阅读说明：本技术 顺丁烯二酰亚胺树脂组成物、预浸体及其硬化物 (Maleimide resin composition, prepreg and cured product thereof ) 是由 松浦一贵 中西政隆 窪木健一 于 2018-04-25 设计创作，主要内容包括：提供一种在制成硬化物的情形时,显示出优异电特性等的顺丁烯二酰亚胺树脂组成物、预浸体及其硬化物。顺丁烯二酰亚胺树脂组成物含有：具有N个顺丁烯二酰亚胺基的顺丁烯二酰亚胺树脂(N为整数,其平均值大于2)及下述式(1)等所表示的特定的含甲基烯丙基的化合物。<Image he="210" wi="700" file="DDA0002242395940000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(式中,R<Sub>2</Sub>及R<Sub>3</Sub>表示甲基烯丙基或氢原子等,Z具有特定的结构,a1表示1～4的整数)。(A maleimide resin composition, a prepreg and a cured product thereof are provided, which exhibit excellent electrical characteristics and the like when formed into a cured product. The maleimide resin composition comprises: a maleimide resin having N maleimide groups (N is an integer having an average value of more than 2) and a specific methallyl group-containing compound represented by the following formula (1). (wherein R2 and R3 each represents a methallyl group, a hydrogen atom, or the like, Z has a specific structure, and a1 represents an integer of 1 to 4).)

1. A maleimide resin composition comprising: a maleimide resin having N maleimide groups (N is an integer and has an average value of more than 2), and at least one of a compound represented by the following formula (1) and a compound represented by any one of the following formulae (3-1) to (3-7),

[ chemical formula 1]

(wherein R2 independently represents a methallyl group or a hydrogen atom; R3 independently represents a methallyl group, a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aromatic group; Z has a structure represented by any one of the following formulas (2-1) to (2-11); a1 represents an integer of 1 to 4.)

[ chemical formula 2]

(wherein R2 represents the same one as R2 in the formula (1); a2 represents an integer of 1 to 4; a2+1 represents an integer of 1 to 5; indicates a bonding site)

[ chemical formula 3]

(wherein, R2 independently represents a methallyl group or a hydrogen atom; R3 independently represents a methallyl group, a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aromatic group; A represents-O-, > NR4 or-C (R4)2-, R4 independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aromatic group; a3 represents an integer of 1 to 4; a3-1 represents an integer of 1 to 3; a3-2 represents an integer of 1 to 2; and n1 is an integer of 1 < n 1. ltoreq.5 in average).

2. The maleimide resin composition of claim 1, wherein the maleimide resin is represented by the following formula (4),

[ chemical formula 4]

(in the formula (4), a plurality of R1 independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aromatic group; a4 represents 1 to 3; and n2 represents an integer, and the average value thereof is 1 < n 2. ltoreq.5).

3. The maleimide resin composition according to claim 1 or 2, which contains a radical polymerization initiator.

4. the maleimide resin composition according to any one of claims 1 to 3, which contains any one or more of a flame retardant, a filler and an additive.

5. A prepreg which retains the maleimide resin composition of any one of claims 1 to 4 in a sheet-like fibrous base material in a semi-cured state.

6. A cured product of the maleimide resin composition of any one of claims 1 to 4.

7. A cured product of the prepreg according to claim 5.

Technical Field

The present invention relates to a maleimide resin composition, a prepreg and a cured product thereof. More specifically, the present invention relates to a maleimide resin composition, a prepreg and a cured product thereof, which are useful for applications of highly reliable semiconductor sealants, electrical and electronic component insulators, various composite material applications including laminates (printed wiring glass fiber reinforced composites) and CFRPs (carbon fiber reinforced composites), various adhesive applications, various coating applications, structural members and the like.

Background

In general, thermosetting resins such as paper-phenol resin having paper as a base material and glass cloth-epoxy resin having glass cloth as a base material have been mainly used as printed wiring boards for electric and electronic devices, particularly copper foil-laminated boards. These thermosetting resins are known to have high reliability because they exhibit high heat resistance, dimensional stability, and other properties due to their specific crosslinked structure. On the other hand, as high-density packaging and high-multilayer structures of printed wiring boards are required to have improved heat resistance, and as high-speed communication demands are required to have lower dielectric constants and lower dielectric loss tangents, thermosetting resins are increasingly required, and novel crosslinked structures are required.

In particular, in recent years, in the M2M market, communication between machines is self-explanatory, and the amount of information is increasing in a large amount while the amount of human-to-human communication is increasing remarkably. On the other hand, since there is a limit to resources that can be allocated to users by a base station, infrastructure maintenance and high functionality of a communication system are continuously developed. Examples thereof include a small base station (ス モ ー ル セ ル). As the number of devices such as small base stations increases, communication substrates are required accordingly, and the amount of information used can also increase significantly, so that extremely high characteristics are required for communication devices such as smartphones (non-patent document 1).

In these applications, low dielectric loss tangent, low water absorption rate, and reliability such that it is not easily changed at a driving temperature are required, and high heat resistance is required. In particular, the dielectric loss tangent is required to be 0.010 or less, particularly 0.007 or less. Further, at the same time, moisture is one of factors that greatly deteriorate dielectric characteristics, and therefore, a lower water absorption rate is required (non-patent document 2).

Further, when the substrate is used for a substrate of a highly functional semiconductor package for communication, it is preferable to have heat resistance of 170 ℃ or higher, and particularly in recent years, it is preferable to have heat resistance of reflow or higher, and Tg of reflow temperature or higher is required, and the required characteristics of the market have become very high (non-patent document 3).

