JPH08199061A - One-component thixotropic polyurethane composition and coating material, sealant, and adhesive - Google Patents

Abstract

PURPOSE: To obtain a polyurethane compsn. excellent in storage stability, surface finish, and adhesion to an adherend by compounding a urethane prepolymer, a specific compd., and a surface-treated calcium carbonate. CONSTITUTION: This compsn. comprises an isocyanate-terminated urethane prepolymer, a compd. which is dissociated by water and generates a compd. having at least two amino groups (pref. a compd. represented by the fromula), and calcium carbonate surface-treated with a metal salt of a fatty acid and having an average particle size of 0.02-0.3μm. In the formula, A is a 1-22C branched or cyclic sec. diamine residue; (CR2 )n is an aliph. ring; R is H or a 1-6C linear, branched, or cyclic alkyl group; E is a residue of an electrophilic compd.; B is a 1-6C linear, branched, or cyclic alkyl group or E; and n is the number of carbon atoms forming the aliph. ring except the carbon atom at the position 1 and the carbon atom adjacent to the position 1, being an integer of 2-4.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyurethane composition having excellent thixotropy, and more particularly to a polyurethane composition excellent in storage stability, surface finish and adhesion to an adherend and the present composition. The present invention relates to coating materials, sealing materials and adhesives using

[0002]

2. Description of the Related Art Polyurethane resins are excellent in various properties such as rubber elasticity, abrasion resistance, durability, etc.
It is used in a wide range of applications such as sealing materials and floor materials.

These polyurethane resins are a one-pack type in which a polyurethane prepolymer having a terminal isocyanate group is cured after being applied, and a curing agent containing a main agent containing a polyurethane prepolymer having a terminal isocyanate group and a polyol chain. The agent can be roughly classified into a two-component type in which it is mixed and cured at the time of construction, but in recent years, one-component polyurethane that can be used by anyone has become particularly noticeable because of its simple construction.

As a method for imparting thixotropy to this one-pack type polyurethane resin, many methods have been conventionally proposed.

For example, a polyurethane composition comprising a combination of hydrophobic colloidal silica, an adduct of polyisocyanate and an amine (Japanese Patent Publication No. 64-24851), a polyurethane comprising a reaction product of hydrophobic silica, an aminosilane compound and a polyisocyanate. Composition (Japanese Patent Publication 64-64)
No. 14269), polyurethane having a composition comprising a combination of hydrophobic colloidal silica and a bisalkoxysilyl compound (Japanese Patent Publication No. 2-16736) Polyurethane comprising colloidal silica and a specific polysiloxane or polyoxyalkylene polymer. Composition (JP-A-61-2
57), surface-siliconized calcium carbonate, surface-hydrophobicized colloidal silica, and a polyurethane composition comprising a polyoxyethylene group-containing siloxane compound (JP-A-4-370146). But,
None of these compositions has sufficient storage stability, and there is a problem that slump is generated if the composition is stirred after storage or the composition thickens after storage, and workability is significantly reduced.

[0006] Further, thixotropic polyurethane using surface-treated calcium carbonate and metal soap (Japanese Patent Publication No. 60-5618).
However, the one-component urethane was not suitable for practical use because the viscosity increased after storage.

[0007]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above problems, and its object is to recover thixotropy even if agitated after storage without thickening during storage. Since it is quick, it does not cause slump, has excellent adhesion to adherends such as tiles and concrete, and has a good surface finish, coating materials such as paints and waterproof materials, adhesives, and sealing. The object is to provide a one-component thixotropic polyurethane composition suitable as a material.

[0008]

The present inventors have completed the present invention as a result of earnest research for solving the above-mentioned problems.

That is, the present invention is a urethane prepolymer (a) having an isocyanate group at a terminal, a compound (b) which is dissociated by water to generate a composition having at least two or more amine groups in the molecule, preferably Is a compound represented by Chemical formula 2,

[0010]

