JP3226605B2 - Molded article having transfer layer and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a molded article having a transfer layer on the surface and a method for producing the same.

[0002]

2. Description of the Related Art As a method of forming a transfer layer on a transfer surface of a molded article, there are (1) a method of thermally transferring a transfer layer of a thermoplastic resin onto a transfer surface of a molded article, and (2) a method of forming a transfer layer. And a method in which a liquid thermosetting resin as an adhesive for dry lamination is applied to the surface to be transferred, and then the transfer layer of the transfer sheet is transferred.

[0003]

In the above-mentioned conventional method for forming a transfer layer on a surface to be transferred, a method for thermally transferring a transfer layer made of a thermoplastic resin uses a thermoplastic resin molded body as a material to be transferred. Therefore, not only the water resistance is poor, but also the surface properties such as wear resistance and stain resistance are poor.

[0004] In addition, a liquid thermosetting resin, which is an adhesive for dry lamination, is applied to a transfer surface of a molded article by utilizing the adhesive force of a coating layer of the thermosetting resin. Because the transfer layer of the transfer sheet is transferred to the coating layer of the thermosetting resin in an uncured state having tackiness and fluidity, the pressure is applied in the transfer step of the transfer layer. The coating layer of the thermosetting resin that forms the adhesive layer flows and deforms. For this reason, cracks, distortions, deformations, etc. occur in the transfer layer transferred to the molded body, or
A good quality transfer layer cannot be obtained due to the occurrence of irregularities on the surface of the formed transfer layer.

[0005] In a method of using a coating layer of a thermosetting resin as an adhesive layer, the transfer is performed after the coating layer of the thermosetting resin forming the adhesive layer is completely cured. In addition, cracks, distortions, deformations, etc., occurring in the transfer layer described above are eliminated, and irregularities on the surface of the transfer layer are also eliminated. In this case, the adhesive layer loses chemical reactivity, heat welding property, etc. Therefore, it is not possible to obtain a good adhesive strength with the transfer layer.

On the other hand, the present invention relates to a thermosetting resin layer formed on a surface of a thermosetting resin layer formed on a transfer surface of a molded article, by applying heat pressure when the transfer layer of the transfer sheet is transferred to the thermosetting resin layer. Is a molded article having a high-quality transfer layer free of cracks, distortions, deformations, etc. without flowing or deforming. The present invention provides a molded article having a transfer layer characterized by being easy to produce from the following, and a method for accurately obtaining a molded article having the transfer layer.

[0007]

The above object can be attained by a molded article having a transfer layer according to the present invention having the following constitution and a method for producing the same. That is, the first aspect of the present invention has a transfer layer on the transfer surface of the molded body, where the transfer layer of the transfer sheet is transferred via a semi-cured non-adhesive solid layer of a thermosetting resin. It consists of a molded body.

Further, the second invention comprises a first step of forming a coating layer of a thermosetting resin on a transfer surface of a molded article used as a transfer object, and drying the coating layer by touch drying. A second step of forming a non-adhesive solid layer in an uncured state by doing so that the transfer sheet having the transfer layer is brought into contact with the transfer layer surface of the transfer sheet and the uncured non-adhesive solid layer surface. And a third step of contacting the uncured non-adhesive solid layer with the non-adhesive solid layer in the uncured state. The fourth step of transferring the transfer layer to the non-adhesive solid layer by heating and pressurizing under conditions that do not cure, and the fifth step of peeling off the portion of the transfer sheet other than the transfer layer, Non-adhesive solid in semi-cured state by thermosetting resin on the transfer surface of the molded body Process for producing a molded article having a transfer layer transfer layer of the transfer sheet through the layer, characterized in that to obtain a molded product that is transferred.

