JP4108827B2 - Inorganic decorative veneer - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention is used for building interior materials, in particular, wall surfaces of bathrooms, washrooms, dressing rooms, etc., and has excellent design properties, good water resistance, warm water resistance, alkali resistance, stain resistance, and mirror gloss. It is related with the inorganic type decorative board which becomes.
[0002]
[Prior art]
Conventionally, as an inorganic decorative board, for example, (1) after forming a printing pattern by direct printing on an inorganic base material such as asbestos slate board, cement slate board, calcium silicate board, etc. A transparent resin paint is applied on top of the printed pattern to form a top coat layer. (2) A decorative sheet on which the printed pattern is formed is pasted on an inorganic base material, and then the top is coated with a transparent resin paint. (3) After providing the pattern by a method such as transferring the pattern onto the surface of the inorganic base material using transfer paper, and then applying a transparent resin paint on the pattern layer A coating layer was known.
[0003]
However, the decorative board of (1) is poor in design, and the decorative board of (2) is coated with an ionizing radiation curable resin paint on the surface after sticking a printing sheet on an inorganic base material, and ionizing radiation is applied. Due to the method of irradiating and curing, the ionizing radiation curable resin may be peeled from the end face of the adhesive layer due to the volume shrinkage of the ionizing radiation curable resin. Since the process cannot be performed continuously, the productivity is poor, and the decorative board (3) is satisfactory in terms of water resistance and design, but the process is complicated, yield is poor, and transfer Since paper is used, there is a drawback of high cost.
[0004]
[Problems to be solved by the invention]
The present invention has been made in view of such problems, and its purpose is to be used for wall surfaces and ceiling surfaces of bathrooms, washrooms, dressing rooms, etc., having excellent design properties, good water resistance, An object of the present invention is to provide an inorganic decorative board having hot water resistance, alkali resistance, and stain resistance.
[0005]
[Means for Solving the Problems]
In order to achieve the above object, the solution means of the present invention is an inorganic decorative board in which a decorative sheet layer is laminated via an adhesive layer on an inorganic base material provided with a sealer layer on the upper surface. , picture-printed layer is provided on the upper surface of the thermoplastic resin film Rutotomoni, the該絵pattern printed layer top surface, the transparent thermoplastic resin film having a surface protective layer made of an ionizing radiation-curable resin as necessary are laminated The adhesive layer is made of a solvent-based moisture-curable polyurethane resin made of a polyester-polyether resin, and the ratio of the polyether groups in the polyester-polyether resin is higher than that of the polyester groups. It is to make it the inorganic type decorative board. With this configuration, the outermost surface of the decorative sheet layer is formed by laminating a transparent thermoplastic resin film, so that foreign matters such as “dust” and “dust” are less likely to adhere, and the surface appearance is excellent. It becomes. In addition, a fine pattern printed layer can be formed on the upper surface of the inorganic base material, and further, the production process is simplified, so that the production efficiency and yield are improved, and an inexpensive inorganic decorative board can be obtained. it can.
[0006]
In addition, by making the thermoplastic resin film layer of a polyolefin resin, it can be a decorative board that can sufficiently withstand the alkali component generated from the inorganic base material, and waste such as slitter scraps. Even when incineration is carried out, a decorative board free from the generation of toxic gas can be obtained.
[0007]
In addition, since the transparent thermoplastic resin film is made of biaxially stretched polyethylene terephthalate film, it has excellent surface properties such as wear resistance, heat resistance, stain resistance, and high visible light transmittance. It becomes an inorganic decorative board excellent in the appearance of the printed layer.
[0008]
In addition, by making the thickness of the biaxially stretched polyethylene terephthalate film from 100 to 200 μm, the outermost surface of the decorative board is formed into a mirror surface by absorbing the irregularities on the surface of the inorganic base material, giving it a high gloss and deep feeling. It becomes the inorganic type decorative board excellent in the designability to have.
[0009]
Moreover, when the adhesive layer is made of a polyester-polyether-based resin, the adhesive layer is affected by an alkaline component eluted from the inorganic base material when the inorganic base material is exposed to an atmosphere such as moisture or moisture. Therefore, it is possible to produce an inorganic decorative board that does not deteriorate the adhesion.
[0010]
In addition, since the adhesive made of the polyester-polyether resin is made of the solvent-based moisture-curable polyurethane resin, it can be applied with conventional equipment, and the adhesive can be easily applied.
