JPH1148695A - Transfer sheet and method for transferring curved surface using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transfer sheet having satisfactory after-coating suitability and a method for satisfactorily transferring to a protrusion and recess surface using the sheet. SOLUTION: The transfer sheet used for the method for transferring a curved surface comprising the steps of opposing a transfer layer side of a transfer sheet S having a support l and transfer layer 2 to a protrusion and recess surface of a base material to be transferred having the protrusion and recess surface, colliding many solid particles to the support side of the sheet, bringing the sheet into pressure contact with the protrusion and recess surface of the base material, adhering the transfer layer to the base material, then releasing to remove the support of the sheet, thereby transferring the transfer layer to the base material, comprises a release layer 3 made of thermoplastic urethane resin having hydroxyl group and a design layer 4 as a transfer layer provided on the layer 3 on a support containing polyolefin resin as releasable resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transfer sheet for producing a transfer product such as a decorative material having a concave and convex decorative surface used for exterior and interior materials of a house, furniture, home electric appliances and the like, and a curved surface transfer method using the same. About.

[0002]

2. Description of the Related Art Conventionally, decorative boards having decorations such as pictures on a substrate surface of the decorative board by a direct printing method, a laminating method, a transfer method or the like have been used for various purposes. In this case, if the surface of the base material is flat, the decoration of the picture can be easily made, but the decoration of the pattern is applied to the uneven surface by a special device. For example, in the case of a columnar shape such as a window frame or a surface border material, the base material decoration surface is a two-dimensional unevenness (a shape having a curvature only in one direction (a direction perpendicular to the generating line or the height direction) like a cylinder). One applicable curved surface decoration technique is proposed in Japanese Patent Publication No. 61-5895. That is, the technique of the publication is a surface decoration method by a laminating method, in which a front cover sheet coated with an adhesive on one side is supplied, while the base material is horizontally conveyed at a speed synchronized with the supply speed of the front cover sheet, and is additionally provided. While maintaining the state in which the end of the facing sheet is not adhered by the large number of holding jigs, the adhesive-applied surface side of the facing sheet is pressed stepwise with respect to the base material for each small area, and the base sheet is used as a base. It is to be adhered by heating to the material surface. This method is called a lapping method. Japanese Patent Application Laid-Open No. 5-139097 proposes a curved surface decoration technique applicable to the case where the surface unevenness is a three-dimensional unevenness such as an embossed shape (that is, a shape having a curvature in two directions like a hemisphere). Have been. That is, the technology of the same publication is a surface decoration method by a transfer method, a thermoplastic resin film is used as a support of a transfer sheet, and a release layer, a pattern layer, and an adhesive layer are sequentially provided on the support. The transfer sheet is placed on a substrate having an uneven surface, and is pressed from the back surface of the support with a heat roller made of rubber having a rubber hardness of 60 ° or less to transfer a picture, thereby obtaining a decorative plate. Further, a foamed layer which foams by heat during transfer is provided between the support and the release layer, and the foaming is also utilized to follow the uneven surface of the substrate.

[0003]

However, in the above-described conventional method, the technique disclosed in Japanese Patent Publication No. 61-5895 can only handle a two-dimensional curved surface. Although the technology proposed in Japanese Patent Application Publication No. H08-27139 can handle three-dimensional curved surfaces, it basically uses elastic deformation of the rotating heat roller by rubber to follow the surface irregularities. Not applicable to irregularities. In addition, the soft rubber roller is liable to be worn by the corners of the unevenness of the transfer-receiving substrate. Also,
In a configuration in which the foam layer is provided on the transfer sheet, the transfer sheet becomes too complicated and expensive. In addition, there is a problem that the substrate is limited to a flat substrate as a whole. In addition, when transferring while forming a transfer layer on the uneven surface as described above, it is necessary to use a thermoplastic resin such as a vinyl chloride-vinyl acetate copolymer or polymethyl methacrylate as a binder resin of the transfer layer. However, those generally used as such thermoplastic binder resins in the past are generally weak in organic solvent resistance, and after transfer, when applying a paint to protect the transfer layer, the paint in the paint is used. There is a drawback that the transferred pattern is dissolved or dissolved by a low molecular weight component such as a diluting solvent or a monomer, and the transferred pattern flows or bleeds. On the other hand, two-component curing type (thermosetting type)
By using a thermosetting resin such as urethane resin or epoxy resin as the binder resin, this disadvantage can be solved.However, another problem that cracks occur in the transfer layer when it is formed into an uneven shape is used instead. occured.

Therefore, according to the present invention, it is possible to obtain a transfer product such as a decorative material which can be transferred to a large three-dimensional uneven surface and has excellent surface decorativeness, and does not require a specially shaped jig for pressing the transfer pressure. As a curved surface transfer method that does not require replacement due to wear of rubber rollers and other parts, and as a transfer sheet used, it has sufficient follow-up formability even on large three-dimensional uneven surfaces, and the flow and bleeding of the pattern during post-painting Another object of the present invention is to provide a transfer sheet having excellent post-coating suitability, such as excellent adhesion to a coating film, and excellent peel strength of a transfer layer over time.

[0005]

In order to solve the above-mentioned problems, the transfer sheet of the present invention has a hydroxyl group on a release resin side of a support having a release resin of a polyolefin resin. A release layer made of a thermoplastic urethane resin,
Further, a pattern layer was provided thereon as a transfer layer. Further, an adhesive layer may be further provided on the picture layer on the support, and the release layer, the picture layer and the adhesive layer may be used as a transfer layer. With the transfer sheet having such a configuration, it is possible to prevent the flow and bleeding occurring in the transfer layer such as a pattern at the time of post-coating after transfer. In addition, the curved surface transfer method of the present invention may include a method in which a transfer layer side of a transfer sheet including a support and a transfer layer is opposed to an uneven surface side of a transfer-receiving substrate having an uneven surface, and a solid is formed on the support side of the transfer sheet. The particles are made to collide, and the pressure of the collision is used to press the transfer sheet against the uneven surface of the substrate to be transferred, and after the transfer layer is adhered to the substrate to be transferred, the support of the transfer sheet is peeled off. In this method, any one of the transfer sheets is used as a transfer sheet to be used in a curved surface transfer method for transferring a transfer layer to a substrate to be transferred.

