JP2012200986A - Decorative board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative board having stably strong (robust) adhesion between an inorganic base material layer and a printed sheet layer (synthetic resin decorative sheet).SOLUTION: In the decorative board, a sealer layer, an adhesive layer and the synthetic resin decorative sheet layer are laminated on one face of the inorganic base material layer in this order, and either or both of the sealer layer and the adhesive layer comprise(s) resin having glass-transition temperature less than 0°C. A surface protective layer is formed on the surface of the synthetic resin decorative sheet layer.

Description

  The present invention relates to a decorative plate used for various furniture, building interior materials, interior materials around a bathroom or kitchen, and the like.

  Conventionally, a decorative board is known in which a paper-based sheet on which a printed pattern is formed is laminated on an inorganic base material using an adhesive, and a transparent resin paint is applied or impregnated on top of it. Since the decorative board of paper is based on a paper-based sheet, when water and oil are dropped, water and oil penetrate to reach the paper-based sheet, so the water resistance and oil resistance are not satisfactory. It was.

  On the other hand, after a thermoplastic resin film having a printed pattern layer formed thereon is stuck on an inorganic base material using a solvent-based adhesive, a resin paint is applied from above the pattern layer. Although a decorative board with a top coat layer is known, this method cannot completely blow off the organic solvent in the adhesive, so that the resin film partially swells due to the influence of the organic solvent. In addition to the occurrence of the homodact phenomenon, the adhesive has a problem in that the volume of the adhesive shrinks during the drying process, thereby impairing the smoothness of the surface. Furthermore, the method of applying the adhesive to the surface of the inorganic base material has a problem that the dryer becomes very long in order to remove the organic solvent in the adhesive, and the adhesive is applied to the back surface of the thermoplastic resin film. The coating method has a problem in terms of productivity because the line speed cannot be increased due to a decrease in film strength due to the organic solvent in the adhesive or curling.

  As one technique for solving these problems, a thermoplastic resin film layer (printing sheet layer) having a sealer layer, an adhesive layer, a pattern printing layer, and a surface protective layer are sequentially laminated on the top surface of the inorganic base material. There is a decorative board (see, for example, Patent Document 1).

  The technique disclosed in Patent Document 1 solves the problems of the conventional decorative board described above by sequentially interposing a sealer layer and an adhesive layer between an inorganic base material and a printed sheet layer. However, due to the resin used to form the sealer layer or the adhesive layer, for example, when the decorative board is cut or perforated, the inorganic base material and the printed sheet layer are peeled off. In addition, when the decorative board is used on the wall surface in such a manner that the end portion is exposed, a problem that the printed sheet layer swells from the inorganic base material may occur, and there has been a demand for a solution to these problems. .

  Therefore, as a result of trying various combinations of materials constituting the sealer layer and the adhesive layer, the above problem is the strength of the interlayer adhesive strength between the inorganic base material and the printing sheet layer, specifically, the inorganic base material and the printing sheet. The inventor has obtained the knowledge that if the peel strength between layers is 20 N / 25 mm width or more, the present invention has been obtained.

Japanese Patent Application Laid-Open No. 11-138689

  Therefore, the present invention has a stable and strong (strong) adhesive strength between the inorganic base material and the printed sheet layer (synthetic resin decorative sheet layer referred to in the present application), and can be easily peeled between the layers. There is no veneer to provide.

  In order to achieve the above object, the inventor of the present invention has a sealer layer, an adhesive layer, and a synthetic resin decorative sheet layer in order on one surface of the inorganic base material layer. It is laminated, and either or both of the sealer layer and the adhesive layer are made of a resin having a glass transition temperature of less than 0 ° C.

  According to a second aspect of the present invention, in the decorative board according to the first aspect, a surface protective layer is formed on a surface layer of the synthetic resin decorative sheet layer.

  According to a third aspect of the present invention, in the decorative board according to the second aspect, the surface protective layer is formed of an ionizing radiation curable resin.

  According to a fourth aspect of the present invention, in the decorative board according to the first aspect, the inorganic base material layer is a gypsum board base material.

  According to the present invention, either or both of the sealer layer and the adhesive layer are composed of a resin having a glass transition temperature of less than 0 ° C., thereby having water resistance and oil resistance, and an inorganic base material and a synthetic resin. The interlayer of the decorative sheet has an excellent effect that it can provide a decorative board that has a stable and strong (strong) adhesive strength and does not easily peel between the layers.

