JP2013209878A - Method of manufacturing flooring decorative material - Google Patents

Method of manufacturing flooring decorative material Download PDF

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JP2013209878A
JP2013209878A JP2013115206A JP2013115206A JP2013209878A JP 2013209878 A JP2013209878 A JP 2013209878A JP 2013115206 A JP2013115206 A JP 2013115206A JP 2013115206 A JP2013115206 A JP 2013115206A JP 2013209878 A JP2013209878 A JP 2013209878A
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layer
acrylic
flooring
resin
coating film
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JP5904159B2 (en
Inventor
Yuka Suzuki
由香 鈴木
Hiroaki Nakayama
寛章 中山
Yoji Masuda
洋史 増田
Takashi Doi
孝志 土井
Masaru Kimura
賢 木村
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Dainippon Printing Co Ltd
大日本印刷株式会社
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Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet for a flooring material having excellent adhesion of a paint film.SOLUTION: The decorative sheet for a flooring material comprises a design composition layer 5, a transparent adhesive layer 4, a transparent resin layer 3 and a primer layer 2 sequentially formed in order on a basic sheet 6 made of a polyolefine resin. The primer layer is a primer layer for forming a paint film composed of (1) an acrylic-urethane copolymer resin having a copolymerization ratio of not more than 65% of an acrylic component and also (2) an isocyanate.

Description

The present invention relates to a decorative sheet for flooring.

  Conventionally, as a flooring material for a detached house or a condominium / apartment, for example, natural wood having a thickness of about several hundred μm to several mm is sliced on a wooden base material such as a lauan plywood having a thickness of about 6 to 15 mm. A veneer with a veneer bonded together and further coated with a veneer surface is widely used. Such natural wood painted floor materials can be painted, polished, and painted repeatedly to achieve a smooth finish with a deep feeling (thick film), and to obtain a beautiful design with a very feeling of painting. Can do.

  On the other hand, there is a need for floor materials having various functions such as durability and heating function in addition to design properties. However, when painting the natural wood, there is a possibility that the natural wood contracts due to heat from a hot carpet, a heater, etc., and the floor surface is cracked or the coating film is peeled off.

  Further, for example, there is a flooring material in which a thin paper provided with a pattern printing layer is laminated on a wooden substrate such as a lauan plywood having a thickness of about 6 to 15 mm and then coated. This flooring material has a feeling of painting, and if an ink having weather resistance is used for the pattern printing layer, durability such as weather resistance and heat resistance can be imparted. However, when coating is performed, it is almost impossible for the uncured paint to penetrate and harden the entire thin paper, so that the remaining paper portion may cause the coating film to peel off at the paper portion.

In recent years, a decorative sheet for flooring has been developed in which a synthetic resin sheet made of an olefin-based thermoplastic resin is laminated on a wooden base material and further provided with a surface protective layer (Patent Document 1). The floor decorative material obtained using this floor decorative sheet is superior to the floor material made of natural wood in terms of scratch resistance, abrasion resistance, water resistance, stain resistance, and the like. Moreover, this floor decorative material is also excellent to some extent in the adhesiveness of a coating film.
On the other hand, in order to obtain a floor decorative material having a sense of depth, it is required to increase the thickness of the coating film formed on the floor decorative material.

  However, when increasing the thickness of the coating film, higher coating film adhesion is required on the coating film forming surface of the floor decorative sheet.

JP 2001-123647 A

  The main object of the present invention is to provide a decorative sheet for flooring that has excellent adhesion of a coating film.

  As a result of intensive studies, the present inventor has found that a specific primer layer for forming a coating film can achieve the above object, and has completed the present invention.

That is, the present invention relates to the following decorative sheet for flooring.
1. A decorative sheet for flooring in which a pattern layer, a transparent adhesive layer, a transparent resin layer, and a primer layer are sequentially formed on a base material sheet made of a polyolefin-based resin,
A decorative sheet for flooring, wherein the primer layer is a primer layer for forming a coating film formed by 1) an acrylic-urethane copolymer resin having an acrylic component copolymerization ratio of 65% or less and 2) an isocyanate.
2. Item 2. The decorative sheet for flooring according to Item 1, wherein the copolymerization ratio of the acrylic component in the acrylic-urethane copolymer resin is 20 to 65%.
3. Item 2. The decorative sheet for flooring according to Item 1, wherein the copolymerization ratio of the acrylic component in the acrylic-urethane copolymer resin is 20 to 40%.
4). Item 4. The flooring according to any one of Items 1 to 3, wherein the primer layer contains 1.5 to 5.5 parts by weight of silica with respect to 100 parts by weight of the total amount of acrylic-urethane copolymer resin and isocyanate. Cosmetic sheet.
5. The decorative sheet for flooring according to any one of claims 1 to 4, wherein the primer layer is colored.
6). Item 6. The decorative sheet for flooring according to any one of Items 1 to 5, which has a synthetic resin layer having a thickness of 150 µm or more on the back surface of the base material sheet.
7). Item 6. The decorative sheet for flooring according to any one of Items 1 to 5, wherein the transparent resin layer has a thickness of 200 µm or more.
8). A floor decorative material comprising the decorative sheet for floor material according to any one of Items 1 to 7, wherein a coating film is formed on the coating film forming primer layer.

  The decorative sheet for flooring of the present invention has a coating film formed on the surface on which a coating film is formed by 1) an acrylic-urethane copolymer resin having an acrylic component copolymerization ratio of 65% or less and 2) an isocyanate. By having the primer layer for coating, high coating film adhesion can be realized.

  In particular, when the copolymerization ratio of the acrylic component of the acrylic-urethane copolymer resin is 20% or more, excellent weather resistance can be imparted to the decorative material for flooring. Furthermore, when the copolymerization ratio of the acrylic component is 40% or less, excellent coating film adhesion can be imparted even to a thick decorative sheet for flooring.

  Moreover, when the said primer layer is colored, the said decorative sheet can give a three-dimensional effect and a depth feeling effectively. In addition, the colored primer layer has little color degradation over time.

  Furthermore, when the decorative sheet for flooring of the present invention has a synthetic resin layer having a thickness of 150 μm or more on the back surface of the base sheet, or when the thickness of the transparent resin layer is 200 μm or more instead of providing the synthetic resin layer, Excellent caster resistance, impact resistance, etc. can be imparted to flooring decorative materials. In particular, when the thickness of the transparent resin layer is 200 μm or more, the design of the design pattern layer becomes more three-dimensional and the design of the decorative material for flooring is improved.

