JP2006231605A - Water pressure transfer film and water pressure transfer body - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydraulic transfer film which can well make a hydraulic transfer medium having excellent stainproofness without spray coating. <P>SOLUTION: This hydraulic transfer film comprises a support film made of a water-soluble or water swelling resin and a transfer layer which is formed on the support film and can be dissolved in an organic solvent. The transfer layer has a curable resin layer which is curable by at least either one of exposure to active energy radiation or heating, and the curable resin layer contains a polymerizable compound with an organosiloxy group and/or a fluoroalkyl group. <P>COPYRIGHT: (C)2006,JPO&NCIPI

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 comprising a support film made of a water-soluble or water-swellable resin and a transfer layer including a decorative layer is floated on the water surface with the support film facing downward, and an activator and In this method, after the transfer layer is softened with a so-called organic solvent, the transfer layer is transferred to the transfer object by being submerged in water while pressing the transfer object from above. Thereby, the decoration layer rich in design property can be provided to the molded product of a complicated three-dimensional shape.

  Usually, the decorative layer is made of printing ink or paint and is inferior in durability. Therefore, for the purpose of protecting the decorative layer, a protective layer is provided on the molded product after hydraulic transfer by spray coating or the like. However, there are problems that the two-step process of spray coating after water pressure transfer is complicated, and that the cost for the spray coating process is high because a coating equipment is required in addition to the water pressure transfer equipment.

On the other hand, a hydraulic transfer film in which a surface protective layer made of a polymer having a radically polymerizable unsaturated group and a glass transition temperature of 0 to 250 ° C. and a decorative layer are provided in advance as a transfer layer is disclosed (for example, , Patent Document 1 and Patent Document 2). After the hydraulic transfer, the surface protective layer and the decorative layer can be applied to the transfer object only by the hydraulic transfer method by curing the surface protective layer with ionizing radiation or heat.
However, although the hydraulic transfer film described in the publication is excellent in solvent resistance, surface hardness, etc., when the hydraulic transfer member is applied to a housing of a household electric appliance, the antifouling property tends to be inferior. .

As general-purpose additives for imparting antifouling properties to paints and the like, fluorine-based additives and silicon-based additives are known, but when the additives are added to the curable resin layer of a hydraulic transfer film, There have been problems such as phase separation, whitening due to bleeding, etc., or no antifouling property obtained even if they are dissolved.
Japanese Patent Laid-Open No. 64-22378 (Japanese Patent Publication No. 7-29084) JP 2004-34393 A

  An object of the present invention is to provide a hydraulic transfer film which gives a hydraulic transfer body excellent in antifouling properties without spray coating.

  The present inventors have found that the above problem can be solved by adding a fluorine-based compound having a polymerizable group or a silicon-based compound to the curable resin layer.

  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 irradiated with active energy rays and heated. A hydraulic transfer film having a curable resin layer curable with at least one kind, wherein the curable resin layer contains a polymerizable compound having an organosiloxy group and / or a fluoroalkyl group. To do.

  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.

  In the present invention, since a fluorine compound having a polymerizable group or a silicon compound is used, bleeding of the antifouling component can be prevented, and the antifouling property can be exhibited continuously.

(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 has a curable resin layer (hereinafter referred to as curable resin layer) that can be cured by irradiation with active energy rays or heating. The transfer layer has a curable resin layer and a decorative layer (hereinafter referred to as a decorative layer) made of a printing ink film or a paint film provided thereon. The curable resin layer in the present invention is not cured at room temperature but is cured by irradiation with active energy rays or heating to form a cured resin layer.

(Curable resin layer)
The curable resin layer contains a polymerizable compound having an organosiloxy group and / or a fluoroalkyl group (hereinafter referred to as component A).

(Polymerizable compound having an organosiloxy group)
Examples of the polymerizable functional group possessed by the polymerizable compound (component A) having an organosiloxy group and / or a fluoroalkyl group include radical polymerizable groups such as a (meth) acryloyl group, a vinyl group, a vinyloxy group, and a maleimide group, And cationically polymerizable groups such as epoxy groups. Of these, a radical polymerizable group is preferable, and a (meth) acryloyl group is most preferable.

  In the polymerizable compound having an organosiloxy group used in the present invention, the organosiloxy group is a general term for groups having at least two basic structural units as shown below.

  For example, specific examples of the organosiloxy group having a repeating structure of the D unit include the following structures. (R is a positive integer)

  Specific examples of the organosiloxy group having a repeating structure of T units include the following structures. (S is a positive integer)

Specifically, the organic group R represents an alkyl group, an aryl group, a polyether group, or a fluoro group. The alkyl group may be linear, branched or cyclic, and in particular, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, It can be selected from cyclopentyl and cyclohexyl groups and other similar groups. A methyl group is particularly preferred. As the aryl group, a phenyl group is preferable. Polyether groups include polyoxyethylene groups, polyoxypropylene groups, or polyoxyethylene / polyoxypropylene groups. Examples of the fluoro group include a linear, branched or cyclic alkyl group, or an alkenyl group having one or more fluorine atoms as a substituent.
The number of the basic structural units is in the range of 2 to 30,000, preferably 2 to 10,000.

