JPS6354418A - Curable resin composition for prepreg - Google Patents

Abstract

PURPOSE:To obtain the title composition which can give a cured product excellent in heat resistance, water resistance and toughness, by mixing an epoxy compound with a cyanate resin, a polysulfone resin and a specified bis(hydroxyphenyl) sulfone or its formalin condensate. CONSTITUTION:A mixture obtained by mixing an epoxy compound (A) having at least two epoxy groups in the molecule (e.g., bisphenol A-derived epoxy resin) with a polycyanate (prepolymer) (B) having at least two cyanato groups in the molecule or a mixture thereof with a polymaleimide (prepolymer) (B) having at least two maleimide groups in the molecule at 9:1-2:8 is mixed with 6-60pts.wt. per 100pts.wt. component B, polysulfone resin (C) of formula I (wherein Ar is a group of formula II, III or IV) and 0.5-20pts.wt., per 100pts.wt. component A, bis(hydroxyphenyl) sulfone of formula VI or its formaline condensate (D).

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a novel resin composition for prepreg. It is suitable as a matrix resin for reinforced plastic (hereinafter abbreviated as FRP) brev legs.

[Conventional technology]

Among thermosetting resins, epoxy resins are widely used in various industrial fields due to their excellent mechanical properties. In particular, epoxy resins are often used in advanced composite materials made of reinforcing fibers such as carbon fibers, glass uA fibers, and aramid fibers and matrix resins. However, the epoxy 8i used in these composite materials still has some unsatisfactory points, and its applications and usage methods are limited. One of these is heat resistance and water resistance. Various curable resins other than epoxy resins have conventionally been used as matrix resins to improve heat and water resistance. Among these, cured products of cyanate ester resins have been known to provide cured products with excellent heat resistance and water resistance. However, these cured products are brittle and have poor toughness, so advanced composite materials using them as matrix resins lack impact resistance and are hardened by reinforced uA'H.
There was a drawback that the strength of No. 1 could not be fully expressed.

Therefore, various efforts have been made to improve the toughness of these cured products. For example, cyanate ester resin compositions have been
There are those containing a modified butadiene resin with an acrylyl group introduced therein (Japanese Patent Laid-Open No. 57-153045), those containing a butadiene-acrylonitrile copolymer (Japanese Patent Laid-Open No. 57-153046), or those containing epoxy Ill. (Japanese Unexamined Patent Publication No. 56-157424.
56-157425) and the like are known.

However, all of these methods inevitably suffer from a decrease in heat resistance and water resistance.

In order to solve these problems and improve the toughness of the cured product without deteriorating its heat resistance and water resistance, Ujl! added polysulfone resin! The composition is disclosed in Japanese Patent Application Laid-open No. 57-165.
451, a resin composition in which an epoxy resin was further added to these was proposed as JP-A-60-250026.

These resin compositions have improved toughness of the cured product by adding polysulfone resin, and the polysulfone resin alone has better heat resistance and water resistance than the above-mentioned butadiene resin. The cured product has excellent physical properties with little deterioration in heat resistance and water resistance.

However, in these cured products, the polysulfone resin is highly dispersed, and because polysulfone resin is a thermoplastic resin, it dissolves in halogenated solvents, so these cured products have a serious drawback of poor solvent resistance. .

As a result of studies by the present inventors, polysulfone B!
When epoxy 8i compositions containing j# were cured, it was found that those that dissolved uniformly and cured as they were, or those that did not dissolve uniformly and were finely dispersed even after phase separation, had almost no problem with solvent resistance. Understood.

However, when cyanate ester resin is used, even if it is uniformly dissolved, the thermoplastic 8i phase separates during the dispersion process, and the final cured product has poor solvent resistance because it is not finely dispersed. Most of the results were unsatisfactory.

[Problems to be solved by the present invention]

An object of the present invention is to provide a jHMB composition for prepregs that becomes finely dispersed and does not have poor solvent resistance even when a polysulfone resin is added to a cyanate ester resin to improve the toughness of the cured product.

[Means for solving problems]

As a result of extensive studies, the present inventors found that bisphenol was used to improve the dispersion state of the polysulfone resin in the cured product in a cyanate ester resin containing a polysulfone resin in order to improve the toughness of the cured product. S
The inventors have discovered that by adding , it is possible to provide a resin composition for prepregs that is finely dispersed and has excellent heat resistance and water resistance without deteriorating solvent resistance and has improved toughness.

That is, in order to achieve the above object, the present invention has the following configuration.

