KR20190137106A - Maleimide resin composition, prepreg and cured product thereof - Google Patents

Abstract

(식 중, R₂ 및 R₃은 메탈릴기 또는 수소원자 등을 나타내고, Z는 특정한 구조를 갖고, a1은 1∼4의 정수를 나타낸다.)When it is set as the hardened | cured material, the maleimide resin composition, prepreg, and its hardened | cured material which show the outstanding electrical property etc. are provided. The maleimide resin composition contains a maleimide resin having N maleimide groups (N is an integer and its average value is greater than 2), and a specific metalyl group-containing compound represented by the following formula (1).

(In formula, R <_2> and R <_3> represents a metalyl group, a hydrogen atom, etc., Z has a specific structure, and a1 represents the integer of 1-4.)

Description

Maleimide resin composition, prepreg and cured product thereof

This invention relates to a maleimide resin composition, a prepreg, and its hardened | cured material. Specifically, high reliability semiconductor sealing materials, electrical and electronic component insulating materials, and various composite materials, including laminated boards (printed wiring glass fiber reinforced composites) and CFRP (carbon fiber reinforced composites), various adhesives, various paints A maleimide resin composition, a prepreg, and its hardened | cured material useful for a use, a structural member, etc.

Generally, as a board | substrate which laminates a printed wiring board for electric and electronic devices, especially copper foil, thermosetting resins, such as paper-phenol resin mainly based on paper and glass cloth-epoxy resin based on glass cloth, are used conventionally. Since these thermosetting resins express characteristics such as high heat resistance and dimensional stability by a unique crosslinked structure, it is known to have high reliability. On the other hand, the demand for thermosetting resins, such as high density mounting of printed wiring boards, improved heat resistance due to high multilayer structure, low dielectric constant and low dielectric tangent contact due to high-speed communication demand, and the like, requires a new crosslinked structure. Getting started.

In particular, in the M2M market, the amount of information is enormously enlarging, as well as the communication between machines as well as the amount of communication between people. On the other hand, there is a limit to the resources that can be allocated to a user (user) by the base station. Therefore, infrastructure maintenance and high functionalization of the communication system are in progress. For example, a small cell may be mentioned. In addition to the need for a communication board as the number of small cells and the like increases, the amount of information to be used can also be particularly increased, so that very high characteristics are required for communication devices such as smartphones (Non-Patent Document 1).

In these applications, low dielectric loss tangent, low water absorption, and reliability that are hard to change at a driving temperature are required, so high heat resistance is required. In particular, the dielectric loss tangent is required to have a property of 0.010 or less, particularly 0.007 or less. At the same time, since moisture is one of the factors that greatly deteriorate the dielectric properties, a lower water absorption is required (Non Patent Literature 2).

In addition, when used for a substrate of a high-performance communication semiconductor package, it is preferable to clear the heat resistance of 170 ° C or higher, particularly, the heat resistance of solder reflow or more, and recently, Tg of a reflow temperature or higher has been required. The required characteristic has been very high (Non-Patent Document 3).

In a fiber reinforced composite material, it consists of matrix resin and reinforcing fibers, such as carbon fiber, glass fiber, alumina fiber, boron fiber, and aramid fiber, and generally has the characteristic of light weight and high strength. Such fiber-reinforced composite materials include insulation materials for electrical and electronic parts and laminated boards (printed wiring boards, build-up boards, etc.), aerospace materials such as aircraft and wings of passenger aircraft, machine tool members represented by robot hand arms, and construction and civil engineering repair materials. It is widely used as a purpose, as a leisure goods use, such as a golf shaft and a tennis racket. In particular, carbon fiber reinforced composite materials (hereinafter referred to as CFRP) in the aerospace materials such as aircraft and wings of passenger aircraft, and machine tool members represented by robotic hand arms maintain rigidity in the temperature range from room temperature to about 200 ° C. Heat resistance, mechanical properties, long-term reliability, i.e., high thermal decomposition temperature and high elastic modulus at high temperature are required. Epoxy resins are widely used as matrix resins of fiber-reinforced composite materials. However, epoxy resins have low heat resistance and are not suitable for aerospace materials and machine tool members.

Maleimide resins are widely known as matrix resins having high heat resistance and being able to withstand the use environment of 200 ° C or higher. Although the bismaleimide compound is used as the subject of maleimide resin, since a molded article falls, various modifiers have been developed in order to improve this. As the solution, various modifications are performed, and for example, compounding a modified butadiene resin having a meta (acryloyl) group introduced into the cyanate ester resin composition (Patent Document 1), butadiene-acrylonitrile air It is known to add a copolymer (patent document 2), or to add epoxy resin to these (patent document 3). However, although these methods alleviate dryness, the heat resistance and the fall of mechanical strength all have the problem which cannot be avoided.

Moreover, the method of modifying a maleimide resin with the allyl compound known as additives, such as a reactive diluent, a crosslinking agent, and a flame retardant, of a maleimide resin is also known. For example, patent document 4 is resin obtained by heat-melting and mixing liquid o, o'- diallyl bisphenol A in 4,4'- diphenylmethane bismaleimide at normal temperature, and can be impregnated to a carbon fiber sheet with a solvent. Do.

Japanese Patent Publication No. 57-153045 Japanese Patent Publication No. 57-153046 Japanese Patent Publication No. 56-157424 Japanese Patent Application Laid-Open No. 09-087460

 Nikkei electronics, June 10, 2013, pp. 30-32  Panasonic Denko Kibo Vol. 59 No. One  Hitachi Chemical Co., Ltd. Technical Report No. 39 (2002-7)

However, even if the prepreg obtained is modified by o, o'- diallyl bisphenol A, patent document 4 is inadequate an electrical characteristic.

Then, this invention is providing the maleimide resin composition, a prepreg, and its hardened | cured material which show an electrical property, especially low hygroscopicity (low water absorption), and heat resistance in the hardened | cured material.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in view of the above fact, the maleimide resin composition containing the maleimide resin which has a functional group more than bifunction, and the compound which has a metalyl group has the electrical characteristics, especially in the hardened | cured material It discovered that the outstanding low hygroscopicity (low water absorption) and heat resistance were shown, and came to complete this invention.

That is, the present invention,

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

(In formula, R <_2> respectively independently represents a metalyl group or a hydrogen atom. R <_3> respectively independently represents a metalyl group, a hydrogen atom, a C1-C10 alkyl group, or an aromatic group. Z is following formula (2-1) It has a structure represented by any one of-(2-11) a1 represents the integer of 1-4.)

(Wherein, R ₂ has the same meaning as R ₂ in the formula (1). A2 represents an integer of 1~4. A2 + 1 is an integer of 1 to 5. * represents a bonding site.)

(Wherein, R ₂ each independently represents a metalyl group or a hydrogen atom. R ₃ each independently represents a metalyl group, a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aromatic group. A represents —O—,> NR _4. Or -C (R ₄ ) _2- , R ₄ each 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 1 to 3 A3-2 represents an integer of 1 to 2. n1 represents an integer and the average value represents 1 <n1≤5.)

[2] the maleimide resin composition according to the above [1], wherein the maleimide resin is a structure represented by the following Formula (4):

(In formula (4), two or more R <_1> represents a hydrogen atom, a C1-C10 alkyl group, or an aromatic group each independently. A4 represents 1-3. N2 is an integer and the average value is 1 <n2 <= 5. Is displayed.)

[3] the maleimide resin composition according to the above [1] or [2], containing a radical polymerization initiator;

[4] the maleimide resin composition according to any one of the preceding [1] to [3], containing 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 semi-cured by holding the sheet-like fibrous substrate;

[6] a cured product of the maleimide resin composition according to any one of the above [1] to [4],

[7] The present invention relates to a cured product of the prepreg according to the above [5].

The maleimide resin composition of the present invention has electrical properties, particularly low hygroscopicity (low absorption) and heat resistance in the cured product thereof, and thus includes insulating materials for electrical and electronic components, laminates (printed wiring boards, build-up substrates, etc.) and CFRP. It is useful for various composite materials, adhesives, paints and the like.

The maleimide resin composition of this invention is demonstrated below.

The maleimide resin composition of this invention contains N maleimide resin (henceforth only called "maleimide resin") which has N (N is an integer and the average value is larger than 2) maleimide groups.

The maleimide resin which can be used in this invention should just be a maleimide resin which has a number exceeding 2 in 1 molecule of a maleimide group on average, and is not specifically limited.