In the molded article having the transfer layer of the present invention having the above-described structure and the method for producing the same, the molded article to be used as the object to be transferred includes, for example, a single piece of wood, a wood composite, a particle board, and a medium density fiberboard. Wood molded products, gypsum, gypsum-based molded products such as gypsum slag, calcium silicate-based molded products such as calcium silicate, asbestos slate, lightweight foamed concrete, hollow extruded cement, pulp cement, asbestos cement, wood chip cement, glass fiber reinforced Cement moldings such as concrete and fiber cement moldings, ceramics moldings such as pottery, porcelain, earthenware, glass, enamel, iron, stainless steel, galvanized steel, polyvinyl chloride sol coated steel, stainless steel, aluminum, titanium, Metals such as copper, polyethylene, polypropylene, polymethyl methacrylate, poly Methyl acrylic acid, poly ethyl methacrylate, polyvinyl chloride, polystyrene, acrylonitrile-butadiene-styrene copolymer, a thermoplastic resin molded article such as a polycarbonate, a phenol resin,
Thermosetting resin moldings such as urea resin, unsaturated polyester resin, polyurethane resin, epoxy resin, melamine resin, etc .; phenolic resin, urea resin, A so-called FRP molded body impregnated with a resin such as an unsaturated polyester resin, a polyurethane resin, an epoxy resin, a melamine resin or a diallyl phthalate resin and cured, and a molded body such as two or more kinds of plates are bonded or bonded by heat. Then, a composite molded body or the like laminated and used is used, and a three-dimensional molded body such as a sheet-like material, a rod-like material, or an injection molded product having a foil shape or a thickness is used. Particularly, an aluminum molded body is preferable.

[0010] The coating layer of the thermosetting resin formed on the transfer surface of the molded article is usually formed as a coating layer of a solvent liquid of the thermosetting resin. Melamine resin, diallyl phthalate resin, phenol resin, urea resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, thermosetting acrylic resin, which has a sufficient degree of polymerization to enable Amino alkyd resin, melamine
Thermosetting resins such as urea copolymer resins, silicon resins, polysiloxane resins, etc., solvents, and additives added as necessary, for example, curing agents such as crosslinking agents and polymerization initiators, polymerization accelerators, and viscosity adjustment It is formed by a coating agent comprising a mixture with an agent or the like. In particular, an epoxy resin is preferable from the viewpoint of the adhesive strength of the non-tacky solid layer in a semi-cured state.

The solvent used in the coating agent is appropriately selected according to the type of the thermosetting resin to be used. Examples of the solvent include esters such as ethyl acetate and butyl acetate, acetone, methyl ethyl ketone, and the like. Ketones such as methyl isobutyl ketone, cyclohexanone, and isophorone; pentane, hexane, heptane, and mixtures thereof; gasoline, mineral spirits, aliphatic hydrocarbons such as petroleum benzine, and aromatics such as benzene, toluene, xylene, and cyclohexane. Hydrocarbons, halogenated hydrocarbons such as trichloroethylene, perchlorethylene, carbon tetrachloride, etc., methyl alcohol, ethyl alcohol,
Monohydric alcohols such as isopropyl alcohol and butyl alcohol, polyhydric alcohols such as ethylene glycol and glycerin, ethers such as ethyl ether and methyl ether, and a mixture of two or more of these are used. Is done.

The transfer sheet used in the present invention comprises a transfer sheet base material and a transfer layer, the transfer sheet base material having a releasable surface, and the transfer sheet base material. And a transfer layer formed on the release surface of the material.

The release surface of the transfer sheet substrate may be used as it is as a transfer sheet substrate, for example, in the case of a plastic sheet having a releasable surface. Is treated with a fluorine resin, silicone, or the like, so that the treated surface has a release surface.

After the transfer sheet having the transfer layer is brought into contact with the uncured non-adhesive solid layer which is the transfer surface of the transfer object, the superposed body of the transfer object and the transfer sheet is removed. The step of transferring the transfer layer to the non-adhesive solid layer by heating and pressurizing under such conditions that the uncured non-adhesive solid layer does not completely cure is performed in the transfer sheet. When the transfer layer has an adhesive force or an adhesive layer formed on a transfer sheet, the transfer step is a temperature and time treatment step capable of activating the adhesive force of the adhesive layer. A heating step of about 180 ° C. for several seconds is sufficient.

Particularly, the molded article having the transfer layer of the present invention is
When used in applications where both heat resistance and water resistance are required, such as exterior materials, interior materials such as bathrooms, window materials for blinds, etc., transfer It is preferable that a release layer is formed in advance on the surface of the sheet substrate with a resin having a glass transition point of 60 ° C. or higher.
It is preferable to form a molded article capable of preventing the transfer layer from being peeled off by hot water, sunlight, or the like and the occurrence of blisters or the like by the action of the surface protective layer by the peeling layer constituting the part.

The release layer is made of a thermoplastic resin, a thermosetting resin, or an ionizing radiation-curable resin, and usually has a thickness of 0.1 to 1.0.
It is preferably formed with a thickness of about 10μ, and in the case of a release layer made of a thermosetting resin or an ionizing radiation-curable resin, it is present on the surface of the transfer sheet substrate as a completely cured release layer. Is used.

