WO2011001490A1 - Tile sheet and process for producing the tile sheet - Google Patents

Tile sheet and process for producing the tile sheet Download PDF

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Publication number
WO2011001490A1
WO2011001490A1 PCT/JP2009/061832 JP2009061832W WO2011001490A1 WO 2011001490 A1 WO2011001490 A1 WO 2011001490A1 JP 2009061832 W JP2009061832 W JP 2009061832W WO 2011001490 A1 WO2011001490 A1 WO 2011001490A1
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meth
acrylate
weight
tile
group
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PCT/JP2009/061832
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French (fr)
Japanese (ja)
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正巳 左右木
伸之 長谷川
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アルファ化研株式会社
有限会社旭工芸
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Priority to PCT/JP2009/061832 priority Critical patent/WO2011001490A1/en
Publication of WO2011001490A1 publication Critical patent/WO2011001490A1/en

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    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
    • E04F13/00—Coverings or linings, e.g. for walls or ceilings
    • E04F13/07—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor
    • E04F13/08—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor composed of a plurality of similar covering or lining elements
    • E04F13/0862—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor composed of a plurality of similar covering or lining elements composed of a number of elements which are identical or not, e.g. carried by a common web, support plate or grid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
    • B44C3/00—Processes, not specifically provided for elsewhere, for producing ornamental structures
    • B44C3/12—Uniting ornamental elements to structures, e.g. mosaic plates
    • B44C3/123—Mosaic constructs

Definitions

  • the present invention relates to a tile sheet suitable for improving the workability of an exterior tile and a method for manufacturing the tile sheet.
  • This tile sheet is made up of a plurality of tiles in the form of a sheet, and the construction of the tile sheet is bonded to the wall surface of the building via an adhesive mortar, and after the mortar is embedded in the joint, the construction surface is washed and finished. It is done.
  • this type of tile sheet there has been provided a sheet obtained by using starch paste or the like, arranging a plurality of tiles vertically and horizontally, and bonding paper to the surface.
  • this tile sheet after being bonded to the building wall via adhesive mortar, it is necessary to apply water to the surface of the tile to peel off the paper, and the peeled paper is a large amount of waste. Therefore, the improvement was strongly demanded from the field. Therefore, a tile sheet in which tiles are spot-bonded with a thermosetting adhesive to form a sheet has been proposed. In this method, vinyl chloride plastisol, acrylic sol, urethane, etc.
  • thermosetting adhesive used as thermosetting adhesive
  • the dotted tile sheet is attached to the wall surface via adhesive mortar, and the mortar is immediately embedded in the joint to finish. Therefore, workability is greatly improved.
  • thermosetting adhesive in order to cure the thermosetting adhesive, it has to be heated at a temperature of 160 ° C. or more for 15 minutes or more. This requires a long heating furnace of several tens of meters that allows the stagnation of the material, the processing apparatus is enlarged, a large amount of energy is required, the productivity is poor, and the cost tends to be high.
  • Patent Document 1 proposes a method using an ultraviolet curable resin in order to integrally connect a plurality of tiles with a predetermined interval.
  • the plurality of tiles are arranged in a state where they are separated by a predetermined joint gap, an ultraviolet curable resin is applied between the plurality of tiles, and the ultraviolet curable resin is cured by irradiation of ultraviolet rays. These tiles are connected together.
  • Patent Document 1 The configuration disclosed in Patent Document 1 described above is only required to irradiate ultraviolet rays, so that it is expected to be easy to manufacture, but no optimum ultraviolet curable resin is specifically proposed in the literature, Normally, commercially available products have poor adhesion to tiles and cannot ensure appropriate flexibility. For this reason, such a configuration has not been realized.
  • the literature suggests that materials using polymerizable acrylic oligomers, acrylic monomers, epoxy resins, silicone resins, thiol compounds, acrylic modified polybutadiene, etc. can be used, multiple tiles are integrated. Therefore, it is necessary to withstand a relatively large load, and further research is required to obtain a configuration having flexibility to be joined uniformly along the wall surfaces of the casings to be joined.
  • An object of the present invention is to provide a tile sheet that can withstand a relatively large load, has a required flexibility, and is suitable for improving the workability of a tile, and a method for manufacturing the tile sheet.
  • a plurality of tiles arranged vertically and horizontally through joint gaps are joined together by a flexible ultraviolet curable resin that is bridged in the joint gap.
  • An ultraviolet curable adhesive composition comprising a reactive (meth) acryloyl group-containing monomer and an oligomer and / or polymer compatible with the monomer as a main component and a photoreaction initiator mixed therewith,
  • a tile sheet characterized by being cured and having a tensile strength of 0.5 Mpa or more and an elongation of 30% or more.
  • the oligomer a photoreactive (meth) acryloyl group-containing oligomer is suitable.
  • the tile sheet becomes too weak, cannot support the tile's own weight, and stretches or breaks.
  • the adhesive becomes too hard, and when the tile sheet is attached to a building wall surface, the sheet is too hard to follow the change in the wall surface, which impairs workability.
  • a photoreactive (meth) acryloyl group-containing monomer and an oligomer and / or polymer compatible with the monomer are placed in the joint gap between the tiles arranged vertically and horizontally through the joint. It is prepared by supplying an ultraviolet curable adhesive composition comprising a main component and mixing a photoinitiator to each tile so as to bridge the tiles, and curing the adhesive composition by irradiating with ultraviolet rays. .
  • the ultraviolet curable resin used for the tile sheet is achieved by an ultraviolet curable resin having a tensile strength of 0.5 Mpa or more, preferably 0.8 Mpa or more and an elongation of 30% or more, preferably 50% or more.
  • an ultraviolet curable resin having a tensile strength of 0.5 Mpa or more, preferably 0.8 Mpa or more and an elongation of 30% or more, preferably 50% or more.
  • the ultraviolet curable adhesive composition used for the tile sheet is mainly composed of a photoreactive (meth) acryloyl group-containing monomer and an oligomer and / or polymer compatible with the monomer, and a photoreaction initiator and
  • the monomer is a (meth) acrylate monomer, and the acryloyl group of the (meth) acrylate monomer has a monofunctional monomer content of 55% or more and a bifunctional or more polyfunctional monomer content of 45% in the monomer composition.
  • the following are used as those having a tensile strength of 0.5 Mpa or more after UV curing and an elongation of 30% or more.
  • some or all of the monomers, oligomers and polymers in the composition are hydroxyl groups, carboxyl groups and salts thereof, epoxy groups, amino groups, amide groups, maleimide groups, alkoxy groups. And those containing one or more functional groups such as a mercapto group, a phosphoric acid group, a phosphoric ester group and a nitro group.
  • These have adhesive modification effects such as improving adhesion to the tile, making it difficult for the tile and adhesive to peel off, strengthening the cohesive strength of the adhesive, and increasing the tensile strength against tension.
  • the adhesiveness of the resin can be improved.
  • the polymers and / or oligomers mentioned above are urethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, epoxy resin, polyvinyl butyral resin, saturated polyester resin, polyamide resin, styrene maleic acid resin, nitrocellulose and the like. 1 type or 2 types or more selected from.
  • the tile sheet of the present invention is formed by bonding each tile vertically and horizontally using an ultraviolet curable resin, and in the production thereof, it is easily prepared by irradiating the adhesive composition with ultraviolet rays and curing. Is done.
  • This tile sheet does not cover the entire tile with a connecting sheet, so there is no need to peel off after construction.
  • the mortar is embedded in the joints, so the UV curable resin supplied in a bridging manner between the tiles is concealed in the mortar. Since it is not exposed later, a beautiful finish can be achieved without requiring post-processing.
  • FIG. 1 It is a top view of the tile sheet U concerning this invention. It is a longitudinal cross-sectional view which shows the joining aspect of the tile T.
  • FIG. It is a top view of the mounting jig 1 which laid the tile T.
  • FIG. It is a longitudinal cross-sectional view of the mounting jig 1 on which tiles T are laid.
  • the present invention will be described in detail below.
  • tiles T are arranged vertically and horizontally through joint gaps s, and ultraviolet curable resin B is arranged in the joint gaps s in a bridging manner. It is provided and each tile T is consolidated.
  • This ultraviolet curable resin B is characterized by having a flexible property having a tensile strength of 0.5 Mpa or more and an elongation of 30% or more. For this reason, when producing a 300 ⁇ 300 mm square tile sheet of 4.5 ⁇ 2 tiles, the total weight of the tile sheet is about 1050 g, and when this is applied to a vertical surface, a large load is applied.
  • the tile sheet cannot withstand its own weight and is not divided at the joint.
  • the joint surface of the frame to which the tile sheet is applied is not necessarily a uniform surface, but has a flexible characteristic having an elongation rate of 30% or more, and therefore follows the unevenness of the joint surface. Thus, surface contact can be achieved.
  • the tile sheet U includes tiles T arranged on a flat plate-shaped mounting jig 1 with joint gaps s, and an ultraviolet curable adhesive composition is placed in the joint gaps s. It can be easily manufactured by supplying and irradiating with ultraviolet rays. That is, the mounting jig 1 has a protruding spacer 4 for forming the joint gap s formed on the bottom surface, and the protruding spacer 4 forms the mounting surface 3 that matches the vertical and horizontal dimensions of the tile T vertically and horizontally. ing. Holes 5 are formed in the bottom surface of the mounting jig 1 at both side positions of the convex spacer 4 in the joint gap s.
  • the mounting jig 1 is provided with a bottom plate 2 on the lower surface, and the hole 5 has a bottomed shape. A reflecting mirror 8 and a through-hole plate 10 are embedded in the hole 5.
  • the ultraviolet curable adhesive composition is injected in the form of dots onto the center of the hole portion 5 in each joint gap s. Further, the mounting jig 1 is irradiated with ultraviolet rays by the light source L while being transferred by the belt conveyor C or the like. By this irradiation step, the ultraviolet curable adhesive composition receives ultraviolet rays, and each component is crosslinked and cured. At this time, the ultraviolet rays are transmitted through the through-hole plate 10 from the light passage portions 7 and 7 on both sides of the ultraviolet curable adhesive composition, reflected by the reflecting mirror 8, and applied to the ultraviolet curable adhesive composition from below. Is also irradiated.
  • the ultraviolet curable adhesive composition is irradiated with ultraviolet rays from above and below, and the curing thereof is made uniform.
  • the ultraviolet irradiation time is about 10 seconds. Therefore, even if irradiation is performed while running on the belt conveyor C, the apparatus does not need to be enlarged, and the tile sheet U can be easily manufactured by a small apparatus. It will be.
  • the ultraviolet curable adhesive composition according to the embodiment of the present invention is mainly composed of a photoreactive (meth) acrylate monomer (acryloyl group-containing monomer), a photoreactive (meth) acrylate oligomer (acryloyl group-containing oligomer), and an organic polymer. And a photoreaction initiator, and if necessary, a vinyl ether compound or the like is mixed therewith, and a sensitizer, an organic polymer, an inorganic modifier or the like is added as necessary. Further, for the purpose of decreasing the viscosity and adjusting the coating amount, it may be diluted with an organic solvent, a plasticizer or the like.
  • the ultraviolet curable adhesive composition is composed mainly of a photoreactive (meth) acrylate monomer and a photoreactive (meth) acrylate oligomer, and a photoreactive (meth) acrylate monomer and an organic substance. It is divided into the structure which has a polymer as a main component.
  • the pulling strength and elongation of the ultraviolet curable resin are as follows.
  • the acryloyl group has a monofunctional monomer of 55% or more, preferably 60% or more, and the acryloyl group has a bifunctional or more. This is achieved by having a monomer content of 45% or less, desirably 40% or less. This is because when the polyfunctional acryloyl group monomer is 40% or more, the cured product is hard and the elongation rate is lowered.
  • Examples of the photoreactive (meth) acryloyl group-containing monomer include monofunctional (meth) acrylate, bifunctional (meth) acrylate, trifunctional or higher (meth) acrylate, and the like.
  • Examples of the monofunctional (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl ( (Meth) acrylate, t-butyl (meth) acrylate, glycidyl (meth) acrylate, acryloylmorpholine, N-vinylpyrrolidone, tetrahydrofurfuryl acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) ) Acrylate, isodecy
  • bifunctional (meth) acrylate examples include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, and nonanediol di (meth).
  • Examples of the trifunctional or higher functional (meth) acrylate compound include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, and tris 2-hydroxy.
  • Trifunctional or higher (meth) acrylate compounds pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol Trifunctional or higher polyfunctionality such as tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane hexa (meth) acrylate, etc. And a polyfunctional (meth) acrylate obtained by substituting a part of these (meth) acrylates with an alkyl group or ⁇ -caprolactone.
  • Examples of the (meth) acryloyl group-containing oligomer include polyester (meth) acrylate, polyurethane (meth) acrylate, epoxy (meth) acrylate, polyether (meth) acrylate, oligo (meth) acrylate, alkyd (meth) acrylate, polyol ( And (meth) acrylate.