As a specific example of the said maleimide resin, the polyfunctional maleimide compound obtained by reaction of 3,4,4'-triaminodiphenylmethane, triaminophenol, and maleic anhydride, a tris- (4-aminophenyl) phosphate, and a tris Trismaleimide compounds, such as the maleimide compound obtained by reaction of (4-aminophenyl) -phosphate, the tris (4-aminophenyl) -thiophosphate, and maleic anhydride, and tris (4-maleimide phenyl) methane, bis ( Tetramaleimide compounds, such as maleimide obtained by reaction of 3, 4- dimarimide phenyl) methane, tetramaleimide benzophenone, tetramaleimide naphthalene, a triethylenetetramine, and maleic anhydride, a phenol novolak-type maleimide Resin, isopropylidene bis (phenoxyphenyl maleimide) phenyl maleimide aralkyl resin, biphenylene type phenyl maleimide aralkyl resin, represented by formula (5) Of Li maleimide, benzene dialdehyde and polyaniline obtained by condensation of aniline is a poly-maleimide and the like. Moreover, the polyamino polymaleimide resin which added aromatic diamine to these polymaleimide can also be used. Moreover, since novolak-type maleimide resin has a molecular weight distribution and high varnish stability, it is suitable for kneading with a metalryl resin. These may use a commercially available thing and can also manufacture it using a well-known method.

(In formula (5), two or more R <_1> represents a hydrogen atom, a C1-C10 alkyl group, or an aromatic group each independently. A4 represents 1-3. A4 + 1 represents 1-4. N3 is an integer. And an average value of 1 <n 3 ≤ 8. Z represents a structure represented by any one of the formulas (2-1) to (2-11).

Preferably, the maleimide resin represented by following formula (4) or the polymaleimide resin represented by said formula (5) is mentioned.

(In formula (4), two or more R <_1> represents a hydrogen atom, a C1-C10 alkyl group, or an aromatic group each independently. A4 represents 1-3. A4 + 1 represents 1-4. N2 is Integer and its average value is 1 <n2≤5.)

As a C1-C10 alkyl group in R <_1> in said Formula (4) and Formula (5), a methyl group, an ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl 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, decyl group, etc. are mentioned. Can be. Especially, a methyl group is preferable.

As an aromatic group in R <_1> in said Formula (4) and Formula (5), aromatic hydrocarbon groups, such as a phenyl group, a biphenyl group, an indenyl group, a naphthyl group, an anthryl group, a fluorenyl group, a pyrenyl group, a furanyl group, a tie And a vinyl group, thienothienyl group, pyrrolyl group, imidazolyl group, pyridyl group, pyrazyl group, pyrimidyl group, quinolyl group, indolyl group and carbazolyl group.

In addition, the value of n2 of Formula (4) is an integer, and the average value of <1 n <= 5 is shown. It is preferable that n2 is 1-10, It is more preferable that it is 2-8, It is especially preferable that it is 2-4. In addition, although the value of n2 can be computed from the value of the weight average molecular weight calculated | required by the measurement of the gel permeation chromatography (GPC) of maleimide resin, it is approximate that of n2 computed from the measurement result of GPC of the compound which is a raw material. You can think of it as almost equal to the value.

As the maleimide resin used in the present invention, those having a melting point and a softening point can be used. Especially when it has a melting point, 200 degrees C or less is preferable, and when it has a softening point, it is preferable that it is 150 degrees C or less. If the melting point or softening point is too high, it is not preferable because the possibility of gelation at the time of mixing increases.

These maleimide resins may use a commercially available thing and can also be synthesize | combined by a well-known method. Below, the manufacturing method of maleimide resin represented by the said Formula (4) is demonstrated.

The manufacturing method of the maleimide resin represented by the said Formula (4) is not specifically limited, You may manufacture by any well-known method known as a synthesis | combining method of a maleimide compound.

When manufacturing the polymaleimide resin of Formula (4), although the compound of following formula (6) is needed as the precursor, For example, patent document (Unexamined-Japanese-Patent No. 3-100016) and patent document (Japan) Japanese Patent Application Laid-open No. Hei 8-16151) describes the reaction of aniline with a dihalogenomethyl compound or dialkoxymethyl compound, but by employing such methods, aniline and bishalogenomethylbiphenyl or bis are described. The compound of Formula (6) is obtained by making an alkoxy methyl biphenyl react.

(In formula (6), two or more R <_1> represents a hydrogen atom, a C1-C10 alkyl group, or an aromatic group each independently. A4 represents 1-3. A4 + 1 represents 1-4. N2 is Integer and its average value is 1 <n2≤5.)

The formula (6) in the alkyl group and an aromatic group having 1 to 10 carbon atoms in the R ₁ may be mentioned that each of the formulas (4) and expression, such as one listed as R ₁ in the (5).

Examples of anilines used in the preparation 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 Alkyl substitution which has single or plural alkyl groups of 1 to 5 carbon atoms, such as -sec-butylaniline, 4-tert-butylaniline, 2,6-diethylaniline, 2-isopropyl-6-methylaniline, and 4-pentylaniline Phenyl aniline which has phenyl groups, such as aniline, 2-amino biphenyl, and 4-amino biphenyl, etc. are mentioned. These may be used independently and may use 2 or more types together.

As bishalogenomethyl biphenyls or bisalkoxy methyl biphenyls used, 4,4'-bis (chloromethyl) biphenyl, 4,4'-bis (bromomethyl) biphenyl, 4,4'- Bis (fluoromethyl) biphenyl, 4,4'-bis (iodomethyl) biphenyl, 4,4'-dimethoxymethylbiphenyl, 4,4'-diethoxymethylbiphenyl, 4,4'- Dipropoxymethylbiphenyl, 4,4'-diisopropoxymethylbiphenyl, 4,4'-diisobutoxymethylbiphenyl, 4,4'-dibutoxymethylbiphenyl, 4,4'-di- tert-butoxymethylbiphenyl etc. are mentioned. These may be used independently and may be used together 2 or more types. The usage-amount of bishalogeno methyl biphenyl or bis alkoxy methyl biphenyl is 0.05-0.8 mol with respect to 1 mol of anilines used, Preferably it is 0.1-0.6 mol.

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, and methanesulfonic acid may be used as necessary. 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, with respect to 1 mol of the aniline used, and if it is 0.8 mol or less, the viscosity of the reaction solution does not become too high and stirring is easy, and if it is 0.1 or more, There is no delay in progress.

Reaction may be performed using organic solvents, such as toluene and xylene as needed, or may be performed in a non-solvent. For example, after adding an acidic catalyst to the mixed solution of aniline and a solvent, when a catalyst contains water, water is removed from a system by azeotropy. Thereafter, bishalogenomethylbiphenyls or bisalkoxymethylbiphenyls are added at 40 to 100 ° C, preferably at 50 to 80 ° C, over 1 to 5 hours, preferably 2 to 4 hours, and then The temperature is increased while removing the solvent from the system, and the reaction is carried out at 180 to 240 ° C, preferably at 190 to 220 ° C for 5 to 30 hours, preferably for 10 to 20 hours. After the reaction was completed, the acidic catalyst was neutralized with an aqueous alkali solution, the water-insoluble organic solvent was added to the oil layer, and the water washing was repeated until the waste water became neutral, and the excess aniline or the organic solvent was distilled off under heating and reduced pressure to obtain a formula ( The compound of 6) is obtained. Although not mentioned in Japanese Patent Application Laid-open No. Hei 8-16151 and Japanese Patent No. 5030297, diphenylamine as a by-product at this stage varies depending on the amount of catalyst, raw material use ratio, temperature, time, etc. It contains -10 mass%. Diphenylamine cannot be removed on the conditions which distill off aniline. Diphenylamine can be removed by blowing water vapor under heating and decompression at a temperature of at least the boiling point of aniline or a large amount of inert gas such as nitrogen gas.

When diphenylamine is contained in the maleimide resin composition of the present invention, for example, when used for curing reaction with maleimide resin, the end of the molecular chain becomes an end, and if the content is large, the curing network is not sufficiently formed. There is a possibility that the mechanical strength is significantly reduced. In addition, when diphenylamine is contained in the aromatic amine resin represented by Formula (6), since diphenylamine remains as it is after maleimation and does not contribute to a reaction, it remains in a hardened | cured material as it is, and it bleeds out during long-term use, There is a possibility that the thermal decomposition resistance is lowered. Therefore, the diphenylamine content is usually 1% by mass or less, preferably 0.5% by mass or less, and more preferably 0.2% by mass or less.

65 degreeC or less is preferable and, as for the softening point of the aromatic amine resin represented by said Formula (6), 60 degreeC or less is more preferable. If the softening point is 65 ° C. or less, the viscosity of the maleimidized resin does not increase, and the carbon fiber or glass fiber is easily impregnated. Moreover, when increasing a dilution solvent and decreasing a viscosity, there exists a possibility that resin may not adhere sufficiently.