  As the polymerizable compound having an organosiloxy group used in the present invention, an organopolysiloxy group-containing urethane (meth) acrylate oligomer is preferably used. The organopolysiloxy group-containing urethane (meth) acrylate oligomer can be obtained by adding an organopolysiloxy group-containing alcohol and a hydroxyl group-containing (meth) acrylate to an organic polyisocyanate.

  The organopolysiloxy group-containing alcohol is preferably an organopolysiloxy group-containing monool and / or an organopolysiloxy group-containing polyol. The organic polyisocyanate and hydroxyl group-containing (meth) acrylate constituting the urethane (meth) acrylate resin derived from this monool and the urethane (meth) acrylate resin derived from this polyol are the same or different. Also good.

This monool-derived urethane (meth) acrylate resin is obtained by subjecting 10 equivalents of an organic polyisocyanate and 0.1 to 6 equivalents of an organopolysiloxy group-containing monool to addition reaction at 60 to 120 ° C. for several hours. It is obtained by adding 5 to 11 equivalents of acrylate followed by addition reaction for several hours, and reacting until a part of the reaction solution is subjected to IR spectrum measurement until the absorption peak of the isocyanate group of 2260 to 2280 cm ⁻¹ disappears. . Similarly, the polyol-derived urethane (meth) acrylate resin is obtained from 10 equivalents of an organic polyisocyanate, 3 to 7 equivalents of an organopolysiloxy group-containing polyol, and 2 to 8 equivalents of a hydroxyl group-containing (meth) acrylate.

  Examples of the raw material organic polyisocyanate include tetramethylene-1,4-diisocyanate, pentamethylene-1,5-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethyl-hexamethylene-1,6-diisocyanate, lysine diisocyanate, Examples include isophorone diisocyanate, 1,3-bis (isocyanatomethyl) -cyclohexane, 4,4′-dicyclohexylmethane diisocyanate, and their isocyanurates.

  Examples of the raw material organopolysiloxy group-containing alcohol include organopolysiloxy group-containing monools exemplified by dialkyl silicone monoalkyl alcohols; organopolysiloxy group-containing polyols exemplified by dialkyl silicone dialkyl alcohols and dialkyl silicone tetraalkyl alcohols. . Examples of the alkyl group in these alkyl silicones include a methyl group, an ethyl group, a propyl group, and a butyl group. The molecular weight of the organopolysiloxy group-containing alcohol is several hundred to several tens of thousands depending on the degree of polymerization of the alkyl silicone. The number average molecular weight of the organopolysiloxy group-containing alcohol is preferably 500 to 50,000. These may be commercially available, and examples include both end silaplanes and one end silaplanes (both are trade names manufactured by Chisso Corporation).

  The raw material hydroxyl group-containing (meth) acrylate is, for example, (meth) acrylic acid ethylene oxide adduct, (meth) acrylic acid propylene oxide adduct, (meth) acrylic acid glycidyl (meth) acrylate adduct, Addition of methylolpropane di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, glycerin ethylene oxide or propylene oxide (Meth) acrylate, pentaerythritol ethylene oxide or propylene oxide adduct tri (meth) acrylate, ditrimethylolpropane ethylene oxide or propylene oxide adduct Tri (meth) acrylate, penta (meth) acrylate of an adduct of ethylene oxide or propylene oxide dipentaerythritol.

(Polymerizable compound having a fluoroalkyl group)
The polymerizable compound having a fluoroalkyl group has a perfluoroalkyl group having 1 to 20 carbon atoms, or a fluoroalkyl group having 1 to 20 carbon atoms in which some of these fluorine atoms are substituted with hydrogen atoms. For example, perfluoromethylmethyl (meth) acrylate, perfluoroethylmethyl (meth) acrylate, 2-perfluorobutylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorooctyl ethyl ( (Meth) acrylate, 2-perfluoroisononylethyl (meth) acrylate, 2-perfluorononylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, perfluoropropylpropyl (meth) acrylate, perfluorooctylpropyl ( Perf having a C1-C20 perfluoroalkyl group such as (meth) acrylate, perfluorooctyl amyl (meth) acrylate, perfluorooctylundecyl (meth) acrylate, etc. Oroalkyl alkyl (meth) acrylates, and fluoroalkyl (meth) acrylates having a C1-C20 fluoroalkyl group in which some of these fluorine atoms are substituted with hydrogen atoms, perfluorobutylethylene, perfluorohexylethylene Perfluoroalkyl such as perfluorooctylethylene and perfluorodecylethylene, alkylenes, and fluoroalkyls and alkylenes in which some of these fluorine atoms are substituted with hydrogen atoms can be used.