  • polyester (meth) acrylate and polyurethane (meth) acrylate are particularly desirable for obtaining a flexible ultraviolet curable resin having strong adhesion to tiles and flexibility.
  • Examples of the vinyl ether compound include ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether, butanediol monovinyl ether, cyclohexanedimethanol monovinyl ether, t-butyl vinyl ether, and t-amyl.
  • some or all of the monomers, oligomers, and polymers in the ultraviolet curable adhesive composition may have hydroxyl groups, carboxyl groups and salts thereof, epoxy groups, amino groups, maleimide groups, alkoxy groups, mercapto groups, and phosphate groups.
  • Adhesiveness of the ultraviolet curable resin can be improved by using a functional group such as a phosphate ester group, an isocyanate group, or a nitro group. This is because they have adhesive modification effects such as enhancing adhesion to the tile, making it difficult for the tile and adhesive to peel off, increasing the cohesive strength of the adhesive, and increasing the tensile strength against tension.
  • Examples of such monomers include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, ethylene glycol mono (meth) ) Acrylate, propylene glycol mono (meth) acrylate, butanediol mono (meth) acrylate, pentanediol mono (meth) acrylate, hexanediol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate , Triethylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, polyethylene Divalent compounds such as glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, neopentyl glycol
  • natural polymer materials and synthetic polymer materials other than the acrylates described above may be further selected and added to the adhesive of the present invention as necessary.
  • natural polymer materials and synthetic polymer materials include various vinyl ester resins, block isocyanates, polyisocyanate compounds, bisphenol A type epoxy resins, bisphenol F type epoxy resins, alicyclic epoxy resins, and other epoxies.
  • Resin polymer or oligomer and derivatives thereof Polyepoxides, polyvinyl butyral resin, polyvinyl alcohol and derivatives thereof, acrylic resins, alkyd resins, urea resins, melamine resins, polyvinyl acetate, vinyl acetate copolymers, polybutadiene Elastomers, saturated polyesters, saturated polyethers, nitrocelluloses, cellulose derivatives such as cellulose acetate butyrate; fats and oils such as linseed oil, tung oil, soybean oil, castor oil or epoxidized oil That.
  • blocked isocyanates, polyisocyanate compounds, bisphenol A type epoxy resins, bisphenol F type epoxy resins, alicyclic epoxy resins and other epoxy resin polymers or oligomers and their derivatives polyepoxides, polyvinyl butyral resins, polyvinyl alcohol and their derivatives, saturation Polyester resin, polyamide, nitrocellulose, etc. are desirable because they increase the adhesion to the tile.
  • plasticizers such as diethyl phthalate, dibutyl phthalate, dioctyl phthalate, and process oil
  • organic solvents such as toluene, xylene, butyl acetate, and isopropyl alcohol can be added to the adhesive composition. wear.
  • the adhesive composition if necessary, titanium oxide, carbon black, petals, colored pigments such as oil dyes, colored dyes, calcium carbonate, talc, alumina, aluminum hydroxide, magnesium hydroxide, kaolin clay, Clay mineral powder, rock wool powder, glass fiber powder, asbestos powder, hydrous fine powder silica (white carbon), ultra fine powder anhydrous silica (Aerosil), silica sand (silica sand), precipitated magnesium carbonate, stearic acid metal salt Inorganic powders such as can be added.
  • colored pigments such as oil dyes, colored dyes, calcium carbonate, talc, alumina, aluminum hydroxide, magnesium hydroxide, kaolin clay, Clay mineral powder, rock wool powder, glass fiber powder, asbestos powder, hydrous fine powder silica (white carbon), ultra fine powder anhydrous silica (Aerosil), silica sand (silica sand), precipitated magnesium carbonate, stearic acid metal salt Inorganic powders such as can be added.
  • Examples of the photoinitiator referred to in the present invention include compounds that generate radicals by hydrogen abstraction such as benzophenone, benzyl, Michler ketone, thioxanthone, or anthraquinone. These compounds generally use a tertiary amine such as methylamine, diethanolamine, N-methyldiethanolamine or tributylamine as a sensitizer.
  • Examples of another type of photopolymerization initiator include compounds that generate radicals by intramolecular cleavage. Specific examples include benzoin, dialkoxyacetophenone, acyloxime ester, benzyl ketal, hydroxyalkylphenone, halogenoketone and the like.
  • the adhesive is selected from one or a mixture of two or more selected from (meth) acrylate oligomers and (meth) acrylate monomers, if necessary, from these oligomers, polymers compatible with the monomers, and oligomers.
  • one or two or more kinds are added, and a photoreaction initiator and, if necessary, a sensitizer, a thickener, a diluent, a colorant, and the like are added.
  • the above-described adhesive composition can be used, for example, by arranging tiles on a release-treated board, injecting adhesive between the tiles in a dotted manner, and then irradiating ultraviolet rays to cure the ultraviolet curable resin. Make a tile sheet.
  • An ultraviolet lamp used for irradiating ultraviolet rays is irradiated with ultraviolet rays from a light source that efficiently generates ultraviolet rays, such as a high-pressure mercury lamp, and cured.
  • a light source that efficiently generates ultraviolet rays, such as a high-pressure mercury lamp
  • CN2256 (Polyerter polyol, manufactured by Sartomer Japan Co., Ltd.) 60 parts by weight, 2-hydroxy 3-phenoxypropyl acrylate, 30 parts by weight, 10 parts by weight of hexanediol diacrylate, 10 parts by weight of ⁇ -carboxypolycaprolactone monoacrylate Parts, photopolymerization initiator [Irgacure 184 (manufactured by Ciba Specialty Chemicals Co., Ltd., 1-hydroxy-cyclohexyl-phenyl-ketone)], 1 part by weight of amino alcohol, Aerosil 200 (manufactured by Nippon Aerosil Co., Ltd.) 1.5 Part by weight was added to obtain an ultraviolet curable adhesive composition.
  • Irgacure 184 manufactured by Ciba Specialty Chemicals Co., Ltd., 1-hydroxy-cyclohexyl-phenyl-ketone
  • Aerosil 200 manufactured by Nippon Aerosil Co., Ltd. 1.5 Part by weight was
  • Epototo YD-011 epoxy resin manufactured by Toto Kasei Co., Ltd.
  • 4-hydroxybutyl acrylate 60 parts by weight of Epototo YD-011 (Epoxy resin manufactured by Toto Kasei Co., Ltd.) was mixed and dissolved in 40 parts by weight of 4-hydroxybutyl acrylate.
  • urethane acrylate oligomer obtained in Example 2 10 parts by weight of phenoxypolyethylene glycol acrylate, 4 parts by weight of Kayamar PM-2 (manufactured by Nippon Kayaku Co., Ltd.), a photopolymerization initiator [Irgacure 184 (Ciba 5 parts by weight of 1-hydroxy-cyclohexyl-phenyl-ketone) manufactured by Specialty Chemical Co., Ltd., 3 parts by weight of amino alcohol and 4 parts by weight of Aerosil 200 (manufactured by Nippon Aerosil Co., Ltd.) are obtained to obtain an ultraviolet curable adhesive composition. It was.
  • Byron 550 (Toyobo Co., Ltd., saturated polyester resin) 35 parts by weight 4-hydroxybutyl acrylate 40 parts by weight, phenoxy polyethylene glycol acrylate 30 parts by weight, polyethylene glycol 600 acrylate (Toagosei Co., Ltd. Aronix M-260) 5 parts by weight The solution was mixed and dissolved in the part.
  • Aronix M-5600 acrylic acid dimer manufactured by Toagosei
  • ⁇ Comparative Example 2 100 parts by weight of the urethane acrylate oligomer obtained in Example 1, 30 parts by weight of lauryl acrylate, 20 parts by weight of 2.2-bis [4- (acryloxy-diethoxy) phenyl] propane, polyethylene glycol 600 diacrylate (Toagosei Co., Ltd.) Aronix M-260) 5 parts by weight photopolymerization initiator [Irgacure 184 (Ciba Specialty Chemicals 1-hydroxy-cyclohexyl-phenyl-ketone)] 4 parts by weight, amino alcohol 2 parts by weight, Aerosil 200 (Nippon Aerosil) 4 parts by weight) were added to obtain an ultraviolet curable adhesive composition.
  • Example 1 In order to verify the characteristics of Examples 1 to 9 and Comparative Examples 1 and 2, tiles T were laid and aligned on the mounting jig 1 shown in FIGS.
  • the ultraviolet curable adhesive composition produced in Example 1 was injected into each joint gap s with a width of about 5 mm and a thickness of 1.5 mm as shown in FIG. Then, using a 150 W / cm high-pressure mercury lamp as the light source L, the coating film portion of the ultraviolet curable resin was irradiated with ultraviolet rays for 10 seconds (distance 25 mm from the lamp) to form a cured coating film.
  • the two upper ends of the produced tile sheet were lifted by hand, and the state of the tile sheet after lightly shaking several times was observed to confirm its adhesiveness. Further, this tile sheet was bent 90 degrees at the bonding portion, and the state of the adhesive was observed.
  • UV curable resin prepared in Examples 1 to 9 and Comparative Examples 1 and 2 was applied to a release-treated board to a thickness of about 1.5 mm and 150 W / cm high-pressure mercury.
  • the coating film portion of the ultraviolet curable resin was irradiated with ultraviolet rays for 10 seconds (distance from the lamp of 25 mm) to form a cured coating film.
  • This cured film was measured according to JIS K 7113, and the tensile strength (Mpa) and elongation of the film were measured with TECHNO K GRAPH 10 KN (manufactured by Minebea Co., Ltd.). The test results are shown below.
  • Adhesion test Comparative Example 2 had poor adhesion to the tile, and the adhesive peeled off the tile interface when the sheet was lifted. There was no abnormality in other things. Bending test: Comparative Example 1 could not be easily bent, and the adhesive was partially cracked. In Comparative Example 2, the adhesive was peeled off from the tile interface by bending.

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Abstract

Provided is a tile sheet which withstands a relatively high load, has necessary flexibility, and is suitable for improving tile applicability.  Also provided is a process for producing the tile sheet. The tile sheet is characterized by comprising a plurality of tiles arranged in the lengthwise and crosswise directions with joint spaces thereamong and bonded to each other with a flexible ultraviolet-cured resin which has bridged each joint space.  The tile sheet is further characterized in that the ultraviolet-cured resin is a resin obtained by curing, by ultraviolet irradiation, an ultraviolet-curable adhesive composition comprising a photoreactive (meth)acryloyl-containing monomer and an oligomer and/or polymer compatible with the monomer, as major components, and a photoreaction initiator mixed therewith, the cured resin having a tensile strength of 0.5 MPa or higher and an elongation of 30% or higher.

Description

タイルシート及び該タイルシートの製造方法Tile sheet and method for manufacturing the tile sheet
　本発明は、外装タイルの施工性を向上するに適したタイルシート及び該タイルシートの製造方法に関するものである。この、タイルシートは、複数個のタイルをシート状としてなり、該タイルシートの施工は、接着モルタルを介して建築物壁面に接着され、目地にモルタルを埋め込んだ後、施工面を洗浄して仕上げられる。 The present invention relates to a tile sheet suitable for improving the workability of an exterior tile and a method for manufacturing the tile sheet. This tile sheet is made up of a plurality of tiles in the form of a sheet, and the construction of the tile sheet is bonded to the wall surface of the building via an adhesive mortar, and after the mortar is embedded in the joint, the construction surface is washed and finished. It is done.
　従来、この種のタイルシートとしては、澱粉糊等を用い、複数個のタイルを縦横に配列し、紙を表面に接着してなるものが提供されていた。しかるにこのタイルシートにあっては、接着モルタルを介して建築物壁面に接着された後、タイルの表面に水をかけて、紙をはがす作業が必要な上、はがした紙が大量の廃棄物となるため、その改善が現場から強く求められていた。そこで、タイル同士を熱硬化性接着剤によって点接着し、シート状としたタイルシートが提案された。この方法では、熱硬化性接着剤として塩化ビニールプラスチゾル、アクリルゾル、ウレタン等を使用し、点付けしたタイルシートを、接着モルタルを介して壁面躯体に貼り付け、直ちに目地にモルタルを埋め込んで仕上げをするものであり、作業性は大幅に改善される。しかしこの方法は、熱硬化性接着剤を硬化させるため、１６０度以上の温度で、１５分以上加熱しなければならず、これを一連のラインで生産する場合には、移動中に１５分以上の滞留を可能とする数十ｍに及ぶ長い加熱炉を要し、加工装置が大型化し、大量のエネルギーを必要とし、生産性が悪く、高コストになりがちであった。 Conventionally, as this type of tile sheet, there has been provided a sheet obtained by using starch paste or the like, arranging a plurality of tiles vertically and horizontally, and bonding paper to the surface. However, in this tile sheet, after being bonded to the building wall via adhesive mortar, it is necessary to apply water to the surface of the tile to peel off the paper, and the peeled paper is a large amount of waste. Therefore, the improvement was strongly demanded from the field. Therefore, a tile sheet in which tiles are spot-bonded with a thermosetting adhesive to form a sheet has been proposed. In this method, vinyl chloride plastisol, acrylic sol, urethane, etc. are used as thermosetting adhesive, and the dotted tile sheet is attached to the wall surface via adhesive mortar, and the mortar is immediately embedded in the joint to finish. Therefore, workability is greatly improved. However, in this method, in order to cure the thermosetting adhesive, it has to be heated at a temperature of 160 ° C. or more for 15 minutes or more. This requires a long heating furnace of several tens of meters that allows the stagnation of the material, the processing apparatus is enlarged, a large amount of energy is required, the productivity is poor, and the cost tends to be high.
