JPS62135528A - Molding composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition low in stickiness, excellent in moldability, capable of giving a high-strength molding and useful for use in prepregs, sealing materials, etc., comprising a compound having an ethylenically unsaturated bond, an amine compound and, optionally, a filler. CONSTITUTION:A compound (A) having an ethylenically unsaturated bond reactive with an NH2 group, such as a glycidyl ether resin obtained from bisphenol A (derivative) and epichlorohydrin, is mixed with an amine compound (B) (e.g., xylylenediamine) in an amount corresponding to 0.01-0.7 equivalent of active hydrogen per equivalent of the unsaturated double bonds of component A and further corresponding to a rate at which component A can be thickened and, optionally 0-10wt%, based on the total of components A and B, reaction rate modifier (C) such as a carboxyl compound or a tert. amine and 10-80wt%, based on the composition, filler (D) such as carbon fiber.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a thickened molding composition useful as a molding material for industrial parts, housing materials, electronic parts, and the like.

[Prior art and its problems]

7'+ used for industrial parts, housing materials, electronic parts, etc.
7 f Ref, BMC (bulk molding compound), SMC (sheet molding compound and land), sealing materials, etc. are polymerized and hardened in order to achieve quick curing and ease of handling to reduce molding costs. There is a need to promote B-stage development and reduce flatness.

To improve the above-mentioned rapid curing properties, use a type of resin that hardens through radical polymerization, and further add metal oxides or hydroxides such as magnesium oxide, polyisocyanate, etc. to make it B-stage. is being carried out.

However, it is also possible to add a radical polymerization catalyst and achieve B-staging through partial polymerization, but this method has the drawback that the curing reaction proceeds and it is extremely difficult to obtain B-staging. There is. In addition, when adding metal oxides and hydroxides, the metal crosslinking reaction with the carboxyl group in the unsaturated compound is significantly accelerated by moisture in the raw material or in the air, so it is necessary to impregnate the reinforcing material. There are disadvantages in the workability during the process, and the molding pressure becomes low because the molding composition becomes soft, resulting in a narrow range of moldability. Furthermore, in the case of adding terisocyanate, the molding composition contains a large amount of air bubbles and becomes soft due to the reaction with moisture in the raw materials or the air and generation of carbon dioxide, resulting in a molding composition with excellent strength. Not only will a molded product not be obtained, but if the moisture content is too high, B-staging will not progress sufficiently, and the product will not be sticky and will be unsatisfactory for molding.

[Means for solving problems]

As a result of research into a molding composition that does not have the above-mentioned drawbacks, is easy to implement industrially, and is inexpensive, the present inventors found that it is possible to remove moisture during 5B-staging, which is different from conventional ones. A molding composition that is not affected by this effect has been found, and the present invention has been achieved.

That is, the present invention provides a molding composition characterized by comprising a compound having an ethylenically unsaturated bond capable of reacting with an amino group, an amine compound, an optional filler, and a thickened viscosity. do.

