JP4710570B2 - Hydraulic transfer film and hydraulic transfer body - Google Patents

Description

  The present invention relates to a hydraulic transfer film having a curable resin layer and a hydraulic transfer body obtained by hydraulic transfer of the film.

  In the hydraulic transfer method, a hydraulic transfer film having a support film made of a water-soluble or water-swellable resin and a transfer layer is floated on the water surface with the support film facing downward, and the transfer layer is formed with an organic solvent called an activator. In this method, after the softening, the transfer layer is transferred to the transfer body by being submerged in water while being pressed from above. Recently, a hydraulic transfer film having a transfer layer in which a curable resin layer serving as a topcoat layer and a decorative layer are integrated has been developed (for example, refer to Patent Document 1). A topcoat layer and a decorative layer can be provided on the transfer object.

Since the water pressure transfer method can easily apply a decoration layer to a transfer object having a complicated three-dimensional shape, it has recently been applied to water members such as bathtubs and counters. These members are required to have hot water resistance in addition to the conventional physical properties such as scratch resistance, heat resistance, chemical resistance and the like. The hot water resistance is required to have no change even when immersed in hot water at 60 to 90 ° C. for about 300 hours.
Since the material of the water-circulating member is usually plastic, the water pressure transfer is usually performed under transfer conditions that do not damage the member. For example, the drying process after the transfer is performed at 100 ° C. or lower so that it is not exposed to a high temperature in the drying or curing process, and light such as ultraviolet rays without heat exposure is used in the curing process. However, when the transfer is performed under such conditions, in the hydraulic transfer film disclosed in Patent Document 1, when the decorative layer is formed of dark ink when immersed in hot water at 60 to 90 ° C. for about 300 hours There was a problem that coating film defects such as blisters occurred.
JP 2004-34393 A

  The subject of the present invention is that even if the material of the transfer object is a member having low heat resistance such as plastic, the transfer can be performed satisfactorily under the conditions suitable for the member. It is an object of the present invention to provide a hydraulic transfer film that does not cause any coating film defects such as blisters even when immersed in the film for 300 hours or longer.

  The present inventors presume that coating film defects such as blisters in the dark ink portion of the decorative layer are caused by an uncured product such as a reactive monomer considered to have migrated from the curable resin layer, and are dried at high temperature. As a film design in which the uncured product does not remain even if there is no heat curing step, a film containing a (meth) acrylate compound having a pentaerythritol skeleton in the curable resin layer and a blocked isocyanate compound in the decorative layer However, it has been found that the above problems can be solved.

A hydraulic transfer film having a transfer layer in which a curable resin layer serving as a topcoat layer and a decorative layer are integrated is a part of the reactive monomer that is a component of the curable resin layer during storage. It is thought that it has migrated.
Among the monomers transferred to the decoration layer, the monomers transferred to the transparent or light-colored portion of the decoration layer are cured because light is transmitted, but the dark-colored portion is difficult to transmit light, and partially remains as an uncured product it is conceivable that. This is considered to cause bleeding at the time of immersion in hot water and cause blister defects on the surface of the coating film.

  The inventors of the present invention made the curable resin layer contain a (meth) acrylate compound having a pentaerythritol skeleton, and the decorative layer contained a blocked isocyanate compound, and used two kinds of crosslinking patterns in combination. Specifically, the blocking agent of the blocked isocyanate group in the decorative layer is dissociated, and a crosslinked pattern that crosslinks the regenerated isocyanate group with a hydroxyl group in the curable resin layer or the ink layer, and a crosslinking pattern by light irradiation. Use together. The presence of the pentaerythritol skeleton in the curable resin layer makes it possible to obtain a hydraulic transfer body that does not cause blistering or the like even in the dark portion of the decorative layer where light is not easily transmitted. The step of dissociating the blocking agent of the blocked isocyanate group can utilize a heat drying step after hydraulic transfer.

  That is, the present invention has a support film made of a water-soluble or water-swellable resin and a transfer layer that can be dissolved in an organic solvent provided on the support film, and the transfer layer is photocurable. A hydraulic transfer film having a resin layer and a decorative layer, wherein the curable resin layer contains a (meth) acrylate compound having a pentaerythritol skeleton, and the decorative layer contains a blocked isocyanate compound To do.

