TWI648303B - Aromatic amine resin, maleimide resin, curable resin composition and cured product thereof - Google Patents

Abstract

An object of the present invention is to provide an aromatic amine resin having a small content of diphenylamine as a by-product, a maleimide resin derived therefrom, a curable resin composition using the same, and the like A cured product obtained by curing the composition and having excellent heat resistance, low hygroscopicity, low dielectric properties, flame retardancy, and toughness. The aromatic amine resin of the present invention contains a compound represented by the following formula (1) obtained by reacting aniline with a dihalogenated methyl aralkyl derivative or an aralkyl alcohol derivative, and a diphenylamine as a by-product. The content is 1% by weight or less.

(wherein, X represents a substituted or unsubstituted aromatic hydrocarbon group having 6 to 18 carbon atoms; n is an average value, indicating 1≦n≦10)

Description

Aromatic amine resin, maleimide resin, curable resin composition and cured product thereof

The present invention relates to an aromatic amine resin and a maleimide resin derived therefrom, a curable resin composition using the same, and a cured product thereof, which are suitably used for a semiconductor sealing material, a printed wiring substrate, and a build-up layer. Lightweight high-strength materials such as electrical and electronic parts such as laminates or carbon fiber reinforced plastics and glass fiber reinforced plastics.

In recent years, laminated boards equipped with electrical and electronic parts have been required to have a wide range of features and heightened as their use range has expanded. For example, in the prior art, a semiconductor wafer is mounted on a metal lead frame as a mainstream, and a semiconductor wafer having a high processing capability such as a CPU is mounted on a laminated board made of a polymer material. An element such as a CPU has been developed in terms of speed, and the clock frequency has become high, and signal transmission delay or transmission loss has become a problem, and it has become required to have a low dielectric constant and a low dielectric loss tangential to the wiring board. At the same time, as the speed of the components is increased, the heat generation of the wafer is increased, so that heat resistance is also required. In addition, mobile electronic devices such as mobile phones have become popular in recent years, and precision electronic devices have been used in the outdoor environment or in the vicinity of the human body. Therefore, it is necessary to withstand the external environment (especially heat and humidity resistance). Furthermore, in the automotive field, electronic technology is rapidly developing, and there are cases where precision electronic equipment is placed near the engine, and heat resistance and moisture resistance are required at a higher level. On the other hand, since it is used for automotive applications or mobile devices, safety such as flame retardancy has become more important. Due to the increased awareness of environmental problems in recent years, halogen-based flame retardants have been gradually avoided, and halogens have not been used. The demand for flame retardancy has increased.

In the prior art, for example, a wiring board using a BT resin which is a resin of a bisphenol A type cyanate compound and a bis-butylene diimide compound, which is described in Patent Document 1, is used for heat resistance, chemical resistance, electrical properties, and the like. It is excellent and has been widely used as a high-performance wiring board, but it needs to be improved in the case where further high performance is required as described above.

In addition, in recent years, due to the need for energy conservation, aircraft, automobiles, trains, and ships have been moving in a lightweight direction. In the field of transportation, research on the use of previously used metal materials for lightweight and high-strength carbon fiber composites has been conducted. For example, the Boeing 787 is lighter by increasing the ratio of composite materials, greatly improving fuel efficiency. In the automotive field, although only a part of the propeller shaft made of composite material is mounted, the trend of using the composite material to manufacture the vehicle body is also applied to the advanced vehicle.

Previously, bisphenol A diglycidyl ether or tetraglycidyl propyl diamine diphenylmethane using epoxy resin, and diaminodiphenylmethane or diaminodiphenyl as a hardener have been utilized. In order to further promote the weight reduction, composite materials such as enamel must promote the application of composite materials, and thus have become a property that cannot be achieved by conventional resins.

Prior technical literature Patent literature

Patent Document 1: Japanese Patent Publication No. 54-30440

Patent Document 2: Japanese Special Fair 8-16151

Patent Document 3: Japanese Patent No. 5030297

An object of the present invention is to provide an aromatic amine resin having a small content of diphenylamine as a by-product, a maleimide resin derived therefrom, a curable resin composition using the same, and the like A cured product obtained by curing the composition and having excellent heat resistance, low hygroscopicity, low dielectric properties, flame retardancy, and toughness.

The inventors of the present invention have made an effort to solve the above problems, and have completed the present invention.

