JPH0326750A - Fiber-reinforced composite material - Google Patents

Abstract

PURPOSE:To obtain a composite material having high toughness and excellent mechanical properties in hot-moist state by compounding specific epoxy resin, reactive oligomer, line plastic particles, curing agent and reinforcing fiber. CONSTITUTION:The objective material is produced by compounding (A) 100 pts.wt. of an epoxy resin having >=2 epoxy groups in one molecule. (B) 10-100 pts.wt. of a reactive oligomer consisting of a polyaryl ether expressed by formula I (Ar is bivalent aromatic group of formula II, III or IV; n is positive integer), (C) 2-15wt.% (based on the whole composition) of resinous fine particles composed of the component A, the component B and a curing agent composed mainly of an aliphatic amine or an acid anhydride, having an average particle diameter of 10-100mum and exhibiting an elastic modulus of 100-500kg/mm<2> in cured state, (D) 0.7-1.05 mol-equivalent of a curing agent consisting of an aromatic amine (in terms of the active hydrogen group of the amine based on the epoxy group) and (E) reinforcing fibers.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a fiber-reinforced composite material that is strong and has excellent mechanical properties at high temperature and humidity.

[Conventional technology]

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

However, cured epoxy resins generally 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.

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

JP-A No. 61-228016 describes a tough thermosetting epoxy resin composition composed 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 is shown to have a two-phase structure of dispersed discontinuous phases.

Further, Japanese Patent Publication No. 62-61216 describes an epoxy composition using an aromatic polysulfone having amine groups at both ends as a curing agent.

Further, JP-A-63-170428 describes a Bripreg having a structure in which fine particles made of resin are dispersed on the surface of the Bripreg, which is 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.

U.S. Pat. No. 4,783,506 describes a fiber-reinforced composite material whose matrix resin is a composition obtained by adding a reactive elastomer to a thermosetting epoxy resin composition similar to that of JP-A-61-228016. has been done.

[Problem to be solved by the invention]

As in Japanese Patent Publication No. 48-5107, in order to obtain a composition with sufficient toughness using a high molecular weight polysulfone resin, it is necessary to increase the amount of polysulfone resin added, and the The viscosity becomes too high, making it difficult to impregnate reinforcing fibers.

Furthermore, it has been found that the larger the molecular weight, the lower the solvent resistance of the cured product containing it.

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 poor anti-drying agent resistance. It is unsatisfactory.

In addition, the aromatic oligomer specifically mentioned in the Examples in Japanese Patent Publication No. 62-61216 has a considerably small molecular weight, and forms a cured product in a homogeneous phase with the epoxy resin, resulting in insufficient toughness.

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. In addition, in order to obtain high toughness, it is necessary to control the arrangement of fine particles present at the prepreg interface, but it is extremely difficult to control the processes of prepreg manufacturing, prepreg lamination, thermosetting molding, etc. It has its drawbacks.

In U.S. Pat. No. 4,783,506, a polyarylene polyether sulfone having amine functional groups at both terminals is mainly used as a reactive oligomer, and a polyarylene polyether sulfone is used as a reactive oligomer. It has the disadvantage of inferior mechanical properties.

[Means to solve the problem]

The present invention provides a fiber-reinforced composite material comprising an epoxy resin composition comprising an epoxy resin, reactive oligomer resinous fine particles, and a curing agent, and reinforcing fibers, wherein the epoxy resin composition has two epoxy groups in one molecule of (al). 100 parts by weight of an epoxy resin having 100 parts by weight or more of an epoxy resin, 10 to 100 parts by weight of a reactive oligomer consisting of a polyaryl ether represented by the formula (b)(I), 0 representing a divalent aromatic group, n being a positive is an integer) (C
) Consisting of an epoxy resin, a reactive elastomer, and a curing agent mainly composed of an aliphatic amine or acid anhydride, and has an elastic modulus of 100 to 500 kg/mm" in a cured state and an average particle size of 10 to 100 μm. Resin-like fine particles are added in an amount of 2 to 15% by weight based on the epoxy resin composition, (a curing agent made of dl aromatic amine is used in an amount of 0.7 to 1.05 molar equivalents of amine hydrogen groups to epoxy groups), and The present invention relates to a fiber-reinforced composite material characterized by the following.

