JPH08118781A - Transfer sheet - Google Patents

Abstract

PURPOSE: To obtain a transfer sheet wherein it is abundant in flexibility as a transfer sheet, excellent in suitability for transfer of a three dimensional product and after transfer, a transfer layer is excellent in hardness, wear resistance, and adhesion bond. CONSTITUTION: In a transfer sheet T having a protective layer 2 by a ionizing radiation curable resin as a transfer layer H on a surface of a substrate sheet having release properties, the protective layer 2 contains silicone acrylate or silicone methacrylate prepolymer which is 1000-100000 in average molecular weight, and has at least total two of any functional groups of acryloyl group, methacryloyl group, acryloyloxy group, or methacryloyloxy group in one molecule.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to home appliances, furniture,
It is related to a hard coat (hard coating) transfer sheet used for the purpose of protecting the surface of a decorative layer provided by transfer of an interior material for construction, a vehicle interior material such as an automobile, and the hard coat layer is particularly excellent in flexibility. The present invention relates to a transfer sheet made of a sheet.

[0002]

2. Description of the Related Art A transfer sheet provided with a hard coat layer of an ionizing radiation curable resin as a protective layer is a pattern layer and an adhesive layer obtained by applying a liquid of an ionizing radiation curable resin to a release layer of a base sheet and curing it. It has excellent hardness and scratch resistance. The stain resistance was formed by adding a releasing compound such as silicone oil to the resin.

[0003]

The above-mentioned hard coat layer containing an ionizing radiation-curable resin as a main component, which is obtained from a transfer sheet, is excellent in hardness, scratch resistance and stain resistance, but is three-dimensionally molded. When transferring to a product, there is a problem that a product having hardness has a low elongation rate and lacks flexibility associated with bending of a molded product. In addition, those having a high elongation rate have flexibility associated with bending of a molded product, but have a problem that they are inferior in scratch resistance and stain resistance. Further, what was formed by adding a releasing compound such as silicone oil to the resin has elution (bleeding) of the releasing agent,
There was a problem that the peeling performance (protective layer breakage, peeling prevention function) of the adhesive tape (cellophane tape or the like) after the durability test was deteriorated.

According to the present invention, the hard coat layer can be cured in a short time, has excellent flexibility even during the transfer sheet manufacturing process and during the use of the three-dimensional molded article of the transfer sheet, and has a surface after transfer. The present invention provides a transfer sheet having excellent scratch resistance, stain resistance, and non-bleeding property. Further, the present invention provides
In addition, it is non-adhesive at room temperature in the uncured state, and it is possible to continuously print and coat the upper layers such as the pattern layer and the adhesive layer without undergoing a step such as special crosslinking or curing when manufacturing the transfer sheet. The curing of the transfer layer by irradiation with ionizing radiation is
An object of the present invention is to provide a transfer sheet that can be freely transferred before and after transfer.

[0005]

In order to solve the above-mentioned problems, the present inventors have found that the transfer sheet of the present invention is at least ionizing radiation cured as a transfer layer on one surface of a base sheet having releasability. In a transfer sheet having a protective layer of mold resin, the protective layer has an average molecular weight of 1,000 to 10,000.
0, 1 acryloyl group, methacryloyl group in the molecule,
A transfer sheet containing a crosslinked cured product of a silicon acrylate or a silicon methacrylate prepolymer having a total of two or more functional groups of either an acryloyloxy group or a methacryloyloxy group. Further, the protective layer of the invention according to claim 2 is a transfer sheet containing an ionizing radiation curable resin and a non-crosslinking type thermoplastic resin compatible with the resin. Furthermore, the invention of claim 3 is a transfer sheet comprising a protective layer according to claim 1 and a laminate of a picture layer and an adhesive layer in this order, and at least one of the picture layer and the adhesive layer It is a transfer sheet containing a prepolymer and / or a monomer having two or more acryloyl groups or methacryloyl groups in the molecule.

As shown in FIG. 1, the transfer sheet T of the present invention.
Has an average molecular weight of 1000 to 1000 including a non-crosslinked thermoplastic resin on one surface of the base sheet 1 if necessary.
00, a protective layer 2 made of an ionizing radiation curable resin containing a silicone acrylate having two or more of an acryloyl group, a methacryloyl group, an acryloyloxy group and a methacryloyloxy group in one molecule, a pattern layer 3, And a transfer layer H in which the adhesive layer 4 is sequentially laminated.

