JP5879872B2 - Floor decorative material - Google Patents

Description

  The present invention has excellent scratch resistance (caster resistance and impact resistance) even when a low specific gravity wood base material is used, and has excellent surface appearance quality, dimensional stability and sheet adhesion. It relates to cosmetics.

  Conventionally, as a wood-based decorative board used for a floor decorative material for a house (for example, a floor board), an adhesive is provided on the upper surface of a wooden base material (for example, a hardwood lauan plywood) obtained from a good quality log. In addition, there is known one in which a decorative sheet having a natural wood design is pasted.

  As the woody base material, the above-mentioned hardwood lauan is frequently used. However, in recent years, raw materials are difficult to obtain due to lack of natural resources, timber cutting restrictions, etc., and the material shortage is progressing. This problem is particularly acute for hardwoods such as Lauan. Therefore, the development of a wood base material that can be used in place of the Lauan plywood is being promoted. As substitute materials for lauan, softwood plywood, early-wood plywood (planted wood plywood) and the like are used.

  These plywoods have a lower specific gravity than Lauan plywood, so the rigidity is low, the hardness is insufficient, and the scratch resistance is poor. In addition, since the appearance quality is also inferior, a wooden board (for example, medium density wooden fiber board: MDF, high density wooden fiber) obtained by molding and solidifying a wooden fiber or a wooden piece separated from a wooden waste material with an adhesive on the surface. In general, it is used as a multi-layer base plate in which plates: HDF, particle boards: PB, etc. are bonded together.

  However, the multi-layer base plate has a larger dimensional change amount per 1% moisture content change of the wood board laminated on the surface than the lower plywood, and is likely to change in size according to changes in the surrounding environment. For this reason, the degree of dimensional change differs between the upper layer and the lower layer of the multi-layer base plate, resulting in a problem that the multi-layer base plate is warped or bent, causing gaps, thrusting, and the like. In particular, the Lauan alternative material described above has low specific gravity and low rigidity, so that it is difficult to maintain the shape and easily follow the dimensional change of the wooden board laminated on the surface. For this reason, especially the said multilayer base plate tends to generate | occur | produce a curvature and bending.

  In addition, plywood such as softwood plywood and early-wood plywood used as a raw material for lauan has a part of early wood and a part of late wood, and the difference in specific gravity between them is large. Therefore, when processing as a multi-layer base plate, if the pressure is applied by laminating a wood board and plywood, the degree of compressive deformation differs between the early and late materials of the plywood, and the surface of the multi-layer base plate Unevenness is likely to occur.

  In addition, it has been studied to attach impregnated paper to the surface. However, if the wood base material has a low specific gravity, there is a problem that the scratch resistance (particularly impact resistance) is insufficient. If the resin-impregnated paper is made too thick in order to improve the scratch resistance, warping may occur in the low specific gravity wood substrate having low rigidity due to curing shrinkage that occurs when the resin in the resin-impregnated paper is thermally cured.

JP 2008-81969 A JP 2008-81972 A

  The present invention has excellent scratch resistance (caster resistance and impact resistance) even when a low specific gravity wood base material is used, and has excellent surface appearance quality, dimensional stability and sheet adhesion. An object is to provide a cosmetic material.

  As a result of intensive studies, the present inventor has found that the above-described object can be achieved when a specific woody base material and a specific resin-impregnated paper are used, and the present invention has been completed.

That is, the present invention relates to the following floor decorative material.
1. A floor decorative material in which a resin-impregnated paper A and a decorative sheet are sequentially laminated on a wooden substrate having a specific gravity of 0.55 g / cm ³ or less,
The paper basis weight of the base paper constituting the resin-impregnated paper is 300 to 800 g / m ² ,
The resin-impregnated paper is impregnated with a thermosetting resin on the base paper,
The resin impregnation rate of the resin impregnated paper is 30 to 100%.
A decorative material for floors.
2. Item 2. The floor decorative material according to Item 1, wherein the decorative sheet has a synthetic resin layer as a lowermost layer.
3. Item 3. The floor decorative material according to Item 1 or 2, wherein a resin-impregnated paper B is laminated on the back side of the wooden substrate.
4). Item 4. The floor decorative material according to any one of Items 1 to 3, wherein the wooden substrate is an early-wood plywood or a softwood plywood.

  Hereinafter, the floor decorative material of the present invention will be described in detail.

Floor decorative material according to the present invention The floor decorative material according to the present invention is a floor decorative material in which a resin-impregnated paper and a decorative sheet are sequentially laminated on a wood base having a specific gravity of 0.55 g / cm ³ or less. And
The paper basis weight of the base paper constituting the resin-impregnated paper is 300 to 800 g / m ² ,
The resin-impregnated paper is impregnated with a thermosetting resin on the base paper,
The resin impregnation rate of the resin impregnated paper is 30 to 100%.
It is characterized by that. Since the floor decorative material of the present invention having the above characteristics uses the above-mentioned specific wood base material and specific resin-impregnated paper, even when a low specific gravity wood base material is used, it has excellent scratch resistance performance (caster resistance and resistance). Impact properties) and excellent surface appearance quality, dimensional stability and sheet adhesion.

