JP2005297429A - Film for hydraulic pressure transfer and hydraulic pressure transfer body - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a film for hydraulic pressure transfer which reduces a loss of beauty such as a washing mark in a process of removing a support film and enables manufacture of a hydraulic pressure transfer article, a manufacturing method thereof, a hydraulic pressure transfer body manufactured by using the film for hydraulic pressure transfer, and a manufacturing method of the body. <P>SOLUTION: The hydraulic pressure transfer film has the support film constituted of a water-soluble or water-swelling resin and a transfer layer provided on the support film and being soluble to an organic solvent. The transfer layer has a curable resin layer of which the viscosity at a shear rate of 0.1 s<SP>-1</SP>on the occasion of being diluted with an organic solvent so that the concentration of the solid content of the resin be 55% is 5-10,000 Pa s and which can be cured by at least one of an activation energy beam and heating. The hydraulic pressure transfer body using the hydraulic pressure transfer film and the manufacturing method of the body are provided. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention uses a hydraulic transfer film capable of simultaneously hydraulically transferring a curable resin layer, or a curable resin layer and a decorative layer, onto the surface of an object to be transferred such as various molded articles, a manufacturing method thereof, and the hydraulic transfer film. The present invention relates to a hydraulic transfer body to be manufactured and a method for manufacturing the same.

  The hydraulic transfer method is a method that can add a decorative layer rich in design to a molded product with a complicated three-dimensional shape, but in order to make the hydraulic transfer film follow the surface of the molded product with a complicated three-dimensional shape, The film itself must have sufficient flexibility.

Making the hydraulic transfer film flexible is activation in a so-called hydraulic transfer method.
Activation is to redissolve the transfer layer formed into a film with an organic solvent. When the transfer layer is composed of a composite layer in which a curable resin layer and a decorative layer are laminated, the decorative pattern must be softened without breaking, and the laminated structure must be maintained. Moreover, when a transfer layer consists of a curable resin layer, it must be made flexible while holding the curable resin layer.

  A normal hydraulic transfer film has a transfer layer on a support film made of a water-soluble or water-swellable resin. The hydraulic transfer body floats the hydraulic transfer film on the water with the transfer layer facing up and the support film down, activates the transfer layer with an organic solvent, and then transfers the transfer layer to the transfer substrate with water pressure. It is obtained by removing the support film.

As methods for removing the support film, there are still water immersion, running water, water discharge, water shower, water spraying, water spraying, etc., but still water immersion requires a long time to remove the support film and is not industrially suitable. Therefore, it is usually performed by a method of removing the support film in a short time by applying water pressure, such as water shower, water spray, or water spray.
However, when a hydraulic transfer film having a curable resin layer is used, when the support film is removed by applying water pressure in this way, the water pressure activates and softens the uncured curable resin with an organic solvent. The layer may have cleaning marks such as sandblast, orange peel, crater, bar, and streak, which may impair the aesthetics of the resulting hydraulic transfer body.

  There is also known a method of pre-curing the curable resin layer in advance before removing the support film to obtain a hydraulic transfer body having no cleaning mark (see, for example, Patent Document 1). Therefore, there is a problem that it is necessary to switch the irradiation amount and intensity of the active energy ray irradiating device, or a plurality of active energy ray irradiating devices must be introduced, resulting in a decrease in efficiency and high cost. It was. In addition, the preliminary curing needs to strictly define the crosslink density of the curable resin layer, and is not a simple method for a three-dimensional molded product.

JP 2003-305998 A

  The problem to be solved by the present invention is a hydraulic transfer film capable of producing a hydraulic transfer product without loss of aesthetics such as washing marks in the support film removal step by hydraulic pressure, a method for producing the same, and the hydraulic transfer It is providing the hydraulic transfer body manufactured using a film, and its manufacturing method.

If the transfer layer, particularly the curable resin layer is too soft when activated, that is, if the viscosity of the curable resin layer is too low during activation, the support film removal step by water pressure I found that there was a trace of washing. Furthermore, the viscosity of the curable resin layer at the time of activation was measured at a shear rate of 0.1 s ⁻¹ by diluting the curable resin layer with an organic solvent used at the time of activation so that the solid concentration was 55%. The above problem was solved by using a curable resin having a viscosity in a specific range for the transfer layer of the hydraulic transfer film.

That is, the present invention includes 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, and the transfer layer includes active energy rays. It has a curable resin layer that can be cured by at least one kind of heating, and the curable resin layer has a shear rate of 0.1 s ⁻¹ when diluted with an organic solvent so as to have a solid content concentration of 55%. A hydraulic transfer film having a viscosity of 5 to 10,000 Pa · s is provided.

In the present invention, the viscosity at a shear rate of 0.1 s ⁻¹ when diluted with an organic solvent to a solid content concentration of 55% on a support film made of a water-soluble or water-swellable resin is 5 to 5. A film (A) provided with a curable resin layer that is 10000 Pa · s and can be cured by at least one of active energy rays and heating;
A film (B) provided with a decorative layer that can be dissolved in an organic solvent comprising a printing ink film or a paint film on a peelable film,
Provided is a method for producing a hydraulic transfer film which is laminated by dry lamination so that the curable resin layer of the film (A) and the decorative layer of the film (B) face each other.

  Further, the present invention provides the hydraulic transfer film described above, after peeling the peelable film from the film, floating in water with the support film down, activating the transfer layer with an organic solvent, There is provided a method for producing a hydraulic transfer body in which a layer is transferred to a transfer medium, the support film is removed, and then the transfer layer is cured by at least one of active energy ray irradiation and heating.

  The present invention also provides a hydraulic transfer member produced by the method described above.

  In the hydraulic transfer film of the present invention, the viscosity of the curable resin layer at the time of activation is in a specific range. Can be produced.

The hydraulic transfer film of the present invention has 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, and the transfer layer has a solid content. A curable resin layer curable by at least one of active energy rays and heating, having a viscosity at a shear rate of 0.1 s ⁻¹ when diluted with an organic solvent so as to have a concentration of 55% is 5 to 10,000 Pa · s. Have.

(Concentration of solid content for viscosity evaluation of curable resin)
The transfer layer, particularly the curable resin layer, inevitably has a viscosity because it is redissolved with an organic solvent that becomes an activator (hereinafter, an organic solvent used as an activator is abbreviated as an activator) during activation. Go down. The activator is usually 90 to 150% by mass of the transfer layer mass per unit area with respect to the transfer layer (the curable resin layer and the decorative layer), although depending on the film thickness of the curable resin layer. Therefore, the transfer layer immediately after spraying, that is, the curable resin layer, is the same as the state in which the activator solution having a solid content concentration of 40 to 53% is applied. Since the transfer is carried out within a few seconds to 1 minute after the activator is sprayed, depending on the composition of the activator, it may volatilize during that time and the solid content concentration may increase. In the present invention, as a result of examining this value and how much the curable resin layer actually contains the activation agent at the time of activation, the solid content concentration of 55% is determined to be that of the curable resin layer at the time of actual activation. It was determined to be close to the solid content concentration and suitable for studying the relationship between the shear rate and the viscosity in evaluating the cleaning trace resistance described later.

