JP2008238688A - Moistureproof sheet, face sheet, and decorative plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a moistureproof sheet which does not degrade commercial value by preventing warpage even when being used in a place with large difference in temperature and humidity environments between both sides, in doors, sliding doors, and partitioning or others, and a decorative sheet using the same, and a moistureproof plate less likely to delaminate even after long-term use or upon accidental exposure to external force and a decorative plate made of the same. <P>SOLUTION: The moisture proof sheet is constituted of a colored synthetic resin made base material layer and a vapor deposited layer and is characterized by being constituted by arranging an adhesive primer layer on the exposed face of the vapor deposited layer. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a moisture-proof sheet to be adhered to a wooden base material, a decorative sheet using the same, and a decorative board comprising the same, and more specifically, by moisture absorption and moisture release of a wooden base material due to changes in environmental temperature and humidity. The present invention relates to a moisture-proof sheet having a function of preventing warping, a decorative sheet using the same, and a decorative board made of them.

  Conventionally, a decorative board in which a decorative sheet is attached to the surface of a woody base material such as plywood, medium density fiber board (MDF), hard board, particle board, etc. has been used as a surface material for doors, sliding doors, partitions, etc. . If the moisture content of the wooden base material is lower than the equilibrium moisture content of the wooden base material under outdoor air conditions, moisture absorption and water absorption will take place from the surface of the decorative board where the decorative sheet is not adhered, and this surface will expand. On the other hand, if the moisture content of the wooden base material is greater than the equilibrium moisture content of the wooden base material under the open air condition, the decorative sheet is attached to the moisture-based and water-releasing shrinkage. Since the surface to which the decorative sheet is applied is almost free from moisture absorption and desorption, the expansion rate or contraction rate differs between the surface on which the decorative sheet of the decorative board is adhered and the surface on which the wooden base material is exposed, and the decorative board warps. As a result, the product value is reduced.

  As a method for preventing such warping, for example, a method of sufficiently reinforcing the decorative plate so as not to be warped with metal or the like, or a decorative plate on the back side of the decorative plate having a decorative sheet attached to the surface is used. A method of applying paint to prevent the moisture content of the wooden base material from changing due to moisture absorption or desorption from the back side, or vinyl chloride, polyethylene, polypropylene, etc. on the back side of the decorative board with a decorative sheet attached to the surface There are known a method of sticking a synthetic resin sheet, or a method of sticking a moisture-proof sheet made of paper / polyethylene / paper (for example, see Patent Document 1).

  Although the method of reinforcing the decorative plate can prevent warping by reinforcing, there is a problem that warping cannot be prevented in the case of a structure that cannot sufficiently perform reinforcement such as a flash door. In addition, the method of coating the paint has a problem that it is difficult to form a uniform moisture-proof and waterproof layer due to strong suction of the paint on the surface of the wooden base material and poor surface smoothness. A method of sticking a synthetic resin sheet or a moisture-proof sheet is adopted and widely used because it can be applied to a flash door and warpage can be prevented to some extent.

However, even if it is a decorative board that adopts a method of sticking a synthetic resin sheet or moisture proof sheet, if it is used for a long time in doors, sliding doors, partitions etc. that have a large difference in temperature and humidity environment on both sides, There is a difference in the moisture distribution of the wood-based substrate between the one surface side and the other surface side. As a result, the degree of expansion and contraction of both surfaces is different, and warping may occur. In addition, as another problem, when using a moisture-proof sheet, both sides are paper layers, and an excellent effect in terms of workability that it can be easily attached to a wooden substrate with an emulsion type adhesive. On the other hand, since the interlayer strength of the paper layer is weak, there is a possibility of peeling from the interlayer of the paper layer when used for a long time or when an external force is applied by force.
Japanese Patent Laid-Open No. 9-29919

  Accordingly, the present invention provides a moisture-proof sheet that prevents warping and does not reduce the commercial value of a door, sliding door, partition, or the like even when the temperature and humidity environment on both sides is greatly different, and a decorative sheet using the moisture-proof sheet And a decorative sheet made thereof, and a moisture-proof sheet that does not have a possibility of peeling when used for a long period of time or when external force is applied forcefully, and a decorative sheet using the moisture-proof sheet and the same To provide a decorative board. Furthermore, since the moisture-proof sheet is used as a constituent material of the decorative sheet, the moisture-proof sheet that does not impair the design properties of the decorative sheet by concealing the surface color and color unevenness of the base material for the decorative sheet when used as a decorative sheet, and the same It is providing the decorative sheet using these, and the decorative board which consists of them.

