JPH0625445A - Prepreg resin composition - Google Patents

Abstract

PURPOSE:To obtain a prepreg resin composition improved in heat, impact and water resistances by mixing a specified aromatic polysulfone with a bisphenol epoxy resin, N,N,N',N'-tetraglycidyldiaminodiphenylmethane and diaminodiphenyl sulfone. CONSTITUTION:15-45wt.% aromatic polysulfone comprising at least 50mol% repeating units of formula I and at most 50mol% at least one kind of repeating unite selected from among those of formulas II-XVII and having a reduced viscosity of 0.35-0.6g/dl as measured in dimethylformamide in a concentration of 1g/dl at 30 deg.C is mixed with 5-60wt.% bisphenol epoxy resin and 50-80wt.% N,N,N',N'-tetraglycidyldiaminodiphenylmethane. 0.7-1.3 equivalents (in terms of the amino group), per equivalent of the epoxy groups in the bisphenol epoxy resin, of a diaminodiphenyl sulfone is added to the obtained composition.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a prepreg resin composition having excellent heat resistance, impact resistance and water resistance.

[0002]

2. Description of the Related Art A composite material composed of an epoxy resin and a reinforcing agent such as carbon fiber, glass fiber and aromatic polyamide fiber is a structural material for aircraft etc. by utilizing its high specific strength, specific elastic modulus and specific rigidity. Is used as. However, these composite materials are limited in applications due to insufficient heat resistance, water resistance and impact resistance of epoxy resin,
Performance improvements are desired.

Epoxy resins currently used as structural materials for aircraft and the like are N, N, and N as matrix resins.
Using an aromatic glucidylamine type epoxy resin such as N ′, N′-tetraglycidyldiaminodiphenylmethane,
Diaminodiphenyl sulfone is used as a curing agent. This resin composition is excellent in heat resistance, mechanical properties, dimensional stability, chemical resistance and weather resistance, but has a small elongation and poor impact resistance.

Further, in order to improve the heat resistance of the epoxy resin, a bismaleimide resin, as a matrix resin,
Thermosetting resins such as cyanate ester resins have been studied,
It is being applied to the primary structural materials of aircraft. Although the composite material made from such a thermosetting resin-based prepreg was confirmed to show good performance, on the other hand,
It has been pointed out that the toughness and impact resistance of the composite material are inferior because the elongation rate of the matrix resin is low and it is brittle, and improvement thereof has been demanded. In particular, when these composite materials are used for aircraft primary structural materials, they may be impacted from the outside by jumping up of pebbles during takeoff and landing, dropping of tools during maintenance, etc. First, it is necessary to improve impact resistance, but this has been an important issue that is difficult to solve.

As a means for improving the toughness of the resin composition for prepreg, a method of mixing a rubber component with a thermosetting resin has been attempted, but its blending amount is lowered because heat resistance and mechanical properties are deteriorated. It is regulated, and depending on the application, it remains at a low compounding amount and does not give a sufficient modifying effect.

As a method for preventing the deterioration of heat resistance and imparting impact resistance, a method of blending a thermosetting resin with a thermoplastic resin has been proposed (Japanese Patent Laid-Open No. 63-2121339).
63-54418). However, the performance required for recent prepregs is not sufficiently satisfied.

Further, as means for improving the heat resistance, water resistance and impact resistance of the epoxy resin, for example, Japanese Patent Publication No.
As disclosed in Japanese Patent No. 3-60056, a method has been proposed in which polyethersulfone is added to an epoxy resin and mixed to improve the impact resistance of the composite material. However, in order to obtain sufficient impact resistance, it is necessary to add a large amount of polyether sulfone, and as a result, the melt viscosity and the solution viscosity when dissolved in a solvent increase, and the processability of the prepreg decreases. There was a drawback. At the same time, the recent demands for heat resistance and impact resistance are becoming more and more stringent, and the applications that cannot be met by the existing technology are increasing.

[0008]

DISCLOSURE OF THE INVENTION The present invention is to solve the above-mentioned conventional problems, and an object thereof is to:
It is intended to provide a resin composition for prepreg excellent in heat resistance, impact resistance and water resistance.

[0009]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that heat resistance is improved by blending a specific aromatic polysulfone with a thermosetting resin for prepreg. It was found that the impact resistance and water resistance can be improved, and the present invention has been completed.

The first resin composition for prepreg of the present invention has at least 50 mol% of repeating units represented by the following formula (I) and at least selected from the group consisting of the following formulas (II) to (XVII). 15-45% by weight of an aromatic polysulfone comprising one or more repeating units of 50 mol% or less, 5-60% by weight of a bisphenol type epoxy resin, and N, N,
A composition consisting of 50 to 80% by weight of N ', N'-tetraglycidyldiaminodiphenylmethane was added in an amount of 0.7 to 10 in terms of amino groups based on 1 equivalent of epoxy groups in the epoxy resin.
1.3 equivalents of diaminodiphenyl sulfone was added, and the reduced viscosity of the aromatic polysulfone was 0.35 to 0.6 dl when measured in dimethylformamide at a concentration of 1 g / dl and a temperature of 30 ° C. / G.

[0011]

[Chemical 7]

[0012]

[Chemical 8]

[0013]

[Chemical 9]

The second resin composition for prepreg of the present invention is a thermosetting resin 30 to 95 containing 10 to 50% by weight of the aromatic polysulfone, a polyfunctional maleimide and a polyfunctional cyanate ester as main components. % By weight and 2 to 60% by weight of an epoxy compound having two or more epoxy groups.

In a preferred embodiment of the first or second prepreg resin composition of the present invention, the aromatic polysulfone has the repeating unit of 50 mol% or more represented by the above formula (I) and the above formula (II). ) The repeating unit represented by 5) to 30 mol% is contained.