FIG. 1 is a conceptual diagram (cross-sectional view) of the floor decorative material produced in Example 1. FIG.

The decorative sheet for flooring of the present invention is a decorative sheet for flooring in which a pattern layer, a transparent adhesive layer, a transparent resin layer, and a primer layer are sequentially formed on a base material sheet made of a polyolefin resin. Because
The primer layer is a coating layer forming primer layer formed by 1) an acrylic-urethane copolymer resin having an acrylic component copolymerization ratio of 65% or less and 2) an isocyanate.

  The thickness of the decorative sheet for flooring of the present invention is not particularly limited, and may be set as appropriate according to the installation location of the flooring decorative material. For example, in a place where high durability is required, the thickness of the decorative sheet for flooring is preferably 250 μm or more, and more preferably 400 to 600 μm. By setting the thickness of the decorative sheet for flooring to 250 μm or more, more excellent dent scratch resistance, impact resistance, caster resistance and the like can be imparted to the decorative material for flooring.

As the base sheet, a sheet made of a polyolefin resin is used. Usually, a film made of polyolefin resin may be used.

  It does not specifically limit as polyolefin resin, What is normally used in the field | area of a decorative sheet can be used. For example, polyethylene, polypropylene, polybutene, polymethylpentene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-propylene-butene copolymer, polyolefin-based thermoplastic elastomer, etc. Is mentioned. Among these, polypropylene, polyolefin-based thermoplastic elastomers and the like are particularly preferable.

  A homopolymer or copolymer having polypropylene as a main component is also preferable, and examples thereof include homopolypropylene resin, random polypropylene resin, and block polypropylene resin.

  In addition, a propylene-α-olefin copolymer containing 15 mol% or more of a comonomer of ethylene, butene-1,4-methylpentene-1, hexene-1, or octene-1 is also preferable.

  The polyolefin-based thermoplastic elastomer is a block polymer using isotactic polypropylene for the hard segment and atactic polypropylene for the soft segment. In particular, a mixture of a hard segment made of isotactic polypropylene and a soft segment made of atactic polypropylene at a weight ratio of 80:20 is preferable.

  The polyolefin resin may be formed into a film by, for example, a calendar method, an inflation method, a T-die extrusion method, or the like.

  The thickness of the base sheet is not particularly limited and can be set according to the product characteristics, but is usually 40 to 150 μm, preferably about 50 to 100 μm.

  An additive may be mix | blended with a base material sheet as needed. Examples of the additives include fillers such as calcium carbonate and clay, flame retardants such as magnesium hydroxide, antioxidants, lubricants, foaming agents, and colorants (see below). The blending amount of the additive can be appropriately set according to the product characteristics.

  It does not specifically limit as a coloring agent, Well-known coloring agents, such as a pigment and dye, can be used. For example, inorganic pigments such as titanium white, zinc white, petal, vermilion, ultramarine blue, cobalt blue, titanium yellow, yellow lead, carbon black; isoindolinone, Hansa Yellow A, quinacridone, permanent red 4R, phthalocyanine blue, indanthrene Organic pigments (including dyes) such as blue RS and aniline black; metal pigments such as aluminum and brass; pearlescent pigments made of foil powder such as titanium dioxide-coated mica and basic lead carbonate. The coloring mode of the base sheet includes transparent coloring and opaque coloring (hiding coloring), and these can be arbitrarily selected. For example, when the ground color of the adherend (base material to which the decorative sheet is bonded) is concealed, opaque coloring may be selected. On the other hand, in order to make the ground pattern of the adherend visible, transparent coloring may be selected.

One or both surfaces of the base sheet may be subjected to surface treatment such as corona discharge treatment, ozone treatment, plasma treatment, ionizing radiation treatment, dichromic acid treatment, etc., as necessary. For example, when the corona discharge treatment is performed, the surface tension of the substrate sheet surface is 30 dyne or more, preferably 4
It may be set to 0 dyne or more. The surface treatment may be performed according to a conventional method for each treatment.

  A back primer layer for facilitating adhesion of the adherend may be provided on the back surface of the base material sheet (attachment adherent surface). Moreover, you may provide the primer layer for printing for making formation of a pattern pattern layer easy in the upper surface (opposite surface to a to-be-adhered material sticking surface) of a base material sheet.

  The said back surface primer layer and the primer layer for printing can be formed by apply | coating a well-known primer agent to the single side | surface or both surfaces of a base material sheet. As the primer agent, one obtained by dispersing a resin component in a solvent can be used. Examples of the resin component include acrylic-urethane resins and urethane-cellulose resins (for example, a resin obtained by adding hexamethylene diisocyanate to a mixture of urethane and nitrified cotton).

Although the application amount of the primer agent is not particularly limited, it is usually 0.1 to 100 g / m 2 , preferably about 0.1 to 50 g / m 2 .

  Although the thickness after drying of the said back surface primer layer and the primer layer for printing is not specifically limited, It is 0.01-10 micrometers normally, respectively, Preferably it is about 0.1-1 micrometer.

A synthetic resin layer having a thickness of 150 μm or more, preferably 250 to 500 μm may be further formed on the synthetic resin layer substrate sheet back surface (adhering material attachment surface) or the back primer layer.

By forming a synthetic resin layer having a thickness of 150 μm or more, a floor decorative material having caster resistance, impact resistance and the like can be suitably obtained.
When a synthetic resin layer having a thickness of 150 μm or more is formed, a decorative sheet for flooring having a thickness of 250 μm or more can be obtained.

  The resin component of the synthetic resin layer is not particularly limited. For example, polyethylene (high density polyethylene, medium density polyethylene, low density polyethylene), vinyl chloride resin, polystyrene, polypropylene, methacrylic resin, acrylonitrile styrene resin, polyamide resin, acrylonitrile butadiene. Styrene resin, polyimide resin, polyamideimide resin, fluororesin, urethane resin, polysulfone, polycarbonate, polyacetal, polyphenylene ether, polyethylene naphthalate (PEN), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyarylate, etc. It is done. Amorphous polyethylene terephthalate (so-called A-PET) [Mitsubishi Chemical Corporation: Nova Clear (trade name)], PETG and the like can also be suitably used. These can be used alone or in combination of two or more. Among these, at least one of polypropylene and A-PET is particularly preferable. Examples of polypropylene include homopolypropylene, random polypropylene, and block polypropylene. Of these, homopolypropylene is particularly desirable. A-PET is desirably used together with PEN for the purpose of imparting heat resistance.