(Viscosity measurement / shear rate)
On the other hand, as a result of examining the relationship between the shear rate and the viscosity, in particular, the effect of suppressing aesthetic loss on the curable resin layer due to the water pressure (water flow) at the time of washing with water is the curable resin layer solution measured at a moderate shear rate. It was well correlated with the viscosity. Among these, the viscosity when the shear rate is 0.1 s ⁻¹ is most correlated with the aesthetic loss such as washing marks in the support film removal step, and the viscosity when the shear rate is 0.1 s ⁻¹ is 5 By setting the pressure to 10000 Pa · s, it is possible to obtain a hydraulic transfer body having no cleaning marks or the like. Among them, the viscosity is preferably 5 to 5000 Pa · s, and most preferably 8 to 1000 Pa · s.

(viscosity)
It is desirable that the viscosity is appropriately adjusted according to the film thickness of the curable resin layer. For example, when the curable resin layer is a thick film having a thickness of about 100 to 200 μm, it is preferably adjusted within a relatively low range of about 5 to 50 Pa · s. On the other hand, when the curable resin layer is a thin film of about 3 to 5 μm, it is preferably adjusted within a relatively high viscosity range of about 500 to 10000 Pa · s, more preferably in the range of 500 to 5000 Pa · s, The range of ˜1000 Pa · s is most preferable.
When the viscosity is less than 5 Pa · s, a cleaning mark is likely to remain particularly in the support film removal step. On the other hand, if the viscosity exceeds 10,000 Pa · s, the followability of the film to a three-dimensional molded product is inferior, and there is a possibility that air bubbles may be bitten.

In the present invention, the viscosity may be measured using a viscometer such as a Brookfield (B) viscometer that can be measured at a shear rate of 0.1 s- ¹ . Examples of the viscometer include a cone plate type and a cylindrical type. In the present invention, a CS-type stress control rheometer manufactured by Calime Co., Ltd. is used and measured under the conditions of a measurement temperature of 25 ° C. and a stress of 5.968 × 10 ^{−3 to} 596.8 Pa, and a shear rate of 0.1 s ⁻ The viscosity at ¹ was calculated.

  In order to adjust the curable resin layer so that the viscosity when diluted with an activator so as to be a solid content concentration of 55% is 5 to 10,000 Pa · s, for example, a high molecular weight curable resin And a method for selecting a curable resin having a high solution viscosity and a method for adjusting the viscosity by adding a viscosity modifier. Among them, the method of adding a viscosity modifier is preferable because it is easy to adjust to a desired viscosity. If the desired design and characteristics are satisfied, there is no limitation on the type of the viscosity modifier, and inorganic or organic substances can be used, which may be soluble or swellable or insoluble in the activator.

(Viscosity modifier)
Inorganic materials include inorganic pigments, inorganic pigments such as carbon, titanium oxide, graphite, zinc white; carbonated lime powder, precipitated calcium carbonate, gypsum, clay (China Clay), silica powder, diatomaceous earth, talc, kaolin, alumina white Inorganic pigments such as barium sulfate, aluminum stearate, magnesium carbonate, barite powder, and abrasive powder; inorganic pigments such as silicone, glass beads, and inorganic crystals.

Examples of organic substances include organic coloring pigments, organic crystals, and polymer fine particles.
Examples of organic coloring pigments include general-purpose pigments such as azo pigments, phthalocyanine pigments, selenium pigments, and quinacridone pigments.
Depending on the particle size and amount of addition, the organic color pigment has a concealing effect on the base layer (transfer base material) in the case where the decorative layer in the transfer layer or the decorative layer is not provided, depending on the particle size and addition amount. What is necessary is just to control a particle size and addition amount.
Examples of the organic crystal include crystalline polyurea, crystalline polyurethane, crystalline polyamide, crystalline amino acid, crystalline polypeptide, crystalline organometallic complex, and the like.
Examples of the polymer particles include crosslinked acrylic particles, crosslinked polystyrene resin particles, crosslinked urethane particles, phenol resin particles, silicone resin particles, polyethylene particles, fluorine particles, melamine particles, polycarbonate particles, and phenol particles. .

  Among the viscosity modifiers, inorganic pigments, organic crystals, and polymer fine particles have a high viscosity adjustment effect, and also appropriately control the viscosity of the curable resin layer in the support film removal step in the hydraulic transfer step, and are curable. This is preferable because design deterioration of the resin surface is suppressed. Inorganic extender pigments and organic crystals are still preferred because they are particularly effective. Among the viscosity modifiers, 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 , Inorganic extender pigments such as abrasive powder, cross-linked acrylic fine particles, cross-linked polystyrene resin fine particles, cross-linked urethane fine particles, phenol resin fine particles, silicone resin fine particles, polyethylene fine particles, fluorine fine particles, melamine fine particles, polycarbonate fine particles, phenol fine particles, etc. Is used as a matting agent, and by using these, it is possible to obtain a hydraulic transfer body that is excellent in surface properties and has a matte tone that gives a high-class design feeling. Among them, silica powder is preferable because a high matting effect can be obtained with a small amount of addition.

  The amount of the viscosity modifier added is not particularly limited as long as the viscosity is 5 to 10,000 Pa · s when the curable resin layer is diluted with an activator so as to have a solid content concentration of 55%. However, the viscosity modifier may be used alone or in combination.

(Support film)
The support film used for the hydraulic transfer film of 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 (curable resin layer, decorative layer))
The transfer layer is composed of a curable resin layer or a composite layer in which a curable resin layer and a decoration layer are laminated.

(Curable resin layer)
The curable resin layer contains a curable resin that can be cured by at least one of active energy ray irradiation and heating. When the decorative layer is laminated, it is preferable that the curable resin layer is transparent because the design of the decorative layer of the obtained hydraulic transfer body can be expressed well. However, depending on the required characteristics and design properties of the hydraulic transfer body, it is sufficient that the color and pattern of the decorative layer of the hydraulic transfer body to be basically obtained can be seen through, and that the curable resin layer is completely transparent. It does not need to include transparent to translucent ones. Moreover, it may be colored.

(Curable resin layer curable resin)
Specific examples of the resin curable by at least one of active energy ray irradiation and heating, which are components of the curable resin layer, include the following (1) to (6).
(1) A curable resin layer containing an active energy ray-curable resin.
(2) A curable resin layer containing an active energy ray-curable resin and a thermoplastic resin.
(3) A curable resin layer containing a thermosetting resin.
(4) A curable resin layer containing a thermosetting resin and a thermoplastic resin.
(5) A curable resin layer containing an active energy ray curable resin and a thermosetting resin.
(6) A curable resin layer containing an active energy ray curable resin, a thermosetting resin, and a thermoplastic resin.
Next, the specific configurations (1) to (6) of the curable resin layer will be described.

(1) Curable resin layer containing active energy ray-curable resin The active energy ray-curable resin is an oligomer and a polymer having a polymerizable group or a structural unit curable by active energy rays in one molecule. The active energy rays referred to here are ultraviolet rays and electron rays, and both oligomers and polymers that are cured by these can be used, but ultraviolet curable resins are particularly suitable.