  The ratio of the polymerizable compound having an organosiloxy group and / or fluoroalkyl group to the total amount of the polymerizable compound in the curable resin layer is preferably in the range of 9 to 70% by mass in terms of percentage. When the polymerizable compound having an organosiloxy group and / or a fluoroalkyl group is less than 9% by mass, the antifouling property is slightly inferior, and when it is 70% by mass or more, the haze increases and the transparency may decrease. Among these, the range of 10% to 65% by mass is preferable.

(Radically polymerizable compound)
The curable resin layer used in the present invention is cured by irradiation with active energy rays or heating. Therefore, it is preferable to contain a general-purpose radical polymerizable compound. Among them, (meth) acrylate is preferable because of its excellent curability, and polyfunctional (meth) acrylate having 2 to 15 (meth) acryloyl groups in one molecule is particularly preferable. Although there is no particular limitation on the radically polymerizable compound, 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 has the aforementioned organosiloxy group and / or fluoroalkyl group. This is preferable because the curing reaction efficiently proceeds with the polymerizable compound.
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 5,000.

(Urethane (meth) acrylate)
Urethane (meth) acrylate is (meth) acrylate having a urethane bond in the molecule, and can be obtained by reacting a hydroxyl group-containing (meth) acrylate, polyisocyanate, and polyol. Depending on the purpose, it is also possible to use urethane (meth) acrylate composed of hydroxyl group-containing (meth) acrylate and polyisocyanate without using polyol as a raw material. Of course, you may use commercially available urethane (meth) acrylate.

(Polyester (meth) acrylate)
The polyester (meth) acrylate used in the present invention is a saturated or unsaturated polyester (meth) acrylate having at least two (meth) acryloyl groups in one molecule. For example, polybasic acid or its anhydride, polyol, polyester (meth) acrylate obtained by esterifying (meth) acrylic acid or its anhydride, polyester (meth) acrylate consisting of polyol and (meth) acrylic acid or its anhydride And polyester (meth) acrylate obtained by reacting a carboxyl group of a polyester synthesized by a conventional method with a (meth) acrylate having an epoxy group. Of course, you may use commercially available polyester (meth) acrylate.
As the polybasic acid, for example, an aromatic polybasic acid, a chain aliphatic polybasic acid, a cyclic aliphatic polybasic acid and the like can be used. As the polyol, for example, an alkylene polyol can be used.

(Epoxya (meth) acrylate)
Epoxy (meth) acrylate is (meth) acrylate obtained by reacting polyepoxide with (meth) acrylic acid or its anhydride. Examples of the polyepoxide include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, and the like, and hydrogenated aromatic rings of bisphenol type epoxy resin. As the epoxy (meth) acrylate, bisphenol A type epoxy acrylate is preferable. Of course, you may use commercially available epoxy (meth) acrylate.

(Polyether (meth) acrylate)
The polyether (meth) acrylate is, for example, (meth) acrylate obtained by esterifying polyether and (meth) acrylic acid or its anhydride. Examples of polyethers that can be used include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and other branched alkyl polyols, combinations of bisphenol A skeletons, polysiloxane chains, and the like.

(Non-polymerizable thermoplastic resin)
When the curable resin layer used in the present invention contains a non-polymerizable thermoplastic resin in addition to the polymerizable compound having an organosiloxy group and / or a fluoroalkyl group and a radical polymerizable compound, a hydraulic transfer body is obtained. The appearance and various physical properties can be improved. As the non-polymerizable thermoplastic resin, a general-purpose thermoplastic resin can be used. However, when it is a (meth) acrylic resin, the drying property of the curable resin layer can be improved, and transparency and solvent resistance can be imparted. A polyester resin is preferable because it can give a sense of depth and flexibility.

((Meth) acrylic resin)
The (meth) acrylic resin is preferably a (meth) acrylic resin having a weight average molecular weight of 70,000 to 250,000. Among these, poly (meth) acrylate is preferable because it has a high Tg and is suitable for improving the drying property of the curable resin layer. In particular, a poly (meth) acrylate having a polymethyl methacrylate as a main component and a weight average molecular weight of 100,000 to 200,000, more preferably 100,000 to 150,000 is preferable in terms of excellent transparency, solvent resistance, and scratch resistance.
Moreover, as a copolymer component of poly (meth) acrylate, a carboxyl group-containing radical polymerizable monomer such as (meth) acrylic acid is used, and the acid value of the polymer is adjusted to about 1 to 10, thereby supporting the support. The adhesion to the film and the adhesion between the transfer target and the curable resin layer can be improved.

(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, and Elitel XA-0611 are preferably used from the viewpoint that desirable physical properties of the coating film can be easily obtained.

  When the curable resin layer contains a thermoplastic resin, it is preferable that the blending ratio satisfies the following three conditions at the same time because the effect of the thermoplastic resin can be expressed more.

