JPH10297192A - Transfer sheet, and manufacture of decorative member using transfer sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transfer sheet which can be transferred to an uneven face and is highly moldable and also whose release strength can be properly adjusted for improving foil retaining properties and foil fin resistance, and to manufacture a decorative member using the transfer sheet. SOLUTION: This transfer sheet is of such a construction that at least, a peelable layer 3 and a pattern layer 4 are formed as a transfer layer 2 on a base 1 made up mainly of an olefinic resin. The peelable layer 3 contains a first resin component and a copolymer of ester methacrylate, ethylene and maleio anhydride as a second resin component. When manufacturing the decorative member, the transfer layer 2 is transferred to a material to which a pattern is transferred using the transfer sheet with the help of a vacuum press process or a concurrent process of injection molding and decorating transfer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of manufacturing a decorative member for applying a pattern to a three-dimensional surface or the like by transfer, and a transfer sheet used in the method.

[0002]

2. Description of the Related Art Conventionally, a polyethylene terephthalate film is generally used as a base material of a transfer sheet for a decorative member having a flat transfer surface. However, in order to transfer a pattern to the surface of various decorative members such as a resin injection molded product or a wood base material, particularly a transfer surface having an uneven surface, the transfer sheet base material needs to be a resin film having moldability. Vinyl chloride resin films have been widely used. Such a transfer film is disclosed in, for example, Japanese Patent Publication No. 6-69759,
Japanese Patent Publication No. 7-29518, Japanese Patent Publication No. 7-10039
No. 8, for example. In the above, there is a configuration in which a pattern layer made of a releasable cellulose-based ink or the like is directly provided on a base material, and in the case of a design layer provided directly on a base material, a release layer provided directly on a base material is provided. Is composed of any one of polyvinyl butyral, cellulose acetate propionate resin, and chlorinated polypropylene resin.

[0003]

However, in the above, when printing is performed to directly provide a pattern layer on a base material, the solvent attacks the vinyl chloride resin film of the base material and the peel strength is unstable. Problem. Further, in the above, there is a problem that the plasticizer contained in the vinyl chloride resin film of the base material bleeds out and the peel strength becomes unstable. Further, in the above, there is a problem that the resin used for the release layer is limited to a specific resin such as polyvinyl butyral, cellulose acetate propionate resin, and chlorinated polypropylene resin. As described above, in the decoration of a transfer object having a three-dimensional uneven surface such as a three-dimensional molded product, the vinyl chloride resin film is excellent in moldability, but is easy to use as a base material of the transfer sheet and is satisfactory. Did not have the performance to be. Therefore, for example, Tokiko 7-1
In Japanese Patent No. 10550, as a base material, in addition to a vinyl chloride resin, a polystyrene resin, an acrylonitrile resin,
A transfer sheet using another plastic film such as an ABS resin is disclosed. However, in the above, it is necessary to provide an anchor layer on the base material in order to improve the adhesion to other layers of the plastic film, and a structure in which a release layer, a picture layer, etc. are provided on the anchor layer will not be provided. I can't get it. Therefore, when the transfer sheet is formed and transferred due to the anchor layer and the release layer, the suitable temperature range for thermoforming is narrowed.

Therefore, the present inventor uses a vinyl chloride resin film base material as a transfer sheet that does not require an additional layer such as an anchor layer on the base material, and has a base material having an appropriate release property and moldability. We have been conducting research on transfer sheets using polyethylene films or polypropylene films as material films. Further, the transfer sheet made of such a polyethylene or polypropylene film is also a measure against the vinyl chloride resin film that generates hydrochloric acid gas as a measure against the global environment. However, in the transfer sheet using these films, the crystallinity of the film is high, and the film softens rapidly at the melting point, so that the range of molding conditions of the transfer sheet is narrow. There has been a problem that the uniformity of the elongation is unstable, that is, the elongation of the whitened portion becomes larger than that of the other portions. When manufacturing a transfer sheet, it is necessary to appropriately adjust the peel strength between the base material and the transfer layer. If the peel strength is too light, the transfer layer itself will spill during handling, failing to function as a transfer sheet. Therefore, an appropriate peel strength is required (foil durability). On the other hand, if the peeling strength is too strong, the base material of the transfer sheet cannot be peeled off between the base material and the transfer layer at the time of peeling, resulting in peeling failure. Therefore, it is also important that the base material of the transfer sheet can have an appropriate peel strength. However, there has been a problem that the base material made of an olefin resin such as polyethylene generally has a peel strength which is too light as compared with a normal resin for a transfer layer. Therefore, there is a method of performing corona treatment on the surface of the base material in contact with the transfer layer, but the peel strength changes with time and is unstable. Attempts have also been made to mix a chlorinated polypropylene resin into the resin of the release layer, but there has been a problem that the chlorinated polypropylene resin generates hydrochloric acid gas during combustion.

