JPH1120392A - Transfer sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To increase peeling strength and enhance wear resistance and further, eliminate a pattern voiding phenomenon at the time of printing. SOLUTION: In the transfer sheet comprising at least, a peeling layer 5, a physical property reinforcing layer 4 and a transparent resin layer 3 formed on a base with peeling properties, the peeling layer 5 is made up of a 0.1-1 μm-thick thermoplastic resin layer, the physical property reinforcing layer 4 is made up of a curable resin containing 5-50% in terms of weight ratio of a fine metal oxide particle with an average particle diameter of 1-10 μm and the transparent resin layer 3 is made up of a curable resin. Further, the fine particle is a fine oxide particle of one or two or more different types of element selected from among silicon, aluminum, titanium, lead, zinc, tin, cerium, zirconium and germanium.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to home appliances and furniture / architecture interior materials, automobile interior / exterior materials, cosmetic lids,
The present invention relates to a transfer sheet used for the purpose of surface protection and cosmetics of miscellaneous goods.

[0002]

2. Description of the Related Art Conventionally, the following transfer sheets have been mainly used as such transfer sheets.

(1) A transfer sheet having a releasable release layer, a pearl ink layer, a coloring layer, and, if necessary, a metal deposition layer on one side of a base sheet such as a polyester film, Transparent filling in which the surface is treated with (a) a curable compound having two or more acryloyl groups or methacryloyl groups in a molecule, and (b) an alkoxysilane having a radical polymerizable unsaturated bond in a molecule. Transfer sheet comprising a cured layer of a composition containing a mixture of (JP-A-63-29309)
No. 9)

(2) At least one of the layers provided on the substrate sheet having a releasing property, at least one layer close to the surface of the substrate sheet,
One metal oxide sphere having an average particle size of 0.01 to 15 μm
A transfer sheet comprising a hard film layer containing 0 to 90% by weight and a next layer formed of a transparent layer made of a light-transmitting resin (or an ionizing radiation-curable resin). (Japanese Patent Laid-Open No. 5
-139093)

[0005]

In the transfer sheet as in (1), when the release layer is made of a thermoplastic resin (exceeding 1 μm) under abrasion conditions, desired abrasion performance cannot be obtained ( There is a problem that the scratch property is poor). In addition, if fine particles are added to obtain abrasion properties, printability is inferior, pattern missing occurs, or fine particles are included, so light peeling, burr easily occurs, and peeling with a slight impact. There was a problem.

[0006] Even in the case of the transfer sheet as described in (2), there is a problem that the range to be selected is limited in consideration of the releasability from the base sheet. In addition, due to the inclusion of fine particles, poor printability, pattern missing or light peeling,
Burr easily. There was a problem that the film was peeled off by a slight impact.

[0007]

In order to solve the above problems, in the present invention, a thin thermoplastic resin is provided on a release layer to improve the peel strength, and a small metal oxide is used as a physical property enhancement layer. By using a curable resin layer to which fine particles were added, a transfer sheet having an appropriate peel strength, no pattern omission during printing, and good abrasion resistance was successfully obtained.

[0008] (1) In a transfer sheet having at least a release layer, a physical property enhancement layer and a transparent resin layer on a base material having release properties, the release layer is thin (0.1 to 1 μm) thermoplastic resin. Wherein the physical property enhancement layer comprises a curable resin containing 5 to 50% by weight of metal oxide fine particles having an average particle diameter of 1 μm to 10 μm, and the transparent resin layer comprises a curable resin. Sheet. (2) The fine particles are silicon, aluminum, titanium, lead,
(1) The transfer sheet according to (1), which is an oxide fine particle of one or more elements selected from zinc, tin, cerium, zirconium, and germanium. (3) The fine particles are spherical in shape (1).
Or the transfer sheet according to (2). (4) The transfer sheet according to (1), (2) or (3), wherein the property enhancing layer is made of an ionizing radiation curable resin. (5) The transfer sheet according to (1), (2), (3) or (4), wherein the property enhancing layer is made of a thermosetting resin. (6) The transfer sheet according to (1), (2), (3), (4) or (5), wherein the transparent resin layer is made of an ionizing radiation-curable resin. (7) The transfer sheet according to (1), (2), (3), (4) or (5), wherein the transparent resin layer is made of a thermosetting resin. Was developed.

[0009]

Embodiments of the present invention will be described below in detail with reference to the drawings. FIG. 1 is a sectional view showing an example of a transfer sheet according to the present invention.

