JPH0569698A - Transfer material and transferred object - Google Patents

Abstract

PURPOSE:To obtain a transfer material which enables a foil decoration firmly on the surface of a molded product. CONSTITUTION:First, aluminum tris (ethylacetate acetate), toluene and a silica grain with an average diameter of 0.5mum are blended and stirred well, then this blend is added to an medium ink consisting of methyl methacrylate resin and toluene to prepare a hard film layer ink, and this ink is applied to a base sheet of polyethylene terephthalate to provide a hard film layer. In addition, a pattern layer consisting of a blue organic pigment and methyl methacrylic resin and an adhesive layer of methacrylate resin are provided to obtain a transfer material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention uses a transfer material which can enhance the commercial value of a plastic product, a woodwork product, a glass product, a metal product, a ceramic product or the like by applying a beautiful and strong painting on the surface thereof and using the transfer material. It concerns a transcript.

[0002]

2. Description of the Related Art The transfer method is a kind of printing technology which has been widely used as a method for forming a pattern on the surface of various base materials. Generally, a transfer material is constituted by providing a release layer, a pattern layer, and an adhesive layer on a base sheet having releasability. When this transfer material is transferred to a molded product and the base sheet is peeled off,
The release layer is designed to be the top layer of the molded product,
It is used as a simple method of painting.

[0003]

When a thermoplastic resin is used for the release layer, the resistance of the transfer material to external effects such as abrasion resistance and impact resistance is weak, so that the transfer material is not easily used during a long period of use. It is easy to get scratches on the surface. Further, when a curable resin such as an ultraviolet ray or electron beam curable resin or a thermosetting resin is used, resistance to external action is improved and scratches are less likely to occur, but the transfer material such as a corner of the transferred object is In the stretched area, cracks are generated on the surface of the transfer material during transfer,
Moreover, even if the transfer material is bent, cracks occur on the surface. In addition, special equipment (hot-air oven, far-infrared heater oven, radiation irradiator such as ultraviolet ray, electron beam, etc.) is necessary because the operation of curing immediately after the operation is required when only the curable resin is printed or coated. Had to be installed adjacent to the printing or coating machine. In addition,
When secondarily processing the surface of the transfer material after the transfer with the normal transfer material, it is necessary to take care so that the transfer material is not scratched during this operation. In addition, dust is attached when the resin for secondary processing is applied, environmental pollution, work efficiency is reduced due to an increase in the number of work steps, and the labor is accompanied by this.

[0004]

In order to solve the above-mentioned drawbacks, the present invention provides a transfer material in which at least one layer of a layer provided on a base sheet having releasability is close to the base sheet surface. Was composed of a hard film layer containing 10 to 90% by weight of metal oxide spheres having an average particle size of 0.2 to 20 μm.

In this transfer material, the metal of the metal oxide spheres is composed of at least one element selected from the group consisting of silicon, aluminum, titanium, magnesium, zirconium, indium, tin and zinc. May be. In the above transfer material, the surface of the metal oxide spheres is treated with at least one surface treatment agent selected from the group consisting of aluminum chelating agents, titanium chelating agents, silane coupling agents and titanate coupling agents. It may be configured as described above.

In the present invention, in order to solve the above drawbacks, at least one layer of the transfer material provided on the base sheet having releasability and close to the base sheet surface is averaged. Metal oxide spherical particles with a particle size of 0.2 to 20 μm
A transfer material composed of a hard film layer containing 10 to 90% by weight was transferred to a molded product. In this transfer, the metal of the metal oxide spheres is silicon, aluminum,
It may be configured to be at least one element selected from the group consisting of titanium, magnesium, zirconium, indium, tin and zinc. Further, in the above-mentioned transfer product, the surface of the metal oxide sphere is treated with at least one surface treatment agent selected from the group consisting of an aluminum chelating agent, a titanium chelating agent, a silane coupling agent and a titanate coupling agent. May be configured so that

The present invention will be described in detail below. Examples of the base sheet having releasability include plastic films such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polypropylene, polyethylene, polyamide, cellophane, polyimide and polyether ether ketone, or composite films of these with paper or metal foil. The thing used as a base sheet of a usual transfer material is used.