  As the ultraviolet ray source, 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.

  Examples of polymerizable groups and structural units that can be cured by active energy rays include groups and structural units having a polymerizable unsaturated double bond such as a (meth) acryloyl group, a styryl group, a vinyl ester, a vinyl ether, and a maleimide group. Of these, a (meth) acryloyl group is preferred. Of these, an active energy ray-curable oligomer or polymer having three or more (meth) acryloyl groups in one molecule is preferable. More specifically, an active energy ray-curable oligomer or polymer having a mass average molecular weight of 300 to 10,000, more preferably 300 to 5,000, having three or more (meth) acryloyl groups in one molecule is preferably used. .

  The oligomer or polymer having a (meth) acryloyl group can be used without any problem as long as it is used as a coating resin. Specific examples include polyurethane (meth) acrylate, polyester (meth) acrylate, poly Examples include acrylic (meth) acrylate, epoxy (meth) acrylate, polyalkylene glycol poly (meth) acrylate, polyether (meth) acrylate, and polyurethane (meth) acrylate, polyester (meth) acrylate, and epoxy (meth) acrylate. Is preferably used.

  In particular, an ultraviolet ray-curable polyurethane (meth) acrylate having three or more (meth) acryloyl groups in one molecule and a weight average molecular weight of 300 to 10,000, more preferably 300 to 5,000, is an active energy ray curable resin. Particularly preferably used. These may be used alone or in combination of two or more.

  The curable resin layer containing these active energy ray-curable resins 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. Acyl phosphine oxide compounds such as oxides; benzophenone, o-benzoylbenzoic acid methyl-4-phenylbenzophenone compounds such as benzophenone compounds; thioxanthone compounds such as 2,4-dimethylthioxanthone; amino compounds such as 4,4'-diethylaminobenzophenone Examples thereof include benzophenone compounds; polyether maleimide carboxylic acid ester compounds, and the like, and these 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

(2) Curable resin layer containing active energy ray curable resin and thermoplastic resin The curable resin layer containing active energy ray curable resin and thermoplastic resin contains the active energy ray curable resin and thermoplastic resin described above. . Use of a thermoplastic resin in combination with an active energy ray curable resin is extremely effective in reducing the tackiness of the curable resin layer, improving the glass transition temperature (Tg), and improving the cohesive fracture strength of the curable resin layer. . However, if the amount of the thermoplastic resin to be included in the curable resin layer is large, the curing reaction of the curable resin is inhibited. Therefore, the thermoplastic resin should be 70 parts by mass with respect to 100 parts by mass of the total resin of the curable resin layer. It is preferable to add in the range which does not exceed.

  The thermoplastic resin is compatible with the active energy ray curable resin to be used, 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 the fluidity of the curable resin and facilitate activation of the curable resin layer with an organic solvent, the mass average molecular weight of the thermoplastic resin is preferably 3,000 to 400,000, more preferably 10,000. The 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.

  Among these, as the curable resin layer containing the active energy ray-curable resin and the thermoplastic resin, a mass average molecular weight of 300 to 10,000 having three or more (meth) acryloyl groups in one molecule, more preferably 300 to 5000 active energy ray-curable resin, and Tg compatible with this active energy ray-curable resin is 35 ° C to 200 ° C, preferably 35 ° C to 150 ° C, and a mass average molecular weight is 3000 to 400,000, A curable resin layer containing a thermoplastic resin that is preferably 10,000 to 200,000 is preferable. Further, the active energy ray-curable resin is a polyurethane (meth) acrylate having three or more (meth) acryloyl groups in one molecule, and the thermoplastic resin is a polymethacrylate, particularly polymethyl methacrylate. An especially preferred resin layer is preferred.

(3) Curable resin layer containing a thermosetting resin The thermosetting resin is a compound having in its molecule a functional group that is polymerized by the action of heat or a catalyst, or a curing agent as a main component of the thermosetting compound. A heat-reactive compound is blended. Examples of the functional group that is polymerized by the action of heat or a catalyst include an N-methylol group, an N-alkoxymethyl group, an epoxy group, a methylol group, an acid anhydride, and a carbon-carbon double bond.

  For those having a carbon-carbon double bond in the molecule and capable of crosslinking reaction by polymerization, curable resins of the same type as the active energy ray curable resin can be used, and these curable resins and radical sources by heating. It can be used as a thermosetting resin by combining with a thermopolymerization initiator that generates. As the thermal polymerization initiator at this time, usual thermal polymerization initiators such as benzoyl peroxide and azobisisobutyronitrile are used.

  Specific combinations of the main agent and the curing agent include, for example, a main resin having a hydroxyl group or an amino group and an isocyanate as a curing agent; a main resin having a hydroxyl group or a carboxyl group and an N-methylol or N-alkoxymethyl as a curing agent. Amino resins such as melamine and benzoguanamine; main resin having epoxy group and hydroxyl group and acid anhydride such as phthalic anhydride as curing agent; main resin having carboxyl group, carbon-carbon double bond, nitrile group and epoxy group A phenol resin as a curing agent; a main resin having a carboxyl group or an amino group and an epoxy group-containing compound as a curing agent can be used.

  Many of these thermosetting resins undergo a gradual curing reaction during storage even at room temperature. If the curing reaction proceeds during the storage period, the transfer layer is not sufficiently activated by the organic solvent, which causes a transfer failure. For this reason, among thermosetting resins, a system using polyol as the main agent and blocked isocyanate as the curing agent is preferable.

  As the blocked isocyanate, those obtained by protecting an isocyanate group with a conventional blocking agent can be used. Examples of the conventional blocking agent include phenol, cresol, aromatic secondary amine, tertiary alcohol, lactam, oxime and the like.

As the block isocyanate, a block isocyanate having a suitable desorption temperature for the block group may be selected in accordance with the heat resistance of the decorative layer and the heat resistance of the transfer target.
Examples of the polyol include acrylic polyol, poly-p-hydroxystyrene, polyester polyol, and polyethylene vinyl alcohol copolymer. Acrylic polyol is particularly preferable, and an acrylic having a mass average molecular weight of 3,000 to 100,000 is particularly preferable. Polyols, more preferably 10,000 to 70,000 acrylic polyols are suitable.

  Since the thermosetting resin also needs printability or coatability, it is preferable that the resin has a high molecular weight before curing, preferably a mass average molecular weight of 1,000 to 100,000, more preferably 3,000 to 30,000. . More specifically, those containing a polyol (particularly preferably acrylic polyol) having a mass average molecular weight of 3,000 to 100,000, more preferably 10,000 to 70,000 as a main component and a blocked isocyanate as a curing agent are preferably used. .

(4) Curable resin layer containing a thermosetting resin and a thermoplastic resin As the curable resin layer containing a thermosetting resin and a thermoplastic resin, the thermosetting resin described in (3), and (2) The thermoplastic resin described is included.
The thermosetting resin to be used is the same as the thermosetting resin described in (3), and the preferred thermosetting resin is also a blocked isocyanate and a polyol as in (3). Particularly, the polyol is an acrylic polyol. The weight average molecular weight is 3,000 to 100,000, more preferably 10,000 to 70,000.