[0010] Transfer is a printing method in which a transfer layer composed of a decorative layer 2, a picture layer, etc. once formed on a base material 7 (peelable base material) is transferred to another transfer object. A release layer 6 may be provided on the base material 7 if necessary. As a transfer layer, a decorative layer 2 such as a metal vapor deposition layer, a transparent resin layer 3, a physical property enhancement layer 4, a release layer 5, It is composed of an adhesive layer 1 and the like.

Here, the release layer means a layer which remains on the substrate side even after the transfer and facilitates the separation from the transfer layer, and the release layer transfers to the transfer object side after the transfer and the transfer. Refers to a layer that becomes a surface protective layer of the layer. Peeling is performed between the release layer and the peeling layer. In addition, the pattern layer and the decorative layer may be provided on the entire surface or partially in the form of a pattern. As the pattern, the design of natural products such as wood grain, stone grain, cloth grain, letters, figures, symbols, various abstract patterns, etc. Either may be used.

The releasable base material used for the transfer sheet includes:
A film having a thickness of 5 to 200 μm, which has good releasability from the transfer layer, is used. Examples of the material include polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene terephthalate / isophthalate copolymer, polyolefin resins such as polyethylene, polypropylene, and polymethylpentene, polyvinyl fluoride, polyvinylidene fluoride, and polytetrafluoroethylene. , Ethylene-
Polyfluoroethylene resin such as tetrafluoroethylene copolymer, polyamide such as nylon 6, nylon 6.6, polyvinyl chloride, vinyl chloride / vinyl acetate copolymer, ethylene / vinyl acetate copolymer, ethylene / Vinyl alcohol copolymer, polyvinyl alcohol, vinyl polymer such as vinylon, cellulose resin such as cellulose triacetate, cellophane, polymethyl methacrylate, polyethyl methacrylate, polyethyl acrylate, polybutyl acrylate, etc. Of a synthetic resin film or sheet of acrylic resin, polystyrene, polycarbonate, polyarylate, polyimide or the like.

[0013] If necessary, a release layer may be provided on the release substrate in order to promote the release property between the transfer layer and the release substrate (release substrate sheet). Examples thereof include forming a paint film by adding a release agent such as a fluorine-based resin, various waxes, and silicone to a known vehicle such as an acrylic resin, a cellulose-based resin, and a vinyl-based resin. For example, a resin formed by applying a resin such as a fluorine-based resin, silicone, a melamine-based resin, a polyolefin resin, or an ionizing radiation-crosslinkable polyfunctional acrylate, polyester, or epoxy resin and forming a film with an extrusion coat is used. In order to adjust the gloss of the surface after the transfer, a known matting agent such as microsilica can be added to the release layer.

Dimensionally stable base material (substrate sheet) For the purpose of transferring a pattern with high dimensional accuracy to a plate-shaped transfer member, particularly, polyethylene terephthalate, polycarbonate, polyimide, polyarylate, polyetheretherketone, cellulose acetate It is preferable to use a resin such as a high-quality paper coated with polymethylpentene that is hardly changed in size by heat or stress.

Formable substrate (substrate sheet) When the surface of the transfer-receiving member is generally a curved surface such as in-mold transfer, polyamide such as 6-nylon and 6-6-nylon, polyolefin such as polyethylene and polypropylene, polyethylene terephthalate, A low-crystalline polyester such as polybutylene terephthalate and polyethylene terephthalate / isophthalate copolymer, a flexible thermoplastic resin film such as polyvinyl chloride, vinylon, and the like, or a laminate thereof is preferable.

The thickness of the substrate (substrate sheet) is usually from 5 to 20.
0 μm, preferably 16 to 100 μm. 16 μm
If it is less than that, the strength is insufficient. If the thickness exceeds 100 μm, the cost is high, and the transfer speed is reduced due to poor heat transfer in the roll transfer method.

[Release Layer] As the release layer, a resin composition having releasability from a releasable substrate and having desired physical properties as a surface protective layer of the transfer layer after transfer is selected. In the present invention, a thermoplastic resin is usually used because it has good releasability from a substrate film. The thickness is also selected depending on desired physical properties and the like, but is usually 0.1 to 1 μm, especially 0.5 to 1 μm.
μm to 1 μm are most effective in terms of abrasion resistance and releasability. If it exceeds 1 μm, the peeling layer made of a thermoplastic resin will be remarkably worn in a wear test or the like, and even if the physical property strengthening layer is provided, no effect on abrasion will be seen. Therefore, the release layer must be thin.