Condition 1) The curable resin layer contains 80% by mass or more in total of three components of a polymerizable compound having an organosiloxy group and / or a fluoroalkyl group, a non-polymerizable thermoplastic resin, and a radical polymerizable compound. 2) The curable resin layer contains a non-polymerizable thermoplastic resin in an amount of 30% by mass to 75% by mass.
Condition 3) The ratio of the polymerizable compound having an organosiloxy group and / or a fluoroalkyl group to the total amount of the polymerizable compound in the curable resin layer is in the range of 9 to 70% by mass in terms of percentage.

  When the curable resin layer contains a polymerizable compound having the organosiloxy group and / or fluoroalkyl group, a radical polymerizable compound, and a non-polymerizable thermoplastic resin, the radical polymerizable compound is an epoxy (meth) acrylate. Polyester (meth) acrylate, urethane (meth) acrylate, or polyether (meth) acrylate is preferable, and the non-polymerizable thermoplastic resin is preferably an acrylic resin or a polyester resin.

  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.

  The photopolymerization initiator is usually added in an amount of 0.5 to 15% by mass, preferably 1 to 8% by mass, based on the active energy ray-curable resin used. 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.

(Active energy rays)
The active energy ray means visible light, ultraviolet ray, electron beam, and gamma ray, and any of them can be used, but ultraviolet ray is particularly preferable. 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.

  In the polymerization reaction, alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve and ethyl cellosolve, esters such as methyl cellosolve acetate and ethyl celloacetate, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone Aromatic compounds such as benzene, toluene, chlorobenzene and dichlorobenzene can be used as the reaction solvent. In the polymerization reaction, hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, 4-methylquinoline, phenothiazine, or the like may be allowed to coexist in the reaction system as a polymerization inhibitor.

(Decoration layer)
The hydraulic transfer film of the present invention may be provided with a decorative layer in addition to the curable resin layer. The printing ink or paint used for the decorative layer is preferably activated by an organic solvent to obtain sufficient flexibility for transfer. After drying of the curable resin layer, the decorative layer is preferably printed by using gravure printing ink. Is preferably formed.

  Base resin used for printing ink or paint is acrylic resin, polyurethane resin, polyamide resin, urea resin, epoxy resin, polyester resin, vinyl resin (vinyl chloride, vinyl acetate, vinyl chloride-vinyl acetate copolymer resin), vinylidene resin (vinylidene) Chloride, vinylidene fluoride), ethylene-vinyl acetate resin, polyolefin resin, chlorinated olefin resin, ethylene-acrylic resin, petroleum-based resin, cellulose derivative resin, and other thermoplastic resins, among which polyurethane resin, polyester resin, vinyl chloride resin are used. -A vinyl acetate copolymer resin is preferably used since it is excellent in solubility in an organic solvent, fluidity, pigment dispersibility, and transferability, and a polyurethane resin is particularly preferable.

  The colorant used in the printing ink or paint 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. These metals include aluminum (Al), gold (Au), silver (Ag), brass (Cu—Zn), titanium (Ti), chromium (Cr), nickel (Ni), nickel chrome (Ni—Cr). Stainless steel (SUS) or the like is preferably used. These metal strips may be surface-treated with a cellulose derivative such as epoxy resin, polyurethane, acrylic resin, nitrocellulose, etc. in order to improve dispersibility, oxidation prevention and strength of the ink layer.

The decorative layer
1) A method of coating or printing on a curable resin layer on a support,
Or
2) It can be provided by a method of dry laminating a film having a curable resin layer formed on a support film and a film having a decorative layer on a peelable film.

  When coating or printing on the curable resin layer on the support of 1), appropriateness for coating or printing such as wettability of the surface of the curable resin layer is required.

  When the decorative layer is formed on the release film in advance in 2), a method of laminating by dry lamination of the film having the decorative layer on the peelable film and the film having the curable resin layer formed on the support film is available. preferable.

  In the step of bonding a film having a curable resin layer on a support and a film having a decorative layer on a peelable film, the heat resistance of the support film including the PVA film is generally low, and 130 When pasting at a temperature exceeding ℃, problems such as film shrinkage and laminating wrinkles are likely to occur. Therefore, drying of the film (A) and pasting by heating and pressing are performed in a temperature range of 40 to 120 ° C. It is preferable to carry out in a temperature range of 40 to 100 ° C.

  The decorative layer is formed on the peelable film or the curable resin layer formed on the support film by using offset printing, screen printing, ink jet printing, thermal transfer printing or the like 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. A colored layer having no pattern and a colorless varnish resin layer can also be formed by coating.

  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.

  The production of the hydraulic transfer film of the present invention is preferably carried out using a dry laminator. That is, a film in which a support is mounted on one feeding roll (first feeding roll) of a dry laminator, and a decorative layer having a pattern is printed on a peelable film in advance on the other feeding roll (second feeding roll). Wear (Y). An organic solvent solution of the curable resin is applied to the surface of the water-soluble or water-swellable resin layer of the support film fed from the first feed roll, and further dried by a drier to be curable resin on the support film. A film (X) having a layer formed thereon is obtained. Next, the curable resin layer of the film (X) and the decorative layer of the film (Y) fed out from the second feeding roll are overlaid so as to face each other, and bonded together with a thermocompression-bonding roll and wound around a winding roll. By being taken, the hydraulic transfer film of the present invention is manufactured.

