WO2018199157A1 - Maleimide resin composition, prepreg and cured product of same - Google Patents

Abstract

Provided are: a maleimide resin composition, a cured product of which exhibits excellent electrical characteristics and the like; a prepreg; and a cured product of the prepreg. A maleimide resin composition according to the present invention contains a maleimide resin that has N maleimide groups (N is an integer and the average thereof is more than 2) and a specific methallyl group-containing compound that is represented by formula (1) or the like. (In the formula, each of R₂ and R₃ represents a methallyl group, a hydrogen atom or the like; Z has a specific structure; and a1 represents an integer of 1-4.)

Description

Maleimide resin composition, prepreg and cured product thereof

The present invention relates to a maleimide resin composition, a prepreg, and a cured product thereof. Specifically, for high-reliability semiconductor encapsulant use, electrical / electronic component insulation material use, and various composite materials use such as laminate (printed wiring glass fiber reinforced composite material) and CFRP (carbon fiber reinforced composite material), The present invention relates to a maleimide resin composition useful for various adhesive applications, various coating applications, structural members, and the like, a prepreg, and a cured product thereof.

In general, printed circuit boards for electrical and electronic equipment, especially as a substrate for laminating copper foil, has been conventionally thermosetting, mainly paper-based paper-phenolic resin, glass cloth-based glass cloth-epoxy resin, etc. Resin is used. These thermosetting resins are known to have high reliability because they exhibit characteristics such as high heat resistance and dimensional stability due to their unique cross-linking structure. On the other hand, new demands for thermosetting resins are increasing, such as high-density mounting of printed wiring boards, improved heat resistance due to higher multi-layer configurations, and lower dielectric constant and lower dielectric loss tangent due to high-speed communication demand. Cross-linking structures are beginning to be needed.

In particular, in recent years, in the M2M market, the amount of information has increased enormously while the amount of communication between machines as well as between people has increased dramatically. On the other hand, since there are limits to the resources that a base station can allocate to users, communication infrastructure development and higher functionality are progressing. An example is a small cell. As the number of equipment such as small cells increases, a communication board is required, and the amount of information used can be dramatically increased, so it has very high characteristics for communication devices such as smartphones. It is calculated | required (nonpatent literature 1).
In these applications, high heat resistance is required because reliability such as low dielectric loss tangent, low water absorption, and resistance to change at driving temperature is required. In particular, the dielectric loss tangent requires a characteristic of 0.010 or less, particularly 0.007 or less. At the same time, moisture is one of the factors that greatly deteriorate the dielectric characteristics, so a lower water absorption is required (Non-Patent Document 2).

Furthermore, when used for a substrate of a high-performance communication semiconductor package, it is preferable to clear heat resistance of 170 ° C. or higher, particularly heat resistance of solder reflow in recent years, and Tg higher than the reflow temperature is required. Therefore, the required characteristics of this market are becoming very high (Non-patent Document 3).

The fiber reinforced composite material is composed of matrix resin and reinforcing fibers such as carbon fiber, glass fiber, alumina fiber, boron fiber and aramid fiber, and generally has light weight and high strength characteristics. Such fiber-reinforced composite materials include insulating materials for electrical and electronic parts and laminated boards (printed wiring boards, build-up boards, etc.), aerospace materials such as passenger aircraft bodies and wings, and machine tool members represented by robot hand arms. In addition, it is widely used for construction and civil engineering repair materials, and for leisure goods such as golf shafts and tennis rackets. In particular, carbon fiber reinforced composite materials (hereinafter referred to as CFRP) maintain rigidity in the temperature range from room temperature to about 200 ° C in aerospace materials such as passenger aircraft and wings, and machine tool members represented by robot hand arms. There is a demand for heat resistance, mechanical properties, long-term reliability, that is, a sufficiently high thermal decomposition temperature and a high elastic modulus at high temperatures. Conventionally, 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 and machine tool member applications.

Maleimide resin is widely known as a matrix resin that has high heat resistance and can withstand a use environment of 200 ° C. or higher. As the main component of the maleimide resin, a bismaleimide compound is used, but since a molded product becomes brittle, various modifiers have been developed to improve this. As a solution to this, various modifications have been performed. For example, a modified butadiene resin in which a meth (acryloyl) group is introduced into a cyanate ester resin composition (Patent Document 1), butadiene-acrylonitrile copolymer Known are those in which a coalescence is added (Patent Document 2), or those in which an epoxy resin is further added (Patent Document 3). However, these methods alleviate the brittleness, but all have a problem in that a decrease in heat resistance and mechanical strength cannot be avoided.

Furthermore, a method of modifying a maleimide resin with an allyl compound known as an additive such as a reactive diluent, a crosslinking agent or a flame retardant for the maleimide resin is also known. For example, Patent Document 4 is a resin obtained by heating and melting and mixing o, o'-diallylbisphenol A, which is liquid at room temperature, with 4,4'-diphenylmethane bismaleimide, and impregnating the carbon fiber sheet without solvent. It is possible.

Japanese Unexamined Patent Publication No. 57-153045 Japanese Unexamined Patent Publication No. 57-153046 Japanese Unexamined Patent Publication No. 56-157424 Japanese Unexamined Patent Publication No. 09-087460

Nikkei Electronics, June 10, 2013, pp. 30-32 Panasonic Electric Works Technical Report Vol. 59 No. 1 Hitachi Chemical Technical Report No. 39 (2002-7)

However, in Patent Document 4, even if the prepreg obtained is modified with o, o′-diallylbisphenol A, the electrical characteristics are insufficient.
Then, this invention is providing the maleimide resin composition, prepreg, and its hardened | cured material which show the electrical property in the hardened | cured material especially the outstanding low hygroscopicity (low water absorption), and heat resistance.

As a result of intensive investigations in view of the actual situation as described above, the present inventors have found that a maleimide resin composition containing a maleimide resin having a functional group exceeding bifunctionality and a compound having a methallyl group has an electrical property in the cured product, In particular, the inventors have found that it has excellent low hygroscopicity (low water absorption) and heat resistance, and has completed the present invention.

That is, the present invention
[1] A maleimide resin having N maleimide groups (N is an integer and the average value is larger than 2), a compound represented by the following formula (1), and the following formulas (3-1) to (3- 7) A maleimide resin composition containing at least one of the compounds represented by any one of

(Wherein R ₂ independently represents a methallyl group or a hydrogen atom. R ₃ independently represents a methallyl group, a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aromatic group. (It has a structure represented by any one of formulas (2-1) to (2-11), a1 represents an integer of 1 to 4)

(Wherein, _{R 2} is .A2 + 1 representing the .A2 is an integer of 1 to 4 represent the same as _{R 2} in the formula (1) represents an integer of 1-5. * Represents a bonding position.)

(In the formula, each R ₂ independently represents a methallyl group or a hydrogen atom. Each R ₃ independently represents a methallyl group, a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aromatic group. A is — O—,> NR ₄ or —C (R ₄ ) ₂ —, wherein R ₄ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aromatic group, a3 is an integer of 1 to 4 A3-1 represents an integer of 1 to 3. a3-2 represents an integer of 1 to 2. n1 is an integer, and an average value thereof represents 1 <n1 ≦ 5.
[2] The maleimide resin composition according to [1], wherein the maleimide resin has a structure represented by the following formula (4):

(In Formula (4), a plurality of R _{1 s} each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aromatic group. A4 represents 1 to 3. n2 is an integer; (The average value represents 1 <n2 ≦ 5.)
[3] The maleimide resin composition according to [1] or [2], which contains a radical polymerization initiator,
[4] The maleimide resin composition according to any one of [1] to [3] above, which contains any one or more of a flame retardant, a filler, and an additive,
[5] A prepreg in which the maleimide resin composition according to any one of [1] to [4] is held on a sheet-like fiber base material and is in a semi-cured state;
[6] A cured product of the maleimide resin composition according to any one of [1] to [4],
[7] A cured product of the prepreg according to [5] above,
About.

Since the maleimide resin composition of the present invention has electrical properties, particularly low hygroscopicity (low water absorption) and heat resistance in the cured product, the insulating material for electrical and electronic parts and laminated boards (printed wiring boards, build-up boards) Etc.) and various composite materials including CFRP, adhesives, paints and the like.