Examples of the thermoplastic resin include cellulose derivatives such as ethyl cellulose, cellulose nitrate, cellulose acetate, ethyl hydroxycellulose and cellulose acetate propionate; styrene resins such as polystyrene and poly α-methylstyrene; and styrene copolymers.
Acrylic resins such as polymethyl methacrylate, polyethyl methacrylate, polyethyl acrylate, and polybutyl acrylate; vinyl polymers such as polyvinyl chloride, polyvinyl acetate, vinyl chloride / vinyl acetate copolymer, polyvinyl butyral, and rosin And rosin ester resins such as rosin-modified maleic resin, rosin-modified phenol resin, and polymerized rosin, and natural or synthetic resins such as coumarone resin, vinyltoluene resin, and polyamide resin.

[Ultraviolet Absorber / Light Stabilizer] In order to impart better weather resistance (light resistance) to the transfer sheet, an ultraviolet absorber and / or a light stabilizer can be added. Both UV absorber and light stabilizer are usually 0.5 to 1
Although it is about 0% by weight, it is generally preferable to use an ultraviolet absorber and a light stabilizer in combination. As the ultraviolet absorber, an organic substance such as benzotriazole, benzophenone, and salicylate, or an inorganic substance such as zinc oxide, cerium oxide, and titanium oxide in the form of fine particles having a diameter of 0.2 μm or less can be used. As a light stabilizer, bis- (2,
Hindered amine radical scavengers such as (2,6,6-tetramethyl-4-piperidinyl) sebacate and radical scavengers such as piperidine radical scavengers can be used. The above-mentioned ultraviolet absorber and light stabilizer are effective when added to the release layer.

[Physical Property Enhancing Layer] The physical property enhancing layer contains fine particles having a small particle diameter and / or a small addition amount in a resin. When the metal oxide is contained, the hardness of the resin layer is increased, and the original performance is exhibited even under abrasion conditions. The smaller the particle size of the metal oxide fine particles, the smaller the unevenness. The smaller the amount of addition, the less the unevenness, and the omission during pattern printing is eliminated.

The physical property-enhancing layer of the present invention may contain an average particle size of 1 μm to 10 μm in a thermosetting resin or an ionizing radiation-curable resin described below.
It contains 5 to 50% by weight of metal oxide fine particles of μm. That is, when the thickness is less than 1 μm, the wear resistance effect is small, and
If it exceeds μm, the transparency will be lowered, the pattern will be lost during pattern printing, or the printability or coating suitability will be poor. A particularly preferred addition amount is 2 to 15%. The particle size is preferably about 0.5 to 3 μm.

The fine particles include silicon, aluminum,
Oxide fine particles of one or more elements selected from titanium, zinc, tin, cerium, zirconium, and germanium have excellent non-coloring properties. For outdoor use, ultraviolet absorption is required, and therefore zinc oxide and cerium oxide are preferred. For general molded products, low cost alumina and cerium oxide are preferred. When antistatic is required, lead oxide can be used.

The surface of the metal oxide fine particles is treated with at least one surface treating agent selected from the group consisting of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, an aluminum chelating agent, a titanium chelating agent and the like. Then, it is excellent in the improvement of the holding power in the binder, the dispersibility in the ink, and the transparency of the coated product. Incidentally, these treatments, treatment agents, fine particle shapes and the like are described in Japanese Unexamined Patent Publication No. Hei.
Column to page 4 and column 5 are the same.

As the thermosetting resin, a phenol resin,
There are urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, amino alkyd resin, melamine / urea co-condensation resin, silicon resin, polysiloxane resin, etc. According to the above, a curing agent such as a crosslinking agent and a polymerization initiator, a polymerization accelerator, a solvent, a viscosity modifier, an extender and the like are added. As a curing agent, isocyanate is usually an unsaturated polyester resin, polyurethane resin, amine is an epoxy resin, peroxide such as methyl ethyl ketone peroxide, radical initiator such as azobisisobutyronitrile is an unsaturated polyester resin. Often used for resins.

As the isocyanate, a divalent or higher aliphatic or aromatic isocyanate can be used, but an aliphatic isocyanate is preferable from the viewpoint of preventing thermal discoloration and weather resistance.
Specific examples include tolylene diisocyanate, xylene diisocyanate, 4,4-diphenylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, and the like.

In order to accelerate the curing reaction, heating may be performed after coating as necessary. For example, in the case of an isocyanate-cured urethane-curable unsaturated polyester-based resin or polyurethane-based resin, it is usually at 40 to 60 ° C. for about 1 to 5 days, and in the case of a polysiloxane resin, it is usually 80 to 150.
C. for about 1 to 300 minutes.