　そこで、複数のタイルを所定の間隔に離間させた状態で一体に連結するために、紫外線硬化性樹脂を用いたものが、特許文献１で提案された。これは、複数のタイルを所定の目地間隙で離間させた状態に配置し、前記複数のタイル間に紫外線硬化性樹脂を塗布し、紫外線の照射により前記紫外線硬化性樹脂を硬化させることにより前記複数のタイルを一体に連結するものである。 Therefore, Patent Document 1 proposes a method using an ultraviolet curable resin in order to integrally connect a plurality of tiles with a predetermined interval. The plurality of tiles are arranged in a state where they are separated by a predetermined joint gap, an ultraviolet curable resin is applied between the plurality of tiles, and the ultraviolet curable resin is cured by irradiation of ultraviolet rays. These tiles are connected together.
特開２００１－１４０４４９号公報Japanese Patent Laid-Open No. 2001-140449
　上述した特許文献１で開示された構成は、紫外線を照射するだけでよいから、製造容易性が期待されるものの、文献中には最適な紫外線硬化性樹脂が具体的に提案されていず、また通常市販されているものでは、タイルとの密着性が悪く、適度の柔軟性が確保できない。このためかかる構成は、実現されるに至っていない。ちなみに文献では、重合可能なアクリルオリゴマー、アクリルモノマー、エポキシ樹脂、シリコン樹脂、チオール化合物、アクリル変性ポリブタジエンなどを原料とするものを用いることができると示唆しているものの、複数のタイルを一体化するため、比較的大きな荷重に耐える必要があり、しかも接合する躯体の壁面に沿って整一に接合される柔軟性を備えた構成とするには、さらなる研究を要するものである。 The configuration disclosed in Patent Document 1 described above is only required to irradiate ultraviolet rays, so that it is expected to be easy to manufacture, but no optimum ultraviolet curable resin is specifically proposed in the literature, Normally, commercially available products have poor adhesion to tiles and cannot ensure appropriate flexibility. For this reason, such a configuration has not been realized. By the way, although the literature suggests that materials using polymerizable acrylic oligomers, acrylic monomers, epoxy resins, silicone resins, thiol compounds, acrylic modified polybutadiene, etc. can be used, multiple tiles are integrated. Therefore, it is necessary to withstand a relatively large load, and further research is required to obtain a configuration having flexibility to be joined uniformly along the wall surfaces of the casings to be joined.
　本発明は、比較的大きな荷重に耐え、所要の柔軟性を有する、タイルの施工性を向上するに適したタイルシート及び該タイルシートの製造方法を提供することを目的とするものである。 An object of the present invention is to provide a tile sheet that can withstand a relatively large load, has a required flexibility, and is suitable for improving the workability of a tile, and a method for manufacturing the tile sheet.
　本発明は、目地間隙を介して縦横に配列した複数個のタイル相互を、目地間隙内に橋渡された可撓性を有する紫外線硬化性樹脂により接合されてなり、前記紫外線硬化性樹脂が、光反応性(メタ)アクリロイル基含有モノマー並びに該モノマーと相溶性のあるオリゴマー及び／又はポリマーを主成分とし、これに光反応開始剤を混合してなる紫外線硬化性接着剤組成物を、紫外線照射により硬化してなり、０.５Ｍｐａ以上の引っ張り強度で、かつ３０％以上の伸び率を有するものであることを特徴とするタイルシートである。ここでオリゴマーとしては、光反応性(メタ)アクリロイル基含有オリゴマーが好適となる。０.５Ｍｐａ未満の強度であると、タイルシートが弱くなりすぎ、タイルの自重を支えきれず、伸びたり破断したりする。３０％未満の伸び率であると、該接着剤が硬くなりすぎ、該タイルシートを建築物壁面に取り付ける場合、シートが硬すぎ壁面の変化に追従しにくくなり、作業性を害する。 In the present invention, a plurality of tiles arranged vertically and horizontally through joint gaps are joined together by a flexible ultraviolet curable resin that is bridged in the joint gap. An ultraviolet curable adhesive composition comprising a reactive (meth) acryloyl group-containing monomer and an oligomer and / or polymer compatible with the monomer as a main component and a photoreaction initiator mixed therewith, A tile sheet characterized by being cured and having a tensile strength of 0.5 Mpa or more and an elongation of 30% or more. Here, as the oligomer, a photoreactive (meth) acryloyl group-containing oligomer is suitable. If the strength is less than 0.5 Mpa, the tile sheet becomes too weak, cannot support the tile's own weight, and stretches or breaks. When the elongation is less than 30%, the adhesive becomes too hard, and when the tile sheet is attached to a building wall surface, the sheet is too hard to follow the change in the wall surface, which impairs workability.
　このタイルシートは、目地を介して縦横に配列した複数個のタイル相互の、その目地間隙内に、光反応性(メタ)アクリロイル基含有モノマー並びに該モノマーと相溶性のあるオリゴマー及び／又はポリマーを主成分とし、これに光反応開始剤を混合してなる紫外線硬化性接着剤組成物を各タイル相互を橋渡しするように供給し、接着剤組成物に紫外線照射して硬化することにより作製される。 In this tile sheet, a photoreactive (meth) acryloyl group-containing monomer and an oligomer and / or polymer compatible with the monomer are placed in the joint gap between the tiles arranged vertically and horizontally through the joint. It is prepared by supplying an ultraviolet curable adhesive composition comprising a main component and mixing a photoinitiator to each tile so as to bridge the tiles, and curing the adhesive composition by irradiating with ultraviolet rays. .
　このタイルシートに用いられる紫外線硬化性樹脂は、引っ張り強度が０.５Ｍｐａ以上望ましくは０.８Ｍｐａ以上で、伸び率が３０％以上望ましくは５０％以上の紫外線硬化性樹脂によって達成されることが、種々の研究の結果、確認された。４.５×２丁タイルの３００×３００ｍｍ角タイルシートを作製する場合、タイルシート全体の重量が１０５０ｇ程度あり、０.５Ｍｐａ以上の引っ張り強度があればタイルシート全体を支えることができ、また３０％以上の伸び率があれば、躯体に追従しやすくなるからである。 The ultraviolet curable resin used for the tile sheet is achieved by an ultraviolet curable resin having a tensile strength of 0.5 Mpa or more, preferably 0.8 Mpa or more and an elongation of 30% or more, preferably 50% or more. As a result of various studies, it was confirmed. When producing a 300 × 300 mm square tile sheet of 4.5 × 2 tiles, the weight of the entire tile sheet is about 1050 g, and if the tensile strength is 0.5 Mpa or more, the entire tile sheet can be supported. This is because an elongation percentage of at least% makes it easier to follow the housing.
　このタイルシートに用いられる紫外線硬化性接着剤組成物は、光反応性(メタ)アクリロイル基含有モノマー並びに該モノマーと相溶性のあるオリゴマー及び／又はポリマーを主成分とし、これに光反応開始剤とを混合してなり、前記モノマーが（メタ）アクリレートモノマーであり、該（メタ）アクリレートモノマーのアクリロイル基が、モノマー組成中で単官能モノマーが５５％以上、２官能以上の多官能モノマーが４５％以下であるものが、紫外線硬化後０.５Ｍｐａ以上の引っ張り強度で、かつ３０％以上の伸び率を有するものとして用いられる。 The ultraviolet curable adhesive composition used for the tile sheet is mainly composed of a photoreactive (meth) acryloyl group-containing monomer and an oligomer and / or polymer compatible with the monomer, and a photoreaction initiator and The monomer is a (meth) acrylate monomer, and the acryloyl group of the (meth) acrylate monomer has a monofunctional monomer content of 55% or more and a bifunctional or more polyfunctional monomer content of 45% in the monomer composition. The following are used as those having a tensile strength of 0.5 Mpa or more after UV curing and an elongation of 30% or more.
　このような紫外線硬化性接着剤組成物は、その組成中のモノマー、オリゴマー、ポリマーの一部または全部が、水酸基、カルボキシル基及びその塩類、エポキシ基、アミノ基、アミド基、マレイミド基、アルコキシ基、メルカプト基、燐酸基、燐酸エステル基、ニトロ基等の官能基の１種または２種以上を含有するものが用いられる。これらは、タイルとの密着性を高め、タイルと接着剤が剥離しにくくしたり、接着剤の凝集力を強め、引張りに対する抗張力を高めるなどの接着剤改質効果があり、これにより紫外線硬化性樹脂の接着性を向上させることができる。 In such an ultraviolet curable adhesive composition, some or all of the monomers, oligomers and polymers in the composition are hydroxyl groups, carboxyl groups and salts thereof, epoxy groups, amino groups, amide groups, maleimide groups, alkoxy groups. And those containing one or more functional groups such as a mercapto group, a phosphoric acid group, a phosphoric ester group and a nitro group. These have adhesive modification effects such as improving adhesion to the tile, making it difficult for the tile and adhesive to peel off, strengthening the cohesive strength of the adhesive, and increasing the tensile strength against tension. The adhesiveness of the resin can be improved.
　上述のポリマー及び／又はオリゴマーはウレタン（メタ）アクリレート、ポリエステル（メタ）アクリレート、エポキシ（メタ）アクリレート、エポキシ樹脂、ポリビニルブチラール樹脂、飽和ポリエステル樹脂、ポリアミド樹脂、スチレンマレイン酸樹脂、ニトロセルロース等の群から選ばれた１種または２種以上含有してなるものとすることができる。 The polymers and / or oligomers mentioned above are urethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, epoxy resin, polyvinyl butyral resin, saturated polyester resin, polyamide resin, styrene maleic acid resin, nitrocellulose and the like. 1 type or 2 types or more selected from.
　本発明のタイルシートは、紫外線硬化性樹脂を用いて、各タイルを縦横に結合してなるものであり、その製造にあっては接着剤組成物に紫外線照射して硬化することにより容易に作製される。 The tile sheet of the present invention is formed by bonding each tile vertically and horizontally using an ultraviolet curable resin, and in the production thereof, it is easily prepared by irradiating the adhesive composition with ultraviolet rays and curing. Is done.
　また、０.５Ｍｐａ以上の引っ張り強度で、かつ３０％以上の伸び率を有するものであるから、タイルシート全体を支えることができ、またタイルを接合する躯体の表面に追従しやすくなり、該接合面に凹凸や変形があっても、容易に接合される。 In addition, since it has a tensile strength of 0.5 Mpa or more and an elongation rate of 30% or more, it can support the entire tile sheet and can easily follow the surface of the casing to which the tile is joined. Even if there are irregularities or deformations on the surface, they can be joined easily.
　このタイルシートは、連結シートでタイル全体を覆うものではないから、施工後の剥離が不要である。また各タイルの裏面にモルタルを塗って接合した後、さら目地にモルタルを埋め込むことにより施工されるものであるから、タイル間に橋渡し状に供給した紫外線硬化性樹脂はモルタル内に隠蔽され、施工後に露出することは無いため、後処理を要することなく、美麗な仕上げが可能となる。 This tile sheet does not cover the entire tile with a connecting sheet, so there is no need to peel off after construction. In addition, after mortar is applied to the back of each tile and joined, the mortar is embedded in the joints, so the UV curable resin supplied in a bridging manner between the tiles is concealed in the mortar. Since it is not exposed later, a beautiful finish can be achieved without requiring post-processing.
本発明にかかるタイルシートＵの平面図である。It is a top view of the tile sheet U concerning this invention. タイルＴの接合態様を示す縦断面図である。It is a longitudinal cross-sectional view which shows the joining aspect of the tile T. FIG. タイルＴを敷設した搭載治具１の平面図である。It is a top view of the mounting jig 1 which laid the tile T. FIG. タイルＴを敷設した搭載治具１の縦断面図である。It is a longitudinal cross-sectional view of the mounting jig 1 on which tiles T are laid.