The maleimide resin composition of the present invention will be described below.
The maleimide resin composition of the present invention contains a maleimide resin having N maleimide groups (hereinafter also simply referred to as “maleimide resin”) (N is an integer and the average value is greater than 2).
The maleimide resin that can be used in the present invention is not particularly limited as long as it is a maleimide resin having an average number of maleimide groups exceeding 2 in one 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, tris- (4-aminophenyl) -phosphate, Trismaleimide compounds such as tris (4-aminophenyl) -phosphate, maleimide compounds obtained by reaction of tos (4-aminophenyl) -thiophosphate with maleic anhydride, trismaleimide compounds such as tris (4-maleimidophenyl) methane, bis (3 , 4-dimaleimidophenyl) methane, tetramaleimide benzophenone, tetramaleimide naphthalene, tetramaleimide compounds such as maleimide obtained by reaction of triethylenetetramine with maleic anhydride, phenol novolac maleimide resin, isopropylidenebis (Phenoxyphenylmaleimide) phenylmaleimide aralkyl resin, biphenylene type phenylmaleimide aralkyl resin, polymaleimide represented by the formula (5), polymaleimide of polyaniline obtained by condensation of benzenedialdehyde and aniline, and the like. Further, polyaminopolymaleimide resins obtained by adding aromatic diamines to these polymaleimides can also be used. Furthermore, novolak-type maleimide resins have a molecular weight distribution and thus have high varnish stability, and are therefore suitable for kneading with methallyl resins. These may use a commercially available thing and can also manufacture using a well-known method.

(In Formula (5), a plurality of R _{1 s} each 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 is an integer, and an average value thereof represents 1 <n3 ≦ 8, and Z represents a structure represented by any one of the formulas (2-1) to (2-11).

Preferably, a maleimide resin represented by the following formula (4) or a polymaleimide resin represented by the above formula (5) may be mentioned.

(In Formula (4), a plurality of R _{1 s} each 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) N2 is an integer, and the average value represents 1 <n2 ≦ 5.)

Examples of the alkyl group having 1 to 10 carbon atoms for R ₁ in the above formulas (4) and (5) include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, and an iso-butyl group. Group, tert-butyl group, sec-butyl group, n-pentyl group, i-pentyl group, amyl group, n-hexyl group, cyclopentyl group, cyclohexyl group, octyl group, 2-ethylhexyl group, nonyl group And decyl group. Of these, a methyl group is preferred.
Examples of the aromatic group in R ₁ in the above formulas (4) and (5) include an aromatic hydrocarbon group such as a phenyl group, a biphenyl group, an indenyl group, a naphthyl group, an anthryl group, a fluorenyl group, and a pyrenyl group, and furanyl. Group, thienyl group, thienothienyl group, pyrrolyl group, imidazolyl group, pyridyl group, pyrazyl group, pyrimidyl group, quinolyl group, indolyl group and carbazolyl group.

Further, the value of n2 in the formula (4) is an integer, and represents an average value of 1 <n ≦ 5. n2 is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 2 to 4. The value of n2 can be calculated from the value of the weight average molecular weight determined by the gel permeation chromatography (GPC) measurement of the maleimide resin, but approximately from the GPC measurement result of the compound as the raw material. It can be considered that it is almost equivalent to the calculated value of n2.

As the maleimide resin used in the present invention, one having a melting point and a softening point can be used. In particular, when it has a melting point, it is preferably 200 ° C. or lower, and when it has a softening point, it is preferably 150 ° C. or lower. If the melting point or softening point is too high, the possibility of gelation increases during mixing, which is not preferable.

These maleimide resins may be commercially available or can be synthesized by known methods. Below, the manufacturing method of maleimide resin represented by said Formula (4) is demonstrated.

The method for producing the maleimide resin represented by the formula (4) is not particularly limited, and any known method known as a method for synthesizing a maleimide compound may be used.
When the polymaleimide resin of the formula (4) is produced, a compound of the following formula (6) is required as a precursor thereof. For example, a patent document (Japanese Patent Laid-Open No. 3-100016) and a patent document (Japan) JP-B-8-16151) describes reactions of anilines with dihalogenomethyl compounds and dialkoxymethyl compounds, and anilines and bishalogenomethylbiphenyls or A compound of the formula (6) is obtained by reacting with bisalkoxymethylbiphenyls.

(In Formula (6), a plurality of R _{1 s} each 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) N2 is an integer, and the average value represents 1 <n2 ≦ 5.)

Examples of the alkyl group having 1 to 10 carbon atoms and the aromatic group for R ₁ in the formula (6) include the same as those exemplified as R ₁ in the formula (4) and the formula (5), respectively. .

Examples of anilines used for the production of 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-sec-butylaniline, 2-tert-butylaniline, 4-butylaniline, 4 -Sec-butylaniline, 4-tert-butylaniline, 2,6-diethyl Alkyl-substituted anilines having one or more alkyl groups having 1 to 5 carbon atoms, such as aniline, 2-isopropyl-6-methylaniline, 4-pentylaniline, phenyl having phenyl groups such as 2-aminobiphenyl, 4-aminobiphenyl, etc. Examples include aniline. These may be used alone or in combination of two or more.
Examples of the bishalogenomethyl biphenyls or bisalkoxymethyl biphenyls used include 4,4′-bis (chloromethyl) biphenyl, 4,4′-bis (bromomethyl) biphenyl, and 4,4′-bis (fluoromethyl). Biphenyl, 4,4'-bis (iodomethyl) biphenyl, 4,4'-dimethoxymethylbiphenyl, 4,4'-diethoxymethylbiphenyl, 4,4'-dipropoxymethylbiphenyl, 4,4'-diisopropoxy Examples include methylbiphenyl, 4,4′-diisobutoxymethylbiphenyl, 4,4′-dibutoxymethylbiphenyl, 4,4′-di-tert-butoxymethylbiphenyl, and the like. These may be used alone or in combination of two or more. The amount of bishalogenomethylbiphenyls or bisalkoxymethylbiphenyls used is 0.05 to 0.8 moles, preferably 0.1 to 0.6 moles per mole of anilines used.

In the reaction, if necessary, an acidic catalyst such as hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, zinc chloride, ferric chloride, aluminum chloride, p-toluenesulfonic acid, methanesulfonic acid and the like may be used. These may be used alone or in combination of two or more. The amount of the catalyst 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. Viscosity does not become too high and stirring becomes easy, and when it is 0.1 or more, the progress of the reaction is not delayed.
The reaction may be carried out using an organic solvent such as toluene or xylene, if necessary, or without solvent. For example, after adding an acidic catalyst to a mixed solution of anilines and a solvent, when the catalyst contains water, the water is removed from the system by azeotropic distillation. Thereafter, bishalogenomethylbiphenyls or bisalkoxymethylbiphenyls are added at 40 to 100 ° C., preferably 50 to 80 ° C. over 1 to 5 hours, preferably 2 to 4 hours, and then the solvent is removed from the system. The temperature is raised and the reaction is carried out at 180 to 240 ° C., preferably 190 to 220 ° C. for 5 to 30 hours, preferably 10 to 20 hours. After completion of the reaction, neutralize the acidic catalyst with an aqueous alkaline solution, add a water-insoluble organic solvent to the oil layer and repeat washing with water until the wastewater becomes neutral, and distill off excess anilines and organic solvent under heating and reduced pressure. This gives a compound of formula (6). Although not mentioned in Japanese Patent Publication No. 8-16151 and Japanese Patent No. 5030297, diphenylamine, which is a by-product at this stage, varies depending on the amount of catalyst, the ratio of raw materials used, temperature, time, etc. Usually 2 to 10% by mass is contained in the resin. Diphenylamine cannot be removed under conditions where aniline is distilled off. Diphenylamine can be removed by blowing steam or an inert gas such as a large amount of nitrogen gas under reduced pressure by heating at a temperature equal to or higher than the boiling point of aniline.

When diphenylamine is contained in the maleimide resin composition of the present invention, for example, when used for a curing reaction with a maleimide resin, it becomes a terminal end of a molecular chain, and if the content is large, a curing network is not sufficiently formed. There is a possibility that the mechanical strength will be significantly reduced. In addition, when diphenylamine is contained in the aromatic amine resin represented by the formula (6), diphenylamine remains as it is after maleimidation and remains in the cured product as it is without contributing to the reaction. Bleed out and thermal decomposition resistance may decrease. Therefore, the diphenylamine content is usually 1% by mass or less, preferably 0.5% by mass or less, more preferably 0.2% by mass or less.

The softening point of the aromatic amine resin represented by the formula (6) is preferably 65 ° C. or less, and more preferably 60 ° C. or less. When the softening point is 65 ° C. or lower, the viscosity of the maleimidized resin does not increase, and carbon fibers and glass fibers are easily impregnated. If the viscosity is lowered by increasing the dilution solvent, the resin may not adhere sufficiently.