  The present invention also provides the hydraulic transfer film described above, wherein the support film is floated on water, the transfer layer is activated with an organic solvent, the transfer layer is transferred to a transfer object, and the support film Then, a hydraulic transfer body in which the transfer layer is cured with light is provided.

  The curable resin layer referred to in the present invention means an uncured layer at the transfer stage, and a layer that forms a cured resin layer after curing. The cured resin layer means a layer produced by a curing reaction after transfer.

According to the present invention, even if the material of the transfer body is a member having low heat resistance such as plastic, it can be transferred satisfactorily under the conditions suitable for the member, and even if it is immersed in warm water at 60 ° C. for 300 hours or more, it can be applied with a blister or the like. A hydraulic transfer body in which no film defects are generated can be obtained.

(Support film)
The support film made of a water-soluble or water-swellable resin used for the hydraulic transfer film of the present invention is a film made of a resin that can be dissolved or swollen with water.
Examples of the support film made of a water-soluble or water-swellable resin (hereinafter abbreviated as support film) include, for example, PVA (polyvinyl alcohol), polyvinylpyrrolidone, acetylcellulose, polyacrylamide, acetylbutylcellulose, gelatin, Films such as sodium alginate, hydroxyethyl cellulose, carboxymethyl cellulose and the like can be used.

  Among them, a PVA film generally used as a hydraulic transfer film is particularly preferable because it is easily dissolved in water, easily available, and suitable for printing a curable resin layer. The thickness of the support film used is preferably about 10 to 200 μm.

(Transfer layer)
The transfer layer provided on the support film of the hydraulic transfer film of the present invention was provided on the photocurable curable resin layer (hereinafter referred to as curable resin layer) and the curable resin layer. It has a decorative layer (hereinafter referred to as a decorative layer) made of a printing ink film or a paint film. In the present invention, the curable resin layer contains a (meth) acrylate compound having a pentaerythritol skeleton, and the ink layer contains a blocked isocyanate compound.

(Curable resin layer)
((Meth) acrylate compound having pentaerythritol skeleton)
As the (meth) acrylate compound having a pentaerythritol skeleton used in the present invention, a known one such as pentaerythritol triacrylate can be used, but the smaller the tackiness when drying the coating film, the better the hydraulic transfer workability. Urethane modified (meth) acrylate is most preferred. This can be obtained, for example, by charging an aliphatic diisocyanate, pentaerythritol triacrylate, and a diol so that NCO / OH ≦ 1 (substance ratio) and reacting them by a conventional method. Any compound preferably has an alcoholic hydroxyl group because it reacts with the blocked isocyanate compound contained in the decorative layer. Moreover, it is preferable that there is no isocyanate residue from a viewpoint of storage stability. Commercial products may be used for these.
The molecular weight is preferably 3,000 to 50,000, and preferably 5,000 to 40,000 in terms of weight average molecular weight, since it exhibits good hydraulic transferability.

  The (meth) acrylate compound having a pentaerythritol skeleton is preferably added so as to be in the range of 20 to 100% by mass in the curable resin layer. If it is less than 20%, the hot water resistance may not be sufficient. If the polymerizable compound (A) is tack-free when dried, the curable resin layer can be composed of only the polymerizable compound (A) and a photopolymerization initiator.

  The reason why the pentaerythritol skeleton is effective for hot water resistance is not clear, but since the sensitivity to light is good, it is considered that a considerable crosslink density can be obtained even in a dark portion where light is difficult to transmit. Alternatively, it may be difficult to move to the ink layer.

