JPH0496962A - Epoxy resin composition and prepreg consisting thereof - Google Patents

Abstract

PURPOSE:To obtain a resin composition suitable as prepreg of fiber-reinforced composite material having heat resistance and toughness comprising epoxy resin, a specific polyimidesiloxane resin and epoxy hardener. CONSTITUTION:The objective resin composition contains (AP 100 pts.wt. epoxy resin, (B) 10-100 pts.wt. polyimidesiloxane resin having 3000-30000 number- averaged molecular weight composed of repeating units expressed by formula IV and formula V (A is aromatic residue; B is a bifunctional group expressed by formula VI and/or formula VII; C is expressed by formula III) obtained by the imidation reaction of an aromatic diamine, an acid anhydride expressed by formula I and/or formula II (R1 is H or C1-10 alkyl; R2 is H, C1-20 alkyl or OH) with a silicone oligomer having diamine terminal, in which the main chain is expressed by formula III (R3 and R4 are C1-5 alkyl and/or phenyl; R5 is C3-10 carbon chain and/or aromatic group; (n) is 1-60) and (C) necessary amount of epoxy hardener.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to an epoxy resin composition with excellent heat resistance and toughness, and a prepreg from which a composite material with excellent heat resistance and toughness can be obtained. It is.

[Conventional technology]

In general, epoxy resins have excellent properties such as curability, mechanical strength, chemical resistance, and adhesion with reinforcing fibers, and are used in a wide range of applications such as molding, lamination, adhesives, and matrix resins for fiber-reinforced composites. used in the field.

However, thermally cured epoxy resins have the disadvantage of poor toughness and brittleness. In particular, in the field of epoxy resins as matrices for fiber-reinforced composite materials, various compositions have been proposed to improve toughness.

For example, as a method to improve the toughness of epoxy resin,
JP-A-57-21450, JP-A-58-1206
No. 39 describes a method in which a rubbery polymer such as an acrylonitrile-butadiene copolymer is added to an epoxy resin to utilize a so-called sea/island structure in which the rubber phase becomes a separate phase.

Japanese Patent Publication No. 48-5107 describes that impact resistance is improved by a composition in which a polysulfone resin is added to an epoxy resin.

JP-A No. 61-228016 describes a tough thermosetting epoxy resin composition consisting of an epoxy resin and an aromatic oligomer, and describes a continuous phase mainly composed of an aromatic oligomer and an island-shaped phase mainly composed of an epoxy resin. The cured product has a two-phase structure of dispersed discontinuous phases.

Further, JP-A-63-170428 describes a prepreg having a structure in which fine particles made of resin are dispersed on the surface of the prepreg made of an epoxy resin composition and reinforcing fibers. According to this publication, it is stated that when the prepregs are laminated, fine particles are present at the interface of the prepregs, so that the toughness of the laminate is improved.

[Problem to be solved by the invention]

However, JP-A No. 57-21450, JP-A No. 5
Although the toughness of the cured epoxy resin is improved in a system in which a rubbery polymer is added as in Japanese Patent No. 8-120639, the environmental resistance is unsatisfactory, such as the heat resistance being lowered.

Furthermore, as disclosed in Japanese Patent Publication No. 48-5107, in order to exhibit sufficient toughness by adding polysulfone, it is necessary to add a large amount, which reduces the processability of the epoxy resin composition. For example, when making a prepreg for fiber-reinforced composite materials from the resin, it is difficult to impregnate the fiber bundle with the resin because the resin has a high viscosity, and the finished prepreg has poor handling properties such as tackiness and drapability. There's a problem.

The two-phase structure of the composition described in JP-A No. 61-228016 means that the aromatic hydrocarbon oligomer forming the continuous phase is easily dissolved in a solvent, and as a result, the composition has unsatisfactory solvent resistance. It has become a thing. In addition, in such a two-phase separated system, the heat resistance of the cured product is dominated by the phase with a lower glass transition temperature (Tg),
It is not possible to obtain a cured product with high heat resistance.

Furthermore, in JP-A-63-170428, the toughness of the matrix resin itself is not improved, so it cannot be said to be perfect. That is, when a perpendicular impact is applied to the surface of a planar laminate, it exhibits high toughness, but there remains concern about the toughness when the shape of the laminate or the angle of impact changes.

The purpose of the present invention is to solve the above problems and improve mechanical strength.
To provide an epoxy resin composition that provides a cured product with excellent heat resistance and toughness, and a prepreg for fiber-reinforced composite material that becomes a fiber-reinforced composite material with excellent mechanical strength, heat resistance, and toughness. be.