  When a blocked isocyanate and a polyol are used as the thermosetting resin, since the polyol generally has a coating film forming ability, the amount of the thermoplastic resin used in combination may be small. The thermoplastic resin to be used must be compatible with the thermosetting resin to be used. When a blocked isocyanate and a polyol are used as the thermosetting resin, a thermoplastic resin that is soluble in the polyol is preferable. As the thermoplastic resin, a thermoplastic resin having a Tg of 35 ° C. to 200 ° C., more preferably a Tg of 35 ° C. to 150 ° C., and a mass average molecular weight of 3000 to 400,000 is preferably used. Methacrylate is preferred. The thermoplastic resin is preferably non-polymerizable.

(5) Curable resin layer containing active energy ray curable resin and thermosetting resin As the curable resin layer containing active energy ray curable resin and thermosetting resin, the active energy rays described in (1), respectively. A curable resin and the thermosetting resin described in (3) can be used. For example, it contains (meth) acrylate having three or more (meth) acryloyl groups in one molecule, blocked isocyanate and polyol.

  Especially, what contains each preferable resin of the active energy ray-curable resin described in (1) and each preferable resin of the thermosetting resin described in (3) is preferable, for example, mass average molecular weight 300-1 More preferably, an oligomer or polymer having three or more (meth) acryloyl groups in one molecule of 300 to 5,000, particularly preferably a polyurethane (meth) acrylate, or a blocked isocyanate and a weight average molecular weight of 3,000 to 3,000. It contains 100,000, more preferably 10,000 to 70,000 acrylic polyols.

(6) Curable resin layer containing active energy ray curable resin, thermosetting resin and thermoplastic resin The curable resin layer containing active energy ray curable resin, thermosetting resin and thermoplastic resin is (1) It is a curable resin layer containing the active energy ray-curable resin described in 1., the thermosetting resin described in (3), and the thermoplastic resin used in combination with the active energy ray-curable resin described in (2). The thermoplastic resin is preferably non-polymerizable.

The curable resin layer must be able to be activated by an activator during hydraulic transfer. Therefore, the curable resin layer must improve the solubility with respect to an activator with the increase in film thickness. However, the curable resin layer also requires shape stability (storage stability) as a hydraulic transfer film having an uncured curable resin layer. In order to balance such contradictory requirements, The thermoplastic resin layer preferably contains a thermoplastic resin.
In the activation of the present invention, the activator lands on the transfer layer, the activator penetrates quickly, and the curable resin layer can be dissolved (activated). In addition, by including a thermoplastic resin, the curable resin layer has a moderate resistance to the penetration of the activator and has a firm self-holding power before curing, and is activated more gently. This makes it possible to suppress uneven dissolution of the curable resin layer and cracking of the decorative layer due to rapid activation.

In order to ensure the solubility of the curable resin layer at the time of transfer, it is preferable to use 45% by mass or more of a resin that can be cured by at least one of highly soluble active energy rays and heating.
On the other hand, the amount of the thermoplastic resin contained in the curable resin layer is preferably 25% by mass or more, more preferably, in order to better ensure the forming ability, drying property, and storage stability of the curable resin layer. Is 30% by mass or more.
Therefore, the mass ratio P of the resin that can be cured by at least one of active energy rays and heating with respect to the thermoplastic resin of the present invention: (mass sum of radical polymerizable compounds) / (mass sum of thermoplastic resins) is 45/55. It is preferably 75/25 or less, more preferably 50/50 or more and 70/30 or less, and most preferably 60/40.

In order to facilitate activation with an organic solvent, it is preferable to use a polyacrylate having a mass average molecular weight of 20,000 to 300,000 or a polyester having a mass average molecular weight of 5,000 to 50,000 as the thermoplastic resin.
When the molecular weight of the thermoplastic resin used exceeds the above range, it is effective in adjusting the viscosity of the curable resin layer at the time of activation, but it is difficult to activate with an activator within the time of hydraulic transfer. Easy to be. On the other hand, if the molecular weight is below the above range, it is difficult to suppress the fluidity and tackiness of the uncured curable resin layer, and the cured resin film moves to the coating film surface at a high temperature. Reduce performance.
Moreover, in order to improve the drying property at the time of coating film formation, it is preferable to use a polyacrylate having a mass average molecular weight of 150,000 or more or a polyester having a mass average molecular weight of 30,000 or more as the thermoplastic resin.
On the other hand, the glass transition temperature (Tg) of the thermoplastic resin is preferably 25 ° C to 250 ° C, more preferably 50 ° C to 150 ° C. If the Tg of the thermoplastic resin is less than 20 ° C., it is difficult to suppress the adhesiveness of the uncured curable resin layer, and adversely affects the heat resistance of the cured coating film. And curable resin become difficult to mix.

The above-described curable resin layer has a greater surface protection effect of the obtained hydraulic transfer body as the dry film thickness is thicker, and has a greater effect of absorbing irregularities of the decorative layer, so that the molded product has an excellent gloss. This is preferable. Therefore, in order to satisfy the function as the protective layer and the effect of absorbing the irregularities of the decorative layer, the dry film thickness of the curable resin layer is preferably 3 to 200 μm, and the uncured curable resin layer is stored. From the viewpoint of stability, it is preferably 100 μm or less. However, if the dry film thickness is too thick, activation (solubilization) of the curable resin layer by the activator tends to be insufficient. Therefore, in order to sufficiently activate the curable resin layer with the activator and satisfy the function as a protective layer and the design, it is preferably 5 to 50 μm, and preferably 10 to 45 μm. Is more preferable.
The curable resin layer can be formed by applying and drying an organic solvent solution (paint) of a curable resin, and the viscosity at the time of application may be appropriately adjusted to a viscosity suitable for the application method. The viscosity can be adjusted by adjusting the paint concentration.

  In the above (1) to (6), the antifoaming agent, the anti-settling agent, the pigment dispersing agent, the anti-blocking agent, the antistatic agent, and the antioxidant, as long as the design property and curability are not impaired in addition to the viscosity modifier Various conventional additives such as an agent, a light stabilizer, an ultraviolet absorber, a silica sol, and an organosilica sol may be added. These additives may be liquid or solid, and may be dissolved or only dispersed.

(Decoration layer)
The printing ink or paint used for forming the decorative layer of the hydraulic transfer film of the present invention is preferably activated by an activator to obtain sufficient flexibility when transferring the transfer layer to the transfer target. From the viewpoint of easily obtaining a high-quality image, it is preferably formed with gravure printing ink. A colored layer having no pattern can also be formed by coating.

