JPH02127421A - Epoxy resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition excellent in storage stability, moist heat resistance and post-impact compression characteristics and useful for a prepreg by blending a bifunctional epoxy resin, trifunctional epoxy resin and respectively specified phenol compound and diaminodiphenyl sulfone. CONSTITUTION:(A) A bifunctional epoxy resin (preferably bisphenol A type or bisphenol F type), (B) a trifunctional epoxy resin (preferably N,N,O- triglycidyl-p- or m-aminophenol, etc.), (C) a phenol compound [e.g., 2,6- dihydroxynaphthalene of the formula I (X1 to X8 are H, Br, Cl, 1-6C alkyl or OH, provided that one of X1 to X4 and one of X5 to X8 are OH) and (D) 4,4'-diaminodiphenyl sulfone or 3,3'-diaminodiphenyl sulfone are blended, thus obtaining the objective composition. In addition the component (C) is preferably used in an amount satisfying formula II.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an epoxy resin composition for Gripreg that provides excellent storage stability, heat and humidity resistance, and impact resistance and compression properties. The resulting composite material can be used in aircraft, automobiles, and general industrial applications.

[Conventional technology]

Conventionally, epoxy resins have been widely used as matrix resins for composite materials due to their excellent adhesion and high rigidity. Among them, n, m, and Is are used as matrix resins for high-performance structures.
M'-tetraglycidyldiaminodiphenylmethane, 4
Compositions containing 4'-diaminodiphenylsulfone as a main component have been in use for many years since 1972.

[Problem that the invention seeks to solve]

However, since the elongation of the matrix resin is low, the composite material obtained by heating and curing the prepreg of this composition cannot be used with recent high elongation reinforcing fibers such as carbon fibers, aramid fibers, and glass having a breaking elongation of T5 or better. It had drawbacks such as being unable to follow fibers, etc., and having a lower tensile elongation than reinforcing fibers. As a result, although the compressive strength after moisture absorption is sufficient in the temperature range of 82°C, the compressive strength after impact is extremely low, making the material completely inadequate for use as a material for secondary structures.

On the other hand 5th 8AMPI European Cha
pter (198A) Paper 15 (T, T
The passage written in attersal'l'J,
Materials with high compressive strength after impact have been reported, but the compressive strength after moisture absorption was insufficient, and the volume content of fibers did not increase due to the inclusion of an intermediate layer called interleaf, so this material is far from practical. Met.

In view of the above, the present inventors found that both the compressive strength in the 82°C temperature range after moisture absorption (110 to 9/1,1111 or more) and the compressive strength after impact (27 to 5F/■ snow or more) were superior. The present invention was arrived at as a result of extensive research into an epoxy resin composition for Gripregs that provides such characteristics.

[Means for solving problems]

That is, the gist of the present invention is (A) in a bifunctional epoxy resin) trifunctional epoxy resin (C) a phenol compound represented by the following formula (however!, ~
X is H, Br, l) a, an alkyl group having 6 or less carbon atoms, or -OH, which may be the same or different, but
Any one of X and any one of X, ~X, ■
Each symbol represents OH. ) φ) 44'-diaminodiphenylsulfone or 43'
- An epoxy resin composition containing diaminodiphenylsulfone as an essential component.

Of these compositions, some or all α), all @), and all (C) are prepared by combining (0) phenolic OE O80 or more with the engineered boxy group of (A) CB) in advance. It is preferable to carry out a preliminary reaction before use.

The present invention further provides an epoxy resin composition containing reinforcing fibers in the epoxy resin composition.

The (A) bifunctional epoxy resin used in the present invention includes bisphenol A type epoxy resin, bisphenol ? type epoxy resins, their brominated epoxy resins, bisphenol B type epoxy resins, and the like.

In order to improve toughness, it is desirable to use bisphenol A type epoxy resin or bisphenol F type epoxy resin as the main component.

