JP2000226424A - Urethane prepolymer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a urethane prepolymer composition improved in adhesion to metallic materials, bonding strength, durability, water resistance, heat resistance, and storage stability by including a specified isocyanato-terminated urethane prepolymer with an isocyanate-type silane coupling agent having an isocyanato group and a hydrolyzable silane group. SOLUTION: A compound having at least two active hydrogen groups in the molecule and having a number-average molecular weight of 500-10,000 is reacted with a polyisocyanate compound having at least two isocyanato groups in isocyanate-excess conditions to obtain an isocyanato-terminated urethane prepolymer. This prepolymer is compounded with 0.005-30 pts.wt., desirably, 0.01-10 pts.wt. isocyanate-type silane coupling agent having both functional groups of an isocyanate group and a hydrolyzable group in the molecule and represented by the formula. In the formula, n is an integer; and X is a hydrolyzable group such as -OCH3, -OC2H6 or -OC2H4OCH3.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a urethane prepolymer composition, and more particularly to an inorganic material which is usually difficult to secure sufficient adhesive performance and adhesion as a polyurethane-based adhesive, a sealing agent, a paint, and the like. The present invention relates to a urethane prepolymer composition capable of exhibiting excellent adhesion performance and adhesion to materials such as metal and metal materials.

[0002]

2. Description of the Related Art Polyurethane-based adhesives, sealants and paints are prepared by mixing a polyisocyanate compound alone or with a substance containing active hydrogen which is liable to react with isocyanate. Alternatively, it is used as a two-liquid type (two-liquid type). That is, it is used in various forms such as a polyisocyanate monomer, a prepolymer, and an isocyanate-modified polymer. The prepolymer includes a polyol having two or more active hydrogens such as a hydroxyl group (OH) and an amine group in a molecule and an isocyanate group (N
CO) with two or more polyisocyanate compounds having an isocyanate group in excess, that is, NC
It is obtained by mixing and reacting both so that the O / OH equivalent ratio is greater than 1, and can be used together with a suitable curing agent as a two-pack type in applications such as adhesives, sealing agents, and paints. However, there is also a one-part type that cures with moisture in the air or surface moisture of a material to be adhesively applied. The two-component type requires work such as weighing and mixing the main agent and the curing agent, and the workability is inferior to the one-component type. Therefore, one-component type adhesives, sealing agents, and paints are often used. It is becoming. One-component urethane prepolymer-based adhesives are used for various purposes such as shoe production and automobile parts attachment, and in the field of construction, they are used for production of building members in factories and construction of construction environments. In general, polyurethane-based adhesives can be used to adjust good adhesion to porous inorganic materials such as wood, concrete and calcium silicate plates, plastics, iron, etc., but inorganic materials such as glass and ceramics can be used. It is inadequate for bonding to materials or metal materials that form an inert oxide film such as aluminum or stainless steel. Adds silane coupling agents to polyurethane adhesives, sealants and paints to improve adhesion to inorganic materials such as glass and porcelain, and metal materials such as aluminum and stainless steel that can easily form inert oxide films. It is possible to do, but to one-part urethane prepolymer adhesive,
If the silane-based coupling agent is previously blended, the storage stability may be impaired or the adhesive performance may be insufficiently improved depending on the type and amount of the silane-based coupling agent. There are also problems with sealing agents and paints, and in the case of one-component urethane prepolymers, inorganic materials such as glass and porcelain, and inactive oxide films such as aluminum and stainless steel are easily formed, as with adhesives. There was a similar problem with respect to adhesion to metal materials.

[0003]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned disadvantages of the prior art, and does not impair the conventional performance of polyurethane-based adhesives, sealing agents, and paints.
Excellent adhesion and bonding strength to inorganic materials including glass and earthenware, and metal materials including metals that easily form inert oxide films such as aluminum and stainless steel, as well as durability and water resistance It is an object of the present invention to provide a one-pack urethane prepolymer composition having improved heat resistance and excellent storage stability. Other objects of the present invention will become clear from the description throughout the present specification.