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the transfer sheet of the present invention and a curved surface transfer method using the same will be described.

[Transfer Sheet] FIG. 1 is a sectional view showing an embodiment of the transfer sheet. FIG. 1A shows a configuration without an adhesive layer, and FIG. 1B shows a configuration with an adhesive layer. As shown in FIG. 1, the transfer sheet S of the present invention includes a support 1 using a polyolefin-based resin as a release resin, a release layer 3 made of a thermoplastic urethane resin having a hydroxyl group as a transfer layer 2, and a pattern layer 4. Consists of In the embodiment shown in FIG. 1A, the transfer layer 2 is composed of only the release layer 3 and the picture layer 4, and the transfer layer 2 shown in FIG.
In the embodiment, the transfer layer 2 is composed of a release layer 3, a picture layer 4, and an adhesive layer 5. The adhesive layer 4 is provided as appropriate.

(Support) The support is made of an olefin resin as a release resin, and at least the side in contact with the transfer layer is made of an olefin resin. As such a support, first, there is a support mainly composed of an olefin resin in its entire thickness. In addition, polyethylene terephthalate, a resin film such as a vinyl chloride resin or a substrate made of a material other than an olefin resin, such as paper, and a transfer layer side, a release layer made of an olefin resin as a release resin. Support may be used. A specific example of the support is, for example, a polypropylene-based thermoplastic elastomer film. Polypropylene-based thermoplastic elastomers have an excellent stretching property that the processing temperature range during molding or transfer is wider because the degree of softening with temperature change is gentler than that of crystalline olefin-based resins. This is one of the preferable supports in that it is suitable for a curved surface transfer method using pressure and that it does not generate hydrochloric acid gas during waste combustion and is environmentally friendly. The thickness of the support is not particularly limited, but is usually 20 to 200 μm in total thickness.

In the case where the support is made of an olefin resin, the olefin resin may be, for example, polyethylene, polypropylene, polybutene-1, ethylene.
Propylene copolymer, ethylene-butene-1 copolymer,
There are propylene / butene-1 copolymer, polymethylpentene, olefin-based thermoplastic elastomer and the like. These resins may be used alone or in combination of two or more. Further, the support may be a laminate composed of different olefin-based resin layers. In order to adjust the physical properties, a resin other than the olefin resin may be mixed and used as an auxiliary component within a range that does not impair the performance of the olefin resin, such as the original moldability and mold releasability.

As the olefin-based thermoplastic elastomer, for example, the following can be used.

[0011] Japanese Patent Publication No. Hei 6-23278,
(A) As a soft segment, the number average molecular weight Mn is 2
Boiling heptane-soluble polypropylene (atactic polypropylene) having a ratio of weight average molecular weight Mw to number average molecular weight Mn of 5,000 or more, Mw / Mn ≦ 7 (atactic polypropylene)
0% by weight and (B) as a hard segment, a boiling index heptane-insoluble polypropylene (isotactic polypropylene) having a melt index of 0.1 to 4 g / 10 min.
90 to 10% by weight of a soft polypropylene.

As described in JP-B-53-21021, (A) an olefin polymer (crystalline polymer) such as polyethylene, polypropylene or polymethylpentene is used as a hard segment, and (B) a partially crosslinked ethylene- Propylene copolymer rubber, unsaturated ethylene-propylene-
An olefin-based elastomer obtained by using a monoolefin copolymer rubber such as a non-conjugated diene terpolymer rubber as a soft segment, and uniformly mixing and mixing these. Incidentally, monoolefin rubber / olefin polymer = 50/50 to 90
/ 10 (weight ratio).

As described in JP-B-53-34210 and the like, (B) uncrosslinked monoolefin copolymer rubber (soft segment) and (A) olefin copolymer (crystalline, hard segment) are crosslinked. An olefin-based elastomer obtained by mixing with an agent, heating and applying shear stress to dynamically partially cross-link. (B) Monoolefin rubber / (A)
Olefin copolymer = 60/40 to 80/20 (weight ratio).

As described in JP-B-56-15741, (A) mixing with a peroxide such as isotactic polypropylene, propylene-ethylene copolymer or propylene-butene-1 copolymer and heating reduces the molecular weight. Mixing and heating with a peroxide-decomposable olefin polymer (hard segment) that increases fluidity and (B) a peroxide such as ethylene-propylene copolymer rubber, ethylene-propylene-non-conjugated diene terpolymer rubber, etc. Mixes with peroxides such as peroxide-crosslinked monoolefin copolymer rubber (soft segment), which crosslinks and reduces fluidity, (C) polyisobutylene, butyl rubber, etc.
Peroxide non-crosslinked hydrocarbon rubber (soft segment and fluidity-modifying component) that does not crosslink even when heated and does not change fluidity, and (D) mineral oils such as paraffinic, naphthenic, and aromatic An olefin-based elastomer obtained by mixing a softener and dynamically heat-treating the mixture in the presence of an organic peroxide. (A) is 90 to 40 parts by weight, (B) is 10 to 60 parts by weight.
(A) + (B) = 100 parts by weight,
(C) and / or (D) have a compounding ratio of 5 to 100 parts by weight.

An olefin-based thermoplastic elastomer comprising an ethylene-styrene-butylene copolymer as described in JP-A-2-139232.

The olefin-based thermoplastic elastomer described above, having a hydroxyl group and / or a carboxyl group as a polar group. For example, an olefin-based thermoplastic elastomer having a hydroxyl group introduced by graft polymerization of an ethylene-vinyl alcohol copolymer or the like and a carboxyl group introduced by a copolymer of maleic acid, fumaric acid, itaconic acid or the like is used. Either of these hydroxyl groups and carboxyl groups,
Alternatively, both may be used in combination, and these polar groups have an effect of adjusting the peel strength of the transfer layer from the release layer.