Materials for the base sheet include polyester films such as polyethylene terephthalate, polybutylene terephthalate and ethylene terephthalate / isophthalate copolymers, polyolefin films such as polyethylene, polypropylene and saponified ethylene / vinyl acetate copolymers, and polychlorinated products. A vinyl film, a nylon film, or a coated paper coated with a release resin such as a silicone resin is used. And the thickness is 10 μm to 2
It is about 00 μ. In particular, at the time of transfer, when used for simultaneous molding transfer such as injection molding simultaneous transfer described later, a polyolefin or polyvinyl chloride film is preferable. Further, if necessary, a release layer using a silicone resin, a melamine resin, a polyolefin or the like may be further formed on the resin film.

Further, when a desired matte or uneven pattern is provided on the surface of the protective layer after transfer, the base sheet,
Alternatively, a concavo-convex pattern having the same shape as the desired concavo-convex shape may be formed on the surface of the release layer. Such uneven patterns include matte, hairline, wood grain conduit, and line grooves.

The silicon acrylate prepolymer has an average molecular weight of 1,000 to 100,000, preferably
An average molecular weight of 1,000 to 20,000, a side chain in one molecule,
It has two or more polymerizable unsaturated groups at the terminal or both. The polymerizable unsaturated group is at least one of a (meth) acryloyl group and a (meth) acryloyloxy group. However, the term "(meth) acryloyl group" is used to mean an acryloyl group or a methacryloyl group. (The same shall apply hereinafter) Examples of silicon (meth) acrylate include the following. (However, the present invention is not limited to these.) Japanese Patent Publication No. 51-42696 and Japanese Patent Publication No. 54-651.
A polysiloxane having a (meth) acryloyl group at the terminal or side chain of the molecule as disclosed in JP-B No. 2 and JP-B No. 58-53656. End-modified polyorganosiloxane as disclosed in JP-A-62-292867. More specifically, (OR ³ ) ₃ SiQ [(R ¹ ) ₂ SiO] _n-1 [(R ¹ ) ₂ Si] QSi (OR ³ ) ₃ or (OR ³ ) ₂ R ³ SiQ [(R ¹ ) ₂ Si0] _n-1 [(R ¹ ) ₂ Si] Q SiR ³ (
0R ³ ) ₂ and a polyorganosiloxane of pentaerythritol di (meth) acrylate, pentaerythritol diacrylate / monomethacrylate, pentaerythritol tri (meth) acrylate or pentaerythritol tetra (meth) acrylate are reacted with A product produced by carrying out a dealcohol reaction between a terminal SiO—OR ³ group of an organosiloxane and a C—OH group in a molecule of the polyfunctional (meth) acrylate of pentaerythritol. (Here, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group which is the same or different from each other, and R ³ is
Alkyl groups which are the same or different from each other, Q represents a polymethylene group or an oxygen atom, and n represents a number of 4 to 100. ) As disclosed in JP-A-48-16991,
A polyorganosiloxane having a (meth) acryloyloxy group as a photofunctional group. A compound obtained by reacting a polyorganosiloxane having a Si—Cl group in the molecule with pentaerythritol tri (meth) acrylate as disclosed in JP-A-55-104320.

When the average molecular weight is 1,000 or less, the silicone acrylate is easily volatilized by the heat of the transfer sheet or the curing step, the silicone content in the cured coating film is reduced, and the adhesion after the durability test is maintained. I can't. Further, even if it is cured by ionizing radiation after transfer, the silicone content in the cured coating film is lowered, and the effect cannot be sufficiently exhibited. Also, the adhesiveness of the uncured coating film after coating and drying the solvent does not completely disappear,
It is unsuitable for applications such as winding the protective layer in an uncured state, overprinting a pattern layer or the like, or transferring. When the average molecular weight is 100,000 or more, the solubility in the paint and the compatibility with other components are poor, and the desired amount of silicone acrylate cannot be included in the paint. It is impossible to form the opaque film by separating in the film, and to exert its effect sufficiently.