[0004]

SUMMARY OF THE INVENTION The present invention relates to a compound having two or more active hydrogen groups in a molecule and an isocyanate group having two or more active hydrogen groups.
The urethane prepolymer having a terminal isocyanate group obtained by mixing and reacting a polyisocyanate compound having at least one polyisocyanate compound with an isocyanate group in excess to give an isocyanate group and a hydrolyzable silane group in one molecule represented by the following formula 1. Or when an isocyanate-based silane coupling agent having both functional groups is blended, or when the terminal isocyanate group urethane prepolymer is obtained, the isocyanate group represented by the formula 1 in one molecule is added to the reaction system. And a isocyanate-based silane coupling agent having both functional groups of a hydrolyzable silane group and a one-component moisture-curable urethane prepolymer composition.

[0005]

[Formula 1] _{O = C = N- (CH 2} ) n-SiX 3 where, n represents an integer, X is _-OCH 3, _-OC 2 _{H 5,} or a hydrolyzable group of _-OC 2 _H 4 OCH ₃ .

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The compound having two or more active hydrogen groups in the molecule (hereinafter referred to as an active hydrogen group-containing compound) used in the present invention includes, for example, a monomer or prepolymer having a terminal hydroxyl group or an amine group. Can be
Specific examples thereof include polymer polyols such as polyester polyol, polyether polyol, polycarbonate polyol, acrylic polyol, and polyether polyamine, polymer polyamines, castor oil, and saccharides. As an active hydrogen group-containing compound, a chain extender such as a low molecular weight alcohol such as ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, and cyclohexane dimethanol or propylene for the purpose of adjusting the molecular weight or introducing a hydroxyl group. Diamines such as diamine and hexamethylene diamine, low molecular weight amino alcohols, and water may be used. Other active hydrogen group-containing compounds include monoalcohols and monoamines, and these and the aforementioned low-molecular-weight amino alcohols are also used as reaction terminators. One or more of these can be used. Among the above-mentioned polymer polyols, specific examples of the polyester polyol include ethylene glycol, diethylene glycol, dipropylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol. Butanediol, 1,4-butanediol, neopentyl glycol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2-methyl-1,5-pentane Diol,
3-methyl-1,5-pentanediol, 1,6-hexanediol, 2,2,4-trimethyl-1,3-propanediol, 2-ethyl-1,3-hexanediol, 2,2-diethyl-1,3 -Propanediol, 2
So-called low molecular weight glycols such as -n-butyl-2-ethyl-1,3-propanediol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, and mixtures thereof; succinic acid, adipic acid, Dehydration condensation with dicarboxylic acids such as sebacic acid, azelaic acid, phthalic acid, isophthalic acid, terephthalic acid, fumaric acid, maleic acid, oxalic acid, naphthylene dicarboxylic acid, their acid esters, acid anhydrides, and mixtures thereof Examples thereof include polyesters having hydroxyl groups at both ends obtained by the reaction, and polycaprolactone diol obtained by ring-opening polymerization of ε-caprolactone. Specific examples of the polyether polyol include, for example, ethylene oxide, propylene oxide, oxirane compounds such as butylene oxide, ethylene glycol, propylene glycol, trimethylolpropane, obtained by polymerizing with a low molecular weight polyol such as glycerin or water as an initiator. Polyether polyols and ethylene oxide,
Examples thereof include polyether polyols obtained by ring-opening polymerization of epoxides such as propylene oxide alone or mixtures, and polytetramethylene glycol obtained by ring-opening polymerization of tetrahydrofuran. Specific examples of the polycarbonate polyol include those obtained by a dephenol reaction between low-molecular glycols used in the synthesis of the polyester polyol and diphenyl carbonate. The number average molecular weight of such a high molecular polyol exhibits excellent adhesion performance and adhesiveness aimed at by the present invention, and also improves durability, water resistance, heat resistance, and storage stability. In order to obtain a one-component urethane prepolymer composition having excellent properties, it is preferably in the range of 500 to 10,000. Examples of the low molecular alcohol include low molecular glycols used for the synthesis of the polyester polyol described above. Specific examples of the low-molecular polyamine include aliphatic diamines such as ethylenediamine and hexamethylenediamine, alicyclic diamines such as isophoronediamine and cyclohexyldiamine, and aromatic diamines such as diaminodiphenylmethane and diaminodiphenylsulfone. . Specific examples of the low-molecular-weight amino alcohol include monoethanolamine and diethanolamine. Specific examples of the monoalcohol include methanol, ethanol, propanol, isopropanol and the like. Specific examples of the monoamine include -monoamines such as ethylamine and butylamine, and secondary monoamines such as diethylamine and dibutylamine.

