by mass relative to 100 parts by mass of the resin composition.

In the resin composition of the present invention, other various curable resins or thermoplastic resins can also be blended as needed.

Examples of hardening resins include epoxy resins, unsaturated polyester resins, hardening maleimide resins, polycyanate resins, phenol resins, ethylene resins having more than one polymerizable unsaturated hydrocarbon group in the molecule. base compounds, etc. From the viewpoint of low dielectric coefficient and low dielectric loss tangent, vinyl compounds having one or more polymerizable unsaturated hydrocarbon groups in the molecule are preferred.

When the hardening resin is an epoxy resin, it is preferably selected from one molecule having two or more One or more epoxy resins on the epoxy base. Relevant epoxy resins include, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, tetramethylbisphenol F type epoxy resin, bisphenol type epoxy resin, cyanoquinone type epoxy resin, bisphenol fennel 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 novolac Varnish type epoxy resin, cresol novolac type epoxy resin, alkyl novolac type epoxy resin, styrenated phenol novolak type epoxy resin, bisphenol novolak type epoxy resin, naphthalene novolak type epoxy resin Oxygen resin, β-naphthol aralkyl type epoxy resin, naphthalene diol aralkyl type epoxy resin, α-naphthol aralkyl type epoxy resin, biphenyl aralkylphenol type epoxy resin, Trihydroxyphenylmethane-type epoxy resins, tetrahydroxyphenylethane-type epoxy resins, dicyclopentadiene-type epoxy resins, alkylene glycol-type epoxy resins, aliphatic cyclic epoxy resins, and the like. These epoxy resins may be used alone, or two or more types of epoxy resins of the same type may be used in combination, and epoxy resins of different types may be used in combination.

Moreover, when an epoxy resin is contained, you may use a hardening|curing agent other than an epoxy resin. The curing agent is not particularly limited, and examples thereof include phenol-based curing agents, amine-based curing agents, imide-based compounds, acid anhydride-based compounds, naphthol-based curing agents, active ester-based curing agents, benzoxazine-based curing agents, Cyanate-based hardeners, etc. These may be used alone, or two or more of the same type may be used in combination with other types.

Furthermore, when compounding an epoxy resin, a hardening accelerator may be used as needed. For example, amines, imidazoles, organic phosphines, Lewis acids, etc. Generally, the addition amount of the hardening accelerator is in the range of 0.2 to 5 parts by mass relative 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, the vinyl compounds may be any as long as they can be crosslinked and cured by reacting with the vinyl compound of the present invention. The polymerizable unsaturated hydrocarbon group is preferably a carbon-carbon unsaturated double bond, more preferably a molecule Compounds with two or more carbon-carbon unsaturated double bonds.

The average number of carbon-carbon unsaturated double bonds per molecule of vinyl compounds as hardening resins (the number of vinyl groups (including substituted vinyl groups), also known as the number of terminal double bonds), although vinyl The Mw of the compound varies, but is preferably, for example, 1 to 20, more preferably 2 to 18. When the number of terminal double bonds is too small, it tends to be difficult to obtain sufficient heat resistance of the cured product. Also, if the number of terminal double bonds is too large, the reactivity may be too high, which may cause problems such as lowered storage stability of the composition or lowered fluidity of the composition.

Vinyl compounds, such as triallyl isocyanurate (TAIC) and other trienyl isocyanurate compounds, modified terminal hydroxyl (meth)acryl or styrene groups Polyphenylene ether (PPE), polyfunctional (meth)acrylate compounds with two or more (meth)acryl groups in the molecule, polybutadiene equal to vinyl groups with two or more vinyl groups in the molecule Compounds (polyfunctional vinyl compounds), vinylbenzyl compounds such as styrene and divinylbenzene, and the like. Among them, those having two or more carbon-carbon unsaturated double bonds in the molecule are preferred, specifically, TAIC, multifunctional (meth)acrylate compounds, modified PPE resins, multifunctional vinyl Compounds, and divinylbenzene compounds, etc. If these are used, it is presumed that crosslinking can be formed more appropriately by the curing reaction, and the heat resistance of the cured product of the resin composition can be improved. In addition, these may be used alone or in combination of two or more. Moreover, it can also be used together with the compound which has one carbon-carbon unsaturated double bond in a molecule|numerator. The compound having one carbon-carbon unsaturated double bond in the molecule may, for example, be a compound having one vinyl group in the molecule (monovinyl compound) and the like.