  To apply the organic solvent solution of the curable resin to the support film, a slit reverse coater, die coater, comma coater, bar coater, knife coater, gravure coater, gravure reverse coater, micro gravure coater, flexo coater, blanket coater A roll coater, an air knife coater or the like can be used.

  In addition, by using a support laminated on a peelable film, the coating or printing substrate is hardly affected by sagging and has good dimensional stability. The film thickness can be precisely controlled.

  The production of the film (Y) having a decorative layer on the peelable film may be applied but is preferably carried out by printing. In particular, when printing a pattern, gravure printing, flexographic printing, offset printing or silk printing is preferred. . A decorative layer is applied or printed on the peelable film and then dried to obtain a film (Y).

(Peelable film)
Examples of the peelable film that can be used in the present invention include polyolefin films such as polypropylene and polyethylene, polyester films, films made of nylon or polyvinyl chloride, and polyolefin films that are relatively inexpensive and easy to recycle are particularly preferable. preferable. The thickness of the film is preferably 0.5 μm to 250 μm from the viewpoint of appropriate adhesion to the decorative layer and strength during printing.
Moreover, it is also possible to further adjust the maximum peeling force by performing a surface treatment on the peelable film as necessary.

  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 molded article having a curable resin layer of the present invention or a decorative layer and a curable resin layer is obtained by floating the hydraulic transfer film of the present invention on water with the support film down, and using an organic solvent. After activating the transfer layer having the curable resin layer or the decorative layer and the curable resin layer, the transfer layer is hydraulically transferred to the transfer target, the support film is removed, and then the transfer layer is irradiated with active energy rays. It is a method of curing, and water pressure transfer can be performed by the same method as a conventional water pressure transfer film. The outline of the manufacturing method of the decorative molded product 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 composed of the curable resin layer and the decorative 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 transferred material taken out of water, and the curable resin layer of the transferred layer transferred to the transferred material is cured by irradiation with active energy rays, so that the curable resin layer or the curable resin layer is obtained. A molded article having a decorative layer is obtained.

  The transfer layer of the hydraulic transfer film of the present invention comprising the curable resin layer or the curable resin layer and the 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 and imparts flexibility to the cured resin layer or the curable resin layer and the decorative layer. 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.

  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.

  The curable resin layer is cured by irradiation with active energy rays after drying water and the activator. Although the curing time depends on the composition and the type of curing agent, it is preferable in the process that curing proceeds within a few minutes to 1 hour.

(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 components 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.

  EXAMPLES 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) <Lattice pattern printing film P2>
On the unstretched polypropylene film “Pyrene CT” made by Toyobo with a thickness of 50 μm, print the printing ink G2 of the following composition by gravure printing with a thickness of 4 g (solid content) / m ² in 3 plates. Thus, a checkered print film P2 was produced.
<Composition of printing ink G2, black, yellow, white>
Polyurethane (Bernock EZL676 manufactured by Dainippon Ink Co., Ltd.): 20 parts by mass, pigment (black, yellow, white): 10 parts by mass, ethyl acetate / toluene (1/1): 60 parts by mass, and additives such as wax: 10 parts by mass Department.

(Production Example 3) <Production Example of Organopolysiloxy Group-Containing Urethane (Meth) acrylate Resin (XA1)>
117.3 parts by weight of dismodule H (trade name: 84 g / eq, manufactured by Sumitomo Bayer Urethane Co., Ltd.), which is hexaethylene diisocyanate, in a four-necked flask equipped with a stirrer, thermometer, condenser, and dropping funnel, both ends X-22-160AS (trade name: 482 g / eq, manufactured by Shin-Etsu Silicone Co., Ltd.), which is a polysiloxane skeleton-containing alcohol, was charged with 336.5 parts by weight, reacted at 70-80 ° C. for 7 hours, and then partially hydroxylated. Add 800 parts by weight of light acrylate DPE-6A (trade name: 1150 g / eq, manufactured by Kyoeisha Chemical Co., Ltd.), which is dipentaerystol hexaacrylate, and 5 drops of dibutyltin dilaurate, and further at 70 to 80 ° C. After reacting for 8 hours, the peak of the isocyanate group at 2270 cm ⁻¹ disappears in IR, and the desired organopolysiloxy group It was judged that the containing urethane acrylate resin was obtained.

