JP5077645B2 - Activator and method for producing hydraulic transfer body - Google Patents

Description

  The present invention relates to an activator for use in the production of a hydraulic transfer body.

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 imparting designability is floated on the water surface with the support film facing downward, and is usually called an activator. In this method, the organic layer is sprayed to soften the transfer layer, and then the transfer layer is transferred to the transfer target by being submerged in water while pressing the transfer target from above. In the hydraulic transfer method, any pattern can be uniformly and neatly imparted to a molded product having a complicated three-dimensional shape made of metal or plastic by selecting the pattern of the transfer layer that imparts design properties. Can do.
Recently, a hydraulic transfer film having a transfer layer in which a curable resin layer serving as a topcoat layer and a decorative layer are integrated has also been developed (see, for example, Patent Document 1). A topcoat layer and a decorative layer can be provided on the transfer object.

In the hydraulic transfer method, the process of softening the transfer layer is usually called activation, and the resin constituting the coated transfer layer is solubilized without completely dissolving it, thereby imparting flexibility to the transfer layer. This is a step of improving the followability and adhesion of the transfer layer to the three-dimensional curved surface of the transfer object. If the activation is not performed properly, there arises a problem that the transfer layer cannot be transferred onto the transfer target material or the pattern of the obtained hydraulic transfer material is broken.
In particular, the activation of a hydraulic transfer film having a transfer layer in which a curable resin layer and a decorative layer are integrated is different between the activation behavior of the curable resin layer and the activation behavior of the decorative layer. An activator that can be activated uniformly over time is appropriately adjusted and used.

As the activator used in this step, conventionally, a mixture of an aromatic hydrocarbon solvent such as xylene or toluene and an organic solvent such as ketone, ester or alcohol has been used. However, in recent years, the use of xylene and toluene has been restricted due to VOC regulations, and the use of activators with low toxicity has been urged.

JP 2004-34393 A

  The problem to be solved by the present invention is to provide an activator which has low toxicity and can be used for a hydraulic transfer film having a transfer layer in which a curable resin layer and a decorative layer are integrated. .

The present inventors have solved the above problem by using monoterpene hydrocarbon as one component of the activator.
That is, the present invention provides a hydraulic transfer body using a support film made of a water-soluble or water-swellable resin and a hydraulic transfer film having a transfer layer soluble in an organic solvent provided on the support film. The activator used in the above is provided with 3 to 50% by mass of a monoterpene hydrocarbon.

  The present invention also provides a hydraulic transfer film having a support film made of a water-soluble or water-swellable resin and a transfer layer soluble in an organic solvent provided on the support film, with the transfer layer facing up. In the method for producing a hydraulic transfer body, the hydraulic transfer film is transferred to the transferred body by pressing the transferred body against the transfer layer which is floated on water and activated by the activator. A method for producing a hydraulic transfer body using the activator described in 1. is provided.

  The present invention can provide an activator that has low toxicity and can be used for a hydraulic transfer film having a transfer layer in which a curable resin layer and a decorative layer are integrated.

(Activator)
The present invention is characterized by the use of monoterpene hydrocarbons as one component of the activator.
Examples of the monoterpene hydrocarbon used in the present invention include limonene, terpinene, sabinene, camphene, binene, osymene, myrcene, cymene, ferrandlene, terpinolene, paracymene, δ-3-carene, himacarene, tricyclene, caralene and the like. It is done. Of these, limonene or terpinene is preferable.
The monoterpene hydrocarbon is preferably used in the range of 3 to 50% by mass, more preferably 5 to 35% by mass, and still more preferably 5 to 25% by mass with respect to the total amount of the activator.

  In the present invention, the organic solvent used in combination with the monoterpene hydrocarbon is not particularly limited, and a known organic solvent can be used. For example, ethyl cellosolve, butyl cellosolve, butyl carbitol acetate, carbitol, carbitol acetate, cellosolve acetate, methyl isobutyl ketone, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl amyl Examples include ketones, methyl isoamyl ketone, isobutyl alcohol, isopropyl alcohol, n-butanol, diacetone alcohol, sol-fit acetate, 3-methoxybutyl acetate, and the like, and mixtures thereof. Of these, methyl isoamyl ketone, isoamyl acetate, and isobutyl alcohol are preferable.

