JP2003154795A - Transfer sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transfer sheet with outstanding adhesive properties of a protecting layer after transfer, in the transfer sheet which can transfer/form a transfer layer including at least the protecting layer which imparts a superb surface physical property to the surface after transfer. SOLUTION: In the transfer sheet having a transfer layer 2 including at least a protecting layer 21 on a base material sheet 1, the protecting layer 21 is composed of an acrylic resin which shows 100 deg.C or higher of a glass transition point and an average molecular weight of 100,000 to 150,000. According to necessity, a release layer 11 may be formed on the face for forming the transfer layer 2 of the base material sheet 1 or a pattern layer 22, an adhesive layer 23 or the like may be formed on the protecting layer 21.

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to various substrates to be transferred, such as, for example, a wood-based substrate, an inorganic-based substrate, a metal-based substrate, and a synthetic resin-based substrate. The present invention relates to a transfer sheet for transfer-forming a transfer layer including at least a protective layer on the surface of the transfer sheet. [0002] Conventionally, for example, in the production of cosmetic materials and the like,
In applying makeup with a protective layer or the like to the surface of each of the above various substrates, a transfer method using a transfer sheet is used as a method capable of easily forming the protective layer or the like by a dry method. [0003] This transfer method means that a protective layer made of a resin composition having excellent surface properties such as hardness and solvent resistance is provided on a base sheet made of paper or a thermoplastic resin film in a releasable manner. If necessary, a transfer layer is prepared by providing a pattern layer, an adhesive layer, and the like (these are referred to as a transfer layer together with the protective layer). After the transfer layer is adhered to the substrate to be transferred by pressure bonding, the transfer layer is transferred and formed on the substrate to be transferred by peeling off the interface between the transfer layer and the substrate sheet and removing the substrate sheet. It is a method of producing a cosmetic material or the like of the intended purpose. [0004] As the protective layer, for example, surface hardness, abrasion resistance, scratch resistance, solvent resistance,
In order to impart excellent surface properties such as chemical resistance, it is general that a curable resin such as a thermosetting resin or an ionizing radiation-curable resin is used.Specifically, a polyol compound and an isocyanate compound are used. Various types have been already used, such as a two-component curable polyurethane-based resin which is a reaction product of the above, and an ionizing radiation-curable acrylate-based resin having a radical polymerizable double bond in the molecule. However, in the transfer sheet using the curable resin as a protective layer as described above, there is a problem that the adhesion of the protective layer after transfer is not good. In other words, curable resins having a three-dimensional cross-linked structure inside, such as thermosetting resins and ionizing radiation-curable resins, tend to have poor adhesion to other materials due to their high internal cohesive strength, and Adhesion with the pattern layer provided on the layer or the adhesive layer for adhesion to the substrate to be transferred, etc. is insufficient. However, there is a problem that the adhesive may peel off together with the cellophane adhesive tape. On the other hand, if the protective layer is formed of a thermoplastic resin in order to avoid the above-mentioned problems, if a general thermoplastic resin is used, the surface properties such as solvent resistance and abrasion resistance will be insufficient. Can not get to. Under such circumstances, the appearance of a transfer sheet capable of transfer-forming a protective layer excellent in both adhesion and surface properties has been desired. SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems in the prior art, and it is an object of the present invention to improve the surface after transfer. Another object of the present invention is to provide a transfer sheet capable of transfer-forming a transfer layer including at least a protective layer imparting surface physical properties and having excellent adhesion of the protective layer after transfer. [0008] The present invention provides a transfer sheet having a transfer layer including at least a protective layer on a base sheet, wherein the protective layer has a glass transition point of 100 ° C or higher, A transfer sheet comprising an acrylic resin having an average molecular weight of 100,000 to 150,000. Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 is a side sectional view showing an embodiment of the transfer sheet of the present invention. As shown in FIG. 1, the transfer sheet of the present invention basically has a transfer layer including at least a protective layer 21 for protecting the surface after transfer on one side of a substrate sheet 1 as a support. 2 is provided so as to be peelable. In the present invention, the protective layer 21 has a glass transition point of 100 ° C. or higher and an average molecular weight of 1000
