JP2006264126A - Hydraulic transfer film and hydraulic transfer medium - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydraulic transfer film which hardly causes a surface defect on a hydraulic transfer article. <P>SOLUTION: The hydraulic transfer film comprises a substrate film which is composed of a water-soluble or water-swelling resin, and a transfer layer which can be dissolved in an organic solvent provided on the substrate film, wherein the transfer layer comprises a curable resin layer which can be cured by at least either active energy ray irradiation or heating, and the curable resin layer comprises Neuburg silica. The hydraulic transfer film is used for a hydraulic transfer medium. <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.

  The hydraulic transfer method is called an activator by floating a hydraulic transfer film consisting of a support film made of a water-soluble or water-swellable resin and a transfer layer including a decorative layer on the water surface with the support film facing down. In this method, after the transfer layer is softened with an organic solvent, the transfer layer is submerged in water while being pressed from above (see, for example, Patent Document 1 and Patent Document 2). ). Thereby, the decoration layer rich in design property can be provided to the molded product of a complicated three-dimensional shape.

In general, the surface of a hydraulic transfer body is required to be free from so-called coating film defects such as wrinkles, bumps, and dents, and a leveling agent or the like is added to the surface layer. However, when the resin blended in the surface layer is poorly compatible with the leveling agent, it cannot be blended, and the addition of the leveling agent causes problems such as a decrease in coating properties such as water resistance. It was. Surface defects can be avoided to some extent by devising the speed and angle of submergence while pressing the transferred object from above without adding a leveling agent, but the optimum conditions differ depending on the shape of the transferred object Therefore, it was very complicated.
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 in which surface defects of a hydraulic transfer product are unlikely to occur.

  The present inventors have found that the above problem can be solved by blending Neuburg silica in 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 by at least one kind, wherein the curable resin layer contains Neuburg silica.

  The present invention also provides the hydraulic transfer film described above, wherein the support film is floated on water, the transfer layer is activated with an organic solvent, the transfer layer is transferred to a transfer target, and the support film Then, a hydraulic transfer body in which the transfer layer is cured by at least one of active energy ray irradiation and heating is provided.

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

(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 Neuburg silica)
The curable resin layer contains Neuburg silica.
Neuburg silica generally refers to a natural combination of lamellar kaolinite and massive quartz. A special method of refining Neuburg dredged clay from Neuburg, Germany, and a thin plate of kaolinite and massive quartz are naturally combined and combined. Specific examples include Siritin V85 (average particle size 3 μm), Siritin V88 (average particle size 3 μm), Siritin N82 (average particle size 2.3 μm), Siritin N85 (average particle size 2.3 μm), Siritin Z86 (average particle size) 1.8 μm in diameter), Siritin Z89 (average particle diameter 1.8 μm), Siricolloid P82 (average particle diameter 1.6 μm), Siricolloid P87 (average particle diameter 1.6 μm), and other surface-treated Actidyl MAM (average particle) Diameter 3 μm), actidyl VM56 (average particle size 1.8 μm) and the like (manufactured by Hoffmann Minerals, Germany). A plurality of Neuburg silicas having different average particle diameters and surface treatments may be used in combination, or an artificially produced combination having the same structure may be used.

  Neuburgh silica has numerous capillaries due to the innumerable silica of nanometer particle size, through which volatile matter can be raised and evaporated from the plate-like surface. In addition, the film strength increases due to the filler effect. For this reason, in the drying process after the hydraulic transfer, the organic solvent / water remaining in the curable resin layer can be efficiently evaporated without substantially destroying the curable resin layer. It is estimated that it can be avoided.

The average particle size of Neuburg silica is preferably 1 to 5 μm. If the average particle size is less than 1 μm, the amount of dust increases, so that the workability of blending may be reduced. If the average particle size exceeds 5 μm, the transparency of the curable resin layer may be impaired.
In the present invention, the average particle diameter refers to an average particle diameter calculated by a weight average particle diameter measuring method. Neuburg silica, strictly speaking, is not a single particle size, but a mixture of different particle sizes. Therefore, when the particle size is displayed, it is indicated by an average particle size.