  In order to achieve the above object, the inventor of the present invention described in claim 1 is a moisture-proof sheet comprising a colored synthetic resin base material layer and a vapor deposition layer, and is bonded to the exposed surface of the vapor deposition layer. A primer layer is provided.

  The decorative sheet according to claim 2 is the moisture-proof sheet according to claim 1, wherein a printed layer is provided on the exposed surface of the synthetic resin base material layer, and the entire surface of the printed layer is made of a curable resin. A protective layer is provided.

  The decorative sheet of the present invention according to claim 3 is the moisture-proof sheet according to claim 1, wherein a printed layer is provided on the exposed surface of the synthetic resin base material layer, and the entire surface of the printed layer is interposed with an adhesive layer. A synthetic resin transparent layer is provided, and a surface protective layer made of a curable resin is provided on the entire surface of the synthetic resin transparent layer.

  The decorative board of the present invention according to claim 4 is the decorative sheet according to any one of claims 2 and 3, wherein the decorative sheet base is provided on the entire surface of the adhesive primer layer of the decorative sheet via an adhesive layer. A material is provided.

  The decorative board of the present invention according to claim 5 is characterized in that the moisture-proof sheet according to claim 1 is provided on the exposed surface of the decorative board according to claim 4.

Since the moisture-proof sheet of the present invention has a moisture permeability (JIS Z 0208) of 2.0 g / m ² · 24 hr or less, the moisture-proof sheet is made of a synthetic resin sheet such as vinyl chloride, polyethylene, polypropylene, or paper / polyethylene / paper. It has much better moisture-proof performance than sheets, and the decorative sheet made of the moisture-proof sheet of the present invention and the decorative sheet using the same has a large difference in the temperature and humidity environment on both sides, such as doors, sliding doors, and partitions. Even if it is used in a certain place, there is an excellent effect of hardly causing warpage. In addition, the moisture-proof sheet of the present invention and the decorative sheet made of a decorative sheet using the same have an excellent effect that there is almost no possibility of peeling when used for a long time or when external force is applied forcefully. . In addition, the moisture-proof sheet of the present invention and the decorative board made of the decorative sheet using the same have the excellent effect of hiding the surface color and color unevenness of the decorative board base material and not impairing the design of the decorative sheet. Play.

The above-described present invention will be described in detail below with reference to the drawings.
FIG. 1 is a layer configuration diagram schematically illustrating one embodiment of a moisture-proof sheet according to the present invention, and FIG. 2 is a layer configuration diagram schematically illustrating a first embodiment of a decorative sheet using the moisture-proof sheet according to the present invention. FIG. 3 is a layer configuration diagram schematically showing a second embodiment of a decorative sheet using the moisture-proof sheet according to the present invention, and FIG. 4 is an example of a decorative board using the moisture-proof sheet and the decorative sheet according to the present invention. FIG. 5 is a schematic view of the layer structure, FIG. 5 is a schematic view of the layer structure of another embodiment of the decorative board using the moisture-proof sheet and the decorative sheet according to the present invention, in which 1 is a moisture-proof sheet, 2, 2 'is a decorative sheet, 3 is a decorative plate, 10 is a colored synthetic resin substrate layer, 11 is a vapor deposition layer, 12 is an adhesive layer, 13 is a synthetic resin transparent layer, and 15 and 16 are adhesion primers. Layer, 17 printed layer, 18 surface protective layer, 19 adhesive layer, 20 decorative plate Each base material is shown.

  FIG. 1 is a schematic diagram of a layer structure of an embodiment of a moisture-proof sheet according to the present invention. The moisture-proof sheet 1 is a colored synthetic resin base material layer (hereinafter referred to as a synthetic resin colored base material layer). The vapor deposition layer 11 and the adhesion primer layer 15 are formed on one surface of 10. An adhesive primer layer 16 (see FIGS. 4 and 5) may be provided on the other surface of the synthetic resin colored substrate layer 10 as necessary. In addition, as a case where the primer layer 16 for adhesion is provided on the other surface, for example, it is provided when used for the original purpose as the moisture-proof sheet 1 on the back surface of the base material for the decorative board, and this moisture-proof sheet 1 is provided. For example, when attaching a decorative plate to a core material such as a door, a sliding door, a partition, etc., the choice of an adhesive for bonding the core material and the decorative plate is widened, thereby facilitating the application work. There is an effect that can be done.