As the epoxy resin having two or more epoxy groups per molecule used in the present invention, epoxy resins having at least three epoxy groups per molecule are suitable from the viewpoint of heat resistance of the cured product.

Examples of these include p-aminophenol, m-aminophenol, 4-amino-m-cresol, 6-amino-m-cresol, 4.4'-diaminodiphenylmethane, 3.3'-diaminodiphenylmethane, 4. 4'-
Diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, l,4-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene , l,3-bis(3-aminophenoxy)benzene,
2,2-bis(4-aminophenoxyphenyl)propane, p-phenylenediamine, m-phenylenediamine, 2.4-}luenediamine, 2.6-toluenediamine, p-xylylenediamine, m- xylylenediamine, l,4-cyclohexane-bis(methylamine), 1
．． Amine-based epoxy resins derived from 3-cyclohexane-bis(methylamine), etc.; novolacs derived from novolak resins, which are reaction products of phenols such as phenol, 0-cresol, m-cresol, p-cresol, and formaldehyde; epoxy resin, phloroglycin, tris(4-hydroxyphenyl)methane,
Glycidyl ether compounds derived from trivalent or higher phenols such as 1,1,2.2-tetrakis(4-hydroquinphenyl)ethane, his[α-(dihydroxyphenyl)1α-methylethyl]benzene, and other glycidyl ether compounds derived from trivalent or higher phenols such as Examples include glycidyl isocyanurate, 2,4.6-triglycidyl-s-triazine, rubbers thereof, urethane-modified compounds, etc., and one or more of these epoxy resins are used, but are not limited to these. do not have.

In the present invention, in addition to the epoxy resin having three or more epoxy groups in one molecule, it is also possible to use an epoxy resin having two epoxy groups in the molecule.

Examples of such epoxy resins include diglycidyl ether compounds derived from bisphenol A, bisphenol F, bisphenol AD, dihydric phenols such as hydroquinone and resonoresin, or halogenated bisphenols such as tetrabromobisphenol A, p- Glycidyl ester compounds derived from aromatic carboxylic acids such as oxybenzoic acid, m-oxybenzoic acid, terephthanoleic acid, isophthalic acid, S,
Hydantoin-based epoxy resin derived from 5-dimethyl hydantoin etc., 2,2-bis(3.4-
Epoxy(hexyl)propane, 2,2-bis(4
-(2.3-epoxycyclohexyl)propane, vinylcyclohexene dioxide, cycloaliphatic epoxy resins such as 3,4-epoxycyclohexyl methyl 3,4-epoxycyclohexanecarboxylate,
Other examples include N,N-diglycidylaniline, and one or more of these epoxy resins may be used.

The reactive oligomer of the present invention is a polyaryl ether represented by formula (I).

When OAr is a polyarylether represented by formula (III), the number average molecular weight is 3,000 to 10,000.
It is preferable that The scope is limited for the reasons mentioned above.

It represents a divalent aromatic group, and n is a positive integer. ) More specifically, when Ar is a polyarylether represented by formula (II), the number average molecular weight is 11,000 to
Preferably, it is 30,000. Number average molecular weight is 11. If it is less than 000, sufficient toughness cannot be obtained. Also, 30. If it exceeds 000, the viscosity of the epoxy composition increases, causing processing problems such as difficulty in impregnating fibers with the composition.

Furthermore, in the present invention, a combination of two or more types of Ar may be used. The preferred number average molecular weight in this case is based on the number average molecular weight range defined for the main component divalent aromatic group among the types of Ar.