In order to impart releasability to the base sheet, the surface of the base sheet may be subjected to a release treatment. For mold release treatment, silicone resin, urethane resin, urea resin,
Thermosetting resin such as epoxy resin, acrylic fluorine resin, vinylidene fluoride resin, fluorine compound resin such as poly (perfluoro) olefin, silicon oligomer, wax oligomer, etc. are coated on the base sheet, and if necessary, A heat treatment may be performed, a wax or the like may be further coated, or a film having excellent releasability such as an oriented olefin, a liquid crystal oligomer or a liquid crystal polymer may be laminated on the base sheet. Further, in some cases, a base sheet may be used in which the surface of the base sheet is processed to have an uneven shape so as to be easily released.

The hard film layer contains 10 to 90% by weight of metal oxide spherical particles. That is, if it is 10% by weight or less, it is difficult to contribute to the improvement of the strength of the present invention, and if it is 90% by weight or more, it becomes very difficult to form a coating film. In the present invention, the inclusion of 10 to 90% by weight, particularly 40 to 80% by weight, of the metal oxide spheres based on the dry solid weight of only the hard film layer portion is excellent in terms of strength improvement and printability. It is particularly advantageous that the hard film layer is provided in contact with the base sheet or a portion close to the base sheet. For example, it is effective to provide the hard film layer in the release layer, the layer next to the release, or the next layer. is there.

Generally, as the metal of the metal oxide spherical particles,
It can be selected from silicon, aluminum, titanium, magnesium, zirconium, indium, tin, zinc, lead, chromium, iron and silver, etc. Spherical particles composed of at least one element selected from the group consisting of aluminum, titanium, magnesium, zirconium, indium, tin and zinc are excellent.

The average particle size of these metal oxide spheres is preferably 0.2 to 20 μm. That is, spheres smaller than 0.2 μm are unlikely to contribute to the improvement of surface strength, and those exceeding 20 μm are not good in printability or coating suitability, and the coating film becomes very rough. Of these, especially 0.4-8
It was found from many experiments that μm is excellent in printability, coating suitability, and coating suitability.

Resins used in the hard film layer of the present invention include thermoplastic resins, thermosetting resins, curable resins such as ultraviolet or electron beam curable resins, and mixed resins thereof. In particular, a resin containing a thermoplastic resin as a main component has advantages that it is excellent in energy saving, equipment saving, and thermal flexibility.

As the thermoplastic resin, a (meth) acrylic ester type resin, vinyl chloride vinyl acetate copolymer type resin, chlorinated rubber type resin, polyester type resin, alkyd type resin, polyamide type resin, hydrocarbon type resin, There are polyvinyl acetal resins and the like, and as the thermosetting resins, there are urea resins, epoxy resins, urethane resins, phenol resins, melamine resins and the like. Examples of the ultraviolet or electron beam curable resin include epoxy resin, unsaturated polyester resin, (meth) acrylic acid ester resin or urethane resin, and oligomers and monomers thereof. Furthermore, as the (meth) acrylate resin, urethane (meth) acrylate resin, polyester (meth) acrylate resin, spiro compound (meth) acrylate resin, polyether (meth) acrylate resin, (meth) acrylic (meth)
There are acrylate resins, silicone (meth) acrylate resins, melamine (meth) acrylate resins and their oligomers and monomers. Of course, a photosensitizer or a photopolymerization initiator may be added if necessary. Moreover, you may add additives, such as a dispersing agent, a leveling agent, and a lubricant.

The surface of the metal oxide spheres is the surface of a metal alkoxide such as an aluminum chelating agent, a titanium chelating agent, a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, an aluminum alcoholate and a titanium alcoholate. When treated with a treating agent, the ink, printing, coating suitability and coating film suitability are improved. In particular, when treated with at least one surface-treating agent selected from the group consisting of aluminum chelating agents, titanium chelating agents, silane coupling agents, titanate coupling agents, etc., ink, printing, coating suitability and film forming suitability, etc. Is the best to improve. Aluminum chelating agents include ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethylacetoacetate), alkylacetoacetate aluminum diisopropylate, aluminum monoacetylacetonate bis (ethylacetoacetate), aluminum tris (acetylacetonate), etc. There is. Examples of titanium chelating agents include diisopropoxybis (acetylacetonato) titanium, di-n-butoxybis (triethanolaminato) titanium, and dihydroxybis (lactato) titanium. As the silane coupling agent, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, vinyltriene For example, ethoxysilane. Examples of titanate coupling agents include isopropyl triisostearoyl titanate, isopropyl tri (N-aminoethyl, aminoethyl titanate, tetraisopropyl bis (dioctyl phosphite) titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraoctyl bis (ditrityl). Decyl phosphite) titanate, etc. Aluminum-based coupling agents include acetoalkoxyaluminum diisopropylate.

