WO2011136068A1

WO2011136068A1 - Thermal transfer film and decorative molded article using same

Info

Publication number: WO2011136068A1
Application number: PCT/JP2011/059506
Authority: WO
Inventors: 永田　寛知; 一彦守屋; 勝仁黒木
Original assignee: Dic株式会社
Priority date: 2010-04-26
Filing date: 2011-04-18
Publication date: 2011-11-03
Also published as: JP4872140B2; KR101287900B1; TW201200352A; CN102695618B; KR20120041742A; JPWO2011136068A1; TWI498214B; CN102695618A

Abstract

Disclosed is a thermal transfer film which comprises, on a base film, a transfer layer wherein a radically polymerizable resin composition layer and a decorative layer are laminated in this order. The thermal transfer film is characterized in that the radically polymerizable resin composition layer contains a (meth)acrylic resin, which contains a radically polymerizable unsaturated group, and a (meth)acrylate of an epoxidized vegetable oil. Also disclosed is a decorative molded article which is obtained using the thermal transfer film, specifically by fitting the thermal transfer film in a mold for injection molding and performing injection molding, or alternatively by bonding and integrating the thermal transfer film to a transfer-receiving base by vacuum molding. The thus-obtained protective layer has excellent surface properties, especially excellent fingerprint resistance.

Description

Thermal transfer film and decorative molded product using the same

In the present invention, for example, a transfer layer including at least a protective layer is transferred and formed on the surface of various transfer substrates such as a synthetic resin substrate, a wood substrate, an inorganic substrate, and a metal substrate. This relates to a transfer film.

Conventionally, as a decoration method of articles, a protective layer or the like can be easily formed on the surface of various transferred substrates such as a synthetic resin base material, a wood base material, an inorganic base material, a metal base material, A transfer method using a transfer film is used. With this transfer method, a protective layer made of a resin composition having excellent surface properties such as hardness and solvent resistance is provided on a base film made of paper, a thermoplastic resin film, etc. in a peelable state, and further required According to the above, a transfer film is prepared by providing a pattern layer, an adhesive layer, etc. (hereinafter these are referred to as a transfer layer together with the protective layer), and the transfer layer surface of the transfer film is used as the surface of the substrate (substrate to be transferred). The transfer layer of the transfer film is bonded to the substrate to be transferred or the injection resin by placing the transfer film in advance in the injection mold and filling with the injection resin. This is a method for producing a desired decorative article in which a transfer layer is transferred and formed on a substrate to be transferred by peeling off at the interface with the material film and removing the substrate film. In recent years, active investigations have been made as a method of decorating automobile interior members, household appliance members, electronic device casings, and the like.

As the protective layer, a thermosetting resin is used to impart excellent surface properties such as surface hardness, abrasion resistance, scratch resistance, solvent resistance, and chemical resistance to the surface of the product after transfer. Alternatively, a curable resin such as an active energy ray curable resin is generally used, and specifically, a two-component curable polyurethane resin that is a reaction product of a polyol compound and an isocyanate compound, Various materials using an ionizing radiation curable acrylate resin having a radical polymerizable double bond have already been used (see, for example, Patent Document 1).
Also, when used as a decoration on home appliances and electronic equipment casings, in addition to the physical properties such as surface hardness, a function to protect against oil stains such as skin and sebum (called fingerprint resistance) Is also required.

As a technique known in the coating field for the fingerprint resistance, for example, a technique of blending a fluorosurfactant with a hard coat agent and making the resulting cured film water repellent (see, for example, Patent Document 2), Hard coat agent utilizing high water repellency derived from fluorine such as a technique using a copolymer of a polymerizable monomer having a chain alkyl group and a polymerizable monomer having a polyfluoroalkyl group (see, for example, Patent Document 3) There is a technology for imparting fingerprint smudge prevention. All of these techniques using fluorine utilize the property that fluorine groups are unevenly distributed at the air interface after coating. However, as described above, the protective layer in the transfer film is provided on the base film in a peelable state, that is, since there is no air interface, fluorine groups are unevenly distributed on the surface that becomes the surface of the protective layer after transfer. There is a problem that fingerprint resistance cannot be obtained.

Japanese Patent Laid-Open No. 7-314995 Japanese Patent Laid-Open No. 10-110118 JP 2010-24283 A

The problem to be solved by the present invention is to provide a transfer film using a curable resin as a protective layer, and to provide a film for thermal transfer which is excellent in surface physical properties, particularly fingerprint resistance.

The present inventors solved the above problems by adding epoxidized vegetable oil (meth) acrylate as a component of the curable resin layer, that is, the radical polymerizable resin composition layer.

That is, the present invention is a thermal transfer film having a transfer layer in which a radical polymerizable resin composition layer and a decorative layer are laminated in this order on a base film, wherein the radical polymerizable resin composition layer is a radical film. A film for thermal transfer containing a (meth) acrylic resin containing a polymerizable unsaturated group and an epoxidized vegetable oil (meth) acrylate is provided.

According to the present invention, a decorative molded product having excellent surface properties, particularly fingerprint resistance, can be obtained.

(Base film)
The base film used in the present invention is not particularly limited, and a known base film for thermal transfer can be used. Specifically, for example, a film made of heat-resistant resin such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyamide 6, 66 (PA6, PA66), polyimide (PI), polyvinyl alcohol (PVA) or the like is preferably used. . Among these, a film made of PET resin is most preferably used because it is excellent in cost and beauty. The thickness of the base resin film 1 is preferably 20 to 125 μm, but is preferably 35 to 75 μm in consideration of the ability to follow a three-dimensional shape.