The fiber-reinforced composite material is composed of a matrix resin and reinforcing fibers such as carbon fibers, glass fibers, alumina fibers, boron fibers, or aramid fibers, and generally has characteristics of light weight and high strength. Such fiber-reinforced composite materials are widely used for insulating materials and laminates (printed wiring boards, build-up boards, etc.) for electric and electronic components, aerospace materials such as bodies and wings of passenger aircraft, machine tool members including robot arms, construction and civil engineering materials, and recreational products such as golf clubs and tennis rackets. In particular, in aerospace materials such as bodies and wings of passenger aircraft and machine tool members represented by robot arms, carbon fiber reinforced composite materials (hereinafter referred to as CFRP) are required to have heat resistance and mechanical properties that maintain rigidity in a temperature range of room temperature to about 200 ℃, long-term reliability, that is, a thermal decomposition temperature sufficiently high, and a high elastic modulus at high temperatures. Epoxy resins have been widely used as matrix resins for fiber-reinforced composite materials, but epoxy resins have low heat resistance and are not suitable for aerospace materials or machine tool members.

As a matrix resin having high heat resistance and also capable of withstanding a use environment of 200 ℃ or higher, a maleimide resin is widely known. A bismaleimide compound is used as a main agent of a maleimide resin, but since a molded article becomes brittle, various modifiers have been developed for improving the maleimide resin. As a solution to this problem, various modifications have been made, and for example, a cyanate ester resin composition is known which is prepared by blending a modified butadiene resin having a methyl (acryloyl) group introduced therein (patent document 1), a cyanate ester resin composition having a butadiene-acrylonitrile copolymer added thereto (patent document 2), or a cyanate ester resin composition having an epoxy resin added thereto (patent document 3). However, these methods have a problem that the brittleness is reduced, but the heat resistance and the mechanical strength are inevitably reduced.

Further, a method of modifying a maleimide resin with an allyl compound known as an additive such as a reactive diluent, a crosslinking agent, and a flame retardant for the maleimide resin is also known. For example, patent document 4 discloses a resin obtained by adding o, o '-diallylbisphenol a, which is liquid at room temperature, to 4,4' -diphenylmethane bismaleimide and hot-melt mixing the mixture, and the carbon fiber sheet can be impregnated with the resin without a solvent.

Disclosure of Invention

Problems to be solved by the invention

However, in patent document 4, the electrical characteristics of the prepreg obtained are not satisfactory even when the prepreg is modified with 2,2' -diallylbisphenol a.

Accordingly, the present invention provides a maleimide resin composition, a prepreg and a cured product thereof, which exhibit electrical characteristics, particularly excellent low hygroscopicity (low water absorption) and heat resistance, in the cured product thereof.

Means for solving the problems

The present inventors have made extensive studies in view of the above-mentioned circumstances, and as a result, have found that a maleimide resin composition comprising a maleimide resin having a more than bifunctional functional group and a compound having a methallyl group exhibits electrical characteristics, particularly excellent low hygroscopicity (low water absorption) and heat resistance, in a cured product thereof, and have completed the present invention.

Namely, the present invention relates to:

[1] A maleimide resin composition comprising: a maleimide resin having N maleimide groups (N is an integer and has an average value of more than 2) and at least one of a compound represented by the following formula (1) and a compound represented by any one of the following formulae (3-1) to (3-7);

[ chemical formula 1]

(wherein R2 independently represents a methallyl group or a hydrogen atom; R3 independently represents a methallyl group, a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aromatic group; Z has a structure represented by any one of the following formulas (2-1) to (2-11); a1 represents an integer of 1 to 4.)

[ chemical formula 2]

(wherein R2 represents the same one as R2 in the formula (1); a2 represents an integer of 1 to 4; a2+1 represents an integer of 1 to 5; indicates a bonding site)

[ chemical formula 3]

(wherein, R2 independently represents a methallyl group or a hydrogen atom; R3 independently represents a methallyl group, a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aromatic group; A represents-O-, > NR4 or-C (R4)2-, R4 independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aromatic group; a3 represents an integer of 1 to 4; a3-1 represents an integer of 1 to 3; a3-2 represents an integer of 1 to 2; and n1 is an integer of 1 < n 1. ltoreq.5 in average).

[2] The maleimide resin composition according to the above item [1], wherein the maleimide resin has a structure represented by the following formula (4);

[ chemical formula 4]

(in the formula (4), a plurality of R1 independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aromatic group; a4 represents 1 to 3; and n2 represents an integer, and the average value thereof is 1 < n 2. ltoreq.5).

[3] The maleimide resin composition as described in the aforementioned item [1] or [2], which contains a radical polymerization initiator;

[4] The maleimide resin composition according to any one of the above items [1] to [3], which comprises at least one of a flame retardant, a filler and an additive;

[5] A prepreg which comprises a fibrous base material in a sheet form and a maleimide resin composition as defined in any one of the above items [1] to [4], the fibrous base material being in a semi-cured state;

[6] A cured product of the maleimide resin composition according to any one of the above items [1] to [4 ];

[7] A cured product of the prepreg according to the above [5 ].

ADVANTAGEOUS EFFECTS OF INVENTION

The maleimide resin composition of the present invention has electrical characteristics, particularly excellent low hygroscopicity (low water absorption) and heat resistance, among cured products thereof, and is therefore useful for insulating materials for electric and electronic parts, laminates (printed wiring boards, build-up boards, etc.), various composite materials represented by CFRP, adhesives, paints, and the like.

Detailed Description

The maleimide resin composition of the present invention will be explained below.