[0005]

Means for Solving the Problems In order to solve the above-mentioned problems, first, the transfer sheet of the present invention comprises a base material mainly composed of an olefin resin and at least a release layer and a picture layer provided as a transfer layer. In the transfer sheet having the above configuration, the release layer contains a second resin component composed of a (meth) acrylate / ethylene / maleic anhydride copolymer in addition to the first resin component. As a result, a transfer sheet having an appropriate peel strength (foil durability) and excellent peelability, and capable of transferring to a three-dimensional surface due to the formability of the sheet was obtained. Furthermore, if the transfer sheet is further provided with an adhesive layer in addition to the release layer and the picture layer as the transfer layer, there is no need to apply an adhesive at the time of transfer, and the transfer sheet can be easily adhered.

Further, the first method of the present invention for producing a decorative member is described.
The method of the above, by a vacuum press method, the transfer sheet,
After being pressed against and adhered to the transfer object by the air pressure and the contraction force of the elastic film, the base material of the transfer sheet was peeled off, and the transfer layer was transferred onto the surface of the transfer object. As a result, it is possible to transfer onto an already-formed transfer object having a three-dimensional uneven surface with good peel strength. Further, a second method of the method of manufacturing a decorative member according to the present invention is a method in which the transfer sheet is inserted between a pair of dies, and both dies are clamped by an injection molding simultaneous painting transfer method. After filling the molten resin into the cavity formed by the above procedure and bringing the transfer sheet into close contact with the surface of the molded product at the same time as molding, the molds are opened, and the base material of the transfer sheet is peeled off. The transfer layer was transferred to the body surface. As a result, at the same time as the resin molding, it is possible to transfer to a transfer object having a three-dimensional uneven surface with good peel strength.

[0007]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a transfer sheet of the present invention and a method for manufacturing a decorative member using the same will be described in detail with reference to the drawings.

FIG. 1 is a sectional view showing one embodiment of the transfer sheet of the present invention. As illustrated in FIG. 1, the transfer sheet 10 of the present invention includes, as a transfer layer 2, at least a release layer 3 made of a specific material on a base material 1 made of an olefin resin.
This is a configuration in which a picture layer 4 is provided. Further, as another form of the transfer sheet of the present invention, for example, a sheet having an adhesive layer on the surface of the picture layer 4 may be used. Needless to say, the adhesive layer may not be provided on the transfer sheet when the picture layer has an adhesive property to the transfer object, or when the adhesive layer is applied to the transfer object side by coating or painting.

[Substrate] As the substrate 1, a resin film containing an olefin resin as a main component is used. Examples of the olefin resin include polyethylene, polypropylene, polybutene-1, ethylene / propylene copolymer, ethylene / butene-1 copolymer, propylene / butene-1 copolymer, polymethylpentene, and olefin-based thermoplastic elastomer. Etc. These resins may be used alone or in combination of two or more. Further, a film of a laminate composed of different resin layers may be used. The thickness of the resin film is not particularly limited, but is, for example, 20 to 200 μm. This resin film may be composed of only an olefin-based resin, but may be mixed with a resin other than the olefin-based resin as an auxiliary component for adjusting physical properties. In addition, among olefin resins, olefin thermoplastic elastomers are:
Since the change in the degree of softening with temperature change is more gradual than that of the crystalline olefin-based resin, the processing temperature range during molding or transfer becomes wider. In addition, necking is hard to occur, which is preferable. As the olefin-based thermoplastic elastomer, for example, the following can be used.

