KR20060051758A - Decorative sheet for flooring material having good impact and scratch resistance - Google Patents

Abstract

The present invention provides a floor covering cosmetic sheet that exhibits excellent impact resistance and scratch resistance without forming a buckler layer.

Specifically, the present invention relates to a transparency comprising a patterned layer, a transparent adhesive layer, a transparent polypropylene resin layer, and an ionizing radiation curable resin or a two-component curable urethane resin on a base sheet made of a polyolefin resin. As a cosmetic sheet for flooring material having a surface protective layer sequentially formed,

(1) The thickness of the transparent polypropylene resin layer is 150 µm or more,

(2) The universal hardness of the transparent polypropylene resin layer is 35 N / mm ² or more,

(3) Provides a floor covering cosmetic sheet, characterized in that the universal hardness of the transparent surface protective layer is 100 N / ㎜ ² or more.

Flooring decorative sheet, polyolefin resin, impact resistance

Description

Flooring sheet with excellent impact resistance and scratch resistance {DECORATIVE SHEET FOR FLOORING MATERIAL HAVING GOOD IMPACT AND SCRATCH RESISTANCE}

1: It is a schematic diagram of the floor cosmetic material produced in Experimental example 1. FIG.

2: It is a schematic diagram of the floor cosmetic material produced in Experimental Example 3. FIG.

Explanation of the sign

1. Transparent surface protective layer

2. Transparent polypropylene resin layer (top polypropylene layer in FIG. 2)

3. Patterned layer and transparency adhesive layer

4. Sheet

5. Adhesive layer

6. Nawang plywood

7. Bottom polypropylene layer

The present invention relates to a flooring decorative sheet excellent in impact resistance and scratch resistance.

DESCRIPTION OF RELATED ART Conventionally, polyvinyl chloride resin sheet is used abundantly as a decorative sheet | seat constituent material for resin flooring materials. When the polyvinyl chloride resin sheet is used, the sheet hardness (hard to soft) can be easily adjusted by adjusting the amount of plasticizer added, and there is an advantage that the embossing can be easily installed.

However, since polyvinyl chloride resin may release harmful graphite, chlorine-based gas and the like upon incineration, polyolefin-based resins which do not emit chlorine-based gas or the like have been used in place of polyvinyl chloride resin in recent years.

As a decorative sheet for a floor covering using a polyolefin resin, it is printed, for example in one side on the backer layer which consists of polyolefin resin in Unexamined-Japanese-Patent No. 8-13740 and 8-1883. Laminates the printing sheet in which the shape layer and the primer layer are sequentially formed, and further laminates the clear sheet made of ionomer resin on the printing sheet, and simultaneously laminates three layers made of the Bucker layer / print sheet / clear sheet. A cosmetic sheet for use is disclosed. Such a floor covering cosmetic sheet adheres a buckler layer side to various to-be-adhered materials, and turns into a floor cosmetic material. Moreover, a bucker layer is a reinforcement layer provided in order to provide hardness, strength, etc. to the flooring decorative sheet.

The makeup sheet for flooring material which has a buckler layer is easy to express predetermined hardness, strength, etc., and shows the outstanding impact resistance.

However, the flooring decorative sheet having a bucker layer requires a step of attaching the buckler layer portion to another portion (for example, a printing sheet) in the manufacturing process, and there is a problem that product loss is likely to occur in the step.

Therefore, it is desired to develop a floor covering cosmetic sheet having a predetermined hardness, strength and the like and exhibiting excellent impact resistance even without forming a buckler layer.

In addition to the outstanding impact resistance, it is also required to have high scratch resistance (bio-immunity). This is because in conventional protrusion plate flow, scratches, dents, and the like caused by sand processing, grooving, and the like can be almost erased by sanding, but sanding can be performed in a flooring material made by adhering a makeup sheet to an adherend. This is because there is no wound left on the final product due to processing or the like.

This invention aims at providing the flooring decorative sheet which exhibits the outstanding impact resistance even if it does not form a buckler layer, and also exhibits the outstanding scratch resistance.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to achieve the said objective, it discovered that the said objective can be achieved by forming a specific polypropylene resin layer and a surface protection layer, and came to complete this invention.

That is, the present invention relates to a flooring decorative sheet having excellent impact resistance and scratch resistance and a floor decorative material using the decorative sheet.

1. A transparent surface protective layer made of a patterned layer, a transparent adhesive layer, a transparent polypropylene resin layer, and an ionizing radiation curable resin or a two-component curable urethane resin is sequentially formed on a base sheet made of a polyolefin resin. As a makeup sheet for flooring,

(1) The thickness of the transparent polypropylene resin layer is 150 µm or more,

(2) The universal hardness of the transparent polypropylene resin layer is 35 N / mm ² or more,

(3) The cosmetic sheet for floor coverings, characterized in that the universal hardness of the transparent surface protective layer is 100 N / mm ² or more.