The third resin composition for prepreg of the present invention comprises 15 to 45% by weight of an aromatic polysulfone copolymer, 5 to 60% by weight of a bisphenol type epoxy resin, and N, N, N ', N'-tetra. A composition comprising 50 to 80% by weight of glycidyl diaminodiphenylmethane is added with 0.7 to 1.3 equivalents of diaminodiphenylsulfone in terms of amino groups with respect to 1 equivalent of epoxy groups in the above epoxy resin. The polysulfone copolymer has 5 to 3 units corresponding to the monomer represented by the following formula (XVIII).
At a proportion of 0 mol% and with the following formulas (XIX) and (XX)
A total of 70 to 9 constitutional units corresponding to the monomer represented by
When contained in a proportion of 5 mol%, and the reduced viscosity of the aromatic polysulfone copolymer is measured in dimethylformamide at a concentration of 1 g / dl and a temperature of 30 ° C.,
It is 0.35-0.6 dl / g.

[0017]

[Chemical 10]

[0018]

[Chemical 11]

[0019]

[Chemical 12]

(However, in the above formula, n1 represents an integer of 3 or 4, R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a methyl group or a halogen atom, and a to
d is independently an integer of 1 to 4, and X ¹ represents a halogen atom. ) A fourth resin composition for prepregs of the present invention is a thermosetting resin 30-containing mainly 10 to 50% by weight of the aromatic polysulfone copolymer, polyfunctional maleimide and polyfunctional cyanate ester. 95% by weight,
And an epoxy compound having two or more epoxy groups 2
It contains 60% by weight.

Next, the present invention will be described in detail.

First, the first resin composition of the present invention will be described.

The aromatic polysulfone contained in the first resin composition of the present invention has the above formula (I) and the above formula (II).
To (XVII) are copolymers of repeating units.
The aromatic polysulfone copolymer has a repeating unit (I)
It contains 50 mol% or more, but preferably contains 5 to 30 mol% of the repeating unit represented by the above formula (II). By containing the repeating unit (II) in a proportion of 5 to 30 mol%, the heat resistance of the molded product obtained from the resin composition is improved. When the content of the repeating unit (II) exceeds 30 mol%, the melt viscosity is increased and the prepreg processability is deteriorated. The molecular weight of the aromatic polysulfone can be based on the reduced viscosity, and the reduced viscosity is 0.35 to 0.6 dl / g when measured at a concentration of 1 g / dl at 30 ° C. in dimethylformamide. . When the reduced viscosity is less than 0.35 dl / g, the impact resistance of the molded product obtained from the resin composition is lowered, which is not practical. 0.
If it exceeds 6 dl / g, the workability of prepreg deteriorates.

The method for producing the aromatic polysulfone copolymer used in the first resin composition of the present invention is not particularly limited, but is preferably in a polar solvent in the presence of an alkali metal or a metal salt. Then, a nucleophilic substitution polycondensation method of polymerizing a monomer having a hydroxyl group and a halogen group at the terminal is used.

As the above-mentioned alkali metal carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate and the like are preferable, but sodium carbonate or potassium carbonate is particularly preferable. As the polar solvent, sulfone-based solvents such as sulfolane, diphenyl sulfone and dimethyl sulfoxide, or amide-based solvents such as dimethylacetamide and dimethylimidazoline are preferably used.

In the production of the copolymer, the polymerization reaction temperature is usually in the range of 80 to 400 ° C., preferably 100 to 350 ° C., although it varies depending on the reaction raw materials, the types of components, the type of polymerization reaction and the like. It is carried out in. Further, it is preferable to mix the monomers in the polymerization in such a range that the total halogen groups are 90 to 110 mol% with respect to the total hydroxyl groups of the monomers. In order to obtain a polymer having a higher molecular weight, it is preferably used within the range of 95 to 105 mol%.

The bisphenol type epoxy resin contained in the first resin composition of the present invention is a liquid or solid bisphenol A type epoxy resin, for example, commercially available Epicoat 828, 825, 1001 (oiled shell epoxy). Incorporated), DER-331 (manufactured by Dow Chemical Co., Ltd.), or bisphenol F type epoxy resin such as Epicron 830 (manufactured by Dainippon Ink and Chemicals Incorporated), and bromides thereof such as Epiclon 1
52 (manufactured by Dainippon Ink and Chemicals, Inc.) and the like.
These epoxy resins may be used alone or as a mixture of several kinds.

The N, N, N ', N'-tetraglycidyldiaminodiphenylmethane contained in the first resin composition of the present invention is, for example, commercially available ELM4.
34 (manufactured by Sumitomo Chemical Co., Ltd.) and YH434 (manufactured by Tohto Kasei Co., Ltd.) are used.

The first resin composition of the present invention comprises, as described above, 15 to 45% by weight of aromatic polysulfone, preferably 15 to 30% by weight; bisphenol type epoxy resin 5 to
60% by weight; and N, N, N ', N'-tetraglycidylaminodiphenylmethane 50 to 80% by weight, preferably 50 to 70% by weight, based on 1 equivalent of the epoxy group in the epoxy resin. , 0.7 to 1.3 equivalents of diaminodiphenyl sulfone in terms of amino groups are added.

Content of aromatic polysulfone copolymer is 1
If it is less than 5% by weight, the heat resistance, impact resistance and water resistance of the molded product obtained from the resin composition will be lowered, and if it exceeds 45% by weight, the prepreg processability of the resin composition will be lowered. When the content of the bisphenol type epoxy resin in the resin composition is less than 5% by weight, the melt viscosity of the resin composition increases and the prepreg processability decreases. On the other hand, when it exceeds 60% by weight, the heat resistance, impact resistance and water resistance of the molded product obtained from the resin composition are deteriorated. N, N, N ',
When the content of N'-tetraglycidylaminodiphenylmethane is less than 50% by weight, the heat resistance of the molded product obtained from the resin composition decreases, and when it exceeds 80% by weight, the heat resistance increases but the impact resistance increases. descend.

The addition amount of the curing agent, diaminodiphenyl sulfone, contained in the first resin composition of the present invention is theoretically 1 equivalent of amino groups to 1 equivalent of epoxy groups in the above epoxy resin. Although it is the amount to be added, it can be selected in the range of 0.7 to 1.3 equivalents depending on the reaction rate, shelf life and the like. If the added amount deviates from this range, unreacted epoxy groups or amino groups remain after the curing reaction, and heat resistance and water resistance decrease.

