JP2002105427A - Adhesive for connection of tile and unit tile using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive for connection of tiles which can be simply unitized using a usual application apparatus and which holds adhesive strength to the tile bases and to glassy surfaces, bent strength, thermal resistance and blocking resistance when piling up the unit tiles, after use, connection strength, alkali resistance, etc., at the same time, as an adhesive used for the unit tile. SOLUTION: An adhesive for connection of tiles comprises: an urethane prepolymer (A) having two or more ethylenic unsaturated groups at the end of a reaction product which reacts a prepolymer having an isocyanate group at the end obtained from reacting at least a polyol (a), an excess polyisocyanate compound (b) and a reactive tertiary amine (c), with an ethylenic unsaturated monomer (d) containing a hydroxyl group; an initiator (B) of radical polymerization; and a filler (C).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive used for connecting tiles of a unit tile formed by connecting tiles with a resin bridge. More specifically, the present invention relates to a radical polymerization cross-linkable urethane adhesive having good workability in a uniting step, good adhesion to a tile base material and a vitreous surface, and excellent in heat resistance, bending strength and blocking resistance.

[0002]

2. Description of the Related Art There is known a unit tile manufactured by a method in which a plurality of tiles are arranged at a predetermined joint interval and an important part is connected with an adhesive on the back side or the side so as to straddle the joint interval. ing. Japanese Patent Application Laid-Open No. H11-314216 discloses a unit tile in which a vinyl chloride sol-based adhesive is connected by heating and curing as the adhesive. However, a vinyl chloride sol-based adhesive is not preferred because of contamination of the tile surface due to migration of the plasticizer and environmental problems. Japanese Patent Application Laid-Open No. 11-62176 discloses a method for producing a unit tile using moisture-curable urethane as a reactive hot-melt adhesive as a coupling agent. The hot-melt type requires a heat-melting type coating apparatus, and requires preheating of the tiles in order to improve the wetting of the tiles on the bonding surface.

[0003] Further, when connecting the side surfaces of the tiles,
In many cases, the vitreous glaze applied to the surface hangs down on the side surface, and the conventional adhesive has low adhesion to the glaze surface, and has a problem that the adhesive surface peels off during bending or construction.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an adhesive for a unit tile which can be easily made into a unit by using an ordinary coating device, and has an adhesive property to a tile base material and a vitreous surface, and a bending property. An object of the present invention is to provide an adhesive for tile connection that maintains strength, heat resistance and blocking resistance when unit tiles are stacked, and connection strength even after construction.

[0005]

Means for Solving the Problems The present inventors have started the development of a solvent-free two-pack type urethane adhesive with a long pot life in consideration of the simplicity and safety in using the adhesive. Then, a resin cross-linked by introducing an amino group into the urethane prepolymer having an ethylenically unsaturated group or by using an amino group-containing acrylic monomer in combination has adhesiveness to a glassy surface and durability of the resin. The inventors have found that they have excellent properties, and have reached the present invention.

That is, the present invention relates to a method in which a hydroxyl-containing ethylenically unsaturated monomer (d) is added to a prepolymer having a terminal isocyanate group obtained by reacting at least a polyol (a) and an excess of a polyisocyanate compound (b). ), And a tile connecting adhesive comprising a urethane prepolymer (A) having two or more ethylenically unsaturated groups at the terminal of the reaction product, a radical polymerization initiator (B), and a filler (C) It is. Further, the present invention is a unit tile in which the adhesive is applied to each of a plurality of tiles arranged at an interval of joints so as to form a bridge, and is cured by heating. Furthermore, in a preferred embodiment of the present invention, the urethane prepolymer (A) having two or more ethylenically unsaturated groups at the terminal of the reaction product is a polyol (a), an excess polyisocyanate compound (b), Is obtained by reacting a hydroxyl group-containing ethylenically unsaturated monomer (d) with an isocyanate group-terminated prepolymer obtained by reacting a reactive tertiary amine (c), or the adhesive An adhesive containing an amino group-containing acrylic monomer (e) instead of the reactive tertiary amine (c).

