JP2013108306A - Tile joint structure and adhesive composition for moisture-curable tiles - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a tile joint structure for not generating discoloration of a joint filler due to an adhesive, its construction method, and an adhesive composition for moisture-curable tiles.SOLUTION: The tile joint structure includes: an adhesive layer 16 formed on a surface of a substrate material 18; a plurality of tiles 12 bonded on an upper surface of the adhesive layer; and an inorganic joint filler 14 filled in a joint gap 15 of the plurality of tiles. An adhesive forming the adhesive layer contains: (A) a moisture-curable organic polymer; (B) a 6-hydroxychroman derivative indicated by the general formula (1); and (C) at least one kind of non-chelate tin compound selected from dialkyl tin alkoxides and a reaction product of dialkyl tin oxides and a silicate compound.

Description

  The present invention relates to a tile joint structure, a construction method thereof, and a moisture-curing tile adhesive composition.

  Conventionally, it is widely known that a tile is bonded to a floor surface or a wall surface using an adhesive. Examples of tile adhesives are listed in Patent Documents 1 and 2.

  In Patent Document 1, in order to cope with the uneven color after the filling process based on the difference in the degree of the efflorescence phenomenon, a granular material is stuck to the joint part.

  In Patent Document 2, high weather resistance plasticizers and low weather resistance plastics are used as tile adhesives that have excellent weather resistance and are less likely to contaminate bonded tiles in order to cope with an open joint method that does not close the joints between tiles. And an adhesive containing an agent.

  On the other hand, components such as antioxidants or antioxidants are often added to tile adhesives for the purpose of preventing aging.

  However, when the tiles are bonded using an adhesive to which components such as an antioxidant or an anti-aging agent are added and the joints are filled between the tiles, the joints are bonded to the joints when the joints are dried. There is a problem that the components such as the anti-aging agent move and the surface of the joint material is discolored (yellowing or the like) as shown in FIG.

  FIG. 3 shows a state in which a discolored portion is generated on the surface of the joint material in the conventional tile joint structure. In FIG. 3, reference numeral 110 denotes a conventional tile joint structure. The tile joint structure 110 includes an adhesive layer 116 formed on the surface of the base material 118, a plurality of tiles 112 adhered to the upper surface of the adhesive layer 116, and joints 115 in the joint gaps 115 of the plurality of tiles 112. It is comprised from the joint material 114 stuffed. And when the joint material 114 dries, components, such as an anti-aging agent of an adhesive agent, move to the joint material 114, and a discoloration spot 120 is generated on the surface of the joint material 114.

  The joints between the tiles are very easily noticeable by humans, and even if the plugging work is done with great care, if the surface of the jointing material changes color later, it will be ruined. Therefore, the appearance of a tile adhesive that does not cause discoloration of the joint material due to the adhesive has been desired.

JP-A-8-144471 2009-22214 gazette

  It is an object of the present invention to provide a tile joint structure, a construction method thereof, and a moisture-curing tile adhesive composition in which discoloration of the joint material caused by the adhesive does not occur.

  In order to solve the above problems, a tile joint structure of the present invention includes an adhesive layer formed on a surface of a base material, a plurality of tiles bonded to the upper surface of the adhesive layer, and a plurality of tiles. And an inorganic joint material filled with joints in the joint gap, and the adhesive forming the adhesive layer is represented by (A) a moisture-curable organic polymer, (B) represented by the following general formula (1) It contains one or more non-chelating tin compounds selected from 6-hydroxychroman derivatives, (C) dialkyltin alkoxides, and reaction products of dialkyltin oxides and silicate compounds.

(In the general formula (1), R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. R ² represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms.)

A tack-free time (23 ° C., 50% RH) suitable as the adhesive is 15 minutes to 120 minutes, more preferably 30 minutes to 60 minutes.

  The (A) moisture curable organic polymer is preferably a crosslinkable silyl group-containing organic polymer.

（前記一般式（１）において、Ｒ^１、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８及びＲ^９は、それぞれ独立に水素原子又は炭素数１〜２０のアルキル基を表し、Ｒ^２は水素原子、炭素数１〜２０のアルキル基又は炭素数２〜２０のアルケニル基を表す。） The construction method of the present invention is a construction method for constructing the tile joint structure of the present invention, and includes a step of forming an adhesive layer on the surface of the base material, and before the surface of the adhesive layer becomes tack-free. A step of providing a joint gap in the base material and bonding a plurality of tiles; and a step of filling the joint material in the joint gap after the surface of the adhesive layer in the joint gap becomes tack-free. The adhesive that forms the adhesive layer includes (A) a moisture-curable organic polymer, (B) a 6-hydroxychroman derivative represented by the following general formula (1), and (C) a dialkyltin alkoxide. And at least one non-chelating tin compound selected from the reaction products of dialkyltin oxides and silicate compounds.

