JP2632939B2 - One-part type thermosetting composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a one-pack type thermosetting composition, and particularly to a storable composition suitable for applications such as adhesives, sealing materials, paints, and resin moldings. The present invention relates to a one-part thermosetting composition.

[Conventional technology]

Conventionally, a thermosetting composition comprising a polyisocyanate compound and a compound having active hydrogen, for example, a polyol compound, has been used as a two-pack type which is stored separately and mixed immediately before use. However, this two-pack type composition has drawbacks such as the necessity of mixing before use and the difficulty of always keeping the mixing ratio of each component constant. A one-part composition in which a compound having hydrogen is preliminarily mixed has been studied.

As this one-pack type composition, one obtained by dispersing a solid polyhydroxy compound in a liquid prepolymer of an aromatic polyisocyanate compound is disclosed in JP-B-61-26927, from a metal complex of an organic polyisocyanate and diphenylaniline. Some are disclosed in JP-A-56-26922 and JP-A-57-177014.

[Problems to be solved by the invention]

However, the composition described in JP-B-61-26927 has a problem that storage stability is low and a high temperature of 130 ° C. or more is required for curing.
The compositions described in JP-A No. 922 and JP-A-57-177014 also have a problem that the thermosetting ability is lost when the composition is stored for about one month.

An object of the present invention is to solve the above-mentioned problems and to provide a one-pack type thermosetting composition having a high storage stability, a short curing time, and a low curing temperature.

[Means for solving the problem]

The above problems, according to the present invention, (A) a mixture of a polyisocyanate compound and a high boiling polar compound, (B) a hydrazino group (-NHNH _2), first an amide group (-C
ONH ₂ ), a solid polyfunctional compound having at least one functional group selected from a primary thioamide group (—CSNH ₂ ) and a sulfamoyl group (—SO ₂ NH ₂ ), an amidino group (—C
(NH) NH ₂ ), and at least one compound selected from the group consisting of a solid compound having a heterocyclic ring and a plurality of amino groups, wherein the one-component thermosetting composition is dispersed. Solved by things.

The polyisocyanate compound as the component (A) used in the composition of the present invention is a compound having a plurality of, preferably 2 to 3 isocyanate groups in a molecule. As this polyisocyanate compound, for example, various polyisocyanate compounds such as aliphatic, aromatic, and alicyclic compounds can be used.

Such polyisocyanate compounds include, for example, xylylene diisocyanate, polyphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, isophorone diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, naphthalene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate A diisocyanate compound such as dicyclohexylmethane diisocyanate, or a polymer thereof; further, an allophanate bond, an isocyanurate bond, a carbodiimide bond, or the like in the molecule, a compound having a plurality of isocyanate groups in the molecule, For example, dimer or trimer of the above diisocyanate compound, polymeric diphenyl methanediyl Or the like can also be used cyanate. Furthermore, the polyisocyanate compound in the present invention may be used in the form of a prepolymer having a plurality of isocyanate groups in a molecule, which is obtained by reacting an active hydrogen compound containing active hydrogen such as a polyol compound and a polyamine compound. it can. Such a prepolymer is, for example, a polyisocyanate compound as described above,
It can be obtained by reacting with an active hydrogen compound at, for example, 20 to 90 ° C. for 1 to 6 hours.

