JPH10315694A - Manufacturing of three-dimensional decorated article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a three-dimensional decorated article having an uneven face with molded-in decoration performed by a transfer process. SOLUTION: This method for manufacturing a three-dimensional decorated article is composed of a first step to place a transfer sheet S with a transfer layer 2 laminated on a support sheet 1 on a base B to which an image is transferred, in such a manner that the transfer layer 2 faces the base B, a second step to pour a fluid resin 3 onto the support sheet 1 side of the transfer sheet S placed on the base B and apply a pressure from the resin side with the help of a pressing roller 5, a third step to solidify the resin 3 by cooling it with cooling rollers 6, 6a, 6b, and a fourth step to peel the support sheet 1 from the base B and transfer the transfer layer 2 onto the base B. Thus the three- dimensional decorated article P is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a three-dimensional painted product. In particular, the present invention relates to a manufacturing method for painting a plate-like object having irregularities on its surface by transfer.

[0002]

2. Description of the Related Art Conventionally, various methods have been used to transfer a picture to a substrate to be transferred having an uneven surface by transfer. For example, Japanese Patent Application Laid-Open Nos.
Japanese Patent Application Laid-Open No. 216599 and the like describe a method in which a soft rubber roller having a low rubber hardness is used as a transfer roller, and a transfer sheet is pressed onto the uneven surface of the base material to be transferred and transferred. Also, Japanese Patent Publication No. 52-17448, Japanese Patent Publication No.
In the publication No. 58014 and the like, as a transfer method by a so-called vacuum press method, a three-dimensional article such as a molded article is used as a base material to be transferred, and a transfer sheet is interposed between the base material and the transfer sheet via an adhesive as necessary. Then, a rubber film is placed on the transfer sheet and pressed, and the air pressure difference between the upper and lower sides of the rubber film created by vacuum suction from the base material to be transferred and the contraction force of the rubber film are used as the transfer pressure. Is described in which the surface of the substrate to be transferred is molded and transferred. Also, Japanese Patent Publication No. 52-41682, Japanese Patent Publication No. 60-
No. 58718 discloses a so-called hydraulic transfer method.
A method of floating a swelled transfer sheet on a water surface, immersing a transfer substrate formed of a three-dimensional article such as a molded product from above, and transferring the transfer sheet while forming the transfer sheet on the uneven surface of the transfer substrate by water pressure. Have been described.

[0003]

However, in the above-mentioned method, the transfer sheet is pressed to follow the surface irregularities by utilizing the elastic deformation of rubber, and the transfer sheet is formed and transferred. The rubber roller cannot completely follow the surface irregularities, and the transfer layer is not partially transferred, resulting in transfer omission, which is not applicable. In addition, there is also a problem that the soft rubber roller is easily worn out by the corners of the unevenness of the base material to be transferred. Further, the above method is not applicable because the rubber film made of silicone rubber or the like cannot completely follow large irregularities on the surface and causes transfer omission. In addition, because of the use of the air pressure difference, vacuum suction is performed from the transfer-receiving substrate side. If the transfer-receiving substrate is not a gas-permeable material such as a wooden substrate, air tends to remain on the unevenness of the transfer-receiving surface. As a result, in the residual air portion, the transfer sheet does not come into contact with the transfer-receiving surface, so that the transfer omission is likely to occur. Also,
In the above method, as compared to the above method, the transfer can be performed on a complicated and large uneven surface, but the swelled support sheet of the transfer sheet remaining on the transfer substrate is the transfer substrate immersed in water. The removal of the support sheet is complicated, for example, it is necessary to take out, remove by washing, and further require a drying step of the product. In addition, a transfer-receiving substrate having water absorbency is not suitable because it takes a long time to dry the product because water permeates. Further, in order to supply and immerse the substrate to be transferred from above toward the water surface, work is performed on an inorganic plate material or the like made of a material such as cement when the substrate is large or heavy. There was a problem that it was difficult.

[0004]

Therefore, in order to solve the above-mentioned problems, in the method for producing a three-dimensional painted article of the present invention, a transfer sheet having a transfer layer on a support sheet is placed on a substrate to be transferred. A first method in which the transfer layer is placed so as to face the substrate to be transferred
A second step of pouring a liquid resin into the support sheet side of the transfer sheet placed on the substrate to be transferred and applying pressure from the resin side, and a third step of solidifying the resin. And a fourth step of peeling the support sheet from the substrate to be transferred and transferring the transfer layer onto the substrate to be transferred. As a result, it is possible to produce a three-dimensional painted molded article in which the uneven surface is painted by transfer without causing transfer omission. Further, in the present invention, the continuous production is performed by using a liquid resin heated and melted in the second step in the above steps, applying pressure by a roller, and cooling and solidifying the resin by a cooling roller in a third step. The production method was suitable for the properties.