  Resin used for the decoration layer, that is, base resin used for printing ink or paint is acrylic resin, polyurethane resin, polyamide resin, urea resin, epoxy resin, polyester resin, vinyl resin (vinyl chloride, vinyl acetate, PVC-vinegar) Uses thermoplastic resins such as vinyl copolymer resins), vinylidene resins (vinylidene chloride, vinylidene fluoride), ethylene-vinyl acetate resins, polyolefin resins, chlorinated olefin resins, ethylene-acrylic resins, petroleum-based resins, and cellulose derivative resins. It is done. Among these, polyurethane resins, polyester resins, and vinyl chloride-vinyl acetate copolymer resins are preferably used because of their excellent solubility in organic solvents, fluidity, pigment dispersibility, and transferability, and polyurethane resins and polyester resins are preferred. A polyurethane resin is particularly preferred.

  The polyurethane resin used in the printing ink or paint has a number average molecular weight (measured by GPC using a polystyrene calibration curve) of 2,000 to 60,000, more preferably 2,500 to 56,000, and even more preferably 2. What is 500-40,000 is preferable from having moderate adhesiveness with the solubility to an organic solvent, and a peelable film. When the number average molecular weight of the polyurethane resin is smaller than 2,000, the weather resistance is lowered, and when the number average molecular weight is larger than 60,000, the glass transition temperature is increased, and the adhesiveness and fluidity of the printing ink or paint are increased. , Pigment dispersibility and transferability are reduced. In addition, the glass transition temperature of the polyurethane resin is preferably −5 ° C. or more and 70 ° C. or less because it has solubility in an organic solvent and appropriate adhesion to a transfer target.

  A polyurethane resin having a low hydroxyl value is preferred, and a polyurethane having no hydroxyl group is preferred. The higher the hydroxyl value of the polyurethane resin, the more easily the polyurethane resin molecules become macromolecules due to hydrogen bonds or the like, and the glass transition temperature tends to increase and the transferability tends to decrease.

  The polyester resin used in the printing ink or coating material preferably has a number average molecular weight of 2,000 to 8,000 in order to have appropriate adhesion to the peelable film, and more preferably 2,500 to 7 , 500, most preferably 2,500 to 7,000. When the number average molecular weight is less than 2,000, the flexibility and elongation at break are lowered, the followability to the transferred material at the time of transfer is lowered, and the image quality of the decorative layer formed on the obtained hydraulic transfer body is improved. descend. If the number average molecular weight is larger than 8,000, the polyester resin molecules tend to become large molecules due to hydrogen bonding or the like, the glass transition temperature becomes high, and the transferability decreases. Moreover, it is preferable that the glass transition temperature of the polyester resin used for printing ink or a coating material is -5 degreeC or more and 70 degrees C or less from having moderate adhesiveness with a to-be-transferred material.

The polyester resin is preferably a polyester having a small number of hydroxyl groups, specifically a polyester having a hydroxyl value of 5 or less.
When the hydroxyl value of the polyester resin is large, the polyester resin molecules tend to become large molecules due to hydrogen bonds or the like, the glass transition temperature becomes high, and the transfer property of the printing ink or paint tends to decrease. When other resins are blended and the glass transition temperature of ink or paint is prepared to be low, it is preferable to use the above polyurethane resin as a resin other than the polyester resin.

In order to adjust the peeling force between the decorative layer and the peelable film, the decorative layer may contain a release agent. The release agent to be used is not limited at all as long as it can be dispersed in the decoration layer formed into an ink or paint. However, it is preferable to use a fluorine-based compound or a silicone-based compound, and it is easy to control the molecular weight and chemical structure. Compounds are particularly preferred. Among silicone compounds, polyether-modified polysiloxanes and polysiloxane-polyether block copolymers can be suitably used.
The content of the silicone compound in the printing ink or paint is preferably 0.01% by mass or more and 6.0% by mass or less, more preferably 0.05% by mass or more and 4.0% by mass or less in the nonvolatile content. It is. If the content is less than 0.01% by mass, the effect of the release agent is insufficient. If the content exceeds 6.0% by mass, repellency or the like occurs during multi-layer printability, which will be described later, and the printability tends to be reduced. When using a hydraulic transfer film, it becomes easy to cause peeling between a decoration layer and a curable resin layer.

  The printing ink or paint contains a colorant such as a pigment or a dye in addition to the base resin. The blending amount of the colorant may be appropriately determined according to the purpose of decoration, but is usually in the range of 1 to 50 parts by mass, more preferably in the range of 3 to 30 parts by mass.

  Examples of the colorant 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, risol red, and pyrazolone. Red, Watching Red Calcium Salt, Lake Red D, Brilliant Carmine 6B, Eosin Lake; Blue Pigment, Bitumen, Cobalt Blue, Alkaline Blue Lake, Victoria Blue Lake, Phthalocyanine Blue, Metal-free Phthalocyanine Blue; Green Pigment, Chrome Green , Chromium oxide, pigment green B, malachite green lake; titanium white or the like can be used as a white pigment.

  The printing ink or paint may contain a plasticizer, a surfactant, an antioxidant, an ultraviolet absorber, a matting agent, a solvent, or the like as necessary.

  The decoration layer can be formed by gravure printing, offset printing, screen printing, ink jet printing, and the like, and gravure printing is preferable because a high-quality image can be easily obtained. It is preferable that the dry film thickness of a decoration layer is 0.5-15 micrometers, More preferably, it is 1-7 micrometers.

  As the organic solvent used for the purpose of diluting the printing ink or paint of the decorative layer, a known one may be used, for example, aromatic hydrocarbons such as toluene and xylene, ester solvents such as ethyl acetate and butyl acetate, Examples thereof include ether solvents such as dimethyl ether and diethyl ether, ketone solvents such as methyl ethyl ketone, and alcohol solvents such as methanol, ethanol and isopropanol. 20-80 mass parts is preferable with respect to 100 mass parts of printing ink or the whole coating material, and, as for the compounding quantity of an organic solvent, More preferably, it is 30-60 mass parts. When the blending amount is less than 20 parts by mass, the viscosity becomes high and workability is lowered, and the colorant is not sufficiently dispersed in the thermoplastic resin. On the other hand, if the blending amount of the organic solvent exceeds 80 parts by mass, it takes a long time for drying after printing, and the productivity is lowered.

  The dry film thickness of the decorative layer is preferably in the range of 0.5 to 15 μm in consideration of the balance between activation and decorativeness during hydraulic transfer. More preferably, it is 1-7 micrometers. As long as the design and spreadability are not impaired, the anti-foaming agent, anti-settling agent, pigment dispersant, fluidity modifier, anti-blocking agent, antistatic agent, antioxidant, light stabilizer in the decorative layer Various conventional additives such as ultraviolet absorbers may be added.

(Peelable film)
The hydraulic transfer film of the present invention may be produced by laminating on a peelable film, and may be used by peeling from the release film during hydraulic transfer.
An example of a method for producing a hydraulic transfer film having a release film is shown below.

  The decorative layer is applied to the peelable film (A) with a peelable film (A) and a support film (B) on which a curable resin layer is laminated by dry lamination (dry lamination method). Can be manufactured together. In that case, it is necessary that the decorative layer is fixed on the peelable film with such a peeling force that the decorative layer is not peeled off by the work or handling such as film feeding.