　以下本発明を詳細に説明する。
　図１、２で示すように、本発明のタイルシートＵは、例えばタイルＴが縦横に目地間隙ｓを介して整一配列され、その目地間隙ｓ内に紫外線硬化性樹脂Ｂが橋渡し状に配設され、各タイルＴを固結してなるものである。この紫外線硬化性樹脂Ｂは、０.５Ｍｐａ以上の引っ張り強度で、かつ３０％以上の伸び率を有する可撓性のある特性を有することを特徴としている。このため、４.５×２丁タイルの３００×３００ｍｍ角タイルシートを作製する場合、タイルシート全体の重量が１０５０ｇ程度あり、これを垂直面に施工する場合には、大きな荷重がかかることとなるが、かかる引張り強度を有するため、タイルシートがその自重に耐え切れず、その接合部で分断することがない。また、タイルシートが貼着施工される躯体の接合面は、必ずしも整一な面ではないが、３０％以上の伸び率を有する可撓性のある特性を有するため、その接合面の凹凸に倣って、面接触させることが可能となる。 The present invention will be described in detail below.
As shown in FIGS. 1 and 2, in the tile sheet U of the present invention, for example, tiles T are arranged vertically and horizontally through joint gaps s, and ultraviolet curable resin B is arranged in the joint gaps s in a bridging manner. It is provided and each tile T is consolidated. This ultraviolet curable resin B is characterized by having a flexible property having a tensile strength of 0.5 Mpa or more and an elongation of 30% or more. For this reason, when producing a 300 × 300 mm square tile sheet of 4.5 × 2 tiles, the total weight of the tile sheet is about 1050 g, and when this is applied to a vertical surface, a large load is applied. However, since it has such tensile strength, the tile sheet cannot withstand its own weight and is not divided at the joint. In addition, the joint surface of the frame to which the tile sheet is applied is not necessarily a uniform surface, but has a flexible characteristic having an elongation rate of 30% or more, and therefore follows the unevenness of the joint surface. Thus, surface contact can be achieved.
　このタイルシートＵは、例えば図３，４で示すように、平板状の搭載治具１にタイルＴを目地間隙ｓを置いて列設し、目地間隙ｓ内に紫外線硬化性接着剤組成物を供給して、紫外線照射することにより、容易に製造することができる。すなわち、搭載治具１は、目地間隙ｓを形成するための凸条スペーサ４が底面部に突成され、該凸条スペーサ４によりタイルＴの縦横寸法に合致した搭載面部３を縦横に形成している。搭載治具１底面部には、目地間隙ｓの凸条スペーサ４の両側位置で、孔部５が形成される。この搭載治具１には、底板２が下面に設けられ、孔部５を有底状としている。この孔部５には、反射鏡８と透孔板１０とが埋設される。 For example, as shown in FIGS. 3 and 4, the tile sheet U includes tiles T arranged on a flat plate-shaped mounting jig 1 with joint gaps s, and an ultraviolet curable adhesive composition is placed in the joint gaps s. It can be easily manufactured by supplying and irradiating with ultraviolet rays. That is, the mounting jig 1 has a protruding spacer 4 for forming the joint gap s formed on the bottom surface, and the protruding spacer 4 forms the mounting surface 3 that matches the vertical and horizontal dimensions of the tile T vertically and horizontally. ing. Holes 5 are formed in the bottom surface of the mounting jig 1 at both side positions of the convex spacer 4 in the joint gap s. The mounting jig 1 is provided with a bottom plate 2 on the lower surface, and the hole 5 has a bottomed shape. A reflecting mirror 8 and a through-hole plate 10 are embedded in the hole 5.
　そして、搭載治具１の搭載面部３に、タイルＴを敷設した後、各目地間隙ｓ内の孔部５の中央上に紫外線硬化性接着剤組成物を点状に注入する。さらに、この搭載治具１をベルトコンベヤＣ等で、移送しながら、光源Ｌにより、紫外線を照射する。この照射工程により、紫外線硬化性接着剤組成物は紫外線を受け、各成分が架橋して硬化する。このとき、紫外線は、紫外線硬化性接着剤組成物の両側の光通過部７，７から透孔板１０を透過して、反射鏡８で反射して、紫外線硬化性接着剤組成物に下方からも照射される。このため、紫外線硬化性接着剤組成物はその上下から紫外線が照射されることとなり、その硬化が均一になされることとなる。この紫外線照射時間は１０秒間程度であり、このためベルトコンベヤＣで走行させながら照射したとしても、装置の大型化を要することは無く、これによりタイルシートＵは、小型装置により容易に製造されることとなる。 Then, after laying the tile T on the mounting surface portion 3 of the mounting jig 1, the ultraviolet curable adhesive composition is injected in the form of dots onto the center of the hole portion 5 in each joint gap s. Further, the mounting jig 1 is irradiated with ultraviolet rays by the light source L while being transferred by the belt conveyor C or the like. By this irradiation step, the ultraviolet curable adhesive composition receives ultraviolet rays, and each component is crosslinked and cured. At this time, the ultraviolet rays are transmitted through the through-hole plate 10 from the light passage portions 7 and 7 on both sides of the ultraviolet curable adhesive composition, reflected by the reflecting mirror 8, and applied to the ultraviolet curable adhesive composition from below. Is also irradiated. For this reason, the ultraviolet curable adhesive composition is irradiated with ultraviolet rays from above and below, and the curing thereof is made uniform. The ultraviolet irradiation time is about 10 seconds. Therefore, even if irradiation is performed while running on the belt conveyor C, the apparatus does not need to be enlarged, and the tile sheet U can be easily manufactured by a small apparatus. It will be.
　本発明の実施に係る紫外線硬化性接着剤組成物は、光反応性(メタ)アクリレートモノマー（アクリロイル基含有モノマー）、光反応性(メタ)アクリレートオリゴマー（アクリロイル基含有オリゴマー）、有機物ポリマーを主成分とし、光反応開始剤、必要に応じてこれにビニルエーテル化合物等を混合してなり、必要に応じて増感剤、有機物ポリマー、無機改質剤等を添加したものである。さらに粘度を低下させ、塗布量を調節させる目的で、有機溶剤、可塑剤等によって希釈したりしてもよい。 The ultraviolet curable adhesive composition according to the embodiment of the present invention is mainly composed of a photoreactive (meth) acrylate monomer (acryloyl group-containing monomer), a photoreactive (meth) acrylate oligomer (acryloyl group-containing oligomer), and an organic polymer. And a photoreaction initiator, and if necessary, a vinyl ether compound or the like is mixed therewith, and a sensitizer, an organic polymer, an inorganic modifier or the like is added as necessary. Further, for the purpose of decreasing the viscosity and adjusting the coating amount, it may be diluted with an organic solvent, a plasticizer or the like.
　かかる構成にあって、紫外線硬化性接着剤組成物は、光反応性(メタ)アクリレートモノマーと光反応性(メタ)アクリレートオリゴマーを主成分とする構成と、光反応性(メタ)アクリレートモノマーと有機物ポリマーを主成分とする構成とに区分される。 In such a configuration, the ultraviolet curable adhesive composition is composed mainly of a photoreactive (meth) acrylate monomer and a photoreactive (meth) acrylate oligomer, and a photoreactive (meth) acrylate monomer and an organic substance. It is divided into the structure which has a polymer as a main component.
　この紫外線硬化性樹脂のひっぱり強度と伸び率は、（メタ）アクリレートモノマー組成中で、アクリロイル基が、単官能であるモノマーが５５％以上、望ましくは６０％以上、アクリロイル基が２官能以上であるモノマーが４５％以下望ましくは４０％以下であることによって達成される。多官能アクリロイル基モノマーが４０％以上になると硬化物が硬く、伸び率が低下するからである。 The pulling strength and elongation of the ultraviolet curable resin are as follows. In the (meth) acrylate monomer composition, the acryloyl group has a monofunctional monomer of 55% or more, preferably 60% or more, and the acryloyl group has a bifunctional or more. This is achieved by having a monomer content of 45% or less, desirably 40% or less. This is because when the polyfunctional acryloyl group monomer is 40% or more, the cured product is hard and the elongation rate is lowered.
　光反応性(メタ)アクリロイル基含有モノマーとしては、例えば、単官能の（メタ）アクリレート、２官能の（メタ）アクリレート、３官能以上の（メタ）アクリレート等が挙げられる。前記単官能の（メタ）アクリレートとしては、例えば、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、グリシジル（メタ）アクリレート、アクリロイルモルフォリン、Ｎ－ビニルピロリドン、テトラヒドロフルフリールアクリレート、シクロヘキシル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、イソデシル（メタ）アクリレート、ラウリル（メタ）アクリレート、トリデシル（メタ）アクリレート、セチル（メタ）アクリレート、ステアリル（メタ）アクリレート、ベンジル（メタ）アクリレート、２－エトキシエチル（メタ）アクリレート、３－メトキシブチル（メタ）アクリレート、エチルカルビトール（メタ）アクリレート、リン酸（メタ）アクリレート、エチレンオキサイド変性リン酸（メタ）アクリレート、フェノキシ（メタ）アクリレート、エチレンオキサイド変性フェノキシ（メタ）アクリレート、プロピレンオキサイド変性フェノキシ（メタ）アクリレート、ノニルフェノール（メタ）アクリレート、エチレンオキサイド変性ノニルフェノール（メタ）アクリレート、プロピレンオキサイド変性ノニルフェノール（メタ）アクリレート、メトキシジエチレングリコール（メタ）アクリレート、メトキシポリチレングリコール（メタ）アクリレート、メトキシプロピレングリコール（メタ）アクリレート、２－（メタ）アクリロイルオキシエチル－２－ヒドロキシプロピルフタレート、２－ヒドロキシ－３－フェノキシプロピル（メタ）アクリレート、２－（メタ）アクリロイルオキシエチルハイドロゲンフタレート、２－（メタ）アクリロイルオキシプロピルハイドロゲンフタレート、２－（メタ）アクリロイルオキシプロピルヘキサヒドロハイドロゲンフタレート、２－（メタ）アクリロイルオキシプロピルテトラヒドロハイドロゲンフタレート、ジメチルアミノエチル（メタ）アクリレート、トリフルオロエチル（メタ）アクリレート、テトラフルオロプロピル（メタ）アクリレート、ヘキサフルオロプロピル（メタ）アクリレート、オクタフルオロプロピル（メタ）アクリレート、オクタフルオロプロピル（メタ）アクリレート、２－アダマンタンおよびアダマンタンジオールから誘導される１価のモノ（メタ）アクリレートを有するアダマンチルアクリレートなどのアダマンタン誘導体モノ（メタ）アクリレート等が挙げられる。 Examples of the photoreactive (meth) acryloyl group-containing monomer include monofunctional (meth) acrylate, bifunctional (meth) acrylate, trifunctional or higher (meth) acrylate, and the like. Examples of the monofunctional (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl ( (Meth) acrylate, t-butyl (meth) acrylate, glycidyl (meth) acrylate, acryloylmorpholine, N-vinylpyrrolidone, tetrahydrofurfuryl acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) ) Acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, benzyl ( ) Acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethyl carbitol (meth) acrylate, phosphoric acid (meth) acrylate, ethylene oxide modified phosphoric acid (meth) acrylate, phenoxy (meth) ) Acrylate, ethylene oxide modified phenoxy (meth) acrylate, propylene oxide modified phenoxy (meth) acrylate, nonylphenol (meth) acrylate, ethylene oxide modified nonylphenol (meth) acrylate, propylene oxide modified nonylphenol (meth) acrylate, methoxydiethylene glycol (meth) Acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl hydrogen phthalate, 2- (meth) acryloyloxypropyl hydrogen phthalate 2- (meth) acryloyloxypropyl hexahydrohydrogen phthalate, 2- (meth) acryloyloxypropyl tetrahydrohydrogen phthalate, dimethylaminoethyl (meth) acrylate, trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, Hexafluoropropyl (meth) acrylate, octafluoropropyl (meth) acrylate, octafluoropropyl (meth) acrylate, 2- And adamantane mono (meth) acrylates such as adamantyl acrylate having a monovalent mono (meth) acrylate derived from adamantane and adamantanediol.
　前記２官能の（メタ）アクリレートとしては、例えば、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、ブタンジオールジ（メタ）アクリレート、ヘキサンジオールジ（メタ）アクリレート、ノナンジオールジ（メタ）アクリレート、エトキシ化ヘキサンジオールジ（メタ）アクリレート、プロポキシ化ヘキサンジオールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、エトキシ化ネオペンチルグリコールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、ヒドロキシピバリン酸ネオペンチルグリコールジ（メタ）アクリレートなどのジ（メタ）アクリレート、ビスフェノールＦ型ジアクリレート、エチレンオキサイド変性ビスフェノールＦ型ジアクリレート、ビスフェノールＡ型ジアクリレート、エチレンオキサイド変性ビスフェノールＡ型ジアクリレート、エチレンオキサイド変性イソシアヌル酸ジアクリレート等が挙げられる。 Examples of the bifunctional (meth) acrylate include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, and nonanediol di (meth). Acrylate, ethoxylated hexanediol di (meth) acrylate, propoxylated hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di ( (Meth) acrylate, neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, tripropylene glycol Di (meth) acrylate, di (meth) acrylate such as hydroxypivalate neopentyl glycol di (meth) acrylate, bisphenol F type diacrylate, ethylene oxide modified bisphenol F type diacrylate, bisphenol A type diacrylate, ethylene oxide modified bisphenol A-type diacrylate, ethylene oxide modified isocyanuric acid diacrylate, and the like.