(Radically polymerizable compound)
The curable resin layer used in the present invention may contain a general-purpose radical polymerizable compound in addition to the (meth) acrylate compound having the pentaerythritol skeleton within a range not impairing the curing of the present invention. A (meth) acrylate is preferable because of excellent curability, and a polyfunctional (meth) acrylate having 2 to 15 (meth) acryloyl groups in one molecule is particularly preferable. There is no particular limitation on the radically polymerizable compound, but when the glass transition temperature before curing is less than 40 ° C., the reactive group is relatively easy to move even in the matrix, and it is efficient as a (meth) acrylate compound having a pentaerythritol skeleton. This is preferable because the curing reaction proceeds.
Specific examples of the radical polymerizable compound include urethane (meth) acrylate, polyester (meth) acrylate, and epoxy (meth) acrylate. These weight average molecular weights are preferably 300 to 10,000. If the weight average molecular weight is less than 300, bleeding out from the coating film is likely to occur, and it may ooze into the decorative layer or induce fluctuations in the coating film thickness. When the weight average molecular weight exceeds 10,000, the compatibility with the (meth) acrylate compound having a pentaerythritol skeleton may be lowered, or the scratch resistance of the resulting coating film may be lowered.

(Non-polymerizable thermoplastic resin)
When the curable resin layer used in the present invention contains a non-polymerizable thermoplastic resin in addition to the (meth) acrylate compound having the pentaerythritol skeleton and the radical polymerizable compound, the appearance and various aspects of the resulting hydraulic transfer body are as follows. It is preferable because the physical properties can be improved. A general-purpose thermoplastic resin can be used as the non-polymerizable thermoplastic resin. If the amount added is too large, the scratch resistance of the resulting coating film tends to decrease, so it is preferable to keep it to 70% or less. Of these, the use of a polyester resin is preferred because it can give a sense of depth.

(polyester)
As the polyester resin, a polyester resin having a weight average molecular weight of 30,000 to 70,000 is preferable. As the polyester resin used in the present invention, a polyester resin obtained by copolymerizing an aromatic or aliphatic dicarboxylic acid and an aromatic or aliphatic diol can be preferably used. Among them, a mixture of one or two or more polyester resins obtained by copolymerizing an aromatic or aliphatic dicarboxylic acid and an aliphatic diol is preferable, which is synthesized from an aromatic dicarboxylic acid and an aliphatic diol. A polyester resin mixture is preferred.

  A commercially available product may be used as the polyester resin synthesized from the aromatic dicarboxylic acid or the aliphatic dicarboxylic acid and the aliphatic diol, and the polyester resin synthesized from the aromatic dicarboxylic acid and the aliphatic diol. Byron 200, Byron 240, Byron 650, Byron GK880 (above, “trade name”, manufactured by Toyobo Co., Ltd.) Elitel XA-0611 (above, “trade name”, Unitika (Made by Co., Ltd.) is preferably used.

(Thermosetting resin)
The curable resin layer used in the present invention may be a photothermosetting type by using a thermosetting compound in addition to the (meth) acrylate compound having the pentaerythritol skeleton and the radical polymerizable compound. When the material to be transferred is a plastic having a low heat resistant temperature, the starting temperature of the thermal polymerization initiator is preferably as low as possible, and is preferably a temperature not exceeding 100 ° C. As the thermosetting compound, known compounds can be used. For example, N-methylol group, N-alkoxymethyl group, epoxy group, methylol group, acid anhydride having a functional group that is polymerized by the action of heat or catalyst. , Compounds having carbon-carbon double bonds, resins, and the like can be used.

(Photopolymerization initiator)
The curable resin layer may contain a conventional photopolymerization initiator or photosensitizer as necessary. Typical photopolymerization initiators include acetophenone compounds such as diethoxyacetophenone and 1-hydroxycyclohexyl-phenyl ketone; benzoin compounds such as benzoin and benzoin isopropyl ether; 2,4,6-trimethylbenzoin diphenylphosphine. Acylphosphine oxide compounds such as oxides; Benzophenone, o-benzoylbenzoic acid methyl-4-phenylbenzophenone compounds such as methyl-4-phenylbenzophenone; Thioxanthone compounds such as 2,4-dimethylthioxanthone; Amino compounds such as 4,4'-diethylaminobenzophenone Examples include benzophenone compounds.

  A photoinitiator is 0.5-15 mass% normally with respect to all the polymeric components, Preferably it is 1-8 mass%. Examples of the photosensitizer include amines such as triethanolamine and ethyl 4-dimethylaminobenzoate. Furthermore, onium salts such as benzylsulfonium salt, benzylpyridinium salt, and arylsulfonium salt are known as photocationic initiators, and these initiators can also be used, and are used in combination with the above-mentioned photoradical generators. You can also.

