JP2006346884A - Hydraulic transfer film and hydraulically transferred body - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydraulic transfer film, in which no adhesion between a curing resin layer under uncured state and a water-soluble support film lowers during the storage of the film. <P>SOLUTION: This hydraulic transfer film has the curing resin layer comprising (1) a (meth)acrylic copolymer having a hydroxyl group in a main chain and a (meth)acryloyl group in a side chain under the condition that a hydroxyl number is 10-150 mg KOH/g and a weight average molecular weight is 5,000-100,000, and (2) a radical polymerizable compound selected from the group consisting of an epoxy acrylate, a polyester acrylate, a urethane acrylate and a polyether acrylate compatible with the (meth)acrylic copolymer and having the weight average molecular weight of not more than 10,000, wherein the (meth)acrylic copolymer is ≥20 mass% and ≤80 mass%. Further, the hydraulically transferred body obtained by employing the hydraulic transfer film is provided. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

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

  In the hydraulic transfer method, a hydraulic transfer film having a support film made of a water-soluble or water-swellable resin and a transfer layer is floated on the water surface with the support film facing downward, and the transfer layer is formed with an organic solvent called an activator. In this method, after the softening, the transfer layer is transferred to the transfer body by being submerged in water while being pressed from above.

  The hydraulic transfer method is a method that can apply a decorative layer rich in design to a complex three-dimensional molded product, but after the hydraulic transfer, a process of spray coating the protective layer with a curable resin is required on the decorative layer that has been hydraulically transferred. Therefore, a two-step process is required to obtain a transfer body. In addition to the water pressure transfer equipment, a painting equipment is also required for the spray painting process, which is expensive. For this reason, a hydraulic transfer method using a one-step process has been demanded in order to simplify the process and reduce costs.

  In response to this requirement, a technique for transferring a thermoplastic resin layer and a decorative layer to a transfer target in one step using a hydraulic transfer film having a thermoplastic resin layer (surface protective layer) and a decorative layer as a transfer layer is disclosed. (For example, refer to Patent Document 1). However, in this technique, the surface protective layer is made of a thermoplastic resin, specifically, a copolymer of butyl acrylate and ethyl acrylate, and is not a curable coating film. Therefore, the surface protective layer has physical properties such as solvent resistance and surface hardness. The chemical and chemical durability was not sufficient.

In addition, as a hydraulic transfer method by a one-step process, the coating layer is made of a polymer having a radically polymerizable unsaturated group and a glass transition temperature of 0 to 250 ° C., is in an uncured state, is solid at room temperature, and There is provided a method for producing a molded article having a cured resin layer, wherein a coating layer is transferred to a transfer target using a hydraulic transfer sheet having an adhesive coating layer, and the coating layer is cured by ionizing radiation or heat. (For example, refer to Patent Document 2). However, because it is non-adhesive at room temperature, the adhesion between the curable resin layer and the water-soluble support film is reduced during storage at room temperature, and peeling occurs at the interface between the curable resin layer and the water-soluble support film. was there.
Japanese Patent Laid-Open No. 4-197699 Japanese Patent Laid-Open No. 64-22378 (Japanese Patent Publication No. 7-29084)

  Accordingly, an object of the present invention is a hydraulic transfer film having a curable resin layer used in a hydraulic transfer method by a one-step process, wherein the curable resin layer and a water-soluble support are in an uncured state during storage of the film. An object of the present invention is to provide a hydraulic transfer film in which the adhesion with a body film does not decrease.

  As a result of intensive studies to solve the above problems, the inventors of the present invention have 1) a hydroxyl group and a (meth) acryloyl group in the side chain, and a hydroxyl value of 10 to 150 mgKOH / g. , A (meth) acrylic copolymer (component A) having a weight average molecular weight of 5000 to 100,000 and a radically polymerizable compound having a weight average molecular weight of 10,000 or less compatible with the (meth) acrylic copolymer are used at a specific ratio. As a result, the inventors have found that the above problems can be solved, and have completed the present invention.

