JPH10166536A - Film for doubling specification decorative plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film for a doubling specification decorative plate having no environmental stain even at the time of incinerating by remarkably improving V-cut processability, notch resistance and adhesive properties. SOLUTION: The film for doubling specification decorative plate comprises a polyester film used to form an inner film layer of the plate obtained by sequentially forming at least an adhesive layer, the inner film layer, a design print layer, an adhesive layer and an outer film layer at least on a base material and provided with a coating layer at least on one surface in such a manner that the polyester film has longitudinal and lateral tensile elastic moduli of 600kg/mm<2> or less.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a doubling specification decorative film, and more particularly, to a doubling specification decorative film which is made of a coated polyester film having specific physical properties and has excellent compatibility with the decorative plate. is there.

[0002]

2. Description of the Related Art A decorative board formed by sequentially forming an adhesive layer, a film layer, and a pattern printing layer on a base material is called a single-layer face printing decorative board. A decorative board formed by sequentially forming an inner film layer, a pattern printing layer, an adhesive layer, and an outer film layer is called a doubling specification decorative board. In addition, as a base material, a wood board (plywood, particle board, etc.), an inorganic board, a steel plate, or the like is appropriately used. The doubling specification decorative board can protect the pattern printing layer by the outer film layer, and can use the transparent film for the formation of the outer film layer to show the luxury of the pattern printing, Is used for a higher-grade use than a single-layer surface-printed decorative board because the film forming the outer film layer can be embossed or the like to give a three-dimensional effect of woodgrain.

[0003] A doubling specification decorative board is used for decorating surfaces of various kinds of furniture, doors and the like, taking advantage of the above-mentioned characteristics. And especially in the case of furniture or doors mainly made of wood-based boards, the edges are finished so that the planes intersect at right angles to form corners, and the corners are formed by bending a decorative board. It is formed. In bending a decorative board, a method called V-shaped cutting is generally employed. In this processing method, a V-shaped cut having a depth slightly smaller than the thickness of the base material is formed on the surface of the base material of the decorative board, and the cut is made so that the cut is located inside. for that reason,
The suitability of the decorative board for bending is strongly dependent on the suitability of the film used for the decorative board for bending. In particular, 2
In the case of a doubling specification decorative board using two films,
A film that is excellent in bending workability is required as compared with a single-layer facing printing decorative board that uses only one film.
If this bending workability is poor, in the case of V-shaped cut processing,
The folded shape of the decorative board returns to its original shape without being fixed,
In this case, a base material and a decorative sheet (a sheet composed of an inner film layer, a pattern printing layer, an adhesive layer, and an outer film layer)
Peels off, and the appearance and design are impaired. Therefore, a doubling specification decorative board is required to have a film excellent in V-shaped cut workability.

[0004] Further, since the decorative board is used as a surface material for furniture, doors and the like, it is inevitable that the decorative board comes into contact with, for example, the tip of a cleaning tool or a nail on a limb. When the self-healing property (restoring property) of the film attached to the base material is poor, a dent is left on the decorative plate due to the above-mentioned contact, and the high printability of the pattern printing layer cannot be maintained. If the attached film does not have an appropriate strength, the plastic deformation at the time of the above-mentioned contact becomes large and the film cannot be restored. Therefore, in the doubling specification decorative board, a film having excellent dent recovery (dent resistance) is required as a film adhered to the substrate as a characteristic combining the above-mentioned self-healing property and appropriate strength. Is done.

Heretofore, a vinyl chloride resin film has been most commonly used as a decorative film, and is often used for a doubling type decorative film. A vinyl chloride resin film is easily deformed, and has advantages such as excellent suitability for V-shaped cutting. On the other hand, lack of appropriate strength results in poor dent resistance, and the film thickness must be sufficiently thick. There is a problem. In addition, a vinyl chloride resin film is strongly demanded as a film for a decorative board in place of the vinyl chloride resin film because of environmental problems at the time of incineration. In addition, when a vinyl chloride resin film is bonded to a base material, a stabilizer or a plasticizer incorporated in the vinyl chloride resin easily migrates to the adhesive layer to cause poor adhesion. In addition, a vinyl chloride resin film originally has poor thermal dimensional stability and large expansion and contraction due to heat, and therefore easily causes wrinkles on the decorative board surface.

Meanwhile, as a doubling specification decorative board using a film other than a vinyl chloride resin film, a decorative board using a laminate of a polyolefin synthetic paper and a flexible polyester film (Japanese Patent Laid-Open No. 7-17005), Decorative board using a laminate of a thermoplastic transparent elastomer film selected from the group consisting of styrene, olefin, urethane, fluororubber, polyamide, and ester and a polyolefin resin (JP-A-6-7983)
No. 0) has been proposed. However, decorative panels using a polyolefin resin film as described above are unsuitable for use in furniture and building interior materials, for example, because they generate a large amount of heat due to combustion in a fire, and use a film other than a polyolefin resin film. There is a need for a decorative veneer.

[0007] Polyester films are advantageous because they do not generate a large amount of heat during combustion, and have less environmental problems during combustion. Also, it has excellent thermal dimensional stability. However, the ordinary V-shaped polyester film is not suitable for the V-cut processing. Also, the bonding with the plywood is often insufficient. Similarly, the adhesion to the pattern printing layer is often insufficient. This is due to poor adhesion between the polyester film and the adhesive or between the polyester film and the printing layer. That is, there has been no doubling-type decorative board which is excellent in V-shape cutting workability, dent resistance, and adhesion, and has little environmental pollution during combustion.

[0008]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances, and an object of the present invention is to significantly improve V-cut workability, dent resistance, and adhesiveness, and to reduce the likelihood of incineration. An object of the present invention is to provide a doubling specification decorative film without environmental pollution.

[0009]

That is, the gist of the present invention is that at least an adhesive layer, an inner film layer,
A polyester film having a coating layer provided on at least one surface, which is used for forming an inner film layer of a doubling specification decorative plate in which a picture printing layer, an adhesive layer, and an outer film layer are sequentially formed. And a polyester film having a tensile modulus in the transverse direction of 600 kg / mm ² or less.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The polyester for the base polyester film referred to in the present invention refers to a polymer containing an ester group obtained by polycondensation from a dicarboxylic acid and a diol or a hydroxycarboxylic acid. Examples of the dicarboxylic acid include terephthalic acid, isophthalic acid, adipic acid, azelaic acid, sebacic acid, 2,6-naphthalenedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid. Examples of the diol include ethylene glycol, 1,4 -Butanediol,
Examples include diethylene glycol, triethylene glycol, neopentyl glycol, 1,4-cyclohexanedimethanol, polyethylene glycol, and the like. As the hydroxycarboxylic acid, p-hydroxybenzoic acid, 6-
And hydroxy-2-naphthoic acid.