A release layer may be provided between the base film and a transfer layer described later. The release layer functions as a layer for releasing the transfer layer and the base material film, which are transferred to the substrate to be transferred or the injection-molded product that is a molded product of the injection resin. The release layer is required to have a release property from the transfer layer, but is also required to have an adhesive property between the base film and the transfer layer so that the transfer layer does not release from the release layer.

As the release layer, a commonly used release agent such as a silicone resin, a fluororesin, a cellulose derivative resin, a urea resin, a polyolefin resin, or a melamine resin can be used. For example, when a PET resin film is used as the base resin film 1, a silicone resin release agent having an appropriate release property is suitably used. The release layer 2 can be applied using a roll coater or the like, and the thickness is preferably 0.01 μm to 5 μm.

(Transfer layer)
In the thermal transfer film of the present invention, the transfer layer includes at least a radical polymerizable resin composition layer that is an outermost layer of a transfer body obtained by transferring to a transfer substrate, and the radical polymerizable resin composition layer. It is a layer which has at least a decorating layer between the transfer target substrate.
On the base film, the radical polymerizable resin composition layer and the decorative layer are laminated in this order so that the decorative layer is between the radical polymerizable resin composition layer and the substrate to be transferred. To be provided. In addition to the radical polymerizable resin composition layer and the decorative layer, an adhesive layer or a layer such as an intermediate layer for concealing unevenness on the surface of the substrate to be transferred may be provided.

(Transfer layer Radical polymerizable resin composition layer)
The radical polymerizable resin composition layer used in the present invention contains a (meth) acrylic resin containing a radical polymerizable unsaturated group and an epoxidized vegetable oil (meth) acrylate.

(Epoxidized vegetable oil (meth) acrylate)
Epoxidized vegetable oil (meth) acrylate is a compound obtained by ring-opening addition polymerization of (meth) acrylic acid to the epoxy group of epoxidized vegetable oil epoxidized with peracetic acid and perbenzoic acid to the double bond of unsaturated vegetable oil. is there.
The vegetable oil in the present invention is a triglyceride in which at least one fatty acid is a fatty acid having at least one carbon-carbon unsaturated bond in the triglyceride of glycerin and a fatty acid. , Asa seed oil, flaxseed oil, Eno oil, Ochishika oil, olive oil, cacao oil, kapok oil, kayak oil, mustard oil, kyounin oil, kiri oil, kukui oil, walnut oil, poppy oil, sesame oil, safflower oil, radish Seed oil, soybean oil, blast oil oil, camellia oil, corn oil, rapeseed oil, niger oil, nuka oil, palm oil, castor oil, sunflower oil, grape seed oil, gentian oil, pine seed oil, cottonseed oil, coconut oil, Peanut oil, dehydrated castor oil, and the like.
Specific examples of the epoxidized vegetable oil (meth) acrylate include epoxidized soybean oil acrylate (CN111 manufactured by Kayaku Sartomer, EBECRYL860 manufactured by UCB, Photomer 3005F manufactured by cognis), epoxidized linseed oil acrylate (Cognis) Photomer 3082) and the like.

The epoxidized vegetable oil (meth) acrylate is preferably added in an amount of 0.1 to 20% by weight, and most preferably in the range of 1 to 10% by weight, based on the total solid content of the radical polymerizable resin composition. Depending on the composition of the radical polymerizable resin composition, if it is less than 0.1%, the anti-fingerprinting ability may be insufficient, and if it exceeds 20%, the radical polymerizable resin composition is plasticized and the film hardness is increased. May decrease.

((Meth) acrylic resin containing radically polymerizable unsaturated group)
The (meth) acrylic resin containing a radically polymerizable unsaturated group used in the present invention is not particularly limited, and a (meth) acrylic resin obtained by a known method can be used. Specifically, for example, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate, cyclohexyl methacrylate, ethyl hexyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, hydroxyethyl acrylate, acrylic acid Mainly composed of (meth) acrylic resins obtained by homo- or copolymerization of (meth) acrylic monomers such as cyclohexyl, ethylhexyl acrylate, methacrylic acid, acrylic acid, acrylonitrile, methacrylonitrile, or the above (meth) acrylates. Monomers having a polymerizable double bond that can be copolymerized therewith, for example, ethylene, butadiene, isoprene, vinyl acetate, vinyl propionate, vinyl butyrate, styrene, α-methylstyrene Vinyl toluene, divinyl benzene, N - cyclohexyl maleimide, N - ethylmaleimide, N - phenylmaleimide and the like is added as a copolymerization component (meth) acrylic resin.
The (meth) acrylic resin can be obtained by polymerizing the (meth) acrylic monomer or a monomer having a polymerizable double bond by a conventional method.

