JPS62184015A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:To increase the storage stability, wet-heat resistance and impact resistance of the obtained composition and improve the fluidity of the composition during molding, by mixing a polymaleimide, polycyanic ester or the like with a pre-reaction product of an epoxy compound with a diamine, a urea compound and a specified polysulfone resin. CONSTITUTION:This thermosetting resin composition contains the following components A-D: (A) at least one selected from among a polymaleimide (I), a polycyanic ester or its oligomer (II) and a pre-reaction product of (I) with (II), (B): a pre-reaction product of a diamine with an epoxy compound having at least two epoxy groups in the molecule, (C): a urea compound, and (D): a polysulfone resin of the formula (wherein A is a bivalent aromatic group which may be interrupted by oxygen or a bivalent aliphatic group and m is an integer >=2).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a thermosetting resin composition having excellent storage stability, flow stability, impact resistance, moist heat resistance and mechanical properties.

[Prior art]

Conventionally, various resin compositions have been used as matrices for composite materials, but in the field of thermosetting resins in particular, in addition to excellent mechanical properties, they have good adhesion to reinforcing materials. Epoxy resins have been widely used because of their superior strength development properties compared to other thermosetting resins.

In recent years, there has been a strong demand for higher performance of composite materials, especially improvements in impact resistance, heat and humidity resistance, etc.

As one of the methods, polyfunctional maleimides, polyfunctional cyanate esters, oligomers thereof, and pre-reacted products thereof are being considered as matrices. As a result, although the rigidity and heat-and-moisture resistance of the resin were improved, the impact resistance was low and was still insufficient for use as a matrix for composite materials. Furthermore, the fluidity of the resin during molding is as high as that of epoxy resin, and improvements in the molding process have also been desired.

[Purpose of the invention]

The present inventors have arrived at the present invention as a result of intensive studies aimed at developing a thermosetting resin composition that has excellent storage stability, heat and humidity resistance, and impact resistance, and has improved fluidity during molding. .

[Structure of the invention]

The present invention relates to polyfunctional maleimide (I), polyfunctional cyanate ester or oligomer thereof (11) and (1), and (
At least one kind selected from the group consisting of the pre-reactants of II) (A) a pre-reactant of an epoxy compound having two or more epoxy groups in one molecule and a diamine (B), a urea compound (C) and General formula (in the formula, 1m is a divalent aromatic group which may be interrupted by an oxygen atom or a divalent aliphatic group)
is an integer of 2 or more).

The polyfunctional maleimide (1) used in the present invention is a compound having two or more maleimide groups, represented by the general formula (wherein R1 represents a divalent aromatic group or an alicyclic group). Examples include prepolymers obtained by reacting these bismaleimides with amines.

Bismaleimide can be produced by a known method in which maleic anhydride is reacted with a diamine to prepare bismaleamic acid, which is then cyclodehydrated. The diamine may be either an aromatic diamine or an alicyclic diamine; for example, the following compounds may be used. m-22 diamine, p-7 22 diamine, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylmethane.

4.4'-diaminodiphenyl ether, 2,2-bis(4-aminophenoxyphenyl)propane, bis(4
-aminophenoxyphenyl) sulfone, bis(4-aminophenoxyphenyl) sulfide, 1,4-bis(
4-aminophenoxy)benzene, 1,3-bis(4-
aminophenoxy)benzene, trimethylenebis(4-
7minobenzo 1-)), 1,4-cyclohexanediamine, hexahydroxylylenediamine, etc. These diamines can be used alone or in combination.

Polyfunctional cyanate ester (II) used in the present invention
is an organic compound having two or more cyanate ester groups represented by the general formula %) (3) (wherein R2 is an aromatic group and n is an integer of 2 to 5) and its oligomer. .