[0010] Japanese Patent Publication No. Hei 6-23278 discloses
(A) As a soft segment, the number average molecular weight Mn is 2
5,000 or more, 10 to 90% by weight of a boiling heptane-soluble polypropylene having a ratio Mw / Mn ≦ 7 of the weight average molecular weight Mw to the number average molecular weight Mn, and (B) a soft segment having a melt index of 0.1 90 to 10% by weight of boiling heptane-insoluble polypropylene of ４4 g / 10 min,
Soft polypropylene consisting of a mixture with:

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, etc., (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 above-mentioned olefin-based thermoplastic elastomer 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 a stretched film or an unstretched film, but it is preferable to use an unstretched film in consideration of moldability for three-dimensional molding. Also, in order to adjust the peel strength between the substrate and the transfer layer to an appropriate one,
The olefin resin used for the substrate may be provided with the polar group as described above, or the substrate may be subjected to corona treatment, plasma treatment, or the like.

In order to three-dimensionally paint a transferred object having a three-dimensional uneven surface, a resin film mainly composed of the above-mentioned olefin resin used as a base material has been conventionally used in a semi-rigid ( (Plasticizer content is 10 to 30 phr in terms of dioctyl phthalate) It is desirable to have the same three-dimensional moldability and mechanical strength as vinyl chloride resin. For that,
Breaking strength at 25 ° C. is 300 to 400 kg / cm ² , 25
Preferably, the material has a breaking elongation at 150 ° C. of 150 to 180%, a breaking strength at 70 ° C. of 200 to 300 kg / cm ² , and a breaking elongation at 70 ° C. of 160 to 200%. The measured value is J
This is a value based on IS-K-6734. If the breaking strength at 25 ° C. exceeds this value or the breaking elongation is less than this value, the three-dimensional formability at room temperature is insufficient, and at 70 ° C., the breaking strength exceeds this value, or If the elongation at break is less than this value, three-dimensional moldability during heat molding (usually about 70 ° C. to 150 ° C.) is insufficient. If the breaking strength at 25 ° C. is less than this value, the transfer sheet is likely to break during three-dimensional molding at normal temperature. If the breaking elongation at 25 ° C. exceeds this value, the registration accuracy during multicolor printing Becomes defective. If the breaking strength at 70 ° C. is less than this value or the breaking elongation exceeds this value, the distortion of the picture during three-dimensional molding becomes remarkable.

If the concave and convex pattern is formed by embossing, sandblasting, and hairline processing by hot pressing on the substrate surface in contact with the transfer layer, the concave and convex pattern can be formed on the surface of the transfer layer after transfer. Can also. 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. .

[Release Layer] The release layer 3 is a part of the transfer layer, and after the transfer, is transferred to the transfer object, and serves as a protective layer for protecting the surface of the transfer object from chemicals, ultraviolet rays, abrasion, and the like.
It is a layer for adjusting the adhesiveness of the transfer layer to the base material to make the releasability necessary and sufficient. The resin constituting the release layer comprises at least a mixture of the first component and the second component. As the resin of the first resin component, a resin excellent in elongation suitability is preferable in order to impart appropriate releasability by itself and to perform three-dimensional molding. The first resin component as the main component is a resin other than a (meth) acrylate / ethylene / maleic anhydride copolymer, for example, an acrylic resin, a polyvinyl butyral resin, or a cellulose resin such as nitrocellulose. Resin, chlorinated polyolefin-based resin such as chlorinated polypropylene, polyamide-based resin, urethane-based resin, vinyl chloride-vinyl acetate copolymer, rubber-based resin, acrylate-based ionizing radiation-curable resin, and the like can be used. Further, in addition to the first resin component, the release layer contains a suitable amount of a (meth) acrylate / ethylene / maleic anhydride copolymer as a second resin component. The content is determined by the adhesion of the first resin component, the resin in contact with both interfaces of the release layer (base resin, resin of the picture layer), and the (meth) acrylate / ethylene / maleic anhydride copolymer itself. In order to obtain a necessary and sufficient peel strength, it is appropriately adjusted according to the properties and the like. The content is in the range of 1 to 49% by weight based on the total amount of the release layer. By including the (meth) acrylate / ethylene / maleic anhydride copolymer as the second resin component, it is possible to appropriately adjust the peel strength. The addition of the (meth) acrylic acid ester / ethylene / maleic anhydride copolymer has an effect of increasing the peel strength of the release layer when only the first resin component is used (to make the release layer heavier). If the content of the (meth) acrylic acid ester / ethylene / maleic anhydride copolymer is too small, the effect is not obtained, the peel strength is low and the foil holding property is lowered, and if the content is too large, the peel strength is strong. It is not preferable because it results in poor peeling. Further, a wax, as a third component,
The peel strength may be adjusted by mixing silicone or the like.