(In the general formula (1), R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. R ² represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms.)

  By constructing as described above, when the joint material dries, components such as an anti-aging agent from the adhesive move to the joint material and prevent the surface of the joint material from discoloring more effectively. be able to.

  The tack-free time (23 ° C., 50% RH) suitable as an adhesive used in the construction method of the present invention is 15 minutes to 120 minutes, more preferably 30 minutes to 60 minutes.

  The moisture-curable tile adhesive composition of the present invention includes (A) a moisture-curable organic polymer, (B) a 6-hydroxychroman derivative represented by the following general formula (1), and (C) dialkyltin alkoxides. And one or more non-chelate tin compounds selected from the reaction products of dialkyltin oxides and silicate compounds.

(In the general formula (1), R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. R ² represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms.)

  When the joint material dries, the adhesive can effectively prevent components such as an anti-aging agent from the adhesive from moving to the joint material and discoloration of the surface of the joint material.

  The (A) moisture curable organic polymer is preferably a crosslinkable silyl group-containing organic polymer.

  ADVANTAGE OF THE INVENTION According to this invention, the remarkable effect that the tile joint structure which prevented discoloration of the joint material resulting from an adhesive agent, its construction method, and a moisture hardening type tile adhesive composition can be provided. Play.

Further, the construction method according to the present invention has an effect that the construction period can be shortened as compared with the conventional method because the adhesive has a high surface hardening rate and a short tack-free time.

One embodiment of the tile joint structure of the present invention is shown, (a) is a schematic plan view, and (b) is a schematic cross-sectional view. It is a flowchart which shows the flow of the construction method of the tile joint structure of this invention. The conventional tile joint structure is shown, (a) is a schematic plan view, and (b) is a schematic cross-sectional view.

  Embodiments of the present invention will be described below, but these are exemplarily shown, and it goes without saying that various modifications are possible without departing from the technical idea of the present invention.

  The moisture-curable tile adhesive composition of the present invention comprises (A) a moisture-curable organic polymer, (B) a 6-hydroxychroman derivative, (C) a dialkyltin alkoxide, and a dialkyltin oxide and a silicate compound. One or more non-chelate tin compounds selected from the reaction products are contained as essential components.

  As the (A) moisture curable organic polymer, a known organic polymer that is cured by moisture can be used, and a crosslinkable silyl group-containing organic polymer and a moisture curable urethane organic polymer are preferable. A crosslinkable silyl group-containing organic polymer is more preferable. The (A) moisture curable organic polymer may be used alone or in combination of two or more. The number average molecular weight of the (A) moisture curable organic polymer is preferably 1,000 to 50,000, and more preferably 2,000 to 30,000.

  The crosslinkable silyl group-containing organic polymer has a hydroxyl group or a hydrolyzable group bonded to a silicon atom and can be crosslinked by forming a siloxane bond, that is, an organic polymer having a crosslinkable silyl group. It is.

  The number of crosslinkable silyl groups is not particularly limited, but is preferably 0.1 to 5 and more preferably 0.5 to 4 in the molecule. The position of the crosslinkable silyl group is not particularly limited, and may be at the end or inside of the organic polymer molecular chain, or may be at both, but is preferably at the end of the molecular chain. Further, the crosslinkable silyl group is preferably one represented by the following general formula (2) which is easily crosslinked and easy to produce.

  In said formula (2), R is a C1-C20 substituted or unsubstituted monovalent organic group, a C1-C20 alkyl group, a C6-C20 aryl group, or C7-C7 Twenty aralkyl groups are preferred, and a methyl group is most preferred. When a plurality of R are present, they may be the same or different. X is a hydroxyl group or a hydrolyzable group, and is selected from a halogen atom, a hydrogen atom, a hydroxyl group, an alkoxyl group, an acyloxyl group, a ketoximate group, an amide group, an acid amide group, a mercapto group, an alkenyloxyl group, and an aminooxyl group. Groups are preferred, alkoxyl groups are more preferred, and methoxyl groups are most preferred. When a plurality of X are present, they may be the same or different. n is 1, 2 or 3.

  In the crosslinkable silyl group-containing organic polymer, when a plurality of crosslinkable silyl groups are present, these may be the same or different, and the number of n in the formula (2) is also the same. Or different. Two or more kinds of organic polymers having different crosslinkable silyl groups may be used.

  The polymer unit in the crosslinkable silyl group-containing organic polymer is not particularly limited. For example, a polyoxyalkylene polymer, a vinyl-modified polyoxyalkylene polymer, a (meth) acryl-modified polyoxyalkylene polymer, ( (Meth) acrylic polymers, vinyl polymers, polyester polymers, (meth) acrylic acid ester polymers, polyisobutylene polymers, and copolymers thereof (for example, JP2003-238895, JP 2000-169544, JP-A-2004-059782, JP-A-2004-51830, JP-A-2003-138151, JP-A-2001-40037 and JP-A-10-182991). It can be mentioned as a suitable example. These polymers may be used alone or in combination of two or more. In the present invention, acryl and methacryl are collectively referred to as (meth) acryl.

