JPH02614A - One-pack thermosetting composition - Google Patents

Abstract

PURPOSE:To obtain a composition giving a cured resin excelling in elongation and strength at break, having high storage stability and a low curing temperature by dispersing a compound selected from among specified solid compounds in a polyisocyanate compound. CONSTITUTION:This one-pack thermosetting composition is obtained by dispersing at least one compound (e.g., adipic dihydrazide or melamine) selected from among a solid polyfunctional compound having at least one functional group selected from a hydrazino group, a prim. amine group, a prim. thioamine group and a sulfamoyl group, a solid compound having an amidino group and a solid compound having a heterocyclic ring and a plurality of active hydrogen atoms in a polyisocyanate compound. This composition gives a cured resin excellent in elongation and strength at break, has high storage stability and a low curing temperature, and is suited for, especially, an adhesive, a sealing material, a coating material, a resin molding, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a corrugated thermosetting composition, particularly a storable composition suitable for use in adhesives, sealants, paints, resin moldings, etc. This invention relates to a one-component thermosetting composition.

[Conventional technology]

Conventionally, thermosetting compositions consisting of a polyisocyanate compound and a compound having active hydrogen, such as a polyol compound, have been used as a two-component type in which the two components are stored separately and mixed immediately before use. However, this two-component composition has drawbacks such as the need for mixing before use and the difficulty of keeping the mixing ratio of each component constant. One-component compositions in which hydrogen-containing compounds are premixed are being considered.

This wave-type composition is prepared by dispersing a solid polyhydroquine compound in a liquid prepolymer of an aromatic polyisocyanate compound. JP-A No. 26927-26927, and those comprising metal complexes of organic polyisocyanate and diphenylaniline are disclosed in JP-A-56-26922 and JP-A-57-177014.

[Problem that the invention seeks to solve]

However, the composition described in Japanese Patent Publication No. 61-26927 has low storage stability and requires 130
There is a problem that a high temperature of ℃ or higher is required, and Japanese Patent Application Laid-Open No. 56-26922 and Japanese Patent Application Laid-open No. 57177014
The composition described in the publication also had a problem in that it lost its thermosetting ability when stored for about one month.

An object of the present invention is to solve the above-mentioned problems and provide a one-component thermosetting composition that has high storage stability and a low curing temperature.

[Means for solving problems]

According to the present invention (1), the above problem can be solved by adding at least one type of sulfamoyl group to the (A) polyisocyanate compound; A solid polyfunctional compound having a functional group; (1) a solid compound having an amidino group; and (2) a solid compound having a heterocycle and a plurality of active hydrogens. According to the present invention (2), (B) a solid polyfunctional compound having active hydrogen is added to (A) a mixture of a polyisocyanate compound and a high-boiling polar compound. With a one-component thermosetting composition characterized by being dispersed,
resolved.

The polyisocyanate compound which is the component (A) used in the compositions of the present invention (1) and (2) is a compound having a plurality of isocyanate groups, preferably 2 to 3 isocyanate groups in the molecule. As this polyisocyanate compound, various polyisocyanate compounds such as aliphatic, aromatic, and alicyclic polyisocyanate compounds can be used.

Examples of such polyisocyanate compounds include xylylene diisocyanate, polyphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, inphorone diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, naphthalene diisocyanate, hydrogenated diphenylmethane diisocyanate, and hydrogenated xylylene diisocyanate. Examples include diisocyanate compounds such as isocyanate, dicyclohexylmethane diisocyanate, and polymers thereof, and furthermore, they contain allophanate bonds, iso/anate bonds, carbodiimide bonds, etc. in the molecule. It is also possible to use compounds having a plurality of incyanate groups, such as the diisocyanate compound, the trichloride compound, and the polymeric diphenylmethane diisocyanate.

Furthermore, the polyisocyanate compounds in the present invention (1) and (2) have multiple iso/anate groups in the molecule, which are obtained by reacting active hydrogen compounds containing active hydrogen such as polyol compounds and polyamine compounds. It can also be used in the form of a prepolymer. Such a prepolymer can be obtained, for example, by reacting a polyisocyanate compound as described above and an active hydrogen compound at, for example, 20 to 90°C for 1 to 6 hours.