Any of the reactive oligomers of formula (I) can be produced using known methods, such as dimethyl sulfoxide, dimethyl formamide, dimethyl acetamide,
In a solvent such as tetrahydrofuran, phenols such as resorcinol, hydroquinone, and bisphenol A, dialkali metal salts of these phenols whose aromatic rings are substituted with halogen, and dihalogen compounds such as 4,4'-dichlorodiphenylsulfone or It is obtained by reacting a compound in which an aromatic ring is further substituted with halogen. In this case, by increasing the molar ratio of the dialkali metal salt, the terminal functional group can be a hydroxyl group.

The molecular weight can be adjusted because the larger the difference in the molar ratio between the two, the smaller the molecular weight becomes.

In the composition of the present invention, the polyarylether of formula (I) is blended in an amount of lO to 100 parts by weight, preferably 20 to 80 parts by weight, per 100 parts by weight of the epoxy resin. If the amount is less than 10 parts by weight, sufficient toughness will not be achieved. Also,
If it exceeds 100 parts by weight, the viscosity of the epoxy composition becomes too high, making it difficult to impregnate fibers, and the prepreg produced by impregnating fibers with the epoxy composition loses drape and tack properties. Problems arise, such as difficulty in molding into a shape.

The resinous fine particles of the present invention are granular cured products made of an epoxy resin, a reactive elastomer, and a curing agent whose main component is an aliphatic amine or an acid anhydride. The cured product has an elastic modulus of 100 to 500 kg/mm2. elastic modulus is 1
If it is less than 00 kg/mm2, the effect of improving toughness is insufficient. An elastic modulus exceeding 500 kg/mm2 cannot be obtained with the cured product of the present invention. Elastic modulus is 150-400kg
/ mm", the toughness improvement effect is almost the same. The average particle size is preferably 10 to 100 μm. If the average particle size is less than 10 μm, the toughness improvement effect is small. 100 μm
If it exceeds this amount, problems such as a decrease in elastic modulus will occur due to factors such as disordering of the arrangement of fibers in the laminate. The shape of the resinous fine particles is preferably spherical, cylindrical, elliptical, fibrous, or the like, but is not particularly limited.

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 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 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 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 obtain a laminate with good industrial reproducibility. I can't.

The epoxy resin used for producing the resinous fine particles is not particularly limited, but the above-mentioned epoxy resins are preferably used. As reactive elastomers, urethane elastomers,
Acrylonitrile butadiene polymers containing terminal carboxy groups can be used, but are not particularly limited. The curing agent is preferably an aliphatic amine or an acid anhydride. Since the Tg of the resinous fine particles cured with aliphatic amine or acid anhydride is lower than the Tg of the cured matrix resin, they have the effect of relieving internal stress caused by cooling after thermosetting the laminate. It is also suggested that the interfacial strength with the cured matrix resin is also good.

Specific examples of aliphatic amines include 1,3-propanediamine, ethylenediamine, 1,6-hexamethylenediamine, triethylenetetramine, 1-aminoethylpiperazine, N,N-dimethyl-1,3-propanediamine,
Examples include, but are not limited to, diethylenetriamine. Specific examples of the acid anhydride include, but are not limited to, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and the like. Furthermore, an epoxy curing agent such as an aromatic amine or a polyhydric phenol can be used in addition to the aliphatic amine or acid anhydride. Similarly, curing accelerators, fillers, and anti-aging agents for rubber can be added.

The phase state of the resinous fine particles used in the present invention is preferably basically a so-called sea-island structure in which the epoxy resin is a continuous phase and the rubbery substance is an island. There is an inverted phase structure in which the epoxy resin is an island and a rubbery substance is a continuous phase, and a semi-IP structure in which both phases are microdispersed.
enetrating network), the Tg and elastic modulus of the resinous fine particles become too low and cannot be used for the purpose of the present invention.

The resinous fine particles used in the present invention are prepared by thermosetting a mixture of 100 parts by weight of an epoxy resin, 0.4 to 1.2 molar equivalents of a curing agent, and 10 to 60 parts by weight of a reactive elastomer.
It can be manufactured by crushing.