The thermosetting resin used for the release layer in the transfer sheet includes, for example, melamine resin, diallyl phthalate resin, phenol resin, urea resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, amino resin Alkyd resin, melamine
Urea copolymer resin, silicon resin, polysiloxane resin and the like.

The ionizing radiation-curable resin formed as a release layer in the transfer sheet may be a mixture of a prepolymer, an oligomer, and / or a monomer having a polymerizable unsaturated bond or an epoxy group in a molecule. A resin composition is used. Specific examples of the prepolymer or oligomer include unsaturated polyesters such as a condensate of an unsaturated dicarboxylic acid and a polyhydric alcohol, and methacrylates such as polyester methacrylate, polyether methacrylate, polyol methacrylate, and melamine methacrylate; Acrylates such as polyester acrylate, epoxy acrylate, urethane acrylate, polyether acrylate, polyol acrylate, and melamine acrylate are used.

Further, specific 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, etc. Methacrylates such as methacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, methoxyethyl methacrylate, ethoxymethyl methacrylate, phenyl methacrylate, 2- (N, N-diethylamino) ethyl acrylate, methacrylic acid- 2- (N, N-dimethylamino) ethyl, 2- (N, N-dibenzylamino) ethyl acrylate, 2- (N, N-dimethylamino) methyl methacrylate, 2- (N Of unsaturated acid with N, diethylamino) propyl Amino alcohol esters, unsaturated carboxylic acid amides such as acrylamide, methacrylamide, etc., ethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate Polyacrylate compounds such as diacrylate compounds such as acrylate, dipropylene glycol diacrylate, ethylene glycol acrylate, propylene glycol dimethacrylate, diethylene glycol dimethacrylate, etc., trimethylolpropane trithioglycolate, trimethylolpropane trithiopropylate, and pentaerythritol Two or more thio groups in the molecule by tetrathioglycol And polythiol compounds having a thiol group.

The release layer made of the ionizing radiation-curable resin is usually formed of 5 to 9 of the aforementioned prepolymer or oligomer.
5% by weight and 9 of the monomer and / or polythiol compound
5 to 5% by weight of the composition.

Further, when the release layer is formed of an ionizing radiation-curable resin and the release layer is cured by irradiation with ultraviolet rays, for example, acetophenones, benzophenones, Michler benzoyl benzoate, α ·
A photopolymerization initiator such as an amiloxime ester, tetramethylmeuram monosulfide, or thioxanthone;
It goes without saying that a coating agent containing a photosensitizer added as needed, for example, a photosensitizer such as n-butylamine, triethylamine, tri-n-butylphosphine, or the like is used.

The transfer layer formed on the release surface of the transfer sheet substrate has at least a decorative layer, and if necessary, a release layer or a release layer directly formed on the transfer sheet substrate. A transfer layer having a laminated configuration including an adhesive layer and the like formed on the decorative layer is used.

The decorative layer includes a printing layer made of printing ink, a metal film layer made of aluminum, chromium, or the like, and may be a solid decorative layer on the entire surface, or may be wood grain, stone grain, polka dot, lattice pattern, character, or the like. , A partial pattern layer expressing a figure, etc., or a combination of a solid decorative layer and a partial pattern layer on the entire surface. The printing layer made of the printing ink is preferably formed of a printing ink using a resin having a glass transition temperature of 60 ° C. or higher as a vehicle in order to provide the decorative layer with hot water resistance and heat resistance.

The adhesive layer, which is the uppermost layer of the transfer layer in the transfer sheet, is formed as needed similarly to the release agent layer. For example, when the decorative layer contains a thermoplastic resin. In the case where the decorative layer has heat welding performance by the presence of the adhesive layer, the adhesive layer is not always necessary, but the decorative layer itself does not have heat welding performance, as in the case where the decorative layer is formed of a metal deposition layer. In some cases, an adhesive layer becomes essential.

For the adhesive layer, a heat-sensitive adhesive, a solvent-activated adhesive or the like is used, and those described below are used.