  FIG. 2 is a layer configuration diagram schematically illustrating a first embodiment of a decorative sheet using the moisture-proof sheet according to the present invention, and the decorative sheet 2 is the synthetic resin-made colored base layer 10 of the moisture-proof sheet 1. The printed layer 17 is provided on the exposed surface, and the surface protective layer 18 made of a curable resin is provided on the entire surface of the printed layer 17.

  FIG. 3 is a layer configuration diagram schematically showing a second embodiment of a decorative sheet using the moisture-proof sheet according to the present invention, and the decorative sheet 2 ′ is the colored base layer 10 made of the synthetic resin of the moisture-proof sheet 1. A printed layer is provided on the exposed surface, a synthetic resin transparent layer 13 is provided on the entire surface of the printed layer 17 via an adhesive layer 12, and a surface protective layer made of a curable resin is formed on the entire surface of the synthetic resin transparent layer 13. 18 is provided.

  FIG. 4 is a layer configuration diagram schematically showing an embodiment of a decorative board using the moisture-proof sheet and the decorative sheet according to the present invention. The decorative board 3 is arranged on one surface of the base material 20 for decorative board. 1 is attached via an adhesive layer 19 so that the surface protective layer 18 is exposed, and the moisture-proof sheet 1 shown in FIG. Attached through the adhesive layer 19 so as to be located on the 20 side.

  FIG. 5 is a layer configuration diagram schematically illustrating another embodiment of the decorative board using the moisture-proof sheet and the decorative sheet according to the present invention, and the decorative board 3 is illustrated on one surface of the base material 20 for the decorative board. The decorative sheet 2 ′ shown in FIG. 3 is stuck through an adhesive layer 19 so that the surface protective layer 18 is exposed, and the vapor-proof layer 1 shown in FIG. It is stuck through the adhesive layer 19 so as to be located on the substrate 20 side.

  4 and 5 show an example in which the adhesion primer layer 16 is provided on the exposed surface of the moisture-proof sheet 1, but as described above, this is applied to a core material such as a door, a sliding door, or a partition. It is provided in order to facilitate the sticking work when wearing.

  Next, materials constituting the moisture-proof sheet 1, the decorative sheets 2, 2 ', and the decorative board 3 will be described. First, as the colored base layer 10 made of synthetic resin, olefinic thermoplastic resin such as polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl alcohol copolymer, or a mixture thereof, polyethylene terephthalate, poly Ester-based thermoplastic resins such as butylene terephthalate, polyethylene naphthalate, polyethylene naphthalate-isophthalate copolymer, polycarbonate, polyarylate, acrylic heat such as polymethyl methacrylate, polyethyl methacrylate, polybutyl acrylate Non-halogen thermoplastic resins such as a plastic resin, polyimide, polyurethane, polystyrene, acrylonitrile-butadiene-styrene resin, and the like can be given. The synthetic resin colored substrate layer 10 may be a sheet stretched in a uniaxial or biaxial direction or may be unstretched. As the colorant, a well-known pigment having excellent weather resistance can be used as appropriate, and the mixing method of the resin and the pigment may be either dry blend or masterbatch, but it is uniform without unevenness. A master batch is preferable in the sense that a colored substrate layer is obtained. The synthetic resin colored substrate layer 10 may be colored transparent, translucent, or opaque (having concealment).

  The vapor deposition layer 11 is an inorganic vapor deposition layer made of a metal thin film typified by aluminum, or an inorganic oxide vapor deposition layer made of an inorganic oxide thin film typified by silicon oxide, magnesium oxide, or aluminum oxide. The vapor deposition layer 11 is formed into a thin film on at least one surface of the synthetic resin colored substrate layer 10 by a known vapor deposition method such as a vacuum vapor deposition method or a plasma activated chemical reaction vapor deposition method. In addition, as the said vapor deposition layer 11, since the vapor deposition layer which consists of a metal thin film represented by aluminum has a metallic luster, it has a design property with respect to the decorative sheets 2 and 2 'which need to form the printing layer 17 In view of the above, there is a problem that the metallic luster must be concealed, and there are cases where adhesion is performed using high frequency during flash door processing, and more preferably, the inorganic oxide whose vapor deposition layer is transparent It is a vapor deposition layer. In addition, for the purpose of further improving the gas barrier property of the vapor deposition layer 11, a composition in which an inorganic oxide typified by silicon oxide, magnesium oxide, and aluminum oxide is added to the vapor deposition layer 11 is polyvinyl alcohol or polyvinyl alcohol. The polyvinyl alcohol layer or the composition layer may be formed by coating by a known coating method such as a roll coating method or a gravure coating method.

