JP2007062320A - Hydraulic transfer film and hydraulic transfer body - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydraulic transfer film that can be excellently transferred to a member on conditions suitable for the member even if a material of a body to be transferred is a low heat-resistant member such as plastics, and also, is capable of completely preventing the occurrence of coating defects such as a blister even if a hydraulic transfer body obtained after the transfer is immersed into warm water at 60°C for more than three hundred hours. <P>SOLUTION: The hydraulic transfer film has a support film composed of a water-soluble or water-swelling resin and a transfer layer which can be dissolved in an organic solvent provided on the support film. The transfer layer has a curable resin layer curable by light and an ornament layer. The hydraulic transfer film is composed so that the curable resin layer includes (1) a (meth)acrylate compound having a pentaerythritol skeleton and a block isocyanate compound or (2) a polymerizable compound having a pentaerythritol skeleton, a block isocyanate group, and a (meth)acryloyloxy group. The hydraulic transfer body is formed by using the hydraulic transfer film. <P>COPYRIGHT: (C)2007,JPO&INPIT

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 decorative 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 of 60 to 90 ° C. for about 300 hours.
Since the material of the water-circulating member is usually plastic, 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 with dark ink when immersed in hot water of 60 to 90 ° C. for about 300 hours There has been a problem that coating film defects such as blisters occur.
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, (1) a (meth) acrylate compound having a pentaerythritol skeleton and a blocked isocyanate compound in the curable resin layer, or
(2) The above problem has been solved by including a polymerizable compound having a pentaerythritol skeleton and having a blocked isocyanate group and a (meth) acryloyloxy group.

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.

  As a constituent component of the curable resin layer, the present inventors have (1) a (meth) acrylate compound and a blocked isocyanate compound having a pentaerythritol skeleton, or (2) a pentaerythritol skeleton having a blocked isocyanate group and The said subject was solved by using the polymeric compound which has a (meth) acryloyloxy group, and using 2 types of crosslinking patterns together. Specifically, a cross-linking pattern for cross-linking an isocyanate group regenerated by dissociating a blocking agent of a blocked isocyanate group and a hydroxyl group in a curable resin layer or a decoration layer, and a cross-linking pattern by light irradiation are used in combination. By having a pentaerythritol skeleton, a hydraulic transfer body that does not cause blistering or the like can be obtained even in a dark color portion of a decorative layer that is difficult to transmit light, although the reason is not clear. 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 has (1) a (meth) acrylate compound and a blocked isocyanate compound having a pentaerythritol skeleton, or (2) a pentaerythritol skeleton. And a hydraulic transfer film containing a polymerizable compound having a blocked isocyanate group and a (meth) acryloyloxy group.

  Further, the present invention provides the above-mentioned hydraulic transfer film, 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 target, and the support After removing the film, a hydraulic transfer body is provided in which the transfer layer is cured with light.

  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 has (1) a (meth) acrylate compound having a pentaerythritol skeleton and a blocked isocyanate compound, or (2) a pentaerythritol skeleton having a blocked isocyanate group and (meth). A polymerizable compound having an acryloyloxy group (hereinafter, (2) a polymerizable compound having a pentaerythritol skeleton and having a blocked isocyanate group and a (meth) acryloyloxy group is abbreviated as a polymerizable compound (A)). It is characterized by that. Among these, a hydraulic transfer film in which the polymerizable compound (A) is contained in the curable resin layer is most effective and preferable.

(Polymerizable compound (A))
The polymerizable compound (A) used in the present invention is particularly preferably a polyfunctional (meth) acrylate having 2 to 5 (meth) acryloyloxy groups in one molecule.
The isocyanate group blocking agent is not particularly limited as long as it is a commonly used one. However, when the material to be transferred is a plastic having low heat resistance, the dissociation temperature of the blocking agent is preferably 70 ° C to 130 ° C. . 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 promote the reaction between the regenerated isocyanate and the hydroxyl group, a known catalyst such as dibutyltin dilaurate may be added to the curable resin layer or the decorative layer. (Blocking agent dissociation temperature of blocked isocyanate group is abbreviated as NCO dissociation temperature.)

The polymerizable compound (A) can be obtained by a known method. For example, aliphatic diisocyanate, pentaerythritol triacrylate, and diol are charged so that NCO / OH ≧ 1 (substance ratio) and reacted in a conventional manner, and then the remaining isocyanate group reacts with the blocking agent. Can be obtained by the following method. Moreover, these may use a commercial item.
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 addition amount of the polymerizable compound (A) is not particularly limited, but in order to obtain the effect of the present invention sufficiently, it is preferably added in the range of 20 to 100% by mass in the curable resin layer. 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.