Moreover, it can be synthetically produced by the production method described in the following example. That is, an epoxy resin and an acrylonitrile butadiene polymer containing a terminal carpoquine group are dispersed in a water-alcohol system using an emulsifier to obtain an emulsion liquid, and then an aliphatic amine is added and the particle size is reduced by curing while standing at room temperature. Resin-like fine particles with a size of 10 to 100 μm can be synthesized. Synthetic production is industrially advantageous because it can be produced at a lower cost than square production, which is produced by pulverizing a cured product.

Aromatic amines used in the present invention include 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4l 4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, m-phenylenediamine. , p-phenyl diamine, 4.4'
-methylene-bis-orthochloroaniline, tetrac-diaminodiphenylmethane, 4,4'-diaminostilbene, 4,4'-diaminodiphenyl sulfide, m
-xylylene diamine, p-xylylene diamine, 1.
4-bis(4-aminophenoxy)benzene, 1.4-
Bis(3-aminophenoxy)benzene, 1.3-1:
's(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenyl ether, 2,4-toluenediamine, 2,6 -Toluenediamine, 5-amino-1-(4'-aminophenyl)
-1.33-trimethylindane, 6-amino-1-(
Examples include 4'-aminophenyl)-1.3.3-}limethylindan.

In the present invention, two or more of the aromatic amines described above can be combined and used as a eutectic. Further, in order to lower the curing temperature condition, it can also be used in combination with a polyhydric phenol curing agent as exemplified below.

As polyhydric phenol curing agents, phenol novolak and its halides, cresol novolak and its halides, bisphenol A1 bisphenol F1 bisphenol S1 tetrabromo bisphenol A
, tetrabromobisphenol S, etc.

In the composition of the present invention, the curing agent is blended in an amount such that active hydrogen in the curing agent is 0.7 to 1.05 moles per mole of epoxy group. However, the active hydrogen equivalent of the reactive oligomer represented by formula (I) is reduced from the above blending amount.

If the amount of the curing agent is too small, curing will be insufficient, and the toughness of the cured product will drop significantly, while if it is too much, the moisture resistance of the cured product will decrease.

Mixing of the four components can be accomplished by conventional methods for preparing epoxy resin compositions. It is preferable that the reactive oligomer represented by formula (I) and the epoxy resin are mutually dissolved before curing. Preferably, the curing agent is also dissolved in the epoxy resin immediately before curing or during the curing process.

The resinous fine particles are blended as an epoxy resin composition, and when they are uniformly dispersed in the composition, the resinous fine particles are applied in the form of a film on the surface of a brev leg made of an epoxy resin composition that does not contain resinous fine particles and reinforcing fibers. Or, the case where it is applied in powder form is exemplified as a method of blending the resinous fine particles. In either compounding method, the resinous fine particles are used in the form of being dispersed on the surface of the prepreg. A laminate produced by laminating the prepregs is thermoset to form a resin layer of 10 to 50 μm containing resinous fine particles. If the resin layer is less than 10 μm, the effect of improving the toughness of the laminate is small, and if it exceeds 50 μm, there will be drawbacks such as a decrease in the elastic modulus of the laminate.

The reactive oligomer shown by the formula (1) and the epoxy resin are mutually dissolved and become a transparent composition during curing.At this point, it is a homogeneous phase, but after that, as curing progresses, it becomes transparent. is lost and phase separation occurs.

This is confirmed by observing the fractured surface of the cured product with a scanning electron microscope as a two-phase structure. The two-phase structure that is generally formed when a composition similar to the composition of the present invention is cured will be described.

A typical example of a two-phase structure is a two-phase structure formed of a continuous phase mainly composed of reactive oligomers and a discontinuous phase mainly composed of epoxy resin. This case is characterized by very high toughness, but on the other hand, it has poor solvent resistance, which is not preferable for the purposes of the present invention.

On the other hand, in the present invention, the discontinuous layer mainly composed of the reactive oligomer represented by formula (I) spreads in an amoeba-like or network shape, and the main component is dispersed as a discontinuous phase in the continuous phase composed of the epoxy resin. A two-phase structure is formed. In this case, since both toughness and solvent resistance are excellent, the object of the present invention is met.