The molar ratio of epoxy groups O in these epoxy resin bodies) to the epoxy resin ω) is M/B = 1/CL 1
~1/12, preferably 1/a2 ~ 4/0. It is O. When j/l is larger than 1, not only hot water resistance but also chemical resistance is reduced, which is not preferable. 1
If it is smaller than /12, the toughness is insufficient, resulting in a decrease in the utilization rate of the reinforcing material and a decrease in the compressive strength after impact (c).

The trifunctional epoxy resin used in the present invention includes:
N, 14. O-)liglycidyl-p- or -m-aminephenol, "p"pO-triglycidyl-4-amino-m- or -5-amino-0-cresol, LLl-(
) liglycidyloxyphenyl) methane, and the like. Among them, N, M.

O-triglycidyl compounds are preferably used in terms of improving solvent resistance.

The phenolic compound (0) in the present invention is a dihydroxy compound having a naphthalene skeleton, such as a 2.6-
Cyhydroxynaphthalene is preferably used.

The amount of (C) used is preferably such that the ratio of the number of moles of phenolic OH in (0) is 1/[11 to 1/α9, and if this ratio is greater than 1/α1, sufficient moist heat resistance and It is not suitable because impact resistance cannot be obtained, and if it is smaller than 1/α9, it is not preferable because heat resistance and solvent resistance decrease.More preferably, it is 1/α2 to 1/0. It is 8.

(D) It is desirable that the following equation be satisfied.

Number of moles of NH in amine =1/Y8~1/1-S A very preferable ratio is 1/IIL9 to 1/12.

If it is larger than 1/0.8, curing will be insufficient and solvent resistance and heat resistance will be poor, and if it is smaller than 1/15, water resistance and solvent resistance will be lowered, which is not preferable.

In addition, all or part of the epoxy resin (A), all (0) in the epoxy resin, and all (0) of the phenolic 0'E1 are mixed in advance to a phenolic 0'E1 of 80 or more, more preferably 90
% or more.

If the reaction rate is lower than this, the 411 impact resistance of the resin composition will decrease, so it is preferable to pre-react to the above-mentioned extent.

Molar ratio of epoxy groups A / B -1 / C of some or all epoxy resins IA), all epoxy resins) used in the preliminary reaction with the phenolic compound (0)
L5~1/A Ol, preferably 1/α5~1
/2. It is O. If it is larger than 1/13, sufficient hot water resistance and solvent resistance cannot be obtained and it is not suitable.

If it is smaller than 1/AO, gelation will occur during the preliminary reaction, which is not preferable.

Further, the amount of (0) used in the pre-reaction is the number of moles of heptanol OHO of (C) = 1/12 to 1/1. It is preferable to set it to i, and more preferably, it is 1/α3 to 1/1.0. If it is larger than 1/α2, sufficient hot water resistance and compressive strength after impact cannot be obtained, which is not preferable. Also, if it is smaller than 1/11, the viscosity during the preliminary reaction will be high (it will be difficult to handle), which is not preferable.

The epoxy resin composition of the present invention has one of the above-mentioned components) to Φ) as an essential component, but other epoxy resins (B) may be added within a range that does not disrupt the overall physical property balance.
Soy milk can also be used in combination with soy milk. Other epoxy resins (
Representative examples of LLMS N'-tetraglycidyldiaminodiphenylmethane and other tetrafunctional epoxy resins, and novolac type epoxy resins. The amount of these @) components used is preferably less than 20 parts by weight of the total epoxy resin components ((A) + (B) + (6)).

In addition, when using the component (6), it is desirable that the ratio of each component satisfies the following formulas.

Molar ratio of epoxy groups in (A)/■) = 1/α1~1/
t2 The resin composition of the present invention may contain other components such as inorganic photoresist agents such as silica powder, Aerosil, microballoons, and flame retardants such as adioxide/thymo7, as well as butadiene-acrylonitrile with carboxyl groups at both terminals. So-called elastomer components such as polymers, thermoplastic resin components such as polyethersulfone, polysulfone, polyetheretherketone, polyetherimide, and polyvinyl butyralide may be used in combination depending on the purpose.