It is a figure showing the basic layer composition of the decorative board concerning the present invention diagrammatically.

The present invention will be described in detail below with reference to the drawings.
FIG. 1 is a diagram schematically showing a basic layer configuration of a decorative board according to the present invention. In the figure, 1 is a decorative board, 10 is a surface protective layer, 11 is a synthetic resin decorative sheet layer, and 12 is An adhesive layer, 13 is a sealer layer, and 14 is an inorganic base layer.

FIG. 1 is a diagram schematically showing a basic layer structure of a decorative board according to the present invention. The decorative board 1 is provided with a sealer layer 13 and an adhesive layer 12 on one surface of an inorganic base layer 14. And a synthetic resin decorative sheet layer 11 and a surface protective layer 10 are sequentially laminated. In addition, the said surface protective layer 10 is provided as needed, and is not essential in this invention.

  Next, each layer which comprises the decorative material 1 of this invention is demonstrated. First, the inorganic base material layer 14 will be described. As the inorganic base material constituting the inorganic base material layer, a publicly known material may be used according to the application. For example, calcium silicate plate, rock wool, volcanic glass multilayer plate (JIS A5440 “ Incombustible volcanic glassy multilayer board ”, asbestos slate board, gypsum board, gypsum board, die light and tiger glass rock [Yoshino Gypsum Co., Ltd .: trade name], etc., cement, ceramics Glass, metal, etc. can be mentioned, and the thickness thereof is generally 2 to 15 mm, preferably 3 to 9 mm, although it depends on the material. This should be determined in consideration of

Further, as a material constituting the sealer layer 13, the alkaline component elution from the inorganic base material layer 14 is prevented, and the adhesive layer 12 is prevented from penetrating into the inorganic base material layer 14. It is provided for the purpose of improving the adhesion with the layer 12, and for example, one or more solvent-based or water-based organic sealers such as urethane-based, epoxy-based, acrylic-based, rubber-based, etc. can be used. In the present invention, any resin is a resin having a glass transition temperature (Tg) of less than 0 ° C. Further, the coating amount of the sealer layer may be appropriately determined depending on the state of the inorganic base material layer 14, and is generally 5 to 25 g / m ² (as solid content).

The material constituting the adhesive layer 12 includes urethane resin [one-part curable type (moisture curable type), two-part curable type], acrylic resin, ethylene-vinyl acetate copolymer resin, rubber resin. Any of the hot melt type, solvent type, aqueous type and the like can be used. However, in the present invention, any resin is a resin having a glass transition temperature (Tg) of less than 0 ° C. Further, the coating amount of the adhesive layer 12 is generally 20 to 40 g / m ² (as solid content) in consideration of the adhesive strength.

  The synthetic resin decorative sheet layer 11 will be described. The synthetic resin decorative sheet layer 11 may be a single-layer synthetic resin decorative sheet decorated on a synthetic resin base sheet, or may be decorated on a synthetic resin base sheet. It may be a composite synthetic resin decorative sheet in which a transparent resin layer is further laminated thereon, a resin constituting a synthetic resin base sheet, a decoration content, a resin constituting a transparent resin layer Can be appropriately used from conventionally known resins.

  Examples of the resin constituting the synthetic resin base sheet and the transparent resin layer include a saturated polyester resin and low-density polyethylene (linear low-density) because it has excellent processability and does not generate harmful gases during combustion. Polyethylene), medium density polyethylene, high density polyethylene, homopolypropylene, ethylene α-olefin copolymer, polymethylpentene, polybutene, ethylene-propylene copolymer, propylene-butene copolymer, ethylene-vinyl acetate copolymer. , Saponified ethylene-vinyl acetate copolymer, or a mixture thereof such as olefinic thermoplastic resin, in either an unstretched state or a uniaxial or biaxially stretched state. The thickness may be about 60 to 300 μm. The In addition, these sheets may be subjected to well-known easy adhesion treatment such as corona discharge treatment, plasma treatment, ozone treatment, etc. on necessary surfaces as necessary.

  Moreover, as a decoration provided in the said synthetic resin decorative sheet layer 11, the pattern printing layer which consists of a pattern and a solid pattern is one of them. The pattern printing layer can be formed using ink by a known printing method such as a gravure printing method, an offset printing method, or a silk screen printing method. The pattern printing layer is, for example, a wood grain pattern, a stone pattern, a cloth pattern, a skin pattern, a geometric pattern, a character, a symbol, a line drawing, various abstract pattern patterns, or a solid pattern. The picture pattern and the solid pattern may be either one or both.