The maleimide resin composition of the present invention contains a maleimide resin having N maleimide groups (N is an integer, and the average value thereof is 2 or more) (hereinafter, also referred to simply as "maleimide resin").

The maleimide resin usable in the present invention is not particularly limited as long as it has a maleimide group number of more than 2 in an average of 1 molecule.

Specific examples of the maleimide resin include polyfunctional maleimide compounds obtained by the reaction of 3,4,4' -triaminodiphenylmethane, triaminophenol and the like with maleic anhydride, maleimide compounds obtained by the reaction of tris (4-aminophenyl) phosphate, tris (4-aminophenyl) thiophosphate and maleic anhydride, tricalimide compounds such as tris (4-maleinimidenyl) methane, bis (3, 4-bismaleimide phenyl) methane, tetramaleimide benzophenone, tetramaleimide naphthalene, tetramaleimide compounds such as maleimide obtained by the reaction of triethylenetetramine with maleic anhydride, tetramaleimide and the like, Phenol novolac type maleimide resin, isopropylidene bis (phenoxyphenylmaleimide) phenylmaleimide aralkyl resin, phenylene (ビ フ ェ ニ レ ン) type phenylmaleimide aralkyl resin, polymaleimide represented by formula (5), polymaleimide of polyaniline obtained by condensation of benzene dialdehyde with aniline, and the like. Also, a polyamide-based polymaleimide resin obtained by adding an aromatic diamine to these polymaleimides may be used. Further, the novolak type maleimide resin has a molecular weight distribution and is therefore highly stable in varnish, and therefore, is suitable for kneading a methallyl resin. These can be produced by a commercially available method or a known method.

[ chemical formula 5]

(in the formula (5), a plurality of R1 independently represent a hydrogen atom, an alkyl group having 10 to 10 carbon atoms or an aromatic group; a4 represents 1 to 3; a4+1 represents 1 to 4; n3 represents an integer having an average value of 1 < n 3.ltoreq.8; and Z represents a structure represented by any one of the formulae (2-1) to (2-11)).

Preferred examples thereof include maleimide resins represented by the following formula (4) and polymaleimide resins represented by the above formula (5).

[ chemical formula 6]

(in the formula (4), a plurality of R1 independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aromatic group; a4 represents 1 to 3; a4+1 represents 1 to 4; and n2 represents an integer, and the average value thereof is 1 < n 2. ltoreq.5).

Examples of the alkyl group having 1 to 10 carbon atoms in R1 in the above formulas (4) and (5) include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, secondary butyl, n-pentyl, isopentyl, pentyl, n-hexyl, cyclopentyl, cyclohexyl, octyl, 2-ethylhexyl, nonyl, decyl and the like. Among them, methyl is preferred.

Examples of the aromatic group in R1 in the above formulas (4) and (5) include: an aromatic hydrocarbon group such as phenyl, biphenyl, indenyl, naphthyl, anthracenyl, fluorenyl and pyrenyl, furyl, thienyl, thienothienyl, pyrrolyl, imidazolyl, pyridyl, pyrazinyl, pyrimidinyl, quinolyl, indolyl and carbazolyl.

The value of n2 in formula (4) is an integer, and represents an average value of 1 < n.ltoreq.5. n2 is preferably 1 to 10, more preferably 2 to 8, and most preferably 2 to 4. The value of n2 can be calculated from the weight-average molecular weight value obtained by Gel Permeation Chromatography (GPC) measurement of the maleimide resin, and can be considered approximately equal to the value of n2 calculated from the GPC measurement result of the raw material compound.

The maleimide resin used in the present invention may have a melting point or a softening point. In particular, when the melting point is present, it is preferably 200 ℃ or lower, and when the softening point is present, it is preferably 150 ℃ or lower. If the melting point or softening point temperature is too high, the possibility of gelation during mixing is high, which is not preferable.

These maleimide resins are commercially available, and can be synthesized by a known method. Hereinafter, a method for producing the maleimide resin represented by the above formula (4) will be described.

The method for producing the maleimide resin represented by the above formula (4) is not particularly limited, and can be produced by any known method known as a method for synthesizing a maleimide compound.

In the case of producing the polymaleimide resin of the formula (4), the compound of the following formula (6) is required as a precursor thereof, and for example, a reaction of anilines with dihalomethyl compounds or dialkoxymethyl compounds is described in patent documents (Japanese patent laid-open No. 3-100016) and patent documents (Japanese patent publication No. 8-16151), and the compound of the formula (6) can be obtained by reacting anilines with bishalomethylbenzyl biphenyls or bisalkoxymethyl biphenyls by the same method as those.

[ chemical formula 7]

(in the formula (6), R1 in a plurality of the R1 independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aromatic group; a4 represents 1 to 3; a4+1 represents 1 to 4; n2 is an integer, and the average value thereof is 1 < n2 ≦ 5).

the alkyl group and the aromatic group having 1 to 10 carbon atoms in R1 in formula (6) are the same as those listed for R1 in formula (4) and formula (5), respectively.

The anilines used for producing the compound of formula (6) include: aniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 2-ethylaniline, 3-ethylaniline, 4-ethylaniline, 2, 3-dimethylaniline, 2, 4-dimethylaniline, 2, 5-dimethylaniline, 2, 6-dimethylaniline, 3, 4-dimethylaniline, 3, 5-dimethylaniline, 2-propylaniline, 3-propylaniline, 4-propylaniline, 2-isopropylaniline, 3-isopropylaniline, 4-isopropylaniline, 2-ethyl-6-methylaniline, 2-dibutylaniline, 2-tributylaniline, 4-butylaniline, 4-dibutylaniline, 4-tributylaniline, 4-methylaniline, 4-t-butylaniline, 4-butylaniline, 2-methylaniline, 4-butylaniline, 2-methylaniline, 4-methylaniline, 2-methylaniline, and phenylanilines having a phenyl group such as alkyl-substituted anilines having one or more alkyl groups having 1 to 5 carbon atoms, e.g., 2, 6-diethylaniline, 2-isopropyl-6-methylaniline and 4-pentylaniline, and 2-aminobiphenyl and 4-aminobiphenyl. These may be used alone or in combination of two or more.