Cellulose derivatives such as ethylcellulose, cellulose nitrate, ethylhydroxyethylcellulose, cellulose acetate propionate and cellulose acetate; styrene resins and styrene copolymer resins such as polystyrene and poly-α-methylstyrene; polymethyl methacrylate and polymethyl methacrylate Acrylic resins such as acrylics such as ethyl methacrylate, polyethyl acrylate and polyacrylbutyl, vinyl polymers such as polyvinyl chloride, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral resin, rosin and rosin Rosin ester resin such as modified maleic acid resin, rosin modified phenol resin, polymerized rosin, polyisoprene rubber, polyisobutyl rubber, rubber resin with styrene / butadiene rubber, butadiene / acrylonitrile rubber, Malonic resin, vinyl toluene resin, polyurethane, polyamide resins, polychlorinated olefins, other resins such as various ionomers, furthermore,
Such as mixtures thereof,

The adhesive layer is preferably formed of a resin having a glass transition temperature of 90 ° C. or higher, for the purpose of imparting hot water resistance and heat resistance to the transfer layer transferred to the transfer object.

In the present invention, after a coating layer of a thermosetting resin is formed on a transfer surface of a molded article used as a transfer object, the coating layer is dried by touch to obtain an uncured non-cured resin. In the step of forming the adhesive solid layer, a part of or all of the solvent in the coating layer is volatilized to bring the surface of the coating layer into a touch-dry state. The thermosetting resin used for the working layer is not completely cured.

That is, in the drying step after forming the coating layer of the thermosetting resin on the transfer surface of the molded body,
In the coating layer, the residual solvent component in the coating layer is volatilized to be in a touch-dry state, and the fluidity and the surface tackiness of the coating layer are lost, but the resin itself in the coating layer is lost. It is preferable to leave or heat dry the resin so that at least the resin does not reach complete curing and retains thermoplasticity.

After the transfer sheet having the transfer layer is brought into contact with the uncured non-adhesive solid layer which is the transfer surface of the transfer object, the superposed body of the transfer object and the transfer sheet is removed. The step of transferring the transfer layer to the non-adhesive solid layer by heating and pressurizing under such conditions that the uncured non-adhesive solid layer does not completely cure is performed in the transfer sheet. Adhesive force of the transfer layer, or, if an adhesive layer is formed on the transfer sheet, a heating step at a temperature to activate the adhesive force of the adhesive layer, for example, heat roller transfer , Vacuum press transfer, etc.
A treatment at 80 to 180 ° C. for several seconds is sufficient.

[0031]

The molded article having the transfer layer of the present invention has good properties such as heat resistance, water resistance, and abrasion resistance, and has no flow, distortion, crack, etc. in the pattern formed by the transfer layer. Since the semi-cured non-adhesive solid layer that forms the transfer surface of the molded body, which is the transfer target, is not completely cured after the transfer of the transfer layer, equipment for long-time heat treatment at high temperature, etc. Is unnecessary, the number of manufacturing steps is small, and the cost is greatly reduced.

Further, according to the method for producing a molded article having a transfer layer of the present invention, a molded article having the above-mentioned characteristics can be obtained accurately.

[0033]

EXAMPLES The concrete structure of a molded article having a transfer layer according to the present invention and a method for producing the molded article will be described below with reference to production examples.

Example 1 (1) Preparation of a transfer sheet: A 26 μm-thick polyethylene terephthalate film “Toray Co., Ltd .: X-45” was coated on the surface of a transfer sheet base material with an acrylic resin. A release layer having a thickness of 2 μm was formed, and the surface of the release layer was mixed with a 2 μm-thick lattice pattern picture layer and a pigment by using a colored ink obtained by adding a pigment to a vehicle of an acrylic resin and a salt / vinyl acetate resin. An undercoat layer and an adhesive layer formed by colored solid printing with a thickness of 2 μm of an acrylic resin are sequentially formed by a gravure coating method, and then subjected to heat drying at 60 ° C. for 1 minute.
A transfer sheet having a tack-free surface was obtained.

(2) Preparation of transfer object: A coating agent of a hardening type epoxy resin containing 10% by weight of silica was applied to the surface of a 0.15 mm-thick aluminum plate (manufactured by Showa Aluminum Co., Ltd.). By performing heat drying at 100 ° C. for 5 minutes, a transfer object made of an aluminum plate having a 20 μm-thick thermosetting resin coating layer formed on the transfer surface was obtained. The surface of the coating layer of the curable epoxy resin is in a state where there is no tack even when touched with a finger, and is made of a semi-cured non-adhesive solid layer.

(3) Transfer step: 200 ° C. at a speed of 10 m / min in a state in which the coating layer surface of the curable epoxy resin of the transfer object is brought into contact with the underprint layer / adhesive layer surface of the transfer sheet. Roll transfer was performed by passing twice under heating.