The maleimide resin of the formula (4) can be obtained by reacting the compound of the formula (6) with maleic anhydride in the presence of a solvent and a catalyst. For example, Patent Document (Japanese Patent Laid-Open No. 3-100016) Or a method described in Japanese Patent Application Laid-Open No. 61-229863.
As the solvent used in the reaction, it is necessary to remove water generated during the reaction from the system, and therefore a water-insoluble solvent is used. For example, 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, methyl isobutyl ketone and cyclopentanone However, it is not limited to these, and two or more kinds may be used in combination.
In addition to the water-insoluble solvent, an aprotic polar solvent may be used in combination. Examples thereof include dimethyl sulfone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, N-methylpyrrolidone, etc., and two or more kinds may be used in combination. When using an aprotic polar solvent, it is preferable to use a solvent having a higher boiling point than the water-insoluble solvent used in combination.
The catalyst is an acidic catalyst and is not particularly limited, and examples thereof include p-toluenesulfonic acid, hydroxy-p-toluenesulfonic acid, methanesulfonic acid, sulfuric acid, and phosphoric acid.
For example, maleic acid is dissolved in toluene, an N-methylpyrrolidone solution of the compound of formula (6) is added with stirring, and then p-toluenesulfonic acid is added to remove water generated under reflux conditions from the system. While doing the reaction.

In the maleimide resin composition of the present invention, the amount of maleimide resin is preferably 5 to 50% by mass based on the total amount of resin in the maleimide resin composition. More preferably, it is 10 to 50% by mass, and particularly preferably 20 to 50% by mass. In the case of the above range, in the physical properties of the cured product, mechanical strength and peel strength are high, dielectric loss tangent is low, and heat resistance tends to be high.

The maleimide resin composition of the present invention includes a compound represented by the following formula (1) and a compound represented by any of the following formulas (3-1) to (3-7) (hereinafter simply referred to as “methallyl group-containing compound”). At least one of them.

(Wherein R ₂ independently represents a methallyl group or a hydrogen atom. R ₃ independently represents a methallyl group, a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aromatic group. (It has a structure represented by any one of formulas (2-1) to (2-11), a1 represents an integer of 1 to 4)

(Wherein, _{R 2} is .A2 is .A2 + 1 represents an integer of 1 to 4 represent the same as _{R 2} in the formula (1) represents an integer of 1-5. * Represents a bonding position.)

(In the formula, each R ₂ independently represents a methallyl group or a hydrogen atom. Each R ₃ independently represents a methallyl group, a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aromatic group. A is — O—,> NR ₄ or —C (R ₄ ) ₂ —, wherein R ₄ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aromatic group, a3 is an integer of 1 to 4 A3-1 represents an integer of 1 to 3. a3-2 represents an integer of 1 to 2. n1 is an integer, and an average value thereof represents 1 <n1 ≦ 5.

When the methallyl group-containing resin used in the present invention is mixed with a maleimide group, a cured product having lower hygroscopicity and better dielectric properties can be obtained than allyl group-containing resins and propenyl group-containing resins having the same skeleton. In addition, unlike the reaction of epoxy groups, polar groups are not generated, so that it is possible to suppress an increase in water absorption (wetness) accompanying an improvement in heat resistance.

In the above formulas (1) and (3-1) to (3-7), it is preferable that 20% or more of R ₃ is a methallyl group. In this case, it is not the definition of one molecular unit of the corresponding compound, but means an average of a plurality of molecules of the corresponding compound.
The proportion of the methallyl group can be confirmed by an analyzer such as high performance liquid chromatography (HPLC).

In the above formulas (1) and (3-1) to (3-7), the alkyl group having 1 to 10 carbon atoms for R ₃ includes a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, n -Butyl, iso-butyl, tert-butyl, sec-butyl, n-pentyl, i-pentyl, amyl, n-hexyl, cyclopentyl, cyclohexyl, octyl, 2- An ethylhexyl group, a nonyl group, a decyl group, etc. are mentioned. A methyl group is preferred.
Examples of the aromatic group represented by R ₃ in the formulas (1) and (3) include an aromatic hydrocarbon group such as a phenyl group, a biphenyl group, an indenyl group, a naphthyl group, an anthryl group, a fluorenyl group, and a pyrenyl group, and a furanyl group. , Thienyl group, thienothienyl group, pyrrolyl group, imidazolyl group, pyridyl group, pyrazyl group, pyrimidyl group, quinolyl group, indolyl group and carbazolyl group.

Also, the values of a2 and a3 in the formula (1) and the formulas (3-1) to (3-7) are integers and are 1 to 4, respectively. In addition, although the value of n1 can be calculated from the value of the weight average molecular weight obtained by the measurement of gel permeation chromatography (GPC) of the methallyl group-containing compound, it is approximately the measurement of the GPC of the compound as a raw material. It can be considered to be almost equivalent to the value of n calculated from the result.

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

The softening point of the methallyl group-containing compound is preferably 120 ° C. or lower. When the softening point is 120 ° C. or lower, the compatibility with the solvent is good, and therefore, it is easy to remove the salt by washing or the like, and there is no concern about corrosion, which is preferable.

In the maleimide resin composition of the present invention, the method for producing the compound represented by the formula (1) or the compound represented by any one of the formulas (3-1) to (3-7) is not particularly limited. It may be produced by any known method known as a synthesis method of a ruether compound. For example, Japanese Patent Application Laid-Open No. 2003-104923 discloses an allyl ether obtained by reacting a polyphenol compound with an allyl halide such as allyl chloride, allyl bromide or methylallyl chloride using a base such as an alkali metal hydroxide. Is disclosed.

For example, it can be obtained by reaction of phenol resin and methallyl halide. Examples of the phenol resin used as a raw material include a reaction product of phenol and 4,4′-bis (chloromethyl) -1,1′-biphenyl, phenol and 4,4′-bis (methoxymethyl) -1,1′- Reaction product of biphenyl, reaction product of phenol and hydroxybenzaldehyde, reaction product of phenol and salicylaldehyde or parahydroaldehyde, reaction product of phenol and 1,4'-bischloromethylbenzene, phenol and 1,4 ' Preferred examples include, but are not limited to, a reaction product of bismethoxymethylbenzene, a reaction product of phenol and dicyclopentadiene, a reaction product of phenol and formaldehyde, and a reaction product of cresol and formaldehyde.

As the methallyl halide (for example, methallyl chloride) used in the present invention, it is preferable to use one having a small amount of the polymer. For example, methallyl chloride tends to polymerize to polymethallyl chloride.
The residual polymethallyl chloride not only increases the total chlorine content, but also contributes to an increase in the molecular weight of the methallyl ether compound, and may leave a trace amount of gel in the product. In addition, in order to reduce the amount of chlorine, it is necessary to add a considerable amount of a basic substance, which is not preferable in the industry and generates highly methallyl alcohol in the system.
These polymethallyl chloride compounds can be easily confirmed by gas chromatography or the like, and the specific amount is a polymer of 1.0 area% or less with respect to the methallyl chloride monomer in the area ratio. More preferably, it is 0.5 area% or less, More preferably, it is 0.2 area% or less, Most preferably, it is 0.05 area% or less.
The purity of methallyl chloride is preferably 90 area% or more, more preferably 97 area% or more, and particularly preferably 99 area% or more.
The amount of methallyl chloride used is usually 1.0 to 1.15 mol, preferably 1.0 to 1.10, relative to 1 mol of hydroxyl group of the phenolic resin (hereinafter also referred to simply as “raw phenolic resin”). Mole, more preferably 1.0 to 1.05 mole.

In the present invention, the base that can be used for etherifying methallyl chloride is preferably an alkali metal hydroxide, and specific examples thereof include sodium hydroxide and potassium hydroxide. The aqueous solution may be used, but in the present invention, it is particularly preferable to use a solid material formed into a flake shape from the viewpoint of solubility and handling.
The amount of the alkali metal hydroxide used is usually 1.0 to 1.15 mol, preferably 1.0 to 1.10 mol, more preferably 1.0 to 1 mol, based on 1 mol of the hydroxyl group of the starting phenol resin. 0.05 mole.

In order to accelerate the reaction, a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide or trimethylbenzylammonium chloride may be added as a catalyst. The amount of the quaternary ammonium salt used is usually 0.1 to 15 g, preferably 0.2 to 10 g, per 1 mol of hydroxyl group in 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 is preferable, and dimethyl sulfoxide is particularly used as a solvent. preferable.
The amount of the aprotic polar solvent used is preferably 20 to 300% by mass, more preferably 25 to 250% by mass, and particularly preferably 25 to 200% by mass with respect to the total mass of the phenol resin. The aprotic polar solvent is not useful for purification such as washing with water, and it is not preferable to use it in a large amount. Moreover, since the boiling point is high and removal of the solvent is difficult, a large amount of energy is consumed, so that it is not preferable that the amount is too large.

