JPH02218715A - Composition for synthetic foam - Google Patents

Abstract

PURPOSE:To obtain the subject readily moldable composition, consisting of a glassy microballoon substance, glycidyl group-containing liquid epoxy compound and specific solid aromatic diamine compound, excellent in heat and pressure resistance and having a long shelf.life. CONSTITUTION:The objective composition obtained by blending (A) a glassy microballoon substance with (B) a liquid epoxy compound (e.g. N,N,N',N'- tetraglycidylaminodiphenylmethane) having >=2 glycidyl groups and (C) as solid aromatic diamine compound (e.g. 4,4'-diaminodiphenyl sulfone), expressed by the formula (X is SO2, CO, etc.; R is CH2CH2, CH2CH2CH2, etc.) and having <=50mu average particle diameter so as to provide (60-80)/(40-20) weight ratio of the components [A/(B+C)]. Furthermore, the microballoon substance having 5-100mu average particle diameter is preferably used as the component (A) and microballoons having different particle diameters are preferably used together.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention provides a composition for syntactic foam that has excellent heat resistance and pressure resistance, has a long shelf life that indicates the useful life of prepregs, etc., and is easy to mold. Regarding.

[Problems to be solved by the prior art and the invention] +? as a composition for syntactic foam? +M Showa 60-1
As proposed in Japanese Patent No. 225.80, it is known to use a liquid epoxy compound and a liquid acid anhydride having glassy microhollow bodies and three or more glycidiμ groups in the molecule. However, since all of these compositions use liquid resin compositions, high-temperature molding in a mold is essential, and the productivity of a single mold is poor, so there has been a demand for improved productivity. Furthermore, a system consisting of a liquid epoxy compound and a liquid acid anhydride has the drawback that the reactivity of the nitrogen-free epoxy compound is low, and that a catalyst must be used in combination, resulting in a short shelf life. Furthermore, when using a nitrogen-containing EBOKI V compound, the compound itself acts as a catalyst and has the disadvantage of shortening its life.

The present inventors have achieved the present invention as a result of intensive studies aimed at obtaining a composition with a long shelf life, excellent moldability, a sufficiently low density syntactic foam, and excellent heat resistance and pressure resistance.

[Means to solve the problem]

The gist of the present invention is a glassy microhollow body (A), a liquid epoxy compound containing two or more glycidyl groups (B),
A solid aromatic diamine compound having an average particle size of 50 μ or less and represented by the following structural formula (I) (C1 o 0 R is -aH2aa, -C! H2-OH! -0 horse- or aTl.

10 horses -0-Oi, - indicates) H3, and the weight ratio of (4)/[F]) + (O) is 60
-8o/40-20 thermosetting syntactic foam composition.

The glassy micro hollow bodies are not particularly limited as long as they are glassy inorganic or organic micro hollow bodies, but the average particle diameter is preferably 5 μm to 100 μm from the viewpoint of uniformity of dispersion. Further, it is more preferable to use these particles having different particle sizes together in order to improve the pressure resistance. The true specific gravity of the glassy hollow body is preferably α4 or less as it is lower for the purpose of reducing the weight of the foam.

The liquid epoxy compound containing two or more glycidyl groups may be liquid at room temperature;
a O-0H2-0-02H4-8-8) n-c+! g
, -o-au, -o-c2H4-si (n represents 0 to 3), polyglyndylthioethers of polysulfide compounds having -B-8- groups, diphenylolpropane, diphenylolmethane, etc. Polyglycide of polyhydric phenols - Polyglycide of alcohols - Nythea L'include or resol
epoxidized products of alicyclic compounds such as cyclohexene, cyclopentadiene, dicyclopentadiene, etc., aliphatic polyoxylic acids such as esters of methanol, ethylene glycol, glycerin, etc. of cyclohexene-6-methylcyclohexane carboxylic acids Poly(epoxyalkyl A/) ethers of compounds, or epoxyalkyl esters of carboxylic acids such as glycidyl esters of aromatic or aliphatic carboxylic acids, diphenylene diamine, xylysine diamine, bis(aminophenyl A/) methane, bis (aminophenyl 1v) ethane, bis(aminophenyl/I/)
Examples include polyglycidyl compounds of polyamines such as propane and bis(aminophene/I/)sulfone, and polyglycidyl compounds of aminophenol-IViA such as aminophenol and aminocresol. These may be used alone or in combination of two or more.

Examples of the solid aromatic diamine (C) represented by structural formula (1) include 4.41-diaminodiphenylene-sulfone, trimethylene-bis(4-aminobenzoate), and 4.4'-diaminodiphenyl ketone. . If X is other than those in E, the basicity of the amine becomes high and the shelf life is shortened, which is not preferable. Liquid aromatic diamines are not preferred because the resulting composition loses its shape when heated in an unrestricted state. If the average particle size exceeds 50 μm, the cured product becomes brittle and is not suitable.

Here, the amount of aromatic amine used may be such that the ratio of the epoxy group of the epoxy compound to the -Nu group of the amine is 1/α5 to 1.5. More preferably 1/(18 to 1.3.α
If it is less than 5, the curing will be insufficient and the material will become brittle, which is not suitable. If it exceeds 1.5, the heat resistance will decrease and it will not be suitable.

In addition to the above-mentioned latent curing agents, the present composition may also contain guanidines such as dianediamide, 0-tolylbiguanide, λ6-xyleni-biguanide, and diphenylguanidine, and dihydrazides such as adipyl dihydrazide and azerai-dihydrazide. No problem.