For this reason, it is preferable to measure the peeling force at the interface between the decorative layer and the peelable film and select a preferable combination of the peelable film and the transfer layer. Further, if necessary, it is possible to further reduce the peeling force by further surface-treating the peelable film.

  Specifically, a film made of a material such as polypropylene, polyethylene, polyester, nylon, or polyvinyl chloride can be used as the peelable film, and the thickness is preferably 20 μm to 250 μm.

(Method for producing hydraulic transfer film)
Next, an example of the manufacturing method of the hydraulic transfer film of the present invention is shown below.
The method for producing a hydraulic transfer film of the present invention comprises a film (A) in which the curable resin layer is provided on a support film made of a water-soluble or water-swellable resin, and a printing ink film or a peelable film. A film (B) provided with a hydrophobic decorative layer that can be dissolved in an organic solvent (that is, an activator) comprising a paint film, a curable resin layer of the film (A), a decorative layer of the film (B), It is preferable that the layers are laminated so as to face each other and bonded together by dry lamination (dry lamination method).

  When the transfer layer does not have a decorative layer and the transfer layer is composed of a curable resin layer, the film (A) having the curable resin layer on the support film and the peelable film are cured with the film (A). The layers are laminated so that the resin layer and the peelable film face each other and are bonded together by dry lamination (dry lamination method).

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

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

  In addition, by using a support film laminated on a peelable film, the coating or printing substrate is hardly affected by sagging and has good dimensional stability. It becomes possible to precisely control the coating film thickness.

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

The decorative layer
(I) A method of coating or printing on a curable resin layer on a support film,
Or
(Ii) In a film for hydraulic transfer by dry laminating a film (A) having a curable resin layer formed on a support film and a film (B) having a decorative layer on a peelable film (2). Can be stacked.
When coating or printing on the curable resin layer on the support film of (i), appropriateness for coating or printing such as wettability of the surface of the curable resin layer is required. In addition, when a decorative layer with a pattern is introduced by multi-layer printing using a gravure printing machine, the order is reversed from printing from a normal solid to a light or dark pattern. It becomes difficult to ensure the smoothness of the solid layer in close contact with the transfer body. Furthermore, in the printing process, a phenomenon in which the ink printed on the previous plate is taken on the subsequent plate, so-called reverse transition, is likely to occur.

  On the other hand, when the decorative layer is previously formed on the release film (ii), it can be handled by ordinary printing, and the above-described problems do not occur. For this reason, the method of laminating | stacking by the dry lamination of the film (A) in which the film (B) which has a decoration layer on the peelable film of (ii), and the curable resin layer was formed on the support body film is preferable.

  In the step of bonding the film (A) having a curable resin layer provided on a support film and the film (B) having a decorative layer provided on a peelable film, generally a support film including a PVA film is used. When the film is pasted at a temperature exceeding 130 ° C., the film tends to shrink or the wrinkle of the laminate easily enters. It is preferable to carry out in a temperature range of 120 ° C, and more preferably in a temperature range of 40 to 100 ° C.

  In order to produce a hydraulic transfer film having only a curable resin layer using a dry laminator, the above curable resin is used until the production of a film (A) having a curable resin layer formed on a support film. This is the same as the production of a hydraulic transfer film having a layer and a decorative layer. Next, the curable resin layer of the produced film (A) and the peelable film fed from the second feeding roll are overlapped, bonded by a thermocompression-bonding roll, and wound on a winding roll, thereby curable resin. A hydraulic transfer film having only a layer is produced.

  The obtained film for hydraulic transfer of the present invention is wound around a roll and covered with light-shielding paper, and if stored in a dark place such as a warehouse, the curing reaction does not proceed unnecessarily, and the film is blocked during storage. It does not occur, it can be fed out from the roll at the time of water pressure transfer, it can transfer the water of a clear decorative layer, and has sufficient market distribution unless it is actively exposed to ultraviolet rays and sunlight. It is. 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 hydraulic transfer body of the present invention floats the hydraulic transfer film of the present invention in water (after peeling the peelable film if there is a peelable film) with the transfer layer up and the support film down. The transfer layer is activated by an activator (activation may be performed before floating in water), the transfer layer is transferred to a transfer target, the support film is removed, and then the curable resin layer of the transfer layer Is cured by at least one of irradiation with active energy rays and heating.

Specifically, the support film of the hydraulic transfer film from which the peelable film has been peeled is floated on the water in the water tank, and the support film is dissolved or swollen with water.
Next, the transfer layer comprising the decorative layer and the cured resin layer is activated by applying or spraying an activator to the transfer layer. The activation of the transfer layer with the activator may be performed before the film is floated on water.
Next, the member to be transferred and the hydraulic transfer film are submerged in water while pressing the member to be transferred against the transfer layer, and the transfer layer is brought into close contact with the member to be transferred by water pressure and transferred.
Finally, the support film is removed from the transfer medium that has been removed from the water, and the cured resin layer of the transfer layer transferred to the transfer medium is cured by at least one of active energy ray irradiation and heating to be cured resin. A hydraulic transfer body having a layer or a cured resin layer and a decorative layer is obtained.

(water)
The water in the water tank in the hydraulic transfer functions as a hydraulic medium that adheres the curable resin layer of the hydraulic transfer film or the curable resin layer and the decorative layer to the three-dimensional curved surface of the transfer object when transferring the transfer layer, The support film is swelled or dissolved. Specifically, water such as tap water, distilled water or ion exchange water may be used. Depending on the support film used, 10 salts of inorganic salts such as boric acid may be added to the water. % Or less, or 50% or less alcohol may be dissolved.

(Activator)
The activator used in the present invention is an organic solvent that solubilizes the transfer layer, that is, the curable resin layer and the decorative layer. As the activator used in the present invention, the same activator used for general hydraulic transfer can be used. Specifically, toluene, xylene, butyl cellosolve, butyl carbitol acetate, carbitol, carbitol acetate , Cellosolve acetate, methyl isobutyl ketone, ethyl acetate, isobutyl acetate, isobutyl alcohol, isopropyl alcohol, n-butanol, solfit acetate, and the like, 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.
In general, the spray amount of the activator is preferably in the range of 90 to 150% by mass per unit area with respect to the transfer layer. In the present invention, if the activator is sprayed too much, it is not preferable because the viscosity may be lower than the viscosity of the designed curable resin layer. By setting the spray amount within this range, the transfer layer immediately after spraying, that is, the curable resin layer, is the same as the state in which an organic solvent solution having a solid content concentration of 40 to 53% is applied.

After the transfer layer is hydraulically transferred to the transfer target, the support film is removed by dissolving or peeling with water and then dried.
In order to dissolve and remove the support film with water, water immersion, running water, water discharge, water shower, water spraying, water spraying, etc. may be used, one of these may be adopted, or a combination of two or more May be.
In still water immersion, it takes a long time to remove the support film, and it is not industrially suitable, so a method of removing the support film in a short time by applying water pressure (running water, water discharge, water shower, water spray, water spray, etc. Is preferred.