Thermoplastic resins include, for example, phenoxy resins, polyurethane resins, polyester resins, polyethylene resins, polypropylene resins, polystyrene resins, ABS resins, AS resins, vinyl chloride resins, polyvinyl acetate resins, Polymethyl methacrylate resin, polycarbonate resin, polyacetal resin, cyclic Polyolefin resins, polyimide resins, thermoplastic polyimide resins, polyimideimide resins, polytetrafluoroethylene resins, polyetherimide resins, polyphenylene ether resins, modified polyphenylene ether resins , polyether resin, polyether resin, polyether ether ketone resin, polyphenylene sulfide resin, polyvinyl formaldehyde resin, or known thermoplastic elastomers (such as styrene-ethylene-propylene copolymer, styrene-ethylene- butene copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, hydrogenated styrene-butadiene copolymer, hydrogenated styrene-isoprene copolymer, etc.), or rubber (e.g. polybutadiene, polyisoprene) and the like. Preferable are polyphenylene ether resins (unmodified), hydrogenated styrene-butadiene copolymers, and the like.

The resin composition of the present invention may also contain other additives such as fillers, silane coupling agents, antioxidants, release agents, defoamers, emulsifiers, thixotropy imparting agents, smoothing agents, flame retardants, pigments, etc. wait.

Specifically, fillers include fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide, silicon nitride, aluminum hydroxide, diaspore, magnesium hydroxide, talc, mica, carbonic acid Calcium, calcium silicate, calcium hydroxide, magnesium carbonate, barium carbonate, 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, microparticle rubber, thermoplastic elastomer, etc. The reason for using the filler is, for example, the effect of improving impact resistance. In addition, when metal hydroxides such as aluminum hydroxide, diaspore, and magnesium hydroxide are used, they function as flame retardant additives to improve flame retardancy. Among them, silicon dioxide, mica and talc are preferable, and spherical silicon dioxide is more preferable. Moreover, these may be used individually by 1 type, and may use them in combination of 2 or more types.

The filler can be used directly, but it can also be surface-treated with silane coupling agents such as epoxy silane type or amino silane type. The silane coupling agent is preferably vinylsilane type, methacryloxysilane type, acryloxysilane type, and styrylsilane type silane coupling agent. In this way, it is possible to increase Adhesion strength with metal foil or interlayer adhesion strength between resins. In addition, instead of using the method of surface-treating the filler in advance, it is also possible to add a silane coupling agent by an integral blending method.

When the resin composition is used as a plate-shaped substrate, from the viewpoint of dimensional stability, bending strength, etc., preferable fillers include, for example, fibrous fillers. A more preferable example is a glass fiber substrate using a filler of a fibrous base material in which glass fibers are woven into a grid.

The compounding quantity of a filler is preferably 1-150 mass parts with respect to 100 mass parts of resin compositions (solid content), More preferably, it is 10-70 mass parts. When the compounding quantity is large, the hardened|cured material will become brittle, and there exists a possibility that sufficient mechanical properties may not be acquired. In addition, if the compounding amount is small, there is a possibility that the effect of compounding the filler such as improving the impact resistance of the cured product cannot be obtained.

It is preferable that the compounding quantity of other additives is the range of 0.01-20 mass parts with respect to 100 mass parts of resin compositions (solid content).

A cured product can be obtained by heating and curing the resin composition of the present invention. The method used to obtain the hardened product is preferably to use casting, compression molding, transfer molding, etc., or laminated in the form of resin sheets, resin-coated copper foil, prepregs, etc., and then heated and pressurized to make a laminate. and so on. 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 can be prepared by uniformly mixing the above-mentioned components. The resin composition can be easily made into a cured product by the same method as a conventional method. Examples of the cured product include molded cured products such as laminates, cast products, molded products, adhesive layers, insulating layers, and films.