(1) Curable composition A for prepreg containing at least the following components; Polyepoxy compound B having at least two or more epoxy groups in one molecule; Cyanate ester resin C; Polysulfone resin D ;Bis(hydroxyphenyl) represented by the following general formula
At least one of sulfone or its formalin condensate The polyepoxy compound used in the present invention is
Most of them can be used without limit. To specifically illustrate, Epicote 828. Ebiko) 1001 (
Liquid or solid Bi-X7z such as DER-331 (manufactured by Dow Chemical Japan Co., Ltd.)
/-7kA type epoxy vd visit, ELM434. ELM1
Glycidylamine type epoxy resins such as 20 (manufactured by Sumima Kagaku Co., Ltd.), YH-434 (manufactured by Kyoto Kasei Co., Ltd.), xY-720 (manufactured by Ciba-Geigy Co., Ltd.), Evicron 830 (manufactured by Dainippon Ink & Chemicals Co., Ltd.), YH-434 (manufactured by Kyoto Kasei Co., Ltd.), Bisphenol F type epoxy 81 visit, Epicote 152. Epicote 154
Phenol novolac type epoxy resin such as (manufactured by Yuka Shell Epoxy Co., Ltd.), brominated bisphenol A type epoxy resin such as Evicron 152 (manufactured by Dainippon Ink & Chemicals Co., Ltd.), cresol novolak such as ESCN-220 (manufactured by Sumima Kagaku Co., Ltd.) Examples include bisphenol S type epoxy resin, bisphenol S type epoxy resin, and alicyclic epoxy resin.

These polyepoxy compounds can be used alone or in a mixture of several types. However, since adding a thermoplastic resin increases the resin viscosity, if the amount added is large, use the low-viscosity, liquid Ebiko) 82B ( Bisphenol A type epoxy resin such as Yuka Shell Epoxy Co., Ltd.), bisphenol F type epoxy tilt? is suitable.

Moreover, the polyfunctional cyanate ester in component B is a compound having two or more cyanate ester groups, and a suitable cyanate ester is a compound represented by the following general formula (1).

R, 40-CmiN), (1) (where m is an integer of 2 or more and 6 or less, R is an aromatic organic group, and the cyanate ester group is an aromatic group of the organic group R. (Bound to a ring) Specifically, dicyanatobenzene, tricyanatobenzene, dicyanatonaphthalene, tricyanatonaphthalene, diaminodiphenyl, bis(cyanatophenyl)methane, bis(cyanatophenyl)
Examples include propane, bis(cyanatophenyl) ether, bis(cyanatophenyl) sulfone, and cyanate ester obtained by reaction of novolac with cyanogen halide. It can also be used as a prepolymer obtained by polymerizing these polyfunctional cyanate esters in the presence of a catalyst such as a Lewis acid, a salt such as sodium carbonate, or lithium chloride.

Moreover, polyfunctional maleimides are compounds represented by the following general formula (2).

+1 (wherein R is an aromatic or aliphatic organic group of 2 or more and 6 or less, X and X are hydrogen, halogen, or an alkyl group, and n is an integer of 2 or more and 6 or less. ) The maleimide represented by the above formula can be obtained by reacting maleic anhydride with a polyamine having 2 to 6 amine groups to prepare maleamic acid, and then performing a dehydration reaction. The polyamine used is preferably an aromatic polyamine in terms of heat resistance, but if it is desired to impart flexibility or softness to UjlR, an aliphatic amine may be used. Suitable amines include phenylene diamine, xylylene diamine, Examples include amine, cyclohexanediamine, diaminodiphenyl, diaminodiphenylmethane, diaminodiphenyl ether, diaminodiphenylsulfone, and the like. Also used are condensation products of maleimide and these amines.

The mixing ratio of component A and component B varies depending on the type of compound used, but generally A:B is 9:1 to 2:8.
is within the range of

The amount of the polysulfone resin (C component) to be added is preferably about 6 to 60 parts per 100 parts by weight of the polyepoxy compound (A component) and the cyanate esters and maleimides (B component). If this happens, the tack and drape of the prepreg will deteriorate.

The amount of bis(hydroxyphenyl)sulfone added as component D is 0,
It is preferably about 5 to 20 parts, and if it is less than this, the effect of addition will be small, and if it is more than this, the tack and drape of the prepreg will deteriorate.

The method of mixing the components of the present invention is not particularly limited, and a preferred method can be selected as appropriate depending on the shape of each component and the mixing state or dispersion state of the intended blend. An example of a mixing method is to use a solvent that dissolves each component to form a homogeneous solution.An example of a mixing method is to dissolve the polyepoxy compound and thermoplastic UJ sushi at a relatively high temperature without using a solvent. There is a method of lowering the temperature by adding cyanate esters and maleimides.

The resin composition of the present invention is a useful epoxy resin composition that, when used as a matrix for FRP prepreg, provides a prepreg with excellent tack and drape properties, good moldability, and high toughness. However, as reinforcing fibers, carbon fibers, glass fibers, aramid fibers, boron fibers, or hybrids thereof can be used. Moreover, any shape can be used, such as a tape arranged in a certain direction, a sheet-like material, a mat-like material, a woven material, etc.

Furthermore, various additives such as fillers, curing accelerators, and diluents can be used within the range that does not impair the properties.