As the ionizing radiation-curable resin, a composition obtained by appropriately mixing a prepolymer, oligomer, and / or monomer having a polymerizable unsaturated bond or an epoxy group in a molecule is used. Examples of the prepolymer and oligomer include unsaturated polyesters such as a condensate of an unsaturated dicarboxylic acid and a polyhydric alcohol, polyester methacrylate,
Examples include methacrylates such as polyether methacrylate, polyol methacrylate, and melamine methacrylate, and acrylates such as polyester acrylate, epoxy acrylate, urethane acrylate, polyether acrylate, polyol acrylate, and melamine acrylate.

Examples of the monomer include styrene, α-
Styrene monomers such as methylstyrene, acrylates such as methyl acrylate, 2-ethylhexyl acrylate, methoxyethyl acrylate, butoxyethyl acrylate, butyl acrylate, methoxybutyl acrylate, phenyl acrylate, Methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, methoxyethyl methacrylate, ethoxymethyl methacrylate, phenyl methacrylate, lauryl methacrylate, 2- (N, N-diethylamino) ethyl acrylate, 2- (N, N-dimethylamino) ethyl methacrylate, 2- (N, N-dibenzylamino) ethyl acrylate, (N, N-dimethylamino) methyl methacrylate, 2- (N , N-didiethylamino) propyl Substituted amino alcohol esters of unsaturated acids, acrylamide, unsaturated carboxylic acid amides such as methacrylamide, Echirerifu' fluoride, polyvinylidene fluoride, polytetrafluoroethylene, ethylene -4
Polyfluoroethylene resins such as fluorinated ethylene copolymers, polyamides such as nylon 6, nylon 6.6, compounds such as polyvinyl chloride, vinyl chloride / vinyl acetate cleat, dipropylene glycol diacrylate, ethylene glycol acrylate, Polyfunctional compounds such as propylene glycol dimethacrylate and diethylene glycol dimethacrylate, and / or polythiol compounds having two or more thiol groups in the molecule, for example, trimethylolpropane trithioglycolate, trimethylolpropane trithiopropylate And pentaerythritol tetrathioglycol.

If necessary, one or two of the above compounds may be used.
The prepolymer or oligomer is used in an amount of 5% by weight or more and the monomer and / or polythiol is used in an amount of 9% or more in order to impart ordinary coating suitability to the resin composition.
It is preferable that the content be 5% by weight or less.

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. A structure having a relatively low crosslink density is used. In addition, when the heat resistance, hardness, solvent resistance, etc. of the cured product are required, the amount of the monomer may be increased within a range that does not hinder coating suitability,
It is preferable to use a tri- or more functional acrylate-based monomer to obtain a structure having a high crosslinking density. It is also possible to adjust the coating suitability and the physical properties of the cured product by mixing a monofunctional or difunctional monomer and a trifunctional or higher functional monomer.

Examples of the monofunctional acrylate monomer as described above include 2-hydroxyacrylate, 2-hexyl acrylate, phenoxyethyl acrylate and the like. Examples of the bifunctional acrylate monomer include ethylene glycol diacrylate and 1,6-hexanediol diacrylate, and examples of the trifunctional or higher acrylate monomer include trimethylolpropane triacrylate,
Pentaerythritol hexaacrylate, dipentaerythritol hexaacrylate and the like can be mentioned.

In order to adjust physical properties such as flexibility and surface hardness of the cured product, at least one of the above prepolymers, oligomers and monomers is used with the following ionizing radiation non-curable resin. 1 to 70% by weight, preferably 5 to 50% by weight can be used as a mixture.

As the ionizing radiation non-curable resin, thermoplastic resins such as urethane, cellulose, polyester, acrylic, butyral, polyvinyl chloride and polyvinyl acetate can be used. From the viewpoint, cellulose, urethane and butyral are preferred.

In particular, in the case of curing and curing with ultraviolet light, acetophenones, benzophenones, Michler benzoyl benzoate, α-amyloxime ester, tetramethyl meuram monosulfide are used as photopolymerization initiators in the ionizing radiation-curable resin composition. , Thioxanthones, and / or n-butylamine, triethylamine, tri-n-butylphosphine, and the like as a photosensitizer may be used in combination.

Here, the ionizing radiation means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing and cross-linking a molecule, and usually an ultraviolet ray or an electron beam is used. As the ultraviolet light source, a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a black light lamp, and a metal halide lamp is used.