Examples of the bishalomethyl biphenyl or the bisalkoxymethyl biphenyl used include: 4,4' -bis (chloromethyl) biphenyl, 4' -bis (bromomethyl) biphenyl, 4' -bis (fluoromethyl) biphenyl, 4' -bis (iodomethyl) biphenyl, 4' -dimethoxymethyl biphenyl, 4' -diethoxymethylbiphenyl, 4' -dipropoxymethylbiphenyl, 4' -diisopropyloxymethylbiphenyl, 4' -diisobutyoxymethylbiphenyl, 4' -dibutoxymethylbiphenyl, 4' -ditridebutoxymethyl biphenyl, etc. These may be used alone or in combination of two or more. The amount of the bishalomethyl biphenyl or the bisalkoxymethyl biphenyl to be used is 0.05 to 0.8 mol, preferably 0.1 to 0.6 mol, based on 1 mol of the aniline to be used.

In the reaction, an acidic catalyst such as hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, zinc chloride, ferric chloride, aluminum chloride, p-toluenesulfonic acid, methanesulfonic acid or the like can be used as necessary. These may be used alone or in combination of two or more. The amount of the catalyst to be used is usually 0.1 to 0.8 mol, preferably 0.5 to 0.7 mol, based on 1 mol of the aniline to be used, and if it is 0.8 mol or less, the viscosity of the reaction solution is not excessively high and stirring is easy, and if it is 0.1 or more, the reaction does not progress slowly.

The reaction may be carried out using an organic solvent such as toluene or xylene, if necessary, or may be carried out without a solvent. For example, when an acidic catalyst is added to a mixed solution of anilines and a solvent and the catalyst contains water, water is removed from the system by azeotropy. Then, bis-halogenomethyl biphenyls or bis-alkoxymethyl biphenyls are added at 40 to 100 ℃ (preferably 50 to 80 ℃) for 1 to 5 hours (preferably 2 to 4 hours), and then the temperature is raised while removing the solvent from the system, and the reaction is carried out at 180 to 240 ℃ (preferably 190 to 220 ℃) for 5 to 30 hours (preferably 10 to 20 hours). After the reaction is completed, the acidic catalyst is neutralized with an alkaline aqueous solution, and then a water-insoluble organic solvent is added to the oil layer, washing with water is repeated until the waste water becomes neutral, and excess aniline or organic solvent is distilled off under heating and reduced pressure, whereby the compound of formula (6) can be obtained. Although not mentioned in Japanese patent publication No. 8-16151 or Japanese patent No. 5030297, diphenylamine as a by-product in this stage varies depending on the amount of catalyst, the ratio of raw materials used, the temperature, the time, etc., and is usually contained in the resin in an amount of 2 to 10% by mass. Diphenylamine cannot be removed under conditions of distillation to remove aniline. Diphenylamine can be removed by introducing steam or a large amount of an inert gas such as nitrogen under reduced pressure while heating at a temperature at least equal to or higher than the boiling point of aniline.

If diphenylamine is contained in the maleimide resin composition of the present invention, for example, in the case of being used for a curing reaction with a maleimide resin, the terminal ends of the molecular chains are formed, and if the content is large, a cured network may not be sufficiently formed, and the mechanical strength may be significantly reduced. Further, when diphenylamine is contained in the aromatic amine resin represented by formula (6), diphenylamine also remains directly after maleinization and remains directly in the cured product without contributing to the reaction, and therefore bleeding may occur during long-term use, and the thermal decomposition resistance may be reduced. Therefore, the diphenylamine content is required to be usually 1 mass% or less, preferably 0.5 mass% or less, and more preferably 0.2 mass% or less.

The softening point of the aromatic amine resin represented by the above formula (6) is preferably 65 ℃ or lower, and more preferably 60 ℃ or lower. If the softening point is 65 ℃ or lower, the maleinized resin is easily impregnated with carbon fibers or glass fibers without increasing the viscosity. Further, if the dilution solvent is increased or the viscosity is decreased, the resin may not be sufficiently adhered.

The maleimide resin of the above formula (4) is obtained by reacting maleic anhydride with the compound of the above formula (6) in the presence of a solvent and a catalyst, and for example, the method described in patent document (jp-a-3-100016) or patent document (jp-a-61-229863) may be used.

Since it is necessary to remove water generated in the reaction from the system, a water-insoluble solvent is used as a solvent used in the reaction. Examples thereof include: aromatic solvents such as toluene and xylene; aliphatic solvents such as cyclohexane and n-hexane; ethers such as diethyl ether and diisopropyl ether; ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as methyl isobutyl ketone and cyclopentanone, but the solvent is not limited thereto, and two or more kinds thereof may be used in combination.

Besides the above-mentioned water-insoluble solvents, aprotic polar solvents may be used in combination. Examples thereof include: dimethyl sulfone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, 1, 3-dimethyl-2-imidazolidinone, N-methylpyrrolidinone, etc., and two or more of them may be used in combination. When an aprotic polar solvent is used, it is preferable to use a water-insoluble solvent having a higher boiling point than that of the solvent used in combination.