Specific examples of the polyol compound to be reacted with the polyisocyanate compound to obtain such a prepolymer include ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, trimethylolpropane, diethylene glycol, triethylene glycol, hexamethylene glycol, and glycerin. Polyhydric alcohols such as 1,3-butylene glycol, 1,4-butanediol, hexanetriol, pentaerythritol derivatives, sorbitol and neopentyl glycol; the polyhydric alcohols and alkylene oxides such as ethylene oxide and propylene oxide A polyether polyol obtained by addition polymerization with the above polyhydric alcohols, maleic acid, succinic acid,
Polyester polyols obtained by a condensation reaction with polybasic acids such as adipic acid, sebacic acid, tartaric acid, terephthalic acid and isophthalic acid; polyester polyols obtained by ring-opening polymerization of lactones such as ε-caprolactone and γ-valerolactone; Hydroxy group-containing polymerizable monomers such as hydroxyethyl acrylate, hydroxybutyl acrylate, and trimethylolpropane monoacrylate are polymerized alone or copolymerizable with them, for example, acrylic acid, methacrylic acid, styrene, acrylonitrile Acrylic polyol obtained by copolymerizing α-methylstyrene, etc .; castor oil or a derivative thereof; obtained by reacting an epoxy resin having epoxy groups at both ends with monoethanolamine, diethanolamine, etc. Such as epoxy polyols can be mentioned.

Specific examples of the polyamine compound to be reacted with the polyisocyanate compound to obtain a prepolymer include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, tetramethylenediamine, pentamethylenediamine, and hexamethylenediamine. Aliphatic polyamine compounds such as cyclohexylenediamine, isophoronediamine, melamine and derivatives thereof; o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane,
Aromatic polyamine compounds such as 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether, 2,4-diaminodiphenylamine, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, and 2,4-diaminotoluene Can be mentioned.

As described above, when a polyol compound is used as an active hydrogen compound that forms a prepolymer having a plurality of isocyanate groups in the molecule, the molecular weight of the polyol compound is preferably 10,000 or less, and particularly preferably 1,000.
0 to 7,000, and in this case, a tough and elastic cured resin is obtained when the obtained composition is cured.

In the present invention, the polyisocyanate compounds can be used alone or in combination of two or more.

Furthermore, in the polyisocyanate compound of the present invention, the ratio of all isocyanate groups to all polyisocyanate compounds is preferably 2 to 20% by weight, particularly preferably 3 to 15% by weight. The composition can be cured at an extremely low temperature, and the storage stability can be kept higher.

In the present invention, all or a part of the isocyanate group of the polyisocyanate compound may be blocked.

Examples of the blocking agent for blocking the isocyanate group include alcohols such as ethanol, propanol, butanol and isobutanol; phenol,
Phenols such as cresol, xylenol, p-nitrophenol; ethyl malonate, ethyl acetoacetate;
Carbonyl compounds such as acetylacetone; acid amides such as acetamide and acrylamide; acid imides such as succinimide and maleic imide; imidazoles such as 2-ethylimidazole and 2-ethyl-4-methylimidazole; 2-pyrrolidone And lactams such as ε-caprolactam; oximes such as acetoxime, methyl ethyl ketoxime, diacetyl monooxime and cyclohexanone oxime; and the like.

These blocking agents, the polyisocyanate compound, in a conventional manner, for example, in a solvent containing no active hydrogen dissolving the blocking agent or without solvent, room temperature to 80 ~
The reaction may be performed at a temperature of about 0.5 to 5 hours.

These blocked polyisocyanate compounds generate isocyanate groups when heated.

In the composition of the present invention, the high-boiling polar compound constituting the component (A) has a melting point not higher than the temperature for curing the obtained composition, and is not higher than the curing temperature or not higher than the use temperature of the composition. It is desirable to have a boiling point that does not evaporate at a temperature of, for example, 140 ° C. or higher. By selecting this high boiling point polar compound, the curing temperature and rate of the composition of the present invention can be controlled, and the curing time can be shortened. However,
Compounds that readily dissolve the active hydrogen of the component (B) at 40 ° C. or lower in a solid polyfunctional compound should be avoided from being used as a high boiling point polar compound from the viewpoint of storage stability.

