JP6913891B1 - Tile construction method and adhesive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a tile construction method capable of enhancing the durability of an adhered tile against vibration and linear expansion of a construction surface and having excellent stain resistance of an adhesive layer. SOLUTION: In a tile construction method, a tile is adhered to a construction surface with an adhesive composition having a storage elastic modulus of 1.0 MPa or more and 10 MPa or less after curing. [Selection diagram] Fig. 1

Description

The present disclosure relates to a tile construction method and an adhesive composition, and more particularly to a tile construction method for adhering tiles to a construction surface and an adhesive composition having specific characteristics.

When a tile is attached to a construction surface such as a wall surface having a non-landing surface, the non-landing adjusting layer is formed using the non-landing adjusting composition, and then the tile is adhered (Patent Document 1 and Patent). Reference 2). As the composition for adjusting non-landing, Patent Document 1 describes that the maximum tensile strength of the cured product is 0.6 N / mm ² or more and the elongation at break is 35% or more. It is disclosed that the maximum tensile strength of the cured product is 0.4 to 2.0 N / mm ² , and the elongation at break is 40 to 200%. It is said that by using such a non-landing adjusting composition, tiles can be stretched on the wall surface with excellent adhesion and followability.

Japanese Unexamined Patent Publication No. 2017-43975 Japanese Unexamined Patent Publication No. 2013-32675

However, according to the findings obtained as a result of the inventor's research and development, a cured product having the same tensile strength and breaking elongation as the non-landing adjusting composition disclosed in Patent Document 1 and Patent Document 2 is provided. When tiles are adhered to a wall surface using an adhesive composition, the adhered tiles may peel off or crack due to vibration caused by an earthquake on the wall surface or linear expansion due to daily temperature changes. There was a problem with durability. In addition, the adhesive composition used for adhering tiles is also required to have excellent stain resistance because it can suppress adhesion of foreign substances and the like to the adhesive layer exposed at the joints between the attached tiles. ..

An object of the present disclosure is to provide a tile construction method and an adhesive composition which can enhance the durability of a tile adhered to a construction surface such as a wall surface and have excellent stain resistance of an adhesive layer.

In the tile construction method according to one aspect of the present disclosure, the tile is adhered to the construction surface with an adhesive composition having a storage elastic modulus of 1.5 MPa or more and 10 MPa or less at 23 ° C. after curing. The adhesive composition is at least one of a composition that cures with moisture in the air and a composition that cures with heat.

The adhesive composition according to one aspect of the present disclosure has an adhesive strength of 0.3 N / mm ² or more and a cohesive fracture rate of 75% or more measured in accordance with JIS-A5557: 2010, and after curing. 23 Ri 10MPa der following storage modulus 1.5 MPa or more at ° C., is at least one of the composition is cured by moisture in the air and compositions that cure by heat, Ru is used for bonding the tiles.

According to the present disclosure, it is possible to provide a tile construction method and an adhesive composition which can enhance the durability of the adhered tile against vibration and linear expansion of a wall surface and have excellent stain resistance of the adhesive layer.

FIG. 1 is a schematic cross-sectional view of a wall structure formed by the tile construction method according to the embodiment of the present disclosure. FIG. 2 is a schematic cross-sectional view of a test piece used for an in-plane shear test.

In the tile construction method according to the present embodiment, a tile is formed on a construction surface having a seam by using an adhesive composition (hereinafter, also referred to as composition (X)) having a storage elastic modulus of 1.0 MPa or more and 10 MPa or less after curing. Glue.

In the bonding of tiles to the construction surface, the present inventors have applied stress generated to the tiles due to displacement of the construction surface due to vibration due to an earthquake or the like or linear expansion due to daily temperature changes, and after curing of the adhesive composition. It was found that there is a relationship with the storage elastic modulus of. That is, if the storage elastic modulus after curing is 10 MPa or less, it is considered that the stress applied to the tile is sufficiently relaxed, and the tile may peel off without being able to withstand the stress caused by vibration or linear expansion of the construction surface. , Cracking can be suppressed, and as a result, the durability of the adhered tile can be improved. If the storage elastic modulus after curing exceeds 10 MPa, it is considered that the stress caused by vibration and linear expansion of the construction surface is insufficiently relaxed, and the stress transmitted to the tile may become too large. There is a risk that peeling and cracking cannot be sufficiently suppressed. In particular, on a construction surface having a seam, strain stress due to displacement is concentrated on the seam portion, so that the effect of suppressing tile peeling and cracking due to stress relaxation is remarkable.

Further, the present inventors have found that there is a relationship between the storage elastic modulus of the composition (X) after curing, the surface tackiness of the adhesive layer to be formed, and the adhesiveness of foreign substances and the like. .. That is, when the storage elastic modulus after curing is 1.0 MPa or more, the surface tackiness of the adhesive layer containing the cured product of the adhesive composition is low, the adhesiveness of foreign substances and the like is suppressed, and good stain resistance. Is obtained. If the storage elastic modulus after curing is less than 1 MPa, the surface tackiness of the adhesive layer becomes large, and there is a possibility that the adhesion of foreign matter or the like cannot be sufficiently prevented.

Here, the "construction surface" is a structural surface of a building to be constructed by attaching tiles, and specifically, in a building such as an inner / outer wall surface, a floor surface, a ceiling surface, and a partition wall surface of the building. Exposed surface, including vertical wall surface, inclined wall surface, horizontal wall surface, etc. In addition, the construction surface includes those under repair.

Hereinafter, a case where tiles are installed on the wall surface as a construction surface will be described.

In the tile construction method according to the present embodiment, for example, first, the composition (X) is applied to the entire surface or a part of the wall surface. The thickness of the composition (X) applied is, for example, 0.1 mm or more and 5 mm or less, and preferably 1 mm or more and 3 mm or less. Next, tiles are placed on the surface of the applied composition (X). This gives a wall-tile bond. In this case, the composition (X) may or may not be applied to the surface of the tile. Then, preferably, the composition (X) is cured. In the case of a composition in which the composition (X) is cured by the humidity in the air, the curing treatment is performed by curing the wall surface-tile adhesive for a predetermined time under a predetermined temperature and humidity condition, and also by curing the composition (X). ) Is a heat-curable composition, it is carried out by heating the wall-tile adhesive body at a predetermined temperature for a predetermined time. In this way, the tile can be glued to the wall surface.

The effect of the tile construction method according to the present embodiment becomes remarkable by applying it to a wall surface having a seam. In this case, the tiles may be overlapped and glued to the seams. According to the tile construction method according to the present embodiment, since the composition (X) is used, the adhesive layer formed by the composition (X) when the wall surface moves at the seam portion even when the wall surface has a seam. Is suitable for stress relaxation, so that it is possible to prevent the tile from peeling or cracking. That is, as a result, the durability of the bonded tile can be increased. Here, the "seam" means a portion where two things (wall base material, etc.) are joined together, but also includes, for example, a cracked portion on the wall surface. At the seams, the two spliced objects may be in contact with each other or apart from each other and there may be a gap between them.