The catalyst is not particularly limited as long as it is an acidic catalyst, and examples thereof include: p-toluenesulfonic acid, hydroxy-p-toluenesulfonic acid, methanesulfonic acid, sulfuric acid, phosphoric acid, and the like.

For example, maleic acid is dissolved in toluene, an N-methylpyrrolidone solution of the compound of formula (6) is added under stirring, p-toluenesulfonic acid is then added, and the reaction is carried out under reflux conditions while removing the produced water from the system.

In the maleimide resin composition of the present invention, the amount of maleimide resin blended is preferably 5 to 50 mass% based on the total amount of resins in the maleimide resin composition. More preferably 10 to 50 mass%, most preferably 20 to 50 mass%. When the amount is within the above range, the mechanical strength and peel strength of the cured product tend to be high, the dielectric loss tangent tends to be low, and the heat resistance tends to be high.

The maleimide resin composition of the present invention contains at least one of a compound represented by the following formula (1) and a compound represented by any one of the following formulae (3-1) to (3-7) (hereinafter, simply referred to as "methallyl group-containing compound").

[ chemical formula 8]

(wherein R2 independently represents a methallyl group or a hydrogen atom; R3 independently represents a methallyl group, a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aromatic group; Z has a structure represented by any one of the following formulas (2-1) to (2-11); a1 represents an integer of 1 to 4.)

[ chemical formula 9]

(wherein R2 represents the same one as R2 in the formula (1); a2 represents an integer of 1 to 4; a2+1 represents an integer of 1 to 5; indicates a bonding site)

[ chemical formula 10]

(wherein, R2 independently represents a methallyl group or a hydrogen atom; R3 independently represents a methallyl group, a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aromatic group; A represents-O-, > NR4 or-C (R4)2-, R4 independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aromatic group; a3 represents an integer of 1 to 4; a3-1 represents an integer of 1 to 3; a3-2 represents an integer of 1 to 2; and n1 is an integer of 1 < n 1. ltoreq.5).

when the methallyl group-containing resin used in the present invention is mixed with a maleimide group, a cured product having a lower hygroscopicity than an allyl group-containing resin or an acryl group-containing resin having the same skeleton and having a better dielectric property can be obtained. Further, since a reaction different from the epoxy group does not generate a polar group, an increase in water (moisture) absorption property accompanying an improvement in heat resistance can be suppressed.

In the above formulae (1) and (3-1) to (3-7), R3 is preferably a methallyl group in not less than 20% of the total number. In this case, it does not mean the specification of 1 molecular unit of the corresponding compound, but means the average of a plurality of molecules of the corresponding compound.

the ratio of methallyl groups can be confirmed by an analysis device such as a High Performance Liquid Chromatography (HPLC).

Examples of the alkyl group having 1 to 10 carbon atoms in R3 in the above formulae (1) and (3-1) to (3-7) include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, secondary butyl, n-pentyl, isopentyl, pentyl, n-hexyl, cyclopentyl, cyclohexyl, octyl, 2-ethylhexyl, nonyl, decyl and the like. Preferably methyl.

Examples of the aromatic group in R3 in formulae (1) and (3) include: an aromatic hydrocarbon group such as phenyl, biphenyl, indenyl, naphthyl, anthracenyl, fluorenyl and pyrenyl, furyl, thienyl, thienothienyl, pyrrolyl, imidazolyl, pyridyl, pyrazinyl, pyrimidinyl, quinolyl, indolyl and carbazolyl.

In the formulae (1) and (3-1) to (3-7), the values of a2 and a3 are integers of 1 to 4, respectively. The value of n1 can be calculated from the weight average molecular weight value obtained by Gel Permeation Chromatography (GPC) measurement of the methallyl group-containing compound, and can be considered to be approximately the same as the value of n calculated from the GPC measurement result of the raw material compound.

The total chlorine content of the methallyl group-containing compound is preferably 500ppm or less, more preferably 300ppm or less, and most preferably 100ppm or less.

The softening point of the methallyl group-containing compound is preferably 120 ℃ or lower. When the softening point is 120 ℃ or lower, the compatibility in a solvent is good, and therefore, the salt can be easily removed by washing or the like, and in a field where electrical reliability is required, corrosion is not concerned, and thus it is preferable.

In the maleimide resin composition of the present invention, the method for producing the compound represented by the above formula (1) or the compound represented by any one of the formulae (3-1) to (3-7) is not particularly limited, and the maleimide resin composition can be produced by any known method known as a method for synthesizing a methallyl ether compound. For example, Japanese patent application laid-open No. 2003-104923 discloses a method of obtaining an allyl ether by reacting a polyphenol compound with an allyl chloride, allyl bromide, allyl chloride or other halogenated allyl group using a base such as an alkali metal hydroxide.

For example, it can be obtained by reacting a phenol resin with a methallyl halide. Examples of the phenol resin as a raw material include: a reactant of phenol and 4,4' -bis (chloromethyl) -1,1' -biphenyl, a reactant of phenol and 4,4' -bis (methoxymethyl) -1,1' -biphenyl, a reactant of phenol and hydroxybenzaldehyde, a reactant of phenol and salicylaldehyde or p-hydroxyaldehyde, a reactant of phenol and 1,4' -bischloromethylbenzene, a reactant of phenol and dicyclopentadiene, a reactant of phenol and formaldehyde, a reactant of cresol and formaldehyde, but not limited thereto.

The methallyl halide (e.g., methallyl chloride) used in the present invention is preferably used in a small amount as a polymer. For example, methallyl chloride tends to polymerize with each other to form polymethacrylic chloride.