  Specifically, the crosslinkable silyl group-containing organic polymer has a (meth) acrylic polymer having a crosslinkable silyl group, a polyoxyalkylene polymer having a crosslinkable silyl group, and a crosslinkable silyl group. A (meth) acryl-modified polyoxyalkylene polymer, a polyisobutylene polymer having a crosslinkable silyl group, and a mixture thereof are preferred.

  As the (meth) acrylic polymer having a crosslinkable silyl group, a polymer or copolymer having a crosslinkable silyl group at the molecular chain end and containing an acrylate ester as a monomer unit, or a crosslinkable silyl A copolymer having a group at the molecular chain terminal and containing an acrylate ester and another monomer unit is preferred. The polymer is preferably a solid at room temperature and a glass transition temperature of 10 ° C. or higher.

  The method for producing the (meth) acrylic polymer having a crosslinkable silyl group at the terminal is not particularly limited, and examples thereof include a free radical polymerization method, an anionic polymerization method, a cationic polymerization method, a UV radical polymerization method, and a living anion polymerization method. In addition, known polymerization methods such as various polymerization methods such as a living cationic polymerization method and a living radical polymerization method can be mentioned, but a controlled radical polymerization method is preferable, and a living radical polymerization method is more preferable.

  Examples of the polyoxyalkylene polymer having a crosslinkable silyl group include a polymer having a crosslinkable silyl group at the molecular chain terminal and having polyoxypropylene as the main chain. The production method of such a polymer is not particularly limited. For example, after the terminal hydroxyl group of polyoxypropylene having a hydroxyl group at the terminal is converted to an unsaturated group such as an allyloxy group, hydrosilane such as methyldimethoxysilane is used. It can be obtained by introducing a crosslinkable silyl group into polyoxypropylene by a hydrosilylation reaction.

  As the moisture-curable urethane-based organic polymer, a polyurethane prepolymer having a known isocyanate group obtained by reacting a polyol and a polyisocyanate can be widely used.

  The polyol is not particularly limited as long as it is an active hydrogen-containing compound having two or more active hydrogen groups. For example, polyether polyol, polyester polyol, amine polyol, polycarbonate polyol, polybutadiene polyol, and acrylic polyol. Polyether polyol, polyester polyol or amine polyol is preferably used, and polyether polyol is particularly preferable. As the polyol, those having a molecular weight of 100 to 12000 and 2 to 4 OH groups in one molecule can be preferably used. These polyols may be used alone or in combination of two or more.

  More specifically, examples of the polyether polyol include diols such as ethylene glycol, propylene glycol and butylene glycol, triols such as glycerin and trimethylolpropane, and one or two amines such as ammonia and ethylenediamine. Examples include polyether polyols such as random or block copolymers obtained by ring-opening polymerization of propylene oxide and / or ethylene oxide in the presence of more than one species.

  Examples of the polyester polyol include polyesters such as copolymers obtained by polycondensation of adipic acid, sebacic acid, terephthalic acid and the like in the presence of ethylene glycol, propylene glycol, 1,4 butanediol, neopentyl glycol and the like. Examples thereof include polyols, and other low molecular active hydrogen compounds having two or more active hydrogen groups such as bisphenol A and ramester of castor oil.

  The amine polyol can be obtained, for example, by addition reaction of an alkylene oxide with an amine compound, and is preferably a triamine or higher polyamine polyol on average. Examples of the amine compound include ethylamine, butylamine, octylamine, laurylamine, ethylenediamine, diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, propylenediamine, methylaminomethylamine, methylaminoethylamine, ethylaminoethylamine, 1,2 -Diaminopropane, 1,3-diaminopropane, methylaminopropylamine, bis (3-aminopropyl) ether, 1,3-bis (3-aminopropyl) ethane, 1,4-diaminobutane, laurylaminopropylamine, Examples include aliphatic polyamines such as iminobispropylamine and methyliminobispropylamine, and aromatic polyamines such as metaxylenediamine, which should be used alone or in combination. It can be. Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, and the like.

  Specific examples of the polyisocyanate include aromatic polyisocyanates such as diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), naphthalene diisocyanate, hexamethylene diisocyanate (HDI), lysine methyl ester diisocyanate, and the like. Aliphatic polyisocyanates, hydrogenated diphenylmethane diisocyanate, isophorone diisocyanate, norbornane diisocyanate, hydrogenated tolylene diisocyanate, and the like. Among these, MDI's are from the standpoint of toxicity and price. Use is preferred.