The seam may include a sealing portion filled with a sealing material. In this case, the tile may be overlapped and adhered to the sealing portion. According to the tile construction method according to the present embodiment, since the composition (X) is used, even when the wall surface has a sealing portion, the durability of the tile bonded across the sealing portion can be enhanced, for example, in-plane. In the shear test, it is possible to suppress cracking of tiles adhered across the sealing portion.

In the tile construction method according to the present embodiment, the tiles may be bonded at intervals of joints. In this case, the joints may or may not be sealed. According to the tile construction method according to the present embodiment, by using the composition (X) having excellent stain resistance, foreign matter or the like adheres to the adhesive layer exposed to the joints even if the joints between the tiles are not sealed. Can be suppressed.

The wall structure formed by the tile construction method according to the present embodiment includes a wall surface, an adhesive layer formed on the wall surface, and tiles fixed to the adhesive layer. The adhesive layer contains a cured product of the composition (X).

FIG. 1 shows a cross-sectional view of an example of a wall structure 1 formed by the tile construction method according to the present embodiment. The wall structure 1 includes a wall base material 2, a sealing portion 3 existing at a joint between the wall base materials 2, an adhesive layer 4 formed on the wall base material 2 and the sealing portion 3, and an adhesive layer 4. Includes a plurality of tiles 5 fixed to. The plurality of tiles 5 are fixed at intervals of joints from each other. The adhesive layer 4 contains a cured product of the composition (X). The adhesive layer 4 is formed so as to be overlapped with at least the sealing portion 3. The tile 5 overlaps the sealing portion 3 via the adhesive layer 4. Even in such a case, by using the composition (X), it is possible to suppress cracking of the tiles adhered across the sealing portion. Further, in the wall structure 1 of FIG. 1, since the joints 6 between the tiles are not sealed, a part of the adhesive layer 4 is exposed to the joints 6. Even in such a case, by using the composition (X) having excellent stain resistance, it is possible to suppress the adhesion of foreign matter or the like to the adhesive layer exposed at the joints of the tiles.

Examples of the wall base material 2 include porous panels such as siding boards, mortar, and stone materials. Examples of the sealing material that gives the sealing portion 3 include various sealing material compositions such as silicone-based, polyisobutylene-based, modified silicone-based, and polyurethane-based. Examples of the tile 5 include exterior tiles, interior tiles, mosaic tiles, acid-resistant tiles, and the like.

[Adhesive composition]
The composition (X) has a storage elastic modulus of 1.0 MPa or more and 10 MPa or less after curing.

(Storage modulus)
The storage elastic modulus of the composition (X) after curing is 1.0 MPa or more and 10 MPa or less. When the storage elastic modulus is 10 MPa or less, the durability of the adhered tile against, for example, vibration of the wall surface or linear expansion can be enhanced. The storage elastic modulus is preferably 8 MPa or less, more preferably 6 MPa or less, and even more preferably 5 MPa or less. Further, when the storage elastic modulus is 1.0 MPa or more, for example, the stain resistance of the cured product of the composition (X) can be made excellent. The storage elastic modulus is preferably 2 MPa or more, more preferably 3 MPa or more, and even more preferably 4 MPa or more.

Here, the storage elastic modulus of the composition (X) after curing is obtained by performing a dynamic viscoelasticity test on the cured product of the composition (X). In the dynamic viscoelasticity test, the composition (X) is cured to prepare a test piece, and the storage elastic modulus (MPa) at 23 ° C. is measured. The method for measuring the storage elastic modulus will be described in the column of Examples described later.

In the present embodiment, as will be described later, such a storage elastic modulus can be realized by the composition of the composition (X).

(Elongation rate at break)
The elongation at break after curing of the composition (X) is preferably 80% or more, more preferably 100% or more, and even more preferably 120% or more. When the elongation at break is 80% or more, the adhesive layer can more closely follow the distortion caused by the movement caused by the vibration of the wall surface and the linear expansion, and the peeling and cracking of the tile can be further suppressed. The upper limit of the elongation at break is not particularly limited, but 200% is sufficient.

Here, the elongation at break after curing of the composition (X) can be obtained by performing a tensile test on the cured product of the composition (X). In the tensile test, the composition (X) is cured to prepare a test piece, and the elongation at break (%) is measured according to the JIS A5557 6.3.4 film physical characteristic test method. The method for measuring the elongation at break will be described in the column of Examples described later.

(Tensile strength)
Tensile strength after curing of the composition (X), it is preferably, more preferably 0.80 N / mm ² or more, 0.90 N / mm ² or more and 0.60N / mm ² or more Is even more preferable. When the tensile strength is 0.60 N / mm ² or more, the occurrence of tack on the adhesive layer is further suppressed, so that the adhesiveness of foreign substances can be further reduced and the stain resistance can be further improved. The upper limit of the tensile strength is not particularly limited, but is, for example, 1.50 N / mm ² .

Here, the tensile strength of the composition (X) after curing is obtained by performing a tensile test on the cured product of the composition (X). In the tensile test, the composition (X) is cured to prepare a test piece, and the tensile strength (N / mm ² ) is measured according to the JIS A5557 6.3.4 film physical characteristic test method. The method for measuring the tensile strength will be described in the column of Examples described later.

(Adhesive strength)
The adhesive strength of the composition (X) ^{is preferably 0.3 N / mm 2} or more. In this case, the durability of the tile adhered to the wall surface can be further improved. Adhesive strength is more preferably 0.6 N / mm ² or more, still more preferably 0.7 N / mm ² or more, and particularly preferably 0.8N / mm ² or more.

(Coagulation fracture rate)
The cohesive failure rate of the composition (X) is preferably 75% or more. In this case, the durability of the tile adhered to the wall surface can be further improved. The cohesive fracture rate is more preferably 85% or more, further preferably 95% or more, and particularly preferably 100%.

Here, the adhesive strength and the cohesive fracture rate of the composition (X) are values measured by an adhesive strength test based on JIS-A5557: 2010. The method for measuring the adhesive strength and the cohesive fracture rate will be described in the column of Examples described later.

The composition (X) is a composition that is cured by moisture in the air (hereinafter, also referred to as composition (X1)) or a composition that is cured by heat (hereinafter, also referred to as composition (X2)) depending on the curing method. ). Since the composition (X1) can be cured by moisture in the air, this allows for easier on-site construction. Since the composition (X2) can be cured by heating, it can be applied in a shorter time.

[Composition that cures with moisture in the air (X1)]
Examples of the composition (X1) include a composition containing a polymer having a crosslinkable silyl group (hereinafter, also referred to as polymer (A)) (hereinafter, also referred to as composition (X11)).

In addition to the polymer (A), the composition (X11) contains, for example, an adhesion-imparting agent (B), a curing agent for epoxy compounds (C), a plasticizer (D), a filler (E), and a catalyst (F). , Additive (G) and the like may be contained.