[Means to solve the problem]

As a result of intensive studies to solve the above problems, the present inventors discovered that the above object could be achieved by blending a polyimide siloxane resin with a specific structure into an epoxy resin, leading to the present invention.

That is, the present invention comprises 100 parts by weight of an epoxy resin, the repeating structural units of which are represented by the following formulas (Ia) and (Ib>).
An epoxy resin composition comprising 10 to 100 parts by weight of a polyimidosiloxane resin having a number average molecular weight in the range of 3.000 to 30.000 and a required amount of an epoxy curing agent, and a fiber reinforced composite comprising the epoxy resin composition and reinforcing fibers. This invention relates to prepreg for materials.

(ABsu (Ia) 云C-B+(Ib) (In the above formula, A is an aromatic residue, B is the following formula (n) and /
Alternatively, it is a divalent group represented by formula (I[I), and C is a divalent group represented by formula (IV). )/ (In the above formula, R1 represents hydrogen or an alkyl group having 1 to 10 carbon atoms, and R2 represents hydrogen, an alkyl group having 1 to 20 carbon atoms, or a hydroxyl group.) R1 The epoxy resin used in the present invention has It is a compound having two or more epoxy groups, and the bifunctional type is superior in improving flexibility, while the polyfunctional type having three or more epoxy groups is superior in terms of heat resistance. One or more of these may be used.

Examples of epoxy resins having two epoxy groups in the molecule include dihydric phenols such as bisphenol A, bisphenol F1 bisphenol AD, hydroquinone, and resorcinol, or dihydric phenols derived from halogenated bisphenols such as tetrabromobisphenol A. Glycidyl ether compounds, glycidyl ester compounds derived from aromatic carboxylic acids such as p-oxybenzoic acid, m-oxybenzoic acid, terephthalic acid, and isophthalic acid; 5.
Hydantoin-based epoxy resin derived from 5-dimethylhydantoin etc., 2,2-bis(3゜4-epoxycyclohexyl)propane, 2,2-bis(4-(2,3
-Epoxypropyl)cyclohexyl]propane, vinylcyclohexene dioxide, alicyclic epoxy resins such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and other N, N
-diglycidylaniline, etc., but are not limited to these.

In addition, examples of epoxy resins having three or more epoxy groups per molecule include p-aminephenol, m-aminophenol, 4-amino-m-cresol, 6-amino-m-cresol, and 4,4-diaminodiphenylmethane. , 3,3°-diaminodiphenylmethane, 4,4″
-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1,4-bis(4-aminophenoxy)benzene, ■, 4-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene , ■, 3-bis(3-aminophenoxy)benzene, 2,2-bis(4-aminophenoxyphenyl)propane, p-phenylenediamine, m-phenylenediamine, 2.4-toluenediamine, 2.6-toluene Diamine, p-xylylene diamine, m-xylylene diamine, 1,4-cyclohexane-bis(methylamine)
, l,3-cyclohexane-bis(methylamine), etc., amine-based epoxy resin, phenol, 0-
Novolak epoxy resin derived from novolac resin, which is a reaction product of formaldehyde and phenols such as cresol, m-cresol, and p-cresol, phloroglycine, tris(4-hydroxyphenyl)methane, 1,1,2° 2-tetrakis(4-hydroxyphenyl)ethane, bis[α-(dihydroxyphenyl)-
Glycidyl ether compounds derived from trivalent or higher phenols such as α-methylethyl]benzene, triglycidyl isocyanurate, 2゜4.6-)liglycidyl-5-triazine, or rubbers thereof, urethane-modified compounds etc., but are not limited to these.

To further explain the polyimide siloxane resin of the present invention, A in the above formula (Ia) is a mononuclear or polynuclear divalent aromatic residue, and the aromatic ring has 1 to 5 carbon atoms.
These include substituted and unsubstituted alkyl groups, halogens, alkoxy groups having 1 to 5 carbon atoms, and the like. Specifically, A can include one or more aromatic diamine residues.

Examples of the aromatic amines include 4,4'-diaminodiphenylmethane, 3
, 3°-diaminodiphenylmethane, 4.4°-diaminodiphenyl ether, 3,4'diaminodiphenyl ether, 4,4-diaminodiphenylpropane', 4
．． 4'-diaminodiphenylsulfone, 3,3°
-diaminodiphenylsulfone, 2,4-toluenediamine, 2゜6-toluenediamine, m-phenylenediamine, p-phenylenediamine, benzidine, 4,4
゜Diamino diphenyl sulfide, 3,3'dichloro-4,4゛-diaminodiphenylsulfone, 3,3'
°-dichloro-4,4′-diaminodiphenylpropane, 3,3′-dimethyl-4°4′-diaminodiphenylmethane, 4,4°-methylene-bis-(2,6
-dimethylaniline), 4,4'-methylene-bis-(
2-methyl-6-nitylaniline), 4.4'-methylene-bis-(2,6-dinitylaniline), 3.3'
-dimethoxy-4,4'-diaminobiphenyl, 3
．． 3′-dimethyl-4,4°-diaminobiphenyl, ■
.