[0005]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, an embodiment of a method for producing a three-dimensional decorative article according to the present invention will be described with reference to the drawings. First, FIG. 1 is a conceptual diagram illustrating one embodiment as a typical embodiment of the method for producing a three-dimensionally painted product of the present invention in the order of steps. In the embodiment shown in the figure, a resin that is heated and melted is used as a liquid resin, pressure is applied to the liquid resin by a pressing roller, and the resin is cooled and solidified by a cooling roller. That is, as shown in FIG. 1A, in the first step, the transfer sheet S having the transfer layer 2 on the support sheet 1 and the transfer layer 2 Place so that it faces.
Next, in the second step, first, as shown in FIG. 1B, the support sheet 1 of the transfer sheet S placed on the transfer-receiving base material B.
In this case, as shown in FIG. 1C, a pressure roller 5 disposed on the resin side is used as a pressing means to apply pressure to the transfer sheet from the resin side. Add. In the embodiment using a pressure roller as shown in the figure, the viscosity of the liquid resin 3 is such that the liquid resin 3 does not flow down or spread too much under its own weight. In FIG. (C), the substrate to be transferred B is transported to the left in the drawing. As a result, the transfer sheet S is pressed against the transfer base material B by the resin to which the pressure is applied, and is formed following the surface unevenness, and the transfer sheet is pressed against the transfer base material. Next, in the third step, as shown in FIG. 1D, the resin is cooled by using the three cooling rollers 6, 6a and 6b as cooling means to solidify the resin. In FIG. 1D, the transfer-receiving base material B is transported to the left in the drawing. Then, in the next fourth step, as shown in FIG. 1E, only the support sheet 1 of the transfer sheet S is peeled off from the base material B to be transferred together with the solidified resin 3a in which the liquid resin 3 is solidified. Then, the transfer layer 2 is assumed to be a three-dimensional decorative article P transferred to the base material B to be transferred. The peeled and removed support sheet 1 may be separated and separated from the solidified resin 3a as shown in FIG. 1 (F).

Hereinafter, the present invention will be described in more detail.

[Transferred Substrate] The substrate to be transferred B can of course be applied to a flat surface to be transferred, but the present invention is most effective when the surface to be transferred is an uneven surface, This is a substrate to be transferred having three-dimensional irregularities. A conventional rubber transfer roller (see the above-mentioned Japanese Patent Application Laid-Open No. 5-139097) is applicable because it has a directionality essentially due to its rotation axis in order to utilize elastic deformation of rubber. Surface irregularities are restricted. That is, even if transfer to three-dimensional unevenness having a curvature in two axial directions is possible, the three-dimensional shape cannot be uniformly applied to an arbitrary direction. For example, unless the longitudinal direction of the wood grain conduit pattern is parallel to the feed direction of the transfer sheet, it cannot be successfully transferred to the concave portion of the conduit. However, in the present invention, since the transfer pressure is applied through a freely-formable fluid such as a liquid resin, the three-dimensional shape of the surface irregularities has essentially no planar direction of the pressure application region. . (This directionality is a direction of a temporal position change of a point on the transfer-receiving substrate to which pressure is applied.) This feature uses a pressing roller as a pressing unit as shown in FIG. Although it is effective even in the case, as will be described later, it becomes more remarkable when a flat pressure type press is used as the pressing means as shown in FIG.
Therefore, in the present invention, a transfer substrate having a shape having irregularities in the feed direction of the transfer sheet or the transfer substrate may be used. That is, it can be applied to two-dimensional unevenness having unevenness only in one direction such as only the feed direction or only the width direction, and three-dimensional unevenness having unevenness in two directions such as both the feed direction and the width direction. .

The substrate to be transferred is not limited to a flat plate material (having an envelope shape) as a whole, but has a two-dimensional unevenness whose cross section is convex or concave in an arc shape and curved in the feeding direction or width direction. Alternatively, the curved surface may have finer three-dimensional surface irregularities (for example, the transfer substrate may be surrounded by a weir as shown in FIG. 2 and a transfer pressure may be applied). Also,
It is also possible to use a substrate to be transferred having an irregular surface having fine irregularities superimposed on large irregularities, or a substrate having a surface to be transferred to the bottom of the concave portion or the inner surface of the concave portion of the irregular surface. The large pattern irregularities and fine irregularities are, for example, composed of large pattern irregularities and fine irregularities on the convex portions thereof, and the large pattern irregularities have a step of 1 to 10 mm and a width of the concave portion of 1 to 10 mm. The width of the projection is 5 mm or more, and the fine unevenness is smaller than the large unevenness in both the step and the width. Specifically, the step is about 0.1 to 5 mm, The width and the width of the convex portion are 0.1 mm or more, and are about less than 1/2 of the width of the convex portion having a large uneven shape. Specific examples of the uneven pattern of the decorative material having a combination of large irregularities and fine irregularities and having three-dimensional surface irregularities include, for example, tiles and bricks having joints and grooves as large irregularities. , Stones and other two-dimensional array patterns, and fine irregularities on the spray-painted surface such as stucco and lysine, as well as stones such as cleaved surfaces of granite and stone surfaces such as travertine marble boards Wood-grained uneven pattern with a contoured pattern, or a large-sized uneven pattern, such as a paneling pattern having grooves, grooves, saury, sane, etc., a floating wood grain pattern, and a conduit groove, a hairline, etc. as fine irregularities thereon Is mentioned. In addition, each surface which forms the uneven surface is not limited to a flat surface, may be a curved surface alone, or may be a combination of a flat surface and a curved surface. Therefore, the curved surface on the substrate to be transferred according to the present invention also means a concavo-convex surface having no curved surface composed of only a plurality of flat surfaces, such as a tooth profile of a clog. Further, the curvature in the present invention includes a case where the curvature is infinite (the radius of curvature = 0) which is angular like the periphery of a side or a vertex of a cube. In order to make the surface of the substrate to be transferred into a desired unevenness, a pressing process, an embossing process, an extrusion process, a cutting process, a forming process, or the like may be used.