  More preferable compositions in the activator of the present invention include, for example, a mixture of limonene / methyl isoamyl ketone / isoamyl acetate / isobutyl alcohol, a mixture of terpinene / methyl isoamyl ketone / isoamyl acetate / isobutyl alcohol, and the like.

In the present invention, various additives such as an antifoaming agent, a fluidity modifier, an antistatic agent, an antioxidant, a light stabilizer, and an ultraviolet absorber are included in the activator as long as the activation performance is not impaired. May be added.
Furthermore, in order to improve the adhesiveness of printing ink or a coating material and a molded article in this activator, you may include 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.

  Since the activator of the present invention has high permeability, a thick hydraulic transfer film having a plurality of layers such as a decorative layer and a curable resin layer can be activated in a short time.

(Hydraulic transfer film)
The activator of the present invention is a known hydraulic transfer film, for example, a hydraulic transfer film having only a decorative layer as a transfer layer, or a decorative layer and a curable resin layer as a transfer layer as described in JP-A-2004-34393. It can be used as an activator of a hydraulic transfer film having Especially, the hydraulic transfer film which has a decoration layer and a curable resin layer as a transfer layer can exhibit the effect of this invention most, and is preferable. Moreover, you may provide the peelable film on the transfer layer as needed. Hereinafter, there is a support film made of a water-soluble or water-swellable resin, which is a preferred form, and a transfer layer that can be dissolved in an organic solvent provided on the support film, and the transfer layer is at least a decorative layer And the film for hydraulic transfer which has a curable resin layer which can be hardened | cured by active energy ray irradiation and at least 1 type of heating is demonstrated.

(Support film)
The support film used for the hydraulic transfer film used in the present invention is a film made of a water-soluble or water-swellable resin.
Examples of resins comprising water-soluble or water-swellable resins include polyvinyl alcohol (PVA), polyvinyl pyrrolidone, acetyl cellulose, polyacrylamide, acetyl butyl cellulose, gelatin, glue, sodium alginate, hydroxyethyl cellulose, carboxymethyl cellulose, etc. it can. 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. These resin layers may be a single layer or multiple layers, and the layer thickness is preferably about 10 to 200 μm.

(Transfer layer (decoration layer, curable resin layer))
Next, the transfer layer (decoration layer, curable resin layer) provided on the support of the hydraulic transfer film of the present invention will be described. The transfer layer is a curable resin layer or a composite layer in which a curable resin layer and a decoration layer are laminated.

(Transfer layer decoration layer)
In the transfer layer of the hydraulic transfer film used in the present invention, the decorative layer is obtained by printing a single layer or a plurality of layers of ink on the support film by a method such as printing. The printing method is not particularly limited, and for example, it can be produced by printing or coating by a method such as gravure printing, offset printing, screen printing, ink jet printing, roll coating, comma coating, rod gravure coating, or micro gravure coating. . The entire surface of the ink layer may be printed or coated with the same ink (100% in the case of halftone dots), or may be partially printed so as to form a pattern.

Furthermore, a resin layer may be provided between the support film and the ink layer, which is preferable. The purpose of the resin layer includes, for example, the purpose as an ink receiving layer, the purpose of increasing the adhesive force with the transfer target, the purpose of suppressing excessive swelling of the film during transfer, and the like, depending on the purpose. Can be selected or additives can be added.
Examples of resins that can be used for these purposes include acrylic resins, polyurethane resins, polyester resins, vinyl chloride resins, vinyl acetate resins, vinyl chloride-vinyl acetate copolymer resins, and other vinyl resins, chlorinated olefin resins, and ethylene-acrylic resins. Known resins such as resins, petroleum-based resins, and cellulose derivative resins can be used. In addition, as a resin used for the purpose of increasing the adhesive force with the transfer target, a polyurethane resin, a polyester resin, a vinyl chloride-vinyl acetate resin copolymer resin, or a cellulose derivative resin is preferable.
Moreover, when using for the purpose of suppressing swelling, what added the inorganic fine particle etc. to the said resin is used.
Moreover, the active energy ray irradiation curable resin layer etc. which are mentioned later may be laminated | stacked.
Thus, the activator of the present invention can be easily activated even by a thick hydraulic transfer film provided with a resin layer and a decorative layer.