  The (meth) acrylic copolymer having a hydroxyl group is excellent in adhesion to a support film having a large polarity. However, if a large amount of hydroxyl group is contained, the adhesiveness is increased and the hydrostatic transfer property is affected. The transfer body tends to be inferior in water resistance, solvent resistance, and the like. In the present invention, by introducing a (meth) acryloyl group that is a polar group and non-hydrophilic to the side chain of the (meth) acrylic copolymer having a hydroxyl group, the amount of the hydroxyl group is minimized and supported. Adhesion with body film was made possible. Since the (meth) acryloyl group can be cured by irradiation with active energy rays, the obtained hydraulic transfer body is excellent in solvent resistance.

  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 film for hydraulic transfer having a curable resin layer curable with at least one of the following: 1) the curable resin layer has 1) a hydroxyl group and a (meth) acryloyl group in a side chain; 150 mg KOH / g, (meth) acrylic copolymer (component A) having a weight average molecular weight of 5,000 to 100,000, 2) epoxy acrylate, polyester acrylate compatible with the (meth) acrylic copolymer (component A), A radical polymerizable compound (component B) having a weight average molecular weight of 10,000 or less selected from the group consisting of urethane acrylate and polyether acrylate; A, of the curable resin layer, wherein (meth) acrylic copolymer (component A) provides a hydraulic transfer film 80 mass% or less than 20 wt%.

  Further, the present invention provides the above-mentioned hydraulic transfer film, wherein the support film is floated on water, the transfer layer is activated with an organic solvent, the transfer layer is transferred to a transfer target, and the support A hydraulic transfer body in which the film is removed and then 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 at least one of active energy ray irradiation and heating. . The transfer layer may have 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 active energy ray irradiation to form a cured resin layer.

(Curable resin layer)
((Meth) acrylic copolymer having (meth) acryloyl group)
A (meth) acrylic copolymer (component A) having a hydroxyl group used in the present invention, a (meth) acryloyl group in the side chain, a hydroxyl value of 10 to 150 mgKOH / g, and a weight average molecular weight of 5,000 to 100,000; Is a (meth) acrylic copolymer having mono (meth) acrylate as a main polymerization component, and the (meth) acrylic copolymer has a (meth) acryloyl group in the side chain. Specifically, a (meth) acryloyl group is pendant on the main chain portion of a (meth) acrylic copolymer having mono (meth) acrylate and mono (meth) acrylate having a hydroxyl group as main polymerization components. The (meth) acrylic copolymer having photocurability.
As a method for obtaining such a (meth) acrylic copolymer having a (meth) acryloyl group, for example, a (meth) acrylate having a reactive group (a) and a mono (meth) acrylate having a hydroxyl group are essentially polymerized. A (meth) acrylic copolymer (hereinafter abbreviated as (meth) acryl main chain) polymerized as a component is reacted with a (meth) acrylate having a reactive group (b) capable of reacting with the reactive group (a). The method of letting it be mentioned.
As a method of pendating a (meth) acryloyl group on the main chain portion of the (meth) acrylic copolymer, for example, (meth) acrylic polymerized with (meth) acrylate having a reactive group (a) as an essential polymerization component. Examples thereof include a method in which a copolymer (hereinafter abbreviated as (meth) acryl main chain) is reacted with (meth) acrylate having a reactive group (b) capable of reacting with the reactive group (a).

  For example, when a hydroxyl group is used as the reactive group (a), for example, an isocyanate group may be used as the reactive group (b). Such (meth) acrylates having a hydroxyl group include, for example, hydroxyl group-containing (meta) such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and glycerin mono (meth) acrylate. ) Acrylates. Examples of the (meth) acrylate having an isocyanate group include (meth) acryloyl isocyanate and (meth) acryloyloxyethyl isocyanate.

  Further, when a carboxyl group is used as the reactive group (a), for example, a glycidyl group may be used as the reactive group (b). Examples of such a (meth) acrylate having a carboxyl group include acrylic acid and methacrylic acid. Examples of the (meth) acrylate having a glycidyl group include glycidyl (meth) acrylate.