Embedded image

And a one-part thixotropic moisture-curable polyurethane composition comprising surface-treated calcium carbonate (c), the surface of which has been treated with a fatty acid metal salt and which has an average particle size of 0.02 to 0.3 micron, More preferably, the content of the surface-treated calcium carbonate (c) is 1.0 to 60.0% by weight, BE.
T specific surface area of 5 to 100 m ² / g, preferably containing a moisture curing accelerator (d), and a moisture curing accelerator (d)
Is one or more selected from the group of inorganic acids, organic acids and their anhydrides, esters, and acidic chlorides, and the moisture curing accelerator (d) is an acid dissociation index in an aqueous solution. pKa is in the range of 2.0 to 6.0, and the moisture curing accelerator (d) is one or more selected from phosphoric acid, phosphoric acid ester, acidic phosphoric acid ester, salicylic acid, acetic anhydride, or silicic acid alumina. That is, the ratio of the number of isocyanate groups of the urethane prepolymer (a) having an isocyanate group at the terminal to the number of active hydrogen generated by hydrolysis from the cross-linking agent (b) composed of an alicyclic enamine derivative is an equivalent ratio. -NCO / -H = 0.5 to 3.0 is provided, and a coating material, a sealing material, and an adhesive comprising the composition are provided. (Constitution)

The composition of the present invention comprises a urethane prepolymer (a) having an isocyanate group at the terminal, a compound (b) which dissociates with water to generate a composition having at least two or more amine groups in the molecule, and A composition comprising a surface-treated calcium carbonate (c), and more preferably a composition containing a moisture curing accelerator (c) in the composition.
The compound (b) is preferably represented by the following chemical formula 3.

[0013]

Embedded image

[A is a molecular or cyclic group having 1 to 22 carbon atoms
It is a residue of secondary diamine, and (CR ₂)_nIs an aliphatic ring
Represent. R is a hydrogen atom or a linear or branched chain having 1 to 6 carbon atoms
Or, it is a cyclic hydrocarbon. E is a residue of an electrophilic compound
Is. B is a linear branched or cyclic alkane having 1 to 6 carbon atoms.
A kill group or E, where n is the 1-position and carbon adjacent to the 1-position
Represents the number of carbon atoms forming an aliphatic ring excluding elementary, 2 to 4
Is an integer. ]

The compound (b) of the present invention refers to JP-A 6-1.
No. 84070, which is an alicyclic enamine compound. Preferably, it is a derivative represented by Chemical formula 3, specifically, 1,4-bis (1-cyclohexyl-2-oil-N, N'-diphenylurea) piperazine, 1,4-
Bis (1-cyclohexyl-2-oil-N, N'-dimethylurea) piperazine, 1,4-bis (1-cyclohexyl-2-oil-N, N'-diethylurea) piperazine, 1,4-bis ( 1-cyclohexyl-2-oil-N, N'-dipropylurea) piperazine, 1,
4-bis (1-cyclohexyl-2-oil-N, N '
-Dioctadecylurea) piperazine, 1,4-bis [1-cyclohexyl-2-oil-N, N'-di (2
-Ethylhexylurea)] piperazine, 1,4-bis [1-cyclohexyl-2-oil-N, N'-di (2
-Ethoxyethoxy) ethoxycarbonylamino-O-
Trilyurea] piperazine, and 1,4-bis [2,2
6-bis (2-methoxycarbonylethyl) -1-cyclohexenyl] piperazine, 1,4-bis [2,6-bis (2-methoxycarbonylpropyl) -1-cyclohexenyl] piperazine, 1,4-bis [ 2,6-bis (2-cyanoethyl) -1-cyclohexenyl] piperazine, N, N′-bis [2,6-bis (2-methoxycarbonylethyl) -1-cyclohexenyl] -N, N ′
Dimethylethylenediamine, 1,3-bis {1- [2,
6-bis (2-methoxycarbonylethyl) -1-cyclohexenyl] piperidin-4-yl} propane, 1,
4-bis [2- (2-methoxycarbonylethyl) -6
-Methyl-1-cyclohexenyl] piperazine (2,6
Position isomer), 1,4-bis (2,6 diacetyl-
1-cyclohexenyl) piperazine and the like.

The polyurethane prepolymer (a) having an isocyanate group at the terminal used in the present invention is a compound having two or more isocyanate groups, and an organic polyisocyanate and an organic polyhydroxyl compound are usually used under an excess of isocyanate. A prepolymer prepared by the method, and an organic polyisocyanate itself.

As the organic polyisocyanate, 2,4
-Tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane diisocyanate, partially carbodiimidated diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, tolidine diisocyanate, naphthalene diisocyanate, phenylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene Examples thereof include aromatic diisocyanates such as diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and cyclohexane diisocyanate, aliphatic diisocyanates, alicyclic diisocyanates, and mixtures of two or more thereof.