(Meth) acrylic acid ester / ethylene /
As the (meth) acrylate component of the maleic anhydride copolymer, for example, methyl (meth) acrylate, ethyl (meth) acrylate, alkyl (meth) acrylate such as butyl (meth) acrylate, or others (Meth) acrylates. One or more of these (meth) acrylic esters are used as a comonomer component. In addition, (meth) acrylic acid means acrylic acid or methacrylic acid.
Depending on the ratio of the (meth) acrylic acid ester, ethylene and maleic anhydride copolymerized monomer, the physical properties of the obtained copolymer change. When the (meth) acrylic ester component increases, the (meth) acrylic ester / ethylene / maleic anhydride copolymer becomes flexible, and when the maleic anhydride increases, the polarity becomes higher. Adhesion is improved.

In the transfer sheet of the present invention, an olefin-based resin is used as a base material, and a (meth) acrylate / ethylene / maleic anhydride copolymer is used as a second resin component in the release layer. Since the union is contained, the advantage that the limitation of the resin that can be used as the first resin component of the release layer can be reduced can be obtained. That is, in the above-mentioned conventional technology, the release layer is limited to a single layer of polyvinyl butyral, cellulose acetate propionate resin, chlorinated polypropylene resin, or the like from the viewpoint of the releasability from the vinyl chloride resin film. However, these resins are poor in abrasion resistance, chemical resistance, solvent resistance,
The use is not particularly required for surface properties after transfer. On the other hand, in the present invention, if necessary, a two-part curable urethane resin having excellent surface properties such as solvent resistance, and an ionizing radiation-curable acrylic resin are used as a surface protective layer for a release layer which becomes the outermost surface after transfer. A system resin or the like can be used as the first resin component. As a result, since there is little restriction on the resin of the release layer that becomes the surface layer of the transferred body after the transfer, the surface physical properties of the obtained decorative member, for example, solvent resistance, scratch resistance,
An excellent transfer sheet can be freely designed as required in terms of surface properties such as abrasion resistance. In addition, since excellent surface properties can be imparted in this manner, the release layer transferred and formed can also be used as a paint finish. Note that the surface protective layer as a decorative member may be formed by spray coating or the like after the transfer layer is transferred. When a chlorinated polypropylene resin is used to adjust the peel strength of the release layer, there is a problem that the resin generates hydrochloric acid gas during combustion. However, in the present invention, chlorine-free (meth) acrylate / ethylene -Since the maleic anhydride copolymer is used, such a problem does not occur. The thickness of the release layer is 0.5 to 30 μm, usually about 2 to 10 μm.

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.

[Pattern Layer] Next, the pattern layer 4 is formed by printing or coating a pattern such as a pattern, a solid pattern, or the like, using a known vehicle mixed with an ink or coating liquid containing a pigment or the like. It is. As a printing method, a conventionally known printing method such as gravure printing, offset printing, letterpress printing, flexographic printing, or silk screen printing can be used.
For the all solid pattern, a conventionally known coating method such as a gravure coat and a gravure reverse coat can be used.

Various printing inks or coating liquids for the picture layer can be used, and a binder resin, a coloring agent, a solvent, and if necessary, an extender pigment, a curing agent, various additives, etc. The added composition can be used. As the binder resin, for example, acrylic resin, chlorinated polyethylene, chlorinated polypropylene, vinyl acetate, vinyl chloride-vinyl acetate copolymer, thermoplastic resin such as cellulose resin, room temperature or thermosetting polyurethane such as polyurethane Conventional resins such as resins and ionizing radiation curable resins such as acrylic resins can be used alone or as a mixture of these resins. In the transfer sheet of the present invention, since the pattern layer is provided on the release layer provided on the base material, compared with the case where the design layer is provided directly on the base material such as vinyl chloride resin, polyethylene, or polypropylene, the binder resin There are few restrictions. In addition, as a coloring agent, titanium white, zinc white, red petals,
Inorganic pigments such as vermilion, ultramarine blue, cobalt blue, titanium yellow, graphite, carbon black and the like, and organic pigments such as isoindolinone, Hansa yellow A, quinacridone, permanent red 4R, phthalocyanine blue, indaslen blue RS, aniline black and the like (or Conventionally known coloring pigments such as metal pigments such as dyes, aluminum and brass, pearlescent (pearl) pigments made of foil powder such as titanium dioxide-coated mica and basic lead carbonate 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 may be entirely or partially laminated in a pattern. The metal thin film may be formed of a metal such as aluminum, chromium, gold, silver, or copper by vacuum evaporation, The film is formed by a method such as sputtering. To form a pattern, a removal layer is formed in a desired pattern with a water-soluble ink on a unnecessary portion of the metal thin film. A known method such as removal of the metal thin film immediately above the surface is used. The picture layer is a layer formed by printing or the like,
A combination with this metal thin film may be used.