((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. 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 blocked isocyanate compound used in the present invention may be a known one, and is not particularly limited. However, when the material to be transferred is a plastic having low heat resistance, the dissociation temperature of the blocking agent is 70 ° C to 130 ° C. Most preferred. 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 and the hydroxyl group, a known catalyst such as dibutyltin dilaurate may be added to the curable resin layer.

  The blending amount of the (meth) acrylate compound having a pentaerythritol skeleton and the blocked isocyanate compound into the curable resin layer is not particularly limited, but the (meth) acrylate compound having a pentaerythritol skeleton is 10 to 100% by mass, the block When the isocyanate compound is 0.1 to 5% by mass, the effects of the present invention are best obtained, which is preferable.

  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.

(Curable resin layer radical polymerizable compound)
The curable resin layer used in the present invention includes the (1) (meth) acrylate compound having a pentaerythritol skeleton and the blocked isocyanate compound, or (2) the polymerizable compound (A), and the curing of the present invention. A general-purpose radically polymerizable compound may be contained within a range not impairing the above. 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 within the matrix, so that the curing reaction with the polymerizable compound (A) is efficient. It is preferable because it goes forward.
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 film thickness fluctuation of the coating film. When the weight average molecular weight exceeds 10,000, the compatibility with the polymerizable compound (A) may decrease, or the scratch resistance of the resulting coating film may decrease.

(Curable resin layer non-polymerizable thermoplastic resin)
The curable resin layer used in the present invention is the (1) (meth) acrylate compound and block isocyanate compound having a pentaerythritol skeleton, or (2) the polymerizable compound (A) and the radical polymerizable compound, When a non-polymerizable thermoplastic resin is contained, the appearance and various physical properties of the obtained hydraulic transfer body can be improved, which is preferable. A general-purpose thermoplastic resin such as an acrylic resin or a polyester 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 is the (1) (meth) acrylate compound and block isocyanate compound having a pentaerythritol skeleton, or (2) the polymerizable compound (A) and the radical polymerizable compound, A thermosetting compound can be used in combination to form a photothermosetting type. 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.

  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.

(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 photocation initiators, and these initiators can also be used, and are used in combination with the above-mentioned photo radical generator. You can also.

(Decoration layer)
The printing ink or paint used for forming the decorative layer of the present invention is a printing ink or paint that can be printed on or applied to a peelable film, has a low peel strength from the peelable film, and is activated by an organic solvent. Thus, it is preferable that sufficient flexibility is obtained when the transfer layer is transferred to the transfer target, and gravure printing ink is particularly preferable. A colored layer having no pattern can also be formed by coating.
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.

  Unless detrimental to design and spreadability, antifoaming agent, anti-settling agent, pigment dispersant, fluidity modifier, anti-blocking agent, antistatic agent, antioxidant in curable resin layer and decorative layer Various conventional additives such as a light stabilizer and an ultraviolet absorber may be added.

  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, solfit 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 group can be dissociated. The drying temperature at this time is preferably a temperature that does not exceed the heat-resistant temperature of the substrate so as not to cause thermal deformation of the transfer object. 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 that does not exceed the heat resistance temperature of the substrate so as not to cause thermal deformation of the transfer target. 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)
The molded product to be transferred is preferably adhered sufficiently 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 “Pyrene CT”, 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 printed 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: 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 2) <Production of blocked isocyanate-containing urethane acrylate XA1>
In a toluene solvent, a reaction product (weight average molecular weight 21,000) obtained by reacting 8 molar equivalents of isophorone diisocyanate with 5 molar equivalents of pentaerythritol triacrylate at 60 ° C. has a residual isocyanate group equivalent to 3,5 -Dimethylpyrazole was reacted to obtain a blocked isocyanate-containing urethane acrylate XA1. XA1 had a weight average molecular weight of 23,000 and a solid content of 55%.

(Production Example 3) <Production of blocked isocyanate-containing urethane acrylate XA2>
A reaction product obtained by reacting 10 mol equivalent of hexamethylene diisocyanate, 3.5 mol equivalent of pentaerythritol triacrylate and 1.5 mol equivalent of 1,3-butanediol at 60 ° C. in a toluene solvent (weight average molecular weight 18, 000) was reacted with the remaining isocyanate group and an equivalent amount of 3,5-dimethylpyrazole to obtain a blocked isocyanate-containing urethane acrylate XA2. XA2 had a weight average molecular weight of 21,000 and a solid content of 55%.

