JPH0352767B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a resin composition that has excellent storage stability, curability and adhesiveness, and suppresses curing heat generation. Conventionally, resins used in the production of fiber-reinforced plastic products such as sheet molding compounds (SMC), bulk molding compounds (BMC), and prepregs do not undergo significant polymerization and hardening, reduce stickiness, and improve fiber retention. Rapid thickening is required to maintain convergence. In order to achieve this purpose, it has generally been proposed to incorporate carboxylic acid into the structure of unsaturated polyester resin compositions, and to increase the viscosity using magnesium oxide (U.S. Pat. No. 2,628,209). . However, since the above method generally involves a reaction between a solid and a liquid, it lacks quantitative and controllability of the reaction, and has the disadvantage that the thickening behavior, especially the thickening level and rate, vary significantly depending on time and temperature. had.
Another problem was that it was limited to only terminal carboxylic acid-containing compounds. Furthermore, since resin compositions based on unsaturated polyester resins generally lack adhesive properties, this has been a problem in terms of performance, especially when used as structural composite materials and adhesives. In view of the above, the present inventors have found that they have excellent adhesive properties, have excellent viscosity increasing properties in quantitative and controllable properties, suppress curing heat generation, can be applied to general compounds containing hydroxyl groups that do not contain carboxylic acids, and are suitable for composite materials, adhesives, etc. As a result of intensive studies on resin compositions useful for agent applications, the present invention was achieved. That is, the gist of the present invention is to provide an ethylenic or allylic unsaturated polyester (A) or a reaction product of a polyepoxide and an ethylenically unsaturated carboxylic acid (B) () copolymerizable with the aquatic group-containing unsaturated polyester (A). Catalyst () capable of polymerizing saturated monomers () (), () Curing agent selected from guanidines and dihydracides capable of curing compounds containing at least one oxirane ring () () () (), ( ) A catalyst () for polyisocyanate () and a reaction accelerator () for the reaction between isocyanate and hydroxyl groups (). After mixing,
()()() is added. As the unsaturated polyester (A) used in the present invention, those produced by known methods using known raw materials can be used. Namely, unsaturated dicarboxylic acids such as fumaric acid and maleic acid and their acid anhydrides, phthalic acid, isophthalic acid, adipic acid,
Saturated dibasic acids and their acid anhydrides such as phthalic anhydride, succinic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride and diethylene glycol, propylene glycol, neopentyl glycol, butanediol, hydrogenated bisphenol A, 2,2 Examples include hydroxyl group-containing unsaturated polyesters obtained by dehydration condensation reaction with glycol components such as -di-(4-hydroxypropoxyphenyl)propane. The polyepoxide used for the reaction product (B) of polyepoxide and ethylenically unsaturated carboxylic acid is not particularly limited, but for example, diphenylol such as diphenylolpropane, diphenylrollethane, diphenylrollmethane, etc. Polyglycidyl ethers of alkanes, polyglycidyl ethers of polyhydric phenols such as novolak or resol, p-aminophenol,
m-aminophenol, polyglycidyl ethers of polyvalent amines such as 4,4'-diaminodiphenylmethane, cyclohexene, cyclopentadiene,
Epoxy resin produced by epoxidation of alicyclic compounds such as dicyclopentadiene, 3,4-
Examples include methyl esters of epoxy-6-methyl-cyclohexanecarboxylic acids, poly(epoxyalkyl)ethers of aliphatic polyepoxy compounds such as ethylene glycol and glycerin, and glycidyl esters of aromatic and aliphatic carboxylic acids. Moreover, preliminary reaction products of these polyepoxides, amine compounds, and acid anhydrides may be used. Further, examples of the ethylenically unsaturated carboxylic acid include methacrylic acid, acrylic acid, and crotonic acid. In the reaction between polyepoxide and ethylenically unsaturated carboxylic acid, the molar ratio of epoxy group to carboxylic acid is preferably 1:0.5 to 1.1. This reaction can be carried out using known methods (e.g. Japanese Patent Publication No. 44-
31472) can be carried out. There is no problem in using compounds (A) and (B) together. Examples of the ethylenically or allylic unsaturated monomer () include styrene, vinyltoluene, styrene derivatives such as chlorostyrene, methacrylates such as methyl methacrylate, methyl acrylate, glycidyl acrylate, and glycidyl methacrylate, acrylates, diallyl phthalate, and triaryl. Examples include allyl esters such as lucyanurate and triallyl isocyanurate. Examples of the polymerization catalyst () in () and () include peroxides active at medium to high temperatures such as benzoyl peroxide and t-butyl perbenzoate, and peroxides active at normal temperatures. Examples of the compound containing at least one oxirane ring include the polyepoxides already mentioned above, as well as monoepoxy compounds such as styrene oxide, butyl glycidyl ether, allyl glycidyl ether, and phenyl glycidyl ether. The curing agent () selected from guanidines and dihydrazides that can cure () is dicyandiamide, 2,6-xylenyl-biguanide, 0
- Guanidines such as -tolylbiguanide, diphenylguanidine, and di-0-tolylguanidine, and dihydrazides such as adipyl dihydrazide and azelyl dihydrazide. The reaction catalyst () for ()() is a compound represented by the following general formula. (X and Y=Cl, Br, CH ₃ , OCH ₃ , OC ₂ H ₅ ,
NO ₂ and H or