As the electron beam source, various electron beam accelerators such as a Cockloft-Walton type, a Vandegraph type, a resonance transformer type, an insulating core transformer type, a linear type, a dynamitron type, and a high frequency type are used. Preferably, electrons having an energy of 100 to 300 keV are irradiated.

[Transparent Resin Layer] A transparent resin layer 3 may be provided as shown in FIG. 1 to improve the adhesion between the decorative layer 2 and the physical property enhancing layer 4 and the printability of the decorative pattern. The forming resin may be any resin as long as it is in close contact with the release layer and the decorative layer. Especially,
When the thermosetting resin or the ionizing radiation-curable resin is used as the transparent resin, the abrasion property is further improved.

As the ink (or paint) for forming the decorative layer and the picture layer, chlorinated polyolefins such as chlorinated polyethylene and chlorinated polypropylene, polyester, polyurethane, acrylic, vinyl acetate, vinyl chloride and vinyl acetate can be used as binders. A polymer, a cellulosic resin, or the like is used, and one kind or a mixture of two or more kinds is used. A material obtained by adding a known pigment as listed below to this is used.

As the pigment, titanium white, zinc white, red stalk,
Inorganic pigments such as vermilion, ultramarine blue, cobalt blue, titanium yellow, graphite, carbon black, etc., and organic pigments such as isoindolinone, Hansa Yellow A, quinacridone, permanent red 4R, phthalocyanine blue, Indathrene Buri RS, aniline black, etc. Dyes), metal pigments such as aluminum, brass, etc., pearlescent (pearl) pigments composed of foil powder such as titanium dioxide-coated mica, basic lead carbonate, etc., depending on the application, transparent coloring pigments or opaque colorings Choose one of the pigments. These are added and dispersed as powder or flaky foil pieces.

As the pattern printing of the decoration and the picture, the pattern is formed by ink (or paint) using a known printing method such as gravure printing, offset printing, silk screen printing, transfer printing from a transfer sheet.

The patterns include a wood grain pattern, a stone grain pattern, a cloth grain pattern, a leather pattern, a geometric figure, a character, a symbol, and a solid image on the entire surface. The pattern is on the front, back, both sides of the sheet,
Alternatively, it is provided between layers.

The adhesive layer is a layer for transferring and adhering the transfer layer to the object to be transferred, and is selected from heat-sensitive adhesives, solvent-activated adhesives, ionizing radiation-curable adhesives and the like according to the application. . When the transfer layer other than the adhesive layer, such as the picture layer and the release layer, has sufficient adhesiveness, the adhesive layer may be omitted.

The heat-sensitive adhesive is a substance which exhibits adhesiveness when heated, and is usually a thermoplastic resin, an ionomer or the like. Examples of the resin include, for example, ethyl cellulose, cellulose nitrate, cellulose acetate, ethyl hydroxyethyl cellulose, cellulose acetate propionate. Cellulose derivatives such as acrylates, polystyrene, styrene resins or styrene copolymers such as poly α-methylstyrene, polymethyl methacrylate, polyethyl methacrylate, polyethyl acrylate, acrylic resins such as polybutyl acrylate,
Polyvinyl chloride, polyvinyl acetate, vinyl chloride / vinyl acetate copolymer, ethylene / vinyl alcohol copolymer,
Vinyl polymers such as polyvinyl butyral, rosin, rosin modified maleic resin, rosin modified phenol resin, rosin ester resins such as polymerized rosin, rubbers such as polyisoprene rubber, polyisobutyl rubber, styrene butadiene rubber, butadiene acrylonitrile rubber Examples of the resin include natural or synthetic resins such as resins, coumarone resins, vinyl toluene resins, polyamide resins, and polychlorinated olefins, and various ionomers.

After the transfer sheet of the present invention is laminated and adhered to another transfer object, the base material is peeled off to obtain a transferred product.
In the case of lamination, the adhesive layer may be omitted if the transfer sheet itself can be adhered to the object to be transferred (at a thermal melting point or the like). When the transfer sheet itself does not adhere to the adherend, the transfer sheet is laminated via an appropriate easy-adhesion layer and an adhesive layer.