[Adhesive Layer] The adhesive layer 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 at the time of transfer, and it is easy to adhere to the transfer target. Further, the adhesive layer may be applied to the transfer object side by a coating method using a roll coat or the like or a coating method using a spray coat or the like. In the case where an adhesive layer is applied to the transfer object, and when the picture layer itself has adhesiveness to the transfer object, the adhesive layer as the transfer layer can be omitted. As the resin of the adhesive layer, an appropriate resin may be selected depending on the adhesiveness to the transfer object and the transfer method to be adopted.

As a resin for such an adhesive layer, for example, an acrylic resin is one of preferred resins. This is because the acrylic resin can easily adjust the adhesion according to the material of the transfer-receiving body by copolymerizing various acrylic esters, methacrylic esters, and other vinyl monomers. For example, when the transfer object is an ABS resin, this acrylic resin is a preferable resin. When the transfer object is a vinyl chloride resin such as a vinyl chloride resin, other resins may be appropriately used depending on the material of the transfer object, such as mixing and using a vinyl chloride-vinyl acetate copolymer in addition to the acrylic resin. In some cases, more excellent adhesion may be obtained by mixing and using. The mechanism for developing the adhesive layer may be a heat-sensitive type in which adhesiveness is developed by heating used in a so-called transfer sheet, or a pressure-sensitive type or a solvent-activated type. 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. The thickness of the adhesive layer is usually about 1 to 50 μm. As described above, in the transfer sheet of the present invention, there is a case where an adhesive is applied to the transfer sheet side and / or the object to be transferred and then transferred without providing the adhesive layer. If the transfer sheet has an adhesive layer and the adhesive is also applied to the transfer object side, there is an effect of further improving the adhesion of the transfer layer. Also, when manufacturing a decorative member such as a three-dimensional three-dimensional molded product to which a transfer layer is transferred by solidifying the resin from a liquid resin such as an injection molding simultaneous painting method, the liquid resin itself functions as an adhesive. There are times when it does.

Here, the transfer object of the transfer sheet of the present invention will be described. The transfer object is not particularly limited to its material and shape. For example, the material may be an acrylic resin, a vinyl chloride-based material. Resin, acrylonitrile-
Butane-styrene copolymer (ABS resin), polycarbonate resin, polyethylene, polypropylene, phenolic resin, or other metal or metal compound such as aluminum, iron, stainless steel, brass, wood plywood, wood veneer, Optionally, wood such as medium density fiberboard (MDF), ceramics such as glass, ceramics and tiles, ALC (lightweight cellular concrete), GRC (fiber reinforced concrete), fiber reinforced calcium board, cement such as ceramic siding, etc. is there. Also, the shape is arbitrary, such as a flat plate, a curved plate, a rod-shaped body, a three-dimensional object, and the like. As for the shape,
In the simultaneous molding and painting transfer method, the shape of the transfer object is formed simultaneously with the transfer.

By the way, the transfer sheet of the present invention as described above can be applied to the case where the transfer surface of the transfer object is flat, but an olefin resin such as an olefin thermoplastic elastomer is used as a base material. The transfer sheet of the present invention exhibits its true value when it is applied to a transfer object having a three-dimensional uneven surface. As a method of transferring the image to the transfer object using the transfer sheet of the present invention, for example, the following various known transfer methods can be used.

