JP2001199029A - Decorative sheet and decorative material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet formed by laminating a resin layer (surface resin layer) having high surface hardness on a base material, excellent in scratch-resistant hardness and hard to generate a cavity even if the decorative sheet is pressed from its surface by a pencil. SOLUTION: The decorative sheet is constituted by providing a resin layer with a surface hardness (universal hardness value) of 100-200 on a base material layer. A substrate is laminated on the rear surface of the decorative sheet directly or through other layer to constitute a decorative material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a decorative sheet and a decorative material having excellent surface hardness, which are used for interior materials of buildings such as walls, fittings such as doors, and surface materials of furniture such as wardrobes.

[0002]

2. Description of the Related Art Conventionally, a paper base material has been used as a base material.
Cosmetic material formed by forming a pattern layer on the surface of the paper substrate by printing or the like in order to impart abrasion resistance and stain resistance, and then forming a surface protective layer comprising a crosslinked product of an ionizing radiation-curable resin. It has been known.

For example, 1) Japanese Patent Publication No. 49-31033 discloses that a picture layer is formed on a paper base material, and a coating of an unsaturated polyester prepolymer is applied on the outermost surface to form a coating film. There is also described a decorative material in which the coating film is crosslinked and cured with an electron beam or ultraviolet light to form a surface protective layer.

[0004] 2) Japanese Patent No. 2856862 discloses that a picture layer is formed on a paper base material, and the outermost surface contains a (meth) acrylate prepolymer, a (meth) acrylate monomer and a silicone acrylate lubricant. There is described a decorative material in which a coating film is formed by applying a paint to be applied, and the coating film is crosslinked and cured by an electron beam or ultraviolet light to form a surface protective layer.

3) Further, Japanese Patent Application Laid-Open No. 8-183147 discloses a decorative sheet having a wear-resistant surface protective layer.

[0006]

However, although these decorative materials have a surface protective layer on the surface, the dents may not be formed when the scratch resistance is insufficient or when the decorative material is pressed from the surface with a pencil or the like. There was a problem that it easily occurred.

[0007] In order to solve such problems, the present invention provides a decorative sheet comprising a substrate and a resin layer having a high surface hardness (surface resin layer) laminated thereon, which has excellent scratch resistance and excellent surface hardness. Even when pressed by a pencil or the like, it is possible to provide a decorative sheet in which dents are unlikely to be formed, and a decorative material obtained by attaching a substrate directly or through another layer to the back side of the decorative sheet. Aim.

[0008]

The present invention firstly provides a decorative sheet having a base material layer and a resin layer having a surface hardness (value of universal hardness) of 100 to 200 on the base material layer. .

In the decorative sheet according to the first aspect,
The surface hardness (the value of universal hardness) of the base material layer is 70.
It is preferably from 200 to 200.

[0010] Secondly, the present invention relates to the decorative sheet according to the first aspect of the present invention, on the back side (the side opposite to the side on which the resin layer is provided), directly or via another layer. To provide a decorative material having a substrate adhered thereto.

Since the decorative sheet of the present invention has a resin surface having excellent surface hardness, that is, a surface hardness (value of universal hardness) of 100 to 200, the decorative sheet has excellent scratch resistance. And a dent is unlikely to occur even when pressed from the surface of the decorative sheet with a pencil or the like.

Further, the decorative material of the present invention is obtained by laminating the decorative sheet of the first invention on a substrate directly or via another layer (such as an adhesive layer). It has excellent scratch resistance as in the case of the decorative sheet, and hardly causes dents even when pressed from the surface of the decorative material with a pencil or the like.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the decorative sheet and the decorative material of the present invention will be described in detail. The decorative sheet of the present invention basically has a surface hardness (value of universal hardness) of 10 on the base material layer 1 like a decorative sheet 10A shown in FIG.
0 to 200 resin layers 2 are formed.

The base material of the base material layer 1 is a paper base material,
A plastics substrate, a metal foil substrate, or the like is used.

Examples of the paper base material include (1) thin paper, kraft paper, titanium paper, linter paper, paperboard, gypsum board paper, and a so-called ball wallpaper material obtained by sol-coating or dry-laminating a polyvinyl chloride resin on paper. Anti-quality paper,
Coated paper, art paper, sulfuric acid paper, glassine paper, parchment paper, paraffin paper, paper such as Japanese paper, (2) glass fiber,
Asbestos, potassium titanate fiber, alumina fiber, silica fiber, inorganic fiber such as carbon fiber, or polyester resin,
A nonwoven fabric made of an organic fiber such as vinylon fiber; (3) a mixed paper made by mixing the papers of the above (1) with an inorganic fiber such as a glass fiber or an organic fiber such as a polyester resin or vinylon fiber;

(4) The papers of the above (1) may be coated with urethane resin, acrylic resin, melamine resin, phenol resin, urea resin, xylene resin, diallyl phthalate resin, guanamine resin, unsaturated polyester resin, epoxy resin, alkyd resin For example, an impregnated paper impregnated with a thermosetting resin such as a silicon resin can be used.

Further, a flame retardant such as aluminum hydroxide powder can be added to these paper base materials. Further, a laminate of the same type or two or more types of the above-described paper-based substrates can be used as the paper-based substrate. The rice basis weight of the paper base material is usually about ²⁰ to 120 g / m ² .