(Polymer (A))
The polymer (A) has a crosslinkable silyl group. The crosslinkable silyl group is a group having a silicon atom and a hydrolyzable group bonded to the silicon atom. In one crosslinkable silyl group, for example, 1 to 3 hydrolyzable groups are bonded to one silicon atom. Examples of the hydrolyzable group include a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an acid amide group, an aminooxy group, a mercapto group, an alkenyloxy group and the like. The hydrolyzable group preferably contains an alkoxy group. That is, the crosslinkable silyl group preferably contains an alkoxysilyl group.

Examples of the alkoxysilyl group include a trialkoxysilyl group such as a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, and a triphenoxysilyl group; a dialkoxysilyl group such as a dimethoxymethylsilyl group and a diethoxymethylsilyl group. Examples thereof include monoalkoxysilyl groups such as methoxydimethylsilyl groups and ethoxydimethylsilyl groups. The alkoxysilyl group preferably contains at least one of a dialkoxysilyl group and a trialkoxysilyl group, and more preferably contains at least one of a dimethoxymethylsilyl group and a trimethoxysilyl group.

The polymer (A) may have various skeletons as long as it has a crosslinkable silyl group. The polymer (A) may have, for example, a polyoxylen skeleton, a vinyl-modified polyoxylen skeleton, a poly (meth) acrylate skeleton, a skeleton containing a vinyl-based polymer, a polyester skeleton, or the like. The skeleton of the polymer (A) may contain an organosiloxane.

The polymer (A) preferably has at least one of a polyoxylene skeleton and a poly (meth) acrylate skeleton. That is, the polymer (A) preferably contains at least one of a polymer having a polyoxylene skeleton (A1) and a polymer having a poly (meth) acrylate skeleton (A2). In this case, the composition (X11) tends to have higher adhesiveness to the sealing portion and the like. In particular, when the polymer (A) is a polymer (A2) having a poly (meth) acrylate skeleton, the composition (X11) and its cured product tend to have better weather resistance and UV resistance. The (meth) acrylate skeleton is composed of at least one of an acrylate skeleton and a methacrylate skeleton. The composition (X11) may contain both the polymer (A1) and the polymer (A2).

(Polymer (A1))
The polymer (A1) has, for example, a polyoxylen skeleton and a crosslinkable silyl group bonded to the polyoxylen skeleton. The polymer (A1) has at least one crosslinkable silyl group per molecule. The crosslinkable silyl group may be bonded as a side chain in the middle of the polyoxylen skeleton, or may be bonded to the end of the polyoxylen skeleton. The crosslinkable silyl group may be bonded to the end of the polyoxylen skeleton via a urethane bond or the like.

Examples of the polyoxylen skeleton include a polyoxyalkylene skeleton and a polyoxyylene skeleton. The polyoxylen skeleton is represented by the formula- (RO) n-, for example. R is, for example, an alkylene group or an arylene group, and the alkylene group has, for example, 1 or more and 14 or less carbon atoms, and the arylene group has, for example, 6 or more and 14 or less carbon atoms. n is a natural number of 2 or more. A plurality of Rs in one polio skeleton may be the same as or different from each other.

The polyoxylen skeleton has a constituent unit such as an ethylene oxide unit, a propylene oxide unit, a butylene oxide unit, a tetramethylene oxide unit, and a phenylene oxide unit.

The polyoxylen skeleton is a bifunctional one using ethylene glycol as a starting material (linear polyoxylen skeleton) and a trifunctional one using 2-hydroxymethylpropane-1,3-diol as a starting material (branched). It is preferable to contain at least one of the polyoxylene skeletons).

The weight average molecular weight of the polymer (A1) is preferably 8000 or more and 25000 or less. When the weight average molecular weight is 8000 or more, the cured product of the composition (X11) tends to have better flexibility. Further, when the weight average molecular weight is 25,000 or less, the viscosity of the composition (X11) is unlikely to increase, and therefore the coatability of the composition (X11) tends to be improved. The weight average molecular weight is more preferably 15,000 or more and 20,000 or less. The weight average molecular weight is a value obtained in terms of styrene from the measurement result by GPC (gel permeation chromatography).

(Polymer (A2))
The polymer (A2) has a poly (meth) acrylate skeleton and a crosslinkable silyl group bonded to the poly (meth) acrylate skeleton. The polymer (A2) has at least one crosslinkable silyl group per molecule. The crosslinkable silyl group may be bonded as a side chain in the middle of the poly (meth) acrylate skeleton, or may be bonded to the end of the poly (meth) acrylate skeleton. It is preferable that one crosslinkable silyl group is bonded to one end of the poly (meth) acrylate backbone and one or more crosslinkable silyl groups are bonded to the side chain. When crosslinkable silyl groups are bonded only to both ends of the poly (meth) acrylate skeleton, the cured product tends to become hard due to the influence of post-crosslinking, and the crosslinkable silyl is applied only to the side chain of the poly (meth) acrylate skeleton. When the groups are bonded, hydrolysis of the acrylic side chain may cause a decrease in the strength of the cured product.

The poly (meth) acrylate skeleton has a structure in which an unsaturated monomer containing a (meth) acrylic compound is polymerized. The (meth) acrylic compound comprises at least one of an acrylic compound and a methacrylic compound. Examples of the (meth) acrylic compound include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and (meth). ) Isobutyl acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, neopentyl (meth) acrylate, n-hexyl (meth) acrylate, (meth) ) N-Heptyl acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, (meth) acrylic Alkyl (meth) acrylates such as dodecyl acid, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate; cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, (meth) acrylic (Meta) acrylic acid alicyclic alkyls such as tricyclodecynyl acid; (meth) acrylic acid aromatic esters such as (meth) phenyl acrylate, (meth) toluyl acrylate, benzyl (meth) acrylate, (meth). ) Hydroxyethyl acrylate, hydroxypropyl (meth) acrylate, hydroxyalkyl (meth) acrylate such as hydroxybutyl (meth) acrylate; 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate , (Meta) 2-aminoethyl acrylate, (meth) dimethylaminoethyl acrylate, (meth) chloroethyl acrylate, (meth) trifluoroethyl acrylate, (meth) trifluoromethylmethyl acrylate, (meth) acrylic Examples thereof include heteroatom-containing (meth) acrylic acid esters such as tetrahydrofurfuryl acid acid and ε-caprolactone addition reaction products of hydroxyethyl (meth) acrylate. The components that can be contained in the (meth) acrylic compound are not limited to the above.