  Further, by using Neuburg silica having an average particle size of 1.7 μm or less, high gloss of 80 or more is exhibited at 20 ° gloss. This is presumed that the Neuburg silica dispersed in the curable resin layer has a plate-like portion dispersed in a direction substantially parallel to the coating film surface and serves as a reflecting mirror for incident light.

  In the curable resin layer, the content of Neuburg silica is preferably 3 to 20% by weight, more preferably 5 to 18% by weight, and even more preferably 7 to 15% by weight. If the content is less than 3%, the effect of eliminating surface defects may be poor, and if it exceeds 35% by weight, the transparency of the curable resin layer may be impaired.

(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.

(Epoxy (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 Neuburg silica and the radical polymerizable compound, the appearance and various physical properties of the obtained hydraulic transfer body can be improved. preferable. A general-purpose thermoplastic resin can be used as the non-polymerizable thermoplastic resin. Among them, the (meth) acrylic resin is preferable because it can improve the drying property of the curable resin layer, and can provide transparency, solvent resistance, and the like. A feeling and flexibility can be imparted, which is preferable.

((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 them, 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.

  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.

  To the curable resin layer, non-reactive thermoplastic resins such as general-purpose (meth) acrylic monomers or acrylic resins and polyester resins are blended for the purpose of improving drying properties, as long as desired physical properties are not impaired. May be.

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

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

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

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

  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 product 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 curing with an organic solvent. After activating the transfer resin layer or the transfer layer having the decorative layer and the curable resin layer, the transfer layer is hydraulically transferred to the transfer target, the support film is removed, and the transfer layer is then cured by irradiation with active energy rays. The 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 a curable resin layer or 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 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.

(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.

(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.

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 an activator (xylene: MIBK: butyl acetate: isopropanol = 5: 2: 2: 1). ): 40 g / m ² was sprayed on 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 1-2)
Hydraulic transfer films F51 to F52 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 C52 shown in Table 3 (C52 was cloudy) Therefore, a hydraulic transfer film was not manufactured). Further, the obtained hydraulic transfer films F51 to F52 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 of 5 m / min) to obtain a hydraulic transfer body.

ＮＫオリゴＥＡ−１０２０：新中村化学(株)製エポキシアクリレート
Ｍ−８５３０：東亞合成(株)製ポリエステルアクリレート（重量平均分子量１，２００）
バイロンＧＫ８８０：東洋紡績(株)製ポリエステル
シリコロイドＰ８７：ドイツ国ホフマンミネラル社製ノイブルクシリカ（平均粒径１．６μｍ）
アクテジルＭＡＭ：ドイツ国ホフマンミネラル社製メタクリルシラン表面処理済ノイブルクシリカ（平均粒径３μｍ）
イルガキュア１８４：チバ・スペシャリティケミカルス社製光重合開始剤
希釈溶剤：ＭＥＫ、酢酸ブチル、トルエンの混合溶剤

NK Oligo EA-1020: Epoxy acrylate M-8530 manufactured by Shin-Nakamura Chemical Co., Ltd .: Polyester acrylate manufactured by Toagosei Co., Ltd. (weight average molecular weight 1,200)
Byron GK880: Polyester silicolloid P87 manufactured by Toyobo Co., Ltd .: Neuburg silica manufactured by Hoffmann Mineral (Germany) (average particle size 1.6 μm)
Actegil MAM: Neuburg silica treated with methacryl silane surface (average particle size 3 μm) manufactured by Hoffmann Minerals, Germany
Irgacure 184: Photopolymerization initiator dilution solvent manufactured by Ciba Specialty Chemicals: Mixed solvent of MEK, butyl acetate, and toluene