As the plastics base material, polyethylene, chlorinated polyethylene, polypropylene, ethylene-
Polyolefin resins such as propylene copolymer, ethylene-propylene-butene copolymer, ethylene-vinyl acetate copolymer, 4-methylpentene-1 resin, ethylene-vinyl alcohol copolymer, polystyrene, acrylonitrile-butadiene-styrene Polystyrene or a copolymer of polystyrene such as a copolymer (ABS resin), an acrylonitrile-styrene copolymer (SAN resin), and an acrylonitrile-chlorinated polyethylene-styrene copolymer (ACS resin);

Poly (methyl) methacrylate, poly (ethyl meth) acrylate, poly (butyl meth) acrylate, methyl (meth) acrylate-butyl (meth) acrylate copolymer, ethyl (meth) acrylate -Butyl (meth) acrylate copolymer, methyl (meth) acrylate-
Acrylic resin such as styrene copolymer, (meth) methyl acrylate-butyl (meth) acrylate- (meth) acrylate-2-hydroxyethyl copolymer (where (meth) acryl is acrylic or methacryl) ), Polyester resins such as polyethylene terephthalate and polybutylene terephthalate,

Polyvinyl chloride, vinyl chloride-acrylate copolymer, vinyl chloride-methacrylate copolymer, vinyl chloride-acrylonitrile copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl acetate-
Vinyl chloride copolymer, vinyl chloride resin such as propylene-vinyl chloride copolymer, vinyl acetate resin, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral,

Cellulose resins such as acetylcellulose, cellulose acetate butyrate, cellulose ether, methylcellulose, cellophane, polyamide resins (nylon 6, nylon 66, etc.), polyacetal, polycarbonate, polyphenylene oxide, polyphenylene sulfide, polysulfone, polyamide imide,
Heat-resistant resin such as polyimide, polyamide bismaleimide, polyether sulfone, polyphenylene sulfone, polyallyl sulfone, polyarylate, polyetheretherketone, polyetherimide, polytetrafluoroethylene, polyfluoroethylenepropylene, tetrafluoroethylene- Perfluoroalkoxy ethylene copolymer, ethylene-
Fluorinated resins such as tetrafluoroethylene copolymer, polyvinylidene fluoride, poly (trifluorochloroethylene), silicone resin,

Phenol resin, urea resin, melamine resin, xylene resin, diallyl phthalate resin, unsaturated polyester, glyptal resin, unsaturated alcohol-modified phthalic resin, isophthalic resin, terephthalic acid resin, aliphatic polyester, polycarbonate, epoxy resin ,
Thermosetting polybutadiene, furan resin, polyurethane,
A sheet-like single layer or a laminate of a thermosetting resin such as an alkylbenzene resin and a guanamine resin alone or a mixture thereof can be used. As specific examples of these thermosetting resins, those similar to those listed as specific examples of the thermosetting resin forming the surface resin layer described later can be used.

As the metal foil substrate, those obtained by forming a metal foil layer on the surface of the above-mentioned paper-based substrate or plastic substrate are used. Examples of the metal used as the metal foil include aluminum, stainless steel, iron, and copper.

The substrate 1 can be colored by itself using a coloring agent. For example, a pattern layer 3 is formed on the substrate 1 like a decorative sheet 10B shown in FIG. Is preferred. The picture layer 3 is formed to improve the decorativeness of the decorative material (giving a design effect).

The pattern layer 3 can be provided, for example, by printing a pattern on the substrate 1. The pattern can be formed with ink (or paint) using a known printing method such as gravure printing, offset printing, silk screen printing, gravure offset printing, ink jet printing, or the like. The amount of ink (paint) applied is usually 1 to
It is about 10 g / m ² (when dried).

The pattern may be a wood pattern, a stone pattern, a cloth pattern, a tile pattern, a brick pattern, a leather pattern, a geometric pattern, a character symbol, a solid pattern, or a combination of these patterns (for example, (Overall solid / grain pattern).

As the ink or paint, a vehicle composed of a binder resin or the like, a coloring agent such as a pigment or a dye, and, if necessary, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent and the like are appropriately mixed. Can be used.

As the binder, for example, cellulosic resins such as nitrocellulose, cellulose acetate and cellulose acetate, urethane resins, acrylic resins, vinyl chloride-vinyl acetate copolymers, polyester resins and the like, or a mixture of two or more thereof Mixtures can be used.

Examples of the coloring agent include inorganic pigments such as titanium white, graphite, carbon black, nickel titanium yellow, red iron oxide, and ultramarine blue; organic pigments such as quinacridone, isoindolinone, phthalocyanine, bisazo dyes and monoazo dyes; Bright pigments such as titanium dioxide-coated mica, foil powder of aluminum or the like, or other dyes can be used.

The surface of the substrate 1 may be embossed with a concavo-convex pattern, or the embossed recesses may be filled with a coloring ink by wiping to be colored.

The decorative sheet of the present invention has a surface resin layer 2 laminated on the base layer 1. As a resin constituting the surface resin layer 2, a Fischer hardness meter (H. Fishe) is used.
It is preferable to use one having a universal hardness value (HU) of 100 to 200, which is calculated in the coating film hardness measurement by R Co.).

If the value of the universal hardness is less than 100, good results cannot be obtained with respect to scratch hardness and the occurrence of dents caused by pencils and the like. On the other hand, when a material having a universal hardness of 200 or more is used, a thin paper or a flexible substrate such as a plastic sheet is used as the substrate, and the flexibility of the resin layer is lost. As a result, it is difficult to form them on a substrate. In addition, there is a problem that the surface resin layer is easily broken or cracked by impact.

The universal hardness of the surface resin layer 2 is as follows: Fisher scope H100V (manufactured by H. Fisher).
And can be determined by measuring with a Vickers pyramid indenter.