JP-B-2-42080, JP-A-6-42080
As described in JP-A-315950, etc., after a transfer sheet is disposed between both male and female molds of injection molding, a molten resin is injected and filled into the mold, and the transfer sheet is formed on the surface of the resin molded product at the same time as molding. So-called injection molding simultaneous painting transfer method, in which a transfer layer is transferred from an image forming apparatus, JP-B-56-45768 (overlay method),
As described in Japanese Patent Publication No. 60-58014 (vacuum pressing method) or the like, a transfer sheet is placed on the surface of a three-dimensional article such as a molded article, facing or placed with an adhesive therebetween as necessary. A transfer method using a so-called vacuum forming and laminating method in which a transfer layer of a transfer sheet is transferred to the surface of a three-dimensional article by a pressure difference caused by vacuum suction from the three-dimensional article side; As described in JP-A-2666, etc., in the major axis direction of a columnar substrate such as a cylinder and a polygonal column, a transfer sheet is supplied in a plurality of directions while appropriately supplying a transfer sheet through an adhesive layer as necessary. With different rollers, the decorative sheet is successively pressed and adhered to a plurality of side surfaces constituting the columnar base material and the transfer layer is transferred, so-called a wrapping method, a transfer method using a so-called wrapping method, and a BMC (Bulk Molding Compound) molding method. S
Various molding methods in FRP (Fiber Reinforced Plastics) such as MC (Sheet Molding Compound) molding method and hand lay-up molding method, or RIM (Reaction Injiction)
Molding), and a molding method such as a matched molding method.

Incidentally, the above-mentioned molding method and the above-mentioned molding method simultaneously transfer the three-dimensional shape of the three-dimensional molded product and develop the same.
And are for transferring a three-dimensional shape to a molded article already formed. In the above method, a resin mold,
Alternatively, there is a method in which after a transfer sheet is preformed by another mold, resin is injection-molded and transferred at the same time as molding. Similarly, in the methods listed, there are cases where the three-dimensional forming of the transfer sheet is performed simultaneously with forming and cases where pre-forming is performed before forming. In the hand lay-up method, the transfer sheet is formed by preliminary forming.

Among the various molding methods described above, the vacuum pressing method and the simultaneous painting transfer method by injection molding are typical molding methods. Therefore, as a method of manufacturing the decorative member of the present invention using the transfer sheet, a manufacturing method using the vacuum press method and the simultaneous injection painting transfer method will be described.

FIG. 2 is an explanatory view of a method of manufacturing a decorative member using a vacuum press method among the transfer methods using the vacuum forming and laminating method. The vacuum pressing method is similar to the vacuum laminating method, but uses not only air pressure but also the contraction force (shrinkage pressure) of a rubber-like elastic film as an elastic film to press the transfer sheet against the transfer target. Is slightly different in that the heating is performed through a rubber-like elastic film heated by a heater, and is characterized by uniform heating of the transfer sheet and a stronger pressing force.

A vacuum press 3 shown in the schematic diagram of FIG.
0 is a vertical movement means 13 such as a hydraulic cylinder
There is an upper chamber 11 which can move up and down, and a lower chamber 21 is provided below and facing the upper chamber 11. An infrared radiation type heater 12 is disposed inside the upper chamber 11. Upper room 11
Is entirely covered with a rubber-like elastic film 15. Silicon rubber or the like is usually used for the rubber-like elastic film 15. The upper surface of the lower chamber 21 is a table 22 having a plurality of exhaust holes 23. The upper chamber 11 and the lower chamber 21 have supply / exhaust ports 14 and 24, respectively, so that their internal pressures can be adjusted independently. In the vacuum press method, first, in a state where the upper chamber 11 moves upward and is separated from the lower chamber 21, the transfer object 20 is arranged on the mounting table 22, and the transfer sheet 10 is arranged from above the transfer object 20. . At that time, the transfer sheet 1
The transfer layer side of “0” faces the transfer-receiving body 20. If the adhesive is to be applied to the outer surface of the transfer sheet or the transfer object, it is applied at this stage. If the adhesive contains a solvent, it is dried at this stage. Next, the upper chamber 11 is moved downward and pressed against the lower chamber 21 to seal the upper chamber 11 and the lower chamber 21. FIG. 2 shows this state. Next, the pressure in the lower chamber 21 is reduced, and the pressure in the upper chamber 11 is increased. Further, the transfer sheet 10 is heated and softened through the rubber-like elastic film 15 using the heater 12 to be in a moldable state. As a result, the transfer sheet 10 is pressed by the pressure difference between the upper chamber 11 and the lower chamber 21 and the contraction pressure of the rubber-like elastic film 15, and is deformed and pressed along the outer surface of the transfer target body 20, and
Comes into close contact with the transfer receiving body 20. Finally, the pressure in the lower chamber 21 is released, and the pressure in the upper chamber 11 is released to bring both chambers to atmospheric pressure. The upper chamber 11 is moved upward to separate the upper chamber 11 and the lower chamber 21 from each other. Transfer receiving body 20 to which 10 is attached
Is taken out and the transfer sheet 10 (substrate 1) is peeled off to obtain a decorative member having a three-dimensionally patterned surface provided with a pattern on which the transfer layer has been transferred.