The above-mentioned olefin-based thermoplastic elastomer or other olefin-based resin can be formed into a film by a conventionally known film forming method such as a calendering method, an inflation method, and a T-die extrusion method. The film may be either a stretched film or an unstretched film. However, when the surface to be transferred has an uneven surface and moldability for three-dimensional molding is considered, it is preferable to use an unstretched film. Further, in order to adjust the peel strength between the support and the transfer layer to an appropriate value, an olefin resin used for the support may have a polar group as described above, or a corona treatment of the substrate, a plasma treatment, or the like. May be applied.

When the support is composed of a base material and a release layer made of an olefin resin, the above-mentioned various olefin resins can be used as the olefin resin. Further, the base material may be paper or nonwoven fabric having no stretchability if the transfer surface is flat or two-dimensional unevenness, or a resin film such as a biaxially stretched polyethylene terephthalate film having low stretchability. When the transfer surface is an uneven surface and moldability for three-dimensional molding is taken into consideration, a stretchable resin film is preferably used as the base material. Of course, even in biaxially stretched polyethylene terephthalate film, depending on the surface unevenness, by setting heating conditions, collision pressure conditions, etc.
Since the necessary and sufficient stretchability can be exhibited, transfer to an uneven surface is possible. However, preferred resin films that easily exhibit stretchability at lower temperatures and lower pressures include, for example,
Ethylene / terephthalate / isophthalate copolymer,
Thermoplastic polyester resin such as polybutylene terephthalate, soft or semi-hard vinyl chloride resin, ethylene-
Thermoplastic resins such as vinyl acetate copolymers, ethylene-vinyl alcohol copolymers, acrylic resins and polyamide resins, or rubbers such as natural rubber, synthetic rubber, urethane-based thermoplastic elastomers, alone or as a mixture, in a single layer or different types Can be used. These resin films are preferably low stretched or unstretched. In order to laminate a substrate and a release layer made of an olefin-based resin to form a support, a known lamination method such as dry lamination, simultaneous extrusion lamination, and coextrusion may be used.

If an uneven pattern is formed by embossing, sandblasting, or hairline processing by hot pressing on the support surface in contact with the transfer layer, the uneven pattern can be formed on the surface of the transfer layer after transfer. it can. The uneven pattern is, for example, a wood channel groove, a stone plate surface uneven pattern (a cleavage surface of granite or the like), a surface texture of a cloth, a satin finish, a grain of sand, a hairline, a linear groove, a skin squeezing, a character, a geometric pattern, or the like. .

(Transfer Layer) The transfer layer 2 includes at least a release layer 3 made of a thermoplastic urethane resin having a hydroxyl group;
It is composed of the picture layer 4 and the adhesive layer 5 may be a component of the transfer layer as appropriate. In the configuration having the adhesive layer, it is possible to omit applying the adhesive to one or both of the transfer sheet and the substrate to be transferred at the time of transfer.

(Transfer Layer: Release Layer) The release layer is made of a thermoplastic urethane resin having a hydroxyl group. As such a thermoplastic urethane resin, a urethane resin composed of a linear polymer having a hydroxyl group remaining by reacting a polyol having a hydroxyl group at a terminal with a polyisocyanate can be used. In order to make the material thermoplastic rather than thermosetting, diisocyanate is generally used as the isocyanate and diol is used as the polyol. In addition, an excess of a polyfunctional polyol exceeding bifunctional may be reacted with diisocyanate. In order to make the thermoplastic urethane resin have a hydroxyl group, preferably, the hydroxyl group of the polyol and the isocyanate group of the polyisocyanate are mixed and reacted so that the number of hydroxyl groups / the number of isocyanate groups becomes 1.05 to 1.40. It is good to The hydroxyl group improves the adhesiveness with the overcoat film (transparent protective layer) without decreasing the releasability of the support and the transfer layer over time. The residual isocyanate groups in the release layer are not preferred. This is because, in the case of a residual isocyanate group, the interlayer adhesion is changed with time, for example, the peeling force between the transfer layer and the support is increased, and the support may not be peeled off. Also, by leaving a hydroxyl group, when a curable urethane resin which cures with isocyanate is used for the overcoating film by post-coating, the adhesion between the two layers can be improved by interlayer crosslinking between the overcoating film and the release layer. On the other hand, even when the release layer has a residual isocyanate group, it is possible to utilize the hydroxyl group and the interlayer crosslinking in the curable urethane resin of the top coat, but the isocyanate group also reacts with moisture in the air. In addition, the adhesion between the coating film and the release layer changes with the lapse of time until the coating after the release, resulting in lack of stability.

Further, even when the transfer sheet is suddenly deformed by the impact pressure due to the concave portion or the like due to the thermoplastic urethane resin,
There is no transfer failure due to cracking or peeling of the release layer. Especially,
When the transfer sheet of the present invention is used in a transfer method using solid particle collision pressure without using an elastic roller as in the conventional transfer method, the stretchability of the transfer sheet support, the setting of the collision pressure, and the transfer target substrate This effect is significant because, when the transfer sheet is formed following the surface irregularities, the transfer sheet is likely to be rapidly deformed by the impact pressure, though it depends on the surface irregularities. In the case of the transfer method using an elastic roller, the transfer sheet deformation speed can be reduced by lowering the transfer speed (reducing the roller rotation speed). This is because in the exposed portion, even if the transfer speed of the transfer sheet or the transfer-receiving substrate is reduced, the deformation speed of the transfer sheet due to the impact pressure cannot be reduced. In terms of forming a release layer corresponding to the moldability of the transfer sheet, thermoplastic resins such as vinyl chloride-vinyl acetate copolymer and polymethyl methacrylate which are conventionally widely used may be used, but these generally have resistance to organic solvents. It is weak and is dissolved by a low molecular weight component such as a diluting solvent or monomer in the paint at the time of post-coating, and the transferred picture flows or bleeds. On the other hand, a thermosetting resin such as a two-component curable (thermosetting) urethane resin or an epoxy resin can solve this drawback, but instead has poor molding suitability and causes cracks in the release layer. However, by using a thermoplastic urethane resin having a hydroxyl group for the release layer as in the present invention, a transfer sheet having good post-coating suitability and also having good moldability can be obtained.