2. On the base sheet made of polyolefin resin, a transparent surface protective layer made of a patterned layer, a transparent adhesive layer, a transparent polypropylene resin layer, and an ionizing radiation curable resin or a two-component curable urethane resin is formed sequentially. As a makeup sheet for flooring,

(A) The transparent polypropylene resin layer is composed of two layers of an upper polypropylene layer and a lower polypropylene layer,

(B) the thickness of the upper polypropylene layer is 100 μm or more,

(C) The universal hardness of the upper polypropylene layer is at least 35 N / mm ² ,

(D) the thickness of the lower polypropylene layer is at least 50 μm,

(E) The universal hardness of the lower polypropylene layer is 20 N / mm ² or less,

(F) The floor covering cosmetic sheet, characterized in that the universal hardness of the transparent surface protection layer is 100 N / mm ² or more.

3. The decorative sheet for flooring according to item 2, wherein the thickness of the upper polypropylene layer is 100 to 300 µm.

4. The decorative sheet for flooring according to any one of items 1 to 3, wherein a colored concealment layer is further formed between the base sheet and the patterned layer.

5. The decorative sheet for flooring according to any one of items 1 to 4, wherein irregularities are formed on the surface of the transparent surface protective layer.

6. Floor decorative material which adhere | attached the base material sheet side of the floor covering decorative sheet of any one of said claim | item 1 to an adherend.

EMBODIMENT OF THE INVENTION Hereinafter, the makeup sheet for floor coverings and the makeup material for floors of this invention are demonstrated in detail.

Flooring Sheet

The decorative sheet for flooring material of the present invention is a transparent surface protection comprising a patterned layer, a transparent adhesive layer, a transparent polypropylene resin layer, and an ionizing radiation curable resin or a two-component curable urethane resin on a base sheet made of a polyolefin resin. Flooring is a makeup sheet for the flooring is formed sequentially,

(1) The thickness of the transparent polypropylene resin layer is 150 µm or more,

(2) The universal hardness of the transparent polypropylene resin layer is 35 N / mm ² or more,

(3) The universal hardness of the transparent surface protective layer is characterized by being 100 N / mm ² or more.

(Base sheet)

As the base sheet, a sheet made of polyolefin resin is used. Usually, you may use the film which consists of polyolefin resin.

It does not specifically limit as polyolefin resin, What is normally used in the field of a cosmetic 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. can be mentioned. Among these, polypropylene, polyolefin thermoplastic elastomer, and the like are particularly preferable.

Single or copolymers containing polypropylene as a main component are also preferred, for example, homo polypropylene resins, random polypropylene resins, block polypropylene resins, and polypropylene crystals, as well as having 2 to 20 carbon atoms other than propylene. (alpha) -olefin is mentioned. In addition, a propylene-α-olefin copolymer or the like containing 15 mol% or more of a comonomer of ethylene, butene-1,4-methylpentene-1, hexene-1 or octene-1 is also preferable.

Polyolefin-based thermoplastic elastomers are block polymers using an aromatic polyester having high crystallinity and high melting point in a hard segment and an amorphous polyether having a glass transition temperature of −70 ° C. or lower in a soft segment. In particular, it is preferable to mix a hard segment made of isotactic polypropylene and a soft segment made of atactic polypropylene in a weight ratio of 80:20.

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.

Although the thickness of a base material sheet is not specifically limited and can be set according to a product characteristic, Usually, it is 40-150 micrometers, Preferably it is about 50-100 micrometers.

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

A coloring agent is not specifically limited, Well-known coloring agents, such as a pigment and dye, can be used. For example, inorganic pigments, such as titanium bag, zinc-ized, red oxide, vermilion, ultramarine blue, cobalt blue, sulfur titanium, sulfur lead, and carbon black; Organic pigments (including dyes) such as isoindolinone, anza yellow A, quinacridone, permanent tread 4R, phthalocyanine blue, indersrene blue JR, and aniline black; Metallic pigments such as aluminum and brass; Pearlescent pigments composed of thin powders such as titanium dioxide-coated mica and basic lead carbonate. The coloring aspect of a base material sheet has transparent coloring and opaque coloring (hiding coloring), These can be selected arbitrarily. For example, when color concealing the background color of the adherend (base material for adhering the cosmetic sheet), an opaque color may be selected. On the other hand, in the case where the background shape of the adherend can be seen by the naked eye, 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, and dichromic acid treatment, as necessary. For example, in the case of corona discharge treatment, the surface tension of the surface of the base sheet may be 30 dxyNe or more, preferably 40 dxynye or more. Surface treatment may follow the usual method of each treatment.