The combination of the reactive group (a) and the reactive group (b) shown above is merely an example. For example,
Reactive when the reactive group (a) is an isocyanate group, the reactive group (b) is a hydroxyl group, the reactive group (a) is a glycidyl group, the reactive group (b) is a carboxyl group, and the reactive group (a) is a glycidyl group. Known combinations such as the group (b) is a hydroxyl group-reactive group (a) is a hydroxyl group, the reactive group (b) is a carboxyl group-reactive group (a) is a hydroxyl group, and the reactive group (b) is a glycidyl group Can be selected.
Especially, since a hydroxyl group can be introduce | transduced simultaneously, it is preferable that a reactive group (a) is a hydroxyl group and a reactive group (b) is an isocyanate group, a carboxyl group, or a glycidyl group, and an isocyanate group is the most preferable.

  The polymerization method of the (meth) acryl main chain having the reactive group (a) is performed by radical polymerization. The form of radical polymerization is not particularly limited, and the polymerization can be performed by a known method such as solution polymerization, emulsion polymerization, suspension polymerization or the like. Among these, a poly (meth) acrylic copolymer containing polymethyl methacrylate and hydroxyl group-containing (meth) acrylate as essential polymerization components is preferable in terms of excellent transparency, solvent resistance, and scratch resistance.

When the hydroxyl value of the (meth) acrylic copolymer having a (meth) acryloyl group is less than 10, an improvement in adhesion between the curable resin layer and the water-soluble support film is not exhibited, and when the hydroxyl value exceeds 150, the adhesiveness is increased. May increase too much.
Especially, the range whose hydroxyl value is 15 or more and 130 or less is more preferable. The hydroxyl value can be adjusted by the amount of hydroxyl group-containing (meth) acrylate used.

When the weight average molecular weight of the (meth) acrylic copolymer having a (meth) acryloyl group exceeds 100,000, the solvent resistance and scratch resistance tend to decrease due to UV curing failure, etc., and curing occurs when the weight average molecular weight is less than 5000. Since the adhesiveness of the curable resin layer increases, it may be difficult to prepare a hydraulic transfer film with a curable resin layer.
Especially, it is preferable that it is a weight average molecular weight 5000-100000, More preferably, it is 10000-90000, Furthermore, 20000-80000 is the most preferable.

Hereinafter, a method for synthesizing a (meth) acrylic copolymer when the reactive group (a) is a hydroxyl group and the reactive group (b) is an isocyanate group will be described as an example.
The amount of 2- (meth) acryloyloxyethyl isocyanate used in the production of a (meth) acrylic copolymer (component A) having a hydroxyl value of 10 to 100 is determined by taking into consideration the reaction rate and the like. It is 0.8-1.2 mol normally with respect to 1.00 mol (theoretical amount) of the hydroxyl group which a copolymer has, and 0.9-1.1 mol is more preferable.
In order to accelerate the reaction between the hydroxyl group of the thermoplastic acrylic resin (component D) and the isocyanate group, for example, tertiary amines such as triethylamine and benzyldimethylamine, dibutyltin dilaurate, dioctyltin dilaurate, etc. A dilaurate compound such as can be used as a catalyst. The addition amount of these catalysts is 0.001-5.0 weight% normally with respect to the weight of the whole reaction mixture, Preferably it is 0.01-1.1 weight%. The reaction time is usually 1 to 10 hours. Moreover, reaction temperature is 20-120 degreeC normally, Preferably it is 30-90 degreeC.

  In the synthesis of the (meth) acrylic copolymer (component A), a solvent inert to the terminal isocyanate group of 2- (meth) acryloyloxyethyl isocyanate can be used as a reaction solvent. Specific examples of the solvent inert to the isocyanate group used at this time include, for example, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, and the like. An aromatic hydrocarbon compound such as

(Radically polymerizable compound (component B))
The radically polymerizable compound (component B) having a weight average molecular weight of 10,000 or less is preferably (meth) acrylate because of its excellent curability, and is a polyfunctional (meth) having 2 to 15 (meth) acryloyl groups in one molecule. Acrylate is particularly preferred. The radically polymerizable compound is not particularly limited, but it is preferable that the glass transition temperature before curing is less than 40 ° C., because the reactive group is relatively easy to move even within the matrix and the curing reaction proceeds efficiently.