Although the maleimide resin of the said Formula (4) is obtained by making maleic anhydride react with the compound of the said Formula (6) in presence of a solvent and a catalyst, For example, the patent document (Unexamined-Japanese-Patent No. 3-100016) What is necessary is just to employ | adopt the method etc. which were described in a patent document (Unexamined-Japanese-Patent No. 61-229863).

Since the solvent used in the reaction needs to remove water generated during the reaction from the system, 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, and methyl isobutyl ketone Although ketone solvents, such as cyclopentanone, etc. are mentioned, It is not limited to these, You may use 2 or more types together.

In addition, an aprotic polar solvent may be used in combination with the non-aqueous solvent. For example, dimethyl sulfone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, N-methylpyrrolidone, etc. may be mentioned, You may use 2 or more types together. . When using an aprotic polar solvent, it is preferable to use what has a boiling point higher than the water-insoluble solvent used together.

The catalyst is an acidic catalyst and is not particularly limited. 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 under stirring, and then p-toluenesulfonic acid is added, and water produced under reflux conditions is removed from the system. The reaction is carried out while removing.

In the maleimide resin composition of this invention, it is preferable to contain 5-50 mass% of compounding quantities of maleimide resin with respect to the total amount of resin in the said maleimide resin composition. More preferably, it is 10-50 mass%, Especially preferably, it is 20-50 mass%. In the case of the said range, mechanical property and peeling strength are high in the physical property of hardened | cured material, there exists a tendency for low dielectric loss tangent and high heat resistance.

The maleimide resin composition of the present invention is a compound represented by any one of the compounds represented by the following formula (1) and the following formulas (3-1) to (3-7) (hereinafter only referred to as "metall group-containing compound") At least one of them.

(In formula, R <_2> respectively independently represents a metalyl group or a hydrogen atom. R <_3> respectively independently represents a metalyl group, a hydrogen atom, a C1-C10 alkyl group, or an aromatic group. Z is following formula (2-1) It has a structure represented by any one of-(2-11) a1 represents the integer of 1-4.)

(Wherein, R ₂ has the same meaning as R ₂ in the formula (1). A2 represents an integer of 1~4. A2 + 1 is an integer of 1 to 5. * represents a bonding site.)

(Wherein, R ₂ each independently represents a metalyl group or a hydrogen atom. R ₃ each independently represents a metalyl group, a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aromatic group. A represents —O—,> NR _4. Or -C (R ₄ ) _2- , R ₄ each 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 1 to 3 A3-2 represents an integer of 1 to 2. n1 represents an integer and the average value represents 1 <n1≤5.)

When the metalyl group-containing resin used in the present invention is mixed with a maleimide group, a cured product having lower hygroscopicity and better dielectric properties than an allyl group-containing resin or a propenyl group-containing resin having the same skeleton can be obtained. In addition, unlike the reaction of the epoxy group, since no polar group is generated, an increase in water supply (wet) property due to improvement in heat resistance can be suppressed.

In said Formula (1) and (3-1)-(3-7), it is preferable that 20% or more in R <_3> is a metalyl group in R <_3> . In this case, the mean of the plural molecules of the corresponding compound is meant, not the definition of one molecule unit of the corresponding compound.

The proportion of the metallyl group can be confirmed by an analytical device such as high performance liquid chromatography (HPLC).

As a C1-C10 alkyl group in R <_3> in said Formula (1) and (3-1)-(3-7), a methyl group, an ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso -Butyl 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, furnace And a silyl group and a decyl group. Methyl groups are preferred.

As an aromatic group in R <_3> in said Formula (1) and (3), aromatic hydrocarbon groups, such as a phenyl group, a biphenyl group, an indenyl group, a naphthyl group, an anthryl group, a fluorenyl group, a pyrenyl group, a furanyl group, a thienyl group And thienothienyl group, pyrrolyl group, imidazolyl group, pyridyl group, pyrazyl group, pyrimidyl group, quinolyl group, indolyl group and carbazolyl group.

In addition, the value of a2 and a3 in Formula (1) and Formula (3-1)-(3-7) is an integer, and is 1-4, respectively. In addition, although the value of n1 can be computed from the value of the weight average molecular weight calculated | required by the measurement of the gel permeation chromatography (GPC) of a metalyl group containing compound, it approximately computed from the measurement result of GPC of the compound which is a raw material. It can be considered that it is almost equivalent to the value of n.

As a total amount of chlorine of the said metallyl group containing compound, 500 ppm or less is preferable, More preferably, it is 300 ppm or less, It is preferable that it is especially 100 ppm or less.

It is preferable that the softening point of the said metallyl group containing compound is 120 degrees C or less. If the softening point is 120 ° C. or lower, the compatibility with the solvent is good, and therefore, it is easy to remove salts by washing or the like, and is preferable because there is no fear of corrosion in the field where electrical reliability is required.

In the maleimide resin composition of the present invention, the method for producing the compound represented by the compound represented by the formula (1) or any one of formulas (3-1) to (3-7) is not particularly limited, and the metalyl ether You may manufacture by what is well-known as a synthesis | combining method of a compound. For example, Japanese Patent Application Laid-Open No. 2003-104923 discloses a method for obtaining allyl ether by reacting a polyhydric phenol compound with a base such as an alkali metal hydroxide and allyl halide such as allyl chloride, allyl bromide, and methyl allyl chloride. .

For example, it is obtained by reaction of a phenol resin and a metalryl halide. As a phenol resin used as a raw material, for example, a reactant of phenol and 4,4'-bis (chloromethyl) -1,1'-biphenyl, phenol and 4,4'-bis (methoxymethyl) -1,1 '-Biphenyl reactant, phenol and hydroxybenzaldehyde, phenol and salicylic or parahydroaldehyde, phenol and 1,4'-bischloromethylbenzene, phenol and 1,4'-bisme Although the reactant of oxymethylbenzene, the reactant of phenol and dicyclopentadiene, the reactant of phenol and formaldehyde, and the reactant of cresol and formaldehyde are mentioned, but it is not limited to these.

It is preferable to use the thing with few polymers for the metalyl halide (for example metalyl chloride) used for this invention. For example, metalyl chloride tends to polymerize with each other to become polymetall chloride.

Residual polymetall chloride not only increases the total amount of chlorine, but also contributes to an increase in the molecular weight of the metalyl ether compound, so that a small amount of gel material may remain during commercialization. In addition, in order to reduce the amount of chlorine, addition of a substantial amount of basic substance is required, which is undesirable in industry and produces highly toxic metalyl alcohol in the system.

These polymetall chloride compounds can be easily identified by gas chromatography and the like, and the specific amount thereof is preferably a polymer of 1.0 area% or less with respect to the metalyl chloride monomer in an area ratio thereof, and more preferably 0.5 area%. Hereinafter, More preferably, it is 0.2 area% or less, Especially preferably, it is 0.05 area% or less.

Moreover, as purity of a metalyl chloride, 90 area% or more is preferable, 97 area% or more is more preferable, and 99 area% or more is especially preferable.

The amount of metalyl chloride used is usually 1.0 to 1.15 moles, preferably 1.0 to 1.10 moles, and more preferably 1.0 to 1.05 moles, per 1 mole of hydroxyl groups of the phenol resin (hereinafter, simply referred to as raw phenol resin) as the raw material. .

As a base which can be used when etherifying a metalyl chloride in this invention, an alkali metal hydroxide is preferable, As a specific example, sodium hydroxide, potassium hydroxide, etc. are mentioned, A solid substance may be used and the aqueous solution may be used, Especially in this invention, the use of the solid material shape | molded in flake shape from the surface of solubility and handling is preferable.

The usage-amount of alkali metal hydroxide is 1.0-1.15 mol normally with respect to 1 mol of hydroxyl groups of a raw material phenol resin, Preferably it is 1.0-1.10 mol, More preferably, it is 1.0-1.05 mol.

In order to accelerate the reaction, quaternary ammonium salts such as tetramethylammonium chloride, tetramethylammonium bromide and trimethylbenzylammonium chloride may be added as a catalyst. As the usage-amount of a quaternary ammonium salt, it is 0.1-15 g normally with respect to 1 mol of hydroxyl groups of a raw material phenol mixture, Preferably it is 0.2-10 g.

In this reaction, aprotic polar solvents such as dimethyl sulfoxide (hereinafter referred to as "DMSO"), dimethylformamide, dimethylacetamide, dimethylimidazolidinone and N-methylpyrrolidone are preferable, and dimethyl is particularly preferred. It is preferable to use sulfoxide as a solvent.

As the usage-amount of an aprotic polar solvent, 20-300 mass% is preferable with respect to the gross mass of a phenol resin, More preferably, it is 25-250 mass%, Especially preferably, it is 25-200 mass%. Aprotic polar solvents are not useful for purification, such as washing with water, and are not preferred for use in large quantities. Moreover, since a boiling point is high and it is difficult to remove a solvent, too much energy is consumed, and too much is not preferable.