As a method for introducing a polymerizable unsaturated group into the (meth) acrylic resin, for example, a carboxyl group-containing polymerizable monomer such as acrylic acid or methacrylic acid, dimethylaminoethyl methacrylate, An amino group-containing polymerizable monomer such as dimethylaminopropylacrylamide is blended and copolymerized to obtain the copolymer having a carboxyl group or an amino group, and then the carboxyl group or amino group and glycidyl such as glycidyl methacrylate. A method of reacting a monomer having a group and a polymerizable unsaturated group,
A hydroxyl group-containing monomer such as 2-hydroxyethyl methacrylate or 2-hydroxyethyl acrylate is previously blended and copolymerized as the copolymer component to obtain the copolymer having a hydroxyl group, and then the hydroxyl group and isocyanate ethyl methacrylate are obtained. A method of reacting a monomer having a polymerizable unsaturated group with an isocyanate group such as
A glycidyl group-containing polymerizable monomer such as glycidyl methacrylate is previously blended and copolymerized as the copolymer component to obtain the copolymer having a glycidyl group, and then the glycidyl group and a carboxyl group of acrylic acid or methacrylic acid. A method of reacting the containing polymerizable monomer,
During polymerization, thioglycolic acid is used as a chain transfer agent to introduce a carboxyl group at the end of the copolymer, and a monomer having a glycidyl group such as glycidyl methacrylate and a polymerizable unsaturated group is added to the carboxyl group. How to react,
As a polymerization initiator, a carboxyl group-containing azo initiator such as azobiscyanopentanoic acid is used to introduce a carboxyl group into the copolymer, and a glycidyl group such as glycidyl methacrylate and a polymerizable unsaturated group are introduced into the carboxyl group. And the like.
Among them, a carboxyl group-containing monomer such as acrylic acid or methacrylic acid or an amino group-containing monomer such as dimethylaminoethyl methacrylate or dimethylaminopropylacrylamide is copolymerized, and the carboxyl group or amino group and glycidyl methacrylate are copolymerized. A method of reacting a monomer having a polymerizable unsaturated group with a glycidyl group such as glycidyl group, or a glycidyl group-containing polymerizable monomer such as glycidyl methacrylate in advance as a copolymerization component, The method of obtaining the above-mentioned copolymer and then reacting the glycidyl group with a carboxyl group-containing polymerizable monomer of acrylic acid or methacrylic acid is the simplest and preferred.

The (meth) acrylic resin containing a radically polymerizable unsaturated group is preferably contained in an amount of 10 to 99.9% by weight of the total solid content of the radically polymerizable resin composition, and ranges from 40 to 99.9% by weight. Is most preferred. If it is less than 10%, tackiness may remain on the surface due to the addition of epoxidized vegetable oil (meth) acrylate that is liquid at room temperature.

(Other components Photopolymerization initiator)
When the thermal transfer film of the present invention is cured with active energy rays, a photopolymerization initiator may be preferably used in the radical polymerizable resin composition layer. Examples of photopolymerization initiators include, for example, acetophenone compounds such as diethoxyacetophenone and 1-hydroxycyclohexyl-phenyl ketone; benzoin compounds such as benzoin and benzoin isopropyl ether; 2,4,6-trimethylbenzoin diphenylphosphine oxide Acyl phosphine oxide compounds such as benzophenone, benzophenone compounds such as methyl-4-phenylbenzophenone o-benzoylbenzoate; thioxanthone compounds such as 2,4-dimethylthioxanthone; aminobenzophenones such as 4,4′-diethylaminobenzophenone Compounds such as polyether-based maleimide carboxylic acid ester compounds, and the like, which can be used in combination. The amount of the photopolymerization initiator used is 0.1 to 20% by mass, preferably 0.5 to 15% by mass, based on the total solid content of the radical polymerizable resin composition. Examples of the photosensitizer include amines such as triethanolamine and ethyl 4-dimethylaminobenzoate. Furthermore, onium salts such as benzylsulfonium salt, benzylpyridinium salt, and arylsulfonium salt are known as photocationic initiators, and these initiators can also be used, and are used in combination with the above photopolymerization initiators. You can also

(Thermal polymerization initiator)
Moreover, when thermosetting the film for thermal transfer of the present invention, a thermal polymerization initiator may be preferably used for the radical polymerizable resin composition layer. Examples of thermal polymerization initiators include various peroxides such as hydrogen peroxide, t-butyl hydroperoxide, di-t-butyl peroxide and cumene hydroperoxide; potassium persulfate, sodium persulfate, ammonium persulfate, etc. Various persulfates of azobisisobutyronitrile, 1-[(1-cyano-1-methylethyl) azo] formamide, 2,2′-azobis [2- (5-methyl-2-imidazoline-2) -Yl) propane] dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] or its dihydrochloride, 2,2′-azobis [2- (4,5,5) 6,7-tetrahydro-1H-1,3-diazepin-2-yl) propane] dihydrochloride, 2,2′-azobis [N- (4-aminophenyl) -2-methylpropion Amidine], dihydrochloride of 2,2′-azobis (2-methylpropionamide) and the like, and various azo initiators. In particular, in the case of the vacuum forming method, a sufficient amount of heat is applied to the film to form it instantaneously, so that a thermal polymerization initiator can also be suitably used.

(Isocyanate compound)
In addition, when the film for thermal transfer of the present invention is thermally cured, radical polymerization is performed by selecting a resin having a hydroxyl group as the (meth) acrylic resin containing the radical polymerizable unsaturated group and adding an isocyanate compound. A urethane crosslinked structure different from the crosslinked structure derived from the unsaturated group can be introduced, which is preferable.
As the (meth) acrylic resin containing a radical polymerizable unsaturated group and having a hydroxyl group, for example, a carboxyl group-containing monomer such as acrylic acid or methacrylic acid is copolymerized, and the carboxyl group and glycidyl are copolymerized. A method in which a monomer having a polymerizable unsaturated group and a glycidyl group such as methacrylate is reacted, or a glycidyl group-containing polymerizable monomer such as glycidyl methacrylate is previously blended and copolymerized as the copolymer component, and then glycidyl (Meth) acrylic resin obtained by a method of reacting a glycidyl group with a carboxyl group-containing polymerizable monomer of acrylic acid or methacrylic acid, or hydroxyethyl acrylate, etc. (Meth) acrylic resin copolymerized with (meth) acrylate having a hydroxyl group of