  Moreover, as the synthetic resin transparent layer 13, the resin described in the synthetic resin colored base material layer 10 or a sheet of the resin can be used, and similarly to the synthetic resin colored base material layer 10. It may be in an unstretched state or a uniaxially or biaxially stretched state, or may be in a state where two or more layers are laminated, and various configurations are appropriately adopted. be able to. The synthetic resin transparent layer 13 may be translucent, or may be colored transparent or translucent.

  The thickness of the synthetic resin-made colored base layer 10 and the synthetic resin-made transparent layer 13 is generally 12 to 300 μm. In addition, these layers 10 and 13 may be subjected to a known easy adhesion treatment such as corona discharge treatment, plasma treatment, ozone treatment, etc. on a necessary surface as necessary. In addition, these layers 2 and 2 'may be appropriately added with known additives such as an antioxidant, a light stabilizer, and an ultraviolet ray inhibitor.

  The printing layer 17 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. As the printing layer 17, for example, a pattern printing layer such as 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 patterns, etc. Although it consists of the solid pattern printing layer which has, any one structure may be sufficient.

  Examples of the ink for forming the printing layer 17 include chlorinated polyolefins such as chlorinated polyethylene and chlorinated polypropylene, polyester, polyurethane composed of isocyanate and polyol, polyacryl, polyvinyl acetate, polyvinyl chloride, and vinyl chloride. It can be used by mixing one or more kinds of vinyl acetate copolymer, cellulose resin, polyamide resin, etc., and adding it to pigments, solvents, various auxiliary agents, etc. to make it into an ink. In view of the above, a non-chlorine vehicle in which one or two or more of polyester, polyurethane, polyacrylic, polyvinyl acetate, cellulose resin, polyamide resin, and the like, which are composed of isocyanate and polyol are mixed, is more preferable. Polyester, isocyanate and polyol Polyurethane consisting of polyacrylic, to one without such a polyamide resin is a mixture of two or more. A pigment, a solvent, various auxiliary agents, etc. added thereto to make an ink can be used.

  Next, the adhesive layer 12 and the adhesion primer layers 15 and 16 will be described. Examples of the resin used for the adhesive layer 12 and the adhesion primer layers 15 and 16 include ester resins, urethane resins, acrylic resins, polycarbonate resins, vinyl chloride-vinyl acetate copolymers, polyvinyl butyral resins, Nitrocellulose-based resins and the like can be mentioned, and these resins can be used alone or mixed to form an adhesive composition, which can be formed using an appropriate application means such as a roll coating method or a gravure printing method.

  However, it is particularly preferable that the adhesive layer 12 and the adhesion primer layers 15 and 16 are formed of a resin comprising (I) a copolymer of an acrylic resin and a urethane resin and (II) an isocyanate. That is, the copolymer of acrylic resin and urethane resin (I) has an acrylic polymer component having a hydroxyl group at the terminal (component A), a polyester polyol component having a hydroxyl group at both ends (component B), and a diisocyanate component (component). C) is mixed and reacted to form a prepolymer, and a chain extender (component D) such as diamine is further added to the prepolymer to extend the chain. By this reaction, polyester urethane is formed and an acrylic polymer component is introduced into the molecule to form an acrylic-polyester urethane copolymer having a hydroxyl group at the terminal. This acrylic-polyester urethane copolymer is formed by reacting the terminal hydroxyl group with the isocyanate (II) and curing it.

  As the component A, a linear acrylate polymer having a hydroxyl group at the terminal is used. Specifically, linear polymethyl methacrylate (PMMA) having a hydroxyl group at the terminal is preferable because it is excellent in weather resistance (particularly the property against photodegradation) and can be easily copolymerized with urethane. . The component A is an acrylic resin component in the copolymer, and those having a molecular weight of 5000 to 7000 (weight average molecular weight) are preferably used because of particularly good weather resistance and adhesiveness. In addition, the component A may be used only having a hydroxyl group at both ends, but a mixture having a conjugated double bond at one end is mixed with the above-mentioned one having a hydroxyl group at both ends. Is also good.