  The urethane prepolymer having an isocyanate group obtained by reacting the polyol and polyisocyanate may be used alone or in combination of two or more. When two or more types are used in combination, the combination is not particularly limited, and prepolymers using different polyols or polyisocyanates, for example, a prepolymer using polypropylene glycol and a prepolymer using amine polyol are used in combination. May be.

  The (B) 6-hydroxychroman derivative is a compound having an antioxidant action represented by the following formula (1).

In the general formula (1), R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, A hydrogen atom or a methyl group is preferred. R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ may be the same or different.

In the general formula (1), R ² represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms, and the steric structure when the carbon to which R ² is bonded is an asymmetric carbon atom. The arrangement represents an R structure and / or an S structure in the R, S display method. R ² is preferably the following formula (3) or the following formula (4).

  The (B) 6-hydroxychroman derivative may be used alone or in combination of two or more. (B) The blending ratio of the 6-hydroxychroman derivative is not particularly limited, but in order to obtain the effect of the present invention, 0.1 part by mass or more is blended with respect to 100 parts by mass of the (A) moisture-curable organic polymer. It is preferably 1 to 10 parts by mass, more preferably 3 to 8 parts by mass.

  Examples of the (C) dialkyltin alkoxides and one or more non-chelate tin compounds selected from the reaction products of dialkyltin oxides and silicate compounds include, for example, dialkyltin alkoxides such as dibutyltin dimethoxide and dibutyltin diphenoxide. A reaction product of a dialkyltin oxide and a silicate compound such as dibutyltin bistriethoxysilicate and dioctyltin bistriethoxysilicate can be used. Among these, from the viewpoint of shortening the tack-free time of the adhesive composition, a reaction product of a dialkyltin oxide and a silicate compound is more preferable, and among them, a reaction product of dibutyltin oxide and normal ethyl silicate is particularly preferably used. it can. In addition, a reaction product of dioctyltin oxide and normal ethyl silicate can be suitably used from the viewpoint of safety of the adhesive composition.

  In addition to the components (A) to (C), the moisture-curable tile adhesive composition of the present invention may include other curing catalysts, adhesion-imparting agents, fillers, and dehydrating agents (storage stability). Improver), diluent, property modifier, plasticizer, thixotropic agent, tackifier, anti-sagging agent, ultraviolet absorber, antioxidant, anti-aging agent, light stabilizer, flame retardant, colorant, heat storage particles Additives such as fragrances and radical polymerization initiators may be blended, or other compatible polymers may be blended.

  As the filler, known fillers can be widely used and are not particularly limited. For example, calcium carbonate, magnesium carbonate, diatomaceous earth hydrous silicic acid, hydrous silicic acid, anhydrous silicic acid, calcium silicate, silica, Examples thereof include titanium dioxide, clay, talc, carbon black, slate powder, mica, kaolin, and zeolite, among which calcium carbonate is preferable, and surface-treated calcium carbonate is more preferable. Further, glass beads, silica beads, alumina beads, carbon beads, styrene beads, phenol beads, acrylic beads, porous silica, shirasu balloons, glass balloons, silica balloons, saran balloons, acrylic balloons, and the like can also be used.

  As the calcium carbonate, any of heavy calcium carbonate, light calcium carbonate, colloidal calcium carbonate, ground calcium carbonate and the like can be used, but colloidal calcium carbonate is more preferable. These calcium carbonates may be used alone or in combination of two or more.

  The primary particle diameter of the calcium carbonate is preferably 0.5 μm or less, and more preferably 0.01 to 0.1 μm. By using such fine powdered calcium carbonate having a small particle diameter, thixotropy can be imparted to the curable composition.

  Further, among calcium carbonates, surface-treated calcium carbonate is preferable, and surface-treated fine calcium carbonate is more preferable from the viewpoint of imparting thixotropy and reinforcing effect on a cured product (cured film). Furthermore, surface-treated fine powdered calcium carbonate is used in combination with other calcium carbonates such as heavy calcium carbonate that has not been surface-treated and has a large particle size, or surface-treated calcium carbonate with a large particle size. May be. When the surface-treated fine calcium carbonate and other calcium carbonate are used in combination, the ratio (mass ratio) between the surface-treated fine calcium carbonate and the other calcium carbonate is preferably 1: 9 to 9: 1, and 3: 7. ~ 7: 3 is more preferred.

  In the said surface treatment calcium carbonate, there is no restriction | limiting in particular in the surface treatment agent used, A well-known surface treatment agent can be used widely. Examples of the surface treatment agent include higher fatty acid compounds, resin acid compounds, aromatic carboxylic acid esters, anionic surfactants, cationic surfactants, nonionic surfactants, paraffin, and titanate couplings. And higher fatty acid compounds and paraffin are more preferable. These surface treatment agents may be used alone or in combination of two or more.