Examples of fibers used as reinforcing materials for fiber-reinforced composite materials using the epoxy resin composition of the present invention include carbon fibers, graphite fibers, glass fibers, silicon carbide fibers, alumina fibers,
titania fiber, boron nitride fiber, aromatic polyamide fiber,
Examples include inorganic or organic fibers having a tensile strength of 0.5 GPa or more and a Young's modulus of 50 GPa or more, such as aromatic polyester fibers and polybenzimidazole fibers.

These fibers can be used in the form of continuous tows, woven fabrics, three-dimensional fabrics such as braids, short fibers, whiskers, etc.

Furthermore, 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, granular materials such as talc, mica, calcium carbonate, alumina hydrate, silicon carbide, carbon black, and silica can also be used to improve the viscosity of the resin composition and facilitate molding of composite materials. It is effective for improving the physical properties of the resulting composite material, such as compressive strength.

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

The resin content of the prepreg is generally 25 to 95% by volume, preferably 30 to 90% by volume. After shaping these prepregs into a desired shape by stacking or winding them, heating, A fiber reinforced composite material can be obtained by applying pressure.

〔Effect of the invention〕

When the epoxy resin composition of the present invention is reinforced with high-strength, high-modulus fibers such as carbon fibers, it becomes a high-performance composite material suitable for aircraft use. In other words, conventional composite materials using epoxy resin as a matrix have poor toughness and therefore poor impact resistance, and once cracks have formed, they easily expand, leading to fatal failure of the material.

The composite material using the epoxy resin composition of the present invention as a matrix takes advantage of the characteristics of the highly tough reactive oligomer that exists independently in the matrix resin, requires a large amount of energy for fracture propagation, and has high impact resistance. .

Furthermore, since the terminal functional group of the reactive oligomer of the present invention is a phenolic hydroxyl group as shown by formula (I), the cured product has a low water absorption rate and good mechanical properties under high temperature and humid conditions. It has the following characteristics. Regarding the water absorption rate, since the blending ratio of the aromatic amine as a curing agent is kept as small as possible, the water absorption rate of the cured product is also low from this point of view.

The resinous fine particles of the present invention have an auxiliary effect of improving the toughness of the resin. Particularly, when the prepreg is used as a laminate in which prepregs are stacked, the resin layer containing resinous fine particles between the prepregs has the effect of relaxing the breaking energy. In addition, since the matrix resin has sufficient toughness even in the absence of resinous fine particles, there is no need to restrict the morphology of the resinous fine particles dispersed on the prepreg surface, making it easy to manufacture industrially. Excellent in that respect.

〔Example〕

The present invention will be described in more detail below based on Examples and Comparative Examples, but the present invention is not limited thereto. In addition, unless otherwise specified below, all units are parts by weight.

Synthesis Example 1 66.1 parts of resorcin and 306 parts of dimethyl sulfoxide are placed in a flask equipped with a stirrer, a thermometer, and a cooling separation device.
parts, 613 parts of chlorobenzene, 100 parts of 48% strength soda
．． Prepare 0 copies. Next, while thoroughly replacing nitrogen,
Raise the temperature to 5°C. Azeotropic dehydration was started at 115°C and 14
Continue azeotropic dehydration until 0°C. After the azeotropic dehydration is completed, the temperature is raised to 160° C. and chlorobenzene is distilled off.

After distilling off chlorobenzene, the temperature was once lowered to below 50°C, and at this temperature 4,4'-dichlorodiphenylsulfone 164. 1 part was charged, the temperature was raised to 160°C, and the polymerization reaction was carried out at this temperature for 3 hours. The number average molecular weight of the resorcinol polysulfone oligomer thus obtained was determined by potentiometric titration of the terminal hydroxyl group, and the result was approximately 15. It was 000.