That is, the present invention provides the following [1] to [7].

[1] An aromatic amine resin comprising a compound represented by the following formula (1) obtained by reacting aniline with a dihalogenated methyl aralkyl derivative or an aralkyl alcohol derivative, as a by-product The content of aniline is 1% by weight or less.

(wherein, X represents a substituted or unsubstituted aromatic hydrocarbon group having 6 to 18 carbon atoms; n is an average value, indicating 1≦n≦10)

[2] The aromatic amine resin according to [1], which comprises a compound represented by the following formula (2) obtained by reacting aniline with a dihalogenated methylbiphenyl derivative or a benzidine derivative, and as a subsidiary The content of the diphenylamine of the product is 1% by weight or less.

(where n is the average value, indicating 1≦n≦10)

[3] The aromatic amine resin according to [1] or [2], which has a softening point of 65 ° C or less.

[4] A maleimide resin obtained by reacting an aromatic amine resin according to any one of [1] to [3] with maleic acid or maleic anhydride. .

[5] The maleimide resin according to [4], wherein the content of the diphenylamine is 1% by weight or less.

[6] A curable resin composition containing at least one of the aromatic amine resin of any one of [1] to [3] and the maleic imide resin of [4] or [5].

[7] A cured product obtained by curing the curable resin composition of [6].

By curing the curable resin composition containing the aromatic amine resin or the maleimide resin of the present invention, it is possible to provide both high heat resistance, low moisture absorption, low dielectric properties, and flame retardancy. A hardened product with excellent toughness. The curable resin composition of the present invention is a material useful for sealing electronic parts, circuit boards, carbon fiber composite materials, and the like.

The aromatic amine resin of the present invention contains the compound represented by the formula (1) or the formula (2), and the content of the by-produced diphenylamine in the production is controlled to 1% by weight or less, preferably 0.5% by weight or less, more preferably It is 0.2% by weight or less.

The method for producing the compound of the formula (1) or the formula (2) is not particularly limited. For example, Japan The reaction of aniline with a dihalogenated methyl aralkyl derivative or an aralkyl alcohol derivative is described in Japanese Patent No. Hei 8-16151 or Japanese Patent No. 5030297, and the aniline is obtained by the same method as the above. The compound of the formula (1) or the formula (2) is obtained by reacting with a bishalogenated methyl aralkyl derivative or an aralkyl alcohol derivative.

The dihalogenated methyl aralkyl derivative or the aralkyl alcohol derivative to be used may, for example, be 1,4-dichloromethylbenzene, 1,3-dichloromethylbenzene or 1,2-dichlorobenzene. Methylbenzene, 1,4-bisbromomethylbenzene, 1,3-dibromomethylbenzene, 1,2-dibromomethylbenzene, 1,4-dimethoxymethylbenzene, 1,3- Dimethoxymethylbenzene, 1,2-dimethoxymethylbenzene, 1,4-diethoxymethylbenzene, 1,3-diethoxymethylbenzene, 1,2-diethyl Oxymethylbenzene, 1,4-dimethylolbenzene, 1,3-dimethylolbenzene, 1,2-dimethylolbenzene, 2,6-dimethylolphthalene, 1,5- Dimethylol naphthalene, 2,6-dimethoxymethylnaphthalene, 1,5-dimethoxymethylnaphthalene, 4,4'-bis(chloromethyl)biphenyl, 4,4'-double (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'-diiso Butoxymethylbiphenyl, 4,4'-dibutoxymethylbiphenyl, 4,4'-di-tertiary butoxymethylbiphenyl, 4,4'-dihydroxymethylbiphenyl, etc. . These may be used alone or in combination of two or more. The amount of the dihalogenated methyl aralkyl derivative or the aralkyl alcohol derivative used is usually 0.05 to 0.8 mol, preferably 0.1 to 0.6 mol, based on the aniline 1 mole used.

In the reaction, an acidic catalyst such as hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, zinc chloride, ferric chloride, aluminum chloride, p-toluenesulfonic acid or methanesulfonic acid may be used as needed. These may be used singly or in combination of two or more. The amount of the catalyst used is usually 0.1 to 0.8 mol, preferably 0.2 to 0.7 mol, relative to the aniline used. If the amount is too large, the viscosity of the reaction solution is too high, and the stirring becomes difficult. If the amount is too small, the reaction proceeds slowly.