  As the surface-treated calcium carbonate, known surface-treated calcium carbonate can be widely used, and is not particularly limited. For example, Vigot 15 (manufactured by Shiraishi Calcium Co., Ltd., light carbonate surface-treated with a fatty acid) Surface treated light calcium carbonate such as calcium, primary particle diameter 0.15 μm; Vigot 10 (manufactured by Shiraishi Calcium Co., Ltd., colloidal calcium carbonate surface treated with fatty acid, primary particle diameter 0.10 μm), white glaze CCR-B ( Shiroishi Calcium Co., Ltd., colloidal calcium carbonate surface-treated with fatty acid, primary particle size 0.08 μm), Shiraka Hana DD (Shiraishi Calcium Co., Ltd., colloidal calcium carbonate surface-treated with resin acid, primary particle size 0 .05 μm), Carlex 300 (manufactured by Maruo Calcium Co., Ltd.), surface treated with fatty acid Loyal calcium carbonate, primary particle diameter 0.05 μm), neolite SS (manufactured by Takehara Chemical Industry Co., Ltd., colloidal calcium carbonate surface-treated with fatty acid, average particle diameter 0.04 μm), neolite GP-20 (takehara chemical industry ( Co., Ltd., colloidal calcium carbonate surface-treated with resin acid, average particle size 0.03 μm), Calsees P (manufactured by Kamishima Chemical Co., Ltd., colloidal calcium carbonate surface-treated with fatty acid, average particle size 0.15 μm) ) Surface treatment colloidal calcium carbonate; MC coat P1 (manufactured by Maruo Calcium Co., Ltd., heavy calcium carbonate surface-treated with paraffin, primary particle size 3.3 μm), AFF-95 (manufactured by Pfematech) Heavy calcium carbonate surfaced with a cationic polymer, primary particle size 0.9 μm), AFF-Z Matec Co., Ltd., heavy calcium carbonate is surface with a cationic polymer and an antistatic agent, and surface treatment of heavy calcium carbonate primary particle size 1.0 .mu.m) and the like.

  A known flame retardant can be used as the flame retardant, and is not particularly limited. For example, metal hydroxides such as aluminum hydroxide and magnesium hydroxide; phosphorus flame retardants such as red phosphorus and ammonium polyphosphate Metal oxide-based flame retardants such as antimony trioxide; bromine-based flame retardants; chlorine-based flame retardants and the like, and metal hydroxides are preferred from the standpoint of toxicity. The metal hydroxide may be a metal hydroxide surface-treated with a surface treatment agent. The said flame retardant may be used independently and may be used together 2 or more types.

  As the other curing catalyst, a known curing catalyst can be widely used as long as it does not affect the performance of the adhesive, and there is no particular limitation, and examples thereof include organometallic compounds and amines, In particular, it is preferable to use a silanol condensation catalyst. Examples of the silanol condensation catalyst include titanic acid esters such as tetrabutyl titanate and tetrapropyl titanate; organoaluminum compounds such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate and diisopropoxyaluminum ethylacetoacetate; dibutyltin diacetyl Chelate compounds such as acetonate, dibutyltin diethyl acetoacetate, zirconium tetraacetylacetonate, titanium tetraacetylacetonate; dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diethylhexanoate, dibutyltin dioctate, dibutyltin dimethylmer Rate, dibutyltin diethylmalate, dibutyltin dibutylmalate, dibutyltin diisooctylmalate, dibutyltin Dialkyltin dicarboxylates such as ridecylmalate, dibutyltin dibenzylmalate, dibutyltin maleate, dioctyltin diacetate, dioctyltin distearate, dioctyltin dilaurate, dioctyltin diethylmalate, dioctyltin diisooctylmalate; Reaction products of dialkyltin oxides such as dibutyltin oxide and dioctyltin oxide and ester compounds such as dioctyl phthalate, diisodecyl phthalate and methyl maleate; and tetravalent compounds such as oxy derivatives (stannoxane compounds) of these dialkyl tin compounds Tin compounds; divalent tin compounds such as tin octylate, tin naphthenate, tin stearate and tin ferzatic acid; or reaction products and mixtures of these with amine compounds such as laurylamine Monoalkyltin compounds such as monobutyltin compounds such as monobutyltin trisoctoate and monobutyltin triisopropoxide and monooctyltin compounds; lead organic acids such as lead octylate and lead naphthenate; bismuth octylate, neodecanoic acid Examples include bismuth organic acids such as bismuth and bismuth rosinate; other acidic catalysts and basic catalysts known as silanol condensation catalysts.

  The antioxidant is used to improve the weather resistance and heat resistance by preventing oxidation of the adhesive composition, and can be added within a range that does not affect the performance of the adhesive. Examples thereof include hindered amine-based and hindered phenol-based antioxidants.

  The ultraviolet absorber is used to improve the weather resistance by preventing photodegradation of the adhesive composition, and can be added within a range that does not affect the performance of the adhesive. Benzotriazole-based, triazine-based, benzophenone-based, benzoate-based ultraviolet absorbers, and the like.