The polyisocyanate compound used in the present invention includes hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate (I
PDI), phenylene diisocyanate, cyclohexyl diisocyanate, 4,4'-dicyclohexyl methane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated trimethyl xylylene diisocyanate, 2-
Methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate, 2,2,4-
Trimethylhexamethylene-1,6-diisocyanate, 2,4,4, trimethylhexamethylene-1,6-diisocyanate
MDl isomers such as diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI) and 2,4'-diphenylmethane diisocyanate; 4,4'-diphenylmethane diisocyanate; , 4,4-dibenzyl diisocyanate, 1,5-naphthalenediisocyanate, paraphenylene diisocyanate, 2,4- or 2,6-
Examples thereof include aromatic diisocyanates such as tolylene diisocyanate or a mixture thereof, tetramethyl xylylene diisocyanate, and 4,4-diphenyl ether diisocyanate, and aromatic aliphatic diisocyanates such as 1,3- or 1,4-xylylene diisocyanate or a mixture thereof. Also, triphenylmethane-4,4 ',
Dimer, trimer, buret derivative derived from the above polyisocyanate monomer such as 4 ″ -triisocyanate, and 2,4,6-oxaziridine trione ring obtained from carbon dioxide and the above polyisocyanate monomer Polyisocyanate, adduct of polyisocyanate with low molecular weight polyol such as ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, cyclohexane dimethanol, modified isocyanate compound with carbodiimide, or polyester polyol And NCO-terminated compounds such as adducts of polyether polyols and high molecular polyols with polyisocyanates, and mixtures of two or more of these.

The isocyanate-based silane coupling agent having both an isocyanate group and a hydrolyzable silane group in one molecule used in the present invention has a limited molecular structure and the number and type of functional groups. However, an isocyanate-based silane coupling agent represented by the following formula 1 is preferred.

[0010]

[Formula 1] _{O = C = N- (CH 2} ) n-SiX 3 where, n represents an integer, X is _-OCH 3, _-OC 2 _{H 5,} or a hydrolyzable group of _-OC 2 _H 4 OCH ₃ . n is preferably 1-3. Specific examples of the isocyanate-based silane coupling agent include γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, and the like.

[0011] The one-pack moisture-curable urethane prepolymer composition of the present invention is characterized in that an active hydrogen group-containing compound and a polyisocyanate compound are prepared so that an isocyanate group becomes excessive, that is, the NCO / OH equivalent ratio is more than 1. So that
It can be obtained by blending and reacting an isocyanate-based silane-based coupling agent represented by the above formula 1 with a terminal isocyanate-based urethane prepolymer obtained by performing a mixing reaction. When obtaining, it may be obtained by blending an isocyanate silane coupling agent having both functional groups of an isocyanate group and a hydrolyzable silane group in one molecule represented by the above formula 1 into the reaction system. As in the latter, a composition excellent in adhesive performance and the like can be obtained even when added and blended into the reaction system at the same time. desirable.

The amount of the isocyanate-based silane coupling agent is preferably 0.005 to 30 parts by weight based on 100 parts by weight of the urethane prepolymer. When the compounding amount of the isocyanate-based silane coupling agent is 0.005
When the amount is less than the parts by weight, excellent adhesive performance and adhesion as intended by the present invention are exhibited, and at the same time, durability, water resistance and heat resistance are improved, and storage stability is excellent. Insufficient to obtain a liquid urethane prepolymer composition;
If the amount is more than 0 parts by weight, the effect is saturated and it is not economically advantageous. More preferably, it is in the range of 0.01 to 10 parts by weight.

When the isocyanate-based silane coupling agent is added to the reaction system, it is preferable that the isocyanate-based silane coupling agent is contained in the composition in an amount of 0.1 to 30% by weight. . The content of the isocyanate-based silane coupling agent,
When the amount is less than 0.1% by weight, excellent adhesion performance and adhesion to materials such as an inorganic material and a metal material, which are the object of the present invention, are exhibited. Is insufficient to obtain a one-pack urethane prepolymer composition having excellent storage stability and 30% by weight.
The effect is saturated even if it is blended beyond the limit, and it is not economically advantageous.