  Examples of the ink for forming the printing layer include chlorinated polyolefin such as chlorinated polyethylene and chlorinated polypropylene as a vehicle, polyester, polyurethane composed of isocyanate and polyol, polyacryl, polyvinyl acetate, polyvinyl chloride, and vinyl chloride. -A mixture of one or more vinyl acetate copolymers, cellulose resins, polyamide resins, etc. can be used, and inks can be used by adding pigments, solvents, various auxiliary agents, etc. In consideration of the problem, a non-chlorine vehicle in which one or two or more types such as polyester, polyurethane composed of isocyanate and polyol, polyacryl, polyvinyl acetate, cellulose resin, and polyamide resin are mixed is suitable, and more preferable. Is polyester, isocyanate and polio Polyurethane consisting Le, polyacrylic, to one without such a polyamide resin is a mixture of two or more.

  In addition to the decorative layer provided on the synthetic resin decorative sheet layer 11, in addition to the printed layer, the synthetic resin base material sheet is colored, embossed to form a concavo-convex pattern, surface gloss adjustment or surface protection. There is a formation of a surface protective layer, etc., and these decorating treatments can be appropriately combined.

  Next, the surface protective layer 10 will be described. Examples of the resin forming the surface protective layer 10 include a curable resin, and a conventionally known resin such as a thermosetting resin or an ionizing radiation curable resin can be used as the curable resin.

  Examples of the thermosetting resin include unsaturated polyester resins, polyurethane resins, epoxy resins, etc. Among them, as main components, polyol components having an OH group such as acrylic polyols, polyester polyols, polyether polyols, epoxy polyols, and the like A two-component curable urethane resin obtained by adding an isocyanate compound such as tolylene diisocyanate, hexamethylene diisocyanate or metaxylene diisocyanate as a curing agent is suitable.

  In addition, the ionizing radiation curable resin has a monomer having a radically polymerizable unsaturated group such as a (meth) acryloyl group or (meth) acryloyloxy group or a cationically polymerizable functional group such as an epoxy group in the molecule. Body, prepolymer or polymer. These monomers, prepolymers or polymers are used alone or in combination. In this specification, (meth) acrylate is used in the meaning of acrylate or methacrylate. The ionizing radiation means an electromagnetic wave or charged particle beam having an energy quantum capable of polymerizing or cross-linking molecules, and is usually an ultraviolet ray or an electron beam.

  Examples of the prepolymer having a radical polymerizable unsaturated group include polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, melamine (meth) acrylate, triazine (meth) acrylate, and polyvinylpyrrolidone. This prepolymer usually has a molecular weight of about 10,000 or less. When the molecular weight exceeds 10,000, the cured resin layer has insufficient surface properties such as scratch resistance, abrasion resistance, chemical resistance, and heat resistance. The acrylate and methacrylate can be used in common, but the acrylate is more advantageous for the purpose of curing efficiently at a high speed and in a short time because the acrylate is faster in terms of the crosslinking curing rate with ionizing radiation. .

  Examples of the prepolymer having a cationically polymerizable functional group include epoxy resins such as bisphenol type epoxy resins, novolac type epoxy resins, and alicyclic epoxy resins, aliphatic vinyl ethers, aromatic vinyl ethers, urethane vinyl ethers, and ester vinyl ethers. And prepolymers such as vinyl ether resins, cyclic ether compounds, and spiro compounds.

  Examples of monomers having a radically polymerizable unsaturated group include (meth) acrylate compound monofunctional monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, methoxyethyl ( (Meth) acrylate, methoxybutyl (meth) acrylate, butoxyethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, N, N-dimethylaminomethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N , N-diethylaminoethyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, N, N-dibenzylaminoethyl (meth) acrylate, lauryl (meth) acrylate, isobornyl (meth) acrylate, ethyl carbitol ( Me ) Acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, methoxypropylene glycol (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, 2 -(Meth) acryloyloxypropyl hydrogen terephthalate and the like.