The unsaturated monomer constituting the poly (meth) acrylate skeleton may contain only the (meth) acrylic compound, or may contain the (meth) acrylic compound and other monomers. Examples of monomers other than the (meth) acrylic compound include styrene, inden, α-methylstyrene, p-methylstyrene, p-chlorostyrene, p-chloromethylstyrene, p-methoxystyrene, and p-tert-butoxystyrene. , Styrene derivatives such as divinylbenzene; compounds having a vinyl ester group such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl benzoate, vinyl cinnate; maleic anhydride, N-vinylpyrrolidone, N-vinyl Morpholine, methacrylonitrile, acrylonitrile, acrylamide, methacrylicamide, N-cyclohexyl maleimide, N-phenylmaleimide, N-lauryl maleimide, N-benzyl maleimide; n-propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether , Tert-Amil vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, 2-chloroethyl vinyl ether, ethylene glycol butyl vinyl ether, triethylene glycol methyl vinyl ether, butyl benzoate (4-vinyloxy), ethylene glycol divinyl ether. , Diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, butane-1,4-diol-divinyl ether, hexane-1,6-diol-divinyl ether, cyclohexane-1,4-dimethanol-divinyl ether , Di (4-vinyloxy) butyl isophthalate, di (4-vinyloxy) glutarate, di (4-vinyloxy) succinate butyl trimethyl propantrivinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 6- Compounds having a vinyloxy group such as hydroxyhexyl vinyl ether, cyclohexane-1,4-dimethanol monovinyl ether, diethylene glycol monovinyl ether, 3-aminopropyl vinyl ether, 2- (N, N-diethylamino) ethyl vinyl ether, urethane vinyl ether, polyester vinyl ether, etc. Can be mentioned.

The weight average molecular weight of the polymer (A2) is preferably 10,000 or more and 70,000 or less. When the weight average molecular weight is 10,000 or more, the cured product of the composition (X11) tends to have better flexibility. Further, when the weight average molecular weight is 70,000 or less, the viscosity of the composition (X11) is unlikely to increase, and therefore the coatability of the composition (X11) tends to be improved. The weight average molecular weight is more preferably 20,000 or more and 60,000 or less. The weight average molecular weight is a value obtained in terms of styrene from the measurement result by GPC (gel permeation chromatography).

The number of crosslinkable silyl groups per molecule of the polymer (A) is preferably 1.3 or more. In this case, the degree of cross-linking between the polymer (A) molecules after curing becomes higher, and the storage elastic modulus and tensile strength of the composition (X11) after curing can be further increased. The number of crosslinkable silyl groups is more preferably 1.5 or more, and even more preferably 2.0 or more. The upper limit of the number of crosslinkable silyl groups is not particularly limited, but is, for example, three.

The polymer (A) preferably contains a polymer (A1) having at least one of a polyoxylene skeleton and a poly (meth) acrylate skeleton and 1.3 or more crosslinkable silyl groups in one molecule.

The ratio of the polymer (A) to the entire composition (X11) is preferably 10% by mass or more and 50% by mass or less. In this case, the curability of the composition (X11) due to moisture in the air can be further improved. The proportion of the polymer (A) is more preferably 15% by mass or more and 40% by mass or less, and further preferably 20% by mass or more and 35% by mass or less.

(Adhesion imparting agent (B))
The adhesion-imparting agent (B) is a substance for enhancing the adhesion of the composition (X11). The composition (X11) can further improve the adhesiveness by containing the adhesion imparting agent (B).

Examples of the adhesion-imparting agent (B) include epoxy compounds, aminosilane compounds, triazine-based compounds, and imidazole-based compounds. The adhesion-imparting agent (B) preferably contains at least one of an epoxy compound and an aminosilane compound. That is, the composition (X11) preferably contains at least one of an epoxy compound and an aminosilane compound.

(Epoxy compound)
Epoxy compounds have at least one epoxy group in one molecule. By containing the epoxy compound as the adhesion imparting agent (B) in the composition (X11), the adhesiveness of the cured product can be further improved. Examples of the epoxy compound include bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, glycidyl ester type epoxy resin, novolak type epoxy resin, and urethane modified epoxy resin. Epoxy such as nitrogen-containing epoxy resin obtained by epoxidizing metaxylene diamine and hydantin, polybutadiene skeleton epoxy resin, NBR (acrylonitrile-butadiene copolymer) skeleton epoxy resin, rubber-modified epoxy resin, and epoxy resin having a long-chain aliphatic skeleton. Resin; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylethyldiethoxysilane, 2- (3,4-) Epoxycyclohexyl) Epoxysilanes such as ethyltrimethoxysilane can be mentioned. Epoxy resin is a compound having two or more epoxy groups in one molecule. The components contained in the epoxy compound are not limited to the above.

The ratio of the epoxy compound to 100 parts by mass of the polymer (A1) is preferably 0.1 parts by mass or more and 10 parts by mass or less. In this case, the flexibility of the cured product of the composition (X11) can be further improved. The proportion of the epoxy compound is more preferably 0.5 parts by mass or more and 6 parts by mass or less, and further preferably 1 part by mass or more and 4 parts by mass or less.

(Aminosilane compound)
The aminosilane compound is a silane compound having an amino group. By containing the aminosilane compound as the adhesion imparting agent (B) in the composition (X11), the adhesiveness of the cured product can be further improved. Further, by using the aminosilane compound as the adhesion imparting agent (B), the composition (X11) can be prevented from containing the epoxy compound, and the cured product of the composition (X11) can be stored when immersed in warm water. Changes in elastic modulus can be suppressed. Examples of the aminosilane compound include 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, and the like.

The ratio of the aminosilane compound to 100 parts by mass of the polymer (A1) is preferably 0.1 parts by mass or more and 6 parts by mass or less. In this case, the flexibility of the cured product of the composition (X11) can be further improved. The proportion of the aminosilane compound is more preferably 0.5 parts by mass or more and 4 parts by mass or less, and further preferably 1 part by mass or more and 3 parts by mass or less.

(Curing agent for epoxy compound (C))
The curing agent (C) is not particularly limited as long as it is a compound capable of curing the epoxy compound. When the composition (X11) contains an epoxy compound, for example, as an adhesion-imparting agent (B), it preferably contains a curing agent (C). By containing the curing agent (C), the composition (X11) can further improve the curability due to moisture in the air.

Examples of the curing agent (C) include ketimine compounds, phenolic curing agents, acid anhydrides, amines, imidazoles, hydrazides, polyethercaptans, Lewis acid-amine complexes and the like. The curing agent (C) preferably contains a ketimine compound. That is, the composition (X11) preferably contains an epoxy compound and a ketimine compound. In this case, the composition (X11) can further suppress deterioration during storage.

The ketimine compound is a compound having a ketimine structure. The ketimine compound is synthesized, for example, by a dehydration condensation reaction between an amine compound having a primary amino group and a ketone compound.

The ketimine compound is difficult to react with the epoxy compound as it is, but the ketimine compound is hydrolyzed to produce a primary amine, and the primary amine reacts with the epoxy compound to cure the composition (X11). Therefore, when the composition (X11) is stored, the curing reaction of the composition (X11) does not easily proceed, so that the composition (X11) can be liquefied.

