JP6194917B2 - Floor decorative material - Google Patents

Description

  The present invention relates to a floor decorative material suitable for directly pasting on a concrete slab.

Conventionally, a floor decorative material using a wooden board is known. In particular, in the case of a flooring decorative material that is directly affixed on a concrete slab in an apartment or the like, a cut groove may be provided on the back surface of the wooden board in consideration of soundproofing and followability to the concrete slab. In addition, a cushion material may be provided on the back surface of the floor decorative material in order to enhance the walking feeling and the like.

When directly applying flooring decorative material on a concrete slab, if the curing reaction of the concrete slab is not completely completed, moisture will be absorbed from the back of the flooring decorative material after construction, and the wooden board will expand and warp. There is a problem that arises. This problem is that when a decorative sheet (especially a decorative sheet having a resin layer and low moisture permeation) is provided on the front surface of the wooden board, the absorbed moisture is absorbed on the front surface of the floor decorative material. This is noticeable because it is difficult to be released from the water.

In order to suppress such expansion and warpage of the decorative material for flooring, there is an attempt to suppress moisture absorption into the wooden board by providing a moisture-proof sheet on the back surface of the cushion material. For example, Patent Literature 1 states that “a moisture-proof sheet in which a cushioning material layer is adhered to the back surface of a flooring base material, and a moisture-proof layer is used as a core layer on the back surface of the cushioning material layer, and a paper layer is formed on the front and back sides thereof. Is a floor material formed by bonding.

However, the floor material described in Patent Document 1 is still insufficient in moisture resistance, and in particular, when a decorative sheet is laminated on the front surface of the floor material, there are harmful effects (expansion, warpage, etc.) due to moisture absorption of the wooden board. It cannot be prevented sufficiently. Therefore, even when a decorative sheet is laminated on the front surface of a wooden board, it is desired to develop a floor covering material in which the occurrence of expansion and warping due to moisture absorption is sufficiently suppressed.

JP-A-10-299234

The present invention improves the above-mentioned problems of the prior art, and even when a decorative sheet is laminated on the front surface of a wooden board, the occurrence of expansion and warping due to moisture absorption is sufficiently suppressed. The purpose is to provide materials. It is another object of the present invention to provide a floor decorative material having excellent adhesion to an adherend.

As a result of intensive studies, the present inventor has found that the above object can be achieved when a specific moisture-proof film is used, and has completed the present invention.

That is, the present invention relates to the following floor decorative material.
1. On the back surface of the decorative sheet is a floor decorative material in which a wooden board, a cushion material, and a moisture-proof film are sequentially laminated,
(I) The moisture-proof film has a moisture permeability of 7 g / m ² · 24 hours or less at a temperature of 40 ° C. and a humidity of 90%,
(Ii) The moisture-proof film is composed of a surface coat layer, a vapor deposition layer, a primer layer 1 and a synthetic resin base material layer in order from the front surface, and the surface coat layer comprises a polyvinyl alcohol resin and It contains at least one selected from the group consisting of urethane resins and has a thickness of 0.1 to 10 μm; the vapor deposition layer is made of a metal thin film or an inorganic oxide thin film; and the primer layer 1 is a urethane resin. And the synthetic resin base material layer includes an ester-based thermoplastic resin, and the thickness is 9 to 60 μm.
(Iii) The cushion material is a laminate of foamed urethane and foamed polyethylene, and has a thickness of 2 to 7 mm.
(Iv) a back surface of the moisture-proof film, is further primer layer 3 formed,
(V) The wood board has a kerf formed on the back surface,
A decorative material for floors.
2 . Item 2. The floor decorative material according to Item 1, wherein a primer layer 2 is further formed on the front surface of the moisture-proof film.
3 . Item 3. The floor decorative material according to Item 1 or 2 , which is a floor decorative material that is directly pasted on a concrete slab via an adhesive layer.