  In addition, as a polyfunctional monomer having a radical polymerizable unsaturated group, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, di Propylene glycol (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tri Propylene glycol di (meth) acrylate, bisphenol-A-di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide tri (meth) acrylate , Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin polyethylene oxide tri (meth) acrylate, tris (meth) acryloyloxy Examples thereof include ethyl phosphate.

  As the monomer having a cationic polymerizable functional group, a prepolymer monomer having the cationic polymerizable functional group can be used.

When the above-mentioned ionizing radiation curable resin is cured by irradiating with ultraviolet rays, a photopolymerization initiator is added as a sensitizer. In the case of a resin system having a radical polymerizable unsaturated group, photoinitiators include acetophenones, benzophenones, thioxanthones, benzoin, benzoin, benzoin methyl ether, Michler benzoylbenzoate, Michler ketone, diphenyl sulfide, dibenzyl disulfide , Diethyl oxide, triphenylbiimidazole, isopropyl-N, N-dimethylaminobenzoate and the like can be used alone or in combination. In the case of a resin system having a cationically polymerizable functional group, an aromatic diazonium salt, an aromatic sulfonium salt, a metallocene compound, a benzoin sulfonic acid ester, a freeroxyxonium diallyl iodosyl salt, etc. should be used alone or as a mixture. Can do. In addition, generally the addition amount of these photoinitiators is about 0.1-10 weight part with respect to 100 weight part of ionizing radiation curable resins. The surface protective layer 10 can be formed by coating the surface layer of the synthetic resin decorative sheet layer 11 by a known coating method such as a gravure coating method or a roll coating method. As a coating amount, 5-200 g / m < ² > is suitable in general as solid content, Preferably it is 15-30 g / m < ² >.

In addition, between the surface protective layer 10 and the synthetic resin decorative sheet layer 11, that is, between the surface protective layer 10 and the printing layer, or between the surface protective layer 10 and the transparent resin layer, or Further improvement in adhesion between the surface protective layer 10 and the synthetic resin decorative sheet layer 11 between the surface protective layer 10 and the synthetic resin base sheet, contamination resistance, and wear resistance Therefore, a transparent or translucent primer layer may be provided. As a coating amount, 1-20 g / m < ² > (as solid content) is suitable, but 3-10 g / m < ² > (as solid content) is more preferable. As the resin constituting the primer layer, urethane resin, epoxy resin, polyester resin, acrylic resin, and the like are used. Of these, urethane resin is preferable. As the urethane resin, a two-component curable urethane resin, a one-component curable (moisture curable) urethane resin, a thermoplastic urethane resin, or the like can be used.

  The surface protective layer 10 may be provided on the surface layer when the synthetic resin decorative sheet layer 10 is produced, and then laminated with the inorganic base material layer 14, or the synthetic resin cosmetic layer may be laminated. It is possible to laminate the inorganic base material layer 14 in the state of the sheet layer 10 and then form the surface protective layer on the surface layer of the synthetic resin decorative sheet layer 10.

  Next, the present invention will be described in more detail with reference to the following examples.

[Production of synthetic resin decorative sheet]
After forming a 2 μm-thick pattern printing layer on one side of an 80 μm-thick polyethylene-based colored sheet with corona discharge treatment on both sides with a printing ink made of acrylic urethane-based resin, urethane-nitrified cotton on the other side A primer obtained by adding 5 parts by weight of hexamethylene diisocyanate to 100 parts by weight of the mixed resin is applied to form a 2 μm-thick back primer layer, and then 100 parts by weight of the acrylic polyol-urethane mixed resin is formed on the pattern printing layer. After applying an adhesive obtained by adding 11 parts by weight of hexamethylene diisocyanate to form a transparent adhesive layer having a thickness of 3 μm, a polypropylene thermoplastic elastomer was applied onto the transparent adhesive layer by a T-die extruder. A transparent resin layer having a thickness of 60 μm is formed by heating and melt extrusion, and an acrylic polyol-urea is formed on the transparent resin layer. A primer formed by adding 6 parts by weight of hexamethylene diisocyanate to 100 parts by weight of a tan mixed resin is applied to form a primer layer for a surface protective layer having a thickness of 2 μm. After applying and drying an electron beam curable resin by a gravure coating method so that the solid content becomes 5 g / m ² , an electron beam is irradiated to form a surface protective layer made of an electron beam curable resin, and the surface A synthetic resin decorative sheet in which an uneven pattern of a wood grain conduit pattern was formed by embossing from the protective layer side was produced.