Compounds of formula (3) include 1, e.g. 1,3- or 1,4
-dicyanatobenzene, 4.4'-dicyanatobiphenyl, bis(4-cyanatophenyl)methane, 2,
2-bis(4-cyanatophenyl)ethane, 2,2-
Bis(4-cyanatophenyl)propane, bis(4-
cyanatophenyl) sulfone and the like. Examples of polyfunctional cyanate ester oligomers include triazine oligomers obtained by trimerizing cyanate. Prepolymers resulting from the reaction of cyanate esters and amines can be used. The amines used in the production of the prepolymer include those used in the synthesis and modification of the polyfunctional maleimide described above.

Component (A) of the present invention includes the polyfunctional maleimide (I), polyfunctional cyanate ester and/or (1
) and (II) in the absence of a catalyst or in the presence of a catalyst.

Examples of the preliminary reaction product (B) of an epoxy compound having two or more epoxy groups in the molecule and a diamine used in the present invention include glycidyl ether type, glycidyl ester type, glycidyl amine type, and chain aliphatic epoxide type. , a reaction product of a known epoxy compound such as an alicyclic epoxide type and a diamine used in the synthesis and modification of the polyfunctional maleimide described above. The diamine preferably has a PKb of 7 or more. When PKb is 7 or less, it is difficult to control the preliminary reaction, and storage stability may decrease. Examples of diamines with PKb of 7 or more include 4,4
'-Diaminodiphenylsulfone, 1,4-His(
4-amino7ethenooxy)benzene, 1,3-bis(
4-aminophenoxy)benzene, trimethylenebis-
(4-aminobenzoate) and the like.

What is the preliminary reaction between an epoxy compound and a diamine?

For example, amino group/ebokey/group = 1/10 to 8/10,
Preferably, it is obtained by reacting at an equivalent ratio of 2/1o to 5/1o. The reaction temperature is 50 to 250°C, preferably 100 to 200°C, and one reaction is completed in 1 minute to 10 hours.

It is preferable to carry out the reaction so that the viscosity of the preliminary reactant is at least 50 times that of the simple mixture.

The urea compound (C) used in the present invention is added as a catalyst for a preliminary reaction between an epoxy compound and a diamine, and is necessary for improving impact resistance. Imidazole or its carboxylic acid adduct, 6th as a catalyst
Even if a class amine or the like is added, not only is storage stability lacking, but the impact resistance is not improved at all.

Examples of urea compounds include 1 such as N-(3-chloro-4-methoxyphenyl)-N', 1/-dimethylurea, N-(
4-chlorophenyl)-', gadimethylurea, N-(
6-chloro-4-ethylphenyl)-N', N'-dimethylurea, N-(6-chloro-4-methylphenyl)-
N',N'-dimethylurea, N-(3,4-dichlorophenyl) -N',N'-dimethylurea%N-(4-methyl-6-nitrophenyl) -N',N'-dimethylurea, 1.1'-(4-methyl-m-7enylene)-bis(3,3-dimethylurea), etc. These may be used alone (or may be used in combination of two or more types). The amount of urea compound (C) used is 1 to 10 parts by weight, preferably 2 to 5 parts by weight, per 10 parts by weight of component (B).

Although the resin composition of the present invention itself has sufficient thermosetting properties, it is necessary to further accelerate curing.

Alternatively, a catalyst other than the urea compound may be added for the purpose of imparting desired properties to the cured product.

Examples of such catalysts include latent curing catalysts such as boron trifluoride amine complex compounds, as well as organic peroxides such as benzoyl peroxide, dicumyl peroxide, and 1-butyl hydroperoxide.

Examples include organic acid metal salts such as zinc octylate, tin octylate, zinc naphthenate, and cobalt naphthenate. The amount of these used is sufficient within a general catalytic amount range, and may be, for example, 5% by weight or less based on the total resin composition.

Polysulfone resin (D) of formula (1) used in the present invention
As % VICTRIIX i 00 P CIC
(manufactured by Company I), oligomers synthesized from bisphenol A and dichlorophenyl sulfone, and the like.

The polysulfone resin is preferably used in a form with enhanced compatibility with other components by directly heating and dissolving it in the epoxy compound, or by dissolving the mixture with the epoxy compound in a solvent and then removing the solvent. The amount of polysulfone resin used is preferably in the range of 5 to 30% by weight based on the total amount of the resin 1 composition. If it is less than 5% by weight, the amount of improvement dust for flow characteristics is low.