  Furthermore, an additive may be blended in the synthetic resin layer as necessary. For example, when polypropylene is used as the resin component of the synthetic resin layer, it is preferable to blend an ultraviolet absorber and a light stabilizer for the purpose of imparting weather resistance. Examples of the ultraviolet absorber include benzophenone ultraviolet absorbers, benzotriazole ultraviolet absorbers, and triazine ultraviolet absorbers. The light stabilizer is not limited, but for example, a hindered amine light stabilizer can be preferably used. Moreover, you may mix | blend the crystallization nucleating agent with the said synthetic resin layer as needed.

  For the synthetic resin layer, the resin component may be laminated on the base sheet by, for example, a calendar method, an inflation method, a T-die extrusion method, or a pre-made film may be used.

A pattern layer is formed on the pattern pattern layer base sheet (opposite to the adherend attachment surface, hereinafter the same side in each layer).

  The design pattern layer imparts design properties with a desired design to the decorative sheet, and the type of design is not particularly limited. Examples thereof include a wood grain pattern, a stone pattern, a grain pattern, a tiled pattern, a brickwork pattern, a cloth pattern, a leather pattern, a geometric figure, a character, a symbol, and an abstract pattern.

  The method for forming the pattern layer is not particularly limited. For example, a colored ink or coating obtained by dissolving (or dispersing) a known colorant (dye or pigment) in a solvent (or dispersion medium) together with a binder resin. What is necessary is just to form by the printing method etc. which used the agent etc.

  Examples of colorants include inorganic pigments such as carbon black, titanium white, zinc white, dial, bitumen, cadmium red; azo pigments, lake pigments, anthraquinone pigments, quinacridone pigments, phthalocyanine pigments, isoindolinone pigments, dioxazine pigments. Organic pigments such as aluminum powder, metal powder pigments such as bronze powder, pearlescent pigments such as titanium oxide-coated mica and bismuth oxide chloride; fluorescent pigments; These colorants can be used alone or in admixture of two or more. These colorants may further contain fillers such as silica, extender pigments such as organic beads, neutralizing agents, surfactants and the like.

  Examples of the binder resin include acrylic resins, styrene resins, polyester resins, urethane resins, acrylic-urethane resins, chlorinated polyolefin resins, vinyl chloride-vinyl acetate copolymer resins, polyvinyl butyral resins. Alkyd resins, petroleum resins, ketone resins, epoxy resins, melamine resins, fluorine resins, silicone resins, fiber derivatives, rubber resins, and the like. These resins can be used alone or in admixture of two or more.

  Examples of the solvent (or dispersion medium) include petroleum organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; ethyl acetate, butyl acetate, 2-methoxyethyl acetate, and acetic acid-2 -Ester-based organic solvents such as ethoxyethyl; alcohol-based organic solvents such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, propylene glycol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone Organic solvents; ether organic solvents such as diethyl ether, dioxane, tetrahydrofuran; dichloromethane, carbon tetrachloride, trichloroethylene, tetrachloroethylene Inorganic solvents and the like, such as water; chlorinated organic solvents. These solvents (or dispersion media) can be used alone or in admixture of two or more.

Examples of the printing method used for forming the pattern layer include a gravure printing method, an offset printing method, a screen printing method, a flexographic printing method, an electrostatic printing method, and an inkjet printing method. When forming a solid pattern pattern layer, for example, roll coating method, knife coating method, air knife coating method, die coating method, lip coating method, comma coating method, kiss coating method, flow coating method, dip coating Various coating methods such as a coating method may be mentioned. In addition, the hand-drawn method, the ink-sink method, the photographic method, the transfer method, the laser beam drawing method, the electron beam drawing method, the metal partial evaporation method, the etching method, etc. may be used or combined with other forming methods. Good.

  The thickness of the pattern layer is not particularly limited and can be set as appropriate according to product characteristics. The layer thickness at the time of coating is about 1 to 15 μm, and the layer thickness after drying is about 0.1 to 10 μm.

A colored concealment layer may be further formed between the colored concealment layer base sheet and the pattern layer, if necessary. The colored masking layer is provided when it is desired to mask the ground color of the adherend from the front surface of the decorative sheet. Of course, when the base sheet is transparent, even when the base sheet is concealed, it may be formed to stabilize the concealment.

  As the ink for forming the colored masking layer, an ink for forming a pattern layer and capable of masking coloring can be used.

  The method for forming the colored concealment layer is preferably a method that can be formed so as to cover the entire base sheet (entirely solid). For example, the roll coating method, knife coating method, air knife coating method, die coating method, lip coating method, comma coating method, kiss coating method, flow coating method, dip coating method and the like described above are preferable.

  The thickness of the colored concealing layer is not particularly limited and can be set as appropriate according to the product characteristics. The layer thickness during coating is about 0.2 to 10 μm, and the layer thickness after drying is about 0.1 to 5 μm.

Transparent adhesive layer A transparent adhesive layer is formed on the pattern layer. The transparent adhesive layer is not particularly limited as long as it is transparent, and includes any of transparent and colorless, colored and translucent. This adhesive layer is formed to bond the pattern layer and the transparent polypropylene resin layer.

  It does not specifically limit as an adhesive agent, A well-known adhesive agent can be used in the field of a decorative sheet.

  Examples of the adhesive known in the field of decorative sheets include thermoplastic resins such as polyamide resin, acrylic resin and vinyl acetate resin, and curable resins such as thermosetting urethane resin. Further, a two-component curable polyurethane resin or polyester resin using isocyanate as a curing agent can also be applied.

  The adhesive layer can be formed, for example, by applying an adhesive on the pattern layer and then drying and curing. Conditions such as drying temperature and drying time are not particularly limited, and may be set as appropriate according to the type of adhesive. The method of applying the adhesive is not particularly limited, and examples thereof include roll coating, curtain flow coating, wire bar coating, reverse coating, gravure coating, gravure reverse coating, air knife coating, kiss coating, blade coating, smooth coating, and comma coating. The method can be adopted.

  Although the thickness of an adhesive bond layer is not specifically limited, The thickness after drying is 0.1-30 micrometers, Preferably it is about 1-20 micrometers.

Transparent resin layer A transparent resin layer is formed on the transparent adhesive layer. The transparent resin layer includes any of colorless and transparent, colored and transparent, and translucent as long as it is transparent.