The compound having an ethylenically unsaturated bond capable of reacting with an amine group used in the present invention includes a compound that substantially reacts with the active hydrogen of the amine compound, that is, a primary or secondary amine 7 group in the amine compound. (Michael-type addition reaction). Specifically, a glycytyl ether type epoxy resin obtained from a jepoxy compound, for example, bisphenol A or its derivative and evichlorohydrin, Vigilon 840, 850.1050 (both products of Dainippon Ink Chemical Industries, Ltd., etc.), Epoxy resin (EP-4000...
- Asahi Denka products, etc.), epoxy resins obtained from bisphenol A and methyl epichlorohydrin (Epicron 800... Inu Nippon Ink Chemical Co., Ltd. products, etc.), alicyclic epoxy resins (Yusox 221.289... Union, etc.) Carbide Co., Ltd. stock products, etc.), epoxy resins based on 7-talic anhydride or its derivatives (Shodyne 508,
...Showa Denko Co., Ltd. product, Epiclon 200...Dainippon Ink Chemical Co., Ltd. product, etc.), hexahydrophthalic anhydride-based 4-oxy resin (Epiclon 400...
Inu Nippon Ink Kagaku Kogyo Co., Ltd. products, etc.), unsaturated basic acids such as acrylic acid, methacrylic acid, crotonic acid, sorbic acid, and optionally small amounts of dibasic acids such as adipic acid,
Vinyl ester compounds obtained from cepacic acid, endomethylenetetrahydrophthalic anhydride, methyltetrahydrophthalic acid, hexahydrophthalic acid, etc. and (meth)acrylic acid -methyl, -ethyl, -furovir, -butyl, -
(meth) such as 2-ethylhexyl, (meth)acrylic acid, etc.
A mixture of acrylic acid monomers, styrene, α-methylstyrene, vinyl acetate, etc. (vinyl ester compound/monomer weight ratio: 1/99 to 90/10,
Preferably 30/70 to 80/20); polyhydric alcohol such as ethylene glycol, propylene glycol, butanediol, neointyl glycol, hexamethylene glycol, trimethylolpropane, trimethylolbutane, glycerin, and the above unsaturated basic acid. unsaturated group-containing esterified products with; unsaturated dibasic acids such as maleic acid (anhydride), fumaric acid, itaconic acid, or their alkyl esters, and optionally terephthalic acid, phthalic acid, endomethylenetetrahydrophthalic anhydride, adipine acid,
A mixture (
Unsaturated polyester/monomer weight ratio: 1/99-9
0/10, preferably 30/70 to 80/20): Among the above unsaturated chilesters, those containing a hydroxyl group and tetramethylene diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, diphenyl Propane
A reaction product with a polyvalent isocyanate such as 4,4'-diisocyanate and inphorone diisocyanate, and a mixture of monomers used in combination with the above unsaturated polyester (the mixing ratio of both may be the same as in the case of the unsaturated polyester); Polyhydric alcohol and/or? polyester polyols (e.g., the saturated dibasic acids described above) are obtained from their alkyl esters and the glycols described above) and/or polyether polyols (e.g., those obtained from the glycols described above and ethylene oxide and/or butylene oxide), An unsaturated urethane resin obtained by reacting the above-mentioned unsaturated basic acid with a terminal hydroxyl group-containing urethane obtained from a polyvalent incyanate, and a mixture of monomers used in combination with the above-mentioned unsaturated polyester (the mixing ratio of both is the same as that of the unsaturated polyester). (The same may be true for the case.)
is preferred, and ethylenically unsaturated monomers such as the above-mentioned (meth)acrylic acid ester monomers, halogenated styrene, vinyl acetate, acrylonitrile, diallyl phthalate, and triallyl isocyanurate can also be used.

Further, the amine compound that can be used in the present invention may be one that reacts with the unsaturated bond of the compound having an ethylenically unsaturated bond, and is usually a primary and/or secondary amine compound.
It has a class amine group. Such amine compounds include aliphatic amines such as ethylenediamine, propylenediamine, tetramethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and hexanediamine; aliphatic amines containing aromatic rings such as xylylenediamine; bisaminomethyl Aliphatic amines containing aliphatic rings such as cyclohexane and Laromine C-160 (BASF product); Aromatic amines such as diaminonophenylmethane and phenylenediamine; Examples include amine group-containing compounds obtained by reaction, and polyvalent amine compounds are preferred.

In the present invention, the mixing ratio of the ethylenically unsaturated compound and the amine compound may be any proportion as long as the amine compound can thicken the ethylenically unsaturated compound. The active hydrogen of the amine compound is 0.0% per unsaturated double bond of the unsaturated compound ff1K.
0.01 to 0.7 equivalent, more preferably 0.05 to 0.3 equivalent. Incidentally, the thickening caused by the addition of an amine compound in the present invention results in a so-called B-staging state.