Examples of applications where the resin composition can be used include printed wiring board materials, resin compositions for flexible wiring boards, insulating materials for circuit boards such as interlayer insulation materials for build-up boards, semiconductor sealing materials, conductive pastes, conductive films, build-up boards, etc. Adhesive films, resin casting materials, adhesives, etc. for layers. Among these various applications, printed wiring board materials, insulating materials for circuit boards, and adhesive films for build-up, Passive elements such as capacitors and active elements such as IC chips can be embedded in substrates, and used as insulating materials for so-called substrates for built-in electronic components. Among them, due to the characteristics of high flame retardancy, low dielectric properties, and solvent solubility, it is preferably used as a printed wiring board material, a resin composition for a flexible wiring board, and an interlayer insulating material for a build-up board. Materials for circuit boards (laminates) and semiconductor sealing materials.

The sealing material obtained by using the resin composition of the present invention can be suitably used for tape-like semiconductor wafers, bonding liquid seals, underfills, and interlayer insulating films of semiconductors. In order to prepare the resin composition as a semiconductor sealing material, for example, the following method can be used. After pre-mixing the inorganic filler, silane coupling agent, mold release agent, etc. The method of fully melting and mixing until uniformity by machine, roller, etc. At this 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, for example, the resin composition can be molded by casting, transfer molding machine, injection molding machine, etc., and then heated and hardened at 180 to 250°C for 0.5 to 5 hours. A method by which a shaped object is made.

When used as a tape sealant, for example, heat it to make a semi-hardened sheet and make a sealant tape, place the sealant tape on a semiconductor wafer, heat it to 100 to 150°C, soften it, and then A method of fully hardening at 180 to 250°C. Also, in the case of a joint type liquid sealing type, the obtained resin composition may be dissolved in a solvent if necessary, and then applied to a semiconductor wafer or an electronic component and cured directly.

The resin composition of the present invention can be dissolved in an organic solvent to prepare a varnish. Usable organic solvents include, for example, 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, dimethyl Acetamide, N-methyl Nitrogen atom-containing solvents such as pyrrolidone, and sulfur atom-containing solvents such as dimethylsulfone can be used alone or in combination of two or more. It is not particularly limited as long as it is an industrially available organic solvent, but methyl ethyl ketone and dimethylformamide are preferable from the viewpoint of solubility and handleability.

After the resin composition of the present invention is dissolved in an organic solvent to make a varnish, it can be impregnated into fibrous materials such as glass fiber cloth, aramid non-woven fabric, polyester non-woven fabric such as liquid crystal polymer, and then the solvent is removed to form a prepreg. body. Furthermore, after coating the composition varnish on a sheet-like material such as copper foil, stainless steel foil, polyimide film, polyester film, etc., it can be made into an adhesive sheet by drying.

When using the above-mentioned prepreg to form a laminate, one or more prepreg bulk layers can be placed on one or both sides to form a laminate, and the prepreg can be made by pressing and heating the laminate. Hardened and integrated to obtain laminates. As the metal foil here, single, alloy or composite metal foils of copper, aluminum, brass, nickel, etc. can be used. The conditions for heating and pressing the laminate can be appropriately adjusted according to the curing conditions of the resin composition for heating and pressing. If the pressure is too low, air bubbles will remain inside the resulting laminate and the electrical properties will be reduced. Therefore, it is expected that Pressing is carried out under conditions that can satisfy moldability. The heating temperature is preferably from 160 to 250°C, more preferably from 170 to 220°C. The pressing pressure is preferably from 0.5 to 10 MPa, more preferably from 1 to 5 MPa. The heating and pressing time is preferably from 10 minutes to 4 hours, more preferably from 40 minutes to 3 hours. Furthermore, it is also possible to make a multi-layer board by using the single-layer laminate plate obtained in this way as an inner layer material. At this time, firstly, the circuit is formed on the laminate plate by the additive process or the subtractive process, and the inner layer material is obtained by blackening the surface of the formed circuit. A prepreg and an adhesive sheet are used to form an insulating layer on one or both sides of the inner layer, and a conductive layer is formed on the surface of the insulating layer to form a multilayer board.

