JPH06322056A - One-pack polyurethane composition - Google Patents

Abstract

(57) [Summary] [Object] To provide a one-pack type polyurethane composition which is cured to a degree such that initial strength is developed in a short time at a relatively low temperature and has excellent storage stability. [Structure] Polyisocyanate compound and 2 of all hydroxyl groups
An equivalent ratio (NCO / OH) of 6% by weight is 0% by weight or more with a polyol compound derived from a polyfunctional polyol having three or more functional groups
A urethane prepolymer obtained by reacting in the following proportions contains a solid curing accelerator dispersed at room temperature.
Further, it is preferable that at least one component selected from the group consisting of the following compounds and compounds is dispersedly contained. Compound At least one selected from a hydrazino group, a primary amide group, a primary thioamide group and a sulfamoyl group
Solid polyfunctional compound compound having certain functional groups Solid compound compound having amidino group Solid compound having heterocycle and plural active hydrogens

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a one-pack type polyurethane composition, and more particularly to a storable one-pack type polyurethane composition suitable for applications such as adhesives, sealing agents, paints and resin moldings. is there.

[0002]

2. Description of the Related Art Conventionally, polyurethane compositions are one-pack type ones in which a urethane polypremer having an isocyanate group at the terminal is cured by moisture or by polymerization between isocyanate groups, and a urethane prepolymer having an activity such as a polyol. A two-pack type in which a compound having hydrogen is mixed and cured is known.

However, in the two-component polyurethane composition, it is necessary to separately store the urethane prepolymer and the compound having active hydrogen and mix them immediately before use, and the mixing ratio of each component is always constant. There is a drawback that handling is complicated, such as having to keep it constant. Therefore, a one-component polyurethane composition that does not require a mixing operation and is easy to handle has been studied.

As such a one-pack type polyurethane 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, which has an isocyanate group at the end. To the urethane prepolymer having 1,8
Cycloamidines such as diazabicyclo (5,4,10) undecene-7 or salts thereof or compounds containing these and a compound having active hydrogen are disclosed in JP-B-46-
It is disclosed in Japanese Patent No. 10549 and Japanese Patent Publication No. 47-25138.

[0005]

However, in the one-component polyurethane composition described in Japanese Patent Publication No. 61-26927, the storage stability is low, and the curing temperature is relatively high at 130 ° C. or higher. There is a problem that a high temperature is required, and the one-component polyurethane compositions described in JP-B-46-10549 and JP-B-47-25138 also have either heat curing property or storage stability. There was a problem of having to sacrifice.

An object of the present invention is to provide a one-pack type polyurethane composition which is cured to such an extent that the required initial strength is developed in a short time by a curing treatment at a relatively low temperature and is excellent in storage stability. Especially. Here, the initial strength means that when the composition is used as an adhesive,
It refers to the strength when it reaches a state that it sufficiently withstands even when an external force is applied to the adhesive part, and when the composition is used as a paint, it is cured to such an extent that the surface of the coating film does not become sticky. The strength of the state.

[0007]

The one-pack type polyurethane composition of the present invention comprises a polyisocyanate compound and a polyol compound in which 20% by weight or more of all hydroxyl groups is derived from a polyfunctional polyol having a trifunctional or higher functionality. (NCO / OH)
The urethane prepolymer obtained by reacting at a ratio of 6 or less contains a solid curing accelerator dispersed at room temperature.

The one-pack type polyurethane composition of the present invention preferably contains at least one solid component selected from the group consisting of the following compounds and compounds in a dispersed manner. Compound At least one selected from a hydrazino group, a primary amide group, a primary thioamide group and a sulfamoyl group
Solid polyfunctional compounds having certain functional groups Compounds Solid compounds having amidino groups Compounds Solid compounds having heterocycles and multiple active hydrogens

The present invention will be specifically described below.
In the urethane prepolymer used in the present invention, the equivalent ratio (NCO / OH) of the polyisocyanate compound and the polyol compound described later is 6 or less, preferably 1.
It is obtained by mixing at a ratio of 1 to 6, particularly preferably 2 to 5, and reacting at 20 to 90 ° C. for 1 to 8 hours.

When the equivalent ratio (NCO / OH) of the polyisocyanate compound and the polyol compound exceeds 6.0, it takes a long time to cure to such an extent that the initial strength is exhibited and the workability deteriorates. . In addition, the equivalent ratio of the polyisocyanate compound and the polyol compound (NCO / O
When H) is less than 1.1, the amount of isocyanate groups in the composition is too small, and the heat curability is deteriorated.