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

The floor decorative material of the present invention is a floor decorative material in which a decorative sheet is laminated on the front surface of a wooden board, and a moisture-proof film is laminated on the back surface of the wooden board via a cushioning material. The moisture-proof film has a moisture permeability of 7 g / m ² · 24 hours or less at a temperature of 40 ° C. and a humidity of 90%. The moisture permeability is a measured value in an environment of a temperature of 40 ° C. and a humidity of 90% RH in accordance with JIS Z0208 (moisture permeability test method (cup method). Hereinafter, the moisture permeability in this specification is a measurement under the above conditions. Indicates the value.

Even if the floor decorative material of the present invention having the above characteristics has a moisture-proof film having a moisture permeability of 7 g / m ² · 24 hours or less, even when the floor decorative material is directly pasted on a concrete slab,
Moisture absorption (water absorption) from the back surface of the floor decorative material is suppressed. Therefore, even when the decorative sheet is laminated on the front surface of the floor decorative material, the occurrence of expansion and warping due to moisture absorption of the wooden board is sufficiently suppressed. Such a flooring decorative material of the present invention is suitable for an application in which the floor decorative material is directly attached onto a concrete slab in an apartment or the like.

  Hereinafter, each structure of the decorative material for floors of this invention is demonstrated.

(Wood board)
As wood board, for example, wood veneer / plywood made of trees such as cedar, firewood, lauan, teak, etc.
Wood boards, such as particle board and medium density fiber board (MDF), are mentioned.

In the present invention, a wood board having a kerf formed on the back surface is preferable. This kerf increases the soundproofing property of the decorative material for flooring and improves the followability to the construction surface when the decorative material for flooring is constructed. The depth and size of the kerf can be appropriately set according to the type of wooden board or construction surface.

Although the thickness of a wooden board is not specifically limited, About 3-15 mm is preferable and about 6-12 mm is more preferable.

(Decorative sheet)
A decorative sheet is laminated on the front side of the wooden board. The decorative sheet is not limited,
For example, it is preferable to have a pattern layer (solid ink layer / pattern ink layer), a transparent resin layer, and a surface protective layer in this order on the substrate sheet. Hereinafter, this decorative sheet will be exemplarily described.

As the base sheet, 1) thin paper, fine paper, craft paper, Japanese paper, titanium paper, resin-impregnated paper,
Paper such as paper-reinforced paper 2) Woven or non-woven fabric made of wood fiber, glass fiber, asbestos, polyester fiber, vinylon fiber, rayon fiber, etc. 3) Polyolefin, polyester, polyacryl, polyamide, polyurethane, polystyrene, etc. 1 or 2 of synthetic resin sheet
A laminate of seeds or more is mentioned.

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. The pattern of the pattern ink layer is, for example, a wood grain pattern, a stone pattern, a cloth pattern, a skin pattern, a geometric pattern, characters, symbols,
Examples include line drawings and various abstract patterns. 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, a curable resin such as a thermosetting resin or an ionizing radiation curable resin is preferable. In particular,
The ionizing radiation curable resin is 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 ionizing radiation include visible light, ultraviolet light (near ultraviolet light, vacuum ultraviolet light, etc.), X-rays, electron beams,
Among these, there are ion beams, among which ultraviolet rays and 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, 10
About 0-300 keV is more preferable. 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, a pattern layer (solid ink layer, pattern ink layer) on one surface of the substrate sheet
Are formed in order by printing, and then a transparent resin layer is laminated on the pattern layer via a known dry lamination adhesive such as a two-component curable urethane resin by the dry lamination method, T-die extrusion method, etc. This can be done by the method of forming the layer.

An uneven pattern may be formed by embossing from 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 (layer that adheres to the wooden board). In addition, a backer layer means the buffer layer aiming at shock absorption etc. in the decorative material for floors. Examples of the material constituting the backer layer include polypropylene, ethylene-vinyl alcohol copolymer, polymethylene, polymethylpentene, polyethylene terephthalate, and high heat-resistant polyalkylene terephthalate [for example, a part of ethylene glycol is 1,4- So-called trade name PET-G (polyethylene terephthalate substituted with cyclohexanedimethanol or diethylene glycol)
Eastman Chemical Company)), polybutylene terephthalate, polyethylene naphthalate, polyethylene naphthalate-isophthalate copolymer, polycarbonate,
Examples include polyarylate, polyimide, polystyrene, polyamide, and ABS. These resins can be used alone or in combination of two or more. Although the upper limit of the thickness of a backer layer is not limited, 300-600 micrometers is suitable.