Representative polyesters include polyethylene terephthalate and polyethylene-2,6-naphthalate. Polyester used in the present invention,
It may be a homopolymer or a copolymer obtained by copolymerizing the third component. The doubling specification decorative film of the present invention is made of the polyester as described above, and therefore has excellent dent recovery (dent resistance) as its own characteristics. The polyester used in the present invention has a tensile modulus in the longitudinal and transverse directions of 600 kg / mm ² from the viewpoint of improving the V-cut workability.
It is important that: The tensile modulus is preferably in the range of 190 to 550 kg / mm ² , more preferably 190 to 500 kg / mm ² .

When the tensile elastic modulus exceeds 600 kg / mm ² , even if a V-shaped cutting process is performed, it is easy to return to the shape before processing due to elastic deformation, and a stable shape can be maintained for a long period of time. Can not. The above tensile modulus is 1
When it is less than 90 kg / mm ² , wrinkles and the like are generated due to tension at the time of sticking to a substrate or the like, and the decorative plate surface tends to be wavy. The thickness of the film of the present invention is selected from the range of usually 5 to 100 μm, preferably 12 to 80 μm. If the film thickness is less than 5 μm,
The degree to which the impact from the surface of the decorative board acts on the base material increases. As a result, particularly when the hardness of the surface of the base material is high, the degree of damage to the clear layer and the printed layer on the surface of the decorative board having a lower hardness than the base material increases. The film thickness is 100
If it exceeds μm, the force required for bending increases, and it is difficult to maintain the shape after processing.

The film of the present invention preferably has concealing properties from the viewpoint of maintaining high designability of the pattern printing applied to the film surface without being affected by the color tone of the substrate. The hiding index can be defined by the transmission density of the film. In the present invention, the transmission density of the film is usually 0.1.
It is set to 1 or more, preferably 0.5 or more. When the transmission density is less than 0.1, the concealing property is insufficient, and the color tone of the pattern printing of the decorative sheet is greatly affected by the color tone of the surface of the base material. As particles used for imparting hiding properties,
Examples thereof include titanium dioxide, barium sulfate, calcium carbonate, and carbon black. Then, in order to improve the dispersibility in the polyester and the weather resistance of the decorative board, particles that have been surface-treated with an oxide such as aluminum, silicon, and zinc and / or an organic compound may be used.

When the color tone of a wooden material can be expressed by a doubling specification decorative board, the polyester film b
Preferably, the value is -5.0 or more. b value is -5.0
If it is less than 3, the bluish tone increases in the surface tone of the decorative board, and the appearance becomes cold, so that the warm tone inherent to the wood-based material is impaired. The following dyes and / or pigments can be used in the film of the present invention. Dyes include natural dyes such as indigo (indigo), azo dyes, anthraquinone dyes, indigoid dyes, sulfur dyes, triphenylmethane dyes, pyrazolone dyes, stilbene dyes, diphenylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes, quinone imine dyes (For example, azine dye, oxazine dye, thiazine dye), thiazole dye, methine dye, nitro dye,
Synthetic dyes such as nitroso dyes and cyanine dyes are exemplified.

Examples of the pigment include phthalocyanine-based, dioxazine-based, anthraquinone-based organic pigments, titanium white, zinc white, lead white, carbon black, red iron, red,
Cadmium red, graphite, ultramarine, cobalt blue, cobalt purple,
Inorganic pigments such as zinc chromate are exemplified. In the present invention, the method for blending the particles, the dye, and the like with the polyester is not particularly limited, and a known method can be employed. The doubling-type decorative polyester film of the present invention has a coating layer on at least one surface. The coating agent for the coating liquid can be arbitrarily selected from known coating agents, but from the viewpoint of adhesiveness, is selected from the group of polyester resin, acrylic resin, polyurethane resin, amino resin, epoxy resin, oxazoline resin, and coupling agent. Preferred are at least one compound.

The polycarboxylic acids constituting the above polyester resin include terephthalic acid, isophthalic acid, orthophthalic acid, phthalic acid, 4,4'-diphenyldicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6- Naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2-potassium sulfoterephthalic acid, 5-sodium sulfoisophthalic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, glutaric acid, succinic acid, trimellitic acid, Examples include trimesic acid, trimellitic anhydride, phthalic anhydride, p-hydroxybenzoic acid, monopotassium trimellitate, and ester-forming derivatives thereof.

The polyvalent hydroxy compound constituting the polyester resin includes ethylene glycol, 1,2
-Propylene glycol, 1,3-propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 2-methyl-1,5-
Pentanediol, neopentyl glycol, 1,4-
Cyclohexane dimethanol, p-xylylene glycol, bisphenol A-ethylene glycol adduct, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polytetramethylene oxide glycol, dimethylolpropionic acid, glycerin,
Trimethylolpropane, sodium dimethylolethylsulfonate, potassium dimethylolpropionate and the like.

A polyester resin can be synthesized by an ordinary polycondensation reaction between the above-mentioned polyvalent carboxylic acid and polyvalent hydroxy compound. In addition, in addition to the above,
A composite polymer having a polyester component such as a so-called acrylic graft polyester described in 65633 can also be used as the polyester resin.
The acrylic resin used in the present invention is a polymer composed of a polymerizable monomer having a carbon-carbon double bond, such as an acrylic or methacrylic monomer. These may be either homopolymers or copolymers. In addition, copolymers of these polymers and other polymers can also be used, and as other polymers,
For example, polyester, polyurethane, epoxy resin and the like can be mentioned. The copolymer may be a block copolymer, a graft copolymer, or the like.

Further, a polymer (a mixture of polymers in some cases) obtained by polymerizing a polymerizable monomer having a carbon-carbon double bond in a polyester solution or a polyester dispersion, a carbon solution in a polyurethane solution or a polyurethane dispersion. A polymer obtained by polymerizing a polymerizable monomer having a carbon double bond (in some cases, a mixture of polymers), polymerizing a polymerizable monomer having a carbon-carbon double bond in another polymer solution or dispersion. The resulting polymer (optionally a polymer mixture) may also be used.

Representative examples of the polymerizable monomer having a carbon-carbon double bond include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid,
Various carboxyl group-containing monomers such as citraconic acid and salts thereof, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, monobutylhydrokilmfumarate, Various hydroxyl-containing monomers such as monobutylhydroxyitaconate, and various kinds of (such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate Various nitrogen-containing vinyl monomers such as (meth) acrylic esters, (meth) acrylamide, diacetone acrylamide, N-methylolacrylamide or (meth) acrylonitrile, styrene, α-methylstyrene, Nylbenzene, various styrene derivatives such as vinyltoluene, vinyl acetate, various vinyl esters such as vinyl propionate, γ-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, Chisso Corporation's “Silaprene FM- 07 "
(Methacryloylo silicon macromer), various silicon-containing polymerizable monomers, phosphorus-containing vinyl monomers, vinyl chloride, viridene chloride, vinyl fluoride, vinylidene fluoride, trifluorochloroethylene, tetrafluoroethylene, chloro Various vinyl halides such as trifluoroethylene and hexafluoropropylene,
Examples include various conjugated dienes such as butadiene.