3-bis(4-aminophenoxy)benzene, 1゜3-
Bis(3-aminophenoxy)benzene, ■.

4-bis(4-aminophenoxy)benzene, 2゜2-
Bis(4-aminephenoxyphenyl)propane, 4.
4'-bis(4-aminophenoxy)diphenylsulfone, 4,4°-bis(3-aminophenoxy)diphenylsulfone, α,α-bis(4-aminophenyl)-m-diisopropylbenzene, α,α′- Screw (4
-aminophenyl)-p-diisopropylbenzene, α
, α-bis(4-amino-3-methyl)-m-diisopropylbenzene, α, α′-bis(4-amino-3-
methyl)-p-diisopropylbenzene, α, α°-bis(4-amino-3,5-dimethylphenyl)-m-diisopropylbenzene, α.

α′-bis(4-amino-3,5-dimethylphenyl)
-p-diisopropylbenzene, 9,9°-bis(4-
(aminophenyl)fluorene, 3゜3゜-dicarboxy-4,4゛-diaminodiphenylmethane, 2,4゜-
Diaminoanisole, bis(3-aminophenyl)methylphosphine oxide, 3,3'-diaminobenzophenone, 0-toluidine sulfon, 4,4°-methylene-bis-chloroaniline, tetrachlorodiaminodiphenylmethane, m-xylylenediamine , p-xylylenediamine, 4,4゛-diaminostilbene, 5
-amino-1-(4' aminophenyl-1,3,3-
Trimethylindane, 6-amino-1-(4'-aminophenyl)-1,3,3-trimethylindane, 5-amino-6-methyl1-(3'-amino-4'-methylphenyl)-1, 3,3-1-limethylindan, 7
-Amino6-methyl-1-(3'-amino-4'-
Methyl 7A/lz) -1,3,3-trimethylindane, 6-amino-5-methyl~1-(4°-amino-3゛-methylphenyl)-1,3,3-trimethylindane, 6- Amino-two-methyl-1-(4゜amino-
3'-methylphenyl)-1,3,3-trimethylindane, ~10).

Further, C in the above formula (Ib) represents a divalent group of the terminal diamine silicone oligomer represented by the formula (rV), n represents an integer of 1 to 60, and the number average molecular weight of the silicone oligomer is is preferably 220 to 5ooo, especially 60
0 to 4000 is preferred.

The proportion of silicone oligomer in the polyimidesiloxane resin is preferably 3 to 70% by weight of the polyimidesiloxane. More preferably 5 to 30% by weight, still more preferably 5 to 20% by weight. If it is less than 3% by weight, toughness will be poor, and if it exceeds 70% by weight, the glass transition temperature will be lowered, which is not preferable.

The number average molecular weight of the polyimide siloxane resin needs to be in the range of 3.000 to 30.000 in order to simultaneously satisfy handleability and toughness of the resin composition. Furthermore, s, ooo to 20,00
A polymer having a number average molecular weight of 0 is preferable because it provides better handling properties and toughness of the cured product.

In the composition of the present invention, the polyimide siloxane resin is blended in an amount of 10 to 100 parts by weight, preferably 20 to 80 parts by weight, per 100 parts by weight of the epoxy resin. The blending amount is 1
If it is less than 0 parts by weight, sufficient toughness will not be exhibited.

Moreover, if it exceeds 100 parts by weight, the viscosity of the epoxy resin composition becomes too high, resulting in poor handling and processability. In particular, when processing prepregs for fiber-reinforced composite materials, there is a problem that it is difficult to impregnate fibers, and prepregs manufactured by impregnating fibers with epoxy compositions have poor drapability.
Problems arise such as loss of tackiness and difficulty in forming into a predetermined shape.

The production of the polyimide siloxane resin consisting of the repeating structural unit formulas (Ia) and (Ib) used in the present invention is as follows:
The above-mentioned aromatic diamine and formula (V) and/or (VI
) The compound represented by the formula and the terminal diamine silicone oligomer whose main chain structure is represented by (IV) can be synthesized by performing a normal imidization reaction. The molecular weight can be adjusted by adjusting the molar ratio of the ingredients.