There is no restriction | limiting in particular in the ink used for a decoration layer. As the colorant contained in the ink, a pigment is preferable, and any of an inorganic pigment and an organic pigment can be used. For example, general-purpose color pigments include carbon black as a black pigment; yellow lead, yellow lead, anthraquinone yellow, mineral fast yellow, titanium yellow; red pigments such as Bengala, cadmium red, quinacridone red, permanent red 4R, and risol red. , Pyrazolone red, watching red calcium salt, lake red D, brilliant carmine 6B, eosin lake; blue pigment, bitumen, cobalt blue, alkali blue lake, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue; Chrome green, chromium oxide, pigment green B, malachite green lake; examples of white pigments include titanium white. Examples of pigments that exhibit a metallic tone include metal powder pigments (aluminum, bronze, etc.), metal foil pigments (aluminum, bronze, etc.), metal vapor-deposited foil pigments (pulverized films of plastics, etc., on which aluminum, bronze, etc. are deposited). It is done. Pearl pigments (such as those obtained by pulverizing natural pearls, flaky materials such as mica, aluminum, glass, etc., coated with titanium oxide, iron oxide, etc.) as pigments that exhibit pearl tone, multicolor effect, polarization effect, hologram, etc. Etc. Inorganic extender pigments such as lime carbonate powder, precipitated calcium carbonate, gypsum, clay (China Clay), silica powder, diatomaceous earth, talc, kaolin, alumina white, barium sulfate, aluminum stearate, magnesium carbonate, barite powder, abrasive powder, Silicone, glass beads and the like can also be used.
The varnish resin contained in the ink is, for example, an acrylic resin system, a polyurethane resin system, a polyester resin system, a vinyl resin system (vinyl chloride, vinyl acetate, vinyl chloride-vinyl acetate copolymer resin), a chlorinated olefin resin system, Known inks such as ethylene-acrylic resin, petroleum resin, and cellulose derivative resin can be used. Among these, polyurethane resins, polyester resins, vinyl chloride-vinyl acetate copolymer resins, cellulose derivative resin systems are preferably used because they are excellent in solubility in organic solvents, fluidity, pigment dispersibility, and transferability. Polyester resin system and cellulose derivative resin system are preferable, and polyurethane resin system and cellulose derivative resin system are particularly preferable.

(Transfer layer curable resin layer)
When the hydraulic transfer film used in the present invention has a curable resin layer as a transfer layer, the curable resin layer is a resin layer containing a resin that can be cured by irradiation with active energy rays or heating. Active energy ray curing and heat curing may be used in combination. The curable resin layer is preferably transparent since the design of the decorative layer of the resulting hydraulic transfer body can be expressed well, but depending on the required properties and design characteristics of the transfer body. Basically, it is sufficient that the color and pattern of the decorative layer of the hydraulic transfer body obtained can be seen through, and it is not necessary to be completely transparent. That is, from transparent to translucent ones are included. Moreover, it may be colored.

(Active energy ray curable resin)
The resin layer containing a resin curable by active energy ray irradiation includes, for example, a known radical polymerizable compound and, if necessary, a photopolymerization initiator. As the radically polymerizable compound, an oligomer or polymer having three or more (meth) acryloyl groups in one molecule is preferable, and a mass average molecular weight having three or more (meth) acryloyl groups in one molecule is 300 to 1. Ten thousand, more preferably 300 to 5,000 active energy ray-curable oligomers or polymers are preferably used. Also, it contains a reactive monomer having a (meth) acryloyl group for the purpose of adjusting the viscosity, reduces the tackiness of the curable resin layer, improves the glass transition temperature (Tg), or cohesive failure of the curable resin layer For the purpose of improving the strength, a thermoplastic resin may be contained.