Examples of the polymerization method of the acrylic monomer include a method of mixing an organic solvent, a monomer and a polymerization initiator and heating the mixture under stirring conditions, and a method of heating and stirring the organic solvent while mixing the monomer and the polymerization initiator. A method of polymerizing by dropping an agent, a method of polymerizing at a high pressure using an autoclave, Using water instead of an organic solvent, and polymerizing in an emulsified form or a suspended form by using a surfactant as necessary. And the like. Examples of the polymerization initiator include inorganic peroxides such as ammonium persulfate and hydrogen peroxide, acyl peroxides such as benzoyl peroxide, tertiary butyl hydroperoxide, and p-menthane hydroperoxide. Various alkyl hydroperoxides, such as di-tert-butyl peroxide, various dialkyl peroxides, azobisisobutyronitrile, azodi-tert-
Various azo compounds such as butane are exemplified.

The above-mentioned inorganic or organic peroxide can be used as a so-called redox catalyst in combination with a reducing agent. In this case, each component
One compound may be used, or a plurality of compounds may be used in combination. As the reducing agent, for example, organic amines, L-ascorbic acid, L-sorbic acid, cobalt naphthenate, cobalt octenoate, iron naphthenate, iron octenoate and the like are used. Examples of the polyurethane resin used in the present invention include, for example, Japanese Patent Publication No. 42-24194.
JP, JP-B-46-7720, JP-B-46-1
0193, JP-B-49-37839, JP-A-50-123197, JP-A-53-12605
No. 8, JP-A-54-138098, and known polyurethane resins or derivatives thereof. Examples of such a derivative include urethane prepolymers having an isocyanate terminal and blocks thereof (sometimes called blocked isocyanates).

Examples of the polyisocyanate include tolylene diisocyanate, phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, 4,4'-dicyclohexyl methane diisocyanate, and isophorone diisocyanate.
Examples of the polyol include polyether polyols such as polyoxyethylene glycol, polyoxypropylene glycol, and polyoxytetramethylene glycol, polyethylene adipates, polyethylene-butylene adipates, polyester polyols such as polycaprolactone, acrylic polyols, castor oil, and the like. Is mentioned. Usually, a polyol having a molecular weight of 300 to 2000 is used.

Examples of the chain extender or crosslinking agent include ethylene glycol, propylene glycol, butanediol, diethylene glycol, trimethylolpropane,
Hydrazine, ethylenediamine, diethylenetriamine, 4,4'-diaminodiphenylmethane, 4,4'-
Diaminodicyclohexylmethane, water and the like. In order to improve the solubility in a solvent containing water as a main medium, the above-mentioned polyurethane resin has an anionic substituent, for example, a —SO ₃ H group, a —OSO ₃ H group, and a —COO.
H groups and their ammonium salts, alkali metal salts,
It preferably has an alkaline earth metal salt. Examples of the method for producing such a polyurethane resin include the following methods (1) to (3).

(1) polyisocyanate, polyol,
A method using a compound having an anionic substituent as a chain extender or the like. For example, a polyisocyanate having an anionic substituent can be obtained by a method of sulfonating an aromatic isocyanate compound. Further, an isocyanate compound having a sulfate salt or diaminocarboxylate of an amino alcohol can also be used. (2) A method of reacting a compound having an anionic substituent with an unreacted isocyanate group of the produced polyurethane. As the compound having an anionic substituent, examples of the anionic substituent include bisulfite, aminosulfonic acid and salts thereof, aminocarboxylic acid and salts thereof, sulfate esters of amino alcohols and salts thereof, and hydroxyacetic acid. And compounds having a salt thereof and the like. (3) Active hydrogen-containing groups (OH, COOH) of polyurethane
Etc.) and a specific compound. Specific compounds include, for example, dicarboxylic anhydride, tetracarboxylic anhydride, sultone, lactone, epoxy carboxylic acid, epoxy sulfonic acid, 2,4-dioxo-oxazolidin, isatoic anhydride, hoston and the like. Can be. Further, a 3- to 7-membered cyclic compound having a salt type group such as carbyl sulfate or a group capable of forming a salt after ring opening can be used.

The amino resin used in the present invention is a polymer, a prepolymer or a derivative thereof formed by reacting an amino compound or an amide compound with an aldehyde. Examples of the amino compound or amide compound serving as a skeleton include, for example, urea, thiourea, ethylene urea,
Dihydroxyethylene urea, triazones, melamine,
Isomeramine, benzoguanamine, glycoluril,
Acetoguanamine, guanylmelamine, dicyandiamide, dicyandiamide homopolymer, dicyandiamide copolymer, aminoacryl ((meth) acrylic monomer containing amino group), aminoacryl homopolymer, aminoacryl copolymer, Aniline and the like. Examples of the above aldehyde compound include formaldehyde and glyoxal.

Examples of the polymer or prepolymer formed by the reaction of an amino compound or an amide compound with an aldehyde include monomethylol urea, dimethylol urea,
Trimethylol urea, tetramethylol urea, methylene urea, methylol methylene urea, methylol methylene urea trimer, monomethylol melamine, dimethylol melamine, trimethylol melamine, tetramethylol melamine, pentamethylol melamine, hexamethylol melamine, monomethylol benzoguanamine, Dimethylol benzoguanamine, trimethylol benzoguanamine, tetramethylol benzoguanamine, monomethylol glycoluril, dimethylol glycoluril,
Examples include trimethylol glycoluril, tetramethylolglycoluril, a homopolymer of N-methylolacrylamide, and a copolymer of N-methylolacrylamide. Some of these compounds may be referred to as methylolated amino resins.

Examples of the derivative of the above polymer or prepolymer include monomethoxymethylurea, monobutoxymethylurea, dimethoxymethylurea, dibutoxymethylurea, trimethoxymethylurea, and the like.
Tributoxymethylurea, tetramethoxymethylurea,
Tetrabutoxymethyl urea, monomethoxymethyl melamine, monobutoxymethylmelamine, dimethoxymethylmelamine, dibutoxymethylmelamine, trimethoxymethylmelamine, tributoxymethylmelamine, tetramethoxymethylmelamine, tetrabutoxymethylmelamine,
Pentamethoxymethyl melamine, pentabutoxymethylmelamine, hexamethylmelamine, hexabutoxymethylmelamine, monomethoxymethylbenzoguanamine, monobutoxymethylbenzoguanamine, dimethoxymethylbenzoguanamine, dibutoxymethylmelamine, trimethoxymethylbenzoguanamine, tributoxymethylbenzoguanamine, Tetramethoxymethylbenzoguanamine, tetrabutoxymethylbenzoguanamine, monomethoxymethylglycoluril, monobutoxymethylglycoluril, dimethoxymethylglycoluril, dibutoxymethylglycoluril, trimethoxymethylglycoluril, tributoxymethylglycoluril, tetramethoxymethylglycoluril , Tetrabutoxymethylgly Ruuriru, homopolymers of N- methoxymethyl acrylamide, N- copolymer of methoxymethyl acrylamide, N- homopolymers of butoxymethyl acrylamide, and a copolymer of N- butoxymethyl acrylamide. Some of these compounds are
It is sometimes called an alkyl etherified amino resin.