(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.

  In the present invention, the (meth) acrylic copolymer (component A) in the curable resin layer is 20% by mass or more and 80% by mass or less. If the amount is less than 20% by mass, the tackiness is too high, and particularly when a peelable film is used, the problem arises that it cannot be peeled off well during hydraulic transfer. Moreover, when it exceeds 80 mass%, peeling may generate | occur | produce between a support body film and a curable resin layer. Among them, the (meth) acrylic copolymer (component A) is preferably 30% by mass or more and 70% by mass or less.

(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.

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

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

(Ink composition G1, black, brown, white)
Bernock EZL676: 20 parts by mass (solid content conversion)
Pigment (black, brown, white): 10 parts by mass (solid content)
Additives such as wax: 10 parts by mass
Solvent: added so as to have a non-volatile content of 30% However, Bernock EZL676 is a polyurethane manufactured by Dainippon Ink & Chemicals, Inc., and the solvent is a mixture of toluene, ethyl acetate, and methyl ethyl ketone in a ratio of 2: 1: 1. Solvent was used.

(Production Example 2) <Production Example of (Meth) acryloyl copolymer (XA1) having (meth) acryloyl group>
As a monomer mixture, 300 parts of a mixture of 28.5 parts of styrene, 126 parts of methyl methacrylate, 45 parts of cyclohexyl methacrylate, 99 parts of hydroxyethyl methacrylate and 1.5 parts of methacrylic acid were prepared.
A 2 L four-necked flask was charged with 120 parts of butyl acetate and 120 parts of toluene, and 6.6 parts of Kayaester O (manufactured by Kayaku Akzo) was added as an initiator to the monomer mixture to prepare a monomer mixture for dropping. After maintaining the temperature of the reaction mixture in the flask at 120 ° C., the dropping monomer mixture was dropped over 6 hours, and 15 parts of butyl acetate was added after the dropping was completed. The reaction mixture temperature was kept at 120 ° C. for 1 hour, and an initiator mixture consisting of 1.2 parts of Kayaester O and 15 parts of butyl acetate was added as an additional initiator three times every 1 hour. Furthermore, after maintaining the reaction mixture temperature in the flask at 120 ° C. for 1 hour, the reaction mixture was allowed to cool to room temperature to obtain an acrylic resin solution (P-1). The acrylic resin solution (P-1) has a solid content of 51 wt%, a hydroxyl value of 144 mg KOH / g (based on solid content), an acid value of 1.6 mg KOH / g (based on solid content), a weight average molecular weight of 45,000, and Tg It was 81 ° C.
In a 1 L separable flask, 500.0 g of the obtained acrylic resin solution (P-1) was added, 0.3 g of dibutyltin dilaurate was added, and the mixture was 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. The same measurement was performed in the following production examples.) Was confirmed to be 0.1% or less. The obtained (meth) acryloyl copolymer (XA1) solution having a (meth) acryloyl group had a solid content of 55% and a hydroxyl value of 81 mgKOH / g (relative to the solid content).

(Production Example 3) <(Meth) acrylic copolymer (XA2) production example>
A 1 L separable flask was charged with 500.0 g of the acrylic resin solution (P-1) obtained in Production Example 2, 0.3 g of dibutyltin dilaurate was added, and the mixture was stirred at 40 ° C. To this solution, 27.1 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 the dropwise addition, the mixture was stirred as it was at 40 to 50 ° C. for 1 hour, further heated and stirred at 70 to 80 ° C. for 3 hours, and it was confirmed that the NCO value was 0.1% by weight or less. The obtained (meth) acryloyl copolymer (XA2) solution having a (meth) acryloyl group had a solid content of 54% and a hydroxyl value of 127 mgKOH / g (relative to the solid content).