　前記３官能以上の（メタ）アクリレート化合物としては、例えば、トリメチロールプロパントリ（メタ）アクリレート、エトキシ化トリメチロールプロパントリ（メタ）アクリレート、プロポキシ化トリメチロールプロパントリ（メタ）アクリレート、トリス２―ヒドロキシエチルイソシアヌレートトリ（メタ）アクリレート、グリセリントリ（メタ）アクリレート等のトリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールトリ（メタ）アクリレート、ジトリメチロールプロパントリ（メタ）アクリレート等の３官能以上の（メタ）アクリレート化合物；ペンタエリスリトールテトラ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート、ジペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジトリメチロールプロパンペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ジトリメチロールプロパンヘキサ（メタ）アクリレート等の３官能以上の多官能（メタ）アクリレートや、これら（メタ）アクリレートの一部をアルキル基やε－カプロラクトンで置換した多官能（メタ）アクリレート等が挙げられる。 Examples of the trifunctional or higher functional (meth) acrylate compound include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, and tris 2-hydroxy. Ethyl isocyanurate tri (meth) acrylate, tri (meth) acrylate such as glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, etc. Trifunctional or higher (meth) acrylate compounds; pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol Trifunctional or higher polyfunctionality such as tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane hexa (meth) acrylate, etc. And a polyfunctional (meth) acrylate obtained by substituting a part of these (meth) acrylates with an alkyl group or ε-caprolactone.
　(メタ)アクリロイル基含有オリゴマーとしては、例えばポリエステル（メタ）アクリレート、ポリウレタン（メタ）アクリレート、エポキシ（メタ）アクリレート、ポリエーテル（メタ）アクリレート、オリゴ（メタ）アクリレート、アルキド（メタ）アクリレート、ポリオール（メタ）アクリレート等が挙げられる。なかでもポリエステル（メタ）アクリレート、ポリウレタン（メタ）アクリレートは、特にタイルとの密着力が強く柔軟性のある紫外線硬化性樹脂を得る上で望ましい。 Examples of the (meth) acryloyl group-containing oligomer include polyester (meth) acrylate, polyurethane (meth) acrylate, epoxy (meth) acrylate, polyether (meth) acrylate, oligo (meth) acrylate, alkyd (meth) acrylate, polyol ( And (meth) acrylate. Among these, polyester (meth) acrylate and polyurethane (meth) acrylate are particularly desirable for obtaining a flexible ultraviolet curable resin having strong adhesion to tiles and flexibility.
　前記ビニルエーテル化合物としては、エチルビニルエーテル、ｎ－プロピルビニルエーテル、イソプロピルビニルエーテル、ｎ－ブチルビニルエーテル、イソブチルビニルエーテル、オクタデシルビニルエーテル、シクロヘキシルビニルエーテル、ブタンジオールモノビニルエーテル、シクロヘキサンジメタノールモノビニルエーテル、ｔ－ブチルビニルエーテル、ｔ－アミルビニルエーテル、エチルヘキシルビニルエーテル、ドデシルビニルエーテル、エチレングリコルモノビニルエーテル、エチレングリコルジビニルエーテル、エチレングリコールブチルビニルエーテル、ヘキサンジオールモノビニルエーテル、ヘキサンジオールジビニルエーテル、ジエチレングリコールモノビニルエーテル、ジエチレングリコールジビニルエーテル、トリエチレングリコールメチルビニルエーテルなどの１価および２価のアルコールのモノビニルエーテルおよびジビニルエーテル等が挙げられる。 Examples of the vinyl ether compound include ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether, butanediol monovinyl ether, cyclohexanedimethanol monovinyl ether, t-butyl vinyl ether, and t-amyl. Vinyl ether, ethyl hexyl vinyl ether, dodecyl vinyl ether, ethylene glycol monovinyl ether, ethylene glycol divinyl ether, ethylene glycol butyl vinyl ether, hexanediol monovinyl ether, hexanediol divinyl ether, diethylene glycol monovinyl ether, diethylene glycol divinyl ether Monovalent and divalent monovinyl ether and divinyl ethers of alcohols, such as triethylene glycol methyl vinyl ether.
　本発明では、紫外線硬化性接着剤組成物中のモノマー、オリゴマー、ポリマーの一部または全部に、水酸基、カルボキシル基及びその塩類、エポキシ基、アミノ基、マレイミド基、アルコキシ基、メルカプト基、燐酸基、燐酸エステル基、イソシアネート基、ニトロ基等の官能基を有するものを用いることによって紫外線硬化性樹脂の接着性を向上させることができる。これらはタイルとの密着性を高め、タイルと接着剤が剥離しにくくなり、接着剤の凝集力を強め、引張りに対する抗張力を高めるなどの接着剤改質効果があるからである。 In the present invention, some or all of the monomers, oligomers, and polymers in the ultraviolet curable adhesive composition may have hydroxyl groups, carboxyl groups and salts thereof, epoxy groups, amino groups, maleimide groups, alkoxy groups, mercapto groups, and phosphate groups. Adhesiveness of the ultraviolet curable resin can be improved by using a functional group such as a phosphate ester group, an isocyanate group, or a nitro group. This is because they have adhesive modification effects such as enhancing adhesion to the tile, making it difficult for the tile and adhesive to peel off, increasing the cohesive strength of the adhesive, and increasing the tensile strength against tension.
　このようなモノマーを例示すれば、２-ヒドロキシエチル（メタ）アクリレート、４-ヒドロキシブチル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、２-ヒドロキシプロピル（メタ）アクリレート、エチレングリコールモノ（メタ）アクリレート、プロピレングリコールモノ（メタ）アクリレート、ブタンジオールモノ（メタ）アクリレート、ペンタンジオールモノ（メタ）アクリレート、ヘキサンジオールモノ（メタ）アクリレート、ジエチレングリコールモノ（メタ）アクリレート、ジプロピレングリコールモノ（メタ）アクリレート、トリエチレングリコールモノ（メタ）アクリレート、トリプロピレングリコールモノ（メタ）アクリレート、テトラエチレングリコールモノ（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート、ポリプロピレングリコールモノ（メタ）アクリレート、ネオペンチルグリコールモノ（メタ）アクリレート、エトキシ化ネオペンチルグリコールモノ（メタ）アクリレート、ヒドロキシピバリン酸ネオペンチルグリコールモノ（メタ）アクリレートなどの２価アルコールのモノ（メタ）アクリレート、イソシアヌル酸エチレンオキサイド変性ジアクリレート、ペンタエリストールジアクリレートモノステアレート、ペンタエリストールトリアクリレート、２-ヒドロキシ３－フェノキシプロピルアクリレート、アクリル酸、メタクリル酸、マレイン酸、フマル酸、イタコン酸、クロトン酸、アトロパ酸シトラコン酸等のα，β-不飽和カルボン酸及びこれらカルボン酸のアンモニウム塩やアミン塩あるいはアルカリ(土類)金属塩、ω－カルボキシーポリカプロラクトンモノアクリレート、アクリル酸ダイマー、フタル酸モノヒドロキシエチルアクリレート、グリシジル（メタ）アクリレート、ジメチルアミノメチル（メタ）アクリレート、カヤマーＰＭ-２(日本化薬株式会社製)、カヤマーＰＭ-２１(日本化薬株式会社製)、γ－メタクリルオキシプロピルトリメトキシシラン、γ－メタクリルオキシプロピルトリエトキシシラン、γ－アクリルオキシプロピルトリメトキシシラン、γ－アクリルオキシプロピルトリエトキシシラン、２-イソシアトエチル（メタ）アクリレート等があげられる。 Examples of such monomers include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, ethylene glycol mono (meth) ) Acrylate, propylene glycol mono (meth) acrylate, butanediol mono (meth) acrylate, pentanediol mono (meth) acrylate, hexanediol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate , Triethylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, polyethylene Divalent compounds such as glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, ethoxylated neopentyl glycol mono (meth) acrylate, and hydroxypivalate neopentyl glycol mono (meth) acrylate Mono (meth) acrylate of alcohol, isocyanuric acid ethylene oxide modified diacrylate, pentaerythritol diacrylate monostearate, pentaerythritol triacrylate, 2-hydroxy 3-phenoxypropyl acrylate, acrylic acid, methacrylic acid, maleic acid, fumar Α, β-unsaturated carboxylic acids such as acid, itaconic acid, crotonic acid, atropic acid citraconic acid, and ammonium or amine salts of these carboxylic acids Alkali (earth) metal salt, ω-carboxy polycaprolactone monoacrylate, acrylic acid dimer, phthalic acid monohydroxyethyl acrylate, glycidyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, Kayamar PM-2 (Nippon Kayaku Kayamar PM-21 (manufactured by Nippon Kayaku Co., Ltd.), γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyl Examples include triethoxysilane, 2-isocyanatoethyl (meth) acrylate, and the like.
　前記有機物ポリマーとしては、更に、天然高分子物質類や前記したアクリレート以外の合成高分子物質類も選ばれ、必要に応じて本発明の接着剤に添加しても良い。天然高分子物質類や合成高分子物質類としては、例えば、各種のビニルエステル樹脂類、ブロックイソシアネート、ポリイソシアネート化合物、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、脂環式エポキシ樹脂等のエポキシ樹脂ポリマーまたはオリゴマーおよびその誘導体ポリエポキシド類、ポリビニルブチラール樹脂、ポリビニルアルコールおよびその誘導体、アクリル樹脂類、アルキド樹脂類、尿素樹脂類、メラミン樹脂類、ポリ酢酸ビニル、酢酸ビニル系共重合体類、ポリブタジエン系エラストマー、飽和ポリエステル類、飽和ポリエーテル類、ニトロセルロース類、セルロースアセテートブチレート等セルロース誘導体類；アマニ油、桐油、大豆油、ヒマシ油またはエポキシ化油類の如き油脂類等が挙げられる。 As the organic polymer, natural polymer materials and synthetic polymer materials other than the acrylates described above may be further selected and added to the adhesive of the present invention as necessary. Examples of natural polymer materials and synthetic polymer materials include various vinyl ester resins, block isocyanates, polyisocyanate compounds, bisphenol A type epoxy resins, bisphenol F type epoxy resins, alicyclic epoxy resins, and other epoxies. Resin polymer or oligomer and derivatives thereof Polyepoxides, polyvinyl butyral resin, polyvinyl alcohol and derivatives thereof, acrylic resins, alkyd resins, urea resins, melamine resins, polyvinyl acetate, vinyl acetate copolymers, polybutadiene Elastomers, saturated polyesters, saturated polyethers, nitrocelluloses, cellulose derivatives such as cellulose acetate butyrate; fats and oils such as linseed oil, tung oil, soybean oil, castor oil or epoxidized oil That.
　なかでもブロックイソシアネート、ポリイソシアネート化合物、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、脂環式エポキシ樹脂等のエポキシ樹脂ポリマーまたはオリゴマーおよびその誘導体ポリエポキシド類、ポリビニルブチラール樹脂、ポリビニルアルコールおよびその誘導体、飽和ポリエステル樹脂、ポリアミド、ニトロセルロース等がタイルとの密着性を高めるので望ましい。 Among them, blocked isocyanates, polyisocyanate compounds, bisphenol A type epoxy resins, bisphenol F type epoxy resins, alicyclic epoxy resins and other epoxy resin polymers or oligomers and their derivatives polyepoxides, polyvinyl butyral resins, polyvinyl alcohol and their derivatives, saturation Polyester resin, polyamide, nitrocellulose, etc. are desirable because they increase the adhesion to the tile.
　該接着剤組成物には必要に応じて、例えばフタル酸ジエチル、フタル酸ジブチル、フタル酸ジオクチル、プロセスオイル等の可塑剤、トルエン、キシレン、酢酸ブチル、イソプロピルアルコール等の有機溶剤を加えることが出きる。また該接着剤組成物には必要に応じて、酸化チタン、カーボンブラック、弁柄、オイル染料等の着色顔料、着色染料、炭酸カルシウム、タルク、アルミナ、水酸化アルミニウム、水酸化マグネシウム、カオリンクレー、粘土鉱物粉体、ロックウール粉体、ガラス繊維粉体、アスベスト粉体、含水微粉シリカ（ホワイトカーボン）、超微粉無水シリカ（アエロジル）、珪砂（シリカサンド）、沈降性炭酸マグネシウム、ステアリン酸金属塩等の無機物粉体等を加えることができる。 If necessary, for example, plasticizers such as diethyl phthalate, dibutyl phthalate, dioctyl phthalate, and process oil, and organic solvents such as toluene, xylene, butyl acetate, and isopropyl alcohol can be added to the adhesive composition. wear. In addition, the adhesive composition, if necessary, titanium oxide, carbon black, petals, colored pigments such as oil dyes, colored dyes, calcium carbonate, talc, alumina, aluminum hydroxide, magnesium hydroxide, kaolin clay, Clay mineral powder, rock wool powder, glass fiber powder, asbestos powder, hydrous fine powder silica (white carbon), ultra fine powder anhydrous silica (Aerosil), silica sand (silica sand), precipitated magnesium carbonate, stearic acid metal salt Inorganic powders such as can be added.