The non-crosslinking type thermoplastic resin which is a constituent of the protective layer made of the ionizing radiation-curable resin in the second invention is, for example, ethyl cellulose, nitrocellulose, cellulose acetate, ethyl hydroxycellulose, cellulose acetate propionate. Cellulose derivatives such as polystyrene, vinyltoluene resin, poly-
Styrene resins such as α-methylstyrene, styrene copolymers, acrylic resins such as poly (meth) acrylate, ethyl poly (meth) acrylate, butyl poly (meth) acrylate, polyvinyl chloride, polyacetic acid vinyl,
Natural or synthetic resins such as vinyl chloride / vinyl acetate copolymer, polyamide resin, rosin, rosin-modified maleic acid resin, rosin-modified phenolic resin and the like can be used. Among these, the most preferable one is that even if the protective layer is in an uncured state, it is non-adhesive and solidified after solvent drying, and sufficient surface hardness and flexibility are exhibited even after curing, and the average molecular weight is 50,000. ~ 600,000, glass transition temperature 50 ~
It is a 130 ° C. thermoplastic acrylic resin. If the numerical range is smaller than this range, the non-adhesiveness during uncured non-drying is insufficient, and if the numerical range is larger than this range, the flexibility and moldability of the cured coating film are insufficient. Become.

The content of the non-crosslinking type thermoplastic resin in the ionizing radiation curable resin layer of the present invention is preferably 5 to 60 parts by weight of the non-crosslinking type thermoplastic resin with respect to 100 parts by weight of the monomer. Here, when the amount of the non-crosslinked thermoplastic resin is 60 parts by weight or more, the crosslink density of the protective layer made of the ionizing radiation curable resin due to ionizing radiation becomes extremely coarse, and after drying the solvent, the uncured state is The coating film becomes brittle, and even after curing, the strength of the protective layer itself is insufficient and the scratch resistance decreases. When the amount of the non-crosslinking type thermoplastic resin is 5 parts by weight or less, the non-adhesiveness of the uncured state of the protective layer made of the ionizing radiation-curable resin after solvent drying is insufficient, and the crosslinking density by the ionizing radiation is high. Since the protective layer is dense, the elongation and flexibility of the protective layer itself are reduced, and deformation, breakage, cracks and the like are likely to occur during transfer.

2 in one molecule in the third invention of the present invention
Examples of the monomer having at least one (meth) acryloyl group include diethylene glycol di (meth) acrylate,
Neopentyl glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9 -Nonanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like can be used.

The prepolymer having two or more acryloyl groups or methacryloyl groups in one molecule in the third invention has a molecular weight of 250 to 5000,
Specifically, polyester acrylate, urethane acrylate, epoxy acrylate and the like can be used. Among these, urethane acrylate having both elongation during transfer and scratch resistance of the surface after transfer is preferable.

When the protective layer made of an ionizing radiation-curable resin is cured with ultraviolet rays, a mixture of acetophenones, benzophenones, Michler benzoyl benzoate, thioxanthones, etc., is used as a photopolymerization initiator. You can If necessary, powder of calcium carbonate, alumina, silica, etc., acrylic beads,
Inorganic and organic fillers such as resin beads such as urethane beads and polycarbonate beads, lubricants such as wax and polyethylene wax, organic solvents, and coloring materials such as dyes and pigments may be added. Also, as a reactive diluent, 1
An acrylic monomer having one or more (meth) acryloyl groups in the molecule may be added. However, it is preferable not to add the reactive diluent as much as possible in order to increase the elongation and flexibility of the protective layer. Also, the organic solvent is
The purpose of this is to impart sufficient fluidity and coating suitability to the prepolymer for forming the protective layer, but it is not necessary to add an organic solvent as long as a fluidity is sufficiently selected without an organic solvent. After applying the protective layer on the transfer sheet and immediately curing it, if the pattern layer is overprinted or rolled up, such a solvent-free prepolymer composition should be selected. Good.

The protective layer comprising the ionizing radiation curable resin composition can be applied by various conventionally known methods such as gravure coating, gravure reverse coating, gravure offset coating, roll coating, reverse roll coating, knife coating and wire bar. A coat, a flow coat, a comma coat, a dip coat, a Wheeler coat, a spinner coat, a spray coat, a silk screen, a pouring coat, a brush coat and the like are applied.

The film thickness of the protective layer made of the ionizing radiation-curable resin composition after removing the solvent is 0.5 to 50 μm, preferably 1 to 10 μm. If it is 0.5 μm or less, scratch resistance is poor, and if it is 50 μm or more, not only the curing rate is delayed, but also flexibility and elongation are lacking.