The amounts of these other components to be used may be appropriately determined depending on the purpose within a range that does not disrupt the overall physical property balance.

The resin composition in the present invention is 4,47-diaminodiphenylsulfone (ζm'-DDEl)
d3,s'-diaminodiphenylsulfone C15'-D
Although sufficient curing can be achieved by using D8) in the above-mentioned ratio, other curing agents or curing accelerators may be used in combination.

Representative examples of other curing agents include aromatic amines such as 44'-diaminodiphenylmethane, trimethylene-bis, (A-aminobenzoate), and dicyandiamide. It is desirable that the amount of these other curing agents used be limited to 20% by weight or less (total amount of curing agent (2)).

Further, as a representative example of the curing accelerator, amine salts of 37 boron fluoride can be mentioned. The amount of the curing accelerator to be used may be appropriately determined depending on the purpose.

Examples of reinforcing fibers include carbon fibers, glass fibers, aramid fibers, boron fibers, silicon carbide fibers, and the like.

The reinforcing fibers can also be used in the form of milled fibers, chopped fibers, unidirectional sheets, or woven fabrics.

〔Example〕

The present invention will be specifically explained below using Examples.

Part represents M1 part. Furthermore, the molar ratio 1 represents the molar ratio of functional groups.

The properties of the covering material were determined by the following measurement method.

The measurement results are converted to a fiber volume content of 60%.

"Hot water resistance" means Qo 16-layer laminated material composite was left in water at 71℃ for 14 days, then Mu8TM D-
695 by a compression test in the 0° direction at 82°C.

"Impact resistance" is based on NA8A RP 1092, by fixing a board with panel dimensions of 4# x 6# on a stand with a 3' x 5' hole, and attaching a bar 'R' nose to the center of it. . υ was determined by dropping a weight (L9kJIZ) and applying an impact of 1 sooz'b·in per inch of plate thickness, and then subjecting the panel to a compression test.

"Resin handling properties" were determined based on the softness of the resin composition at room temperature. Soft items were rated as 0 and hard items were rated as ×.

"M, 1, 1 iK resistance" was determined by the change in appearance of the cured resin product after being immersed at room temperature for 7 days, and those with no change were rated ○, and those with a large change were rated ×.

Example 1 Bisphenol FJ epoxy resin, Epicote 807
C Yuka'zL Epoxy Co., Ltd. trade name, epoxy equivalent 1
70) 100 parts, N, N, N, O-)liglycidyl-P
-Aminophenol (epoxy @94) 1 #6 parts, 2
．． 12.2 parts of 6-hydroxynaphthalene, 4. j'−
DD8 5 parts 9 parts were mixed, and silicon oxide fine powder (A
erosil 580, manufactured by Nippon Aerosil Co., Ltd.)
25 parts were added thereto and thoroughly mixed in a kneader at 60°C to obtain a resin composition 0). 2 parts of this composition were applied to a glass plate and cured at 180° C. for 2 hours to obtain a resin plate.

In addition, this resin composition 'JIJ<1) was impregnated into carbon fibers aligned in one direction (Pyrofil M-1, manufactured by Mitsubishi Rayon Co., Ltd.) by hot melt method to obtain a yarn weight of 145.
A 17 m2 one-sided prepreg with a resin content of 35 layers was made. This prepreg [0°] 1. and [+4
5°107-45°/90°]4. The composite materials were laminated in a superiorly isotropic manner and cured at 180° C. for 2 hours to obtain a composite material. The test results for these are shown in Table 1.

Examples 2 to 6, Comparative Columns 1 to 6 Tests were conducted by changing the theory of the compounds used in Example 1 as shown in Table 1. The results are shown in Table 1.