(Production Example 4) <Production Example of (Meth) acryloyl copolymer (XA3) having (meth) acryloyl group>
As a monomer mixture, a mixture 300 of 28.5 parts of styrene, 126 parts of methyl methacrylate, 60 parts of ethyl methacrylate, 45 parts of butyl methacrylate, 24 parts of cyclohexyl methacrylate, 15 parts of hydroxyethyl methacrylate and 1.5 parts of methacrylic acid 300 A department was created.
A 2 L four-necked flask was charged with 120 parts of butyl acetate and 120 parts of toluene, and 6.6 parts of Kayaester O (manufactured by Kayaku Akzo) was added as an initiator to the monomer mixture to prepare a monomer mixture for dropping. After maintaining the temperature of the reaction mixture in the flask at 120 ° C., the dropping monomer mixture was dropped over 6 hours, and 15 parts of butyl acetate was added after the dropping was completed. The reaction mixture temperature was kept at 120 ° C. for 1 hour, and an initiator mixture consisting of 1.2 parts of Kayaester O and 15 parts of butyl acetate was added as an additional initiator three times every 1 hour. Furthermore, after maintaining the reaction mixture temperature in the flask at 120 ° C. for 1 hour, the reaction mixture was allowed to cool to room temperature to obtain an acrylic resin solution (P-2). The acrylic resin solution (P-2) has a solid content of 51 wt%, a hydroxyl value of 22 mgKOH / g (based on solid content), an acid value of 1.4 mgKOH / g (based on solid content), a weight average molecular weight of 52,000, and Tg is It was 75 ° C.
In a 1 L separable flask, 500.0 g of the obtained acrylic resin solution (P-2) was added, 0.3 g of dibutyltin dilaurate was added, and the mixture was stirred at 40 ° C. To this solution, 6.2 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 it was confirmed that the NCO value was 0.1% or less. The obtained (meth) acryloyl copolymer (XA3) solution having a (meth) acryloyl group had a solid content of 55% and a hydroxyl value of 11 gKOH / g (vs. solid content).

(Production Example 5) <(Meth) acrylic copolymer (XA4) production example>
A 1 L separable flask was charged with 500.0 g of the acrylic resin solution (P-2) obtained in Production Example 5, 0.3 g of dibutyltin dilaurate was added, and the mixture was stirred at 40 ° C. To this solution, 18.1 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 the dropwise addition, the mixture was stirred as it was at 40 to 50 ° C. for 1 hour, further heated and stirred at 70 to 80 ° C. for 3 hours, and it was confirmed that the NCO value was 0.1% by weight or less. The obtained (meth) acryloyl copolymer (XA4) solution having a (meth) acryloyl group had a solid content of 54% and a hydroxyl value of 8 mgKOH / g (relative to the solid content).

(Production Example 6) <Production Example of (Meth) acryloyl copolymer (XA5) having (meth) acryloyl group>
As a monomer mixture, 300 parts of a mixture of 28.5 parts of styrene, 126 parts of methyl methacrylate, 24 parts of cyclohexyl methacrylate, 120 parts of hydroxyethyl methacrylate and 1.5 parts of methacrylic acid were prepared.
A 2 L four-necked flask was charged with 120 parts of butyl acetate and 120 parts of toluene, and 6.6 parts of Kayaester O (manufactured by Kayaku Akzo) was added as an initiator to the monomer mixture to prepare a monomer mixture for dropping. After maintaining the temperature of the reaction mixture in the flask at 120 ° C., the dropping monomer mixture was dropped over 6 hours, and 15 parts of butyl acetate was added after the dropping was completed. The reaction mixture temperature was kept at 120 ° C. for 1 hour, and an initiator mixture consisting of 1.2 parts of Kayaester O and 15 parts of butyl acetate was added as an additional initiator three times every 1 hour. Furthermore, after maintaining the reaction mixture temperature in the flask at 120 ° C. for 1 hour, the reaction mixture was allowed to cool to room temperature to obtain an acrylic resin solution (P-3). The acrylic resin solution (P-3) has a solid content of 51 wt%, a hydroxyl value of 176 mg KOH / g (based on solid content), an acid value of 1.6 mg KOH / g (based on solid content), a weight average molecular weight of 42,000, and Tg is It was 78 ° C.
In a 1 L separable flask, 500.0 g of the obtained acrylic resin solution (P-3) was added, 0.3 g of dibutyltin dilaurate was added, and the mixture was stirred at 40 ° C. To this solution, 11.5 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 it was confirmed that the NCO value was 0.1% or less. The obtained (meth) acryloyl copolymer (XA5) solution having a (meth) acryloyl group had a solid content of 55% and a hydroxyl value of 161 mgKOH / g (relative to the solid content).