The reaction may be carried out by using an organic solvent such as toluene or xylene, or may be carried out without a solvent. For example, when an acidic catalyst is added to a mixed solution of aniline and a solvent, and water is contained in the catalyst, water is removed from the system by azeotropy. Thereafter, a dihalogenated methyl aralkyl derivative or an aralkyl alcohol derivative is added at 40 to 100 ° C, preferably 50 to 80 ° C for 1 to 5 hours, preferably 2 to 4 hours, followed by The solvent is removed from the system while 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 5 to 20 hours. After completion of the reaction, the acidic catalyst was neutralized with an aqueous alkaline solution, and then a water-insoluble organic solvent was added to the oil layer, followed by washing with water until the wastewater became neutral. Japanese Patent Publication No. Hei 8-16151 or Japanese Patent No. 5030297 does not mention that diphenylamine as a by-product differs depending on the amount of catalyst, the ratio of use of raw materials, temperature, time, etc., and is usually in a resin. Contains 2 to 10% by weight. Diphenylamine cannot be removed under conditions in which aniline is distilled off. The diphenylamine can be removed by blowing water vapor under reduced pressure or a large amount of inert gas such as nitrogen gas at a temperature higher than the boiling point of the aniline.

When diphenylamine is contained in the curable resin composition, it is used as a terminal of a molecular chain when it is used for hardening reaction with an epoxy resin, for example, and if it contains a large content, it cannot fully form a hardening net, and mechanical strength is acquired. obviously decased. Further, when the aromatic amine resin contains diphenylamine, the diphenylamine remains directly after the imidization of the maleimide, and does not contribute to the reaction and remains directly in the cured product, so that it will bleed out during long-term use. The thermal decomposition resistance is lowered. Therefore, the content of the diphenylamine is required to be 1% by weight or less, preferably 0.5% by weight or less, and more preferably 0.2% by weight or less.

The softening point of the aromatic amine resin of the present invention is preferably 65 ° C or lower, more preferably 60 ° C or lower. If the softening point is higher than 65 ° C, the viscosity of the maleimide-modified resin becomes higher. It becomes difficult to be immersed in carbon fiber or glass fiber. If the dilution solvent is increased to lower the viscosity, there is a possibility that the resin is insufficiently adhered.

The maleimide resin of the present invention is an aromatic amine containing a compound of the formula (1) or the formula (2) in the presence of a solvent or a catalyst in the presence of maleic acid or maleic anhydride. For example, the method described in JP-A-3-100016 or JP-A-61-229863 may be employed. In this case, since the water formed in the reaction must be removed from the system, the solvent used in the reaction uses a solvent which is not water-soluble. For example, an aromatic solvent such as toluene or xylene, an aliphatic solvent such as cyclohexane or n-hexane, an ether such as diethyl ether or diisopropyl ether, an ester solvent such as ethyl acetate or butyl acetate, or a methyl group may be mentioned. A ketone-based solvent such as butyl ketone or cyclopentanone is not limited thereto, and two or more kinds thereof may be used in combination. Further, in addition to the above water-insoluble solvent, an aprotic polar solvent may be used in combination. For example, dimethyl hydrazine, dimethyl hydrazine, dimethylformamide, dimethyl acetamide, 1,3-dimethyl-2-imidazolidinone, N-methylpyrrolidine A ketone or the like may be used in combination of two or more kinds. In the case of using an aprotic polar solvent, it is preferred to use a solvent having a boiling point higher than that of the non-aqueous solvent to be used in combination. The catalyst is not particularly limited, and examples thereof include acidic catalysts such as p-toluenesulfonic acid, hydroxyp-toluenesulfonic acid, methanesulfonic acid, sulfuric acid, and phosphoric acid.

For example, dissolving maleic acid in toluene, adding an N-methylpyrrolidone solution containing an aromatic amine resin of the compound of the formula (1) or the formula (2) with stirring, and then adding p-toluenesulfonic acid The water generated under reflux conditions is removed from the system for reaction.

The compound which can be cross-linked with the aromatic amine resin which is one of the essential components of the curable resin composition of the present invention has an epoxy group, a maleimide group, an aldehyde group, a ketone group, Anhydride group, isocyanate group, carbonyl group, etc. can be mixed with an aromatic amine resin The compound of the functional group (or structure) of the coupling reaction is not particularly limited.