Examples of the isocyanate compound include aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane-4,4′-diisocyanate, meta-xylylene diisocyanate, α, α, α ′, α′-tetramethyl-meta-xylylene diisocyanate. Polyisocyanates mainly composed of aralkyl diisocyanates such as tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4- (or 2,4,4-trimethyl- 1,6-hexamethylene diisocyanate, lysine isocyanate, isophorone diisocyanate, hydrogenated xylene diisocyanate, hydrogenated diphenylmethane diisocyanate, 1,4-diisocyanate cyclohexane, 1,3 Aliphatic diisocyanates such as bis (diisocyanatemethyl) cyclohexane and 4,4′-dicyclohexylmethane diisocyanate, allophanate type polyisocyanates, biuret type polyisocyanates, adduct type polyisocyanates and isocyanurates which are aliphatic polyisocyanates obtained from aliphatic diisocyanates Type polyisocyanate, and any of them can be suitably used.

In addition, as the above-described polyisocyanate, so-called blocked polyisocyanate compounds blocked with various blocking agents can be used. Examples of the blocking agent include alcohols such as methanol, ethanol and lactic acid ester; phenolic hydroxyl group-containing compounds such as phenol and salicylic acid ester; amides such as ε-caprolactam and 2-pyrrolidone; oximes such as acetone oxime and methyl ethyl ketoxime Active methylene compounds such as methyl acetoacetate, ethyl acetoacetate and acetylacetone can be used. By using the block polyisocyanate compound, it becomes possible to use a hydroxyl group-containing solvent such as alcohol for the coating material for forming the radical polymerizable resin composition layer described later.

(Other ingredients)
Moreover, an inorganic or metal compound, organic fine particles, etc. can also be added to a radically polymerizable resin composition layer. Examples of the inorganic or metal compound include silica, silica gel, silica sol, silicone, montmorillonite, mica, alumina, titanium oxide, talc, barium sulfate, aluminum stearate, magnesium carbonate, glass beads and the like. Further, organosilica sol, acrylic-modified silica, closite, etc. obtained by organically treating the inorganic or metal compound may be used. Examples of the organic fine particles include fine particles such as polyethylene resin, acrylic resin, styrene resin, fluorine resin, melamine resin, polyurethane resin, polycarbonate resin, and phenol resin. These may be used alone or in combination. In addition, a general-purpose additive such as an ultraviolet absorber, a leveling agent, an antiblocking agent and the like can be added within a range not impairing the effects of the present invention.

The thickness of the radical polymerizable resin composition layer used in the present invention is preferably 1 to 50 μm, more preferably 3 to 40 μm, from the viewpoint of surface protection of the substrate to be transferred or the injection-molded product and coating properties.

(Decoration layer)
A general-purpose printing ink or paint can be used for the decorative layer, and can be formed using gravure printing, offset printing, screen printing, inkjet printing, thermal transfer printing, and the like. The dry film thickness of the decorative layer is preferably 0.5 to 15 μm, more preferably 1 to 7 μm. A colored layer having no pattern and a colorless varnish resin layer can also be formed by coating.
In addition, the printed pattern for printing can be any printed pattern as long as it is a pattern or character that can wake up or print. A solid version may also be used.

As a coloring material used for printing ink or paint, printing can be performed using a known organic pigment or inorganic pigment, which is preferable.
Examples of the organic pigment include quinacridone pigments, phthalocyanine pigments, selenium pigments, perylene pigments, phthalone pigments, dioxazine pigments, isoindolinone pigments, methine / azomethine pigments, and diketopyrrolopyrrole pigments. Azo lake pigments, insoluble azo pigments, condensed azo pigments, and the like.
Examples of inorganic pigments include inorganic pigments such as carbon black, iron oxide and titanium oxide, metal powder pigments such as aluminum powder and bronze powder, and pearlescent pigments such as titanium oxide-coated mica.

The resin for varnish contained in the ink is not particularly limited. For example, acrylic resin, polyurethane resin, polyester resin, vinyl resin (vinyl chloride, vinyl acetate, vinyl chloride-vinyl acetate copolymer resin), chlorine Known inks such as olefinic olefin resin, ethylene-acrylic resin, petroleum resin, and cellulose derivative resin can be used.

In addition, the organic solvent contained in the ink can be used without particular limitation as long as it does not attack the radical polymerizable resin composition layer or the peelable film described later. Specific examples include, for example, toluene, xylene, cyclohexane, n -Hydrocarbon organic solvents such as hexane or mineral spirit, esters such as methyl acetate, ethyl acetate, n-butyl acetate, isobutyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol monobutyl ether acetate or amyl acetate Organic solvents, ether organic solvents such as n-butyl ether, dioxane, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether or diethylene glycol, acetate Ketone-based organic solvents such as N, methyl ethyl ketone, methyl isobutyl ketone, methyl amino ketone, diisobutyl ketone or cyclohexanone, nitrogen-containing systems such as N-methylpyrrolidone, “Swazole 310, Swazole 1000, Swazol 1500” [manufactured by Cosmo Oil Co., Ltd. An aromatic petroleum solvent system such as These organic solvents may be used alone or in combination of two or more.

In addition to the base resin and the colorant, the printing ink or paint may contain a plasticizer, a surfactant, an antioxidant, an ultraviolet absorber, a matting agent, a solvent, and the like as necessary.