It is also possible to use another solvent in this reaction. When using, it is preferable to use together C1-C5 alcohol. Examples of the alcohol having 1 to 5 carbon atoms include alcohols such as methanol, ethanol and isopropyl alcohol. Moreover, although non-aqueous solvents, such as methyl ethyl ketone, methyl isobutyl ketone, and toluene, can also be used together, use of 100 mass% or less with respect to dimethyl sulfoxide is preferable. Especially preferably, it is 0.5-50 mass%. Excessive use of non-aqueous solvents such as methyl ethyl ketone, methyl isobutyl ketone, toluene, etc., leads to the rise of the Klyzen transition during the reaction, which results in the formation of new phenolic hydroxyl groups, increasing the metalyl chloride in the system, further increasing the metalyl and metal It may have a product having a aryl 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 increase the reaction temperature by dividing into two or more stages for higher purity etherification. The first step is particularly preferably 35 to 50 ° C, and the second step is 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, the by-products cannot be produced, which is preferable.

Content of the compound which has a metalyl group in the maleimide resin composition of this invention can be suitably set according to the kind of compound to be used, and is not specifically limited. From the viewpoint of the fluidity of the maleimide resin composition and the heat resistance of the cured product obtained by curing this, the content ratio of the compound having a metalyl group is preferably 5 to 30% by mass, more preferably 7 to 25% by mass with respect to the total amount of the composition. desirable. By setting the content ratio of the compound having a metalyl group to 5 to 30% by mass based on the total amount of the composition, comparatively low temperature molding is possible, and a thermosetting resin composition having a viscosity is easily obtained, and a cured product having high heat resistance can be obtained. Tends to be easy.

The maleimide resin composition of this invention may contain a radical polymerization initiator (henceforth only a "catalyst" hereafter) as needed.

Examples of the radical polymerization initiator include benzoin compounds such as benzoin and benzoin methyl, acetophenone compounds such as acetophenone and 2,2'-dimethoxy-2-phenylacetophenone, thioxanthone and 2,4-diethylthione. Bisazides such as thioxanthone-based compounds such as oxaanthone, 4,4'-diazidochalcone, 2,6-bis (4'-azidobenzal) cyclohexanone, and 4,4'-diazidobenzophenone Azo compounds, such as a compound, azobisisobutyronitrile, 2,2'- azobispropane, a hydrazone, 2, 5- dimethyl- 2, 6- di (t-butylperoxy) hexane, 2, 5'- And organic peroxides such as dimethyl-2,5'-di (t-butylperoxy) hexyne-3 and dicumylperoxide.

Content of the radical polymerization initiator in a maleimide resin composition can be suitably set according to the kind of radical polymerization initiator to be used, and is not specifically limited. It is preferable that it is 0.01-5 mass parts with respect to 100 mass parts of maleimide resin compositions from a viewpoint of making a hardening promoting effect and the heat resistance of hardened | cured material compatible, More preferably, it is 0.05-4 mass parts, More preferably, it is 0.1-3 mass parts. to be. If the amount of the radical polymerization initiator is too small, it may cause curing failure. If the amount of the radical polymerization initiator is too large, there is a risk of adversely affecting the curing properties of the resin composition.

The maleimide resin composition of this invention can use together a hardening accelerator other than a radical polymerization initiator as needed. As a curing accelerator which can be used, 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 1-cyano Imidazoles such as ethyl-2-ethyl-4-methylimidazole, triethylamine, triethylenediamine, 2- (dimethylaminomethyl) phenol, 1,8-diaza-bicyclo (5,4,0 Amines such as undecene-7, tris (dimethylaminomethyl) phenol and benzyldimethylamine, phosphines such as triphenylphosphine, tributylphosphine and trioctylphosphine and tin octylate, zinc octylate and dibutyl Organometallic compounds such as tin dimaleate, zinc naphthenate, cobalt naphthenate and tin oleate, and organometallic compounds such as metal chlorides such as zinc chloride, aluminum chloride and tin chloride, and the like, and benzoyl peroxide, dicumyl peroxide and methyl. Organic peroxides such as ethyl ketone peroxide and t-butylperbenzoate. When there are too few hardening accelerators, it will become a cause of a hardening defect, and when there are too many hardening accelerators, it may adversely affect the hardening physical property of a resin composition. Therefore, Preferably it is 0.01-20 mass% with respect to maleimide resin, More preferably, it is 0.01-10 mass%.

You may mix | blend a cyanate ester compound with the maleimide resin composition of this invention. As a cyanate ester compound which can be mix | blended with the maleimide resin composition of this invention, a conventionally well-known cyanate ester compound can be used. Specific examples of the cyanate ester compound include polycondensates of phenols and various aldehydes, polymers of phenols and various diene compounds, polycondensates of phenols and ketones, and polycondensates of bisphenols and various aldehydes with halogenated cyanide. Although a compound is mentioned, It is not limited to these. These may be used independently and may use 2 or more types.

In addition, the cyanate ester compound described in Japanese Patent Laid-Open No. 2005-264154 is particularly preferred as a cyanate ester compound because of its excellent low hygroscopicity, flame retardancy, and dielectric properties.

Moreover, any 1 or more types of a flame retardant, a filler, and an additive can be mix | blended with the maleimide resin composition of this invention as needed.

Although it does not specifically limit as a filler, The filler chosen from metal complex salt, activated carbon, a layered clay mineral, a metal oxide, etc. are mentioned.

As the metal complex salt, a hydrotalcite compound is preferable. The hydrotalcite compound is a compound represented by the general formula [M ²⁺ _1-X M ³⁺ _X (OH) ₂ ] [A ^n- _{X /} nmH ₂ O], and M ²⁺ and M ³⁺ are For divalent and trivalent metal ions, A ^n- _{X / n} represents an interlayer anion. Specifically, representative hydrotalcites are compounds represented as Mg ₆ Al ₂ (OH) ₁₆ CO ₃ · H ₂ O. As a commercial item, the KYOWAAD series by Kyowa Chemical Industry Co., Ltd. is effective. KYOWAAD 500, KYOWAAD 1000, KYOWAAD 700, KYOWAAD 600, KYOWAAD 200, KYOWAAD 2000, etc. are mentioned. In the present invention, a particularly preferable composition is magnesium oxide> aluminum oxide, and magnesium oxide> silicon dioxide in the ratio of magnesium oxide, aluminum oxide, and silicon dioxide. Specifically, KYOWAAD 500 or KYOWAAD 1000 is preferable.

As activated carbon which can be used, chemically activated carbon is preferable. The chemical activated carbon is not particularly limited as long as it has been treated with zinc chloride, phosphoric acid, or the like, but the activated carbon is particularly preferably phosphate activated carbon, since it is likely to introduce chlorine into the product. In addition, depending on the conditions for treating activated carbon obtained by the physical method of making it porous with water vapor, air, carbon dioxide or the like, it may be used in combination with chemically activated activated carbon, and the ratio is at least 50% based on the total amount of activated carbon. The proportion exceeding mass% is preferable.

Examples of the raw material include wood (sawdust, etc.), coal (atan, pit, kohl, etc.), coconut shell, phenol resin, and the like, but in the present invention, wood is particularly preferred. Commercially available products include TAIKO series (series of CG, CW, G, QW, S, ACF, etc.) manufactured by Futamura Chemical Co., Ltd., and HOKUETSU series (SD, BA, F, manufactured by Ajinomoto Fine-Techno Co., Inc.). Series such as ZN, Y-180C, H-10CL, H-8CL, G-10F, CL-K), SHIRASAGI (C, LGK-400, G series, DO series, Wc) made by Japan Enviro Chemicals Co., Ltd. , Sx, WHA etc.), PK series, PKDA series, ELORIT, AZO, DARCO series, HYDRODARCO series, PETRODARCO, GAC, series, GCN, C GRAN, ROW, ROY, ROX, ROB, etc. R, R. EXTRA, SORBNORIT, GF Series, CNR, ROZ, RBAA, RBHG, RZN, RGM, SX, SA, D 10, VETERINAIR, PN, ZN, SA-SW, W, GL, SAM, HB PLUS, EUR RP-20 made by Kuraray Co., Ltd., such as USP, CA, CG, GB, CAP SUPER, CGP SUPER, S-51 series, HDB, HDC, HDR, HDW, GRO SAFE, FM-1, PAC series , YP-17D, and the like.

As the clay mineral, a smectite-based layered clay mineral is preferable, and bentonite, montmorillonite, Weidelite, nontronite, saponite, hectorite, synthetic smectite and the like can be given. As a commercial item, it is Kunimine Industries Co., Ltd. make; SUMECTON (synthetic smectite), bentonite (sodium salt type, calcium salt type), KUNIPIA F (montmorillonite), HOJUN., Co. Ltd .; Bengel series, Bengel W series, Bengel Bright series, Bengel SH, Bengel A, Co-op Chemical Co., Ltd. make; Lucentite series.