[0007]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The configuration of the present invention will be described below in detail. The urethane prepolymer (A) having two or more ethylenically unsaturated groups at the terminal of the reaction product of the present invention is obtained by first reacting at least a polyol (a) with an excess of a polyisocyanate compound (b), Produce a prepolymer having more than one isocyanate group. Subsequently, it is obtained by reacting an excess of a hydroxyl group-containing ethylenically unsaturated monomer (d) with an isocyanate group.

The polyol (a) used in the present invention has a number average molecular weight of 40 to 1 having two or more active hydrogen groups.
000 hydroxyl group-containing compounds, specifically, polyethers obtained by addition polymerization of monomers alone or two or more of ethylene oxide, propylene oxide, glycidyl ether, methyl glycidyl ether and the like by a known method. Diols such as ethylene glycol, propylene glycol, 1,4 butanediol, neopentyl glycol and adipic acid, sebacic acid,
Terephthalic acid, various polyester polyols obtained by polycondensation of isophthalic acid, etc., lactone polyols obtained by ring-opening polymerization of ε-caprolactam, etc., polycarbonate di or polyols, acrylic polyols, polybutadiene polyols, Examples include amine or amino alcohol-based mono- or polyols.
It is preferable to use one or a mixture of two or more selected from polyethers and polyester polyols in view of the liquid properties of the prepolymer, the adhesive strength, the toughness of the cured resin, and the like.

As the polyisocyanate compound (b) used in the present invention, an isocyanate compound having two isosonate groups in one molecule can be used.
Specifically, diphenylmethane diisocyanate (MD
I), aromatic polyisocyanates such as tolylene diisocyanate (TDI) and naphthalene diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate (HDI) and lysine methyl ester diisocyanate, hydrogenated diphenylmethane diisocyanate, isophorone diisocyanate (IPDI) ), Alicyclic polyisocyanates such as norbornene diisocyanate and hydrogenated tolylene diisocyanate, and one or more selected from these groups are used.

In order to synthesize a prepolymer having two or more isocyanate groups at the terminal of the reaction product, the reaction between the polyol (a) and the polyisocyanate compound (b) is carried out as follows.
The reaction is carried out at an NCO / OH ratio of 1.25 to 2.0, preferably 1.5 to 2.0, with an equivalent ratio of isocyanate groups to hydroxyl groups. When it is less than 1.25, the molecular weight becomes large and the viscosity becomes too high to be used substantially without a solvent, and there is a problem in coatability. If it exceeds 2.0,
Since the excess polyisocyanate compound remains in a state of low molecular weight, it becomes difficult to exhibit sufficient bending strength of the adhesive.

The reaction between the polyol (a) and the polyisocyanate compound (b) can be carried out under ordinary reaction conditions, for example, at a temperature of about 30 to 80 ° C. in an atmosphere of dry nitrogen gas. Further, a catalyst can be used if necessary. Examples of specific catalysts that can be used include amine catalysts such as triethylamine, triethylenediamine, N-methylmorpholine, methylimidazole, pyridine, α-picoline, monoethanolamine, diethanolamine, triethanolamine, N, N, N Amine catalysts having active hydrogen such as -trimethylaminoethyl-ethanolamine; and metal catalysts such as dibutyltin dilaurate, dioctyltin dilaurate, calcium naphthenate, tin octylate, and zinc octylate.

In the reaction between the polyol (a) and the polyisocyanate compound (b), a part of the polyol (a) is replaced with a reactive tertiary amine (c) and reacted to give a vitreous surface to the tile. Is improved in adhesiveness.
The reactive tertiary amine (c) used in the present invention includes:
OH group, -COOH group, -NCO group, -NH ₂ Oyobi N
Reactive tertiary amines containing two or more HR groups, where R is an alkyl group containing 1 to 25 carbon atoms. Of these, tertiary amines containing -OH groups are preferred. Specifically, N, N-dimethylethanolamine, N-methyldiethanolamine, N, N-dimethyl-2- (2-dimethylaminoethoxy) -ethanol, N, N, N-trimethyl-N-hydroxyethyldiaminoethane Bisaminoethyl ether, N, N-bis- (3-dimethylaminopropyl) -N-isopropanolamine, N- (3-dimethylaminopropyl) -N, N
-Diisopropanolamine and the like, and N, N-dimethylethanolamine and N-methyldiethanolamine are preferred.