  Component B reacts with diisocyanate to form polyester urethane and constitutes a urethane resin component in the copolymer. The component B is a polyester diol having hydroxyl groups at both ends. Examples of the polyester diol include an addition reaction product of a diol compound having an aromatic or spiro ring skeleton and a lactone compound or a derivative thereof, or an epoxy compound, a condensation product of a dibasic acid and a diol, and a cyclic ester compound. Examples thereof include a derived polyester compound. Examples of the diol include short-chain diols such as ethylene glycol, propylene glycol, diethylene glycol, butanediol, hexanediol, and methylpentenediol, and alicyclic short-chain diols such as 1,4-cyclohexanedimethanol. it can. In addition, examples of the basic acid include adipic acid, phthalic acid, isophthalic acid, terephthalic acid, and the like. The polyester polyol is preferably adipic acid or a mixture of adipic acid and terephthalic acid as an acid component, particularly preferably adipic acid, and an adipate system using 3-methylpentenediol and 1,4-cyclohexanedimethanol as diol components. Polyester.

  In the adhesive layer 12 and the adhesion primer layers 15 and 16, the urethane resin component formed by the reaction between the component B and the component C is the adhesive layer 12 and the adhesion primer layers 15 and 16. Gives flexibility and improves adhesion. The acrylic resin component made of an acrylic polymer contributes to weather resistance and blocking resistance in the adhesive layer 12 and the adhesion primer layers 15 and 16. In the urethane resin, the molecular weight of the component B may be within a range in which a urethane resin capable of sufficiently exhibiting flexibility in the adhesive layer 12 and the adhesion primer layers 15 and 16 is obtained, and adipic acid or In the case of a polyester diol composed of a mixture of adipic acid and terephthalic acid and 3-methylpentanediol and 1,4-cyclohexanedimethanol, 500 to 5000 (weight average molecular weight) is preferable.

  As the component C, an aliphatic or alicyclic diisocyanate compound having two isocyanate groups in one molecule is used. Examples of the diisocyanate include tetramethylene diisocyanate, 2,2,4 (2,4,4) -1,6-hexamethylene diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, and 1,4′-cyclohexyl. A diisocyanate etc. can be mentioned. As the diisocyanate component, isophorone diisocyanate is preferable in terms of excellent physical properties and cost. When the above-mentioned components A to C are reacted, the equivalent ratio of the total hydroxyl group (may be an amino group) of the acrylic polymer, polyester polyol and chain extender described below and the isocyanate group is such that the isocyanate group becomes excessive. To.

  When the above three components A, B and C are reacted at 60 to 120 ° C. for about 2 to 10 hours, the isocyanate group of the diisocyanate reacts with the hydroxyl group at the end of the polyester polyol to form a polyester urethane resin component and an acrylic polymer. A compound in which a diisocyanate is added to a terminal hydroxyl group is also mixed, and a prepolymer is formed in a state where excess isocyanate groups and hydroxyl groups remain. As a chain extender, for example, a diamine such as isophorone diamine or hexamethylene diamine is added to this prepolymer, the isocyanate group is reacted with the chain extender, and the chain is extended so that the acrylic polymer component is contained in the polyester urethane molecule. The (I) acrylic-polyester urethane copolymer introduced and having a hydroxyl group at the terminal can be obtained.

  Addition of isocyanate of (II) to acrylic-polyester urethane copolymer of (I), coating method, coating solution adjusted to necessary viscosity in consideration of coating amount after drying, gravure coating method, roll The adhesive layer 12 and the adhesion primer layers 15 and 16 may be formed by application by a known application method such as a coating method. The isocyanate of (II) is not limited as long as it can be crosslinked and cured by reacting with the hydroxyl group of the acrylic-polyester urethane copolymer of (I). An aliphatic isocyanate can be used, and an aliphatic isocyanate is particularly desirable from the viewpoint of thermal discoloration prevention and weather resistance. Specifically, a monomer such as tolylene diisocyanate, xylylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, or a multimer such as a dimer or trimer thereof, or And polyisocyanates such as derivatives (adducts) obtained by adding these isocyanates to polyols.

Incidentally, as the coating amount after drying of the adhesive layer 12 and the adhesive primer layer 15 and 16, a from 1 to 20 g / m ^2, preferably from 1 to 5 g / m ^2. Further, the adhesive layer 12 and the adhesion primer layers 15 and 16 may be layers to which an additive such as a filler such as silica powder, a light stabilizer, or a colorant is added as necessary.

  Next, the surface protective layer 18 will be described. This surface protective layer 18 is provided for imparting surface physical properties such as scratch resistance, abrasion resistance, stain resistance, water resistance, and weather resistance required for the decorative sheets 2 and 2 '. The resin for forming the protective layer 18 is suitably formed using a curable resin such as a thermosetting resin or an ionizing radiation curable resin, but more preferably has a high surface hardness and excellent productivity. To ionizing radiation curable resin.