The organic polyhydroxyl compounds used in the present invention are polyether polyols, polyester polyols, other polyols and mixed polyols thereof. For example, a polyol produced by using a complex metal cyanide compound complex as a catalyst is also included.

As the polyether polyol, one or more polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin, trimethylolpropane, glucose, sorbitol and sucrose are added to propylene oxide and ethylene. Examples thereof include polyols and polyoxytetramethylene polyols obtained by adding one kind or two or more kinds of oxides, butylene oxides, styrene oxides and the like.

As the polyester polyol, for example, one or two of ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, cyclohexanedimethanol, glycerin, trimethylolpropane or other low molecular weight polyols is used.
And one or more of glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, terephthalic acid, isophthalic acid, dimer acid, hydrogenated dimer acid or other low molecular weight dicarboxylic acid or oligomer acid. Examples thereof include condensation polymers and ring-opening polymers such as propiolactone, caprolactone and valerolactone.

Other polyols include, for example, polycarbonate polyols, polybutadiene polyols,
Examples thereof include hydrogenated polybutadiene polyol and acrylic polyol. In addition, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, pentanediol,
Low molecular weight polyols such as hexanediol, cyclohexanedimethanolglycerin, trimethylolpropane, glucose, sorbitol and sucrose are also included.

The amount of the urethane prepolymer (a) having an isocyanate group at the terminal is produced by hydrolysis from the number of isocyanate groups of the urethane prepolymer (a) and the crosslinking agent (b) composed of an alicyclic enamine derivative. The ratio with the number of active hydrogen is equivalent to -NCO / -H = 0.5-
It is preferably in the range of 3.0, particularly -NCO /-
It is preferable to use H = 1.0 to 2.0. -NC
This is because if O / -H is larger than 3.0, foaming of the coating film is accompanied during curing, and if -NCO / -H is smaller than 0.5, the cured physical properties are remarkably deteriorated.

The surface-treated calcium carbonate (c) used in the present invention can be produced by a known method. For example, limestone is fired in a firing furnace and decomposed into carbon dioxide and quicklime, then quicklime is hydrated and refined by adding water to form lime milk, which is then reacted by blowing carbon dioxide. Alternatively, calcium carbonate can be produced by injecting lime milk in a carbon dioxide gas stream and contacting them in a countercurrent or a cocurrent to react with each other. The calcium carbonate used in the present invention is calcium carbonate surface-treated with a fatty acid metal salt for the purpose of preventing secondary aggregation. The fatty acid metal salt is preferably a salt of sodium, potassium, calcium or aluminum having a molecular weight of fatty acid of 10 to 25 carbon atoms. Examples of commercially available products thereof include white luster flower CC, white luster flower CCR, and white luster flower R0.
6, VIGOT-10, VIGOT-15, STAVI
GOT-15A, EDS-D10, EDS-D15, E
DR-U10 (all manufactured by Shiraishi Kogyo), Neolite SP-T
(Nitto powder) etc. can be used.

The surface-treated calcium carbonate (c) has an average particle size of 0.02 to 0.3 micron, preferably a BET specific surface area of 5 to 100 m ² / g, and more preferably an average particle size of 0.03. ~ 0.15 micron with BET specific surface area of 1
It is from 0 to 60 m ² / g. When the average particle size is smaller than 0.02 micron and the BET specific surface area is larger than 100 m ² / g, the secondary aggregation of calcium carbonate is severe and it is difficult to uniformly disperse it in a usual closed-type production machine. If the BET specific surface area is larger than 0.3 microns and the BET specific surface area is smaller than 5 m ² / g, desired thixotropy cannot be exhibited. The content of surface-treated calcium carbonate in the composition should preferably be 1 to 60% by weight. When appropriate fluidity and thixotropy are required for the material used in the flat scene, the content of the surface-treated calcium carbonate is preferably 1 to 30% by weight, and the material used for the inclined surface is 30 to 60% by weight. desirable. When used in flat fields such as flat roofs and balconies, if the content of surface-treated calcium carbonate is less than 1% by weight, the desired thixotropy cannot be expressed, and problems such as accumulation of material in the gutters occur, and 30% by weight If it is more than that, viscosity and thixotropy are high, and self-leveling of the material cannot be expected. On the other hand, when it is used for an inclined surface, the self-leveling property of the material is unnecessary, and high thixotropic property that does not sag on the inclined surface is required. Therefore, the content of the surface-treated calcium carbonate should be 30% by weight or more. Is preferred. However, when it is more than 60% by weight, the viscosity becomes high and a problem occurs in workability, which is not preferable.