(Examples 1-9)
The curable resin compositions C1 to C9 described in Tables 1 and 2 were prepared as curable resin layer compositions. These NCO dissociation temperatures (the temperature at which 80% or more is dissociated) were 80 ° C. The curable resin compositions C1 to C9 are applied to a 30 μm-thick PVA film manufactured by Aicero Chemical Co., Ltd. with a lip coater so as to have a solid film thickness of 20 μm, 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 produced in Production Example 1 were faced and laminated at 60 ° C. The laminated film was wound up as it was to produce hydraulic transfer films F1 to F9.

The hydraulic transfer films F1 to F9 after light-shielding storage were 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 onto 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).

Note) In Tables 1 and 2, the blending amount is expressed in terms of solid content.
Unidic 17-813: Polyurethane poly (meth) acrylate manufactured by Dainippon Ink & Chemicals, Inc. (solid content: 80%, weight average molecular weight: 1,500)
Aronix M-8530: Polyester acrylate manufactured by Toagosei Co., Ltd. (weight average molecular weight 1,200)
Aronix M-305: Pentaerythritol triacrylate paraloid A-60 manufactured by Toagosei Co., Ltd .: Acrylic resin manufactured by Rohm and Haas (Tg 100 ° C., weight average molecular weight 125,000)
Elitel XA-0611: Polyester duranate manufactured by Unitika Ltd. MF-K60X: Block isocyanate aluminum chelate A (W) manufactured by Asahi Kasei Chemicals Corporation Aluminum tris (acetylacetonate) manufactured by Kawaken Fine Chemicals Co., Ltd.
Irgacure 184: Photopolymerization initiator dilution solvent manufactured by Ciba Specialty Chemicals: C1-5 is toluene, C6-C8 is MEK, butyl acetate, toluene mixed solvent

(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, 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 ×: bulge was observed

(Gloss retention after hot water resistance test)
The hydraulically transferred sample was held in warm water (water temperature 60 ° C.) for 300 hours, and then the gloss retention rate before and after the hot water treatment was calculated by measuring 60 ° gloss with a gloss meter.

(Adhesion after hot water resistance test)
The hydraulically transferred sample is kept in warm water (water temperature 60 ° C.) for 300 hours, and then 100 100 × 1 mm grids are made on the coating film with a cutter. 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.

(Solvent resistance test)
Absorbent cotton containing MEK was rubbed 100 times with a rubbing tester under a load of 1 kg, and the surface of the coating film was observed.

(Abrasion resistance)
About the sample which carried out the hydraulic transfer to the ABS resin board (flat plate: 100mmx100mmx3mm) used by the adhesive test, the surface gloss retention after 100 times of dry wiping was evaluated with the rubbing tester (load 800g).

(Chemical resistance 1: Alcohol resistance)
For the sample that was hydraulically transferred to the ABS resin plate (flat plate: 100 mm × 100 mm × 3 mm) used in the adhesion test, a rubbing test (load 800 g, 100 reciprocations) was performed using absorbent cotton containing 1-butanol, The surface gloss retention after the test was measured.

(Chemical resistance 2: acid resistance / alkali resistance)
Measurement of surface gloss retention after immersion in a 5% aqueous acetic acid solution or 5% aqueous sodium hydroxide solution for 72 hours for a sample that was hydraulically transferred to an ABS resin plate (flat plate: 100 mm × 100 mm × 3 mm) used in the adhesion test did.

Examples 1 to 6 using the polymerizable compound (A) were excellent in hot water resistance and other physical properties. On the other hand, Comparative Examples 1 and 2, which are two-component systems of polyurethane poly (meth) acrylate and blocked isocyanate, could not improve hot water resistance.

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 having:
The curable resin layer is
(1) a (meth) acrylate compound having a pentaerythritol skeleton and a blocked isocyanate compound, or
(2) A hydraulic transfer film comprising a polymerizable compound having a pentaerythritol skeleton and having a blocked isocyanate group and a (meth) acryloyloxy group. The hydraulic transfer film according to claim 1, wherein the curable resin layer comprises (2) a polymerizable compound having a pentaerythritol skeleton and having a blocked isocyanate group and a (meth) acryloyloxy group. The curable resin layer contains a) at least one thermoplastic resin selected from a polyester resin, an acrylic resin, and the like, and b) a radical polymerizable compound having a weight average molecular weight of 300 to 10,000. The hydraulic transfer film as described. The hydraulic transfer film according to claim 1, wherein an isocyanate dissociation temperature of the polymerizable compound having a pentaerythritol skeleton and having a blocked isocyanate group and a (meth) acryloyloxy group is 70 to 130 ° C. 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, wherein a material of the transfer body is plastic.