A compound which can be crosslinked with a maleimide resin which is one of the essential components of the curable resin composition of the present invention, as long as it has an amine group, a cyanate group, a phenolic hydroxyl group, or an alcoholic hydroxyl group. a compound (or structure) of a functional group (or structure) which can be crosslinked with a maleimide resin such as an allyl group, an acryl group, a methacryl group, a vinyl group or a conjugated dienyl group, and is not particularly specific. limited.

Since the amine compound and the maleimide compound are subjected to a crosslinking reaction, the aromatic amine resin of the present invention and the maleimide resin can be used in combination. Since the maleimide resin can also be self-polymerized, it can also be used alone. Further, an amine compound other than the aromatic amine resin of the present invention or a maleic imide compound other than the maleimide resin of the present invention may be used in combination.

The content of the aromatic amine resin or the maleimide resin of the present invention in the curable resin composition of the present invention is usually 10% by weight or more, preferably 15% by weight or more, and more preferably 20% by weight or more. .

As the amine compound which can be blended into the curable resin composition of the present invention, a previously known amine compound can be used. Specific examples of the amine compound include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, m-xylylenediamine, trimethylhexamethylenediamine, 2-methylpentanediamine, and diethylamine. Propylamine, isophoronediamine, 1,3-bis(aminomethyl)cyclohexane, bis(4-aminocyclohexyl)methane, bis(4-amino-3-methylcyclohexyl) Methane, norbornene diamine, 1,2-diaminocyclohexane, diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylphosphonium, dicyandiamide, polyoxypropylene Amine, polyoxypropylene triamine, N-aminoethyl pipe An aniline-formalin resin or the like, but is not limited thereto. These may be used alone or in combination of two or more. The blending amount of the amine compound is preferably 5 times or less, more preferably 2 times or less, in terms of the weight ratio of the aromatic amine resin of the present invention.

As the maleimide compound which can be blended into the curable resin composition of the present invention, a previously known maleimide compound can be used. Specific examples of the maleimide compound include 4,4'-diphenylmethanebis-n-butyleneimine, polyphenylmethane-p-butyleneimine, and inter-phenylene bisexene. Maleimide, 2,2'-bis[4-(4-methyldinimidophenoxy)phenyl]propane, 3,3'-dimethyl-5,5' -diethyl-4,4'-diphenylmethane bis-n-butyleneimine, 4-methyl-1,3-phenylenebissuccinimide, 4,4'-diphenyl Diethylsuccinimide, 4,4'-diphenylfluorene bis-n-butylene imide, 1,3-bis(3-maleoximineiminophenoxy)benzene And 1,3-bis(4-m-butylenediminophenoxy)benzene or the like, but is not limited thereto. These may be used alone or in combination of two or more. The blending amount of the maleimide compound is preferably 5 times or less, more preferably 2 times or less, in terms of a weight ratio of the maleimide resin of the present invention.

In the curable resin composition of the present invention, a cyanate compound can also be formulated.

As the cyanate compound which can be blended into the curable resin composition of the present invention, a previously known cyanate compound can be used. Specific examples of the cyanate ester compound include a polycondensate of a phenol and various aldehydes, a polymer of a phenol and various diene compounds, a polycondensate of a phenol and a ketone, and a bisphenol. A polycondensate of various aldehydes and the like, and a cyanate compound obtained by a reaction with a halogenated cyanide, but is not limited thereto. These may be used alone or in combination of two or more.

Examples of the phenols include phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, and dihydroxynaphthalene.

Examples of the various aldehydes include formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, and cinnamaldehyde.

Examples of the various diene compounds include dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinyl norbornene, tetrahydroanthracene, divinylbenzene, and divinylene. Benzene, diisopropenylbiphenyl, butadiene, isoprene, and the like.

Examples of the ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, and benzophenone.

In addition, the cyanate compound of the synthesis method is excellent in low hygroscopicity, flame retardancy, and dielectric properties, and is particularly preferable as a cyanate compound.

In the curable resin composition of the present invention, an epoxy resin may also be formulated.