Hereinafter, each structure of the decorative material for floors of this invention is demonstrated.
≪Wooden base material≫
The floor decorative material of the present invention has a low specific gravity wood base material (hereinafter also simply referred to as a wood base material) having a specific gravity of 0.55 g / cm ³ or less.

  As the material of the wood base material, it is preferable to use a Lauan alternative material (a material that replaces a conventional Lauan plywood or the like). Specifically, it is preferable to use softwood plywood and / or early mature plywood. Examples of the above-mentioned mature trees include poplar, falkata, acacia, chamelere, eucalyptus, terminaria and the like. In addition, examples of the conifer include pine pine and karamatsu. Of these, it is preferable to use Falkata.

  Further, the wood base material may be present only in one layer in the flooring decorative material, or may be a laminate of two or more layers. Especially, the wooden base material which consists of 3-7 layers which bonded together the several single plate is preferable.

A woody base material can be used combining 1 type (s) or 2 or more types of materials.
≪Resin impregnated paper (resin impregnated paper A) ≫
Resin-impregnated paper (resin-impregnated paper A) is laminated on the front surface of the wooden substrate. As the resin-impregnated paper, the base paper constituting the resin-impregnated paper has a paper basis weight of 300 to 800 g / m ² , the base paper is impregnated with a thermosetting resin, and the resin impregnation rate is 30 to 100%. Use things. Thereby, even when a low specific gravity woody base material is used, it is possible to obtain a floor decorative material having excellent scratch resistance and excellent surface appearance quality, dimensional stability and sheet adhesiveness.

The resin impregnation rate indicates the ratio of the weight (g) of the resin to the unit paper basis weight (g / m ² ). Specifically, a resin-impregnated paper in which 50 g of resin is impregnated with a base paper having a paper basis weight of 100 g / m ² has a resin impregnation rate of 50% (= [50 g] ÷ [100 g / m ² ] × 100). It can be expressed as resin impregnated paper.

  Since the resin impregnation rate of the resin-impregnated paper used in the present invention is 30 to 100%, the resin-impregnated paper can be firmly bonded to the adhesive for attaching the decorative sheet. If the resin impregnation rate is less than 30%, the amount of resin contained in the resin-impregnated paper (the amount of resin entering the base paper) is small, so that the interlayer strength required when used as a flooring decorative material cannot be obtained. If it exceeds 100%, the resin-impregnated paper after thermosetting does not have a paper-like portion necessary for firmly adhering to the adhesive, and as a result, it may not be able to adhere firmly to the decorative sheet. .

The paper basis weight of the base paper constituting the resin-impregnated paper used in the present invention is 300 to 800 g / m ² . If the paper basis weight of the base paper is less than 300 g / m ² , it is not possible to obtain a flooring decorative material excellent in scratch resistance, and if it exceeds 800 g / m ² , the curing shrinkage of the resin-impregnated paper that occurs when the resin is thermally cured. Accordingly, warping may occur in the wooden base material.

The base paper for impregnation used for the resin-impregnated paper is not particularly limited as long as the paper basis weight is 300 to 800 g / m ² , but is a paper base such as thin paper, kraft paper, titanium paper, cotton cloth, or woven made of various materials. Cloth base materials, such as cloth and a nonwoven fabric, can be mentioned.

  A thermosetting resin is used as the resin constituting the resin-impregnated paper. Specifically, unsaturated polyester resin, polyurethane resin (including two-component curable polyurethane), epoxy resin, amino alkyd resin, phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, melamine-urea cocondensation A thermosetting resin such as a resin, a silicon resin, or a polysiloxane resin can be used. 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. In addition, thermosetting resin compositions (adhesives, etc.) mainly composed of the above listed resins can also be used. For example, if it is a resin composition (adhesive etc.) which has a phenol resin as a main component, only a main component can be specified and it can also be abbreviated as a phenol-type resin.

  As a method of obtaining an uncured resin-impregnated paper by impregnating the base paper for impregnation with resin, the solution resin is impregnated by well-known double-sided or single-sided coating such as dipping method, roll coating method, gravure coating method and dried. Just do it.

  As a method for laminating the resin-impregnated paper on the wooden substrate, for example, the resin-impregnated paper is placed on the wooden substrate and hot-pressed.

The temperature, pressure, and time during the hot press molding are not particularly limited as long as the wooden base material and the resin-impregnated paper are bonded to such an extent that they can be used without problems as a flooring decorative material, and can be set as appropriate. For example, when the resin contained in the resin-impregnated paper is a phenol resin and the temperature is 140 ° C. and the pressure is 7 kg / cm ² , the hot pressing can be completed in about 4 minutes.