[Formula] R ₁ and R ₂ = an alkyl group, an allyl group, an alkoxy group, an alkenyl group, an aralkyl group, or an alicyclic compound containing R ₁ and R ₂ at the same time. ) For example, N-(3-chloro-4-methoxyphenyl)-
N',N'-dimethyluria N-(4-chlorophenyl)-N',N'-dimethyluria N-(3-chloro4-ethylphenyl)-N',
N'-dimethyluria N-(4-chlorophenyl)-N', N'-dipropyluria N-(3-chloro-4-methylphenyl)-N',
N'-1 dimethyluria N-(3,4-dichlorophenyl)-N',N'-
Dimethyluria N-(4-methyl-3nitrophenyl)-N',
N'-dimethyluria N-(3-chloro-4methylphenyl)-N',
N'-dimethyluria N-(3-chloro-4-ethylphenyl)-N',
N'-dimethyluria N-(4-ethoxyphenyl)-N',N'-dimethyluria N-(3-chloro-4-methoxyphenyl)-
N',N'-dimethyluria N-(4-methyl-3-nitrophenyl)-
Examples include N'N'-dimethyluria, N-(4-chlorophenyl-carbamoyl)piperidine, N-(4-chlorophenylcarbamoyl)morpholine, N-(4-chlorophenylcarbamoyl)pyrrolidine, and the like. As polyisocyanate (), 4,4-
Aromatic and aliphatic polyisocyanates such as diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hexamethylene diisocyanate, metaxylylene diisocyanate and their crude Examples include refined products. The reaction accelerator () is not particularly limited as long as it promotes the reaction between general isocyanates and alcoholic OH groups, but the coexistence of tertiary amines is not appropriate, and dibutyltin dilaurate, dibutyltin dilaurate, Examples include organic tin compounds such as tin octoate, and naphthenic acid metal salts such as lead naphthenate and cobalt naphthenate. In the present invention, the blending ratio of ()()() is sufficient as long as it satisfies general radical polymerization systems, but generally the ratio of ()/()/() is 0.
~100/100~0/0.1~5 is appropriate. If the catalyst () is less than 0.1, a sufficient curing rate cannot be obtained, so it is not appropriate, and if it exceeds 5, the curing will be too rapid and is not appropriate. The blending ratio of ()()() is not particularly limited as long as it satisfies the conditions necessary for curing general epoxy resins, but the ratio is ()/()/
The ratio in parentheses is suitably in the range of 100/0 to 50/0 to 10. ()/()/() mixture and ()/
The blending ratio of ()/() is 97~3/3~
97 is appropriate. If the amount of the ()/()/() blend is less than 3, the adhesion will be insufficient and unsuitable. If it exceeds 97, it is not suitable because the substantial rapid curing property becomes poor. More preferably the ratio is 97-40/3-60. The amount of () added is for () to () formulations.
The OH/NCO functional group ratio can be arbitrarily selected within the range of 1/0.1 to 1, and depending on the amount added, it is possible to control the hardness, handleability, etc. of the resin composition. The amount of () added is 100 of the mixture of () to ().
A suitable amount is 0 to 5 parts. The amount added is OH group,
It only controls the reaction rate between NCO groups, and a small amount is desirable from a physical standpoint. The mixing method of () to () is () () ()
After preparing the mixture of ()(), ()()
The method of adding () is appropriate for improving tack and flowability. Generally, it is appropriate to leave the obtained resin composition at room temperature to 60°C, more preferably at room temperature to 40°C, to thicken it. For these compositions, fillers such as kaolin, calcium carbonate, clay, etc. can be added in an amount of 5 to 70% of the total amount.
It is also possible to add additives such as a coloring agent and a mold release agent as necessary. Furthermore, it is also possible to add homo or copolymers of styrene, ethylene, methacrylic acid esters, etc. in an amount of 0 to 30% by weight of the total amount as other additives. The resin composition of the present invention has an appropriate thickening property compared to conventionally known thickening methods and compositions, and has excellent adhesion to various materials, and has extremely high practical value. The present invention will be explained in detail with reference to Examples below. In addition, parts in Examples indicate parts by weight. Example 1 50 parts of maleic anhydride, diethylene glycol
Esterified at 140-230°C for 3.5 hours with a composition of 108 parts, then 50 parts of phthalic anhydride and 0.02 parts of hydroquinone.
1 part and esterified at 140-230°C for 3.1 hours. Unsaturated polyester with 19.8% unsaturated acid content
100 parts, part diallyl phthalate monomer, t-
Three parts of butyl perbenzoate were added and kneaded on a three-roll roll at 50°C for 30 minutes to obtain composition (a). On the other hand, 100 parts of diglycidyl ether type epoxy resin of bisphenol A (epoxy equivalent: 200), 5 parts of dicyandiamide, 3 parts of 1-(3,4-dichlorophenyl),
3 parts of 3-dimethylurea using a homomixer.
Composition (b) was obtained by kneading for 30 minutes. For (a), polymethylene polyphenyl isocyanate (viscosity 25℃,
150 cps, NCO content 31%) was added thereto, and then 0.3 part of butyltin dilaurate was added and stirred thoroughly. After standing at room temperature for 20 hours, mix so that the (b)/(a) ratio becomes as shown in Table 1. A resin composition (B) was obtained by aging the present composition (A) at 40° C. for 48 hours under closed conditions. The resin composition (B) had the properties shown in Table 1.