The material of the substrate to be transferred is arbitrary.
Non-porcelain ceramic plates such as calcium silicate plate, extruded cement plate, ALC (lightweight foamed concrete) plate, GRC (glass fiber reinforced concrete) plate, veneer veneer, wood plywood, particle board, or wood Wood plates such as medium density fiberboard (MDF), metal plates such as iron, aluminum and copper, ceramics such as ceramics and glass,
A resin molded product such as polypropylene, ABS resin, and phenol resin may be used. In particular, in the present invention, a substrate to be transferred, which could not be applied by the above-mentioned hydraulic transfer method, can be applied without problem even to a water-absorbing material such as a wood board or a calcium silicate board or a heavy material. In addition, these transfer receiving substrate surfaces are coated in advance with an easy-adhesion primer for assisting the adhesion with the adhesive, or a sealer agent for sealing and sealing fine irregularities and porosity on the surface. Is also good. A resin such as an isocyanate, a two-part curable urethane resin, an epoxy resin, an acrylic resin, or a vinyl acetate resin is applied as an easy-adhesion primer or a sealer.

[Transfer Sheet] The transfer sheet S is composed of a support sheet 1 and a transfer layer 2 to be transferred. The transfer layer comprises at least a decorative layer. Further, the adhesive may be formed on the transfer sheet as an adhesive layer that becomes a part of the transfer layer.

(Support Sheet) As the support sheet 1, a stretchable material is used at least at the time of transfer in order to follow the uneven surface of the substrate to be transferred. Therefore, besides the conventionally known thermoplastic resin film,
A rubber film that can be stretched even at room temperature can be used. In the case of a thermoplastic resin film, when forming a transfer layer such as a decorative layer, there is almost no stretchability, and when heated during transfer, sufficient stretchability is exhibited, and after cooling, the deformed shape is maintained, and the shape due to elasticity is maintained. As a transfer sheet that does not cause restoration, a transfer sheet that can be used in the present invention can be prepared as easily as a conventionally known ordinary transfer sheet. As a specific example of the support sheet, a biaxially stretched polyethylene terephthalate film, which has been widely used in the past, is required to have sufficient and sufficient stretchability by setting heating conditions, transfer pressure conditions, and the like, depending on the surface unevenness. Surface transfer is possible because it can be expressed, but a low temperature, low pressure, easy to develop extensibility, for example, polybutylene terephthalate, or copolymer polyester film such as terephthalate isophthalate copolymer, polypropylene film, Polyolefin films such as polyethylene films and polymethylpentene films,
Low-stretch or non-stretch films such as polyvinyl chloride resin films and nylon films, and rubber (elastomer) films such as natural rubber, synthetic rubber, urethane elastomers and olefin-based elastomers are also preferred support sheets. The thickness of the support sheet is usually 20 to 200 μm.

The support sheet may be provided, if necessary, with a release layer on the transfer layer side in order to improve the releasability from the transfer layer. This release layer is removed together with the support sheet from the transfer layer when the support sheet is peeled off. As the release layer, for example, a simple substance such as a silicone resin, a melamine resin, a polyamide resin, a urethane resin, a polyolefin resin, a wax, or a mixture containing these is used. If necessary, the support sheet may be provided on the other surface (rear surface) where the transfer layer is not provided, that is, on the surface into which the liquid resin is poured.
After the liquid resin is solidified, a back layer may be provided in order to make the resin (solidified resin) easy to peel off. When the solidified resin and the support sheet are separated, the back layer becomes the support sheet side or the solidified resin side, or is separated into the support sheet and the solidified resin by cohesive failure. The material used for the release layer and the release layer can be used as the back layer.
Specifically, a simple substance such as a silicone resin, a melamine resin, a polyamide resin, a urethane resin, a polyolefin resin, a wax, or a mixture containing these is used. In addition,
The release layer and the back layer are formed by a conventionally known coating method and printing method.

Further, if an uneven pattern is provided on the support sheet surface in contact with the transfer layer, the uneven pattern can be formed on the transfer layer surface after the transfer. The uneven pattern is, for example,
There are pears, hairlines, parallel grooves, irregularities on the cleavage face of granite, wood conduit grooves, wood rings, patterns on the surface of cloth, squeezing, letters, geometric patterns, etc. In addition, the formation of the concavo-convex pattern is performed on a support sheet made of a resin film by embossing, sandblasting, or hairline processing by hot pressing, or on the support sheet.
Desired unevenness using an ink (made of two-component cured urethane, silicone resin, melamine resin, polyfunctional acrylate or methacrylate monomer or prepolymer crosslinked by ultraviolet light or electron beam, etc.) using a resin having a releasing property as a binder There is a method of forming a support sheet having a shaping layer by providing a shaping layer by embossing and printing the pattern by silk screen printing or the like. The shaping layer has the function of the release layer.