Examples of the metal oxides 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 the additive that can be used include curing agents for epoxy resins, polyamide resins, silicone resins, fluorine resins such as polytetrafluoroethylene, acrylic resins such as polymethyl methacrylate, and crosslinked products of benzoguanamine, melamine and formaldehyde. , Polybutadiene and its modified product, modified product of acrylonitrile copolymer, polyphenylene ether, polystyrene, polyethylene, polyimide, fluororesin, maleimide compound, cyanate ester compound, silicone gel, silicone oil, and And coloring agents such as surface treatment agents of inorganic fillers such as silane coupling agents, mold release agents, carbon black, phthalocyanine blue, and phthalocyanine green. The compounding quantity of these additives becomes like this. Preferably it is 1,000 mass parts or less with respect to 100 mass parts of curable resin compositions, More preferably, it is the range of 700 mass parts or less.

Although the preparation method of the maleimide resin composition of this invention is not specifically limited, You may just mix each component uniformly, or may prepolymerize. For example, the metalyl group containing compound and maleimide resin used in this invention are prepolymerized by heating in presence or absence of a catalyst, presence or absence of a solvent. Similarly, the prepolymerization is carried out by adding a metalyl group-containing compound, a maleimide resin, a amine compound, a maleimide compound, a cyanate ester compound, a phenol resin, an acid anhydride compound, and the like, to be used in the present invention. Also good. Mixing or prepolymerization of each component uses an extruder, a kneader, a roll, etc. in absence of a solvent, for example, and uses the reaction tank etc. provided with a stirring apparatus in presence of a solvent.

An organic solvent can be added to the maleimide resin composition of this invention, and it can be set as a varnish-like composition (henceforth only a varnish). 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 and the like according to necessity. As a varnish, the prepreg obtained by impregnating the base material, such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, and heat-drying, was heat-press-molded, and the diameter of the maleimide resin composition of this invention You can do with cargo. The solvent at this time is 10-70 mass% normally in the mixture of the maleimide resin composition of this invention and the said solvent, The quantity which preferably occupies 15-70 mass% is used. Moreover, if it is a liquid composition, the hardened | cured material of the maleimide resin containing carbon fiber can also be obtained as it is, for example by an RTM system.

Moreover, the maleimide resin composition of this invention can also be used as a modifier of a film type composition. Specifically, it can be used when improving the flexibility and the like in the B stage. Such a film-shaped resin composition is obtained as a sheet-like adhesive by applying the maleimide resin composition of the present invention as the maleimide resin composition varnish on a release film, removing the solvent under heating, and then performing B stage formation. . This sheet adhesive can be used as an interlayer insulation layer in a multilayer substrate or the like.

The prepreg of this invention can be obtained by heat-melting the maleimide resin composition of this invention, making it low-viscosity, and impregnating into reinforcing fibers, such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, and alumina fiber.

The prepreg of the present invention can also be obtained by impregnating the varnish with a reinforcing fiber and heating it to dryness.

After the prepreg is cut into a desired mold and laminated with copper foil or the like as necessary, the laminate is heated by curing the maleimide resin composition for laminated plates while applying pressure to the laminate by a press molding method, an autoclave molding method, a sheet winding molding method, or the like. You can get it.

In addition, a circuit is formed on a laminated plate formed by laminating copper foil on the surface, and a prepreg, a copper foil, or the like is superimposed thereon, and the above operation can be repeated to obtain a multilayer circuit board.

By heat-hardening the maleimide resin composition of this invention, hardened | cured material (thermosetting resin molded object) is obtained. The hardening method of a maleimide resin composition is not specifically limited. For example, the said maleimide resin composition is heated at 80 degreeC, it casts between two glass plates release-processed using the spacer of 1.5 mm thickness, the 1st hardening of 170-200 degreeC 2 hours is performed, and a glass plate is thereafter. The hardened | cured material (maleimide resin molded object) can be obtained by removing a primary hardened | cured material from the inside, and hardening after 2 hours at 230-260 degreeC.

The maleimide resin composition of this invention is applicable to various uses, and the use is not specifically limited. In particular, since the maleimide resin composition of the present invention is excellent in heat resistance and strength, handling property, and manufacturing efficiency, it is necessary to use such a performance, for example, a matrix resin for fiber-reinforced composite materials, a sealing agent for electric and electronic parts, and the like. It is particularly useful in the field of.

Example

Next, although an Example demonstrates this invention further more concretely, a part is a "mass part" unless there is particular notice below. In addition, this invention is not limited to these Examples.

Below, the various analysis methods used in the Example are described.

Absorbent: 20% 0.1% hydrogen peroxide

The obtained water supply liquid was measured by ion chromatography.

Hydroxyl equivalent: Based on JIS K0070.

Epoxy equivalent: based on JIS K 7236 (ISO 3001)

Amine equivalent: based on the method described in Annex A of JIS K-7236

Diphenylamine content: measured by gas chromatography

ICI melt viscosity: based on JIS K 7117-2 (ISO 3219)

Softening point: Complies with JIS K 7234

Total chlorine: Complies with JIS K 7243-3 (ISO 21672-3)

Gel Permeation Chromatography (GPC):

Analysis condition

Column (Shodex KF-603, KF-602.5, KF-602, KF-601x2)

The connecting 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 condition

The 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 condition

Column HP-530m × 0.32mm × 0.25㎛

Carrier Gas Helium 1.0mL / min Split 1/50

Injector temperature 300 ℃

Detector temperature 300 ℃

After holding for 5 minutes at 50 ° C in an oven temperature program, the temperature was kept at 300 ° C for 10 minutes as it was at 10 ° C / min from 50 ° C to 300 ° C.

Curing exotherm: measurement of curing start temperature, curing exothermic peak top temperature and exothermic end temperature by MDSC measurement

Analysis condition

Analysis Mode: MDSC Measurement

Meter: Made in Q2000 TA Instruments

Temperature rise rate: 3 ℃ / min

Synthesis Example 1

In a flask equipped with a stirrer, a reflux condenser, and a stirring device, 720 parts by mass of dimethyl sulfoxide, 510 parts by mass of bisphenol A (hydroxyl equivalent (120 g / eq. Softening point: 65 ° C), metalyl chloride (99% of purity, Junsei Chemical Co. , Ltd.) 486 mass parts (1.1 mol equivalent with respect to 1 mol equivalent of hydroxyl groups of a phenol resin) were added, and it heated up at 27 degreeC, and was made to melt | dissolve. Subsequently, 134 mass parts of 46.3 mass% sodium hydroxide aqueous solution is added slowly, so that it may not exceed 35 degreeC of internal temperature, and then 70.0 mass parts of flake-shaped caustic soda (99% of purity, manufactured by Tosoh Corporation) (with respect to 1 mol equivalent of hydroxyl groups of a phenol resin) 1.1 molar equivalents) was added over 60 minutes. The reaction was carried out as it is for 4 hours at 30 to 35 ° C, for 1 hour at 40 to 45 ° C, and for 1 hour at 55 to 60 ° C.

After completion | finish of reaction, water, dimethyl sulfoxide, etc. were distilled off by the rotary evaporator. Then, 30 parts by mass of acetic acid (purity 99.5%, manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added to neutralize, 700 parts by mass of methyl isobutyl ketone was added, and water washing was repeated to confirm that the aqueous layer became neutral. Thereafter, 750 parts by mass of a compound having a metallyl group (hereinafter, referred to as "MEP1") were obtained by distilling off the solvents while bubbling nitrogen under reduced pressure using a rotary evaporator from the oil layer.

Synthesis Example 2

720 mass parts of dimethyl sulfoxide, 330 mass parts of phenol resins (tetramethylbiphenol hydroxyl group equivalent 122g / eq.), Metalyl chloride (99% of purity, Tokyo Kasei Kogyo) to the flask equipped with a stirrer, a reflux condenser, and a stirring apparatus. Co., Ltd.) 300 mass parts (1.1 mol equivalent with respect to 1 mol equivalent of hydroxyl groups of a phenol resin) were added, and it heated up at 27 degreeC, and was made to melt | dissolve. Subsequently, 134 mass parts of 46.3 mass% sodium hydroxide aqueous solution is added slowly, so that it may not exceed 35 degreeC of internal temperature, and then 70.0 mass parts of flake-shaped caustic soda (99% of purity, manufactured by Tosoh Corporation) (with respect to 1 mol equivalent of hydroxyl groups of a phenol resin) 1.1 molar equivalents) was added over 60 minutes. The reaction was carried out as it is for 4 hours at 30 to 35 ° C, for 1 hour at 40 to 45 ° C, and for 1 hour at 55 to 60 ° C.