[0011]
Further, in the solvent-based moisture-curable polyurethane resin made of polyester-polyether resin, the ratio of the polyether group is increased. By doing so, it can be set as the adhesive bond layer strong against an alkali component.
[0012]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, specific embodiments of the present invention will be described with reference to the drawings.
FIG. 1 is a laminated sectional view showing an embodiment of the inorganic decorative board of the present invention. FIG. 2 is a laminated sectional view showing another embodiment of the inorganic decorative board of the present invention. Plate, 2 is an inorganic base material, 3 is a sealer layer, 4 is an adhesive layer, 5 'is a decorative sheet layer, 6 is a thermoplastic resin film, 7 is a pattern printing layer, 7a is a solid ink layer, 7b is a pattern Ink layer, 8 is an adhesive layer, 9 is a transparent thermoplastic resin film, and 10 is a surface protective layer.
[0013]
As shown in FIG. 1, the structure of the inorganic decorative board 1 of the present invention is such that an inorganic base material 2 having a sealer layer 3 surface on the upper surface and a pattern on the upper surface of a thermoplastic resin film 6 with an adhesive layer 4 interposed therebetween. The print layer 7 is provided, and a decorative sheet 5 in which a transparent thermoplastic resin film 9 is laminated on the upper surface of the pattern print layer 7 via an adhesive layer 8 is adhered. Since it is formed by sticking the thermoplastic resin film 9, foreign matter such as “dust” and “dust” is less likely to adhere to it, and the surface of an inorganic decorative board having a specular gloss is also caused by minute surface defects. It will be less likely to be defective. Moreover, the transparent thermoplastic resin film 9 forming the surface layer is a biaxially stretched polyethylene terephthalate film having a thickness of 100 to 200 μm, so that irregularities on the surface of the inorganic base material 2 are absorbed, and the mirror gloss of the surface of the inorganic decorative board is obtained. Improved.
[0014]
The inorganic base material 2 used for the inorganic decorative board 1 of the present invention is generally a cement board such as calcium silicate board, asbestos slate board, lightweight foamed concrete board, hollow extruded cement board, gypsum board, gypsum slag. Examples thereof include fiber cement boards such as plaster boards such as boards, pulp cement boards, asbestos cement boards, and wood chip cement boards.
[0015]
The sealer layer 3 is provided for the purpose of preventing alkaline component elution from the inorganic base material 2 and for smoothening the surface of the inorganic base material 2 and increasing the strength of the inorganic base material 2 surface. Yes, the constitution is arbitrary, and it is of course possible to adopt a single layer constitution by the resin composition having both of the above-mentioned physical properties. However, as a method for improving the quality performance, a polyisocyanate resin is used to prevent elution of alkali components. It is desirable to use a curable resin such as a moisture curable urethane resin or an epoxy resin.
[0016]
The adhesive layer 4 is a layer for adhering the decorative sheet layer 5 made of the thermoplastic resin film 6 provided with the pattern printing layer 7 to the inorganic base material 2, for example, a one-component curable urethane resin, A reactive resin-based adhesive such as a two-component curable urethane resin or a two-component mixed epoxy resin can be used. Further, as performance required for the adhesive, not only initial adhesion but also adhesion after water resistance, warm water resistance, boiling resistance test and the like are required, and a one-component curable urethane resin is preferable.
[0017]
The one-component curable urethane-based resin adhesive is a composition containing a urethane prepolymer having an isocyanate group at a molecular terminal as an essential component. The urethane prepolymer is usually a polyisocyanate prepolymer having one or more isocyanate groups at both ends of the molecule, and the isocyanate groups react with each other by moisture in the air to cause a chain extension reaction, resulting in a molecular chain. A reaction product having a urea bond is generated therein, and an isocyanate group at the molecular end further reacts with this urea bond to cause a biuret bond to branch to cause a crosslinking reaction. The framework concept of the molecular chain of the prepolymer having an isocyanate group at the molecular end is arbitrary, but specifically, a polyurethane skeleton having a urethane bond, a polyester skeleton having an ester bond, a polyether skeleton having an ether bond, and a polybutadiene skeleton The physical properties of the adhesive can be adjusted by appropriately adopting one or more of these skeleton structures.