It is characterized by comprising an acrylic resin of 00 to 150,000. The acrylic resin includes methyl methacrylate, ethyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate, cyclohexyl methacrylate, ethylhexyl methacrylate, methyl acrylate,
It is a homo- or copolymer composed of (meth) acrylic monomers such as ethyl acrylate, butyl acrylate, hydroxyethyl acrylate, cyclohexyl acrylate, ethylhexyl acrylate, methacrylic acid, acrylic acid, acrylonitrile, methacrylonitrile, etc. Monomers having a polymerizable double bond copolymerizable therewith, for example, ethylene, butadiene, isoprene, vinyl acetate, vinyl propionate, vinyl butyrate, styrene, α-methylstyrene, vinyltoluene, divinylbenzene, N A copolymer in which -cyclohexylmaleimide, N-ethylmaleimide, N-phenylmaleimide, or the like is added as a copolymer component may be used. Among these various acrylic resins, a homopolymer of methyl methacrylate or a copolymer mainly composed of methyl methacrylate is most suitable for the purpose of the present invention. The acrylic resin has a glass transition point of 1
00 ° C. or higher and average molecular weight of 100,000 to 150
Within the range of 000 is important in the present invention. When the glass transition point is less than 100 ° C. or the average molecular weight is less than 100,000, the solvent resistance, abrasion resistance and heat resistance of the surface after transfer are insufficient, and the average molecular weight is 1
If it exceeds 50,000, the adhesion of the protective layer after transfer is reduced, and burrs are likely to occur during transfer. The thickness of the protective layer 21 is not particularly limited in the present invention, but if it is too thin, the protective effect is insufficient, and if it is too thick, it loses flexibility and is liable to crack. In general, it is appropriately designed within a range of about 1 to 50 μm, more preferably about 5 to 20 μm. The protective layer 21 may include, in addition to the above-mentioned acrylic resin, another resin component such as a thermoplastic resin or a thermosetting resin, if necessary, as long as the surface physical properties and adhesion are not impaired. Various additives such as colorants, fillers, ultraviolet absorbers, light stabilizers, heat stabilizers, gloss regulators, lubricants, antistatic agents, antibacterial agents, fungicides, flame retardants, lubricants, etc. It can also be added. As a method of forming the protective layer 21, various printing methods such as a gravure printing method, an offset printing method, a gravure offset printing method, a flexographic printing method and a screen printing method, a gravure coating method, Various coatings such as gravure coating, roll coating, rod coating, kiss coating, knife coating, air knife coating, comma coating, die coating, lip coating, flow coating, dip coating, spray coating, etc. A construction method can be appropriately used. In the transfer sheet of the present invention, the layer constitution other than the protective layer 21 and the constituent materials thereof are not limited at all, and the base sheet 1 as a support is indispensable. The layers can be arbitrarily added as required. Examples of the base sheet 1 include polyolefin resins such as polyethylene, polypropylene, polybutene and polymethylpentene, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene- (meth) acrylic acid ( Ester) copolymers, olefin copolymer resins such as ethylene-unsaturated carboxylic acid copolymer metal neutralized products (so-called ionomer resins), acrylic resins such as polyacrylonitrile, polymethyl methacrylate, polyethyl methacrylate, and polystyrene ,
Styrene resin such as AS resin and ABS resin, polyvinyl acetal, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyvinyl resin such as vinyl chloride-vinyl acetate copolymer, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate , A film or sheet made of a thermoplastic resin such as a polyester resin such as polyarylate and polycarbonate, a fluororesin such as polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, and ethylene-tetrafluoroethylene copolymer, and paper. , Woven or non-woven fabric, metal foil, etc.