[Effect]

In the present invention, in a resin composition in which polysulfone 4B11 is added to a cyanate ester resin to improve the toughness of the cured product, the dispersion state of polysulfone [11] in the cured product is improved by adding bis(hydroxyphenyl)sulfone. tal1 for prepreg, which does not deteriorate solvent resistance, has excellent heat resistance and water resistance, and has improved toughness.
It has now become possible to provide a composition.

〔Example〕

The invention will be explained in more detail by the following examples. The amount of each component in the examples represents i1 part, and the contents of the resin are as follows.

Epoxy resin; Bisphenol A epoxy resin, Epicoat 828 (manufactured by Yuka Shell Epoxy Co., Ltd.) I3T resin, pre-reacted product of 2,2'-bis(4-cyanatophenyl)propane, BT-2160RX (manufactured by Mitsubishi Gas Chemical Co., Ltd.) ) Example 1 Bo IJ ether sulfo 7 VICTREX 100P having the following chemical structure based on 100 parts by weight of epoxy resin
(1, C.

When 20 parts of 4,4'- and Suphenol S (manufactured by NICCA Chemical Co., Ltd.) were added at 150°C and stirred with PAff, a transparent viscous liquid was obtained after 30 minutes. This mixture was cooled to 80° C., and 200 parts of B1 resin was added to obtain a 111#J1 composition. This resin composition was cast and cured at 180° C. for 2 hours to obtain a cured product.

When the glass transition temperature (1 g) of this cured product was measured using a differential scanning calorimeter, it was 201°C, indicating that it was a cured product with high heat resistance.

Further, this cured product was immersed in methylene chloride and left for one day, but no change occurred.

Example 2 A resin composition was obtained in the same manner as in Example 1 except that 2,4'-bisphenol S (manufactured by NICCA Chemical Co., Ltd.) was used instead of 4,4'-bisphenol S. This resin composition was cast and cured at 180'C for 2 hours to obtain a cured product.

When the glass transition temperature (Tg) of this cured product was measured using a differential scanning calorimeter, it was 200°C, indicating that the cured product had high heat resistance.

Further, this cured product was immersed in methylene chloride and left for one day, but no change occurred.

Comparative Example 1 A vdj1 composition was obtained in the same manner as in Example 1 except for the step of adding 4.4'-bisphenol S. This resin composition was cast and cured at 180° C. for 2 hours to obtain a feces product.

When the glass transition temperature (Tg) of this cured product was measured using a differential scanning calorimeter, it was 202°C, and as in Example 1, the cured product had high heat resistance.

However, when this cured product was immersed in methylene chloride and left for one day, the surface turned white and began to crumble from the edges.

Comparative Example 2 A 1B pilgrimage composition was obtained in the same manner as in Example 1 except for the step of adding polyether sulfone. This t
The composition was cast and cured at 180'C for 2 hours to obtain a cured product.

When this cured product was immersed in methylene chloride and left for one day, no change was observed as in Example 1.

Come! M3 A resin film was prepared by heating the UI composition obtained in Example 1 to lower its viscosity and then stretching it onto paper that had been subjected to a release treatment with silicone. 6th carbon m dark blue trading card T-8
00 (manufactured by Toshisha Co., Ltd.) were aligned in one direction and arranged on a resin film, heated and pressurized to obtain a prepreg. The obtained prepreg has moderate tack.

It had drape and was of good quality.

This prepreg (+45/90/-4510) 4G
Laminated in a quasi-isotropic manner with the configuration of 6.
A composite was obtained by molding under the conditions of kgf/cm2 and 1130°C for 2 hours.

This composite has a weight of 680kgc with a RX6mm tip.
Falling weight f of m/c+w [gave impact energy. When the damage caused by this impact test was measured using an ultrasonic damage imaging device (manufactured by Canon Holosonic), the damage area was 20.4 cm2.

Comparative Example 3 Prepreg was prepared in the same manner as in Example 3 except that the resin of Comparative Example 2 was used instead of the resin of Example 1.
A composite was obtained.

Furthermore, when an impact test of 11 was conducted in the same manner as in Example 9'13, the damage area was 44 J ci2.

Claims (3)

[Claims] (1) Curable resin composition A for prepreg containing at least the following components; polyepoxy compound B having at least two or more epoxy groups in one molecule; cyanate ester resin C; polysulfone resin D; Bis(hydroxyphenyl) represented by the general formula below
At least one type of sulfone or its formalin condensate▲There are mathematical formulas, chemical formulas, tables, etc.▼ (2) Curable resin composition for prepreg according to claim 1, wherein the polysulfone resin of component C is polyallyl ether sulfone represented by the following general formula -(Ar-SO_2)-_n Ar; ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (3) The cyanate ester resin of component B is a mixture with (a) a polyfunctional cyanate ester containing two or more cyanato groups in the molecule or a prepolymer thereof, or a mixture with the above (a) in the molecule. The curable resin composition for prepregs according to claim 1, which comprises a polyfunctional maleimide containing two or more maleimide groups or a mixture thereof with a prepolymer thereof.