In addition, compounds having an intermediate structure between the above compounds are industrially included in the amino resin, but of course, these are included in the amino resin used in the present invention. Examples of commercially available amino resins include urea resins, melamine resins, benzoguanamine resins, glycoluril resins, co-condensates thereof, co-condensates of these with other resins (eg, alkyd resins) (amino alkyd resins), and the like. Is mentioned. For example, one example of an industrially produced melamine resin is produced as a co-condensate of melamine-formaldehyde-methanol (or butanol). Therefore, various melamine resin components are formed depending on the ratio of melamine, formaldehyde, and methanol (or butanol). Further, methanol and butanol may be used in combination.

The self-curing reaction of the amino resin and the reaction with other functional groups are promoted by heat and a catalyst. As the catalyst, an organic acid or an inorganic acid is effective, and specific examples thereof include:
Phosphoric acid, hydrochloric acid, sulfuric acid, methanesulfonic acid, paratoluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, dinonylnaphthalenedisulfonic acid,
These include partial salts thereof, their partial esters, their ammonium salts, their amine salts and the like. The epoxy resin used in the present invention is a compound containing an epoxy group in a molecule, a prepolymer and a cured product thereof. A representative example is a condensate of epichlorohydrin and bisphenol A. In particular, a reaction product of a low molecular weight polyol with epichlorohydrin gives an epoxy resin having excellent water solubility. The epoxy resin used in the present invention is not necessarily required to be water-soluble, and may be an aqueous dispersion type or a solvent-soluble type.

Specific examples of the epoxy resin used in the present invention include sorbitol polyglycidyl ether, sorbitan polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, triglycidyl tris (2 -Hydroxyethyl) isocyanurate, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether,
Resorcin diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polytetramethylene glycol Examples include diglycidyl ether, diglycidyl ether of adipic acid, diglycidyl ether of orthophthalic acid, hydroglycone diglycidyl ether, diglycidyl ether of bisphenol S, glycidyl terephthalate, and dibromoneopentyl glycol diglycidyl ether.

Commercially available epoxy resin emulsions include, for example, "Denacol" manufactured by Nagase Kasei Kogyo Co., Ltd.
EM-125 "," Denacol EX-1101 ",
"Denacol EX-1102", "Denacol EX"
-1103 "and the like. The oxazoline resin (polymer of the oxazoline compound) used in the present invention is a polymer containing an oxazoline compound as at least one of the raw material monomers or a polymer having at least one oxazoline ring in the produced polymer. Examples of the oxazoline compound include 2-oxazoline, 3-oxazoline, and 4-oxazoline compounds, and among these, a 2-oxazoline compound that is highly reactive and practically used industrially is preferable.

Vinyl oxazolines include azoisobutyronitrile (AIBN) and benzoyl peroxide (B
PO), the polymer easily undergoes radical polymerization to produce a polymer having an oxazoline ring in a side chain. Vinyl oxazolines produce similar poly (vinyl oxazolines) by anionic polymerization using n-butyllithium or the like as a catalyst. On the other hand, under a cationic polymerization catalyst such as an oxazolium salt or trifluoromethanesulfonic acid, a polymer having (meth) acrylamide in a side chain is produced. The polymer having an oxazoline ring in the side chain or the above-described polymer having a (meth) acryloyl group in the side chain can crosslink the polymer by a reaction of the side chain. Of course, in the above polymerization, a copolymer having no oxazoline ring may be introduced to form a copolymer. Examples of the coupling agent used in the present invention include silicon-based coupling agents, titanium-based coupling agents, zirconium-based coupling agents, aluminum-based coupling agents, zirconium-aluminum-based coupling agents, and derivatives thereof. No.

Examples of the silicon-based coupling agent include so-called silane coupling agents and alkyl (phenyl)
Alkoxysilanes, alkyl silicates (alkoxysilanes), chlorosilanes and the like can be mentioned, and among these, a silane coupling agent is preferable. The term silane coupling agent refers to a silane compound having an organic functional group bonded to a silicon atom via a carbon atom (carbon functional silane), especially an organic functional group having reactivity and affinity for an organic polymer. Is a general term for compounds containing In other words, a reactive functional group represented by an amino group, an epoxy group, a vinyl group, a methacryl group, and a mercapto group, and a hydrolyzable group represented by an alkoxy group (for example, a methoxy group, an ethoxy group, and an isopropenoxy group) Are silane compounds each bonded to a silicon atom.

Specific examples of the silane coupling agent include:
γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-β (N-vinylbenzylaminoethyl) -γ -Aminopropyltrimethoxysilane hydrochloride, γ-glycidoxypropyltrimethoxysilane, γ
-Mercaptopropyltrimethoxysilane, vinyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-anilinopropyltrimethoxysilane, vinyltrimethoxysilane, octadecyldimethyl [3-
(Trimethoxysilyl) propyl] ammonium chloride, γ-chloropropylmethyldimethoxysilane, γ
-Mercaptopropylmethyldimethoxysilane, vinyltris (β-methoxyethoxy) silane, β- (3,4
-Epoxycyclohexyl) ethyltrimethoxysilane, ureidopropyltrimethoxysilane, triaminopropyl-trimethoxysilane, γ-4,5 dihydroimidazolepropyltriethoxysilane, γ-cyanopropyltriethoxysilane and the like.

Among the above compound examples, there are many so-called trifunctional silane coupling agents in which three hydrolyzable groups represented by an alkoxy group are bonded to a silicon atom. However, a compound in which the number of alkoxy groups bonded to silicon atoms is 2 or less can also be effectively used as silane coupling. A reaction product of the above compound,
For example, oligomers as the above-mentioned condensates, reaction products with polyvinyl alcohol, and the like can also be effectively used as silane couplings. Furthermore, a so-called polymer silane coupling agent can also be used.

The polymer type silane coupling agent is a compound containing both a reactive functional group and a hydrolyzable group represented by an alkoxy group in a side chain of polydimethylsiloxane. Specific examples thereof include trade names “MAC-2101” (manufactured by Nippon Unicar Co., Ltd.) (polydimethylsiloxane containing an alkoxy group, an epoxy group, and a polyether group), and “MAC-2301” (an alkoxy group, a hydroxyl group,
Polydimethylsiloxane containing a polyether group). Examples of the titanium coupling agent include an alkyl titanate and a titanium chelate in addition to a so-called titanium coupling agent. Among them, the titanium coupling agent is preferable.