  The anti-aging agent is used to prevent heat deterioration of the adhesive composition and improve heat resistance, and can be added within a range that does not affect the performance of the adhesive. Examples thereof include an amine-ketone-based anti-aging agent, an aromatic secondary amine-based anti-aging agent, a benzimidazole-based anti-aging agent, a thiourea-based anti-aging agent, and a phosphorous acid-based anti-aging agent.

  The plasticizer is added for the purpose of improving elongation properties after curing or adjusting the hardness to reduce the modulus. The type of the plasticizer is not particularly limited. For example, phthalates such as diisoundecyl phthalate; aliphatic dibasic esters such as dioctyl adipate; glycol esters such as diethylene glycol dibenzoate Aliphatic esters such as butyl oleate; Phosphate esters such as tricresyl phosphate; Epoxy plasticizers such as epoxidized soybean oil; Polyester plasticizers; Polyethers such as polypropylene glycol derivatives Polyoxyethylene alkyl ethers such as tetraethylene glycol diethyl ether; polystyrene oligomers such as poly-α-methylstyrene; hydrocarbon oligomers such as polybutadiene; chlorinated paraffins; UP-1000 ( Acrylic plasticizers such as Toagosei Co., Ltd., UP-1080 (Toagosei Co., Ltd.), UP-1110 (Toagosei Co., Ltd.) and UP-1061 (Toagosei Co., Ltd.). Hydroxyl group-containing acrylic plasticizers such as UP-2000 (manufactured by Toagosei Co., Ltd.), UHE-2012 (manufactured by Toagosei Co., Ltd.); UC-3510 (manufactured by Toagosei Co., Ltd.), etc. Carboxyl group-containing acrylic polymers; epoxy group-containing acrylic polymers such as UG-4000 (manufactured by Toagosei Co., Ltd.); US-6110 (manufactured by Toagosei Co., Ltd.), US-6120 (manufactured by Toagosei Co., Ltd.) Acrylic polymers containing less than 0.5 silyl groups such as oxyalkylene resins containing less than 0.5 silyl groups.

  Examples of the thixotropic agent include inorganic thixotropic agents such as colloidal silica and asbestos powder, organic thixotropic agents such as organic bentonite, modified polyester polyol, and fatty acid amide, hydrogenated castor oil derivative, fatty acid amide wax, and aluminum stearylate. And barium stearylate.

  The dehydrating agent is added for the purpose of removing moisture during storage. Examples of the dehydrating agent include silane compounds such as vinyltrimethoxysilane, dimetholdimethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, zeolite, and oxidation. Examples include calcium, magnesium oxide, and zinc oxide.

  The diluent is added for the purpose of adjusting physical properties such as viscosity. As the diluent, known diluents can be widely used, and are not particularly limited. For example, saturated hydrocarbon solvents such as normal paraffin and isoparaffin, linearlen dimer (trade name of Idemitsu Kosan Co., Ltd.), etc. α-olefin derivatives, aromatic hydrocarbon solvents such as toluene and xylene, alcohol solvents such as ethanol, propanol, butanol, pentanol, hexanol, octanol, decanol, diacetone alcohol, ethyl acetate, butyl acetate, amyl acetate, Examples include various solvents such as ester solvents such as cellosolve acetate, citrate solvents such as acetyltriethyl citrate, and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone.

  The flash point of the diluent is not particularly limited, but considering the safety of the resulting adhesive composition, it is desirable that the flash point of the adhesive composition is high, and the volatile matter from the adhesive composition is low. Is preferred. Therefore, the flash point of the diluent is preferably 65 ° C. or higher. When two or more diluents are mixed and used, the flash point of the mixed diluent is preferably 65 ° C. or higher. However, since a diluent having a high flash point generally tends to have a low dilution effect on the adhesive composition, the flash point is preferably 250 ° C. or lower.

  Considering both safety and dilution effect of the adhesive composition of the present invention, a saturated hydrocarbon solvent is preferable as the diluent, and normal paraffin and isoparaffin are more preferable. The normal paraffin and isoparaffin preferably have 10 to 16 carbon atoms. Specifically, N-11 (normal paraffin, manufactured by JX Nippon Oil & Energy Corporation, carbon number 11, flash point 68 ° C), N-12 (normal paraffin, manufactured by JX Nippon Oil & Energy Corporation, carbon number) 12, flash point 85 ° C.), IP solvent 2028 (isoparaffin, manufactured by Idemitsu Kosan Co., Ltd., carbon number 10 to 16, flash point 86 ° C.) and the like.

  Examples of the adhesion-imparting agent include known silane coupling agents such as amino group-containing silanes, epoxy group-containing silanes, mercapto group-containing silanes, vinyl unsaturated group-containing silanes, isocyanate-containing silanes, and Examples include hydrosilanes.