Alternatively, a mixture or complex of two or more kinds selected from these,
A sheet formed of a laminate or the like can be used. On the surface of the base sheet 1 on the transfer layer 2 side, if necessary, the transfer layer 2 can be easily separated from the base sheet 1, and after the separation, remains on the surface of the base sheet 1. Alternatively, a release layer 11 made of a release material may be provided.
As the release layer 11, for example, an olefin-based resin such as polyethylene, polypropylene, and polymethylpentene;
Polyvinyl fluoride, polyvinylidene fluoride, ethylene-
Low surface tension resin compositions such as fluororesins such as tetrafluoroethylene copolymer, silicone resins such as dimethylpolysiloxane and methylphenylpolysiloxane, and thermosetting such as melamine resins and phenolic resins Generally, a resin composition having a high crosslinking density, such as an ionizing radiation curable resin such as a hydrophilic resin and a (meth) acrylate resin, is used. The surface properties of the transfer layer 2 after the transfer onto the substrate to be transferred are the reverse of the surface properties of the substrate sheet 1 (or the release layer 11). Therefore, the base sheet 1
If a mirror-like material having a smooth surface is used, the surface of the transfer layer 2 after the transfer can be smooth and mirror-finished, and the base sheet 1 has a matte surface or embossed unevenness. If a material having a shape is used, the gloss state and the embossed shape can be formed on the surface of the transfer layer 2 after the transfer. As a method for making the surface of the base material sheet 1 matte, a method of kneading a matting agent composed of inorganic particles or synthetic resin particles into the base material sheet 1 or a method of making the surface of the base material 1 matte is used. A method of performing a surface finish using a metal roll, a method of performing a matte finish on a surface by sandpaper processing or sandblasting, a method of providing a release layer 11 of a coating composition to which a matting agent is added, and the like. be able to. As the method of forming the embossed shape, in addition to the hot-press embossing method using a metal embossing plate, a method in which the release layer 11 is partially provided in a desired pattern may be used. Between the base sheet 1 (or the release layer 11) and the protective layer 21, if necessary, the weight of the peeling of the transfer layer 2 from the base sheet 1 (or the release layer 11) is provided. In order to adjust the thickness within an appropriate range, a release layer (not shown) that separates from the base sheet 1 (or the release layer 11) may be provided together with the protective layer 21 at the time of the release. Examples of the release layer include natural rubber derivatives such as chloride rubber and cyclized rubber; waxes such as natural wax and synthetic wax; cellulose derivatives such as nitrocellulose and cellulose acetate propionate;
Thermoplastic resins such as polyurethane, polyamide, polyimide, polyester, polyacetal, chlorinated polyolefin, vinyl chloride-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, melamine, epoxy, polyurethane It can be appropriately selected from conventionally known various release agents made of a thermosetting resin such as a silicone resin and the like. On the surface of the protective layer 21 opposite to the substrate sheet 1 side, for example, a picture layer 22, a concealing layer (not shown), a metal deposition layer (not shown), an adhesive One or more selected from the layer 23 and the like can be provided. The pattern layer 22 is provided for imparting a design with a pattern to a product after transfer using the transfer sheet of the present invention, and the type of the pattern is not particularly limited. , For example, wood pattern, stone pattern, cloth pattern, abstract pattern,
A geometric figure, a character or a symbol, or a combination of two or more selected from them is optional as desired. The picture layer 22 is formed by using a printing ink or paint obtained by kneading a coloring agent such as a dye or a pigment with a coloring agent (binder) such as a resin and a diluent such as an organic solvent. Or, it is generally formed by a coating method. Examples of the coloring agent include organic pigments such as condensed azo, insoluble azo, quinacridone, isoindolinone, anthraquinone, phthalocyanine, and diketopyrrolopyrrole, and carbon black, iron oxide, and titanium oxide. Inorganic pigments, metal powder pigments such as aluminum powder and bronze powder, and pearlescent pigments such as mica coated with titanium oxide are often used. Examples of the above vehicle include nitrocellulose, cellulose acetate, cellulose acetate propionate, vinyl chloride-vinyl acetate copolymer, chlorinated polyolefin, polyvinyl butyral, polystyrene, polyamide, alkyd, and fluorine. Resin compositions, polyurethane-based, (meth) acrylic, polyester-based, metal alkoxide-based resin compositions, or modified products thereof, can be used alone or in any combination of two or more. As a printing method of the picture layer 22, for example, a gravure printing method, an offset printing method, a gravure offset printing method, a screen printing method, a flexographic printing method, a relief printing method, a dry offset printing method, an ink jet printing method,