The following acid anhydrides can be synthesized by known methods.

[In the formula, R,, R, are the same as above. ]

To illustrate, styrenes represented by the formula (wherein R,, R2 are the same as above) and maleic anhydride are used in a molar ratio of 1.
/2 in the absence of a radical polymerization catalyst and in the presence or absence of a radical polymerization inhibitor.

In the synthesis of the polyimide, formulas (V) and (VI
) The acid anhydride shown in ) and some aromatic tetracarboxylic acid anhydrides may be used in combination. There are no particular limitations on the tetracarboxylic anhydride that is preferably used in combination, and tetracarboxylic anhydrides, which are common raw materials for polyimide, are used.

For example, pyromellitic acid, 3.3', 4゜4゛-
Benzophenonetetracarboxylic acid, 2,3゜6.7-naphthalenetetracarboxylic acid, 3,34.4'-biphenyltetracarboxylic acid, 1,2゜5.6-naphthalenetetracarboxylic acid, 2,2'3.3 °-biphenyltetracarboxylic acid, 3,4°9.10-pyrenetetracarboxylic acid, 2.2-bis(3,4-dicarboxyphenyl)propane, 2.2-bis(4-(2,3-dicarboxyphenyl)propane) carboxyphenoxy)phenyl]propane, 2,2-bis[4-(3
,4-dicarboxyphenoxy)phenyl]propane,
Examples include dianhydrides of tetracarboxylic acids such as bis(3,4-dicarboxyphenoxy)diphenylsulfone and 1,4-bis(2,3-dicarboxyphenoxy)benzene, and one or more of these can be used.

The epoxy resin containing the polyimidosiloxane resin of the present invention further requires an epoxy curing agent.

Examples of the epoxy curing agent include amine curing agents such as the above-mentioned aromatic amines and aliphatic amines, polyphenol compounds such as phenol novolak and cresol novolak, and acid anhydrides, dicyandiamide, and hydrazide compounds.

The ratio of the epoxy resin to the curing agent is such that the amount of active hydrogen in the curing agent is 0.5 to 1.5 moles per mole of epoxy group.

Furthermore, a curing accelerator can be added if necessary. For example, curing accelerators include amines such as benzyldimethylamine, 2,4.6-1-lis(dimethylaminomethyl)phenol, 1,8-diazabicycloundecene, and 2-ethyl 4-methylimidazole. imidazole compounds, boron trifluoride amine complexes, etc.

Furthermore, depending on the purpose of use, the resin composition of the present invention may be mixed with particulate materials such as talc, mica, calcium carbonate, alumina hydrate, silicon carbide, carbon black, and silica, to improve processability and handling. Effective for improvement.

In the prepreg of the present invention, fibers used as reinforcing materials include carbon fibers, graphite fibers, glass fibers, silicon carbide fibers, silica alumina fibers, alumina fibers, titania fibers, aromatic polyamide fibers, aromatic polyester fibers, and polyester fibers. Examples include organic and inorganic fibers such as benzimidazole fibers, but are not limited to these. In particular, in order to provide a composite material in which the prepreg has excellent toughness, fibers having a tensile strength of 50 kg/am2 or more and an elastic modulus of 5 t/mm2 or more are preferable. In addition, depending on the purpose of use, it is also possible to use two or more types of fibers or fibers with different shapes.

Furthermore, in addition to reinforcing fibers, mixing granular materials such as talc, mica, calcium carbonate, alumina hydrate, silicon carbide, carbon black, and silica improves the viscosity of the resin composition and makes it easier to mold the composite material. It is also effective for improving the physical properties of the resulting composite material, such as compressive strength.

As a method for manufacturing the prepreg, a conventionally known manufacturing method using an epoxy resin as a matrix can be adopted.

The resin content of the prepreg is generally 20 to 90% by volume.
, particularly preferably 25 to 70% by volume. A fiber-reinforced composite material can be obtained by forming these prepregs into a desired shape by stacking or winding them, and then heating and pressurizing them.

In the prepreg of the present invention, fine particles made of resin may be dispersed. These resinous fine particles act synergistically with the highly tough resin composition of the present invention to inhibit cracks from propagating in the composite material. In particular, it is preferable that the resinous fine particles have high toughness. Examples include so-called engineering plastics such as polysulfone, polyethersulfone, polyneetimide, polyetherketone, polyetheretherketone, nylon, polyarylate, polycarbonate, and polyamideimide.