As the epoxy resin which can be blended into the curable resin composition of the present invention, any of the previously known epoxy resins can be used. Specific examples of the epoxy resin include polycondensates of phenols and various aldehydes, polymers of phenols and various diene compounds, polycondensates of phenols and ketones, and aggregation of bisphenols and various aldehydes. a propylene oxide-based epoxy resin obtained by epoxidizing a condensate or an alcohol, or 4-vinyl-1-cyclohexene diepoxide or 3,4-epoxycyclohexylmethyl- 3,4'-epoxycyclohexane carboxylate, etc. represented by alicyclic epoxy resin, tetraethoxypropyldiaminediphenylmethane (TGDDM) or trisepoxypropyl-p-amino group The epoxy propylamine epoxy resin, the glycidyl ester epoxy resin, etc. represented by phenol etc. are not limited to these. These may be used alone or in combination of two or more.

Further, a phenol aralkyl resin obtained by subjecting a phenol to a condensation reaction with the above-mentioned bis-halogenated methyl aralkyl derivative or aralkyl alcohol derivative as a raw material is desalted with epichlorohydrin The acid reaction obtained by the acid reaction is excellent in low hygroscopicity, flame retardancy, and dielectric properties, and therefore it is particularly preferable as an epoxy resin.

A phenolic resin can also be formulated in the curable resin composition of the present invention.

As the phenolic resin which can be blended in the curable resin composition of the present invention, any of the previously known phenolic resins can be used. Specific examples of the phenol resin include bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), and phenols (phenol, alkyl-substituted phenol, and aromatic-substituted phenol). , naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzene) Polycondensates of formaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc., phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, Polymers, phenols and derivatives of norbornadiene, vinyl norbornene, tetrahydroanthracene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc. Polycondensates of ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), phenols and aromatic dimethanols (benzene dimethanol, α, α, Polycondensates of α',α'-benzenedimethanol, biphenyldimethanol, α,α,α',α'-biphenyldiethanol, etc., phenols and aromatic dichloromethyls (α,α) '-Dichloroxylene, dichloro Biphenyl group and the like) of the polycondensate, of an aldehyde with a variety of bisphenols polycondensate, and of such quality was modified, but is not limited to such. These may be used alone or in combination of two or more.

Further, the phenol aralkyl resin obtained by subjecting a phenol to a condensation reaction with the above-mentioned bis-halogenated methyl aralkyl derivative or aralkyl alcohol derivative has low hygroscopicity, flame retardancy, and dielectric properties. It is excellent, so it is especially preferable as a phenol resin.

In the curable resin composition of the present invention, a compound having an acid anhydride group can also be formulated.

As the compound having an acid anhydride group which can be blended into the curable resin composition of the present invention, any of the previously known ones can be used. Specific examples of the compound having an acid anhydride group include 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2, 3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, pyrogallic anhydride, 5-(2,5-di-oxytetrahydrofuranyl)- 3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 4-(2,5-di-oxytetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1 , 2-dicarboxylic anhydride, and the like.

The compound having an acid anhydride group may be used singly or in combination of two or more. In addition, when the acid anhydride group is reacted with an amine, it is a proline acid. When it is further heated at 200 to 300 ° C, it is a quinone imine structure by a dehydration reaction, and it is a material excellent in heat resistance.

In the curable resin composition of the present invention, a catalyst for curing (hardening accelerator) may be blended as needed. For example, 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-ethyl Imidazoles such as 4-methylimidazole, triethylamine, triethylenediamine, 2-(dimethylaminomethyl)phenol, 1,8-diazabicyclo[5.4.0]undecene An amine such as -7, tris(dimethylaminomethyl)phenol or benzyldimethylamine; a phosphine such as triphenylphosphine, tributylphosphine or trioctylphosphine; tin octylate, zinc octoate, and Organic metal salts such as dibutyltin maleate, zinc naphthenate, cobalt naphthenate, tin oleate, metal chlorides such as zinc chloride, aluminum chloride, tin chloride, dibutyl butyl peroxide, An organic peroxide such as dicumyl peroxide, an azo compound such as azobisisobutyronitrile or azobisdimethylvaleronitrile, a mineral acid such as hydrochloric acid, sulfuric acid or phosphoric acid, or a Lewis acid such as boron trifluoride. Salts such as sodium carbonate or lithium chloride. The blending amount of the catalyst for curing is preferably 10 parts by weight or less, more preferably 5 parts by weight or less, based on 100 parts by weight of the total of the curable resin composition.