Such high boiling point polar compounds include, for example, propylene carbonate, γ-butyrolactam, γ-valerolactone, δ-valerolactone, N-methyl-ε-caprolactone, N-methylpyrrolidone, cyclohexanone, furfural, N-methylformamide, N-methylformamide , N-dimethylacetamide, diethylene glycol monoethyl ether acetate, diethylene glycol diacetate, acetonylacetone, methyl cyanoacetate, tetramethylurea, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, etc.
C., a compound having a temperature of less than 0 ° C., ethylene carbonate, α-piperidone, sulfolene, succinonitrile, diaminomaleonitrile, p-nitroanisole, methyl carbamate,
Compounds having a melting point of 20 ° C. or more such as isopropyl carbamate, acetamide, N-methylacetamide, succinic anhydride, diphenyl carbonate, and the like can be given. Of these, carbonates such as propylene carbonate and ethylene carbonate, and lactones such as γ-butyrolactone, γ-valerolactone, and δ-valerolactone are preferred.

In the present invention, the high boiling point polar compounds can be used alone or in combination of two or more. The high boiling point polar compound is preferably 0.1 to 20 parts by weight, particularly 1 to 10 parts by weight, based on 100 parts by weight of the polyisocyanate compound. In this case, a composition which can be cured at a low temperature and has particularly good storage stability. Can be obtained.

In the present invention, a solid polyfunctional compound having at least one functional group selected from a hydrazino group, a primary amide group, a primary thioamide group and a sulfamoyl group, which can be used as the component (B), an amidino group And at least one compound selected from solid compounds having a heterocycle and a plurality of active hydrogens (hereinafter referred to as “specific solid compounds”).

The hydrazino group, the primary amide group, the primary thioamide group and a solid polyfunctional compound having at least one functional group selected from sulfamoyl groups, in addition to these groups, a group having reactivity with an isocyanate group, such as an amino group , A hydroxyl group or the like. Further, the solid compound having an amidino group may also have a group having reactivity with an isocyanate group.

Examples of solid polyfunctional compounds having a hydrazino group include succinic dihydrazide, adipic dihydrazide,
Sebacic dihydrazide, dodecane diacid dihydrazide,
Hexadecanedioic acid dihydrazide, eicosane diacid dihydrazide, azelaic acid dihydrazide, oxalic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, hexahydroisophthalic acid dihydrazide, hexahydroterephthalic acid dihydrazide, methylaminodipropionic acid phenyl dihydrazide Compounds having two hydrazino groups in the molecule, such as, methylaminodibutyric acid dihydrazide, ethylaminodivalic acid dihydrazide, 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin; citric acid trihydrazide, cyclohexanetricarboxylic acid trihydrazide Compounds having three or more hydrazino groups in the molecule, such as semicarbazide; having a hydrazino group and an amino group in the molecule, such as semicarbazide That compound; salicylic hydrazide, may be a compound having a hydrazino group and a hydroxyl group in the molecule, such as p- hydroxybenzoic acid hydrazide.

Examples of solid polyfunctional compounds having a primary amide group include succinic diamide, adipic diamide, maleic diamide, malonic diamide, sebacic diamide,
Compounds having two or more primary amide groups in the molecule such as dodecane diacid diamide, hexadecane diacid diamide, eicosane diacid diamide, biuret, and isophthalic acid diamide; in the molecules such as citric acid triamide and cyclohexanetricarboxylic acid triamide A compound having three or more primary amide groups; a compound having a primary amide group and an amino group in a molecule such as urea; a compound having a hydrazino group and a primary amide group in a molecule such as oxamic hydrazide; Can be mentioned.

Examples of solid polyfunctional compounds having a primary thioamide group include succinic dithioamide, adipic dithioamide, maleic dithioamide, malonic dithioamide,
Sebacic acid dithioamide, dodecane diacid dithioamide,
Compounds having two or more primary thioamide groups in a molecule such as hexadecane diacid dithioamide, eicosane diacid dithioamide, and isophthalic acid dithioamide; three or more primary thioamide groups in a molecule such as citric acid trithioamide and cyclohexanetricarboxylic acid trithioamide Compounds having one thioamide group and compounds having a first thioamide group and an amino group in a molecule such as thiourea can be given.