The object to be transferred may be a plate material of various materials such as a flat plate or a curved surface plate, a three-dimensionally shaped article (molded article), or an article of various shapes such as a sheet (or film). As a material used for any of a board material, a three-dimensionally shaped article, and a sheet (film), a wood board such as a wood veneer, a wood plywood, a particle board, a medium density fiber board (MDF) and a wood board such as a wood fiber board , Iron, aluminum, etc., acrylic, polycarbonate, ethylene / vinyl acetate copolymer, ethylene vinyl acetate, polyester, polystyrene, polyolefin, ABS, phenolic resin, polyvinyl chloride, cellulose resin, rubber and other resins, exclusively board materials Or, as a material used as a three-dimensional article, ceramics such as glass, ceramics, etc., cement such as ALC (foamed lightweight concrete), non-cement ceramic materials such as calcium silicate, gypsum, and exclusively as a sheet (or film) Materials used include high-quality paper, paper such as Japanese paper, carbon, Cotton, there potassium titanate, glass, consisting of fibers such as synthetic resin nonwoven fabric or woven fabric or the like.

As a method of laminating these transfer objects (adherends), for example, a method of laminating by pressing a plate-like base material with a pressure roller via an adhesive layer, and a method of injection-molding a transfer sheet The mold is inserted between the male and female molds, the molds are closed, the molten resin is injected and filled from the gate of the male mold, and then cooled, and the transfer sheet is bonded and laminated on the surface of the resin molded article at the same time as molding. And a so-called simultaneous injection molding laminating method.

[0047]

Embodiments of the present invention will be described below in detail.

Example 1 As a base film, 0.3 g / m ² of a melamine resin-based ink (manufactured by The Inktec) was applied to the surface of a 25 μm biaxially stretched polyethylene terephthalate film.
The film was baked at 20 ° C. for 20 seconds to form a release layer, thereby producing a release substrate film. Next, the following release layer composition (A) is dissolved and diluted in a mixed solvent of methyl ethyl ketone and toluene, and then applied on the release substrate film, and the mixed solvent is volatilized by drying at 60 ° C. for 1 minute. , Remove and apply 1 g / m ²
A release layer having a thickness of 1 μm was obtained. Next, the composition for physical property enhancement layer (X) was diluted with the same mixed solvent as in (A), and applied and dried on the release layer to obtain a physical property enhancement layer having a coating amount of 6 g / m ² . Next, the composition (Y) for a transparent resin layer was diluted with the same mixed solvent as in (A), and was applied and dried on the property enhancing layer to obtain a transparent resin layer having an application amount of 4 g / m ² . Next, the decorative layer composition (Z) was diluted with the same mixed solvent as in (A), and the grain was gravure-printed on the transparent resin layer and dried to obtain a decorative layer (pattern layer). . Next, on the transparent resin layer, a polyamide-based adhesive was applied by gravure coating, and the applied amount after drying was 2 g / g.
An m ² adhesive layer was obtained.

-Composition for release layer (A) 50 parts by weight of acrylic resin-Composition for physical property enhancement layer (X) 50 parts by weight of acrylic resin 2 parts by weight of polyfunctional acrylate Silica treated with γ-methacryloxypropyltrimethoxysilane (particles) 1.7 μm in diameter) 5 parts by weight-Composition for transparent resin layer (Y) 50 parts by weight of acrylic resin 2 parts by weight of polyfunctional acrylate-Composition for decorative layer (for pattern layer) (Z) 50 parts by weight of acrylic resin Vinyl chloride Vinyl acetate copolymer 50 parts by weight Pigment 5 parts by weight

Using the transfer sheet, a decorative layer (pattern layer) of the transfer sheet is superposed on the surface of a medium density fiber board as a transfer object at 200 ° C., 10 kg
/ Cm ^{2 at} a rate of 2 m / min.

Comparative Example 1 A melamine resin-based ink (manufactured by The Inktec) was applied at 0.3 g / m ² to the surface of a 25 μm biaxially stretched polyethylene terephthalate film as a base film, and 170
The film was baked at 20 ° C. for 20 seconds to form a release layer, thereby producing a release substrate film. Next, the following release layer composition (A) is dissolved and diluted in a mixed solvent of methyl ethyl ketone and toluene, and then applied on the release substrate film, and the mixed solvent is volatilized by drying at 60 ° C. for 1 minute. , Remove and apply 6 g / m ²
Was obtained. Next, the transparent resin layer composition (Y) was diluted with the same mixed solvent as in (A), and applied and dried on the release layer to obtain a transparent resin layer having an application amount of 4 g / m ² . Next, the decorative layer composition (Z) was diluted with the same mixed solvent as in (A), and the grain was gravure-printed on the transparent resin layer and dried to obtain a decorative layer (pattern layer). . Next, an adhesive layer having a coating amount of 2 g / m ² was obtained after drying the polyamide adhesive by gravure coating on the transparent resin layer.