The ionizing radiation means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing and cross-linking a molecule, and usually an ultraviolet ray or an electron beam is used. As the ultraviolet ray source, a light source having a spectral component in the wavelength range of 2000 to 4000 Å such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a black light lamp, and a metal halide lamp can be used. Electron beam sources include Cockloft-Walton type, Van de Graft type,
Resonant transformer type, insulation core transformer type, or straight line type,
Using various electron beam accelerators such as Dynamitron type and high frequency type, 100 to 1000 KeV, preferably 100 to 3
A device that irradiates electrons having an energy of 00 KeV can be used. The irradiation of the ionizing radiation may be performed either before or after the transfer sheet is transferred to the transfer target, during the manufacturing of the transfer sheet, or before or after the base sheet is removed after the transfer sheet is transferred onto the transfer target. it can.

In the constitution of the present invention, the pattern layer can be formed by printing or applying a pattern layer ink or paint. As the ink or paint, a known one formed by appropriately mixing a vehicle such as an acrylic resin with a colorant such as a pigment or a dye, an extender pigment, a solvent, etc. can be used.

The pattern may be a wood grain pattern, a stone grain pattern, letters, figures, a solid layer, or a combination thereof. Alternatively, in addition to a pattern formed by printing or coating, a metal film formed on the entire surface by vapor deposition or in a pattern can be used as the pattern layer. Further, when the purpose is merely to provide a protective layer on the surface, the pattern layer may be omitted.

In the constitution of the present invention, an adhesive layer may be provided on the protective layer of the ionizing radiation curable resin or on the pattern layer. The adhesive layer can be selected as a layer for transferring and adhering the transfer layer to the transfer-receiving material from among heat-sensitive adhesives, pressure-sensitive adhesives, solvent-activated adhesives, ionizing radiation-curable adhesives, etc. according to the application. . Note that the adhesive layer of the transfer sheet may be omitted when the transfer layer itself such as the picture layer or the entire solid layer other than the adhesive layer has sufficient adhesiveness, or when the adhesive layer is provided on the transfer target side. .

The heat-sensitive adhesive exhibits adhesiveness by heating, and a thermoplastic resin or the like is usually used.
Examples of the resin include cellulose derivatives such as methyl cellulose, ethyl cellulose and cellulose acetate, polystyrene, styrene resins such as poly α-methylstyrene, or styrene copolymers, methyl poly (meth) acrylate, ethyl poly (meth) acrylate. Acrylic resins such as poly (meth) butyl acrylate, vinyl chloride / vinyl acetate copolymers, vinyl polymers such as ethylene / vinyl alcohol copolymers, rosins, rosin-modified maleic acid resins, rosin derivatives such as ester gums, Natural or synthetic rubbers such as polyisoprene rubber and styrene-butadiene rubber, and various ionomers are used.

As the pressure-sensitive adhesive, any of the pressure-sensitive adhesives conventionally used for pressure-sensitive adhesive tapes and seals can be used.
For example, rubber-based resins such as polyisoprene rubber, polyisobutyl rubber, styrene butadiene rubber, and butadiene acrylonitrile rubber, methacrylic acid ester-based resins,
Acrylic ester-based resin, vinyl ether-based resin, vinyl acetate-based resin, vinyl chloride / vinyl acetate copolymer-based resin, vinyl butyral-based resin, urethane-based resin, etc. A suitable tackifier, coumarone-indene resin, etc. are added to the resin system in an appropriate amount, and if necessary, softeners, fillers, anti-aging agents, cross-linking agents, etc. are formed. To do.

The material to be transferred may be various materials such as resin, metal, glass and ceramics. The form of the transferred material can be applied not only to the flat portion of the plate or the molded product but also to the molded product having a three-dimensional shape. In particular, when transferring to the surface of a three-dimensional molded article, it is preferable to transfer the protective layer in an uncured state while maintaining flexibility and high elongation, and then to cure the protective layer with ionizing radiation. .

As a transfer method, transfer to a three-dimensional molded article can be carried out by the following method, in which the characteristics of the transfer sheet of the present invention can be fully utilized. Japanese Patent Publication No. 2-4080, Japanese Patent Publication No. 4-19924
Injection molding simultaneous transfer method as disclosed in Japanese Patent Publication No. First, a transfer sheet is inserted between the female mold and the male mold so that the transfer layer faces the male mold side having the injection holes. If necessary, a transfer sheet is preformed on the surface of the female mold, then both molds are closed, and the cavity between the injection hole and the mold (molding cavity)
After injecting the molten resin into the inside and cooling and solidifying the injected resin,
Both molds are opened, the molded product and the transfer sheet in close contact with the molded product are taken out from the mold, and only the releasable base sheet is peeled off to transfer the transfer layer to the molded product.