The composition of the present invention may contain, if necessary, a filler, a thixotropic agent, a plasticizer, a solvent, an adhesion-imparting agent other than the above-mentioned isocyanate-based silane coupling agent, a catalyst, and other polyurethanes. The additives used can also be arbitrarily added. As specific examples of the filler, for example,
Clay, calcined clay, talc, silica, alumina, calcium carbonate, magnesium oxide, calcium silicate, calcium aluminate, sodium aluminate, magnesium silicate, calcium hydroxide, barium sulfate, carbon black, silica sand, mica, titanium oxide And inorganic powders such as silica balloons, glass balloons and zeolites, and organic powders such as vinyl chloride powders, rubber powders and organic balloons. Specific examples of the thixotropic agents include fatty acid amide waxes, ultrafine silica, asbestos powder, asbestos powder, inorganic thixotropic agents such as sepiolite, organic pentonite, modified polyester polyol-based organic thixotropic agents, and amide-based waxes. And surface-treated calcium carbonate, mica powder, short fiber polyethylene and the like. Specific examples of the plasticizer include dioctyl phthalate (DOP), dibutyl phthalate (DBP), and dilauryl phthalate (DL).
P), butylbenzyl phthalate (BBP), dioctyl adipate (DOA), isodecyl adipate (DI
DA), trioctyl phosphate (TOP), tris (chloroethyl) phosphate (TCEP), tris (dichloropropyl) phosphate (TDCPP), propylene glycol adipate polyester, butylene glycol adipate polyester, Alkyl epoxy stearate, epoxidized soybean oil, and the like. These can be used alone or in combination. The solvent can be used widely from low boiling point to high boiling point. Specific examples include, for example, toluene, xylene, acetone, MEK,
An aliphatic, alicyclic, or aromatic liquid low molecular organic solvent having no active hydrogen in the molecule, such as gasoline, kerosene, light oil, isoparaffin, liquid paraffin, chlorinated paraffin, and polybutene, can be used. Specific examples of the adhesion-imparting agent include various titanate-based coupling agents, reaction products of coupling agents and isocyanate compounds, and reaction products of two or more coupling agents (for example, reaction products of various aminosilanes and epoxysilanes). And a condensation reaction product of an alkoxy group of two or more coupling agents) and the like, and these can be used alone or as a mixture. Specific examples of the catalyst include organometallic catalysts such as dibutyltin dilaurate, tin octenoate, lead octenoate and lead naphthenate, N-triethylamine, N-methylmorpholine bis (2-dimethylaminoethyl) ether, N, N , N ', N ".
N ", N" -pentamethyldiethylenetriamine,
N, N, N'-trimethylaminoethyl-ethanolamine, bis (2-dimethylaminoethyl) ether, N
Tertiary amines such as -methyl-N'-dimethylaminoethylpiperazine, and an imidazole compound in which the secondary amine functional group of the imidazole ring is linearized with a cyanoethyl group, and the like, and one or a mixture of two or more thereof can be used. Other additives include stabilizers, various antioxidants, and ultraviolet absorbers. It should be noted that these auxiliary materials are previously subjected to a dehydration treatment so as not to affect the prepolymer composition. It should be noted that depending on the amount of the auxiliary material added to these prepolymers, the adhesive performance may be impaired with an adhesive, and the adhesion to a substrate may be impaired with a paint or sealing agent.

[0015]

Next, the present invention will be described with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, parts mean parts by weight.

Example 1 Polyoxypropylene diol (number average molecular weight 200
0) 100 parts were subjected to vacuum heat dehydration treatment and polymer MD
80 parts of I was added and reacted at 80 ° C. for 2 hours under a nitrogen atmosphere to obtain a urethane prepolymer containing about 12% by weight of NCO groups. Then, the mixture was cooled to 40 ° C. or lower, 0.2 parts of a catalyst (U-CAT2041 manufactured by San Apro Co.) and 2 parts by weight of γ-isocyanatopropyltrimethoxysilane were added, and the viscosity was 80 poise (BH type viscometer No. 4 rotor). 20
rpm / 25 ° C.) to obtain a urethane prepolymer composition.