  The thicker the curable resin layer, the greater the protective effect of the resulting molded product, and the greater the effect of absorbing the irregularities of the decorative layer, so that the molded product can have excellent gloss. Therefore, the film thickness of the curable resin layer is specifically 3 μm or more, preferably 15 μm or more. When the thickness of the curable resin layer exceeds 200 μm, it is difficult to sufficiently activate the curable resin layer with an organic solvent. From the viewpoints of sufficient activation of the curable resin layer by the organic solvent, function as a protective layer for the decoration layer, absorption of unevenness of the decoration layer, and the like, the dry film thickness of the curable resin layer should be 3 to 200 μm. More preferably, it is 15-70 micrometers.

(Decoration layer Block isocyanate compound)
The decorative layer provided on the curable resin layer contains a blocked isocyanate compound. Although there is no restriction | limiting in particular as a block isocyanate compound, When the to-be-transferred material is a plastic etc. with low heat resistance, it is preferable that the dissociation temperature of a blocking agent is 70 to 130 degreeC. If it is less than 70 degreeC, there exists a possibility of dissociation by the temperature rise etc. in a preservation | save atmosphere during storage. In this case, diethyl malonate, 3,5-dimethylpyrazole, etc. can be used as the blocking agent. In order to lower the dissociation temperature of the blocking agent, a known catalyst such as aluminum tris (acetylacetonate) may be added. In order to accelerate the reaction between the regenerated isocyanate group and the hydroxyl group, a known catalyst such as dibutyltin dilaurate may be added to the curable resin layer. The blocked isocyanate compound is added to the printing ink or paint used for forming the decorative layer.

The decorative layer is usually a layer that is in direct contact with the transfer target during transfer.
The decoration layer may be composed of a single layer or a plurality of layers, and is usually composed of a plurality of layers when a pattern is formed. In the case of a decorative layer composed of a plurality of layers, the blocked isocyanate compound is not added to the layer that contacts the transferred object at the time of transfer, but is added to one or more layers other than the layer that contacts the transferred object at the time of transfer It is preferable to keep it. This method is particularly excellent in the adhesion between the transfer medium and the transfer film, and the effects of the present invention can be most effectively obtained. Specifically, a hydraulic transfer body can be obtained in which coating film defects such as swelling are not generated even when immersed in warm water at 60 ° C. for 500 hours or longer.

  The printing ink or paint used for forming the decorative layer of the present invention is preferably activated with an organic solvent so that sufficient flexibility can be obtained when the transfer layer is transferred to the transfer target. When used, a printing ink or paint that can be printed or coated on the peelable film and has a low peel strength from the peelable film is preferable. In particular, gravure printing ink is preferable. Further, a colored layer having no pattern or a colorless varnish resin layer can be formed by printing or coating as a part of the decorative layer.

  Varnish resins used for printing ink or paint are acrylic resin, polyurethane resin, polyamide resin, urea resin, epoxy resin, polyester resin, vinyl resin (vinyl chloride, vinyl acetate copolymer resin), vinylidene resin (vinylidene chloride, vinylidene fluoride) ), Thermoplastic resins such as ethylene-vinyl acetate resin, polyolefin resin, chlorinated olefin resin, ethylene-acrylic resin, petroleum resin, and cellulose derivative resin are preferably used.

(Colorant in the decoration layer)
The colorant in the decorative layer is preferably a pigment, and any of inorganic pigments and organic pigments can be used. It is also possible to use a metallic gloss ink containing a metal fine particle obtained from a paste of metal cutting particles or a deposited metal film as a pigment. As these metals, aluminum, gold, silver, brass, titanium, chromium, nickel, nickel chrome, stainless steel and the like are preferably used. These metal strips may be surface-treated with a cellulose derivative such as an epoxy resin, polyurethane, acrylic resin, or nitrocellulose in order to improve dispersibility, oxidation prevention, and ink layer strength.

(Method for forming decorative layer)
As a method for forming the decoration layer, offset printing, screen printing, ink jet printing, thermal transfer printing, and the like can be used in addition to gravure printing. It is preferable that the dry film thickness of a decoration layer is 0.5-15 micrometers, More preferably, it is 1-7 micrometers.