More specifically, a Vickers pyramid indenter is used as an indenter, and a load of 20 mN (Newton) is continuously applied from the surface of the resin layer 2 every 6 seconds until the surface resin layer 2 undergoes irreversible elastic deformation. The measurement is performed by measuring the load value at that time and the penetration depth of the indenter.

From the obtained maximum load value (F _max ) and maximum penetration depth (h _max ), HU = F (N) /26.43.
h ² [mm ² ] (where F (N) is the maximum value of the load, h (m
m) represents the maximum value of the penetration depth. ), The universal hardness (HU) can be calculated.

Regarding the universal hardness test, provisional DIN HU-1 and VDI / VDE standards 26
26 sheets ("Material Testing Technology", Vol. 43, N
o. 2, Sep. 1998, and the references cited in this reference. ).

The value of universal hardness (HU) is
It is preferable to measure and determine under such a condition that the penetration depth of the Vickers indenter into the measurement coating film (surface resin layer) is less than 1/10 of the measurement coating film. If the penetration depth exceeds 1/10 with respect to the measured coating film, good measurement results cannot be obtained because of the influence of the base of the measured coating film.

The resin used for the surface resin layer 2 includes
It is preferable to use a crosslinkable resin. As such a crosslinkable resin, a resin used as a conventionally known crosslinkable resin such as an ionizing radiation-curable resin or a thermosetting resin (including a room-temperature-curable resin and a two-component reactive resin) may be used. it can. Among these, ionizing radiation-curable resins tend to have a higher curing density and a higher universal hardness as the number of functional groups increases. Therefore,
It is possible to change the universal hardness after curing by changing the number of functional groups, it is easy to set a predetermined value, and it is preferable from the viewpoint of high-speed productivity and the like.

The crosslink density can be represented by, for example, the average molecular weight between crosslinks represented by the following formula (A).

[0040]

## EQU1 ## Average molecular weight between crosslinks = Total molecular weight / Number of crosslink points (A)

In the formula (A), the total molecular weight is Σ (the number of moles of each component × the molecular weight of each component), and the number of crosslinking points is Σ [Σ (the number of functional groups of each component −1) × 2｝ × the number of moles of each component]. The average molecular weight between crosslinks is
Usually it is in the range of 100-2000. Generally, the larger the average molecular weight between crosslinks, the better the flexibility.

The ionizing radiation-curable resin used as the crosslinkable resin is, specifically, a prepolymer, oligomer and / or oligomer having a polymerizable unsaturated bond or an epoxy group in the molecule.
Alternatively, a composition curable by ionizing radiation in which monomers are mixed at a predetermined ratio is used. Here, the ionizing radiation means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing or crosslinking a molecule.

When an ionizing radiation curable resin is used as the crosslinkable resin, the ionizing radiation source for curing is as follows:
As the ultraviolet light source, an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light, a metal halide lamp and the like are used. As the wavelength of the ultraviolet light, a wavelength range of 190 to 380 nm can be used.

As the electron beam source, various electron beam accelerators such as a Cockcroft-Walton type, a Van degraft type, a resonance transformer type, an insulating core transformer type, a linear type, a dynamitron type and a high frequency type can be used. . The electron beam used is 100 to 1000 keV, preferably 10 to 1000 keV.
Those having 0 to 300 keV are used. The irradiation amount of the electron beam is usually about 2 to 15 Mrad.

Examples of the above prepolymers and oligomers include unsaturated polyesters such as condensates of unsaturated dicarboxylic acids and polyhydric alcohols, methacrylates such as polyester methacrylate, polyether methacrylate, polyol methacrylate and melamine methacrylate, and polyester acrylates. Acrylates such as polyether acrylate, polyol acrylate, melamine acrylate, bisphenol type epoxy resin,
Cationic polymerization type epoxy compounds such as novolak type epoxy compounds are exemplified.

Examples of the urethane acrylate include a polyether-based urethane (meth) acrylate represented by the following formula 1 obtained by reacting a polyether diol with a diisocyanate.

[0047]

## STR1 ## ^{_{CH 2 = C (R 1)}} -COOCH 2 CH 2 O-
CONH-X-NHCOO - ^{[- CH (R 2) - (} CH
_{2) n} -O-] _{m -CONH-X-NHCOO-CH} 2
CH ₂ OCOC (R ¹ ) = CH ₂

(Wherein, R ¹ and R ² each represent a hydrogen atom or a methyl group, X represents a diisocyanate residue, n represents an integer of 1 to 3, and m represents an integer of 6 to 60.)

Examples of the diisocyanate used for the polyether-based urethane (meth) acrylate include, for example, isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, and tolylene diisocyanate. Examples of the polyether diol include polyoxypropylene glycol, polyoxyethylene glycol, and polyoxytetramethylene glycol having a molecular weight of 500 to 3,000.