(Production Example 4) <Production example of organopolysiloxy group-containing urethane (meth) acrylate resin (XA2)>
In a four-necked flask equipped with a stirrer, thermometer, condenser, and dropping funnel, 6.2 parts by weight of hexamethylene diisocyanate and Silaplane FM-0421 (organopolysiloxy group-containing monool having a hydroxyl group at one end) 60 parts by weight of trade name: 5400 g / eq) manufactured by Chisso Corporation, 1 drop of dibutyltin dilaurate is added, and after reacting at 75-80 ° C. for 1 hour, light acrylate PE which is pentaerythritol triacrylate -3A (trade name: 498.3 g / eq, manufactured by Kyoeisha Chemical Co., Ltd.) and 3 drops of dibutyltin dilaurate were added, and the mixture was further reacted at 75-80 ° C for 6 hours. It was judged that the desired organopolysiloxy group-containing urethane acrylate resin was obtained by the disappearance of the absorption peak of the isocyanate group at 2250 cm −1 in the infrared absorption spectrum measurement method.

(Production Example 5) <Production Example of Organopolysiloxy Group-Containing Urethane (Meth) acrylate Resin (XA3)>
A four-necked flask equipped with a stirrer, thermometer, condenser, and dropping funnel was charged with 12.2 parts by weight of hexaethylene diisocyanate and silaplane FM-0411, which is an organopolysiloxy group-containing monool having a hydroxyl group at one end. 21.8 parts by weight of a product name manufactured by Chisso Corporation: 1100 g / eq), 1 drop of dibutyltin dilaurate was added and reacted at 75-80 ° C. for 1 hour, then light acrylate PE-3A (Kyoeisha Chemical) (Product name: 498.3 g / eq) 66.0 parts by weight and 1 drop of dibutyltin dilaurate were added, and further reacted at 75-80 ° C. for 6 hours. It was judged that the desired organopolysiloxy group-containing urethane acrylate resin was obtained by disappearance of the absorption peak of the isocyanate group at 2250 cm ^{−1 in} the infrared absorption spectrum measurement method.

(Production Example 6) <Production Example of Silicone Modified Polyester (XA4) Having Polymerizable Group>
In a flask equipped with a temperature controller, a nitrogen inlet tube, and a stirrer (double helical blade), 236 parts of dimethyl isophthalate, 38 parts by weight of dimethyl terephthalate, 89 parts by weight of dimethyl glutarate, 21 parts by weight of neopentyl glycol, Kurapol P -0510 (manufactured by Kuraray Co., Ltd., poly-3-methylhexanediol adipate) 29 parts by weight, 35 parts by weight of trimethylolpropane and 2.4 parts of calcium acetate as a catalyst were charged at 180 ° C. for 2 hours under nitrogen inflow. Stirring was continued while removing methanol. Subsequently, 440 parts of modified polysiloxane (Shin-Etsu Chemical Co., Ltd. KF-6003) and 1.0 part of tetrabutyl titanate were added as a catalyst. Furthermore, the reaction was allowed to proceed at 210 ° C. for 2 hours while removing excess distillate such as ethylene glycol under a reduced pressure of 130 Pa. Next, the pressure was reduced to 13 Pa while slowly raising the temperature to 300 ° C., and the mixture was reacted for 1 hour to obtain a silicone-modified polyester (XA4M).
To a 1 L separable flask, 250 g of the obtained silicone-modified polyester (XA4M), 300 g of toluene / 2-butanone = 1/1 mixed solvent, and 0.3 g of dibutyltin dilaurate were added and stirred at 40 ° C. To this solution, 41.0 g of 2-acryloyloxyethyl isocyanate (manufactured by Showa Denko KK, trade name: Karenz AOI) was added dropwise at a temperature of 40 to 50 ° C. over 2 hours while paying attention to heat generation. After dropping, the mixture was stirred as it was at 40 to 50 ° C. for 1 hour, further heated up and stirred at 70 to 80 ° C. for 3 hours, and the NCO value (representing the remaining isocyanate group in weight%. NCO value is DIN 53). 185, measured in accordance with ASTM D 1638.) was 0.1% or less. The resulting radical polymerizable compound (XA4) solution had a solid content of 55%.

Example 1
A curable resin composition C1 was 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 40 μm, and then dried at 60 ° C. for 2 minutes to produce a film. The composition of the curable resin composition C1 is shown in Table 1. 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 a hydraulic transfer film F1.
This hydraulic transfer film F1 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: 40 g / m ² was sprayed onto the film. Further, after standing for 10 seconds, water pressure was transferred from the vertical direction to the primer-treated galvanized steel sheet (petroleum fan heater housing). After the transfer, the transfer object was washed with water and dried at 90 ° C. for 20 minutes. Next, the sample was passed once through a UV irradiation device (output: 160 W / cm, conveyor speed: 5 m / min) to obtain a hydraulic transfer body having a glossy cured film.

(Examples 2 to 8)
Hydraulic transfer films F2 to F8 were produced in the same manner as in Example 1 except that the curable resin composition C1 in Example 1 was changed to the curable resin compositions C2 to C8 shown in Tables 1 and 2. Further, the obtained hydraulic transfer films F2 to F8 were hydraulically transferred in the same manner as in Example 1, the transfer target was washed with water, and dried at 90 ° C. for 20 minutes. Next, the sample was passed once through a UV irradiation device (output: 160 W / cm, conveyor speed: 5 m / min) to obtain a hydraulic transfer body having a glossy cured film.