[0018]
In particular, when an inorganic base material is exposed to an atmosphere such as moisture or moisture, it becomes a strong alkali state due to an alkali component eluted from the inorganic base material. As a result, it is a cause that causes poor adhesion, and since a strong alkali resistance is required, a polyether polyol group having a strong alkali resistance property is suitable. A polyester-polyether resin obtained by copolymerizing a polyester polyol group excellent in that point is particularly preferable because of its slightly inferior properties.
[0019]
Examples of the polyester-polyether resin include a structure in which a polyester skeleton obtained by adding a polyester polyol and a polyether polyol to polyisocyanate in any order and subjected to an addition reaction and a polyether skeleton are bonded by a urethane bond. And a polyester-polyether urethane prepolymer having an isocyanate group at the molecular end, ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, trimethylolpropane, diethylene glycol, triethylene glycol, hexamethylene glycol, glycerin 1,3-butylene glycol, 1,4 butanediol, hexanetriol, pentaerythritol, sorbitol, neopentyl glycol, etc. Polyhydric alcohols, polyether polyols obtained by addition polymerization of the above polyhydric alcohols and alkylene oxides such as ethylene oxide and propylene oxide, prepolyhydric alcohols and maleic acid, succinic acid, adipic acid, sebacic acid, isophthalic acid, Polyester polyols obtained by condensation reaction with polybasic acids such as terephthalic acid, polyester polyols obtained by ring-opening polymerization of lactones such as ε-caprolactone and γ-pererolactone, and the like are used.
[0020]
In the polyester-polyether resin, if the ratio of the polyether group is less than 50%, the adhesive strength in the initial adhesion state and the like is excellent, but it is exposed to an alkaline atmosphere such as a hot water adhesion test. If the ratio of the polyether group exceeds 90%, the influence of hydrolysis of the polyester group is increased and the adhesive strength is reduced. Even if exposed, the influence of hydrolysis of the polyester group is small and the adhesive force is not lowered, but the initial adhesion is weak and the productivity is poor. Therefore, when directly touching water such as around the bathroom, alkali resistance is strongly demanded, and therefore, those having a high ratio of polyether groups are preferred, and polyether groups: polyester groups are 80:20 to 90:10 (% ) Is preferred. As the coating amount of the adhesive layer 4, for providing on the surface irregularities of the inorganic base material, those that require coating amount of 150g / m ² ~200g / m ² in order to obtain sufficient adhesion is there.
[0021]
Examples of the thermoplastic resin film 6 for forming the pattern printing layer 7 on the inorganic decorative board 1 include polyolefin resins such as polyethylene, polypropylene, ethylene-propylene copolymer, polymethylpentene, polyvinyl chloride resin, polycarbonate, Polyamide, ABS resin, and other films can be used, but in view of the fact that they do not generate hydrogen chloride, cyan gas, etc. during incineration, and have alkali resistance and are inexpensive. Is preferably used. The thickness of the film is not particularly limited, but is generally about 80 to 120 μm from the viewpoint of economy, practicality, and printability.
[0022]
The pattern printing layer 7 is provided with a solid ink layer 7a for printing on the entire surface and a pattern ink layer 7b for expressing, for example, stone pattern, cloth pattern, surface pattern of natural leather, abstract pattern, etc., and an ink vehicle for providing them. For example, a known one can be used, for example, an acrylic, vinyl chloride, vinyl chloride-vinyl acetate copolymer, chlorinated polyolefin, nitrocellulose, urethane, etc. , Pigments, dyes and other colorants, extender pigments, solvents and the like can be used as appropriate. The solid ink layer 7a can contain a bright pigment together with a colored pigment. Further, the solid ink layer 7a can contain only a colored pigment, and does not contain a bright pigment. It is also possible to comprise so that a luster pigment may be included.
[0023]
The transparent thermoplastic resin film 9 preferably has a visible light transmittance of 80 to 90%, and examples thereof include polyester, polycarbonate, polyvinyl alcohol, polypropylene, polymethylpentene, cellulose triacetate, and cellulose diacetate. Among these, polyester is particularly preferable, and the polyester is particularly oriented in at least a uniaxial direction, preferably in a biaxial direction, by a known stretching method. In particular, a polyethylene terephthalate resin film oriented in the biaxial direction is preferable because it is excellent in mechanical strength and heat resistance. As the thickness of the film, a range of 50 to 350 μm can be used, and a range of 100 to 200 is preferable. When the thickness is 50 μm or less, the printing depth is poor, the surface roughness of the inorganic base material 2 is affected, the specularity is inferior, and handling at the time of film lamination is difficult. When it is 350 μm or more, bending becomes difficult and the economy is deteriorated.