The polyisocyanate compound used for obtaining the urethane prepolymer is a compound having a plurality of, preferably 2-3, isocyanate groups in the molecule. As the polyisocyanate compound, various polyisocyanate compounds such as aliphatic, aromatic, and alicyclic compounds can be used.

Examples of such polyisocyanate compounds include xylylene diisocyanate, polyphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, isophorone diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, naphthalene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated Diisocyanate compounds such as xylylene diisocyanate and dicyclohexylmethane diisocyanate, or polymers thereof can be mentioned. Furthermore, allophanate bonds in the molecule,
Compounds containing isocyanurate bond, carbodiimide bond, etc., having a plurality of isocyanate groups in the molecule,
For example, a dimer or trimer of the above diisocyanate compound, polymeric diphenylmethane diisocyanate or the like can be used. These polyisocyanate compounds can be used alone or in combination of two or more kinds.

In the polyol compound to be reacted with the above polyisocyanate compound to obtain the urethane prepolymer, the ratio of the hydroxyl groups derived from the trifunctional or higher polyfunctional polyol to the total hydroxyl groups in the polyol compound is
It is 20% by weight or more, preferably 50% by weight or more, particularly preferably 80% by weight or more.

When the ratio of the hydroxyl groups derived from the polyfunctional polyol having three or more functional groups to the total hydroxyl groups in the polyol compound used is less than 20% by weight, the heat curability of the obtained one-pack type polyurethane composition is deteriorated. .

Specific examples of the polyol compound include ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, trimethylolpropane, diethylene glycol, triethylene glycol, hexamethylene glycol, glycerin, 1,
Polyhydric alcohols such as 3-butylene glycol, 1,4-butanediol, hexanetriol, pentaerythritol derivative, sorbitol, neopentyl glycol; the polyhydric alcohols and ethylene oxide,
Polyether polyols obtained by addition polymerization with alkylene oxides such as propylene oxide; polyhydric alcohols and polybasic acids such as maleic acid, succinic acid, adipic acid, sebacic acid, tartaric acid, terephthalic acid and isophthalic acid Polyester polyol obtained by condensation reaction; Polyester polyol obtained by ring-opening polymerization of lactones such as ε-caprolactone and γ-valerolactone; Contains hydroxyl groups such as hydroxyethyl acrylate, hydroxybutyl acrylate, and trimethylolpropane monoacrylate Acrylic polymer obtained by polymerizing a polymerizable monomer to be used alone or copolymerizable with these, for example, acrylic acid, methacrylic acid, styrene, acrylonitrile, α-methylstyrene, etc. It can be exemplified an epoxy resin having an epoxy group at both ends, monoethanolamine, epoxy polyols obtained by reacting with diethanolamine and the like; Lumpur; castor oil or a derivative thereof. These polyol compounds can be used singly or in combination of two or more if trifunctional or higher polyfunctional polyol is used in such a proportion that the hydroxyl group resulting from this is 20% by weight or more.

The number average molecular weight of the polyol compound is preferably 10,000 or less, and particularly 10
It is preferably from 00 to 7000. By curing the one-pack type polyurethane composition obtained by using the polyol compound having such a molecular weight,
A cured resin that is tough and elastic is obtained.

Further, in order to obtain a urethane prepolymer, a polyamine compound may be used together with the above-mentioned polyol compound. Specific examples of the polyamine compound include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, cyclohexylenediamine, isophoronediamine, melamine and derivatives thereof. Aliphatic polyamine compound of o;
Phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4,4 '
-Diaminodiphenyl ether, 2,4-diaminodiphenylamine, 1,5-diaminonaphthalene, 1,8-
Examples thereof include aromatic polyamine compounds such as diaminonaphthalene and 2,4-diaminotoluene.

In the urethane prepolymer used in the present invention, the proportion of all isocyanate groups in the urethane prepolymer is preferably 0.1 to 20% by weight, and in this case, the composition obtained is relatively low. It can be cured at temperature.

Further, all or some of the isocyanate groups of the urethane prepolymer 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 acid imide; imidazoles such as 2-ethylimidazole and 2-ethyl-4-methylimidazole; 2-pyrrolidone , Ε-caprolactam and other lactams; acetoxime, methyl ethyl ketoxime, diacetyl monooxime, cyclohexanone oxime and other oximes; and others.

These blocking agents are treated with a urethane prepolymer in a conventional manner, for example, in a solution containing no active hydrogen for dissolving the blocking agent or in the absence of a solvent, from 20 to 80.
By reacting at a temperature of ℃ for 0.5 to 5 hours,
A blocked urethane prepolymer is obtained. These blocked urethane prepolymers generate isocyanate groups when heated.