  Similarly to the curable resin layer, the decorative layer is preferably activated by an organic solvent to obtain sufficient flexibility for transfer. It is formed using gravure printing, offset printing, screen printing, ink jet printing, thermal transfer printing, or the like. It is preferable that the dry film thickness of a decoration layer is 0.5-15 micrometers, More preferably, it is 1-7 micrometers. A colored layer having no pattern and a colorless varnish resin layer can also be formed by coating.

  The decorative layer is formed by a method of coating or printing on a curable resin layer on a support, or a drying of a film having a curable resin layer formed on a support film and a film having a decorative layer on a peelable film. It can be laminated in a film for hydraulic transfer by a laminating method. Among these, lamination is preferable in the film for hydraulic transfer by the latter dry lamination method.

  In addition, the antifoaming agent, the anti-settling agent, the pigment dispersant, the fluidity modifier, the anti-blocking agent, the lubricant, and the antistatic agent in the curable resin layer and the decorative layer as long as the designability and spreadability are not impaired. Various conventional additives such as antioxidants, light stabilizers, ultraviolet absorbers, silica sols and organosilica sols can be added. These additives may be liquid or solid, and may be dissolved or only dispersed.

In addition to the curable resin layer and the decorative layer, the hydraulic transfer film of the present invention may be provided with other resin layers as long as the effects of the present invention are not impaired. For example, if necessary, a resin layer such as a known thermoplastic resin may be provided between the curable resin layer and the decorative layer for the purpose of improving adhesion, and activation described later In this case, a resin layer such as a thermoplastic resin containing an organic or inorganic pigment or resin fine particles may be provided for the purpose of suppressing excessive elongation of the decorative layer.

  The water pressure transfer film of the present invention can be subjected to water pressure transfer in the same manner as the water pressure transfer of a conventional water pressure transfer film.

(Method for producing hydraulic transfer body)
The method for producing a hydraulic transfer body of the present invention is such that the hydraulic transfer film of the present invention is floated on water with the support film down, and the transfer layer having a decorative layer and a curable resin layer is activated with an organic solvent. In this method, the transfer layer is hydraulically transferred to a transfer target, the support film is removed, and then the transfer layer is cured with light, and hydraulic transfer can be performed in the same manner as a conventional hydraulic transfer film. The outline of the manufacturing method of the hydraulic transfer body using the hydraulic transfer film is as follows.

(1) The hydraulic transfer film is floated on water in a water tank with the support film facing down, the transfer layer facing up, and the support film is dissolved or swollen with water.
(2) The transfer layer is activated by applying or spraying an activator to the transfer layer of the hydraulic transfer film.
The activation of the transfer layer with an organic solvent may be performed before the film is floated on water.
(3) While the transfer target is pressed against the transfer layer of the hydraulic transfer film, the transfer target and the hydraulic transfer film are submerged in water, and the transfer layer is brought into close contact with the transfer target by water pressure and transferred.
(4) The support film is removed from the transfer medium taken out of water, and after drying, the curable resin layer of the transfer layer transferred to the transfer medium is cured by light irradiation to obtain a hydraulic transfer body.

  The transfer layer of the hydraulic transfer film of the present invention comprising a curable resin layer and a decorative layer is activated by applying or spraying an organic solvent, and is sufficiently solubilized or softened. The activation mentioned here means that the transfer layer is solubilized without being completely dissolved by applying or spraying an organic solvent to the transfer layer, and the transfer layer is transferred to the transfer layer by providing flexibility. It means improving the followability and adhesion to the body. This activation may be performed to such an extent that when the transfer layer is transferred from the hydraulic transfer film to the transfer body, these transfer layers are softened and can sufficiently follow the three-dimensional curved surface of the transfer body.

  The water in the water tank in the hydraulic transfer functions as a hydraulic medium that swells or dissolves the support film and also causes the hydraulic transfer film to adhere to the three-dimensional curved surface of the transfer target when transferring the transfer layer. Specifically, water such as tap water, distilled water and ion exchange water may be used, and depending on the support film used, inorganic salts such as boric acid and alcohols may be dissolved in water within 10%. But you can.