Example 2 Polyoxypropylene diol (number average molecular weight 200
0) 100 parts were subjected to vacuum heat dehydration treatment and polymer MD
80 parts of I was added and reacted at 80 ° C. for 2 hours under a nitrogen atmosphere to obtain a urethane prepolymer containing 12% by weight of NCO groups. Then, the mixture was cooled to 40 ° C. or lower, and 0.2 parts of a catalyst (U-CAT2041 manufactured by San Apro Co., Ltd.), 2 parts of γ-isocyanatopropyltrimethoxysilane, and dried calcium carbonate (trade name: Whiten, manufactured by Shiraishi Industry Co., Ltd.) P-
30) After adjusting thixotropic properties with 100 parts of hydrophobized ultrafine silica particles (trade name: Aerosil R972, manufactured by Nippon Aerosil Co., Ltd.), the viscosity was adjusted with DBP, vacuum degassing was performed, and a one-component urethane-based The composition was prepared. The viscosity of this urethane prepolymer composition was 150 poise (BH type viscometer No. 5, rotor 20 rpm / 25 ° C.).

Example 3 Polyoxypropylene diol (number average molecular weight 200
0) 85 parts and 15 parts of adipic acid propylene glycol ester polyol (number-average molecular weight 2000) are subjected to vacuum heating and dehydration treatment, 75 parts of 4,4'-diphenylmethane diisocyanate is added, and the mixture is reacted under a nitrogen atmosphere at 80 ° C. for 2 hours. A urethane prepolymer containing 12% by weight of a group was obtained. Then, the mixture was cooled to 40 ° C. or lower, and 0.2 parts of a catalyst (U-CAT2041 manufactured by San Apro Co., Ltd.), 2.0 parts of γ-isocyanatopropyltrimethoxysilane, and dried calcium carbonate (trade name, manufactured by Shiraishi Industry Co., Ltd.) After adjusting the thixotropic properties with 100 parts of whiten P-30) hydrophobized ultrafine silica particles (manufactured by Nippon Aerosil Co., Ltd., trade name: Aerosil R972), the viscosity was adjusted with DBP, and vacuum degassing was performed. A liquid urethane composition was prepared. The viscosity of this urethane prepolymer composition is 200 poise (BH
Type viscometer No. 5 rotor 20 rpm / 25 ° C.).

Example 4 Polyoxypropylene diol (number average molecular weight 200
0) 80 parts and 20 parts of polypropylene glycol (number average molecular weight 4800) were subjected to vacuum heating and dehydration treatment, and 36 parts of 4,4'-diphenylmethane diisocyanate was added thereto and reacted at 80 ° C. for 2 hours under a nitrogen atmosphere to contain 5% by weight of NCO group. A urethane prepolymer was obtained. Next, the mixture was cooled to 40 ° C. or lower, and the catalyst (U-CAT204 manufactured by San Apro Co., Ltd.) was added.
1) 0.2 parts, 2.0 parts of γ-isocyanatopropyltrimethoxysilane, 30 parts of dried calcium carbonate (trade name: Whiten P-30, manufactured by Shiraishi Kogyo Co., Ltd.), hydrophobized ultrafine silica (Nippon Aerosil Co., Ltd.) And its viscosity was adjusted with DBP, followed by vacuum defoaming to prepare a one-part urethane composition. The viscosity of this urethane prepolymer composition is 100 poise (BH type viscometer No. 5 rotor 20 rpm).
/ 25 ° C).

Example 5 Polyoxypropylene diol (number average molecular weight 200
0) 80 parts and 20 parts of polypropylene glycol (number average molecular weight 4800) were subjected to vacuum heating and dehydration treatment, and 36 parts of 4,4'-diphenylmethane diisocyanate and 2.0 parts of γ-isocyanatopropyltrimethoxysilane were added, and 80 ° C. under a nitrogen atmosphere. And reacted for 2 hours at 5% by weight of NCO group
A urethane containing prepolymer was obtained. Next, the mixture was cooled to 40 ° C. or lower, and a catalyst (U-CAT20 manufactured by San Apro Co., Ltd.) was added.
41) 0.2 parts, 2.0 parts of γ-isocyanatopropyltrimethoxysilane, 30 parts of dried calcium carbonate (trade name: Whiten P-30, manufactured by Shiraishi Kogyo Co., Ltd.), hydrophobized ultrafine silica (Nippon Aerosil Co., Ltd.) And its viscosity was adjusted with DBP, followed by vacuum defoaming to prepare a one-part urethane composition. The viscosity of this urethane prepolymer composition was 130 poise (BH type viscometer No. 5 rotor 20 rpm).
m / 25 ° C.).