(Examples 1-8)
The curable resin compositions C1 to C8 described in Tables 1 and 2 were prepared as curable resin layer compositions. The curable resin compositions C1 to C8 are applied to a 30 μm thick PVA film manufactured by Aicero Chemical Co., Ltd. with a lip coater so as to have a solid film thickness of 20 μm, and then dried at 60 ° C. for 2 minutes. Manufactured. The curable resin layer of this film and the decorative layer of the printed film P1 produced in Production Example 1 were faced and laminated at 60 ° C. The laminated film was wound up as it was to produce hydraulic transfer films F1 to F8. The obtained hydraulic transfer films F1 to F8 were stored for 3 months in a light-shielded environment at a temperature of 25 ° C. and a humidity of 60%, but no decrease in adhesion between the uncured curable resin layer and the PVA film was observed. .

The film F1 to F8 for water pressure transfer after light-shielding storage was floated in a 30 ° C. water bath with the ink surface facing upward, allowed to stand for 2 minutes, and then activator S: 40 g / m ² was sprayed on the film. Further, after standing for 10 seconds, the water pressure was transferred from the vertical direction to an ABS automobile door panel coated with primer. After the transfer, the transfer object was washed with water and dried at 90 ° C. for 20 minutes. Next, the door panel was passed once through a UV irradiation device (output: 160 W / cm, conveyor speed: 5 m / min) to obtain a door panel having a glossy cured film.

(Comparative Example 1)
In the same manner as in Example 1, after applying the curable resin layer composition C51 on the PVA film, the decorative layer of the printed film P1 produced in Production Example 1 was faced and laminated at 60 ° C. The decorative film was laminated to obtain a hydraulic transfer film F51. When this hydraulic transfer film F51 is stored for 3 months in a light-shielded environment at a temperature of 25 ° C. and a humidity of 60%, peeling occurs at the interface between the uncured curable resin layer and the PVA film, and it can be applied to hydraulic transfer. There wasn't.

(Comparative Example 2)
In the same manner as in Example 1, after the curable resin layer composition C52 was applied on the PVA film, the decorative layer of the printed film P1 produced in Production Example 1 was faced and laminated at 60 ° C. The decorative film was laminated to obtain a hydraulic transfer film F52. When the hydraulic transfer film F52 is stored for 3 months in a light-shielded environment at a temperature of 25 ° C. and a humidity of 60%, peeling occurs at the interface between the uncured curable resin layer and the PVA film, and it can be applied to hydraulic transfer. There wasn't.

(Comparative Example 3)
In the same manner as in Example 1, after applying the curable resin layer composition C53 on the PVA film, the decorative layer of the printed film P1 produced in Production Example 1 was faced and laminated at 60 ° C. The decorative film was laminated to obtain a hydraulic transfer film F53. The hydraulic transfer film F53 was stored for 3 months in a light-shielded environment at a temperature of 25 ° C. and a humidity of 60%. However, there was no decrease in adhesion between the uncured curable resin layer and the PVA film.
Although it tried to float the film F53 for hydraulic transfer after shading storage in a 30 degreeC water bath so that the ink surface may become upper, the adhesiveness of curable resin layer composition is too large, and is a protective film. The PP film could not be peeled off and hydraulic transfer could not be performed.