When laminating the decorative sheet on the wooden board, 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.

(Cushion material)
A cushion material is provided on the back of the wooden board.

The cushioning material is not particularly limited as long as the cushioning material is a material that can impart cushioning to the flooring decorative material and improve the walking feeling and the like. For example, what laminated | stacked 1 type, or 2 types, such as a foaming polyurethane, a foaming polyester, a foaming polypropylene, a compression polyurethane, is mentioned.

More specifically, examples include 1) a laminate of foamed polyurethane and foamed polyester, 2) a laminate of foamed polyurethane and foamed polypropylene, and 3) a laminate of foamed polyurethane and compressed polyurethane. These types are selected according to the desired degree of cushioning.

In addition, various nonwoven fabrics, so-called spunbond (for example, a mixture of polystyrene and polyethylene) or a laminate thereof can also be used. The thickness of the cushion material is not limited, but 2
About 7 mm is appropriate.

When laminating the cushion material on the wooden board, 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.

(Dampproof film)
The moisture-proof film is provided on the back surface of the wooden board via the cushion material. In the present invention,
A moisture-proof film having a moisture permeability of 7 g / m ² · 24 hours or less at a temperature of 40 ° C. and a humidity of 90% is used. More preferably, 5 g / m ² · 24 hours or less is used. The moisture-proof film is not limited as long as the moisture permeability is satisfied, and a synthetic resin base material layer such as an olefin-based thermoplastic resin or an ester-based thermoplastic resin described later; polyvinyl alcohol, polyvinylidene chloride, etc. on the above-mentioned synthetic resin base material layer A surface coating layer of the above; a synthetic resin base material layer provided with a vapor deposition layer; a synthetic resin base material layer provided with a vapor deposition layer;
Those provided with a surface coat layer such as polyvinylidene chloride; When the moisture-proof film has a synthetic resin substrate layer and a surface coat layer, the layer in the moisture-proof film that adheres to the cushion material may be a synthetic resin substrate layer or a surface coat layer. From the viewpoint of preventing the floor decorative material from being damaged, it is preferable that the layer adhered to the cushion material is a surface coat layer. On the other hand, when the layer that adheres to the cushioning material is a synthetic resin base material layer and the layer that adheres to the adherend is a surface coat layer, the surface coat layer also has a function as a primer layer described later, Adhesion with an adherend such as a concrete slab (or an adhesive when an adhesive is applied onto the adherend) is improved.

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 base material layer may be a uniaxial or biaxially oriented sheet, or may be unstretched, but has a high mechanical strength because it is a base material on which a vapor deposition layer described later is formed. A sheet stretched in the biaxial direction is preferable for reasons such as excellent dimensional stability. The appropriate thickness of the synthetic resin base material layer is approximately 9 to 60 μm.

Examples of the surface coat layer include polyvinyl alcohol resin (PVA), urethane resin, and polyvinylidene chloride resin. The polyvinyl alcohol resin has a general formula R ¹ _n M
(OR ² ) _m (wherein, R ¹ and R ² are the same or different and are a phenyl group or halogen having a C 1-8 alkyl group, a phenyl group, a C 1-2 alkyl substituent) Represents a phenyl group having a substituent, M represents a metal atom, n represents an integer of 0 or more, and m represents 1
And at least one alkoxide represented by the following formula: n + m represents the valence of M), a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer, and a sol-gel Examples thereof include a composition prepared by polycondensation by a sol-gel method in the presence of a process catalyst, an acid, water and an organic solvent. Polyvinyl alcohol and ethylene
By combining the 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. The urethane resin is preferably a two-component curable resin.

A surface coat layer is obtained by applying these resins or compositions on a synthetic resin base material layer by a known coating method such as a roll coating method or a gravure coating method. Its thickness is 0.1-1
0 μm is appropriate. In addition, since the polyvinyl alcohol-based resin has not only gas barrier properties but also adhesiveness, adhesion to an adherend such as a concrete slab (or an adhesive when an adhesive is applied on the adherend). It contributes to the improvement of the durability of flooring decorative materials.

