JP2003154794A - Transfer sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transfer sheet with an outstanding resistance to foil burrs which hardly allows the generation of burrs on a transfer layer during transfer, in the transfer sheet which can transfer/form the transfer layer including at least a 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 formed on a base material sheet 1, the protecting layer 21 is formed of a two-part curable polyurethane resin, as a reaction product between a polyol compound as a principal agent and an isocyanurate modified isocyanate compound as a curing agent. 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. [0005] By the way, in the above-mentioned transfer method, in order to save the labor of cutting the transfer sheet and to eliminate the need for precise alignment between the transfer sheet and the transfer-receiving surface of the transfer-receiving substrate, the transfer method is performed. A transfer sheet having a larger area than the transfer surface is prepared, and the transfer layer in a portion (non-transfer portion) deviating from the transfer surface is used when the base sheet is peeled off after being pressed onto the transfer surface of the transfer sheet. In general, a method is employed in which the sheet is broken between a transfer layer on the transfer surface (transfer portion) and removed together with the base sheet. In this method, however, there is no problem if the transfer layer is a picture layer made of ordinary printing ink. However, when the protective layer is provided as described above, a sufficient surface of the product after transfer is obtained. In order to impart surface properties, if a tough material having excellent surface properties is adopted as the protective layer, it becomes difficult to break the transfer layer at the time of peeling the above-described base sheet, and as a result, in the vicinity of the boundary with the transfer portion All or a part of the transfer layer in the non-transfer portion is peeled off from the base sheet while being connected to the transfer layer in the transfer portion, which is likely to cause so-called burr. For this reason, even if the transfer method makes it possible to form a simple protective layer by a dry method, it is necessary to remove burrs after the transfer in order to obtain a good quality product. Therefore, as a result, the advantage of the simplification of the process by the dry method is not always fully utilized, and in order to solve this problem, it is difficult to generate burrs at the time of transfer, There has been a strong demand for the development of a transfer sheet having an excellent protective layer. 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 provide an excellent surface after transfer. Another object of the present invention is to provide a transfer sheet capable of transferring and forming a transfer layer including at least a protective layer that imparts surface properties to the transfer sheet. According to the present invention, there is provided a transfer sheet having a transfer layer including at least a protective layer on a base sheet, wherein the protective layer comprises a reaction between a polyol compound and an isocyanurate-modified isocyanate compound. A transfer sheet comprising a product. 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 one protective layer 21 for protecting the surface after transfer on one side of a base sheet 1 as a support. 2 is provided so as to be peelable. In the present invention, the protective layer 21 is a two-component curable polyurethane resin which is a reaction product of a polyol compound as a main agent and an isocyanate compound as a curing agent, and the isocyanate compound of the curing agent But,
It is an isocyanurate-modified isocyanate compound. The isocyanurate-modified isocyanate compound is defined as three isocyanate groups (—N ＝ C ＝ O)
Is a double bond between its nitrogen and carbon atoms (N =
The isocyanurate compound formed by forming a cyclic bond (isocyanurate ring) in which three nitrogen atoms and three carbon atoms are alternately arranged by the addition reaction of C). Is an isocyanate compound having an isocyanate group on the side chain bonded to three nitrogen atoms of the isocyanurate ring. The raw material polyisocyanate compound used for producing the isocyanurate-modified isocyanate compound is not particularly limited in the present invention. For example, tolylene diisocyanate (TDI),
Aromatic diisocyanate compounds such as diphenylmethane diisocyanate (MDI) and xylylene diisocyanate (XDI), and hexamethylene diisocyanate (H
An aliphatic diisocyanate compound such as DI), an alicyclic diisocyanate compound such as isophorone diisocyanate (IPDI), hydrogenated diphenylmethane diisocyanate (hydrogenated MDI), hydrogenated xylylene diisocyanate (hydrogenated XDI), or A plurality of types can be arbitrarily mixed and used. When a two-component curable polyurethane resin using this isocyanurate-modified isocyanate compound as a curing agent is used for the protective layer 21 of the transfer sheet,
The reason why the burr of the transfer layer during transfer is less likely to occur is that the resin is hardly stretched and bent as a whole due to the rigid planar structure of the isocyanurate ring, so that the area is larger than the transfer surface of the transfer substrate. When the transfer sheet is pressed against the surface to be transferred and a portion (non-transfer portion) other than the pressed portion (transfer portion) is gripped and the transfer sheet is separated from the transfer substrate, the transfer portion and the transfer It is considered that the protection layer 21 is easily broken by the stress concentrated on the transfer layer 2 at the boundary with the transfer portion. The type of the polyol compound which is the main component of the two-component curable polyurethane resin constituting the protective layer 21 is not particularly limited in the present invention, and may be, for example, an acrylic polyol, a polyester polyol, a polyether polyol, an epoxy polyol. , Polybutadiene polyol, ethylene-vinyl acetate copolymer partially saponified,