Synthesis Example 2 The amount of 4,4'-dichlorodiphenylsulfone in Synthesis Example 1 was changed to 165. The same reaction as in Synthesis Example 1 was performed except that 5 g was used. The number average molecular weight of this resorcinol polysulfone oligomer was 25,000.

Synthesis Example 3 66.1 parts of resorcin in Synthesis Example 1 was added to 45.6 parts of resorcin.
Part and bisphenol A 44. The same reaction as in Example 1 was carried out except that 0 part was used instead. The number average molecular weight of this resorcinol polysulfone oligomer was 11,000.

Synthesis Example 4 66.1 parts of resorcin from Synthesis Example 1 was added to bisphenol A1.
The same reaction as in Synthesis Example 1 was carried out except that the amount was changed to 46.5 parts.

The number average molecular weight of this bisphenol A polysulfone oligomer was 5,000.

Synthesis Example 5 Bisphenol 8 glycidyl ether (manufactured by Sumitomo Chemical Co., Ltd.) was placed in a flask equipped with a stirrer, thermometer, and cooling device.
ELA-128) 38 g, carboxy-terminated acrylonitrile-butadiene copolymer (Goodric
h (manufactured by CT RoN 1008 sp) 1 2 g
, and 3 g of an emulsifier (Emulgen@920, manufactured by Kao Corporation) were added and mixed. Next, 30 g of a mixed solution (I) of isopropyl alcohol and pure water was added to form an emulsion solution. A solution obtained by dissolving 6.9 g of 1-aminoethylpiperazine in 60 g of mixture (I) and 5 g of Aerosil (manufactured by Nippon Aerosil Co., Ltd., OX50) were added and mixed to this emulsion, and then aged at room temperature for 1 day. Next, 270 g of the mixture was added and mixed, and the insoluble portion was filtered off, washed with water, and dried to obtain resinous fine particles.

The resinous fine particles had an average particle size of 23 μm and a glass transition temperature of 135°C. Elastic modulus is 150kg/m
It was m2.

Synthesis example 6 ELA-128 long, CTBN 1008 s
50 g of methyl hexahydrophthalic anhydride (manufactured by Hitachi Chemical Co., Ltd. HN 5500), and 1 g of 2,4,6}-(dimethylaminomethyl)phenol were mixed.
After curing at 20°C for 2 hours, it was further cured at 150°C for 1 hour to obtain a cured product. This cured product was freeze-pulverized and then separated to obtain fine resinous particles with an average particle size of 30 μm. The glass transition temperature of these resinous particles is 150°C, and the elastic modulus is 25
It was 0 kg/mm2.

Comparative Synthesis Example 1 1333 g (5.8 mol) of bisphenol A was added to a 1247 flask equipped with a nitrogen inlet, a thermometer, a stirrer and a Dean-Stark trap under nitrogen purge.
, 1420g of 44.8% potassium hydroxide aqueous solution (
11.3 mol) and 160 g of water were added. The contents of the flask were heated to 60°C and held at that temperature for 30 minutes, at which point a homogeneous solution was obtained. Next 96
0g toluene, 200g potassium carbonate and 1900g
g of dimethyl sulfoxide was added to the flask and the contents were heated to reflux temperature (approximately 120°C).
Water was removed by water-toluene dimethyl sulfoxide azeotrope, yielding 1200 g of azeotrope. The contents of the flask were cooled to 105°C, and a solution of 1887 g of 4,4'-dichlorodiphenyl sulfone (6.57 mol) in 2000 g of dimethyl sulfoxide and 160 g of toluene was added to obtain the obtained product. 160% of the mixture
The mixture was kept at ℃ for 16 hours to remove distilled toluene. The reaction mixture was cooled to 120°C.