The resin component contained in the transparent resin layer is not limited, but is preferably a thermoplastic resin, particularly preferably polypropylene, and more preferably homopolypropylene. It is preferable that the transparent resin layer is substantially formed of the polypropylene resin.

  If necessary, additives such as fillers, flame retardants, lubricants, antioxidants, light stabilizers (ultraviolet absorbers, radical scavengers, etc.) can be added to the transparent resin layer. In particular, in order to improve the weather resistance, it is preferable to add a light stabilizer.

  Examples of the ultraviolet absorber include organic ultraviolet absorbers such as triazine, benzotriazole, benzophenone, and salicylic acid ester. Further, inorganic ultraviolet absorbers such as fine particles of zinc oxide, cerium oxide, titanium oxide having a particle diameter of 0.2 μm or less can be used.

Examples of the radical scavenger include hindered amine radical scavengers such as bis- (2,2,6,6-tetramethyl-4-piperidinyl) sebacate and radical scavengers such as piperidine radical scavengers.
For example, the transparent resin layer is formed of a resin by a calendar method, an inflation method, a T-die extrusion method, or the like. An existing film may be used.

  The thickness of the transparent resin layer is usually about 20 to 300 μm.

  In particular, in the decorative sheet for flooring of the present invention, instead of forming the synthetic resin layer on the back surface of the base material sheet (or the back surface primer layer), the thickness of the transparent resin layer is increased. By setting the thickness of the resin layer to 200 μm or more, preferably 350 to 600 μm, it is possible to impart caster resistance, impact resistance, and the like comparable to or higher than those for forming the synthetic resin layer to the floor decorative material.

  Moreover, instead of forming the synthetic resin layer, by making the thickness of the transparent resin layer 200 μm or more, the design of the design pattern layer can be seen more three-dimensionally, and the design of the decorative material for floors Will improve.

  When the thickness of the transparent resin layer is 200 μm or more, a decorative sheet for flooring having a thickness of 250 μm or more can be obtained.

A primer layer for forming a coating film is formed on the transparent resin layer for forming a coating film.

The primer layer for forming a coating film is formed of an acrylic-urethane copolymer resin and isocyanate.
The copolymerization ratio of the acrylic component in the acrylic-urethane copolymer resin is 65% or less, preferably 20 to 65%, more preferably 20 to 40%. When the copolymerization ratio of the acrylic component is 65% or less, excellent coating film adhesion can be imparted to the decorative sheet for flooring.
Moreover, when the copolymerization ratio of the acrylic component is 20% or more, excellent weather resistance can be imparted to the decorative material for flooring.
Furthermore, when the copolymerization ratio of the acrylic component is 40% or less, better coating film adhesion can be imparted. Usually, as the thickness of the decorative sheet for flooring increases, the shear stress generated by the difference in expansion / contraction ratio between the coating film and the decorative sheet for flooring tends to increase. Therefore, due to the influence of environmental conditions (light, temperature, etc.), the adhesion between the primer layer for forming a coating film and the coating film may deteriorate with time, and the coating film may be peeled off.
In the decorative sheet for flooring of the present invention, when the copolymerization ratio of the acrylic component in the acrylic-urethane copolymer resin is 40% or less, the thickness of the decorative sheet for flooring is large (for example, the decorative sheet for flooring) Even when the thickness is 250 μm or more, excellent coating film adhesion can be exhibited.

  As a primer layer for forming a coating film formed of an acrylic-urethane copolymer resin and an isocyanate, for example, it is formed of a two-component curable urethane resin having an acrylic-urethane block copolymer as a main component and an isocyanate as a curing agent. The resin layer formed is mentioned.

  Hereinafter, the primer layer for forming a coating film will be specifically described with a resin layer formed of the two-component curable urethane resin as a representative example.

  The acrylic-urethane block copolymer has a chain part (acrylic component) (A) of an acrylic monomer obtained by a polymerization reaction of an acrylic monomer, and a chain of acrylic monomers (or A hydroxyl group containing a chain part other than at least a chain of an acrylic monomer (or a chain by copolymerization with another monomer), which may contain a part of the chain by copolymerization with another monomer) It is a compound having a group-containing compound (B) and a urethane bond-containing portion (urethane component) (D) obtained by a reaction (urethane reaction) between the hydroxyl group-containing compound and the isocyanate group-containing compound (C).

  The hydroxyl group-containing compound (B) may be an acrylic polyol (for example, polycarbonate polyol) obtained by utilizing a polymerization reaction of an acrylic monomer, but physical properties can be adjusted by using other polyols. The degree of freedom increases, and a polymer suitable for a wider range of applications can be obtained.

  The acrylic-urethane block copolymer is, for example, a polycarbonate polyurethane (D) obtained by reacting a polycarbonate polyol (B) and a polyisocyanate (C), and an acrylic polyol (A ). In addition, it can be obtained by reacting three compounds of an acrylic polyol (A), a polycarbonate polyol (B) and a polyisocyanate (C) containing an acrylic monomer as a main component.

  Examples of the acrylic monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, and (meth) acrylic acid. And (meth) acrylic acid esters such as 2-hydroxyethyl and (meth) acrylic acid-2-hydroxy-3-phenoxypropyl. These acrylic monomers may be used alone or in combination of two or more. In addition, (meth) acrylic acid means acrylic acid or methacrylic acid.

  The acrylic component of the acrylic-urethane block copolymer is an acrylic monomer composed of one or more of a polymer composed of the above exemplified acrylic monomers, or a prepolymer composed of the above exemplified monomers. It is a chain part of a mer.

  As the polyol component constituting the urethane component of the acrylic-urethane block copolymer, polycarbonate polyol, polyester polyol, polyether polyol, acrylic polyol, and the like can be used. These may be used alone or in combination of two or more.

Moreover, as an isocyanate component which comprises this urethane component, what has a weather resistance is preferable. As the isocyanate having weather resistance, alicyclic isocyanate and aliphatic isocyanate are preferable. In addition, you may use together alicyclic isocyanate and aliphatic isocyanate. By using an aliphatic or alicyclic isocyanate, the hydrolysis resistance, heat resistance, etc. of these isocyanates themselves are excellent, and therefore the weather resistance of the primer layer itself can be enhanced. Therefore, it is possible to prevent a decrease in adhesion between the primer layer for forming a coating film and the coating film over time.