In this reaction, other solvents can be used. When used, it is preferable to use an alcohol having 1 to 5 carbon atoms in combination. Examples of the alcohol having 1 to 5 carbon atoms include alcohols such as methanol, ethanol and isopropyl alcohol. Further, a non-aqueous solvent such as methyl ethyl ketone, methyl isobutyl ketone, and toluene can be used in combination, but the use of 100% by mass or less with respect to dimethyl sulfoxide is preferable. Particularly preferred is 0.5 to 50% by mass. When non-aqueous solvents such as methyl ethyl ketone, methyl isobutyl ketone, and toluene are used in excess, Claisen transition occurs during the reaction, and a phenolic hydroxyl group is newly generated, increasing methallyl chloride in the system, further increasing methallyl and Can have products with methallyl ether.

The reaction temperature is usually 30 to 90 ° C, preferably 35 to 80 ° C. In particular, in the present invention, it is preferable to raise the reaction temperature in two or more steps for higher purity etherification. The first stage is particularly preferably 35 to 50 ° C., and the second stage is particularly preferably 45 to 70 ° C. The reaction time is usually 0.5 to 10 hours, preferably 1 to 8 hours, particularly preferably 1 to 5 hours. If the reaction time is 0.5 hours or more, the reaction proceeds sufficiently, and if the reaction time is 10 hours or less, a by-product is not formed, which is preferable.

The content of the compound having a methallyl group in the maleimide resin composition of the present invention can be appropriately set according to the type of the compound to be used, and is not particularly limited. From the viewpoint of the fluidity of the maleimide resin composition and the heat resistance of the cured product obtained by curing the maleimide resin composition, the content of the compound having a methallyl group is 5 to 30% by mass with respect to the total amount of the composition. The content is preferably 7 to 25% by mass. By setting the content ratio of the compound having a methallyl group to 5 to 30% by mass with respect to the total amount of the composition, a relatively low temperature molding is possible, and a thermosetting resin composition having a viscosity can be easily obtained. The cured product having high heat resistance tends to be easily obtained.

The maleimide resin composition of the present invention may contain a radical polymerization initiator (hereinafter also simply referred to as “catalyst”) as necessary.
Examples of radical polymerization initiators include benzoin compounds such as benzoin and benzoin methyl, acetophenone compounds such as acetophenone, 2,2′-dimethoxy-2-phenylacetophenone, thioxanthone compounds such as thioxanthone and 2,4-diethylthioxanthone, Bisazide compounds such as 4,4′-diazidochalcone, 2,6-bis (4′-azidobenzal) cyclohexanone, 4,4′-diazidobenzophenone, azobisisobutyronitrile, 2,2′-azobispropane Azo compounds such as hydrazone, 2,5-dimethyl-2,6-di (t-butylperoxy) hexane, 2,5′-dimethyl-2,5′-di (t-butylperoxy) hexyne-3 And organic peroxides such as dicumyl peroxide.

The content of the radical polymerization initiator in the maleimide resin composition can be appropriately set according to the type of the radical polymerization initiator to be used, and is not particularly limited. From the viewpoint of achieving 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 with respect to 100 parts by mass of the maleimide resin composition. More preferably, it is 0.1 to 3 parts by mass. If the amount of the radical polymerization initiator is too small, it may cause curing failure, and if it is too large, the cured material properties of the resin composition may be adversely affected.

The maleimide resin composition of the present invention can be used in combination with a curing accelerator in addition to a radical polymerization initiator, if necessary. Examples of curing accelerators that can be used include 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole. Such as imidazoles, triethylamine, triethylenediamine, 2- (dimethylaminomethyl) phenol, 1,8-diaza-bicyclo (5,4,0) undecene-7, tris (dimethylaminomethyl) phenol, benzyldimethylamine, etc. Phosphines such as amines, triphenylphosphine, tributylphosphine, trioctylphosphine and organometallic salts such as tin octylate, zinc octylate, dibutyltin dimaleate, zinc naphthenate, cobalt naphthenate, tin oleate, Zinc, aluminum chloride, include organometallic compounds such as metal chlorides such as tin chloride, benzoyl peroxide, dicumyl peroxide, there is a methyl ethyl ketone peroxide, etc. t- butyl perbenzoate organic peroxide. If the amount of the curing accelerator is too small, it may cause a curing failure, and if it is too large, the cured material properties of the resin composition may be adversely affected. Therefore, it is preferably added in an amount of 0.01 to 20% by mass, more preferably 0.01 to 10% by mass with respect to the maleimide resin.

A cyanate ester compound can also be blended in the maleimide resin composition of the present invention. A conventionally well-known cyanate ester compound can be used as a cyanate ester compound which can be mix | blended with the maleimide resin composition of this invention. Specific examples of cyanate ester compounds include polycondensates of phenols and various aldehydes, polymers of phenols and various diene compounds, polycondensates of phenols and ketones, and polycondensations of bisphenols and various aldehydes. Examples include, but are not limited to, cyanate ester compounds obtained by reacting a product with cyanogen halide. These may be used alone or in combination of two or more.
In addition, cyanate ester compounds described in Japanese Patent Application Laid-Open No. 2005-264154 are particularly preferable as cyanate ester compounds because they are excellent in low moisture absorption, flame retardancy, and dielectric properties.

Furthermore, in the maleimide resin composition of the present invention, any one or more of a flame retardant, a filler, and an additive can be blended as necessary.
Although it does not specifically limit as a filler, The filler etc. which are selected from a metal complex salt, activated carbon, a layered clay mineral, a metal oxide, etc. are mentioned.
As the metal composite salt, a hydrotalcite-like compound is preferable. The hydrotalcite-like compound is a compound represented by the general formula [M ²⁺ _1−X M ³⁺ _X (OH) ₂ ] [A ⁿ⁻ _{X / n} · mH ₂ O], and M ²⁺ and M ³⁺ are Divalent and trivalent metal ions, and A ⁿ⁻ _{X / n} represents an interlayer anion. Specifically, a typical hydrotalcite is a compound represented as Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O. The Kyoward series, a product of Kyowa Chemical Industry Co., Ltd., is effective as a commercial product. Examples include Kyoword 500, Kyoword 1000, Kyoword 700, Kyoword 600, Kyoword 200, Kyoword 2000, and the like. In the present invention, among the components to be contained, it is preferable that magnesium oxide> aluminum oxide and magnesium oxide> silicon dioxide in the quantity ratio of magnesium oxide, aluminum oxide, and silicon dioxide. Specifically, Kyoto word 500, Kyoto word 1000, etc. are preferable.

As activated carbon which can be used, chemical activated carbon is preferable. The chemical activated charcoal is not particularly limited as long as it has been treated with, for example, zinc chloride, phosphoric acid, etc., but the product activated with zinc chloride is particularly preferable because it may introduce chlorine into the product. Phosphoric acid activated charcoal. In addition, activated carbon obtained by a physical method that is made porous with water vapor, air, carbon dioxide, etc., can be used in combination with chemically activated carbon depending on the conditions to be treated. A proportion exceeding 50% by mass with respect to the amount of is preferable.
Examples of the raw material include wood (sawdust, etc.), coal (lignite, peat, coal, etc.), coconut shell, phenol resin, etc. In the present invention, wood is particularly preferred. Commercially available products include Futamura Chemical Co., Ltd., Dazai series (CG, CW, G, QW, S, ACF, etc. series), Ajinomoto Fine Techno Hokuetsu series (SD, BA, F, ZN, Y-180C, H -10CL, H-8CL, G-10F, CL-K, etc. series), Shirataka (C, LGK-400, G series, DO series, Wc, Sx, WHA, etc.), Nihon Enviro Chemicals Co., , Etc. PK series, PKDA series, ELORIT, AZO, DARCO series, HYDRODACO series, PETRODARCO, GAC, series, GCN, C GRAN, ROW, ROY, ROX, RO, RB, R, R., etc. 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 SUPER, CGP SUPER, S-51 series, HDB, HDC, HDR, HDW, GRO SAFE, FM-1, PAC series, Kuraray Co., Ltd., RP-20, YP-17D, etc. Can be mentioned.

The clay mineral is preferably a smectite-based layered clay mineral, and examples include bentonite, montmorillonite, beidellite, nontronite, saponite, hectorite, and synthetic smectite. Commercially available products are Kunimine Kogyo Co., Ltd .; smecton (synthetic smectite), bentonite (sodium salt type, calcium salt type), Kunipia F (montmorillonite), Hojun Co., Ltd .; , Bengel SH, Bengel A, manufactured by Coop Chemical Co., Ltd .; Lucentite series.

Examples of the metal oxide include 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.