On one side or both sides of the base sheet, if necessary, a primer layer (for example, a back side primer layer for facilitating adhesion of the adherend and a primer layer for facilitating formation of a patterned layer) may be formed. good. By forming a primer layer, interlayer adhesion with an adjacent layer (for example, adherend) can be improved.

The primer layer can be formed by applying a known primer on one side or both sides of the base sheet. Examples of the primer include a urethane resin primer made of an acrylic modified urethane resin and the like, a primer made of urethane-cellulose resin (e.g., a resin obtained by adding hexamethylene diisocyanate to a mixture of urethane and vaginal screen). Can be mentioned.

Although the application amount of a primer agent is not specifically limited, Usually, 0.1-100 g / m <^2> , Preferably it is about 0.1-50 g / m <^2> .

Although the thickness of a primer layer is not specifically limited, Usually, 0.01-10 micrometers, Preferably it is about 0.1-1 micrometer.

(Pattern-like layer)

A patterned layer is formed on the base sheet (the opposite side of the adherend adhesive surface, pointing to the same side in each layer below).

The pattern-shaped layer imparts designability by a desired pattern to the makeup sheet, and the kind of pattern is not particularly limited. Examples include wood grains, stone grains, sand grains, tile albums, brick piles, cloth textures, thongs, geometric shapes, letters, symbols, abstract shapes, and the like.

The formation method of a pattern-shaped layer is not specifically limited, For example, the coloring ink, coating agent, etc. which are obtained by dissolving (or dispersing) a well-known coloring agent (dye or pigment) with a binder resin in a solvent (or a dispersion medium). What is necessary is just to form by the printing method etc. which used.

As a coloring agent, For example, Inorganic pigments, such as carbon black, a titanium bag, zincation, a red oxide, a blue wire, and a cadmium red; Organic pigments such as azo pigments, lake pigments, anthraquinone pigments, quinacridone pigments, phthalocyanine pigments, isoindolinone pigments and dioxadine pigments; Metal powder pigments such as aluminum powder and bronze powder; Pearlescent pigments such as titanium oxide coated mica and bismuth oxide; Fluorescent pigments; Luminous pigments; and the like. These coloring agents can be used individually or in mixture of 2 or more types. You may further mix | blend fillers, such as a silica, and extender pigments, such as organic beads, a neutralizing agent, surfactant, etc. with these coloring agents.

Examples of the binder resin include acrylic resins, styrene resins, polyester resins, urethane resins, chlorinated polyolefin resins, vinyl chloride-vinyl acetate copolymer resins, polyvinyl butylal resins, alkyd resins, and petroleum resins. , Ketone resins, epoxy resins, melamine resins, fluorine resins, silicone resins, fibrin derivatives, rubber resins and the like. These resin can be used individually or in mixture of 2 or more types.

As a solvent (or a dispersion medium), For example, petroleum organic solvents, such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, methylcyclohexane; Ester organic solvents such as ethyl acetate, butyl acetate, 2-methoxy ethyl acetate and 2-ethoxy ethyl acetate; Alcohol-based organic solvents such as methanol, ethanol, normal propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol and propylene glycol; Ketone organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; Ether organic solvents such as diethyl ether, dioxane and tetrahydrofuran; Chlorine organic solvents such as dichloromethane, carbon tetrachloride, trichloroethylene and tetrachloroethylene; Inorganic solvents, such as water, etc. are mentioned. These solvents (or dispersion medium) can be used individually or in mixture of 2 or more types.

As a printing method used for formation of a patterned layer, the gravure printing method, the offset printing method, the screen printing method, the fresco print method, the electrostatic printing method, the inkjet printing method, etc. are mentioned, for example. In the case of forming the front beta patterned layer, for example, the roll coat method, the knife coat method, the air knife coat method, the die coat method, the lip coat method, the comma coat method, the kiss coat method, the flow coat method, Various coating methods, such as a dip coat method, are mentioned. In addition, it may be used by a hand dyeing method, a silencing method, a photographing method, a transfer method, a laser beam drawing method, an electron beam drawing method, a partial vapor deposition method such as metal, an etching method, or the like, or in combination with other forming methods.

The thickness of the patterned layer is not particularly limited and may be appropriately set according to product characteristics, but 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.

(Colored concealment layer)

Between the base sheet and the patterned layer, you may additionally form a colored concealment layer. The colored hiding layer is provided when the background color of the adherend is to be concealed on the surface of the makeup sheet. Not only when the base sheet is transparent but also when the base sheet is concealed colored, it may be formed in order to stabilize the concealment.