Specific examples of polyol compounds reacted with polyisocyanate compounds to obtain such prepolymers include ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, L-rimethylolpropane, diethylene glycol, triethylene glycol, and pehexamethylene glycol. Polyhydric alcohols such as nopeglycerin, 1,3 butylene glyconope 1,4-butane dionopehexanetriol, penquerythritol derivatives, sorbitol, neopentyl glycol; the above polyhydric alcohols, ethylene oxide, propylene oxide Polyether polyols obtained by addition polymerization with alkylene oxides such as; condensation reaction of the polyhydric alcohols with polybasic acids such as maleic acid, succinic acid, adipic acid, sebacic acid, tartaric acid, terephthalic acid, and isophthalic acid. Polyester polyol obtained by ring-opening polymerization of lactones such as ε-caprolactone and γ-valerolactone; Polymerization containing hydroxyl groups of hydroxyethyl acrylate, hydroxybutyl acrylate, and trimethylolpropane monoacrylate monomers that can be polymerized alone or copolymerized with these monomers, such as acrylic acid, methacrylic acid, styrene,
Acrylic polyol obtained by copolymerizing acrylonitrile, α-methylstyrene, etc.; Castor oil or its derivatives; Acrylic polyol obtained by reacting an epoxy resin having epoxy groups at both ends with monoethanolamine, jetanolamine, etc. Examples include epoxy polyols.

In addition, specific examples of polyamine compounds to be reacted with polyisocyanate compounds to obtain prepolymers include:
Aliphatic polyamine compounds such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, cyclohexylenediamine, inphorondiamine, melamine and derivatives thereof; 0 phenylene diamine, m-phenylene diamine, p-phenylene diamine, 4.4°-diaminodiphenylmethane, 4
．． 4'-'; aminodiphenyl sulfone, 4.4°-
Aromatic polyamine compounds such as diaminodiphenyl ether, 2.4-diaminodiphenylamine, 1.5-diaminonaphthalene, 1.8-diaminonaphthalene, and 2.4-diaminotoluene can be mentioned.

As mentioned above, when a polyol compound is used as an active hydrogen compound to form a prepolymer having a plurality of incyanate groups in the molecule, the molecular weight of the polyol compound is preferably 10.000 or less, particularly preferably 1. ,000 to 7.000, and in this case, when the resulting composition is cured, a tough and elastic cured resin can be obtained.

In the present inventions (1) and (2), the polyisocyanate compounds can be used alone or in combination of two or more.

Furthermore, in the polyisocyanate compounds in the present invention (1) and (2), the ratio of all isocyanate groups to the total polyisocyanate compound is 2 to 20% by weight,
In particular, it is preferably 3 to 15% by weight; in this case, the resulting composition can be cured at a relatively low temperature, and can maintain even higher storage stability.

In addition, in the present inventions (1) and (2), all or part of the isocyanate groups of the polyisocyanate compound may be blocked.

Examples of blocking agents for blocking this isocyanate group include ethanol, propatool, butanol,
Alcohols such as isobutanol; Phenols such as phenol, cresol, xylenol, and p-nitrophenol; Carbonyl compounds such as ethyl malonate and acetoacetate etynopearacetylacetone; Acid amides such as acetamide and acrylamide; Succinimide,
Acid imides such as maleic imide; imidazoles such as 2-ethylimidazole and 2-ethyl-4-methylimidazole; lactams such as 2-pyrrolidone and ε-caprolactam; acetoxime, methyl ethyl ketoxime, diacetyl monoxime, cyclohexanone oxime oximes such as; and others.

These blocking agents include polyisocyanate compounds and
A normal method, for example, in a solvent that does not contain active hydrogen that dissolves the blocking agent or in the absence of a solvent, from room temperature to 80°C.
Pressure reaction may be carried out at a temperature of 0.5 to 5 hours.

These blocked polyisocyanate compounds are
It produces incyanate groups upon heating.

In the present invention (1), those that can be used as component (B) are: (1) solid polyfunctional having at least one functional group selected from a hydrazino group, a primary amide group, a primary thioamide group, and a sulfamoyl group; (hereinafter referred to as "
"Specified Solid Compounds").