As the titanium coupling agent, for example,
Isopropyl triisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisoprolylbis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetra (2,2- Diallyloxymethyl-1-butyl) bis (di-tridecyl)
Phosphite titanate, bis (dioctylbirophosphate) oxyacetate titanate, bis (dioctylbirophosphate) ethylene titanate, isopropyltrioctanoyl titanate, isopropyldimethacrylisostearoyl titanate, isopropylisostearoyldiacryl titanate, isopropyltri (dioctylphosphate) titanate Isopropyltricumylphenyltitanate, isopropyltri (N-amidoethylaminoethyl) titanate, dicumylphenyloxyacetate titanate, diisostearoylethylene titanate and the like.

As the zirconium-based coupling agent,
Alkyl zirconate, zirconium chelate and the like can be mentioned. Examples of the alkyl zirconate include zirconium butyrate, zirconium acetylacetonate, acetylacetone zirconium butyrate, zirconium lactate, and zirconium butyrate stearate. Examples of zirconium chelates include zirconium-di-isopropoxide-di-methylacetoacetate.

As the aluminum-based coupling agent,
Examples thereof include alkyl aluminates and aluminum chelates. The alkyl aluminate is also called an aluminate ester, and examples thereof include trimethoxy aluminum, triethoxy aluminum, tri-isopropoxy aluminum, and tri-benzyl alkoxy aluminum. Examples of the aluminum chelate include, for example, aluminum-di-n-butoxide-mono-ethylacetoacetate, aluminum-di-n-butoxide-mono-methylacetoacetate, aluminum-di-isobutoxide-mono-methylacetoacetate, aluminum- Di-sec-butoxide-mono-ethylacetoacetate; aluminum-di-isopropoxide-mono-ethylacetoacetate;

Examples of the zirconium-aluminum coupling agent include so-called zirconaluminate coupling agents. This is a kind of reactive compound containing zirconium and aluminum, and commercially available products thereof include, for example, US CAVEDON CHEMICA
L CO. , INC. Product name "CAVCO MO"
DA, CAVCO MOD C, CAVCO
MOD C-1 "," CAVCO MOD F ",
"CAVCO MOD M", "CAVCO MOD
M-1 "," CAVCO MOD S "," CAVCO
MOD APG "," CAVCO MOD CP "
G ”,“ CAVCO MOD CPM ”,“ CAVCO
MOD FPM ”,“ CAVCO MOD MP ”
G "," CAVCOMMOD MPM "and the like.

Examples of the above-mentioned derivative include a hydrolyzate of at least a part of the above-mentioned compound, a condensate containing at least one of the above-mentioned compound or its hydrolyzate, and a reaction product of these with another compound (for example, silane). A reaction product of a partially hydrolyzed coupling agent and polyvinyl alcohol). The coating layer in the present invention may contain various compounds in addition to the above compounds, and specific examples thereof include a binder polymer other than the above, a crosslinking agent other than the above, a filler or particles, a wax, and an antistatic agent. , A surfactant, an antifoaming agent, a coating improver, a thickener, an antioxidant, an ultraviolet absorber, a foaming agent, a dye, and a pigment.

The coating solution used in the present invention is preferably a coating solution using water as a medium for safety and health. However, even if the coating solution contains an organic solvent as an auxiliary of a water-soluble or water-dispersible resin. Alternatively, a coating solution using an organic solvent as a medium may be used. When water is used as the main medium, a coating solution in which the above compound is forcibly dispersed with a surfactant or the like may be used, but a self-dispersion type coating solution is preferable from the viewpoint of the dispersion stability of the coating agent. The self-dispersing coating solution is prepared from a coating agent in which a hydrophilic group is introduced into each of the above compounds. For example, as the nonionic group, a hydroxyl group, a polyether, as the anionic group, sulfonic acid, carboxylic acid, phosphoric acid and salts thereof, and as the cationic group, an onium salt such as a quaternary ammonium salt may be mentioned. . As a method for introducing a hydrophilic group into a compound, various copolymerization reactions including grafting can be employed.

Among the above coating agents, a water-soluble or water-dispersed coating agent having an anionic group is particularly preferred. The lower limit of the content of the anionic group is usually 0.05% by weight from the viewpoint of water solubility or water dispersibility imparted to the coating agent, and the upper limit is not particularly limited. It is 15% by weight from the viewpoint of producing a high molecular weight polyester sufficient to give film strength. The content of the anionic group refers to the ratio of the anionic group residue containing no counter ion to the compound. As a coating method, for example, a reverse roll coater, a gravure coater, a rod coater, as shown in “Coating System”, written by Yuji Harasaki, Maki Shoten, 1979,
An air doctor coater or other coating device can be used.

The coating layer in the present invention is preferably provided by in-line coating. In-line coating is a method in which coating is performed in the process of manufacturing a polyester film, and specifically, coating is performed at any stage from melt extrusion of polyester to biaxial stretching, heat setting, and winding. Is the way. Usually, a substantially amorphous unstretched sheet obtained by melting and quenching, then applied to either a uniaxially stretched film stretched in the longitudinal direction (longitudinal direction) or a biaxially stretched film before heat setting. I do. Among these, a method of stretching the film in the lateral direction after applying it to the uniaxially stretched film is excellent. According to such a method, there is an advantage in manufacturing cost because film formation and coating and drying can be performed simultaneously, thin film coating is easy because stretching is performed after coating, and heat treatment performed after coating is another. Because of the high temperature which cannot be achieved by the above method, the coating film and the polyester film adhere firmly.

The thickness of the coating layer is usually 0.001 to 10 μm, preferably 0.010 to 5 μm, as the thickness after drying.
m, more preferably 0.015 to 2 μm. When the thickness of the coating layer is less than 0.001 μm, the adhesiveness of the polyester film for decorative board or decorative sheet of the present invention to the substrate is not sufficiently improved. The thickness of the coating layer is 10
If it exceeds μm, the coating layer acts as an adhesive, so that the films wound up on the roll are likely to adhere to each other, so-called blocking.

An arbitrary adhesive can be used for laminating the polyester film for a decorative board or decorative sheet of the present invention with a substrate. Examples of the adhesive include a urea resin adhesive, a melamine resin adhesive, a phenol resin adhesive, an α-olefin resin adhesive, an adhesive made of a mixture of an aqueous polymer and an isocyanate, an epoxy adhesive, and a solution type. Vinyl acetate resin adhesive, emulsion type vinyl acetate resin adhesive, acrylic emulsion adhesive, hot melt adhesive, cyanoacrylate adhesive, polyurethane adhesive, chloroprene rubber adhesive, nitrile rubber adhesive, SBR adhesive, modified rubber emulsion adhesive, ethylene copolymer resin adhesive,
Examples include resorcinol-based adhesives, natural rubber-based adhesives, cellulose-based adhesives, starch pastes, and dextrins.