(Activator)
The activator is an organic solvent that solubilizes the curable resin layer and the decorative layer and imparts flexibility. It is preferable not to evaporate until the hydraulic transfer process is completed. As the activator used in the present invention, an activator used for general hydraulic transfer can be used. Specifically, toluene, xylene, ethylbenzene, hexane, cyclohexane, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, propyl acetate, isobutyl acetate, 1-propanol, 2-propanol, 1-butanol, 2-butanol, ethyl Examples include cellosolve, cellosolve acetate, butyl cellosolve, carbitol, carbitol acetate, butyl carbitol acetate, sorbite acetate, and mixtures thereof.

  In order to improve the adhesion between the printing ink or paint and the molded product, this activator may contain some resin components. For example, adhesion may be increased by including 1 to 10% of an ink binder having a similar structure such as polyurethane, acrylic resin, or epoxy resin.

  For the same purpose, the above-mentioned radical polymerizable compound and photopolymerization initiator may be dissolved in the activator and used.

(Film removal, drying)
After the transfer layer is hydraulically transferred to the transfer target, the support film is removed by dissolving or peeling with water and drying. The support film is removed from the transfer target by dissolving or peeling the support film with a water flow in the same manner as in the conventional hydraulic transfer method.
It is preferable that the drying step is heat drying because drying can be performed in a short time and the blocking agent of the blocked isocyanate compound can be dissociated. The drying temperature at this time is preferably a temperature that does not exceed the heat resistance temperature of the base material so that the material to be transferred does not cause thermal deformation when the material to be transferred is a plastic having a low heat resistance temperature. In this case, it is preferable that the NCO dissociation temperature of the polymerizable compound (A) in the hydraulic transfer film to be used is designed to be in the range of 70 ° C. or higher and 130 ° C. or lower. When not heating at the time of a drying process, in order to dissociate a blocking agent, it is also possible to perform post-heating after light irradiation. Also in this case, it is preferable to carry out at a temperature not exceeding the heat-resistant temperature of the base material so as not to cause thermal deformation of the transferred body. For these, an oven or a drying furnace can be used.

  The curable resin layer is cured by light irradiation after drying water and the activator. The light is not particularly limited as long as it has a wavelength used for coating film curing in the field of paint and the like, but usually visible light or ultraviolet light is used. In particular, ultraviolet rays are suitable. As the ultraviolet light source, sunlight, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like is used.

(Molded product to be transferred)
It is preferable that the molded product to be transferred is sufficiently adhered to the surface of the curable resin layer or the decorative layer. For this reason, a primer layer is provided on the surface of the molded product as necessary. As the resin forming the primer layer, a conventional resin can be used as the primer layer without particular limitation, and examples thereof include a urethane resin, an epoxy resin, and an acrylic resin. Further, the primer treatment is not necessary for a molded product made of a resin component having a high solvent absorbability such as an ABS resin or SBS rubber having good adhesion. If the material of the molded product is even primed and has a level of waterproofness that will not cause a quality problem even if submerged in water, metal, plastic, wood, pulp mold, glass, etc. There is no particular limitation.

  Specific examples of molded products to which the present invention can be applied include household appliances such as televisions, videos, air conditioners, radio cassettes, mobile phones, refrigerators, OA equipment such as personal computers and printers, and other households such as petroleum fan heaters and cameras. Applicable to the housing part of the product. Also, furniture components such as tables, chests, and pillars, building materials such as bathtubs, system kitchens, doors, window frames, surrounding edges, writing utensils, calculators, electronic notebooks, cases and other miscellaneous goods, stationery, automobile interior panels, automobiles, etc. And motorcycle outer panels, wheel caps, ski carriers, car carrier bags, golf clubs, yachts and other ship parts, skis, snowboards, helmets, goggles, monuments, etc., and require design It is particularly useful for molded articles and can be used in a very wide range of fields.

  The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, “part” and “%” are based on mass.

(Production Example 1) <Wood pattern printing film P1>
On a 30 μm-thick Toyobo non-stretched polypropylene film, a printing ink G1 having the following composition was printed by gravure printing with a solid 2 plate and a pattern 3 plate to obtain a printing film P1.