(Comparative Example 4)
In the same manner as in Example 1, after applying the curable resin layer composition C54 on the PVA film, the decorative layer of the printed film P1 produced in Production Example 1 was faced and laminated at 60 ° C. The decorative film was laminated to obtain a hydraulic transfer film F54. When the hydraulic transfer film F54 is stored for 3 months in a light-shielded environment at a temperature of 25 ° C. and a humidity of 60%, peeling occurs at the interface between the uncured curable resin layer and the PVA film, and it can be applied to hydraulic transfer. There wasn't.

(Comparative Example 5)
In the same manner as in Example 1, after applying the curable resin layer composition C55 on the PVA film, the decorative layer of the printed film P1 prepared in Production Example 1 was faced and laminated at 60 ° C. The decorative film was laminated to obtain a hydraulic transfer film F55. The hydraulic transfer film F55 was stored for 3 months in a light-shielded environment at an ambient temperature of 25 ° C. and a humidity of 60%, but no decrease in adhesion between the uncured curable resin layer and the PVA film was observed.
Although it tried to float the film F55 for hydraulic transfer after shading storage in a 30 degreeC water bath so that the ink surface might become upper, the adhesiveness of curable resin layer composition is too large, and it is a protective film. The PP film could not be peeled off and hydraulic transfer could not be performed.

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）
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

Unidic 17-813: Polyurethane poly (meth) acrylate manufactured by Dainippon Ink & Chemicals, Inc. (solid content: 80%, weight average molecular weight: 1,500)
Irgacure 184: Photopolymerization initiator dilution solvent manufactured by Ciba Specialty Chemicals: Mixed solvent of MEK, butyl acetate, and toluene

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）
ユニディックＶ５５００：大日本インキ化学工業（株）社製エポキシアクリレート
（重量平均分子量：１，０７０）
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

Unidic 17-813: Polyurethane poly (meth) acrylate manufactured by Dainippon Ink & Chemicals, Inc. (solid content: 80%, weight average molecular weight: 1,500)
Unidic V5500: Epoxy acrylate (weight average molecular weight: 1,070) manufactured by Dainippon Ink & Chemicals, Inc.
Irgacure 184: Photopolymerization initiator dilution solvent manufactured by Ciba Specialty Chemicals: Mixed solvent of MEK, butyl acetate, and toluene

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）
アクリペットＶＨ：三菱レーヨン（株）社製非反応性熱可塑アクリル樹脂
（重量平均分子量：２００，０００、Ｔｇ：１００℃、水酸基価１ｍｇＫＯＨ／ｇ以下）
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

Unidic 17-813: Polyurethane poly (meth) acrylate manufactured by Dainippon Ink & Chemicals, Inc. (solid content: 80%, weight average molecular weight: 1,500)
Acrypet VH: Non-reactive thermoplastic acrylic resin manufactured by Mitsubishi Rayon Co., Ltd. (weight average molecular weight: 200,000, Tg: 100 ° C., hydroxyl value: 1 mgKOH / g or less)
Irgacure 184: Photopolymerization initiator dilution solvent manufactured by Ciba 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 door panel obtained in each Example.

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

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

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

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

Claims (2)

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 film for hydraulic transfer having a curable resin layer, wherein the curable resin layer has 1) a hydroxyl group and a (meth) acryloyl group in a side chain, and a hydroxyl value of 10 to 150 mgKOH / g, (Meth) acrylic copolymer (component A) having a weight average molecular weight of 5,000 to 100,000, and 2) epoxy acrylate, polyester acrylate, urethane acrylate and polyether acrylate compatible with the (meth) acrylic copolymer (component A). A radically polymerizable compound (component B) having a weight average molecular weight of 10,000 or less selected from the group consisting of: Hydraulic transfer film characterized in that, the resistance resin layer in the above (meth) acrylic copolymer (component A) is 80 mass% or less than 20 wt%. The hydraulic transfer film according to claim 1, 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 removed. Then, the transfer layer is cured by at least one of active energy ray irradiation and heating.