As the ink for forming the colored concealment layer, an ink for concealing coloring can be used as the ink for forming the patterned layer.

As for the formation method of a colored concealment layer, the method which can form so that the whole base material sheet may be coat | covered (front-beta shape) is preferable. For example, the roll coat method, the knife coat method, the air knife coat method, the die coat method, the lip coat method, the comma coat method, the kiss coat method, the flow coat method, the dip coat method, etc. are mentioned as a preferable example.

Although the thickness of a colored concealing layer is not specifically limited, Although it can set suitably according to a product characteristic, the layer thickness at the time of coating is about 0.2-10 micrometers, and the layer thickness after drying is about 0.1-5 micrometers.

(Transparent adhesive layer)

On the pattern-shaped layer, the transparent adhesive bond layer is formed. The transparent adhesive layer is not particularly limited as long as it is transparent, and any one of colorless transparent, colored transparent, translucent and the like is included. This adhesive bond layer is formed in order to adhere | attach a pattern-shaped layer and a transparent polypropylene resin layer.

An adhesive is not specifically limited, A well-known adhesive agent can be used in the field of a cosmetic sheet.

As adhesives well-known in the field of a cosmetic sheet, curable resins, such as thermoplastic resins, such as a polyamide resin, an acrylic resin, and a vinyl acetate resin, and a thermosetting urethane resin, are mentioned, for example. Moreover, the two-component curable polyurethane resin or polyester resin which uses an isocyanate as a hardening | curing agent can also be used.

For example, the adhesive layer is coated with an adhesive on a patterned layer, and dried and cured after coating the transparent polypropylene resin constituting the transparent polypropylene resin layer (the upper polypropylene layer or the lower polypropylene layer described later). It can form by making it. Conditions, such as drying temperature and drying time, are not specifically limited, What is necessary is just to set suitably according to the kind of adhesive agent. The method of applying the adhesive is not particularly limited, and for example, a roll coat, a curtain coat, a wire bar coat, a reverse coat, a gravure coat, a gravure reverse coat, an air knife coat, a kiss coat, a blade coat, a smooth coat, a comma coat And the like can be used.

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 Polypropylene Resin Layer)

On the transparent adhesive layer, a transparent polypropylene resin layer (single layer) is formed. The transparent polypropylene resin layer has a thickness of 150 μm or more and a universal hardness of 35 N / mm ² or more. By forming such a transparent polypropylene-based resin layer, high load area scratch resistance can be imparted to the flooring decorative sheet.

Here, the high load resistance scratch resistance means that scratches, indentations, etc. are hardly generated when the surface of the makeup sheet is hardly scratched with a high load (meaning a large load per unit area). The degree of scratch resistance of the high load region can be evaluated, for example, by a pencil hardness test (WIS K 5600-5-4), a Clemens test, or the like.

Universal hardness in this specification is hardness measured using the Fisherscope H100V (made by Fisher Instruments Co., Ltd.) which is useful for hardness measurement of a thin film coating, an elastic material, etc. The hardness measurement by the said Fisherscope H100V is what is called the ultramicro beaker hardness test method. Specifically, it is a method of measuring the sample hardness by directly reading the pressing depth of the dent in a state where the indenter is pressed on the sample surface (for example, a transparent polypropylene resin layer) and the load is applied. The measured value (universal hardness) is defined as follows (see: ISO Technical Report). The indenter uses a diamond indenter (φ 0.4 mm ball indenter) and measures the depth of depression under the test load. Universal hardness is expressed as the ratio of the test load divided by the surface area of the indentations resulting from the test load.

Universal Hardness (N / mm ² ) = F / S

F: Test load (N)

S: Surface area of the ball indenter (φ 0.4 mm) under test load (mm ² )

Although the thickness of a transparent polypropylene resin layer should just be 150 micrometers or more, 300 micrometers or more are preferable and 400 micrometers or more are more preferable.

The universal hardness of the transparent polypropylene resin layer may be 35 N / mm ² or more, but 40 N / mm ² or more is preferable.

The transparent polypropylene resin layer may be laminated on the transparent adhesive layer by, for example, a calendar method, an inflation method, a T-die extrusion method, or the like, or a ready-made film.

Although a transparency polypropylene resin layer is a single layer (1 layer) above, you may make it a multilayer (two or more layers) as needed. For example, the transparent polypropylene-based resin layer is composed of two layers of the upper polypropylene layer and the lower polypropylene layer described later, thereby providing both the high load region scratch resistance and the low load region scratch resistance described later in the flooring decorative sheet. It can be given.

Hereinafter, the case where a transparent polypropylene resin layer is made into a 2-layered structure is demonstrated.