The mixing method of each component of the first resin composition of the present invention is not particularly limited, and may be appropriately selected depending on the shape of each component or the mixed state or dispersed state of the intended compound.
The preferred method can be selected. For example, there is a method of forming a uniform solution using a solvent in which each component is dissolved, and the reinforcing fiber can be impregnated with the solution by a conventional method. As another example, an aromatic polysulfone, a bisphenol type epoxy resin, and N, N, N ', N'-tetraglycidyldiaminodiphenylmethane are dissolved and mixed at a relatively high temperature, and then the temperature is lowered to a temperature at which a curing reaction does not occur. A method of adding diaminodiphenyl sulfone is preferably used.

The first resin composition of the present invention provides a fiber reinforced plastic (FRP) prepreg which is particularly excellent in heat resistance, impact resistance and water resistance. As the reinforcing fibers used in the first resin composition of the present invention, carbon fibers,
Examples include glass fiber, aramid fiber, boron fiber, and hybrids thereof. As the shape of the reinforcing fiber, any shape such as a tape arranged in a certain direction, a sheet-shaped material, a mat-shaped material, and a woven fabric can be used. Further, various additives such as a filler, a curing accelerator and a diluent can be used as long as the characteristics are not impaired.

Next, the second resin composition of the present invention will be described.

The aromatic polysulfone contained in the second resin composition of the present invention is the same as the aromatic polysulfone contained in the first resin composition of the present invention.

The polyfunctional maleimides contained in the second resin composition of the present invention are compounds represented by the following general formula (XXI).

[0037]

[Chemical 13]

(In the formula, R ⁵ is 2 or more and 6 or less aromatic or aliphatic organic groups, X ² and X ³ are hydrogen, halogen, or an alkyl group, and n 2 is 2 or more and 6 or less. The maleimides represented by the above formula are obtained by reacting maleic anhydrides with polyamines having 2 to 6 amino groups to prepare maleamic acid, and then by dehydration reaction. . The polyamine used is preferably an aromatic polyamine in terms of heat resistance, but an aliphatic amine may be used when it is desired to impart flexibility or flexibility to the resin. Suitable amines include phenylenediamine, xylylenediamine, cyclohexanediamine, diaminodiphenyl, diaminodiphenylmethane, diaminodiphenyl ether, diaminodiphenyl sulfone and the like. Condensation products of maleimides with these amines can also be used.

The polyfunctional cyanate ester contained in the second resin composition of the present invention is a compound having two or more cyanate ester groups, and suitable cyanate esters are represented by the following general formula: It is a compound represented by (XXII).

[0040]

[Chemical 14]

[0041] (wherein, n3 is 2 or more, 6 is an integer not less than, R ⁶ is an aromatic organic group, the cyanate ester group is attached to the aromatic ring of the organic group R ⁶ .) The cyanates include dicyanate benzene,
Tricyanate benzene, dicyanate naphthalene, tricyanate naphthalene, dicyanate biphenyl, bis (cyanate phenyl) methane, bis (cyanate phenyl) propane, bis (cyanate phenyl) ether, bis (cyanate phenyl) sulfone, And cyanate ester obtained by the reaction of novolac and cyanogen halide. It can also be used as a prepolymer obtained by polymerizing these polyfunctional cyanates in the presence of a catalyst such as Lewis acid, sodium carbonate or salts such as lithium chloride.

Thermosetting resins containing the above-mentioned polyfunctional maleimide and polyfunctional cyanates as main components are known (for example, Japanese Patent Publication No. 52-31279 and Japanese Patent Publication No. 54-30440). Commercially available BT resin (manufactured by Mitsubishi Gas Chemical Co., Inc.) can be used as the resin.

The epoxy compound contained in the second resin composition of the present invention is not particularly limited, but for example, Epicoat 828, Epicoat 1001 (produced by Yuka Shell Epoxy Co., Ltd.), DER-331 (Dow Chemical Japan). Liquid type or solid bisphenol A type epoxy resin such as; ELM434, ELM120 (Sumitomo Chemical Co., Ltd.), YH-434 (Toto Kasei Co., Ltd.), MY-720.
Glycidylamine type epoxy resin such as (manufactured by Ciba Geigy); Bisphenol F type epoxy resin such as Epicron 830 (manufactured by Dainippon Ink and Chemicals); Epicoat 152, Epicoat 154 (manufactured by Yuka Shell Epoxy) Such phenol novolac type epoxy resin;
Brominated bisphenol A type epoxy resin such as Epicron 152 (manufactured by Dainippon Ink and Chemicals, Inc.); ESCN
A cresol novolac type epoxy resin such as -220 (Sumitomo Chemical Co., Ltd.); a bisphenol S type epoxy resin; and an alicyclic epoxy resin.

These epoxy compounds may be used alone or as a mixture of several kinds. However, when the thermoplastic resin is added, the resin viscosity increases, so when the addition amount is large, the low-viscosity liquid Epicoat 82 is used.
A bisphenol A type epoxy resin such as 8 (manufactured by Yuka Shell Epoxy Co., Ltd.); and a bisphenol F type epoxy resin such as Epicron 830 (manufactured by Dainippon Ink and Chemicals, Inc.) are preferably used.

The second resin composition of the present invention comprises, as described above, 10 to 50% by weight of aromatic polysulfone; 30 to 95% by weight of a thermoplastic resin containing polyfunctional maleimide and cyanates as main components. ; And epoxy compound 2-60
%, Preferably 2-49% by weight.