Comparative Example 1 Polyoxypropylene diol (number average molecular weight 200
0) 100 parts were subjected to vacuum heat dehydration treatment and polymer MD
80 parts of I was added and reacted at 80 ° C. for 2 hours under a nitrogen atmosphere to obtain a urethane prepolymer containing about 12% by weight of NCO groups. Next, the mixture was cooled to 40 ° C. or lower, and 0.2 parts of a catalyst (U-CAT2041 manufactured by San Apro Co., Ltd.) was added.
Viscosity 80 poise (BH type viscometer No. 4 rotor 20 rpm
/ 25 ° C) to obtain a urethane prepolymer composition.

Comparative Example 2 Polyoxypropylene diol (number average molecular weight 200
0) 100 parts were subjected to vacuum heat dehydration treatment and polymer MD
80 parts of I was added and reacted at 80 ° C. for 2 hours under a nitrogen atmosphere to obtain a urethane prepolymer containing 12% by weight of NCO groups. Then, the mixture was cooled to 40 ° C. or lower, 0.2 parts of a catalyst (U-CAT2041 manufactured by San Apro Co., Ltd.), and dried calcium carbonate (trade name: Whiten P-3 manufactured by Shiraishi Industry Co., Ltd.)
0) 100 parts, after performing thixotropic adjustment with hydrophobized ultrafine silica particles (manufactured by Nippon Aerosil Co., Ltd., trade name: Aerosil R972), adjusting the viscosity with DBP, performing vacuum defoaming, and performing a one-component urethane-based composition. Was adjusted. The viscosity of this urethane prepolymer composition was 150 poise (BH type viscometer 5
No. rotor 20 rpm / 25 ° C.).

Comparative Example 3 Polyoxypropylene diol (number average molecular weight 200
0) 85 parts and 15 parts of adipic acid propylene glycol ester polyol (number average molecular weight 2000) are subjected to vacuum heating dehydration treatment, 75 parts of 4,4'-diphenylmethane diisocyanate is added, and the mixture is reacted under a nitrogen atmosphere at 80 ° C. for 2 hours. A urethane prepolymer containing weight% was obtained. Next, the mixture was cooled to 40 ° C. or lower, 0.2 parts of a catalyst (U-CAT2041 manufactured by San Apro Co., Ltd.), and dried calcium carbonate (trade name: Whiten P-3 manufactured by Shiraishi Industry Co., Ltd.)
0) After 100 parts, thixotropic adjustment was performed with hydrophobic ultrafine silica particles (manufactured by Nippon Aerosil Co., Ltd., trade name: Aerosil R972), the viscosity was adjusted with DBP, vacuum degassing was performed, and the one-component urethane-based composition was used. I adjusted things. The viscosity of the urethane prepolymer composition was 200 poise (8H type viscometer No. 5, rotor 20 rpm / 25 ° C.).

Comparative Example 4 Polyoxypropylene diol (number average molecular weight 200
0) 80 parts and 20 parts of polypropylene glycol (number average molecular weight 4800) were subjected to vacuum heating and dehydration treatment, and 36 parts of 4,4'-diphenylmethane diisocyanate was added thereto and reacted at 80 ° C. for 2 hours under a nitrogen atmosphere to contain 5% by weight of NCO group. A urethane prepolymer was obtained. Next, the mixture was cooled to 40 ° C. or lower, and the catalyst (U-CAT204 manufactured by San Apro Co., Ltd.) was added.
1) 0.2 parts, 30 parts of dried calcium carbonate (trade name: Whiten P-30, manufactured by Shiraishi Kogyo), hydrophobized ultrafine silica (trade name: Aerosil R97, manufactured by Nippon Aerosil Co., Ltd.)
After the thixotropic adjustment was performed in 2), the viscosity was adjusted with DBP, and degassing was performed under vacuum to prepare a one-component urethane composition. The viscosity of the urethane prepolymer composition is 10
0 poise (BH type viscometer No. 5 rotor 20 rpm / 25
° C).