When laminating the resin-impregnated paper on the wooden substrate, a known adhesive can be used. Examples of the adhesive include polyvinyl acetate, polyvinyl chloride, vinyl chloride / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ionomer, butadiene / acrylonitrile rubber, neoprene rubber, natural rubber, phenol, melamine, urea. And the like having an active ingredient as an active ingredient. Of these, at least one thermosetting adhesive selected from the group consisting of phenol, melamine and urea is preferred. Although the thickness of an adhesive bond layer is not limited, About 0.1-50 micrometers is preferable.
≪Makeup sheet≫
A decorative sheet is laminated on the front surface of the resin-impregnated paper (resin-impregnated paper A). The structure of the decorative sheet is not limited, but for example, a decorative sheet having a pattern layer (solid ink layer / pattern ink layer), a transparent resin layer, and a surface protective layer in order on the base sheet is preferable. Hereinafter, this decorative sheet will be exemplarily described.

  The base sheet is 1) paper such as thin paper, fine paper, kraft paper, Japanese paper, titanium paper, resin-impregnated paper, inter-paper reinforced paper, etc. 2) wood fiber, glass fiber, asbestos, polyester fiber, vinylon fiber, rayon Examples thereof include one or two or more laminates of woven or non-woven fabric made of fibers and the like, and 3) sheets of synthetic resin such as polyolefin, polyester, polyacryl, polyamide, polyurethane, and polystyrene.

  As for the thickness of a base material sheet, about 20-300 micrometers is preferable. The substrate sheet may be colored as necessary. Further, the surface may be subjected to surface treatment such as corona discharge treatment, plasma treatment, or ozone treatment.

  The pattern layer is composed of a pattern ink layer and / or a solid ink layer. The pattern layer can be formed by a printing method such as gravure printing, offset printing or silk screen printing. Examples of the pattern of the pattern ink layer include a wood grain pattern, a stone pattern, a cloth pattern, a skin pattern, a geometric pattern, characters, symbols, line drawings, various abstract patterns, and the like. The solid ink layer is obtained by solid printing of colored ink. The pattern layer is composed of one or both of a pattern ink layer and a solid ink layer.

  As the ink used for the pattern layer, as a vehicle, chlorinated polyolefin such as chlorinated polyethylene and chlorinated polypropylene, polyester, polyurethane composed of isocyanate and polyol, polyacryl, polyvinyl acetate, polyvinyl chloride, and vinyl chloride-vinyl acetate are used. A polymer, a cellulose-based resin, a polyamide-based resin, or the like may be used alone or in combination, and a pigment, a solvent, various auxiliary agents, and the like may be added thereto to make an ink. Among these, from the viewpoint of environmental problems, adhesion to the printing surface, and the like, one or a mixture of two or more of polyester, polyurethane composed of isocyanate and polyol, polyacryl, polyamide-based resin, and the like is preferable.

  A transparent resin layer will not be specifically limited if it is a transparent resin layer, For example, it can form suitably with a transparent thermoplastic resin. Specifically, soft, semi-rigid or rigid polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer Examples include polymers, ionomers, acrylic esters, and methacrylic esters. Among the above, polyolefin resins such as polypropylene are preferable.

  The transparent resin layer may be colored. In this case, a colorant may be added to the thermoplastic resin. As the colorant, pigments or dyes used in the picture layer can be used.

  For the transparent resin layer, fillers, matting agents, foaming agents, flame retardants, lubricants, antistatic agents, antioxidants, UV absorbers, light stabilizers, radical scavengers, soft components (eg rubber) Various additives such as may be included.

  The surface protective layer (transparent surface protective layer) is provided for imparting surface physical properties such as scratch resistance, abrasion resistance, water resistance and stain resistance required for a decorative sheet. As the resin for forming the surface protective layer, curable resins such as thermosetting resins and ionizing radiation curable resins are preferable. In particular, ionizing radiation curable resins are preferable from the viewpoint of high surface hardness, productivity, and the like.

  Examples of thermosetting resins include 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, and melamines. -Urea co-condensation resin, silicon resin, polysiloxane resin and the like.

  A curing agent such as a crosslinking agent and a polymerization initiator, and a polymerization accelerator can be added to the resin. For example, as curing agents, isocyanates, organic sulfonates, etc. can be added to unsaturated polyester resins, polyurethane resins, etc., organic amines, etc. can be added to epoxy resins, peroxides such as methyl ethyl ketone peroxide, azoisobutyl nitrile, etc. A radical initiator can be added to the unsaturated polyester resin.

  Examples of the method for forming the surface protective layer with a thermosetting resin include a method in which a solution of a thermosetting resin is applied by a coating method such as a roll coating method or a gravure coating method and then dried and cured. The coating amount of the solution is about 5 to 30 μm, preferably about 5 to 20 μm in terms of solid content.

  The ionizing radiation curable resin is not limited as long as it is a resin that undergoes a crosslinking polymerization reaction upon irradiation with ionizing radiation and changes to a three-dimensional polymer structure. For example, one or more prepolymers, oligomers and monomers having a polymerizable unsaturated bond or epoxy group that can be crosslinked by irradiation with ionizing radiation in the molecule can be used. Examples thereof include acrylate resins such as urethane acrylate, polyester acrylate, and epoxy acrylate; silicon resins such as siloxane; polyester resins; epoxy resins and the like.