[Example]

The following examples and comparative examples are given to specifically illustrate the present invention, but the present invention is not limited to etc. Unless otherwise specified, "part" means a mass part, "%" means a "mass %", and "ppm" means a mass ppm. In addition, the measurement method was measured by the following method, respectively.

‧Hydroxyl equivalent:

Measured in accordance with JIS K0070, and the unit is "g/eq." Moreover, unless otherwise specified, the hydroxyl equivalent of a polyhydric hydroxyl resin means the equivalent of a phenolic hydroxyl group.

‧Softening Point:

Measured in accordance with JIS K7234 and the ring and ball method. Specifically, an automatic softening point device (manufactured by Meitec Co., Ltd., ASP-MG4) was used.

‧Glass transition temperature (Tg):

Measurement was performed in accordance with JIS C6481. It is represented by the peak value of tan δ when the measurement is performed with a dynamic viscoelasticity measuring device (manufactured by Hitachi High-Tech Co., Ltd., EXSTAR DMS6100) at a temperature increase of 5°C/min.

‧Relative permittivity dielectric loss tangent:

According to IPC-TM-650 2.5.5.9, use a material analyzer (manufactured by AGILENT Technologies Co., Ltd.) to obtain the dielectric loss tangent of the relative permittivity at a frequency of 1 GHz by the volumetric method, and evaluate it by this.

‧GPC (gel permeation chromatography) determination:

It is used when the body (HLC-8220GPC, Toso Co., Ltd.) is equipped with a column (manufactured by Toso Co., Ltd., TSKgelG4000HXL, TSKgelG3000HXL, TSKgelG2000HXL) in series, and the temperature of the column is 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. As a measurement sample, 0.1 g of the sample was dissolved in 10 mL of THF, and 50 μL of the sample was filtered with a microfilter. For data processing, GPC-8020 model II version 6.00 manufactured by Toso Co., Ltd. was used.

‧IR:

Using a Fourier transform infrared spectrometer (manufactured by Perkin Elmer Precisely, Spectrum One FT-IR Spectrometer 1760X), use KRS-5 in the tank, dissolve the sample in THF, apply it on the tank, dry it, and measure the wave number from 650 to 4000 cm Absorbance of ^-1 .

‧ESI-MS:

Using a mass spectrometer (manufactured by Shimadzu Corporation, LCMS-2020), using acetonitrile and water as mobile phases, a sample dissolved in acetonitrile was measured to perform mass spectrometry.

Abbreviations used in Examples and Comparative Examples are as follows.

[Allyl ether compound]

R1: the allyl ether compound (resin) obtained in Example 1

R2: the allyl ether compound (resin) that embodiment 2 gains

R3: the allyl ether compound (resin) that embodiment 3 gains

S1: Allyl ether compound obtained in Comparative Example 1

S2: Allyl ether compound obtained in Comparative Example 2

S3: 4,4'-(1-methylethylene)bis(2-allylphenol) (manufactured by Fujifilm Hako Pure Chemical Industries, Ltd., allyl equivalent weight 154)

[Polyhydroxy resin]

P1: Polyhydric hydroxyl resin obtained in Synthesis Example 1

P2: Polyhydric hydroxyl resin obtained in Synthesis Example 2

P3: Polyhydric hydroxyl resin obtained in Synthesis Example 3

P4: Polyhydric hydroxyl resin obtained in Synthesis Example 4

MEH: biphenyl aralkyl type polyhydric hydroxyl resin (Meiwa Kasei Co., Ltd., MEH-7851, hydroxyl equivalent 210, softening point 75°C)

PN: Phenol novolak resin (manufactured by AICA Industry Co., Ltd., Shonol BRG-557, hydroxyl equivalent 105, softening point 85° C.)

[Maleimide compound]

M1: phenylmethanemaleimide (manufactured by Daiwa Chemical Industry Co., Ltd., BMI-2300)

M2: The 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 group equivalent 274, softening point 60° C.)

[hardening accelerator]

C1: Dicumyl peroxide (manufactured by NOF Co., Ltd., PERCUMYL D)

C2: 2-Ethyl-4-methylimidazole (manufactured by Shikoku Chemical Industry Co., Ltd., CUREZOL 2E4MZ)

Synthesis Example 1

500 parts of 2,6-xylenol (the following structural formula) were filled in a reaction device including a glass separable flask equipped with a stirrer, a thermometer, a nitrogen blowing tube, a dropping funnel, and a cooling tube.