Furthermore, a cured product of an epoxy resin, a reactive elastomer, and a curing agent is preferable from the viewpoint of adhesion to the epoxy resin and toughness. As the reactive elastomer, urethane elastomer, acrylonitrile-butadiene copolymer containing a terminal carboxyl group, etc. can be used, but there is no particular limitation. Furthermore, a rubbery resin made of an acrylonitrile-butadiene copolymer or nitrile rubber can also be used.

The shape of the resinous fine particles is not particularly limited and may be either spherical or amorphous, but preferably has an average particle size of 5 to 100 μm. When the average particle size is less than 5 μm, the crack suppressing effect is small, and when it exceeds 100 μm, the fiber arrangement is disturbed, leading to deterioration of the physical properties of the molded composite material.

Among the cured products of a system consisting of an epoxy resin, a reactive elastomer, and a curing agent, the following cured products are particularly preferred as the resinous fine particles used in the present invention. That is, (
a) 100 parts by weight of an epoxy resin having two or more glycidyl groups in the molecule, (b) 0.5 to 1 part by weight per glycidyl group
．． Epoxy resin-based fine particles comprising 2 equivalents of an aromatic amine and (C) 5 to 100 parts by weight of an elastomer having a functional group capable of reacting with a glycidyl group or an aromatic amino group;
or (a) 100 parts by weight of an epoxy resin having two or more glycidyl groups in the molecule, (b) 1 to 8 parts by weight of an imidazole compound such as 2-ethyl-4-methylimidazole, and (C) capable of reacting with a glycidyl group. Examples include epoxy resin-based fine particles comprising 5 to 100 parts by weight of an elastomer having a functional group.

In the present invention, the toughness of the matrix resin is sufficiently high even when resinous fine particles are not blended, so that the desired toughness can be obtained by adding a small amount of resinous fine particles. That is, the resinous fine particles are preferably blended in an amount of 2 to 15% by weight based on the total epoxy resin composition. If the blending amount is less than 2% by weight, the toughness will be almost the same as when no additive is added, and the blending will have no effect. Even if the amount exceeds 15% by weight, the toughness is almost the same as that when the amount is less than 15% by weight, and on the other hand, it becomes difficult to control the distribution state of the resinous fine particles, making it difficult to produce a laminate with good industrial reproducibility. This is not desirable because it cannot be obtained.

〔Effect of the invention〕

The resin composition according to the present invention provides a cured epoxy resin having excellent mechanical strength, heat resistance, and toughness. Also,
The prepreg according to the present invention provides a fiber-reinforced composite material with excellent mechanical strength, heat resistance, and toughness.

〔Example〕

The present invention will be explained in more detail below with reference to Examples, but the present invention is not limited thereto.

In addition, as raw materials for the synthesis of the imide-based polymer, the following were synthesized and used using the exemplified production method.

Note that the quantity ratio of the X component and the X component is 1 in this example.
0.6 was used. Hereinafter, this mixture of the X component and the X component will be referred to as ASM.

Further, the number average molecular weight of the obtained product was determined by gel permeation chromatography (hereinafter abbreviated as GPC). The column is Showa Denko (immediately manufactured AD-805/S
and AD-803/S were used in combination, and 0.0
A 1 mol/l LiBr solution in DMF and polyethylene glycol were used as a standard substance.

Synthesis Example 1 ASM was placed in a 11-four flask equipped with a stirrer, a thermometer, a cooling condenser, and a Dean-Stark water drainer.
84.0 g (0,267 mol), 150 g of N-methylpyrrolidone, and 76 g of tetrahydrofuran were charged.
Dissolved at room temperature under nitrogen atmosphere, amine equivalent weight 650g/
eq diaminodimethyl silicone olicomer BY 1
6-853 (manufactured by Toshi/Dow Corning) 10.1
g dissolved in 177 g of tetrahydrofuran, 3
The mixture was added dropwise at room temperature over 0 minutes, and stirring was continued for 1 hour.

2. 111.7 g (0,272 mol) of 2-bis(4-aminophenoxyphenyl)propane was added to 165 g of N
A solution of methylpyrrolidone dissolved in 61.5 g of tetrahydrofuran was added dropwise at room temperature, and stirring was continued for 1 hour.

After raising the temperature to 70°C and keeping it warm for 2 hours, the temperature was raised to 160°C. At that time, when the internal temperature reached 100° C., distillation of tetrahydrofuran started and 247 g was distilled out. Prepare 126g of xylene and raise the temperature to 160-170°C.
It was azeotropically dehydrated for 30 hours. The amount of distilled water was 20.4 g. After xylene was distilled off at 180 DEG C., the resin solution was cooled to room temperature and added dropwise to methyl alcohol 2000-ml under high speed stirring to obtain a precipitate.