  Examples of the ionizing radiation include visible light, ultraviolet light (near ultraviolet light, vacuum ultraviolet light, etc.), X-rays, electron beams, ion beams, etc. Among them, ultraviolet light or electron beams are desirable.

  As the ultraviolet light source, a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light fluorescent lamp, or a metal halide lamp can be used. The wavelength of ultraviolet light is about 190 to 380 nm.

  As the electron beam source, various electron beam accelerators such as a cockcroft-wald type, a bandegraft type, a resonant transformer type, an insulating core transformer type, a linear type, a dynamitron type, and a high frequency type can be used. The energy of the electron beam is preferably about 100 to 1000 keV, more preferably about 100 to 300 keV. The irradiation amount of the electron beam is preferably about 2 to 15 Mrad.

  The ionizing radiation curable resin is sufficiently cured when irradiated with an electron beam, but it is preferable to add a photopolymerization initiator (sensitizer) when it is cured by irradiation with ultraviolet rays.

  Photopolymerization initiators in the case of resin systems having radically polymerizable unsaturated groups include, for example, acetophenones, benzophenones, thioxanthones, 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. In the case of a resin system having a cationic polymerizable functional group, for example, at least one kind such as an aromatic diazonium salt, an aromatic sulfonium salt, a metallocene compound, a benzoin sulfonic acid ester, and a freeloxysulfoxonium diallyl iodosyl salt. Can be used.

  Although the addition amount of a photoinitiator is not specifically limited, Generally it is about 0.1-10 weight part with respect to 100 weight part of ionizing radiation curable resins.

  As a method for forming a protective layer with an ionizing radiation curable resin, for example, a solution of an ionizing radiation curable resin may be applied by a coating method such as a gravure coating method or a roll coating method. The coating amount of the solution is generally about 5 to 30 μm, preferably about 5 to 20 μm as a solid content.

  In order to further impart scratch resistance and abrasion resistance to the surface protective layer formed from the ionizing radiation curable resin, an inorganic filler may be blended. Examples of inorganic fillers include powdered aluminum oxide, silicon carbide, silicon dioxide, calcium titanate, barium titanate, magnesium pyroborate, zinc oxide, silicon nitride, zirconium oxide, chromium oxide, iron oxide, boron nitride, Examples include diamond, gold sand and glass fiber.

  The addition amount of the inorganic filler is about 1 to 80 parts by weight with respect to 100 parts by weight of the ionizing radiation curable resin.

  Lamination of each layer is, for example, by forming a pattern layer (solid ink layer, pattern ink layer) on one side of the base sheet by printing in order, and then bonding a known dry lamination such as a two-component curable urethane resin on the pattern layer. A transparent resin layer can be laminated by a dry lamination method, a T-die extrusion method or the like via an agent, and a surface protective layer can be formed.

  An uneven pattern may be formed by embossing from the transparent resin layer side or the surface protective layer side. The concavo-convex pattern can be formed by heating press, hairline processing or the like. Examples of the uneven pattern include a conduit groove, a stone plate surface unevenness, a cloth surface texture, a satin finish, a grain, a hairline, and a line groove.

  The decorative sheet may have a synthetic resin layer (so-called backer layer) having a thickness of 100 μm or more in the lowermost layer (the lowermost layer bonded to the wooden substrate). In addition, a backer layer means the buffer layer aiming at shock absorption etc. in the decorative material for floors. As a material constituting the backer layer, for example, polyethylene, polypropylene, ethylene-vinyl alcohol copolymer, polymethylene, polymethylpentene, polyethylene terephthalate, heat-resistant polyalkylene terephthalate (for example, a part of ethylene glycol is 1, Polyethylene terephthalate substituted with 4-cyclohexanedimethanol, diethylene glycol or the like, so-called trade name PET-G (manufactured by Eastman Chemical Company)], polybutylene terephthalate, polyethylene naphthalate, polyethylene naphthalate-isophthalate copolymer, polycarbonate , Polyarylate, polyimide, polystyrene, polyamide, ABS and the like. These resins can be used alone or in combination of two or more. The upper limit of the thickness of the backer layer is not limited, but 600 μm is appropriate. The thickness of a preferable backer layer is 200 to 400 μm. The backer layer may be a laminate of two or more layers.

  The method for forming the backer layer is not particularly limited. For example, it can be easily formed by extrusion of molten resin. For example, it can also be formed by a known dry lamination method using a two-component curable polyurethane adhesive composed of a polyol component and an isocyanate component.

  When the coextrusion method is used as a method for forming the backer layer, a backer layer made of a laminate can be easily formed. For coextrusion film formation, for example, a multi-manifold type or feed block type T-die can be used.