47%BF₃醚錯合物7.3份(相對於最初添加之二環戊二烯為0.1倍莫耳)，一邊進行攪拌進行加溫至100℃。保持於相同溫度之情況下，以1小時滴入二環戊二烯(下述結構式)67.6份(相對於2,6-二甲苯酚為0.12倍莫耳)。

7.3 parts of 47% BF ₃ ether complex (0.1 mole relative to the dicyclopentadiene added first) were heated to 100° C. while stirring. While maintaining the same temperature, 67.6 parts of dicyclopentadiene (the following structural formula) was dripped over 1 hour (0.12 times mol with respect to 2,6-xylenol).

再以115至125℃之溫度反應4小時。之後，於5mmHg之減壓下，加溫至200℃以使未反應之原料蒸發除去，加入MIBK 46.7份以溶解生成物。裝填47%BF₃醚錯合物3.3份後，加溫至100℃，保持於相同溫度之情況下，以1小時滴入二環戊二烯74.7份。再以115至125℃之溫度反應4小時。加入氫氧化鉀5份。再添加10%之草酸水溶液9份。加入MIBK 350份以溶解生成物，加入80℃的溫水120份進行水洗，將下層的水層分離除去。加溫至200℃進行回流脫水，過濾後，於5mmHg之減壓下，加溫至160℃以使MIBK蒸發除去，製得紅褐色之多元羥基樹脂(P1)259份。

Then react at a temperature of 115 to 125° C. for 4 hours. Thereafter, under a reduced pressure of 5 mmHg, it was heated to 200° C. to evaporate and remove unreacted raw materials, and 46.7 parts of MIBK was added to dissolve the product. After filling with 3.3 parts of 47% BF ₃ ether complex, it was heated to 100°C, and 74.7 parts of dicyclopentadiene was added dropwise over 1 hour while maintaining the same temperature. Then react at a temperature of 115 to 125° C. for 4 hours. Add 5 parts of potassium hydroxide. Then add 9 parts of 10% oxalic acid aqueous solution. 350 parts of MIBK was added to dissolve the product, 120 parts of warm water at 80° C. was added and washed with water, and the lower water layer was separated and removed. Heat to 200°C for reflux dehydration, filter, then heat to 160°C under reduced pressure of 5 mmHg to remove MIBK by evaporation, and obtain 259 parts of reddish-brown polyhydroxy resin (P1).

The obtained polyhydric hydroxyl resin (P1) is a resin with a hydroxyl equivalent of 323 and a softening point of 97°C, and the absorption ratio (A ₃₀₄₀ /A ₁₂₁₀ ) is 0.27. The Mw obtained by GPC is 740, the Mn is 490, the n=0 body content accounts for 6.6 area%, the n=1 body content accounts for 70.1 area%, and the n=2 body content accounts for 23.3 area%. As a result of mass spectrometry by ESI-MS (negative ion), it was confirmed that M-=375, 507, 629, 639, and 761.

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 charged, and heated to 100° C. while stirring. While maintaining the same temperature, 67.6 parts of dicyclopentadiene (0.12 times mole relative to 2,6-xylenol) was added dropwise over 1 hour. Then react at a temperature of 115 to 125° C. for 4 hours. Thereafter, under a reduced pressure of 5 mmHg, it was heated to 200° C. to evaporate and remove unreacted raw materials, and 46.7 parts of MIBK was added to dissolve the product. After filling 3.3 parts of 47% BF ₃ ether complex, it was heated to 100° C., and while maintaining the same temperature, 56.0 parts of dicyclopentadiene was added dropwise over 1 hour. Then react at a temperature of 115 to 125° C. for 4 hours. Add 5 parts of potassium hydroxide. Then add 9 parts of 10% oxalic acid aqueous solution. 350 parts of MIBK was added to dissolve the product, 110 parts of warm water at 80° C. was added and washed with water, and the lower water layer was separated and removed. Heat to 120°C for reflux dehydration, filter, then heat to 160°C under a reduced pressure of 5mmHg to evaporate and remove MIBK to obtain 240 parts of reddish-brown polyhydroxy resin (P2).