The ketimine compound can include at least one of a ketimine compound having a hydrolyzable silyl group and a ketimine compound having no hydrolyzable silyl group. When the ketimine compound particularly contains a ketimine compound having a hydrolyzable silyl group, the crosslinkable silyl group of the polymer (A) and the crosslinkable silyl group of the ketimine compound can react to form a crosslinked structure. Therefore, the curability of the composition (X11) is increased. However, if the composition (X11) has sufficient curability even if a crosslinked structure is not formed between the polymer (A) and the ketimine compound, the ketimine compound is a ketimine compound having a hydrolyzable silyl group. Does not necessarily have to be included.

A ketimine compound having a hydrolyzable silyl group is synthesized, for example, by a dehydration condensation reaction between an amine compound having at least one crosslinkable silyl group and at least one primary amino group and a ketone compound. The amine compound has, for example, _{a structure of X-R "-NH 2.} X is a crosslinkable silyl group. R" is a divalent hydrocarbon group. The carbon number of R "is, for example, 1 or more and 10 or less. Examples of the ketone compound include cyclic ketones such as cyclopentanone, trimethylcyclopentanone, cyclohexanone, methylcyclohexanone, and trimethylcyclohexanone; acetone, methylethylketone, methylpropylketone, and methyl. Aliphatic ketones such as isopropyl ketone, methyl isobutyl ketone, methyl-tert-butyl ketone, diethyl ketone, dipropyl ketone, diisopropyl ketone, dibutyl ketone and diisobutyl ketone; aromatic ketones such as acetophenone, benzophenone and propiophenone can be mentioned. ..

Examples of the ketimine compound having no hydrolyzable silyl group include 2,5,8-triaza-1,8-nonadiene and 2,10-dimethyl-3,6,9-triaza-2,9-undecadiene, 2. , 10-Diphenyl-3,6,9-Triaza-2,9-Undecadien, 3,11-dimethyl-4,7,10-Triaza-3,10-Tridecadien, 3,11-diethyl-4,7,10 -Triaza-3,10-Tridecadien, 2,4,12,14-Tetramethyl-5,8,11-Triaza-4,11-Pentadecadene, 2,4,20,22-Tetramethyl-5,12 , 19-Triaza-4,19-Trieicosaziene, 2,4,5,17-Tetramethyl-5,8,11,14-Tetraaza-4,14-Octadecadene and the like. The components contained in the ketimine compound having no hydrolyzable silyl group are not limited to the above.

The molar ratio of the ketimine structure of the ketimine compound to the epoxy group of the epoxy compound as the adhesion-imparting agent (B) is preferably 0.4 or more and 0.8 or less. In this case, it is possible to suppress a change in the storage elastic modulus of the cured product of the composition (X11) when immersed in warm water. The molar ratio of the ketimine structure of the ketimine compound to the epoxy group of the epoxy compound (number of mol parts of ketimine / number of mol parts of epoxy group) is the primary amine generated when all the ketimine compounds are hydrolyzed to the epoxy group of the epoxy compound. It can be said that it is the molar ratio of the primary amino group having. This molar ratio is more preferably 0.45 or more and 0.75 or less, and further preferably 0.45 or more and 0.6 or less. When the epoxy compound contains a plurality of different types of epoxy compounds, the epoxy group of the epoxy compound is the total number of epoxy groups of the plurality of types of epoxy compounds. When the ketimine compound contains a plurality of different types of ketimine compounds, the ketimine structure of the ketimine compound is the total number of ketimine structures of the plurality of types of ketimine compounds. From these facts, it is possible to calculate the molar ratio of the ketimine structure of the ketimine compound to the epoxy group of the epoxy compound even when a plurality of different kinds of epoxy compounds and ketimine compounds are contained.

(Plasticizer (D))
The composition (X11) may contain a plasticizer (D). By containing the plasticizer (D) in the composition (X11), the flexibility of the cured product can be further improved. Further, the composition (X11) can reduce the viscosity by containing the plasticizer (D), and therefore can improve the coatability.

Examples of the plasticizer (D) include phosphoric acid ester, phthalate ester, aliphatic monobasic acid ester, aliphatic dibasic acid ester, polyalkylene glycol, aliphatic ester, epoxy plasticizer, polyester plasticizer, and polyether. , Polysyl, (meth) acrylic polymer and the like.

Examples of the phthalate ester include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dinormal hexyl phthalate, bis (2-ethylhexyl) phthalate, dinormal octyl phthalate, diisononyl phthalate, and phthalic acid. Examples thereof include dinonyl, diisodecyl phthalate, diisoundecyl phthalate, and bisbutylbenzyl phthalate.

Examples of the polyalkylene glycol include diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, polypropylene glycol and the like.

The (meth) acrylic polymer is a polymer of unsaturated monomers containing at least one of an acrylic compound and a methacrylic compound. Examples of the (meth) acrylic polymer include polymers of unsaturated monomers containing (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylonitrile, (meth) acrylamide and the like. The unsaturated monomer may contain at least one of an acrylic compound and a methacrylic compound, and may contain a vinyl-based monomer or the like other than these.

The plasticizer (D) may or may not have a crosslinkable silyl group.

The plasticizer (D) preferably contains at least one of polypropylene glycol having a weight average molecular weight of 1000 or more and 5000 or less and a (meth) acrylic polymer. In this case, it is easier to reduce the viscosity of the composition (X11) and improve the flexibility of the cured product. Further, the plasticizer (D) is less likely to elute into water, so that the cured product is less likely to become brittle even when the cured product is exposed to water. When the weight average molecular weight is 1000 or more, the plasticizer (D) is particularly difficult to elute in water. Further, when the weight average molecular weight is 5000 or less, it is easier to reduce the viscosity of the composition (X11) and improve the flexibility of the cured product. The weight average molecular weight is more preferably 1500 or more and 4000 or less, and further preferably 2000 or more and 3000 or less. The weight average molecular weight is a value obtained in terms of styrene from the measurement result by GPC (gel permeation chromatography).

The ratio of the plasticizer (D) to 100 parts by mass of the polymer (A1) is preferably 30 parts by mass or more and 80 parts by mass or less. When this ratio is 30 parts by mass or more, it is particularly easy to reduce the viscosity of the composition (X11) and improve the flexibility of the cured product. Further, when this ratio is 80 parts by mass or less, better curability of the composition (X11) can be easily ensured. This ratio is more preferably 40 parts by mass or more and 75 parts by mass or less, and further preferably 45 parts by mass or more and 60 parts by mass or less.

(Filler (E))
The composition (X11) may contain a filler (E). The fluidity of the composition (X11) can be controlled by adjusting the amount of the filler (E), for example, the fluidity can be made more suitable for the adhesive composition. Further, the filler (E) may contain a pigment. In that case, the composition (X11) and the cured product can be colored with the pigment.

Examples of the filler (E) include heavy calcium carbonate, light calcium carbonate, magnesium carbonate, hydrous silicic acid, silicic acid anhydride, calcium silicate, silica, fumed silica, titanium dioxide, clay, talc, carbon black, and glass. Examples include balloons. The filler (E) may be subjected to surface treatment such as fatty acid treatment or hydrophobization in order to improve dispersibility.