Examples of monomers used for the ionizing radiation-curable resin include styrene monomers such as styrene and α-methylstyrene, methyl acrylate, acrylic acid 2
-Hydroxyhexyl, methoxyethyl acrylate, butoxyethyl acrylate, butyl acrylate, methoxybutyl acrylate, acrylates such as phenyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, methoxyethyl methacrylate, Methacrylic esters such as ethoxymethyl methacrylate, phenyl methacrylate, lauryl methacrylate, 2- (N, N-dimethylamino) ethyl acrylate, 2- (N, N-dimethylamino) methyl methacrylate, acrylic Acid-2- (N, N-dibenzylamino)
Methyl, acrylic acid-2- (N, N-diethylamino)
Substituted amino alcohol esters of unsaturated acids such as propyl,

Compounds such as unsaturated carboxylic acid amides such as acrylamide and methacrylamide, ethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, triethylene glycol diacrylate, and the like, diethylene glycol Diacrylate, propylene glycol diacrylate, trimethylolpropane triacrylate, dipentaerythritol acrylate, dipentaerythritol hexaacrylate, diethylene glycol methacrylate, propylene glycol methacrylate, trimethylolpropane trimethacrylate, dipentaerythritol methacrylate, dipentaerythritol hexamethacrylate, etc. Multifunctionalization Thing,

Alternatively, polythiol compounds having two or more thiol groups in the molecule, for example, trimethylolpropane thioglycolate, trimethylolpropane trithiopropylate, pentaerythritol tetrathioglycol and the like can be mentioned.

In selecting a monomer, if the flexibility of the cured product is required, the amount of the monomer may be reduced within a range that does not impair coating suitability, or a monofunctional or bifunctional acrylate monomer may be used. The structure has a low degree of crosslinking.
Further, when the abrasion resistance, heat resistance, solvent resistance, etc. of the cured product are required, the amount of the monomer is increased or a trifunctional or higher functional acrylate monomer is used as long as the coating suitability is not hindered. Thereby, a structure having a high crosslinking density can be obtained.
In addition, a monofunctional or bifunctional monomer and a trifunctional or higher functional monomer may be mixed to adjust coating aptitude and physical properties of a cured product.

The above-mentioned monofunctional acrylate monomer includes 2-hydroxyhexyl acrylate, phenoxyethyl acrylate and the like. Also, 2
Examples of the functional acrylate include ethylene glycol diacrylate and 1,6-hexanediol diacrylate, and examples of the trifunctional or higher acrylate include trimethylolpropane triacrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol hexaacrylate. Is mentioned.

Further, a non-ionizing radiation curable resin may be added to the ionizing radiation curable resin in order to adjust physical properties such as flexibility and surface hardness of the cured product. As such ionizing radiation non-curable resin, for example, urethane-based resin,
Cellulose resin, polyester resin, acrylic resin,
Thermosetting resins such as butyral-based resin, polyvinyl chloride-based resin, and polyvinyl acetate are used. In particular, use of cellulose-based resin, urethane-based resin, and butyral-based resin is preferable from the viewpoint of flexibility.

When irradiating ultraviolet rays to cure the ionizing radiation-curable resin having the above composition, acetophenones, benzophenols, Michler benzoyl benzoate, α-aminoxime ester may be used as a photopolymerization initiator. , Tetramethylthiuram monosulfite,
Thioxanthones, aromatic diazonium salts, aromatic sulfonium salts, metallocenes and the like are used. The addition amount of these photopolymerization initiators is about 0.1 to 10 parts by weight based on 100 parts by weight of the ionizing radiation-curable resin. Further, n-butylamine, triethylamine, tri-n-butylphosphine and the like can be further mixed and used as a photopolymerization accelerator (sensitizer).

The thermosetting resin used as the crosslinkable resin is generally a mixture of a low molecular weight monomer and a liquid having an appropriate viscosity as a raw material, and is cured to an insoluble and infusible state by heating. Refers to resin. In each case, the cured resin has a spatial network structure.

Examples of the thermosetting resin include urethane resin, acrylic resin, melamine resin, phenol resin, urea resin, xylene resin, diallyl phthalate resin, guanamine resin, unsaturated polyester resin, epoxy resin, alkyd resin, and the like. Silicon resin and the like can be mentioned.

Further, if necessary, a curing agent such as a crosslinking agent and a polymerization initiator, a polymerization accelerator and the like may be added and used. As such a curing agent, isocyanate or organic sulfonate is usually used for unsaturated polyester resin or polyurethane resin, amine is used for epoxy resin, radical reaction such as peroxide such as methyl ethyl ketone peroxide or diazoisobutyronitrile is started. The agent is used for unsaturated polyesters and the like.

As the isocyanate, a divalent or higher valent aliphatic or aromatic isocyanate can be used, but an aliphatic isocyanate is desirable from the viewpoint of prevention of discoloration of the thermosetting resin and weather resistance. For example, tolylene diisocyanate, xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate and the like are used.

Examples of the urethane resin include a two-component curable urethane resin and a one-component curable (moisture-curable) urethane resin.

The two-component curable urethane resin has a polyol as a main component, an isocyanate as a crosslinking agent (curing agent), and an equivalent ratio of hydroxyl group to isocyanate group of the polyol of 0.7.
It is a urethane resin compounded to be about 1.5. The polyol has two or more hydroxyl groups in the molecule, and examples thereof include polyethylene glycol, polypropylene glycol, acrylic polyol, polyester polyol, polyether polyol, polycarbonate polyol, and polyurethane polyol.

As the isocyanate, a polyvalent isocyanate having two or more isocyanate groups in the molecule is used. For example, aromatic isocyanates such as 2,4-tolylene diisocyanate, xylene diisocyanate, and 4,4'-diphenylmethane diisocyanate, fats such as 1,6-hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated diphenylmethane diisocyanate Group (or alicyclic) isocyanates and the like. Further, adducts of the above various isocyanates or trimers of tolylene diisocyanate can also be used.