The surface-treated calcium carbonate (c) used in the present invention has a urethane prepolymer (a) having an isocyanate group at the terminal, and at least two or more amine groups in the molecule dissociated by water. By mixing with the compound (b) represented by the chemical formula 3 for generating the composition, it is possible to obtain stable thixotropy with little increase in viscosity after storage.

The moisture curing accelerator (d) preferably added and used in the present invention is preferably one or more selected from the group consisting of inorganic acids, organic acids and their anhydrides, esters and acid salts. Is used, for example, hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, silicic acid, aluminic acid, perchloric acid, formic acid,
Examples thereof include acetic acid, chloroacetic acid, propionic acid, caproic acid, oxalic acid, succinic acid, adipic acid, maleic acid, phthalic acid, benzoic acid, salicylic acid, and the like, or their anhydrides, esters, acid salts and the like.

Among these, as the moisture curing accelerator (d), the acid dissociation index pKa in the aqueous solution is preferably 2.0 to 6.0, and particularly preferably 2.0 to 3.0.
Here, the acid dissociation index pKa is an index indicating the acid strength, and the lower the value, the higher the acid strength. The value of the acid dissociation index pKa in the aqueous solution can be found in "The Chemical Society of Japan, edited by the Chemical Handbook, Basic Edition, Revised 4th Edition, II-316-3.
21 ”etc. can be referred to. Further, among these acids, phosphoric acid, phosphoric acid ester, acidic phosphoric acid ester, salicylic acid, chloroacetic acid, acetic anhydride and silicic acid alumina are preferable, and when phosphoric acid ester is used, the number of phosphoric acid groups and The ratio with the number of active hydrogen produced by hydrolyzing the compound (b) represented by is in the range of -P (O) OH / -H = 0.1 to 1.0 in terms of equivalent ratio. Particularly, -P (O) OH / -H = 0.2 to
0.6 is preferred. When -P (O) OH / -H <0.1, the curing rate is very slow, and -P (O) OH / -H>
When it is 1.0, the curing speed is slow and the cured physical properties tend to be remarkably poor.

The moisture-curable polyurethane composition of the present invention may be further added with a plasticizer, a stabilizer, an inorganic filler, a tackifier, an adhesion promoter, a catalyst or the like in addition to a coating material, a sealing material or an adhesive. It can be used as an agent.

Examples of the plasticizer include ester-based plasticizers such as dibutyl phthalate, dioctyl phthalate, dilauryl phthalate, butylbenzyl phthalate, diisodecyl phthalate, dibutyl adipate, dioctyl adipate, diisodecyl adipate, dioctyl azelate, dioctyl sebacate, and trioctyl sebacate. Examples thereof include phosphoric acid ester plasticizers such as octyl phosphate and triphenyl phosphate.

Examples of stabilizers include antioxidants and ultraviolet absorbers. Examples of the inorganic filler include calcium carbonate, calcium oxide, clay, talc,
Examples thereof include powders of inorganic compounds such as titanium oxide, calcium hydroxide, aluminum sulfate, kaolin, zeolite, diatomaceous earth and glass balloons. The amount added is preferably 50% by weight or less, more preferably 45% by weight or less in the composition.

[0031]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to the examples. Parts in the examples indicate parts by weight.

Synthesis Example 1 <Example of Synthesis of Urethane Prepolymer> Polyoxypropylene diol (molecular weight 2000) 40
0 parts and polyoxypropylene triol (molecular weight 30
00) 600 parts and 2,4-tolylene diisocyanate 1
A urethane prepolymer was obtained by reacting 46.2 parts with each other at 80 ° C. for 18 hours. The terminal NCO group was 2.50% and the viscosity was 87,000 cps / 25 ° C.

Synthesis Example 2 <Synthesis of alicyclic enamine derivative> 86.1 parts (1.0 mol) of piperazine was mixed with 196.2 parts (2.0 mol) of cyclohexanone and 200 parts of toluene, and the mixture was separated in a water drop separator under nitrogen. Heat with.