  Examples of the oligomer or polymer having a (meth) acryloyl group include, for example, polyurethane (meth) acrylate, polyester (meth) acrylate, polyacryl (meth) acrylate, epoxy (meth) acrylate, and polyalkylene glycol poly (meth) acrylate. , Polyether (meth) acrylate, etc., among which polyurethane (meth) acrylate, polyester (meth) acrylate and epoxy (meth) acrylate are preferably used.

  Examples of the reactive monomer having a (meth) acryloyl group include, for example, methyl acrylate, methyl methacrylate (hereinafter collectively referred to as methyl (meth) acrylate), ethyl (meth) acrylate, n-butyl (meta ) Acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, phenyl ( (Meth) acrylate, phenyl cellosolve (meth) acrylate, 2-methoxyethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-acryloyloxyethyl Monofunctional monomers such as idrogen phthalate, dimethylaminoethyl (meth) acrylate, trifluoroethyl (meth) acrylate, trimethylsiloxyethyl methacrylate, N-vinylpyrrolidone, styrene, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) ) Acrylate, 1,6-hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 2,2-bis (4- (meth) acryloyloxypolyethyleneoxyphenyl) propane, 2,2′-bis (4 -3 functional groups such as bifunctional monomers such as (meth) acryloyloxypolypropyleneoxyphenyl) propane, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate Monomers, tetrafunctional monomers such as pentaerythritol tetra (meth) acrylate, hexafunctional monomers such as dipentaerythritol hexaacrylate. A maleimide compound such as butylene glycol bis (maleimide acetate) can also be used. Of course, it is also possible to use a mixture of two or more of these monomers.

  Examples of photopolymerization initiators include, for example, acetophenone compounds such as diethoxyacetophenone and 1-hydroxycyclohexyl-phenyl ketone; benzoin compounds such as benzoin and benzoin isopropyl ether; 2,4,6-trimethylbenzoin diphenylphosphine oxide Acyl phosphine oxide compounds such as benzophenone, benzophenone compounds such as methyl-4-phenylbenzophenone o-benzoylbenzoate; thioxanthone compounds such as 2,4-dimethylthioxanthone; aminobenzophenones such as 4,4'-diethylaminobenzophenone Compounds such as polyether-based maleimide carboxylic acid ester compounds, and the like, which can be used in combination. The usage-amount of a photoinitiator is 0.1-15 mass% normally with respect to the active energy ray curable resin to be used, Preferably it is 0.5-8 mass%. Examples of the photosensitizer include amines such as triethanolamine and ethyl 4-dimethylaminobenzoate. Furthermore, onium salts such as benzylsulfonium salt, benzylpyridinium salt, and arylsulfonium salt are known as photocationic initiators, and these initiators can also be used, and are used in combination with the above photopolymerization initiators. You can also

The thermoplastic resin used is preferably compatible with the active energy ray curable resin, and specific examples include polymethacrylate, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, and polyester. These may be a homopolymer or a copolymer of a plurality of monomers. The thermoplastic resin is preferably non-polymerizable.
Among them, polystyrene and polymethacrylate are preferable because they have high Tg and are suitable for reducing the adhesiveness of the curable resin layer, and in particular, polymethacrylate mainly composed of polymethyl methacrylate is transparent, solvent resistant, and It is preferable at the point which is excellent in abrasion resistance.