When the substrate is wood, a urea resin adhesive, a melamine resin adhesive, an α-olefin resin adhesive, an adhesive made of a mixture of an aqueous polymer and an isocyanate, an emulsion type vinyl acetate resin adhesive, Acrylic emulsion adhesives, chloroprene rubber adhesives, modified rubber emulsion adhesives, and cellulose adhesives are mainly used.

Commercially available urea resin adhesives include, for example, "Euroid 310" manufactured by Mitsui Toatsu Chemicals, Inc.
“Euroid 320”, “Euroid 701”, “Euroid 755”, “Euroid 730” and the like. Commercially available melamine resin adhesives include, for example,
"Euroid 350", "Euroid 775", "Euroid 781", "Stract Bond C-1", "Stract Bond C-10" (manufactured by Mitsui Toatsu Chemicals, Inc.)
Melamine / urea resin), "Euroid 883", "Euroid 811" (all melamine / phenol resins) manufactured by Mitsui Toatsu Chemicals, Inc. and the like.

Commercially available phenolic resin adhesives include, for example, "Euroid PL-" manufactured by Mitsui Toatsu Chemicals, Inc.
261 "," Euroid PL-281 "," Euroid PL-211 "," Euroid PL-222 "," PR22 "manufactured by Konishi Co., Ltd., and the like. Examples of commercially available α-olefin resin adhesives include “SH2”, “SH3”, “SH5W”, “SH6” and “SH2” manufactured by Konishi Corporation.
"SH20", "SH20L2" and the like. Commercially available adhesives based on a mixture of an aqueous polymer and an isocyanate include, for example, "CU1" and "CU
5 "," CU51 "and the like.

Commercially available epoxy adhesives include, for example, “Esdine 3008” manufactured by Sekisui Chemical Co., Ltd.
"Esdine 3200", "Esdine 3710",
"Esdine 3730", "Esdine 3740",
"Esdine 3750", "Esdine 3600",
"Esdine 3611", "Esdine 3450", and the like. Commercially available solvent-type vinyl acetate resin-based adhesives include, for example, “ESDINE 1” manufactured by Sekisui Chemical Co., Ltd.
011 ”,“ Esdine 1013 ”,“ Esdine 10
15 "," Esdine 1020 "," Esdine 105 "
7 "and the like.

Commercially available emulsion-type vinyl acetate resin adhesives include, for example, “65” manufactured by Cemedine Co., Ltd.
6 "," 605 "," EM-65 "," EM-90 ",
"602 (T)", "Esdine 5100", "Esdine 5165", "Esdine 5" manufactured by Sekisui Chemical Co., Ltd.
200 "," Esdine 5300 "," Esdine 53 "
01 "," Esdine 5320 "," Esdine 540 "
0 ”,“ Esdine 5403 ”,“ Esdine 540 ”
5 "," Esdine 5406 "," Esdine 540 "
8 "," Esdine 5410 "," Esdine 544 "
0 ”,“ Esdine 5500 ”,“ Esdine 570 ”
0 ”,“ Esdine 5800 ”,“ Esdine 580 ”
3 "," Esdine 5815 ", Konishi Co., Ltd." CH
2 "," CH2W "," CH3 "," CH5 "," CH
18 "," CH20 "," CH7 "," CH7L ",
“CH27”, “CH1000”, “CH63”, “C
H65 "," CH131 "," CH133 "," CH1 "
15 "," CX10 "," CX55 "," CH150
0 "," CH1600 "," CH3000L "," CH
72 "," CH73 "," CH74 "," CH77 ",
"With CH107 curing agent", "PTS (A / B)", "C
H7000 / PTS7000 ".

Commercially available acrylic emulsion adhesives include, for example, “EM-31” manufactured by Cemedine Co., Ltd.
5, "EM-370A / B", "Molcon 68"
5 "," EM-326 "," 679 "," EM-702 "
Kai ”,“ CEL10 ”,“ CEL2 ”manufactured by Konishi Co., Ltd.
0 ”,“ CEL22 ”,“ CEL25N ”,“ CEL6 ”
0 ”,“ CEL63 ”,“ CVC33 ”,“ CVC3 ”
6 "," CVC36F "," CV3105 series ",
"SP65", "SP85", "SP200", "SP
210 "," SP220 "," SP281 "," SP2 "
85 "," SP290 "," SP291 "," SP30
55 ”,“ CN520 ”,“ CZ100 ”,“ CZ22 ”
0, "CE780", "CE801", "Nedabond A", "Nedabond W1000" and the like.

Commercially available chloroprene rubber-based adhesives include, for example, “ESDINE 276A” manufactured by Sekisui Chemical Co., Ltd.
L "," Esdine 276FS "," Esdine 276
M ”,“ ESDINE SG202D ”,“ ESDINE 27
8 "," Esdine SG2005E "," G10 "," G11 "," G12 "," Super G Ace "," G17 "," G18 "," G19 "," G5 "manufactured by Konishi Co., Ltd.
000 "," G5800 "," GS5 "," GU55 Blue "," GU68F Green "," G77 "," G7
8, "Nedabond G", "Super G Spray",
"GW150" and the like. Commercially available modified rubber emulsion adhesives include, for example, Cemedine Co., Ltd.
"CL-5N" and "CL-7N" manufactured by Konishi Co., Ltd. "FL200", "FL105S", "HB2", "H"
B10 "and the like. Commercial products of the resorcinol-based adhesive include, for example, Konishi Co., Ltd. "KR15", and commercial products of the cellulose-based adhesive include, for example, Konishi Co., Ltd. "bond for work (K)".

[0055]

EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples unless it exceeds the gist. The measuring method used in the present invention is as follows. (1) Transmission Density The light transmittance under a G filter was measured using a Macbeth densitometer (TD-904). The larger this value is, the higher the hiding power is. (2) Color tone analyzer (TC-180 manufactured by Tokyo Denshoku Co., Ltd.)
0MKII type), and the color tone was measured as L, a, b values according to the method of JIS Z-8722.

(3) Tensile modulus Tensile tester ("Intesco Model 2" manufactured by Intesco Corporation)
001 type), in a room adjusted to a temperature of 23 ° C. and a humidity of 50% RH, length 300 mm, width 20 mm
Was pulled at a strain rate of 10% / min, and was calculated by the following equation using the first linear part of the tensile stress-strain curve. In the formula, E is the tensile modulus (kg /
mm ² ), Δσ is a stress difference due to the original average cross-sectional area between two points on the straight line, and Δε is a strain difference between the same two points.

[Equation 1] E = △ σ / △ ε

(4) Suitability for processing A decorative sheet having the following structure is stuck to a plywood having a black surface as a flat base material to prepare a decorative sheet. After the decorative board was subjected to V-shaped cutting and bent, the suitability for V-shaped cutting was determined based on whether the decorative board returned to its original shape. The case where the decorative board did not return was represented by ○, and the case where it returned was represented by ×. Further, among ○, extremely good cases were represented by ◎.