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, the above-described surface coat layer may be provided on the vapor deposition layer. The surface coat layer also functions as a protective layer for the vapor deposition layer, and its thickness is about 0.1 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 (primer layer 1) may be provided between the synthetic resin substrate layer and the vapor deposition layer. Further, a primer layer (primer layer 2 and / or primer layer 3) may be provided on one side or both sides of various moisture-proof films. For example, “surface coat layer / deposition layer / primer layer 1 / synthetic resin substrate layer” improves adhesion between the synthetic resin substrate layer and the deposition layer, and “primer layer 2 / moisture-proof film / primer layer”. If it is set to “3”, the adhesion between the moisture-proof film and the cushioning material, and the moisture-proof film and an adherend such as a concrete slab (or an adhesive when an adhesive is applied onto the adherend) is improved.

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 comprises (i) a copolymer of acrylic resin and urethane resin and (ii)
) And 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)
Are mixed 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 and curing the terminal hydroxyl group with the isocyanate (ii).

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 having a conjugated double bond at one end is mixed with the above-mentioned one having a hydroxyl group at both ends. 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. 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 and coating liquid 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) 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, monomers of tolylene diisocyanate, xylylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate,
Examples thereof include multimers such as dimers and trimers, and polyisocyanates such as derivatives (adducts) obtained by adding these isocyanates to polyols.

The application amount of the primer layer after drying is 0.1 to 20 μm, preferably 0.
. 1-10 μm. 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.

The floor decorative material of the present invention has a moisture-proof film having a moisture permeability of 7 g / m ² · 24 hours or less, so that even when the floor decorative material is directly pasted on a concrete slab, Moisture absorption (water absorption) is suppressed. Therefore, even when the decorative sheet is laminated on the front surface of the floor decorative material, the occurrence of expansion and warping due to moisture absorption of the wooden board is sufficiently suppressed. Such a flooring decorative material of the present invention is suitable for an application in which the floor decorative material is directly attached onto a concrete slab in an apartment or the like.

It is a schematic diagram (an example) of the decorative material for floors of the present invention. 2 is a schematic diagram of a water resistance test performed in Test Example 1. FIG.

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
(1) Apply a decorative sheet (0.16mm) containing a synthetic resin layer to Chuo Rika Kogyo's adhesive (BA-10L / BA-11
(B, 9 g / scale angle) and 9 mm thick lauan plywood (5ply).
(2) The above was triturated into a 313 mm width × 1840 mm length with a gang saw.
(3) The back side groove, the back side vertical groove, and the split processing (155 mm width × 918 mm length) were performed with the back groove processing machine.
(4) Using the tenona processing machine, the above was subjected to sag processing and end chamfering (145 mm width × 900 mm length).
(5) A groove coating was applied to the chamfered portion on the four sides of the groove coating line as described above (groove coating: W-SF manufactured by Showa Ink Industries, Ltd.).
(6) The cushion material which consists of a nonwoven fabric was affixed on the said back surface through the adhesive agent, and also the moisture-proof film was laminated | stacked. This produced a flooring decorative material.

The moisture-proof film was produced as follows. That is, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was prepared, and a primer layer 1 made of a two-component curable urethane resin was provided on one side. Further, an aluminum vapor deposition layer was provided on the primer layer 1. The film thus obtained is referred to as “deposited PET film”.

A surface coat layer (thickness 0.2) comprising a PVA / silicate system on the vapor-deposited PET film.
μm (dry state)) was formed, and a laminate (synthetic resin base material layer (PET) / deposition layer / surface coat layer) was produced. After both surfaces of the laminate are subjected to corona discharge treatment, a two-part curable resin in which a curing agent (isocyanate) is added to the main agent (a mixture of urethane resin and nitrified cotton-based resin) is solidified by a gravure printing method to 5 μm each The primer layers 2 and 3 for adhesion were formed on both sides. Thereby, a moisture-proof film was obtained. The moisture permeability of this moisture barrier film is
It was 1 g / m ² · 24 hours.