The vacuum forming simultaneous transfer method disclosed in Japanese Patent Application Laid-Open Nos. 4-288214 and 5-57786. This is placed so that the transfer layer of the transfer sheet faces the transfer target side. Then, the transfer sheet is vacuum suctioned to cover the surface of the transfer sheet with the transfer sheet. When a heat-sensitive adhesive is used as the adhesive, the transfer sheet is heated with a heater to develop the transfer layer before, at the same time as, or after coating the transfer sheet on the surface of the transfer target. It is to be glued.

Lapping simultaneous transfer method. This is a lapping method, that is, Japanese Patent Publication No. 59-5190.
No. 0, Japanese Patent Publication No. 61-5895, Japanese Patent Publication No. 3-2
It is disclosed in Japanese Patent No. 666, etc. When attaching the sheet to the columnar body, the sheets are sequentially attached to each side surface of the columnar body by using a pressing roller (for example, in the case of attachment to a square pole, the sheets are sequentially attached to the upper side surface, left and right side surfaces). , And the lower side and finally the four side surfaces). As described above, with the adhesive layer side of the transfer sheet facing the transfer target, the transfer sheets are sequentially attached to each side by lapping, and the transfer layer and the transfer target are bonded by heating or the like. In addition, only the base sheet is peeled off. As described above, it is particularly effective to transfer the transfer sheet of the present invention in an uncured state when transferring a hard coating film by a molding transfer method in which a transfer sheet is stretched and deformed during transfer. Is. Further, it can be used for a transfer method such as hot stamping onto a flat surface which is not deformed by stretching the transfer sheet. In this case, the cured protective layer may be transferred onto the transfer sheet.

[0028]

In the transfer sheet constructed as described above, the silicon acrylate prepolymer is cross-linked by ionizing radiation, so that the hard coat can be cross-linked and cured in a short time. Even when used in a three-dimensional molded product, it is excellent in flexibility, and also has excellent scratch resistance and stain resistance of the surface after transfer. According to the invention of claim 2, the ionizing radiation-curable resin layer of the transfer layer is non-adhesive at room temperature after solvent drying by addition of the non-crosslinking type thermoplastic resin. The upper layers such as the pattern layer and the adhesive layer can be continuously applied and processed without undergoing a step such as curing, and the transfer layer can be cured by ionizing radiation irradiation before or after transfer to the transfer target. . In particular, in the case of curing after transfer, it can be handled in the same manner as a transfer sheet prepared by using an ordinary thermoplastic vehicle, such that it can be temporarily wound and stored without being irradiated with ionizing radiation when a transfer sheet is manufactured.

[0029]

EXAMPLES Next, examples of the transfer sheet according to the present invention will be specifically described.

Example 1 In FIG. 1, the base film 1
As a biaxially oriented polyethylene terephthalate film (Lumirror X-42 # 25 surface mat type manufactured by Toray Industries, Inc.)
The following ionizing radiation curable resin composition (A) is applied to the entire mat surface of the above with a roll coater,
The solvent was volatilized and removed by drying for 1 minute to obtain a non-adhesive solid protective layer 2 in an uncured state with an ionizing radiation curable resin having a film thickness of 3 μm. [Ionizing radiation curable resin composition (A)] 50 parts by weight of silicon acrylate prepolymer (manufactured by Shin-Etsu Chemical Co., Ltd.) (average molecular weight 22500, 11 functional groups in one molecule) 50 parts by weight of toluene Gravure printing is performed on the protective layer 2 of the ionizing radiation curable resin using a gravure printing ink having a vinyl chloride / vinyl acetate copolymer resin as a vehicle and a woodgrain printing plate,
The solvent was volatilized and removed by drying at 60 ° C. for 1 minute to form a woodgrain pattern layer 3. Further, an acrylic heat-sensitive adhesive was applied by a roll coater, and then the solvent was evaporated and removed by drying at 80 ° C. for 1 minute to obtain an adhesive layer 4 having a film thickness of 5 μm. Next, an electron beam of 175 KeV, 2
Irradiation was performed under the condition of Mrad to crosslink and cure the protective layer 2 made of the ionizing radiation-curable resin to obtain a transfer sheet T. Using this transfer sheet T, an ABS resin plate (Styrac ABS767 manufactured by Asahi Chemical Co., Ltd.) as a transfer target and the adhesive layer 4 of the transfer sheet are contacted with each other, and a pressure of 10 kg / cm ² , transport speed 2
After heating under pressure at m / min, the base sheet 1 of the transfer sheet T was peeled off by cooling and a transfer layer H having an ionizing radiation curable resin as a protective layer was provided on the outermost surface of the ABS resin plate.