The one-component curable urethane resin is a polymer formed from a composition containing a prepolymer having an isocyanate group at a molecular terminal as an essential component. The prepolymer generally has one isocyanate group at each terminal of the molecule.
And a polyisocyanate prepolymer having a main skeleton of a polycarbonate skeleton, a polyurethane skeleton, a polybutadiene skeleton, a polyester skeleton, or the like. The isocyanate groups react with each other due to moisture in the air to cause a chain elongation reaction. As a result, the isocyanate groups react to form biuret bonds and branch, and a cross-linking reaction forms a spatial network structure. .

The acrylic resin is mainly composed of acrylic acid (including methacrylic acid) and its derivatives such as acrylamide and acrylonitrile, and other monomers such as acrylic acid ester, ethylene and styrene. And a copolymer resin.

Examples of the acrylic resin include poly (meth) acrylate, poly (ethyl) acrylate, poly (butyl) acrylate, and methyl (meth) acrylate-butyl (meth) acrylate. Coalescing,
(Meth) acrylic acid such as methyl (meth) acrylate-2-hydroxyethyl (meth) acrylate, ethylene-methyl (meth) acrylate, and styrene-methyl (meth) acrylate Those composed of a homo- or copolymer containing an ester are exemplified. Here, (meth) acrylate is used in the meaning of acrylate and methacrylate.

The melamine resin is a resin obtained by subjecting methylol melamine obtained by reacting melamine and formaldehyde to polycondensation. Further, a melamine-based resin such as an acrylic melamine resin, a urea melamine resin, and a phenol melamine resin can also be used.

The phenol resin is a resin obtained by polycondensing a phenol such as phenol, cresol and xylenol with an aldehyde such as formaldehyde, acetaldehyde and furfural. Examples of the phenol resin include a novolak type phenol-formalin polymer and resol Phenol-formalin polymer, rubber phenol resin and the like.

The urea resin is a resin obtained by reacting urea (urea) with formaldehyde under neutral or basic conditions to obtain methylol urea, followed by dehydration or heat dehydration with an acid, and condensation polymerization. is there.

The xylene resin is obtained by subjecting o-xylene, m-xylene, p-xylene or a mixture thereof and formalin to polycondensation with strong acid to obtain methylol xylene, which is further added with phenol, cresol, A resin obtained by adding an organic acid, an amine or the like, and adding a meta-xylene sulfonic acid catalyst to carry out polycondensation.

The diallyl phthalate resin is a resin obtained by polymerizing diallyl phthalate or allyl isophthalate with a peroxide catalyst.

The unsaturated polyester resin is obtained by obtaining a condensation polymer of an unsaturated dibasic acid and a polyhydric alcohol, and then adding a crosslinking agent such as styrene monomer, vinyl acetate, acrylate, methacrylate and the like. It is a resin obtained by adding a catalyst to carry out vinyl polymerization.

As unsaturated dibasic acids, for example, maleic anhydride, fumaric acid, itaconic acid, citraconic acid and the like can be used, and as polyhydric alcohols, ethylene glycol, propylene glycol, diethylene glycol, pentaerythritol and the like can be used. it can.

The saturated alkyd resin is a polyester obtained by condensing a saturated organic acid with a polyhydric alcohol. Examples of the saturated alkyd resin include a glyphtal resin, a modified glyptal resin, an isophthalic acid resin, a fatty acid polyester, a polyethylene terephthalate, and a polycarbonate. In addition, amino alkyd resins can also be used.

The epoxy resin has two epoxy groups in the molecule.
At least one precondensate, amines, polyamides,
It is a resin obtained by adding and reacting a curing agent such as a polysulfide or an organic acid anhydride so that the equivalent ratio of the epoxy group to the active hydrogen of the amine is about 0.7 to 1.5. Examples of the epoxy resin include a bisphenol A condensation polymerization type epoxy resin, a novolak type epoxy resin, and an aliphatic epoxy resin.

The silicon resin is a polymer having silicon (Si) as a main chain, and a type having a silane chain (—Si—Si—Si—) in a molecule and a siloxane chain (—Si—O—Si).
There is a type having —O—) in the molecule. For example, polydimethylsiloxane, polymonomethylsiloxane, and the like can be given.

If necessary, a crosslinking agent may be added to the low molecular weight monomer, oligomer or prepolymer of the thermosetting resin.
A thermosetting resin composition (thermosetting resin liquid) to which a polymerization initiator, a solvent, a viscosity modifier, a modified pigment and the like are added is used as a raw material.

As a crosslinking agent, an organic sulfonate, an isocyanate, an amine, an organic peroxide, azobisisobutyronitrile and the like can be used.

Further, in order to impart abrasion resistance to the surface resin layer 2, if necessary, hard inorganic particles can be added. Examples of such inorganic particles include particles of alumina (such as α-alumina), silica, glass, silicon carbide, and diamond.

The shape of the inorganic particles includes a sphere, a polygon, a scale, an irregular shape, and the like. The average particle size of the inorganic particles is preferably about 3 to 30 μm. If the average particle size is too small, the effect of improving the abrasion resistance is poor, and if it is too large, the surface smoothness decreases. The amount of the inorganic particles to be added is about 5 to 40% by weight based on the total amount of the resin.

The coating composition containing a crosslinkable resin as the binder may further contain various additives as required. Examples of these additives include vinyl chloride-vinyl acetate copolymers, vinyl acetate resins, acrylic resins, thermoplastic resins such as cellulose resins, extenders made of fine powders such as calcium carbonate, barium sulfate, and silicone resins. Lubricants such as waxes, dyes, pigments, dispersants, coloring agents such as reactive silicones, and other paints such as known matting agents such as calcium carbonate barium sulfate and nylon beads, defoamers, leveling agents, and thixotropic agents. And additives usually added to inks and the like.