159.4 g (1.46 mol) p-aminophenol in the second flask, 177. 5 g (1.
42 mol) of a 44.8% aqueous solution of potassium hydroxide, 60
A dehydration reaction was carried out on compound d, which was made up of 1 g of water, 240 g of toluene, and 900 g of dimethyl sulfoxide at 120° C. for 4 hours. The dehydrated mixture was transferred into a 12 liter flask under a nitrogen atmosphere and the resulting mixture was heated to 140°C and held at 140°C for 2 hours, at which point the reaction mixture was Cooled to room temperature. The cooled compound was then filtered to remove the solid inorganic salts and the filtrate was washed with dimethylsulfokind. Slowly add the washed filtrate (+21) to 48
f! of methanol to precipitate the p-amine phenol terminated polysulfone oligomer as a solid product. The precipitate was then washed with water until free of free chloride ions, and the washed product was heated to +00°C.
The solution viscosity was 11,000 poise (22
(0°C), an oligomer with a number average molecular weight of 4,000 was obtained.

Examples 1 to 6 and Comparative Examples 1 to 5 Among the components of the matrix resin composition shown in Table 1, the components other than the curing agent, which is an aromatic amine, were charged into a universal mixer, and mixed under reduced pressure while degassing. ~30 minutes at 150'C~
A resin composition was obtained by kneading for 1 hour. Next, the temperature was lowered to 60 to 80°C, a curing agent which was an aromatic amine was charged, and the mixture was kneaded at 60 to 80°C for 30 minutes while degassing under reduced pressure to obtain a matrix resin composition.

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

ELM434... Tetraglycidyl diaminodiphenylmethane (manufactured by Sumitomo Chemical Co., Ltd.) Sumiepoxy @ ELM4
34) ELMIOO...Triglycidyl of paraaminometacresol (manufactured by Sumitomo Chemical Co., Ltd.) Sumiepoxy@EL
MIOO) Resin A... Tetraglycidyl of 3,4°-diaminodiphenyl ether Epiclon 830... Diglycidyl of bisphenol F (manufactured by Dainippon Ink Co., Ltd.) Epiclon@830
) ELA-128... Diglycidyl of bisphenol A (Sumitomo Chemical Co., Ltd. Sumiepoxy @ ELA-128)
Resin B: Molecular distillation product R-710 of ELA-128
... Diglycidyl of bisphenol AD (1.1'-dihydroxydiphenylethane) (Mitsui Petrochemical Co., Ltd. R-710) 3,3゜-DDS...-3,3゛-diaminodiphenylsulfone (curing agent) 4. 4'-DDS...4.4'-diaminodiphenylsulfone (curing agent) 3. 4'-DDE...3,4°-diaminodiphenyl ether (curing agent) Resin C...Resorcin-based polysulfone resin D of Synthesis Example 1...Resorcin-based polysulfone resin E of Synthesis Example 2 ... Resorcinol-based polysulfone resin F of Synthesis Example 3 ... Bisphenol-based polysulfone resin G of Synthesis Example 4 ... Polysulfone containing terminal amino groups PES5003p of Comparative Synthesis Example I... Polyethersulfone (IC
Victrex made by I @PES5003p) Fine powder A...
-Resinous fine particles of Synthesis Example 5 Powder B Resinlike particles of Synthesis Example 6 The matrix resin composition obtained in the above-mentioned method was molded into specimens for measuring physical properties. All curing conditions were 180° C. for 2 hours. G. c indicates the strain energy release rate (according to NASA PR-1092).

The water absorption rate was expressed as a percentage increase in weight after immersing the sample in boiling water for 48 hours under atmospheric pressure. The elastic modulus is the bending property (ASTM
D-790).

Table 2 shows the physical properties of the carbon fiber reinforced molded product.

Experiment numbers correspond to Table 1. Prepreg, which is a precursor of the certain shape, was produced using a blibreg manufacturing machine in the following manner. That is, surface-treated carbon fibers (Magnamite IM? manufactured by Hercules) are continuously pulled out from a bobbin, arranged in a width of 50cm+, and 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 with a fiber date of 150 glrd was obtained, which was made of carbon fiber impregnated with a matrix resin.