The ratio of the filler (E) to 100 parts by mass of the polymer (A) is preferably 50 parts by mass or more and 300 parts by mass or less, and more preferably 100 parts by mass or more and 200 parts by mass or less.

(Catalyst (F))
The composition (X11) may contain a catalyst (F) that promotes the reaction of crosslinkable silyl groups. Examples of the catalyst (F) include 1,1,3,3-tetrabutyl-1,3-dilauryloxycarbonyl-distanoxane, dibutyltin dilaurate, dibutyltin oxide, dibutyltin diacetate, and dibutyltin phthalate bis (dibutyltin laurin). Acid) Oxide, dibutyltin bisacetylacetonate, dibutyltin bis (monoestermalate), tin octylate, dibutyltin octate, dibutyltin dioctate, dioctylate oxide, tin compound having an alkoxysilyl group, stanas octoate, Organic tin compounds such as dibutyltin maleate, dibutyltin bistriethoxysilicate, dibutyltin distearate, dioctyltin dilaurate, dioctyltin diversate, tin naphthenate; reactants of dibutyltin oxide and phthalate ester; tetrabutyl titanate, tetrapropyl titanate , Tetra-n-butoxytitanate, tetraisopropoxytitanate and other phthalates; organoaluminum compounds such as aluminum trisacetylacetonate, aluminumtrisethylacetate, diisopropoxyaluminum ethylacetate; zirconium tetraacetylacetonate, titanium Chelate compounds such as tetraacetylacetonate; lead octylate; dibutylamine-2-ethylhexoate and the like can be mentioned.

The ratio of the catalyst (F) to 100 parts by mass of the polymer (A) is preferably 0.01 parts by mass or more and 1 part by mass or less, and more preferably 0.05 parts by mass or more and 0.5 parts by mass or less. preferable.

(Additive (G))
The composition (X11) may contain components other than the above as the additive (G). Examples of the additive (G) include a dehydrating agent, a light stabilizer, an ultraviolet absorber, an aggregate, an antioxidant, an antioxidant, a solvent, a fragrance and the like.

When the composition (X11) contains at least one of a light stabilizer and an ultraviolet absorber, the light resistance and UV resistance of the composition (X11) and its cured product tend to be enhanced. Examples of the light stabilizer include a hindered amine-based light stabilizer (HALS) such as bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate. Examples of the ultraviolet absorber include a benzotriazole-based ultraviolet absorber, a triazine-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, a benzoate-based ultraviolet absorber, and the like.

The conditions for curing the composition (X1) are, for example, a temperature of 0 ° C. or higher and 50 ° C. or lower, a humidity of 20% RH or higher and 100% RH or lower, a time of 1 hour or longer and 1 year or lower, a temperature of 20 ° C. or higher and 30 ° C. or lower, and a humidity of 40. It is preferably% RH or more and 70% RH or less, and the time is preferably 20 days or more and 40 days or less.

[Composition that cures with heat (X2)]
Examples of the composition (X2) include a composition containing a thermosetting resin (hereinafter, also referred to as resin (P)) (hereinafter, also referred to as composition (X21)).

The composition (X21) may contain, for example, an epoxy resin curing agent (Q) in addition to the resin (P).

(Resin (P))
The resin (P) is a thermosetting resin. Examples of the resin (P) include epoxy resin, urethane resin, phenol resin, acrylic resin, unsaturated polyester resin and the like.

The ratio of the resin (P) to the entire composition (X21) is preferably 10% by mass or more and 70% by mass or less. In this case, the heat curability of the composition (X21) can be further improved. The proportion of the resin (P) is more preferably 20% by mass or more and 60% by mass or less, and further preferably 30% by mass or more and 50% by mass or less.

The resin (P) preferably contains an epoxy resin. In this case, the composition (X21) can further improve the adhesiveness.

(Epoxy resin)
Epoxy resins have two or more epoxy groups in one molecule. Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, glycidyl ester type epoxy resin, novolak type epoxy resin, and urethane modified epoxy resin. Examples include nitrogen-containing epoxy resin obtained by epoxidizing metaxylene diamine and hydantin, polybutadiene skeleton epoxy resin, NBR (acrylonitrile-butadiene copolymer) skeleton epoxy resin, rubber-modified epoxy resin, and epoxy resin having a long-chain aliphatic skeleton. Be done. The components contained in the epoxy resin are not limited to the above.

The epoxy resin contains at least one epoxy resin selected from the group consisting of hydrogenated bisphenol A type epoxy resin, urethane-modified epoxy resin, polybutadiene skeleton epoxy resin, rubber-modified epoxy resin, and epoxy resin having a long-chain aliphatic skeleton. Is preferable. In this case, the composition (X21) can be in a liquid state before curing, and the cured product has more flexibility than when a bisphenol A type epoxy resin is used as the epoxy resin. can do.

(Epoxy resin curing agent (Q))
When the resin (P) contains an epoxy resin, for example, the composition (X21) preferably contains an epoxy resin curing agent (Q). In this case, the heat curability of the composition (X21) can be further improved.

Examples of the curing agent (Q) include amine-based curing agents, isocyanate-based curing agents, imidazole-based curing agents, phenol-based curing agents, acid anhydride-based curing agents, and thiol-based curing agents.

Examples of the amine-based curing agent include aliphatic polyamines such as dicyandiamide, diethylenetriamine, triethylenetetramine and diethylaminopropylamine; aromatic polyamines such as m-xylenediamine and diaminodiphenylmethane; and alicyclic polyamines such as isophoronediamine and mensendiamine. ; Polyamine and the like can be mentioned.

Examples of the isocyanate-based curing agent include aliphatic isocyanates such as xylylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, lysine methyl ester diisocyanate, trimethylhexamethylene diisocyanate, and n-pentane-1,4-diisocyanate; isophorone diisocyanate and cyclohexane-1. , 4-Diisocyanate, methylcyclohexyldiisocyanate, dicyclohexylmethane-4,4'-diisocyanate and other alicyclic isocyanates; tolylene diisocyanate, diphenylmethane diisocyanate and other aromatic isocyanates; these blocked isocyanates and the like.

Examples of the imidazole-based curing agent include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole and the like.

Examples of the phenol-based curing agent include a resol-type phenol resin and a novolak-type phenol resin.

Examples of the acid anhydride-based curing agent include alicyclic acid anhydrides such as hexahydrophthalic anhydride and methyltetrahydrophthalic anhydride; aromatic acid anhydrides such as trimellitic anhydride, pyromellitic anhydride and benzophenonetetracarboxylic acid. And so on.

Examples of the thiol-based curing agent include an ester-bonded thiol compound, an aliphatic ether-bonded thiol compound, and an aromatic ether-bonded thiol compound.