Next, FIG. 3 is an explanatory view of a method for manufacturing a decorative member by the simultaneous painting transfer method of injection molding. The figure shows a state in which the molten resin has already been injected and filled into the cavity, and the transfer sheet 10 has also been formed and adhered to the resin. A female die 81 having a concave cavity is fixed to a movable die plate (movable plate) 71, and a male die 82 having an injection hole is fixed to the other die plate (fixed plate) 72, and a nozzle is provided on the back surface thereof. 73 is located. The die plate 71 is moved left and right by a hydraulic cylinder 74 on the rear surface in the drawing, and the female mold 81 and the male mold 82 are pressed against each other to perform mold clamping. The transfer sheet 10 is inserted between the female mold 81 and the male mold 82 when the mold is opened. Further, a suction hole connected to a vacuum pump VP through a suction pipe is formed in the cavity surface of the female mold 81, and the transfer sheet 10 is heated by a heating plate (not shown) using the cavity surface of the female mold 81 before clamping. Is preheated and softened for preliminary vacuum forming. Then, after the heating plate is retracted out of the mold, the mold is clamped, and the nozzle 73 is inserted into the cavity (molding cavity).
After the molten resin 83 is injected, filled and cooled to solidify the resin, the mold is opened. Thereafter, when the transfer sheet 10 (base material) is peeled from the molded product, the transfer layer is transferred.
A decorative member having a three-dimensional uneven surface with a pattern is obtained.

The decorative member according to the present invention may be used for interior decoration of buildings such as walls, ceilings, floors, etc., surface decoration of fittings such as window frames, doors, handrails, and furniture and cabinets for light electric / OA equipment. It is used as surface makeup, vehicle interiors such as automobiles, trains, and aircraft, or containers such as bottles, cans, boxes, and cups.

[0037]

EXAMPLES The present invention will be described more specifically with reference to examples and comparative examples.

An olefin-based thermoplastic elastomer obtained by mixing 10 parts by weight of a partially crosslinked hydrogenated styrene / butazine rubber as a soft segment with 100 parts by weight of crystalline isotactic polypropylene as a hard segment is used as a thermoplastic resin. The film was extruded from a die to a thickness of 100 μm to obtain a film for a base material. On this substrate, Table 1
In addition to the first resin component as the release layer, as shown in FIG.
A layer obtained by adding an acrylate / ethylene / maleic anhydride copolymer in a range of 0 to 40% by weight based on the total amount of the release layer as a resin component of the gravure coat, (Based on solid content, the same applies hereinafter) 2 g / m ² , and a woodgrain pattern layer made of a mixed resin of an acrylic resin and a nitrocellulose resin is formed on the release layer by gravure printing. An adhesive layer made of a polyamide resin is coated with a gravure coat at a coating amount of 30 g / m ^2.
To form a transfer sheet.

Next, in each of the above transfer sheets, the peel strength, foil holding property and foil burr resistance were measured on a three-dimensional uneven surface of a wooden molded product made of MDF by a vacuum press transfer method using the apparatus and method shown in FIG. The results of trial transfer and transfer by simultaneous injection molding and painting transfer method using the apparatus and method shown in FIG. 3 using ABS resin were evaluated as follows. The results are shown in Tables 2 and 3.