The obtained Bripreg sheet was cut and laminated so that the reinforcing fibers were oriented in the same direction, then inserted between hot plates of a hydraulic press heated to 180°C, and gradually pressurized until the reinforcing fiber content was 60 vol. While reducing the amount of resin so that
O kg/crlG, hardened in 1 hour.

The formed body was then further heated at 180'C in a hot air oven for 1 hour.
A time post-cure was performed to obtain a cured composite plate having a thickness of about 21II1.

The 0° bending strength and interlaminar shear strength of the obtained composite material cured plate were determined by ASTM-D790 and ASTM-D.
Measured in accordance with 2344.

Next, the obtained composite material cured plate was immersed in boiling water for 48 hours, and then the composite material cured plate after water absorption was heated to 82°C and 121°C.
The 0° bending strength in C was measured in the same manner. The results are shown in Table 2.

Subsequently, 24 plies of the prepreg were laminated in a quasi-isotropic manner, and 18
Press hardening molding was performed at 0°C for 2 hours. A falling impact of 400 kg-cm/cm was applied to the obtained laminate, and the damaged area was measured by ultrasonic C-scan. The measurement results are shown in Table 2.

The results in Tables 1 and 2 will be explained below. Comparative Example 1 is Example 1 without resinous fine particles, but there is no difference in G and c, which are indicators of resin toughness, and Example 1 is slightly better in terms of damage area on a pseudo-isotropic plate. Ta. In Comparative Example 3, in which the resin had low toughness, the damaged area in the pseudo-isotropic plate was large, and the performance was significantly inferior. In Comparative Example 3, in order to reduce the damage area by adding resinous fine particles to the matrix resin system, it is necessary to add a large amount of resinous fine particles, but as shown in Comparative Example 5, the damaged area may become smaller. However, there were some cases where it did not improve much. The cause of this is
Although the dispersion state of the resinous fine particles at the prepreg interface is an important factor, it is suggested that this is because the dispersion state of the resinous fine particles largely depends on the manufacturing method of the prepreg and pseudo-isotropic plate, making it difficult to obtain reproducibility. Ta. Comparative Example 2 uses a polysulfone containing terminal amino groups. In this system, the resin has high toughness and a small damage area;
et ) was low. In Comparative Example 4, the amount of curing agent was 1. There is an excess of 2 molar equivalents,
It showed the same performance as Comparative Example 2.

In contrast to the above comparative examples, in the examples of the present invention, since the resin had high toughness, the damage area was small and the reproducibility was high just by adding a small amount of resinous fine particles. Moreover, the high-temperature wet properties were also excellent.

Claims (3)

[Claims] (1) A fiber-reinforced composite material consisting of an epoxy resin composition consisting of an epoxy resin, a reactive oligomer, resinous fine particles, and a curing agent, and reinforcing fibers, in which the epoxy resin composition (a) contains an epoxy group in one molecule; 100 parts by weight of an epoxy resin having two or more epoxy resins, 10 to 100 parts by weight of a reactive oligomer made of polyaryl ether represented by formula (b) (I), ▲ mathematical formula,
There are chemical formulas, tables, etc. ▼ (I) (In the formula, Ar is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲
Represents at least one type of divalent aromatic group selected from ▼, ▲ ▲ ▼, where n is a positive integer. ) (c) Consisting of an epoxy resin, a reactive elastomer, and a curing agent mainly composed of an aliphatic amine or an acid anhydride, and has an elastic modulus of 100 to 500 kg/mm^2 in the cured state.
2 to 15% by weight of resinous fine particles having an average particle size of 10 to 100 μm based on the epoxy resin composition; A fiber-reinforced composite material characterized by having a molar equivalent of 0.7 to 1.05. (2) Ar of the polyaryl ether is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, and the number average molecular weight is 11.0
00 to 30,000, the fiber reinforced composite material according to claim 1. (3) The fiber according to claim 1, characterized in that Ar of the polyarylether is ▲ ▲ as shown in the formula, chemical formula, table, etc. ▼ and the number average molecular weight is 3,000 to 10,000. Reinforced composite material.