JPH09234994A - Transfer sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve properties such as weather-proof, abrasionresistant and scratch-resistant by adding fine particles of zinc oxide with a surface coated with a vitreous layer to at least, one of the constituent layers of a transfer layer, in a transfer sheet consisting of a transfer layer comprising a protecting layer and a decorative layer formed on one of the faces of a support sheet with mold-parting properties. SOLUTION: This transfer sheet 1 is used for forming a decorative pattern on a finished product or transferring to and forming on the finished product a transfer layer consisting of a decorative layer 4 and a protecting layer 3 for the purpose to protect the surface of the finished product. In addition, the transfer sheet 1 is composed of the protecting layer 3, the decorative layer 4 and an adhesive layer 5 stack in that order as the transfer layer 6. In this case, at least, one of the constituent layers of the transfer layer 6 contains fine particles of zinc oxide, titanium oxide, cerium oxide or ferric oxide with the surface coated with a vitreous layer. The vitreous layer is, for example, formed of a vitreous substance such as quartz glass or soda glass and allows penetration of an ultraviolet beam. Besides, the vitreous layer should be transparent and hard.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a transfer sheet,
More specifically, the present invention relates to a transfer sheet having a transfer layer having weather resistance, abrasion resistance, scratch resistance, etc. that can withstand outdoor use.

[0002]

2. Description of the Related Art Conventionally, a transfer layer such as a decorative layer or a protective layer is provided on a product for the purpose of decorating various products or protecting the surface thereof. A transfer sheet for transfer formation is known, and in such a transfer sheet, a transfer layer transferred to a transfer target contains an organic ultraviolet absorber such as a benzophenone-based or benzotriazole-based ultraviolet absorbent and the transfer layer itself. Furthermore, it has been proposed to improve the weather resistance of the transferred material (Japanese Patent Publication No. 60-7779, Japanese Patent Publication No. 6-9).
8849, etc.).

However, when the transfer layer to which the above-mentioned organic ultraviolet absorber is added is exposed to sunlight, the ultraviolet absorber bleeds (exudes) to the surface of the transfer layer due to heating over time due to exposure to sunlight and the like. Is not only whitened, but if the ultraviolet absorbent near the surface of the transfer layer flows out due to rain dew or the like, the amount of the ultraviolet absorbent contained in the transfer layer is naturally reduced and sufficient weather resistance cannot be obtained. Especially when a transfer layer is formed on a product to be used outdoors, discoloration with time, cracks, deterioration, etc. are likely to occur.
It has also been a factor of impairing the appearance of the transfer target product.

By the way, it has been known to use a crosslinkable resin in which a cured film having a three-dimensional crosslinked structure is formed as a base resin forming a transfer layer to improve wear resistance, scratch resistance and the like of the transfer layer. The applicant has used a reactive ultraviolet absorber having a functional group such as a vinyl group in the molecule to bind it to the above crosslinkable resin, thereby preventing bleeding and outflow of the ultraviolet absorber. It was attempted to impart desired weather resistance to the transfer layer together with abrasion resistance, scratch resistance, etc. (JP-A-7-51902).

However, the reactive ultraviolet absorbers as described above have a large molecular weight because they have a functional group such as a vinyl group, and in order to obtain the same level of ultraviolet absorbing performance as compared with an ultraviolet absorber having no such functional group. However, it is necessary to add a large amount of the reactive ultraviolet absorber, which is disadvantageous in terms of cost. Further, when the reactive ultraviolet absorber is bonded to the crosslinkable resin, the original crosslink reaction of the crosslinkable resins is inhibited, so that the crosslink density of the crosslinkable resin is reduced depending on the amount added, and the abrasion resistance and However, there is a problem in that scratch resistance may not be sufficiently obtained.

On the other hand, as an ultraviolet absorber, the average particle size is 0.1.
It is also known to use an inorganic ultraviolet absorber such as titanium oxide in the form of ultrafine particles of μm or less (JP-A-5-9267).
No. 0, Japanese Patent Publication No. 2-32159, etc.), such an inorganic ultraviolet absorber has a certain particle size, unlike an organic ultraviolet absorber having a molecular level size, and therefore has a surface of a protective layer. Has an advantage that bleeding to the surface is suppressed, and the above-mentioned problems unlike in the case of using an organic ultraviolet absorber are unlikely to occur.