  About the curable resin layer which consists of active energy ray curable resin, after drying a hydraulic transfer body, active energy ray irradiation is performed and the curable resin layer is hardened. If it is a curable resin layer which consists of a thermosetting resin, hardening of a curable resin layer can be performed with drying.

It is preferable that the transfer layer is sufficiently adhered to the surface of the transfer object, and a primer layer is provided on the transfer object surface 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 necessary for a transfer medium composed of a resin component having high solvent absorbability such as ABS resin or SBS rubber having good adhesion. The material of the transfer object may be any of metal, plastic, wood, pulp mold, glass, etc., as long as the shape does not collapse even if it is submerged in water by applying a waterproof process as required. It is not limited.

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

(Viscosity measurement method)
Using a CS-type stress-controlled rheometer manufactured by Carimé, the viscosity was measured at a measurement temperature of 25 ° C. and a stress of 5.968 × 10 ^{−3 to} 596.8 Pa, and the viscosity at a shear rate of 0.1 s ⁻¹ was calculated. .

(Measurement method of peel strength of hydraulic transfer film)
According to JIS K6854, using a precision force meter manufactured by Maruhishi Chemical Machinery Co., Ltd., PP-650-D digital gauge, PGDII at a speed of 10 mm / min, peelability from a hydraulic transfer film (200 mm × 25 mm) The peel strength of the film was measured.

(Surface design)
The surface appearance of the hydraulic transfer body was visually evaluated.
: Maintains surface smoothness △: Slight unevenness (repairable level)
×: There are fine irregularities (levels that cannot be repaired such as water marks)

(Surface gloss measurement method)
The 60-degree specular gloss (JIS K5400) of the hydraulic transfer member was measured. Generally, the gloss value is 90 ± 10% full gloss, 70 ± 10% gloss for 7 minutes, 50 ± 10% semi-gloss (semi-matte), 30 ± 10% gloss for 3 minutes, 10 ± 10% Is referred to as all matte.

(Example of adjusting composition for curable resin layer)
According to the composition of Table 1, a composition for the curable resin layer was prepared. Moreover, about this composition A1, A2, A4, A5, the organic solvent (toluene / diacetonal alcohol / butyl acetate / Solfit acetate / isobutanol = 40/25/15/15/5) used as an activator is used. Table 1 shows the viscosities obtained when the solid content was adjusted to 55%. For the compositions A3 and A6, the viscosity when dissolved in an activator (xylene / MIBK / butyl acetate / isopropanol = 50/20/20/10) and adjusted to a solid content concentration of 55% is shown in Table 1. Indicated.

In Table 1,
UA-1: Urethane acrylate "Unidic 17-813" (mass average molecular weight 1,500) manufactured by Dainippon Ink & Chemicals, Inc.
AP-1: Acrylic polyol (mass average molecular weight 25,000) obtained by copolymerizing hydroxyethyl methacrylate, methyl methacrylate, ethyl acrylate, butyl acrylate and styrene in a molar ratio of 20: 30: 15: 15: 20
Paraloid A-11: Acrylic resin manufactured by Rohm and Haas (Tg 100 ° C., mass average molecular weight 125,000)
Paraloid B-60: Acrylic resin manufactured by Rohm and Haas (Tg 75 ° C., weight average molecular weight 50,000)
I-184: Photopolymerization initiator “Irgacure 184” manufactured by Ciba Specialty Chemicals
PI-1: Mixture of hexamethylene diisocyanate phenol adduct and hexamethylene diisocyanate trimer phenol adduct Silica: “Silicia 350D” manufactured by Fuji Silysia
Polyurea: BYK410 made by Big Chemie Japan
Represents.

(Production of film (B) B1 having a decorative layer)
As the peelable film, a 50 μm thick unstretched polypropylene film (hereinafter abbreviated as “PP film”) manufactured by Toyobo Co., Ltd. was used, and urethane ink (trade name: Univia A) was applied to the film with a gravure 4-color printing machine. A decorative film (B) B1 was produced by printing a 3 μm wood grain pattern.

<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

(Example 1: Production of hydraulic transfer film)
The composition A1 for the curable resin layer is mixed with a mixed solvent of ethyl acetate and toluene (mixing ratio 1: 1) to a 30 μm-thick PVA film made by Aicero Chemical Co., which is a support film, and a solid content concentration of 50%. The solution so dissolved is applied with a comma coater so as to have a predetermined dry film thickness (20 μm), then dried at 60 ° C. for 2 minutes, and then the curable resin layer and the decorative layer of the decorative film B1 are combined. The film C1 for hydraulic transfer was produced by facing and laminating at 60 ° C., and aging at 40 ° C. for 18 hours. When the peelable film was peeled from the hydraulic transfer film C1, the ink layer was transferred to the PVA film side without any defects. The peel force between the peelable film and the decorative layer (ink layer) was 1 N / cm or less, and no wrinkles, streaks, defects, etc. that would affect the hydraulic transfer were generated on the PVA film and the decorative layer.

(Example 2: Production of hydraulic transfer film)
Using the composition A2 for the curable resin layer, a hydraulic transfer film C2 was produced in the same manner as in Example 1. When the peelable film was peeled from the hydraulic transfer film C2, the ink layer was transferred to the PVA film side without any defects. The peel force between the peelable film and the decorative layer (ink layer) was 1 N / cm or less, and no wrinkles, streaks, defects, etc. that would affect the hydraulic transfer were generated on the PVA film and the decorative layer.

(Example 3: Production of hydraulic transfer film)
The composition A3 for the curable resin layer is applied to a 30 μm-thick PVA film manufactured by Aicero Chemical Co., which is a support film, and a solid content concentration of 30% in a mixed solvent of ethyl acetate and toluene (mixing ratio 1: 1). The solution so dissolved is applied with a comma coater so as to have a predetermined dry film thickness (20 μm), and then dried at 60 ° C. for 4 minutes, and then the curable resin layer and the decorative layer of the decorative film B1 are combined. The film C3 for hydraulic transfer was produced by facing and laminating at 60 ° C., and aging at 40 ° C. for 18 hours. When the peelable film was peeled from the hydraulic transfer film C3, the ink layer was transferred to the PVA film side without any defects. The peel force between the peelable film and the decorative layer (ink layer) was 1 N / cm or less, and no wrinkles, streaks, defects, etc. that would affect the hydraulic transfer were generated on the PVA film and the decorative layer.

(Comparative Example 1: Production of hydraulic transfer film)
Using the composition A4 for the curable resin layer, a hydraulic transfer film C4 was produced in the same manner as in Example 1. When the peelable film was peeled from the hydraulic transfer film C4, the ink layer was transferred to the PVA film side without any defects. The peel force between the peelable film and the decorative layer (ink layer) was 1 N / cm or less, and no wrinkles, streaks, defects, etc. that would affect the hydraulic transfer were generated on the PVA film and the decorative layer.