As thermosetting resins, unsaturated polyester resins, polyurethane resins (including two-component curable polyurethane), epoxy resins, amino alkyd resins, phenol resins, urea resins, diallyl phthalate resins, melamine resins, guanamine resins, melamine-ureas Examples thereof include a cocondensation resin, a silicon resin, and a polysiloxane resin. If necessary, a curing agent such as a crosslinking agent or a polymerization initiator, or a polymerization accelerator is added to the resin. For example, as a curing agent, isocyanate or organic sulfonate is added to unsaturated polyester resin or polyurethane resin, organic amine is added to epoxy resin, peroxide such as methyl ethyl ketone peroxide, azoisobutyl nitrile, etc. The radical initiator is added to the unsaturated polyester resin. As a method for forming the surface protective layer with the thermosetting resin, for example, the above-mentioned thermosetting resin is made into a solution, applied to a predetermined surface by a known coating method such as a roll coating method or a gravure coating method, and then dried. And can be formed by curing. The coating amount of the surface protective layer 18 is generally 5 to 200 g / m ^{2 in} terms of solid content, and preferably 5 to 30 g / m ² .

  In addition, as the ionizing radiation curable resin, a monomer having a radically polymerizable unsaturated group such as (meth) acryloyl group or (meth) acryloyloxy group or a cationically polymerizable functional group such as epoxy group in the molecule. , Consisting of a 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 radically polymerizable unsaturated group, photopolymerization initiators include acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ether, Michler benzoylbenzoate, Michler ketone, diphenyl sulfide, dibenzyl disulfide, diethyl Oxite, 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 18 can be formed by forming the ionizing radiation curable resin into a solution and applying the solution to a predetermined surface by a known application 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 5-30 g / m < ² >.

  The surface protective layer 18 may be formed of, for example, a well-known organic ultraviolet absorber such as benzotriazole, benzophenone, or triazine, or titanium dioxide having an average particle size of about 5 to 120 nm, depending on required physical properties. Inorganic ultraviolet absorbers such as cerium oxide and zinc oxide, known light stabilizers such as hindered amines, or known additives such as antistatic agents and leveling agents can be added.

  Next, the adhesive layer 19 will be described. The adhesive layer 19 is a layer used for adhering the moisture-proof sheet 1 and the decorative sheets 2, 2 ′ and the decorative board substrate 20, and as an adhesive forming the adhesive layer 19, for example, Any type of adhesive such as a thermoplastic resin system, a thermosetting resin system, and a rubber (elastomer) system may be used. These can be used by appropriately selecting known products or commercially available products. Examples of the thermoplastic resin adhesive include polyvinyl acetate resin, polyvinyl alcohol, polyvinyl acetal (polyvinyl formal, polyvinyl butyral, etc.), cyanoacrylate, polyvinyl alkyl ether, polyvinyl chloride, polyamide, polymethyl methacrylate, nitrocellulose. , Cellulose acetate, thermoplastic epoxy, polystyrene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, etc., and thermosetting resin adhesives include urea resin, melamine resin Phenol resin, resorcinol resin, furan resin, epoxy resin, unsaturated polyester resin, polyurethane resin, polyimide resin, polyamideimide, polybenzimidazole, polybenzothiazole, etc. That. Rubber adhesives include natural rubber, recycled rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, chloroprene rubber, butyl rubber, polysulfide rubber, silicone rubber, polyurethane rubber, stereo rubber (synthetic natural rubber), ethylene propylene rubber, block Examples include copolymer rubber (SBS, SIS, SEBS, etc.). In particular, the adhesive layer 19 for adhering the decorative sheets 2 and 2 'and the decorative board substrate 20 is made of a pigment or the like in order to conceal the surface color of the decorative board substrate 20 and improve the design. It may be colored.

  Moreover, as the base material 20 for decorative boards, the base material which consists of flash structures, such as plywood, a particle board, a medium density fiber board (MDF), a high density fiber board (HDF), and the wood-type base material can be mentioned. .