  When the decorative sheet is laminated on the resin-impregnated paper (resin-impregnated paper A), a known adhesive can be used. Examples of the adhesive include a two-component curable polyurethane adhesive composed of a polyol component and an isocyanate component, polyvinyl acetate, polyvinyl chloride, vinyl chloride / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ionomer, Examples thereof include water-based (water-based emulsion) adhesives containing butadiene / acrylonitrile rubber, neoprene rubber, natural rubber and the like as active ingredients; and reactive hot-melt adhesives such as PUR. In particular, when a water-based adhesive is used, the present invention uses a resin-impregnated paper having a resin impregnation rate of 30 to 100%, so the water in the water-based adhesive is not only impregnated with the side surface of the flooring decorative material. Evaporation drying can also be performed from the paper side. Therefore, a water-based adhesive can be preferably used.

  In the case of using a two-component curable polyurethane adhesive, examples of the polyol component include polyester polyol, polyester polyurethane polyol, polyether polyol, polyether polyurethane polyol, and the like, and isocyanate components include TDI, MDI, Examples thereof include diisocyanates such as HDI, PIDI, and XDI, and modified products using these as starting materials. In consideration of the coating amount, workability and working environment, an emulsion type curable adhesive is preferable, and a moisture curable hot melt adhesive is more preferable.

Although the thickness of an adhesive bond layer is not limited, About 0.1-50 micrometers is preferable.
≪Resin impregnated paper (resin impregnated paper B) ≫
A resin-impregnated paper (resin-impregnated paper B) may be provided on the back surface of the wooden substrate. By providing the resin-impregnated paper B, it is possible to further suppress the warpage of the floor decorative material as a whole. As the resin-impregnated paper B, the same resin-impregnated paper A can be used.

The method of laminating the resin-impregnated paper B on the back side of the wood base is the same as the case of laminating the resin-impregnated paper A on the wood base described above. Moreover, when using an adhesive agent when laminating the resin-impregnated paper B on the wood base material, the same adhesive as that for adhering the wood base material and the resin-impregnated paper A described above can be used.
≪Dampproof film≫
A moisture-proof film may be provided on the back surface of the wooden substrate or the resin-impregnated paper B. The moisture-proof film preferably has a moisture permeability of 7 g / m ² · 24 hours or less at a temperature of 40 ° C. and a humidity of 90%, and more preferably has a moisture permeability of 5 g / m ² · 24 hours or less.

  The moisture-proof film is not particularly limited, and for example, a synthetic resin film such as an olefin-based thermoplastic resin such as polyethylene or polypropylene, or an ester-based thermoplastic resin such as polyethylene terephthalate, polybutylene terephthalate, or polyethylene naphthalate can be used. Among these, those having at least a synthetic resin base material layer and a vapor deposition layer are particularly preferable. Hereinafter, this aspect will be described by way of example.

  Synthetic resin base layers include polyethylene, polypropylene, ethylene-propylene copolymers, ethylene-vinyl alcohol copolymers, olefinic thermoplastic resins such as mixtures thereof; polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, Ester thermoplastic resins such as polyethylene naphthalate-isophthalate copolymer, polycarbonate, and polyarylate; Acrylic thermoplastic resins such as polymethyl methacrylate, ethyl polymethacrylate, and polybutyl acrylate; polyimide, polyurethane, Non-halogen thermoplastic resins such as polystyrene and acrylonitrile-butadiene-styrene resin are exemplified.

  The synthetic resin substrate layer may be a sheet stretched in a uniaxial or biaxial direction, or may be unstretched. It is preferable that the synthetic resin base material layer is further laminated with a vapor deposition layer. From the positioning as the base material on which the vapor deposition layer is formed, the mechanical strength is strong and the dimensional stability is biaxial. The sheet | seat extended | stretched is preferable. The appropriate thickness of the synthetic resin base material layer is approximately 9 to 25 μm.

  Examples of the vapor deposition layer include an inorganic vapor deposition layer composed of a metal thin film typified by aluminum, and an inorganic oxide vapor deposition layer composed of an inorganic oxide thin film typified by silicon oxide, magnesium oxide, and aluminum oxide. The vapor deposition layer is formed on the synthetic resin base material layer by a known vapor deposition method such as a vacuum vapor deposition method or a plasma activated chemical reaction vapor deposition method. More preferably, it is an inorganic oxide vapor deposition layer whose vapor deposition layer is transparent.

In order to further improve the gas barrier property of the vapor deposition layer, a surface coat layer may be provided on the vapor deposition layer. Examples of the surface coat layer include polyvinyl alcohol resins. Moreover, the general formula ^{_{R 1 n M (OR 2)}} m ( where in the ^formula, R 1, ^{R 2} represents an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more M represents an integer of 1 or more, and n + m represents a valence of M), and a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer. Furthermore, a composition prepared by polycondensation by a sol-gel method in the presence of a sol-gel method catalyst, an acid, water and an organic solvent can be mentioned. Further, by combining polyvinyl alcohol and an ethylene / vinyl alcohol copolymer, gas barrier properties, water resistance, weather resistance and the like are remarkably improved. A silane coupling agent or the like may be added to the composition. A surface coat layer is obtained by applying these resins or compositions on the vapor deposition layer by a known coating method such as a roll coating method or a gravure coating method. The surface coat layer also functions as a protective layer for the vapor deposition layer, and a thickness of about 1 to 10 μm is appropriate.