Specific examples of additives that can be used include epoxy resin curing agents, polyamide resins, silicone resins, fluorine resins such as polytetrafluoroethylene, acrylic resins such as polymethyl methacrylate, cross-linked products of benzoguanamine, melamine, and formaldehyde, polybutadiene And this modified product, modified product of acrylonitrile copolymer, polyphenylene ether, polystyrene, polyethylene, polyimide, fluororesin, maleimide compound, cyanate ester compound, silicone gel, silicone oil, and inorganic such as silane coupling agent Coloring agents such as surface treatment agents for fillers, mold release agents, carbon black, phthalocyanine blue, and phthalocyanine green can be used. The compounding amount of these additives is preferably 1,000 parts by mass or less, more preferably 700 parts by mass or less with respect to 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, but each component may be mixed evenly or prepolymerized. For example, the methallyl group-containing compound and maleimide resin used in the present invention are prepolymerized by heating in the presence or absence of a catalyst and in the presence or absence of a solvent. Similarly, a methallyl group-containing compound used in the present invention, a maleimide resin, and if necessary, a curing agent such as an amine compound, a maleimide compound, a cyanate ester compound, a phenol resin, an acid anhydride compound, and other additives are added. It may be prepolymerized. For mixing or prepolymerization of each component, for example, an extruder, a kneader, a roll or the like is used in the absence of a solvent, and a reaction vessel with a stirrer is used in the presence of a solvent.

An organic solvent can be added to the maleimide resin composition of the present invention to form a varnish-like composition (hereinafter simply referred to as varnish). If necessary, the maleimide resin composition of the present invention is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone to obtain a maleimide resin composition varnish, and glass fiber. A cured product of the maleimide resin composition of the present invention is obtained by hot press molding a prepreg obtained by impregnating a substrate such as carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc. and drying by heating. Can do. The solvent used here is usually 10 to 70% by mass, preferably 15 to 70% by mass in the mixture of the maleimide resin composition of the present invention and the solvent. Moreover, if it is a liquid composition, the hardened | cured material of the maleimide resin containing a carbon fiber can also be obtained as it is, for example by the RTM system.

The maleimide resin composition of the present invention can also be used as a modifier for film-type compositions. Specifically, it can be used to improve flexibility in the B-stage. Such a film-type resin composition is formed by applying the maleimide resin composition of the present invention on the release film as the maleimide resin composition varnish, removing the solvent under heating, and then performing B-stage formation. Obtained as an adhesive. This 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 melting the maleimide resin composition of the present invention with heat, lowering the viscosity, and impregnating it with reinforcing fibers such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, and alumina fiber.
Moreover, the prepreg of this invention can also be obtained by impregnating the said varnish in a reinforced fiber and heat-drying.
The above prepreg is cut into the desired shape, laminated with copper foil if necessary, and then the maleimide resin composition for laminates is heated and cured while applying pressure to the laminate by press molding, autoclave molding, sheet winding molding, etc. By doing so, a laminated board can be obtained.
Furthermore, a circuit can be formed on a laminated board made by superimposing copper foil on the surface, and a multilayer circuit board can be obtained by superimposing a prepreg or copper foil thereon and repeating the above operation.

A cured product (thermosetting resin molding) can be obtained by heat-curing the maleimide resin composition of the present invention. The method for curing the maleimide resin composition is not particularly limited. For example, the maleimide resin composition is heated to 80 ° C. and cast between two glass plates that have been subjected to release treatment using a spacer having a thickness of 1.5 mm, and primary curing is performed at 170 to 200 ° C. for 2 hours, Thereafter, the primary cured product is removed from the glass plate and post-cured at 230 to 260 ° C. for 2 hours, whereby a cured product (maleimide resin molded product) can be obtained.

The maleimide resin composition of the present invention can be applied to various uses, and the use is not particularly limited. In particular, since the maleimide resin composition of the present invention is excellent in heat resistance and strength, handleability and production efficiency, it is used in applications requiring such performance, for example, matrix resins for fiber reinforced composite materials and electric and electronic parts. It is particularly useful in the field of sealants and the like.

EXAMPLES Next, the present invention will be described in more detail with reference to examples. In the following, “parts” means “parts by mass” unless otherwise specified. The present invention is not limited to these examples.
The various analysis methods used in the examples are described below.

Absorbent: 20% 0.1% hydrogen peroxide solution
The obtained water absorption liquid was measured by ion chromatography.
-Hydroxyl equivalent: Conforms to JIS K0070.
・ Epoxy equivalent: Conforms to JIS K 7236 (ISO 3001) ・ Amine equivalent: Conforms to the method described in JIS K-7236 Appendix A ・ Diphenylamine content: measured by gas chromatography ・ ICI melt viscosity: JIS K 7117-2 (ISO 3219) compliant ・ Softening point: JIS K 7234 compliant ・ Total chlorine: JIS K 7243-3 (ISO 21672-3) compliant

Gel permeation chromatography (GPC):
Analysis conditions Column (Shodex KF-603, KF-602.5, KF-602, KF-601x2)
The coupled eluent is tetrahydrofuran and the flow rate is 0.5 ml / min.
Column temperature is 40 ° C, detection: RI (differential refraction detector)
・ High performance liquid chromatography (HPLC):
Analysis conditions Column ODS2 Eluent is acetonitrile-water gradient,
Column temperature 40 ° C. Detection UV 274 nm, flow rate 1.0 ml / min.
-Gas chromatography (GC):
Analysis conditions Column HP-5 30m × 0.32mm × 0.25μm
Carrier gas Helium 1.0mL / min Split1 / 50
Injector temperature 300 ° C
Detector temperature 300 ° C
Oven temperature program After holding at 50 ° C. for 5 minutes, increase the temperature from 50 ° C. to 300 ° C. at 10 ° C./min. Hold at 300 ° C. for 5 minutes.
・ Curing heat generation: Measurement of curing start temperature, curing heat generation peak top temperature and heat generation end temperature by MDSC measurement Analysis conditions Analysis mode: MDSC measurement
Measuring instrument: Q2000 manufactured by TA-instruments Inc. Temperature rising rate: 3 ° C./min

(Synthesis Example 1)
In a flask equipped with a stirrer, a reflux condenser, and a stirrer, 720 parts by mass of dimethyl sulfoxide, 510 parts by mass of bisphenol A (hydroxyl equivalent: 120 g / eq. Softening point: 65 ° C.), methallyl chloride (purity: 99%, Junsei Chemical) 486 parts by mass (1.1 molar equivalents relative to 1 molar equivalent of the hydroxyl group of the phenol resin) was added, and the mixture was heated to 27 ° C. and dissolved. Next, 134 parts by mass of a 46.3% by mass aqueous sodium hydroxide solution was slowly added so that the internal temperature did not exceed 35 ° C., and then 70.0 parts by mass of flaky caustic soda (purity 99%, manufactured by Tosoh) (hydroxyl group 1 of phenol resin) 1.1 molar equivalents to molar equivalents) was added over 60 minutes. The reaction was carried out at 30-35 ° C for 4 hours, at 40-45 ° C for 1 hour, and at 55-60 ° C for 1 hour.
After completion of the reaction, water, dimethyl sulfoxide and the like were distilled off with a rotary evaporator. Then, 30 parts by mass of acetic acid (purity 99.5%, manufactured by Tokyo Chemical Industry Co., Ltd.) was added for neutralization, 700 parts by mass of methyl isobutyl ketone was added, washing was repeated, and the aqueous layer became neutral. confirmed. Thereafter, using a rotary evaporator from the oil layer, 750 parts by mass of a compound having a methallyl group (hereinafter referred to as “MEP1”) was obtained by distilling off the solvents while bubbling nitrogen under reduced pressure.

(Synthesis Example 2)
In a flask equipped with a stirrer, a reflux condenser, and a stirrer, 720 parts by mass of dimethyl sulfoxide, 330 parts by mass of phenol resin (tetramethylbiphenol hydroxyl group equivalent: 122 g / eq.), Methallyl chloride (purity 99%, manufactured by Tokyo Chemical Industry Co., Ltd.) 300 parts by mass (1.1 molar equivalents relative to 1 molar equivalent of the hydroxyl group of the phenol resin) was added, and the mixture was heated to 27 ° C. and dissolved. Next, 134 parts by mass of a 46.3% by mass aqueous sodium hydroxide solution was slowly added so that the internal temperature did not exceed 35 ° C., and then 70.0 parts by mass of flaky caustic soda (purity 99%, manufactured by Tosoh) (hydroxyl group 1 of phenol resin) 1.1 molar equivalents to molar equivalents) was added over 60 minutes. The reaction was carried out at 30-35 ° C for 4 hours, at 40-45 ° C for 1 hour, and at 55-60 ° C for 1 hour.
After completion of the reaction, water, dimethyl sulfoxide and the like were distilled off with a rotary evaporator. Then, 30 parts by mass of acetic acid (purity 99.5%, manufactured by Tokyo Chemical Industry Co., Ltd.) was added for neutralization, 700 parts by mass of methyl isobutyl ketone was added, washing was repeated, and the aqueous layer became neutral. confirmed. Thereafter, using a rotary evaporator from the oil layer, 470 parts by mass of a compound having a methallyl group (hereinafter referred to as “MEP2”) was obtained by distilling off the solvents while bubbling nitrogen under reduced pressure.