This precipitate was filtered and diluted with 2,000 ml of methyl alcohol.
Washed twice. The precipitate was filtered and dried under reduced pressure at 80°C.
4 g of powdered product was obtained.

As measured by GPC, the number average molecular weight of the obtained product was 15,000, and the amine equivalent by titration was 730.
It was 0 g/eq.

Synthesis Example 2 The amount of ASM prepared in Synthesis Example 1 was changed to 81.1 g (0,258
mole) 2,2-bis(4-aminophenoxyphenyl)
The reaction was carried out in the same manner as in Synthesis Example 1, except that the amount of propane charged was changed to 104.7 g (0,255 mol) and the amount of BY16-853 was changed to 19.5 g.
I got g.

As measured by GPC, the number average molecular weight of the obtained product was 15,000, and the amine equivalent by titration was 800.
It was 0 g/eq.

Synthesis Example 3 Synthesis except that BY 16-853 in Synthesis Example 1 was changed to 9.7 g of diaminodimethyl silicone oligomer BY 16-853 C (manufactured by Toshi/Dow Corning Co., Ltd.) with an amine equivalent of 385 g/eq. The same reaction as in Example 1 was carried out to obtain 195 g of a powdered product.

As measured by GPC, the number average molecular weight of the polymer was 15,000, and the amine equivalent by titration was 7,200.
g/eq.

Synthesis Example 4 The amount of ASM prepared in Synthesis Example 1 was 84.0 g (0,267 mol), 2.2-bis(4-aminophenoxyphenyl)
The amount of propane charged was 104.4g (0,254 mol)
, BY16-853 The reaction was carried out in exactly the same manner as in Synthesis Example 1 except that the amount of charged BY16-853 C was changed to 19.9 g, and white powder 1 was obtained.
94g was obtained.

As measured by GPC, the number average molecular weight of the obtained product was 15,000, and the amine equivalent by titration was 800.
It was 0 g/eq.

Synthesis Example 5 In Synthesis Example 1, instead of BY 16-853, diaminodimethyl silicone oligomer X-22-161B (Shin-Etsu Chemical Co., Ltd. (conversion type) 20.7 g with an amine equivalent of 1600 g/eq, the amount of ASM charged was 84 .Og (0,
The same reaction as in Synthesis Example 1 was carried out except that the amount of 2.2-bis(4-aminophenoxyphenyl)propane charged was changed to 112.3 g, and a powder product of 195 mol) was carried out.
I got g.

As measured by GPC, the number average molecular weight of the polymer was 15,000, and the amine equivalent by titration was 7,200.
g/eq.

Synthesis Example 6 The charged amount of ASM of Synthesis Example I was 84.0 g (0,267 mol), 2.2-bis(4-aminephenoxyphenyl)
The amount of propane charged was 113.7g (0,277mol)
, The reaction was carried out in the same manner as in Synthesis Example 1 except that the amount of X22-161B was changed to 10.4 g, and 194 g of white powder was obtained.
I got it.

As measured by GPC, the number average molecular weight of the obtained product was 13,000, and the amine equivalent by titration was 689.
It was 0 g/eq.

Synthesis Example 7 In Synthesis Example 1, instead of BY 16-853, dianilinodimethyl silicone oligomer X-22-161B (Shin-Etsu Chemical side type) with an amine equivalent of 1600 g/eQ was used, and the amount of ASM charged was 84.0 g. g(
0,267 mol) and 2.2-bis(4-aminophenoxyphenyl)propane, the reaction was carried out in the same manner as in Synthesis Example 1, except that the amount of 2.2-bis(4-aminophenoxyphenyl)propane charged was changed to 112.3 g.
5g was obtained.

As measured by GPC, the number average molecular weight of the polymer was 15,000, and the amine equivalent by titration was 7,200.
There was g/eq.

Synthesis Example 8 In a flask equipped with a stirrer, a thermometer, and a cooling device, glycidyl ether of bisphenol A (manufactured by Sumitomo Chemical Co., Ltd.
LA-128) 100 g, carboxy-terminated acrylonitrile-butadiene copolymer (CTBN 1008sp manufactured by Goodrich) 30 g were prepared, and 150
Dissolved at ℃ for 2 hours. Next, the mixture was cooled to 80° C., triphenylphosphine Ig (Wako Tsugiyaku (Yokoso)) was charged, and 5 g of 2-ethyl-4-methylimidazole was added and dissolved.

This resin liquid was added to methyl cellulose (Metrose 90SH4).
000, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.7% aqueous solution 200g
and stirred with an autohomogen mixer (manufactured by Tokushu Kikai ■) to obtain a suspension liquid. 60% of this suspension liquid
After stirring at °C for 15 hours, methylcellulose was removed and resinous fine particles were separated.