  As the alicyclic isocyanate, for example, IPDI (isophorone diisocyanate), hydrogenated MDI (hydrogenated diphenylmethane diisocyanate) or the like can be used.

  As the aliphatic isocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, or the like can be used. In addition, these can be used by 1 type (s) or 2 or more types.

  As the isocyanate used as the curing agent, the above aliphatic or alicyclic isocyanates are preferable from the viewpoint of hydrolysis resistance and heat resistance of the isocyanate itself.

  If necessary, an additive can be added to the primer layer for forming a coating film. Silica is particularly preferable as the additive. By adding silica, blocking that occurs when the decorative sheet for flooring is wound can be effectively prevented.

  Silica is generally used in the form of powder. In this case, the average particle diameter of silica is not particularly limited, but is preferably about 1 to 5 μm. A known or commercially available silica powder may be used.

  The addition amount of silica is preferably 1.5 to 5.5 parts by weight, and more preferably 3.5 to 4.5 parts by weight with respect to 100 parts by weight of the total amount of acrylic-urethane copolymer resin and isocyanate.

  The primer layer for forming a coating film has high adhesion. Since the decorative sheet for flooring of the present invention has such a primer layer on the outermost surface, blocking tends to occur when it is rolled up. In the decorative sheet for flooring of the present invention, blocking can be more effectively prevented by setting the addition amount of silica to 1.5 parts by weight or more.

  Moreover, when adding silica, when there is too much addition amount, there exists a possibility of causing the fall of the adhesiveness of the primer layer for coating-film formation and a coating film with time. In particular, the adhesion of the coating film tends to be lowered in a high temperature and high humidity atmosphere. In the decorative sheet for flooring of the present invention, by reducing the addition amount of silica to 5.5 parts by weight or less, it is possible to effectively prevent a decrease in the adhesion of the coating film in a high temperature and high humidity atmosphere.

  You may add a coloring agent to the primer layer for coating-film formation further. The primer layer can be colored by adding a colorant. When the primer layer is colored, the decorative sheet for flooring of the present invention can effectively have a three-dimensional effect and a sense of depth. In addition, the colored primer layer has little color degradation over time.

  As said colorant, the colorant used for formation of the said pattern pattern layer can be used.

  Moreover, you may add a ultraviolet absorber to the primer layer for coating-film formation. Examples of the ultraviolet absorber include organic ultraviolet absorbers such as benzotriazole, benzophenone, triazine, and salicylic acid ester.

The primer layer for forming a coating film may be formed by a known coating method such as roll coating. At that time, prior to the formation of the primer layer for forming a coating film, the surface to be formed, that is, the surface of the transparent resin layer, may be appropriately subjected to surface easy adhesion treatment such as corona discharge treatment, plasma treatment, ozone treatment and the like as necessary.

  A concavo-convex pattern may be formed by embossing on the primer layer for forming a coating film, if necessary. By forming a coating film on the concavo-convex pattern, a design expression with a feeling of painting becomes possible. In addition, before forming the primer layer for forming a coating film, a concavo-convex pattern may be formed on the transparent resin layer. Hateful. Therefore, after forming the primer layer for forming a coating film, it is preferable to form a concavo-convex pattern thereon.

Flooring decorative material The flooring decorative sheet of the present invention can be made into a flooring decorative material by joining with various adherends. The material of the adherend is not particularly limited, and examples thereof include inorganic non-metallic materials, metallic materials, wood materials, and plastic materials.

  Specifically, in inorganic non-metallic systems, for example, papermaking cement, extruded cement, slag cement, ALC (lightweight cellular concrete), GRC (glass fiber reinforced concrete), pulp cement, wood chip cement, asbestos cement, calcium oxalate, Non-ceramic ceramic materials such as gypsum and gypsum slag, ceramic materials such as earthenware, ceramics, porcelain, setware, glass, and glazing.

  In a metal system, metal materials (metal steel plate), such as iron, aluminum, and copper, are mentioned, for example.

  In the wood system, for example, a single board, plywood, particle board, fiber board, laminated timber and the like made of cedar, straw, firewood, lauan, teak and the like can be mentioned.

  In the plastic system, for example, resin materials such as polypropylene, ABS resin, and phenol resin can be used.

  The shape of such an adherend is not particularly limited, and may be a flat plate in consideration of installation on a flooring or the like.

  After joining with the adherend, for example, according to the characteristics of the final product, cutting, use of a tenor, sag processing, provision of V-shaped grooves, chamfering on four sides, etc. may be performed.

Formation of Coating Film The floor decorative material of the present invention is a floor decorative material having the above-mentioned decorative sheet for flooring, and is formed by forming a coating film on the primer layer for coating film formation. In particular, in the floor decorative material of the present invention, the coating film is firmly adhered to the primer layer for coating film formation.

  Various coating films can be formed on the primer layer for forming a coating film of the floor decorative material. Examples of the resin component constituting the coating film include curable resins such as epoxy resins, urethane resins, acrylic resins, ester resins, and unsaturated polyester resins, or one or more of these. Examples thereof include mixed resins.

  The coating film can be formed of one layer or two or more layers.

As the coating film, a transparent surface protective layer formed by using an ionizing radiation curable resin is particularly preferable. By forming a transparent surface protective layer using an ionizing radiation curable resin, a flooring decorative material having more excellent scratch resistance, weather resistance and the like can be obtained. In particular, the decorative sheet for flooring of the present invention is excellent in that high adhesion can be secured even when an ionizing radiation curable resin, which is difficult to ensure adhesion, is applied as a coating film.

  Hereinafter, the transparent surface protective layer will be specifically described as a representative example of the coating film that can be formed on the primer layer for coating film formation of the decorative sheet for flooring of the present invention.

  A well-known thing or a commercial item can be used for ionizing radiation curable resin. Specifically, a composition containing at least one of a prepolymer, an oligomer and a monomer having a polymerizable unsaturated bond or an epoxy group in the molecule is used.

  Examples of the prepolymer or oligomer include methacrylates such as polyester methacrylate, polyether methacrylate, polyol methacrylate, and melamine methacrylate, urethane acrylates such as urethane acrylate, urethane dimethyl acrylate, and urethane trimethyl acrylate, and polyester. Examples include acrylates such as acrylate, polyether acrylate, polyol acrylate, and melamine acrylate.