A. Top Polypropylene Layer

The upper polypropylene layer is formed in order to obtain scratch resistance particularly in the high load region, among the scratch resistance.

The thickness of the upper polypropylene layer should just be 100 micrometers or more, about 100-300 micrometers is preferable, and about 250 micrometers is especially preferable.

The universal hardness of the upper polypropylene layer may be 35 N / mm ² or more, and 40 N / mm ² or more is preferable.

B. Bottom Polypropylene Layer

The lower polypropylene layer is formed in order to obtain scratch resistance in the low-heavy region, among scratch resistance. Here, high scratch resistance in the low-heavy region means that scratches, indentations, etc. are hardly generated when the surface of the makeup sheet is hardly scratched at low weight (meaning that the load per unit area is small). The degree of scratch resistance in the low-heavy region can be evaluated by, for example, the Hoffman scratch test.

The formation method of a lower polypropylene layer should just be the same as the formation method of the above-mentioned transparent polypropylene resin layer. If necessary, the upper and lower ends may be co-extruded to be formed.

Although the thickness of a lower polypropylene layer should just be 50 micrometers or more, 100 micrometers or more are preferable. The upper limit of the lower polypropylene layer is not limited, but is about 200 μm.

The universal hardness of the lower polypropylene layer may be 20 N / mm ² or less, but 15 N / mm ² or less is preferable.

By forming the lower polypropylene layer in addition to the upper polypropylene layer, it is possible to impart low-heavy region scratching property to the flooring decorative sheet.

As the surface of the upper polypropylene layer, a surface treatment such as a corona discharge treatment, an ozone treatment, a plasma treatment, an ionizing radiation treatment, a dichromic acid treatment or the like may be applied to the surface on which the transparent surface protective layer to be described later is formed. Surface treatment should just follow the normal method according to each treatment.

If necessary, a primer layer (primer layer for facilitating formation of a surface protective layer) may be formed on the surface.

The primer layer can be formed by applying a known primer on one side or both sides of the base sheet. Examples of the primer include a urethane resin primer composed of an acrylic modified urethane resin and the like, a resin primer composed of a block copolymer of acryl and urethane, and the like.

Although the application amount of a primer agent is not specifically limited, Usually, it is 0.1-100 g / m <^2> , Preferably it is about 0.1-50 g / m <^2> .

Although the thickness of a primer layer is not specifically limited, Usually, 0.01-10 micrometers, Preferably it is about 0.1-1 micrometer.

(Transparent surface protective layer)

On the transparent polypropylene resin layer, a transparent surface protective layer made of an ionizing radiation curable resin or a two-liquid curable urethane resin is formed. By forming a surface protective layer made of an ionizing radiation curable resin or a two-liquid curable urethane-based resin, wear resistance, impact resistance, stain resistance, scratch resistance, weather resistance, and the like of the makeup sheet can be improved.

The ionizing radiation curable resin is not particularly limited, and includes a prepolymer (including an oligomer) and / or a monomer containing a radical polymerizable double bond in a molecule thereof capable of polymerizing crosslinking reaction by ionizing radiation irradiation such as ultraviolet rays or electron beams. Transparency resin can be used. These prepolymers or monomers can be used singly or in combination. The curing reaction is usually a crosslinking curing reaction.

Specifically, as said prepolymer or monomer, the compound which has radical polymerizable unsaturated groups, such as a (meth) acryloyl group and a (meth) acryloyloxy group, cationically polymerizable functional groups, such as an epoxy group, etc. are mentioned in a molecule | numerator. Also preferred are polyene / thiol based prepolymers with combinations of polyenes and polythiols. Here, (meth) acryloyl group means acryloyl group or methacryloyl group.

As a prepolymer which has a radically polymerizable unsaturated group, it is polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, melamine (meth) acrylate, triadine (meth) acrylate, for example. And silicone (meth) acrylates. As for these molecular weights, about 250-100000 are usually preferable.

As a monomer which has a radically polymerizable unsaturated group, methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenoxyethyl (meth) acrylate, etc. are mentioned as a monofunctional monomer, for example. Moreover, as a polyfunctional monomer, For example, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethyl propane tri (meth) acrylate, trimethylol propane ethylene oxide tri (meth) acrylate, Dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like.

As a prepolymer which has a cationically polymerizable functional group, the prepolymer of vinyl ether resins, such as epoxy resins, such as a bisphenol-type epoxy resin and a novolak-type epoxy compound, fatty acid type vinyl ether, and aromatic type vinyl ether, is mentioned, for example. . Moreover, as a thiol, polythiol, such as a trimethylol propane trithioglycolate and pentaerythritol tetrathioglycolate, is mentioned, for example. As polyene, what added aryl alcohol to the both ends of the polyurethane by diol and diisocyanate is mentioned, for example.