The solid polyfunctional compound having at least one functional group selected from the above-mentioned hydrazino group, primary amide group, primary thioamide group, and sulfamoyl group contains, in addition to these groups, a group reactive with an incyanate group, such as an amino group. It may have a group, a hydroxyl group, etc. Further, the above-mentioned solid compound having an amidino group may also have a group reactive with an incyanate group.

Examples of solid polyfunctional compounds having a hydrazino group include succinic acid dihydrazide, adipic acid dihydrazide, sebanic acid dihydrazide, dodecanedioic acid dihydrazide, hexadecanedioic acid dihydrazide, eicosaniic acid dihydrazide, carboxylic acid dihydrazide, azelaic acid dihydrazide, and oxalic acid dihydrazide. Dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, hexahydroisophthalic acid dihydrazide, hexahydroterephthalic acid dihydrazide, methylamino dipropionic acid dihydrazide, phenylaminopropionic acid dihydrazide, methylamino dibutyric acid dihydrazide, ethylamino divaleric acid dihydrazide, 1,3-bis( Compounds with two hydrazino groups in the molecule such as hydrazinocarboethyl-5-isopropylhydantoin; compounds with 3 hydrazino groups in the molecule such as citric acid trihydrazide and cyclohexanetricarboxylic acid trihydrazide
Compounds having more than 3 hydrazino groups; Compounds having a hydrazino group and an amino group in the molecule such as semicarbazide; Compounds having a hydrazino group and a hydroxyl group in the molecule such as salicylic acid hydrazide and p-oxybenzoic acid hydrazide. Examples of solid polyfunctional compounds having primary amide groups include succinic acid diamide, adipic acid diamide, maleic acid diamide, malonic acid diamide, sebanic acid diamide, dodecanoic acid diamide, hexadecanoic acid diamide, eicosanniic acid diamide, Compounds having two or more primary amide groups in the molecule such as biuret and isophthalic acid diamide; Compounds having three or more primary amide groups in the molecule such as citric acid triamide and cyclohexanetricarboxylic acid triamide; Compounds having a primary amide group and an amino group in the molecule; Compounds having a hydrazino group and a primary amide group in the molecule, such as oxamic hydrazide.

Examples of solid polyfunctional compounds having primary thioamide groups include succinic acid dithioamide, adipic acid dithioamide, maleic acid dithioamide, malonic acid dithioamide, sebacic acid dithioamide, dodecanoic acid dithioamide, hexadecaniic acid dithioamide, eicosanniic acid dithioamide, and isophthalic acid dithioamide. Compounds having two or more primary thioamide groups in the molecule such as acid dithioamide; compounds having three or more primary thioamide groups in the molecule such as citric acid trithioamide and cyclohexanetricarboxylic acid trithioamide; thiourea, etc. Examples include compounds having a primary thioamide group and an amine group in the molecule.

Examples of solid polyfunctional compounds having sulfamoyl groups include compounds having two or more sulfamoyl groups in the molecule, such as butane disulfamide, hexane disulfamide, benzenedisulfamide, and the like.

Examples of solid compounds having an amidino group include compounds having one amidino group in the molecule such as dicyandiamide and cyclohexanecarboxamidine; pentanediamidine, oxalcyamidine, isophthalcyamidine;
Compounds with two amidino groups in the molecule such as biguanide; Compounds with three or more amidino groups in the molecule such as 1133-propanetetracarboxamidine; Compounds with an amidino group and an amine group in the molecule such as guanidine. Compounds having an amidino group and a primary amide group in the molecule, such as 3-guanidinopropionamide.

Multiple s1! The solid compound having a plurality of active hydrogens preferably has an amino group as a group having active hydrogen, such as melamine, monomethylolmelamine, diallylmelamine, aminoimidazoylmelamine, 2.4
-Diamino-6-[2methylimidazolyl-(1) coethyltriazine, 2,4-diamino-6-[2-ethyl-4-methylimidazolyl-(1)]-diethylriazine, 2.4diamino-6- Examples include [2-undecylimidazolyl-(1)]-diethylriazine, benzoguanamine, trithiocyanuric acid, and derivatives thereof.