The remaining polymethacrylic chloride not only increases the total chlorine amount, but also contributes to an increase in the molecular weight of the methallyl ether compound, and may leave a slight amount of gel during the preparation. Further, in order to reduce the chlorine amount, it is necessary to add an equivalent amount of an alkaline substance, which is not only industrially disadvantageous, but also produces highly toxic methallyl alcohol in the system.

These polymethacrylic chloride compounds can be easily confirmed by gas chromatography or the like, and the specific amount thereof is preferably 1.0 area% or less, more preferably 0.5 area% or less, further preferably 0.2 area% or less, and most preferably 0.05 area% or less, relative to the methallyl chloride monomer, in terms of the area ratio thereof.

the purity of methallyl chloride is preferably 90 area% or more, more preferably 97 area% or more, and most preferably 99 area% or more.

The amount of methallyl chloride to be used is usually 1.0 to 1.15 mol, preferably 1.0 to 1.10 mol, and more preferably 1.0 to 1.05 mol, based on 1 mol of hydroxyl groups of the phenol resin as a raw material (hereinafter, also simply referred to as a raw phenol resin).

In the present invention, the alkali usable in etherification of methallyl chloride is preferably an alkali metal hydroxide, and specific examples thereof include sodium hydroxide, potassium hydroxide and the like, and solid matters can be used, and aqueous solutions thereof can also be used.

The amount of the alkali metal hydroxide used is usually 1.0 to 1.15 mol, preferably 1.0 to 1.10 mol, and more preferably 1.0 to 1.05 mol, based on 1 mol of the hydroxyl group of the raw material phenol resin.

To accelerate the reaction, a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride, or the like may be added as a catalyst. The amount of the quaternary ammonium salt used is usually 0.1 to 15g, preferably 0.2 to 10g, based on 1 mol of the hydroxyl group of the raw material phenol mixture.

In this reaction, an aprotic polar solvent such as dimethyl sulfoxide (hereinafter, referred to as "DMSO"), dimethylformamide, dimethylacetamide, dimethylimidazolidinone, N-methylpyrrolidone, or the like is preferable, and dimethyl sulfoxide is most preferably used as the solvent.

The amount of the aprotic polar solvent used is preferably 20 to 300 mass%, more preferably 25 to 250 mass%, and most preferably 25 to 200 mass% based on the total mass of the phenol resin. Aprotic polar solvents are not conducive to purification such as washing with water, and are not preferred when used in large amounts. Further, since the boiling point is high, it is difficult to remove the solvent, and a large amount of energy is consumed, so that it is not preferable if it is too much.

In this reaction, other solvents may be used. When used, an alcohol having 1 to 5 carbon atoms is preferably used in combination. The alcohol having 1 to 5 carbon atoms is an alcohol such as methanol, ethanol, or isopropyl alcohol. Further, a nonaqueous solvent such as methyl ethyl ketone, methyl isobutyl ketone, or toluene may be used in combination, and it is preferable to use 100% by mass or less based on dimethyl sulfoxide. Most preferably 0.5 to 50 mass%. When a nonaqueous solvent such as methyl ethyl ketone, methyl isobutyl ketone, or toluene is used in an excessive amount, clethon rearrangement occurs during the reaction, a new phenolic hydroxyl group is generated, and methallyl chloride in the system is increased, whereby a product having methallyl group and methallyl ether can be further included.

The reaction temperature is usually 30 to 90 ℃, preferably 35 to 80 ℃. In particular, in the present invention, it is preferable to increase the reaction temperature in 2 stages or more for higher-purity etherification. Most preferably, the temperature of the 1 st stage is 35-50 ℃, and the temperature of the 2 nd stage is 45-70 ℃. The reaction time is usually 0.5 to 10 hours, preferably 1 to 8 hours, and most preferably 1 to 5 hours. The reaction time is preferably 0.5 hour or more because the reaction proceeds sufficiently, and 10 hours or less because a by-product is not produced.

The content of the compound having a methallyl group in the maleimide resin composition of the present invention may be appropriately set according to the kind of the compound used, and is not particularly limited. From the viewpoint of the flowability of the maleimide resin composition and the heat resistance of the cured product obtained by curing the maleimide resin composition, the content ratio of the compound having a methallyl group is preferably 5 to 30% by mass, more preferably 7 to 25% by mass, relative to the total amount of the composition. When the content of the compound having a methallyl group is 5 to 30 mass% based on the total amount of the composition, the composition can be molded at a relatively low temperature, a thermosetting resin composition having a viscosity can be easily obtained, and a cured product having high heat resistance tends to be easily obtained.

The maleimide resin composition of the present invention may optionally contain a radical polymerization initiator (hereinafter, also simply referred to as "catalyst").

Examples of the radical polymerization initiator include: benzoin-based compounds such as benzoin and benzoin methyl ether; acetophenone compounds such as acetophenone and 2,2' -dimethoxy-2-phenylacetophenone; xanthenes such as thioxanthones, 2, 4-diethylthioxanthones, and the like; diazide compounds such as 4,4' -diazide chalcone, 2, 6-bis (4' -diazide benzylidene) cyclohexanone, 4' -diazide benzophenone, and the like; azo compounds such as azobisisobutyronitrile, 2' -azobispropane, hydrazone, and the like; organic peroxides such as 2, 5-dimethyl-2, 6-di (t-butylperoxy) hexane, 2,5 '-dimethyl-2, 5' -di (t-butylperoxy) hexyne-3, and bisisopropenylperoxide.