Aromatic polysulfone content of 10% by weight
If it is less than 50% by weight, there is no effect of improving the heat resistance and impact resistance of the molded product obtained from the resin composition, and if it exceeds 50% by weight, the moldability decreases and the performance as a prepreg is impaired. If the content of the thermosetting resin containing polyfunctional maleimide and polyfunctional cyanate ester as the main component is less than 30% by weight or more than 95% by weight, the curing reaction with the epoxy compound becomes insufficient, Both the heat resistance and the impact resistance of the molded product obtained from the resin composition decrease. Similarly, when the content of the epoxy compound is less than 2% by weight or more than 60% by weight, the curing reaction with the thermosetting resin becomes insufficient, and the heat resistance and impact resistance of the molded product obtained from the resin composition are similarly increased. Is reduced. Epoxy compound and thermosetting resin
Although depending on the structure of the epoxy resin, the content of each is preferably in the range of 9: 1 to 2: 8.

The mixing method of each component of the second resin composition of the present invention is not particularly limited, and a preferable method is appropriately selected according to the shape of each component and the mixed state or dispersed state of the intended compound. be able to. For example, there is a method to make a uniform solution using a solvent in which each component is dissolved,
The solution can be impregnated into the reinforcing fibers by a conventional method. As another example, an epoxy compound and an aromatic polysulfone are heated and dissolved without using a solvent, and after mixing, a thermosetting resin containing a polyfunctional maleimide and a polyfunctional cyanate ester as a main component is used. There is a method of adding at a temperature at which the curing reaction does not occur.

The second resin composition of the present invention may contain the same reinforcing fibers and additives as those of the first resin composition of the present invention, and provides a prepreg excellent in heat resistance and impact resistance. obtain.

Next, the third resin composition of the present invention will be described.

The aromatic polysulfone copolymer contained in the third resin composition of the present invention has the general formula (XIII) or (XI
It is a copolymer of monomer units represented by X) and (XX), and is composed of repeating units excluding X ¹ and a hydroxyl group from the general formula, which are linearly linked via an ether bond. The mole fraction of the monomer unit (XIII) is 5 to 30 mol%, preferably 10 to 25 mol%. When the mole fraction is less than 5 mol%, the effect of improving the heat resistance and impact resistance of the molded product obtained from the resin composition is not sufficient, and when it exceeds 30 mol%, the resin composition obtained is The melt viscosity increases, and the processability of the prepreg and the properties of the resin composition deteriorate. The molecular weight of the aromatic polysulfone can be based on the reduced viscosity, and the reduced viscosity is 0.35 to 0.6 dl / g when measured at a concentration of 1 g / dl at 30 ° C. in dimethylformamide. . When the reduced viscosity is less than 0.35 dl / g, the impact resistance of the molded product obtained from the resin composition is lowered, which is not practical.
If it exceeds 0.6 dl / g, the workability of prepreg deteriorates.

Examples of the monomer represented by the above general formula (XVIII) include, for example, 4,4 ′ ″-dihydroxy-p-
Dihydroxy compounds such as terphenyl and 4,4 ″ ′-dihydroxy-p-quaterphenyl are preferably used. In addition, 4,4 ′ ″-dihydroxy-p-quarterphenyl is, for example, Journal of Che.
medical Society 1379-85 (194
It can be synthesized according to the method described in 0).

In the monomer represented by the general formula (XIX), R ¹ and R ² are hydrogen atom, methyl group and halogen atom. The halogen atom is preferably chlorine or bromine. As a preferable compound, a monohalogen monohydroxy sulfone compound represented by the following formula can be exemplified.

[0053]

[Chemical 15]

X ^{1 in the} monomer represented by the general formula (XX)
Examples of the halogen atom represented by are fluorine, chlorine and iodine, with fluorine and chlorine being particularly preferable. R ³ and R ⁴ are each independently a hydrogen atom,
It is a methyl group or a halogen atom. Chlorine or bromine is preferable as the halogen atom. As a preferable compound, a dihalodiphenyl sulfone compound represented by the following formula can be exemplified.

[0055]

[Chemical 16]

The method for producing the aromatic polysulfone copolymer contained in the third resin composition of the present invention is basically the same as the method for producing the aromatic polysulfone contained in the first resin composition. is there.

Contained in the third resin composition of the present invention,
The bisphenol type epoxy resin is the same as the bisphenol type epoxy resin contained in the first resin composition.

The N, N, N ', N'-tetraglycidyldiphenylmethane contained in the third resin composition of the present invention is the same as the N, N, N contained in the first resin composition.
It is the same as N ', N'-tetraglycidyl diphenylmethane.

The third resin composition of the present invention contains, as described above, 15 to 45% by weight, preferably 15 to 30% by weight of aromatic polysulfone; bisphenol type epoxy resin 5 to
60% by weight; and N, N, N ', N'-tetraglycidylaminodiphenylmethane 50 to 80% by weight, preferably 50 to 70% by weight, based on 1 equivalent of the epoxy group in the epoxy resin. 0 in terms of amino groups.
7 to 1.3 equivalents of diaminodiphenyl sulfone are added.

Content of aromatic polysulfone copolymer is 1
If it is less than 5% by weight, the heat resistance, impact resistance and water resistance of the molded product obtained from the resin composition will be lowered, and if it exceeds 45% by weight, the prepreg processability of the resin composition will be lowered. When the content of the bisphenol type epoxy resin in the resin composition is less than 5% by weight, the melt viscosity of the resin composition increases and the prepreg processability decreases. On the other hand, when it exceeds 60% by weight, the heat resistance, impact resistance and water resistance of the molded product obtained from the resin composition are deteriorated. N, N, N ',
When the content of N'-tetraglycidylaminodiphenylmethane is less than 50% by weight, the heat resistance of the molded product obtained from the resin composition decreases, and when it exceeds 80% by weight, the heat resistance increases but the impact resistance increases. descend.

The addition amount of the curing agent, diaminodiphenyl sulfone, contained in the third resin composition of the present invention is 1 amino group to 1 equivalent of epoxy group in the above epoxy resin.
The equivalent amount is the theoretical addition amount, but it can be selected within the range of 0.7 to 1.3 equivalents depending on the reaction rate, shelf life and the like. If the addition amount deviates from this range, unreacted epoxy groups or amino groups remain after the curing reaction, and the heat resistance and water resistance decrease.

The method of mixing the components of the third resin composition of the present invention is the same as the method of mixing the components of the first resin composition of the present invention.