Further, the molecular weight and Tg of the thermoplastic resin have a great influence on the film-forming ability. In order to suppress fluidity of the curable resin and facilitate activation of the curable resin layer, the mass average molecular weight of the thermoplastic resin is preferably 3,000 to 400,000, more preferably 10,000 to 200,000. Tg is preferably 35 ° C to 200 ° C, more preferably 35 ° C to 150 ° C. When using a thermoplastic resin having a relatively low Tg of around 35 ° C., the mass average molecular weight of the thermoplastic resin is preferably 100,000 or more.
If the amount of the thermoplastic resin is too large, the curing reaction of the curable resin is inhibited. Therefore, the thermoplastic resin is preferably added in a range not exceeding 70 parts by mass with respect to 100 parts by mass of the total resin amount of the curable resin layer. .

  Among these, the curable resin layer containing the active energy ray-curable resin and the non-polymerizable thermoplastic resin has a mass average molecular weight of 300 to 10,000 having three or more (meth) acryloyl groups in one molecule. More preferably, the active energy ray-curable resin is 300 to 5,000, and the Tg compatible with the active energy ray curable resin is 35 ° C to 200 ° C, preferably 35 ° C to 150 ° C, and the mass average molecular weight is 3000. A curable resin layer containing a non-polymerizable thermoplastic resin of ˜400,000, preferably 10,000 to 200,000 is preferred. Further, the active energy ray-curable resin is a polyurethane (meth) acrylate having three or more (meth) acryloyl groups in one molecule, and the non-polymerizable thermoplastic resin is a polymethacrylate, particularly polymethylmethacrylate. A curable resin layer that is an acrylate is particularly preferred.

(Thermosetting resin)
The resin layer containing a resin curable by heating is a compound having a functional group that polymerizes by the action of heat or a catalyst in the molecule, or a thermoreactive compound that becomes a curing agent to a thermosetting compound that becomes a main agent including. Further, similar to the active energy ray curable resin, the thermoplastic resin is used for the purpose of reducing the tackiness of the curable resin layer, improving the glass transition temperature (Tg), or improving the cohesive fracture strength of the curable resin layer. May be included.

The thermal polymerization initiator is not particularly limited. However, when the transfer object is a plastic having a low heat resistant temperature, it is preferable to use a thermal polymerization initiator having a starting temperature as low as possible. It is preferred to use a thermal polymerization initiator having an initiation temperature.
Moreover, a well-known thing can be used as a thermosetting compound, for example, it has a functional group which superposes | polymerizes by the effect | action of a heat | fever or a catalyst, for example, N-methylol group, N-alkoxymethyl group, an epoxy group, a methylol group, an acid. A compound or resin having an anhydride, a carbon-carbon double bond, or the like can be used.

  The thicker the curable resin layer, the greater the protective effect of the resulting molded product, and the greater the effect of absorbing the irregularities of the decorative layer, so that the molded product can have excellent gloss. Accordingly, the film thickness of the curable resin layer is specifically 3 μm or more, preferably 10 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. Preferably, it is 10-70 micrometers. Since the activator of the present invention has high permeability, even a curable resin layer having a thickness of 10 μm or more can be easily activated.

In the curable resin layer, an inorganic / metal compound or an inorganic / metal compound subjected to organic treatment can be added.
There are no restrictions on these compounds that can be added, and for example, organic treatments such as silica gel, silica sol, montmorillonite, mica, alumina, titanium oxide, glass beads, and other inorganic / metal compounds, organosilica sol, acrylic-modified silica, and closite are performed. Inorganic / metal compounds prepared can be used.

(Method for producing hydraulic transfer body)
The hydraulic transfer body of the present invention is not particularly limited except that the activator of the present invention is used, and can be produced by a known transfer method.
Specifically, for example, after the release film is peeled off as necessary, the hydraulic transfer film to be used is floated in water with the transfer layer facing up and the support facing down, and the activator of the present invention The transfer layer is activated by (the activation may be performed before floating in water), the transfer layer is transferred to the transfer target, the support is removed, and then the transfer layer has a curable resin layer. The curable resin layer is cured by at least one of active energy ray irradiation and heating. Hereinafter, a method for producing a hydraulic transfer body when a hydraulic transfer film having a decorative layer and a curable resin layer is used as the transfer layer will be described in detail. Details of the process are as follows.