(4) Step of peeling the transfer sheet base material: Next, the transfer sheet base material (polyethylene terephthalate film) in the transfer sheet is peeled off.
Transfer the underprinting layer / adhesive layer, grid pattern layer and release layer by colored solid printing to the coating layer surface of a curable epoxy resin, which is a semi-cured non-adhesive solid layer on the surface of the transferred object As a result, a molded article having an intended transfer layer was obtained. In addition, in the obtained molded body, a 2 μm-thick release layer made of an acrylic resin functions as a protective layer in the transfer layer.

Comparative Example 1 (1) Preparation of a transfer sheet: A 26 μm thick polyethylene terephthalate film “Toray Co., Ltd .: X-45” was coated on the surface of a transfer sheet substrate with an acrylic resin. A release layer having a thickness of 2 μm was formed, and the surface of the release layer was mixed with a 2 μm-thick lattice pattern picture layer and a pigment by using a colored ink obtained by adding a pigment to a vehicle of an acrylic resin and a salt / vinyl acetate resin. An undercoat layer and an adhesive layer formed by colored solid printing with a thickness of 2 μm of an acrylic resin are sequentially formed by a gravure coating method, and then subjected to heat drying at 60 ° C. for 1 minute.
A transfer sheet having a tack-free surface was obtained.

(2) Preparation of Transferred Object: A coating agent made of an uncured polyurethane obtained by mixing acrylic polyol and tolylene diisocyanate was coated on the surface of a 0.15 mm thick aluminum plate (manufactured by Showa Aluminum Co., Ltd.). After the application, only the solvent was evaporated by drying to obtain a transfer-receiving body composed of an aluminum plate having an uncured and still-adhesive coating layer formed on the transfer-receiving surface.

(3) Transfer step: With the thermosetting resin coating layer surface of the transfer object brought into contact with the underprint layer / adhesive layer surface of the transfer sheet, application is performed by a 150 ° C. heated rubber roll. The pressure was at a running speed of 10 m / min.

(4) Peeling-off step of the transfer sheet base material: Next, the transfer sheet base material (polyethylene terephthalate film) in the transfer sheet is peeled off.
(3) The laminated sheet obtained in the step is cured at 40 ° C. for 3 days, and after the polyurethane is completely cured, the transfer sheet substrate (polyethylene terephthalate film) in the transfer sheet is peeled off, and the colored solid sheet is removed. A molded article having a transfer layer for comparison in which an underprinting layer / adhesive layer by printing and a lattice pattern layer were transferred to the coating layer surface of the thermosetting resin of the transferred body was obtained.

In the molded article having the transfer layer obtained in the comparative example, the colored portion and a part of the picture layer were eluted by the action of the roller pressure in the transfer step and the uncured polyurethane coating layer. In addition, spots occurred in the coloring layer, and blurring occurred in the picture layer. However, the example product did not have these inconveniences, and a high-quality transfer layer was obtained.

[0043]

According to the molded article having a transfer layer of the present invention, a molded article having a transfer layer with high quality characteristics can be supplied at low cost.

Further, according to the method for producing a molded article having a transfer layer of the present invention, a molded article having a transfer layer having high quality characteristics can be easily and reliably obtained.

Claims (2)

(57) [Claims] To a transfer surface according to claim 1 molded body, transfer layer non-tacky solid layer transfer layer transcription sheet through a semi-cured state by thermal curing resin is characterized in that it is transferred Molded articles having. 2. A first step of forming a coating layer of a thermosetting resin on a transfer surface of a molded article used as a transfer object, and an uncured state by touch-drying the coating layer. A second step of forming a non-adhesive solid layer, and transferring the transfer sheet having a transfer layer so that the transfer layer surface of the transfer sheet is in contact with the uncured non-adhesive solid layer surface; non third step of sticky solid layer is Setto, the overlay body between the transfer sheet and the transfer-receiving member, said such the possible non-tacky solid layer of uncured to cured completely FAIL of heating under matters, by pressurizing, and a fourth step of transferring the transfer layer to a non-tacky solid layer, Ri by the the fifth step of peeling the portion other than the transfer layer in the transfer sheet, the molded body Suffered
Non-adhesive solid in semi-cured state with thermosetting resin on transfer surface
Molding in which the transfer layer of the transfer sheet is transferred through the layer
A method for producing a molded article having a transfer layer , characterized by obtaining a molded article.