The third resin composition of the present invention may contain the same reinforcing fibers and additives as those of the first resin composition of the present invention, and provides a prepreg excellent in heat resistance, impact resistance and water resistance. Can be provided.

Next, the fourth resin composition of the present invention will be described.

Contained in the fourth resin composition of the present invention,
The aromatic polysulfone copolymer is the same as the aromatic polysulfone copolymer contained in the third resin composition of the present invention.

The polyfunctional maleimide contained in the fourth resin composition of the present invention is the same as the polyfunctional maleimide contained in the second resin composition of the present invention.

Contained in the fourth resin composition of the present invention,
The polyfunctional cyanate ester is the same as the polyfunctional cyanate ester contained in the second resin composition of the present invention.

The epoxy compound contained in the fourth resin composition of the present invention is the same as the epoxy compound contained in the second resin composition of the present invention.

The fourth resin composition of the present invention comprises, as described above, 10 to 50% by weight of an aromatic polysulfone copolymer; a thermoplastic resin 30 containing polyfunctional maleimide and cyanate ester as main components. 95% by weight; and 2 to 60% by weight, preferably 2 to 49% by weight of an epoxy compound.

Aromatic polysulfone content of 10% by weight
If it is less than 50% by weight, there is no effect of improving the heat resistance and impact resistance of the molded product obtained from the resin composition, and if it exceeds 50% by weight, the moldability decreases and the performance as a prepreg is impaired. If the content of the thermosetting resin containing polyfunctional maleimide and polyfunctional cyanate ester as the main component is less than 30% by weight or more than 95% by weight, the curing reaction with the epoxy compound becomes insufficient, Both the heat resistance and the impact resistance of the molded product obtained from the resin composition decrease. Similarly, when the content of the epoxy compound is less than 2% by weight or more than 60% by weight, the curing reaction with the thermosetting resin becomes insufficient, and the heat resistance and impact resistance of the molded product obtained from the resin composition are similarly increased. Is reduced. Epoxy compound and thermosetting resin
Although depending on the structure of the epoxy resin, the content of each is preferably in the range of 9: 1 to 2: 8.

The method of mixing the components of the fourth resin composition of the present invention is the same as the method of mixing the components of the second resin composition of the present invention.

The fourth resin composition of the present invention may contain the same reinforcing fibers and additives as those of the second resin composition of the present invention, and provides a prepreg excellent in heat resistance and impact resistance. obtain.

[0073]

EXAMPLES The present invention will be described below with reference to examples, but these are merely examples and the present invention is not limited thereto.

Example 1 [Production Method of Aromatic Polysulfone (I)] 4-Chloro-4 was placed in a polymerization reaction vessel equipped with a stirrer, a gas introduction tube, a thermometer and a condenser with a receiver at the tip. Then, 100 parts by weight of '-(p-hydroxyphenyl) diphenyl sulfone, 22.1 parts by weight of anhydrous potassium carbonate, and 290 parts by weight of sulfolane were charged, and nitrogen substitution was performed. Next, stirring and temperature increase are started under a nitrogen atmosphere, and the system temperature is maintained at 220 ° C. for 1 hour, 230 ° C. for 30 minutes, and 240 ° C. for 3 hours.
The reaction was carried out. After the reaction is completed, the reaction solution is cooled to room temperature,
The potassium chloride precipitated in the reaction solution was removed by filtration, and the filtrate was poured into a large amount of methanol to precipitate a polymer powder. The reduced viscosity of the obtained polymer was 0.4 dl / g (3
It was 1 g / dl in dimethylformamide at 0 ° C.

[Preparation of prepreg] Aromatic polysulfone (I) was added to bisphenol A type epoxy resin (Epicote 825 (trade name) manufactured by Yuka Shell Epoxy Co., Ltd.), N, N,
N ′, N′-tetraglycidyldiaminodiphenylmethane (ELM434 (trade name) manufactured by Sumitomo Chemical Co., Ltd.) and diaminodiphenylsulfone having the composition shown in Table 1 were dissolved in dimethylformamide to obtain a solution having a concentration of 10% by weight. This solution is applied to a plain weave cloth made of "Torayca" T300 (trade name) manufactured by Toray Industries, Inc. so that the resin content becomes 35%, impregnated, and dried by heating at 150 ° C to obtain a homogeneous prepreg. It was Laminate 24 sheets of this prepreg for 200
It was cured at ² ° C. for 2 hours under a pressure of 8 kg / cm ² to obtain a composite material having a thickness of about 5 mm. Tip R16mm to this composite
The falling weight impact energy of 680 kg · cm / cm (sample thickness) was applied using the weight. The damaged area generated by this impact test was observed. As a heat resistance test, the glass transition temperature of the cured product was measured by TMA. The water absorption rate is 5
A cm × 5 cm test piece was cut and boiled for 20 hours, and the weight change before and after was calculated as the water absorption amount. The results are shown in Table 1.
Shown in. The results of Examples 2 to 15 and Comparative Examples 1 to 9 described later are also shown in Table 1.

(Examples 2 to 5, Comparative Examples 1 and 2) Aromatic polysulfone (I), bisphenol A type epoxy resin (Epicote 825 (trade name) manufactured by Yuka Shell Epoxy Co., Ltd.), N, N, N ', N'-tetraglycidyl diaminodiphenylmethane (ELM434 manufactured by Sumitomo Chemical Co., Ltd.
(Trade name)) and diaminodiphenyl sulfone are shown in Table 1.
A resin composition was prepared in the same manner as in Example 1 except that the resin composition was blended in the composition ratio shown in Table 1, and the same test as in Example 1 was performed.

Example 6 [Production Method of Aromatic Polysulfone (II)] 4-Chloro-4 '
-(P-Hydroxyphenyl) diphenyl sulfone 10
0 parts by weight, 4,4 '''-dihydroxy-p-quarterphenyl 32.8 parts by weight, 4,4'-dichlorodiphenyl sulfone 27.9 parts by weight (the mole fractions of these components are shown in Table 1). Then, 33.0 parts by weight of anhydrous potassium carbonate and 290 parts by weight of sulfolane were polymerized in the same manner as in Example 1 to obtain an aromatic polysulfone. The reduced viscosity of the obtained polymer was 0.40 dl / g (30 ° C., 1 g / dl in dimethylformamide).