(1) The hydraulic transfer film from which the peelable film has been peeled is floated on water in a water tank with the support film facing down, 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 the activator of the present invention to the transfer layer. The activation may be performed before the film is floated on water.
(3) While the transfer medium is pressed against the transfer layer, the transfer object and the hydraulic transfer film are submerged in water, and the transfer layer is brought into close contact with the transfer object by water pressure and transferred.
(4) The cured resin obtained by removing the support film from the transfer medium taken out of water and curing the curable resin layer of the transfer layer transferred to the transfer medium by at least one of irradiation with active energy rays and heating. A hydraulic transfer body having a layer and a decorative layer is obtained.

(water)
The water in the water tank in hydraulic transfer functions as a hydraulic medium that closely adheres the curable resin layer and decorative layer of the hydraulic transfer film to the three-dimensional curved surface of the transfer target when transferring the transfer layer, and also swells the support film. Or, specifically, water such as tap water, distilled water, ion-exchanged water, etc., and depending on the support film used, 10% or less of inorganic salts such as boric acid in the water or alcohol 50% or less may be dissolved.

(Application method of activator)
Examples of a method for applying the activator of the present invention in the activation step include a method of applying or spraying. Specifically, there is no limitation as long as the activator can be applied to the film, and a roll coater, a die coater, a curtain coater, a spray nozzle, an inkjet nozzle, or the like can be used. Although the amount of the activator is not particularly limited, usually used in an amount of ^20g / ^{m 2 ~60g} / m 2 to the hydraulic transfer film 1 m @ 2. Range of 30g ^{/ m 2} ~40g ^/ m 2 is further preferable.

  The activated transfer layer is transferred to a transfer target. Specifically, 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. .

The support film is removed from the transfer target after transfer. Specifically, the support film is removed from the transfer medium taken out of water and dried.
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 drying step is preferably heat drying because it can be performed in a short time. The drying temperature at this time is preferably a temperature that does not exceed the heat resistance temperature of the substrate so that the material to be transferred is a plastic or the like having a low heat resistance temperature so as not to cause thermal deformation of the material to be transferred. An oven or a drying furnace can be used.

  When the hydraulic transfer film to be used has a curable resin layer, the curable resin layer is cured by active energy rays or heat. As the active energy ray to be used, it is usually preferable to use visible light or ultraviolet light. In particular, ultraviolet rays are suitable. As the ultraviolet light source, sunlight, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like is used. Moreover, as a heat source, well-known heat sources, such as a hot air and a near infrared ray, are applicable.

(Primer layer)
It is preferable that the curable resin layer and the decoration layer are sufficiently adhered to the surface of the transferred body, and a primer layer is provided on the surface of the transferred body 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. In addition, primer treatment is not required for a transfer medium comprising a resin component having high solvent absorbability such as ABS resin or SBS rubber having good adhesion. The material of the transferred material may be any of metal, plastic, wood, pulp mold, glass, etc., as long as it has a waterproof property so that its shape does not collapse even if it is submerged in water by applying a waterproof process. There is no particular limitation.

  Hereinafter, the present invention will be described with reference to examples. Unless otherwise specified, “part” and “%” are based on mass.

Production Example 1 Production of Curable Resin A1 60 parts of an average hexafunctional urethane acrylate (UA1) obtained by reacting 2 molar equivalents of pentaerythritol, 7 molar equivalents of hexamethylene diisocyanate and 6 molar equivalents of hydroxyethyl methacrylate at 60 ° C. The weight average molecular weight 890), Rohm and Haas acrylic resin paraloid A-11 (Tg 100 ° C., mass average molecular weight 125,000) 40 parts, and a mixed solvent of ethyl acetate and methyl ethyl ketone (mixing ratio 1/1) A 50% curable resin A1 was produced.