The curable resin composition of the present invention can be prepared by adding an organic solvent. A lacquer-like composition (hereinafter simply referred to as varnish). Examples of the solvent to be used include γ-butyrolactone, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N,N. - a guanamine solvent such as dimethylimidazolidone, an anthraquinone such as tetramethylene hydrazine, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether single ethyl An ether solvent such as an acid ester or propylene glycol monobutyl ether; a ketone solvent such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone or cyclohexanone; or an aromatic solvent such as toluene or xylene. The solvent is used in the obtained varnish, and the concentration of the solid content of the solvent to be removed is usually from 10 to 80% by weight, preferably from 20 to 70% by weight.

Further, in the curable resin composition of the present invention, a known additive may be blended as needed. Specific examples of the additives which can be used include a curing agent for an epoxy resin, a polybutadiene and a modified product thereof, a modified product of an acrylonitrile copolymer, a polyphenylene ether, a polystyrene, a polyethylene, and a polyfluorene. Amine, fluororesin, maleimide compound, cyanate compound, polyoxyxide gel, polyoxygenated oil, and cerium oxide, aluminum oxide, calcium carbonate, quartz powder, aluminum powder, graphite , talc, clay, iron oxide, titanium oxide, aluminum nitride, asbestos, mica, glass powder and other inorganic fillers, surface treatment agents for filling materials such as decane coupling agents, mold release agents, carbon black, phthalocyanine blue, phthalocyanine A coloring agent such as green. The amount of the additives to be added is preferably 1,000 parts by weight or less, and more preferably 700 parts by weight or less based on 100 parts by weight of the curable resin composition.

The method for preparing the curable resin composition of the present invention is not particularly limited, and only the components may be uniformly mixed or may be prepolymerized. For example, the prepolymerization is carried out by heating the maleimide resin and the cyanate compound in the presence or absence of a catalyst, in the presence or absence of a solvent, or in the absence of a solvent. Similarly, the aromatic amine resin of the present invention and/or the maleic imide resin of the present invention may be added with an epoxy resin, an amine compound, or a butene. Prepolymerization is carried out by a diterpene imine compound, a cyanate compound, a phenol resin, an acid anhydride compound, and other additives. For the mixing or prepolymerization of the respective components, for example, an extruder, a kneader, a roll or the like may be used in the absence of a solvent, and a reaction vessel equipped with a stirring device or the like may be used in the presence of a solvent.

The precured resin can be obtained by heat-melting the curable resin composition of the present invention to a low viscosity and impregnating it with reinforcing fibers such as glass fibers, carbon fibers, polyester fibers, polyamide fibers, and alumina fibers. body.

Further, the varnish may be stained in the reinforced fiber and dried by heating to obtain a prepreg.

By cutting the prepreg into a desired shape, if necessary, laminating with a copper foil or the like, and applying pressure to the laminate by press molding, autoclave molding, sheet winding molding, or the like, The curable resin composition is heat-hardened to obtain a laminate (printed wiring board) or a carbon fiber reinforced material for electric and electronic use.

Example

Hereinafter, the present invention will be specifically described by way of examples and comparative examples. In addition, "parts" and "%" in this document mean "parts by weight" and "% by weight", respectively. The softening point and the melt viscosity were measured by the following methods.

. Softening point: measured by the method according to JIS K-7234

. Melt viscosity: viscosity at 150 ° C by cone and plate method

. Diphenylamine content: determined by gas chromatography

Example 1

Installed with thermometer, cooling tube, Dean-Stark azeotropic distillation To the flask of the separator and the mixer, 372 parts of aniline and 200 parts of toluene were added, and 146 parts of 35% hydrochloric acid was added dropwise at room temperature for 1 hour. After the completion of the dropwise addition, the mixture was heated, and the azeotropic water and toluene were cooled and separated, and only the toluene as the organic layer was returned to the system to be dehydrated. Then, 125 parts of 4,4'-bis(chloromethyl)biphenyl was added while being kept at 60 to 70 ° C for 1 hour, and further reacted at the same temperature for 2 hours. After completion of the reaction, toluene was distilled off while raising the temperature, and the inside of the system was set to 195 to 200 ° C, and the reaction was carried out at this temperature for 15 hours. Thereafter, 330 parts of a 30% aqueous sodium hydroxide solution was slowly added dropwise while cooling, and the toluene distilled off at a temperature of 80 ° C or lower was returned to the system at 70 ° C. The mixture was allowed to stand at 80 °C. The aqueous layer of the lower layer was removed, and the reaction liquid was washed successively until the washing liquid became neutral. Then, excess aniline and toluene were removed from the oil layer by heating under reduced pressure (200 ° C, 0.6 KPa) using a rotary evaporator, whereby 173 parts of the aromatic amine resin (a1) was obtained. The diphenylamine in the aromatic amine resin (a1) was 2.0%.