(Comparative Examples 1-4)
Hydraulic transfer films F51 to F54 were produced in the same manner as in Example 1 except that the curable resin composition C1 in Example 1 was changed to the curable resin compositions C51 to C54 shown in Table 3. Further, the obtained hydraulic transfer films F51 to F54 were hydraulically transferred in the same manner as in Example 1, and the transfer target was washed with water and dried at 90 ° C. for 20 minutes. Next, the sample was passed once through a UV irradiation device (output: 160 W / cm, conveyor speed: 5 m / min) to obtain a hydraulic transfer body having a glossy cured film.

NK Oligo EA-1020: Epoxy acrylate Unidic 17-813 manufactured by Shin-Nakamura Chemical Co., Ltd .: Polyurethane poly (meth) acrylate manufactured by Dainippon Ink & Chemicals, Inc. (solid content: 80%, weight average molecular weight: 1, 500)
M-8530: Toagosei Co., Ltd. polyester acrylate (weight average molecular weight 1,200)
Byron GK880: Polyester manufactured by Toyobo Co., Ltd. (weight average molecular weight 54,000, Tg = 84 ° C.)
Byron 240: Polyester manufactured by Toyobo Co., Ltd. (weight average molecular weight 41,000, Tg = 60 ° C.)
Irgacure 184: Photopolymerization initiator dilution solvent manufactured by Ciba Specialty Chemicals: Mixed solvent of MEK, butyl acetate, and toluene

V8F: Osaka Organic Chemical Co., Ltd. Chemical Name: 1H, 1H, 5H-Octafluoropentyl acrylate NK Oligo EA-1020: Shin-Nakamura Chemical Co., Ltd. Epoxy Acrylate Unidic 17-813: Dainippon Ink & Chemicals, Inc. ) Polyurethane poly (meth) acrylate produced by the company (solid content: 80%, weight average molecular weight: 1,500)
M-8530: Toagosei Co., Ltd. polyester acrylate (weight average molecular weight 1,200)
Byron GK880: Polyester manufactured by Toyobo Co., Ltd. (weight average molecular weight 54,000, Tg = 84 ° C.)
Paraloid A-11: Acrylic resin Irgacure 184 manufactured by Rohm & Haas Co., Ltd. Photopolymerization initiator dilution solvent manufactured by Ciba Specialty Chemicals Co., Ltd. Mixed solvent of MEK, butyl acetate, and toluene

NK Oligo EA-1020: Epoxy acrylate Unidic 17-813 manufactured by Shin-Nakamura Chemical Co., Ltd .: Polyurethane poly (meth) acrylate manufactured by Dainippon Ink & Chemicals, Inc. (solid content: 80%, weight average molecular weight: 1, 500)
M-8530: Toagosei Co., Ltd. polyester acrylate (weight average molecular weight 1,200)
Byron GK880: Polyester manufactured by Toyobo Co., Ltd. (weight average molecular weight 54,000, Tg = 84 ° C.)
SILWET L-77: Nippon Unicar Co., Ltd. silicone-based (non-polymerizable) surfactant Defensa MCF-350SF: Dainippon Ink & Chemicals (non-polymerizable) fluoro-surfactant Irgacure 184: Ciba Photopolymerization initiator dilution solvent manufactured by Specialty Chemicals: Mixed solvent of MEK, butyl acetate, and toluene

(Testing method of transfer body)
The following various physical property tests were performed using the hydraulic transfer bodies obtained in Examples 1 to 8 and Comparative Examples 1 to 4.

(Water pressure transferability)
The case where there was no surface defect and the pattern reproducibility was good was marked with ◯, and the case where significant surface defect or pattern collapse occurred was marked with x.

(Surface gloss evaluation)
According to JIS-K5400 “7.6 Specular Gloss”, the 60 ° specular gloss was measured.

(Anti-fouling property 1: Anti-fouling property of straight line drawing with oil-based ink on coating layer)
On the surface of the coating layer, draw a 3 cm long straight line with oil-based ink, Himacky Black (trade name, manufactured by Zebra Co., Ltd.), wipe it off with tissue paper after 30 seconds, repeat this, and trace after repeating 20 times None was marked with ◯, and after 20 times, there was a mark with x.

(Anti-fouling property 2: Anti-fouling property of straight line drawing with oil-based ink on dry-wiped coating layer)
The surface of the coating layer was wiped dry with tissue paper, and then evaluated in the same manner as antifouling property 1.

(Anti-fouling property 3: Anti-fouling property after drawing with oil-based ink on coating layer)
On the surface of the coating layer, draw a 3cm long straight line with oil-based inks, Himacky Black, Red, and Blue (trade names made by Zebra Co., Ltd.), leave them for 24 hours and wipe them off with tissue paper. The surface was observed. The coating layer surface was evaluated in two steps, with ○ indicating that there was no trace of oil-based ink and X indicating that there was a trace.