The resin composition of the present invention is preferably used in a composition ratio of component (A) and component (B) / A = 1/1 to 9/1. When B/A is 1/1 or less, the heat and humidity resistance is excellent, but the impact resistance may be low. Further, when B/A is 9 parts 1 or more, the #* resistance is excellent, but sufficient heat and humidity resistance is not obtained, and the mechanical properties of the resulting composite material are also insufficient.

The thermosetting resin composition of the present invention is particularly useful for composite materials.
Excellent as J Lux fat. Glass fiber and carbon fiber are used as reinforcing materials for composite materials.

In addition to inorganic fibers such as poron fiber and silicon carbide 1' fiber, poly-p-phenylene terephthalamide and poly-p
- Chopped, yarn, tape, sheet, knitted fabric, mat, and paper products made of organic fibers such as benzamide and polyamide hydrazide, as well as glass powder and glass spheres.

Examples include mica, talc, asbestos, aluminum, iron, and copper. These can be used alone or in combination of two or more. Depending on the purpose, additives such as flow control agents such as fine silicon oxide powder, pigments, dyes, stabilizers, and plasticizers may be used in appropriate combinations.

The thermosetting resin composition of the present invention has excellent storage stability, workability, and processability, and particularly has excellent flow stability during molding.
When used as an IJ lux resin for composite materials, molding time can be shortened and auxiliary materials etc. can be significantly rationalized. Moreover, the cured product has excellent impact resistance and heat and humidity resistance.

Parts in the following Examples and Comparative Examples mean parts by weight.

Example 1 Epicoat 834 (manufactured by Yuka Shell Co., Ltd., epoxy ff1
250) 5000 parts and polyether sulfo 7 VICT
REX 100 P (manufactured by ICI) 1500 copies to 50
5000 parts of methyl ethyl ketone was added thereto and stirred at 70° C. for 6 hours to completely dissolve the mixture. Next, methyl ethyl ketone was removed to obtain a uniform resin composition (hereinafter referred to as (a)).

50 parts of bis(4-maleimidophenyl)methane, 2,
A preliminary reaction product was obtained by preliminarily reacting 450 parts of 2-bis(4-cyanatophenyl)propane at 120°C for 20 minutes.

To this, Epicoat 834 (manufactured by Yuka Shell Co., Ltd., epoxy 1250) was added to 4.4'-diaminodiphenylsulfone at an equivalent ratio of amine group/epoxy group = 1/4 at 160°C.
After 4 hours of reaction, Epicor 807 (manufactured by Yuka Shell Co., Ltd.,
Pre-reactant 2 diluted to 80% with epoxy [170]
000 parts and 1000 parts of the above (a), and heated to 70°C.
Mix uniformly for 30 minutes, then add 100 parts of N-(5,4-dichlorophenyl)-N',l/-dimethylurea and 1 part of dicumyl(-oxide) and stir at 70°C for 1 hour to mix uniformly. A resin composition was obtained. This resin composition was sandwiched between glass plates to a predetermined thickness and heated at 180°C for 2 hours.
A resin plate was obtained by curing for a period of time. In addition, this resin composition was used to form a film using a hot-melt method, and Pyrofil T-3 (manufactured by Mitsubishi Rayon Co., Ltd.) was further used to form a unidirectional prepreg (thread weight 145 g/'''', resin content 64.0%).
It was created. This prepreg is (0)+a and [+45
707'-45/+90) stacked on 4s, 180
A composite material was obtained by curing at ℃ for 2 hours.