In the present invention, the urethane prepolymer contains a solid curing accelerator dispersed at room temperature. When the curing accelerator used is a liquid at room temperature, the storage stability of the obtained one-pack type polyurethane composition is lowered. Further, even if it is a solid at room temperature, a catalyst having the action of promoting the curing, dimerization and trimerization of the polyisocyanate compound at room temperature lowers the storage stability of the composition, which is not preferable. .

Here, as an example of the curing accelerator, 1,8
-Diaza-dicyclo (5,4,0) undecene-7 (hereinafter referred to as "DBU") salts, for example, DBU salts such as orthophthalic acid mono-DBU salt, adipic acid mono-DBU salt and partial DBU salt of phenol novolac resin ; Iron (II
Acetylacetonates such as I) acetylacetonate, manganese (III) acetylacetonate and zinc (II) acetylacetonate; 2-methylimidazole, 2
-Imidazoles such as heptadecyl imidazole; and curing accelerators for epoxy resins. Among these accelerators, DBU salts, particularly DBU salt of phenol novolac resin, are preferable in terms of heat-curability and storage stability. These curing accelerators are also available as commercial products, for example "U-CAT SA-831",
Examples include "U-CAT SA-841" (all of which are manufactured by San-Apro Co., Ltd.).

The above-mentioned curing accelerator is used in an amount of 0.1 to 35 parts by weight, especially 0.1% by weight, based on 100 parts by weight of the urethane prepolymer.
It is preferably dispersed and contained in a proportion of 1 to 20 parts by weight. In this case, the obtained one-pack type polyurethane composition is one to which heat curability is imparted without impairing storage stability. .

The composition of the present invention may contain at least one solid component selected from the group consisting of the following compounds and compounds (hereinafter referred to as "specific solid compound") dispersed therein. preferable. Compound Solid polyfunctional compound having at least one functional group selected from hydrazino group, primary amide group, primary thioamide group and sulfamoyl group Compound Solid compound having amidino group Compound Solid having heterocycle and multiple active hydrogens Compound of

In addition to the hydrazino group, the primary amide group, the primary thioamide group and the sulfamoyl group, the above compound may have a group reactive with an isocyanate group, such as an amino group or a hydroxyl group. Further, the above compound may also have a group reactive with an isocyanate group.

Examples of solid polyfunctional compounds having a hydrazino group include succinic acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, dodecanedioic acid dihydrazide, hexadecanedioic acid dihydrazide, eicosane diacid dihydrazide, carboxylic acid dihydrazide, azelaic acid. Dihydrazide, oxalic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, hexahydroisophthalic acid dihydrazide, hexahydroterephthalic acid dihydrazide, methylaminodipropionic acid dihydrazide, phenylaminopropionic acid dihydrazide, methylaminodibutyric acid dihydrazide, ethylaminodivaleric acid, ethylaminodivaleric acid 2 in the molecule such as 3-bis (hydrazinocarboethyl) -5-isopropylhydantoin
Compounds having 3 hydrazino groups; compounds having 3 or more hydrazino groups in the molecule such as citric acid trihydrazide and cyclohexane tricarboxylic acid trihydrazide;
Examples thereof include 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 a primary amide group include succinic acid diamide, adipic acid diamide, maleic acid diamide, malonic acid diamide, sebacic acid diamide, dodecanedioic acid diamide, hexadecanedioic acid diamide, eicosane. Compounds having two or more primary amide groups in the molecule such as diacid diamide, 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 A compound having a primary amide group and an amino group in the molecule such as urea; a compound having a hydrazino group and a primary amide group in the molecule such as an oxamic hydrazide.

Examples of solid polyfunctional compounds having a primary thioamide group include succinic acid dithioamide, adipic acid dithioamide, maleic acid dithioamide, malonic acid dithioamide, sebacic acid dithioamide, dodecanedioic acid dithioamide, hexadecanedioic acid dithioamide, eicosane. Compounds having two or more primary thioamide groups in the molecule, such as diacid dithioamide and isophthalic acid dithioamide; Compounds having three or more primary thioamide groups in the molecule, such as citric acid trithioamide and cyclohexanetricarboxylic acid trithioamide Examples thereof include compounds having a primary thioamide group and an amino group in the molecule such as thiourea.

Examples of solid polyfunctional compounds having sulfamoyl groups include butanedisulfamide, hexanedisulfamide, benzenedisulfamide, and other compounds having two or more sulfamoyl groups in the molecule. .