(Transfer Layer) The transfer layer 2 is composed of at least a decorative layer, and a release layer, an adhesive layer, etc. may also be a component of the transfer layer as appropriate. In the configuration having the adhesive layer,
It is possible to omit applying an adhesive to one or both of the transfer sheet and the substrate to be transferred at the time of transfer. The decoration layer is partially formed using a conventionally known method such as gravure printing, silk screen printing, offset printing, a pattern layer obtained by printing a pattern with a material, a metal such as aluminum, chromium, gold, and silver using a known vapor deposition method or the like. Alternatively, a metal thin film layer or the like formed on the entire surface and used in accordance with the application is used. As the pattern, according to the surface irregularities of the transferred substrate, wood pattern, stone pattern, cloth pattern,
Tile patterns, brick patterns, leather squeezing patterns, letters, geometric patterns, solid colors, etc. are used. In addition, the ink for the picture layer is a vehicle composed of a binder or the like, a coloring agent such as a pigment or a dye,
It consists of various additives appropriately added to this. Acrylic resin, vinyl chloride-vinyl acetate copolymer,
A simple substance such as a polyester resin, a cellulosic resin, a polyurethane resin, and a fluororesin, or a mixture containing these is used. As the pigment of the colorant, inorganic pigments such as titanium white, carbon black, red iron oxide, graphite, and ultramarine blue, and organic pigments such as aniline black, quinacridone, isoindolinone, and phthalocyanine blue are used. Conventionally, a release layer is provided between the support or the release layer and the decorative layer to adjust the releasability between the decorative layer and to protect the surface of the decorative layer after transfer. This is the same as a known transfer sheet. The release layer is transferred to the transfer-receiving substrate together with the decorative layer during transfer, and covers the surface of the decorative layer. Further, as a means for easily removing air remaining between the transfer sheet and the transfer-receiving substrate at the time of transfer, a large number of small holes penetrating all layers of the transfer sheet may be formed in the transfer sheet as necessary. .

[Adhesive] The adhesive is applied in advance or immediately before transfer as an adhesive layer constituting a transfer layer of a transfer sheet or as an adhesive layer on a substrate to be transferred. When applied to a substrate to be transferred, the adhesive layer of the transfer sheet transfer layer can be omitted.
The adhesive to be used may be appropriately selected depending on the application, required physical properties, and the like. Examples of the adhesive include a heat-sensitive adhesive, a moisture-curable heat-sensitive adhesive, a hot-melt adhesive, a moisture-curable hot-melt adhesive, a two-part curable adhesive, an ionizing radiation-curable adhesive, and an aqueous adhesive. Various kinds of adhesives such as a pressure-sensitive adhesive of a pressure-sensitive adhesive type or a microcapsule breaking type can be used. As the heat-sensitive adhesive, any of a heat-sealing adhesive using a thermoplastic resin and a thermosetting adhesive using a thermosetting resin can be used. However, from the viewpoint that the bonding is completed in a short time, a heat fusion type (heat-sensitive adhesive) is preferable. The adhesive may be diluted with a solvent or without a solvent, or may be a liquid or a solid at room temperature. In the case of an adhesive other than a pressure-sensitive adhesive exhibiting tackiness, a transfer layer can be formed with only a single adhesive layer. If a coloring agent such as a pigment is added to the adhesive layer, it can be said that the entire layer is a decorative layer composed of a solid ink layer.

For example, heat-sensitive adhesives are obtained by condensation polymerization of polyvinyl acetate resin, vinyl chloride-vinyl acetate copolymer, acrylic resin, thermoplastic polyester resin, thermoplastic urethane resin, dimer acid and ethylenediamine. A conventionally known adhesive such as a polyamide resin can be used. As the thermosetting adhesive, a phenol resin, a urea resin, a diallyl phthalate resin, a thermosetting urethane resin, an epoxy resin, or the like can be used.

A moisture-curable heat-sensitive adhesive, which is a kind of heat-sensitive adhesive, causes a crosslinking / curing reaction with moisture in the air when left in a natural state, so that it can be used immediately before transfer in terms of work stability. Apply. Immediately after transfer, the moisture-curable heat-melt adhesive has the same adhesive strength as a normal heat-melt adhesive, but after crosslinking and curing, there is no creep deformation or heat melting, and it has excellent heat resistance, etc. Can be The moisture-curable heat-sensitive adhesive is a composition containing a prepolymer having an isocyanate group at a molecular terminal as an essential component. The prepolymer is usually a polyisocyanate prepolymer having one or more isocyanate groups at both molecular terminals, and is a solid thermoplastic resin at normal temperature. The isocyanate groups react with each other due to moisture in the air to cause a chain extension reaction. As a result, a reactant having a urea bond in the molecular chain is generated, and the isocyanate group at the molecular end further reacts with the urea bond. , Causing biuret bonding and branching to cause a crosslinking reaction. Although the skeleton structure of the molecular chain of the prepolymer having an isocyanate group at the molecular terminal is arbitrary, specific examples include a polyurethane skeleton having a urethane bond, a polyester skeleton having an ester bond, and a polybutazine skeleton. Adhesive properties can be adjusted by appropriately employing one or more of these skeletal structures. If a urethane bond is present in the molecular chain, the terminal isocyanate group also reacts with the urethane bond to form an allophanate bond, which also causes a cross-linking reaction.