(Ink composition G1, black, brown, white)
Bernock EZL676: 20 parts by mass (solid content conversion)
Pigment (black, brown, white): 10 parts by mass (solid content)
Additives such as wax: 10 parts by mass
Solvent: Duranate added to have a nonvolatile content of 30% MF-K60X: 3 parts However, Bernock EZL676 is a polyurethane manufactured by Dainippon Ink & Chemicals, Inc.
Duranate MF-K60X is a block isocyanate manufactured by Asahi Kasei Chemicals Corporation, and a solvent in which toluene, ethyl acetate, and methyl ethyl ketone were mixed at a ratio of 2: 1: 1 was used.

(Production Example 2) <Wood pattern printing film P2>
On a 30 μm-thick Toyobo non-stretched polypropylene film, a printing ink G2 having the following composition was printed by gravure printing with a solid 2 plate and a 3 pattern, and a printing film P2 was obtained.

(Ink composition G2, black, brown, white)
Bernock EZL676: 20 parts by mass (solid content conversion)
Pigment (black, brown, white): 10 parts by mass (solid content)
Additives such as wax: 10 parts by mass
Solvent: added so as to have a non-volatile content of 30%. However, Bernock EZL676 is a polyurethane manufactured by Dainippon Ink & Chemicals, Inc., and the solvent is a mixture of toluene, ethyl acetate, and methyl ethyl ketone in a ratio of 2: 1: 1. Solvent was used.

(Production Example 3) <Wood pattern printing film P3>
On the 30-micrometer-thick Toyobo unstretched polypropylene film, the wood grain pattern was printed by the gravure printing of the printing inks G1 and G2 in order of the following Table 1, and the printing film P3 was obtained.

(Production Example 4) <Wood pattern printing film P4>
On the 30-micrometer-thick Toyobo non-stretched polypropylene film, the wood grain pattern was printed by the gravure printing of the printing inks G1 and G2 in order of the following Table 1, and the printing films P3 and P4 were obtained.

(Examples 1-7, Comparative Examples 1-3)
The curable resin compositions C1 to C4 shown in Table 1 were prepared as curable resin layer compositions. The curable resin compositions C1 to C4 are applied to a 30 μm-thick PVA film manufactured by Aicero Chemical Co., Ltd. so as to have a solid film thickness of 20 μm with a lip coater, and then dried at 60 ° C. for 2 minutes. Manufactured. The curable resin layer of this film and the decorative layer of the printed film P1 or P2 produced in Production Example 1 or 2 were faced and laminated at 60 ° C. The laminated film was wound up as it was to produce hydraulic transfer films F1 to F6.

The film F1 to F6 for water pressure transfer after shading storage was floated in a 30 ° C. water bath with the ink surface facing up, and allowed to stand for 2 minutes, and then activator S: 30 g / m ² was sprayed on the film. After standing for 10 seconds, the water pressure was transferred from the vertical direction to the ABS bathroom panel. After the transfer, the transfer object was washed with water and dried at 90 ° C. for 30 minutes. Next, the bathroom panel having a glossy cured film was obtained by passing the bathroom panel once through a UV irradiation device (output: 160 W / cm, conveyor speed: 5 m / min).

Art Resin AH-51T: Acrylate Aronix M-305 having a pentaerythritol skeleton manufactured by Negami Kogyo Co., Ltd .: Pentaerythritol triacrylate Unidic 17-813 manufactured by Toagosei Co., Ltd .: Dainippon Ink & Chemicals, Inc. Polyurethane poly (meth) acrylate produced (solid content: 80%, weight average molecular weight: 1,500)
Elitel XA-0611: Polyester Irgacure 184 manufactured by Unitika Ltd. Photopolymerization initiator dilution solvent manufactured by Ciba Specialty Chemicals Co., Ltd. Mixed solvent of MEK, butyl acetate and toluene

(Testing method of transfer body)
The following various physical property tests were performed using the bathroom panel obtained in each Example.

(Water pressure transferability)
In the hydraulic transfer performed in the examples and comparative examples, “◯” indicates that there is no surface defect and the pattern reproducibility is good, and “x” indicates that the remarkable surface defect or pattern collapse occurred.