(Synthesis Example 3)
In a flask equipped with a stirrer, a reflux condenser, and a stirrer, 720 parts by mass of dimethyl sulfoxide, 535 parts by mass of a phenol resin (phenol-dicyclopentadiene type hydroxyl group equivalent 178 g / eq. Softening point 106 ° C.), methallyl chloride (purity) 99% Tokyo Chemical Industry Co., Ltd.) 272 parts by mass (1.1 molar equivalents relative to 1 molar equivalent of the hydroxyl group of the phenolic resin) was added, and the mixture was heated to 27 ° C. and dissolved. Next, 134 parts by mass of a 46.3% by mass aqueous sodium hydroxide solution was slowly added so that the internal temperature did not exceed 35 ° C., and then 70.0 parts by mass of flaky caustic soda (purity 99%, manufactured by Tosoh) (hydroxyl group 1 of phenol resin) 1.1 molar equivalents to molar equivalents) was added over 60 minutes. The reaction was carried out at 30-35 ° C for 4 hours, at 40-45 ° C for 1 hour, and at 55-60 ° C for 1 hour.
After completion of the reaction, water, dimethyl sulfoxide and the like were distilled off by heating on a rotary evaporator at 120 ° C. or lower under reduced pressure. Then, 30 parts by mass of acetic acid (purity 99.5%, manufactured by Tokyo Chemical Industry Co., Ltd.) was added for neutralization, 700 parts by mass of methyl isobutyl ketone was added, washing was repeated, and the aqueous layer became neutral. confirmed. Thereafter, 690 parts by mass of a compound having a methallyl group (hereinafter referred to as “MEP3”) was obtained by distilling off the solvents from the oil layer using a rotary evaporator while bubbling nitrogen under reduced pressure.

(Synthesis Example 4)
720 parts by mass of dimethyl sulfoxide, cresol resin OCN-100 ° C. (hydroxyl equivalent: 120 g / eq. Softening point: 105 ° C., manufactured by Meiwa Kasei Kogyo Co., Ltd.) 360 parts by mass and 299 parts by mass of methallyl chloride (purity 99%, manufactured by Tokyo Chemical Industry Co., Ltd.) (1.1 molar equivalents relative to 1 molar equivalent of the hydroxyl group of the cresol resin) were added, and the mixture was heated to 27 ° C. and dissolved. Next, 132.0 parts by mass of caustic soda (purity 99%, manufactured by Tosoh Corporation) (1.1 molar equivalents relative to 1 molar equivalent of hydroxyl group of cresol resin) and 72 parts by mass of water were added over 60 minutes. The reaction was carried out at 30 to 35 ° C. for 4 hours, at 40 to 45 ° C. for 1 hour, and at 60 to 65 ° C. for 1 hour.
After completion of the reaction, water, dimethyl sulfoxide and the like were distilled off by heating on a rotary evaporator at 120 ° C. or lower under reduced pressure. And 600 mass parts of methyl isobutyl ketone was added, and water washing was repeated, and it confirmed that the water layer became neutral. Thereafter, 523 parts by mass of a compound having a methallyl group (hereinafter referred to as “MEP4”) was obtained by distilling off the solvent from the oil layer using a rotary evaporator while bubbling nitrogen under reduced pressure.

(Synthesis Example 5)
A flask equipped with a stirrer, a reflux condenser, and a stirrer is purged with nitrogen, while 720 parts by mass of dimethyl sulfoxide, phenol novolac resin 550PL (hydroxyl equivalent 97 g / eq. Softening point 114 ° C., manufactured by Meiwa Kasei Kogyo) 291 masses Part, allyl chloride (purity 99%, manufactured by Junsei Chemical Co., Ltd.) 253 parts by mass (1.1 molar equivalent with respect to 1 molar equivalent of hydroxyl group of phenol novolac resin) was heated to 27 ° C. and dissolved. Next, 132.0 parts by mass of caustic soda (purity: 99%, manufactured by Tosoh Corp.) (1.1 molar equivalents relative to 1 molar equivalent of hydroxyl group of phenol novolac resin) and 72 parts by mass of water were added over 60 minutes. The reaction was carried out at 30 to 35 ° C. for 4 hours, at 40 to 45 ° C. for 1 hour, and at 60 to 65 ° C. for 1 hour.
After completion of the reaction, water, dimethyl sulfoxide and the like were distilled off by heating on a rotary evaporator at 120 ° C. or lower under reduced pressure. And 600 mass parts of methyl isobutyl ketone was added, and water washing was repeated, and it confirmed that the water layer became neutral. Thereafter, using a rotary evaporator from the oil layer, 440 parts by mass of a compound having a methallyl group (hereinafter referred to as “MEP5”) was obtained by distilling off the solvents while bubbling nitrogen under reduced pressure.

(Synthesis Example 6)
In a flask equipped with a stirrer, a reflux condenser, and a stirrer, 720 parts by weight of dimethyl sulfoxide, 2-phenyl-3,3-bis (4-hydroxyphenyl) phthalimide (hydroxyl equivalent: 201 g / eq. Softening point: 65 ° C.), 590 parts by weight Part, 420 parts by mass of methallyl chloride (purity: 99%, manufactured by Junsei Chemical Co., Ltd., 1.1 mol equivalent to 1 mol equivalent of hydroxyl group of the phenol resin) was added and heated to 27 ° C. to dissolve. Next, 134 parts by mass of a 46.3% by mass aqueous sodium hydroxide solution was slowly added so that the internal temperature did not exceed 35 ° C., and then 70.0 parts by mass of flaky caustic soda (purity 99%, manufactured by Tosoh) (hydroxyl group 1 of phenol resin) 1.1 molar equivalents to molar equivalents) was added over 60 minutes. The reaction was carried out at 30-35 ° C for 4 hours, at 40-45 ° C for 1 hour, and at 55-60 ° C for 1 hour.
After completion of the reaction, water, dimethyl sulfoxide and the like were distilled off with a rotary evaporator. Then, 30 parts by mass of acetic acid (purity 99.5%, manufactured by Tokyo Chemical Industry Co., Ltd.) was added for neutralization, 700 parts by mass of methyl isobutyl ketone was added, washing was repeated, and the aqueous layer became neutral. confirmed. Then, 710 parts by mass of a compound having a methallyl group (hereinafter referred to as “MEP6”) was obtained by distilling off the solvents from the oil layer using a rotary evaporator while bubbling nitrogen under reduced pressure.

(Synthesis Example 7)
In a flask equipped with a stirrer, reflux condenser, and stirrer, 720 parts by weight of dimethyl sulfoxide, 4,4 ′-(1- {4- [2- (4-hydroxyphenyl) propan-2-yl] phenyl} ethane -1,1-diyl) diphenol (hydroxyl equivalent 150 g / eq) 370 parts by mass, methallyl chloride (purity 99%, Junsei Chemical) 420 parts by mass (1.1 molar equivalents relative to 1 molar equivalent of the hydroxyl group of the phenol resin) ) And heated to 27 ° C. to dissolve. Next, 134 parts by mass of a 46.3% by mass aqueous sodium hydroxide solution was slowly added so that the internal temperature did not exceed 35 ° C., and then 70.0 parts by mass of flaky caustic soda (purity 99% manufactured by Tosoh) (hydroxyl group of phenol resin) 1.1 molar equivalents to 1 molar equivalent) was added over 60 minutes. The reaction was carried out at 30-35 ° C for 4 hours, at 40-45 ° C for 1 hour, and at 55-60 ° C for 1 hour.
After completion of the reaction, water, dimethyl sulfoxide and the like were distilled off with a rotary evaporator. Then, 30 parts by mass of acetic acid (purity 99.5%, manufactured by Tokyo Chemical Industry Co., Ltd.) was added for neutralization, 700 parts by mass of methyl isobutyl ketone was added, washing was repeated, and the aqueous layer became neutral. confirmed. Thereafter, the solvent was distilled off from the oil layer using a rotary evaporator under nitrogen bubbling under reduced pressure to obtain 510 parts by mass of a compound having a methallyl group (hereinafter referred to as “MEP7”).