The obtained polyhydric hydroxyl resin (P2) is a resin with a hydroxyl equivalent of 276 and a softening point of 94°C, and the absorption ratio (A ₃₀₄₀ /A ₁₂₁₀ ) is 0.17. The Mw obtained by GPC is 670, the Mn is 490, the n=0 body content accounts for 6.6 area%, the n=1 body content accounts for 70.3 area%, and the n=2 body content accounts for 23.1 area%. As a result of mass spectrometry by ESI-MS (negative ion), it was confirmed that M-=375, 507, 629, 639, and 761.

Synthesis example 3

In the same reaction device 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 relative to the initially added dicyclopentadiene) were charged. It heated up to 100 degreeC, stirring. While maintaining the same temperature, 67.6 parts of dicyclopentadiene (0.12 times mole relative to 2,6-xylenol) was added dropwise over 1 hour. Then react at a temperature of 115 to 125° C. for 4 hours. Thereafter, under a reduced pressure of 5 mmHg, it was heated to 200° C. to evaporate and remove unreacted raw materials, and 46.7 parts of MIBK was added to dissolve the product. After filling 3.3 parts of 47% BF ₃ ether complex, it was heated to 100°C, and 28.0 parts of dicyclopentadiene was added dropwise over 1 hour while maintaining the same temperature. Then react at a temperature of 115 to 125° C. for 4 hours. Add 5 parts of potassium hydroxide. Then add 9 parts of 10% oxalic acid aqueous solution. 280 parts of MIBK were added to dissolve the product, 100 parts of warm water at 80° C. was added and washed with water, and the lower water layer was separated and removed. Heat to 120°C for reflux dehydration, filter, then heat to 160°C under reduced pressure of 5mmHg to evaporate and remove MIBK to obtain 213 parts of reddish-brown polyhydroxy resin (P3).

The obtained polyhydric hydroxyl resin (P3) is a resin with a hydroxyl equivalent of 234 and a softening point of 86°C, and the absorption ratio (A ₃₀₄₀ /A ₁₂₁₀ ) is 0.11. The Mw obtained by GPC is 560, the Mn is 470, the n=0 body content accounts for 6.2 area%, the n=1 body content accounts for 74.0 area%, and the n=2 body content accounts for 19.8 area%. As a result of mass spectrometry by ESI-MS (negative ion), it was confirmed that M-=375, 507, 629, 639, and 761.

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 charged, and heated to 100° C. while stirring. While maintaining the same temperature, 211.7 parts of dicyclopentadiene (0.10 times mole relative to phenol) was added dropwise over 1 hour. Then react at a temperature of 115 to 125° C. for 4 hours, and add 36 parts of potassium hydroxide. Then add 60 parts of 10% oxalic acid aqueous solution. Thereafter, it was heated to 160° C. for dehydration, and then 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, 100 parts of warm water at 80° C. was added and washed with water, and the lower water layer was separated and removed. Heat to 120°C for reflux dehydration, after filtration, heat to 160°C under a reduced pressure of 5mmHg to evaporate and remove MIBK to obtain a reddish-brown polyhydroxy resin (P4) represented by the following general formula (5) ) 480 copies.

The obtained polyhydric hydroxyl resin (P4) had a hydroxyl equivalent of 175 and a softening point of 90°C. The Mw obtained by GPC is 470, the Mn is 410, the s=0 body content accounts for 1.0 area%, the s=1 body content accounts for 68.7 area%, and the content of s=2 or more bodies accounts for 30.3 area%. As a result of mass spectrometry by ESI-MS (negative ion), it was confirmed that M-=375, 507, 629, 639, and 761.