(Method for producing thermal transfer film)
The film for thermal transfer of the present invention is most preferably a method in which a decorative layer is directly printed or coated on a base film provided with the radical polymerizable resin composition layer. Further, an intermediate (primer) layer may be provided in order to ensure interlayer adhesion between the radical heavy synthetic resin layer and the decorative layer.
The method for providing the radical polymerizable resin composition layer on the base film or the method for providing the decorative layer is not particularly limited. For example, a gravure printing method, an offset printing method, a gravure offset printing method, a flexographic printing method. , Various printing methods such as screen printing method, gravure coating method, micro gravure coating method, roll coating method, rod coating method, kiss coating method, knife coating method, air knife coating method, comma coating method, die coating method, lip coating method Various known coating methods such as a flow coating method, a dip coating method, and a spray coating method can be appropriately used. In particular, the decoration layer can be formed by gravure printing, offset printing, screen printing, ink jet printing, and the like, and gravure printing is preferable because a high-quality image can be easily obtained. The dry film thickness of the decorative layer is preferably 0.5 to 15 μm, more preferably 1 to 7 μm.

Further, by dry lamination (dry lamination method), the base film provided with the radical polymerizable resin composition layer and the optional peelable film provided with the decoration layer are combined with the polymerizable resin layer and the decorative layer. Can be manufactured by a method in which they are stacked so as to face each other and bonded together by dry lamination (dry lamination method) and transferred.
The bonding temperature by drying and heating and pressing is not particularly limited, and may be performed while taking into consideration the heat-resistant temperature of the substrate film to be used.

The produced thermal transfer film may be aged as necessary, for example, to improve interlayer adhesion.

(Film thickness for thermal transfer)
The total film thickness of the thermal transfer film of the present application is not particularly limited because it depends on the thermal transfer method, but is preferably 21.5 to 200 μm, more preferably 30 to 150 μm, from the viewpoint of shape followability to the transfer substrate.

(Adhesive layer)
In addition, an arbitrary layer can be further laminated as long as the effects of the present invention are not impaired. For example, when the thermal transfer film of the present invention is attached to a substrate to be transferred, it is preferable to provide an adhesive layer or an adhesive layer on the surface of the decorative layer in contact with the substrate to be transferred. The adhesive layer or the pressure-sensitive adhesive layer is a layer provided for the purpose of increasing the adhesive force with the adherend, and may be an adhesive or a pressure-sensitive adhesive, and appropriately select a material that adheres to the resin film and the adherend. Is possible.

For example, as an adhesive, for example, acrylic resin, urethane resin, urethane modified polyester resin, polyester resin, epoxy resin, ethylene-vinyl acetate copolymer resin (EVA), vinyl chloride resin, vinyl chloride-vinyl acetate copolymer resin, natural Examples thereof include synthetic rubbers such as rubber, SBR, NBR, and silicone rubber. Solvent type or solventless type can be used.

The pressure-sensitive adhesive is not particularly limited as long as it has tackiness at the temperature at which it is thermoformed. For example, solvents such as acrylic resin, isobutylene rubber resin, styrene-butadiene rubber resin, isoprene rubber resin, natural rubber resin, and silicone resin Type adhesive, acrylic emulsion resin, styrene butadiene latex resin, natural rubber latex resin, styrene-isoprene copolymer resin, styrene-butadiene copolymer resin, styrene-ethylene-butylene copolymer resin, ethylene-vinyl acetate resin Solvent-free pressure-sensitive adhesives such as polyvinyl alcohol, polyacrylamide, and polyvinyl methyl ether.

When the adhesive layer or the pressure-sensitive adhesive layer is provided on the thermal transfer film of the present invention, it is directly printed or coated on the film provided with the radical polymerizable resin composition layer and the decorative layer, or the radical polymerizable resin composition. It can be obtained by a method in which the layer and the decorative layer are stacked so as to face each other and transferred by dry lamination. In the latter case, it is preferable to transfer the decorative layer having an adhesive layer, but the adhesive layer may be provided after the decorative layer is transferred.

(Thermal transfer method)
The thermal transfer film of the present invention can be used in a known transfer method. Specifically, if necessary, a pre-formed thermal transfer film is placed on the surface of the female mold, both molds are closed, and molten resin is injected from the injection hole into the cavity between the molds (molded cavity). After the resin was cooled and solidified, both molds were opened, the molded product and the thermal transfer film adhered to the molded product were taken out of the mold, only the base film was peeled off, and the transfer layer was transferred and formed on the transfer substrate. After obtaining the decorative product, after the thermal transfer film is placed above the molded transfer substrate and the transfer layer faces the transfer substrate, and the film is heated above the softening temperature. In addition, molding is performed using a substrate to be transferred without using a mold in a vacuum, and at the same time, thermal transfer is performed during thermal transfer, such as a vacuum molding simultaneous pasting method, a lapping simultaneous transfer method, etc. A three-dimensional shape that stretches and deforms Thermal transfer film particularly suitable for the present invention to transfer method may be used. However, the thermal transfer film of the present invention may be used for a transfer method such as hot stamping that extends to the thermal transfer film and does not undergo deformation.

(Active energy ray irradiation)
The radical polymerizable resin composition layer of the decorative product to which the film for thermal transfer of the present invention is transferred is cured with active energy rays or the like. As the active energy ray, it is usually preferable to use visible light or ultraviolet light. In particular, ultraviolet rays are suitable. As the ultraviolet light source, sunlight, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like is used. In addition, as a heating source when heat is used in combination, a known heat source such as hot air or near infrared light can be applied.
The irradiation dose at this time, it is preferable that the curable resin layer is irradiation amount as fully cured, specifically preferably in the range of ^{250mJ / cm 2 ~ 3000mJ / cm} 2. In particular, 1000 mJ / cm ² to 3000 mJ / cm in order to sufficiently cure the radical reactive diluent or radical polymerizable oligomer that has moved to the interface with the decorative layer and improve the adhesion to the substrate to be transferred. A range of ² is more preferred.
The timing at which the substrate film is peeled may be before or after the irradiation with the active energy ray.