A conventionally known printing method such as an electrostatic printing method can be used. When a solid layer is provided, in addition to the above-described various printing methods, for example, a gravure coating method, a microgravure coating method, a roll coating method, a rod coating method, a knife coating method, an air knife coating method, a kiss coating method, a die coating method , A coating method such as a lip coating method, a comma coating method, a flow coating method, a dip coating method, and a spray coating method. The concealing layer is provided when it is necessary to conceal undesired colors and color tone variations, surface defects, etc. on the surface of the substrate to be transferred in order to obtain a transferred product of uniform quality in design. The constituent material and the forming method are basically the same as those of the picture layer 22 described above. However, in order to ensure sufficient hiding properties, for example, opaque inorganic pigments such as titanium oxide, zinc oxide, iron oxide, and carbon black; metal powder pigments such as aluminum powder; and pearls such as titanium oxide-coated mica. A printing ink or paint containing a large amount of opaque pigments such as glittering pigments such as gloss pigments is used. The metal deposition layer is provided when it is necessary to impart a metallic luster to the surface after transfer. Examples of the metal used include gold, silver, copper, aluminum, nickel, and chromium. , Aluminum is the most common. The formation method may be a conventional vacuum deposition method, or may be a sputtering method, an ion plating method, a chemical vapor deposition method, or the like. In addition, a special design feeling due to a change in gloss can be provided by partially providing a metal deposition layer in any desired pattern by an etching method, a lift-off method, or the like. The adhesive layer 23 is provided to adhere the transfer layer 2 to the surface of the substrate to be transferred, and the type of the adhesive is not particularly limited in the present invention. In general, when a heat-sensitive adhesive is used, it is a non-tacky solid that can be stored and distributed in a rolled state at room temperature, and has the property of softening and melting to develop adhesiveness when heated. There are many. Examples of the heat-sensitive adhesive include ethylene-vinyl acetate copolymer resin, ethylene-ethyl acrylate copolymer resin, polyamide resin, polyester resin, polyolefin resin, chlorinated polyolefin resin, and the like. Examples thereof include a polyurethane resin, a polyvinyl ether resin, and a cellulose derivative. Further, for the purpose of preventing blocking during winding storage, the adhesive layer 2
Addition of an extender made of an inorganic powder such as silica to 3, etc., can also be performed arbitrarily. The present invention will be described in more detail with reference to Examples and Comparative Examples of the transfer sheet of the present invention. Example 1 A polyester resin film (E513) having a thickness of 25 μm
1: Toyo Boseki Co., Ltd.) as a base sheet, and on its surface an acrylic melamine resin (a mixture of TCM01 medium and mat medium: Dainippon Ink and Chemicals, Inc.)
Was applied to a thickness of 1 μm after drying, and was baked and cured at a temperature of 200 ° C. to form a release layer. Subsequently, an acrylic resin (UC having a glass transition point of 105 ° C. and an average molecular weight of 120,000) was used. Clear EXP10627E: Organic solvent solution of Dainippon Ink and Chemicals, Inc. (solvent: ethyl acetate / methyl ethyl ketone = 50/50, solid content: 2)
(0% by weight) to a thickness of 6 μm after drying to form a protective layer, and a gravure using a printing ink (TRC: manufactured by Dainippon Ink and Chemicals, Inc.) using an acrylic resin as a binder. A pattern layer is formed by printing by a printing method, and finally, a polyamide-based heat-sensitive adhesive (TAK) comprising a mixture of 50 parts by weight of a polyamide-based resin having an average molecular weight of 5,000 and 50 parts by weight of a polyamide-based resin having an average molecular weight of 10,000.