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

The solid compound having a heterocycle and a plurality of active hydrogens preferably has an amino group as a group having an active hydrogen, and examples thereof include melamine, monomethylolmelamine, diallylmelamine, aminoimidazoylmelamine, 2, and the like. 4-diamino-6- [2-methylimidazolyl- (1)]-ethyltriazine, 2,4-diamino-6- [2-ethyl-4-methylimidazolyl-
(1)]-Ethyltriazine, 2,4-diamino-6-
Examples include [2-undecylimidazolyl- (1)]-ethyltriazine, benzoguanamine, trithiocyanuric acid and derivatives thereof.

Of the above-mentioned specific solid compounds, particularly preferable ones include adipic acid dihydrazide, eicosane diacid dihydrazide, melamine, aminoimidazoyl melamine and the like. The specific solid compound may be used alone or in combination of two or more kinds.

The specific solid compound has an equivalent ratio of the isocyanate group of the urethane prepolymer to the total amount of the groups reactive with the isocyanate group of the specific solid compound (isocyanate group / group reactive with isocyanate). , Usually 0.3 to 20, preferably 0.5 to 1
Used to be 5.

In the present invention, a solid polyhydroxy compound having no hydrazino group, primary amide group, primary thioamide group, sulfamoyl group, amidino group or heterocycle may be used together with the specific compound. When this solid polyhydroxy compound is used in combination, the equivalent ratio (NCO / OH) between the isocyanate group of the urethane prepolymer and the hydroxyl group of the hydroxy compound.
Is preferably 2.5 or more. This equivalence ratio is 2.
When it is less than 5, the proportion of hydroxyl groups is large, so that the storage stability of the obtained composition decreases.

Specific examples of the solid polyhydroxy compound include pentaerythritol, dipentaerythritol, tripentaerythritol, methyl alpha glucoside of corn starch, corn starch, sucrose, lactose, d-mannitol, anhydrous sorbitol, dulcitol, and Erythritol, isopropylidene-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 etc. can be mentioned.

The specific solid compound in the present invention preferably has a melting point higher than the curing temperature of the resulting composition, for example, a melting point of 60 ° C. or higher.
A compound having a melting point of about 70 to 200 ° C. is particularly preferable because it is performed at 0 to 150 ° C.

Further, since the specific solid compound is dispersed in the urethane prepolymer, it is preferable that the specific solid compound be finely pulverized. Particularly, when the particle size is about 50 μ or less, the cured resin is It has excellent toughness and elasticity.

It is preferable that the composition of the present invention further contains a high boiling point polar compound. The high-boiling polar compound has a melting point that is equal to or lower than the curing temperature for the composition, and has a boiling point that is equal to or higher than the curing temperature or the temperature at which the composition is applied. It is preferable. By selecting this high boiling point polar compound, the curing temperature and speed of the composition of the present invention can be controlled.

Examples of such a high boiling point polar compound include propylene carbonate, γ-butyrolactone, γ-valerolactone, δ-valerolactone and N-methyl-ε-.
Caprolactam, N-methylpyrrolidone, cyclohexanone, furfural, N-methylformamide, N, N
-Dimethylacetamide, diethylene glycol monoethyl ether acetate, diethylene glycol diacetate, acetonylacetone, methyl cyanoacetate, tetramethylurea, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and other compounds having a melting point of less than 20 ° C, ethylene carbonate, α-piperidone, Sulfolane, succinonitrile,
Examples thereof include compounds having a melting point of 20 ° C. or higher such as diaminomaleonitrile, p-nitroanisole, methyl carbamate, isopropyl carbamate, acetamide, N-methylacetamide, succinic anhydride and diphenyl carbonate. Among these, carbonic acid esters such as propylene carbonate and ethylene carbonate, γ-butyrolactone, γ-valerolactone, δ-
Lactones such as valerolactone are preferred.

The above-mentioned high boiling point polar compounds can be used alone or in combination of two or more kinds. Further, the high boiling point polar compound is preferably 0.1 to 30 parts by weight, and particularly preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the urethane prepolymer. And a composition having relatively good storage stability can be obtained.

A filler may be added to the composition of the present invention if necessary. Examples of fillers are talc,
Examples thereof include calcium carbonate, clay, synthetic silica, synthetic zeolite, bentonite, zinc white, titanium dioxide, dry carbon black, glass particles, and surface-treated ones thereof.

In addition to the above, the composition of the present invention may contain a colorant, a stabilizer, a plasticizer, a thickener, an anti-sagging agent, if necessary.
A non-polar solvent or the like can be added.