Among the above components (B), preferred specific solid compounds include adipic dihydrazide, eicosanniic acid dihydrazide, melamine, aminoimidazoyl melamine, and the like.

In the present invention (1), the specific solid compounds can be used alone or in combination of two or more.

The specific solid compound has an equivalent ratio of the incyanate group of component (A) and the groups reactive with the incyanate group of the specific solid compound, usually 0.3 to 5.
, preferably 0.5 to 3 (incyanate group/group reactive with isocyanate).

In addition, in the present invention (1), together with the above compound,
A solid polyhydroxy compound having no hydrazino group, primary amide group, primary thioamide group, sulfamoyl group, amidino group, or heterocycle may be used in combination. When this solid polyhydroxy compound is used in combination, the equivalent ratio of incyanate groups to hydroxyl groups (incyanate groups/hydroxyl groups) is preferably 2.5 or more. If this equivalent ratio is less than 2.5, the proportion of hydroxyl groups will increase,
The storage stability of the resulting composition will be reduced. Here, solid polyhydroxy compounds include pentaerythritol, dipentaerythritol, tripentaerythritol, corn starch methyl alpha glucoside, corn starch, sucrose, lactose, d-mannitol, anhydrous sorbitol, dulcitol, erythritol, Isopropylidene-bis(β-hydroxyethoxyphenol), 1,4-di(β-hydroxyethoxyphenol)phenol, 5-methylol-5-ethyl-2-(
1,1-dimethyl-2-hydroxyethyl)-1゜3-
Examples include dioxane, 5,5-dimethylol-2-(11 dimethyl-2-hydroxyethyl)-1,3-dioxane, and the like.

The specific solid compound in the present invention (1) preferably has a melting point higher than the curing temperature of the resulting composition, for example, 60°C or higher, but since curing is usually performed at 80 to 200°C, Particularly preferred are compounds having a melting point of about ~200°C.

In addition, in the present invention (1), since the specific solid compound is dispersed in the polyisocyanate compound, it is preferable that it is finely pulverized, and in particular, when it has a particle size of about 50μ or less, it can be used in the cured resin. has excellent toughness and elasticity.

A curing accelerator may be added to the composition of the present invention (1), if necessary. However, catalysts that promote curing, dimerization, and trimerization of the polyisonanate compound at room temperature are not preferred because they reduce the storage stability of the composition. Here, examples of curing accelerators include ■,
8-Diaza-dicyclo(5,4,0) undecene-
7 (hereinafter referred to as rDBUJ), DBU salts such as orthophthalic acid mono DBU salt, adipic acid mono DBU salt, partial DBU salt of phenol novolac resin; iron (I) acetylacetonate, manganese (II [) acetylacetonate] Examples include acetylacetonates such as acetylacetonate and zinc (II) acetylacetonate; imidazoles such as 2-methylimidazonope-2-heptadecyl imidazole; and curing accelerators for epoxy resins.

These curing accelerators are also available as commercial products, such as rU-CATSA-821J, rU-
CAT5A-831J, rU-CAT5A-841J
, rU-CATS^-851J (all of the above are manufactured by San-Apro ■), and the like.

Further, a filler can be added to the composition of the present invention (1) if necessary. Examples of fillers include talc, calcium carbonate, clay, synthetic silica, synthetic zeolite,
Examples include bentonite, zinc white, titanium dioxide, dry carbon black, glass particles, and surface-treated products of these.

Among these fillers, synthetic silica is preferred as a filler that prevents blurring during heat curing of the composition of the present invention (1), and among these, hydrophobic silica whose surface has been treated with an organic silicon compound is preferred. It is particularly preferred without changing the properties of the composition of invention (1).

In addition to the above, colorants, stabilizers, plasticizers, thickeners, etc. can be added to the composition of the present invention (1), if necessary.

The high-boiling polar compound constituting component (A) in the composition of the present invention (2) has a melting point below the temperature for curing the resulting composition, and has a melting point below the curing temperature or the temperature of the composition. It is desirable to have a boiling point that does not evaporate at a temperature below the use temperature, for example, a boiling point of 140° C. or higher.