[0024]
FIG. 2 shows a cross-sectional view of a laminated structure of an inorganic decorative board 1 ′ of another embodiment of the inorganic decorative board of the present invention. Hereinafter, the same reference numerals as those of the components already described are used, and duplicate descriptions are omitted.
The inorganic decorative board 1 ′ of the present embodiment is configured such that a surface protection layer 10 is provided on the upper surface of the transparent thermoplastic resin film 9 of the inorganic decorative board 1. A film having excellent surface properties such as contamination is formed, and the formation method is such that after the surface protective layer 10 made of ionizing radiation curable resin is provided on the upper surface of the transparent thermoplastic resin film 9, the pattern printing layer 7 This is made by sticking the thermoplastic resin film 6 provided with the adhesive layer 8 through the adhesive layer 8 to the upper surface of the inorganic base material 2.
[0025]
Specifically, as the ionizing radiation curable resin, a polyfunctional prepolymer having two or more polymerizable unsaturated bonds such as acryloyl group, methacryloyl group, acryloyloxy group, epoxy group, thiol group, etc. in the molecule. A composition that can be cured by ionizing radiation, in which oligomers and / or monomers are appropriately mixed, is used. Here, the ionizing radiation means an electromagnetic wave or charged particle beam having an energy quantum capable of polymerizing or cross-linking molecules, and usually an ultraviolet ray or an electron beam is used, and the curing speed is high and the workability is good. In addition, it is preferable because the physical properties of the resin such as flexibility and hardness can be easily adjusted and the scratch resistance, contamination resistance, solvent resistance, etc. are excellent.
[0026]
Examples of the above prepolymers and oligomers include unsaturated polyesters such as condensation products of unsaturated dicarboxylic acids and polyhydric alcohols, polyester methacrylates, polyether methacrylates, polyol methacrylates, methacrylates such as silicon methacrylate, melamine methacrylate, polyester acrylates, Examples thereof include acrylates such as epoxy acrylate, urethane acrylate, polyether acrylate, polyol acrylate, silicon acrylate, and melamine acrylate, and cationic polymerization type epoxy compounds.
[0027]
Examples of the monomers include styrene monomers such as styrene and α-methylstyrene, methyl acrylate, 2-ethylhexyl acrylate, methoxyethyl acrylate, butoxyethyl acrylate, butyl acrylate, methoxybutyl acrylate, acrylic acid Acrylic esters such as phenyl, methacrylic esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, methoxyethyl methacrylate, ethoxymethyl methacrylate, phenyl methacrylate, lauryl methacrylate, acrylic acid-2- ( N, N-diethylamino) ethyl, methacrylic acid-2- (N, N-dimethylamino) ethyl, acrylic acid-2- (N, N-dibenzylamino) methyl, acrylic acid-2- (N, N-diethylamino) ) Tired of propyl etc. Acid substituted amino alcohol esters, unsaturated carboxylic acid amides such as acrylamide and methacrylamide, ethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, 1,6 hexanediol diacrylate, triethylene glycol diacrylate, etc. A polyfunctional compound such as dipropylene glycol diacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, diethylene glycol dimethacrylate, and / or a polythiol compound having two or more thiol groups in the molecule, such as trimethylol Propane trithioglycolate, trimethylol propane trithiopropylate, pentaerythritol tetrathioglycol, etc. I can get lost.
[0028]
【Example】
Example 1
A gravure-printed abstract pattern was gravure-printed on a colored polypropylene resin film having a thickness of 80 μm using an acrylic resin ink to prepare a printed sheet. Next, a polyester-polyol-based resin adhesive is applied to the back surface of a 125 μm thick biaxially stretched polyethylene terephthalate film so as to have a thickness of 45 μm (wet). Was made. Next, a moisture-curable urethane coating as a sealer layer was applied to a 5 mm thick asbestos slate plate with a 6 g / m ² (wet) sponge roll coat and dried at 150 ° C. for 1 minute to prepare a sealer-treated inorganic substrate. Got ready. Next, after applying 200 μm (wet) of urethane resin moisture curable adhesive on the back side of the mirror surface decorative sheet with a flow coater, irradiating with infrared rays and drying, the adhesive layer surface of the mirror surface decorative sheet on the sealer layer surface of the inorganic substrate Are laminated at a pressure roll temperature of 60 ° C. and a laminating speed of 3 m / min to prepare an inorganic decorative board having a specular gloss.