These surface treatments are usually carried out on the metal oxide spheres before the hard film layer coating material or ink is prepared. When the coating material or ink is prepared, a surface treatment agent is added and the mixture is stirred or kneaded. You may process with meat etc. Before preparing the paint or ink, for example, the metal oxide spheres are dispersed in a solvent, and a surface treatment agent is added to the mixture and the mixture is stirred, heated, etc. to achieve a uniform and expected effect. Of course, it is especially good from the point of view.

The spherical shape of the metal oxide spherical particles may be an ellipsoidal sphere or an uneven sphere depending on the case, but most of them are close to a true sphere and have a smooth surface. However, the effect is remarkable. Of course, it is satisfactory if all spherical particles are spherical with the same particle size.

Generally, the transfer material is formed by providing a release layer, a pattern layer, and an adhesive layer on a base sheet having releasability, but the hard film layer may also serve as these layers, or independently. It may be used as a single layer or a multilayer. The effect is remarkable when the hard film layer also serves as the peeling layer or when it is used as a layer near the peeling layer.

The pattern layer is formed by using a dye and pigment of an appropriate color and an ink binder. Generally, a thermoplastic resin is suitable as the ink binder, and a vinyl chloride vinyl acetate copolymer resin, a polyamide resin, a polyester resin, a (meth) acrylic ester resin, a methacrylic resin, a thermoplastic urethane resin, polyvinyl Acetal-based resins, chlorinated rubber-based resins, chlorinated polyethylene-based resins, chlorinated polypropylene-based resins, alkyd-based resins, phenol-based resins, etc. may be used alone or as a mixture of two or more, but some may be used to strengthen the pattern layer. You may use together thermosetting resin and ultraviolet curable resin.

As one of the pattern layers, a metal vapor deposition pattern layer may be used. In this case, in order to facilitate vapor deposition and to improve the adhesion strength, a vapor deposition anchor layer is provided before the metal vapor deposition pattern layer or It may be formed after the metal vapor deposition pattern layer. The vapor deposition anchor layer may have the above-mentioned thermoplastic resin, thermosetting resin, or a mixture of these resins as a main component, and may be mixed with dyes and pigments if necessary. For vapor deposition of metal, a vacuum vapor deposition method, an ion plating method, a sputtering method or the like is applied, and the metal is not particularly limited, but aluminum, nickel, chromium, copper, gold and the like are often used.

The adhesive layer differs depending on the transferred material, and it is advisable to use a material that is well compatible with the surface of the transferred material.
When the material to be transferred is a polystyrene molded product, a material mainly composed of vinyl chloride / vinyl acetate copolymer resin or styrene copolymer resin can be used. When the transferred material is an acrylic molded product, an acrylic resin-based material can be used.

Each of the above layers is formed by a gravure printing method, a screen printing method, an offset printing method, a gravure coater method,
A roll coater method, a reverse coater method, a comma coater method spraying method, a brush coating method and the like are used to successively form layers on a base sheet having releasability. To obtain a transfer using this transfer material, superimpose this transfer material on the molded product,
Heat and pressure are applied, and then the base sheet having releasability is peeled off. The transfer conditions are not particularly limited, but in many cases
At 100 to 250 ° C, 0.1 second to 5 minutes is suitable. Alternatively, a transfer product may be obtained by simultaneously transferring (molding simultaneous transfer method) and peeling the base sheet having releasability when a resin molded product is manufactured.

[0022]

Function: The metal oxide spherical particles are incomparably harder than the resin. For example, a hard resin has a pencil hardness of 2H to 8H, while a metal oxide spherical particle has a Mohs hardness of 3 or more, and a hard resin has a Mohs hardness of 4 to 7. Therefore, the hard film layer containing 10 to 90% by weight of the metal oxide spheres becomes a very hard layer. In addition, since it is a spherical particle of 0.2 to 20 μm, it has excellent flexibility and does not cause cracks even when the transfer material is stretched during transfer such as the corners of the molded product, and does not crack even when the transfer material is bent. It never happens. Since the present spherical particles are translucent or non-colored, they do not have a bad influence on the design, and in some cases, can give gloss like opal. Even when using a curable resin by ultraviolet rays, electron beams or heat, since 10 to 90% by weight of the present spherical particles are present, the tack of these resins is reduced to the extent that they are not felt by finger corrosion. Immediately after, without the need for ultraviolet rays, electron beams or heat treatment, the pattern layer,
Printing or coating of the adhesive layer can be performed in subsequent steps, and can be performed very effectively and with good operability.