  As monomers, styrene monomers such as styrene and α-methylstyrene; acrylics such as methyl acrylate, 2-ethylhexyl acrylate, methoxyethyl acrylate, butoxyethyl acrylate, butyl acrylate, and phenyl acrylate Acid esters; and methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, ethoxymethyl methacrylate, phenyl methacrylate, and lauryl methacrylate.

  As substituted amino alcohol esters of unsaturated acids, acrylic acid-2- (N, N-diethylamino) ethyl, methacrylic acid-2- (N, N-diethylamino) ethyl, acrylic acid-2- (N, N- Dibenzylamino) methyl, acrylic acid-2- (N, N-diethylamino) propyl, and the like.

  Other unsaturated carboxylic acid amides such as acrylamide and methacrylamide; monofunctional compounds such as ethyl carbitol acrylate and ethylene glycol acrylate; ethylene glycol diacrylate, propylene glycol diacrylate, neobenzyl glycol diacrylate, 1,6 -Multifunctional compounds such as hexanediol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, dipropylene glycol diacrylate, diethylene glycol dimethacrylate, polyethylene glycol diacrylate ;, trimethylolpropane trithioglycolate, trimethylolpropane Thiols in molecules such as trithiopropiolate and dipentaerythritol tetrathioglycol The polythiol compound having 2 or more;, trimethylol propane triacrylate, pentaerythritol hexaacrylate, there is acrylate monomer having 3 or more functional groups such as dipentaerythritol hexa methacrylate.

  Although the formation method of the transparent surface protection layer by ionizing radiation curable resin is not limited, For example, it can form by irradiating ionizing radiation to the coating film of the composition (paint) containing ionizing radiation curable resin. The ionizing radiation may be any ionizing radiation curable resin contained in the paint and any energy that can act on the radical photopolymerization initiator / sensitizer as an additive to initiate a radical polymerization reaction. And electromagnetic waves such as γ rays. Among these, the electron beam is most practical from the viewpoint of the curing ability of the coating film and the simplicity of the irradiation device. In the case of electron beam irradiation, for example, the film may be crosslinked and cured by electron beam irradiation under conditions of 175 keV and 5 Mrad (50 kGy).

Although the thickness of a transparent protective layer is not limited, Usually, it is desirable to set it as 5-150 g / m < 2 > as solid content, especially 15-60 micrometers.

  In addition, the transparent protective layer of the decorative material for floors obtained may have surface unevenness | corrugation. This surface unevenness is caused by unevenness of the adherend (for example, a wooden substrate) itself, uneven application of the adhesive, and the like. In this case, it is preferable to polish the surface of the transparent protective layer. Thereby, the floor decorative material with a smooth surface of the protective layer can be suitably obtained.

  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 for flooring A decorative sheet for flooring having the structure shown in FIG. 1 was prepared by the following method.

An acrylic-urethane resin (a resin obtained by adding 5 parts by weight of hexamethylene diisocyanate to 100 parts by weight of acrylic polyol) on a base sheet 6 made of a colored polyolefin film having a thickness of 60 μm is used as a mixed solvent of methyl ethyl ketone and butyl acetate. The dissolved solution was applied by a gravure printing method so that the solid content was 2 g / m 2 to form a printing primer layer (not shown).

  By a gravure printing method using a printing ink with an acrylic-urethane resin (a resin obtained by adding 5 parts by weight of hexamethylene diisocyanate to 100 parts by weight of an acrylic polyol) on a printing primer layer (not shown). A woodgrain pattern layer 5 was formed.

A reverse primer layer 7 was formed by applying a urethane-cellulose resin solution on the surface of the base sheet 6 opposite to the pattern layer 5 by a gravure printing method so that the solid content was 2 g / m 2 .

  The urethane-cellulose-based resin solution is prepared by adding urethane and nitrified cotton to a mixed solvent of methyl ethyl ketone and methyl isobutyl ketone, and further adding hexamethylene diisocyanate to 5 parts by weight with respect to 100 parts by weight of the mixture of urethane and nitrified cotton. It was prepared by adding a part.

A thermosetting urethane resin adhesive is applied on the pattern layer 5 so that the solid content is 8 g / m 2 , and a polypropylene resin is heated and melt extruded by a T-die extruder to obtain a thickness of 8 μm. A transparent adhesive layer 4 and a transparent resin layer 3 having a thickness of 80 μm were formed.
After the surface of the transparent resin layer 3 is subjected to corona discharge treatment, an acrylic-urethane block having a copolymerization ratio of acrylic component of 50% (acrylic component: urethane component = 50: 50) on the transparent resin layer 3 Copolymer resin (acrylic component: acrylic polyol mainly composed of methyl methacrylate, urethane component: obtained by reaction of polyester polyol with isophorone diisocyanate and hydrogenated MDI (C)) as main agent, hexamethylene as curing agent A coating solution of a two-component curable urethane resin containing a diisocyanate curing agent was applied to form a coating layer forming primer layer 2 having a thickness of 2 μm.
Prior to coating, the coating liquid contains 6.5 parts by weight and 3 parts by weight of silica having an average particle diameter of 3 μm and a triazine-based ultraviolet absorber for a total amount of 100 parts by weight of the main agent and the curing agent. .7 parts by weight were added.

  By the above method, a decorative sheet for flooring having a thickness of about 160 μm was produced.

Preparation of flooring decorative material A floor decorative material was prepared by sticking 12 mm lauan plywood to the back primer layer 7 of the decorative sheet for flooring. For the sticking, urethane-modified ethylene / vinyl acetate emulsion adhesive (9 g / scale 2 wet) was used.

  The floor decorative material was produced by the above method.

Coating film formation On the primer layer 2 for coating film formation, a urethane acrylate electron beam curable resin is applied and dried so as to have a solid content of 50 g / m 2 by a roll coating method, and then uncured electron beam. A curable resin layer was formed. Thereafter, in an atmosphere having an oxygen concentration of 200 ppm, the uncured resin layer is irradiated with an electron beam under the conditions of an acceleration voltage of 125 KeV and 5 Mrad to cure the resin, and a 50 μm thick electron beam curable resin layer 8 (transparent surface protective layer) ) Was formed.

Example 2
By the same method as in Example 1 except that an acrylic-urethane block copolymer having an acrylic component copolymerization ratio of 30% (acrylic component: urethane component = 30: 70) was used as the acrylic-urethane block copolymer. A floor decorative material having a coating film formed thereon was prepared.