Vinyl chloride-vinyl acetate copolymer partially saponified, cellulose derivative, hydroxyl group-containing fluororesin, etc., each alone,
Alternatively, a plurality of types can be arbitrarily mixed and used. Among them, it is most desirable to use an acrylic polyol compound from the viewpoint of the physical properties of the cured product. 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. In addition to the reaction product of the above-mentioned polyol compound and the isocyanurate-modified isocyanate compound, the protective layer 21 may be made of a thermoplastic resin or a thermoplastic resin, if necessary, as long as the surface properties and the foil burr resistance are not impaired. Other resin components such as thermosetting resins, colorants, fillers,
UV absorbers, light stabilizers, heat stabilizers, gloss regulators, lubricants,
Various additives such as an antistatic agent, an antibacterial agent, an antifungal agent, a flame retardant, and a lubricant can be appropriately 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, 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 essential. 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 base 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 sheet 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 chlorinated 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 base sheet 1 side, if necessary, 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 together 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, gravure printing, offset printing, gravure offset printing, screen printing, flexo printing, letterpress printing, dry offset printing, ink jet printing,
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 variations, surface defects, and the like 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, and 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 for bonding 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.)
Is applied to a thickness of 1 μm after drying, and is baked and cured at a temperature of 200 ° C. to form a release layer. Subsequently, an acrylic polyol compound (UC Clear EXP1071) is used as a main agent.
1TR-H: 100 parts by weight of Dainippon Ink and Chemicals, Inc., and tolylene diisocyanate (T
DI) isocyanurate-modified isocyanate compound (EXP10424Y: Dainippon Ink and Chemicals, Inc.)
(Solvent: ethyl acetate / methyl ethyl ketone = 50/50, solid content: 2)
0 wt%) to a thickness of 6 μm after drying to form a protective layer, and a printing ink (EBT: manufactured by Toyo Ink Manufacturing Co., Ltd.) using a mixture of a urethane resin and a nitrified cotton resin as a binder. A print layer is formed by gravure printing using a gravure printing method. Finally, a polyamide-based heat-sensitive adhesive comprising a mixture of 50 parts by weight of a polyamide-based resin having an average molecular weight of 5000 and 50 parts by weight of a polyamide-based resin having an average molecular weight of 10,000 is used. TAK Dyne: manufactured by Dainichi Seika Co., Ltd.) was applied to a thickness of 16 μm after drying to form an adhesive layer, thereby producing a transfer sheet of the present invention. Example 2 In Example 1, the mixture of the acrylic polyol compound for forming the protective layer and the isocyanurate-modified isocyanate compound was further added with 20 parts by weight of a urethane resin binder and 40 parts by weight of glass beads having a particle size of 1 to 10 μm. Parts, 50 parts by weight of methyl ethyl ketone (MEK) and 5 parts of ethyl acetate
A transfer sheet of the present invention was used under the same conditions as in Example 1 except that 25 parts by weight of a filler composition (0 parts by weight, manufactured by Dainippon Ink and Chemicals, Inc.) was added. Produced. Comparative Example 1 In Example 1 described above, instead of the isocyanurate-modified isocyanate compound in the composition for forming a protective layer,
A normal tolylene diisocyanate (TDI) -based curing agent not modified with isocyanurate (D-750: manufactured by Dainippon Ink and Chemicals, Inc.) is used, and the other conditions are the same as those in Example 1 above. Was prepared. Transfer Test The transfer sheets of Examples 1 and 2 and Comparative Example 1 were transferred to a transfer surface of a transfer substrate made of a medium density fiberboard (MDF) by a normal hot roll transfer method. The cosmetic material was prepared by transferring and peeling. As a result, when the transfer sheets of Examples 1 and 2 were used, the length of the burr of the transfer layer at the end of the transfer-receiving substrate was 0.5 mm or less, and the appearance quality was not required without removing the burr. A good transfer product could be obtained. On the other hand, when the transfer sheet of Comparative Example 1 was used, burrs having a length of about 2 to 5 mm were generated, and a burr removal step was required for commercialization. As described in detail above, the transfer sheet of the present invention is characterized in that the protective layer contained in the transfer layer is formed by the reaction product of a polyol compound and an isocyanurate-modified isocyanate compound. Despite being a protective layer made of a curable resin that gives good surface properties to the surface after transfer, it has an excellent effect that burrs are hardly generated at the time of transfer and a good quality transfer product can be easily manufactured. To play.

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 EC30 FA08 FB13 FC09Y                       GA04 GB03                 4F100 AK25 AK36 AK41 AK51B                       AL01 AT00A BA02 BA07                       GB90 JL00                 4J034 AA04 BA03 DA01 DB03 DB07                       DF01 DG00 DK02 DP15 DP16                       DP17 DP18 DP19 EA08 HA01                       HA07 HC03 HC12 HC17 HC22                       HC35 HC46 HC52 HC61 HC64                       HC67 HC71 HC73 QB13 QC08                       RA07

Claims (1)

Claims: 1. A transfer sheet having a transfer layer including at least a protective layer on a base sheet, wherein the protective layer comprises a reaction product of a polyol compound and an isocyanurate-modified isocyanate compound. A transfer sheet characterized by the following.