Examples of the polyol include poly (ethylene adipate), poly (butylene adipate), poly (neopentyl adipate), poly (hexamethylene adipate), poly (butylene azelate), poly (butylene sebacate), Polyester diols such as polycaprolactone, polyethylene oxide, polypropylene oxide, polyether diols such as poly (tetramethylene ether), polycarbonate polyols such as poly (butylene carbonate) and poly (hexamethylene carbonate), or acrylic polyols;
Examples include urethane polyol, fluorine-based polyol, acrylic silicone-based polyol, polyethylene glycol, and polypropylene glycol.

Examples of the diisocyanate component include various aliphatic (or alicyclic) or aromatic diisocyanates conventionally known in the field of polyurethane. For example, aliphatic (or alicyclic) systems include divalent isocyanates such as hexamethylene diisocyanate and isophorone diisocyanate, and aromatic systems include:
2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylene diisocyanate, 4,
4'-diphenylmethane diisocyanate, 1,5-naphthalenediisocyanate, hydrogenated tolylene diisocyanate and the like. In addition, from the viewpoint of weather resistance for exterior use and the like, and from the viewpoint of appropriate reaction delay, an aliphatic (or alicyclic) system such as hexamethylene diisocyanate and isophorone diisocyanate is preferable.

Specific examples of the thermoplastic urethane resin having a hydroxyl group include, for example, adipate diol and polycarbonate diol as a polyol component, and IPDI (isophorone diisocyanate) and MDI (hexamethylene diisocyanate) as isocyanate components. Resin. For example, a resin composed of polyester polyol and IPDI (isophorone diisocyanate), a resin composed of polycarbonate diol and IPDI and MDI (hexamethylene diisocyanate), a tree composed of adipate diol and IPDI, and the like. The thermoplastic urethane resin to be the transfer layer has, for example, a breaking elongation of 500 to 1000%, a stress at 100% elongation of 20 to 50 [kg / cm ² ], and a thermal softening temperature of 70 to 1.
30 [° C.], molecular weight of 40,000 to 60,000,
A preferable result is obtained when each characteristic value falls within the respective ranges.

In order to further improve the weather resistance (light resistance), one or both of an ultraviolet absorber and a light stabilizer can be added to the release layer. Both the agent and the light stabilizer are usually about 0.5 to 10% by weight, but it is generally preferable to use an ultraviolet absorber and a light stabilizer in combination. If the amount is less than this, the effect of improving the weather resistance cannot be sufficiently obtained, and if it is more than this, coloring occurs, and even if it is contained in a large amount, there is no effective change, which is not preferable. Examples of the ultraviolet absorber include benzotriazole-based, benzophenone-based, salicylic acid-based and other organic ultraviolet absorbers, and fine particles of zinc oxide and cerium oxide having a particle size of 0.2 μm or less.
An inorganic substance such as titanium oxide can be used. As a light stabilizer, a hindered amine radical scavenger such as bis- (2,2,2,6,6-tetramethyl-4-piperidyl) sebacate can be used.

(Transfer Layer: Picture Layer) The picture layer 4 is not particularly limited, and includes a pattern layer and a solid layer. The colored transparent layer is also a solid layer. As the printing ink or coating liquid for the picture layer, various kinds can be used, and a binder resin, a coloring agent, a solvent, and, if necessary, a composition containing an extender pigment, a curing agent, various additives, and the like as appropriate. Things can be used. As the binder resin, for example, acrylic resin, chlorinated polyethylene, chlorinated polypropylene, polyvinyl butyral resin, vinyl acetate, vinyl chloride-vinyl acetate copolymer, cellulose resin, thermoplastic urethane resin and the like Usable resins such as a resin at room temperature or a thermosetting resin such as a two-component curable urethane resin, and an ionizing radiation curable resin such as an acrylic resin can be used. Examples of coloring agents include inorganic pigments such as titanium white, zinc white, red petals, vermilion, ultramarine blue, cobalt blue, titanium yellow, graphite, carbon black, isoindolinone, Hansa Yellow A, quinacridone, permanent red 4R, and phthalocyanine blue. And organic pigments (or dyes) such as Indaslen Blue RS and aniline black; metal pigments such as aluminum and brass; pearlescent (pearl) pigments made of foil powder such as titanium dioxide coated mica and basic lead carbonate; Conventionally known coloring pigments can be used. As the extender pigment, calcium carbonate, silica, alnami, barium sulfate and the like are used. Further, the ultraviolet absorber and / or the light stabilizer described in the release layer may be mixed and used. In addition, the pattern of the picture layer may be, for example, a wood pattern, a stone pattern, a cloth pattern, a leather pattern, a character, a geometric figure, a symbol, a line drawing, various abstract patterns, a solid pattern, or a combination thereof. Ah.

As the picture layer, a metal thin film layer may be entirely or partially laminated in a pattern. The metal thin film layer is made of a metal such as aluminum, chromium, gold, silver, copper, etc. A film is formed by a method such as vapor deposition or sputtering.
To form a pattern, a removal layer is formed in a desired pattern with a water-soluble ink on an unnecessary portion of the metal thin film layer, and a metal thin film is formed on the entire surface by vapor deposition or the like, and then washed with water. In addition, a known method such as removal of the metal thin film immediately above is used. The picture layer may be a combination of the layer formed by printing or the like and this metal thin film layer.

(Transfer Layer: Adhesive Layer) The adhesive layer 5 can be provided as a part of the transfer layer if necessary. If an adhesive layer is provided, there is no need to apply an adhesive to the transfer sheet at the time of transfer, and it is easy to adhere to the substrate to be transferred.

