JPH0148291B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel and useful curable resin composition, and more particularly to a low temperature curable resin composition comprising a specific compound containing at least one ethylene carbonate group and a specific amino group-containing compound. The present invention relates to a polyamine-curable resin composition that provides a cured product with excellent curability and adhesion to substrates. Up to now, epoxy resin-polyamine systems, poly(meth)acrylate-polyamine systems, and epoxy resin-poly(meth)acrylate-polyamine systems have been known as room-temperature polyamine-curable resin compositions, among others. ,Epoxy resin-
Polyamine-based materials have excellent mechanical, thermal, chemical, and electrical properties, and are therefore widely used as adhesives, paints, cast products, and the like. However, when such conventional compositions are cured at low temperatures, especially below 10°C, they require a long time to cure, resulting in reduced workability and poor adhesion to substrates such as metal, wood, and glass. The problem is that it is enough. However, in view of the above-mentioned drawbacks, the present inventors conducted extensive research to obtain a curable resin composition with excellent low-temperature curability and adhesion to substrates, and as a result, the general formula [However, in the formula, Y represents an n+1-valent organic group, X represents an ethylene carbonate group, an epoxy group, an acryloyl group, or a methacryloyl group, R represents a hydrogen atom or a methyl group, and n represents 1
It shall be an integer greater than or equal to ] Compounds having at least one ethylene carbonate group in the molecule shown in the formula have extremely high reactivity with compounds having two or more amino groups per molecule, such as polyamines and polyamides, and furthermore, they are highly reactive to compounds having two or more amino groups per molecule, such as polyamines and polyamides. It was discovered that the adhesion of
The present invention has now been completed. That is, the present invention provides a curable resin composition comprising a compound (A) represented by the above general formula [] and a compound (B) having two or more amino groups per molecule. The composition of the present invention having such a structure is characterized in that the reactivity of the ethylene carbonate group based on compound (A) with polyamines and polyamides is higher than that of epoxy groups and (meth)acryloyl groups with them. This difference in reactivity is particularly noticeable at low temperatures.Furthermore, since urethane bonds and hydroxyl groups are generated when this ethylene carbonate group reacts with polyamines or polyamides, stress due to shrinkage during curing is It has excellent adhesion strength and impact strength, and particularly has a high adhesive strength to substrates. The above compound (A) constituting the composition of the present invention is () a compound having two or more ethylene carbonate groups per molecule (when X is an ethylene carbonate group), () a compound having one or more ethylene carbonate groups per molecule A compound having a group and one or more epoxy groups (when X is an epoxy group), or ()
It refers to a compound having one or more ethylene carbonate groups and one or more (meth)acryloyl groups per molecule (when X is a (meth)acryloyl group). Here, typical examples of the above compound () include compounds represented by the following general formula. (In the formula, J represents a residue of a polyisocyanate compound, K represents a residue of a polybasic acid, L represents a residue of a polyhydroxy compound, M represents a residue of a polyepoxy compound excluding the epoxy group, j, k, l
Alternatively, m represents an integer of 2 or more. ) Among them, first, the compound belonging to formula [-1] is one obtained by reacting glycerin carbonate obtained from alkylene carbonate and glycerin with a polyisocyanate compound, and the polyisocyanate compound includes tolylene diisocyanate, These include metaphenylene diisocyanate, naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and isophorone diisocyanate, and furthermore, the above polyisocyanate compounds and low molecular weight polyols, polyesterols, and polyalkylenes. It is a prepolymer having a terminal isocyanate group obtained by reacting a polyhydroxy compound such as a polyol, polybutadiene polyol, or acrylic polyol, and these polyisocyanate compounds can be used alone or in a mixture. Next, compounds belonging to formula [-2] are those obtained by reacting glyceryl carbonate with lower alkyl esters, acid anhydrides, or chlorides of polybasic acids, such as lower alkyl esters of polybasic acids, Acid anhydrides or acid chlorides include dimethyl adipate, dimethyl sebatate, dimethyl maleate, dimethyl fumarate, dimethyl terephthalate, succinic anhydride, maleic anhydride,