Examples of the solid polyfunctional compound having a sulfamoyl group include compounds having two or more sulfamoyl groups in a molecule, such as butanedisulfamide, hexanedisulfamide, and benzenedisulfamide.

Examples of solid compounds having an amidino group include compounds having one amidino group in a molecule such as dicyandiamide and cyclohexanecarboxamidine; pentanediamidine, oxaldiamidine, isophthaldiamidine, and biguanide. Compound having two amidino groups; compound having three or more amidino groups in a molecule such as 1,1,3,3-propanetetracarboxamidine; having amidino group and amino group in a molecule such as guanidine Compounds: Compounds having an amidino group and a primary amide group in the molecule, such as 3-guanidinopropionamide, may be mentioned.

Examples of solid compounds having a heterocyclic ring and a plurality of amino groups include, for example, melamine, monomethylol melamine, diallyl melamine, aminoimidazoyl melamine, 2,4-
Diamino-6- [2-methylimidazolyl- (1)]-
Ethyl triazine, 2,4-diamino-6- [2-ethyl-4-methylimidazolyl- (1)]-ethyltriazine, 2,4-diamino-6- [2-undecylimidazolyl- (1)]-ethyl Triazine, benzoguanamine,
Examples thereof include trithiocyanuric acid and derivatives thereof.

Among the above-mentioned component (B), preferred specific solid compounds include adipic dihydrazide, eicosane diacid dihydrazide, melamine, aminoimidazoyl melamine and the like.

In the present invention, the specific solid compound is used alone or
More than one species can be used in combination.

In the specific solid compound, the total amount of the isocyanate group of the component (A) and the group having reactivity with the isocyanate group of the specific solid compound is usually 0.3 to
5, preferably 0.5 to 3 (isocyanate group / group reactive with isocyanate).

Further, in the present invention, together with the above specific solid compound, a hydrazino group, a primary amide group, a primary thioamide group,
A solid polyhydroxy compound having no sulfamoyl group, amidino group or heterocycle may be used in combination. When this solid polyhydroxy compound is used in combination, the equivalent ratio of isocyanate group to hydroxyl group (isocyanate group / hydroxyl group) is preferably 2.5 or more. If the equivalent ratio is less than 2.5, the ratio of hydroxyl groups will increase,
The storage stability of the resulting composition will be reduced. Here, as the solid polyhydroxy compound, pentaerythritol, dipentaerythritol, tripentaerythritol, methyl alpha glycoside of corn starch, corn starch, sucrose, lactose, d-mannitol, anhydrous sorbitol, dulcitol, erythritol, isopropylate Riden-bis (β-hydroxyethoxyphenol), 1,4-di (β-hydroxyethoxy) phenol, 5-methylol-5-ethyl-2-
(1,1-dimethyl-2-hydroxyethyl) -1,3-dioxane, 5,5-dimethylol-2- (1,1-dimethyl-2
-Hydroxyethyl) -1,3-dioxane.

The specific solid compound in the present invention has a melting point higher than the curing temperature of the obtained composition, for example, preferably has a melting point of 60 ° C. or higher, but since curing is usually performed at 80 to 200 ° C., 85 to 200 ° C. Compounds having a moderate melting point are particularly preferred.

Further, in the present invention, since the specific solid compound is dispersed in the polyisocyanate compound, it is preferable that the specific resin is finely pulverized. And excellent elasticity.