As the adhesive, an appropriate one may be selected and used depending on the material of the substrate to be transferred and the like, and there is no particular limitation. For example, a so-called heat-fusion type (heat-sensitive type adhesive) adhesive which is commonly used for a conventionally known transfer sheet may be used, and a pressure-sensitive type or a solvent activated type may be used. In the case of the pressure-sensitive type, the transfer sheet usually has a configuration in which a release paper or a release film is laminated on the surface of the adhesive layer in order to protect the adhesive layer until immediately before transfer. Examples of the heat-sensitive adhesive include polyvinyl acetate resin, vinyl chloride-vinyl acetate copolymer, acrylic resin, thermoplastic polyester resin, thermoplastic urethane resin, polyamide resin obtained by polycondensation of dimer acid and ethylenediamine, and the like. Can be used. For example, when the substrate to be transferred is an ABS resin, an acrylic resin is one of the preferable resins used for the adhesive. Acrylic resin, by copolymerizing various acrylates and methacrylates, other vinyl monomers,
This is because it is easy to appropriately adjust the adhesiveness according to the material of the substrate to be transferred. Further, when the substrate to be transferred is a vinyl chloride resin such as a vinyl chloride resin, in addition to the acrylic resin, a mixture of vinyl chloride-vinyl acetate copolymer is used. By mixing and using resins,
In some cases, better adhesion may be obtained. The substrate to be transferred is a non-porcelain ceramic-based inorganic substrate such as an asbestos cement board, an asbestos calcium silicate board, a gypsum board, a calcium silicate board, a wood chip cement board, a slag cement board, and an ALC (lightweight foamed concrete) board. In the case of the alkaline base material, an adhesive such as a urethane resin using an acrylic polyol having excellent alkali resistance is preferable. The thickness of the adhesive layer is usually about 1 to 50 μm.

The release layer, the solid pattern layer, and the adhesive layer may be formed by a conventionally known coating method such as gravure coating or gravure reverse coating. Conventionally known printing methods such as printing, letterpress printing, flexographic printing, and silk screen printing may be used. When the adhesion between the release layer and the pattern layer is poor, a primer layer may be provided between these layers.

The transfer sheet may be provided with a plurality of small holes penetrating the entire transfer sheet as necessary, as a means for easily removing air remaining between the transfer sheet and the base material during transfer. The sheet may be perforated.

As described above, in the transfer sheet of the present invention, an adhesive layer is not provided, and an adhesive is applied to the transfer sheet and / or the substrate to be transferred at the time of transfer and then transferred. There is also. If the transfer sheet also has an adhesive layer and the adhesive layer also on the side of the substrate to be transferred, there is an effect of further improving the adhesion of the transfer layer. In order to form an adhesive layer on the substrate to be transferred having an uneven surface, it may be formed by a coating method such as roll coating using a roll such as a soft rubber roll or a sponge roll, curtain flow coating, spray coating, and melt coating. . The thickness of the adhesive layer of the substrate to be transferred varies depending on the type and surface condition of the substrate, but is usually 10 to 20 in the amount of application.
It is about 0 g / m ² (solid content).

[Transfer Method] As the transfer method using the above-described transfer sheet, various transfer methods can be applied. However, the transfer sheet of the present invention is most effective when the transfer method using solid particle collision pressure is used. Is the way. As a typical example of the transfer method using the solid particle collision pressure, an example of the case where a curved surface is transferred to a transfer-receiving substrate having an uneven surface will be described with reference to the conceptual diagram of FIG. That is, the transfer sheet S composed of the support 1 and the transfer layer 2 has at least a release layer of the above-described specific composition and a picture layer as a transfer layer, and a sheet having an adhesive layer or the like as appropriate. . In the example of FIG.
Is provided with an adhesive layer A in advance on the uneven surface. Then, the transfer layer 2 side of the transfer sheet S is opposed to the uneven surface side of the base material B on which the adhesive layer A is already provided [FIG.
(A)], a large number of solid particles P collide against the support 1 side of the transfer sheet S, and the transfer sheet S is pressed against the base material B to be transferred by utilizing the collision pressure. Transfer substrate B
The transfer sheet S is pressed into contact with the base material B to be transferred (FIG. 1B). Here, the solid particles P
The arrow attached to indicates the velocity vector of the solid particles. In the figure, the transfer layer is adhered to the substrate to be transferred by at least the adhesive layer A on the substrate B to be transferred. Then, after the transfer layer 2 of the transfer sheet is adhered to the base material B, the support 1 of the transfer sheet S is peeled off from the base material B to remove the transfer layer 2 from the base material B. A transferred product such as a cosmetic material D which is transferred to the uneven surface and has good post-painting suitability is obtained [FIG.
(C)].

(Solid Particles) Solid particles P include inorganic particles such as glass beads, metal particles such as zinc and iron, and organic particles such as resin beads such as nylon beads and crosslinked rubber beads.
Alternatively, inorganic / resin composite particles composed of inorganic particles such as a metal and a resin are used. The particle shape is preferably spherical, but other shapes can also be used. Particle size is usually 10 to 10
It is about 00 μm.

(Application of Impact Pressure by Solid Particles) Solid particles are ejected from an ejector toward a transfer sheet, and the impact pressure of the impact on the transfer sheet becomes the transfer pressure. Typically, an impeller or a blowing nozzle is used for the ejector. The impeller accelerates the solid particles by its rotation, and the blowing nozzle accelerates the solid particles with a high-speed fluid flow. Sandblasting, shot blasting, shot peening and the like used in the blasting field can be used for the impeller and the blowing nozzle. For example, a centrifugal blast device is used for the impeller, and a pressurized or suction blast device, a wet blast device, or the like is used for the blowing nozzle. The centrifugal blast device accelerates and ejects solid particles by the rotational force of the impeller. A pressurized blasting device ejects solid particles together with air while being mixed with compressed air. The suction-type blast device sucks solid particles into a negative pressure portion generated by a high-speed flow of compressed air, and ejects the solid particles together with the air. The wet blast device mixes and ejects solid particles with a liquid.