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

The polyvinyl alcohol solution is dried to 0.2 g / m ^{2 on} the vapor deposition layer surface of a 50 μm thick colored biaxially stretched polyethylene terephthalate film (hereinafter referred to as a colored PET film) having an alumina vapor deposition layer on one surface. Gravure printing method using a two-part curable printing ink consisting of a vehicle consisting mainly of nitrified cotton resin on a colored PET film surface subjected to corona discharge treatment and added with isocyanate as a curing agent. Then, a solid pattern printing layer is formed, and then a pattern printing layer (wood grain pattern) is formed using a printing ink containing a nitrified cotton resin as a vehicle, and then an isocyanate as a curing agent is added to an acrylic polyol resin as a main agent. The added two-component curable resin is applied to the entire surface on which the solid print layer and the pattern print layer are formed by the gravure printing method. A surface protective layer was formed by printing so that the solid content was 16 g / m ^2, and an isocyanate as a curing agent was added to a urethane resin / nitrified cotton-based resin as a main agent on a vapor deposition layer surface coated with polyvinyl alcohol. A decorative sheet on which an adhesive primer layer having a coating amount of 2 g / m ² as a solid content was formed by a gravure printing method using a liquid curable resin was prepared. The decorative sheet is applied to a 3 mm thick MDF with a vinyl acetate adhesive in a wet state at 8 g / scale ² and dried, and then adhered to the coated surface with a roll laminator so that the vapor deposition layer side of the decorative sheet is positioned on the coated surface. A decorative veneer was made.

Gravure printing method so that a polyvinyl alcohol solution is dried to 0.2 g / m ^{2 on} a vapor deposition layer surface of a colored polypropylene film (hereinafter referred to as a colored PP film) having a thickness of 60 μm provided with an alumina vapor deposition layer on one surface. After coating, the surface of the colored PP film subjected to corona discharge treatment is a gravure printing method using a two-part curable printing ink consisting of a vehicle mainly composed of polyurethane / acrylic polyol resin and isocyanate added as a curing agent. A solid pattern printing layer is formed, then a pattern printing layer (wood grain pattern) is formed using a printing ink containing a polyurethane / acrylic polyol resin as a vehicle, and then the main layer is applied to the vapor deposition layer surface coated with polyvinyl alcohol. Two-component curing by adding isocyanate as a curing agent to urethane resin / nitrified cotton-based resin An intermediate sheet on which an adhesive primer layer having a coating amount of 2 g / m ² as a solid content was formed by a gravure printing method using a mold resin was prepared. Further, an adhesive layer (2 g / m ² as a solid content) made of a two-component curable urethane resin is formed on the entire printing layer surface of the intermediate sheet, and an ethylene / propylene / butene copolymer is formed on the adhesive layer surface. Polypropylene thermoplastic elastomer containing benzotriazole UV absorber and hindered amine radical scavenger as main component is heated and melt extruded with a T-die extruder to form a transparent resin layer with a thickness of 80 μm, and then the transparent A transparent primer layer (1 g / m ² as solid content) is formed on the entire surface of the resin layer by applying a two-component curable urethane-based resin containing an acrylic / urethane block copolymer as a main ingredient and isocyanate added as a curing agent. A urethane acrylate ionizing radiation curable resin is applied to the entire surface of the transparent primer layer and an electron beam [acceleration : 175KeV, dose: 5 Mrad] transparent surface protective layer is irradiated with to form a (5 g / m ² as solid content), prepared decorative sheet provided with a recessed pattern embossed from the surface protective layer side did. The decorative sheet is applied to a 3 mm thick MDF with a vinyl acetate adhesive in a wet state at 8 g / scale ² and dried, and then adhered to the coated surface with a roll laminator so that the vapor deposition layer side of the decorative sheet is positioned on the coated surface. A decorative veneer was made.

[Comparative Example 1]
On one side, 23 g / m ² inter-paper reinforced paper and 30 g / m ² inter-paper reinforced paper that have been subjected to corona discharge treatment are placed with the corona discharge treatment surface facing each other, and PE is 40 μm using a T-die extruder. A laminated body (23 g / m ² paper-reinforced paper / 40 μm PE / 30 μm PE paper / 30 g / m ² paper reinforced paper) laminated by a so-called sandwich lamination method was prepared by heating and extruding to a thickness. Next, gravure printing is performed on the exposed surface of the 30 g / m ² inter-paper reinforced paper of the laminate using a two-component curable printing ink comprising a vehicle in which isocyanate as a curing agent is added to a nitrified cotton-based resin as a main agent. A two-component solution in which a solid print layer is formed by the above method, a pattern print layer is then formed using a printing ink containing a nitrified cotton-based resin as a vehicle, and then an isocyanate is added as a curing agent to an acrylic polyol-based resin as a main agent. A decorative sheet having a surface protective layer formed by printing the curable resin by gravure printing on the entire surface on which the solid printing layer and the pattern printing layer were formed to a solid content of 16 g / m ² was produced. After the decorative sheet is coated with 8 g / sq ^{2 of} vinyl acetate adhesive on MDF having a thickness of 3 mm in a wet state and dried, the exposed surface of 23 g / m ² of inter-sheet reinforced paper of the decorative sheet is exposed on the coated surface. A decorative board adhered with a roll laminator so as to be positioned was prepared.