Examples include phthalic anhydride, adipic acid chloride, and terephthalic acid chloride, and these can be used alone or in combination. Next, as a compound belonging to formula [-3], for example, 2, which is obtained from phosgene and glycerin,
It is obtained by reacting 3-carbonate propyl chloroformate with a polyhydroxy compound, and polyhydric alcohols such as ethylene glycol, propylene glycol, butanediol, glycerin or trimethylolpropane; diethylene glycol, polyethylene Examples include polyether polyols such as glycol and polypropylene glycol; polyester polyols; and acrylic polyols, and these can be used alone or in combination. Further, compounds belonging to formula [-4] are those obtained by reacting a polyepoxy compound having two or more epoxy groups per molecule with carbon dioxide, and examples of the polyepoxy compound include bisphenol A, bisphenol A, Glycidyl ether type which is a reaction product of polyhydroxy compounds such as bisphenol F, halogenated bisphenol A, catechol, resorcinol, glycerin, trimethylolpropane or bisphenol A, alkylene oxide adducts, and (β-methyl)epichlorohydrin. Polyepoxy compounds, novolac type polyepoxy compounds which are compounds of novolac resin and (β-methyl) epichlorohydrin, glycidyl ester type polyepoxy compounds which are reaction products of polyhydric carboxylic acid and epichlorohydrin,
Furthermore, there are vinyl polymers having epoxy groups in their side chains, and these can be used alone or in combination. Next, typical compounds (A) belonging to the above () include [-1) a compound obtained by reacting a polyisocyanate compound with glyceryl carbonate and a hydroxyl group-containing epoxy compound;
-2] A compound obtained by reacting a polybasic acid chloride with glyceryl carbonate and a hydroxyl group-containing epoxy compound, [-3] A compound obtained by reacting a 2,3-carbonate propylchloroformate hydroxyl group-containing epoxy compound, or [- 4] There are compounds in which a polyepoxy compound having two or more epoxy groups per molecule is reacted with carbon dioxide, and a portion of the epoxy groups are further converted into ethylene carbonate groups. Among these, [-1], [-2] and [-
Typical examples of hydroxyl group-containing epoxy compounds used in the synthesis of 3) include glycidol, glycidyl ether type polyepoxy compounds, glycidyl ester type polyepoxy compounds, and combinations of the polyhydroxy compound, the polyisocyanate compound, and glycidol. There are prepolymers obtained by reaction, and these can be used alone or in combination. On the other hand, the polyisocyanate compound used when synthesizing [-1], the polybasic acid chloride used when synthesizing [-2], and [
-4] As specific examples of the polyepoxy compound used in the synthesis, those described above can be used. Next, typical compounds (A) belonging to the above () include [-1] a compound obtained by reacting a polyisocyanate compound with glyceryl carbonate and a hydroxyl group-containing (meth)acrylic compound; A compound obtained by reacting a basic acid chloride with glyceryl carbonate and a hydroxyl group-containing (meth)acrylic compound, [-
3] Compound obtained by reacting 2,3-carbonate propyl chloroformate with a hydroxyl group-containing (meth)acrylic compound, [-4] 1 per molecule
[-5] (meth)acrylic acid chloride, a compound obtained by reacting a compound having one or more epoxy groups and one or more (meth)acrylic groups with carbon dioxide, and further converting the epoxy group into an ethylene carbonate group. , a compound obtained by reacting an anhydride or a lower alkyl ester with glyceryl carbonate, or a compound obtained by reacting a (meth)acrylic compound having an adjacent [-6] hydroxyl group with phosgene or chloroformate. Among these, [-1], [-2] and [-
Typical examples of hydroxyl group-containing (meth)acrylic compounds used in the synthesis of 3) include mono(meth)acrylates of the polyhydroxy compounds;
An addition reaction product between the polyepoxy compound and (meth)acrylic acid, an addition reaction product between a monofunctional epoxy compound such as phenyl glycidyl ether or butyl glycidyl ether, and (meth)acrylic acid, or glycidyl (meth)acrylate or β - Addition reaction products of methylglycidyl (meth)acrylate and monobasic acids such as (meth)acrylic acid, benzoic acid, or stearic acid, etc., and can be used alone or in combination. Also, used when synthesizing [-4],