The reactive tertiary amine (c) can be used by replacing 0.05 to 0.1 mol% of the polyol (a) to be used with the reactive tertiary amine (c). When the amount used is less than 0.05 mol%, the effect introduced is small, and when it exceeds 0.1 mol%, gelation tends to occur due to side reactions and the like. The use of the reactive tertiary amine (c) does not require the use of the above-mentioned catalyst, since it has a catalytic action in the reaction between the isocyanate and the polyol.

Urethane prepolymer (A) having two or more ethylenically unsaturated groups at the terminal of the reaction product of the present invention
Can be obtained by subjecting a hydroxyl-containing ethylenically unsaturated monomer (d) to an addition reaction with a prepolymer having a terminal isocyanate group obtained by reacting a polyol (a) and a polyisocyanate compound (b). . Specific examples of the hydroxyl group-containing ethylenically unsaturated monomer (d) used in the present invention include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) Acrylate, tetrapropylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, polytetramethylene glycol mono (meth) acrylate, 2- (meth) acryloyloxyethyl hydrogencaprolactonate, 2- (meth) acryloyl Oxyethyl hydrogen dicaprolactonate, 2- (meth) acryloyloxyethyl hydrogen poly (degree of polymerization 3 to 5) caprolactonate, 2 (Meth) acryloyloxyethyl-2-hydroxy-6-hexanoate Lactobacillus sulfonate, 2-
(Meth) acryloyloxyethyl-2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerin mono (meth) acrylate, pentaerythritol mono ( (Meth) acrylates, hydroxyl-containing (meth) acrylate monomers such as polyethylene oxide-modified pentaerythritol mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, and polyethylene oxide-modified trimethylolpropane mono (meth) acrylate; 2-hydroxyethyl vinyl ether, 2-
Hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 2-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, triethylene glycol monovinyl ether, tetraethylene glycol monovinyl ether, dipropylene glycol monovinyl ether, tripropylene glycol monovinyl ether, tetrapropylene glycol monovinyl ether, Examples include hydroxyl group-containing vinyl ether monomers such as trimethylolpropane monovinyl ether, and allyl alcohol. One selected from these groups
Species or two or more can be used. Preferably, it is a (meth) acrylate-based monomer selected from 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.

The amount of the hydroxyl group-containing ethylenically unsaturated monomer (d) used in the reaction with the isocyanate group-terminated prepolymer is excessive with respect to the NCO equivalent of the isocyanate group-terminated prepolymer. It is necessary. The reason for using excessively is to completely eliminate free isocyanate groups, reduce the viscosity during the reaction, and at the stage of curing the adhesive of the present invention with a radical polymerization initiator, the preferable viscosity and the curing resin. It also functions as a diluent for obtaining strength physical properties, and it is necessary to set the amount to be used in consideration of the viscosity during the reaction and the cured physical properties of the adhesive. The preferred amount of the hydroxyl group-containing ethylenically unsaturated monomer (d) used is 1.5 to the NCO equivalent of a prepolymer having an isocyanate group at the terminal.
~ 5.0 equivalents.

Urethane prepolymer (A) having two or more ethylenically unsaturated groups at the terminal of the obtained reaction product
Is mixed with a radical polymerization initiator (B), a filler (C) and, if necessary, an amino group-containing acrylic monomer (e), a silane coupling agent and a plasticizer, and the adhesive for tile connection of the present invention is obtained. Obtainable.

In the synthesis of the urethane prepolymer (A) having an ethylenically unsaturated group, the amino group-containing acrylic monomer (e) used in the present invention is obtained by mixing the polyol (a) and the polyisocyanate compound ( It is preferably used when the reactive tertiary amine (c) is not used during the reaction of b). By mixing and using the amino group-containing acrylic monomer (e), the adhesiveness to the glassy surface of the tile can be further improved. Specific examples of the amino group-containing acrylic monomer (e) include N, N-dimethylamineethyl (meth) acrylate and N, N-diethylaminoethyl (meth) acrylate.
At least one selected from these groups can be used. The amount of the amino group-containing acrylic monomer (e) is 0.1 to 10 parts by weight based on 100 parts by weight of the urethane prepolymer (A) having two or more ethylenically unsaturated groups at the terminal of the reaction product. Parts, preferably 1 to 6 parts by weight. When the amount is less than 0.1 part by weight, the effect of improving the adhesion to the glassy surface of the tile is small, and
When the amount is more than the weight part, the pot life of the adhesive becomes short, and the workability is deteriorated.