(Transfer substrate)
The transfer substrate to which the thermal transfer film of the present invention can be transferred is not particularly limited, and various shapes such as resin, metal, glass, wood, and paper can be used, and the shape can be painted, plated, or scratched. It may be decorated by a common decoration method such as.
Further, when the material of the adherend surface of the substrate to be transferred and the material of the thermoplastic resin or ink binder used in the thermal transfer film of the present invention are materials that can be thermally bonded or heat-bonded, it is more closely attached Excellent in properties and preferable. For example, when the material of the adherend surface of the substrate to be transferred is an acrylic resin or a styrene resin, the thermoplastic resin used for the thermal transfer film is preferably an acrylic resin.

Hereinafter, the present invention will be described by way of examples. Unless otherwise specified, “parts” and “%” are based on weight.

(Evaluation methods)
<Adhesion>
Adhesiveness was evaluated by a peel test of cross-cut cello tape (cello tape is a registered trademark) of JIS K-5400. Since PC / ABS resin was used as the substrate, the evaluation was performed at 2 mm square and 100 squares. The case where the number of remaining cells was 100 was evaluated as ◯, the case where 100 cells remained but there were not more than 10 cells was determined as Δ, and the others were determined as ×.

<Fingerprint visibility>
After 10 μL of oleic acid is dropped on a Teflon sheet (Teflon is a registered trademark) and wiped off with a urethane sponge (3M Scotch Bright) cut into 3 cm square, the surface of the sponge with oleic acid attached is removed. The surface of the product to be evaluated was pressed for 10 seconds to adhere oleic acid.
By using a color difference meter to calculate dL * before and after oleic acid adhesion, it is used as a substitute characteristic value for visibility when a fingerprint is adhered, dL * ≦ 1.5 is ○, 1.5 <dL * ≦ 3 is Δ and dL * <3 were evaluated as x.

<Fingerprint wiping>
Similar to the evaluation of fingerprint visibility, after attaching oleic acid and then wiping twice with absorbent cotton (each using a new surface), use a color difference meter to recover from dL * before and after oleic acid attachment By calculating the rate, a substitute characteristic value for the fingerprint wiping property was obtained. Evaluation was made with dL * ≦ 80% as ◯, 50% ≦ dL * <80% as Δ, and dL * <50% as ×.

(Method for producing (meth) acrylic resin containing radically polymerizable unsaturated group)
<Reference Example 1>
A four-necked flask equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen gas inlet tube was charged with 950 parts of butyl acetate and heated to 80 ° C. When the temperature reached that temperature, 970 parts of butyl acrylate Then, a mixture of 30 parts of methacrylic acid and 7 parts of 2,2′-azobis (2-methylbutyronitrile) was added dropwise over 4 hours, and after completion of the addition, the temperature was raised to 90 ° C. and maintained for 10 hours. Continued.
The temperature of the reaction solution was lowered to 50 ° C., a solution in which 0.2 part of t-butylpyrocatechol was dissolved in 20 parts of butyl acetate was added, and 20 parts of glycidyl methacrylate and 3 parts of dimethylaminoethanol were added. The solution was heated to 80 ° C. and reacted at the same temperature for 10 hours to obtain a solution of (meth) acrylic resin (A1) containing a radical polymerizable unsaturated group.

(Molding method)
<Injection molding method>
The thermal transfer film obtained by the method described later was placed on an injection molding machine “EC75N-1.5Y” manufactured by Toshiba Machine Co., and the mold was then closed. The mold has a tray shape in which the shape of the injection-molded body is 100 (L) × 100 (W) × 9 (H) mm, corner R = 10 mm, rising portion R = 5R, draft angle 18.5 °. I used something.
The temperature of the mold was adjusted to 50 ° C. with a heater, and injection resin “Multilon TN-3715B” manufactured by Teijin Chemicals Ltd. was injected at an injection resin temperature of 265 ° C. The injection molded body was removed from the mold, the peelable film was peeled off, and an injection molded body on which the radical polymerizable resin composition layer and the decorative layer of the thermal transfer film were transferred was obtained. Then, a decorative molded product was obtained by performing ultraviolet irradiation with a total irradiation amount of 1000 mJ / cm ² (peak intensity 180 mW / cm ² ).

<Vacuum forming simultaneous pasting method>
Thermoforming was performed using “NGF-0709 molding machine” manufactured by Fuse Vacuum Co., Ltd.
After completely fixing the periphery of the thermal transfer film obtained by the method described below with a clamp, close the upper and lower boxes of the molding machine and make the inside of the box almost completely vacuumed, then use a Helius mid-infrared heater as the heater. After indirectly heating the thermal transfer film from the upper surface, the table on which the adherend is placed is raised, 0.2 MPa of compressed air is blown into the upper box, and the thermal transfer film is attached to the adherend and integrally molded. It was.
In addition, the distance of a heater and the resin sheet S was about 250 mm, and the adherend used the flat plate of length 80mm * width 150mm * thickness 2mm.
The peelable film was peeled off, and a decorative molded product was obtained by performing ultraviolet irradiation with a total irradiation amount of 1000 mJ / cm ² (peak intensity 180 mW / cm ² ).