After completion | finish of reaction, water, dimethyl sulfoxide, etc. were distilled off by the rotary evaporator. Then, 30 parts by mass of acetic acid (purity 99.5%, manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added to neutralize, 700 parts by mass of methyl isobutyl ketone was added, and water washing was repeated to confirm that the aqueous layer became neutral. Thereafter, 470 parts by mass of a compound having a metalyl group (hereinafter, referred to as "MEP2") was obtained by distilling off the solvents while nitrogen bubbling under reduced pressure using a rotary evaporator from the oil layer.

Synthesis Example 3

720 mass parts of dimethyl sulfoxide, phenol resin (phenol-dicyclopentadiene type hydroxyl group equivalent 178g / eq. Softening point 106 degreeC) 535 mass parts, metalyl chloride (purity) to the flask equipped with a stirrer, a reflux condenser, and a stirring apparatus. 99%, Tokyo Kasei Kogyo Co., Ltd.) 272 mass parts (1.1 mol equivalent with respect to 1 mol equivalent of hydroxyl groups of a phenol resin) were added, and it heated up at 27 degreeC, and was made to melt | dissolve. Subsequently, 134 mass parts of 46.3 mass% sodium hydroxide aqueous solution is added slowly, so that it may not exceed 35 degreeC of internal temperature, and then 70.0 mass parts of flake-shaped caustic soda (99% of purity, manufactured by Tosoh Corporation) (with respect to 1 mol equivalent of hydroxyl groups of a phenol resin) 1.1 molar equivalents) was added over 60 minutes. The reaction was carried out as it is for 4 hours at 30 to 35 ° C, for 1 hour at 40 to 45 ° C, and for 1 hour at 55 to 60 ° C.

After completion of the reaction, water, dimethyl sulfoxide, and the like were distilled off under reduced pressure by heating at 120 ° C. or lower with a rotary evaporator. Then, 30 parts by mass of acetic acid (purity 99.5%, manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added to neutralize, 700 parts by mass of methyl isobutyl ketone was added, and water washing was repeated to confirm that the aqueous layer became neutral. Thereafter, 690 parts by mass of a compound having a metalyl group (hereinafter, referred to as "MEP3") were obtained by distilling off the solvents while nitrogen bubbling under reduced pressure using a rotary evaporator from the oil layer.

Synthesis Example 4

720 mass parts of dimethyl sulfoxide, cresol resin OCN-100 degreeC (hydroxyl equivalent 120g / eq. Softening point 105 degreeC, Meiwa Plastic Industries, Ltd.), performing nitrogen purge to the flask provided with the stirrer, the reflux condenser, and the stirring apparatus. Made) 360 parts by mass, metalyl chloride (99% pure, made by Tokyo Kasei Kogyo Co., Ltd.), 299 parts by mass (1.1 molar equivalents to 1 molar equivalent of hydroxyl group of cresol resin) were added, and the temperature was raised to 27 ° C. Dissolved. Subsequently, 132.0 parts by mass of caustic soda (99% pure, manufactured by Tosoh Corporation) (1.1 molar equivalents 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 as it is for 4 hours at 30 to 35 ° C, for 1 hour at 40 to 45 ° C, and for 1 hour at 60 to 65 ° C.

After completion of the reaction, water, dimethyl sulfoxide, and the like were distilled off under reduced pressure by heating at 120 ° C. or lower with a rotary evaporator. And 600 mass parts of methyl isobutyl ketones were added, water washing was repeated, and it was confirmed that the water layer became neutral. Thereafter, 523 parts by mass of a compound having a metalyl group (hereinafter, referred to as "MEP4") were obtained by distilling off the solvents while bubbling nitrogen under reduced pressure using a rotary evaporator from the oil layer.

Synthesis Example 5

720 mass parts of dimethyl sulfoxide, 550PL of phenol novolak resins (hydroxyl equivalent 97g / eq. Softening point 114 degreeC, product made by Meiwa Plastic Industries, Ltd.), performing nitrogen purge to the flask provided with the stirrer, the reflux condenser, and the stirring apparatus. ) 291 parts by mass, allyl chloride (99% pure, manufactured by Junsei Chemical Co., Ltd.), 253 parts by mass (1.1 molar equivalents to 1 molar equivalent of hydroxyl group of the phenol novolak resin) were added, and the temperature was raised to 27 ° C. for dissolution. I was. Subsequently, 132.0 parts by mass of caustic soda (99% pure, manufactured by Tosoh Corporation) (1.1 molar equivalents to 1 molar equivalent of hydroxyl group of the phenol novolak resin) and 72 parts by mass of water were added over 60 minutes. The reaction was carried out as it is for 4 hours at 30 to 35 ° C, for 1 hour at 40 to 45 ° C, and for 1 hour at 60 to 65 ° C.

After completion of the reaction, water, dimethyl sulfoxide, and the like were distilled off under reduced pressure by heating at 120 ° C. or lower with a rotary evaporator. And 600 mass parts of methyl isobutyl ketones were added, water washing was repeated, and it was confirmed that the water layer became neutral. Thereafter, 440 parts by mass of a compound having a metalyl group (hereinafter, referred to as "MEP5") were obtained by distilling off the solvents while bubbling nitrogen under reduced pressure using a rotary evaporator from the oil layer.

Synthesis Example 6

720 mass parts of dimethyl sulfoxide, 2-phenyl-3,3 bis (4-hydroxyphenyl) phthalimide (hydroxyl equivalent 201 g / eq. Softening point 65 degreeC) to the flask provided with the stirrer, the reflux condenser, and the stirring apparatus. 590 mass parts and metal yl chloride (99% of purity, Junsei Chemical Co., Ltd.) 420 mass parts (1.1 mol equivalent with respect to 1 mol equivalent of hydroxyl groups of a phenol resin) were added, and it heated up at 27 degreeC and dissolved. Subsequently, 134 mass parts of 46.3 mass% sodium hydroxide aqueous solution is added slowly, so that it may not exceed 35 degreeC of internal temperature, and then 70.0 mass parts of flake-shaped caustic soda (99% of purity, manufactured by Tosoh Corporation) (with respect to 1 mol equivalent of hydroxyl groups of a phenol resin) 1.1 molar equivalents) was added over 60 minutes. The reaction was carried out as it is for 4 hours at 30 to 35 ° C, for 1 hour at 40 to 45 ° C, and for 1 hour at 55 to 60 ° C.

After completion | finish of reaction, water, dimethyl sulfoxide, etc. were distilled off by the rotary evaporator. Then, 30 parts by mass of acetic acid (purity 99.5%, manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added to neutralize, 700 parts by mass of methyl isobutyl ketone was added, and water washing was repeated to confirm that the aqueous layer became neutral. Thereafter, 710 parts by mass of a compound having a metalyl group (hereinafter, referred to as "MEP6") were obtained by distilling off the solvents while bubbling nitrogen under reduced pressure using a rotary evaporator from the oil layer.

Synthesis Example 7

720 parts by mass of dimethyl sulfoxide, 4,4'-1- {4- [2- (4-hydroxyphenyl) propan-2-yl] phenyl} ethane in a flask equipped with a stirrer, a reflux condenser and a stirring device. 370 parts by mass of -1,1-diyl) diphenol (hydroxyl equivalent 150 g / eq) and 420 parts by mass of metalyl chloride (99% pure, manufactured by Junsei Chemical Co., Ltd.) (with respect to 1 molar equivalent of hydroxyl groups of the phenol resin) 1.1 molar equivalent) was added, and it heated up at 27 degreeC and dissolved. Subsequently, 134 mass parts of 46.3 mass% sodium hydroxide aqueous solution is added slowly, so that it may not exceed 35 degreeC of internal temperature, and then to 70.0 mass parts of flake shaped caustic soda (99% of purity, product made by Tosoh Corporation) (1 molar equivalent of hydroxyl group of a phenol resin) Per mole) was added over 60 minutes. The reaction was carried out as it is for 4 hours at 30 to 35 ° C, for 1 hour at 40 to 45 ° C, and for 1 hour at 55 to 60 ° C.

After completion | finish of reaction, water, dimethyl sulfoxide, etc. were distilled off by the rotary evaporator. Then, 30 parts by mass of acetic acid (purity 99.5%, manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added to neutralize, 700 parts by mass of methyl isobutyl ketone was added, and water washing was repeated to confirm that the aqueous layer became neutral. Thereafter, 510 parts by mass of a compound having a metalyl group (hereinafter, referred to as "MEP7") were obtained by distilling off the solvents while bubbling nitrogen under reduced pressure using a rotary evaporator from the oil layer.