The composition of the present invention includes carboxyl compounds such as benzoic acid, acetic acid, and adipic acid; methanol;
Alcohols such as ethanol, n-propanol and ethylene glycol; tertiary amines such as pyridine and trimethylamine can be added in an amount of 0 to 10% by weight based on the total amount of the ethylenically unsaturated compound and amine compound.

The composition of the present invention may also contain fillers such as carbon fibers, boron fibers, alumina fibers, silicon carbide fibers, inorganic fibers such as glass fibers, aramid P, etc. IJ amide fiber,
Organic fibers such as polyester fibers and polyethylene fibers, whiskers of potassium titanate, silica, calcium carbonate, clay, kaolin, etc.; internal mold release agents, such as zinc stearate; Vinyl acetate, polyacrylic acid ester, saturated polyester, etc. can be added. In particular, fibrous fillers are preferred because they can impart strength. The amount of the filler added is usually 10 to 80% by weight in the composition.

Furthermore, the composition of the present invention may contain a polymerization initiator such as zocumilno, monooxide, t-butyl/'P-oxide,
Add benzoyl peroxide, potassium persulfate, sodium persulfate, etc. to the ethylenically unsaturated compound at a rate of 0.
It can be added in an amount of 01 to 5% by weight.

Furthermore, the composition of the present invention may contain polyethylene, propylene, polybutene, etc. to the extent that the effects of the present invention are not impaired.
Thermoplastic resins such as polyethylene terephthalate, polybutylene terephthalate, polyvinyl chloride, acrylonitrile-butadiene-styrene polymer, polyurethane, polyamide, polyphenylene ether, polyphenylene sulfide; thermosetting such as epoxy resin, phenol resin, melamine resin, urea cutting, etc. Rubber-like substances such as natural rubber, butadiene rubber, and styrene-butadiene rubber can be added.

The composition of the present invention can be generally molded at 100 to 140°C by applying pressure (for example, 10 to 3001 #/α2) K if necessary.

〔Effect of the invention〕

The composition of the present invention has less flatness, excellent moldability, and is almost unaffected by moisture, so it can produce molded products with excellent strength.
It is useful as a C1 sealing material, etc.

〔Example〕

The present invention will be described below with reference to Examples and Comparative Examples. still,
Parts in the examples are by weight.

Example 1 Epiclon 850 (bisphenol A diglycidyl ether type epoxy resin: Dainippon Ink & Chemicals Co., Ltd.)
(trade name) 370 parts (1.0 mol) and 141 parts (1.96 mol) of acrylic acid, 3.7 parts of dimethylbenzylamine,
80-100 in the presence of 200 ppm hydroquinone
An ethylenically unsaturated compound was produced by dissolving 70 parts of a vinyl ester compound having an acid value of 0.1 obtained by reaction at 0.degree. C. in 30 parts of ethylene glycol dimethacrylate. Its moisture content was 0.01%. To 100 parts (0.57 equivalents) of the ethylenically unsaturated compound thus obtained, 3.3 parts (0.1 equivalents) of m-xylylenediamine and 3 parts of
Add 1 part of M (product name of Nippon Oil & Fats Co., Ltd., peroxide), mix well, and impregnate 104 parts of chopped carbon fiber strands. When left in an atmosphere, SM becomes non-stick after 12 hours.
C was obtained. This SMCi-1 was pressure-molded at a molding temperature of 125° C. and a molding pressure of 100 kg/α to give a molded product having a bending strength of 56 and a sea strength.

Example 2 A pre-impregnated product obtained in the same manner as in Example 1 was left in an atmosphere of 23° C. and 85% relative humidity, and a non-tacky SMC was obtained after 12 hours. This SMC was molded at a temperature of 125°C.
A molded product with a bending strength of 57 kg/(1) was obtained by pressure molding at a molding pressure of 100 kg/(1).