Specific examples of the polyisocyanate prepolymer include, for example, an isocyanate group at a molecular terminal obtained by reacting an excess polyisocyanate with a polyol;
There is a urethane prepolymer having a polyurethane skeleton having a urethane bond in a molecular chain. Also, Japanese Unexamined Patent Publication No.
No. 14287, a polyester skeleton and a polybutadiene skeleton obtained by adding a polyester polyol and a polyol having a polybutadiene skeleton in an arbitrary order to a polyisocyanate and subjecting them to an addition reaction are bonded by a urethane bond. Crystalline urethane prepolymer having an isolated structure and having an isocyanate group at the molecular terminal, or a molecule obtained by reacting a polycarbonate polyol with a polyisocyanate as disclosed in JP-A-2-305882. A polycarbonate-based urethane prepolymer having two or more isocyanate groups therein, a polyester-based urethane prepolymer having two or more isocyanate groups in a molecule obtained by reacting a polyester polyol and a polyisocyanate, and the like. It is.

The moisture-curable heat-sensitive adhesive includes:
In addition to the above-mentioned various polyisocyanate prepolymers, if necessary to adjust various physical properties, for example, ethylene-
Tackifiers such as vinyl acetate copolymers, low molecular weight polyethylene, modified polyolefins, atactic polypropylene, linear polyesters, thermoplastic resins such as ethylene-ethyl acrylate (EAA), terpene-phenol resins, and rosin abietate, and plastics Agent, curing catalyst,
Additives such as a moisture removing agent, a storage stabilizer and an antioxidant are added.

The ionizing radiation-curable resin which can be used as the ionizing radiation-curable adhesive is a composition curable by ionizing radiation, and specifically includes a radical polymerizable unsaturated bond or a cationic polymerizable functional group in the molecule. A prepolymer (including a so-called oligomer) having a group and / or a composition which is appropriately mixed with a monomer and which can be cured by ionizing radiation is preferably used. These prepolymers or monomers are used alone or as a mixture of two or more.

The above prepolymer or monomer specifically has a radical polymerizable unsaturated group such as a (meth) acryloyl group and a (meth) acryloyloxy group, a cationic polymerizable functional group such as an epoxy group in the molecule. Consisting of a compound having Further, a polyene / thiol prepolymer based on a combination of polyene and polythiol is also preferably used. In addition, for example, a (meth) acryloyl group is
It means an acryloyl group or a methacryloyl group. Examples of the prepolymer having a radical polymerizable unsaturated group include polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, melamine (meth) acrylate, and triazine (meth) acrylate. The molecular weight is usually 250
Approximately 100,000 are used. Examples of the monomer having a radical polymerizable unsaturated group include monofunctional monomers such as methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and phenoxyethyl (meth) acrylate. As polyfunctional monomers, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylpropane tri (meth) acrylate, trimethylolpropane ethylene oxide tri (meth) acrylate, dipentaerythritol penta (meth) acrylate And dipentaerythritol hexa (meth) acrylate. Examples of the prepolymer having a cationically polymerizable functional group include bisphenol type epoxy resins, epoxy resins such as novolak type epoxy compounds,
There are prepolymers of vinyl ether resins such as fatty acid vinyl ethers and aromatic vinyl ethers. Examples of the thiol include polythiols such as trimethylolpropane trithioglycolate and pentaerythritol tetrathioglycolate. Examples of the polyene include those obtained by adding allyl alcohol to both ends of a polyurethane made of a diol and a diisocyanate.

When curing with ultraviolet light or visible light, a photopolymerization initiator is further added to the ionizing radiation-curable resin. In the case of a resin system having a radical polymerizable unsaturated group, acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ethers can be used alone or in combination as a photopolymerization initiator. In the case of a resin system having a cationically polymerizable functional group, an aromatic diazonium salt, an aromatic sulfonium salt, an aromatic iodonium salt, a metallocene compound, a benzoinsulfonic acid ester, or the like is used alone or as a mixture as a photopolymerization initiator. be able to. In addition,
The addition amount of these photopolymerization initiators is about 0.1 to 10 parts by weight based on 100 parts by weight of the ionizing radiation-curable resin. In addition, as the ionizing radiation, an electromagnetic wave or a charged particle having energy capable of crosslinking the molecules in the adhesive is used. Usually, ultraviolet rays or electron beams are used, but it is also possible to use visible rays, X-rays, ion beams or the like. 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 lamp, a black light, and a metal halide lamp is used. As a wavelength of the ultraviolet light, a wavelength range of 190 to 380 nm is usually mainly used. As an electron beam source, various electron beam accelerators such as a Cockcroft-Walton type, a Van degraft type, a resonance transformer type, an insulating core transformer type, or a linear type, a dynamitron type, and a high frequency type are used.
One that irradiates electrons with energy of 1000 keV, preferably 100 to 300 keV is used.

If necessary, a thermoplastic resin such as a vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, an acrylic resin, or a cellulose resin may be added to the ionizing radiation-curable resin. If used without adding a diluting solvent, it becomes a hot melt adhesive.

Further, various additives may be further added to the various resins used for the adhesive, if necessary. These additives include, for example, extenders (fillers) composed of fine powders such as calcium carbonate, barium sulfate, silica, and alumina, and thixotropic agents such as organic bentonite (especially for transfer-receiving substrates having a large uneven step). In this case, the adhesive may be added to prevent the adhesive from flowing into the concave portion from the convex portion.), A coloring pigment, and the like.