The surface resin layer 2 made of an ionizing radiation-curable resin was formed into an organic solution or a water-based emulsion (solubilized) of the mixture obtained by adding the above prepolymer or monomer and, if desired, the above-mentioned additives. It can be formed by applying the resin composition on the substrate 1 and irradiating the coated surface with ionizing radiation to cure the resin composition. The coating amount of the resin composition is preferably about 5 to 35 g / m ² (based on solid content).

As the solvent, those which are usually used for paints and inks can be used. For example, water, aromatic hydrocarbons such as toluene and xylene, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, and acetic acid Examples thereof include acetates such as ethyl, isopropyl acetate and amyl acetate, alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol, ethers such as dioxane, tetrahydrofuran and diisopropyl ether, and two or more of these.

Examples of the method for forming the surface resin layer 2 using the above-mentioned coating composition include a direct coating method in which the coating composition is directly transferred to the surface of the substrate, and a method in which the surface resin layer 2 is formed on the surface of the peelable substrate. A transfer coating method in which the layer is transferred to the surface of a substrate after being formed in advance is exemplified. Generally, substrate 1
When the coating composition does not penetrate as a material, or when a substrate having irregularities on the surface, and when uniformity of the coating film thickness is required, it is preferable to use the above transfer coating method. preferable.

Examples of the direct coating method include gravure coat, gravure reverse coat, gravure offset coat, spinner coat, roll coat, reverse roll coat, kiss coat, wheeler coat, dip coat, solid coat by silk screen, wire bar coat , A flow coat, a comma coat, a pouring coat, a brush coat, a spray coat and the like can be used. Of these, a gravure coat is preferred.

The transfer coating method is a method in which a coating film is once formed on a thin sheet (film) substrate, cross-linked and cured, and then coated on the surface of the substrate. A lamination method that adheres to a three-dimensional object together with the base material. Once a coating film and an adhesive layer are formed on a release support sheet once, a transfer sheet formed by crosslinking and curing the coating film is coated on the coating film side. Can be used, such as a transfer method in which only the support sheet is peeled off after bonding to the three-dimensional object. In addition,
As a method for forming a surface resin layer on a thin sheet substrate, various coating means similar to the above-described direct coating method can be used.

These methods are more specifically described in, for example, the following documents (a) to (d).
That is, (a) JP-B-2-42080, JP-B-4-42080
Injection molding simultaneous transfer method disclosed in Japanese Patent Application Laid-Open No. 19924/1992 or injection molding simultaneous lamination method disclosed in Japanese Patent Publication No. 50-19132.
No. 88214, Japanese Patent Application Laid-Open No. 5-57786, a vacuum forming simultaneous transfer method, or Japanese Patent Publication No. 56-57786.
No. 45768, a simultaneous vacuum forming laminating method, and (c) a simultaneous lapping method disclosed in JP-B-59-51900, JP-B-61-5895, and JP-B-3-2666. Transfer method or lapping simultaneous lamination method, (d) Jitsugakudai 15-3112
No. 2, Japanese Patent Publication No. 56-7866 and the like, and a V-cut simultaneous transfer method disclosed in Japanese Patent Publication No. 56-7866.

As one of the transfer coating methods, for example, when an ionizing radiation-curable resin is used as the crosslinkable resin, a method of sequentially performing the following steps (A) to (D) may be used. (Japanese Unexamined Patent Publication No. 2-26673)
Reference).

(A) a step of applying an uncured liquid ionizing radiation-curable resin composition to a non-absorbable and releasable synthetic resin sheet, and (B) a surface coated with the ionizing radiation-curable resin composition. Laminating so that is in contact with the substrate, (C)
A step of irradiating the coating film of the ionizing radiation-curable resin composition with ionizing radiation to crosslink and cure, and (D) a step of peeling and removing the synthetic resin sheet.

In the above step, when using a resin diluted with a solvent as the ionizing radiation-curable resin, a step of drying the solvent is performed between steps (A) and (B).
According to the above method, even in the case of a highly permeable material such as paper as the base material, the resin escapes to the back side of the base material,
It is possible to form a surface resin layer having a predetermined universal hardness value on the surface of the base material by reliably preventing the so-called "unevenness".

When a thermosetting resin is used as the crosslinkable resin, the coated surface may be heated after the application of the thermosetting resin composition in order to promote thermosetting. The heating time is, for example, usually 40 to 40 in the case of an isocyanate-curable unsaturated polyester resin or a polyurethane resin.
At 60 ° C. for about 1 to 5 days, and in the case of a polysiloxane resin, usually at 80 to 150 ° C. for about 1 to 300 minutes.

As shown in FIG. 2, for example, the decorative material 11 of the present invention is provided on the back side of the decorative sheet 10C of the present invention (that is, on the surface opposite to the surface on which the surface resin layer 2 is formed). 4
Is adhered via the adhesive layer 5 (or directly).

The material and shape of the substrate 4 are not particularly limited as long as the substrate 4 can be attached to the substrate 1. Examples of the shape of the substrate include a flat plate shape, a curved plate shape, and a polygonal column shape.