After 5 hours, half of the water had separated, and after 20 hours, the calculated amount of water had separated. When the solvent toluene was distilled off and the residue was recrystallized with 200 parts of dehydrated acetone, plate-like crystals were deposited. This was filtered to obtain a colorless and transparent solid of Chemical formula 4.

[0035]

[Chemical 4]

This product is 1,4-bis (1-cyclohexyl) piperazine and is abbreviated as BCP-1. Next, 123 parts (0.5 mol) of BCP-1 and 200 parts of dehydrated methanol were charged into a reaction vessel having a content of 1 liter. 200 parts (2 mol) of ethyl acrylate was transferred to the dropping funnel, and the dropping funnel was attached to the reactor.

While stirring at 55 ° C. in a nitrogen stream, dropping was started while paying attention to heat generation, and the dropping was carried out for 2 hours. After the dropping, stirring was continued under reflux for 10 hours. The mixture was cooled to room temperature and desolvated under reduced pressure. A yellow-red-brown solid was obtained, which was recrystallized from dehydrated acetone. Filtration and vacuum drying gave colorless needle crystals. Measurement of the infrared absorption spectrum, was observed a characteristic absorption of ester 1740 cm ^-1, characteristic absorption of enamine was observed in 1640 cm ^-1. The formation of the target compound was also confirmed from the NMR spectrum. The abbreviation of this compound is BCP4EA.

Synthesis Example 3 <Synthesis of alicyclic enamine derivative> 123 parts (0.5 mol) of BCP-1 obtained above and 204 parts (2 mol) of acetic anhydride were reacted in the same manner as above.
The product becomes a liquid reddish brown, the measurement of the infrared spectrum, characteristic absorption of a carbonyl group was observed at 1710 cm ^-1, characteristic absorption of enamine was observed in 1640 cm ^-1. The abbreviation for this compound is BCP4AC.

<Preparation of One-Component Moisture-Cure Polyurethane Composition> Example 1 In a planetary mixer, white luster CC (average particle size 0.04 micron, BET specific surface area 26 m ² / g, Shiraishi Industry) was used as surface-treated calcium carbonate. 1373 parts, Irganox 1010 (weatherproof stabilizer), and stirred at room temperature for 15 minutes, followed by kneading at 100 ° C.,
The dehydration operation was carried out in vacuum for 2 hours. Next, after cooling to room temperature, 1800 parts of the polyurethane prepolymer and 268 parts of the alicyclic enamine derivative BCP4EA were added, and the mixture was kneaded at room temperature for 15 minutes. Furthermore, as a moisture curing accelerator, acidic phosphoric acid ester (trade name AP-3 Daihachi Chemical Industry) 3
Charge 2 parts and 315 parts of toluene, and make 1 at room temperature in vacuum.
The mixture was stirred for 0 minutes to obtain a one-pack type polyurethane composition.

Example 2 In Example 1, as the surface-treated calcium carbonate, VIGOT15 (average particle size 0.15 micron, BET specific surface area 11.5 m ² / g, manufactured by Shiraishi Kogyo Co., Ltd.) 2 was used in place of the white luster CC. 2
A one-pack type polyurethane composition was obtained by the same method except that 500 parts and 12 parts of salicylic acid were used instead of AP-3 as a moisture curing accelerator.

Example 3 In Example 1, BCP4 was used as the alicyclic enamine derivative.
200 parts of BCP-4AC was used instead of EA, and white luster CCR was used in place of white luster CC (average particle diameter 0.08 micron, BET specific surface area 18 m ² / g, manufactured by Shiraishi Kogyo) 200
A one-pack type polyurethane composition was obtained by the same method except that 0 part and 10 parts of chloroacid acid were used instead of AP-3 as a moisture curing accelerator.

Example 4 In Example 1, as the surface-treated calcium carbonate, 180 parts of VIGOT 10 (average particle size: 0.10 micron manufactured by Shiraishi Kogyo Co., Ltd.) instead of white luster flower CC, surface-untreated calcium carbonate NS-200 (BET specific surface area 1 0.2 m ² / g, average particle size 1.85 μm, manufactured by Nitto Koka Co., Ltd.) 1193 parts were obtained by the same method except that 1-component polyurethane composition suitable for a flat field coating material was obtained.