(Synthesis Example 8)
In a flask equipped with a stirrer, a reflux condenser, and a stirrer, 720 parts by weight of dimethyl sulfoxide, 510 parts by weight of bisphenol A (hydroxyl equivalent: 120 g / eq. Softening point: 65 ° C.), allylic chloride (purity: 99%, Junsei Chemical) 298 0.8 parts by mass (1.1 molar equivalents relative to 1 molar equivalent of the hydroxyl group of the phenol resin) was added, and the mixture was heated to 27 ° C. and dissolved. Next, 134 parts by mass of a 46.3% by mass aqueous sodium hydroxide solution was slowly added so that the internal temperature did not exceed 35 ° C., and then 70.0 parts by mass of flaky caustic soda (purity 99%, manufactured by Tosoh) (hydroxyl group 1 of phenol resin) 1.1 molar equivalents to molar equivalents) was added over 60 minutes. The reaction was carried out at 30-35 ° C for 4 hours, at 40-45 ° C for 1 hour, and at 55-60 ° C for 1 hour.
After completion of the reaction, water, dimethyl sulfoxide and the like were distilled off with a rotary evaporator. Then, 30 parts by mass of acetic acid (purity 99.5%, manufactured by Tokyo Chemical Industry Co., Ltd.) was added for neutralization, 700 parts by mass of methyl isobutyl ketone was added, washing was repeated, and the aqueous layer became neutral. confirmed. Thereafter, by using a rotary evaporator from the oil layer, 750 parts by mass of a compound having an allyl group (hereinafter referred to as “AEP1”) was obtained by distilling off the solvents while bubbling nitrogen under reduced pressure.

(Synthesis Example 9)
A flask equipped with a thermometer, a condenser, a Dean-Stark azeotropic distillation trap, and a stirrer was charged with 372 parts of aniline and 200 parts of toluene, and 146 parts of 35% hydrochloric acid was added dropwise at room temperature over 1 hour. After completion of the dropwise addition, the mixture was heated to cool and separate azeotropic water and toluene, and then only the organic layer of toluene was returned to the system for dehydration. Subsequently, 125 parts of 4,4′-bis (chloromethyl) biphenyl was added over 1 hour while maintaining the temperature at 60 to 70 ° C., and the reaction was further carried out at the same temperature for 2 hours. After completion of the reaction, toluene was distilled off while raising the temperature to bring the inside of the system to 195 to 200 ° C., and the reaction was carried out at this temperature for 15 hours. Then, with cooling, 330 parts of 30% aqueous sodium hydroxide solution was slowly added dropwise so that the system did not circulate vigorously, and the toluene distilled off at a temperature of 80 ° C. or lower was returned to the system and allowed to stand at 70 ° C. to 80 ° C. I put it. The separated lower aqueous layer was removed, and the reaction solution was washed with water until the washing solution became neutral. Subsequently, 173 parts of aromatic amine resin (a1) was obtained by distilling off excess aniline and toluene from the oil layer with a rotary evaporator under heating and reduced pressure (200 ° C., 0.6 KPa). Diphenylamine in the aromatic amine resin (a1) was 2.0%.
The obtained resin (a1) was again added in small portions in place of steam blowing in a rotary evaporator under heating and reduced pressure (200 ° C., 4 KPa). As a result, 166 parts of aromatic amine resin (A1) was obtained. The aromatic amine resin (A1) obtained had a softening point of 56 ° C., a melt viscosity of 0.035 Pa · s, and diphenylamine of 0.1% or less.

(Synthesis Example 10)
After adding 147 parts of maleic anhydride and 300 parts of toluene to a flask equipped with a thermometer, condenser, Dean-Stark azeotropic distillation trap, and stirrer, cooling and separating the water and toluene azeotropically heated. Then, only toluene which is an organic layer was returned to the system for dehydration. Next, a resin solution obtained by dissolving 195 parts of the aromatic amine resin (A1) obtained in Synthesis Example 9 in 195 parts of N-methyl-2-pyrrolidone was added over 1 hour while maintaining the system at 80 to 85 ° C. It was dripped. After completion of the dropping, the reaction is carried out at the same temperature for 2 hours, 3 parts of p-toluenesulfonic acid is added, condensed water and toluene azeotroped under reflux conditions are cooled and separated, and only toluene which is an organic layer Was returned to the system and reacted for 20 hours while dehydrating. After completion of the reaction, 120 parts of toluene was added, and washing with water was repeated to remove p-toluenesulfonic acid and excess maleic anhydride, followed by heating to remove water from the system by azeotropy. Next, the reaction solution was concentrated to obtain a resin solution containing 70% maleimide resin (hereinafter referred to as “MI1”).

(Synthesis Example 11)
In a flask equipped with a stirrer, a reflux condenser, and a stirrer, 720 parts by mass of dimethyl sulfoxide, 2,2′-diallyl-4,4′-sulfonyldiphenol (TGSH hydroxyl group equivalent 263 g / eq. Softening point 65 ° C.) 540 Mass parts, 299 parts by mass of methallyl chloride (purity 99%, manufactured by Tokyo Chemical Industry Co., Ltd.) (1.1 molar equivalents relative to 1 molar equivalent of the hydroxyl group of the phenol resin) were added, and the mixture was heated to 27 ° C. and dissolved. Next, 134 parts by mass of a 46.3% by mass aqueous sodium hydroxide solution was slowly added so that the internal temperature did not exceed 35 ° C., and then 70.0 parts by mass of flaky caustic soda (purity 99% manufactured by Tosoh) (hydroxyl group of phenol resin) 1.1 molar equivalents to 1 molar equivalent) was added over 60 minutes. The reaction was carried out at 30-35 ° C for 4 hours, at 40-45 ° C for 1 hour, and at 55-60 ° C for 1 hour.
After completion of the reaction, water, dimethyl sulfoxide and the like were distilled off with a rotary evaporator. Then, 30 parts by mass of acetic acid (purity 99.5%, manufactured by Tokyo Chemical Industry Co., Ltd.) was added for neutralization, 700 parts by mass of methyl isobutyl ketone was added, washing was repeated, and the aqueous layer became neutral. confirmed. Thereafter, using a rotary evaporator from the oil layer, 630 parts by mass of a compound having a methallyl group (hereinafter referred to as “MEP8”) was obtained by distilling off the solvents while bubbling nitrogen under reduced pressure.

Example 1
35 parts by mass of the compound (MEP1) having a methallyl group obtained in Synthesis Example 1 and 65 parts by mass of the maleimide resin (MI1) obtained in Synthesis Example 10 are blended and stirred uniformly at 150 ° C., and then 100 0.5 parts by mass of dicumyl peroxide (Catalyst 1, manufactured by Kayaku Akzo Co., Ltd.) was mixed at 0 ° C., stirred, and uniformly dissolved to obtain a maleimide resin composition of the present invention. This maleimide resin composition was cured under curing conditions of 200 ° C. × 2 hours at 230 ° C. × 2 hours to obtain a cured product of the present invention. Table 1 shows the measurement results of the physical properties of the cured product.

(Example 2)
38 parts by mass of the compound having a methallyl group (MEP2) obtained in Synthesis Example 2 and 62 parts by mass of the maleimide resin (MI1) obtained in Synthesis Example 10 were blended and stirred uniformly at 150 ° C., and then 100 0.5 parts by mass of dicumyl peroxide (Catalyst 1, manufactured by Kayaku Akzo Co., Ltd.) was mixed at 0 ° C., stirred, and uniformly dissolved to obtain a maleimide resin composition of the present invention. This maleimide resin composition was cured under curing conditions of 200 ° C. × 2 hours at 230 ° C. × 2 hours to obtain a cured product of the present invention. Table 1 shows the measurement results of the physical properties of the cured product.

(Example 3)
45 parts by mass of the compound (MEP3) having a methallyl group obtained in Synthesis Example 3 and 55 parts by mass of the maleimide resin (MI1) obtained in Synthesis Example 10 were blended and stirred uniformly at 150 ° C., and then 100 0.5 parts by mass of dicumyl peroxide (Catalyst 1, manufactured by Kayaku Akzo Co., Ltd.) was mixed at 0 ° C., stirred, and uniformly dissolved to obtain a maleimide resin composition of the present invention. This maleimide resin composition was cured under curing conditions of 200 ° C. × 2 hours at 230 ° C. × 2 hours to obtain a cured product of the present invention. Table 1 shows the measurement results of the physical properties of the cured product.

Example 4
38 parts by mass of the compound having a methallyl group (MEP4) obtained in Synthesis Example 4 and 62 parts by mass of the maleimide resin (MI1) obtained in Synthesis Example 10 were blended and stirred uniformly at 150 ° C., and then 100 0.5 parts by mass of dicumyl peroxide (Catalyst 1, manufactured by Kayaku Akzo Co., Ltd.) was mixed at 0 ° C., stirred, and uniformly dissolved to obtain a maleimide resin composition of the present invention. This maleimide resin composition was cured under curing conditions of 200 ° C. × 2 hours at 230 ° C. × 2 hours to obtain a cured product of the present invention. Table 1 shows the measurement results of the physical properties of the cured product.