If necessary, a curing accelerator may be added to the composition of the present invention. However, a catalyst having an effect of promoting the curing, dimerization and trimerization of the polyisocyanate compound at room temperature is not preferred because it reduces the storage stability of the composition. Here, examples of the curing accelerator include 1,8-diaza-dicyclo (5,4,0) undecene-7 (hereinafter, “DBU”).
), For example, mono-DBU salt of orthophthalic acid, mono-DBU salt of adipic acid, part D of phenol novolak resin
DBU salts such as BU salt; iron (III) acetylacetonate;
Acetylacetonates such as manganese (III) acetylacetonate and zinc (II) acetylacetonate; 2-
Imidazoles such as methylimidazole and 2-heptadecylimidazole; and curing accelerators for epoxy resins. These curing accelerators can also be obtained as commercial products, for example, “U-CAT SA-821”,
"U-CAT SA-831", "U-CAT SA-841", "U-CA
TSA-851 "(all manufactured by San Apro Co., Ltd.).

A filler can be added to the composition of the present invention as needed. Examples of the filler include talc, calcium carbonate, clay, synthetic silica, synthetic zeolite, bentonite, zinc white, titanium dioxide, dry carbon black, glass particles, and those obtained by surface-treating these.

Of these fillers, synthetic silica is preferred as a filler that prevents sagging during heat curing of the composition of the present invention, and hydrophobic silica whose surface is treated with an organosilicon compound is particularly preferred. Particularly preferred without changing the properties of the product.

In addition to the above, a coloring agent, a stabilizer, a plasticizer, a thickener, and the like can be added to the composition of the present invention as needed.

EXAMPLES Hereinafter, examples of the present invention will be described, but the present invention is not limited thereto. In addition, "part" shows a weight part and "%" shows a weight%.

Comparative Example 1 46 parts of polyether polyol "Exenol 2020" having an average molecular weight of 2,000 (manufactured by Asahi Glass Co., Ltd.) and polymeric 4,4'-diphenylmethane diisocyanate "Sumidur 44V-20" (manufactured by Sumitomo Bayer Urethane Co., Ltd.) twenty five
Parts and hydrogenated xylylene diisocyanate “Takenate 60
8 "(manufactured by Takeda Pharmaceutical Co., Ltd.) at a temperature of 80 ° C. for 2 hours to obtain a prepolymer having a plurality of isocyanate groups, to which 15 parts of synthetic zeolite" 5A "and 15 parts of talc" Kuniminetalc TF " 6 parts of (Munimine Kogyo Co., Ltd.) was added to obtain a polyisocyanate component containing 9.4% of isocyanate groups based on the total of the prepolymer having a plurality of isocyanate groups, synthetic zeolite and talc.

Based on 100 parts of this polyisocyanate component, 25.7 parts of sebacic acid dihydrazide (equivalent ratio of NCO: NH ₂ is 1: 1), a partial DBU salt of phenol novolak resin “U-CAT
SA 841 ”(San Apro Co., Ltd.) 5 parts and hydrophobic silica“ AEROSIL RY20 ”surface-treated with an organosilicon compound
0 "(manufactured by Nippon Aerosil Co., Ltd.) was added to obtain a one-part thermosetting composition.

Comparative Example 2 57 parts of polyether polyol "Exenol 850" having an average molecular weight of 7,000 (manufactured by Asahi Glass Co., Ltd.) and 23 parts of polymeric 4,4'-diphenylmethane diisocyanate "Sumidur 44V-20" at 80 ° C. for 6 hours. A prepolymer having a plurality of isocyanate groups is reacted, and 20 parts of a synthetic zeolite “4A” is added to the prepolymer. An isocyanate component was obtained.

To 100 parts of this polyisocyanate component, 5.2 parts of adipic amide (NCO: NH ₂ equivalent ratio is 2: 1) and a partial DBU salt of phenol novolak resin “U-CAT SA 83
1 "(manufactured by San Apro Co., Ltd.) was added to obtain a one-part thermosetting composition.