Dyne: manufactured by Dainichi Seika Co., Ltd.)
To form an adhesive layer, thereby producing a transfer sheet of the present invention. Example 2 In Example 1, the acrylic resin for forming the protective layer was replaced with a urethane resin binder of 20 parts by weight and a particle size of 1 to 10 μm.
m glass beads 40 parts by weight, methyl ethyl ketone (M
EK) 50 parts by weight of a filler and 50 parts by weight of ethyl acetate (Dai Nippon Ink Chemical Industry Co., Ltd.)
A transfer sheet of the present invention was prepared under the same conditions as in Example 1 except that 25 parts by weight of acrylic resin (solid content) was used per 100 parts by weight of the acrylic resin. Comparative Example 1 In Example 1, the acrylic resin for forming the protective layer was a glass transition point of 105 ° C. and an average molecular weight of 27000.
Acrylic resin (BR-85: Mitsubishi Rayon Co., Ltd.)
A transfer sheet was produced under the same conditions as in Example 1 except for the above. Comparative Example 2 In Example 1, the acrylic resin for forming the protective layer was a glass transition point of 105 ° C. and an average molecular weight of 40000.
Acrylic resin (BR-83: Mitsubishi Rayon Co., Ltd.)
A transfer sheet was produced under the same conditions as in Example 1 except for the above. Comparative Example 3 In Example 1, the acrylic resin having a glass transition point of 75 ° C. and an average molecular weight of 70,000 (BR-60: manufactured by Mitsubishi Rayon Co., Ltd.) was used as the acrylic resin for forming the protective layer.
And a transfer sheet was produced under the same conditions as in Example 1 except for the above. Comparison of Performance Using the transfer sheets of Examples 1 and 2 and Comparative Examples 1 to 3, a normal hot roll transfer method was performed on the transfer surface of a transfer substrate made of a medium density fiberboard (MDF). Transfer and peel off at
A cosmetic material was produced for each. About these makeup materials,
When a cellophane tape peeling test, a solvent resistance test (MEK rubbing) and an alkali resistance test (2% sodium carbonate) were carried out, the cosmetics using the transfer sheets of Examples 1 and 2 had no particular problem. The decorative material using the transfer sheet of Comparative Example 1 failed the cellophane tape peeling test, and the decorative material using the transfer sheets of Comparative Examples 2 and 3 failed the solvent resistance test and the alkali resistance test. . As described in detail above, in the transfer sheet of the present invention, the protective layer contained in the transfer layer has a glass transition point of 100 ° C. or higher and an average molecular weight of 100,000 to 15
By using an acrylic resin of 0000, the surface properties after transfer are good, and an excellent effect of easily producing a transfer product having a protective layer with excellent adhesion can be obtained. is there.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a side sectional view showing an embodiment of a transfer sheet of the present invention. [Description of Signs] 1 Base sheet 11 Release layer 2 Transfer layer 21 Protective layer 22 Picture layer 23 Adhesive layer

Continuation of front page    F-term (reference) 3B005 EB01 EC01 EC30 FA08 FB13                       FC08Y FD03Y FD05Y GA04                       GB03                 4F100 AK25 AK25B AK36 AK42                       AL01 AT00A BA02 BA07                       GB90 JA05B JA07B JL13                       YY00B                 4J100 AA02Q AB02Q AB03Q AB04Q                       AB16Q AG02Q AG04Q AJ02P                       AL03P AL08P AL09P AM02P                       AM45Q AM47Q AS02Q AS03Q                       BC04P BC04Q BC43Q CA01                       CA04 DA01 DA25 JA01

Claims (1)

1. A transfer sheet having a transfer layer including at least a protective layer on a base sheet, wherein the protective layer has a glass transition point of 100 ° C. or higher and an average molecular weight of 100 ° C.
A transfer sheet comprising 000 to 150,000 acrylic resins.