To apply the adhesive to a sheet such as a transfer sheet or a substrate to be transferred, a solvent (or a dispersion medium) such as water or an organic solvent is used.
In the form of a solution (or dispersion) dissolved (or dispersed) in
Alternatively, a hot-melt thermoplastic composition or a room-temperature liquid uncured resin is applied in the form of a solvent-free resin liquid. As a coating method,
What is necessary is just to apply by the solution coating by a gravure roll coat etc. which are a conventionally well-known coating method, or the fusion coating (melt coating) method by an applicator etc. The transfer substrate having large surface irregularities can be applied by a coating method such as spray coating, flow coating, or brush coating. When used without adding a diluting solvent, solvent drying is unnecessary. For example, heat-sensitive adhesives can be used as solventless hot-melt adhesives, respectively. In addition, an ionizing radiation-curable adhesive or the like can be applied without a solvent. When used as a hot-melt adhesive, there is no solvent, so solvent drying is unnecessary even immediately before transfer, and high-speed production is possible. The amount of the adhesive applied varies depending on the composition of the adhesive, the type of the substrate to be transferred, and the surface condition.
Usually, it is about 10 to ²⁰⁰ g / m ² (solid content).

(Adhesion method) The adhesion method of the transfer layer to the substrate to be transferred with an adhesive has various modes depending on the kind of the adhesive. In particular, in the present invention, the heat of heating the liquid resin for pressurization,
Alternatively, heat for heating can be used. Further, pressure from a liquid resin for pressing can also be used for bonding. For example, when the adhesive is a heat-fusible or thermosetting adhesive, it is heated and then cooled. When the liquid resin for pressurization is a thermoplastic resin, the heating uses the heat of the resin as a heated molten resin. When the liquid resin for pressurization is an uncured resin liquid of a thermosetting resin, heat applied to the liquid resin is used to cure the uncured resin liquid. In the case of a curable resin cured at room temperature, heat is applied for the purpose of bonding itself. Further, when the adhesive is a pressure-sensitive adhesive, a pressure for forming the transfer sheet into an uneven shape on the surface of the substrate to be transferred is used. In the case where the adhesive is bonded by heat fusion, cooling of the adhesive may be promoted. The cooling is performed by cooling a cooling roller, cold air, or flat pressure press by cooling the press plate itself. The cooling of the adhesive is performed by cooling the hot melt resin when the hot melt resin is used as the liquid resin. Therefore, the cooling roller crawls on the heated molten resin. The cooling of the adhesive may be performed by blowing cool air from the transfer-receiving substrate side. The cool air may be blown from the transfer sheet side.

[Liquid Resin] The liquid resin 3 is a medium for applying a transfer pressure to the transfer sheet by fluid pressure. The liquid resin is not particularly limited as long as it is a liquid resin at least when pressurized. As the liquid resin, a heated melt such as a thermoplastic resin or a wax, or an uncured resin liquid of a curable resin such as a thermosetting resin can be used. Note that the thermoplastic resin and the wask may be a mixture thereof. The liquid resin is also used as a heat source for the adhesive when the adhesive is a heat-sealing type or a thermosetting type, as described in the aforementioned bonding method. In addition, when the support sheet is a thermoplastic resin, the liquid resin is also used as a heating source for improving the stretchability. Therefore, the liquid resin is also used as a means for supplying heat required for transfer, such as heating the adhesive and improving the stretchability of the support sheet. As the liquid resin, a resin exhibiting a viscosity sufficiently along the surface irregularities of the substrate to be transferred is selected and used. In the case of a thermoplastic resin or wax, it is the viscosity at the time of melting by heating, and in the case of an uncured resin liquid, it is the viscosity of the liquid. In addition, cost is also important as a liquid resin. Therefore, the liquid resin is preferably a resin that can be collected and reused, and in this regard, a thermoplastic resin,
Waxes are preferred. These resins are heated and melted again after the step of FIG.
It can be used in the step of FIG. If the liquid resin, for example, is wax alone and has a too low viscosity and flows sideways, a mixture with a thermoplastic resin may be used. Conversely, if the thermoplastic resin has a high viscosity, wax or the like may be added.
Examples of the thermoplastic resin include polyolefin resins such as polyethylene and polypropylene, fluorine resins such as polyvinyl fluoride and polyvinylidene fluoride, ABS (acrylonitrile-butadiene-styrene copolymer) resin, styrene resin, acrylic resin, and polyvinyl chloride resin. And vinyl acetate resin. Examples of the wax include wood wax, montan wax, and paraffin wax. Examples of the curable resin (an uncured product thereof) include a phenol resin, a two-component curable urethane resin, an unsaturated polyester resin, and a thermosetting resin such as an epoxy resin.

[Method of Supplying Liquid Resin] As a method of supplying the liquid resin to the support sheet side of the transfer sheet, a method of simply pouring the liquid resin may be used. If the liquid resin is a hot melt resin, it may be poured by heating with an extruder. Alternatively, a curable resin that is liquid at room temperature may be poured from a tank. The amount of the liquid resin to be poured is appropriately adjusted in accordance with the size of the surface irregularities of the substrate to be transferred, the resin viscosity, and the like so that the transfer sheet follows the surface irregularities and has a thickness necessary and sufficient for molding. The thickness is, for example, about 0.1 to 10 mm as a thickness from a convex portion of the surface irregularities of the transfer-receiving substrate.