Typical examples of compounds having an epoxy group and a (meth)acrylic group include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, and addition of a part of the epoxy group of the above polyepoxy compound with (meth)acrylic acid. Reacted product, or the polyisocyanate compound, the hydroxyl group-containing epoxy compound, and the hydroxyl group-containing (meth)
There are prepolymers obtained by reacting with acrylic compounds, and they can be used alone or in combination. Next, typical examples of (meth)acrylic compounds with adjacent hydroxyl groups used when synthesizing [-6] are 2,3-dihydroxypropyl (meth)acrylate or 4,5-dihydroxypentyl (meth)acrylate. These can be used alone or in combination. Furthermore, as specific examples of the polyisocyanate compound used when synthesizing [-1] and the polybasic acid chloride used when synthesizing [-2], those described above are used. be done. As the component (A), compounds selected from the group consisting of (), (), and () described above can be used alone or in combination. On the other hand, the compound (B) constituting the composition of the present invention refers to a polyamine or a polyamide having a terminal amino group, but the compound (A) has two ethylene carbonate groups. In certain cases, it is preferable to use polyamides as the compound (B). put it here,
Examples of polyamines include aliphatic polyamines, aromatic polyamines, composite polyamines, modified aliphatic polyamines, and heterocyclic polyamines. Specific examples include diethylenetriamine, triethylenetetramine, hexamethylenediamine, iminobispropylamine, and metaphenylenediamine. , diaminodiphenylmethane, phenylenediamine or xylylenediamine; epoxy resin-diethylenetriamine adduct; amine-ethylene oxide adduct; or oligoester (meth)
Examples include adducts of acrylate and polyamines as described above. On the other hand, as a specific example of polyamide, any known and commonly used polyamide can be used, and a typical commercially available product is "Ratsukamide".
(Dainippon Ink & Chemicals Co., Ltd. product) "Tomide"
There are polyamide amine resins such as ``Sanmide'' (product of Sanwa Chemical Industry Co., Ltd.) (product of Fuji Chemical Industry Co., Ltd.). Component (B) is used singly or as a mixture of two or more, and the amount used is 2 to 200 parts by weight per 100 parts by weight of component (A). The thus obtained curable resin composition of the present invention contains a reactive diluent containing a compound having one or more functional groups per molecule that can react with amines other than ethylene carbonate groups within a range that does not impair the characteristics of the present invention. It can be added as Specific examples thereof include the above-mentioned polyepoxy compounds, monofunctional epoxy compounds such as butyl glycidyl ether, phenyl glycidyl ether, styrene oxide, poly(meth)acrylates of polyhydric alcohols, poly(meth)acrylates of polyesters, etc. ) acrylate,
Poly(meth)acrylates such as epoxy(meth)acrylate or polyurethane poly(meth)acrylate; lauryl(meth)acrylate, tetrahydrofurfuryl(meth)acrylate or polyhydric alcohol and non-functional monobasic acid and (meth)acrylic Monofunctional (meth)acrylates such as addition reaction products with acids; further examples include glycidyl (meth)acrylate and β-methylglycidyl (meth)acrylate. Furthermore, the composition of the present invention may contain fillers such as quartz powder, silica, calcium carbonate, calcium silicate, hydrated alumina, asbestos powder, tar, or cement, or various inorganic or organic pigments. Can be added. The composition of the present invention has excellent curability at low temperatures, and the curing temperature of such a composition is usually 0 to 100%.
℃, but it is sufficiently effective even at low temperatures of about 0 to 20℃. The curable resin composition of the present invention thus obtained can be used as it is or in the form of a solution or emulsion.
For adhesion, paint, dipping or impregnation.
Furthermore, it can be used for casting, molding, filling, and other uses. Next, the present invention will be specifically explained with reference to Examples and Comparative Examples, and in the following, "parts" means "parts by weight." Example 1 Glyceryl carbonate was placed in a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a reflux condenser.
236 parts of ethyl acetate, 300 parts of ethyl acetate, and 0.10 parts of dibutyltin laurate were charged, stirred under nitrogen atmosphere,
℃, and further 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate.
174 parts of an 80/20 (weight ratio) mixture was added dropwise over about 80 minutes while keeping the reaction temperature from exceeding 80°C.