Contrary to the above advantages, however, the use of an inorganic UV absorber having a large particle size causes a problem that the transparency of the protective layer containing the same is impaired, and the inorganic UV absorber is also used. Even if the absorbent is processed into ultrafine particles and evenly dispersed in the base resin that forms the transfer layer to ensure transparency, the ultrafine inorganic UV absorber has a cohesive force. There is a problem that it is difficult to obtain transparency due to poor dispersion. Therefore, for example, it is unsuitable to use an inorganic ultraviolet absorber in the case where a part or the whole of the transfer layer is made transparent and the lower layer thereof is made visible after the transfer. Similarly, when hard inorganic particles such as alumina, talc, and silica are added to impart abrasion resistance, scratch resistance, etc. to the transfer layer, the same phenomenon occurs. In addition, since such an inorganic ultraviolet absorber causes a chemical reaction with an acid (particularly in the case of a metal oxide), when the transferred transfer layer is exposed outdoors, carbon dioxide and sulfite in rain are used. There was also a problem that whitening and discoloration were caused by acids such as nitrous acid.

The present inventors have conducted extensive studies in view of the above problems, and as a result, have excellent weather resistance as well as surface physical properties such as abrasion resistance and scratch resistance, and are also suitable for outdoor use. It is sufficient even if it is possible to form a transfer layer that can withstand sufficiently on a transfer target and to make a part or all of the transfer layer transparent so that the lower layer can be visually observed after transfer. The present invention has been completed which can ensure high transparency.

[0009]

That is, the transfer sheet of the present invention is a transfer sheet having a transfer layer comprising at least a protective layer and / or a decorative layer on one surface of a support sheet having releasability, At least one of the layers constituting the transfer layer, zinc oxide surface-embedded with a vitreous layer,
It is characterized by containing fine particles of titanium oxide, cerium oxide or iron oxide.

[0010]

Embodiments of the present invention will be described below in detail. 1 is a sectional view showing an example of the transfer sheet 1 of the present invention.

In an example of the transfer sheet 1 of the present invention shown in FIG. 1, a protective layer 3, a decorative layer 4, and an adhesive layer 5 are sequentially laminated on a support sheet 2, and these layers are transferred. Although it is configured as the layer 6, in the present invention, the transfer layer 6 including at least the protective layer 3 and / or the decorative layer 4 may be provided on one surface of the support sheet 2, and the transfer layer 6 may be the protective layer 3. Only, or a mode including only the decorative layer 4, and a mode including other layers such as a metal vapor deposition layer are also included in the technical scope of the present invention.

In the present invention, in at least one of the layers constituting the transfer layer 6, fine particles of zinc oxide, titanium oxide, cerium oxide, or iron oxide whose surface is embedded with a glassy layer (hereinafter referred to as fine particles) , And these fine particles are abbreviated as “vitreous-embedded fine particles” as necessary), and the vitreous layer for embedding the surface of the metal oxide is, for example, quartz (silica) glass or soda glass. , Potassium glass, borosilicate glass, and the like, but the material is particularly preferable as long as it has ultraviolet transparency and transparency and hardness within the range in which the effects of the present invention described below can be obtained. Not limited.

Here, it is known that the above metal oxides have an ultraviolet absorbing property, and in the present invention, these metal oxides are used as an ultraviolet absorbing agent and are embedded in a glass layer. It has technical significance.

That is, since the glass-embedded microparticles of the present invention have their hardness increased by embedding in the glassy layer, abrasion resistance and scratch resistance are imparted to the layer containing such microparticles. In addition, the UV resistance of the embedded metal oxide can impart weather resistance to the layer. In addition, since the acid resistance of the metal oxide can be improved by embedding the vitreous substance, sufficient weather resistance can be maintained even in an area with a lot of acid rain.