(Ejector: Impeller) FIGS. 4 and 5 are conceptual diagrams showing an example of an ejector using an impeller. Impeller 81
2 is a plurality of blades 813 having two side plates 81 on both sides thereof.
4 and a hollow portion 815 without a blade 813 at the center of rotation. A direction controller 816 is provided in the hollow portion.
(See FIG. 5). The direction controller has a hollow cylindrical shape having an opening 817 with a part of the outer periphery opened in the circumferential direction, has the same rotation axis as the rotation axis of the impeller 812, and is rotatable independently of the impeller. It has become. In use, the ejection direction of the solid particles is adjusted by setting the direction of the opening of the direction controller. Furthermore, another impeller having an internal hollow and the same rotation axis as the impeller 812 has a sprayer 818 in the direction controller (see FIG. 5). The spreader rotates with the outer impeller 812. A rotating shaft 819 is fixed to the center of rotation of the side plate 814. The rotating shaft 819 is rotatably supported by a bearing 820, and is driven and rotated by a rotating power source (not shown) such as an electric motor. Rotate. Then, the solid particles P are supplied from a hopper or the like to the inside of the sprayer 818.
Then, the solid particles scatter outside with the impeller of the sprayer,
It is emitted only in the direction allowed by the opening 817 of the direction controller 816 and is supplied between the blades 813 of the outer impeller 812. Then, the solid particles collide with the blade 813 and are accelerated by the rotational force of the impeller 812,
It gushing from the impeller. In addition, the impeller 8
The size of 12 is usually about 5 to 60 cm in diameter, the width of the blade is about 5 to 20 cm, the length of the blade is about the diameter of the impeller, and the rotation speed of the impeller is about 500 to 5000 [rpm]. The ejection speed of the solid particles is 10 to 50.
[M / s], and the projection density (total weight of solid particles colliding per unit area of the base material) is 10 to 150 [kg / m ² ].
It is about.

(Ejector: Ejector Nozzle) FIG. 6 is a conceptual diagram showing an example of an ejector using an ejector nozzle. An ejector 840 shown in the figure is an example of an ejector in which a gas such as air is used as a solid particle accelerating fluid, and the gas and the solid particles are mixed and ejected when ejecting the solid particles. The ejector 840
An induction chamber 841 for mixing the solid particles P and the fluid F, an internal nozzle 842 for jetting a fluid into the induction chamber, and a blowing nozzle unit 8 for jetting solid particles and a fluid from a nozzle opening 843.
44. A fluid F in a pressurized state from a compressor or the like is ejected from an internal nozzle 842 and passes through an induction chamber 841 to a nozzle 8.
When jetting from the nozzle opening 843 of the nozzle 44, a negative pressure is created by the action of the fluid flow flowing at high speed in the guide chamber 841 in the ejector, and the negative pressure guides and mixes the solid particles into the fluid flow, The nozzle 844 accelerates and transports the solid particles by the flow.
Are ejected from the nozzle opening 843 together with the fluid flow. In addition, there is a blowing nozzle or the like that uses a liquid as a solid particle acceleration fluid. Fluid pressure is spraying pressure, usually 0.1 to 10 kg
/ Cm ² . The flow velocity of the fluid flow is usually 1
About 20 to 20 m / sec, and usually about 5 to 80 m / sec for air flow.

(How to Use the Spouting Device) If the pressurized area cannot be formed into a desired shape and size by using only one spouting device, a plurality of spouting devices are used. For example, in order to make the entire width in the width direction perpendicular to the feeding direction of the transfer sheet and the base material, a plurality of strips are arranged in a straight line in the width direction, and a wide strip shape is linear in the width direction. Pressure region. Further, in order to lengthen the collision pressure application time, the ejectors are arranged in a multistage arrangement in which, for example, two or more rows are arranged in the feed direction of the transfer sheet and the base material. When a plurality are arranged, it is preferable that the adjacent pressurized regions of the individual ejectors partially overlap each other. The collision pressure of the solid particles can be set non-uniformly, for example, a peak-shaped pressure distribution or the like that is maximum in the width direction perpendicular to the transfer sheet feeding direction and decreases as it approaches the both ends in the width direction. . With this setting, the crimping is performed in a stepwise manner from the center to both ends to prevent the air from being trapped inside. of course,
The collision pressure is set within an appropriate pressure range that is equal to or higher than the pressure at which the transfer can be completely performed and is equal to or lower than the pressure at which the transfer sheet is not deformed and the transfer-receiving substrate is not deformed or damaged. When a plurality of ejectors are used, if each of the envelope surfaces (the cross-sectional shape perpendicular to the transport direction) of the transfer surface of the transfer-receiving substrate is a cylindrical convex curved surface having a circular shape, each ejector is The ejector can also be arranged with the direction of the envelope normal to the adjacent substrate to be transferred so that the solid particles collide substantially perpendicularly with the respective primary collision surfaces. In addition, when actually transferring using solid particles, it is preferable that the solid particles are circulated and reused without being scattered in the surrounding atmosphere. Therefore, it is preferable that the transfer pressure is applied by causing the solid particles to collide with the transfer sheet in a chamber that separates the collision space for pressing the transfer pressure due to the solid particle collision pressure from the surrounding space. The support may be peeled off the chamber.

(Heating of Transfer Sheet, Substrate to be Transferred, Adhesive, etc.) Even in the case where solid particle collision pressure is used for transfer pressure pressing, as in the case of the conventional transfer method using an elastic roller, it is possible to perform transfer pressure pressing, Before that, the transfer sheet, the substrate to be transferred, and the like can be appropriately heated. For example, before pressing against the collision pressure, the transfer sheet may be heated by any heating means such as infrared radiation heating or roller heating, and the substrate to be transferred (and the adhesive layer thereon) may be heated by infrared radiation heating or the like. The heating means may be used. For the heating at the time of pressing with the collision pressure, heated solid particles can be used as the solid particles, or in the case of the ejector using the blowing nozzle, the solid particle acceleration fluid can also use the heated fluid. Of course, heating before and during the pressing of the collision pressure, or heating only during the pressing, may be used as appropriate. However, if the hot air heating is performed in a chamber that isolates the collision space, gas flows into the chamber and affects the chamber pressure balance, so it is preferable to perform the heating outside the chamber.