As the substrate material, for example, cedar, cypress, zelkova,
Gypsum concrete such as wood veneer, wood plywood, particle board, wood fiber board such as medium density fiber board (MDF), gypsum board, gypsum slag board etc. Board, asbestos slate board,
Cement board such as lightweight foam concrete board, hollow extruded cent board, pulp cement board, asbestos cement board, fiber cement board such as wood chip cement board, pottery, magnetism, stoneware, earthenware,
Ceramic plates such as glass and enamel, iron plates, galvanized steel plates, polyvinyl chloride sol coated steel plates, aluminum plates,
Metal plate such as copper plate, thermoplastic resin plate such as polyolefin resin plate, acrylic resin plate, ABS resin plate, polycarbonate plate, phenol resin plate, urea resin plate, unsaturated polyester plate, polyurethane resin plate, epoxy resin plate, melamine Thermosetting resin plate such as resin plate, phenolic resin, urea resin, unsaturated polyester resin, polyurethane resin, epoxy resin, melamine resin, diallyl phthalate resin, etc., glass fiber non-woven fabric, fabric, paper, other fibrous A so-called FRP plate or the like obtained by impregnating and curing a base material may be used. Further, the base material may be made of these laminates, and may be colored with a coloring agent.

The adhesive for bonding the decorative sheet 10C of the present invention to the substrate 4 is, for example, one composed of a vinyl acetate resin, a polyamide resin, a one- or two-part curable urethane resin, an epoxy resin, a polyester resin or the like. Can be used.

The decorative sheet and the decorative material of the present invention configured as described above are suitable for various uses. For example, it is useful for decoration of surfaces of buildings, vehicle ships, furniture, musical instruments, cabinets and the like, and decoration of packaging materials. Particularly preferably, the decorative sheet and the decorative material of the present invention are used by being installed in a place or a part where a scratch or a dent due to a projection is likely to occur. For example, as interior materials for buildings such as walls and ceilings, as surface materials for fittings such as doors, door frames, and window frames, as surface materials for building members such as rims and baseboards, and as surface materials for furniture such as chests and cabinets. Can be used.

[0097]

Next, the cosmetic material of the present invention will be described in more detail by way of examples. It is to be noted that the following is an example of the decorative material of the present invention, and the decorative material of the present invention is not limited within the scope of the present invention, and includes a base material, a substrate, a resin constituting a surface resin layer, and the like. The design of the type, the formation method of each layer, the layer configuration, and the like can be appropriately changed.

Example 1 A resin composition having the following composition (A) was applied to a surface of a decorative paper having a basis weight of 50 g / m ² on which a wood grain pattern was printed, at a rate of 25 g / m ² (when dried), and an electron beam was irradiated at 5 Mrad. (175 kV) to form a surface resin layer on the surface of the decorative paper,
A decorative sheet of Example 1 was produced.

(Resin Composition A) Urethane acrylate monomer composition having 3 functional groups [CH ₂ ＣＨCHCOO (CH ₂ CH ₂ O) CH ₂ ] ₃ —CCH ₂ CH ₃ : 63 parts by weight Reactive dispersant (reactive phosphorus Acid ester type quaternary ammonium salt): 1.6 parts by weight Particle size 2 μm silica: 9.4 parts by weight Solvent (ethyl acetate): 26 parts by weight

Example 2 A resin composition having the following composition (B) was applied to a surface of a decorative paper having a basis weight of 50 g / m ² on which a wood grain pattern was printed, at a rate of 25 g / m ² (when dried), and an electron beam of 5 Mrad was applied. (175 kV) to form a surface resin layer on the surface of the decorative paper,
A decorative sheet of Example 2 was produced.

(Resin Composition B) Urethane acrylate monomer composition having 5.5 functional groups (CH ₂ ＣＨCHCOCH ₂ ) ₃ —CCH ₂ OCH ₂ C— (CH ₂ OCOCHＣＨCH ₂ ) ₃ and (CH ₂ ＣＨCHCOOCH ₂₎ ) _3- CCH ₂ OCH ₂ —C (CH ₂ OCOCH ＝ CH ₂ ) ₂ (CH ₂ OCOCH ₂ OH) mixture: 63 parts by weight Reactive dispersant (reactive phosphate ester type quaternary ammonium salt): 1 6.6 parts by weight Particle size 2 μm silica: 9.4 parts by weight Solvent (ethyl acetate): 26 parts by weight

Example 3 A resin composition having the following composition (C) was applied on a surface of a decorative paper having a basis weight of 50 g / m ² on which a wood grain pattern was printed, at a rate of 25 g / m ² (when dried), and an electron beam was irradiated at 5 Mrad. (175 kV) to form a surface resin layer on the surface of the decorative paper,
A decorative sheet of Example 3 was produced.

(Resin Composition C) Urethane acrylate monomer composition having 6 functional groups (CH ₂ ＣＨCHCOOCH ₂ ) ₃ —CCH ₂ OCH ₂ C— (CH ₂ OCOCH CH ₂ ) ₃ : 63 parts by weight Reactive dispersant ( Reactive phosphate ester type quaternary ammonium salt): 1.6 parts by weight Particle size 2 μm silica: 9.4 parts by weight Solvent (ethyl acetate): 26 parts by weight

Comparative Example 1 A resin composition having the following composition (D) was applied at 25 g / m ² (when dried) on the surface of a decorative paper having a wood grain pattern printed thereon and having a basis weight of 50 g / m ² , and an electron beam of 5 Mrad was applied. (175 kV) to form a surface resin layer on the surface of the decorative paper,
A decorative sheet of Comparative Example 1 was produced.