<Example 1 Production Method of Thermal Transfer Film (D1)>
5% by weight of epoxidized soybean oil acrylate (Cognis Photomer 3005F) and 1% by weight based on the nonvolatile content of the solution of the (meth) acrylic resin (A1) containing the radical polymerizable unsaturated group obtained in Reference Example 1 % Photopolymerization initiator Irgacure 184 (manufactured by Ciba Specialty) was added to prepare a radical polymerizable resin composition (B1).
Using a rod gravure coater, the radical polymerizable resin composition (B1) was applied onto a polyethylene terephthalate (PET) sheet “Therapy HP2 / TB (S)” (film thickness 50 μm) manufactured by Toray Film Processing Co., Ltd. at 100 ° C. By drying for 1 minute, a film (C1) having a radically polymerizable resin composition (B1) layer having a film thickness of 5 μm after drying was obtained.
A film (D1) for thermal transfer is obtained by directly applying an aluminum hairline pattern to the radical polymerizable resin composition (B1) layer with a gravure printing machine using DIC XS-756IM ink on the film (C1). Obtained.

<Example 2 Production Method of Thermal Transfer Film (D2)>
A radically polymerizable resin composition comprising a film (C1) having the radically polymerizable resin composition layer and an OPP film (pyrene P2002 manufactured by Toyobo Co., Ltd.) obtained by gravure printing of an aluminum hairline pattern using a DIC XS-756IM ink. After performing dry lamination at 60 ° C. so that the layer and the gravure printing layer face each other, the OPP film was peeled off to obtain a thermal transfer film (D2).

<Example 3 Production Method of Thermal Transfer Film (D3)>
5% by weight of epoxidized soybean oil acrylate (Photomer 3005F manufactured by Cognis) and 10% by weight based on the nonvolatile content of the solution of the (meth) acrylic resin (A1) containing the polymerizable unsaturated group obtained in Reference Example 1. % Of the photoinitiator Irgacure 184 (manufactured by Ciba Specialty Co., Ltd.), and then added to the polyisocyanate “Bernock DN— so that the equivalent ratio is 36% with respect to the hydroxyl group of the (meth) acrylic resin (A1). 981 "(manufactured by DIC Corporation) was added to prepare a radical polymerizable resin composition (B2).
By applying the composition (B2) onto a PET sheet “Therapy HP2 / TB (S)” (film thickness 50 μm) manufactured by Toray Film Processing Co., Ltd. using a rod gravure coater and drying at 100 ° C. for 1 minute. Then, a film (C2) having a radically polymerizable resin composition (B2) layer having a film thickness of 5 μm after drying was obtained.
A film for thermal transfer (D3) is obtained by giving an aluminum hairline pattern to the radically polymerizable resin composition (B2) layer with a gravure printing machine using DIC XS-756IM ink on the film (C2). It was.

<Example 4 Production Method for Thermal Transfer Film (D4)>
5% by weight of epoxidized linseed oil acrylate (Cognis photomer 3082) and 10% by weight based on the nonvolatile content of the solution of the (meth) acrylic resin (A1) containing a polymerizable unsaturated group obtained in Reference Example 1 After adding the photopolymerization initiator Irgacure 184 (manufactured by Ciba Specialty), the polyisocyanate “Bernock DN-981” (DIC ()) was added so that the equivalent ratio was 36% with respect to the hydroxyl group of the (meth) acrylic resin (A1). Co., Ltd.) was added to prepare a coating of the radical polymerizable resin composition (B3).
By applying the composition (B3) onto a PET sheet “Therapy HP2 / TB (S)” (film thickness 50 μm) manufactured by Toray Film Processing Co., Ltd. using a rod gravure coater and drying at 100 ° C. for 1 minute. Then, a film (C3) having a radically polymerizable resin composition (B3) layer having a thickness of 5 μm after drying was obtained.
A film for thermal transfer (D4) is obtained by giving an aluminum hairline pattern to the radically polymerizable resin composition (B3) layer with a gravure printing machine using DIC XS-756IM ink on the film (C3). It was.

(Examples 5 to 8: Method for producing injection molded article)
By using the thermal transfer films (D1) to (D4) obtained in Examples 1 to 4 according to the injection molding method, an injection molded body having a pattern was obtained. The obtained injection-molded product had a performance in which fingerprints were difficult to see and easy to wipe off. The results are shown in Table 1.

(Example 9: Manufacturing method of vacuum formed body)
The film for thermal transfer (D1) obtained in Example 1 was subjected to the vacuum forming simultaneous pasting method to obtain a vacuum formed body having a pattern. The obtained vacuum molded body was hard to see the fingerprint and showed the performance of being easily wiped off. The results are shown in Table 1.

<Comparative Example 1 An example of an injection molded article using a thermal transfer film that does not contain epoxidized vegetable oil (meth) acrylate]
10% by weight of photopolymerization initiator Irgacure 184 (manufactured by Ciba Specialty) is added to the nonvolatile content of the solution of the (meth) acrylic resin (A1) containing the polymerizable unsaturated group obtained in Reference Example 1, A radical polymerizable resin composition (H1) was prepared.
Using a rod gravure coater, the radical polymerizable resin composition (H1) was applied onto a polyethylene terephthalate (PET) sheet “Therapy HP2 / TB (S)” (film thickness 50 μm) manufactured by Toray Film Processing Co., Ltd. at 100 ° C., By drying for 1 minute, a film (HC1) having a radically polymerizable resin composition (H1) layer having a film thickness of 5 μm after drying was obtained.
The film for transfer of heat (HD1) is applied to the film (HC1) by applying an aluminum hairline pattern directly to the radical polymerizable resin composition (H1) layer with a gravure printing machine using DIC-made XS-756IM ink. Obtained.
Using the obtained thermal transfer film (HD1), an injection-molded body having a pattern was obtained according to the injection molding method. The obtained injection-molded product was easy to see fingerprints and difficult to wipe off. The results are shown in Table 2.