Further, a silane coupling agent can be used as an adhesion improver in the adhesive of the present invention. Specific examples of the silane coupling agent include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β
Aminosilanes such as (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane;
Epoxysilanes such as (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane; vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane And vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane and the like; hexamethyldisilazane, γ-mercaptopropyltrimethoxysilane and the like. Preferably, it is an aminosilane-based silane coupling agent. The amount of the silane coupling agent used is determined based on the urethane prepolymer (A) 10 having an ethylenically unsaturated group.
0.1 to 10 parts by weight relative to 0 parts by weight, preferably
0.5 to 6 parts by weight. If the amount is less than 0.1 part by weight, the effect of the adhesive property is small, and if it is more than 10 parts by weight, the flexibility of the adhesive is reduced.

A reactive diluent can be used in the adhesive of the present invention. The reactive diluent controls the viscosity of the adhesive of the present invention containing the obtained urethane prepolymer having an ethylenically unsaturated group (A) as a main component, and the urethane prepolymer is controlled by a radical polymerization initiator (B). It is a monomer whose molecular weight is increased by radical polymerization with the terminal unsaturated group of (A). In particular, the hydroxyl group-containing ethylenically unsaturated monomer (d) used in the above-mentioned reaction for introducing an ethylenically unsaturated group into an isocyanate terminal group can be used as a diluent, and further, 2- (2-ethoxy) is used. ) Ethyl acrylate,
Phenoxyethyl acrylate, 1,6-hexanediol diacrylate, tetraethylene glycol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate hydroxypivalate, polyethylene glycol diacrylate, trimethylolpropane triacrylate Acrylic monomers such as pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, styrene, vinyltoluene, α-methylstyrene, N-vinylpyrrolidone and the like are used as reactive diluents for hydroxyl-containing ethylenically unsaturated monomers ( It can be used in combination with d).

The urethane prepolymer having an ethylenically unsaturated group (A) of the present invention is a radical polymerization initiator (B)
To cure by polymerization. As the radical polymerization initiator, a radical generator activated by heat or light energy can be used. Examples of the radical polymerization initiator activated by heat include organic peroxides such as benzoyl peroxide, cumene hydroperoxide, tertiary butyl hydroperoxide, and cyclohexanone peroxide; Nitrile), 2,2'-azobis (2-methyl-butyronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-
Dimethyl-valeronitrile), 2,2′-azobis (2
-Amidino-propane) dihydrochloride), 2,
2'-azobis [2- (2-imidazolin-2-yl) propane], azobis-tert-octane, 2-cyano-2-propylazoformamide, dimethyl 2,2 '
-Azobis (2-methylpropionate), 2,2'-
Azobis such as azobis (2-hydroxymethylpropionitrile), 2,2′-azobis (N-butyl-2-methylpropionamide), 2,2′-azobis (N-cyclohexyl-2-methylpropionamide) Based compounds can be used. In addition, benzophenones such as benzophenone, P-chlorobenzophenone, and P-dimethylaminobenzophenone can be used as the initiator activated by light, particularly ultraviolet light. The amount used is 0.05 to 2 parts by weight based on 100 parts by weight of the urethane prepolymer having an ethylenically unsaturated group.

The plasticizer used as necessary for the adhesive of the present invention is used to reduce the viscosity of the adhesive composition, and any ordinary plasticizer can be used. For example, phthalic acid-based plasticizer, adipic acid-based plasticizer, specifically,
DOP (dioctyl phthalate), DBP (dibutyl phthalate), DOA (dioctyl adipate), DBE
(A mixture of dibasic acid esters manufactured by DuPont) and the like.

The filler (C) used in the adhesive of the present invention is, for example, clay, talc or calcium carbonate.
(Heavy and light), calcium oxide, silica sand, slate powder,
Examples include inorganic fillers having a particle diameter of 1 to 500 μm, such as mica powder, alumina, glass powder, zinc oxide, titanium dioxide, and carbon black, and at least one selected from these groups can be used. Although the amount of the filler used is not particularly limited, it is preferable that the filler be used in the adhesive of the present invention in the range of 30 to 70% by weight in view of the viscosity, viscosity, and physical strength of the cured resin. preferable.