[Preparation of prepreg] A resin composition was prepared in the same manner as in Example 1 except that the aromatic polysulfone (II) was used in the composition ratio shown in Table 1, and the same test as in Example 1 was carried out. I went.

(Examples 7 to 10, Comparative Examples 3 and 4) Aromatic polysulfone (II), bisphenol A type epoxy resin (Epicote 825 (trade name) manufactured by Yuka Shell Epoxy Co., Ltd.), N, N, N ', N'-tetraglycidyl diaminodiphenylmethane (ELM434 manufactured by Sumitomo Chemical Co., Ltd.
(Trade name)) and diaminodiphenyl sulfone are shown in Table 1.
A resin composition was prepared in the same manner as in Example 1 except that the resin composition was blended in the composition ratio shown in Table 1, and the same test as in Example 1 was performed.

Example 11 [Production Method of Aromatic Polysulfone (III)] 4-Chloro-
100 parts by weight of 4 '-(p-hydroxyphenyl) diphenyl sulfone, 77.9 parts by weight of 4-chloro-4'-hydroxyphenyl sulfone (the molar fractions of these components are shown in Table 1), anhydrous potassium carbonate 44. 1 part by weight and 290 parts by weight of sulfolane were polymerized in the same manner as in Example 1 to obtain an aromatic polysulfone. The reduced viscosity of the obtained polymer was 0.42 dl / g (30 ° C., 1 g / dl in dimethylformamide).

[Preparation of prepreg] A resin composition was prepared in the same manner as in Example 1 except that the aromatic polysulfone (III) was used in the composition ratio shown in Table 1, and the same test as in Example 1 was carried out. I went.

(Examples 12 to 15, Comparative Examples 5 and 6)
Aromatic polysulfone (III), bisphenol A type epoxy resin (Epicote 825 manufactured by Yuka Shell Epoxy Co., Ltd.
(Trade name)), N, N, N ', N'-tetraglycidyl diaminodiphenylmethane (Sumitomo Chemical Co., Ltd. ELM4
34 (trade name)) and diaminodiphenyl sulfone were mixed in the composition ratios shown in Table 1, a resin composition was prepared in the same manner as in Example 1, and the same test as in Example 1 was performed.

Comparative Examples 7 to 9 As the aromatic polysulfone, Victrex 4100G (trade name) manufactured by ICI was used, and bisphenol A type epoxy resin (Epicote 825 (trade name) manufactured by Yuka Shell Epoxy Co., Ltd.), N, N ,.
A resin composition was prepared in the same manner as in Example 1 except that N ′, N′-tetraglycidyldiaminodiphenylmethane (ELM434 (trade name) manufactured by Sumitomo Chemical Co., Ltd.) and diaminodiphenylsulfone were mixed in the composition ratio shown in Table 1. It was created and the same test as in Example 1 was performed.

[0084]

[Table 1]

A: 4-chloro-4 '-(p-hydroxyphenyl) diphenylsulfone molar fraction B: 4,4 "'-dihydroxy-p-quarterphenyl molar fraction C: 4,4'-dichloro Molar fraction of diphenyl sulfone D: Molar fraction of 4-chloro-4′-hydroxyphenyl sulfone E ₁ : Weight fraction of aromatic polysulfone F ₁ : Bisphenol A type epoxy resin (Epicoat 8
25) Weight fraction G: Weight fraction of N, N, N ', N'-tetraglycidyldiaminodiphenylmethane (ELM434) H: Addition equivalent of diaminodiphenylsulfone in terms of amino group (1 equivalent of epoxy group in epoxy resin) *): The glass transition temperature is measured by TMA manufactured by Seiko Instruments Inc.
And a heating rate of 20 ° C./min by a penetration method.

Example 16 Aromatic Polysulfone (I)
In addition, bisphenol A type epoxy resin (Epicote 828 (trade name) manufactured by Yuka Shell Epoxy Co., Ltd.) and thermosetting resin (BT-2160 (trade name) manufactured by Mitsubishi Gas Chemical Co., Inc.) were used in the composition ratios shown in Table 2 for dimethylformamide To obtain a solution having a concentration of 10% by weight. This solution was applied and impregnated on a plain weave cloth using "Torayca" T300 (trade name) manufactured by Toray Industries, Inc. so that the resin content would be 35%.
It was heated and dried at ℃ to obtain a homogeneous prepreg. Twenty-four layers of this prepreg are laminated, 200 ° C, 2 hours, pressure 8 kg
It was cured under the condition of / cm ² to obtain a composite material having a thickness of about 5 mm. 680 by using the weight of the tip R16mm for this composite material
A falling weight impact energy of kg · cm / cm (sample thickness) was applied. The damaged area generated by this impact test was observed. The glass transition temperature of the cured product is TMA as a heat resistance test.
It was measured by. The results are shown in Table 2. The results of Examples 17 to 30 and Comparative Examples 10 to 18 described later are also shown in Table 2.

(Examples 17 to 20, Comparative Examples 10 and 1)
1) Aromatic polysulfone (I), bisphenol A type epoxy resin (Epicote 828 manufactured by Yuka Shell Epoxy Co., Ltd.
(Trade name) and thermosetting resin (B manufactured by Mitsubishi Gas Chemical Co., Inc.)
A resin composition was prepared in the same manner as in Example 16 except that T-2160 (trade name) was blended in the composition ratio shown in Table 2, and the same test as in Example 16 was performed.

(Examples 21 to 25, Comparative Examples 12 and 1)
3) Aromatic polysulfone (II), bisphenol A type epoxy resin (Epicote 828 manufactured by Yuka Shell Epoxy Co., Ltd.
(Trade name) and thermosetting resin (B manufactured by Mitsubishi Gas Chemical Co., Inc.)
A resin composition was prepared in the same manner as in Example 16 except that T-2160 (trade name) was blended in the composition ratio shown in Table 2, and the same test as in Example 16 was performed.