With respect to the obtained resin, a small amount of water was successively dropped by a rotary evaporator under heating and reduced pressure (200 ° C, 4 KPa) instead of water vapor blowing. As a result, 166 parts of the aromatic amine resin (A1) was obtained. The obtained aromatic amine resin (A1) had a softening point of 56 ° C, a melt viscosity of 0.035 Pa·s, and a diphenylamine of 0.1% or less.

Example 2

In the same manner as in the first embodiment, 372 parts of aniline was changed to 457 parts, and the same operation was carried out to obtain 181 parts of an aromatic amine resin (a2). The diphenylamine in the aromatic amine resin (a2) was 3.0%. With respect to the obtained resin, a small amount of water was successively dropped by a rotary evaporator under heating and reduced pressure (200 ° C, 4 KPa) instead of water vapor blowing. As a result, 166 parts of the aromatic amine resin (A2) was obtained. The obtained aromatic amine resin (A2) has a softening point of 53 ° C and a melt viscosity of 0.025 Pa. ‧ S, diphenylamine is 0.1% or less.

Example 3

In the same manner as in the first embodiment, 372 parts of aniline was changed to 186 parts, and the same operation was carried out to obtain 181 parts of an aromatic amine resin (A3). The obtained aromatic amine resin (A3) had a softening point of 64 ° C, a melt viscosity of 0.1 Pa ‧ and a diphenylamine of 0.16%.

Example 4

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 separator, and a stirrer, and heated, and the azeotropic water and toluene were cooled and divided. After the liquid, only the toluene as the organic layer was returned to the system to be dehydrated. Then, while maintaining the temperature in the system at 80 to 85 ° C, 195 parts of the aromatic amine resin (A1) obtained in Example 1 was dissolved in 195 parts of N-methyl-2-pyrrolidone dropwise over 1 hour. The obtained resin solution. After the completion of the dropwise addition, the reaction was carried out for 2 hours at the same temperature, and 3 parts of p-toluenesulfonic acid was added. After the azeotropic condensation water and toluene were cooled under reflux, the mixture was separated, and only the toluene as an organic layer was returned to the system. Inside, the reaction was carried out for 20 hours while dehydrating. After completion of the reaction, 120 parts of toluene was added and washed with water to remove p-toluenesulfonic acid and an excess of maleic anhydride, and the mixture was heated to remove water from the system by azeotropy. Then, the reaction solution was concentrated to obtain a resin solution containing 70% of maleimide resin (M1). The content of diphenylamine in the maleimide resin (M1) is 0.1% or less.

Comparative example 1

In the same manner as in Example 4, the aromatic amine resin (A1) was changed to the aromatic amine resin (a1), and the same operation was carried out to obtain a 70% resin solution of the maleimide resin (m1). . The content of diphenylamine in the maleimide resin (m1) was 1.4%.

Examples 5 to 6 and Comparative Examples 2 to 3

Using the aromatic amine resins (A1) and (a1) obtained in Example 1, various epoxy resins were blended in the ratio (parts by weight) of Table 1, and kneaded by a mixing roll and plated, and then prepared by transfer molding. The resin molded body was cured at 160 ° C for 2 hours, and further cured at 180 ° C for 8 hours. Further, when the composition was liquid at room temperature, each component was heated and melted and mixed in a metal container, directly poured into a mold, cured at 160 ° C for 2 hours, and further cured at 180 ° C for 8 hours. With respect to the physical properties of the cured product thus obtained, the following items were measured, and the results are shown in Table 1.

. Glass transition temperature: The temperature at which tan δ is the maximum value measured by a dynamic viscoelasticity tester.

. Moisture absorption rate: The weight increase rate after 24 hours at 121 ° C / 100%. The test piece was a disk having a diameter of 50 mm and a thickness of 4 mm.

. Izod impact test value: performed in accordance with JIS K7110.

(A1), (a1): the aromatic amine resin synthesized in Example 1.