(Surface gloss evaluation)
According to JIS-K5400 “7.6 Specular Gloss”, 20 ° and 60 ° Specular Gloss were measured.

(Pencil hardness)
The pencil hardness of the coating film was measured using JIS-K5401 "Pencil scratch test machine for coating film". The length of the core was 45 degrees with a 3 mm coated cotton, the load was 1 kg, the scratching speed was 0.5 mm / min, the scratching length was 3 mm, and the pencil used was Mitsubishi Uni.

(Adhesion)
The ink adhesion of the sample that was hydraulically transferred to an ABS resin plate (flat plate: 100 mm × 100 mm × 3 mm) was evaluated according to the cross-cut tape method (JIS K5400) (full score of 10).

(Hot water resistance test)
The hydraulically transferred sample was held in warm water (water temperature 60 ° C.) for 300 hours, 400 hours, and 500 hours, respectively, and then the surface state of the hydraulic transfer member was visually observed and evaluated in the following three stages.
A: No blistering was observed at all.
○: Cannot be determined as bulge, but some appearance abnormality was observed Δ: Fine bulge was observed with loupe (5 times magnification) ×: bulge was observed with naked eyes

(Gloss retention after hot water resistance test)
The hydrostatically transferred sample was kept in warm water (water temperature 60 ° C.) for 300 hours and 500 hours, and then 60 degree gloss was measured with a gloss meter to calculate the gloss retention before and after the hot water treatment.

(Adhesion after hot water resistance test)
The hydraulically transferred sample is held in warm water (water temperature 60 ° C.) for 300 hours and 500 hours, and then 100 1 × 1 mm grids are made on the coating film with a cutter, and an adhesive tape is applied to the part, and then this adhesive The tape was peeled off rapidly, and the peeled state of the coating film was visually observed and evaluated in the following three stages.

(Double-circle): Peeling was not recognized at all.
○: 1 to 30% of the whole peeled off.
X: 31-100% of the whole peeled off.

In Examples 1 to 3, in which the curable resin layer contains a (meth) acrylate compound having a pentaerythritol skeleton and the ink layer contains a blocked isocyanate compound, the warm water resistance is good. Furthermore, Examples 4-7 which contain a block isocyanate compound in layers other than the layer which contacts a to-be-transferred object among multiple layers of decoration layers were able to maintain hot water resistance for 500 hours.
On the other hand, in Comparative Examples 1 and 2 in which the blocked isocyanate compound is not contained in the ink layer, the warm water resistance is poor. It was found that even when the curable resin layer did not contain (meth) acrylate having a pentaerythritol skeleton, there was no effect of improving warm water resistance (Comparative Example 3).

Claims (7)

A support film made of a water-soluble or water-swellable resin and a transfer layer that can be dissolved in an organic solvent provided on the support film, the transfer layer being a photocurable curable resin layer and a decorative layer A hydraulic transfer film, wherein the curable resin layer contains a (meth) acrylate compound having a pentaerythritol skeleton, and the decorative layer contains a blocked isocyanate compound. The curable resin layer contains 1) at least one thermoplastic resin selected from a polyester resin and an acrylic resin, and 2) a radical polymerizable compound having a weight average molecular weight of 300 to 10,000. Hydraulic transfer film. The hydraulic transfer film according to claim 1 or 2, wherein an isocyanate dissociation temperature of the blocked isocyanate compound is 70 ° C to 130 ° C. The decorative layer is composed of a plurality of decorative layers including a layer in contact with the transfer target, and any one or a plurality of layers other than the layer in contact with the transfer target contains a blocked isocyanate compound. The hydraulic transfer film according to any one of the above. The hydraulic transfer film according to claim 1 is floated on water with the support film down, the transfer layer is activated with an organic solvent, the transfer layer is transferred to a transfer target, and the support film is removed. A hydraulic transfer body, wherein the transfer layer is cured with light. The hydraulic transfer body according to claim 5, wherein after the support film is removed, heat drying is performed at 100 ° C. or lower. The hydraulic transfer body according to claim 5 or 6, wherein a material of the transfer body is plastic.