(Comparative Example 2: Production of hydraulic transfer film)
Using the composition A5 for the curable resin layer, a hydraulic transfer film C5 was produced in the same manner as in Example 1. When the peelable film was peeled from the hydraulic transfer film C5, the ink layer was transferred to the PVA film side without any defects. The peel force between the peelable film and the decorative layer (ink layer) was 1 N / cm or less, and no wrinkles, streaks, defects, etc. that would affect the hydraulic transfer were generated on the PVA film and the decorative layer.

(Comparative Example 3: Production of hydraulic transfer film)
Using the composition A6 for the curable resin layer, a hydraulic transfer film C6 was produced in the same manner as in Example 3. When the peelable film was peeled from the hydraulic transfer film C6, the ink layer was transferred to the PVA film side without any defects. The peel force between the peelable film and the decorative layer (ink layer) was 1 N / cm or less, and no wrinkles, streaks, defects, etc. that would affect the hydraulic transfer were generated on the PVA film and the decorative layer.
Table 2 summarizes the specifications and production methods of the hydraulic transfer films obtained in Examples 1 to 3 and Comparative Examples 1 to 3.

表中、実は実施例を、比は比較例を表す。

In the table, the examples are actually examples, and the ratios are comparative examples.

(Example 4) Water pressure transfer Water at 25 ° C was put in a water tank, and the water pressure transfer film C1 from which the peelable film was peeled was floated on the water surface with the PVA side facing down. An activator (toluene / diacetonal alcohol / butyl acetate / Solfit acetate / isobutanol = 40/25/15/15/5) was sprayed at 30 g / m ² , and after 15 seconds, an A4 plate ABS plate (thickness) 3 mm) was inserted from the hydraulic transfer film into the water, and was hydraulically transferred.
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, using a UV irradiation apparatus, the curable resin layer was cured by irradiating with UV light of 2400 mJ / cm ² , and a decorative hydraulic transfer body having a cured resin layer and having a clear pattern was obtained. . The evaluation results are shown in Table 3.

(Example 5) Water pressure transfer A water pressure transfer film C2 was used to obtain a decorative water pressure transfer body having a cured resin layer and a clear pattern by the same method as in Example 4. The evaluation results are shown in Table 3.

(Example 6) Water pressure transfer Warm water at 25 ° C was put in a water tank, and the water pressure transfer film C3 from which the peelable film was peeled was floated on the water surface with the PVA side facing down. Activating agent (xylene / MIBK / butyl acetate / isopropanol = 50/20/20/10) was sprayed at 25 g / m ² , and after 15 seconds, an A4 size ABS plate (thickness 3 mm) was transferred from the hydraulic transfer film to the water. It was inserted and water pressure was transferred.
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 heated at 90 ° C. for 60 minutes. Curing was performed to obtain a decorative hydraulic transfer body having a cured resin layer and having a clear pattern. The evaluation results are shown in Table 3.

(Comparative example 4) Water pressure transfer The water pressure transfer body was obtained by the method similar to Example 4 using the film C4 for water pressure transfer. The evaluation results are shown in Table 3.

(Comparative example 5) Water pressure transfer The water pressure transfer body was obtained by the method similar to Example 4 using the film C5 for water pressure transfer. The evaluation results are shown in Table 3.

(Comparative Example 6) Water pressure transfer A water pressure transfer member was obtained in the same manner as in Example 6 using the water pressure transfer film C6. The evaluation results are shown in Table 3.

  As shown in this Example, a hydraulic transfer film can be easily produced by coating and laminating on a PVA film, and a hydraulic transfer body having a curable resin layer can be obtained. Table 3 shows the transfer conditions and physical properties of the transfer.

  From the above results, Examples 4 to 6 using A1 to A3 as the composition for the curable resin layer were excellent in surface design. In Examples 4 and 6, a hydraulic transfer body excellent in design and exhibiting a matte tone was obtained. In Example 5, a hydraulic transfer body having excellent design and high glossiness was obtained.

  The hydraulic transfer body of the present invention is a home appliance such as a television, video, air conditioner, radio cassette, mobile phone, refrigerator, etc .; OA equipment such as a personal computer, fax machine or printer; a housing part of a home product such as a fan heater or a camera; Furniture components such as tables, chests, and pillars; building components such as bathtubs, system kitchens, doors, and window frames; miscellaneous goods such as calculators and electronic notebooks; automotive interior panels, automobile and motorcycle skins, wheel caps, ski carriers, automobiles Car interior items such as carrier bags for cars; sports equipment such as golf clubs, skis, snowboards, helmets, goggles, etc .; three-dimensional images for advertising, signboards, monuments, etc., moldings that have curved surfaces and require design It is particularly useful for products and can be used in a very wide range of fields.

It is sectional drawing of the film for hydraulic transfer which concerns on embodiment in this invention. It is sectional drawing of the film for hydraulic transfer which concerns on embodiment in this invention, and a film (A) (film which laminated | stacked the support body film and the curable resin layer (topcoat layer) in this order) and a film (B) ( It is a figure explaining the case where the hydraulic transfer film of this invention is manufactured by bonding together the film which laminated | stacked the decoration layer on the peelable film by dry lamination.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Hydraulic transfer film 2 Support film 3 Curable resin layer (topcoat layer)
4 decorative layer 5 peelable film 6 laminated film (A)
7 Laminated film (B)

Claims (8)

It has 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, and the transfer layer is cured by at least one of active energy rays and heating. The curable resin layer has a viscosity at a shear rate of 0.1 s ⁻¹ when diluted with an organic solvent so that the solid content concentration is 55%. -Hydraulic transfer film characterized by being s. The hydraulic transfer film according to claim 1, wherein the organic solvent is an activator used for hydraulic transfer. The film for hydraulic transfer according to claim 1 or 2, wherein the curable resin layer contains a viscosity modifier. The film for hydraulic transfer according to claim 3, wherein the viscosity modifier is an inorganic extender pigment or an organic crystal. The curable resin layer contains a resin curable with at least one of active energy rays and heating, and a thermoplastic resin, and is a resin curable with at least one of active energy rays and heating with respect to the thermoplastic resin. 2. The hydraulic transfer film according to claim 1, wherein the mass ratio P: (mass sum of radical polymerizable compounds) / (mass sum of thermoplastic resin) is 45/55 or more and 75/25 or less. On a support film made of a water-soluble or water-swellable resin, the viscosity at a shear rate of 0.1 s ⁻¹ when diluted with an organic solvent to a solid content concentration of 55% is 5 to 10,000 Pa · s, A film (A) provided with a curable resin layer curable by at least one of active energy rays and heating;
A film (B) provided with a decorative layer that can be dissolved in an organic solvent comprising a printing ink film or a paint film on a peelable film,
A method for producing a hydraulic transfer film, wherein the curable resin layer of the film (A) and the decorative layer of the film (B) are stacked so as to face each other and are bonded together by dry lamination. The hydraulic transfer film according to any one of claims 1 to 5, floating in water with the support film facing down, activating the transfer layer with an organic solvent, transferring the transfer layer to a transfer target, A method for producing a hydraulic transfer body, comprising removing the support film and then curing the transfer layer by at least one of active energy ray irradiation and heating. A hydraulic transfer member produced by the method of claim 7.

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