  The method for producing the moisture curable tile adhesive composition of the present invention is not particularly limited, and for example, it can be produced by blending a predetermined amount of a compounded substance and degassing and stirring.

  The moisture-curable tile adhesive composition of the present invention can be made into a one-part type or a two-part type as required, and can be suitably used as a one-part type. The moisture-curable tile adhesive composition of the present invention can be cured at room temperature by atmospheric moisture, and is suitably used as a room temperature moisture-curable tile adhesive composition. If necessary, curing may be accelerated by heating.

  The moisture-curable tile adhesive composition of the present invention can be used for various applications such as for buildings, automobiles, civil engineering, and electrical / electronic fields, but is particularly preferably used as an adhesive for tiles. . The moisture-curable tile adhesive composition of the present invention includes an adhesive layer formed on the surface of a base material, a plurality of tiles bonded to the upper surface of the adhesive layer, and a joint gap between the plurality of tiles. Particularly suitable as an adhesive for forming an adhesive layer in a tile joint structure including an inorganic joint material filled with joints.

  In FIG. 1, the code | symbol 10 shows the tile joint structure of this invention. The tile joint structure 10 includes an adhesive layer 16 formed on the surface of the base material 18, a plurality of tiles 12 adhered to the upper surface of the adhesive layer 16, and joints 15 in the joint gaps 15 of the plurality of tiles 12. It is set as the structure containing the inorganic type joint material 14 stuffed. As the adhesive for forming the adhesive layer 16, the moisture-curable tile adhesive composition of the present invention is used.

  Although the construction method for constructing the tile joint structure of the present invention is not particularly limited, as shown in FIG. 2, the step of forming the adhesive layer 16 on the surface of the base material 18 (S20), and the adhesive Before the surface of the layer becomes tack-free, a step (S22) of bonding the plurality of tiles 12 by providing joint gaps 15 in the base material 18, and the surface of the adhesive layer 16 in the joint gap 15 is tack-free. After that, a construction method including the step (S24) of filling the joint material 14 into the joint gap 15 is suitably used. As the adhesive for forming the adhesive layer 16, the moisture-curable tile adhesive composition of the present invention is used.

  The tile 12 is not particularly limited as long as it is a tile. For example, a ceramic tile, a stone tile, an asphalt tile, a plastic tile, and a rubber tile are preferably used.

  The inorganic joint material 14 is not particularly limited as long as it is an inorganic joint material, and examples thereof include a cement joint material mainly composed of cement.

  Although there is no restriction | limiting in particular as the said base material 18, For example, mortar, concrete, wood, stone, etc. are mentioned.

  The present invention will be described more specifically with reference to the following examples. However, it is needless to say that these examples are shown by way of illustration and should not be construed in a limited manner.

(Examples 1-6)
Each compounding substance was mixed and stirred with the composition shown in Table 1 to prepare the moisture-curable tile adhesive composition of the present invention.

In Table 1, the compounding quantity of each compounding substance is shown by a mass part, and the detail of each compounding substance is as follows.
* 1) Moisture curable organic polymer A1: Trade name Cyryl SAT200 (manufactured by Kaneka Corporation, polymer having a main chain of polyoxypropylene and a dimethoxysilyl group at the molecular end)
* 2) Moisture curable organic polymer A2: Trade name MA440 (manufactured by Kaneka Corporation), polymer (MS) having a main chain of polyoxypropylene and a dimethoxysilyl group at the molecular end, and a main chain of polymethacrylate A mixture of a copolymer (MA) having a dimethoxysilyl group in the molecule (mixing ratio: MS: MA = 60: 40)).
* 3) 6-hydroxychroman derivative: trade name Irganox (registered trademark of Ciba Holding Inc.) E201, manufactured by Ciba Specialty Chemicals Co., Ltd., 3,4-dihydro-2,5,7,8-tetramethyl -2- (4,8,12-trimethyltridecyl) -2H-benzopyran-6-ol [the following formula (5)].

* 4) Plasticizer: Trade name Actol D-3000 (manufactured by Mitsui Chemicals, Inc., polyoxypropylene polymer, number average molecular weight 3000)
* 5) Filler: Product name Whiteon SB (Shiraishi Calcium Co., Ltd., calcium carbonate)
* 6) Adhesion imparting agent: trade name KBM-603 (manufactured by Shin-Etsu Chemical Co., Ltd., N-2 (aminoethyl) 3-aminopropyltrimethoxysilane)
* 7) Moisture-absorbing agent: Brand name Ethylsilicate 28 (manufactured by Colcoat Co., Tetraethoxysilane)
* 8) Non-chelating tin compound: Trade name Neostan U-700ES (manufactured by Nitto Kasei Co., Ltd., reaction product of dibutyltin oxide and normal ethyl silicate)
* 12) Non-chelated tin compound: Trade name Neostan S-1 (Nitto Kasei Co., Ltd., reaction product of dioctyltin oxide and normal ethyl silicate)