Synthesis Example 5

In a flask equipped with a thermometer, a cooling tube, a Dean-Stark azeotropic distillation trap, and a stirrer, fill 100 parts of aniline and 50 parts of toluene, and dissolve 39.2 parts of 35% hydrochloric acid at room temperature for 1 hour drop enter. After the dropwise addition, heat to make it azeotropic, cool the produced water and methanol, separate the liquids, and pour only the toluene in the organic layer back into the system for dehydration. 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 the reaction was carried out at the same temperature for 2 hours. After completion of the reaction, toluene was distilled off while raising the temperature, the temperature in the system was adjusted to 195 to 200° C., and the reaction was carried out at this temperature for 15 hours. Afterwards, under cooling, slowly drop 86 parts of 30% sodium hydroxide aqueous solution in such a way as not to cause violent reflux in the system, pour the toluene distilled off when the temperature rises below 80°C into the system, and place it in a static place. 70 to 80°C. The water layer of the lower layer after separation was removed, and this was repeated until the washing solution obtained by washing the reaction solution with water became neutral. Next, excess aniline and toluene were distilled off from the oil layer under heating and reduced pressure (200° C., 0.6 KPa) with a rotary evaporator, whereby 47 parts of aromatic amine resins were obtained.

Next, 75 parts of maleic anhydride and 150 parts of toluene were filled in the above-mentioned flask, and the water and toluene produced by heating and azeotroping were cooled and separated, and only the toluene in the organic layer was poured back into the system for dehydration. Next, a resin solution in which 100 parts of the above-mentioned aromatic amine resin was dissolved in 100 parts of N-methyl-2-pyrrolidone was dropped into a system maintained at 80 to 85°C over 1 hour. After dropping, react at the same temperature for 2 hours, add 1.5 parts of p-toluenesulfonic acid, carry out azeotropy under reflux conditions, cool the resulting condensation water and toluene, and separate the liquids, then pour only the toluene in the organic layer back into the system , and reacted for 20 hours under dehydration. After the reaction, 100 parts of toluene was added, water washing was repeated to remove p-toluenesulfonic acid and excess maleic anhydride, and water was removed from the system by azeotropic heating. Next, the reaction liquid was concentrated to obtain 133 parts of a maleimide compound (M2). Here, maleimide (M2), in formula (4), a=b, b=0, r=1, q=1, R ⁵ are all hydrogen atoms, m is 1.3.

Example 1

In the same reaction device as in Synthesis Example 1, fill 100 parts of the valent hydroxyl resin (P1) obtained in Synthesis Example 1 and 150 parts of diethylene glycol dimethyl ether, heat to 100°C to form a uniform solution, and then cool to 35°C about. add Add 27 parts of 50% sodium hydroxide solution (1.1 times mole relative to polyhydric hydroxyl resin) to make a phenoxide solution, then drop in 45 bromide propene (the following structural formula) in the range of 30 to 40°C for 1 hour Parts (1.2 times the mole relative to the polyhydroxy resin),

After completion|finish of dripping, it heated up to 60 degreeC, and was made to react at the same temperature for 3 hours. After completion of the reaction, 220 parts of MIBK was added, 70 parts of warm water was added to perform water washing, and the lower layer was separated and removed. Thereafter, MIBK was evaporated and removed by heating to 130° C. under a reduced pressure of 5 mmHg to obtain 109 parts of a brown allyl ether compound (R1).

The resulting propylene ether compound (R1) has a softening point of 61°C, a hydroxyl equivalent of 12870, and a melt viscosity of 0.14Pa at 150°C. s, the total chlorine content is 68ppm. The Mw obtained by GPC is 790, the Mn is 510, the n=0 body content accounts for 5.9 area%, the n=1 body content accounts for 70.5 area%, and the n=2 body content accounts for 23.6 area%. As a result of mass spectrometry by ESI-MS (negative ion), it was confirmed that 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. 2.

Example 2

In the same reaction device as in Synthesis Example 1, fill 100 parts of valent hydroxyl resin (P2) obtained in Synthesis Example 2 and 150 parts of diethylene glycol dimethyl ether, heat to 100°C to form a uniform solution, and then cool to 35°C about. Add 32 parts of 50% sodium hydroxide solution (1.1 times the mole relative to the polyhydroxy resin) to make a phenoxide solution, and drop in 52.5 propylene bromide (the following structural formula) in the range of 30 to 40 ° C for 1 hour part (1.2 times the mole relative to the polyhydric hydroxyl resin), after the completion of the dropping, 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, 70 parts of warm water was added to perform water washing, and the lower layer was separated and removed. Thereafter, MIBK was evaporated and removed by heating to 130° C. under a reduced pressure of 5 mmHg to obtain 110 parts of a brown allyl ether compound (R2).