By selecting this high boiling point polar compound, the present invention (
2) The curing temperature and speed of the composition can be controlled. However, from the viewpoint of storage stability, compounds that easily dissolve the active hydrogen component (B) in the solid polyfunctional compound at 40° C. or lower should be avoided as high-boiling polar compounds.

Such high-boiling polar compounds include, for example, propylene carbonate, T-butyrolactone, T-valerolactone, δ-valerolactone, N-methyl-ε-caprolactam, N-methylpyrrolidone, cyclohexanone, furfural, N-methylformamide, and N-methylpyrrolidone. , N-dimethylacetamide, diethylene glycol monoethyl ether acetate, diethylene glycol diacetate, acetonyl acetone, methylcyanoacetate, tetramethylurea, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, etc., with a melting point of 2.
Compounds below 0°C, ethylene carbonate, α-piperidone, sulfolene, succinonitrile, diaminomaleonitrile, methyl p-nitroanisonopelbamate, impropinopeacetamide carbamate, N-methylacetamide, succinic anhydride, diphenyl carbonate Compounds having a melting point of 20°C or higher can be mentioned. Among these, propylene carbonate,
Carbonate esters such as ethylene carbonate, lactones such as T-butyrolactone, γ-valerolactone, and δ-valerolactone are preferred.

In the present invention (2), the high-boiling polar compounds can be used alone or in combination of two or more. The high boiling point polar compound is preferably used in an amount of 0.1 to 20 parts by weight, particularly 1 to 10 parts by weight, per 100 parts by weight of the polyisocyanate compound. A good composition can be obtained.

As the component (B) in the present invention (2), a solid polyfunctional compound having active hydrogen (hereinafter referred to as "active hydrogen solid compound") is used. What can be used as this active hydrogen solid compound is a solid polyfunctional compound having active hydrogen that is reactive with incyanate groups, such as hydrazide used as component (B) in the present invention (1). a solid polyfunctional compound having at least one functional group selected from a group consisting of a primary amide group, a primary thioamide group, and a sulfamoyl group; a solid compound having an amidino group; a solid compound having a heterocycle and a plurality of active hydrogen atoms; Compounds and the same solid polyhydroxy compounds that can be used as needed in the present invention (1) can be mentioned.

Among the above, preferred active hydrogen solid compounds include adipic acid dihydrazide, eicosanniic acid dihydrazide,
Examples include melamine and aminoimidazoyl melamine.

In the present invention (2), the active hydrogen solid compounds can be used alone or in combination of two or more.

The active hydrogen solid compound in the present invention (2) has an equivalent ratio of the total amount of the incyanate groups of the component (A) and the groups that are reactive with the incyanate groups of the active hydrogen solid compound, usually 0. 3-5, preferably 0.5-3
(isocyanate group/group reactive with isocyanate).

Further, the melting point and particle size of the active hydrogen solid compound in the present invention (2) are the same as those of the specific solid compound in the present invention (1).

The composition of the present invention (2) may optionally include the composition of the present invention (1).
Curing accelerators, fillers, colorants, stabilizers, plasticizers, thickeners, etc. similar to those in the composition can be added.

Examples Examples of the present invention (1) and (2) will be described below, but the present invention is not limited thereto. Note that "part" indicates part by weight, and "%" indicates 1% by weight.

Example 1 46 parts of polyether polyol "Efcenol 2020 J (manufactured by Asahi Glass ■) having an average molecular weight of 2.000,
25 parts of polymeric 4.4°-diphenylmethane diisocyanate [Sumidur 44V-20J (manufactured by Sumitomo Bayer Urethane) and 8 parts of hydrogenated xylylene diisocyanate [Takenate 600J (manufactured by Takeda Pharmaceutical Company)] were heated at 80°C for 2 hours. The reaction produces a prepolymer having multiple incyanate groups, which is then coated with synthetic zeolite'
Add 15 parts of 5AJ and 6 parts of Kunimine Talc TFJ (manufactured by Kunimine Kogyo@) to create a polyisocyanate component containing 9.4% incyanate groups based on the total of the prepolymer having multiple incyanate groups, synthetic zeolite, and talc. I got it.