Further, in the present invention, when a part or all of the transfer layer 6 is made transparent so that the lower layer thereof can be visually observed after transfer (specifically, the transfer layer 6 is formed as shown in the illustrated example). In the case where the protective layer 3 is composed of the protective layer 3 and the decorative layer 4, and the protective layer 3 is transparently formed so that the decorative layer 4 located below the protective layer 3 after transfer is visible through the protective layer 3) Even if the layer contains glass-embedded fine particles in order to impart abrasion resistance, scratch resistance, and weather resistance, the glass layer on the surface of the fine particles has transparency, and a substrate forming a transparent layer. Since the difference in the refractive index with the resin is small and the reflection at the interface between them can be reduced, sufficient transparency should be maintained even if the glass-embedded fine particles have a relatively large particle size. You can

The average particle size of the vitreous embedded particles is 1 to 40 μm, preferably 1 to 10 in consideration of dispersibility of the particles.
It is preferably in the range of μm, and such a range makes it possible to improve scratch resistance and abrasion resistance without impairing transparency. When the average particle size of the glass-embedded particles is less than the above range, the transparency is excellent, but the cohesive force of such particles is strong, so that dispersion failure tends to occur, and scratch resistance and abrasion resistance are improved. It will not be possible to improve it sufficiently. When the average particle size of the glass-embedded particles exceeds the above range, the abrasion resistance and the scratch resistance are improved, but the particle size becomes too large and the transparency is lowered. When importance is attached to transparency rather than abrasion resistance and scratch resistance, glass-embedded particles having a particle diameter smaller than the above range may be used as long as dispersion treatment is sufficiently performed.

The shape of the vitreous embedded particles is scaly, spherical,
It is appropriately selected from an elliptic sphere having a flat sphere, a shape close to the true sphere or an ellipsoid, a polyhedron, or an amorphous shape,
Scale-like or amorphous shapes having sharp corners may cause abrasion of rolls or doctor knives of a coating device when coating-forming a layer containing such vitreous embedded particles. It is not preferable because there are no protrusions or corners on the particle surface
A spherical shape whose surface is surrounded by a smooth curved surface or an elliptical shape is preferable.

The content of the vitreous embedded particles is appropriately selected within the range where desired abrasion resistance, scratch resistance, weather resistance and transparency are obtained, but is usually 1 to 20% by weight, preferably Is 3 to 10% by weight. If it is less than 3% by weight, abrasion resistance, scratch resistance and weather resistance are insufficient. When it exceeds 10% by weight, transparency and coating suitability are deteriorated, and the performance of the transfer layer is not improved despite the cost increase.

As described above, in the present invention, the transfer layer 6 contains fine particles of zinc oxide, titanium oxide, cerium oxide, or iron oxide, the surfaces of which are embedded in the vitreous layer. Not only can the weather resistance be imparted to the layer 6, but also abrasion resistance and scratch resistance can be imparted, and the layer 6 can sufficiently withstand outdoor use. Moreover, such a vitreous-embedded fine particle can be dispersed uniformly in the base resin without fear of impairing the transparency of the layer containing the fine particle, even if the particle size is relatively large with less aggregation. it can.

In the present invention, as described above, at least one of the layers constituting the transfer layer 6 contains fine particles of vitreous embedding, and when the transfer sheet 1 of the present invention is constructed as in the illustrated example. In addition, it is possible to contain the glass-embedded fine particles in both the protective layer 3 and the decorative layer 4, or either one of them, but the transfer layer 6 is transferred to the transfer target and the support sheet is formed. It is most preferable that the protective layer 3 appears on the surface side when peeling off 2, and the protective layer 3 serves as the surface protective layer 3 of the transferred material, and that the protective layer 3 contains the vitreous embedded fine particles. . When only the decorative layer 4 contains the glass-embedded fine particles, the protective layer 3 may be worn out to expose the decorative layer 4. However, at this time, the decorative layer 4 has abrasion resistance, If the scratch resistance and the weather resistance are shown, the object can be achieved only by preventing deterioration of the decoration itself applied to the transferred material with time.