The resulting propylene ether compound (R2) has a softening point of 48°C, a hydroxyl equivalent of 20,000, and a melt viscosity of 0.07Pa at 150°C. s, the total chlorine content is 132ppm. The Mw obtained by GPC is 670, the Mn is 490, the n=0 body content accounts for 6.1 area%, the n=1 body content accounts for 71.7 area%, and the n=2 body content accounts for 22.1 area%. As a result of mass spectrometry by ESI-MS (negative ion), it was confirmed that M-=455, 587, 719, and 749.

Example 3

In the same reaction device as in Synthesis Example 1, fill 100 parts of valent hydroxyl resin (P3) obtained in Synthesis Example 3 and 150 parts of diethylene glycol dimethyl ether, heat to 100°C to form a uniform solution, and then cool to 35°C about. Add 38 parts of 50% sodium hydroxide solution (1.1 times the mole relative to the polyhydroxy resin) to make a phenoxide solution, and drop in propylene bromide (the following structural formula) 62.2 in the range of 30 to 40°C for 1 hour part (1.2 times the mole relative to the polyhydric hydroxyl resin), after the completion of the dropping, 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, 70 parts of warm water was added to perform water washing, and the lower layer was separated and removed. Thereafter, MIBK was evaporated and removed by heating to 130° C. under a reduced pressure of 5 mmHg to obtain 114 parts of a brown allyl ether compound (R3).

The obtained propylene propylene ether compound (R3) is a semi-solid resin at room temperature with a hydroxyl equivalent of 69,000 and a melt viscosity of 0.03Pa at 150°C. s, the total chlorine content is 148ppm. The Mw obtained by GPC is 560, the Mn is 460, the n=0 body content accounts for 6.0 area%, the n=1 body content accounts for 74.1 area%, and the n=2 body content accounts for 20.0 area%. As a result of mass spectrometry by ESI-MS (negative ion), it was confirmed that 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 polyvalent hydroxy resin was changed to the valent hydroxy resin (P4) obtained in Synthesis Example 4.

Comparative example 2

Except having changed polyhydric hydroxyl resin into MEH, it carried out similarly to Example 1, and obtained the allyl ether compound (S2).

Example 4

Prepare 100.0 parts of maleimide compound (M1), 196.1 parts of allyl ether compound (R1) obtained in Example 1 (1 times mole relative to maleimide compound), hardening accelerator (G1) 3.0 parts (1phr relative to the total amount of resin), stirred on a heating plate at 140°C for 10 minutes.

The obtained resin composition was placed in a mold made of fluororesin, and vacuum pressurized at 2 MPa at a temperature of 150°C x 30 minutes + 220°C x 100 minutes to obtain a hardened resin test piece with a side length of 50mm x a thickness of 2mm. 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

The compounding amount (parts) shown in Table 1 was prepared, and the resin composition was prepared in the same manner, and the same test as in Example 4 was carried out, and the results are shown in Table 1.

[Table 1]

[Industrial availability]

The resin composition of the present invention can be widely used in various fields such as coatings, civil engineering bonding, casting, electrical and electronic materials, film materials, etc., and is especially useful for laminates and electronic circuits that require low dielectric coefficient and low dielectric loss tangent. substrate.

Claims (7)

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

In the formula, ^R1 independently represents a hydrocarbon group with a carbon number of 1 to 8, ^R2 independently represents a hydrogen atom or a dicyclopentenyl group, and more than one of them is a dicyclopentenyl group, and ^R3 independently represents a hydrogen atom or a dicyclopentenyl group. In the hydrocarbon group with 1 to 4 carbons, n represents the number of repetitions, and the average value is a number of 1 to 5. A resin composition containing the allyl ether compound and the maleimide compound described in claim 1. A hardened product, which is obtained by hardening the resin composition described in claim 2. A sealing material using the resin composition described in claim 2. A material for circuit boards using the resin composition described in claim 2. A prepreg using the resin composition described in claim 2. A laminate using the resin composition described in claim 2.

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