Peel strength: The base material of the transfer sheet on the transfer object was peeled off at 90 ° at a speed of 1 m / min with a width of 25 mm.
The strength was measured. Foil holding property: In the form of a transfer sheet, it was evaluated whether the transfer layer peeled off from the substrate when rubbed by hand.れ な い indicates that the film was not peeled off, Δ indicates that the film was slightly peeled but was acceptable, and x indicates that the film could not be used. Foil burr resistance: The evaluation was made on whether or not burrs were formed due to adhesion of the transfer layer so as to protrude to a portion such as a corner on the transfer object that does not require transfer. Items without burrs were rated as ○, those with some burrs and acceptable were rated as △, and those with severe burrs were rated as x.

[0041]

[Table 1]

[0042]

[Table 2]

[0043]

[Table 3]

As described above, the transfer sheet in each of the examples had good foil holding properties without the transfer layer peeling off before setting, and also had problems with foil burrs after the transfer sheet was in close contact with the object to be transferred. Foil burr resistance was not so good. On the other hand, in each of the comparative examples, the transfer layer was peeled off by the time of setting, and foil burrs were severely generated and the foil burrs were poor. In each of the embodiments, the transfer sheet follows the three-dimensional uneven surface of the transfer object, does not cause transfer failure, and is affected by necking of the substrate (film) and temperature unevenness during heating of the transfer sheet. As a result, there was obtained a decorative member which was free from unevenness, distortion and the like of the pattern, and which was excellent in aesthetic appearance and was decorated with an uneven surface.

[0045]

According to the transfer sheet of the present invention, an olefin resin is used as a main component of the base material, and the first layer is used as a release layer of the transfer layer.
Since the (meth) acrylic acid ester / ethylene / maleic anhydride copolymer is contained as the second resin component with respect to the resin of the component, peeling is performed by adjusting the content of the second resin component. The strength can be easily adjusted, the foil holding properties are excellent, the foil burr resistance is good, and excellent peelability is obtained. Also,
Compared to the case where the peel strength is adjusted by corona treatment, the stability of the peel strength over time is also excellent. In addition, even when the surface to be transferred has an uneven surface, it is excellent in elongation suitability, so that decoration of a three-dimensional decorative member can be transferred similarly to the conventionally used vinyl chloride resin. In addition, since the base material produced as transfer sheet waste material is an olefin resin, it does not generate hydrogen chloride gas even when incinerated like the conventional base material vinyl chloride resin, and is suitable for global environmental measures. Is excellent.

[Brief description of the drawings]

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

FIG. 2 is an explanatory view by a vacuum press transfer method as an embodiment of a method for manufacturing a decorative member of the present invention.

FIG. 3 is an explanatory view showing another embodiment of the method of manufacturing a decorative member according to the present invention, which is a simultaneous painting and painting transfer method by injection molding.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Base material 2 Transfer layer 3 Release layer 4 Pattern layer 10 Transfer sheet 11 Upper chamber 12 Heater 13 Vertical movement means 14, 24 Supply / exhaust port 15 Rubber-like elastic film 20 Transfer object 21 Lower chamber 22 Mounting stand 23 Exhaust hole 30 Vacuum press Equipment 71 Die plate (movable plate) 72 Die plate (fixed plate) 73 Nozzle 74 Hydraulic cylinder 81 Female 82 Male 83

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI B32B 27/00 B32B 27/00 Z // B29L 9:00

Claims (4)

[Claims] 1. A transfer layer comprising at least a release layer and a picture layer provided on a base material containing an olefin resin as a main component, wherein the release layer has a (meth) acrylic acid ester in addition to the first resin component. -A transfer sheet containing a second resin component comprising an ethylene / maleic anhydride copolymer. 2. The transfer sheet according to claim 1, further comprising an adhesive layer in addition to the release layer and the picture layer as the transfer layer. 3. The method according to claim 1, wherein the vacuum press method is used.
After the transfer sheet described above is pressed against and adhered to the object to be transferred by air pressure and the contraction force of the elastic film, the base material of the transfer sheet is peeled off, and the transfer layer is transferred to the object to be transferred. Production method. 4. In a state in which the transfer sheet according to claim 1 or 2 is inserted between a pair of molds, both molds are clamped by an injection molding simultaneous painting transfer method, and a cavity formed by both molds is closed. After filling the transfer sheet with the surface of the molded product at the same time as molding, the molds are opened, the base material of the transfer sheet is peeled off, and the transfer layer is transferred to the transfer object made of the molded product. To manufacture a decorative member.