Comparative Example 5 Polyoxypropylene diol (number average molecular weight 200
0) 80 parts and 20 parts of polypropylene glycol (number average molecular weight 4800) were subjected to vacuum heating and dehydration treatment, and 36 parts of 4,4'-diphenylmethane diisocyanate was added thereto and reacted at 80 ° C. for 2 hours under a nitrogen atmosphere to contain 5% by weight of NCO group. A urethane prepolymer was obtained. Next, the mixture was cooled to 40 ° C. or lower, and the catalyst (U-CAT204 manufactured by San Apro Co., Ltd.) was added.
1) 0.2 part, 2 parts of γ-glycidoxypropyltrimethoxysilane, 30 parts of dry-dried calcium carbonate (trade name: Whiten P-30, manufactured by Shiraishi Industry Co., Ltd.), hydrophobized ultrafine silica (Nippon Aerosil) Company name, trade name Aerosil R9
After the thixotropic adjustment was performed in 72), the viscosity was adjusted with DBP, and the mixture was degassed under vacuum to prepare a one-part urethane composition. The urethane prepolymer composition has a viscosity of 1
00 poise (BH type viscometer No. 5 rotor 20 rpm / 2
5 ° C.).

Comparative Example 6 Polyoxypropylene diol (number average molecular weight 200
0) 80 parts and 20 parts of polypropylene glycol (number average molecular weight 4800) were subjected to vacuum heating and dehydration treatment, and 36 parts of 4,4'-diphenylmethane diisocyanate was added thereto and reacted at 80 ° C. for 2 hours under a nitrogen atmosphere to contain 5% by weight of NCO group. A urethane prepolymer was obtained. Next, the mixture was cooled to 40 ° C. or lower, and the catalyst (U-CAT204 manufactured by San Apro Co., Ltd.) was added.
1) 0.2 parts, 2 parts of vinyltrimethoxysilane, 30 parts of dried calcium carbonate (trade name: Whiten P-30, manufactured by Shiraishi Kogyo), hydrophobized ultrafine silica (trade name, Aerosil manufactured by Nippon Aerosil Co., Ltd.) After the thixotropic adjustment was performed in R972), the viscosity was adjusted with DBP, and the mixture was degassed under vacuum to prepare a one-component urethane composition. The viscosity of this urethane prepolymer composition was 100 poise (BH type viscometer No. 5, rotor 20 rpm / 25 ° C.).

<Composition Evaluation 1> Examples 1 to 5, Comparative Example 1
Adhesive performance and storage stability of the moisture-curable polyurethane compositions obtained in Nos. To 6 were evaluated by the following methods. The results are shown in Tables 1 and 2. <Test material> One of the test materials is a 25 mm wide ordinary plywood adjusted to a water content of 7 to 10%, and the other dressing material is
A 0.2 mm aluminum sheet, a 0.1 mm stainless sheet and a 0.5 mm soft PVC sheet were used. <Adhesion operation> The composition was uniformly applied to plywood at about 150 g / m ² , and each sheet was placed thereon and clamped under a pressure of 0.1 MPa for 16 hours in an atmosphere of 20 ° C to prepare an adhesive body. <Curing> The bonded body was cured at 20 ° C. and 65% RH for 7 days. <Normal state> After curing was completed, the adhesive performance was evaluated in a 20 ° C. atmosphere by the following adhesive performance evaluation method. <Heat resistance> The cured test pieces were left in an 80 ° C. environment for 3 hours, and then evaluated in an 80 ° C. atmosphere by the following adhesive performance evaluation method. <Boiling resistance> The cured test specimen was immersed in boiling water for 4 hours, dried in a 60 ° C dry machine for 20 hours, further immersed in boiling water for 4 hours, and allowed to acclimatize to room temperature in room temperature water and then to 20 ° C. While wet in an atmosphere, the adhesive performance was evaluated by the following adhesive performance evaluation method. <Evaluation of adhesion performance> The sheet was placed in the direction of 90 degrees with respect to the plywood.
The film was pulled at a speed of 00 mm / min, and its peeling resistance was measured. The value was expressed in kg / 25 mm and compared and evaluated. <Preservability> The composition whose viscosity at 25 ° C. was measured was 300 c
After storing for 1 month in a 40 ° C constant temperature room, the temperature was returned to 25 ° C and the viscosity was measured. The case where the viscosity after storage relative to the initial viscosity was less than 40% was passed, and the case where the viscosity increased by 40% or more was rejected.