  The synthetic resin substrate layer and / or the surface coat layer may be subjected to a surface treatment such as a corona treatment, if necessary. By such surface treatment, the adhesive strength with the adjacent layer can be further increased.

  In the present invention, a primer layer may be further provided between the synthetic resin substrate layer and the vapor deposition layer and on one or both sides of the moisture-proof film. Therefore, a suitable aspect of the moisture-proof film is, for example, an aspect of “synthetic resin substrate layer / primer layer / deposition layer / surface coat layer”, and further provided with a primer layer on one or both sides of the moisture-proof film. An aspect may be sufficient.

  These primer layers are provided in order to increase the adhesion between the synthetic resin base material layer and the vapor deposition layer and to increase the adhesion when the moisture-proof film is laminated on another layer.

  Examples of the resin used for such a primer layer include ester resins, urethane resins, acrylic resins, polycarbonate resins, vinyl chloride-vinyl acetate copolymers, polyvinyl butyral resins, nitrocellulose resins, and the like. These resins can be used alone or in combination. The primer layer can be formed using an appropriate application means such as a roll coating method or a gravure printing method.

  Among these, the primer layer is preferably formed from (i) a copolymer of an acrylic resin and a urethane resin and (ii) an isocyanate. That is, the copolymer of (i) an acrylic resin and a urethane resin is composed of 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. The acrylic-polyester urethane copolymer is formed by reacting the terminal hydroxyl group with the isocyanate (ii) and curing.

  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, characteristics 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 in which a conjugated double bond remains at one end is mixed with the one having a hydroxyl group at both ends. Also good.

  The 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. Examples of the dibasic acid include adipic acid, phthalic acid, isophthalic acid, terephthalic acid and the like. Preferred as the polyester polyol is adipic acid using adipic acid or a mixture of adipic acid and terephthalic acid as the acid component, particularly preferably adipic acid, and 3-methylpentenediol and 1,4-cyclohexanedimethanol as the diol component. Polyester.

  In the primer layer, the urethane resin component formed by the reaction of the component B and the component C gives flexibility to the primer layer and contributes to improvement in adhesion. Moreover, the acrylic resin component which consists of an acrylic polymer contributes to a weather resistance and blocking resistance in the said primer layer. 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 primer layer is obtained. Adipic acid or a mixture of adipic acid and terephthalic acid, and 3-methylpentanediol In the case of polyester diol composed of 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 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 diisocyanate is added to the terminal hydroxyl group is also mixed, and a prepolymer is formed in a state where excess isocyanate group and hydroxyl group 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 primer layer may be formed by coating by a known coating method such as a coating method. The isocyanate of (ii) may be any isocyanate that 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, tolylene diisocyanate, xylylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate monomers, dimers, trimers and other multimers, or these And polyisocyanates such as derivatives (adducts) obtained by adding the above isocyanate to a polyol.

As the coating amount after drying of the primer layer is from 1 to 20 g / ^{m 2,} preferably from 1 to 5 g / ^{m 2.} Moreover, the said primer layer is good also as a layer which added additives, such as fillers, such as a silica powder, a light stabilizer, and a coloring agent, as needed.

  When the moisture-proof film is laminated on the wood substrate or the resin-impregnated paper B, a known adhesive can be used. Examples of the adhesive include polyvinyl acetate, polyvinyl chloride, vinyl chloride / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ionomer, butadiene / acrylonitrile rubber, neoprene rubber, natural rubber, and the like as active ingredients. Adhesives to be used. Although the thickness of an adhesive bond layer is not limited, About 0.1-50 micrometers is preferable.

  The floor decorative material of the present invention is suitable as a floor decorative material to be applied to floor surfaces of various buildings and as a floor decorative material used for floor heating as a special application.

The floor decorative material of the present invention has a resin-impregnated paper and a decorative sheet laminated in order on a wood base having a specific gravity of 0.55 g / cm ³ or less, and the base paper of the base paper constituting the resin-impregnated paper. When the amount is 300 to 800 g / m ² and the resin impregnation rate of the resin impregnated paper is 30 to 100%, excellent scratch resistance (caster resistance and Impact resistance) and excellent surface appearance quality, dimensional stability and sheet adhesion.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the examples.

Example 1
≪Preparation of decorative sheet≫
A pattern printing layer having a thickness of 2 μm was formed on one surface of a 60 μm-thick polypropylene film subjected to corona discharge treatment on both sides with a printing ink made of a two-part curable acrylic urethane resin. Next, an urethane resin adhesive was applied onto the pattern print layer so that the solid content was 3 g / m ² to form an adhesive layer. On the adhesive layer, a polypropylene resin was heated and melt extruded with a T-die extruder to form a transparent resin layer having a thickness of 80 μm. Next, after the corona discharge treatment is applied to the surface of the transparent resin layer, an acrylic urethane resin is applied to the surface subjected to the corona discharge treatment so that the solid content is 1 g / m ^2. Thus, a primer layer was formed.