Composition for release layer (A) 50 parts by weight of acrylic resin 2 parts by weight of polyfunctional acrylate 5 parts by weight of silica treated with γ-methacryloxypropyltrimethoxysilane (particle size 1.7 μm) 2 parts by weight of film reinforcing agent Composition for transparent resin layer (Y) 50 parts by weight of acrylic resin 2 parts by weight of polyfunctional acrylate-Composition for decorative layer (for pattern layer) (Z) 50 parts by weight of acrylic resin 50 parts by weight of vinyl chloride-vinyl acetate copolymer Pigment 5 parts by weight

Using this transfer sheet, a decorative layer (picture layer) of the transfer sheet is superposed on the surface of a medium-density fiber board as an object to be transferred, and is placed at 200 ° C., 10 kg.
/ Cm ^{2 at} a rate of 2 m / min.

Comparative Example 2 As a base film, a melamine resin ink (manufactured by The Inktec) 0.3 g / m ^{2 was} applied to the surface of a biaxially stretched polyethylene terephthalate film 25 μm, and 170
The film was baked at 20 ° C. for 20 seconds to form a release layer, thereby producing a release substrate film. Next, the following release layer composition (A) is dissolved and diluted in a mixed solvent of methyl ethyl ketone and toluene, and then applied on the release substrate film, and the mixed solvent is volatilized by drying at 60 ° C. for 1 minute. , Remove and apply 6 g / m ²
Was obtained. Next, the transparent resin layer composition (Y) was diluted with the same mixed solvent as in (A), and applied and dried on the release layer to obtain a transparent resin layer having an application amount of 4 g / m ² . Next, the decorative layer composition (Z) was diluted with the same mixed solvent as in (A), and the grain was gravure-printed on the transparent resin layer and dried to obtain a decorative layer (pattern layer). . Next, an adhesive layer having a coating amount of 2 g / m ² was obtained after drying the polyamide adhesive by gravure coating on the transparent resin layer.

Composition for release layer (A) Acrylic resin 25 parts by weight Vinyl chloride vinyl acetate copolymer 25 parts by weight Polyfunctional acrylate 2 parts by weight γ-methacryloxypropyltrimethoxysilane-treated silica (1.7 μm particle size) 5 parts by weight-Composition for transparent resin layer (Y) 50 parts by weight of acrylic resin 2 parts by weight of polyfunctional acrylate-Composition for decorative layer (for pattern layer) (Z) 50 parts by weight of acrylic resin Vinyl chloride-vinyl acetate copolymer 50 parts by weight Pigment 5 parts by weight

Using the transfer sheet, a decorative layer (pattern layer) of the transfer sheet is superimposed on the surface of a medium density fiber board as a transfer object at 200 ° C. and 10 kg.
/ Cm ^{2 at} a rate of 2 m / min.

Comparative Example 3 As a base film, 0.3 g / m ² of a melamine resin-based ink (manufactured by The Inktec) was applied to the surface of a 25 μm biaxially stretched polyethylene terephthalate film.
The film was baked at 20 ° C. for 20 seconds to form a release layer, thereby producing a release substrate film. Next, the following release layer composition (A) is dissolved and diluted in a mixed solvent of methyl ethyl ketone and toluene, and then applied on the release substrate film, and the mixed solvent is volatilized by drying at 60 ° C. for 1 minute. , Remove and apply 6 g / m ²
Was obtained. Next, the transparent resin layer composition (Y) was diluted with the same mixed solvent as in (A), and applied and dried on the release layer to obtain a transparent resin layer having an application amount of 4 g / m ² . Next, the decorative layer composition (Z) was diluted with the same mixed solvent as in (A), and the grain was gravure-printed on the transparent resin layer and dried to obtain a decorative layer (pattern layer). . Next, an adhesive layer having a coating amount of 2 g / m ² was obtained after drying the polyamide adhesive by gravure coating on the transparent resin layer.

Peeling layer composition (A) Acrylic resin 25 parts by weight Butyral resin 25 parts by weight Polyfunctional acrylate 2 parts by weight γ-methacryloxypropyltrimethoxysilane-treated silica (particle size 1.7 μm) 5 parts by weight Composition for transparent resin layer (Y) 50 parts by weight of acrylic resin 2 parts by weight of polyfunctional acrylate-Composition for decorative layer (for pattern layer) (Z) 50 parts by weight of acrylic resin 50 parts by weight of vinyl chloride-vinyl acetate copolymer Pigment 5 parts by weight

Using this transfer sheet, a decorative layer (pattern layer) of the transfer sheet is superimposed on the surface of a medium density fiber board as an object to be transferred at 200 ° C., 10 kg
/ Cm ^{2 at} a rate of 2 m / min.