(Example 5)
35 parts by mass of the compound (MEP5) having a methallyl group obtained in Synthesis Example 5 and 65 parts by mass of the maleimide resin (MI1) obtained in Synthesis Example 10 were blended and stirred uniformly at 150 ° C., and then 100 0.5 parts by mass of dicumyl peroxide (Catalyst 1, manufactured by Kayaku Akzo Co., Ltd.) was mixed at 0 ° C., stirred, and uniformly dissolved to obtain the thermosetting resin composition of the present invention. This maleimide resin composition was cured under curing conditions of 200 ° C. × 2 hours at 230 ° C. × 2 hours to obtain a cured product of the present invention. Table 1 shows the measurement results of the physical properties of the cured product.

(Example 6)
47 parts by mass of the compound having a methallyl group (MEP6) obtained in Synthesis Example 6 and 53 parts by mass of the maleimide resin (MI1) obtained in Synthesis Example 10 were blended and stirred uniformly at 150 ° C., and then 100 0.5 parts by mass of dicumyl peroxide (Catalyst 1, manufactured by Kayaku Akzo Co., Ltd.) was mixed at 0 ° C., stirred, and uniformly dissolved to obtain the thermosetting resin composition of the present invention. This maleimide resin composition was cured under curing conditions of 200 ° C. × 2 hours at 230 ° C. × 2 hours to obtain a cured product of the present invention. Table 1 shows the measurement results of the physical properties of the cured product.

(Example 7)
39 parts by mass of the compound (MEP7) having a methallyl group obtained in Synthesis Example 7 and 61 parts by mass of the maleimide resin (MI1) obtained in Synthesis Example 10 were mixed and stirred uniformly at 150 ° C., and then 100 ° C. Then, 0.5 part by mass of dicumyl peroxide (Catalyst 1, manufactured by Kayaku Akzo Co., Ltd.) was mixed, stirred, and uniformly dissolved to obtain the maleimide resin composition of the present invention. This maleimide resin composition was cured under curing conditions of 200 ° C. × 2 hours at 230 ° C. × 2 hours to obtain a cured product of the present invention. Table 1 shows the measurement results of the physical properties of the cured product.

(Comparative Example 1)
46 parts by mass of the allyl group-containing compound (AEP1) obtained in Synthesis Example 8, maleimide compound (4,4′-bismaleimide diphenylmethane BMI-1000, manufactured by Daiwa Kasei Kogyo Co., Ltd., hereinafter abbreviated as “MI2”) 54 Mix parts by mass and stir uniformly at 150 ° C., then mix 100 parts by mass of dicumyl peroxide (Catalyst 1, manufactured by Kayaku Akzo Co., Ltd.), stir and dissolve uniformly. The maleimide resin composition of the comparative example was obtained. The maleimide resin composition was cured under curing conditions of 200 ° C. × 2 hours at 230 ° C. × 2 hours to obtain a cured product of a comparative example. Table 1 shows the measurement results of the physical properties of the cured product.

(Comparative Example 2)
38 parts by weight of the allyl group-containing compound (AEP1) obtained in Synthesis Example 8 and 62 parts by weight of the maleimide resin (MI1) obtained in Synthesis Example 10 were blended and stirred uniformly at 150 ° C., and then 100 ° C. Then, 0.5 parts by weight of dicumyl peroxide (Catalyst 1, manufactured by Kayaku Akzo Co., Ltd.) was blended, stirred and uniformly dissolved to obtain the maleimide resin composition of the present invention. This maleimide resin composition was cured under curing conditions of 200 ° C. × 2 hours at 230 ° C. × 2 hours to obtain a cured product of the present invention. Table 1 shows the measurement results of the physical properties of the cured product.

<Heat resistance>
Tg: The peak point of tan δ (tan δ MAX) in DMA measurement was defined as Tg.
Analysis conditions Dynamic viscoelasticity measuring instrument: manufactured by TA-instruments, Q-800 Measurement temperature range: 30 ° C. to 350 ° C. Temperature rate: 2 ° C./min Test piece size: 5 mm × 50 mm cut out was used (thickness is About 800 μm).
<Dielectric constant test and dielectric loss tangent test>
-Using a 1 GHz cavity resonator manufactured by Kanto Electronics Co., Ltd., a test was performed by the cavity resonator perturbation method. However, the test was conducted with a sample size of 1.7 mm wide × 100 mm long and a thickness of 1.7 mm.
<Water absorption rate>
Water absorption: 100 ° C. × 24 h Weight increase% of the cured product immersed.

From Table 1, it can be confirmed that the cured product of the maleimide resin composition of the present invention exhibits high heat resistance, low water absorption, and low dielectric properties.

(Example 8)
A varnish was prepared by adding 35 parts by mass of the compound (MEP1) having a methallyl group obtained in Synthesis Example 1, 65 parts by mass of the maleimide resin (MI1) obtained in Synthesis Example 10, and 100 parts by mass of methyl ethyl ketone (MEK). The obtained varnish was allowed to stand at 25 ° C. for 72 hours, and then the presence or absence of precipitates was confirmed. The results are shown in Table 2.

Example 9
In addition to 55 parts by mass of the compound having methallyl group (MEP1) obtained in Synthesis Example 1, 45 parts by mass of maleimide resin (BMI-2300, manufactured by Daiwa Kasei Kogyo Co., Ltd., hereinafter referred to as “MI3”) and 100 parts by mass of MEK Created a varnish. The obtained varnish was allowed to stand at 25 ° C. for 72 hours, and then the presence or absence of precipitates was confirmed. The results are shown in Table 2.

(Comparative Example 3)
A varnish was prepared by adding 47 parts by mass of the compound (MEP1) having a methallyl group obtained in Synthesis Example 1, 53 parts by mass of a maleimide compound (MI2), and 100 parts by mass of MEK. The obtained varnish was allowed to stand at 25 ° C. for 72 hours, and then the presence or absence of precipitates was confirmed. The results are shown in Table 2.

According to Table 2, in the present invention, a composition using a maleimide resin having N maleimide groups (N is an integer, the average value being greater than 2) is a maleimide resin having N maleimide groups with high crystallinity. It can be confirmed that the stability of the varnish is higher than that of using varnish.

Although the invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
The present application is based on a Japanese patent application (Japanese Patent Application No. 2017-090437) filed on April 28, 2017, and is incorporated by reference in its entirety. Also, all references cited herein are incorporated as a whole.

Since the maleimide resin composition of the present invention has electrical properties, particularly low hygroscopicity (low water absorption) and heat resistance in the cured product, the insulating material for electrical and electronic parts and laminated boards (printed wiring boards, build-up boards) Etc.) and various composite materials including CFRP, adhesives, paints and the like.

Claims (7)

A maleimide resin having N maleimide groups (N is an integer and the average value is larger than 2), a compound represented by the following formula (1), and the following formulas (3-1) to (3-7) A maleimide resin composition containing at least one of the compounds represented by any of the above.

(Wherein R ₂ independently represents a methallyl group or a hydrogen atom. R ₃ independently represents a methallyl group, a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aromatic group. (It has a structure represented by any one of formulas (2-1) to (2-11), a1 represents an integer of 1 to 4)

(Wherein, _{R 2} is .A2 is .A2 + 1 represents an integer of 1 to 4 represent the same as _{R 2} in the formula (1) represents an integer of 1-5. * Represents a bonding position.)

(In the formula, each R ₂ independently represents a methallyl group or a hydrogen atom. Each R ₃ independently represents a methallyl group, a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aromatic group. A is — O—,> NR ₄ or —C (R ₄ ) ₂ —, wherein R ₄ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aromatic group, a3 is an integer of 1 to 4 A3-1 represents an integer of 1 to 3. a3-2 represents an integer of 1 to 2. n1 is an integer, and an average value thereof represents 1 <n1 ≦ 5. The maleimide resin composition according to claim 1, wherein the maleimide resin has a structure represented by the following formula (4).

(In Formula (4), a plurality of R _{1 s} each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aromatic group. A4 represents 1 to 3. n2 is an integer; (The average value represents 1 <n2 ≦ 5.) The maleimide resin composition according to claim 1 or 2, which contains a radical polymerization initiator. The maleimide resin composition according to any one of claims 1 to 3, comprising at least one of a flame retardant, a filler, and an additive. A prepreg in which the maleimide resin composition according to any one of claims 1 to 4 is held on a sheet-like fiber base material and is in a semi-cured state. A cured product of the maleimide resin composition according to any one of claims 1 to 4. A cured product of the prepreg according to claim 5.