The curing agent (Q) preferably contains a latent curing agent used for a one-component epoxy resin. The latent curing agent means that even if the latent curing agent is mixed with an epoxy resin, curing does not substantially proceed while a temperature near room temperature is applied, and the material is heated to a temperature equal to or higher than a predetermined temperature. It is a kind of curing agent in which the progress of curing is recognized only when it is used. Examples of the latent curing agent for epoxy resins include modified amine-based latent curing agents. Examples of the modified amine-based latent curing agent include an epoxy compound-added amine compound obtained by adding an amine compound to an epoxy compound, a polyamine-based phenol salt, and the like.

The curing agent (Q) preferably contains at least one of a modified amine-based latent curing agent and a blocked isocyanate, and more preferably contains both a modified amine-based latent curing agent and a blocked isocyanate. In this case, the heat curability of the composition (X21) can be further improved.

The ratio of the curing agent (Q) to 100 parts by mass of the epoxy resin is preferably 50 parts by mass or more and 300 parts by mass or less, and more preferably 100 parts by mass or more and 150 parts by mass or less.

In addition to the above-mentioned components, the composition (X21) contains, for example, a plasticizer (D), a filler (E), an additive (G), and the like mentioned as components that the composition (X11) may contain. You may.

When the composition (X21) contains the filler (E), the ratio of the filler (E) to 100 parts by mass of the resin (P) is preferably 0.1 parts by mass or more and 100 parts by mass or less. It is more preferable that the amount is 10 parts by mass or more and 10 parts by mass or less.

The conditions for curing the composition (X2) are, for example, a temperature of 80 ° C. or higher and 200 ° C. or lower, a time of 1 minute or more and 1 day or less, a temperature of 80 ° C. or higher and 120 ° C. or lower, and a time of 30 minutes or longer and 2 hours or shorter. It is preferable to have.

The composition (X) can be suitably used for adhering tiles such as exterior tiles and interior tiles.

Hereinafter, the present disclosure will be specifically described with reference to Examples, but the present disclosure is not limited to the Examples.

1. 1. Preparation of Composition The raw materials shown in the “Composition” column of Table 1 were mixed to prepare a composition. The details of the raw materials are as follows. The blending amount of the raw materials shown in Table 1 is shown in parts by mass.
-Polymer 1: A polymer having a branched polyoxylen skeleton and a crosslinkable silyl group. Product name Excelster ES-S3430 manufactured by AGC Inc. Weight average molecular weight 17,000. The average number of crosslinkable silyl groups in one molecule is 2.2.
-Polymer 2: A polymer having a poly (meth) acrylate skeleton and a crosslinkable silyl group (one-terminal one-side chain dimethoxysilyl group-substituted poly (meth) acrylic resin). Made by Soken Chemical Co., Ltd. Development product number NE4003DD6. Weight average molecular weight 51000. The average number of crosslinkable silyl groups in one molecule is two.
-Polymer 3: A polymer having a linear polyoxylen skeleton and a crosslinkable silyl group. Made by AGC. Product name Excelstar ES-S4530. Weight average molecular weight 18,000. The average number of crosslinkable silyl groups in one molecule is 1.5.
-Polymer 4: A polymer having a linear polyoxylen skeleton and a crosslinkable silyl group. Made by AGC. Product name Excelstar ES-2410. Weight average molecular weight 17,000. Average number of crosslinkable silyl groups in one molecule 1.2-Epoxy compound 1: Bisphenol A type epoxy resin. Made by DIC. Product name Epicron 850S, epoxy equivalent 188.
-Epoxy compound 2: Epoxysilane. Made by Shin-Etsu Chemical Co., Ltd. Part number KBM403. Epoxy equivalent 236.3.
-Ketimine compound 1: A ketimine compound having a crosslinkable silyl group. N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propaneamine. Made by JNC. Product name Sila Ace S340. Primary amine equivalent after hydrolysis 303 g / mol.
Ketimine compound 2: Divalent ketimine compound. Made by Nitto Kaseisha. Product name Ebonit K100. Primary amine equivalent after hydrolysis 209 g / mol.
-Aminosilane compound: 3- (2-aminoethylamino) propyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd. Part number KBM603.
-Plasticizer 1: Polypropylene glycol. Made by AGC. Product name Excelol 3020.
-Plasticizer 2: (meth) acrylic polymer. Made by Toagosei. Product number UP1000.
-Filler 1: Light calcium carbonate. Made by Shiraishi Kogyo. Product name CCR.
-Filler 2: Heavy calcium carbonate. Made by Shiraishi Kogyo. Product name Whiten 305.
-Filler 3: fumed silica. Made by Aerosil Japan. Product name RY200.
-Catalyst: Tin catalyst, manufactured by Nitto Kasei Co., Ltd., product number U220H.
-Epoxy resin 1: Hydrogenated bisphenol A type epoxy resin. Made by Mitsubishi Chemical Corporation. Product name jER YX8000. Epoxy equivalent 205.
-Epoxy resin 2: Bisphenol A type epoxy resin. Made by DIC. Product name Epicron 850S, epoxy equivalent 188.
-Modified amine-based latent curing agent: Polyamine-based phenol salt. Made by ADEKA. EH-5030S.
-Block isocyanate: Made by Mitsui Chemicals, Inc. Product name Takenate B-7010K.

2. Wall surface construction After the composition was uniformly applied to the entire wall surface with a thickness of 1.5 mm, tiles were placed, fixed and adhered to the surface of the applied composition. The obtained wall-tile adhesive was cured at 23 ° C. and 50% RH for 28 days for the moisture-curing composition, and cured at 100 ° C. for 60 minutes for the thermosetting composition to bond the tiles to the wall surface. rice field.

3. 3. Evaluation (1) Storage elastic modulus A coating film having a thickness of 1.5 mm was prepared using the composition, and the coating film was cured at 23 ° C. and 50% RH for 28 days with a moisture curing composition, and the thermosetting composition was obtained. The product was cured at 100 ° C. for 60 minutes. A test piece having a width of 5 mm and a length of 30 mm to 40 mm was prepared from the cured coating film. Using a dynamic viscoelasticity measuring device (DMS6100 manufactured by Seiko Instruments Inc.), the storage elastic modulus of this test piece at 23 ° C. was measured under the conditions shown below.
Mode: Tension measurement length: 20 mm
Measurement temperature range: 0 ° C to 30 ° C
Temperature rise rate: 5 ° C / min setting SS setting: Start, end 50mN
Strain amplitude: 10 μm
Minimum tension: 50mN
Tension gain: 1.2
Frequency: 1Hz
Initial force amplitude: 50 mN
Creep: 0