Example 2 A transfer sheet was prepared in the same manner as in Example 1 except that the following ionizing radiation-curable resin composition (B) was used instead of the ionizing radiation-curable resin composition (A). Created. [Ionizing radiation curable resin composition (B)] Silicon acrylate prepolymer 20 parts by weight (Shin-Etsu Chemical Co., Ltd. average molecular weight 22,500, number of functional groups in one molecule: 11) Non-crosslinking thermoplastic resin polymethylmeta Acrylate 60 parts by weight (Mitsubishi Rayon Co., Ltd., Dianal BR-80 average molecular weight 95,000, glass transition temperature 105 ° C.) Toluene 20 parts by weight Using this transfer sheet, an ABS resin plate as a transfer target was prepared in the same manner as in Example 1. Then, the transfer layer H was provided on the ABS resin plate.

(Embodiment 3) A polyethylene terephthalate film for molding (Dia foil #
25 Mitsubishi Plastics Co., Ltd.) on one surface, the following ionizing radiation curable resin composition (C) was applied by a roll coater, and then the solvent was evaporated and removed by drying at 50 ° C. for 1 minute,
A protective layer 2 made of an ionizing radiation curable resin having a film thickness of 3 μm was obtained. [Ionizing radiation curable resin composition (C)] 50 parts by weight of silicon acrylate prepolymer (Shin-Etsu Chemical Co., Ltd. average molecular weight 50000 22 functional groups in one molecule) Toluene 50 parts by weight Next, the ionizing radiation Gravure printing is performed on the protective layer 2 made of a curable resin using the following pattern layer ink (X) and a wood grain printing plate, and the solvent is volatilized and removed by drying at 50 ° C. for 1 minute to obtain a wood grain pattern layer 3 Got [Vehicle of pattern layer ink (X)]-Vinyl chloride vinyl acetate copolymer resin 45 parts by weight-Polyethylene glycol diacrylate monomer 5 parts by weight-Methyl ethyl ketone 25 parts by weight-Toluene 25 parts by weight Further, an acrylic heat-sensitive adhesive is used. After coating with a roll coater, the solvent was volatilized and removed by drying at 60 ° C. for 1 minute to obtain an adhesive layer 4 having a film thickness of 5 μm. Next, an electron beam was irradiated from the adhesive layer 4 side under the conditions of 175 KeV and 2 Mrad to cure the ionizing radiation effect type resin and obtain a transfer sheet T. Using this transfer sheet T, a plate having an upward convex curved surface made of medium density fiber board is placed as a transfer target on a mounting table having vacuum suction holes, and the surface of the transfer sheet T The adhesive layer 4 and the adhesive layer 4 are superposed on each other, vacuum suction is applied from the transfer target side to coat the transfer sheet on the surface of the transfer target, and the transfer sheet T side is heated by a heater 180 ° C. for 1 minute to perform transfer and ionization. A transfer layer H having a radiation curable resin as the protective layer 2 was provided.

Comparative Example 1 As shown in FIG. 3, as a base sheet 1, a biaxially stretched polyethylene terephthalate film (T-60 # 50 manufactured by Toray) was formed on the surface of a melamine resin varnish (Zinc Tech Co., Ltd.). 0.3 g / m ² ) and baked at 170 ° C. for 20 seconds to form the release layer 6,
A releasable substrate sheet R was produced. Next, the following ionizing radiation curable resin composition (D) is applied on the entire surface of the releasable substrate sheet R by a roll coating method, and the solvent is volatilized and removed by drying at 60 ° C. for 1 minute, and then applied. 175 electron beam from the layer side
KeV, 2 Mrad irradiation under the conditions of cross-linking, film thickness 3
A protective layer 2 made of an ionizing radiation curable resin having a thickness of μm was obtained. [Ionizing radiation curable resin composition (D)]-Urethane acrylate prepolymer 50 parts by weight (average molecular weight 5000, number of functional groups per molecule 3) -Toluene 50 parts by weight Next, the same pattern layer 3 as in Example 1 Then, the adhesive layer 4 was formed to obtain a transfer sheet T, and the transfer was performed on the ABS resin plate in the same manner as in Example 1.