Example 5 In Example 1, 700 parts of VIGOT15 (average particle size 0.15 micron manufactured by Shiraishi Kogyo Co., Ltd.) was used as the surface-treated calcium carbonate in place of white luster CC, and surface-untreated calcium carbonate NS-200 (average particle size 1 A one-pack type polyurethane composition suitable for a flat-field coating material was obtained by the same method except that 673 parts of 0.85 micron manufactured by Nitto Koka Co., Ltd. was used.

Comparative Example 1 A one-pack type polyurethane composition was obtained in the same manner as in Example 1 except that the alicyclic enamine derivative BCP4EA was not used.

Comparative Example 2 Carmos (lignin-treated calcium carbonate, average particle size 0.04 micron, BET specific surface area 26 m ² instead of white luster CC as the surface-treated calcium carbonate in Example 1)
/ G, manufactured by Shiraishi Kogyo Co., Ltd.) was used to obtain a one-pack type polyurethane composition by the same method as above.

Comparative Example 3 Hydrophobic fumed silica Aerosil R-97 in place of the surface-treated calcium carbonate white luster flower CC in Example 1.
2 (made by Nippon Aerosil) 100 parts by weight, untreated calcium carbonate NS-200 (average particle size 1.85 microns,
A one-pack type polyurethane composition was obtained by the same method except that 1273 parts by weight of Nitto Koka Co., Ltd.) and 10 parts by weight of silicone oil SH-3771 (manufactured by Toray Dow Corning) were used as a thixotropic agent.

Comparative Example 4 In Example 1, the alicyclic enamine derivative BCP4EA was not used, and the surface-treated calcium carbonate white luster CC was replaced with hydrophobic fumed silica Aerosil R-972.
(Nippon Aerosil Co., Ltd.) 100 parts by weight, untreated calcium carbonate NS-200 (average particle size 1.85 microns, manufactured by Nitto Koka Co., Ltd.) 1273 parts by weight and silicone oil SH-3771 (Toray Dow Corning Co., Ltd.) as a thixotropic agent. A one-pack type polyurethane composition was obtained by the same method except that 10 parts by weight of (produced) was used.

Comparative Example 5 NCC3010 (average particle size 0.74 micron, BET specific surface area 3 m ² / g, Nitto Koki Co., Ltd.) was used as the surface-treated calcium carbonate in Example 1 instead of white luster CC.
A one-pack type polyurethane composition was obtained by the same method except that 100 parts by weight was used.

[Test Method] Measurement of initial viscosity, initial thixo index, initial slump property, initial coating fluidity Immediately after production, the sample was stored in a closed container and left at 25 ° C. for 5 hours, and then 450 g of a sample was put in a 500 CC container. And the rotation speed is 100 with a hand mixer equipped with a stirring blade.
Stir for 60 seconds at 0 rpm / min. Viscosity immediately measured with a BH type rotational viscometer at 2 rpm and 20 rpm.
The viscosity of is measured. (The unit is expressed in poise.)

The thixo index is 20 and the measured viscosity at 2 rpm.
Expressed as the ratio of measured viscosity at rpm. Regarding the slump property, test pieces were prepared according to the slump (vertical) test method specified in 4.3.2 of JIS-5758 (1992 version), and the slump length was measured by leaving it in a dryer at 50 ° C. To do. (Unit is expressed in mm.)

Regarding the initial coating fluidity, the gradient 1 /
25 on a 10 * 10 cm slate plate tilted at 50
After uniformly coating the sample with a trowel at a coating amount of 2 kg / cm ^{2 in} an atmosphere of ℃, the sample is allowed to stand for 24 hours, and then the sample is cured.
When the flow of the coating film is not recognized, it is rated as O. When the flow of the coating film is recognized, it is rated as X.

<Measurement of viscosity after storage, thixo index after storage, slump property after storage> 5
After being left in a 0 ° C. dryer for 7 days, the temperature is adjusted to 25 ° C., and the measurement is performed in the same manner as in the measurement of initial viscosity, initial thixo index, initial slump property, and initial coating film fluidity.

<Foamability> The surface of the sample is 20 * 10c.
After being evenly applied to a slate plate of m with a thickness of 2 mm,
Immediately, it is left to stand in a constant temperature and humidity chamber adjusted to a temperature of 60 ° C. and a relative humidity of 50% RH until it is completely cured. Then, the presence or absence of foaming on the surface is observed.