In addition, as a curing catalyst, N-(5-chloro-4-methoxyphenylv)-Nl,
Nl-dimethylurea N-(4-chloropheniA/)-N; N'-dimethylurea N-(5-chloro-4-ethymuphenitv) -N'
.

Lewis! asymmetric urea compounds such as N'-dimethylurea, boron trifluoride, monoethylamine, etc. 'l! It is also possible to use salt together.

Glassy soy small hollow body (A), liquid Epoquine compound + E)
, the heavy electric ratio of the aromatic diamine compound (C) is (4) 103
) + (C) is preferably 60/40 to ao/20, and if it is less than 60/40, it is not suitable because it not only has a high density but also tends to lose its shape. If it is larger than 80/20, the compressive strength of the resulting syntactic foam will decrease, which is not suitable.

This composition can be heat-cured as it is, or compression molded, removed from the mold, and then heat-cured to produce a syntactic foam.

A more specific method for preparing this composition is to put it in a kneading machine preheated to about 25 to 90°C, then add (0) and knead well, then add (A) and be careful not to damage the hollow body. However, it is desirable to mix and stir until the mixture becomes uniform.At this time, it is also preferable to use a mixing aid.

The composition obtained here is placed in a mold heated to a temperature of up to 50° C. and preformed under a pressure of 100 ky/α2 or less.

After demolding, it can be cured outside the mold in a hot air oven at temperatures up to 180° C., without causing deformation.

Therefore, the exclusive use time of the mold is short and the productivity is extremely high.

The present composition can be used in many fields such as inclusions for lightweight golf heads, rackets, etc., and as a substitute for honeycombs.

Furthermore, lightweight reinforcing materials such as carbon fibers, aramid fibers, fibrous materials such as silicon carbide, whiskers, etc. may be included in the composition.

〔Example〕

Hereinafter, the present invention will be specifically explained with reference to Examples. Parts represent parts by weight.

Example 1 N, N, N: 100 parts of N'-tetraglycidyldiaminodiphenylmethane (Epicote 604IJ, manufactured by Yuka Shell Epoxy ■), 32 parts of 4°4'-diaminodiphenylsulfone with an average particle size of 15 μm, boron trifluoride 5 parts of Monoethylamine Complex Q were placed in a kneader heated to 50°C and stirred until thoroughly homogeneous. Next, a glass micro hollow body (D32/a so o, manufactured by 3M) 3
After adding 09 parts and stirring carefully so as not to destroy the hollow body, the mixture was immediately cooled to obtain a composition (I3).

Composition (I) was placed in a mold at 40°C as shown in Fig. 1 for 50'n.
/crR'' was applied to obtain a golf rad core shape as shown in Fig. 2.The shape was maintained even after demolding.

The resulting shaped product was heated at a rate of 2° C./min, cured at 180° C. for 2 hours, and then cooled to room temperature, but the shape did not change from the initial shape. Specific gravity was 058. Then 2c from this one
When we cut out a corner cube and conducted a compression test at 25°C, the result was 2'! It had a strength of g/-2. When a similar test was conducted at 150° C., the strength was 1.5 kg and 7 m”. The shelf life of the composition fil was confirmed by leaving it at room temperature and observing the change in hardness.

After 20 days, it was still soft enough to be pressed with a finger.

Example 2 Example 1 except that the composition of the resin composition was changed as shown in Table 1.
A composition was obtained in the same manner as in Example 1, and after preforming and heat curing in the same manner as in Example 1, a syntactic 7 ohm was obtained. The specific gravity and compressive strength are also shown in Table 1.

Comparative Example 1 The composition of the resin composition was the same as in Example 1 of JP-A-60-122580, the glassy micro hollow bodies were changed, and the results were evaluated in the same manner as in Example 1 of the present application. Table 1 shows the results. It is also shown in .

[Brief explanation of the drawing]

FIG. 1 shows a mold suitable for molding the composition of the present invention, and FIG. 2 shows a shaped article obtained with the mold of FIG. 1. 1 Upper mold 2 Cylinder 3 Lower mold 4 Shape space procedure amendment No. 2 Figure 1, Case indication Patent application No. 1-39527 2 Name of invention Syntactic foam composition & correction person case Relationship Patent applicant: 2-3-19 Kyobashi, Chuo-ku, Tokyo (603) Mitsubishi Rayon Co., Ltd. President Yatabe Nagai 4; Agent: 5-2-6-19 Kyobashi, Chuo-ku, Tokyo 104; Amendment amend the subject specification as follows. Page 6, line 15, insert ``If a curing accelerator is not used together'' next to ``...Used.'' Page 7, line 16, after "...there is no problem." j (Add the following section: "When a curing accelerator is used in combination, the ratio of the epoxy group of the epoxy compound to the -NH group of the amine is 110.4 to 1. .0 is appropriate.''

Claims (1)

[Claims] 1. Glassy micro hollow bodies (A), liquid epoxy compound containing two or more glycidyl groups (B), average particle size 50
A solid aromatic diamine compound (C) with a particle size of less than μ and represented by the following structural formula (I) ▲There are numerical formulas, chemical formulas, tables, etc.▼(I) (In the formula, X is -SO_2-, -CO-, or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, R is -CH_2CH_2-, -C
H_2-CH_2-CH_2- or ▲There are mathematical formulas, chemical formulas, tables, etc.▼), and the weight ratio of (A) / (B) + (C) is 60 to 8
A composition for thermosetting syntactic foam having a ratio of 0/40 to 20.