The physical properties of the transfer molded articles prepared in the examples and comparative examples were measured and evaluated by the following methods. [Measurement / Evaluation Method] (Pencil hardness) Based on JIS K5400. (Abrasion resistance) 1 protective layer of # 0000 steel wool
Rubbing back and forth 0 times, and the state of the scratch is evaluated. ○ There are no scratches. △ Slightly scratched. (Stain resistance) Oil-based magic ink (black) on the sample surface
Then, after 2 hours, wipe off with ethanol and evaluate for contamination. ○ Can be completely removed with ethanol. △ Traces of contamination are slightly visible. (Cellotape releasability) The sample was left for 300 hours under the condition of 60 ° C and 95% RH, cross-cut at 1 mm intervals, and subjected to a peeling test using cellophane tape (cellophane adhesive tape) manufactured by Nichiban Co., Ltd. Evaluate according to the degree. ○ No peeling × 3/10 or more peeling.

[0035]

[Table 1] Evaluation results

[0036]

According to the transfer sheet of the present invention having the above-mentioned constitution, the transferred protective layer has good abrasion resistance, stain resistance and cellophane tape peeling property. Further, in the transfer sheet according to the second aspect, in addition to this, the ionizing radiation curable resin layer contained in the transfer layer can be made non-tacky only by evaporation of the solvent. Therefore, since it is non-adhesive at room temperature in the uncured state, it is possible to continuously print and process the upper layers such as the pattern layer and the adhesive layer without passing through steps such as crosslinking and curing during the production of the transfer sheet. . The curing of the transfer layer by irradiation with ionizing rays can be performed before or after the transfer to the transfer target. In particular, the fact that a curing step can be provided after transfer is
Even if a transfer step is provided during the processing of the transfer sheet during the processing of a three-dimensional molded article, the transfer sheet having excellent flexibility can be transferred without causing cracks in the pattern layer, and the surface after transfer curing is scratch resistant. It has excellent adhesion and adhesion strength after durability test. The transfer sheet is suitable for the injection molding simultaneous transfer method, the vacuum molding simultaneous transfer method, and the lapping simultaneous transfer method. In particular, even in the case of irradiation after transfer, there is an effect that it can be handled in the same manner as a transfer sheet created using a normal thermoplastic vehicle, such as being able to be temporarily stored in a wound state without being irradiated with ionizing radiation when manufacturing a transfer sheet. .

[Brief description of drawings]

FIG. 1 is a schematic sectional view of a transfer sheet of the present invention.

FIG. 2 is a schematic sectional view of a transfer sheet that can be used for the three-dimensional molded article of the present invention.

FIG. 3 is a schematic sectional view of a transfer sheet provided with a release layer.

[Explanation of symbols]

 1 Base Sheet 11 Base Sheet for Molding 2 Protective Layer 3 Picture Layer 4 Adhesive Layer 6 Release Layer H Transfer Layer R Releasable Base Sheet T Transfer Sheet

Claims (3)

[Claims] 1. A transfer sheet having, as a transfer layer, at least a protective layer of an ionizing radiation curable resin on one surface of a base sheet having releasability, the protective layer having an average molecular weight of 1,000 to 100,000 and one molecule. Acryloyl group, a methacryloyl group, an acryloyloxy group, or a silicone acrylate having a total of two or more functional groups of any of the methacryloyloxy groups, or a crosslinked cured product of a silicon methacrylate prepolymer, characterized in that Transfer sheet. 2. The transfer sheet according to claim 1, wherein the protective layer contains a non-crosslinking thermoplastic resin compatible with the ionizing radiation curable resin. 3. A transfer sheet comprising a protective layer according to claim 1 and a pattern layer and an adhesive layer laminated in this order on the protective layer, wherein 2 are contained in one molecule of at least one of the pattern layer and the adhesive layer.
A transfer sheet comprising a prepolymer and / or a monomer having one or more acryloyl groups or methacryloyl groups.