[0023]

【Example】

Example 1 A medium ink composed of 5 kg of aluminum tris (ethylacetoacetate), 25 kg of toluene, and 40 kg of silica spheres having an average particle size of 0.5 μm, and well stirred, and then 10 kg of methylmethacrylate resin and 20 kg of toluene. In addition to the above, a hard film layer ink was prepared, and the thickness when dried on a 25 μm-thick polyethylene terephthalate substrate sheet was 2.5
A hard film layer is provided by coating with a gravure coater to a thickness of μm, and a pattern layer consisting of 5% by weight of blue organic pigment and 95% by weight of methylmethacrylic resin and an adhesive layer of methylmethacrylic acid ester resin are gravure coated. A transfer material was obtained by printing. Then, transfer this transfer material to a molded product of methyl methacrylic acid ester resin by a roll transfer machine at 210 ° C for 5 seconds under heat and pressure, and then use steel wool # 3.
A transfer product having a blue pattern without cracks, which was excellent in surface strength and was not scratched by rubbing, was obtained.

Comparative Examples 1 to 3 As comparative examples, a conventional thermoplastic resin, an ultraviolet curable resin or a thermosetting resin was used in place of the hard film layer of Example 1 to prepare a transfer material and a transfer product, and the surface strength and The degree of crack generation was compared with that in Example 1. As Comparative Example 1, Example 1
In place of the hard film layer of No. 3, a layer provided with a methylmethacrylate resin was prepared. Similarly, Comparative Example 2
As the above, an article provided with a layer formed of a urethane acrylate resin and irradiated with ultraviolet rays was prepared. Similarly, Comparative Example 3
As the above, a product having a layer formed of a polyacrylic polyol resin and a polyisocyanate and heat-treated was prepared. Table 1 shows a comparison of the surface strength of steel wool # 4 (# 0000) and # 3 (# 000) and the degree of cracking at the corner (2R) of the molded product.

[0025]

[Table 1]

Example 2 of diisopropoxybis (acetylacetonato) titanium
Transparent silica spheres having an average particle size of 1 μm were immersed in a 5% toluene solution, and then heated with stirring and dried. The thickness of a hard film layer consisting of 50% by weight of these silica spheres and 50% by weight of alkyd resin coated with epoxy resin and heat-treated.
It was provided by screen printing on a 50 μm polyethylene terephthalate substrate sheet. Next, a pre-deposition anchor layer consisting of an acrylic polyol resin containing a yellow dye and an oligomer of polytoluidine diisocyanate was provided by screen printing, heat-treated at 160 ° C. for 30 seconds, and then aluminum was deposited. Further, a post-deposition anchor layer made of vinyl chloride-vinyl acetate copolymer resin was provided, and an adhesive layer made of butyl acrylate resin was further provided to obtain a transfer material. Using this transfer material, it can be transferred to a polystyrene molded product by the simultaneous molding molding method, and it will not be scratched by rubbing with Steel Wool # 4. It has excellent surface strength and has no cracks in the corners of the molded product. It was

Example 3 A layer made of a methylmethacrylate resin was provided on a base sheet obtained by laminating oriented polypropylene on a polyamide film, and then 10 kg of polyethylene terephthalate resin and 1 kg of γ-glycidoxypropyltrimethoxysilane were added. After spraying a spray ink consisting of 10 kg of alumina spheres having an average particle size of 20 μm, 60 kg of toluene and 19 kg of methyl ethyl ketone, and drying to form a hard film layer, 10% by weight of titanium oxide and 90% by weight of polyethylene terephthalate resin. A pattern layer composed of and was provided by brush coating, and an adhesive layer composed of a chlorinated polyethylene resin was applied by spraying to provide a transfer material. This transfer material was transferred to a polypropylene resin molded product by heating and pressurizing at 180 ° C. for 10 seconds to obtain a transfer product having no crack and excellent surface strength with no damage by Steel Wool # 3.