As the base resin for forming the protective layer 3, a thermoplastic resin such as an acrylic resin or a vinyl chloride-vinyl acetate copolymer which forms a solid film by solvent drying, or itself is also used outdoors. A curable resin having physical properties such as abrasion resistance and scratch resistance that can be sufficiently provided is preferably used, and a curable resin such as an ionizing radiation curable resin is preferably used. Combined or
A composition in which a photopolymerization initiator and / or a photopolymerization accelerator are added to a prepolymer, a polymer, and / or a monomer having an epoxy group, and a composition curable by ionizing radiation is used.

The ionizing radiation means an electromagnetic wave or a charged particle beam having energetic particles capable of polymerizing and cross-linking molecules, and usually ultraviolet rays, electron beams and the like are used. In the present invention, the protective layer 3 is made of glass. In the case of containing the substance-embedded fine particles, as the ionizing radiation curable resin forming the protective layer 3, in order to prevent the curing reaction from being hindered by the added ultraviolet absorber (glass-embedded fine particles), It is preferable to use a so-called electron beam curable resin that is cured by electron beam irradiation, but in the case of curing with ultraviolet rays,
The ionizing radiation curable resin (ultraviolet curable resin) used may be shifted so that the photosensitive wavelength does not overlap with the absorption wavelength of the ultraviolet absorber.

As the ultraviolet ray source, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a black light lamp, a metal halide lamp or the like can be used. Also, as the electron beam source, Cockloft-Walton type,
Various electron beam accelerators such as bandegraph type, resonance transformer type, insulating core transformer type, linear type, dynamitron type, and high frequency type can be used, and 100 to 1000 keV can be used to cure the electron beam curable resin. Preferably 100
An electron having an energy of ˜300 keV is irradiated, and the irradiation dose is usually about 0.5 to 30 Mrad.

Examples of the above prepolymers and polymers include unsaturated polyesters such as condensation products of unsaturated dicarboxylic acids and polyhydric alcohols, polyester methacrylates, polyether methacrylates, polyol methacrylates,
Methacrylates such as melamine methacrylate, polyester acrylate, epoxy acrylate, urethane acrylate, polyether acrylate, polyol acrylate, and acrylates such as melamine acrylate are available.

Examples of the monomer include styrene and α
Styrene-based monomers such as methylstyrene, methyl acrylate, 2-ethylhexyl acrylate, methoxyethyl acrylate, butoxyethyl acrylate, butyl acrylate, methoxybutyl acrylate, acrylates such as phenyl acrylate, methacrylic acid Methacrylic acid esters such as methyl, ethyl methacrylate, propyl methacrylate, methoxyethyl methacrylate, ethoxymethyl methacrylate, phenyl methacrylate and lauryl methacrylate, 2- (N, N-diethylamino) ethyl acrylate, memethacryl 2- (N, N-dimethylamino) ethyl acrylate, 2- (N, N-dibenzylamino) methyl acrylate, 2- (N, N-diethylamino) propyl acrylate Substituted amino alcohol ester , Acrylamide, unsaturated carboxylic acid amides such as methacrylamide, ethylene glycol diacrylate, dipropylene glycol diacrylate,
Compounds such as propylene glycol diacrylate, neopentyl glycol diacrylate, 1,6 hexanediol diacrylate, triethylene glycol diacrylate, and other compounds such as dipropylene glycol diacrylate, ethylene glycol diacrylate, propylene glycol dimethacrylate, and diethylene glycol dimethacrylate. There are functional compounds and / or polythiol compounds having two or more thiol groups in the molecule, such as trimethylolpropane trithioglycolate, trimethylolpropane trithiopropylate and pentaerythritol tetrathioglycol.

The above compounds may be used alone or in combination as necessary.
Although a mixture of two or more species is used, in order to impart ordinary coating aptitude to the radiation curable paint, the prepolymer or polythiol is 5% by weight or more, and the monomer and / or polythiol is 95% by weight or less. preferable.

In selecting the monomer, when flexibility of the cured product is required, the amount of the monomer may be reduced within a range that does not hinder coating suitability, or a monofunctional or bifunctional acrylate monomer may be used. The structure has a relatively low crosslinking density. In addition, when heat resistance, hardness, solvent resistance, etc. of the cured product are required, increase the amount of the monomer within a range that does not hinder the coating suitability, or use a trifunctional or higher functional acrylate monomer to achieve a structure with a high crosslinking density. Is preferred. It is also possible to mix a mono- or di-functional monomer and a tri- or more-functional monomer to adjust the coating suitability and the physical properties of the cured product.