[Method of Applying Transfer Pressure] The method of applying the transfer pressure applied to the transfer sheet via the liquid resin is not particularly limited. However, in addition to the above-described embodiment in which a pressing roller is used as a pressing unit as shown in FIG. As shown in FIG. 2, there is a mode using a flat pressure type press (up-down type). FIG. 2 shows a state in which a transfer sheet S is placed on a transfer base material B placed on a table 7 such that the transfer layer faces the transfer base material side. This is a method in which the resin 3 is poured from a nozzle 4 or the like (see FIG. 2A). Then, as shown in FIG. 2 (B), pressure is applied to the liquid resin 3 by a flat press plate 9. However,
From the viewpoint of continuous productivity, it is more desirable to use a roller system in which a continuous belt-shaped transfer sheet can be easily handled. Further, a plurality of pressure rollers may be used for sub-pressing several times. Note that the pressure roller and the press plate can also be used as a heating means for the liquid resin. The pressure roller is, for example, an internal hollow metal roller that circulates steam or hot oil through the hollow portion. The press plate is heated by an electric heater provided inside. In order to prevent the liquid resin 3 from leaking in the lateral direction due to the pressure and to escape the pressure, it is preferable to provide a weir that is thicker than the thickness of the substrate to be transferred, around the portion to which the pressure is applied.
In the case of the up-down system as shown in FIG. In the case of the roller system as shown in FIG.
It is preferable to provide weirs on both sides in the width direction (not shown). The pressure value is
It is set as appropriate depending on the liquid resin, the surface irregularity of the substrate to be transferred, the adhesive, and the like. The pressure value is usually 1 to 30 kg / cm ²
It is about.

The transfer method of the present invention is a laminating method. Japanese Patent Application Laid-Open No. 53-71163, which is similar to JP-A-53-71163, has a similar feature in that the uneven surface having minute concave portions such as conduit holes is painted.
On the substrate to be transferred, a thermoplastic resin film on which a pattern is printed is placed, and an auxiliary film is further placed on the resin film, and the auxiliary film is made to be in a fluid state by applying heat and pressure, thereby utilizing the fluidity thereof. A painting method is described in which the resin film is pressed into the minute recesses and adheres to the substrate, and after cooling, only the auxiliary film is peeled off. However, the present invention uses a liquid resin as a pressure transmission medium, and the resin is supplied in a liquid state from the beginning. Therefore, the transfer sheet sufficiently follows and forms the inside of the concave portion of the surface unevenness of the transfer-receiving base material, and the liquid resin is completely filled in the concave portion, and further the transfer sheet portion on the convex portion of the transfer-receiving base material. The amount of resin necessary and sufficient to cover the entire surface, including the entire area, can be supplied.
Therefore, it is possible to transfer to large surface irregularities. However, in JP-A-53-71163, the auxiliary film as thin as 25 μm or the like is used. It cannot deal with deeper surface irregularities such as bricks and brickwork patterns.

[Solidifying Step] In order to solidify the liquid resin, if the liquid resin is a hot-melt resin, it is cooled, and if it is a curable resin, the curing reaction is advanced. To advance the curing reaction, the thermosetting resin is heated, and the ionizing radiation curable resin is irradiated with ultraviolet rays or electron beams. The cooling of the heated molten resin includes a cooling roller as a cooling means as shown in FIG. 1 and a press plate as shown in FIG. The cooling roller is, for example, a metal roller having a hollow inside, and circulates cold water through the hollow portion. The press plate circulates cold water through piping provided inside. Although a single cooling roller may be used, as shown in FIG. 1, a plurality of cooling rollers can be used in series to perform sub-several times to achieve faster cooling. Cooling of the heated molten resin is preferably performed while applying pressure with a cooling roller, a press plate or the like. As a result, it is possible to prevent the transfer sheet formed following the inside of the concave portion of the concave-convex surface of the transfer-receiving substrate from returning to the case where there is a restoring force after the pressure release. In addition, in the case of surrounding the four sides with a weir, since the pressure can be received by the weir, separately in the case of roller pressing, the pressure tends to escape in the front and rear direction, so that the pressure of the roller is directly transmitted to the transfer sheet, Also, between the liquid resin / transfer sheet and the transfer sheet /
In order to expel air between transfer-receiving substrates, it is not possible to transmit unless the viscosity of the liquid resin is high to some extent. Therefore, in this sense, it is desirable to apply pressure while cooling. Cooling also increases the production speed. The cooling roller, the base material to be transferred, and the transfer sheet may be transported with the former fixed at the position, fixed at the latter position with the former moved, or both moved. The same applies to the pressure roller.

[Removal of Supporting Sheet] After the liquid resin is solidified into a solidified resin, the supporting sheet of the transfer sheet is released from the substrate to be transferred, whereby the transfer is completed. The peeled support sheet and the solidified resin may be peeled together, or separately, that is, the solidified resin may be peeled first, and then the support sheet may be peeled. Further, if the support sheet and the solidified resin are the same resin, they may be re-melted and reused as a liquid resin raw material as they are. Further, when the support sheet and the solidified resin are different resins, for example, after separation, only the solidified resin may be re-melted and reused.

The term "painting" as used in the present invention means, in addition to simply giving a visible pattern such as a picture, a character or a figure to a molded product, a pattern which is not visible, or a hard coating, a conductive film or the like. And the like. Known patterns such as an ink layer formed by printing or the like and a metal thin film formed by vacuum evaporation or the like are examples of a visible pattern. Examples of an invisible pattern are transparent to visible light and fluorescent by ultraviolet irradiation. Is used.