　本発明でいう光反応開始剤とは例えば、ベンゾフェノン、ベンジル、ミヒラーケトン、チオキサントンまたはアントラキノン等の水素引き抜きによってラジカルを発生するタイプの化合物等が挙げられる。これらの化合物は、メチルアミン、ジエタノールアミン、Ｎ－メチルジエタノールアミン、トリブチルアミン等の第三アミンを増感剤として併用するのが一般的である。 Examples of the photoinitiator referred to in the present invention include compounds that generate radicals by hydrogen abstraction such as benzophenone, benzyl, Michler ketone, thioxanthone, or anthraquinone. These compounds generally use a tertiary amine such as methylamine, diethanolamine, N-methyldiethanolamine or tributylamine as a sensitizer.
　別のタイプの光重合開始剤としては、例えば、分子内開裂によってラジカルを発生するタイプの化合物等が挙げられる。具体的には、例えば、ベンゾイン、ジアルコキシアセトフェノン、アシルオキシムエステル、ベンジルケタール、ヒドロキシアルキルフェノン、ハロゲノケトン等が挙げられる。 Examples of another type of photopolymerization initiator include compounds that generate radicals by intramolecular cleavage. Specific examples include benzoin, dialkoxyacetophenone, acyloxime ester, benzyl ketal, hydroxyalkylphenone, halogenoketone and the like.
　かくして該接着剤は、（メタ）アクリレートオリゴマー、（メタ）アクリレートモノマーから選ばれた１種または２種以上の混合物に、必要に応じてこれらオリゴマー、モノマーと相溶性のあるポリマー、オリゴマーからえらばれた１種または２種以上を添加し、光反応開始剤と、必要に応じてその増感剤、増粘剤や希釈剤、着色剤等を添加して作製される。 Thus, the adhesive is selected from one or a mixture of two or more selected from (meth) acrylate oligomers and (meth) acrylate monomers, if necessary, from these oligomers, polymers compatible with the monomers, and oligomers. In addition, one or two or more kinds are added, and a photoreaction initiator and, if necessary, a sensitizer, a thickener, a diluent, a colorant, and the like are added.
　上述した接着剤組成物は、たとえば離型処理された盤上にタイルを整列させ、このタイル間に接着剤を点状に注入し、次に紫外線を照射し、該紫外線硬化性樹脂を硬化させタイルシートを作製する。紫外線を照射する際に用いる紫外線ランプは、高圧水銀灯などの紫外線を効率的に発生する光源から紫外線を照射し、硬化させる。タイルの裏に回って光の届かない箇所はたとえばタイルシートを反転させ、光を当てることによって硬化させたり、離型処理された盤に紫外線透過率に優れたガラス、プラスチックスを用い、裏面からも光を照射させるか、この透光盤に光の反射面を設け、上から照射した光を反射面で反射させることにより、上から照射した場合に影になる箇所も同時に硬化させることによって達成される。 The above-described adhesive composition can be used, for example, by arranging tiles on a release-treated board, injecting adhesive between the tiles in a dotted manner, and then irradiating ultraviolet rays to cure the ultraviolet curable resin. Make a tile sheet. An ultraviolet lamp used for irradiating ultraviolet rays is irradiated with ultraviolet rays from a light source that efficiently generates ultraviolet rays, such as a high-pressure mercury lamp, and cured. For example, turn the tile sheet upside down and harden it by shining light on the back of the tile, or use a glass or plastic with excellent UV transmittance on the release-treated panel. This is achieved by irradiating light or providing a light reflecting surface on this translucent board, and reflecting the light irradiated from above by the reflecting surface, thereby simultaneously curing the shadowed area when irradiated from above. Is done.
　以下実施例により、本発明をさらに具体的に説明する。本発明の範囲はこれら実施例に限定されるものではない。 Hereinafter, the present invention will be described more specifically with reference to examples. The scope of the present invention is not limited to these examples.
　攪拌機、コンデンサー、滴下ロートおよび温度計を備えた２リットルの清浄なセパラブルフラスコに、２官能ポリエステルポリオール（アデカポリエステルＮＳ-２４００　旭電化工業株式会社製）１０００重量部、イソホロンジイソシアネート２２５重量部を加え、攪拌しながら９０℃に昇温し、３時間反応させた。この反応物に、２-ヒドロキシエチルアクリレト１２０重量部、ターシャリーブチルハイドロキノン０.５重量部を加え、８０℃にてさらに３時間反応させ、ウレタンアクリレートオリゴマーを得た。 To a 2 liter clean separable flask equipped with a stirrer, condenser, dropping funnel and thermometer, 1000 parts by weight of bifunctional polyester polyol (Adeka Polyester NS-2400, manufactured by Asahi Denka Kogyo Co., Ltd.) and 225 parts by weight of isophorone diisocyanate were added. While stirring, the temperature was raised to 90 ° C. and reacted for 3 hours. To this reaction product, 120 parts by weight of 2-hydroxyethyl acrylate and 0.5 part by weight of tertiary butyl hydroquinone were added and reacted at 80 ° C. for 3 hours to obtain a urethane acrylate oligomer.
　上記オリゴマー１００重量部に、２ヒドロキシエチルアクリレート３０重量部、フェノキシポリエチレングリコールアクリレート１５重量部、アクリル酸１０重量部、ジメチルアミノメチルメタアクリレート１０重量部、光重合開始剤〔イルガキュア１８４（チバ・スペシャリテイーケミカル社製　１－ヒドロキシ－シクロヘキシル－フェニル-ケトン）〕５重量部、アミノアルコール２重量部、酸化チタン０.０５重量部、カーボンブラック０.００５重量部、アエロジル２００（日本アエロジル株式会社製）３重量部を加え、紫外線硬化性接着剤組成物を得た。 To 100 parts by weight of the above oligomer, 30 parts by weight of 2-hydroxyethyl acrylate, 15 parts by weight of phenoxypolyethylene glycol acrylate, 10 parts by weight of acrylic acid, 10 parts by weight of dimethylaminomethyl methacrylate, a photopolymerization initiator [Irgacure 184 (Ciba Specialty) Chemical 1-hydroxy-cyclohexyl-phenyl-ketone)] 5 parts by weight, amino alcohol 2 parts by weight, titanium oxide 0.05 parts by weight, carbon black 0.005 parts by weight, Aerosil 200 (manufactured by Nippon Aerosil Co., Ltd.) 3 Part by weight was added to obtain an ultraviolet curable adhesive composition.
　攪拌機、コンデンサー、滴下ロートおよび温度計を備えた２リットルの清浄なセパラブルフラスコに、プラクセル２２０（ポリカプロラクトンジオール　ダイセル化学工業株式会社製）１０００重量部、ヘキサメチレンジイソシアネート１５０重量部、を加え、攪拌しながら９０℃に昇温し、３時間反応させた。この反応物に、２-ヒドロキシエチルアクリレト９５重量部、ターシャリーブチルハイドロキノン０.５重量部重量部をさらに加え、８０℃にてさらに３時間反応させ、ウレタンアクリレートオリゴマーを得た。 To a 2 liter clean separable flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer, 1000 parts by weight of Plaxel 220 (polycaprolactone diol, manufactured by Daicel Chemical Industries, Ltd.) and 150 parts by weight of hexamethylene diisocyanate were added and stirred. Then, the temperature was raised to 90 ° C. and reacted for 3 hours. To this reaction product, 95 parts by weight of 2-hydroxyethyl acrylate and 0.5 parts by weight of tertiary butyl hydroquinone were further added and reacted at 80 ° C. for 3 hours to obtain a urethane acrylate oligomer.
　上記オリゴマーに１００重量部に、アロニックスＭ-５６００（アクリル酸ダイマー　東亞合成株式会社製）３０重量部、４-ヒドロキシブチルアクリレート３０重量部、１．６ヘキサンジオールジアクリレート１０重量部、γ－アクリルオキシプロピルトリエトキシシラン２重量部、光重合開始剤〔イルガキュア１８４（チバ・スペシャリテイーケミカル社製　１－ヒドロキシ－シクロヘキシル－フェニル-ケトン）〕５重量部、アミノアルコール２重量部、酸化チタン０.０５重量部、カーボンブラック０.００５重量部、アエロジル２００（日本アエロジル株式会社製）３重量部を加え、紫外線硬化性接着剤組成物を得た。 100 parts by weight of the above oligomer, 30 parts by weight of Aronix M-5600 (acrylic acid dimer, manufactured by Toagosei Co., Ltd.), 30 parts by weight of 4-hydroxybutyl acrylate, 10 parts by weight of 1.6 hexanediol diacrylate, γ-acryloxy 2 parts by weight of propyltriethoxysilane, photopolymerization initiator [Irgacure 184 (manufactured by Ciba Specialty Chemicals Co., Ltd., 1-hydroxy-cyclohexyl-phenyl-ketone)], 2 parts by weight of amino alcohol, 0.05 weight of titanium oxide Part, carbon black 0.005 part by weight, and Aerosil 200 (manufactured by Nippon Aerosil Co., Ltd.) 3 parts by weight were added to obtain an ultraviolet curable adhesive composition.
　攪拌機、コンデンサー、滴下ロートおよび温度計を備えた２リットルの清浄なセパラブルフラスコに、ＵＲＩＣ Ｈ-５６（ひまし油ポリオール　伊藤製油株式会社製）１３１０重量部、トリレンジイソシアネート３１５重量部を加え攪拌しながら９０℃に昇温し、３時間反応させた。この反応物に、２-ヒドロキシプロピルアクリレート２１０重量部ターシャリーブチルハイドロキノン０.５重量部をさらに加え、８０℃にてさらに３時間反応させ、ウレタンアクリレートオリゴマーを得た。 To a 2 liter clean separable flask equipped with a stirrer, condenser, dropping funnel and thermometer, 1310 parts by weight of URIC H-56 (castor oil polyol, manufactured by Ito Oil Co., Ltd.) and 315 parts by weight of tolylene diisocyanate were added and stirred. The temperature was raised to 90 ° C. and reacted for 3 hours. To this reaction product, 210 parts by weight of 2-hydroxypropyl acrylate and 0.5 parts by weight of tertiary butyl hydroquinone were further added and reacted at 80 ° C. for 3 hours to obtain a urethane acrylate oligomer.
　上記オリゴマーに１００重量部に、アロニックスＭ-５６００（アクリル酸ダイマー　東亞合成株式会社製）３０重量部、４ヒドロキシブチルアクリレート３０重量部、γ－アクリルオキシプロピルトリエトキシシラン２重量部、光重合開始剤〔イルガキュア１８４（チバ・スペシャリテイーケミカル社製　１－ヒドロキシ－シクロヘキシル－フェニル-ケトン）〕５重量部、アミノアルコール２重量部、アエロジル２００（日本アエロジル株式会社製）３重量部を加え、紫外線硬化性接着剤組成物を得た。 100 parts by weight of the above oligomer, 30 parts by weight of Aronix M-5600 (acrylic acid dimer, manufactured by Toagosei Co., Ltd.), 30 parts by weight of 4 hydroxybutyl acrylate, 2 parts by weight of γ-acryloxypropyltriethoxysilane, photopolymerization initiator [Irgacure 184 (Ciba Specialty Chemical Co., Ltd. 1-hydroxy-cyclohexyl-phenyl-ketone)] 5 parts by weight, amino alcohol 2 parts by weight, Aerosil 200 (Nippon Aerosil Co., Ltd.) 3 parts by weight are added, and UV curable An adhesive composition was obtained.
　攪拌機、コンデンサー、滴下ロートおよび温度計を備えた２リットルの清浄なセパラブルフラスコに、３官能ポリエーテルポリオール（アデカポリエーテルＧ-１５００　旭電化工業株式会社製）１０００重量部、トリレンジイソシアネート３４５重量部、を加え、攪拌しながら９０℃に昇温し、３時間反応させた。この反応物に、２―ヒドロキシエチルアクリレト２３５重量部、１２％ジブチルチンジラウレート０.２重量部、ターシャリーブチルハイドロキノン０.５重量部重量部をさらに加え、８０℃にてさらに３時間反応させ、ウレタンアクリレートオリゴマーを得た。 To a 2 liter clean separable flask equipped with a stirrer, condenser, dropping funnel and thermometer, 1000 parts by weight of trifunctional polyether polyol (Adeka Polyether G-1500, manufactured by Asahi Denka Kogyo Co., Ltd.), 345 weights of tolylene diisocyanate The mixture was heated to 90 ° C. with stirring and reacted for 3 hours. To this reaction product, 235 parts by weight of 2-hydroxyethyl acrylate, 0.2 part by weight of 12% dibutyltin dilaurate and 0.5 part by weight of tertiary butyl hydroquinone were further added and reacted at 80 ° C. for another 3 hours. A urethane acrylate oligomer was obtained.