Example 3
Except for using an acrylic-urethane block copolymer having an acrylic component copolymerization ratio of 15% (acrylic component: urethane component content ratio = 15: 85) as the acrylic-urethane block copolymer, the same as in Example 1. By this method, a floor decorative material having a coating film formed thereon was produced.

Comparative Example 1
According to the same method as in Example 1, except that an acrylic-urethane block copolymer having an acrylic component copolymerization ratio of 70% (acrylic component: urethane component = 70: 30) was used as the acrylic-urethane block copolymer. A floor decorative material having a coating film formed thereon was prepared.

Example 4
A floor decorative material having a coating film was produced in the same manner as in Example 1 except that the amount of silica added was 5.0 parts by weight with respect to 100 parts by weight of the total amount of the main agent and the curing agent. .

Example 5
A floor decorative material having a coating film was produced in the same manner as in Example 1 except that the amount of silica added was 4.0 parts by weight with respect to 100 parts by weight of the total amount of the main agent and the curing agent. .

Example 6
A floor decorative material having a coating film formed thereon was prepared in the same manner as in Example 1 except that the amount of silica added was 3.0 parts by weight with respect to 100 parts by weight of the total amount of the main agent and the curing agent. .

Example 7
A floor decorative material having a coating film was produced in the same manner as in Example 1 except that the amount of silica added was 2.0 parts by weight with respect to 100 parts by weight of the total amount of the main agent and the curing agent. .

Example 8
Into the coating liquid of the two-component curable urethane resin, an inorganic pigment (trade name “PER weather resistant yellow” manufactured by Showa Ink Industries, Ltd.) as a colorant is added to 100 parts by weight of the total amount of the main agent and the curing agent.
A floor decorative material having a coating film was produced in the same manner as in Example 1 except that the addition of parts by weight was performed.

Example 9
A decorative sheet for flooring having a thickness of 460 μm is formed on the back primer layer 7 by further forming a synthetic resin layer having a thickness of 300 μm, and Example 1 is applied except that a 12 mm lauan plywood is adhered to the synthetic resin layer. Similarly, a floor decorative material having a coating film formed thereon was produced.

  The synthetic resin layer was formed by heat-melt-extruding a composition containing homopolypropylene, bis (p-methylbenzylidene) sorbitol, a triazine-based ultraviolet absorber and a hindered amine-based light stabilizer with a T-die extruder. The amount of bis (p-methylbenzylidene) sorbitol used was 0.1 parts by weight with respect to 100 parts by weight of homopolypropylene. The amount of the triazine-based ultraviolet absorber used was such that the concentration of the triazine-based ultraviolet absorber in the resin composition was 2000 ppm. Further, the amount of the hindered amine light stabilizer used was such that the concentration of the hindered amine light stabilizer in the resin composition was 1000 ppm.

Example 10
The same method as in Example 9 except that an acrylic-urethane block copolymer having an acrylic component copolymerization ratio of 30% (acrylic component: urethane component- = 30: 70) was used as the acrylic-urethane block copolymer. Thus, a floor decorative material having a coating film formed thereon was produced.

Example 11
As an acrylic-urethane block copolymer resin, an acrylic-urethane block copolymer resin having an acrylic component copolymerization ratio of 30% (acrylic component: urethane component = 30: 70) (acrylic component: methyl methacrylate as a main component) Acrylic polyol, urethane component: polycarbonate polyurethane obtained by reaction of polycarbonate polyol and 1,6-hexamethylene diisocyanate), and a floor decorative material having a coating film formed in the same manner as in Example 9. Was made.
Example 12
A flooring decorative material in which a coating film was formed by the same method as in Example 1 was prepared except that the thickness of the transparent resin layer 3 was set to 400 μm.

Comparative Example 2
According to the same method as in Example 9, except that an acrylic-urethane block copolymer having an acrylic component copolymerization ratio of 70% (acrylic component: urethane component = 70: 30) was used as the acrylic-urethane block copolymer. A floor decorative material having a coating film formed thereon was prepared.

Test Example 1 (Coating film adhesion)
The coating-film adhesiveness of the decorative material for flooring which formed the coating film obtained in Examples 1-3 and 8-11 and Comparative Examples 1-2 was confirmed. Specifically, after making a crosscut on the surface of the paint film, applying the Nichiban cello tape (registered trademark) and abruptly removing it five times in a row, visually observing whether the paint film peels off. Confirmed by
○ when the coating film was not peeled off, △ when the coating film was partially peeled (one part of the test area was peeled off), and one where the coating film was peeled off entirely (the whole test area was peeled off) ) Was evaluated as x.
The results are shown in Tables 1 and 2.

Test Example 2 (Weather resistance)
The weather resistance of the decorative materials for floors on which the coating films obtained in Examples 1 to 3 and 8 to 11 and Comparative Examples 1 and 2 were formed was confirmed.
Specifically, ultraviolet rays having an illuminance of 60 mW / cm 2 are applied to the surface of the electron beam curable resin layer of the floor decorative material by a super accelerated weathering tester (“I Super UV Tester SUV-131” manufactured by Iwasaki Electric Co., Ltd.).
After irradiating for 00 hours, when the operation of putting a crosscut on the surface of the coating film (electron beam curable resin layer) and attaching and peeling the Nichiban cello tape (registered trademark) five times in succession, the coating film peels off. It was confirmed by visual observation.
The case where there was no peeling of the coating film was evaluated as ○, and the case where the coating film was peeled off was evaluated as ×.
The results are shown in Tables 1 and 2.

Test Example 3 (Blocking test)
The flooring decorative sheets obtained in Examples 4 to 7 were cut into a square of 5 cm in length and 5 cm in width, and the sheets were laminated so that the primer layer 2 for forming a coating film of the sheet and the base sheet 6 were in contact with each other. . The obtained laminate was left in an oven at 40 ° C. for 24 hours under a pressure of 0.49 MPa. Thereafter, the laminate was taken out from the oven, the sheets constituting the laminate were peeled off by hand, the peel resistance at that time was confirmed, and the appearance of the laminate was visually confirmed.
The sheet constituting the laminate can be easily peeled off without peeling resistance, and there is no change in the appearance of the contact portion between the sheets of the laminate. When peeling the sheet constituting the laminate, the peeling resistance is Yes, and the gloss of the contact portion between the sheets of the laminate was changed (the gloss of the base sheet 6 was transferred to the surface of the primer layer 2), and the sheets constituting the laminate were easy And those where transfer of the primer layer 2 for coating film formation (to the base material sheet 6) or cohesive failure of the primer layer 2 is recognized at the contact portion between the sheets of the laminate. evaluated.