Further, the adhesive of the present invention may optionally contain a commonly used thixotropic agent in order to adjust the viscosity. Specifically, inorganic thixotropic agents such as silica powder, bentonite and wollastonite can be used.

Further, the adhesive of the present invention may contain a polymerization inhibitor in order to prevent a curing reaction during storage. Specifically, hydroquinone, monoethylhydroquinone and the like can be used. Its usage is 100 ~ 1,0
00 ppm is preferred.

The adhesive of the present invention is used as an adhesive for connecting tiles, by arranging a plurality of tiles at a predetermined joint interval, and connecting the required points so as to straddle the joint interval on the back side or side surface. Can be applied to various methods and devices. The method of applying to the tile may be applied directly to the tile by a known nozzle method, a gravure plate method, or the like, or applied to a release paper, and then transferred to the tile and applied to the tile by a method such as heat or heat. It can be cured by ultraviolet irradiation or the like.

The adhesive of the present invention is characterized in that it has good workability in the uniting process, has high adhesive strength to the tile base material and the vitreous surface, and has excellent heat resistance, bending resistance and blocking resistance. You.

[0027]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited by these examples.
In the examples and comparative examples, “parts” or “%” means “parts by weight” or “% by weight” unless otherwise specified.

Synthesis Example 1 (Polyurethane prepolymer A-
1) After filling nitrogen into a reactor equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen inlet tube, polyester diol (Kuraray Polyol P-101 manufactured by Kuraray Co., Ltd.)
5), hexamethylene diisocyanate (Duranate 50M, manufactured by Asahi Kasei Corporation) (14.4 g).
g, and reacted at 60 ° C. for 3 hours under a nitrogen atmosphere. Then, 28.2 g of 2-hydroxyethyl methacrylate (trade name: Light Ester HO manufactured by Kyoeisha Chemical Co., Ltd.) was added, and the reaction was further performed at 60 ° C. for 2 hours. And cool to room temperature. A polyurethane prepolymer A-1 having a double bond at a terminal having a viscosity of 10,000 was obtained.

Synthesis Example 2 (Amino-Modified Polyurethane Prepolymer A-2) After filling nitrogen into a reactor equipped with a stirrer, thermometer, reflux condenser and nitrogen inlet tube, polyester diol P-101
0 (manufactured by Kuraray Co., Ltd.), 20.3 g of polyester diol P-2010 (manufactured by Kuraray Co., Ltd.), 40.7 g, hexamethylene diisocyanate (Duranate 50M, manufactured by Asahi Kasei Corporation) 12.8 g, N-methyldiethanolamine After charging 1.2 g of amino alcohol MDA (trade name, manufactured by Nippon Emulsifier Co., Ltd.) and reacting at 60 ° C. for 3 hours under a nitrogen atmosphere, 2-hydroxyethyl methacrylate (trade name, Light Ester H, manufactured by Kyoeisha Chemical Co., Ltd.)
O) 25.0 g is added, and the mixture is further reacted at 60 ° C. for 2 hours and cooled to room temperature. Amino-modified polyurethane prepolymer A having a terminal double bond having a viscosity of 15,000
-2 was obtained.

Synthesis Examples 3 and 4 (Polyurethane Prepolymers A-3 and A-4) Synthesis Example 3 was similar to Synthesis Example 1 except that hexamethylene diisocyanate of Synthesis Example 1 was changed to tolylene diisocyanate.
Was synthesized in the same manner as in Synthesis Example 1 except that hexamethylene diisocyanate in Synthesis Example 1 was changed to isophorone diisocyanate. The amount and the viscosity are shown in Table 1.

[0031]

[Table 1]

In Table 1, the abbreviations of the raw materials are as follows. HDI: Hexamethylene diisocyanate (Duranate 50M, manufactured by Asahi Kasei Corporation) TDI: Tolylene diisocyanate (Sumidur T80, manufactured by Sumitomo Bayer Urethane Co., Ltd.) IPDI: Isophorone diisocyanate (Vestanat, manufactured by Daicel-Hüls, Ltd.) IPD
I) P-1010: Polyester diol, number average molecular weight 1,000 (Kuraray Co., Ltd. product name Kuraray polyol P-1010) P-2010: Polyester diol, number average molecular weight 2,000 (Kuraray Co., Ltd. product name) Kuraray polyol P-2010) N-methyldiethanolamine: (Amino Alcohol MDA manufactured by Nippon Emulsifier Co., Ltd.) Light ester HO: 2-hydroxyethyl methacrylate (Light ester HO manufactured by Kyoeisha Chemical Co., Ltd.)