　上記ウレタンアクリレートオリゴマー６０重量部に、エスレックＢＬ-３（ブチラール樹脂　積水化学株式会社製）３０量部を４ヒドロキシブチルアクリレート７０重量部にて混合溶解したもの１００重量部、Ｎ－ビニル２－ピロリドン２０重量部、γ－アクリルオキシプロピルトリエトキシシラン２重量部、光重合開始剤〔イルガキュア１８４（チバ・スペシャリテイーケミカル社製　１－ヒドロキシ－シクロヘキシル－フェニル-ケトン）〕５重量部、アミノアルコール２重量部、アエロジル２００（日本アエロジル株式会社製）３重量部を加え、紫外線硬化性接着剤組成物を得た。 100 parts by weight of 60 parts by weight of the urethane acrylate oligomer, 30 parts by weight of ESREC BL-3 (butyral resin, manufactured by Sekisui Chemical Co., Ltd.) mixed with 70 parts by weight of 4 hydroxybutyl acrylate, 20 parts of N-vinyl 2-pyrrolidone Parts by weight, 2 parts by weight of γ-acryloxypropyltriethoxysilane, 5 parts by weight of photopolymerization initiator [Irgacure 184 (Ciba Specialty Chemicals Co., Ltd., 1-hydroxy-cyclohexyl-phenyl-ketone)], 2 parts by weight of amino alcohol 3 parts by weight of Aerosil 200 (manufactured by Nippon Aerosil Co., Ltd.) was added to obtain an ultraviolet curable adhesive composition.
　ＣＮ２２５６（ポリエルテルポリオール　サートマー・ジャパン株式会社製）６０重量部、２-ヒドロキシ３－フェノキシプロピルアクリレート、３０重量部、１．６ヘキサンジオールジアクリレート１０重量部、ω－カルボキシーポリカプロラクトンモノアクリレート１０重量部、光重合開始剤〔イルガキュア１８４（チバ・スペシャリテイーケミカル社製　１－ヒドロキシ－シクロヘキシル－フェニル-ケトン）〕２重量部、アミノアルコール１重量部、アエロジル２００（日本アエロジル株式会社製）１.５重量部を加え、紫外線硬化性接着剤組成物を得た。 CN2256 (Polyerter polyol, manufactured by Sartomer Japan Co., Ltd.) 60 parts by weight, 2-hydroxy 3-phenoxypropyl acrylate, 30 parts by weight, 10 parts by weight of hexanediol diacrylate, 10 parts by weight of ω-carboxypolycaprolactone monoacrylate Parts, photopolymerization initiator [Irgacure 184 (manufactured by Ciba Specialty Chemicals Co., Ltd., 1-hydroxy-cyclohexyl-phenyl-ketone)], 1 part by weight of amino alcohol, Aerosil 200 (manufactured by Nippon Aerosil Co., Ltd.) 1.5 Part by weight was added to obtain an ultraviolet curable adhesive composition.
　エポトートＹＤ-０１１（東都化成株式会社製エポキシ樹脂）６０重量部を４-ヒドロキシブチルアクリレート４０重量部にて混合し溶解した。 60 parts by weight of Epototo YD-011 (Epoxy resin manufactured by Toto Kasei Co., Ltd.) was mixed and dissolved in 40 parts by weight of 4-hydroxybutyl acrylate.
　上記混合物に実施例２で得たウレタンアクリレートオリゴマー１５０重量部、フェノキシポリエチレングリコールアクリレート１０重量部、カヤマーＰＭ-２（日本化薬株式会社製）４重量部、光重合開始剤〔イルガキュア１８４（チバ・スペシャリテイーケミカル社製　１－ヒドロキシ－シクロヘキシル－フェニル-ケトン）〕５重量部、アミノアルコール３重量部、アエロジル２００（日本アエロジル株式会社製）４重量部を加え、紫外線硬化性接着剤組成物を得た。 150 parts by weight of the urethane acrylate oligomer obtained in Example 2, 10 parts by weight of phenoxypolyethylene glycol acrylate, 4 parts by weight of Kayamar PM-2 (manufactured by Nippon Kayaku Co., Ltd.), a photopolymerization initiator [Irgacure 184 (Ciba 5 parts by weight of 1-hydroxy-cyclohexyl-phenyl-ketone) manufactured by Specialty Chemical Co., Ltd., 3 parts by weight of amino alcohol and 4 parts by weight of Aerosil 200 (manufactured by Nippon Aerosil Co., Ltd.) are obtained to obtain an ultraviolet curable adhesive composition. It was.
　ＳＭＡ３０００（スチレンマレイン酸樹脂、サートマージャパン株式会社製）３３部をヒドロキシブチルアクリレート３３部、フェノキシレートポリエチレングリコールアクリレート３３部にて溶解した溶液４０重量部、エポトートＹＤ－０１１（東都化成株式会社製エポキシ樹脂）６０重量部を４－ヒドロキシブチルアクリレート４０重量部にて混合し溶解した溶液１００重量部、実施例１で得たウレタンアクリレートオリゴマー１１０重量部、ノニルフェノールＥＯ変性アクリレート（東亞合成株式会社製アロニックスＭ－１１１）５０重量部、ヒドロキシブチルアクリレート３０重量部、エトキシレートビスフェノールＡジアクリレート１０重量部、光重合開始剤〔イルガキュア１８４（チバ・スペシャリテイーケミカル社製　１－ヒドロキシ－シクロヘキシル－フェニル－ケトン）〕８重量部、アエロジル２００（日本アエロジル株式会社製）７重量部を加え、紫外線硬化性接着剤組成物を得た。 40 parts by weight of a solution prepared by dissolving 33 parts of SMA 3000 (styrene maleic acid resin, manufactured by Sartomer Japan Co., Ltd.) with 33 parts of hydroxybutyl acrylate and 33 parts of phenoxylate polyethylene glycol acrylate, Epototo YD-011 (epoxy manufactured by Toto Kasei Co., Ltd.) Resin) 100 parts by weight of a solution prepared by mixing 60 parts by weight of 4-hydroxybutyl acrylate with 40 parts by weight, 110 parts by weight of the urethane acrylate oligomer obtained in Example 1, nonylphenol EO-modified acrylate (Aronix M manufactured by Toagosei Co., Ltd.) -111) 50 parts by weight, hydroxybutyl acrylate 30 parts by weight, ethoxylate bisphenol A diacrylate 10 parts by weight, photopolymerization initiator [Irgacure 184 (manufactured by Ciba Specialty Chemicals 1- Dorokishi - cyclohexyl - phenyl - ketone)] 8 parts by weight of Aerosil 200 (Nippon Aerosil Co., Ltd.) 7 parts by weight was added to obtain an ultraviolet-curable adhesive composition.
　攪拌機、コンデンサー、滴下ロートおよび温度計を備えた２リットルの清浄なセパラブルフラスコに、アデカポリエーテルＰ-３０００（２官能ポリエーテルポリオール　旭電化工業株式会社製）１５００重量部、ヘキサメチレンジイソシアネート１３５重量部、１２％ジブチルチンジラウレート０.３重量部を加え、攪拌しながら９０℃に昇温し、３時間反応させた。この反応物に、４―ヒドロキシブチルアクリレト８７重量部、ターシャリーブチルハイドロキノン０.５重量部をさらに加え、８０℃にてさらに３時間反応させ、ウレタンアクリレートオリゴマーを得た。 In a 2 liter clean separable flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer, 1500 parts by weight of ADEKA polyether P-3000 (bifunctional polyether polyol, manufactured by Asahi Denka Kogyo Co., Ltd.), 135 weight of hexamethylene diisocyanate Part, 0.3% by weight of 12% dibutyltin dilaurate was added, the temperature was raised to 90 ° C. with stirring, and the mixture was reacted for 3 hours. To this reaction product, 87 parts by weight of 4-hydroxybutyl acrylate and 0.5 parts by weight of tertiary butyl hydroquinone were further added and reacted at 80 ° C. for 3 hours to obtain a urethane acrylate oligomer.
　エポトートＹＤ-０１１（東都化成株式会社製エポキシ樹脂）６０重量部を４-ヒドロキシブチルアクリレート４０重量部にて混合し溶解した溶液に、上記ウレタンアクリレートオリゴマー９０重量部、カヤマーＰＭ-２（日本化薬株式会社製）４重量部、光重合開始剤〔イルガキュア１８４（チバ・スペシャリテイーケミカル社製　１－ヒドロキシ－シクロヘキシル－フェニル-ケトン）〕６重量部、アミノアルコール３重量部、アエロジル２００（日本アエロジル株式会社製）５重量部を加え、紫外線硬化性接着剤組成物を得た。 In a solution obtained by mixing and dissolving 60 parts by weight of Epototo YD-011 (epoxy resin manufactured by Toto Kasei Co., Ltd.) with 40 parts by weight of 4-hydroxybutyl acrylate, 90 parts by weight of the urethane acrylate oligomer and Kayamer PM-2 (Nippon Kayaku) 4 parts by weight, photopolymerization initiator [Irgacure 184 (Ciba Specialty Chemicals 1-hydroxy-cyclohexyl-phenyl-ketone)] 6 parts by weight, amino alcohol 3 parts by weight, Aerosil 200 (Nippon Aerosil Co., Ltd.) (Made by company) 5 parts by weight was added to obtain an ultraviolet curable adhesive composition.
　バイロン５５０（東洋紡績株式会社製飽和ポリエステル樹脂）３５重量部を４-ヒドロキシブチルアクリレート４０重量部、フェノキシポリエチレングリコールアクリレート３０重量部、ポリエチレングリコール６００アクリレート（東亞合成株式会社製アロニックスＭ-２６０）５重量部にて混合溶解した。この溶液に、アクリル酸マグネシウム４重量部、光重合開始剤〔イルガキュア１８４（チバ・スペシャリテイーケミカル社製　１－ヒドロキシ－シクロヘキシル－フェニル-ケトン）〕４重量部、アミノアルコール２重量部、アエロジル２００（日本アエロジル株式会社製）３重量部を加え、紫外線硬化性接着剤組成物を得た。 Byron 550 (Toyobo Co., Ltd., saturated polyester resin) 35 parts by weight 4-hydroxybutyl acrylate 40 parts by weight, phenoxy polyethylene glycol acrylate 30 parts by weight, polyethylene glycol 600 acrylate (Toagosei Co., Ltd. Aronix M-260) 5 parts by weight The solution was mixed and dissolved in the part. To this solution, 4 parts by weight of magnesium acrylate, 4 parts by weight of a photopolymerization initiator [Irgacure 184 (manufactured by Ciba Specialty Chemicals Co., Ltd., 1-hydroxy-cyclohexyl-phenyl-ketone)], 2 parts by weight of amino alcohol, and Aerosil 200 ( Nippon Aerosil Co., Ltd.) (3 parts by weight) was added to obtain an ultraviolet curable adhesive composition.
　＜比較例１＞
　実施例２で得られたウレタンアクリレートオリゴマーを１００重量部、アロニックスＭ-５６００（アクリル酸ダイマー　東亞合成株式会社製）２０重量部、４-ヒドロキシブチルアクリレート２０重量部、１．６ヘキサンジオールジアクリレート３５重量部、γ－アクリルオキシプロピルトリエトキシシラン２重量部、光重合開始剤〔イルガキュア１８４（チバ・スペシャリテイーケミカル社製　１－ヒドロキシ－シクロヘキシル－フェニル-ケトン）〕５重量部、アミノアルコール２重量部、酸化チタン０.５重量部、カーボンブラック０.０１重量部、アエロジル２００（（日本アエロジル株式会社製）３重量部を加え、紫外線硬化性接着剤組成物を得た。 <Comparative Example 1>
100 parts by weight of the urethane acrylate oligomer obtained in Example 2, 20 parts by weight of Aronix M-5600 (acrylic acid dimer manufactured by Toagosei Co., Ltd.), 20 parts by weight of 4-hydroxybutyl acrylate, 35 hexanediol diacrylate 35 Parts by weight, 2 parts by weight of γ-acryloxypropyltriethoxysilane, 5 parts by weight of a photopolymerization initiator [Irgacure 184 (Ciba Specialty Chemicals 1-hydroxy-cyclohexyl-phenyl-ketone)], 2 parts by weight of amino alcohol Then, 0.5 parts by weight of titanium oxide, 0.01 parts by weight of carbon black, and 3 parts by weight of Aerosil 200 (manufactured by Nippon Aerosil Co., Ltd.) were added to obtain an ultraviolet curable adhesive composition.