(Examples 26 to 30, Comparative Examples 14 and 1)
5) Aromatic polysulfone (III), bisphenol A type epoxy resin (Epicote 82 manufactured by Yuka Shell Epoxy Co., Ltd.
8 (trade name)) and a thermosetting resin (BT-2160 (trade name) manufactured by Mitsubishi Gas Chemical Co., Inc.) in the composition ratio shown in Table 2 to prepare a resin composition in the same manner as in Example 16. Then, the same test as in Example 16 was performed.

(Comparative Examples 16 to 18) As an aromatic polysulfone, Victrex 4100G (trade name) manufactured by ICI was used, and bisphenol A type epoxy resin (Epicoat 828 (trade name) manufactured by Yuka Shell Epoxy Co., Ltd.) and thermosetting resin. Example 1 except that (BT-2160 (trade name) manufactured by Mitsubishi Gas Chemical Co., Inc.) was blended in the composition ratio shown in Table 2.
A resin composition was prepared in the same manner as in Example 6, and the same test as in Example 16 was performed.

[0091]

[Table 2]

A: 4-chloro-4 '-(p-hydroxyphenyl) diphenyl sulfone molar fraction B: 4,4'"-dihydroxy-p-quarterphenyl molar fraction C: 4,4'-dichloro Molar Fraction of Diphenyl Sulfone D: Molar Fraction of 4-Chloro-4′-hydroxyphenyl Sulfone E ₁ : Weight Fraction of Aromatic Polysulfone F ₂ : Bisphenol A Epoxy Resin (Epicoat 8
28) Weight fraction I: Weight fraction of thermosetting resin (BT-2160) *: Glass transition temperature is measured by Seiko Denshi TMA
And a heating rate of 20 ° C./min by a penetration method.

Example 31 [Production Method of Aromatic Polysulfone (IV)] 2 equipped with a stirrer, a gas introduction pipe, a thermometer and a condenser with a receiver at the end
In a 00 ml eggplant-shaped flask, 3.39 g (10 mmo) of 4,4 ′ ″-dihydroxy-p-quarterphenyl.
l), 4,4'-dihydroxydiphenyl sulfone 2.
51 g (10 mmol), 4,4'-dichlorodiphenyl sulfone 5.76 g (20 mmol), anhydrous potassium carbonate 2.73 g (20 mmol), diphenyl sulfone 40 g, and toluene 25 ml were charged and nitrogen substitution was carried out. Then, stirring and temperature increase were started in a nitrogen atmosphere,
Toluene was azeotropically distilled at 0 to 170 ° C. to remove water in the system. Approximately 1 hour later, after confirming that distillation stopped, 1 hour at 220 ° C, 30 minutes at 250 ° C, 280
The reaction was carried out at 30 ° C. for 30 minutes and 320 ° C. for 3 hours. After completion of the reaction, the reaction solution was cooled to room temperature, potassium chloride precipitated in the reaction solution was removed by filtration, and the filtrate was poured into a large amount of methanol to precipitate a polymer. The reduced viscosity of the obtained polymer was 0.45 dl / g (30 ° C., 1 g / dl in dimethylformamide).

[Preparation of prepreg] A prepreg was prepared using the aromatic polysulfone (IV) in the same manner as in Example 1, and an impact resistance test, a heat resistance test and a water resistance test were conducted. The results are shown in Table 3. Examples 32 to 4 described below
The results of 0 and Comparative Examples 19 to 25 are also shown in Table 2.

(Examples 32 to 35, Comparative Examples 19 and 2)
0) Aromatic polysulfone (IV), bisphenol A type epoxy resin (Epicote 825 manufactured by Yuka Shell Epoxy Co., Ltd.
(Trade name)), N, N, N ', N'-tetraglycidyl diaminodiphenylmethane (Sumitomo Chemical Co., Ltd. ELM4
34 (trade name)) and diaminodiphenyl sulfone were blended in the composition ratios shown in Table 3, a resin composition was prepared in the same manner as in Example 31, and the same test as in Example 31 was performed.

(Examples 36 to 40, Comparative Examples 21 and 2)
2) Polymerize an aromatic polysulfone copolymer by replacing 4,4 ″ ′-dihydroxy-p-quarterphenyl, 4,4′-dihydroxydiphenylsulfone and 4,4′-dichlorodiphenylsulfone with the composition ratios shown in Table 3. Bisphenol A type epoxy resin (Epicote 825 (trade name) manufactured by Yuka Shell Epoxy Co., Ltd.), N, N, N ', N'-
A resin composition was prepared in the same manner as in Example 31 except that tetraglycidyl diaminodiphenylmethane (ELM434 (trade name) manufactured by Sumitomo Chemical Co., Ltd.) and diaminodiphenyl sulfone were blended in the composition ratios shown in Table 3, and Example 3 was prepared.
The same test as 1 was performed.

Comparative Examples 23 to 25 As the aromatic polysulfone, Victrex 4100G (trade name) manufactured by ICI was used, and bisphenol A type epoxy resin (Epicote 825 (trade name) manufactured by Yuka Shell Epoxy Co., Ltd.), N,
Resin composition in the same manner as in Example 31 except that N, N ′, N′-tetraglycidyldiaminodiphenylmethane (ELM434 (trade name) manufactured by Sumitomo Chemical Co., Ltd.) and diaminodiphenylsulfone were mixed in the composition ratio shown in Table 3. A product was prepared and the same test as in Example 31 was performed.

[0098]

[Table 3]

B: 4,4'-dihydroxy-p-quarterphenyl molar fraction J: 4,4'-dihydroxydiphenyl sulfone molar fraction C: 4,4'-dichlorodiphenyl sulfone molar fraction E ₂ : Weight fraction of aromatic polysulfone F ₁ : Bisphenol A type epoxy resin (Epicoat 8
25) Weight fraction G: Weight fraction of N, N, N ', N'-tetraglycidyldiaminodiphenylmethane (ELM434) H: Addition equivalent of diaminodiphenylsulfone in terms of amino group (1 equivalent of epoxy group in epoxy resin) *): The glass transition temperature is measured by TMA manufactured by Seiko Instruments Inc.
And a heating rate of 20 ° C./min by a penetration method.