After further reaction at 60°C for 4 hours, ethyl acetate was distilled off under reduced pressure to obtain a pale yellow addition product having the following structure and a melting point of 82°C. Hereinafter, this will be abbreviated as "(A-1)". 100 copies of (A-1) “Ratsukamide TD-”
100 parts of ``966H'' (a 60% non-volatile solution of paint polyamide resin manufactured by Dainippon Ink and Chemicals Co., Ltd. in a mixed solvent of xylene and butanol), 50 parts of ethyl acetate,
30 parts of xylene and 20 parts of methyl ethyl ketone were added and mixed well to prepare a paint. This paint was then applied to a tin plate to a film thickness of 6 mils, dried at 10°C for 4 days, and then a film test was conducted. Example 2 In a reaction vessel equipped with a stirring device, a thermometer, and a carbon dioxide blowing device, 340 parts of “Epicron 850” (bisphenol type epoxy resin manufactured by Dainippon Ink Chemical Co., Ltd.), 39 parts of triphenylphosphine, and Add 3.3 parts of anhydrous aluminum chloride and heat to 50 to 100℃.
After 80 hours of blowing in carbon dioxide while stirring, the epoxy group changed to ethylene carbonate group by 100
% conversion (measurement of residual amount of oxirane oxygen), the reaction was terminated. Next, it was dissolved in 400 parts of benzene, washed with water, and the benzene was distilled off under reduced pressure to obtain a pale yellow reaction product having the following structure and a melting point of 86°C. Below, this will be referred to as “(A-
2)". Example 1 except that 100 copies of (A-2) were used.
A paint was prepared in the same manner as above, and a coating film test was conducted. Example 3 146 parts of adipic acid, 212 parts of diethylene glycol, and 0.10 parts of tetraisopropyl titanate were placed in a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a distillation head, and the mixture was heated at 125°C under a nitrogen stream.
After dehydration condensation for 5 hours, the inside of the reaction system was
After reducing the pressure to mmHg and maintaining the same temperature for 1 hour,
A pale yellow liquid oligoester with a hydroxyl value of 353 was obtained. Next, 322 parts of this oligoester was mixed with 600 parts of ethyl acetate and 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate.
348 parts of a mixture of 80/20 (weight ratio) was added and reacted at 80°C for 2 hours to obtain a prepolymer having isocyanate groups at the ends. Next, add 0.10 parts of dibutyltin dilaurate and glyceryl carbonate.
118 parts and 74 parts of glycidol, and
After reacting at 80° C. for 4 hours, ethyl acetate was distilled off under reduced pressure to obtain a highly viscous polyester urethane resin having ethylene carbonate groups and epoxy groups at the ends. Hereinafter, this will be abbreviated as "(A-3)". Example 1 except that 100 copies of (A-3) were used.
A paint was prepared in the same manner as above, and a coating film test was conducted. Example 4 In a reaction vessel equipped with a stirrer, a thermometer, and a dropping funnel, 118 parts of glyceryl carbonate, 101 parts of triethylamine, and 2,6-di-t-butyl-p-
1 part of cresol and 400 parts of chloroform were charged, the temperature was maintained at 0 to 10°C, and 90.5 parts of acrylic acid chloride was added dropwise over 1 hour while stirring, and the mixture was further maintained at this temperature for 2 hours. After the reaction was completed, triethylamine hydrochloride was filtered, washed successively with 5% aqueous hydrochloric acid and water, dried over magnesium sulfate, and chloroform was removed under reduced pressure at 50°C, resulting in an oily 2,3-carbonate. Propyl acrylate was obtained. Below, this will be referred to as “(A-
4)" for short. Thereafter, a coating material was prepared in the same manner as in Example 1 except that 100 parts of (A-4) was used, and a coating film test was conducted. Comparative example 1 100 copies of “Epicron 850”, “Ratsukamide TD”
-966H'', 50 parts of ethyl acetate, 30 parts of xylene and 20 parts of methyl ethyl ketone were added and mixed well to prepare a paint, and thereafter a coating film test was conducted in the same manner as in Example 1. Example 5 To 100 parts of the resin (A-3) synthesized in Example 3,
"Ratsukamide EA-631" (Dainippon Ink and Chemicals
100 parts of adhesive polyamide resin (manufactured by Co., Ltd.) and 200 parts of calcium carbonate powder were added and mixed well to prepare an adhesive. Next, apply this adhesive to an aluminum plate (thickness
It was sandwiched between two sheets (0.2 mm, hardness 1/2H; surface treated with a mixture of sulfuric acid and monochromic acid) and compressed at 10° C. for 20 hours. Thereafter, the pressure was released and the sample was left at a temperature of 10°C for 7 days, and then the peel strength and tensile shear strength were measured using a tensile tester. Comparative Example 2 A polyester urethane resin having epoxy groups at both ends was synthesized in the same manner as in Example 3, except that 74 parts of glycidol was used instead of 118 parts of glyceryl carbonate. Next, 100 parts of this resin was added with ``Ratsucamide EA''.