(Adhesion)
For samples subjected to hydraulic transfer to the following primer-treated galvanized steel plate (flat plate: 100 mm × 100 mm × 0.5 mm) or ABS resin plate (flat plate: 100 mm × 100 mm × 3 mm), according to the cross-cut tape method (JIS K5400) Ink adhesion was evaluated (full score of 10).

<Primer-treated galvanized steel sheet>
Dai Nippon Ink Chemical Co., Ltd. Beckolite 57-206-40 (linear polyester resin having a hydroxyl group at its terminal, number average molecular weight 10,000) 45 parts in terms of solid content, titanium white 50 parts, cyclohexanone / isophorone / xylol = Mixing 20 parts of 30/50/20 mixed solvent, bead milling, and after finishing, 5 parts xylene diisocyanate (XDI) and 0.5 parts dibutyltin dilaurate (TK-1) as curing agents In addition, the top coating obtained was applied to a chromate-treated hot-dip galvanized steel sheet (plating coverage 60 g / m ² ) with a bar coater to a dry film thickness of 40 μm, and baked at a maximum plate temperature of 235 ° C. A treated galvanized steel sheet was obtained.

(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.

(Abrasion resistance)
A rubbing tester (load 800 g) is used for a sample that has been hydraulically transferred to a primer-treated galvanized steel plate (flat plate: 100 mm × 100 mm × 0.5 mm) or ABS resin plate (flat plate: 100 mm × 100 mm × 3 mm) used in the adhesion test. The surface gloss retention after 100 times of dry wiping was evaluated.

(Chemical resistance 1: Alcohol resistance)
1-butanol was included in the sample that was hydraulically transferred to the primer-treated galvanized steel plate (flat plate: 100 mm × 100 mm × 0.5 mm) or 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, and the surface gloss retention after the test was measured.

(Chemical resistance 2: acid resistance / alkali resistance)
Protective films (made by Nitto Denko Corporation) on the end face (from the end to 3 mm inside) and back face of the sample that was hydraulically transferred to the primer-treated galvanized steel sheet (flat plate: 100 mm x 100 mm x 0.5 mm) used in the adhesion test The surface gloss retention rate after immersion in a 5% aqueous acetic acid solution or a 5% aqueous sodium hydroxide solution for 72 hours was measured with a Nitoflon adhesive tape No. 903UL).

(Adhesion after hot water treatment)
The hydraulically transferred sample was heat treated in hot water (water temperature 98 ° C.) for 2 hours, and then 100 100 × 1 × 1 mm grids were made on the coating film. Was peeled off rapidly, and the peeled state of the coating film was visually observed and evaluated in the following three stages.

○: No peeling was observed.
(Triangle | delta): 1-30% of the whole peeled.
X: 31-100% of the whole peeled off.

(Gloss retention after hot water treatment)
The hydrostatically transferred sample was heat-treated in hot water (water temperature 98 ° C.) for 2 hours, and then the gloss retention before and after the hydrothermal treatment was calculated by measuring 60 ° gloss with a gloss meter.

  Tables 4 to 6 show the evaluation results of the transfer product of the hydraulic transfer body obtained by hydraulic transfer of the hydraulic transfer film of the present invention together with comparative examples.

In Examples 1 to 8, which are examples of the present invention, antifouling properties are imparted to the hydraulic transfer member, and other physical properties are maintained at a level that causes no practical problems. On the other hand, Comparative Example 1 not containing a polymerizable compound having an organosiloxy group and / or a fluoroalkyl group, a comparison in which a non-polymerizable compound having an organosiloxy group or a fluoroalkyl group was blended in place of the polymerizable compound (component A) In Examples 2 and 3, the antifouling property was insufficient, and Comparative Example 4 in which the amount of the non-polymerizable compound having a fluoroalkyl group was increased was whitened.

Claims (5)

It 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 can be cured by at least one of active energy ray irradiation and heating. A hydraulic transfer film having a curable resin layer, wherein the curable resin layer contains a polymerizable compound having an organosiloxy group and / or a fluoroalkyl group. The film for hydraulic transfer according to claim 1, wherein the polymerizable compound having an organosiloxy group and / or a fluoroalkyl group is (meth) acrylate. The curable resin layer is
1) a polymerizable compound having an organosiloxy group and / or a fluoroalkyl group;
2) a radically polymerizable composition comprising urethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, or polyether (meth) acrylate;
3) The film for hydraulic transfer according to claim 1, comprising (meth) acrylic resin or polyester resin. The ratio for which the polymerizable compound which has the said organosiloxy group and / or fluoroalkyl group with respect to the polymeric compound whole quantity in the said curable resin layer is the range of 9-70 mass% converted into a percentage. The film for hydraulic transfer described in 1. The film for hydraulic transfer according to claim 1 is floated on water with the support film facing 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. The transfer layer is then cured by at least one of active energy ray irradiation and heating.