(Production Example 3) Production of film (B) B1 having a decorative layer As a peelable film, a 50 μm-thick unstretched polypropylene film (hereinafter abbreviated as PP film) manufactured by Toyobo Co., Ltd. was used, and urethane ink ( A decorative film (B) B1 was manufactured by printing a 3 μm-thick grain pattern on a product name: Univia A) with a gravure four-color printing machine.

(Ink composition, black, brown, white)
Polyurethane (Polyurethane 2569 made by Arakawa Chemical): 20 parts
Pigment (black, brown, white): 10 parts
Ethyl acetate / toluene (1/1): 60 parts
Additives such as wax: 10 parts

(Production Example 4) Manufacture of hydraulic transfer film C1 As a support film, the curable resin A1 of Production Example 1 is applied to the glossy surface of PVA (film thickness 30 μm, width 360 mm) manufactured by Aicello Chemical Co., Ltd. with a comma coater and the solid content film thickness 10 μm. And then dried at 60 ° C. for 2 minutes to produce a film (A). The curable resin layer of this film (A) and the ink layer of the film (B) B1 having a decorative layer are laminated at 60 ° C., and the laminated film is wound up as it is and the film C1 for hydraulic transfer. Manufactured.

Table 1 summarizes the film specifications and production conditions of the hydraulic transfer film C1 obtained in Production Example 4.

(Activator)
As the activator, D1 to D10 (the ratio is described in Table 2) are used in Examples and Comparative Examples, and D11 to D13 (the ratio is described in Table 3) are used as Reference Examples.

Mixed solvent A: isobutyl alcohol / isoamyl alcohol / isoamyl acetate = 56.25 / 37.5 / 6.25

Mixed solvent B: isobutyl alcohol / butyl acetate / isoamyl acetate / 3-methoxybutyl acetate = 53.3 / 6.7 / 26.7 / 13.3

( Comparative Example 1)
Water at 25 ° C. was placed in a water tank and floated on the water surface with the PVA side of the hydraulic transfer film C1 from which the peelable film was peeled down. Activating agent D1 was sprayed at 30 g / m ² , and after 15 seconds, an A4-size ABS plate (thickness: 3 mm) was inserted into the water from the hydraulic transfer film to perform hydraulic transfer.
The PVA was washed with water using a jet washer JW-350B manufactured by Nisshin Seiki Co., Ltd. under conditions of 28 Hz, 20 ° C., 2 minutes, and then dried at 80 ° C. for 30 minutes. Next, by using a UV irradiation apparatus manufactured by Nihon Batteries Co., Ltd., by irradiating 1100 mJ / cm ² of UV light, the curable resin layer was cured to obtain a hydraulic transfer body having a clear pattern. .

(Example 1 )
As a result of hydraulic transfer using the activator D2 in the same manner as in Comparative Example 1, a hydraulic transfer body having a very clear pattern was obtained.

(Example 2 )
As a result of hydraulic transfer using the activator D3 in the same manner as in Comparative Example 1, a hydraulic transfer body having a very clear pattern was obtained.

(Example 3 )
As a result of hydraulic transfer using the activator D4 in the same manner as in Comparative Example 1, a hydraulic transfer body having a very clear pattern was obtained.

( Comparative Example 2 )
As a result of hydraulic transfer using the activator D5 in the same manner as in Comparative Example 1, a hydraulic transfer body having a clear pattern was obtained.

( Comparative Example 3 )
As a result of hydraulic transfer using the activator D6 in the same manner as in Comparative Example 1, a hydraulic transfer body having a clear pattern was obtained.

(Example 4 )
As a result of hydraulic transfer using the activator D7 in the same manner as in Comparative Example 1, a hydraulic transfer body having a very clear pattern was obtained.

(Example 5 )
As a result of hydraulic transfer using the activator D8 in the same manner as in Comparative Example 1, a hydraulic transfer body having a very clear pattern was obtained.

(Example 6 )
As a result of hydraulic transfer using the activator D9 in the same manner as in Comparative Example 1, a hydraulic transfer body having a very clear pattern was obtained.