As ionizing radiation used for curing an ionizing radiation curable resin, electromagnetic waves or charged particles having energy capable of curing reaction of molecules in the ionizing radiation curable resin (composition) can be used. Usually, ultraviolet rays or electron beams may be used, but visible rays, X rays, ion rays or the like may be used.

As the ultraviolet light source, for example, 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 or a metal halide lamp can be used. As a wavelength of an ultraviolet-ray, 190-380 nm is usually preferable.

As the electron beam source, for example, various electron beam accelerators such as coke croft Walton type, van degraf type, resonant transformer type, insulated core transformer type, or linear type, dynatron type and high frequency type can be used. Especially, it is especially preferable to be able to irradiate the electron which has an energy of 100-1000 Pa, preferably 100-300 Pa.

Although it does not specifically limit as a two-component curable urethane type resin, Although the polyol component (acryl polyol, polyester polyol, polyether polyol, epoxy polyol, etc.) which has an OH group as a main component, and the isocyanate component (trilene diisocyanate, hexamethylene di) which are hardening | curing agent components Isocyanate, metha xylene diisocyanate, etc.) can be used.

These surface protective layers may contain plasticizers, stabilizers, fillers, dispersants, dyes, colorants, such as pigments, solvents, etc. as needed.

For example, the surface protective layer may be formed by coating ionizing radiation curable resin or two-component curable urethane resin on a transparent polypropylene resin layer by a known coating method such as gravure coat or roll coat, and then curing the resin. have. In the case of an ionizing radiation curable resin, the resin is cured by electron beam irradiation.

Although the thickness of a surface protection layer is not specifically limited, Although it can set suitably according to the characteristic of a final product, it is usually 0.1-50 micrometers, Preferably it is about 1-20 micrometers.

As for the hardness of a surface protection layer, the said universal hardness should just be 100 N / mm <^2> or more, Preferably it is 150 N / mm <^2> or more. If the universal hardness of the surface protective layer is less than 100 N / mm ^2, there is a fear that sufficient scratch resistance cannot be exhibited. Moreover, 45 N / mm <^2> or more is preferable and, as for the universal hardness of the whole makeup sheet formed to the surface protection layer, 50 N / mm <^2> or more is more preferable.

Unevenness may be formed in the surface (surface exposed to air) of the surface protection layer. Usually, an uneven shape is formed by embossing. The embossing processing method is not specifically limited, For example, the method of heat-softening the surface of a transparent acrylic resin layer, and pressing and shaping | molding by an embossing board, and cooling is an example of a preferable method. In the embossing process, a well-known single sheet or a rotating embossing machine can be used. As the concave-convex shape, for example, wood-coated conduits, slab surface concave-convex (granite rock wall surface, etc.), cloth surface texture, easy, sand grain, hairline, and many fine groove patterns have.

Floor Cosmetic

The flooring decorative sheet of the present invention can be formed into a flooring decorative material by bonding to various adherends. The material of the adherend is not particularly limited, and materials such as inorganic nonmetal, metal, wood, and plastic may be used.

Specifically, the inorganic non-metallic type may be, for example, cement, extruded cement, slag cement, ALC (lightweight foamed concrete), RC (glass fiber reinforced concrete), pulp cement, wood cement, asbestos cement, calcium silicate, gypsum, Non-ceramic ceramic industry materials, such as gypsum slug, ceramic materials, such as earthenware, ceramics, porcelain, stoneware, glass, and enamel, etc. are mentioned.

Examples of the metal type include metal materials such as iron, aluminum, and copper (metal steel sheet).

Examples of the wood-based system include veneers, plywood, particle boards, fiberboards, and aggregates made of cedar, cypress, oak, nawang, and teak.

Examples of the plastics include resin materials such as polypropylene, ABS resins, and phenol resins.

The shape of such a to-be-adhered body is not specifically limited, Usually, what is necessary is just to set it as a flat board considering installation in a flooring etc.

After joining to the adherend, for example, cutting may be performed using a cutting or tenon, a V-shaped thin groove, chamfering or the like depending on the characteristics of the final product.

The flooring decorative sheet of the present invention exhibits excellent impact resistance even without forming a buker layer, and further exhibits excellent scratch resistance.

In addition, since it is not necessary to form a bucker layer, the manufacturing process of the flooring decorative sheet can be made easy, and the manufacturing loss which arose in the conventional bucker layer forming process can be eliminated.

EXAMPLE

Hereinafter, the present invention will be described in more detail through experimental examples.

Experimental Example  One

(Makeup sheet for flooring)

A patterned layer was formed by printing on a colored polypropylene film (base sheet) having a thickness of 0.06 mm.