[Production of decorative board]
The 6 mm thick Tiger Glass Rock [Yoshino Gypsum Co., Ltd .: trade name] and the synthetic resin decorative sheet produced above were changed to a surface protective layer of the synthetic resin decorative sheet by changing the combination of sealer and adhesive. No. shown in Table 1 1 to 13 decorative plates were produced, and the peel strength of the decorative sheet made of Tiger Glass Rock and synthetic resin was measured for this decorative plate (measurement conditions: peel speed 200 mm / min, 180 ° peel), and the peel strength was 20 N / 25 mm. The above was evaluated as shown in Table 1 with good marks as ◯ and with less than 20 N / 25 mm as bad marks as shown in Table 1.

  In addition, the sealer used what was previously apply | coated and formed on the tiger glass lock. In addition, in the case of water-based adhesive, the adhesive is applied to the synthetic resin decorative sheet (the back side), wet-laminated with the sealer surface of the tiger glass lock, and then deaerated and sandwiched between 30 cm square plates. After applying a load of 20 kg for 12 hours, it was cured at room temperature for 3 days. In the case of a hot melt adhesive, a synthetic resin decorative sheet (the back surface) was pressure-bonded and laminated immediately after it was applied to the sealer surface of Tiger Glass Rock. In the case of a pressure-sensitive adhesive, a pressure-sensitive adhesive sheet in which a pressure-sensitive adhesive is applied to the release-treated surface of a polyester film (PET film) that has been subjected to a release treatment is used, and this pressure-sensitive adhesive sheet is pressure-bonded to a synthetic resin decorative sheet (back surface). Later, the PET film was peeled off, and the peeled surface was pressure-bonded to the sealer surface of Tiger Glass Rock.

Abbreviations in Table 1 <Sealer>:
A: Acrylic water-based sealer manufactured by Chuo Rika Kogyo <Glass transition temperature Tg: 30 ° C.>
[SA-95 (main agent) / EX-8 (curing agent) / water = 100/10/60 (weight ratio)]
B: Acrylic water-based sealer (prototype) <Tg: 5 ° C>
C: Yayoi Chemical's chloroprene solvent sealer <Tg: -30 ° C>
<Adhesive>:
D: Chloroprene-based water-based adhesive manufactured by Konishi Co., Ltd. <Tg: −45 ° C.>
[Konishi WG22]
E: Chuo Rika Kogyo Co., Ltd. ethylene-vinyl acetate copolymer aqueous adhesive <Tg: 0 ° C.>
[BA-10L (main agent) / BA-11B (curing agent) = 100 / 2.5]
F: Moisture curable hot-melt adhesive manufactured by Hitachi Chemical Polymer <Tg: 30 ° C.>
[Hybon W4836]
G: Acrylic adhesive <Tg: −30 ° C.> manufactured by Soken Chemical Co., Ltd.
[SK Dyne 1309 (main agent) / E-AX (curing agent) = 100/3 (weight ratio)]

  As is apparent from Table 1, either a sealer layer or an adhesive layer, or both are made of a resin having a glass transition temperature of less than 0 ° C., so that a synthetic resin decorative sheet and a tiger glass lock are formed. The interlaminar strength (peel strength) can be 20 N / 25 mm or more, and it has water resistance and oil resistance, and the interlayer between the inorganic base material and the synthetic resin decorative sheet is stable and strong (strong). It can be set as a decorative board which does not peel easily between these layers.

  The present invention can be suitably used for an incombustible decorative board, and is particularly useful for a decorative board comprising a gypsum board-based inorganic base material and a synthetic resin decorative sheet.

DESCRIPTION OF SYMBOLS 1 Decorative board 10 Surface protective layer 11 Synthetic resin decorative sheet layer 12 Adhesive layer 13 Sealer layer 14 Inorganic base material layer

Claims (4)

On one surface of the inorganic base material layer, a sealer layer, an adhesive layer, and a synthetic resin decorative sheet layer are sequentially laminated, and either the sealer layer or the adhesive layer, or both have a glass transition temperature. A decorative board comprising a resin of less than 0 ° C. The decorative board according to claim 1, wherein a surface protective layer is formed on a surface layer of the synthetic resin decorative sheet layer. 3. The decorative board according to claim 2, wherein the surface protective layer is formed of an ionizing radiation curable resin. The decorative board according to claim 1, wherein the inorganic base material layer is a gypsum board base material.

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