(2) Breaking elongation and tensile strength The breaking elongation and tensile strength were measured in accordance with JIS A5557 (2010). A coating film having a thickness of about 1.5 mm was prepared from the composition, and the coating film was cured at 23 ± 2 ° C. for a moisture-curing composition and 50% ± 10 RH for 28 days, and at 100 ° C. for a thermosetting composition. The curing treatment was performed for 60 minutes. From the coating film after the curing treatment, a tensile No. 6 dumbbell-shaped test piece was prepared. This test piece was subjected to a tensile test at a tensile speed of 100 mm / min using a tensile tester (manufactured by Shimadzu Corporation, model number AGS-X) according to the JIS A5557 6.3.4 film physical property measurement method. From the measurement results, the elongation at break and the tensile strength were determined by the following formulas.
Break elongation (%) = (distance between marked lines at break (mm) -distance between marked lines (mm)) x 100 / distance between marked lines (mm)
Tensile strength (N / mm ² ) = maximum load (N) / original cross-sectional area of test piece (mm ² )

(3) In-plane shear test The structure of the test piece 101 used in the in-plane shear test is shown in FIG. The test body 101 was prepared by the following procedure. A wall base material panel 102 having a height of 3000 mm and a width of 1600 mm was joined by a sealing material 103 having a width of 10 mm (manufactured by Yokohama Rubber Co., Ltd., product number Hamatite SC-MS1NB-LM) to prepare a wall base material. After the adhesive composition is uniformly applied on the wall base material panel 102 and the sealing material 103 with a thickness of 1.5 mm, half of the adhesive composition is applied to the sealing portion at intervals of 5 mm in joint width on the applied adhesive composition 104. The tiles 105 were arranged and adhered in such a manner. This test piece was cured at 23 ± 2 ° C. and 50% ± 10 RH for 28 days with a moisture-curing composition, and cured at 100 ° C. for 60 minutes with a thermosetting composition. In the in-plane shear test, the test piece 101 after the hardening treatment was deformed by applying a load to the equivalent of 1/100 rad (maximum joint deviation of 4.5 mm), and then the presence or absence of cracks in the tile was confirmed. When there was no crack in the tile, it was evaluated as "OK", and when there was a crack in the tile, it was evaluated as "NG".

(4) Contamination test After the adhesive composition was uniformly applied to the wall base material to a thickness of 1.5 mm, the moisture-curing composition was cured at 23 ± 2 ° C. and 50 ± 10% RH for 28 days, and then thermosetting. The composition was cured at 100 ° C. for 60 minutes to form a coating film of the cured product. After spraying 200 mesh of sieved volcanic ash on the surface of this coating film, the volcanic ash was removed using a brush. When the volcanic ash could be removed, it was evaluated as "OK", and when it could not be removed, it was evaluated as "NG".

(5) Adhesive strength test The adhesive strength of tiles to the wall base material was measured in accordance with JIS A5557 (2010).
(I) The test body was prepared by the following procedures (a) to (e).
(A) As the wall base material, a base exterior material sealer plate (70 mm × 70 mm × thickness 16 mm) or a mortar plate (70 mm × 70 mm × thickness 20 mm) specified for the materials and tools used in the JIS A5557 6.2 test was used. ..
(B) As the tile, the exterior mosaic tile specified in JIS A5209 was used. The tile size was 45 mm × 45 mm. However, the height of the back legs of the tile was about 0.5 mm, or there was no back legs.
(C) After uniformly applying the adhesive composition to the wall base material with a thickness of 1.5 mm, the tile was adhered to the central portion of the wall base material to obtain a wall base material-tile adhesive body.
(D) The obtained adhesive was cured at 23 ± 2 ° C. and 50 ± 10% RH for 28 days for the moisture-curing composition, and cured at 100 ° C. for 60 minutes for the thermosetting composition.
(E) An iron piece for an adhesion test was attached to the tile side of the bonded body after the curing treatment, and a cut (a notch reaching the base material) was made around the tile with a cutter knife or the like to obtain a test body.
(Ii) The tensile adhesion test was carried out according to the following procedures (f) to (i).
(F) The prepared test piece was subjected to a tensile test at a tensile speed of 3 mm / min, and the maximum tensile load until fracture was measured.
(G) The tensile adhesive strength was calculated by the following formula.
Adhesive strength (N / mm ² ) = maximum tensile load (N) / total area of fracture surface (tile area (45 mm x 45 mm) (mm ² ))
(H) The cohesive fracture rate was determined as follows.
The fracture surface was observed, and the fracture positions were classified into B (tile), AB (adhesive and tile interface), A (adhesive), GA (base material and adhesive interface), and G (base material).
The cohesive fracture rate was calculated by the following formula.
Aggregate fracture rate (%) = (Area of A + G + B) x 100 / Area of the entire fracture surface (Tile area (45 mm x 45 mm) (mm ² ))
(I) ^{"OK" when the adhesive strength is 0.3 N / mm 2} or more and the cohesive fracture rate is 75% or more, and the adhesive strength is ^{less than 0.3 N / mm 2} or the cohesive fracture rate is 75%. If it was less than, it was evaluated as "NG".

The evaluation results are shown in Table 1.

1 Wall structure 2 Wall base material 3 Sealing part 4 Adhesive layer 5 Tile 6 Joint

Claims (10)

A tile construction method in which tiles are adhered to a construction surface with an adhesive composition having a storage elastic modulus at 23 ° C. after curing of 1.5 MPa or more and 10 MPa or less.
A tile construction method in which the adhesive composition is at least one of a composition that cures with moisture in the air and a composition that cures with heat. The construction surface has a seam
The tile construction method according to claim 1, wherein the tiles are laminated and adhered to the seams. A sealing portion filled with a sealing material is formed at the seam.
The tile construction method according to claim 2, wherein the tile is laminated and adhered to the sealing portion. The tile construction method according to any one of claims 1 to 3, wherein the tiles are adhered to a construction surface at intervals of joints, and a cured product of the adhesive composition is exposed at the joints. Any of claims 1 to 4, wherein the adhesive strength measured in accordance with JIS-A5557: 2010 of the adhesive composition is 0.3 N / mm ² or more, and the cohesive fracture rate is 75% or more. The tile construction method described in item 1. Adhesive strength measured in accordance with JIS-A5557: 2010 is 0.3 N / mm ² or more, cohesive fracture rate is 75% or more, and storage elastic modulus at 23 ° C. after curing is 1.5 MPa or more and 10 MPa. Ri der below,
At least one of a composition that cures with moisture in the air and a composition that cures with heat.
The adhesive composition that is used for bonding the tiles. Contains a polymer having a crosslinkable silyl group,
The polymer has at least one of a polyoxylene skeleton and a poly (meth) acrylate skeleton and 1.3 or more crosslinkable silyl groups in one molecule.
The adhesive composition according to claim 6, which is cured by moisture in the air. The adhesive composition according to claim 7, further containing a plasticizer, wherein the ratio of the plasticizer to 100 parts by mass of the polymer is 30 parts by mass or more and 80 parts by mass or less. The adhesive composition according to claim 7 or 8, further comprising at least one of an epoxy compound and an aminosilane compound. The adhesive composition according to claim 7 or 8, further comprising an epoxy compound and a ketimine compound.

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