The content of the radical polymerization initiator in the maleimide resin composition may be appropriately set according to the kind of the radical polymerization initiator used, and is not particularly limited. From the viewpoint of satisfying both the curing acceleration effect and the heat resistance of the cured product, the amount is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 4 parts by mass, and still more preferably 0.1 to 3 parts by mass, based on 100 parts by mass of the maleimide resin composition. If the amount of the radical polymerization initiator is too small, curing failure may occur, and if it is too large, the curing properties of the resin composition may be adversely affected.

the maleimide resin composition of the present invention may be used in combination with a curing accelerator, if necessary, in addition to the radical polymerization initiator. Examples of the hardening accelerator that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, and 1-cyanoethyl-2-ethyl-4-methylimidazole; amines such as triethylamine, triethylenediamine, 2- (dimethylaminomethyl) phenol, 1, 8-diaza-bicyclo (5,4,0) undecene-7, tris (dimethylaminomethyl) phenol, and benzyldimethylamine; phosphines such as triphenylphosphine, tributylphosphine, and trioctylphosphine; and organic metal salts such as tin octylate, zinc octylate, dibutyltin dimaleate, zinc naphthenate, cobalt naphthenate, and tin oleate; examples of the organic metal compounds include metal chlorides such as zinc chloride, aluminum chloride and tin chloride, and also include organic peroxides such as benzoyl peroxide, bisisopropyl peroxide, methyl ethyl ketone peroxide and tert-butyl perbenzoate. If the curing accelerator is too small, curing failure may occur, and if too large, the curing physical properties of the resin composition may be adversely affected. Therefore, the amount of the maleimide resin is preferably 0.01 to 20% by mass, more preferably 0.01 to 10% by mass.

Cyanate ester compounds may also be formulated in the maleimide resin composition of the present invention. As the cyanate ester compound which can be formulated into the maleimide resin composition of the present invention, conventionally known cyanate ester compounds can be used. Specific examples of the cyanate ester compound include, but are not limited to, cyanate ester compounds obtained by reacting cyanogen halides with polycondensates of phenols and various aldehydes, polymers of phenols and various diene compounds, polycondensates of phenols and ketones, polycondensates of bisphenols and various aldehydes, and the like. These may be used alone or in combination of two or more.

Further, Japanese patent application laid-open No. 2005-264154 discloses that a cyanate ester compound obtained by a synthesis method is most preferable as a cyanate ester compound because of its low hygroscopicity, flame retardancy and excellent dielectric properties.

Further, the maleimide resin composition of the present invention may contain any one or more of a flame retardant, a filler and an additive as required.

The filler is not particularly limited, and examples thereof include fillers selected from metal complex salts, activated carbons, layered clay minerals, metal oxides, and the like.

The metal complex salt is preferably a hydrotalcite-like compound. The hydrotalcite-like compound is a compound represented by the general formula [ M2+ 1-XM 3+ X (OH)2] [ An-X/n.mH 2O ], wherein M2+ and M3+ represent metal ions having 2-and 3-valences, and An-X/n represents An interlayer anion. Specifically, a representative hydrotalcite compound is a compound represented by Mg6Al2(OH)16CO3 · 4H 2O. As a commercially available product, キ ョ ー ワ ー ド series, which is a product of Cogeneration chemical industries, Inc., is effective. Examples thereof include: キ ョ ー ワ ー ド 500, キ ョ ー ワ ー ド 1000, キ ョ ー ワ ー ド 700, キ ョ ー ワ ー ド 600, キ ョ ー ワ ー ド 200, キ ョ ー ワ ー ド 2000, etc. In the present invention, the components preferably contained in the composition have a composition of magnesia > alumina and magnesia > silica in terms of the amount ratio of magnesia, alumina and silica. Specifically, キ ョ ー ワ ー ド 500, キ ョ ー ワ ー ド 1000, or the like is preferable.

As the activated carbon that can be used, chemically activated carbon is preferable. The chemically activated carbon is not particularly limited as long as it is treated with zinc chloride, phosphoric acid, or the like, and is most preferably phosphoric acid activated carbon because activation with zinc chloride may introduce chlorine into the product. Further, activated carbon obtained by a physical method of forming a porous body by using water vapor, air, carbon dioxide, or the like may be used in combination with chemically activated carbon depending on the conditions of treatment, and the ratio is preferably at least more than 50% by mass of chemically activated carbon relative to the amount of the whole activated carbon.

As the raw materials, there can be mentioned: wood (sawdust, etc.), coal (brown coal, peat, coal char, etc.), coconut shell, phenol resin, etc., but wood-based is most preferable in the present invention. Examples of commercially available products include: フ タ ム ラ Taige series (CG, CW, G, QW, S, ACF series, etc.) manufactured by Chemicals GmbH, ホ ク エ ツ series (SD, BA, F, ZN, Y-180C, H-10CL, H-8CL, G-10F, CL-K series) manufactured by Siberian フ ァ イ ン テ ク ノ; white eagle (C, LGK-400, G series, DO series, Wc, Sx, WHA, etc.), カ ル ボ ラ フ ィ ン, etc., manufactured by Japan エ ン バ イ ロ ケ ミ カ ル ズ GmbH; PK series, PKDA series, ELORIT, AZO, DARCO series, HYDRODARCO series, PETRODACO, GAC series, GCN, C GRAN, ROW, ROY, ROX, RO, RB, R, R.EXTRA, SORBNORIT, GF series, CNR, ROZ, RBAA, RBHG, RZN, RGM, SX, SA, D10, VETERINAIR, PN, ZN, SA-SW, W, GL, SAM, HB PLUS, EUR, USP, CA, CG, GB, CAP, CGP SUPER, S-51 series, HDB, HDC, HDR, HDW, GRO SAFE, SAFFM-1, SAFPAC series, etc., manufactured by NORIT GmbH; ク ラ レ RP-20 and YP-17D manufactured by Ltd.