[0034]

【Example】

[Preparation of transfer sheet] A polyethylene terephthalate film having a thickness of 50 μm was prepared, and a release layer composed of a mixed system of melamine resin and acrylic resin was applied on one side thereof to a thickness of 1 μm (solid content basis, the same applies hereinafter) and supported. Body sheet. A transfer layer comprising the following release layer, pattern layer and adhesive layer was formed by printing on the release layer surface of the support sheet to obtain a transfer sheet. The release layer was formed to a thickness of 1 μm using an acrylic resin ink manufactured by Showa Ink Industry Co., Ltd. The pattern layer (decorative layer) uses a mixed resin ink of 1: 1 weight ratio of acrylic resin and vinyl chloride-vinyl acetate copolymer manufactured by Showa Ink Kogyosho Co., Ltd. The design with the design of was formed. The adhesive layer
2 μm thick using hot-melt adhesive of acrylic resin
Formed.

[Preparation of substrate to be transferred]
A calcium silicate plate (12 mm thick) was prepared. On the surface to be the transfer surface, a stone-like unevenness was formed, and the depth of the recesses of the unevenness was 2.5 mm at the maximum, and the width of the recesses was 3 mm at the shortest interval. The average depth of the concave portions was 1.5 mm in depth and 5 mm in width. A water-based acrylic emulsion-based adhesive was applied to the transfer surface having the surface irregularities by a spray gun at 10 g / m ² to form an adhesive layer also on the transfer substrate side.

[Transfer] As a liquid resin for pressurization, a polypropylene resin (AZ5 manufactured by Sumitomo Nogataku Co., Ltd.)
64, and a melt index of 30 [g / 10 minutes]). This resin was heated to 180 ° C. by an extruder and melted, and extruded as a liquid resin onto a support sheet side of a transfer sheet covered with the transfer layer facing the base material to be transferred. Thereafter, the pressure (about 10 ° C.) is applied by a hollow metal roller (surface temperature: 100 ° C.) in which heated and pressurized steam is circulated from the resin side to the inside of the hollow.
kg / cm ² ), and the molten resin is spread over the entire surface of the substrate to be transferred with the transfer sheet interposed therebetween.
In addition, the residual air between the molten resin / transfer sheet and the transfer sheet / transferred substrate was expelled and defoamed. At this point, the thickness of the resin is about 2 mm (from the transfer surface of the transfer substrate)
Met. Then, it consists of a hollow metal roller in which cold water is circulated in the internal cavity.
The resin was cooled while applying pressure in this order with three cooling rolls of 30 ° C. and 30 ° C., and the resin was completely solidified. afterwards,
Only the support sheet of the transfer sheet and the solidified resin were integrally peeled off from the substrate to be transferred to obtain a three-dimensional painted product in which the transfer layer was transferred to the substrate to be transferred. In the obtained three-dimensionally painted product, the transfer sheet, which is a phenomenon in which the transfer layer is not partially transferred, because the transfer sheet was completely formed along the surface irregularities of the base material to be transferred by the heat and pressure of the molten resin. I was not able to admit. Also, a polypropylene resin used as a resin for pressurization,
Since the polyethylene terephthalate film of the support sheet was not firmly bonded, the polypropylene resin and the support sheet could be separated. Therefore, the polypropylene resin was cut into pellets, which could be reused.

[0037]

According to the present invention, it is possible to easily obtain a three-dimensional painted article in which a large three-dimensional uneven surface is decorated. In addition, the transfer can be performed on the convex portion of the large irregular surface and in the concave portion (the bottom portion or the side surface which is the connecting portion between the convex portion and the bottom portion) without causing transfer omission. Also,
On the convex part of large irregularities, a finer irregular pattern (for example,
Even if there is a hairline, satin finish, etc., it is possible to paint by transfer even in the concave portions of the fine irregularities. Further, unlike the conventional rubber roller pressing method, there is no wear of parts such as the roller due to the concave and convex portions of the substrate to be transferred. As a result of the above, a three-dimensional painted article having an extremely excellent design property is obtained, which has not been achieved in the past.

[Brief description of the drawings]

FIG. 1 is a conceptual diagram illustrating one embodiment of a method for producing a three-dimensional decorative article of the present invention.

FIG. 2 is a conceptual diagram illustrating another embodiment of the method for producing a three-dimensional painted article of the present invention.

[Description of Signs] 1 Support sheet 2 Transfer layer 3 Liquid resin 3a Solidified resin 4 Nozzle 5 Pressure roller 6, 6a, 6b Cooling roller 7 Placement stand 8 Weir 9 Press plate B Transfer receiving substrate P Three-dimensional painting S Transfer sheet

Claims (2)

[Claims] 1. A first step of placing a transfer sheet having a transfer layer on a support sheet so that the transfer layer faces the transfer target substrate on a transfer target substrate; A second step in which a liquid resin is poured into the support sheet side of the transfer sheet placed thereon and pressure is applied from the resin side; a third step in which the resin is solidified; And a fourth step of peeling the transfer layer from the material and transferring the transfer layer onto the substrate to be transferred. 2. The method according to claim 1, wherein the liquid resin heated and melted in the second step is used, pressure is applied by a roller, and the resin is cooled and solidified by a cooling roller in the third step.
The method for producing the three-dimensional painted article described.