[Comparative Example 2]
A decorative board was prepared in the same manner as in Example 2 except that a colored PP film having a vapor deposition layer was used instead of a colored PP film having a thickness of 60 μm provided with an alumina vapor deposition layer on one side. . Of course, no polyvinyl alcohol solution was applied because there was no vapor deposition layer.

  The decorative plates in Examples 1 and 2 and Comparative Examples 1 and 2 produced above were evaluated for moisture permeability and plane tensile strength by the evaluation methods described below, and the results are summarized in Table 1.

〔Evaluation methods〕
-Moisture permeability: Conforms to JIS Z 0208 "Moisture permeability test method for moisture-proof packaging materials (cup method)"
The moisture permeability is calculated by measuring the decorative sheets of Examples 1 and 2 and Comparative Examples 1 and 2.
Out.
Planar tensile strength: JAS plywood Measured according to the plane tensile test to calculate the plane tensile strength.
In addition, the decorative board used for evaluation calls the moisture-proof sheet and MDF for 24 hours.
Using a pressed material, cut the decorative board into 5cm square and the bottom is 2cm square
A metal jig is attached to the moisture-proof sheet surface with a cyanoacrylate adhesive.
After curing at room temperature (about 23 ° C) for 4 hours, follow the metal jig with a cutter knife.
Make a notch that reaches the MDF,
In contrast, pull in the direction of the vertical plane, and visually observe and evaluate the peeling interface.
And tensile strength was measured.

  As is apparent from Table 1, the decorative sheet of the present invention is provided with an alumina vapor-deposited layer, so that the moisture vapor transmission performance is improved, and the alumina vapor-deposited layer causes warpage of the decorative board caused by changes in environmental temperature and humidity. The effect that it can reduce compared with the conventional product (Comparative Examples 1 and 2) which does not exist in a layer structure can be expected. Moreover, in the plane tensile strength, since Comparative Example 1 consisting of a paper layer results in separation between papers, Examples 1 and 2 result in delamination (material failure = material failure) of the base material for decorative plate. The peel strength can be improved.

It is a layer block diagram showing an example of a moisture-proof sheet concerning the present invention diagrammatically. It is a layer lineblock diagram showing diagrammatically a 1st embodiment of a decorative sheet using a moisture-proof sheet concerning the present invention. It is a layer lineblock diagram showing a 2nd embodiment of a decorative sheet using a moisture-proof sheet concerning the present invention. It is a layer block diagram which shows one Example of the decorative board using the moisture-proof sheet | seat and decorative sheet concerning this invention schematically. It is a layer block diagram which shows schematically the other Example of the decorative board using the moisture-proof sheet | seat and decorative sheet concerning this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Moisture-proof sheet 2,2 'decorative sheet 3 decorative board 10 Colored synthetic resin base material layer 11 Vapor deposition layer 12, 19 Adhesive layer 13 Synthetic resin transparent layer 15, 16 Adhesive primer layer 17 Print layer 18 Surface protective layer 20 Base material for decorative board

Claims (5)

A moisture-proof sheet comprising a colored synthetic resin base layer and a vapor-deposited layer, wherein an adhesion primer layer is provided on the exposed surface of the vapor-deposited layer. The moisture-proof sheet according to claim 1, wherein a printed layer is provided on the exposed surface of the synthetic resin base material layer, and a surface protective layer made of a curable resin is provided on the entire surface of the printed layer. 2. The moisture-proof sheet according to claim 1, wherein a printed layer is provided on an exposed surface of the synthetic resin base material layer, a synthetic resin transparent layer is provided on the entire surface of the printed layer via an adhesive layer, and the synthetic resin transparent layer is provided. A decorative sheet comprising a surface protective layer made of a curable resin on the entire surface. The decorative sheet according to any one of claims 2 and 3, wherein a decorative sheet base material is provided on the entire surface of the adhesion primer layer of the decorative sheet via an adhesive layer. A decorative board comprising the moisture-proof sheet according to claim 1 on the exposed surface of the decorative board according to claim 4.

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