The decorative sheet was prepared as follows. That is, first, an arbitrary pattern is printed on the inner film, and a 50 μm polyester film (“T6 manufactured by Diafoil Hoechst Co., Ltd.”) is formed thereon as the outer film.
00-50 ”) or a 50 μm acrylic film (“ Acryprene HBS ”manufactured by Mitsubishi Rayon Co., Ltd.) is laminated to form a decorative sheet. For the lamination, a saturated polyester resin adhesive ("Nichigo Polyester (LP-035)" manufactured by Nippon Synthetic Chemical Co., Ltd.) was used. Next, the decorative sheet was bonded to a plywood as a flat base material to prepare a doubling specification decorative board. The above bonding was performed so that the inner film surface was bonded to the plywood, and the following five types of adhesives were used. The workability was changed in each case with the adhesive changed, and their average was taken as the final result. Emulsion type vinyl acetate resin adhesive; "605" manufactured by Cemedine Co., Ltd. Emulsion type vinyl acetate resin adhesive; Konishi Co., Ltd.
"CH18" Acrylic emulsion adhesive: "679" manufactured by Cemedine Co., Ltd. Acrylic emulsion adhesive: "CV" manufactured by Konishi Co., Ltd.
C36 "Rubber adhesive:" G17 "manufactured by Konishi Co., Ltd.

(5) Indentation resistance The above decorative board was placed horizontally so that the decorative sheet surface was on the upper side, and from a height of 50 cm, a mass of 100 g and a diameter of 3 c.
The iron ball of m was dropped on the decorative board, and the pattern of the portion where the iron ball fell was observed. The symbol "o" indicates no drop mark, the symbol "x" indicates a clear drop mark, and the symbol "△" indicates the middle. (6) Concealment Observation of the change in the color tone of the pattern printed from the surface of the decorative sheet was observed, and the case where the design was retained was evaluated as good. The case where the color change was remarkable and the design was deteriorated was evaluated as x. Is represented by △. In addition, among 場合, the case where it was held very well was represented by ◎.

(7) Adhesive The decorative sheet was prepared as follows. That is, first, an arbitrary pattern is printed on the inner film, and a 50 μm polyester film (“T600-5” manufactured by Diafoil Hoechst Co., Ltd.) is formed thereon as the outer film.
0 ”) or 50 μm acrylic film (“ Acryprene HBS ”manufactured by Mitsubishi Rayon Co., Ltd.) to form a decorative sheet. For the lamination, a saturated polyester resin adhesive ("Nichigo Polyester (LP-035)" manufactured by Nippon Synthetic Chemical Co., Ltd.) was used. Next, the decorative sheet was bonded to a plywood as a flat base material to prepare a doubling specification decorative board. This bonding is as follows. First, 110 g / m ² of an adhesive is uniformly applied on a plywood by wet. The film is placed on the plywood to which the adhesive has been applied so that the surface to be evaluated of the film faces the adhesive, and bonded. This sample was pressed at 2 kg / c with a press.
Leave for 1 hour while applying a pressure of m ² . Thereafter, the sample is taken out and left at room temperature for one day. Using the prepared sample, the adhesiveness was evaluated by the following method. The following five types of adhesives were used, and the average of the evaluation results of the five types was adopted. Emulsion type vinyl acetate resin adhesive; "605" manufactured by Cemedine Co., Ltd. Emulsion type vinyl acetate resin adhesive; Konishi Co., Ltd.
"CH18" Acrylic emulsion adhesive: "679" manufactured by Cemedine Co., Ltd. Acrylic emulsion adhesive: "CV" manufactured by Konishi Co., Ltd.
C36 "Rubber adhesive:" G17 "manufactured by Konishi Co., Ltd.

It is the interface between the plywood and the inner film that is most easily peeled among the layers of the decorative board. The adhesiveness of this part was evaluated as follows. Peeling by hand: The film was peeled from the plywood by hand, and the peeling interface was visually judged. The case where the plywood was delaminated was evaluated as ○, the case where the plywood was separated at the interface between the film and the adhesive was evaluated as x, and the case where both were mixed was evaluated as Δ. High temperature creep peel test: The film was scored 1 inch wide. The film was partially peeled from the cut. Thereafter, the plywood was leveled and the plywood was fixed such that the partially peeled film hangs vertically. A 500 g load was applied to the edge of the hanging film, and the film was allowed to stand in a dry hot air oven at 60 ° C. The distance at which the film peeled off the plywood was measured after one hour. When the peel length after one hour is less than 2 mm, ◎ 2 mm or more and 5 mm
Is less than ○, 5 mm or more and less than 20 mm is Δ,
A case of 20 mm or more was evaluated as x.

COMPARATIVE EXAMPLE 1 Polyethylene terephthalate to which 13.5% by weight of titanium dioxide and 0.5% by weight of wet silica were added was dried at 180 ° C. for 4 hours, then extruded at 290 ° C. by a melt extruder, and electrostatically applied. By applying the method, the mixture was cooled and solidified on a cooling roll having a surface temperature set to 40 ° C. to obtain an unstretched sheet. The obtained sheet was stretched at 85 ° C. 2.5 times in the machine direction to obtain a film. Next, the obtained film was guided to a tenter and stretched 3.2 times in the transverse direction at 120 ° C.
Heat fixing was performed at 10 ° C. to obtain a 50 μm biaxially stretched polyester film (I). This biaxially stretched polyester film was used as an inner film, and the above-mentioned polyester film was used as an outer film. A decorative doubling board was prepared in the same manner as described above and evaluated. The results are shown in Table 1 below.

Comparative Example 2 7.0% by weight of titanium dioxide, 0.5% by weight of wet silica
A biaxially stretched polyester film (II) obtained in the same manner as in Example 1 except that polyethylene terephthalate to which was added was used. The biaxially stretched polyester film was used as an inner film, and the acrylic film was used as an outer film. A doubling specification decorative board was prepared in the same manner as described above and evaluated. Table 1 shows the results.

Comparative Example 3 7.3% by weight of titanium dioxide, 0.01 of carbon black
2 obtained in the same manner as in Example 1 except that polyethylene terephthalate to which 0.5% by weight of anthraquinone-based yellow pigment was added and 0.5% by weight of wet silica was used. An axially stretched polyester film (III) was obtained. This biaxially stretched polyester film was used as an inner film, and the above-mentioned polyester film was used as an outer film. A decorative doubling board was prepared in the same manner as described above and evaluated. Table 1 shows the results.

Comparative Example 4 7.3% by weight of titanium dioxide, 0.01 of carbon black
Polyethylene terephthalate containing 30 mol% of an isophthalic acid component containing 0.5% by weight of wet-process silica at 70 ° C. After drying for one week, it was extruded at 250 ° C. by a melt extruder, applied with an electrostatic contact method, and cooled and solidified on a cooling roll having a surface temperature set at 10 ° C. to obtain an unstretched sheet. The obtained sheet was stretched in the longitudinal direction by 2.5 times at 50 ° C. to obtain a film.