Examples of the monofunctional acrylate monomer as described above include 2-hydroxy acrylate, 2-hexyl acrylate and phenoxyethyl acrylate.
Further, as the bifunctional acrylate, ethylene glycol diacrylate, 1,6-hexanediol diacrylate, and the like, and as the trifunctional or higher functional acrylate, trimethylolpropane triacrylate, pentaerythritol tri (tetra) acrylate, dipentaerythritol hexaacrylate. Etc.

Further, in order to adjust the physical properties such as flexibility and surface hardness of the cured product, the following ionizing radiation non-curable resin is added to at least one of the above prepolymer, polymer and monomer. %, Preferably 5 to 50% by weight can be mixed and used.

As the ionizing radiation non-curable resin, a thermoplastic resin such as urethane type, fiber type, polyester type, acrylic type, butyral type, polyvinyl chloride, polyvinyl acetate, etc. can be used. From the viewpoint of film flexibility (deformation during transfer sheet 1 production or transfer, and prevention of cracks due to bending), fibrin-based, urethane-based, and butyral-based films are preferable.

When such an ionizing radiation curable resin is cured with ultraviolet rays, acetophenones, benzophenones, Michler benzoyl benzoate, α-aminoxime ester, tetramethyl thiuram monosulfide, thioxanthone are used as photopolymerization initiators. As the photopolymerization accelerator (sensitizer), n-butylamine, triethylamine, tri-n-butylphosphine and the like can be mixed and used.

To form the protective layer 3 by applying the above ionizing radiation curable resin, for example, roll coating, curtain flow coating, wire bar coating, reverse coating, gravure coating, gravure reverse coating, air knife coating. , Kiss coating, blade coating, smooth coating, comma coating, etc.
It is preferable to form the film with a film thickness of 00 μm, preferably about 1 to 20 μm.

The decorative layer 4 is provided for the purpose of imparting decorative properties, and is gravure-printed by using a known thermoplastic resin or thermoplastic resin, or an ink in which a pigment or the like is dispersed in the above-mentioned ionizing radiation curable resin, It can be formed by known printing means such as offset gravure printing, silk screen printing, offset printing, electrostatic printing, jet printing printing, transfer means, partial vapor deposition, gross matte printing and the like. The printing pattern of the decorative layer 4 can be appropriately selected from patterns such as lattices, polka dots and the like, abstract patterns, patterns of natural products such as stones and woods, letters, symbols and the like as desired.
As in the case where the protective layer 3 contains the glass-embedded fine particles, the decoration layer 4 contains the glass-embedded fine particles, and at this time, an ionizing radiation curable resin is used as a binder for forming the decoration layer 4 by printing. When used, an electron beam curable resin is used as the ionizing radiation curable resin.

The adhesive layer 4 is provided as needed when the transfer layer 6 does not have adhesiveness to the transferred material, and is made of acrylic resin, vinyl acetate resin, vinyl chloride-vinyl acetate. Using a thermoplastic resin such as a polymer or a thermoplastic polyurethane-based resin, or a thermosetting resin such as a two-component curable polyurethane having a blocked isocyanate as a curing agent, a coating means similar to that of the protective layer 1 is used to form 1 to 20 μm.
The coating is formed to a thickness of m.

As the support sheet 2, one having releasability from the transfer layer 6 is used. Specifically, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyester resin such as polyethylene terephthalate-isophthalate copolymer, polyolefin resin such as polyethylene, polypropylene, polymethylpentene, polyvinyl fluoride, polyvinylidene fluoride, poly Tetrafluoroethylene, ethylene-4
Polyfluorinated ethylene resin such as fluorinated ethylene copolymer, polyamide such as nylon 6, nylon 66, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer Polymers, polyvinyl alcohol, vinyl polymers such as vinylon, cellulose triacetate, cellulosic resins such as cellophane, acrylic resins such as methyl polymethacrylate, ethyl polymethacrylate, ethyl polyacrylate, and polybutyl acrylate, Molded into a sheet shape by adding a release agent such as melamine resin, silicone, fluororesin, paraffin, etc. to synthetic resin such as polystyrene, polycarbonate, polyarylate, polyimide, etc., or fine paper, thin paper The release agent for papers such as glass, glassine paper, and sulfuric acid paper. For forming coating films of paints added to well-known vehicles such as acrylic resins, fibrin resins, vinyl resins, etc., and extruding releasable resins such as melamine resins, silicones, fluorine resins, and paraffin. The thing etc. which formed the film by a coat etc. can be illustrated.