[0029]
Example 2
A polyester-acrylate UV curable resin coating is applied to the upper surface of a 125 μm thick biaxially stretched polyethylene terephthalate film with a gravure coater so that the coating thickness is 2 μm (dry), and an 80 w / cm ozone UV lamp is applied. An inorganic decorative board having a specular gloss was prepared in the same manner as in Example 1 except that a film which was passed through a lamp-mounted irradiation device at a speed of 5 m / min and was irradiated with ultraviolet rays and cured.
[0030]
【The invention's effect】
In the present invention, as described above, a decorative sheet laminated in the order of a thermoplastic resin layer, a pattern printing layer, and a transparent thermoplastic resin layer is provided on the upper surface of an inorganic base material with a sealer layer on the upper surface, with an adhesive layer interposed therebetween. As a result, a fine pattern can appear, and the surface of the decorative board is less likely to have foreign matter such as “dust” and “dust” on it, resulting in an excellent surface appearance. . Moreover, since the production process is simplified, production efficiency and yield are improved, and an inexpensive inorganic decorative board can be obtained.
[0031]
In addition, by making the thermoplastic resin film that forms the decorative sheet layer into a polyolefin resin, it is possible to make a decorative board that can sufficiently withstand the alkali component generated from the inorganic base material. An incineration process can be used for the treatment of objects.
[0032]
In addition, by using a biaxially stretched polyethylene terephthalate resin film of 100 to 200 μm for the transparent thermoplastic resin film, it is formed by absorbing irregularities on the surface of the inorganic base material, so it has a specular gloss, stain resistance, etc. An inorganic decorative board having excellent surface properties can be obtained.
[0033]
Moreover, since an adhesive bond layer consists of polyester-polyether-type resin, the inorganic type decorative board used as surface materials, such as a bathroom wall surface and a ceiling surface excellent in warm water resistance and alkali resistance, can be obtained. Furthermore, by using a solvent-based moisture-curable polyurethane resin as the adhesive and increasing the ratio of the polyether group, the coating becomes easy and it is resistant to alkaline components.
[0034]
In addition, by providing a surface protective layer with ionizing radiation curable resin on the upper surface of the transparent thermoplastic resin layer that forms the decorative sheet layer, the surface hardness, wear resistance, solvent resistance, and contamination resistance of the decorative board The surface physical properties such as properties can be further improved.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view showing an embodiment of an inorganic decorative board according to the present invention.
FIG. 2 is a laminated cross-sectional view showing another embodiment of the inorganic decorative board of the present invention.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1, 1 'Inorganic decorative board 2 Inorganic base material 3 Sealer layer 4 Adhesive layer 5, 5' Makeup sheet layer 6 Thermoplastic resin film 7 Picture printing layer 7a Solid ink layer 7b Picture ink layer 8 Adhesive layer 9 Transparent heat Plastic resin film 10 Surface protective layer

Claims (4)

The inorganic base material subjected to sealer layer on the upper surface, the inorganic-based decorative laminate obtained by laminating the decorative sheet layer through an adhesive layer, the decorative sheet layer, picture-printed layer is provided on the upper surface of the thermoplastic resin film Rutotomoni, the該絵pattern printed layer top surface, the transparent thermoplastic resin film having a surface protective layer made of an ionizing radiation curable resin is made of those formed by laminating optionally the adhesive layer, a polyester An inorganic decorative board comprising a solvent-based moisture-curable polyurethane resin made of a polyether resin, wherein the ratio of polyether groups in the polyester-polyether resin is higher than that of polyester groups .   2. The inorganic decorative board according to claim 1, wherein the thermoplastic resin film layer is made of a polyolefin resin. 2. The inorganic decorative board according to claim 1, wherein the transparent thermoplastic resin film comprises a biaxially stretched polyethylene terephthalate film. The inorganic decorative board according to claim 3, wherein the biaxially stretched polyethylene terephthalate film has a thickness of 100 to 200 µm.

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