The composition of the present invention is cured to such an extent that the initial strength is developed in a short time by heat treatment at a relatively low temperature, but thereafter, it is cured by continuing heat treatment and / or applying moisture. The reaction can be completed.

[0044]

EXAMPLES Examples of the present invention will be described below.
The present invention is not limited to these. In the following, "parts" means parts by weight and "%" means% by weight.
Indicates.

[Example 1] Trifunctional polyether polyol having a number average molecular weight of 5000 "Excenol 823"
28 parts (manufactured by Asahi Glass Co., Ltd.) and Polymeric 4,4'-
Diphenylmethane diisocyanate "Sumijour 44
V-20 "(manufactured by Sumitomo Bayer Urethane Co., Ltd.) was reacted at 90 ° C for 2 hours to obtain a urethane prepolymer having a plurality of isocyanate groups. Here, the equivalent ratio of isocyanate groups to hydroxyl groups (NCO / OH) is 4.
The ratio of the hydroxyl groups derived from the trifunctional or higher polyfunctional polyol to the total hydroxyl groups in the polyol compound (hereinafter, referred to as "OH / total OH") is 100%. 11 parts of dioctyl phthalate (hereinafter referred to as "DOP"), 20 parts of calcium carbonate, 26 parts of synthetic zeolite "5A" and 6 parts of talc were added to the urethane prepolymer.
Parts were added to prepare a formulation containing a prepolymer having isocyanate groups. For 100 parts of this formulation,
Partial DBU salt of phenol novolac resin "U-CAT
SA831 "(manufactured by San-Apro Ltd.) was added to obtain a one-component polyurethane composition.

Example 2 In Example 1, 25 parts of the trifunctional polyether polyol “Excenol 823” was added.
Parts, 12 parts of polymeric 4,4′-diphenylmethane diisocyanate “Sumijour 44V-20” (equivalent ratio (NCO / OH) is 5.6, OH / total OH is 1).
It is 00%. A one-pack type polyurethane composition was obtained in the same manner except that the urethane prepolymer was obtained as the above).

Example 3 In Example 1, 29 parts of the trifunctional polyether polyol “Excenol 823” was used.
Parts, 8 parts of polymeric 4,4′-diphenylmethane diisocyanate “Sumijour 44V-20” (equivalent ratio (NCO / OH) is 3.5 and OH / total OH is 10).
It is 0%. A one-pack type polyurethane composition was obtained in the same manner except that the urethane prepolymer was obtained as the above).

[Example 4] 28 parts of trifunctional polyether polyol "EXCENOL 823" and 9 parts of polymeric 4,4'-diphenylmethane diisocyanate "SUMIDUR 44V-20" (equivalent ratio (NCO / OH) was 4. And OH / total OH is 100%) at 90 ° C. for 2 hours to obtain a prepolymer having a plurality of isocyanate groups. D to this urethane prepolymer
A formulation containing a prepolymer having isocyanate groups was prepared by adding 11 parts of OP, 30 parts of calcium carbonate, 13 parts of synthetic zeolite "5A" and 9 parts of talc. To 100 parts of this blend, 4 parts of a partial DBU salt of a phenol novolac resin "U-CAT SA831" was added to obtain a one-pack type polyurethane composition.

[Example 5] In Example 4, instead of 28 parts of the trifunctional polyether polyol "Exenol 823", 14 parts of the trifunctional polyether polyol "Exenol 823" and a bifunctional compound having a number average molecular weight of 4000 were used. Polyether polyol "EXCENOL 510"
(Asahi Glass Co., Ltd.) 14 parts (equivalent ratio (NCO / OH) is 4.0 and OH / total OH is 55%) were used in the same manner except that a urethane prepolymer was obtained. ,
A one-pack type polyurethane composition was obtained.

[Example 6] In Example 4, instead of 28 parts of the trifunctional polyether polyol "Excenol 823", 7 parts of the trifunctional polyether polyol "Excenol 823" and the difunctional polyether polyol "Excenol 510" were used. 21 parts (equivalent ratio (NCO / O
H) is 4.0 and OH / total OH is 30%. )
A one-pack type polyurethane composition was obtained in the same manner except that the urethane prepolymer was obtained by using.

Example 7 In Example 4, a partial DBU salt of phenol novolac resin “U-CATSA83” was used.
1 ”instead of 4 parts, mono-DBU salt of o-phthalic acid“ U
-CAT SA810 "(manufactured by San-Apro Ltd.) 0.7
A one-pack type polyurethane composition was obtained in the same manner except that parts were used.