Example 1 Polyurethane prepolymer A-1 obtained in Synthesis Example 1
100 parts by weight of calcium carbonate (Maruo Calcium Co., Ltd.)
4. 100 parts by weight (trade name, manufactured by Superno S), 3.3 parts by weight of powdered silica (trade name: Carplex 80, manufactured by Shionogi Co., Ltd.), dimethylaminoethyl methacrylate (methacrylic ester DM, manufactured by Mitsui Chemicals, Inc.) 3 parts by weight were added and mixed, and 0.6 part by weight of a radical polymerization initiator dimethyl 2,2'-azobis (2-methylpropionate) (trade name: V-601, manufactured by Wako Pure Chemical Industries, Ltd.) was further added. To obtain a curable composition. A film having a thickness of 1 mm was prepared and cured at 150 ° C. for 15 minutes, and the tensile strength was measured to obtain a result equivalent to that of a vinyl chloride sol-based adhesive for tiles. 95m
3 x 18 vertical tiles for exterior walls measuring mx 45mm
Adhesives of the present invention are injected into the joints with a nozzle at 0.15 g per point as shown in FIG. 1 and cured at 150 ° C. for 15 minutes. Then, a unit tile sample was obtained. The samples were tested for adhesion, heat resistance, blocking resistance, and bending resistance, and all were good. The results are shown in Table 2.

Example 2 100 parts by weight of calcium carbonate (trade name: Super S manufactured by Maruo Calcium Co., Ltd.) was added to 100 parts by weight of the amino-modified polyurethane prepolymer A-2 obtained in Synthesis Example 2, and powdered silica (Yoshio Shiono Co., Ltd.) ) Product name Carplex 8
0) 12.5 parts by weight were added and mixed, and a radical polymerization initiator dimethyl 2,2'-azobis (2-methylpropionate) (trade name: V-60, manufactured by Wako Pure Chemical Industries, Ltd.)
1) A curable composition was obtained by adding 0.6 parts by weight. A unit tile sample was obtained by heating and curing in the same manner as in Example 1, and measurements and tests were performed in the same manner to obtain good results. Table 2 shows the results
Shown in

Examples 3 and 4 Example 3 is based on the polyurethane prepolymer A-
1 was changed to polyurethane prepolymer A-3, and a silane coupling agent (N-β (aminoethyl) γ-aminopropyltrimethoxysilane Shin-Etsu Silicone KBM603 manufactured by Shin-Etsu Chemical Co., Ltd.) was replaced with polyurethane prepolymer A-3. Except that 0.4 part is added to 100 parts, Example 4 is cured in exactly the same manner as Example 1 except that the polyurethane prepolymer A-1 of Example 1 is changed to polyurethane prepolymer A-4. The composition was obtained. Heat-cured in the same manner as in Example 1 to obtain a unit tile sample,
Similarly measured and tested, Examples 3 and 4 all gave good results. The results are shown in Table 2.

Comparative Example 1 This is a type in which dimethylaminoethyl methacrylate, which is the amino group-containing acrylic monomer of Example 1, is omitted. A unit tile sample was obtained by heating and curing in the same manner as in the example, and the measurement and test were performed in the same manner. Adhesion to tiles, heat resistance and bending resistance at -5 ° C were poor. The results are shown in Table 2.

REFERENCE EXAMPLE 1 Using a PVC sol adhesive for tiles (trade name: X-199-901, manufactured by Seiden Chemical Co., Ltd.), cured at 180 ° C. for 15 minutes, and referred to tensile strength, adhesiveness and blocking resistance. did.