Example 4 1 kg of isopropyltriisostearoyl titanate, 1.5 kg of zinc oxide spheres each having an average particle size of 0.2 μm and 0.5 μm, 3 kg of silica spheres having an average particle size of 2 μm, and 40 kg of methylmethacrylate resin A hard film ink consisting of 14 kg of urethane acrylate resin and 39 kg of toluene is coated with a roll coater on the wax-coated surface of a polyethylene terephthalate film to form a hard film layer, dried, and then made of methylmethacrylate resin. After providing a transparent layer by gravure printing, irradiating with ultraviolet light, and further providing a pattern layer consisting of 10% by weight of a blue organic pigment and 90% by weight of vinyl chloride vinyl acetate copolymer resin by gravure printing, An adhesive layer made of a polymer resin was provided by gravure printing to obtain a transfer material. This transfer material is used to transfer to an ABS resin molded product by the simultaneous molding transfer method, and it is not scratched even if it is rubbed with Steel Wool # 4. It has excellent surface strength and has no cracks in the corners of the molded product. It was

Example 5 1 kg of ethyl acetoacetate aluminum diisopropylate was dissolved in 10 kg of toluene, and then 30 kg of magnesia spheres having an average particle diameter of 2 μm was immersed in the mixture, stirred and heated, and air-cooled. After mixing with a medium ink consisting of 10 kg of resin and 10 kg of polyester resin and stirring, a polybutylene terephthalate film was coated with a reverse coater to form a hard film layer. A pattern layer consisting of 30% by weight of black pigment and 70% by weight of modified alkyd resin is provided by offset printing, and heat treated at 120 ° C for 30 seconds,
An adhesive layer made of polyester resin was provided by gravure printing to obtain a transfer material. This transfer material is used to transfer to a polyester molded product by the simultaneous molding and transfer method so that it will not be scratched by rubbing with Steel Wool # 4. It has excellent surface strength and a beautiful transferred product with no cracks in the corners of the molded product. Obtained.

Example 6 Di-n-butoxybis (triethanolaminato) titanium 5
20 kg of titanium oxide spheres with an average particle size of 0.5 μm and an average particle size of 0.5 μm
An ink consisting of 5 kg of zirconium oxide (20 kg), urethane resin (20 kg) and toluene (35 kg) was coated on the film surface of a paper laminated with a polyethylene terephthalate film with a reverse coater to form a hard film layer. Next, a transparent layer made of urethane resin was provided, and an adhesive layer made of modified polystyrene resin was provided to obtain a transfer material. This transfer material is transferred to an acrylonitrile / butadiene / styrene copolymer resin molded product at 200 ° C for 8 seconds by heating and pressing with a roll transfer machine, and with steel wool # 3 cracks with excellent surface strength without scratches. No transcript was obtained.

Example 7 1 kg of γ-glycidoxypropylmethyldiethoxysilane, 15 kg of indium oxide having an average particle size of 8 μm, 3 kg of tin oxide having an average particle size of 3 μm, 2 kg of alkyd resin and butyl acetate 79
A coating consisting of kg and a polyethylene terephthalate film is spray-coated to form a hard film layer, and a transparent layer of methylmethacrylate resin is spray-coated to provide a black pigment 30% by weight and urethane resin 70% by weight. % To provide a pattern layer, and an adhesive layer made of vinyl chloride / vinyl acetate copolymer resin was provided by spraying to provide a transfer material. This transfer material was transferred onto an acrylonitrile / styrene copolymer resin molded product at 210 ° C. for 20 seconds by an up-down transfer machine to obtain a transfer product having no crack and excellent surface strength with no damage by Steel Wool # 4.

[0032]

EFFECTS OF THE INVENTION Since the surface strength is strong, scratches are unlikely to occur even if the transfer material is used for a long period of time, and even if the transfer material such as corners is stretched at the time of transfer, the transfer material is not cracked. A transfer material is formed, and cracks do not occur on the surface even when the transfer material is bent, so a transfer material that does not impair its beauty, and a transfer material can be easily manufactured with good workability and economically. The industrial effect is enormous.

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[Procedure amendment]

[Submission date] December 4, 1991

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 5

[Correction method] Change

[Correction content]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 6

[Correction method] Change

[Correction content]

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0006

[Correction method] Change

[Correction content]

In the present invention, in order to solve the above drawbacks, at least one layer of the transfer material provided on the base sheet having releasability and close to the base sheet surface is averaged. Use metal oxide spheres with a particle size of 0.2 to 20 μm.
A transfer material composed of a hard film layer containing 10 to 90% by weight was transferred to a molded product. In this transcript, the metal of the metal oxide spherules body, silicon, aluminum, titanium, magnesium, zirconium, indium, may be configured to be at least one element selected from the group consisting of tin and zinc .. In the above transcripts, the surface of the metal oxide spherules body, aluminum chelating agent, titanium chelate agent, at least one surface treatment agent a silane coupling agent and selected from the group consisting of titanate coupling agent treatment It may be configured as described above.