[Example 8] In Example 4, a partial DBU salt of a phenol novolac resin "U-CATSA83" was used.
A one-pack type polyurethane composition was obtained in the same manner except that 1.6 parts of zinc (II) acetylacetonate (manufactured by Kishida Chemical Co., Ltd.) was used instead of 4 parts of 1 ”.

Comparative Example 1 In Example 4, the trifunctional polyether polyol “Excenol 823” was used in an amount of 23
Parts, 14 parts of polymeric 4,4′-diphenylmethane diisocyanate “Sumijour 44V-20” (equivalent ratio (NCO / OH) is 7.4, and OH / total OH is 1).
It is 00%. A one-pack type polyurethane composition was obtained in the same manner except that the urethane prepolymer was obtained as the above).

Comparative Example 2 In Example 4, 28 parts of the difunctional polyether polyol “Excenol 510” (equivalent ratio (NCO / OH)) was used instead of 28 parts of the trifunctional polyether polyol “Excenol 823”. 4.
0 and OH / total OH is 0%. A one-pack type polyurethane composition was obtained in the same manner except that the urethane prepolymer was obtained by using (1).

Comparative Example 3 In Comparative Example 1, instead of 23 parts of the trifunctional polyether polyol “Excenol 823”, 23 parts of the bifunctional polyether polyol “Excenol 510” (equivalent ratio (NCO / OH) was 7.
4 and OH / total OH is 0%. A one-pack type polyurethane composition was obtained in the same manner except that the urethane prepolymer was obtained by using (1).

Comparative Example 4 In Example 4, a partial DBU salt of phenol novolac resin “U-CATSA83” was used.
A one-pack type polyurethane composition was obtained in the same manner except that "1" was removed.

[Comparative Example 5] In Example 4, a partial DBU salt of a phenol novolac resin "U-CATSA83" was used.
1 "in the same manner except that 0.07 part of DBU salt of phenol" U-CAT SA1 "(manufactured by San-Apro Co., Ltd.), which is a liquid curing accelerator at room temperature, was used instead of 4 parts of" 1 ". A liquid polyurethane composition was obtained.

[Example 9] 28 parts of trifunctional polyether polyol "EXCENOL 823" and 9 parts of polymeric 4,4'-diphenylmethane diisocyanate "SUMIDUR 44V-20" (equivalent ratio (NCO / OH) was 4. And OH / total OH is 100%) at 90 ° C. for 2 hours to obtain a prepolymer having a plurality of isocyanate groups. To this urethane prepolymer, 11 parts of DOP, 20 parts of calcium carbonate, 26 parts of synthetic zeolite "5A" and 6 parts of talc were added to prepare a formulation containing a prepolymer having an isocyanate group. 4 parts of partial DBU salt "U-CAT SA831" of phenol novolac resin and 1.31 parts of adipic dihydrazide (equivalent ratio (NC
O / NH ₂ ) is 3.5. ) And were added to obtain a one-pack type polyurethane composition.

Example 10 In Example 9, 2 parts of the trifunctional polyether polyol “Excenol 823” was added.
5 parts, 12 parts of polymeric 4,4′-diphenylmethane diisocyanate “Sumijour 44V-20” (equivalent ratio (NCO / OH) is 5.6 and OH / total OH is 100%) as urethane pre. A one-pack type polyurethane composition was obtained in the same manner except that the polymer was obtained.

[Example 11] 28 parts of trifunctional polyether polyol "EXCENOL 823" and 9 parts of polymeric 4,4'-diphenylmethane diisocyanate "SUMIDUR 44V-20" (equivalent ratio (NCO / OH) was 4. And OH / total OH is 100%) at 90 ° C. for 2 hours to obtain a prepolymer having a plurality of isocyanate groups. To this urethane prepolymer, 11 parts of DOP, 20 parts of calcium carbonate, 26 parts of synthetic zeolite "5A" and 6 parts of talc were added to prepare a formulation containing a prepolymer having an isocyanate group. 4 parts of partial DBU salt "U-CAT SA831" of phenol novolac resin and 1.31 parts of adipic dihydrazide (equivalent ratio (NC
O / NH ₂ ) is 3.5. ) And were added to obtain a one-pack type polyurethane composition.

Example 12 The trifunctional polyether polyol “EXCENOL 823” 2 in Example 11 was used.
Instead of 8 parts, 14 parts of the trifunctional polyether polyol “Excenol 823” and 14 parts of the difunctional polyether polyol “Excenol 510” (equivalent ratio (NC
O / OH) is 4.0 and OH / total OH is 55%. A one-pack type polyurethane composition was obtained in the same manner except that the urethane prepolymer was obtained by using (1).