<Adhesiveness> A concrete surface having a surface of 30 * 30 cm
Sanding the surface of the REIT specimen with sandpaper
After that, the test piece is set vertically. Dry the sample at 50 ℃
After curing for 7 days, adjust the temperature to 25 ° C and stir with a spatula for 1 minute.
After stirring, apply 600 g with a comb-like iron on the vertical surface of the test piece.
/ M²It is applied so that the surface is 4.5 cm * 4.
5cm mosaic tiles (Sugiura ceramics) are pasted together
It After leaving it at room temperature for 7 days, use the instant adhesive to display the tiles.
Attach a built-in type tension holder to the surface and pull with a built-in type tensile tester.
Conduct a tension test to check the adhesive strength between the sample and the mosaic tile.
taking measurement. Unit is kg / cm ²Expressed by

Of the samples prepared this time, the initial B
Initial viscosity (20 rpm) with H type rotational viscometer is 350 ps
The following items were omitted from the slump property and adhesiveness tests on the assumption that they are used as coating materials for flat fields and applications.

[0056]

[Table 1]

[0057]

[Table 2] ^* Among the results of the adhesiveness test that are not measurable, the thixotropy of the sample was reduced, so the tiles were misaligned or peeled off after the tiles were bonded, and the adhesive strength could not be measured.

[0058]

EFFECT OF THE INVENTION The one-pack thixotropic urethane resin composition of the present invention does not cause slump and does not cause slump because the thixotropy is recovered rapidly even after stirring without storage thickening. , Has excellent adhesiveness to an adherend such as concrete, and has a good surface finish, and exhibits excellent performance as a coating material such as a coating material and a waterproof material, an adhesive agent, and a sealing material.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display area C08G 18/65 NEV

Claims (9)

[Claims] 1. A urethane prepolymer (a) having an isocyanate group at the terminal, a compound (b) which dissociates with water to generate a compound having at least two amine groups in the molecule, and a fatty acid metal salt on the surface. A one-component thixotropic polyurethane composition, characterized in that it contains surface-treated calcium carbonate (c) which has been treated with 1. and has an average particle size of 0.02 to 0.3 micron. 2. The one-component thixotropic polyurethane composition according to claim 1, wherein the compound (b) is a compound represented by Chemical formula 1. Embedded image [A in the formula is a residue of a branched or cyclic secondary diamine having 1 to 22 carbon atoms, and (CR ₂ ) _n represents an aliphatic ring. R is a hydrogen atom or a linear, branched or cyclic hydrocarbon having 1 to 6 carbon atoms. E is the residue of the electrophilic compound. B is a linear branched or cyclic alkyl group having 1 to 6 carbon atoms, or E, and n represents the number of carbon atoms forming an aliphatic ring excluding the carbon atoms at the 1-position and adjacent to the 1-position, and 2 Is an integer of ~ 4. ] 3. The one-pack thixotropic polyurethane composition according to claim 1, wherein the content of the surface-treated calcium carbonate (c) is 1.0 to 6.0% by weight. 4. BET of surface-treated calcium carbonate (c)
The one-component thixotropic polyurethane composition according to claim 1, which has a specific surface area of 5 to 100 m ² / g. 5. A moisture curing accelerator (d) is further included, and the moisture curing accelerator (d) is selected from the group consisting of inorganic acids, organic acids and their anhydrides, esterified products and acidic chlorides.
The one-component thixotropic polyurethane composition according to claim 1, which is a composition containing one or more kinds. 6. The one-component thixotropic polyurethane composition according to claim 3, wherein the moisture curing accelerator (d) has an acid dissociation index pKa in an aqueous solution of 2.0 to 6.0. 7. The moisture curing accelerator (d) is one or more selected from phosphoric acid, phosphoric acid ester, acidic phosphoric acid ester, salicylic acid, acetic anhydride, or alumina silicate. The one-component thixotropic polyurethane composition described. 8. The ratio of the number of isocyanate groups of the urethane prepolymer (a) having an isocyanate group at the terminal to the number of active hydrogen produced by hydrolysis from the crosslinking agent (b) composed of an alicyclic enamine derivative is Equivalent ratio is -NCO /
The one-component thixotropic polyurethane composition according to claim 1, wherein -H = 0.5 to 3.0. 9. A coating material, a sealing material, and an adhesive, each of which comprises the composition according to any one of claims 1 to 7.