The resinous fine particles had an average particle size of 23 μm and a glass transition temperature of 135°C. The elastic modulus is 150 kg/.

It was m2.

Synthesis Example 9 In a flask equipped with a stirrer, a thermometer, and a cooling device, 100 g of glycidyl ether of bisphenol A (Jumin Chemical Industry Co., Ltd. (Yokozai ELA-128)) and a carboxy-terminated acrylonitrile-butadiene copolymer (C manufactured by Goodrich Co., Ltd.) were added.
Pour 30g of TBN 1008sp) and heat to 150°C.
It was dissolved for 3 hours. Next, the mixture was cooled to 80° C., and 20 g of 3,4°-diaminodiphenyl ether was added and dissolved.

This resin liquid was added to methyl cellulose (Metrose 90SH4).
000, 0.7% aqueous solution 200 of Shin-Etsu Chemical (Yokosaki)
g and stirred with an autohomo mixer (manufactured by Tokushu Kikai ■) to obtain a suspension liquid. Add this suspension liquid to 6
After stirring at 0° C. for 15 hours, methylcellulose was removed and resinous fine particles were separated.

The resinous fine particles had an average particle size of 31 μm and a glass transition temperature of 143°C. Elastic modulus is 170kg/
It was mm2.

Comparative Synthesis Example 1 In a 500-Yoturo flask equipped with a stirrer, thermometer, cooling condenser, and Dean-Stark water drainer, 2
, 2-bis(4-aminophenoxyphenyl)propane 41.05g (0.1 mol), mixed cresol 280
ASM 31.42g (0.1 mol)
was added and kept at the same temperature for 4 hours after the addition.

After keeping warm, add 110g of xylene, 160~1708
The temperature was raised at C and azeotropically dehydrated for 14 hours. The amount of distilled water was 3.3 g. After xylene was distilled off at 180° C., the resin solution was cooled to room temperature and added dropwise to methyl alcohol 1400° C. with high speed stirring to obtain a precipitate. The precipitate was separated by filtration, washed three times with methyl alcohol 50 (W), and further washed with stirring for 1 hour under reflux with methyl alcohol 500.
I took my time. The precipitate was filtered, washed with 100% methyl alcohol, filtered, and dried under reduced pressure at 80°C to obtain 64.2 g of a powder product. As measured by GPC, the number average molecular weight of the obtained product was 9,200.

Comparative Synthesis Example 2 In Comparative Synthesis Example 1, the amount of 2.2-bis(4-aminephenoxyphenyl)propane charged was 41.05 g (0
, 1 mol) to 59. The reaction was carried out in the same manner as in Synthesis Example 1 except that the amount was changed to 1 g (0,144 mol), and white powder 6.
6.1 g was obtained. The number average molecular weight of the product was 2000 as determined by GPC.

Examples 1 to 8 and Comparative Examples 1 to 3 Among the components of the resin composition shown in Table 1, the components other than the curing agent were kneaded at 120 to 150°C for 30 minutes to 1 hour while degassing under reduced pressure to obtain a uniform and transparent material. A resin composition was obtained.

Next, the temperature is lowered to 60-80℃, a hardening agent is added, and the temperature is lowered to 60-80℃.
A resin composition was obtained by kneading at 80°C. 1 of the resin composition
It was cured at 80° C. for 2 hours and its performance was evaluated. The evaluation results are shown in Table 1.

The physical properties were measured as follows.

The glass transition temperature (Tg) was defined as the peak temperature of loss modulus measured by dynamic viscoelasticity measurement.

Bending strength, bending modulus and bending strain at break are JISK-6
911 compliance.

The strain energy release rate was based on ASTM E-399.

The contents of each component shown in Table 1 are shown below.