Example 13 In Example 11, the partial DBU salt of phenol novolac resin “U-CATSA” was used.
A one-pack type polyurethane composition was obtained in the same manner except that 0.7 part of o-phthalic acid mono-DBU salt "U-CAT SA810" was used instead of 831 "4 parts.

Example 14 In Example 11, a partial DBU salt of phenol novolac resin “U-CATSA” was used.
A one-pack type polyurethane composition was obtained in the same manner except that 1.6 parts of zinc (II) acetylacetonate was used instead of 4 parts of 831 ″.

Example 15 In Example 11, 1.75 parts of sebacic acid dihydrazide (equivalent ratio (NCO / NH ₂ ) is 3.5) is used instead of 1.31 part of adipic acid dihydrazide. A one-component polyurethane composition was obtained in the same manner except that it was used.

Example 16 In Example 11, 1.09 parts of adipic acid diamide (equivalent ratio (NCO / NH ₂ ) was 3.10 parts) instead of 1.31 parts of adipic acid dihydrazide.
It is 5. A one-pack type polyurethane composition was obtained in the same manner except that (1) was used.

Example 17 In Example 11, 0.64 parts of melamine (equivalent ratio (NCO / NH ₂ ) is 3.5) was used in place of 1.31 parts of adipic dihydrazide. A one-pack type polyurethane composition was obtained in the same manner except for the above.

[Comparative Example 6] In Example 9, the trifunctional polyether polyol "EXCENOL 823" was used in an amount of 23.
Parts, 14 parts of polymeric 4,4′-diphenylmethane diisocyanate “Sumijour 44V-20” (equivalent ratio (NCO / OH) is 7.4, and OH / total OH is 1).
It is 00%. A one-pack type polyurethane composition was obtained in the same manner except that the urethane prepolymer was obtained as the above).

Comparative Example 7 In Example 11, the trifunctional polyether polyol “EXCENOL 823” 28 was used.
In place of the parts, 28 parts of the bifunctional polyether polyol "EXCENOL 510" (equivalent ratio (NCO / OH) is 4.0 and OH / total OH is 0%) is used to prepare the urethane prepolymer. A one-pack type polyurethane composition was obtained in the same manner except that the above was obtained.

Comparative Example 8 In Comparative Example 6, 23 parts of the difunctional polyether polyol “Excenol 510” (equivalent ratio (NCO / OH)) was used instead of 23 parts of the trifunctional polyether polyol “Excenol 823”. 7.
4 and OH / total OH is 0%. A one-pack type polyurethane composition was obtained in the same manner except that the urethane prepolymer was obtained by using (1).

[Example 18] 28 parts of trifunctional polyether polyol "EXCENOL 823" and 9 parts of polymeric 4,4'-diphenylmethane diisocyanate "SUMIDUR 44V-20" (equivalent ratio (NCO / OH) was 4. And OH / total OH is 100%) at 90 ° C. for 2 hours to obtain a prepolymer having a plurality of isocyanate groups. To this urethane prepolymer, 11 parts of DOP, 30 parts of calcium carbonate, 13 parts of synthetic zeolite "5A" and 9 parts of talc were added to prepare a compound containing a prepolymer having an isocyanate group. To 100 parts of this blend, 4 parts of a partial DBU salt of "U-CAT SA831" of a phenol novolac resin and 1 part of propylene carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) were added to obtain a one-pack type polyurethane composition. It was

Example 19 A one-pack type polyurethane composition was obtained in the same manner as in Example 18 except that 4 parts of propylene carbonate was used.

Example 20 A one-pack type polyurethane was prepared in the same manner as in Example 18 except that 1 part of γ-valerolactone (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of 1 part of propylene carbonate. A composition was obtained.

Example 21 A one-pack type polyurethane composition was prepared in the same manner as in Example 18 except that 1 part of γ-butyrolactone (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of 1 part of propylene carbonate. I got a thing.

Example 22 28 parts of trifunctional polyether polyol "Excenol 823" and 9 parts of polymeric 4,4'-diphenylmethane diisocyanate "Sumijour 44V-20" (equivalent ratio (NCO / OH) was 4. And OH / total OH is 100%) at 90 ° C. for 2 hours to obtain a prepolymer having a plurality of isocyanate groups. To this urethane prepolymer, 11 parts of DOP, 30 parts of calcium carbonate, 13 parts of synthetic zeolite "5A" and 9 parts of talc were added to prepare a compound containing a prepolymer having an isocyanate group. 4 parts of partial DBU salt "U-CAT SA831" of phenol novolac resin and 1.31 parts of adipic dihydrazide (equivalent ratio (NC
O / NH ₂ ) is 3.5. ) And 1 part of propylene carbonate were added to obtain a one-pack type polyurethane composition.