Example 2
In the above (6), a flooring decorative material was produced in the same manner as in Example 1 except that a laminate of foamed urethane and foamed polyethylene was used as the cushioning material. Specifically, as a cushioning material, a laminate of foamed urethane made by Achilles and foamed polyethylene made by Toray (total thickness 5 mm)
Was used.

Example 3
In the above (6), a flooring decorative material was produced in the same manner as in Example 1 except that the surface coat layer of the moisture-proof film was a urethane resin. The moisture permeability of this moisture-proof film is 3 g / m ² · 24
It was time.

Example 4
In (6) above, as a moisture-proof film, a biaxially stretched polypropylene film (OPP film, thickness 20 μm) is coated with a surface coating of polyvinyl alcohol resin (thickness 0.1 μm).
A flooring decorative material was produced in the same manner as in Example 1 except that a material provided with the above was used. The moisture permeability of this moisture-proof film was 4.5 g / m ² · 24 hours.

Example 5
In the above (6), as the moisture-proof film, one surface of the OPP film (thickness 20 μm) is provided with a polyvinyl alcohol resin surface coat (thickness 0.1 μm), and the other is provided with an adhesion primer layer 3. A flooring decorative material was produced in the same manner as in Example 1 except that a material was used. The moisture permeability of this moisture-proof film was 4.5 g / m ² · 24 hours.

Example 6
In the above (6), a flooring decorative material was produced in the same manner as in Example 1 except that an OPP film (thickness 30 μm) was used as the moisture-proof film. The moisture permeability of this moisture-proof film is 6 g / m
Was ² · 24 hours.

Example 7
In the above (6), as the moisture-proof film, the OPP film (thickness 30 μm) is provided with the adhesion primer layer 3, and the adhesion primer layer 3 is provided so as to adhere to the base. A flooring decorative material was prepared in the same manner as in Example 1 except that a film was used. The moisture permeability of this moisture-proof film was 6 g / m ² · 24 hours.

Example 8
In the above (6), a 60 μm polyethylene resin film (P
E, a floor decorative material was produced in the same manner as in Example 1 except that the moisture permeability was 7 g / m ² · 24 hours.

Comparative Example 1
In the above (6), a flooring decorative material was produced in the same manner as in Example 1 except that a laminate of a nonwoven fabric and spunbond (polystyrene + polyethylene) was used as a cushioning material and a moisture-proof sheet was not further laminated. Specifically, for the cushion material, L45 type made by Kureha Tech was used. As a reference value, the moisture permeability of spunbond is 20 g / m ² · 24 hours.

Comparative Example 2
In Example (6) above, Example 1 was used except that moisture-proof paper (polyethylene (thickness 30 μm) as a core layer and laminated on both sides with paper: moisture permeability 10 g / m ² · 24 hours) was used as the moisture-proof sheet. Similarly, a flooring decorative material was produced.

<The layer structure of the moisture-proof film of an Example and a comparative example>
Example 1: (Lawan plywood) / (nonwoven fabric cushioning material) / primer layer 2 / PVA / aluminum deposition / primer layer 1 / PET / primer layer 3 / (mortar base)
Example 2: (Lawan plywood) / (foamed urethane / foamed polyethylene cushion material) / primer layer 2 / PVA / aluminum deposition / primer layer 1 / PET / primer layer 3 / (mortar base)
Example 3: (Lawan plywood) / (nonwoven fabric cushion material) / primer layer 2 / urethane resin / aluminum deposition / primer layer 1 / PET / primer layer 3 / (mortar base)
Example 4: (Lawan plywood) / (nonwoven cushion material) / OPP / PVA / (mortar base)
Example 5: (Lawan plywood) / (nonwoven cushion material) / PVA / OPP / primer layer 3
/ (Mortar base)
Example 6: (Lawan plywood) / (nonwoven cushion material) / OPP / (mortar base)
Example 7: (Lawan plywood) / (nonwoven cushion material) / OPP / primer layer 3 / (mortar base)
Example 8: (Lawan plywood) / (nonwoven cushion material) / PE / (mortar base)
Comparative Example 1: (Lawan plywood) / (nonwoven cushion material) / spunbond (polystyrene / P
E) / (mortar base)
Comparative Example 2: (Lawan plywood) / (nonwoven cushion material) / paper / PE / paper / (mortar base)