The thickness of the support sheet 2 is appropriately selected according to the intended use, and a thickness of about 12 to 200 μm is usually used, but a preferable thickness is 25 to 100 μm. When the thickness of the support sheet 2 is less than the above range, the transfer sheet 1
Inconveniences such as breakage and wrinkles are likely to occur during manufacturing or transfer. In addition, when the thickness of the support sheet 2 exceeds the above range, not only is it disadvantageous in terms of cost, but also it is liable to cause inconvenience that heat during transfer is difficult to transfer. Particularly, transfer is performed by the injection molding simultaneous transfer method. In this case, the sheet may not stretch and may hinder the transfer.

The transfer sheet 1 of the present invention is suitable for various uses, for example, a polyvinyl chloride deck material (container),
Decorative decoration by transfer to exterior members such as doors and window frame materials (sashes), protective material for preventing light fading of the image surface printed by a thermal sublimation transfer printer (in this case, a transparent protective layer 3, or The transfer layer 6 is composed of a transparent protective layer 3 and a transparent adhesive layer), or even an interior material such as an automobile interior material, a cabinet of light electric current / OA equipment, etc., which wants to prevent fading due to sunlight irradiation from windows etc. It is also suitable for use as a decorative decoration by transfer to a member used for a long period of time.

[0038]

EXAMPLES The present invention will be described in more detail with reference to specific examples of the present invention.

Example 1 Biaxially stretched polyester sheet having a thickness of 38 μm (manufactured by Toray;
HP-7) is coated with a melamine resin to form a releasable support sheet, and an ink having the following composition is gravure-printed on the support sheet at a dry coating amount of 2 g / m ² to form a protective layer. Was formed.

Ink composition Acrylic resin: 20 parts by weight Trimethylolpropane triacrylate: 10 parts by weight Glass silica-embedded zinc oxide (average particle size: 4 μm): 3 Parts by weight Polyethylene wax: 1 part by weight Methyl ethyl ketone: 33 parts by weight Toluene: 33 parts by weight

Next, a mixture of an acrylic resin and a vinyl chloride-vinyl acetate copolymer was used as a binder resin, and a gravure ink (manufactured by Showa Ink Mfg. Co., Ltd.) containing a color pigment added thereto was used to gravure-print the protective layer. A decorative layer is formed by printing on the above, and then an adhesive layer is laminated on the decorative layer by gravure printing with an acrylic adhesive (manufactured by Showa Ink Kogyo Co., Ltd.) so that the coating amount is 2 g / m ² to form a transfer sheet. Obtained.

Example 2 A transfer sheet was obtained in the same manner as in Example 1 except that the ink having the following composition was used as the ink for forming the protective layer.

Ink composition Acrylic resin: 20 parts by weight Trimethylolpropane triacrylate: 10 parts by weight Vitreous silica-embedded cerium oxide (average particle size: 4 μm): 3 Parts by weight Polyethylene wax: 1 part by weight Methyl ethyl ketone: 33 parts by weight Toluene: 33 parts by weight

Comparative Example 1 A transfer sheet was obtained in the same manner as in Example 1 except that the ink having the following composition was used as the ink for forming the protective layer.

Ink composition Acrylic resin: 20 parts by weight Trimethylolpropane triacrylate: 10 parts by weight Benzotriazole-based UV absorber: 3 parts by weight Polyethylene wax:・ ・ ・ 1 part by weight Methyl ethyl ketone ・ ・ ・ ・ ・ 33 parts by weight Toluene ・ ・ ・ ・ ・ 33 parts by weight

Comparative Example 2 A transfer sheet was obtained in the same manner as in Example 1 except that the ink having the following composition was used as the ink for forming the protective layer.