Tests shown in the table below were conducted on resin plates and composite materials. The results are shown in the table. Glass transition point (Tg) in the table
and minη were each measured using a dynamic mechanical spectrometer manufactured by Rheometrics. The heat and humidity resistance of the composite material is (O)+a laminate composite 7
After 14 days of immersion in 1°C water, ASTM D 6
It was measured by carrying out a compression test in the 0° direction at 82° C. in accordance with 95. Impact resistance is C+4510/-45/
+90) A 4.9 kg piece of 4° laminated plate composite cut to 4 x 6 inches and fixed onto a 6 x 5 inch holed steel plate with a 0.5 inch R1 nose in the center. The measurement was performed by dropping a weight and applying an impact of 15,001 b-in per inch of plate thickness, and then performing a compression test. Non-bleeding moldability is determined by the uniformity of the thickness of the composite material obtained by molding it in an autoclave without using a bleeder, and those with high uniformity are rated ◎.

The lowest value is marked with an X.

Example 2 As a preliminary reaction product of an epoxy compound and a diamine, Ebiko) 828 (manufactured by Yuka Shell Co., Ltd., epoxy equivalent: 189)
with 4,4L diaminodiphenyl sulfone and amine group/
Epoxy group=! A resin plate and a composite material were obtained in the same manner as in Example 1 except that the resin plate was reacted at 160° C. for 4 hours at an equivalent ratio of 1/100. The test results are shown in the table below.

Example 3 Epicoat 152 (manufactured by Yuka Shell Co., Ltd., epoxy compound [177]) was used as a preliminary reaction product of an epoxy compound and a diamine.
was reacted with 4,4'-diaminodiphenylsulfone at an equivalent ratio of amino group/epoxy group = 3/100 at 160°C for 6 hours, and the other conditions were the same as in Example 1 to produce a resin plate and a composite material. I got it. The test results are shown in the table below.

Example 4 As a preliminary reaction product of an epoxy compound and a diamine, Epicote 864 was reacted with 1,4-bis(4-aminophenoxy)benzene in the same manner as in Example 1, and
A resin plate and a composite material were obtained in the same manner as in Example 1 in other respects. The test results are shown in the table below.

Example 5 As a preliminary reaction product of an epoxy compound and a diamine, Epicote 834 was reacted with trimethylene bis(4-aminobenzoate) under the same conditions as in Example 1, and the other conditions were the same as in Example 1 to prepare a resin. Boards and composites were obtained.

The test results are shown in the table below.

Comparative Example 1 A resin plate and a composite material were obtained in the same manner as in Example 1 except that no polysulfone resin was added. The test results are shown in the table below.

Comparative Example 2 A resin composition was prepared in the same manner as in Example 1 except that the epoxy compound and diamine were used without pre-reacting, but the resin had poor storage stability and could not be made into a prepreg.

Comparative Example 6 Resin plates and composites were produced in the same manner as in Example 1, except that the polysulfone resin was not added and the pre-reacted product of epoxy and diamine was diluted to 80% with Epikote 807, but the amount used was changed to 100 parts. I got the material. The following table shows all the fruits.

Claims (1)

[Claims] 1. Polyfunctional maleimide (I), polyfunctional cyanate ester or oligomer thereof (II), and (I) and (II)
At least one kind selected from the group consisting of preliminary reactants (
A), a preliminary reaction product of an epoxy compound having two or more epoxy groups in the molecule and a diamine (B), a urea compound (
C) and general formulas ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (1) (In the formula, A is a divalent aromatic group which may be interrupted by an oxygen atom or a divalent aliphatic group, and m is 2 or more. A thermosetting resin composition containing a polysulfone resin (D) represented by (indicating an integer of ). 2. The ratio of component (B) to component (A) is B/A=1/
The thermosetting resin composition according to claim 1, wherein the thermosetting resin composition is in the range of 1 to 9/1. 3. The thermosetting resin composition according to claim 1, wherein the preliminary reaction product of the epoxy compound and diamine is obtained at an equivalent ratio of amino group/epoxy group = 1/10 to 8/10. . 4, diamine is 4,4-diaminodiphenylsulfone,
1,4-bis(4-aminophenoxy)benzene, 1,
The thermosetting resin composition according to claim 1, which is 3-bis(4-aminophenoxy)benzene or trimethylenebis(4-aminobenzoate). 5. The urea compound is N-(3,4-dichlorophenyl)-
The thermosetting resin composition according to claim 1, which is N',N'-dimethylurea.