[Procedure correction 4]

[Document name to be amended] Statement

[Correction target item name] 0007

[Correction method] Change

[Correction content]

The present invention will be described in detail below. As the substrate sheet having releasing property, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polypropylene, polyethylene, polyamide, cellophane, polyimide, and composite films of plastic film or these and paper or metal foil, such as Porieterue over Teruketon Normal The material used as the base sheet of the transfer material is used.

[Procedure amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0011

[Correction method] Change

[Correction content]

The average particle size of these metal oxide spherical particles is preferably 0.2 to 20 μm. That is, spherical particles smaller than 0.2 μm hardly contribute to the improvement of surface strength, and if it exceeds 20 μm, it is not good in printability or coating suitability,
The coating film also becomes very rough. Of these, especially 0.4
It was found from many experiments that ~ 8 μm is excellent in printability, coating suitability, and coating suitability. However,
This average particle size is smaller than the primary particles (for example, the average particle size).
Diameter of 0.005 to 0.2 μm)
But it doesn't matter.

[Procedure Amendment 6]

[Document name to be amended] Statement

[Name of item to be corrected] 0019

[Correction method] Change

[Correction content]

As one of the pattern layers, a metal vapor deposition pattern layer may be used. In this case, in order to facilitate vapor deposition and to improve the adhesion strength, a vapor deposition anchor layer is provided before the metal vapor deposition pattern layer or It may be formed after the metal vapor deposition pattern layer. The vapor deposition anchor layer may contain the above-mentioned thermoplastic resin, thermosetting resin, or a mixture of these resins as a main component, and may be mixed with dyes and pigments if necessary. Deposition of the metal vacuum evaporation method, the ion plating Ti packaging method or sputtering method is applied, it is not particularly restricted but includes metal, aluminum, nickel, chromium, copper, gold is often used.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Name of item to be corrected] 0023

[Correction method] Change

[Correction content]

[0023]

Example 1 5 kg of aluminum tris (ethylacetoacetate), 25 kg of toluene and 40 kg of silica spheres having an average particle size of 0.5 μm were mixed and stirred well, and then 10 kg of methylmethacrylate resin and 20 kg of toluene. In addition to the medium ink consisting of, a hard film layer ink was prepared, and a thickness of 2.5 μm when dried on a polyethylene terephthalate substrate sheet with a thickness of 25 μm.
coated with a gravure coater so as to μm the hard film layer provided consists more blue organic pigment 5 wt% of methyl methacrylate ester resin 95% by weight consists of the pattern layer and methyl methacrylate ester resin adhesive layer Was provided by gravure printing to obtain a transfer material. Next, this transfer material is transferred to a molded product of methylmethacrylic acid ester resin by a roll transfer machine at 210 ° C for 5 seconds under heat and pressure, and it is not scratched even if it is rubbed with Steel Wool # 3. A transfer with a crack-free blue pattern was obtained.

Claims (6)

[Claims] 1. At least one layer of a layer provided on a base sheet having releasability close to the surface of the base sheet contains 10 to 90% by weight of metal oxide spheres having an average particle size of 0.2 to 20 μm. A transfer material comprising a hard film layer. 2. The transfer material according to claim 1, wherein the metal of the metal oxide spheres is at least one element selected from the group consisting of silicon, aluminum, titanium, magnesium, zirconium, indium, tin and zinc. .. 3. The surface of the metal oxide spheres is treated with at least one surface treatment agent selected from the group consisting of aluminum chelating agents, titanium chelating agents, silane coupling agents and titanate coupling agents. The transfer material according to claim 1. 4. Among the layers provided on the base sheet having releasability, at least one layer close to the base sheet surface contains 10 to 90% by weight of metal oxide spheres having an average particle size of 0.2 to 20 μm.
A transfer product obtained by transferring a transfer material composed of a hard film layer containing the transfer material to a molded product. 5. The metal of the metal oxide spherical particles is silicon, aluminum, titanium, magnesium, zirconium,
The transcript according to claim 4, which is at least one element selected from the group consisting of indium, tin and zinc. 6. The surface of the metal oxide sphere is treated with at least one surface treatment agent selected from the group consisting of an aluminum chelating agent, a titanium chelating agent, a silane coupling agent and a titanate coupling agent. The transcript according to item 4.