The following test was done with respect to the obtained moisture-curable tile adhesive composition. The results are shown in Table 1.
(1) Tile joint discoloration confirmation test
Apply an adhesive composition of 500 g / m ² on an ISO mortar base material (70 cm x 70 cm x 20 cm) using a standard comb iron of JIS A 5548, and immediately apply the tile (45 mm x 45 mm) as shown in Fig. 1. paste. The tile joint was filled with an inorganic joint material (cement joint material) immediately after tacking and freezing after 23 hours and 50% RH under manual pressure. The thickness of the inorganic joint material of the tile joint was 2 mm. After curing at 23 ° C. and 50% RH for 3 days, the sample was immersed in warm water at 50 ° C. for 7 days, and the discoloration of the joint part of the test body before and after immersion in the warm water was visually confirmed. The case where no discoloration was confirmed was evaluated as ◯, and the discoloration was evaluated as ×.

(2) Tack-free time
A tack-free test was conducted according to JIS A 1439 5.19. Apply the adhesive composition to the flexible board with a thickness of 3mm, and check the cured state by finger touch every 5 minutes at 23 ° C and 50% RH, and after 30-60 minutes, the adhesive composition must adhere to the finger. ○ If less than 15 to 30 minutes or more than 60 minutes to 120 minutes later if the adhesive composition does not adhere to the finger, Δ, if less than 15 minutes if the adhesive composition does not adhere to the finger × or after exceeding 120 minutes When the adhesive composition adheres, it is set as x.

(Comparative Examples 1-3)
As shown in Table 2, an adhesive composition was prepared and tested in the same manner as in Example 1 except that the compounding substances were changed. The results are shown in Table 2.

In Table 2, the compounding quantity of each compounding substance is shown by a mass part, * 1, * 3- * 8 is the same as Table 1, and the detail of another compounding substance is as follows.
* 9) Hindered phenolic antioxidants: Brand name ADK STAB AO-60 (manufactured by Adeka)
* 10) Product name Neostan U-220H (Nitto Kasei Co., Ltd., dibutyltin diacetylacetonate)
* 11) Non-chelated tin compound: Trade name Neostan U-100 (Nitto Kasei Co., Ltd., dibutyltin dilaurate)

  As shown in Table 1, in the tile joint structures shown in Examples 1 to 6, no discoloration of the joint material was observed. Also, the curing rate was good.

  As shown in Table 2, in the tile joint structures shown in Comparative Examples 1 to 3, the curing rate was good, but discoloration of the joint material was observed. In the tile joint structure shown in Comparative Example 4, no discoloration of the joint material was observed, but the curing rate exceeded 60 minutes, and the curing rate was slightly poor.

  10: Tile joint structure of the present invention, 12, 112: Tile, 14, 114: Joint material, 15, 115: Joint gap, 16, 116: Adhesive layer, 18, 118: Base material, 110: Conventional tile Joint structure.

Claims (5)

An adhesive layer formed on the surface of the base material, a plurality of tiles bonded to the upper surface of the adhesive layer, and an inorganic joint material filled with joints between joints of the plurality of tiles,
An adhesive forming the adhesive layer,
(A) a moisture curable organic polymer,
(B) a 6-hydroxychroman derivative represented by the following general formula (1), and (C) one or more non-chelating tin compounds selected from the reaction products of dialkyltin alkoxides and dialkyltin oxides and silicate compounds A tile joint structure comprising:

(In the general formula (1), R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. R ² represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms.)   The tile joint structure according to claim 1, wherein the moisture curable organic polymer (A) is a crosslinkable silyl group-containing organic polymer. A construction method for constructing the tile joint structure according to claim 1 or 2,
Forming an adhesive layer on the surface of the base material;
Before the surface of the adhesive layer becomes tack-free, a step of providing a joint gap in the base material and bonding a plurality of tiles;
After the surface of the adhesive layer of the joint gap is tack-free, filling the joint material into the joint gap,
An adhesive forming the adhesive layer,
(A) a moisture curable organic polymer,
(B) a 6-hydroxychroman derivative represented by the following general formula (1), and (C) one or more non-chelating tin compounds selected from the reaction products of dialkyltin alkoxides and dialkyltin oxides and silicate compounds A method for constructing a tile joint structure, comprising:

(In the general formula (1), R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. R ² represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms.) (A) a moisture curable organic polymer,
(B) a 6-hydroxychroman derivative represented by the following general formula (1), and (C) one or more non-chelating tin compounds selected from the reaction products of dialkyltin alkoxides and dialkyltin oxides and silicate compounds A moisture-curing tile adhesive composition comprising:

(In the general formula (1), R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. R ² represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms.)   5. The moisture-curable tile adhesive composition according to claim 4, wherein the (A) moisture-curable organic polymer is a crosslinkable silyl group-containing organic polymer.

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