Example 7 and Comparative Example 4

50 parts of 2,2-bis(4-cyanatephenyl)propane was dissolved in the maleimide resin (M1) obtained in Example 4, and the maleic acid obtained in Comparative Example 1 In 643 parts of the quinone imine resin (m1) solution, pre-reaction was carried out at 130 ° C for 10 hours to obtain a prepolymer. 150 parts of the above epoxy resin (E2) and 2 parts of zinc octoate were added thereto, and uniformly mixed. The solution thus obtained was applied thinly on a glass plate, hardened at 170 ° C for 2 hours, and hardened at 250 ° C for 1 hour. The obtained hardened material was pulverized, and the particle size was concentrated to 42 mesh mesh-on and mesh-pass sifting, each taken in 5 parts, dispersed in 50 parts of ion-exchanged water at 121 ° C A 20-hour autoclave test was performed. Thereafter, the powder was removed, and the results of measuring the conductivity of the extracted water are shown in Table 2.

Example 8 and Comparative Example 5

The aromatic amine resins (A1) and (a1) obtained in Example 1 were blended in the ratio (parts by weight) of Table 3, kneaded by a mixing roll, and plated, and then a resin molded body was prepared by transfer molding. It was hardened at 160 ° C for 2 hours, and further hardened at 180 ° C for 8 hours. With respect to the physical properties of the cured product thus obtained, the following items were measured, and the results are shown in Table 3.

. Flame retardancy test

Determination of flame retardancy: according to UL94. The sample size is set to be 12.5 mm wide by 150 mm long. The test was carried out under the conditions of a thickness of 0.8 mm.

Remnant flame time: total residual flame time of the test piece of 0.8mm

According to Table 1, the glass transition temperature and the Ehrlich impact test value were higher in the examples in which the diphenylamine content was less than that in the comparative example, and it was concluded that the cross-linking network was consolidated. Further, according to Table 2, it is considered that the cured product of the maleimide resin derived from the aromatic amine resin having a small content of diphenylamine is an example, and the conductivity of the extracted water is lower than that of the comparative example. In the case of electrical and electronic parts, it is difficult to cause defects in various use environments. According to Table 3, it is considered that the examples using the aromatic amine resin having a small content of diphenylamine have good flame retardancy and excellent heat decomposition resistance as compared with the comparative examples, and are safer when used for electric or electronic parts and the like. .

The present invention has been described in detail above with reference to the specific embodiments thereof. It is understood that various changes and modifications may be made without departing from the spirit and scope of the invention.

Furthermore, this application is based on a Japanese patent application filed on April 2, 2014 (Day Bento 2014-076160), by reference, uses all of its contents. Further, all references cited herein are incorporated herein by reference in their entirety.

[Industrial availability]

The curable resin composition containing the aromatic amine resin or the maleimide resin of the present invention is cured by heat curing, low hygroscopicity, low dielectric property, and flame retardant. Excellent in properties and toughness, it can be used for electrical and electronic parts such as semiconductor sealing materials, printed wiring boards, and laminated laminates, or lightweight high-strength materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics.

Claims (7)

An aromatic amine resin containing a compound represented by the following formula (1) obtained by reacting aniline with a dihalogenated methyl aralkyl derivative or an aralkyl alcohol derivative, and a diphenylamine content as a by-product 0.5% by weight or less, (wherein, X represents a substituted or unsubstituted aromatic hydrocarbon group having 6 to 18 carbon atoms; n is an average value, and represents 1≦n≦10). The aromatic amine resin according to the first aspect of the patent application contains a compound represented by the following formula (2) obtained by reacting aniline with a dihalogenated methylbiphenyl derivative or a benzidine derivative, as a by-product The content of diphenylamine is 0.5% by weight or less, (where n is the average value, indicating 1≦n≦10). The aromatic amine resin of claim 1 or 2 has a softening point of 65 ° C or less. A maleimide resin obtained by reacting an aromatic amine resin according to any one of claims 1 to 3 with maleic acid or maleic anhydride. For example, the maleimide resin of claim 4, wherein the content of diphenylamine It is 1% by weight or less. A curable resin composition comprising at least one of an aromatic amine resin according to any one of claims 1 to 3 and a maleimide resin of claim 4 or 5. A cured product obtained by hardening a curable resin composition of claim 6 of the patent application.