ELMloo ・Triglycidyl-4-amino-m
-Cresol [Sumi Epoxy E
LM100), EPICLON830 ° diglycidyl bisphenol F [Dainippon Ink (1'ri) EPICLON■8
30] ELA121--Diglycidyl bisphenol A [Sumie Kagaku Kogyo (ready made Sumiepoxy ELA128)
] 3.3° DDS-・-3,3' diaminodiphenylsulfone [Mitsui Toatsu Chemical (immediately manufactured)], 4.4'DDS...°4,4' diaminodiphenylsulfone [manufactured by Sumikagaku Kogyo ■ Sumicure@ S
], Polymer A...-Imide polymer of Synthesis Example 1 Polymer B...-Imide polymer of Synthesis Example 2 Polymer C...-Imide polymer of Synthesis Example 3 Polymer D...
・Imide-based polymer Polymer E′ of Synthesis Example 4・Imide-based polymer Polymer F of Synthesis Example 5・・Imide-based polymer Polymer G of Synthesis Example 6 −Imide-based polymer Polymer H of Synthesis Example 7 Polymer Polymer I - Polymer Polymer J of Comparative Synthesis Example 2
Polyethersulfone 5003P manufactured by ICI Corporation Examples 9 to 12 and Comparative Examples 4 to 6 Among the components of the resin composition shown in Table 2, components other than the curing agent were removed under reduced pressure at 120 to 150°C for 30 minutes. Kneaded for hours. Next, the temperature of the resin composition was lowered to 60 to 80°C, a curing agent was added, and the mixture was kneaded at 60 to 80°C to obtain a resin composition. The resin composition was used as a matrix resin for prepreg for carbon fiber reinforced composite materials.

The contents of the resin components shown in Table 2 are the same as those used in Table 1. Further, the contents of the fine powder used are as shown below.

Fine powder A is the fine powder of Synthesis Example 8, fine powder B is the fine powder of Synthesis Example 9, and fine powder C is a frozen pulverized product of polyamideimide resin (manufactured by Mitsui Toatsu Chemical Co., Ltd.), and has an average particle size of 35 μm.

Table 3 shows the physical properties of the carbon fiber reinforced molded product.

Experiment numbers correspond to Table 2. A prepreg, which is a precursor of the molded body, was produced using a prepreg manufacturing machine in the following manner. That is, surface-treated carbon fibers (Magnamite IM7 manufactured by Hercules) are continuously pulled out from a bobbin, arranged in a 50 cm width, and then a release paper coated with the above-mentioned matrix resin in a thin film is pressed with a roll. do. In this way, a unidirectionally aligned fiber prepreg made of carbon fiber impregnated with matrix resin and having a fiber basis weight of 150 g/rrr was obtained.

The obtained prepreg sheet was cut and laminated so that the reinforcing fibers were oriented in the same direction, and the sheets were inserted between hydraulic press hot plates heated to 180°C and gradually pressurized until the reinforcing fiber content was 60% by volume. 20kg while reducing the amount of resin so that
/cnf weight for 1 hour.

Next, the molded body was further post-cured at 180° C. for 1 hour in a hot air oven to obtain a cured composite plate having a thickness of about 211Il111.

The 0″ compression degree and interlaminar shear strength of the obtained composite material cured board were determined by ASTM-D695 and ASTM-D23, respectively.
Measured in accordance with 44.

Next, the obtained composite material cured board was immersed in boiling water for 48 hours, and then the composite material cured board after water absorption was heated at 82°C and 121'c.
The 0° compressive strength and interlaminar shear strength were measured in the same manner. The results are shown in Table 3.

In addition, the prepregs were laminated in a 24-ply pseudo-isotropic manner, and 1
Press hardening molding was performed at 80°C for 2 hours. The obtained laminate was cut into 80 squares, the four sides were fixed at each If)n+m, and 60 squares were cut out.
A falling weight impact of 350 kg-cm/cm was applied to the center of a mm square, and the damaged area was quantified using ultrasonic C-5can. The measurement results are shown in Table 3.

Claims (3)

[Claims] (1) 100 parts by weight of an epoxy resin, 10 to 100 parts by weight of a polyimide siloxane resin whose repeating structural units are of the following formulas (Ia) and (Ib) and whose number average molecular weight is in the range of 3,000 to 30,000. and an epoxy resin composition containing the required amount of an epoxy curing agent. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I a) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I b) (In the above formula, A is an aromatic residue, B is the following formula (II) and /
or a divalent group represented by formula (III), and C is a divalent group represented by formula (III), and C is a divalent group represented by formula (III);
It is a divalent group represented by IV). ) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) (In the above formula, R_1 is hydrogen or an alkyl group with 1 to 10 carbon atoms, R_2 is hydrogen, carbon number 1 to 20 alkyl groups or hydroxyl groups.) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (IV) [In the above formula, R_3 and R_4 are alkyl groups having 1 to 5 carbon atoms and/or phenyl groups, R_5 represents a carbon chain having 3 to 10 carbon atoms and/or an aromatic residue, and n represents an integer of 1 to 60. ] (2) A prepreg for a fiber-reinforced composite material, comprising the resin composition according to claim 1 and reinforcing fibers. (3) A prepreg for a fiber-reinforced composite material, comprising the resin composition according to claim 1, resinous fine particles, and reinforcing fibers.