[Table] Yes.
Adhesion was determined by adding 3 parts of zinc stearate to 100 parts of composition A, then impregnating 120 parts of chopped strand glass fiber mat, and then adding 40 parts of zinc stearate to 100 parts of composition A.
SMC with low stickiness was obtained by leaving it under closed conditions at ℃ for 48 hours. A good molded product of this SMC was obtained under the molding conditions shown in Table 1. Cut out a specimen 10 mm wide and 15 mm long from a 3 mm thick plate.
The results of interlaminar shear strength determined at L/D=3.5 according to ASTMD-2344-76 are shown. Example 2 39 parts of methacrylic acid, 0.7 parts of lithium chloride, and 0.05 parts of hydroquinone were added to 95 parts of diglycidyl ether type epoxy resin of bisphenol A (epoxy equivalent: 190), and 60 parts of vinyl ester obtained by adding 39 parts of methacrylic acid, 0.7 parts of lithium chloride, and 0.05 parts of hydroquinone at 100°C. 40 parts of styrene and 2.5 parts of t-butyl perbenzoate were mixed, and then polymethylene polyphenyl isocyanate (viscosity 25°C,
Add 10 parts of 150 cps, NCO content 31%) and 0.3 parts of dibutyltin dilaurate and stir well to form a composition.
I got (C). Composition (d) was obtained by kneading 100 parts of the above epoxy resin, 5 parts of dicyandiamide, and 3 parts of 1-(3,4-dichlorophenyl)3,3-dimethylurea in a homomixer for 30 minutes. (C) at room temperature for 20
After standing for a period of time, composition (d) was mixed so that the (d)/(c) ratio was as shown in Table 2. A resin composition (D) was obtained by aging the present composition (C) at 40° C. for 48 hours under closed conditions. Table 2 shows the properties of the resin composition.