[0038]

[Table 2]

In Table 2, the product names and abbreviations are as follows. X-199-901: PVC adhesive for tiles manufactured by Seiden Chemical Co., Ltd. Methacryl ester DM: Dimethylaminoethyl methacrylate manufactured by Mitsui Chemicals, Inc. Super S: Calcium carbonate carplex manufactured by Maruo Calcium Co., Ltd. 80: Yoshio Shiono Powdered silica KBM603: Silane coupling agent (Shin-Etsu Chemical Co., Ltd. N-β (aminoethyl) γ-aminopropyltrimethoxysilane V-601: Dimethyl 2,2′-azobis (2-methylpro Pionate) (radical polymerization initiator manufactured by Wako Pure Chemical Industries, Ltd.)

Test Method Tensile Strength The adhesive of the present invention was prepared in a sheet having a thickness of 1 mm,
The composition was cured at 15 ° C. for 15 minutes to obtain a test sample. A test piece obtained by punching the sample with a dumbbell No. 1 was left at 23 ° C. and 65% RH for 1 hour, and the tensile strength was measured by an autograph (manufactured by Shimadzu Corporation) at a tensile speed of 100 mm / min. The unit of measurement is Kg / cm ² . Adhesive property Three 18 tiles for exterior walls of 95 mm x 45 mm in size are arranged vertically and 6 horizontally, and a joint space of 5 mm width is taken, and the adhesive of the present invention is applied to the joint at one point as shown in FIG. 0.15g
Then, the mixture is cured by a nozzle at 150 ° C. for 15 minutes to obtain a unit tile sample, and the adhesion to the tile is observed at room temperature. A: Good adhesion. ×: Poor adhesion Heat resistance adhesion The unit tile obtained in the adhesion test was used as a heat resistance test sample. The unit tile is left at 60 ° C. for 3 days and peeled off at that temperature to check the adhesiveness. ：: Does not peel. ×: easily peeled off. Blocking resistance An adhesive sheet was obtained in the same manner as in the tensile strength. Similarly, the cured sheet is cut into 50 mm × 50 mm,
A load was applied to the constant temperature bath at 100 g / cm ² , and the mixture was allowed to stand for 3 days, returned to room temperature, and observed for blocking properties. ：: easily peeled off. X: Peeling off with strong force. Folding resistance The unit tile obtained in the adhesion test was used as a bending resistance sample. Unit tile at -5 ℃, 25 ℃, 3
Leave in each thermostat at 5 ° C for 7 days and bend at that temperature to see peeling and cracking of the adhesive. ：: No peeling or cracking. ×: Peeling or cracking is observed.

[0041]

The urethane-based adhesive of the present invention has excellent adhesiveness, heat-resistant adhesiveness, blocking resistance and bending resistance, and is useful as an adhesive for connecting unit tiles.

[Brief description of the drawings]

FIG. 1 is a plan view of a unit tile in which a bridge is formed by a tile connecting adhesive of the present invention.

[Explanation of symbols]

 A: Unit tile 1: Tile 2: Adhesive 3: Joint space

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2E110 AA42 AB04 AB05 BA13 GA15W GA34W GA44Z GB26W GB42Z 4J040 EF051 EF061 EF111 EF121 EF131 EF191 EF251 EF351 FA141 FA142 FA291 GA14 GA15 HA026 HA136 HA156 HA196 HA346 HA356 HB19 HC24 LA41 LA08 LA11 MA04 NA14

Claims (4)

[Claims] 1. A hydroxyl group-containing ethylenically unsaturated monomer (d) is reacted with a prepolymer having a terminal isocyanate group obtained by reacting at least a polyol (a) and an excess of a polyisocyanate compound (b). And a tile connecting adhesive comprising a urethane prepolymer (A) having two or more ethylenically unsaturated groups at the terminal of the reaction product, a radical polymerization initiator (B), and a filler (C). 2. A prepolymer having a terminal isocyanate group obtained by reacting a urethane prepolymer (A) with a polyol (a), an excess polyisocyanate compound (b), and a reactive tertiary amine (c). And reacting a hydroxyl group-containing ethylenically unsaturated monomer (d).
The adhesive for tile connection according to item 1. 3. The adhesive for tile connection according to claim 1, which comprises an amino group-containing acrylic monomer (e). 4. A urethane prepolymer having at least two ethylenically unsaturated groups at the terminal of the reaction product (A), a radical polymerization initiator (B), and a filler (C)
A unit formed by applying the tile connecting adhesive according to any one of claims 1 to 3 so as to form a bridge on each of a plurality of tiles arranged at an interval between joints, and curing by heating. tile.