Synthesis Example 8

In a flask equipped with a stirrer, a reflux condenser and a stirring device, 720 parts by mass of dimethyl sulfoxide, 510 parts by mass of bisphenol A (hydroxyl equivalent (120 g / eq. Softening point 65 ° C.), allyl chloride (99% of purity, Junsei Chemical Co., Ltd.) 298.8 mass parts (1.1 mol equivalent with respect to 1 mol equivalent of hydroxyl groups of a phenol resin) were added, and it heated up at 27 degreeC, and was made to melt | dissolve. Subsequently, 134 mass parts of 46.3 mass% sodium hydroxide aqueous solution is added slowly, so that it may not exceed 35 degreeC of internal temperature, and then 70.0 mass parts of flake-shaped caustic soda (99% of purity, manufactured by Tosoh Corporation) (with respect to 1 mol equivalent of hydroxyl groups of a phenol resin) 1.1 molar equivalents) was added over 60 minutes. The reaction was carried out as it is for 4 hours at 30 to 35 ° C, for 1 hour at 40 to 45 ° C, and for 1 hour at 55 to 60 ° C.

After completion | finish of reaction, water, dimethyl sulfoxide, etc. were distilled off by the rotary evaporator. Then, 30 parts by mass of acetic acid (purity 99.5%, manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added to neutralize, 700 parts by mass of methyl isobutyl ketone was added, and water washing was repeated to confirm that the aqueous layer became neutral. Thereafter, 750 parts by mass of a compound having an allyl group (hereinafter, referred to as "AEP1") were obtained by distilling off the solvents while bubbling nitrogen under reduced pressure using a rotary evaporator from the oil layer.

Synthesis Example 9

372 parts of aniline and 200 parts of toluene were thrown into the flask with a thermometer, a cooling tube, a Dean Stark azeotropic trap, and a stirrer, and 146 parts of 35% hydrochloric acid were added dropwise at room temperature for 1 hour. After completion | finish of dripping, after cooling and liquid-separating water and toluene azeotropically, only toluene which is an organic layer was returned to the system, and dehydration was performed. Subsequently, 125 parts of 4,4'-bis (chloromethyl) biphenyl were added over 1 hour, maintaining 60-70 degreeC, and reaction was performed further at the same temperature for 2 hours. After completion | finish of reaction, while heating up, toluene was distilled off and system inside was 195-200 degreeC, and reaction was performed at this temperature for 15 hours. Thereafter, 330 parts of a 30% aqueous sodium hydroxide solution was slowly added dropwise while cooling to prevent the system from refluxing violently. Toluene, which had been distilled off at elevated temperature at 80 ° C or lower, was returned to the system and left at 70 ° C to 80 ° C. The separated lower aqueous layer was removed, and water washing of the reaction solution was repeated until the washing solution became neutral. Subsequently, 173 parts of aromatic amine resin (a1) were obtained by distilling excess aniline and toluene from the oil layer under the reduced pressure (200 degreeC, 0.6 KPa) from an oil layer. Diphenylamine in the aromatic amine resin (a1) was 2.0%.

Instead of blowing water vapor under heating and decompression (200 degreeC, 4 KPa), the obtained resin (a1) was dripped again at the water level little by little. As a result, 166 parts of aromatic amine resin (A1) were obtained. The softening point of the obtained aromatic amine resin (A1) was 56 degreeC, melt viscosity was 0.035 Pa.s and diphenylamine was 0.1% or less.

Synthesis Example 10

147 parts of maleic anhydride and 300 parts of toluene were added to a flask equipped with a thermometer, a cooling tube, a Dean Stark azeotropic distillation trap, and a stirrer, and the azeotropically heated water and toluene were cooled and separated. It returned and dehydrated. Next, the resin solution which melt | dissolved 195 parts of aromatic amine resins (A1) obtained by the synthesis example 9 in 195 parts of N-methyl- 2-pyrrolidone was dripped over 1 hour, maintaining system inside at 80-85 degreeC. After completion of the dropwise addition, the reaction was carried out at the same temperature for 2 hours, 3 parts of p-toluenesulfonic acid was added, the condensate and toluene condensed under reflux conditions were cooled and separated, and only toluene, which is an organic layer, was returned to the system for dehydration. The reaction was carried out for 20 hours. 120 parts of toluene was added after completion | finish of reaction, water washing was repeated, p-toluenesulfonic acid and excess maleic anhydride were removed, and it heated and removed water from the system azeotropically. Next, the reaction solution was concentrated to obtain a resin solution containing 70% maleimide resin (hereinafter referred to as "MI1").

Synthesis Example 11

720 parts by mass of dimethyl sulfoxide, 2,2'-diallyl-4,4'-sulfonyldiphenol (TGSH hydroxyl equivalent 263 g / eq. Softening point 65 ° C) in a flask equipped with a stirrer, a reflux condenser and a stirring device. 299 mass parts (1.1 mol equivalent with respect to 1 mol equivalent of hydroxyl groups of a phenol resin) of a mass part and metalyl chloride (99% of purity, product made from Tokyo Kasei Kogyo Co., Ltd.) were added, and it heated up at 27 degreeC and dissolved. Subsequently, 134 mass parts of 46.3 mass% sodium hydroxide aqueous solution is added slowly, so that it may not exceed 35 degreeC of internal temperature, and after that, to 70.0 mass parts of flake shaped caustic soda (99% of purity, manufactured by Tosoh Corporation) (1 mole equivalent of hydroxyl group of a phenol resin) Per mole) was added over 60 minutes. The reaction was carried out as it is for 4 hours at 30 to 35 ° C, for 1 hour at 40 to 45 ° C, and for 1 hour at 55 to 60 ° C.

After completion | finish of reaction, water, dimethyl sulfoxide, etc. were distilled off by the rotary evaporator. Then, 30 parts by mass of acetic acid (purity 99.5%, manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added to neutralize, 700 parts by mass of methyl isobutyl ketone was added, and water washing was repeated to confirm that the aqueous layer became neutral. Thereafter, 630 parts by mass of a compound having a metalyl group (hereinafter, referred to as "MEP8") were obtained by distilling off the solvents while bubbling nitrogen under reduced pressure using a rotary evaporator from the oil layer.

(Example 1)

35 mass parts of compounds (MEP1) which have a metalyl group obtained by the synthesis example 1, and 65 mass parts of maleimide resin (MI1) obtained by the synthesis example 10 are mix | blended, and it stirs uniformly on 150 degreeC conditions, and after that, it is diku at 100 degreeC. 0.5 mass part of milperoxides (catalyst 1, Kayaku Akzo Corporation make) were mix | blended, it stirred, and was made to melt | dissolve uniformly, and the maleimide resin composition of this invention was obtained. This maleimide resin composition was hardened | cured at 200 degreeC * 2 hours and 230 degreeC * 2 hours of hardening conditions, and the hardened | cured material of this invention was obtained. Table 1 shows the measurement results of the physical properties of the cured product.

(Example 2)

38 mass parts of compounds (MEP2) which have a metalyl group obtained by the synthesis example 2, and 62 mass parts of maleimide resin (MI1) obtained by the synthesis example 10 are mix | blended, and it stirs uniformly on 150 degreeC conditions, and after that, it is diku at 100 degreeC. 0.5 mass part of milperoxides (catalyst 1, Kayaku Akzo Corporation make) were mix | blended, it stirred, and was made to melt | dissolve uniformly, and the maleimide resin composition of this invention was obtained. This maleimide resin composition was hardened | cured at 200 degreeC * 2 hours and 230 degreeC * 2 hours of hardening conditions, and the hardened | cured material of this invention was obtained. Table 1 shows the measurement results of the physical properties of the cured product.

(Example 3)

45 mass parts of compounds (MEP3) which have a metalyl group obtained by the synthesis example 3, and 55 mass parts of maleimide resin (MI1) obtained by the synthesis example 10 are mix | blended, and it stirs uniformly on 150 degreeC conditions, and after that, it is diku at 100 degreeC. 0.5 mass part of milperoxides (catalyst 1, Kayaku Akzo Corporation make) were mix | blended, it stirred, and was made to melt | dissolve uniformly, and the maleimide resin composition of this invention was obtained. This maleimide resin composition was hardened | cured at 200 degreeC * 2 hours and 230 degreeC * 2 hours of hardening conditions, and the hardened | cured material of this invention was obtained. Table 1 shows the measurement results of the physical properties of the cured product.