The cohesive failure means a state in which the primer layer 2 is destroyed and the resin components constituting the primer layer are attached to both surfaces (primer layer 2 and base material sheet 6) of the peeled sheet.
The results are shown in Table 3.
Test example 4 (moisture and heat resistance test)
The floor decorative materials obtained in Examples 4 to 7 were left in a constant temperature and humidity chamber of 60 ° C. and 90% relative humidity for 500 hours, and then a crosscut was put on the surface of the coating film to obtain a Nichiban cello tape (registered trademark). ) Was affixed and peeled off abruptly for five times, it was confirmed by visual observation whether the coating film peeled off.
○ when the coating film was not peeled off, △ when the coating film was partially peeled (one part of the test area was peeled off), and one where the coating film was peeled off entirely (the whole test area was peeled off) ) Was evaluated as x.

  The results are shown in Table 3.

Test Example 5 (Caster resistance)
The castor resistance of the floor decorative material on which the coating films obtained in Examples 1, 9 and 12 were formed was evaluated using a caster resistance test apparatus L6-O4 (manufactured by Asano Machinery Co., Ltd.). The evaluation procedure is as follows. That is, the floor decorative material to be tested was fixed on the sample fixing base. After the caster fixing base was raised by the adjustment handle so that the three casters did not contact the surface of the flooring decorative material, a weight was placed on the load base so that the weight would be 70 kg. Next, the load placed on the three casters was applied using the adjustment handle. The rotational speed was 20 rpm, counter-rotated every 5 minutes, set to 1000 rotations, and after completion of 1000 rotations, the adjustment handle was turned to float the caster fixing base, and the floor decorative material to be tested was taken out.
Table 4 shows the dent depth of the floor decorative material taken out.

From Table 4, it can be seen that the floor decorative materials obtained in Examples 9 and 12 are more excellent in castor resistance than the floor decorative material obtained in Example 1. In particular, since the floor decorative materials obtained in Examples 9 and 12 have a dent depth of less than 100 μm, they can be used effectively in places where caster resistance is required.

DESCRIPTION OF SYMBOLS 1 ... Decorative sheet for flooring 2 ... Primer layer 3 for coating film formation ... Transparent resin layer 4 ... Transparent adhesive layer 5 ... Picture pattern layer 6 ... Base material sheet 7 ... Back primer layer 8 ... Electron beam curable resin layer (coating)
9 ... Lawan plywood

That is, this invention relates to the manufacturing method of the following decorative materials for floors .
1. At least adherend substrate made of a polyolefin resin on sheet, picture pattern layer, a transparent adhesive layer, a transparent resin layer, primer layer, and the manufacturing method of the floor decorative material having a coating film in this order There,
(I) Step I of obtaining a decorative sheet for flooring by laminating a pattern layer, a transparent adhesive layer, a transparent resin layer, and a primer layer in this order on a substrate sheet,
(II) Step II of joining the base sheet side surface of the decorative sheet for flooring and the adherend,
(III) Step III of forming a coating film on the primer layer,
In this order,
The method for producing a flooring decorative material, wherein the primer layer is a primer layer for forming a coating film formed by 1) an acrylic-urethane copolymer resin having an acrylic component copolymerization ratio of 65% or less and 2) an isocyanate. .
2. The manufacturing method of said claim | item 1 whose application quantity of the said coating film is 5-150 g / m < 2 > as solid content .
3. The manufacturing method of said claim | item 1 whose application quantity of the said coating film is 50-150 g / m < 2 > as solid content .
4 . Item 4. The method according to any one of Items 1 to 3 , wherein a copolymerization ratio of the acrylic component in the acrylic-urethane copolymer resin is 20 to 65%.
5 . Item 4. The method according to any one of Items 1 to 3 , wherein the copolymerization ratio of the acrylic component in the acrylic-urethane copolymer resin is 20 to 40%.
6 . Item 6. The method according to any one of Items 1 to 5 , wherein the primer layer contains 1.5 to 5.5 parts by weight of silica with respect to 100 parts by weight of the total amount of acrylic-urethane copolymer resin and isocyanate. .
7 . It said primer layer is colored, the production method according to any one of items 1-6.
8 . Item 8. The method according to any one of Items 1 to 7 , wherein a synthetic resin layer having a thickness of 150 μm or more is provided on the back surface of the base sheet.
9 . Item 8. The manufacturing method according to any one of Items 1 to 7 , wherein the transparent resin layer has a thickness of 200 µm or more.

Claims (8)

  1. A decorative sheet for flooring in which a pattern layer, a transparent adhesive layer, a transparent resin layer, and a primer layer are sequentially formed on a base material sheet made of a polyolefin-based resin,
    A decorative sheet for flooring, wherein the primer layer is a primer layer for forming a coating film formed by 1) an acrylic-urethane copolymer resin having an acrylic component copolymerization ratio of 65% or less and 2) an isocyanate.
  2.   The decorative sheet for flooring according to claim 1, wherein the copolymerization ratio of the acrylic component in the acrylic-urethane copolymer resin is 20 to 65%.
  3.   The decorative sheet for flooring according to claim 1, wherein the copolymerization ratio of the acrylic component in the acrylic-urethane copolymer resin is 20 to 40%.
  4.   The flooring material according to any one of claims 1 to 3, wherein the primer layer contains 1.5 to 5.5 parts by weight of silica with respect to 100 parts by weight of the total amount of acrylic-urethane copolymer resin and isocyanate. Cosmetic sheet.
  5.   The decorative sheet for flooring according to any one of claims 1 to 4, wherein the primer layer is colored.
  6.   The decorative sheet for flooring according to any one of claims 1 to 5, further comprising a synthetic resin layer having a thickness of 150 µm or more on the back surface of the base material sheet.
  7.   The decorative sheet for flooring according to any one of claims 1 to 5, wherein a thickness of the transparent resin layer is 200 µm or more.
  8.   A flooring decorative material comprising the decorative sheet for flooring according to any one of claims 1 to 7, wherein a coating film is formed on the primer layer for coating film formation.
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KR101627732B1 (en) * 2015-10-28 2016-06-07 주식회사 폴리사이언텍 Non-pvc recyclable environmental-friendly floors with excellent abrasion -resistance and dimensional stability
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