Ink composition Acrylic resin: 20 parts by weight Trimethylolpropane triacrylate: 10 parts by weight Benzotriazole-based UV absorber: 3 parts by weight α-alumina (average) Particle size 4μm) ··· 3 parts by weight polyethylene wax ··· 1 part by weight methyl ethyl ketone ··· 32 parts by weight toluene ··· 31 parts by weight

Comparative Example 3 A transfer sheet was obtained in the same manner as in Example 1 except that the ink having the following composition was used as the ink for forming the protective layer.

Ink composition Acrylic resin: 20 parts by weight Trimethylolpropane triacrylate: 10 parts by weight Zinc oxide (average particle size 0.015 μm, no vitreous embedding layer)・ ・ ・ 3 parts by weight Polyethylene wax ・ ・ ・ ・ ・ ・ 1 part by weight Methyl ethyl ketone ・ ・ ・ ・ ・ 33 parts by weight Toluene ・ ・ ・ ・ ・ 33 parts by weight

A transfer layer was transferred from each of the transfer sheets obtained in Examples 1 and 2 and Comparative Examples 1 to 3 onto a test piece, and the transfer layer after transfer was subjected to the following tests to evaluate the results. . The results are shown in Table 1.

Test 1 (Transparency Test) The surface of the transfer layer was visually observed. Those with no white turbidity or coloration were defined as “excellent”.

Test 2 (Abrasion resistance test) The Taber abrasion test CS-10F was rotated 100 times with a load of 500 g and then the surface of the transfer layer was observed. The case where the picture (decorative layer) did not disappear was defined as "excellent".

Test 3 (Scratch resistance test) Steel wool # 0000 was pressed under a load of 1 kg for 100 reciprocations, and then the surface of the transfer layer was observed. Those with visible scratches were rated "inferior" and those with no visible scratches were rated "excellent".

Test 4 (Weather resistance test) Using a sunshine weatherometer (manufactured by Suga Test Instruments), irradiation time 3000 hr, black panel temperature 63 ° C.
The weather resistance test was conducted under the conditions for accelerated weather resistance test. The change in color difference before and after irradiation with ultraviolet rays was measured and evaluated by ΔE = (Δa ² + Δb ² + Δc ² ) ^1/2 in the Hunter color difference formula Lab.

Test 5 (acid resistance test) The sample was immersed in a 0.1% sulfuric acid aqueous solution for 1000 hours, and its appearance was visually observed.

[0056]

[Table 1] *: Surface whitening due to bleeding of the ultraviolet absorber was observed.

[0057]

As described above, according to the transfer sheet of the present invention, in at least one of the layers constituting the transfer layer, zinc oxide, titanium oxide, cerium oxide whose surface is embedded with a glassy layer, Alternatively, by incorporating fine particles of iron oxide, not only can weather resistance be imparted to the transfer layer, but also abrasion resistance, scratch resistance, and acid resistance can be imparted, making it suitable for outdoor use. Is also well tolerated. Moreover, such a vitreous-embedded fine particle can be dispersed uniformly in the base resin without fear of impairing the transparency of the layer containing the fine particle, even if the particle size is relatively large with less aggregation. The present invention is particularly useful when a part or the whole of the transfer layer is made transparent to make the lower layer visible after the transfer, and the transparent layer does not impair the transparency of the transparent layer. It becomes possible to impart abrasion resistance, scratch resistance, and weather resistance.

[Brief description of drawings]

FIG. 1 is a sectional view showing an example of a transfer sheet of the present invention.

[Explanation of symbols]

 1 Transfer Sheet 2 Support Sheet 3 Protective Layer 4 Decorative Layer 6 Transfer Layer

Claims (1)

[Claims] 1. A transfer sheet having a transfer layer comprising at least a protective layer and / or a decorative layer on one surface of a support sheet having releasability, wherein at least one of the layers constituting the transfer layer is present. A transfer sheet characterized by containing fine particles of zinc oxide, titanium oxide, cerium oxide, or iron oxide whose surface is embedded in a glassy layer.