Thereafter, a 0.3 mm (300 μm) thick transparent polypropylene resin film was bonded with a urethane dry laminate adhesive to form a transparent polypropylene resin layer.

Subsequently, the electron beam hardening type transparent surface protection layer (15 micrometers) of universal hardness 170N / mm <^2> was formed on the transparent polypropylene resin layer.

Next, an embossing process was performed on the transparent surface protective layer side to prepare a floor covering decorative sheet.

(Making Floor Cosmetics)

A 12 mm roughness plywood was affixed to the base sheet side of the floor covering decorative sheet, and the floor decorative material was produced. Urethane modified ethylene-vinyl acetate emulsion adhesive (100 g / m <^2> ) was used for adhesion | attachment.

(Scratch resistance of flooring material)

The scratch resistance of the produced floor decorative material was evaluated. The following pencil hardness test and Clemens test is to evaluate the scratch resistance of the high load area. In addition, the Hoffman scratch test evaluates scratch resistance in underloaded areas. Each test method is as follows.

1. Pencil hardness test (high load evaluation)

The test was done by the pencil hardness tester. The test was conducted in accordance with JIS K 5600-5-4 except that the tester was set so that the front of the pencil applied a load of 1000 g to the makeup sheet when the tester was in the horizontal position.

2. Hoffman scratch test (low load evaluation)

The test was done using the Hoffman scratch test machine by a U.S.-RAD DEC company. Specifically, a scratch knife (φ7 mm columnar knife) was installed so as to contact the surface of the cosmetic material at an angle of 45 °, and the tester was moved onto the cosmetic material. While increasing the load gradually, the test was repeated until swelling, indentation, etc. appeared on the surface of the cosmetic material.

3. Clemens test (high load evaluation)

The test was carried out in accordance with JIS K 5600-5-5. Needles for scratching the surface of the cosmetic material were made of diamonds.

These test results are shown in Table 1 below.

HB of PF layer 15 20 25 30 35 40 45 HＵ of the makeup sheet 25 30 35 40 45 50 55 Pencil Hardness ^{＊ 1} 6B 4B 3B 2B HB HB HB Hoffman scratches ^{＊ 2} 400 400 400 400 400 400 400 Clemens Scratches ^{＊ 3} 70 80 80 80 90 90 90

Ｕ: Universal hardness (N / mm ² ) PP: Polypropylene

* 1: hardness that does not occur with white burns and dents

＊ 2: Maximum load without white burn (g)

* 3: Maximum load without whitening (g) These units are as follows.

Experimental Example  2

A flooring decorative material was produced in the same manner as in Experimental Example 1 except that the universal hardness of the transparent polypropylene resin layer was fixed at 40 N / mm ² and the thickness thereof was cut.

The scratch resistance (pencil hardness) of the produced floor decorative material was evaluated. The evaluation results are shown in Table 2 below.

Pp layer thickness (㎛) 60 80 100 150 300 400 500 Pencil hardness 3B 3B 2B HB HB HB HB

Experimental Example  3

(Makeup sheet for flooring)

A patterned layer was formed by printing on a colored polypropylene film (base sheet) having a thickness of 0.06 mm.

Then, the film extruded together with the upper polypropylene layer having a universal hardness of 40 N / mm ² and the lower polypropylene layer having a uniform hardness of 0.15 mm thickness (two-layer configuration: 0.3 mm layer thickness) was bonded with an urethane-based dry laminate adhesive. did.

Then, to form the electron beam curing type transparent surface protection layer (15 ㎛) of the universal hardness of 170 N / mm ² on the top of the polypropylene layer.

Next, an embossing process was performed on the transparent surface protective layer side to prepare a floor covering decorative sheet.

(Production of the makeup material for the floor)

A 12 mm roughness plywood was affixed to the base sheet side of the floor covering decorative sheet, and the floor decorative material was produced. Urethane modified ethylene-vinyl acetate emulsion adhesive (100 g / m <^2> ) was used for adhesion | attachment.

(Scratch resistance of flooring material)

The scratch resistance (pencil hardness, Hoffman scratch, Clemens scratch) of the produced floor decorative material was evaluated. The evaluation results are shown in Table 3 below.

HB of upper P layer 40 HB of lower P layer 15 20 35 35 40 Hoffman scratches 600 600 400 400 400 Pencil hardness HB HB HB HB HB Clemens Scratches 90 90 90 90 90

Experimental Example  4

Except for fixing the HV of the upper polypropylene layer to 40 N / mm ² and the Hp of the lower polypropylene layer to 15 N / mm ² , extruding together, and seating both of them so that the upper / lower sum was 0.3 mm. In the same way, the flooring cosmetics were produced.