The clay mineral is preferably a bentonite-based layered clay mineral, and examples thereof include: bentonite, montmorillonite, aluminum bentonite, nontronite, saponite, lithium bentonite, synthetic bentonite, etc. Examples of commercially available products include: ク ニ ミ ネ manufactured by industrial products corporation, ス メ ク ト ン (synthetic bentonite), bentonite (sodium salt type, calcium salt type), ク ニ ピ ア F (montmorillonite); ホ ー ジ ュ ン, ベ ン ゲ ル series, ベ ン ゲ ル W series, ベ ン ゲ ル ブ ラ イ ト series, ベ ン ゲ ル SH, ベ ン ゲ ル A; コ ー プ ケ ミ カ ル series ル ー セ ン タ イ ト manufactured by GmbH.

As the metal oxide, there can be mentioned: inorganic fillers such as silica, alumina, calcium carbonate, quartz powder, aluminum powder, graphite, talc, clay, iron oxide, titanium oxide, aluminum nitride, asbestos, mica, and glass powder.

As specific examples of additives that can be used, there can be cited: a curing agent for epoxy resins, a polyamide resin, a silicone resin, a fluororesin such as polytetrafluoroethylene, an acrylic resin such as polymethyl methacrylate, a crosslinked product of benzoguanamine or melamine and formaldehyde, polybutadiene and a modified product thereof, a modified product of an acrylonitrile copolymer, polyphenylene oxide, polystyrene, polyethylene, polyimide, a fluororesin, a maleimide compound, a cyanate ester compound, silicone gel, silicone oil, a surface treatment agent for inorganic fillers such as silane coupling agents, a release agent, carbon black, phthalocyanine blue, and a colorant such as phthalocyanine green. The amount of these additives is preferably 1,000 parts by mass or less, and more preferably 700 parts by mass or less, per 100 parts by mass of the curable resin composition.

The method for preparing the maleimide resin composition of the present invention is not particularly limited, and the respective components may be uniformly mixed or may be prepolymerized. For example, the prepolymerization is carried out by heating the methallyl group-containing compound used in the present invention with a maleimide resin in the presence or absence of a catalyst and in the presence or absence of a solvent. Similarly, the prepolymer may be prepared by adding a methallyl group-containing compound used in the present invention, a maleimide resin, an optional amine compound, a maleimide compound, a cyanate ester compound, a phenol resin, an acid anhydride compound, and other curing agents, and other additives. For the mixing or prepolymerization of the respective components, for example, an extruder, a kneader, a roll or the like is used in the absence of a solvent, and a reaction tank or the like with a stirring device is used in the presence of a solvent.

The maleimide resin composition of the present invention may be prepared as a varnish-like composition (hereinafter, simply referred to as varnish) by adding an organic solvent thereto. The maleimide resin composition of the present invention is optionally dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. to prepare a maleimide resin varnish, which is impregnated with a base material such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc. and then heated and dried, and the prepreg thus obtained is hot-press molded to prepare a cured product of the maleimide resin composition of the present invention. The solvent used in this case is usually 10 to 70 mass% (preferably 15 to 70 mass%) in the mixture of the maleimide resin composition of the present invention and the solvent. Further, if the resin composition is a liquid composition, a cured product of a maleimide resin containing carbon fibers can be obtained directly by, for example, the RTM method.

The maleimide resin composition of the present invention may be used as a modifier for a film-type composition. Specifically, it can be used for improving the flexibility in the B-stage. The resin composition of this film type can be obtained as a sheet-like adhesive by preparing the maleimide resin composition of the present invention into the above maleimide resin composition varnish, applying the varnish to a release film, heating the varnish to remove the solvent, and then subjecting the varnish to a B-stage treatment. The sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like.

the prepreg of the present invention can be obtained by heating and melting the maleimide resin composition of the present invention to lower the viscosity and impregnating the resin composition with reinforcing fibers such as glass fibers, carbon fibers, polyester fibers, polyamide fibers, and alumina fibers.

The prepreg of the present invention can also be obtained by impregnating reinforcing fibers with the varnish and drying the impregnated reinforcing fibers by heating.

The prepreg is cut into a desired shape, and laminated with a copper foil or the like as necessary, and then the laminate is heat-cured with a maleimide resin composition while applying pressure to the laminate by a press molding method, an autoclave molding method, a sheet winding molding method or the like, thereby obtaining a laminate.

Further, a multilayer circuit board can be obtained by forming a circuit on a laminate made by laminating copper foil on the surface, laminating a prepreg, copper foil, or the like thereon, and repeating the above operation.

The maleimide resin composition of the present invention is cured by heating to obtain a cured product (thermosetting resin molded product). The method for curing the maleimide resin composition is not particularly limited. For example, the maleimide resin composition is heated to 80 ℃, cast between 2 glass plates which have been subjected to mold release treatment using a spacer having a thickness of 1.5mm, and once cured at 170 to 200 ℃ for 2 hours, and then the once cured product is removed from the glass plate and cured at 230 to 260 ℃ for 2 hours, thereby obtaining a cured product (maleimide resin molded product).

The maleimide resin composition of the present invention can be applied to various uses, and the use thereof is not particularly limited. In particular, the maleimide resin composition of the present invention is excellent in heat resistance and strength, handling properties and production efficiency, and therefore is particularly useful in applications requiring such properties, for example, in the fields of matrix resins for fiber-reinforced composite materials, sealants for electric and electronic parts, and the like.