(Example 4)

38 mass parts of compounds (MEP4) which have a metalyl group obtained by the synthesis example 4, and 62 mass parts of maleimide resin (MI1) obtained by the synthesis example 10 are mix | blended, and it stirs uniformly on 150 degreeC conditions, and after that, it is diku at 100 degreeC. 0.5 mass part of milperoxides (catalyst 1, Kayaku Akzo Corporation make) were mix | blended, it stirred, and was made to melt | dissolve uniformly, and the maleimide resin composition of this invention was obtained. This maleimide resin composition was hardened | cured at 200 degreeC * 2 hours and 230 degreeC * 2 hours of hardening conditions, and the hardened | cured material of this invention was obtained. Table 1 shows the measurement results of the physical properties of the cured product.

(Example 5)

35 mass parts of compounds (MEP5) which have a metalyl group obtained by the synthesis example 5, and 65 mass parts of maleimide resin (MI1) obtained by the synthesis example 10 are mix | blended, and it stirs uniformly on 150 degreeC conditions, and after that, it is diku at 100 degreeC. 0.5 mass part of milperoxides (catalyst 1, Kayaku Akzo Corporation make) were mix | blended, and it stirred, and made it melt | dissolve uniformly, and obtained the thermosetting resin composition of this invention. This maleimide resin composition was hardened | cured at 200 degreeC * 2 hours and 230 degreeC * 2 hours of hardening conditions, and the hardened | cured material of this invention was obtained. Table 1 shows the measurement results of the physical properties of the cured product.

(Example 6)

47 mass parts of compounds (MEP6) which have a metalyl group obtained by the synthesis example 6, and 53 mass parts of maleimide resin (MI1) obtained by the synthesis example 10 are mix | blended, and it stirs uniformly on 150 degreeC conditions, and after that, it is diku at 100 degreeC. 0.5 mass part of milperoxides (catalyst 1, Kayaku Akzo Corporation make) were mix | blended, and it stirred, and made it melt | dissolve uniformly, and obtained the thermosetting resin composition of this invention. This maleimide resin composition was hardened | cured at 200 degreeC * 2 hours and 230 degreeC * 2 hours of hardening conditions, and the hardened | cured material of this invention was obtained. 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 metalyl group obtained in Synthesis Example 7 and 61 parts by mass of the maleimide resin (MI1) obtained in Synthesis Example 10 were mixed, stirred uniformly at 150 ° C., and then dicu at 100 ° C. 0.5 mass part of milperoxides (catalyst 1, Kayaku Akzo Corporation make) were mix | blended, it stirred, and was made to melt | dissolve uniformly, and the maleimide resin composition of this invention was obtained. This maleimide resin composition was hardened | cured at 200 degreeC * 2 hours and 230 degreeC * 2 hours of hardening conditions, and the hardened | cured material of this invention was obtained. Table 1 shows the measurement results of the physical properties of the cured product.

(Comparative Example 1)

46 parts by mass of the compound (AEP1) having an allyl group obtained in Synthesis Example 8, a maleimide compound (4,4'-bismaleimide diphenylmethane BMI-1000, manufactured by Daiwa Kasei Industry Co., Ltd., hereinafter referred to as "MI2") Omitted) 54 parts by mass are blended, and the mixture is stirred uniformly at 150 ° C., then 0.5 parts by mass of dicumyl peroxide (catalyst 1, manufactured by Kayaku Akzo Corporation) is blended at 100 ° C., stirred and uniformly dissolved to obtain a comparative example. The maleimide resin composition was obtained. This maleimide resin composition was hardened | cured at 200 degreeC * 2 hours and 230 degreeC * 2 hours of hardening conditions, and the hardened | cured material of the comparative example was obtained. Table 1 shows the measurement results of the physical properties of the cured product.

(Comparative Example 2)

38 weight part of compounds (AEP1) which have an allyl group obtained by the synthesis example 8, and 62 weight part of maleimide resin (MI1) obtained by the synthesis example 10 are mix | blended, and it stirred uniformly on 150 degreeC conditions, and after that, dicumylper at 100 degreeC 0.5 weight part of oxides (catalyst 1, Kayaku Akzo Corporation make) were mix | blended, and it stirred and was made to melt uniformly, and the maleimide resin composition of this invention was obtained. This maleimide resin composition was hardened | cured at 200 degreeC * 2 hours and 230 degreeC * 2 hours of hardening conditions, and the hardened | cured material of this invention was obtained. Table 1 shows the measurement results of the physical properties of the cured product.

<Heat resistance>

Tg: The peak point (tanδMAX) of Tanδ in the DMA measurement was referred to as Tg.

Analysis conditions Dynamic viscoelasticity measuring instrument: The product made by TA Instruments, Q-800 Measurement temperature range: 30 degreeC-350 degreeC Temperature rising rate: 2 degreeC / min The test piece size: It cut out to 5 mm x 50 mm (thickness about 800 micrometers).

Dielectric constant test, Dielectric tangent test

The test was carried out by a cavity resonator perturbation method using a 1 GHz cavity resonator manufactured by KANTO Electronic Application and Development Inc. However, the sample size was 1.7 mm in width x 100 mm in length, and thickness was 1.7 mm and tested.

<Absorption rate>

Absorption rate: 100% of weight increase of the hardened | cured material immersed in 24 * 24h.

It can be confirmed from Table 1 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)

35 mass parts of compounds (MEP1) which have a metalyl group obtained by the synthesis example 1, 65 mass parts of maleimide resin (MI1) obtained by the synthesis example 10, and 100 mass parts of methyl ethyl ketone (MEK) were added, and the varnish was created. After leaving the obtained varnish at 25 ° C x 72 h, the presence or absence of precipitates was confirmed. The results are shown in Table 2.

(Example 9)

55 parts by mass of the compound (MEP1) having a metalyl group obtained in Synthesis Example 1, 45 parts by mass of maleimide resin (BMI-2300, manufactured by Daiwa Kasei Industry Co., Ltd., hereinafter referred to as "MI3"), and 100 parts by mass of MEK The varnish was prepared by adding wealth. After leaving the obtained varnish at 25 ° C x 72 h, the presence or absence of precipitates was confirmed. The results are shown in Table 2.

(Comparative Example 3)

47 mass parts of compounds (MEP1) which have a metalyl group obtained by the synthesis example 1, 53 mass parts of maleimide compounds (MI2), and 100 mass parts of MEK were added, and the varnish was created. After leaving the obtained varnish at 25 ° C x 72 h, the presence or absence of precipitates was confirmed. The results are shown in Table 2.

According to Table 2, in this invention, the composition using the maleimide resin which has N maleimide groups (N is an integer and the average value is larger than 2) uses the maleimide resin which has N maleimide groups with high crystallinity. It can be confirmed that stability is higher as varnish than that.

Although this invention was demonstrated in detail with reference to the specific aspect, it is clear for those skilled in the art for various changes and correction to be possible, without leaving | separating the mind and range of this invention.

In addition, this application is based on the JP Patent application (patent application 2017-090437) of an application on April 28, 2017, The whole is taken in into consideration. Also, all references cited herein are incorporated in their entirety.

(Industrial availability)

The maleimide resin composition of the present invention has electrical properties, particularly low hygroscopicity (low absorption) and heat resistance in the cured product thereof, and thus includes insulating materials for electrical and electronic components, laminates (printed wiring boards, build-up substrates, etc.) and CFRP. It is useful for various composite materials, adhesives, paints and the like.

Claims (7)

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

[Wherein, R _{2 's} each independently represent a metalyl group or a hydrogen atom. R ₃ each independently represents a metalyl 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 following formula (2-1)-(2-11). a1 represents the integer of 1-4.]

[Wherein, R ₂ is Formula (1) of the same meaning as R _2. a2 represents the integer of 1-4. a2 + 1 represents the integer of 1-5. * Indicates a bonding position.]

[Wherein, R _{2 's} each independently represent a metalyl group or a hydrogen atom. R ₃ each independently represents a metalyl group, a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aromatic group. A represents -O-,> NR ₄ or -C (R ₄ ) _2- , and R ₄ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aromatic group. a3 represents the integer of 1-4. a3-1 represents the integer of 1-3. a3-2 represents the integer of 1-2. n1 is an integer whose average value is 1 <n1≤5.] The method of claim 1,
Maleimide resin composition whose said maleimide resin is a structure represented by following formula (4).

[In formula (4), two or more R <_1> represents a hydrogen atom, a C1-C10 alkyl group, or an aromatic group each independently. a4 represents 1-3. n2 is an integer whose average value is 1 <n2≤5.] The method according to claim 1 or 2,
Maleimide resin composition containing a radical polymerization initiator. The method according to any one of claims 1 to 3,
Maleimide resin composition containing any 1 or more types of a flame retardant, a filler, and an additive. The prepreg which hold | maintains the maleimide resin composition of any one of Claims 1-4 in the sheet-like fiber base material, and is in the semi-hardened state. Hardened | cured material of the maleimide resin composition in any one of Claims 1-4. Hardened | cured material of the prepreg of Claim 5.