Example 23 A one-pack type polyurethane composition was obtained in the same manner as in Example 22 except that 4 parts of propylene carbonate was used.

Example 24 A one-pack type polyurethane composition was obtained in the same manner as in Example 22 except that 1 part of γ-valerolactone was used instead of 1 part of propylene carbonate.

Example 25 A one-pack type polyurethane composition was obtained in the same manner as in Example 22 except that 1 part of γ-butyrolactone was used instead of 1 part of propylene carbonate.

Example 26 A one-pack type polyurethane composition was prepared in the same manner as in Example 22 except that 1 part of ethylene carbonate (manufactured by Kishida Chemical Co., Ltd.) was used instead of 1 part of propylene carbonate. Obtained.

[Test Example 1 (Measurement of Initial Strength Development Time)]
In order to obtain the initial strength development time at 90 ° C. for each of the compositions obtained in Examples 1 to 26 and Comparative Examples 1 to 8, the curing degree of the composition at 90 ° C. was measured with a measuring machine “JSR.
"Curastometer type III" (manufactured by Nigo Shoji Co., Ltd.) was measured according to the following measurement conditions, and the heat curing time until the composition cured and the measured torque value reached 0.5 kg · cm was measured. It was measured. In addition, regarding Example 4, 8
The above heat-curing times at 0 ° C. and 140 ° C. were similarly measured. Note that the state of the composition having a torque value of 0.5 kg · cm is, for example, when the composition is used as an adhesive, has a strength sufficient to withstand an external force applied to the adhesive part. It is a state that has been reached, that is, a state in which it can be considered that the clamp-off has reached the possible strength. Measurement conditions: Amplitude angle ¼ degree Vibration frequency 100 cycles / 1 minute The results are shown in Table 1.

[Test Example 2] The compositions obtained in Examples 1 to 26 and Comparative Examples 1 to 8 were put in a glass sample bottle with a lid having a capacity of 100 ml and stored in a constant temperature bath at 50 ° C.
The number of days to cure during storage was examined. The results are shown in Table 1.
Shown in.

[0081]

[Table 1]

[Test Example 3 (Measurement of Adhesive Shear Strength)] Length 1
A set of two SMC plates having a size of 00 mm, a width of 25 mm, and a thickness of 3 mm was used, and the bonding portion of 25 mm × 25 mm was used for Example 4,
Each of the compositions obtained in Example 11, Comparative Example 1 and Comparative Example 2 was applied, and Example 4, Comparative Example 1 and Comparative Example 2 were processed according to the following processing conditions, processing conditions and processing conditions. For 11, the following processing conditions,
Shear test pieces were prepared by curing according to treatment conditions and treatment conditions. Using this test piece, at a pulling rate of 5 mm / min, "Autograph AG-5000" was used.
The shear strength was measured by "B". Treatment conditions Treatment was performed at 90 ° C. for 7 minutes and 30 seconds. Treatment conditions Treatment was performed at 90 ° C. for 6 minutes. Treatment conditions The treatment was performed at 90 ° C. for 120 minutes. Treatment condition After treatment at 90 ° C for 7 minutes and 30 seconds,
It was treated at 23 ° C. and 60% relative humidity for 7 days. Treatment condition After treatment at 90 ° C for 6 minutes, further 23
Treatment was carried out for 7 days at 60 ° C. and 60% relative humidity. The results are shown in Table 2.

[0083]

[Table 2]

[0084]

As described above, the one-pack type polyurethane composition according to the present invention is cured to such an extent that the required initial strength is developed in a short time by the curing treatment at a relatively low temperature, and the storage stability is stable. It has excellent properties.

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Claims (2)

[Claims] 1. An equivalent ratio (NCO / OH) of a polyisocyanate compound and a polyol compound in which 20% by weight or more of all hydroxyl groups is derived from a polyfunctional polyol having a functionality of 3 or more.
The one-component polyurethane composition is characterized in that the urethane prepolymer obtained by reacting at a ratio of 6 or less contains a solid curing accelerator dispersed at room temperature. 2. The urethane prepolymer according to claim 1 contains a curing accelerator which is solid at room temperature and at least one solid component selected from the group consisting of the compounds shown below: A one-pack type polyurethane composition comprising: Compound At least one selected from a hydrazino group, a primary amide group, a primary thioamide group and a sulfamoyl group
Solid polyfunctional compounds having certain functional groups Compounds Solid compounds having amidino groups Compounds Solid compounds having heterocycles and multiple active hydrogens