ＮＫオリゴＥＡ−１０２０：新中村化学(株)製エポキシアクリレート
ユニディック１７−８１３：大日本インキ化学工業(株)社製ポリウレタンポリ（メタ）クリレート（固形分：８０％、重量平均分子量：１，５００）
Ｍ−８５３０：東亞合成(株)製ポリエステルアクリレート（重量平均分子量１，２００）
バイロン２４０：東洋紡績(株)製ポリエステル
シリチンＶ８８：ドイツ国ホフマンミネラル社製ノイブルクシリカ（平均粒径３μｍ）
アクテジルＭＡＭ：ドイツ国ホフマンミネラル社製メタクリルシラン表面処理済ノイブルクシリカ（平均粒径３μｍ）
イルガキュア１８４：チバ・スペシャリティケミカルス社製光重合開始剤
希釈溶剤：ＭＥＫ、酢酸ブチル、トルエンの混合溶剤

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 240: Polyester Siritin V88 manufactured by Toyobo Co., Ltd .: Neuburg Silica manufactured by Hoffmann Mineral (Germany) (average particle size 3 μm)
Actegil MAM: Neuburg silica treated with methacryl silane surface (average particle size 3 μm) manufactured by Hoffmann Minerals, Germany
Irgacure 184: Photopolymerization initiator dilution solvent manufactured by Ciba Specialty Chemicals: Mixed solvent of MEK, butyl acetate, and toluene

ＮＫオリゴＥＡ−１０２０：新中村化学(株)製エポキシアクリレート
Ｍ−８５３０：東亞合成(株)製ポリエステルアクリレート（重量平均分子量１，２００）
バイロンＧＫ８８０：東洋紡績(株)製ポリエステル
ＡＳＰ−２００：林化成株式会社製６角板状カオリナイト（平均粒径０．４μｍ）
イルガキュア１８４：チバ・スペシャリティケミカルス社製光重合開始剤
希釈溶剤：ＭＥＫ、酢酸ブチル、トルエンの混合溶剤
エリーテルＸＡ−０６１１：ユニチカ(株)製ポリエステル
エマルゲンＡ−６０：花王(株)製非イオン性界面活性剤（ＨＬＢ＝１２．８）

NK Oligo EA-1020: Epoxy acrylate M-8530 manufactured by Shin-Nakamura Chemical Co., Ltd .: Polyester acrylate manufactured by Toagosei Co., Ltd. (weight average molecular weight 1,200)
Byron GK880: Polyester ASP-200 manufactured by Toyobo Co., Ltd .: Hexagonal plate-shaped kaolinite manufactured by Hayashi Kasei Co., Ltd. (average particle size 0.4 μm)
Irgacure 184: Photopolymerization initiator dilution solvent manufactured by Ciba Specialty Chemicals: Mixed solvent of MEK, butyl acetate, and toluene
Elitel XA-0611: Polyester Emulgen A-60 manufactured by Unitika Ltd .: Nonionic surfactant manufactured by Kao Corporation (HLB = 12.8)

(Testing method of transfer body)
The following various physical property tests were conducted using the hydraulic transfer bodies obtained in Examples 1 to 8 and Comparative Examples 1 to 3.

(Existence of surface defects)
The case where the surface defect was not observed visually was marked with ◯, and the surface defect observed with x.

(Pattern reproducibility)
The one with good pattern reproducibility was marked with ◯, and the one with pattern collapse was marked with x.

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

(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, the hydraulic transfer body has no surface defects, and other physical properties are maintained at a level that causes no practical problems. On the other hand, Comparative Example 1 containing no Neuburg silica could not eliminate the surface defects. In Comparative Example 2 in which hexagonal plate-shaped kaolinite was blended instead of Neuburg silica, surface defects could not be eliminated. Since the comparative example 3 which put surfactant in the coating film became cloudy, creation of the hydraulic transfer film was not performed.

Claims (3)

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 Neuburg silica. The hydraulic transfer film according to claim 1, wherein the Neuburg silica has an average particle diameter of 1 to 5 μm. The hydraulic transfer film according to claim 1 or 2, 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 film is A hydraulic transfer body, which is removed and then cured by at least one of active energy ray irradiation and heating.