(Example 41) Aromatic polysulfone (IV)
Was used to prepare a prepreg in the same manner as in Example 16, and an impact resistance test and a heat resistance test were performed. The results are shown in Table 4. Examples 42 to 50 described below and Comparative Example 2
The results of 6 to 32 are also shown in Table 4.

(Examples 42 to 45, Comparative Examples 26 and 2)
7) Aromatic polysulfone (IV), bisphenol A type epoxy resin (Epicote 828 manufactured by Yuka Shell Epoxy Co., Ltd.
(Trade name) and thermosetting resin (B manufactured by Mitsubishi Gas Chemical Co., Inc.)
A resin composition was prepared in the same manner as in Example 41 except that T-2160 (trade name) was blended in the composition ratio shown in Table 4, and the same test as in Example 41 was performed (Examples 46 to 5).
0, Comparative Examples 28 and 29) 4,4 ′ ″-dihydroxy-p-quarterphenyl, 4,4′-dihydroxydiphenylsulfone and 4,4′-dichlorodiphenylsulfone were replaced by aromatic compounds in place of the composition ratios shown in Table 4. The polysulfone copolymer is polymerized, and a bisphenol A type epoxy resin (Epicote 828 (trade name) manufactured by Yuka Shell Epoxy Co., Ltd.) and a thermosetting resin (BT-2160 (trade name) manufactured by Mitsubishi Gas Chemical Co., Inc.) are shown in Table 4. A resin composition was prepared in the same manner as in Example 41 except that the composition ratios shown were used, and the same tests as in Example 41 were performed.

(Comparative Examples 30 to 32) As an aromatic polysulfone, Victrex 4100G (trade name) manufactured by ICI was used, and a bisphenol A type epoxy resin (Epicote 825 (trade name) manufactured by Yuka Shell Epoxy Co., Ltd.) and a thermosetting resin. Example 4 except that (BT-2160 (trade name) manufactured by Mitsubishi Gas Chemical Co., Inc.) was blended in the composition ratio shown in Table 4.
A resin composition was prepared in the same manner as in Example 1, and the same test as in Example 41 was performed.

[0103]

[Table 4]

B: 4,4 '''-dihydroxy-p-quarterphenyl mole fraction J: 4,4'-dihydroxydiphenyl sulfone mole fraction C: 4,4'-dichlorodiphenyl sulfone mole fraction E ₂ : Weight fraction of aromatic polysulfone F ₂ : Bisphenol A type epoxy resin (Epicoat 8
28) Weight fraction I: Weight fraction of thermosetting resin (BT-2160) *: Glass transition temperature is measured by Seiko Denshi TMA
And a heating rate of 20 ° C./min by a penetration method.

[0105]

The resin composition obtained by the present invention is
It has good heat resistance, impact resistance and water resistance, and is suitable as a resin composition for prepreg.

Claims (5)

[Claims] 1. The repeating unit represented by the following formula (I) is 5
Aromatic polysulfone 15 to 45% by weight consisting of 0 mol% or more and 50 mol% or less of at least one repeating unit selected from the group consisting of the following formulas (II) to (XVII), bisphenol epoxy resin 5 To 60% by weight and 50 to 80% by weight of N, N, N ', N'-tetraglycidyldiaminodiphenylmethane in an amount of 0.7 to 10 in terms of amino groups based on 1 equivalent of epoxy groups in the epoxy resin. A resin composition for prepreg, to which 1.3 equivalents of diaminodiphenyl sulfone is added, wherein the reduced viscosity of the aromatic polysulfone was measured in dimethylformamide at a concentration of 1 g / dl and a temperature of 30 ° C. At this time, it is 0.35-0.6 dl / g and the resin composition for prepregs. [Chemical 1] [Chemical 2] [Chemical 3] 2. The aromatic polysulfone 1 according to claim 1.
Thermosetting resin 30 to 9 containing 0 to 50% by weight of polyfunctional maleimide and polyfunctional cyanate ester as main components
A resin composition for prepreg, containing 5% by weight and 2 to 60% by weight of an epoxy compound having two or more epoxy groups. 3. The resin composition for prepreg according to claim 1 or 2, wherein the aromatic polysulfone has a repeating unit of 50 mol% or more represented by the formula (I), and the formula (II). A resin composition for prepreg containing 5 to 30 mol% of the repeating unit shown. 4. Aromatic polysulfone copolymers 15-45
% By weight, 5-60% by weight of bisphenol type epoxy resin, and 50-80% by weight of N, N, N ', N'-tetraglycidyldiaminodiphenylmethane, relative to 1 equivalent of epoxy group in the epoxy resin. A prepreg resin composition to which 0.7 to 1.3 equivalents of diaminodiphenyl sulfone in terms of amino group is added, wherein the aromatic polysulfone copolymer corresponds to a monomer represented by the following formula (XVIII). The aromatic polysulfone is contained in an amount of 5 to 30 mol%, and a total of 70 to 95 mol% of units corresponding to the monomers represented by the following formulas (XIX) and (XX). The reduced viscosity of the copolymer is 0.35 to 0.6 dl / when measured in dimethylformamide at a concentration of 1 g / dl and a temperature of 30 ° C.
The resin composition for prepreg which is g. [Chemical 4] [Chemical 5] [Chemical 6] (However, in the above formula, n1 represents an integer of 3 or 4,
R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom,
It represents a methyl group or a halogen atom, a to d are each independently an integer of 1 to 4, and X ¹ represents a halogen atom. ) 5. The aromatic polysulfone copolymer according to claim 4, 10 to 50% by weight, a polyfunctional maleimide and a thermosetting resin containing polyfunctional cyanates as main components, 30 to 95% by weight, And a resin composition for prepreg containing 2 to 60% by weight of an epoxy compound having two or more epoxy groups.