[Table] Yes.
Example 3 To 60 parts of a vinyl ester resin obtained by adding 95 parts of novolac type epoxy resin (Epicoat 152 manufactured by Shell Chemical Co., Ltd., epoxy equivalent weight 175), 42 parts of methacrylic acid, 0.7 parts of lithium chloride, and 0.05 parts of hydroquinone and reacting at 100°C. 40 parts of styrene and 29 parts of t-butyl perbenzoate were mixed with the mixture, and then polymethylene polyphenyl isocyanate (viscosity 25
C, 150 cps, NCO content 31%) and 0.3 parts of dibutyltin dilaurate were added and thoroughly stirred to obtain a composition (e). On the other hand, 100 parts of diglycidyl phthalate type epoxy resin (epoxy equivalent: 154), 5 parts of dicyandiamide, 1-(3,4-dichlorophenyl)
3 parts of 3,3-dimethylurea in a homomixer.
A composition (f) was obtained by kneading the mixture. After leaving (e) at room temperature for 20 hours, composition (f) was mixed so that the (f)/(e) ratio was as shown in Table 3. A resin composition (F) was obtained by aging the present composition (E) at 40° C. for 48 hours under closed conditions. Table 3 shows the properties of the resin composition.

[Table] Yes.
Example 4 Immediately after adjusting (e) in Example 3, (f) was mixed to obtain a composition (E'), which was aged at 40°C for 48 hours under closed conditions, and then a resin composition (F') I got it. Table 4 shows the properties of the resin composition.

[Table] Yes.
Comparative Example 1 98 parts of maleic anhydride was added to 144 parts of the vinyl ester obtained in Example 2, and the mixture was reacted at 100° C. for about 1 hour to produce a maleic acid half ester group.
40 parts of styrene was added to 60 parts of the reactant, and 2.9 parts of t-butyl perbenzoate was mixed therein.
Next, 5 parts of magnesium oxide was added to obtain a composition (g). Next, the composition (d) of Example 2 was adjusted to a d/g ratio.
25/75 mixture and the composition of Example 2 with a d/e ratio of 25/75 at 40°C for 48 hours, 72 hours,
It was left for 96 hours and 192 hours. These thickening properties are shown in Table 5.
It was hot on the street.

【table】

Claims (1)

[Claims] 1 Ethylenically or allylic unsaturated monomer copolymerizable with hydroxyl group-containing unsaturated polyester (A) or reaction product of polyepoxide and ethylenically unsaturated carboxylic acid (B) () () () Catalyst capable of polymerizing () () () A compound containing at least one oxirane ring () A curing agent selected from guanidines and hydrazides capable of curing () () Catalyst for () () Compounds represented by the following general formula as () (X and Y=Cl, Br, CH ₃ , OCH ₃ , OC ₂ H ₅ ,
NO ₂ and H or [Formula] R ₁ and R ₂ = alkyl group, allyl group, alkoxy group, alkenyl group, or aralkyl group, or an alicyclic compound containing R ₁ and R ₂ at the same time. 1.) A curable resin composition comprising: a polyisocyanate compound (); and a reaction promoter between an isocyanate and a hydroxyl group (). 2. The composition according to claim 1, wherein the compound ()()()()() is added after pre-mixing the compound ()()()()().