A urethane acrylate ionizing radiation curable resin is applied to the primer layer surface by a roll coating method so that the solid content is 15 g / m ^2, and then an electron beam irradiation apparatus is used in an environment with an oxygen concentration of 200 ppm or less. Then, the surface protective layer was formed by irradiating and curing an electron beam under conditions of an acceleration voltage of 125 KeV and 5 Mrad. Next, a decorative sheet (total thickness: 160 μm) was prepared by forming an uneven pattern of a wood grain conduit pattern having a depth of 30 μm by embossing from the surface protective layer side.
≪Preparation of decorative material for floors≫
An uncured resin-impregnated paper having a resin impregnation ratio of 50% was produced by impregnating a kraft paper (impregnating base paper) having a paper basis weight of 500 g / m ² with a phenol resin. The phenolic adhesive was applied to a 11.4 mm thick Falkata plywood at 10 g / scale angle, and the uncured resin-impregnated paper was placed on the hot press machine at 140 ° C., 7 kg / cm ² for 4 minutes. Hot pressing was performed under the conditions.

  Next, a decorative sheet was bonded onto the resin-impregnated paper via an aqueous adhesive (BA-10L / BA-11B, manufactured by Chuo Rika Kogyo Co., Ltd.). The decorative sheet was bonded so that the polypropylene film of the decorative sheet was in contact with the aqueous adhesive. As a result, a floor decorative material having a width of 303 mm and a length of 1818 mm was produced on the floor processing line.

Example 2
Two uncured resin-impregnated papers with a resin impregnation rate of 50% were prepared by impregnating a kraft paper (impregnating base paper) with a paper basis weight of 800 g / m ² with a resin impregnation ratio of 50% Cured resin impregnated paper A, B). On the 11.4 mm thick Falkata plywood, phenolic adhesive was applied at 10 g / scale angle, and the uncured resin-impregnated paper A (resin-impregnated paper (surface side)) was placed. What is the phenolic adhesive? The uncured resin-impregnated paper B (resin-impregnated paper (back side)) was placed on the opposite Falkata plywood. Then, it hot-press-molded on the conditions of 140 degreeC and 7 kg / cm < ² > for 4 minutes with the hot press machine.

  Next, a decorative sheet was bonded onto the resin-impregnated paper A via an aqueous adhesive (BA-10L / BA-11B, manufactured by Chuo Rika Kogyo Co., Ltd.). The decorative sheet was bonded so that the polypropylene film of the decorative sheet was in contact with the aqueous adhesive. As a result, a floor decorative material having a width of 303 mm and a length of 1818 mm was produced on the floor processing line.

Example 3
A polypropylene resin film (250 μm) is bonded to the back surface (polypropylene film surface) of the decorative sheet obtained in Example 1 via a urethane resin adhesive, and this is used as a decorative sheet (total thickness: 410 μm). It was. As the uncured resin-impregnated paper, uncured resin-impregnated paper having a paper basis weight of 300 g / m ² and a resin impregnation rate of 50% was used. About others, it carried out similarly to Example 1, and produced the decorative material for floors.

Example 4
A polypropylene resin film (400 μm) is bonded to the back surface (polypropylene film surface) of the decorative sheet obtained in Example 1 via a urethane resin adhesive, and this is used as a decorative sheet (total thickness: 560 μm). It was. As the uncured resin-impregnated paper, uncured resin-impregnated paper having a paper basis weight of 300 g / m ² and a resin impregnation rate of 50% was used. About others, it carried out similarly to Example 1, and produced the decorative material for floors.

Example 5
A polypropylene resin film (250 μm) is bonded to the back surface (polypropylene film surface) of the decorative sheet obtained in Example 1 via a urethane resin adhesive, and this is used as a decorative sheet (total thickness: 410 μm). It was. About others, it carried out similarly to Example 1, and produced the decorative material for floors.

Example 6
Instead of the 11.4 mm thick Falkata plywood, a 11.4 mm thick softwood plywood was used. As the uncured resin-impregnated paper, uncured resin-impregnated paper having a paper basis weight of 300 g / m ² and a resin impregnation rate of 50% was used. About others, it carried out similarly to Example 1, and produced the decorative material for floors.

Example 7
A flooring decorative material was produced in the same manner as in Example 1 except that a 11.4 mm thick softwood plywood was used instead of the 11.4 mm thick Falkata plywood.

Example 8
As the uncured resin-impregnated paper, a floor decorative material was prepared in the same manner as in Example 1 except that uncured resin-impregnated paper having a paper basis weight of 500 g / m ² and a resin impregnation rate of 100% was used. Produced.

Comparative Example 1
An uncured resin-impregnated paper having a base paper weight of 200 g / m ² and a resin impregnation rate of 150% is placed on a 11.4 mm thick softwood plywood, and 140 ° C. and 7 kg / cm ² in a hot-pressing machine. Hot pressing was performed for 4 minutes.