[Substrate to be Transferred] As the substrate to be transferred B to be transferred with the transfer sheet of the present invention, the surface to be transferred may of course be a flat surface, but a curved surface transfer method using solid particle collision pressure is really useful. What is exhibited is a transferred substrate whose surface to be transferred is an uneven surface, and in particular, the transferred substrate has three-dimensional unevenness (however, the transfer sheet has an extensible Use those that exist). Conventional holding jigs that come into rotational contact (the above-mentioned Japanese Patent Publication No. 61-5895) and rubber transfer rollers (the above-mentioned JP-A-5-139).
No. 097) essentially has the directionality of the rotation axis, so that the applicable surface unevenness is limited. That is, the former is limited to two-dimensional unevenness having a curvature only in one axis direction, and the latter can be transferred to a three-dimensional unevenness having a curvature in two axis directions, but the three-dimensional shape can be changed in any direction. Cannot be applied homogeneously. Moreover, in the latter case, the shape of the base material is practically limited to a flat plate shape, and otherwise, it is impossible unless a transfer roller having a special shape tailored to each base material shape is used. In the transfer by the solid particle collision pressure, since a large number of solid particles can behave fluidly, two-dimensional unevenness having unevenness only in one direction such as only in the feed direction or only in the width direction, and in the feed direction and the width direction. The present invention can also be applied to three-dimensional unevenness having unevenness in both directions and two directions. Therefore, the shape is arbitrary, such as a flat plate, a curved plate, a rod, a three-dimensional object, and the like.

As the substrate to be transferred, a substrate to be transferred having an uneven surface superimposed on large irregularities and having fine 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. Transfer substrates are also possible. The large irregularities and the minute irregularities are, for example, a plan view of FIG. 3A and a plan view of FIG.
As shown in an example of a perspective view of the main part of FIG. 1, the unevenness of the substrate to be transferred is composed of large irregularities 401, 402 and fine irregularities 403 on the convex portion 402. 10 to 10 mm, the width of the concave portion is 1 to 10 mm, and the width of the convex portion is 5 mm or more. The fine unevenness is smaller than the large unevenness in both the step and the width. The step is about 0.1 to 5 mm, the width of the concave portion and the width of the convex portion are 0.1 mm or more, and is less than about 1/2 of the width of the convex portion having a large irregular shape. As a specific example of a concave-convex pattern of a cosmetic material having a combination of large pattern irregularities and fine irregularities, and having a three-dimensional surface irregularity, for example,
It has a two-dimensional array pattern of tiles, bricks, stones, etc. with joints, grooves, etc. as large irregularities, and irregularities on the spray painted surface such as stucco, ricin, etc. as fine irregularities on it,
It has a stone-grained uneven pattern such as a cleaved surface of granite or a stone material surface such as a travertine marble plate, or a large-sized uneven pattern, a paneling pattern having joints, grooves, shawls, sane, etc., and a floating woodgrain pattern. A wood-grained uneven pattern having a conduit groove, a hairline, and the like as fine unevenness on the upper side is given. 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.
If it is a board material, a non-porcelain ceramic board such as a calcium silicate board, a slag cement board, an ALC (lightweight foamed concrete) board, a GRC (glass fiber reinforced concrete) board, a wood veneer or a wood plywood, a particle board, or a wood board 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 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. Easy adhesion primer,
Alternatively, a resin such as an isocyanate, a two-component cured urethane resin, an epoxy resin, an acrylic resin, and a vinyl acetate resin is applied as a sealer. Also, the shape is flat,
A curved plate, a rod-shaped body, a three-dimensional object, or the like is optional, but the transfer can be performed by employing an appropriate transfer method described later, depending on the uneven shape of the surface to be transferred. In the injection molding simultaneous painting transfer method, the shape of the substrate to be transferred is formed simultaneously with the transfer (resin molding).

[Post-coating] The transfer sheet of the present invention is excellent in post-coating suitability, and is further provided with a transparent protective layer (top coat layer) in order to impart durability, design feeling, etc. to the surface of the transferred product after transfer. ) May be painted. Examples of such a transparent protective layer include a one- or two-component curable urethane resin, an ionizing radiation-curable resin cured by ultraviolet light or an electron beam, a fluororesin such as polytetrafluoroethylene and polyvinylidene fluoride, and polymethacrylic acid. One or two or more of acrylic resin such as methyl, silicone resin, etc. are used as a binder, and if necessary, a UV absorber such as benzotriazole or ultrafine cerium oxide (if not cured by UV), a hindered amine type A paint to which a light stabilizer such as a radical scavenger, a coloring pigment, an extender pigment, a lubricant and the like are added is used. Of course, the transparent protective layer may be colored and transparent. In particular, in the transfer sheet of the present invention, a thermoplastic urethane resin having a hydroxyl group is used for the release layer. Thus, interlayer crosslinking occurs due to interlayer urethane bonding, and the adhesion between the two layers is good. At this time, in order to make the interlayer cross-linking more reliable, a one-component curable (moisture-curable) urethane resin composed of only an isocyanate-based prepolymer is used as a coating material, or a component of a two-component curable urethane resin. It is preferable to mix the polyol and the polyisocyanate such that the number of isocyanate groups / the number of hydroxyl groups = 1.05 to 1.40. The coating may be performed by spray coating, flow coating, roll coating using a soft rubber roll or sponge roll, or the like. The thickness of the transparent protective layer is 1 to 10
It is about 0 μm.

[Uses of Transfer Products] The transfer products obtained from the above-described transfer sheet can be used for various applications as articles having a flat or irregular surface such as a three-dimensional shape. For example, cosmetic materials include exterior materials such as exterior walls, fences, roofs, gates, and gable plates, architectural interior materials such as walls and ceilings, window frames, doors, handrails, thresholds, doors and other fixtures, and furniture such as chests of drawers. It can be used in various fields such as a surface material, a cabinet for light electric / OA equipment, or a vehicle interior material such as an automobile.

[0046]

The present invention will be further described with reference to the following examples.