To 100 parts of this polyisocyanate component, 25.7 parts of sebacic acid dihydrazide (the equivalent ratio of NCO:NH is 1:1), a portion of phenol novolac resin DB
U Salt rU-CAT SA 841J (Sun Appro ■
5 parts (manufactured by Nippon Aerosil Ltd.) and 3 parts of hydrophobic silica "^εROSIL RY200J" (manufactured by Nippon Aerosil ■) surface-treated with an organic silicon compound were added to obtain a -wave type thermosetting composition.

Example 2 57 parts of a polyether polyol "Efsenol 850J (manufactured by Asahi Glass Co., Ltd.) having an average molecular weight of 7.000 and 23 parts of a polymeric 4,4°-diphenylmethane diisocyanate "Sumidur 44V-20J" were mixed at 80°C for 6 hours.
A prepolymer having a plurality of incyanate groups is obtained by reacting for a period of time, and 20 parts of synthetic zeolite "4A" is added to this to obtain a prepolymer having 6.0 parts of isocyanate groups based on the total of the prepolymer having a plurality of incyanate groups and the synthetic zeolite. A polyisocyanate component containing 0% was obtained.

To 100 parts of this polyisocyanate component, 5.2 parts of adipic acid amide (the equivalent ratio of NCO:NH is 2:1) and a partial DBU salt of phenol novolac resin rU-CAT SA 831J (manufactured by San Avro@)
3 parts were added to obtain a -wave type thermosetting composition.

Example 3 43.8 parts of a polyester polyol "Kurapol P-3D101J (manufactured by Kuraray ■) having an average molecular weight of 3.000 and 2 parts of polymeric 4,4°-diphenylmethane diisocyanate [SumiDur 44 V-20436] were heated at 80°C. The reaction was carried out for 2 hours to obtain a prepolymer having multiple incyanate groups, and this was mixed with synthetic zeolite "5".
A" 10 parts, talc "Kunimine Talc TF Js part, and bentonite "Kuch0RBENJ (manufactured by Shiraishi Kogyo@) 2 parts"
A polyisocyanate component containing 10% of incyanate groups based on the total of the prepolymer having a plurality of isocyanate groups, synthetic zeolite, talc and bentonite was obtained.

For 100 parts of this polyisocyanate component, 3.1 parts of pentaerythritol (NCO:OH equivalent ratio is 2.6
:1), 6.2 parts of dicyandiamide (NCO:
The equivalent ratio of N H2 is 3.2:1), partial DBU salt of phenolic novolak resin rU-CAT SA 8
31J 2 parts and zinc (II) acetylacetate) 0
．． 1 part was added to obtain a wave-shaped thermosetting composition.

Example 4 A - wave type was prepared in the same manner as in Example 2 except that 6 parts of melamine (the equivalent ratio of NCO:NH2 was 1:1) was used instead of 5.2 parts of adipic acid amide in Example 2. A thermosetting composition was obtained.

Example 5 A one-component thermosetting composition was obtained in the same manner as in Example 1 except that 2 parts of propylene carbonate was further added to 100 parts of the polyisocyanate compound.

Example 6 In Example 2, 4 parts of T-valerolactone was further added to 100 parts of the polyisocyanate compound, and the other conditions were the same as in Example 2 to obtain a -wave type thermosetting composition.

Example 7 In Example 4, 2 parts of r-butyrolactone was further added to 100 parts of the polyisocyanate compound, and the other conditions were the same as in Example 4 to obtain a -wave type thermosetting composition.

Example 8 Partial DB of phenol novolac resin in Example 1
A -wave type thermosetting composition was obtained in the same manner as in Example 1 except that 8 parts of ethylene carbonate was used instead of 5 parts of U salt rU -CAT SA 841J.

Comparative Example 1 7.6 parts of pentaerythritol (NGO 20H) was used instead of 25.7 parts of sebacic acid dihydrazide in Example 1.
A wave-shaped thermosetting composition was obtained in the same manner as in Example 1 except that the partial DBU salt of the phenol novolac resin was removed.