  Next, a decorative sheet similar to that of Example 1 was bonded onto the resin-impregnated paper via a PUR adhesive. The decorative sheet was bonded so that the polypropylene film of the decorative sheet was in contact with the PUR adhesive. As a result, a floor decorative material having a width of 303 mm and a length of 1818 mm was produced on the floor processing line.

Comparative Example 2
As the uncured resin-impregnated paper, a floor decorative material was prepared in the same manner as in Example 1 except that uncured resin-impregnated paper having a paper basis weight of 900 g / m ² and a resin impregnation ratio of 50% was used. Produced.

Comparative Example 3
As the uncured resin-impregnated paper, a floor decorative material was prepared in the same manner as in Example 1 except that uncured resin-impregnated paper having a paper basis weight of 500 g / m ² and a resin impregnation ratio of 150% was used. Produced.

Test example 1 (surface appearance quality evaluation test)
The floor decorative materials produced in Examples 1 to 8 and Comparative Examples 1 to 3 were visually evaluated. The evaluation criteria were as follows.

○: No strange appearance.
Δ: Slightly uncomfortable, but no problem in use.
×: There is a problem in use.

Test Example 2 (Sheet adhesion evaluation test)
A peeling test was performed on the floor decorative materials produced in Examples 1 to 8 and Comparative Examples 1 to 3. Specifically, a floor decorative material test piece having a width of 25 mm is prepared, the decorative sheet at the tip is peeled off, and the peeled decorative sheet is 180 ° at a tensile speed of 200 mm / min with a Tensilon tester. The remaining part of the decorative sheet was peeled by pulling in the direction, and the integrated average load value at that time was measured. The evaluation criteria were as follows.

○: 24.5 N or more / 25 mm width ×: less than 24.5 N / 25 mm width

Test Example 3 (Caster Resistance Evaluation Test)
The floor decorative materials produced in Examples 1 to 8 and Comparative Examples 1 and 2 were evaluated by the following procedure. That is, the load of 25 kg was applied to the twin wheel caster, and the depth of the dent after the test specimen surface was reciprocated 25000 times was evaluated. The evaluation criteria were as follows.

○: Recess depth is 100 μm or less ×: Recess depth is greater than 100 μm
Test example 4 (impact resistance evaluation test)
According to the DuPont impact test of JIS K5600, a shooting mold having a hemispherical tip with a radius of 6.35 mm was allowed to stand on the surface of the floor decorative material produced in Examples 1-8 and Comparative Examples 1-2. The weight was evaluated by dropping a weight of 500 g on the shooting mold from a height of 30 cm. The evaluation criteria were as follows. In addition, △ evaluation and ○ evaluation were judged as pass.

○: Depression depth is 300 μm or less Δ: Depression depth is larger than 300 μm, 400 μm or less X: Depression depth is larger than 400 μm

Test example 5 (warp amount evaluation test)
The temporal deformation (warpage amount) of the decorative materials for floors produced in Examples 1 to 8 and Comparative Examples 1 to 2 was measured. Specifically, the amount of warp arrow height after each floor decorative material was completed for floor use was measured. The evaluation criteria were as follows. In addition, △ evaluation and ○ evaluation were judged as pass.

○: Warpage amount in the longitudinal direction is 10 mm or less. Δ: Warpage amount in the longitudinal direction is greater than 10 mm and 15 mm or less. X: Warpage amount in the longitudinal direction is greater than 15 mm. In addition, Table 1 shows the overall scratch resistance evaluation that combines the caster resistance evaluation and the impact resistance evaluation. The evaluation criteria for the overall damage resistance evaluation were as follows. In addition, △ evaluation and ○ evaluation were judged as pass.

○: Both caster resistance evaluation and impact resistance evaluation ○ evaluation △: Castor resistance evaluation is ○ evaluation and impact resistance evaluation is △ evaluation ×: At least one of caster resistance evaluation and impact resistance evaluation is X Evaluation In addition, since the sheet adhesive evaluation was x in Test Example 2, the floor decorative material produced in Comparative Example 3 was not performed in Test Examples 3 to 5.

Claims (4)

A floor decorative material in which a resin-impregnated paper A and a decorative sheet are sequentially laminated on a wooden substrate having a specific gravity of 0.55 g / cm ³ or less,
The paper basis weight of the base paper constituting the resin-impregnated paper is 300 to 800 g / m ² ,
The resin-impregnated paper is impregnated with a thermosetting resin on the base paper,
The resin impregnation rate of the resin impregnated paper is 30 to 100%.
A decorative material for floors.   The floor decorative material according to claim 1, comprising a synthetic resin layer in a lowermost layer of the decorative sheet.   The flooring decorative material according to claim 1 or 2, wherein a resin-impregnated paper B is laminated on the back side of the wooden substrate.   The flooring decorative material according to any one of claims 1 to 3, wherein the wooden substrate is an early-wood plywood or a softwood plywood.