(Transfer Sheet) As a support made of a polyolefin resin having a total thickness of a release resin, 90% by weight of isotactic polypropylene, 10% by weight of atactic polypropylene, 1000 pp of erucamide
m, a polypropylene-based olefin-based thermoplastic elastomer is extruded from a T-die to a thickness of 100 μm.
Was obtained. On this support, a release layer, a pattern layer, and an adhesive layer were sequentially formed by gravure printing to form a transfer layer, and a transfer sheet of the present invention was obtained. The release layer is formed of a thermoplastic polyurethane resin having a hydroxyl group, which is obtained by reacting an acrylic polyol (having a hydroxyl value of 20) with a polyol component and isophorodiisocyanate with an isocyanate component in a ratio of the number of hydroxyl groups / the number of isocyanate groups = 1.2 / 1. A release layer ink was prepared by mixing 3 parts by weight of silica powder, 25 parts by weight of methyl ethyl ketone, 25 parts by weight of toluene, and 25 parts by weight of xylene in 100 parts by weight of the thermoplastic urethane resin. The thermoplastic urethane resin used for the release layer had a molecular weight of 40,000, a glass transition temperature of -45 ° C, and a breaking elongation of 60.
0%, 100% elongation stress was 36 [kg / cm ² ], and thermal softening temperature was 100 ° C. The picture layer was printed using a thermoplastic polyurethane resin as a binder resin and an ink using a reddish pattern, isoindolinone, carbon black, and titanium white as a coloring pigment to form a brick-patterned picture pattern having joints.

(Substrate to be Transferred) FIG.
As shown in the plan view of (A) and the perspective view of the main part of FIG. 3 (B), a groove-like concave portion 401 serving as a joint of a brick having a width of 6 mm and a depth of 2 mm on the surface and a flat convex portion 402 of a brick portion are provided. Is prepared as large irregularities, and a calcium silicate plate having a thickness of 12 mm is prepared on a flat convex portion 402 having a fine unevenness 403 having a satin finish like a center line average roughness (JIS-B-0601) of 100 μm. A urethane-based adhesive was spray-coated on the surface.

(Transfer) The transfer sheet was placed on the transfer substrate such that the transfer layer side faced the transfer substrate side. Next, after the transfer sheet is heated to 100 ° C. and softened, spherical zinc spheres having an average particle diameter of 0.3 mm are used as solid particles.
The transfer was performed by colliding the transfer sheet with the support side at an average speed of 35 m / s to press the transfer pressure, and after cooling, peeling off the support body (see FIG. 2). Finally, a transparent curable urethane coating was applied to the surface to form a transparent protective layer. At that time, the acrylic polyol and hexamethylene diisocyanate were blended so that the number of isocyanate groups / the number of hydroxyl groups = 1.2 / 1. As a result, there is no flow or bleeding of the pattern at the time of post-coating, and the transfer sheet follows the uneven surface of the base material to be transferred, and the peelability of the support is also good, so that the transfer drop defect does not occur, A decorative board for exterior was obtained as a transfer product excellent in aesthetic appearance.

[0050]

According to the present invention, it is possible to obtain a transfer product excellent in post-coating suitability without causing flow or bleeding of a transfer layer such as a picture during post-coating after transfer. When a curable urethane resin that is cured with isocyanate is used in the post-coating, it reacts with the hydroxyl group in the release layer, and the adhesion of a coating film such as a transparent protective layer formed in the post-coating is good. Therefore, the durability of the transferred product can be improved. Further, in the curved surface transfer by the solid particle collision pressure, a decorative material in which a large three-dimensional uneven surface is decorated can be easily obtained.
Of course, two-dimensional irregularities such as a window frame and a sash are also possible, and in addition to a flat plate material, a tile having a wavy shape (envelope shape) as a whole, or a convex or concave curve Even those with shapes can be easily obtained. In addition, it is possible to transfer on the convex portion of the large irregular surface and also inside the concave portion (the bottom portion or the side surface which is the connecting portion between the convex portion and the bottom portion). Further, even when there is a finer uneven pattern (for example, a hairline, a satin finish, etc.) on the convex part of the large unevenness, the decoration can be transferred to the concave part of the fine unevenness. 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. The peel strength between the support and the release layer also becomes constant over time,
There is no phenomenon that the film hardly peels off over time.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view illustrating a transfer sheet according to an embodiment of the present invention.

FIG. 2 is a conceptual diagram outlining a curved surface transfer method of the present invention.

FIGS. 3A and 3B are explanatory diagrams showing an example having three-dimensional surface irregularities as an example of a substrate to be transferred, where FIG. 3A is a plan view and FIG.
FIG.

FIG. 4 is a perspective view conceptually illustrating an example of an ejector using an impeller.

FIG. 5 is a conceptual diagram illustrating the inside of the impeller of FIG. 4;

FIG. 6 is a cross-sectional view conceptually illustrating an example of an ejector using an ejection nozzle.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Support body 2 Transfer layer 3 Release layer 4 Picture layer 5 Adhesive layer 401 Groove-shaped concave part 402 Flat convex part 403 Fine unevenness 812 Impeller 813 Blade 814 Side plate 815 Hollow part 816 Direction controller 817 Opening part 818 Sprayer 819 Rotation Shaft 820 Bearing 840 Jetting device using blowing nozzle 841 Induction chamber 842 Internal nozzle 843 Nozzle opening 844 Nozzle A Adhesive layer B Substrate D Decorative plate P Solid particles S Transfer sheet

Claims (3)

[Claims] 1. A release layer composed of a thermoplastic urethane resin having a hydroxyl group on a release resin side of a support using a polyolefin resin as a release resin, and a pattern layer thereon as a transfer layer. Transfer sheet provided. 2. The transfer sheet according to claim 1, wherein a release layer, a picture layer, and an adhesive layer are provided in this order as a transfer layer on the support. 3. The transfer layer side of a transfer sheet composed of a support and a transfer layer is opposed to the uneven surface side of the transfer-receiving base material having the uneven surface, and solid particles collide with the support side of the transfer sheet. Utilizing the collision pressure, the transfer sheet is pressed against the uneven surface of the substrate to be transferred, and after the transfer layer adheres to the substrate to be transferred, the support of the transfer sheet is peeled off to remove the transfer layer. A curved surface transfer method for transferring to a transfer-receiving substrate, wherein the transfer sheet according to claim 1 or 2 is used.
Curved surface transfer method.