Test example 1 (water resistance test)
(1) A plastic plate (1.5 m × 2 m) with a sponge mat attached to the surface was prepared. A metal frame was fixed on the mount with a distance of 900 mm.
(2) Water was sprayed on the surface of the mount so that the surface of the mount was always wet.
(3) The flooring was set in a state where the floor material short portion hits the upper and lower metal frames (a schematic diagram of the set state is shown in FIG. 2). That is, it was set in a state where the elongation in the longitudinal direction was suppressed.
(4) Observation of the flooring condition (warp, undulation, etc.) and moisture content measurement over time (1 week, 2 weeks). Watering was performed regularly to keep the surface of the base plate wet. The moisture content was measured using a wood moisture meter (product name “Turk” manufactured by Kett Science Laboratory).

  The results are shown in Table 1.

[In Table 1, the unit of moisture permeability is g / m ² · 24 hours. Although the moisture permeability indicates the moisture permeability of the moisture permeable film, Comparative Example 1 is a reference value indicating the moisture permeability of the spunbond. ]
As is clear from the results in Table 1 above, the floor decorative material of the present invention provided with a moisture-proof film having a moisture permeability of 7 g / m ² · 24 hours or less effectively absorbs moisture to the wood board due to the presence of the moisture-proof film. As a result, warpage and expansion of the floor decorative material are prevented.

Test example 2 (adhesion test)
・ A flooring decorative material was applied to the mortar base using KONISHI adhesive (KU928RS). The application amount of the adhesive was 400 g / m ² .

・ After curing the floor covering material constructed above by the following method, the adhesiveness (peeled state) was evaluated by forced peeling.

・ Grow for 1 week at room temperature. (Normal adhesiveness)
-Cured for 1 week in a 50 ° C x 90% RH environment. (Moist heat adhesion)
The results are shown in Table 2.

The “cushion material / material breakage” in the peeled state means that the cushion material itself was destroyed when the floor decorative material was forcibly peeled off. Further, “film / adhesive interface” means that the moisture-proof film has been peeled off from the mortar base. Furthermore, “peeling between moisture-proof papers” means that the moisture-proof paper has been peeled off from the floor decorative material.

What provided the primer layer 3 on the moisture-proof film improved the adhesiveness with the mortar base. Further, when the moisture-proof film of Comparative Example 2 was moisture-proof paper, the peel strength between the moisture-proof papers decreased because the paper absorbed moisture.

1. Cosmetic sheet 2. 2. Wood board with kerf formed on the back side Cushion material4. 4. Moisture-proof film Metal frame 6. Base plate (sponge / plastic plate)
7). Floor decorative material

Claims (3)

On the back surface of the decorative sheet is a floor decorative material in which a wooden board, a cushion material, and a moisture-proof film are sequentially laminated,
(I) The moisture-proof film has a moisture permeability of 7 g / m ² · 24 hours or less at a temperature of 40 ° C. and a humidity of 90%,
(Ii) The moisture-proof film is composed of a surface coat layer, a vapor deposition layer, a primer layer 1 and a synthetic resin base material layer in order from the front surface, and the surface coat layer comprises a polyvinyl alcohol resin and It contains at least one selected from the group consisting of urethane resins and has a thickness of 0.1 to 10 μm; the vapor deposition layer is made of a metal thin film or an inorganic oxide thin film; and the primer layer 1 is a urethane resin. And the synthetic resin base material layer includes an ester-based thermoplastic resin, and the thickness is 9 to 60 μm.
(Iii) The cushion material is a laminate of foamed urethane and foamed polyethylene, and has a thickness of 2 to 7 mm.
(Iv) a back surface of the moisture-proof film, is further primer layer 3 formed,
(V) The wood board has a kerf formed on the back surface,
A decorative material for floors. The flooring decorative material according to claim 1, wherein a primer layer 2 is further formed on the front surface of the moisture-proof film. The flooring decorative material according to claim 1 or 2 , which is a flooring decorative material that is directly pasted on a concrete slab via an adhesive layer.

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