( Comparative Example 4 )
As a result of hydraulic transfer using the activator D10 in the same manner as in Comparative Example 1, a hydraulic transfer body having a clear pattern was obtained.

(Reference Example 1)
As a result of hydraulic transfer using the activator D11 in the same manner as in Comparative Example 1, a hydraulic transfer body having a very clear pattern was obtained.

(Reference Example 2)
As a result of hydraulic transfer using the activator D12 in the same manner as in Comparative Example 1, a hydraulic transfer body having a pattern collapse was obtained.

(Reference Example 3)
As a result of hydraulic transfer using the activator D13 in the same manner as in Comparative Example 1, a hydraulic transfer body having a very clear pattern was obtained.

Evaluation Methods of Examples and Comparative Examples , and Reference Examples 1 to 3 The pattern reproducibility was evaluated by visually comparing the pattern density of the hydraulic transfer body with a film having a decorative layer. The pattern in which the shading of the pattern was reproduced was marked with ◯, and the sharp pattern was marked with ◎. The case where pattern collapse occurred and the pattern was unclear was rated as x.
The results are shown in Tables 4 and 5.

(Acts 1 to 6 are the abbreviations of Examples 1 to 6 , and the ratios 1 to 4 are the Comparative Examples 1 to 4, respectively . References 1 to 3 are abbreviations of Reference Examples 1 to 3.)

From the above results, Examples 1 6 using D 2 to D 9 as activator, pattern reproducibility of the active agent and the level to use xylene, toluene or listed in Reference Example 1 and 3 are very An excellent product was obtained .

  The hydraulic transfer body obtained by the production method of the present invention includes home appliances such as televisions, videos, air conditioners, radio cassettes, mobile phones and refrigerators; OA equipment such as personal computers, fax machines and printers; homes such as fan heaters and cameras. Housing parts of products; furniture parts such as tables, chests and pillars; building parts such as bathtubs, system kitchens, doors and window frames; miscellaneous goods such as calculators and electronic notebooks; automobile interior panels, automobile and motorcycle skins, wheel caps Car interiors and accessories such as ski carriers and automobile carrier bags; sports equipment such as golf clubs, skis, snowboards, helmets and goggles; 3D images for advertising, signboards, monuments, etc. Is particularly useful for molded products that require It is possible to use.

Claims (7)

Activation for use in the production of a hydraulic transfer body using a support film made of a water-soluble or water-swellable resin and a hydraulic transfer film having a transfer layer soluble in an organic solvent provided on the support film. An activator comprising 3 to 50% by mass of a monoterpene hydrocarbon.
The monoterpene hydrocarbon is limonene or terpinene, activator of claim 1. The activator according to claim 2, comprising methyl isoamyl ketone or isoamyl acetate . The activator according to any one of claims 1 to 3 , wherein the transfer layer has at least a decorative layer and a curable resin layer that can be cured by at least one of active energy ray irradiation and heating. The decorative layer contains a polyurethane resin, a polyester resin, a vinyl chloride-vinyl acetate copolymer resin or a cellulose derivative resin, and the curable resin layer is an oligomer or polymer having three or more (meth) acryloyl groups in one molecule. The activator according to claim 4. A support film made of a water-soluble or water-swellable resin, and a hydraulic transfer film having a transfer layer soluble in an organic solvent provided on the support film, floated in water with the transfer layer facing up, 2. The activation according to claim 1 as an activator in a method for producing a hydraulic transfer body in which a film for hydraulic transfer is transferred to a transfer body by pressing the transfer body against the transfer layer activated by an activator. A method for producing a hydraulic transfer body, characterized by using an agent. The transfer layer has at least a decorative layer and a curable resin layer that can be cured by at least one of active energy ray irradiation and heating, and after transferring the hydraulic transfer film to the transfer target, the transferred curable resin The method for producing a hydraulic transfer member according to claim 6, wherein the layer is cured.