[0028]

[Table 1]

[0029]

[Table 2] <Composition evaluation 2> The adhesion performance of the moisture-curable polyurethane-based compositions obtained in Example 4 and Comparative Example 4 was evaluated by a method different from the above, and the results are shown in Table 3. <Testing Material> Concrete was used as one of the materials to be adhered, and porcelain tile and glass tile were used as the other materials to be adhered. <Adhesion work> The composition was uniformly applied to the concrete with a comb iron, and the respective materials were placed thereon and left as it was. <Curing> The bonded body was cured at 20 ° C. and 65% RH for 7 days. <Normal state> After curing was completed, the adhesive performance was evaluated in a 20 ° C. atmosphere by the following adhesive performance evaluation method. <Boiling resistance> The cured test specimen was immersed in boiling water for 4 hours, dried in a drier at 60 ° C. for 20 hours, further immersed in boiling water for 4 hours, and allowed to acclimate to room temperature in room temperature water. The adhesive performance was evaluated in the following manner while wet in an atmosphere of ° C. <Evaluation of adhesion performance> An iron jig was attached to concrete and tile and pulled in a uniaxial direction. The tensile resistance was measured, the fracture surface at that time was observed, and the strength was measured in MPa.
And evaluated by comparison.

[0030]

[Table 3] A: adhesive cohesive fracture, AB: adhesive-tile interface fracture

[0031]

As described above, according to the present invention, as a polyurethane-based adhesive, sealing agent, paint or the like, inorganic materials and metal materials, etc., for which it is difficult to ensure sufficient adhesive performance and adhesion, are used. Demonstrate excellent adhesive performance and adhesion to
In addition, a one-part urethane prepolymer composition having improved durability, water resistance, and heat resistance and excellent storage stability can be obtained.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Koji Fukuda 4-13-1, Itabashi, Itabashi-ku, Tokyo Fukushima Shinko Co., Ltd. F-term (reference) 4J034 BA08 CA04 CA15 CB03 DA01 DB04 DC02 DC03 DC50 DF01 DF02 DF14 DF16 DF20 DF21 DF22 DG03 DG04 DG05 DN03 DP18 HA01 HA02 HA07 HA08 HB05 HB08 HB11 HB12 HC03 HC12 HC17 HC22 HC61 HC64 JA42 QB12 QB19 RA07 RA08 4J038 DG261 DG291 GA15 JC35 NA03 NA04 NA11 NA14 NA26 PC1 EF EF EF EF EF EF EF JA12 JB04 KA16 LA05 LA06 LA07 LA08 MA01 MA02 MA04 MA05

Claims (4)

[Claims] 1. An urethane prepolymer having a terminal isocyanate group obtained by mixing and reacting a compound having two or more active hydrogen groups in a molecule with a polyisocyanate compound having two or more isocyanate groups so that the isocyanate group becomes excessive. A one-component moisture-curable composition comprising a polymer and an isocyanate-based silane coupling agent represented by the following formula 1 and having both functional groups of an isocyanate group and a hydrolyzable silane group in one molecule: Urethane prepolymer composition. [Formula 1] _{O = C = N- (CH 2} ) n-SiX 3 where, n represents an integer, X is _-OCH 3, _-OC 2 _{H 5,} or a hydrolyzable group of _-OC 2 _H 4 OCH ₃ . 2. The one-component moisture-curable urethane prepolymer according to claim 1, wherein 0.005 to 30 parts by weight of an isocyanate silane coupling agent is blended with 100 parts by weight of the urethane prepolymer having terminal isocyanate groups. Polymer composition. 3. A urethane prepolymer having a terminal isocyanate group is obtained by mixing and reacting a compound having two or more active hydrogen groups in the molecule with a polyisocyanate compound having two or more isocyanate groups so that the isocyanate group becomes excessive. In this case, the reaction system is characterized by being mixed with an isocyanate silane coupling agent represented by the following formula 1 and having both isocyanate groups and hydrolyzable silane groups in one molecule. One-component moisture-curable urethane prepolymer composition. [Formula 1] _{O = C = N- (CH 2} ) n-SiX 3 where, n represents an integer, X is _-OCH 3, _-OC 2 _{H 5,} or a hydrolyzable group of _-OC 2 _H 4 OCH ₃ . 4. The one-pack moisture-curable urethane prepolymer composition according to claim 3, wherein the isocyanate-based silane-based coupling agent is contained in the composition in an amount of 0.1 to 30% by weight.