Next, the obtained film was guided to a tenter, stretched 3.0 times in the transverse direction at 90 ° C., and heat-set at 150 ° C. to obtain a 50 μm biaxially stretched polyester film (IV). . This biaxially stretched polyester film was used as an inner film, and the above-mentioned polyester film was used as an outer film. A decorative doubling board was prepared in the same manner as described above and evaluated. Table 1 shows the results.

Comparative Example 5 0.6% by weight of titanium dioxide, 0.5% by weight of wet silica
Using a polyethylene terephthalate to which styrene was added, extrusion was performed in the same manner as in Example 1, and the mixture was cooled and solidified on a cooling roll to obtain a 100 μm unstretched film (V) (biaxial stretching was not performed). This unstretched polyester film was used as an inner film, and the above-mentioned polyester film was used as an outer film. A doubling specification decorative board was prepared in the same manner as described above, and evaluated. Table 1 shows the results.

Comparative Example 6 Using polyethylene terephthalate to which 5% by weight of titanium dioxide and 0.5% by weight of wet silica were added, Example 1 was used.
According to the same manufacturing method as described above, the tensile modulus is 500 in the longitudinal direction.
A biaxially stretched polyester film (VI) adjusted to kg / mm ² and 550 kg / mm ^{2 in} the transverse direction was obtained. This 2
An axially stretched polyester film was used as an inner film, and the polyester film was used as an outer film. A doubling specification decorative board was prepared in the same manner as described above, and its evaluation was performed. Table 1 shows the results.

Comparative Example 7 Using a polyethylene terephthalate and the same production method as in Example 1, the tensile modulus was 610 kg / m in the longitudinal direction.
mm ^2, to obtain a biaxially oriented polyester film which has been adjusted in the transverse direction to 570kg / mm ² (VII). Using this biaxially stretched polyester film as the inner film,
Using the polyester film for the outer film,
A doubling specification decorative board was prepared in the manner described above and evaluated. Table 1 shows the results.

Example 1 A biaxially stretched polyester film provided with a coating layer was prepared. The combination of the applied coating layer and the base film was as shown in Table 1-1. That is, the coating layer 1 was provided on one surface of the polyester film (I) prepared in Comparative Example 1. The composition of the coating film was as shown in Table 2-1 below. That is, the coating layer 1 was prepared by blending the coating raw material A and the coating raw material J such that the ratio of the dry solid content was 95/5, diluted with water as needed, and coated with a bar coater. The film thickness after drying was 0.3 μm. The contents of the coating raw materials were as shown in Tables 3-1 to 3-3 below.
That is, the coating material A is a polyester aqueous dispersion,
The coating material J is an aqueous dispersion of silicon oxide. Table 3
As described in Tables 1 to 3, the coating raw materials mainly consist of aqueous dispersions, but the compositions of the coating layers described in Tables 2-1 to 2-2 below show that the water content was removed. It is a composition relating to a dry solid content later. The same applies to the film thickness, which is the film thickness after drying. The properties of the obtained coated film are shown in Table 4 below.
-1. The decorative board characteristics were good including the adhesiveness. In addition, evaluation of adhesiveness was performed on the coating layer surface side.

Examples 2 to 14 and Comparative Example 8 A coated film was prepared in the same manner as in Example 1. However, the combination of the base film and the coating layer, and the composition and thickness of the coating layer were prepared as shown in Tables 1-1, 2-1 and 3-1 to 3-3 below. The properties of the obtained film were as shown in Table 4-1. Examples 2 to 14
All had excellent decorative board properties including adhesiveness.
Comparative Example 8 was excellent in adhesiveness and the like, but poor in workability.

Example 15 A coated film was prepared in the same manner as in Example 1. However, it was applied during stretching in the vertical and horizontal directions. Specifically, after stretching in the longitudinal direction, applied to one side of the film before the transverse stretching,
Thereafter, the film was subjected to transverse stretching and heat setting to prepare a coated polyester film. The coating agent was adjusted in the same manner as in Example 1. This was applied by a roll coater. For horizontal stretching,
The thickness of the dried coating film was 1/3 of that of the example, but the adhesion was good. This is the effect of in-line coating. The properties of the obtained coated film are shown in Table 4-1.
The decorative plate properties were good.

Examples 16 to 92 Coated films were prepared in the same manner as in Example 15, that is, by in-line coating. The combinations of the base film and the coating layer in each example were as shown in Tables 1-1 to 1-5. In each case, after the base film was stretched in the longitudinal direction, it was applied to one surface of the film before the transverse stretching, and then heat-fixed in the transverse direction to prepare a coated polyester film. The coating method was the same as in Example 15. The composition and film thickness of the coating layer were as shown in Tables 2-1 to 2-2, and details of the compounds constituting the coating layer were as shown in Tables 3-1 to 3-3. The production conditions other than the application were the same as those of the respective base films. The properties of the obtained coated film are shown in Tables 4-1 to 4-6. In each case, the thickness of the coating film was 1/3 as compared with Examples 1 to 14, but the decorative plate characteristics were good including the adhesiveness. In particular, when a crosslinking agent is contained, high adhesiveness is often exhibited even at a high temperature.

[0074]

[Table 1]

[0075]

[Table 2]

[0076]

[Table 3]

[0077]

[Table 4]

[0078]

[Table 5]

[0079]

[Table 6]

[0080]

[Table 7]

[0081]

[Table 8]

[0082]

[Table 9]

[0083]

[Table 10]

[0084]

[Table 11]

[0085]

[Table 12]

[0086]

[Table 13]

[0087]

[Table 14]

[0088]

[Table 15]

[0089]

[Table 16]

[0090]

According to the present invention described above, there is provided a doubling-type decorative board film which has remarkably improved V-cut workability, dent resistance and adhesiveness, and has no environmental pollution during incineration. The industrial value of the present invention is great.

Claims (4)

[Claims] 1. A doubling specification decorative plate comprising at least an adhesive layer, an inner film layer, a pattern printing layer, an adhesive layer, and an outer film layer formed on a substrate in this order, which is used for forming an inner film layer. A doubling-specific decorative film, comprising: a polyester film having a coating layer provided on at least one surface, wherein the polyester film has a tensile modulus in the longitudinal and transverse directions of not more than 600 kg / mm ^2. . 2. Tensile elastic modulus in both longitudinal and transverse directions is 1
^{2. The} pressure is at least 90 kg / mm ^2.
The polyester film as described. 3. The coating layer according to claim 1, wherein the coating layer contains at least one selected from the group consisting of polyester, acrylic polymer, polyurethane, amino resin, epoxy resin, polymer of oxazoline compound, and compound of coupling agent. 3. The polyester film according to 1 or 2. 4. The polyester film according to claim 1, wherein the coating layer is provided by in-line coating.