　＜比較例２＞
　実施例１で得たウレタンアクリレートオリゴマーを１００重量部、ラウリルアクリレート３０重量部、２．２－ビス〔４－（アクリロキシ・ジエトキシ）フェニル〕プロパン２０重量部、ポリエチレングリコール６００ジアクリレート（東亞合成株式会社製アロニックスＭ-２６０）５重量部光重合開始剤〔イルガキュア１８４（チバ・スペシャリテイーケミカル社製　１－ヒドロキシ－シクロヘキシル－フェニル-ケトン）〕４重量部、アミノアルコール２重量部、アエロジル２００（日本アエロジル株式会社製）４重量部を加え、紫外線硬化性接着剤組成物を得た。 <Comparative Example 2>
100 parts by weight of the urethane acrylate oligomer obtained in Example 1, 30 parts by weight of lauryl acrylate, 20 parts by weight of 2.2-bis [4- (acryloxy-diethoxy) phenyl] propane, polyethylene glycol 600 diacrylate (Toagosei Co., Ltd.) Aronix M-260) 5 parts by weight photopolymerization initiator [Irgacure 184 (Ciba Specialty Chemicals 1-hydroxy-cyclohexyl-phenyl-ketone)] 4 parts by weight, amino alcohol 2 parts by weight, Aerosil 200 (Nippon Aerosil) 4 parts by weight) were added to obtain an ultraviolet curable adhesive composition.
　実施例１から実施例９及び比較例１から２の特性を検証するため、図３，４で示した搭載治具１にタイルＴを敷設して整列させ、実施例１から実施例９及び比較例１にて作製された紫外線硬化性接着剤組成物を、同図のように各目地間隙ｓ内に約５ｍｍ幅１.５ｍｍ厚で注入した。そして１５０Ｗ／ｃｍの高圧水銀ランプを光源Ｌとして用いて、上記紫外線硬化性樹脂の塗膜箇所に紫外線を１０秒間照射し（ランプからの距離２５ｍｍ）、硬化被膜を形成した。作製されたタイルシートの上端２箇所を手で持ちあげ、軽く数回ゆすった後のタイルシートの状態を観察し、その接着性を確認した。またこのタイルシートを接着箇所で９０度折り曲げ、接着剤の状態を観察した。 In order to verify the characteristics of Examples 1 to 9 and Comparative Examples 1 and 2, tiles T were laid and aligned on the mounting jig 1 shown in FIGS. The ultraviolet curable adhesive composition produced in Example 1 was injected into each joint gap s with a width of about 5 mm and a thickness of 1.5 mm as shown in FIG. Then, using a 150 W / cm high-pressure mercury lamp as the light source L, the coating film portion of the ultraviolet curable resin was irradiated with ultraviolet rays for 10 seconds (distance 25 mm from the lamp) to form a cured coating film. The two upper ends of the produced tile sheet were lifted by hand, and the state of the tile sheet after lightly shaking several times was observed to confirm its adhesiveness. Further, this tile sheet was bent 90 degrees at the bonding portion, and the state of the adhesive was observed.
　さらに実施例１から実施例９及び比較例１、比較例２にて作製された紫外線硬化性樹脂を、離型処理された盤上に約１.５ｍｍ厚に塗布し、１５０Ｗ／ｃｍの高圧水銀ランプを用いて、上記紫外線硬化性樹脂の塗膜箇所に紫外線を１０秒間照射し（ランプからの距離２５ｍｍ）、硬化被膜を形成した。この硬化皮膜を、ＪＩＳ Ｋ７１１３に準拠し、皮膜の引っ張り強度（Ｍｐａ）、伸び率をＴＥＣＨＮＯ ＧＲＡＰＨ １０ＫＮ(ミネベア株式会社製)にて測定した。以下にその試験結果を示す。 Further, the UV curable resin prepared in Examples 1 to 9 and Comparative Examples 1 and 2 was applied to a release-treated board to a thickness of about 1.5 mm and 150 W / cm high-pressure mercury. Using a lamp, the coating film portion of the ultraviolet curable resin was irradiated with ultraviolet rays for 10 seconds (distance from the lamp of 25 mm) to form a cured coating film. This cured film was measured according to JIS K 7113, and the tensile strength (Mpa) and elongation of the film were measured with TECHNO K GRAPH 10 KN (manufactured by Minebea Co., Ltd.). The test results are shown below.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　接着性試験：比較例２はタイルへの密着が悪く、シートを持ち上げたときにタイル界面から接着剤が剥離した。他のものでは異常が起きなかった。
　曲げ試験：比較例１は容易に曲げることができず、部分的に接着剤にクラックが入った。比較例２は曲げることにより、接着剤がタイル界面から剥離した。 Adhesion test: Comparative Example 2 had poor adhesion to the tile, and the adhesive peeled off the tile interface when the sheet was lifted. There was no abnormality in other things.
Bending test: Comparative Example 1 could not be easily bent, and the adhesive was partially cracked. In Comparative Example 2, the adhesive was peeled off from the tile interface by bending.
　Ｕ　タイルシート
　Ｔ　タイル
　Ｂ　紫外線硬化性樹脂
　ｓ　目地間隙
　１　搭載治具 U tile sheet T tile B UV curable resin s Joint gap 1 Mounting jig

Claims (6)

  1. 　目地間隙を介して縦横に配列した複数個のタイル相互を、目地間隙内に橋渡された可撓性を有する紫外線硬化性樹脂により接合されてなり、
    　前記紫外線硬化性樹脂が、光反応性(メタ)アクリロイル基含有モノマー並びに該モノマーと相溶性のある光反応性オリゴマー及び／又は有機物ポリマーを主成分とし、これに光反応開始剤を混合してなる紫外線硬化性接着剤組成物を、紫外線照射により硬化してなり、０.５Ｍｐａ以上の引っ張り強度で、かつ３０％以上の伸び率を有するものであることを特徴とするタイルシート。     A plurality of tiles arranged vertically and horizontally through the joint gap are joined by a flexible ultraviolet curable resin bridged in the joint gap,
    The ultraviolet curable resin is mainly composed of a photoreactive (meth) acryloyl group-containing monomer and a photoreactive oligomer and / or organic polymer that is compatible with the monomer, and a photoreaction initiator is mixed therewith. A tile sheet obtained by curing an ultraviolet curable adhesive composition by ultraviolet irradiation, having a tensile strength of 0.5 Mpa or more and an elongation of 30% or more.
  2. 　目地間隙を介して縦横に配列した複数個のタイル相互の、その目地間隙内に、光反応性(メタ)アクリロイル基含有モノマー及び／又は光反応性ビニルモノマー並びに該モノマーと相溶性のあるオリゴマー及び／又はポリマーを主成分とし、これに光反応開始剤を混合してなる紫外線硬化性接着剤組成物を、各タイル相互を橋渡しするように供給し、接着剤組成物に紫外線照射して硬化することにより、０.５Ｍｐａ以上の引っ張り強度で、かつ３０％以上の伸び率を有する可撓性のある紫外線硬化性樹脂を生成し、該紫外線硬化性樹脂により複数個のタイル相互を接合してタイルシートを作製することを特徴とするタイルシートの製造方法。 A plurality of tiles arranged vertically and horizontally through the joint gap, and within the joint gap, a photoreactive (meth) acryloyl group-containing monomer and / or a photoreactive vinyl monomer and an oligomer compatible with the monomer and / Or UV curable adhesive composition composed mainly of polymer and mixed with photoinitiator is supplied to bridge each tile and cured by irradiating the adhesive composition with ultraviolet light. Thus, a flexible ultraviolet curable resin having a tensile strength of 0.5 Mpa or more and an elongation rate of 30% or more is generated, and a plurality of tiles are joined to each other by the ultraviolet curable resin. A method for producing a tile sheet, comprising producing a sheet.
  3. 　オリゴマーが光反応性(メタ)アクリロイル基含有オリゴマーであることを特徴とする請求項２に記載のタイルシートの製造方法。 The method for producing a tile sheet according to claim 2, wherein the oligomer is a photoreactive (meth) acryloyl group-containing oligomer.
  4. 　紫外線硬化性接着剤組成物中の光反応性(メタ)アクリロイル基含有モノマーのアクリロイル基が、モノマー組成中で単官能モノマーが５５重量％以上、２官能以上の多官能モノマーが４５重量％以下であることを特徴とする請求項２又は請求項３に記載のタイルシートの製造方法。 The acryloyl group of the photoreactive (meth) acryloyl group-containing monomer in the ultraviolet curable adhesive composition is such that the monofunctional monomer is 55% by weight or more and the bifunctional or higher polyfunctional monomer is 45% by weight or less in the monomer composition. The tile sheet manufacturing method according to claim 2, wherein the tile sheet is provided.
  5. 　紫外線硬化性接着剤組成物が、その組成中のモノマー、オリゴマー、ポリマーの一部または全部が、水酸基、カルボキシル基及び／又はその塩類、エポキシ基、アミノ基、アミド基、マレイミド基、アルコキシ基、メルカプト基、燐酸基、燐酸エステル基、ニトロ基等の官能基の１種または２種以上を含有するものであることを特徴とする請求項２乃至請求項４の何れか１項に記載のタイルシートの製造方法。 The ultraviolet curable adhesive composition has a monomer, oligomer or polymer part or all of which is a hydroxyl group, carboxyl group and / or salt thereof, epoxy group, amino group, amide group, maleimide group, alkoxy group, The tile according to any one of claims 2 to 4, comprising one or more functional groups such as a mercapto group, a phosphoric acid group, a phosphoric ester group, and a nitro group. Sheet manufacturing method.
  6. 　紫外線硬化性接着剤組成物が、その組成中のポリマー及び／又はオリゴマーがウレタン（メタ）アクリレート、ポリエステル（メタ）アクリレート、エポキシ（メタ）アクリレート、エポキシ樹脂、ポリビニルブチラール樹脂、飽和ポリエステル樹脂、ポリアミド樹脂、スチレンマレイン酸樹脂、ニトロセルロース等の群から選ばれた１種または２種以上含有してなるものであることを特徴とする請求項２乃至請求項５の何れか１項に記載のタイルシートの製造方法。 UV curable adhesive composition, polymer and / or oligomer in the composition is urethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, epoxy resin, polyvinyl butyral resin, saturated polyester resin, polyamide resin The tile sheet according to any one of claims 2 to 5, wherein the tile sheet is one or more selected from the group consisting of styrene maleic acid resin and nitrocellulose. Manufacturing method.
PCT/JP2009/061832 2009-06-29 2009-06-29 Tile sheet and process for producing the tile sheet WO2011001490A1 (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57165417A (en) * 1981-04-03 1982-10-12 Nippon Synthetic Chem Ind Co Ltd:The Photo-setting urethane acrylic resin composition
JPH05255631A (en) * 1992-03-12 1993-10-05 Hayakawa Rubber Co Ltd Ultraviolet-curable ink composition, formation of cured coating films and use of ultraviolet-curable ink composition
JPH07330835A (en) * 1994-06-10 1995-12-19 Toagosei Co Ltd Low-viscosity quick-curing (meth)acrylate composition
JPH08231655A (en) * 1995-02-28 1996-09-10 Dainippon Ink & Chem Inc Resin composition, lining agent and molding material
JP2001140449A (en) * 1999-11-18 2001-05-22 Nogawa Chemical Co Ltd Tile coupling agent and connection method of tile
JP2003192750A (en) * 2001-12-26 2003-07-09 Kuraray Co Ltd Ultraviolet curing resin composition
JP2009191496A (en) * 2008-02-13 2009-08-27 Alpha Kaken Kk Tile sheet and method of manufacturing the same

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57165417A (en) * 1981-04-03 1982-10-12 Nippon Synthetic Chem Ind Co Ltd:The Photo-setting urethane acrylic resin composition
JPH05255631A (en) * 1992-03-12 1993-10-05 Hayakawa Rubber Co Ltd Ultraviolet-curable ink composition, formation of cured coating films and use of ultraviolet-curable ink composition
JPH07330835A (en) * 1994-06-10 1995-12-19 Toagosei Co Ltd Low-viscosity quick-curing (meth)acrylate composition
JPH08231655A (en) * 1995-02-28 1996-09-10 Dainippon Ink & Chem Inc Resin composition, lining agent and molding material
JP2001140449A (en) * 1999-11-18 2001-05-22 Nogawa Chemical Co Ltd Tile coupling agent and connection method of tile
JP2003192750A (en) * 2001-12-26 2003-07-09 Kuraray Co Ltd Ultraviolet curing resin composition
JP2009191496A (en) * 2008-02-13 2009-08-27 Alpha Kaken Kk Tile sheet and method of manufacturing the same

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