(Resin Composition D) Urethane acrylate monomer composition having a functional group number of 2.5 [CH ₂ CHCOO (CH ₂ CH ₂ O) CH ₂ ] ₃ -CCH ₂ CH ₃ and [CH ₂ ＣＨCHCOO (CH ₂ CH) ₂ O) CH _{2] 2 [(CH 2 OH) COO (CH} 2 CH 2 O) CH 2 ] -CCH mixture of ₂ CH _3: 63 parts by weight reactive dispersant (reactive phosphate ester type quaternary ammonium Salt): 1.6 parts by weight Particle size 2 μm silica: 9.4 parts by weight Solvent (ethyl acetate): 26 parts by weight

Comparative Example 2 A two-part curable urethane varnish was coated with a gravure coat on the surface of a decorative paper having a basis weight of 50 g / m ² on which a wood grain pattern was printed.
The decorative sheet of Comparative Example 2 was produced by applying 5 g / m ² (at the time of drying) to form a surface resin layer made of a two-component curable urethane resin on the surface of the decorative paper.

Comparative Example 3 A resin composition having the following composition (E) was applied on the surface of decorative paper having a basis weight of 50 g / m ² on which a wood grain pattern was printed at a rate of 25 g / m ² (when dried).
Coating was performed and electron beam irradiation was performed at 5 Mrad (175 kV). However, cracks occurred on the coat surface and a flat coat film (surface resin layer) could not be obtained. A resin composition having the following composition (E) was applied to the surface of the glass substrate at a rate of 25 g / m ² (when dried), and the surface of the surface resin layer was irradiated with an electron beam at 5 Mrad (175 kV).
The value of universal hardness was 250 when measured by 00V (manufactured by H. Fisher).

(Resin Composition E) Tricyclodecane dimethanol diacrylate: 63 parts by weight Reactive dispersant (reactive phosphate ester type quaternary ammonium salt): 1.6 parts by weight Particle size 2 μm silica: 9.4 Parts by weight Solvent (ethyl acetate): 26 parts by weight

Measurement of Universal Hardness Value The value of the universal hardness of the surface resin layer surface of each decorative sheet of the working examples and comparative examples (excluding Comparative Example 3) was measured under the following conditions using a Fisher scope H100V (H. Fish).
er).

That is, a Vickers pyramid indenter is used as an indenter, and a load of 20 mN (Newton) is continuously applied from the surface resin layer surface every 6 seconds until the surface resin layer undergoes irreversible elastic deformation. HU = F (N) /26.43 from the obtained maximum load value (F _max ) and maximum penetration depth (h _max ).
h ² [mm ² ] (where F (N) is the maximum value of the load, h (m
m) represents the maximum value of the penetration depth. ) Was used to calculate the value of universal hardness. The measurement results are shown in Table 1 below.

[0111]

[Table 1]

From Table 1, it can be seen that the values of the universal hardness of the surface resin layer of the decorative sheet of the examples are 70-200.
The value of the universal hardness of the surface resin layer of the decorative sheets of Comparative Examples 1 and 2 was less than 70.

[0113] Using each decorative material obtained in the scratched hardness and pencil dent Test Examples and Comparative Examples (excluding Comparative Example 3), were subjected to the following scratch hardness test and pencil hardness test.

(1) Pencil hardness test A pencil dent test according to JIS K5400 was performed. That is, a pencil lead having a hardness of 9H was placed on the surface of the decorative material while applying a load of 500 g, and the depression was measured by a surface roughness meter. The test results are shown in Table 2 below.

(2) Scratch hardness test A scratch hardness test based on the JAS special plywood scratch hardness B test was performed. That is, the surface of the cosmetic material was scratched with a diamond needle while applying a load of 200 g, and then the depth of the scratch on the surface of the cosmetic material was measured using a two-dimensional surface roughness meter (manufactured by Kosaka Laboratory Co., Ltd.). It was measured. The test results are shown in Table 2 below.

[0116]

[Table 2]

Table 2 shows that the decorative materials of Examples 1 to 3 have excellent scratch hardness and pencil dent resistance as compared with the decorative materials of Comparative Examples 1 and 2.

[0118]

As described above, the decorative sheet of the first invention of the present application has a resin layer having excellent surface hardness on the surface, that is, a surface hardness (value of universal hardness) of 100 to 200. Has excellent scratch resistance, and
Even when pressed from the surface of the decorative sheet with a pencil or the like, dents are unlikely to occur.

The decorative material of the second invention is obtained by laminating the decorative sheet of the first invention directly on a substrate or via another layer (such as an adhesive layer). It has excellent scratch resistance similarly to the decorative sheet of the invention of the above-mentioned invention, and hardly causes dents even when pressed from the surface of the decorative material with a pencil or the like.

[Brief description of the drawings]

FIG. 1 is a sectional view of a decorative sheet of the present invention.

FIG. 2 is a sectional view of the decorative material of the present invention.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Base material layer, 2 ... Surface resin layer, 3 ... Picture layer, 4 ... Substrate,
5 ... adhesive layer

 ──────────────────────────────────────────────────の Continued on the front page F term (reference) 4F100 AA20B AK01B AK25B AK51B AT00A BA02 DG10A EH462 EJ532 GB07 GB08 GB81 HB01A HB31A JK12B JK14 JL06 YY00B

Claims (4)

[Claims] 1. A decorative sheet comprising: a base material layer; and a resin layer having a surface hardness (value of universal hardness) of 100 to 200 on the base material layer. 2. The decorative sheet according to claim 1, wherein the surface hardness (a value of universal hardness) of the base material layer is 70 to 200. 3. A backing side of a decorative sheet having a base material layer and a resin layer having a surface hardness (value of universal hardness) of 100 to 200 on the base material layer, directly or through another layer. A decorative material with a substrate attached. 4. The decorative material according to claim 3, wherein said base material layer has a surface hardness (a value of universal hardness) of 70 to 200.