Comparative Example 3 43.8 parts of a polyether polyol having an average molecular weight of 3,000 "Clapol P-3D101" (manufactured by Kral Co., Ltd.) and 36.2 parts of polymeric 4,4'-diphenylmethane diisocyanate "Sumidur 44V-20" at 80.degree. After reacting for 2 hours to obtain a prepolymer having a plurality of isocyanate groups, 10 parts of synthetic zeolite “5A”, 8 parts of talc “Kunimine talc TF”, and bentonite “D ORBEN” (manufactured by Shiraishi Industry Co., Ltd.) 2 Part of the prepolymer having a plurality of isocyanate groups, synthetic zeolite, talc, and bentonite.
% Of a polyisocyanate component was obtained.

3.1 parts of pentaerythritol (the equivalent ratio of NCO: OH is 2.6: 1) to 100 parts of this polyisocyanate component,
6.2 parts of dicyandiamide (equivalent ratio of NCO: NH ₂ is 3.2: 1), partial DBU salt of phenol novolak resin “U-CAT
SA 831 ”2 parts and zinc (II) acetyl acetate 0.1
Was added to obtain a one-part thermosetting composition.

Control Example 4 In the same manner as in Control Example 2 except that 6 parts of melamine (the equivalent ratio of NCO: NH ₂ is 1: 1) was used instead of 5.2 parts of adipic amide in Control Example 2, a one-pack type heat was used. A curable composition was obtained.

Example 1 A one-part thermosetting composition was obtained in the same manner as in Comparative Example 1, except that 2 parts of propylene carbonate was added to 100 parts of the polyisocyanate compound.

Example 2 In Comparative Example 2, 4 parts of γ-valerolactone were further added to 100 parts of the polyisocyanate compound, and otherwise the same as in Comparative Example 2, to obtain a one-part thermosetting composition.

Example 3 In Comparative Example 4, 2 parts of γ-butyrolactone were further added to 100 parts of the polyisocyanate compound, and the others were the same as in Comparative Example 4, to obtain a one-part thermosetting composition.

Example 4 Partial DB of phenol novolak resin in Control Example 1
A one-part thermosetting composition was obtained in the same manner as in Control Example 1, except that 8 parts of ethylene carbonate was used instead of 5 parts of U salt “U-CAT SA 841”.

Comparative Example 1 Instead of 25.7 parts of sebacic acid dihydrazide in Comparative Example 1, 7.6 parts of pentaerythritol (the equivalent ratio of NCO: OH was
1: 1) and the phenol novolak resin part D
A one-part thermosetting composition was obtained in the same manner as in Control Example 1 except that the BU salt was omitted.

Comparative Example 2 Instead of 5.2 parts of adipic amide in Control Example 2,
One-pack type compound was prepared in the same manner as in Control Example 2 except that 14.3 parts of 3,4'-diaminodiphenyl ether (the equivalent ratio of NCO: NH ₂ was 1: 1) was used and the partial DBU salt of the phenol novolak resin was removed. An attempt was made to obtain a thermosetting composition, which gelled during mixing.

Comparative Example 3 One-part heat was prepared in the same manner as in Comparative Example 2 except that 7.4 parts of pentaerythritol (equivalent ratio of NCO: OH was 1: 2) instead of 5.2 parts of adipic amide in Comparative Example 2. A curable composition was obtained.

Test Example 1 [Measurement of Storage Stability] Control Examples 1-4, Examples 1-4, and Comparative Examples 1 and 3
Was placed in a glass sample bottle with a lid having a capacity of 50 ml, stored in a thermostat at 40 ° C., and the number of days until curing during storage was determined. Table 1 shows the results.

Test Example 2 [Measurement of Heat-Hardening Time] Control Examples 1-4, Examples 1-4, and Comparative Examples 1 and 3
In order to determine the curing rate at various temperatures for each of the compositions obtained in the above, the degree of curing of the composition at various temperatures was measured using a measuring instrument "JSR Curastometer III" (manufactured by Nichigo Corporation). The composition was cured according to the following measurement conditions, and the heat curing time until the measured torque value of the composition reached 1.0 kg · cm was measured. The state of the composition having a torque value of 1.0 kgcm is, for example, when the composition is used as an adhesive, has reached a strength enough to withstand even when an external force is applied to the bonded portion. This is the state, that is, the state where it can be considered that the strength at which the clamp-off is possible has been reached.