Comparative Example 2 14.3 parts of 3,4'-diaminodiphenyl ether (N
An attempt was made to obtain a wave-shaped thermosetting composition in the same manner as in Example 2, except that the equivalent ratio of CO:NH was 1:1 and the partial DBU salt of the phenol novolac resin was removed. However, it gelled during mixing.

Comparative Example 3 The same procedure as in Example 2 was carried out except that 2.4 parts of pentaerythritol (the equivalent ratio of NCO:OH was 1:2) was used instead of 5.2 parts of adipic acid amide in Example 2.
- A corrugated thermosetting composition was obtained.

Test Example 1 [Measurement of storage stability] The compositions obtained in Examples 1 to 8 and Comparative Examples 1 and 3 were placed in a glass sample bottle with a lid of 150 + nl and stored in a constant temperature bath at 40°C. The number of days required for hardening during storage was investigated. The results are shown in Table 1.

Test Example 2 [Measurement of heat curing time] In order to determine the curing rate depending on various temperatures for each of the compositions obtained in Examples 1 to 8 and Comparative Examples 1 and 3, the compositions at various temperatures were measured. A device to measure the degree of hardening of
JsR Curastometer ■type” (Nichirei Shoji @nfs
), and measured the heat curing time until the composition was cured and the measured torque value reached 1, Q kg-cm. Note that this torque value is 1.
0 kg-cm The state of the proposed composition is, for example, when the composition is used as an adhesive, a state in which it has reached a strength sufficient to withstand even when an external force is applied to the adhesive part, that is, clamp-off. This is a state where it can be considered that the strength has reached the level where it is possible.

Measurement condition; Amplitude angle 1 part 4 degrees Vibration frequency: 100 cycles/1 minute The results are shown in Table 1.

Table 1 Test Example 3 [Measurement of physical properties of cured resin sheet] Each of the compositions obtained in Examples 1 to 8 and Comparative Examples 1 and 3 was sandwiched between Teflon sheets. for 2 hours at 120°C for the compositions of Examples 5-8.
For the composition of J
An IS No. 2 dumbbell-shaped test piece was punched out. The Teflon sheet was peeled off from this dumbbell-shaped test piece, a tensile test was conducted at a tensile speed of 2 QQ mm/min, and the strength and elongation at break were measured using an Autograph A G-5000B J (manufactured by Shimadzu Corporation). The results are shown in Table 2.

Table 2 Test Example d CT Peel Strength Measurement] A 0.8 mm thick steel plate with a bonded area of 150 x 25 positive was coated with Braimer rMIGHTYGRIP 9025J.
(manufactured by Japan Synthetic Rubber) and using each of the compositions obtained in Examples 1 to 8 and Comparative Examples 1 and 3, the compositions of Examples 1 to 4 and Comparative Examples 1 and 3 were 2 hours at 120°C, 1 for the compositions of Examples 5-8.
A T-shaped peel test piece was prepared by heating and curing at 00° C. for 1 hour in a constant temperature bath. Using this test piece, the T-peel strength was measured using "Autograph A [:, -5000B"] at a bowing speed of 100 sequences/min. For the T-peel strength, the fracture equilibrium value during the test was taken as the value. The results are shown in Table 3.

Test Example 5 [Measurement of shear strength] 1.6 m+ with dimensions of 100 + n + n x 25 mm
Using n-thick steel plate, ply the adhesive part of 12.5 mm x 25 mm. -rMIGHTYGRIP9G25
using each of the compositions obtained in Examples 1 to 8a and Comparative Examples 1 and 3; For the compositions of Examples 5 to 8, at 100°C for 1 hour,
A shear test piece was prepared by heating and curing in a constant temperature bath. Using this test piece, “Autograph A
Shear strength was measured using C-5000B J. The results are shown in Table 3.

No. table 〔Effect of the invention〕

Claims (2)

[Claims] (1) (A) A polyisocyanate compound, (B) [1] 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, [2] ] A one-component thermosetting composition characterized by dispersing at least one compound selected from a solid compound having an amidino group, and [3] a solid compound having a heterocycle and a plurality of active hydrogens. thing. (2) A one-component thermosetting composition comprising (A) a mixture of a polyisocyanate compound and a high-boiling polar compound, and (B) a solid polyfunctional compound having active hydrogen dispersed therein.