Comparative Example 4 As a substrate film, 0.3 g / m ² of a melamine resin-based ink (manufactured by The Inktec) was applied to the surface of a 25 μm biaxially stretched polyethylene terephthalate film,
The film was baked at 20 ° C. for 20 seconds to form a release layer, thereby producing a release substrate film. Next, the following release layer composition (A) is dissolved and diluted in a mixed solvent of methyl ethyl ketone and toluene, and then applied on the release substrate film, and the mixed solvent is volatilized by drying at 60 ° C. for 1 minute. , Remove and apply 6 g / m ²
Was obtained. Next, the transparent resin layer composition (Y) was diluted with the same mixed solvent as in (A), and applied and dried on the release layer to obtain a transparent resin layer having an application amount of 4 g / m ² . Next, the decorative layer composition (Z) was diluted with the same mixed solvent as in (A), and the grain was gravure-printed on the transparent resin layer and dried to obtain a decorative layer (pattern layer). . Next, an adhesive layer having a coating amount of 2 g / m ² was obtained after drying the polyamide adhesive by gravure coating on the transparent resin layer.

• Composition for release layer (A) 25 parts by weight of acrylic resin 2 parts by weight of polyfunctional acrylate 5 parts by weight of silica treated with γ-methacryloxypropyltrimethoxysilane (particle size 1.7 μm) • Composition for transparent resin layer (Y) Acrylic resin 50 parts by weight Polyfunctional acrylate 2 parts by weight Composition for decorative layer (for pattern layer) (Z) Acrylic resin 50 parts by weight Vinyl chloride vinyl acetate copolymer 50 parts by weight Pigment 5 parts by weight

Using this transfer sheet, a decorative layer (picture layer) of the transfer sheet is superposed on the surface of a medium-density fiber board as a transfer object at 200 ° C., 10 kg
/ Cm ^{2 at} a rate of 2 m / min.

[Results of Performance Test] Table 1 shows the results of comparison of the transferred material of the transfer sheet of Example 1 and the transferred materials of the transfer sheets of Comparative Examples 1 to 4 in various physical properties.

[Test Method] Peeling strength: 0 hr and 24 hr. Heavy and light ones with hand peel feeling are rejected. 2. Printability Visually evaluate the printing condition of the pattern (the degree of pattern omission)

[0065]

[Table 1]

[0066]

According to the transfer sheet and the transfer product of the present invention, the release strength is improved by providing a release layer (0.1 to 1 μm) made of a thin thermoplastic resin on the physical property enhancement layer. The abrasion resistance was improved by adding small metal oxide fine particles to the physical property enhancement layer. Further, by applying a transparent resin layer containing no fine particles between the physical property enhancement layer and the pattern layer, pattern omission during printing was eliminated.

[Brief description of the drawings]

FIG. 1 is a sectional view showing an example of a transfer sheet according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Adhesive layer 2 Decorative layer 3 Transparent resin layer 4 Physical property enhancement layer 5 Release layer 6 Release layer 7 Base material (base sheet) 8 Transfer sheet 9 Metal oxide fine particles 10 Transfer object

Claims (7)

[Claims] 1. A transfer sheet having at least a release layer, a physical property enhancement layer, and a transparent resin layer on a release substrate, wherein the release layer comprises a thermoplastic resin layer having a thickness of 0.1 to 1 μm. A transfer sheet, wherein the physical property enhancing layer is made of a curable resin containing 5 to 50% by weight of metal oxide fine particles having an average particle diameter of 1 μm to 10 μm, and the transparent resin layer is made of a curable resin. 2. The fine particles are oxide fine particles of one or more elements selected from silicon, aluminum, titanium, lead, zinc, tin, cerium, zirconium, and germanium. The transfer sheet according to claim 1, wherein 3. The transfer sheet according to claim 1, wherein the fine particles have a spherical shape. 4. The transfer sheet according to claim 1, wherein the property enhancing layer is made of an ionizing radiation curable resin. 5. The transfer sheet according to claim 1, wherein the property enhancing layer is made of a thermosetting resin. 6. The transfer sheet according to claim 1, wherein said transparent resin layer is made of an ionizing radiation-curable resin. 7. The transfer sheet according to claim 1, wherein the transparent resin layer is made of a thermosetting resin.