Measurement conditions: Amplitude angle 1/4 degree Frequency 100 cycles / 1 minute The results are shown in Table 1.

Test Example 3 [Measurement of Physical Properties of Cured Resin Sheet] Control Examples 1-4, Examples 1-4, and Comparative Examples 1 and 3
Each of the compositions obtained in the above was sandwiched between Teflon sheets, and the compositions of Control Examples 1 to 4 and Comparative Examples 1 and 3 were
2 hours at 120 ° C., 100 ° C. for the compositions of Examples 1-4
To form a cured resin sheet having a thickness of 2 mm, and a JIS No. 2 dumbbell-shaped test piece was punched out. The Teflon sheet was peeled off from the dumbbell-shaped test piece, a tensile test was performed at a tensile speed of 200 mm / min, and the strength and elongation at break were measured by “Autograph AG-5000B” (manufactured by Shimadzu Corporation). . The results are shown in Table 2.

Test Example 4 [Measurement of T-Type Peeling Strength] A 0.8 mm thick steel plate having an adhesive portion of 150 mm × 25 mm was previously treated with a primer “MIGHTYGRIP 9025” (manufactured by Japan Synthetic Rubber Co., Ltd.), Each of the compositions obtained in Examples 1 to 4 and Comparative Examples 1 and 3 was used, and Comparative Examples 1 to 4 were used.
4 and the compositions of Comparative Examples 1 and 3 were heated and cured in a thermostat at 120 ° C. for 2 hours and the compositions of Examples 1 to 4 at 100 ° C. for 1 hour to produce T-peel test pieces. . Using this test piece, T-type peel strength was measured at a pulling speed of 100 mm / min by "Autograph AG-5000B". T
The mold peel strength was determined by taking the fracture equilibrium value at the time of the test. The results are shown in Table 3.

Test Example 5 [Measurement of shear strength] Using a 1.6 mm thick steel plate of 100 mm x 25 mm, 12.5 mm x
A 25 mm adhesive portion was previously treated with a primer "MIGHTYGRIP 9025", and the compositions obtained in Comparative Examples 1 to 4, Examples 1 to 4 and Comparative Examples 1 and 3 were used, and Comparative Examples 1 to 4 and Comparative Examples 2 hours at 120 ° C. for the compositions of Examples 1 and 3, 1 hour at 100 ° C. for the compositions of Examples 1-4,
Heat-curing was performed in a thermostat to prepare a shear test piece. Using this test piece, "Autograph AG-50" at a pulling speed of 5 mm / min.
00B "to measure the shear strength. The results are shown in Table 3.

(Effect of the Invention) The one-part thermosetting composition of the present invention has excellent elongation at break and strength at break of the cured resin, high storage stability, short curing time, and low curing temperature, Particularly, the composition is suitable for an adhesive, a sealing material, a paint, a resin molded article, and the like.

 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Yukihiro Okubo 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd. (56) References JP-A-58-120627 (JP, A) JP-A Sho JP-A-62-116635 (JP, A) JP-A-61-235414 (JP, A) JP-A-57-177014 (JP, A) JP-A-56-26922 (JP, A) A)

Claims (1)

(57) [Claims] 1. A mixture of (A) a polyisocyanate compound and a high boiling point polar compound, (B) a hydrazino group (-NHNH ₂ ), a primary amide group (-C
ONH ₂ ), a solid polyfunctional compound having at least one functional group selected from a primary thioamide group (—CSNH ₂ ) and a sulfamoyl group (—SO ₂ NH ₂ ), an amidino group (—C (NH) NH ₂ ) And a solid compound having at least one compound selected from the group consisting of a solid compound having a heterocyclic ring and a plurality of amino groups.