Comparative Example 1 To 100 parts of the mixture of 70 parts of the vinyl ester compound in Example 1 and 30 parts of ethylene glycol dimethacrylate, 28 parts of MTL (trade name, Crude MDI, manufactured by Nippon Polyurethane Co., Ltd.) and 1 part of Perhexa-3M were added. Add chopped strands of carbon fiber and mix well.
The pre-impregnated product obtained by impregnating 30 parts was left in an atmosphere of 23° C. and a relative humidity of 55° C. After 12 hours, an SMC was obtained which was not sticky but contained many bubbles. This SMC was pressure molded at a molding temperature of 125° C. and a molding pressure of 100 kg/cm 2 to obtain a molded product with a bending strength of 38 kg/m.

Comparative Example 2 When the pre-impregnated material obtained in the same manner as Comparative Example 1 was left in an atmosphere of 23°C and relative humidity of 85°C, it was very soft and sticky even after one week, and a good SMC could not be obtained. .

Example 3 To 100 parts of an ethylenically unsaturated compound obtained by dissolving 70 parts of the vinyl ester compound in Example 1 in 30 parts of ethylene glycol dimethacrylate, 50 parts of calcium carbonate was added and mixed well. The moisture content of this mixture was 0.2%. Add 3.3 m-xylylene diamine to this mixture.
1 part of Perhexa-3M were added and mixed, and the mixture was impregnated into 50 parts of chopped carbon fiber strands and left in an atmosphere of 23° C. and relative humidity of 55° C. After 12 hours, an SMC without any stickiness was obtained. When this SMC was pressure molded at a molding temperature of 125°C and a molding pressure of 100 kg/m2, the bending strength was 2.
8 kg/deaf molded product was obtained ◇ Example 4 Ethylenically unsaturated compound 10 obtained in the same manner as Example 1
50 parts of slightly moisture-absorbed calcium carbonate was added to 0 parts and mixed well. The water content of this mixture was 0.6 inches.

3.3 parts of m-xylene diamine and 1 part of 9-hexane 3M were added to this mixture, mixed, impregnated into 50 parts of carbon fiber chimney strands, and left in an atmosphere at 23°C and 85% relative humidity. After 12 hours, SMC without any stickiness was obtained. This SMC was molded at a molding temperature of 125°C and a molding pressure of 100 J.
,/m, a molded product with a bending strength of 27 kg/a was obtained.

Comparative Example 3 28 parts of maleic anhydride was added to 100 parts of the ethylenically unsaturated compound of Example 3, and 50 parts of calcium carbonate was added to 100 parts of the reaction product obtained by reacting at 100° C. for about 1 hour and mixed. . The water content of this mixture was 0.2%. 3 parts of magnesium oxide and 1 part of Perhexa-3M were added to 150 parts of this mixture, mixed, and impregnated into 50 parts of chopped carbon fiber strands at 23°C and 55% relative humidity.
Leave it in an atmosphere of
I got a C. This SMC was molded at a molding temperature of 125°C and a molding pressure of 1
When pressure-formed with 00kg/6n2, the bending strength was 25k.
A molded product weighing 1 g/min was obtained.

Comparative Example 4 To a reaction product obtained by reacting 100 parts of the ethylenically unsaturated compound of Example 3 with 28 parts of maleic anhydride, 50 parts of calcium carbonate which had absorbed some moisture was added and mixed. The moisture content of this mixture was 0.6%.

3 parts of magnesium oxide and 1 part of Perhexa 3M were added and mixed to 150 parts of this mixture, and the mixture was impregnated into 950 parts of chopped carbon fiber strands and left in an atmosphere at 23° C. and 85% relative humidity. This product did not lose its flatness even after one week, and it was not possible to obtain a good SMC.

Claims (1)

[Claims] Consists of a compound having an ethylenically unsaturated bond that can react with an amino group, an amine compound, and a filler if necessary,
A molding composition characterized by being thickened and thickened.