<Comparative example 2> Example of injection-molded body using thermal transfer film containing fluorine-based additive>
2% by weight of MegaFac RS-75 (fluorine-containing UV curable resin manufactured by DIC) based on the nonvolatile content of the solution of the (meth) acrylic resin (A1) containing a polymerizable unsaturated group obtained in Reference Example 1 And 10 weight% of photoinitiator Irgacure 184 (made by Ciba Specialty) was added, and the radical polymerizable resin composition (H2) was prepared.
Using a rod gravure coater, the radical polymerizable resin composition (H2) was applied onto a polyethylene terephthalate (PET) sheet “Therapy HP2 / TB (S)” (film thickness 50 μm) manufactured by Toray Film Processing Co., Ltd. at 100 ° C. By drying for 1 minute, a film (HC2) having a radically polymerizable resin composition (H2) layer having a film thickness of 5 μm after drying was obtained.
The film for transfer of heat (HD2) is applied to the film (HC2) by directly applying an aluminum hairline pattern to the radical polymerizable resin composition (H2) layer with a gravure printing machine using DIC-made XS-756IM ink. Obtained. At this time, the printability of the hairline pattern was slightly poor and some patterns were missing.
Using the obtained thermal transfer film (HD2), an injection-molded article having a pattern was obtained according to the injection molding method. The obtained injection-molded product was inferior in terms of adhesion, although the fingerprint wiping property was slightly improved. This is presumed that the fluorine-containing additive was segregated at the air interface during coating, resulting in poor adhesion. The results are shown in Table 2.

<Comparative Example 3> Example of injection-molded article using thermal transfer film containing fine particles of Teflon>
2% by weight of Teflon fine particles (KTL-4N manufactured by Kitamura) and 10% by weight of light with respect to the nonvolatile content of the solution of the (meth) acrylic resin (A1) containing a polymerizable unsaturated group obtained in Reference Example 1. A polymerization initiator Irgacure 184 (manufactured by Ciba Specialty) was added to prepare a radical polymerizable resin composition (H3).
Using a rod gravure coater, the radical polymerizable resin composition (H3) was applied onto a polyethylene terephthalate (PET) sheet “Therapy HP2 / TB (S)” (film thickness 50 μm) manufactured by Toray Film Processing Co., Ltd. at 100 ° C. By drying for 1 minute, a film (HC3) having a radically polymerizable resin composition (H3) layer having a film thickness of 5 μm after drying was obtained.
The film for transfer of heat (HD3) is applied to the film (HC3) by directly applying an aluminum hairline pattern to the radical polymerizable resin composition (H3) layer with a gravure printing machine using DIC-made XS-756IM ink. Obtained. At this time, the printability of the hairline pattern was slightly poor and some patterns were missing.
Using the obtained thermal transfer film (HD3), an injection-molded article having a pattern was obtained according to the injection molding method. The obtained injection-molded product was slightly inferior in fingerprint visibility, although the fingerprint wiping property was slightly improved. The results are shown in Table 2.

<Comparative example 4> Example of injection-molded article using thermal transfer film containing fluorine-based additive>
2% by weight of Sandoma 28-3F (manufactured by DH Materials, silicon-modified urethane acrylate) with respect to the nonvolatile content of the solution of the (meth) acrylic resin (A1) containing the polymerizable unsaturated group obtained in Reference Example 1. ) And 10% by weight of a photopolymerization initiator Irgacure 184 (manufactured by Ciba Specialty) were added to prepare a radical polymerizable resin composition (H4).
Using a rod gravure coater, the radical polymerizable resin composition (H4) was applied onto a polyethylene terephthalate (PET) sheet “Therapy HP2 / TB (S)” (film thickness 50 μm) manufactured by Toray Film Processing Co., Ltd. By drying for 1 minute, a film (HC4) having a radically polymerizable resin composition (H4) layer having a film thickness of 5 μm after drying was obtained.
A film (HD4) for thermal transfer is applied to the film (HC4) by directly applying an aluminum hairline pattern to the radical polymerizable resin composition (H4) layer with a gravure printing machine using an DIC-made XS-756IM ink. Obtained. At this time, the printability of the hairline pattern was slightly poor and some patterns were missing.
Using the obtained thermal transfer film (HD4), an injection-molded article having a pattern was obtained according to the injection molding method. The obtained injection-molded product was inferior in adhesion, although the fingerprint wiping property was slightly improved. This is presumed to be inferior because the silicon-containing additive segregates at the air interface during coating. The results are shown in Table 2.

Claims

A thermal transfer film having a transfer layer in which a radical polymerizable resin composition layer and a decorative layer are laminated in this order on a base film, wherein the radical polymerizable resin composition layer is a radical polymerizable unsaturated group A film for thermal transfer, comprising (meth) acrylic resin containing epoxidized vegetable oil (meth) acrylate.
The film for thermal transfer according to claim 1, wherein the epoxidized vegetable oil (meth) acrylate is epoxidized soybean oil (meth) acrylate.
The film for thermal transfer according to claim 1 or 2, wherein the (meth) acrylic resin containing the radically polymerizable unsaturated group has a hydroxy group.
The film for thermal transfer according to claim 3, comprising an isocyanate compound and partially cured with the hydroxy group.
A decorative molded product obtained by mounting the thermal transfer film according to any one of claims 1 to 4 in an injection mold and injection molding.
A decorative molded product obtained by affixing and integrating the thermal transfer film according to any one of claims 1 to 4 on a substrate to be transferred by a vacuum molding method.