Examples 7 to 12 Tests were conducted by changing the compounds used in Example 1 as shown in Table 1. M fruits are also shown in Table 1.

The compound Epicoat 828 used is a bifunctional engineered glycidyl ether type EVO Φ
Part name manufactured by Yuka Shell Epoxy Co., Ltd., epoxy equivalent: 188).

Run 15 The composition of Run 1 was used, but Epikote 807 was divided into two parts and a portion was pre-reacted. That is, 30 parts of Epicote 807, N, LO-)liglycidyl-p-
16-6 parts of amine phenol, 112 parts of 2.6-dihydroxynaphthalene, reacted at 130°C for 2 hours, cooled to 60°C, and added 70 parts of Epicor) 807, 57.9 parts of 44'-DDS. , and further added 25 parts of silicon oxide fine powder and thoroughly mixed in a kneader (kept at 60°C) to obtain a resin composition (n). this composition value)
Resin plates and composites were tested in the same manner except that the composition was used instead of composition (1) in Example 1. Table 2 shows the results.
It was shown to.

Examples 14 to 20 Tests were carried out in the same manner as in the practical series, except that the theory of compounds used in the preliminary reaction and the reaction rate were changed as shown in Table 2.

The results are shown in Table 2.

Actual Series 21 Tests were conducted in exactly the same manner as Actual Series 1, except that 1 SO part of powdered polyether sulfone was further mixed with each compound described in Example Series 1.

The resulting composition had good handling properties and the MIX resistance of the cured resin, and the carbon fiber composite material produced using this resin composition had a pressure a strength of 118 Yu/11 after water absorption at 82°C.
11”, compressive strength after impact at room temperature 35k!97m
”The physical properties as a composite material were also extremely good.

Claims (1)

[Claims] 1. An epoxy resin composition characterized by containing the following components (A), (B), (C), and (D) as essential components (A) a bifunctional epoxy resin (B) a trifunctional epoxy Resin (C) Phenolic compound represented by the following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. (D) 4,4'-diaminodiphenylsulfone or 3,
3'-Diaminodiphenylsulfone 2, The composition according to claim 1, wherein the (A) bifunctional epoxy resin is a bisphenol A type and/or bisphenol F type epoxy resin. 3. (B) The trifunctional epoxy resin is N,N,O-triglycidyl-p- or -m-aminophenol, N,N,O
-Triglycidyl-4-amino-m- or -5-amino-o-cresol, 1,1,1-(triglycidyloxyphenyl)methane or a mixture of two or more thereof. 1. The composition according to item 1. 4. The molar ratio of epoxy groups in (A)/(B) is 4/0.1
Composition according to claim 1, characterized in that it is 1/1.2 to 1/1.2, preferably 1/0.2 to 1/1.0. 5. The composition according to claim 1, wherein the amount of (C) used satisfies the following formula. Sum of moles of epoxy groups in (A) and (B)/number of moles of phenolic OH in (C) = 1/0.1 to 1/0.96,
2. The composition according to claim 1, wherein the amount of (D) used satisfies the following formula. (Sum of moles of epoxy groups in (A) and (B)) - ((C
) / NH of amine (D)
The number of moles of (C) = 1/0.8 to 1/1.57, some or all (A), all (B), and all (C) are preliminarily added to the phenolic OH of (C). More than 80% (A
2. The composition according to claim 1, wherein the composition is used after preliminary reaction with the epoxy group of (B). 8. The composition according to claim 7, wherein the molar ratio of the epoxy groups of (A)/(B) used in the preliminary reaction is 1/0.3 to 1/3.0. 9. The composition according to claim 7, wherein the amount of (C) used in the preliminary reaction satisfies the following formula. Sum of moles of epoxy groups in (A) and (B)/number of moles of phenolic OH in (C) = 1/0.2 to 1/1.110
2. The composition according to claim 1, further comprising reinforcing fibers.