(Scratch resistance of flooring material)

The scratch resistance (pencil hardness, Hoffman scratch, Clemens scratch) of the produced flooring cosmetics was evaluated. The evaluation results are shown in Table 4 below.

Top P Layer Thickness 300 280 250 200 150 100 100 Lower Pp Thickness 0 20 50 100 150 200 50 Hoffman scratches 400 400 600 600 600 800 700 Pencil hardness HB HB HB HB HB B B Clemens Scratches 90 90 90 90 90 80 80

 At the end of Table 4, the evaluation result in the case where the thickness of an upper PPU is made into 100 micrometers and the thickness of a lower PPU is made into 50 micrometers is shown together. The evaluation result shows that even when the upper P layer is set to 100 µm and the lower P layer is set to 50 µm, the usefulness is high as a floor covering decorative sheet.

Experimental Example  5

The lower polypropylene layer was fixed to HV: 15 N / mm ² and 50 µm in thickness, and both layers were extruded and sheeted together by dividing the thickness of the upper polypropylene layer (HW: 40 N / mm ² ). In the same way, the flooring cosmetics were produced.

(Scratch resistance of flooring material)

The scratch resistance (pencil hardness, Hoffman scratch, Clemens scratch) of the produced flooring cosmetics was evaluated. The evaluation results are shown in Table 5 below.

Top P Layer Thickness 250 350 450 Lower Pp Thickness 50 50 50 Hoffman scratches 600 500 500 Pencil hardness HB HB HB Clemens Scratches 90 90 90

(Impact resistance of flooring cosmetics)

The impact resistance of the cosmetics (3 types) of Table 5 was evaluated using the DuPont impact tester (according to JIS K 5600-5-3). Specifically, the weight of the prescribed weight was dropped from the height of 30 cm on the surface of the cosmetic material, and the evaluation was made by measuring the amount of depression. The evaluation results are shown in Table 6 below.

Top P Layer Thickness 250 350 450 Lower Pp Thickness 50 50 50 Dupont depression: μm 350 300 250

 Moreover, the flooring material which has a conventional bucketer has a depression amount of about 250 micrometers by the same impact test, and it can be said that the flooring decorative material of this invention has almost equivalent impact resistance. In the case of the protrusion plate flooring of a conventional product, since the surface is hard and it is hard to buffer an impact, a coating film is fragile and it becomes the depression amount of about 400 micrometers.

Experimental Example  6

Experimental Examples 1-5 were performed instead of the transparent surface protection layer which consists of two-component hardening type urethane type resins for an electron beam curing type transparent surface protection layer.

Each evaluation result was the same grade as shown in Tables 1-6. It turned out that the surface protection layer can obtain the same effect even if it forms from either an electron beam curable resin or two-component curable urethane type resin.

The present invention provides a floor covering decorative sheet that exhibits excellent impact resistance and scratch resistance without forming a buckler layer.

Claims (6)

On the base sheet made of polyolefin-based resin, a makeup for flooring material having a patterned layer, a transparent adhesive layer, a transparent polypropylene-based resin layer, and a transparent surface protective layer made of an ionizing radiation curable resin or a two-component curable urethane-based resin sequentially formed. As a sheet, (1) The thickness of the transparent polypropylene resin layer is 150 µm or more, (2) The universal hardness of the transparent polypropylene resin layer is 35 N / mm ² or more, (3) The universal hardness of the transparent surface protective layer is 100 N / mm ² or more. Floor covering sheet. On the base sheet made of polyolefin-based resin, a makeup for flooring material having a patterned layer, a transparent adhesive layer, a transparent polypropylene-based resin layer, and a transparent surface protective layer made of an ionizing radiation curable resin or a two-component curable urethane-based resin sequentially formed. As a sheet, (A) The transparent polypropylene resin layer is composed of two layers of an upper polypropylene layer and a lower polypropylene layer, (B) the thickness of the upper polypropylene layer is 100 μm or more, (C) The universal hardness of the upper polypropylene layer is at least 35 N / mm ² , (D) the thickness of the lower polypropylene layer is at least 50 μm, (E) The universal hardness of the lower polypropylene layer is 20 N / mm ² or less, (F) The universal hardness of the transparent surface protective layer is 100 N / mm ² or more. Floor covering sheet. The method of claim 2, The top polypropylene layer has a thickness of 100 to 300 μm Floor covering sheet. The method according to claim 1 or 2, The colored concealment layer is further formed between the base sheet and the patterned layer. Floor covering sheet. The method according to claim 1 or 2, Irregularities are formed on the surface of the transparent surface protection layer. Floor covering sheet. Floor cosmetic material made by adhering the base material sheet side of the floor covering cosmetic sheet according to claim 1 to the adherend.

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