631'' and 200 parts of calcium carbonate powder were added and mixed well to prepare an adhesive, which was then subjected to an adhesion test.

【table】

[Table] Example 6 5-methyl-5-hydroxymethyl-1,3-dioxapentane-2 was placed in the same reactor as in Example 1.
-392 parts of methyl ethyl ketone, 896 parts of dibutyltin dilaurate and Burnock DN-950
(Ethyl acetate solution of a 3:1 molar ratio adduct of hexamethylene diisocyanate and trimethylolpropane manufactured by Dainippon Ink Chemical Co., Ltd., non-volatile content 75
%, isocyanate group content 12.5%, average of 3 isocyanate groups per molecule) was charged and the temperature was gradually raised to 60° C. with stirring under a nitrogen atmosphere. The temperature was then maintained at the same temperature for 8 hours to obtain a 50% non-volatile solution of a compound having an average of 3 ethylene carbonate groups per molecule. Hereinafter, this will be abbreviated as (A-5). 100 parts of hexamethylene diamine of (A-5)
7.3 parts were added and thoroughly mixed to prepare a paint. Afterwards, apply this paint to the tin plate to a dry film thickness.
The coating was applied using a doctor blade to a thickness of 50 μm, and after drying at 10° C. for 4 days, a coating film test was conducted. Example 7 In a reactor similar to Example 1, 286 parts of a 1:1 molar ratio adduct of glyceryl carbonate and heximethylene diisocyanate and 0.2 parts of dibutyltin dilaurate were added.
220 parts of methyl ethyl ketone, 228 parts of dimethacrylate of trimethylolpropane and 2,
0.5 part of 6-di-t-butyl-p-cresol was charged and the temperature was gradually raised to 60°C with stirring under a nitrogen atmosphere, and the temperature was maintained for 8 hours until 1 mol per molecule was added.
A 70% non-volatile solution of a compound having 1 ethylene carbonate groups and 2 methacryloyl groups was obtained. Hereinafter, this will be abbreviated as (A-6). 100 parts of (A-6) and 35 parts of decamethylene diamine
A paint was prepared by adding 50% of the total amount and mixing thoroughly. Thereafter, a coating film was prepared in the same manner as in Example 6, and then a coating test was conducted. Example 8 In a reactor similar to Example 1, a 1:1 molar ratio of glyceryl carbonate and hexamethylene diamine was added.
286 parts of the adduct, 0.2 parts of dibutyltin dilaurate, 210 parts of methyl ethyl ketone, and 204 parts of diglycidyl ether of trimethylolpropane were charged, and the temperature was gradually raised to 60°C with stirring under a nitrogen atmosphere, and then maintained at the same temperature for 8 hours. A 70% non-volatile solution of a compound having one ethylene carbonate group and two epoxy groups per molecule was obtained. Below, this is (A
-7). The molar ratio of ethylenediamine and bisphenol A diglycidyl ether to 100 parts of (A-5) is 1:
1 adduct was added and mixed thoroughly to prepare a paint. Thereafter, a coating film was prepared in the same manner as in Example 6, and then a coating test was conducted. Table 3 summarizes the coating film performance test results of Examples 6 to 8.

【table】

Claims (1)

[Claims] 1 (A) General formula [] [However, Y in the formula represents an n+1 valent organic group,
is an ethylene carbonate group, an epoxy group, an acryloyl group or a methacryloyl group,
R represents a hydrogen atom or a methyl group, and n is an integer of 1 or more. ] A compound represented by (B) a compound having two or more amino groups per molecule selected from polyamines and/or polyamides having terminal amino groups [provided that in the formula [], X is an ethylene carbonate group When n=1, it refers to a polyamide having a terminal amino group. ] A curable resin composition comprising: