JP2006051672A - Hydraulic transferring film and hydraulically transferred body - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydraulic transferring film, in which pigments each having a flake-like shape such as metal pigment are employed so as to be able to manufacture a hydraulically transferred article having a reproduced design equilavent to one employed in printing or in painting, and its manufacturing method and, at the same time, a hydraulically transferred body employed with this film. <P>SOLUTION: This hydraulic transferring film consists of a support film made of a water-soluble or a water-swellable resin and an organic solvent-soluble transferring layer provided on the support film, in which at least a curable resin layer curable by at least either one between the irradiation of activating energy rays and heating, a decorative layer including a flake-like pigment and a resin film layer in the order named, and its manufacturing method and a hydraulically transferred body employed with the hydraulic transferring film are also disclosed. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a hydraulic transfer film capable of simultaneously hydraulically transferring a curable resin layer and a metal-like decorative layer onto the surface of an object to be transferred such as various molded articles, a method for producing the hydraulic transfer film, and the hydraulic transfer film. The present invention relates to a hydraulic transfer body manufactured using a film.

  In painting or printing, a metallic design is expressed by painting or printing a paint or ink containing a metal pigment such as aluminum. In general, a metal pigment is obtained by crushing a film-like or foil-like metal into a flake shape, and has a flat shape. In order to achieve a more metallic design on the coated or printed surface, it is necessary to orient these high-brightness metal pigments, and the coating thickness is reduced and the metal pigment is applied to the painted surface. The orientation is urged. In particular, leafing type pigments with high brightness need to be segregated on the surface of the coating film and fully oriented. Therefore, in painting, orientation is improved by brushing or polishing (rubbing) after painting. In printing, cell-freefing on the surface of the printing substrate is performed by back printing, and brightness due to metallic luster is efficiently expressed.

On the other hand, attempts have been made to obtain a metallic design by a hydraulic transfer method.
The hydraulic transfer method is a method that can impart a decorative layer rich in design to a molded article having a complicated three-dimensional shape (see, for example, Patent Documents 1 and 2). Normally, a hydraulic transfer film in which a transfer layer in which decorative layers such as a curable resin layer and an ink layer are laminated in this order on a support is formed on a support, the transfer layer is on the top, the support is on the bottom, and the water is transferred to the water. It is obtained by activating the transfer layer by spraying an organic solvent on the transfer layer (that is, on the decorative layer), transferring the transfer layer to a transfer target, and removing the support.
In order to make the hydraulic transfer film follow the surface of the transfer target having a complicated three-dimensional shape, the hydraulic transfer film needs to have sufficient flexibility in the activation process. Usually, the transfer is coated with an organic solvent. The layer is redissolved to gain flexibility.

However, when the decorative layer includes a flaky metal pigment, the organic solvent is directly contacted and redissolved in the decorative layer in the activation step, so that the orientation of the metal pigment is lost and the luminance is lowered. That is, with a hydraulic transfer film using a conventional ink containing a flaky metal pigment, a hydraulic transfer product reproducing a sufficient metallic decoration could not be obtained.
Japanese Unexamined Patent Publication No. 64-22378 Japanese Patent Laid-Open No. 2003-200698

  The problem to be solved by the present invention is to produce a hydraulic transfer product that reproduces a design equivalent to printing or painting using a pigment having a flake shape such as a metal pigment (hereinafter abbreviated as flake pigment). It is in providing the film for hydraulic transfer, its manufacturing method, and the hydraulic transfer body using this film.

The present inventors solved the above-mentioned problems by using a hydraulic transfer film having a layer structure in which the decorative layer having a flake pigment is not directly sprayed with an organic solvent in the activation step.
That is, a resin film layer was provided on a decorative layer containing a flake pigment, and a layer structure in which the organic solvent was not in direct contact during the activation process was obtained.
By providing the resin coating layer, the decorative layer having the flaky pigment has a structure laminated with the curable resin layer. Therefore, since the flake pigment does not come into direct contact with the organic solvent, the orientation of the pigment is not disturbed, and a hydraulic transfer product that reproduces the design equivalent to printing or painting using the flake pigment can be manufactured.

  That is, 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 is the support film. Provided is a hydraulic transfer film in which at least a curable resin layer curable by at least one of active energy ray irradiation and heating, a decorative layer containing a flake pigment, and a resin coating layer are laminated in this order. To do.

Further, the present invention is a method for producing the hydraulic transfer film as described above,
(1) A peelable film (a) having a decorative layer containing a flaky pigment and a peelable film (b) having a resin coating layer are arranged so that the decorative layer and the resin coating layer face each other. After laminating, peeling the peelable film (a), forming the decorative layer on the resin coating layer on the peelable film (b),
(2) The support film on which the curable resin layer is formed, and the peelable film (b) produced in the step (1) and having a decorative layer formed on the resin coating layer, the curable resin layer There is provided a method for producing a hydraulic transfer film, comprising a step of laminating the decorative layer so as to face each other.

Further, the present invention is a method for producing the hydraulic transfer film as described above,
(1 ′) A peelable film (a ′) in which a decorative layer containing a flaky pigment is formed on a resin coating layer or a pattern layer, and a peelable film (b) in which a resin coating layer is formed, and the decorative layer After laminating so as to face the resin coating layer, the peelable film (a ′) is peeled off, and the decorative layer and the resin coating layer or the pattern are formed on the resin coating layer on the peelable film (b). Forming layers in order,
(2 ′) A support film on which a curable resin layer is formed, and a peelable film (b) in which a decorative layer and a resin coating layer or a pattern layer are sequentially formed on the resin coating layer produced in the step (1 ′). And a step of laminating the curable resin layer and the resin coating layer or the picture layer so as to face each other.

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

Since the film for hydraulic transfer of the present invention has a resin coating layer on the decorative layer, the flake pigment such as a metal pigment does not come into direct contact with the organic solvent during activation, and the orientation of the pigment is not disturbed. It is possible to produce a hydraulic transfer product that closely reproduces the same design as printing and painting.
The present invention is not limited to metal pigments, and can be applied to all flake pigments that exhibit design properties by orientation. When the flake pigments are used, the metal feeling, glitter feeling, metallic luster, It is possible to produce a hydraulic transfer product that well reproduces the pearl tone, interference effect, multicolor effect, polarization effect, hologram decoration and the like.

(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 A, resin coating layer))
Next, the transfer layer provided on the support for the hydraulic transfer film of the present invention will be described.
The transfer layer is at least on the support film,
A curable resin layer (hereinafter abbreviated as curable resin layer) curable by at least one of active energy ray irradiation and heating, a decorative layer (hereinafter abbreviated as decorative layer A) containing a flake pigment, and a resin coating The layers are laminated in order, and the uppermost layer is a resin coating layer. That is, the resin coating layer serves as an adhesive surface with the substrate to be transferred. The transfer layer is not particularly limited except that these three layers are laminated in this order, and the layers need not necessarily be in close contact with each other. For example, a resin coating layer, a resin coating layer, a pattern layer, a color clear layer, or the like may be provided between the respective layers. Specifically, the transfer layer may have a three-layer structure in which the decorative layer A and the resin coating layer are stacked in close contact with each other on the curable resin layer, or the transfer layer may include the curable resin layer and the decorative layer A. A four-layer structure having a layer made of the same material as the resin coating layer or a pattern layer therebetween may be used.

(Curable resin layer)
The curable resin layer is a layer having a role as a top coat for protecting the decorative layer in the hydraulic transfer body. Moreover, the disorder of orientation is suppressed by sandwiching the decorative layer A with the resin coating layer.
The curable resin layer contains a curable resin that can be cured by at least one of active energy ray irradiation and heating. 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.
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.

  In the above (1) to (6), an antifoaming agent, an anti-settling agent, a pigment dispersant, a fluidity modifier, an anti-blocking agent, an antistatic agent, and an antioxidant are provided so long as the design and curability are not impaired Various conventional additives such as 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.

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 Acrylic (meth) acrylates, epoxy (meth) acrylates, polyalkylene glycol poly (meth) acrylates, polyether (meth) acrylates, etc. are mentioned, among them 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. Acylphosphine oxide compounds such as oxides; Benzophenone, benzophenone compounds such as methyl-4-phenylbenzophenone o-benzoylbenzoate; 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 organic solvent during hydraulic transfer. Therefore, the curable resin layer must have improved solubility in organic solvents as the film thickness increases. However, the curable resin layer also requires shape stability (storage stability) as a hydraulic transfer film having an uncured curable resin layer, and 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, activation of the curable resin layer with an organic solvent tends to be difficult. 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.

(Curable resin layer with fine particles added)
When the curable resin layer contains an appropriate amount of fine particles, it can prevent excessive swelling at the time of activation. In addition to its role as a top coat for protecting the decorative layer, the decorative layer A can be enlarged, colored spots, and colors. It plays a role in preventing deterioration in design properties such as blurring.
The purpose of activation during transfer is to improve the followability and adhesion of the transfer layer to the three-dimensional curved surface of the transfer target. Therefore, the organic solvent serving as the activator has the ability to dissolve all of the transfer layer, that is, the resin coating layer, the decorative layer A, and the curable resin layer. However, at this time, if the printing ink of the decorative layer A or the resin component of the paint is completely dissolved in the organic solvent, the colorant particles such as dyes and pigments are separated from each other or mixed, and the design is This may cause enlargement or color blur.

The curable resin layer containing fine particles can resist the swelling of the resin, and the adjacent decorative layer A can be prevented from excessively swelling due to its suppressed swelling state. Therefore, it is preferable that the fine particles do not dissolve or swell in an organic solvent for activation, a resin used for the curable resin layer, or the like.
Further, since the fine particles impart thixotropic properties to the activated curable resin layer, if the curable resin layer contains the fine particles, the transferred material is transferred to the obtained hydraulic transfer film at a low speed. When pressing, the resistance is generated against the shear stress applied to the hydraulic transfer film, so that the design of the transfer layer can be prevented from being lowered in the transfer process, and the three-dimensional curved surface can be easily followed.

Examples of the fine particles include inorganic fine particles and organic fine particles.
As inorganic fine particles, inorganic pigments such as inorganic pigments, carbon, titanium oxide, kraftite, zinc white; carbonated lime powder, precipitated calcium carbonate, gypsum, clay (China Clay), silica powder, diatomaceous earth, talc, kaolin, Inorganic pigments such as alumina white, barium sulfate, aluminum stearate, magnesium carbonate, barite powder, abrasive powder, etc .; silicone, glass beads and the like.

  Examples of the organic fine particles 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 fine particles, inorganic pigments, organic crystals, and polymer fine particles are preferable because they have a high swelling suppression effect, and inorganic extender pigments and organic crystals are preferable because they are particularly effective.
What is necessary is just to determine suitably content in the case of containing the said fine particle according to the absorption amount of an organic solvent, 0.1-40 mass% is preferable, More preferably, it is 0.2-30 mass%, More preferably, it is 0. .2 to 20% by mass.

  The fine particles may be spherical or amorphous, but are preferably spherical or have a shape close thereto. In addition, the size of the fine particles is preferably 0.001 to 30 μm from the viewpoint of dispersibility in the coating material and surface smoothness. Of course, the range of the optimum particle diameter differs in relation to the film thickness, but for example, in the case of a film thickness of about 20 μm, it is preferably 0.001 to 10 μm.

  The fine particles also affect the appearance of the transferred product and can control the design from gloss to matte. Further, it is possible to control from a smooth surface to an embossed surface by changing the shape and size of the fine particles. Therefore, the composition and concentration of the fine particles may be adjusted so as to obtain a desired design by combining with a base such as a decoration layer.

  In particular, among the fine particles, 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, Organic extender pigments such as abrasive powders, 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 These are used as matting agents, 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 matting agent may have a spherical shape or an indefinite shape, but preferably has a spherical shape or a shape close thereto. Further, the size of the fine powder is preferably 0.05 to 30 μm from the viewpoint of dispersibility in paint, matteness of efficiency, and surface smoothness. Of course, the range of the optimum particle diameter varies depending on the film thickness, but for example, in the case of a film thickness of about 20 μm, it is preferably 0.5 to 10 μm.

  The use method and addition amount of the matting agent may be the same as the method and addition amount used for paints and inks, which are general purpose uses of the matting agent. For example, when using a matting agent that provides a matting effect by adding 20% to the resin solid content of the paint, add 10% to the resin solid content of the curable resin layer used in the present invention. By doing so, a sufficient matting effect can be obtained after the hydraulic transfer.

  The refractive index of the fine particles when used as a matting agent can scatter light more efficiently, so it is preferable that the difference from the refractive index of the coating resin is large. By using and transferring by hydraulic pressure, the matte property can be efficiently exhibited, so that there is no need to provide a restriction. Rather, fine particles having a small difference in refractive index can be used so as to make full use of the pattern and color of the base.

  The degree of matte tone can be evaluated by surface gloss. It can be said that the smaller the surface gloss, the more matte. It can be said that the gloss of the surface gloss (%) is preferably 20 or less. More preferably, it has a matte tone having a gloss of 10 or less.

  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 organic solvent tends to be insufficient. Therefore, in order to sufficiently activate the curable resin layer with an organic solvent and to satisfy the function as a protective layer and the designability, the thickness is preferably 5 to 30 μm.

(Decoration layer A)
The decoration layer A is a layer having a role of imparting decoration expressed by a flaky pigment to the hydraulic transfer body.
The decorative layer A is obtained by applying a paint or ink containing a flaky pigment and a resin. The flake pigment is not particularly limited as long as it is a general-purpose flake pigment having a scale-like aspect ratio, among others, metallic tone, metallic luster, glitter, pearl tone, interference effect, multicolor effect A flake pigment capable of expressing a design such as a polarizing effect and a hologram has a great effect of the present invention and can be suitably used. Specifically, it is preferable to include 70% or more of a pigment having a shape having a major axis of 5 to 20 μm, a minor axis of 0.5 μm or less, and a foil area of 20 to 2000 μm ² . (Hereinafter, paint or ink containing flake pigment and resin is abbreviated as flake pigment paint or ink)
Examples of flake pigments include metal powder pigments (aluminum, bronze, etc.), metal foil pigments (aluminum, bronze, etc.), metal vapor-deposited foil pigments (plastics with aluminum, bronze, etc. deposited) And a pulverized film). 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.

In addition, a general-purpose colorant may be contained. General-purpose pigments include, for example, 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, Pyrazolone Red, Watching Red Calcium Salt, Lake Red D, Brilliant Carmine 6B, Eosin Lake; Blue Pigment, Bituminous, Cobalt Blue, Alkaline Blue Lake, Victoria Blue Lake, Phthalocyanine Blue, Metal-Free Phthalocyanine Blue; Chrome as Green Pigment Green, chromium oxide, pigment green B, malachite green lake; examples of white pigments include titanium white.
The blending amount of the flake pigment and 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.

  As the resin used in the flaky pigment paint or ink, a resin usually used in printing ink or paint may be used. For example, acrylic resin, polyurethane resin, polyamide resin, urea resin, epoxy resin, polyester resin, vinyl resin (Vinyl chloride, vinyl acetate, vinyl chloride-vinyl acetate copolymer resin), vinylidene resin (vinylidene chloride, vinylidene fluoride), ethylene-vinyl acetate resin, polyolefin resin, chlorinated olefin resin, ethylene-acrylic resin, petroleum resin, cellulose A thermoplastic resin such as a derivative resin is used. 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 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 2,500 to 40,000. The following are preferable because they have solubility in an organic solvent and appropriate adhesiveness with a peelable film when a peelable film is used. 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. Further, the glass transition temperature of the polyurethane resin is preferably −5 ° C. or more and 70 ° C. or less from the viewpoint of 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 preferably has a number average molecular weight of 2,000 to 8,000 in order to have appropriate adhesiveness with the peelable film when the peelable film is used, and more preferably 2500 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 body.
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 the manufacturing process of the hydraulic transfer film of the present invention to be described later, when a peelable film is used, a flake pigment paint or ink contains a release agent in order to adjust the peel force between the decorative layer A and the peelable film. You may let them. The release agent to be used is not limited as long as it can be dispersed in the flaky pigment paint or ink, but it is preferable to use a fluorine-based compound or a silicone-based compound, and since the molecular weight and chemical structure are easily controlled, the silicone-based compound is used. 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 flaky pigment paint or ink 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 in the nonvolatile content. % Or less. 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 the hydraulic transfer film is used, peeling tends to occur between the decorative layer A and the curable resin layer.
In addition, as long as the design and spreadability are not hindered, in the flaky pigment paint or ink, plasticizer, surfactant, antioxidant, UV absorber, matting agent, antifoaming agent, anti-settling agent, Various conventional additives such as pigment dispersants, fluidity modifiers, antiblocking agents, antistatic agents, antioxidants, light stabilizers, and ultraviolet absorbers may be added.

  The organic solvent used in the flaky pigment paint or ink may be any organic solvent that dissolves the printing ink or paint. Examples thereof include aromatic hydrocarbons such as toluene and xylene, ester solvents such as ethyl acetate and butyl acetate, and dimethyl ether. And ether solvents such as diethyl ether, ketone solvents such as methyl ethyl ketone, and alcohol solvents such as methanol, ethanol and isopropanol. The blending amount of the organic solvent is preferably 20 to 80 parts by mass, more preferably 30 to 60 parts by mass with respect to 100 parts by mass of the entire flake pigment paint or ink. 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 decorative layer A is produced by printing or coating a flake pigment paint or ink 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. Of these, gravure printing, rod gravure coating, and micro gravure coating are preferred because they facilitate the orientation of flake pigments. The dry film thickness of the decorative layer A is preferably from 0.5 to 15 μm, more preferably from 1 to 7 μm, since good decorative properties and activation during hydraulic transfer are possible. The decorative layer A may be printed or coated on the entire surface with the same flaky pigment paint or ink (100% in the case of halftone dots), or may be partially printed or coated to form a pattern. Good.

(Picture layer, color clear layer)
In addition to the decorative layer A, the hydraulic transfer film of the present invention may have a pattern layer, a color clear layer, and the like for the purpose of decoration. The pattern layer and the color clear layer have a role of giving a high-design decoration to the hydraulic transfer body integrally with the decoration layer A. Hereinafter, layers that play a role of decoration such as a pattern layer, a color clear layer, and a decoration layer A are collectively referred to as “decoration layer A ′”.
The pattern layer referred to here is an overprinted pattern in which ink is placed only on the portion forming the pattern of each color in a plurality of versions corresponding to the number of colors forming the pattern. For example, in the case of gravure printing, the decorative layer A may be printed on the entire surface (so as to have a halftone dot of 100%), and a pattern layer may be laminated, or a pattern layer may be formed so as to form a pattern together with the decorative layer A. You may print or apply.
Further, the color clear layer is a layer for coloring so as not to conceal the lower pattern and the like. The entire surface (100% in the case of halftone dots) may be printed or coated with the same color paint or ink, or a pattern may be formed with a plurality of colors. Note that the pattern layer and the color clear layer do not necessarily cover the entire surface of the decoration layer A, and therefore do not always have a function of protecting the decoration layer A upon activation.

(Resin coating layer)
The hydraulic transfer film of the present invention has a resin coating layer so as to cover the surface of the decorative layer A. The resin coating layer protects the surface of the decorative layer A from an organic solvent and activates the transfer process, and favorably adheres to the transfer target. Therefore, it suppresses the leafing reduction of the flake pigment due to the activation, and plays a role of preventing deterioration in design properties such as color spots and color blurs of the decoration layer A ′ including the decoration layer A. In the present invention, it is sufficient that the surface of the decorative layer A is covered at the time of activation, and therefore it is not necessary to be a complete continuous film. In addition to the continuous film by the coating method or the like, the halftone dot 100 of the gravure printing method is used. It may be a film having halftone dots by solid printing of%. At this time, the gap between the plates is preferably less than 100 μm, more preferably 50 μm or less, and further preferably 20 μm or less.

The resin coating layer used in the present invention is not particularly limited as long as it is a resin coating that can uniformly cover the surface of the decorative layer A by a simple coating method and can be easily activated by an activator. Among them, it is preferable to use a resin as used in the decorative layer A or the decorative layer A ′ because of excellent adhesion to the decorative layer A or the decorative layer A ′ as a lower layer. Specifically, it is preferable to use a resin used for the above-mentioned flake pigment paint or ink. At the time of activation, in order to suppress induction of delamination due to phase separation by an activator, the resin coating layer preferably contains 50% by mass or more of the resin used in the decorative layer A ′. The content is more preferably 80% by mass or more, and still more preferably 90% by mass or more.
Examples of resins that are used in the decorative layer A ′ and that are preferably used in the resin coating layer include polyurethane and polyester.
Resins used for the resin coating layer include plasticizers, surfactants, matting agents, solvents, antifoaming agents, anti-settling agents, pigment dispersants, fluidity modifiers, antiblocking agents, if necessary. Various conventional additives such as antistatic agents, antioxidants, light stabilizers and ultraviolet absorbers may be added.

  Moreover, the resin film layer may be colored and may contain a general purpose pigment for the purpose of coloring. For example, when titanium oxide is contained, a white resin coating layer is obtained, and when a carbon pigment is contained, a black resin coating layer is obtained. For example, when aiming at the effect of concealing the underlayer, since the titanium oxide pigment is a so-called white pigment, white ink or white paint can be used as it is. The carbon-based pigment is a so-called black pigment, and black ink or black paint can be used as it is. Among them, when a black ink layer or a black paint layer is provided as a resin coating layer so as to be the base of the decorative layer A ′, (the curable resin layer / the decorative layer A / the black ink layer or the black paint layer are laminated in this order). In the case of ()), it is particularly preferable to apply a pigment having a metallic tone as the flaky pigment because it is effective in expressing the contrast between the highlight and the shade.

In addition, the fine particles described in the section of the curable resin layer may be contained in an amount of 30% by mass or more to have a swelling suppression effect. The content of the fine particles at this time may be appropriately determined according to the absorption amount of the organic solvent, but is preferably 30 to 80% by mass, more preferably 30 to 80% by mass, and still more preferably 40 to 80% by mass. .
In order to give a swelling inhibiting effect, the fine particles used are preferably fine inorganic powders. For example, when aiming at the effect of utilizing the base of the transfer target, it is preferable to add an inorganic extender pigment such as silica, talc, kaolin, barium sulfate so as to be translucent.

Furthermore, in order to adjust the peeling force between the resin coating layer and the peelable film, the resin coating 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 resin film layer formed into an ink or paint, like the decorative layer A ′, but it is preferable to use a fluorine-based compound or a silicone-based compound, and its molecular weight or chemical structure. Since it is easy to control, a silicone type compound is particularly preferable. 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 the hydraulic transfer film is used, peeling tends to occur between the resin coating layer and the decorative layer.

The resin coating layer is formed by coating machines such as slit reverse, slot die, comma, bar, knife, gravure, gravure reverse, micro gravure, rod gravure, offset gravure, flexo, blanket, roll, air knife, screen, inkjet, etc. It can be performed by a printing machine or the like. The dry film thickness of the resin coating layer is preferably 0.1 to 10 μm, more preferably 0.2 to 7 μm, and still more preferably 0.3 to 4 μm.
When laminating a resin film layer with a pattern layer or the like, gravure printing is preferable. However, when the resin film layer having the fine particles is solid-plate printed by gravure printing, the gap between the solid printing plate is 100 μm or more. As a result, the effect of the fine particles contained in the resin coating layer is diminished, the plates become discrete, and the handle is liable to crack. Therefore, when the resin coating layer is formed by a method in which gaps between the plate marks are generated, the gaps between the plate marks are preferably less than 100 μm, more preferably 50 μm or less, and 20 μm or less. Further preferred.
As the organic solvent used for the resin coating layer, the same solvents as those used for the ink or paint used in the decorative layer A ′ can be used.
Also, a plurality of resin coating layers can be stacked. For example, when the resin coating layer is produced by gravure printing, a plurality of solid plates with halftone dot printing 100% can be stacked in order to completely cover with ink.

In the case where the decorative layer A ′ is formed by printing, the pattern is composed of dots referred to as a plate and is not a complete continuous film. Accordingly, the pattern of the decorative layer A ′ has a property of being easily enlarged upon activation. Therefore, when an activator is applied to the transfer layer, the pattern may stretch so that the handle can be broken. Therefore, the resin coating layer is provided between the curable resin layer and the decorative layer A, that is, the support film / the curable resin layer / the resin coating layer / the decorative layer including the decorative layer A / the resin coating layer are laminated in this order. The pattern of the decoration layer A is preferably reinforced, and the flexibility of the decoration layer by activation and the reproducibility of the pattern can both be achieved.
The resin coating layer provided between the curable resin layer and the decorative layer A ′ is integrated with the decorative layer A ′ to give a high-design decoration to the hydraulic transfer body after being transferred to the transfer target. Therefore, it may be appropriately colored from transparent to opaque according to the required design properties.

(Method for producing hydraulic transfer film)
The hydraulic transfer film of the present invention is
A peelable film in which at least two layers of the decorative layer A and the resin coating layer are laminated so that the resin coating layer is in contact with the peelable film;
A support film made of a water-soluble or water-swellable resin provided with a curable resin layer that can be cured by at least one of irradiation with active energy rays and heating, and activated with an organic solvent, and a curable layer It can obtain by the method of laminating | stacking so that it may oppose with a resin layer, and bonding by dry lamination (dry lamination method).
Among them, a peelable film in which two layers of the decorative layer A and the resin coating layer are laminated, a peelable film (a) in which the decorative layer A is formed, and a peelable film (b) in which the resin coating layer is formed. When the decorative layer A and the resin coating layer are laminated so that they face each other and then the peelable film (a) is peeled off, the flake pigment is in the back-printed state, This is preferable because it is easy to obtain orientation.
Hereinafter, this method will be described in detail.

As a specific process,
(1) The peelable film (a) on which the decorative layer A is formed and the peelable film (b) on which the resin coating layer is formed are laminated so that the decorative layer A and the resin coating layer face each other, and then the peelable film is peeled off. Peeling the film (a) and forming the decorative layer A on the resin coating layer on the peelable film (b);
(2) A support film having a curable resin layer formed thereon, and a peelable film (b) having a decorative layer A formed on the resin coating layer produced in the step (1), It has the process of laminating so that the decoration layer A may oppose.

Further, when the resin coating layer is provided between the curable resin layer and the decoration layer A, or when the decoration layer A ′ includes a pattern layer or a color clear layer,
(1 ′) A peelable film (a ′) in which a decorative layer A is formed on a resin coating layer or a pattern layer, and a peelable film (b) in which a resin coating layer is formed, After laminating so as to face each other, the peelable film (a ′) is peeled off, and the decorative layer A and the resin film layer or the pattern layer are sequentially formed on the resin film layer on the peelable film (b),
(2 ′) A support film on which a curable resin layer is formed, and a peelable film (b) in which a decorative layer A and a resin coating layer or a pattern layer are sequentially formed on the resin coating layer produced in the step (1). Can be manufactured by a process of laminating such that the curable resin layer and the resin coating layer or the pattern layer face each other.
Here, the peelable film (a), the peelable film (a ′), and the peelable film (b) are the peelable films themselves that are independent of the decorative layer A and the resin coating layer, respectively.
The peelable film (a) on which the decorative layer A is formed is hereinafter referred to as “laminated film (a)”,
The peelable film (a ′) having the decorative layer A formed on the resin film layer or the pattern layer is “laminated film (a ′)”, and the peelable film (b) having the resin film layer formed is “laminated film (b)”. "

((1) Description of process)
The laminated film (a), the laminated film (a ′), and the laminated film (b) can all be produced by the same method. That is, in the laminated film (a) or the laminated film (a ′), in the laminated film (a ′), after the resin coating layer or the pattern layer is first applied or printed, the decorative layer A may be applied or printed. . Moreover, what is necessary is just to apply | coat or print a resin coating layer directly for laminated film (b).
For coating or printing, slit reverse coaters, die coaters, comma coaters, bar coaters, knife coaters, gravure coaters, gravure reverse coaters, micro gravure coaters, flexo coaters, blanket coaters, roll coaters, air knife coaters, etc. may be used. I can do it.

The laminated film (a) and the laminated film (a ′) are laminated so that the laminated film (b) and the laminated layers face each other. The laminating method is preferable because the dry lamination (dry laminating method) method is carried out in a state in which no unnecessary solvent is contained, so that the orientation of the flake pigment is not lowered.
The temperature in the step of laminating the laminated film (a) and the laminated film (a ′) and the laminated film (b) is 10 ° C. lower than the glass transition temperature of the resin used for each surface to be laminated. It is preferably performed between the higher deformation temperatures of the film (a), the peelable film (a ′), or the peelable film (b). Specifically, the lamination film (a) and the lamination film (a ′) and the lamination film (b) are preferably bonded together by heating and pressing in a temperature range of 30 to 150 ° C. More preferably, it is carried out in the temperature range.

After laminating the laminated film (a) and the laminated film (a ′) with the laminated film (b), the peelable film (a) and the peelable film (a ′) are peeled off. This method is preferable because the decorative layer A is once printed on the back side, so that the orientation of the pigment can be easily obtained. When the pigment is a flaky pigment exhibiting a metallic tone, a metallic tone with increased brightness can be expressed.
In this way, the decorative layer A, or the decorative layer A and the resin coating layer or the picture layer can be sequentially formed on the resin coating layer of the laminated film (b).
As the peelable film (a), the peelable film (a ′), and the peelable film (b), it is preferable to use films having different peel forces. Specifically, the peelable film (a) and the peelable film (a ′) have a peel force weaker than the peel force between the peelable film (b) and the resin coating layer (however, the peel force referred to here is It is preferable to have a peeling force with a layer formed on the outermost interface of the peelable film (a) and the peelable film (a ′).
Specifically, it is preferable to measure the peel force between each peelable film and the layer at the outermost interface, and to select a preferable combination of the peelable film and the layer. Moreover, it is also possible to make a peeling force still smaller by surface-treating to a peelable film as needed.
For example, when a polyethylene terephthalate film subjected to non-silicone release treatment is used for the peelable film (a) and the peelable film (a ′) and a biaxially stretched polypropylene film is used for the peelable film (b), both films After bonding, the peelable film (a) and the peelable film (a ′) can be peeled from the decorative layer A or the handle or the resin coating layer without any defects. Furthermore, since the coating or printing substrate is hardly affected by sagging and has good dimensional stability, it becomes possible to perform precise coating or printing.

  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. Moreover, in order to control peeling strength, the film which performed the peeling process etc. on the surface of a raw material can also be used.

((2) Description of process)
A peelable film (b) in which a decorative layer A or a decorative layer A and a resin coating layer or a pattern layer are formed in this order on the resin coating layer, and a support film on which a curable resin layer is formed, The hydraulic transfer film of the present invention can be produced by laminating the curable resin layer and the decorative layer A so as to face each other.

  Specifically, the support film on which the curable resin layer is formed can be cured by at least one of active energy ray irradiation and heating on a support made of a water-soluble or water-swellable resin, and an organic solvent. It is a film provided with an activated curable resin layer. In order to apply the organic solvent solution of the curable resin to the support, a slit reverse coater, die coater, comma coater, bar coater, knife coater, gravure coater, gravure reverse coater, micro gravure coater, flexo coater, blanket coater A roll coater, an air knife coater or the like can be used.

  A curable resin layer comprising a decorative film A or a peelable film (b) in which a decorative film A and a resin film layer or a pattern layer are sequentially formed on the resin film layer, and a support film on which the curable resin layer is formed. As a method of laminating so that the decorative layer A and the decorative layer A face each other, a dry lamination method is preferable as described above. Bonding by drying and heating and pressing is preferably performed in a temperature range of 40 to 120 ° C, and more preferably in a temperature range of 40 to 100 ° C. In general, the heat resistance of a support film such as a PVA film is low, and when the films are bonded at a temperature exceeding 130 ° C., a problem that the film shrinks or the wrinkles of the laminate easily occur.

  In addition, when the curable resin layer contains the fine particles or the like, the adhesive force during lamination is weakened, and peeling occurs at the interface between the curable resin layer and the decorative layer A when peeling the peelable film. May end up. As described above, when the adhesive force between the decorative layer and the curable resin layer is insufficient, it is preferable to provide an adhesive layer for increasing the adhesion to the decorative layer after providing the curable resin layer on the support film. . As the adhesive layer, it is preferable to use a curable resin layer that does not contain fine particles or the like, or a resin layer obtained by removing a colorant from an ink layer or a paint layer that is a decorative layer. The adhesive layer is usually formed on the curable resin layer of the support film on which the curable resin layer is formed.

An example of the manufacturing method of the hydraulic transfer film of this invention is shown.
For example, a peelable film (b) is attached to one feeding roll (first feeding roll) of a dry laminator, and a decorative layer is previously applied to the peeling film (a) on the other feeding roll (second feeding roll). A laminated film (a) printed with A is attached. The laminated film in which the resin film layer ink is applied to the peelable film (b) fed from the first feed roll, and further dried with a drier to form the resin film layer on the peelable film (b). (b) is obtained. Next, the resin coating layer of the laminated film (b) and the decorative layer A of the laminated film (a) fed out from the second feeding roll are overlaid so as to face each other, and bonded together with a thermocompression-bonding roll and wound up. Rolled up. By peeling the peelable film (a) at the time of winding on a roll or at the time of production of a hydraulic transfer film, the decorative layer A, or the decorative layer A and the resin coating layer or pattern layer is formed on the resin coating layer. A peelable film (b) formed sequentially is obtained.

Next, a support is attached to one feeding roll (first feeding roll) of the dry laminator, and the other feeding roll (second feeding roll) is decorated on the resin coating layer obtained by the above method. A peelable film (b) (hereinafter abbreviated as a laminated film (b2)) in which the layer A or the decorative layer A and the resin coating layer or the pattern layer are sequentially formed is mounted. 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 with a layer formed is obtained. Next, the curable resin layer of this film and the decorative layer or the resin coating layer of the laminated film (b2) fed out from the second feeding roll are overlaid so as to oppose each other, and are laminated by a thermocompression-bonding roll. The film for hydraulic transfer according to the present invention is manufactured by being wound around.
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 is floated on water with the transfer layer facing up and the support layer facing down after peeling off the peelable film of the hydraulic transfer film of the present invention, if a peelable film is attached. , Activate the transfer layer with an organic solvent (activation may be performed before floating in water), transfer the transfer layer to the transfer target, remove the support, and then activate the curable resin layer of the transfer layer It is obtained by curing with at least one of energy ray irradiation and heating.

Specifically, 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.
Next, the transfer layer composed of the decorative layer and the cured resin layer is activated by applying or spraying an organic solvent as an activator to the transfer layer. The activation of the transfer layer with an organic solvent 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.

The activation of the transfer layer with an organic solvent is such that when the transfer layer is transferred from the hydraulic transfer film to the transfer target, the transfer layer is softened and can sufficiently follow the three-dimensional curved surface of the transfer target. It only has to be done.
Note that the resin film layer, the decorative layer A, and the curable resin layer are all softened here, but the decorative layer A is covered with the resin film layer, so that it can be in direct contact with an organic solvent. Therefore, the orientation of the flaky pigment is not disturbed, and only the softening is achieved.

  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, and ion-exchanged water may be used. Depending on the support film used, inorganic salts such as boric acid may be added to the water. % Or less, or 50% or less alcohol may be dissolved.

  The activator used in the present invention is an organic solvent that solubilizes the transfer layer, that is, the resin coating layer, the decorative layer, and the curable resin layer. As the activator used in the present invention, the same activator used for general hydraulic transfer can be used. Specifically, toluene, xylene, ethyl cellosolve, butyl cellosolve, methoxypropanol, butyl carbitol acetate, Carbitol, carbitol acetate, cellosolve acetate, diisobutyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, isobutyl acetate, amyl acetate, isoamyl acetate, isobutyl alcohol, isopropyl alcohol, n-butanol, methoxybutyl acetate, solfit acetate, Examples thereof include diacetone alcohol 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.

  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. 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.

  About the curable resin layer containing 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 containing a thermosetting resin, the curable resin layer can be cured together 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.

(Hydraulic transfer body)
Specific examples of the hydraulic transfer body to which the present invention can be applied include home appliances such as televisions, videos, air conditioners, radio cassettes, mobile phones, refrigerators; OA equipment such as personal computers, fax machines and printers; fan heaters, cameras, etc. Housing parts for household products; 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; automobile interior panels, outer panels of automobiles and motorcycles, wheels Car interior and exterior items such as caps, ski carriers, and automobile carrier bags; sports equipment such as golf clubs, skis, snowboards, helmets, goggles, etc .; three-dimensional images for advertising, signboards, monuments, etc. Especially useful for molded products that require high performance It can be used in the field.

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

<Testing method for hydraulic transfer film>

(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 called matte, but when it has the property of reflecting light, the 60 degree specular gloss is high regardless of the surface state. For example, the glossy surface of aluminum foil is about 500%, and the matte surface is about 140%. Such a phenomenon increases the 60-degree specular gloss when the flake pigment is oriented parallel to the surface even in a metallic pigment or a pearl pigment.
(Adhesion)
The ink adhesion of a sample that was hydraulically transferred to an ABS resin plate (flat plate: 100 mm × 100 mm × 3 mm) was evaluated based on a cross-cut tape method (JIS K5400) on a 10-point scale.

(Production Example 1: Production of curable resin composition A1)
As a curable resin, urethane acrylate “UA-1” obtained by reacting 2 molar equivalents of pentaerythritol, 7 molar equivalents of hexamethylene diisocyanate and 6 molar equivalents of hydroxyethyl methacrylate at 60 ° C. (average number of acryloyl groups 6 in one molecule) , Mass average molecular weight 890) 51 parts, Rohm and Haas acrylic resin “Paraloid A-11” (Tg 100 ° C., mass average molecular weight 125,000) 34 parts as a thermoplastic resin, and Ciba Specialty as a polymerization initiator 3 parts of a photopolymerization initiator “Irgacure 184” manufactured by Chemicals Inc. was dissolved in a mixed solvent of ethyl acetate and methyl ethyl ketone (mixing ratio 1: 1). Next, 15 parts of kaolin “Katalpo” manufactured by Tsuchiya Kaolin Industry was added as inorganic fine particles and stirred to obtain a curable resin composition A1 having a resin solid content of 42%. Table 1 shows the detailed composition.

(Production Example 2: Production of curable resin composition A2)
In the same manner as in Production Example 1, a curable resin composition A2 was obtained. The detailed composition is shown in Table 1.

(Production Example 3: Production of Curable Resin Composition A3)
As a curable resin, acrylic polyol “AP-1” (mass average molecular weight 25,000) obtained by copolymerizing hydroxyethyl methacrylate, methyl methacrylate, ethyl acrylate, butyl acrylate and styrene at a molar ratio of 20: 30: 15: 15: 20. ) 69 parts, a hexamethylene diisocyanate phenol adduct having an isocyanate value 1.1 times equivalent to the hydroxyl value of acrylic polyol “AP-1” and a trimer phenol adduct of hexamethylene diisocyanate as a curing agent 16 parts of “PI-1” was dissolved in a mixed solvent of toluene and ethyl acetate (1: 1). Next, 10 parts of silica “Silisia 350D” manufactured by Fuji Silysia was added as inorganic fine particles and stirred to obtain a curable resin composition A3 having a resin solid content of 35%.

In Table 1,
UA-1: urethane acrylate obtained by reacting 2 molar equivalents of pentaerythritol, 7 molar equivalents of hexamethylene diisocyanate and 6 molar equivalents of hydroxyethyl methacrylate at 60 ° C. (average number of acryloyl groups in one molecule, mass average molecular weight of 890)
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)
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
Kaolin: “Catalupo” made by Tsuchiya Kaolin Industry
Represents.

Further, the gloss value after UV curing is determined by applying a curable resin to an ABS plate used for hydraulic transfer with a bar coater (No. 30), drying at 80 ° C. for 30 minutes, and UV at an irradiation amount of 1200 mJ / cm ^2. The gloss value after irradiation and complete curing of the curable resin layer is expressed, and the gloss value after thermosetting is applied to an ABS plate using a curable resin for hydraulic transfer with a bar coater (No. 44). Then, the gloss value after drying for 60 minutes at 80 ° C. to completely cure the curable resin layer is expressed.

(Production Example 4: Production of film (a) B1 having a decorative layer containing a flaky pigment)
As the peelable film (a), a 38 μm-thick non-silicone-treated polyethylene terephthalate film NK281 (hereinafter abbreviated as release PET film) manufactured by Toyobo Co., Ltd. was used, and ink-1 (silver) having the following composition was rodd to the film. A solid coating with a thickness of 3 μm was applied with a gravure coater to produce a metallic decorative film B1.

<Ink-1 Silver>
Polyurethane (Polyurethane 2569 made by Arakawa Chemical): 20 parts
Pigment (deposited aluminum foil flakes): 10 parts
Ethyl acetate / toluene (1/1): 60 parts
Additives such as wax: 10 parts

(Production Example 5: Production of film (a) B2 having a decorative layer containing a flaky pigment)
As the peelable film (a), a release PET film with a thickness of 38 μm manufactured by Toyobo Co., Ltd. was used, and ink-1 (silver) and ink-2 (transparent red) were applied to the film using a gravure four-color printing machine. Using the 3rd plate, transparent red, silver, and silver were continuously printed in this order to produce a metallic decorative film B2 having a color clear layer with a thickness of 3 μm.

<Ink-2 transparent red>
Polyurethane (Polyurethane 2569 made by Arakawa Chemical): 20 parts
Pigment (red): 3 parts
Ethyl acetate / toluene (1/1): 60 parts
Additives such as wax: 10 parts

(Production Example 6: Production of film (a) B3 having a decorative layer containing a flaky pigment)
As the peelable film (a), a release PET film having a thickness of 38 μm manufactured by Toyobo Co., Ltd. was used, and ink-1 (silver) and ink-3 (black) were applied to the film with a gravure four-color printing machine. Using this, continuous printing was performed in the order of black (mesh-like abstract pattern), silver (solid), and silver (solid) to produce a metallic decorative film B3 having a color clear layer with a thickness of 3 μm.

<Ink-3 ink>
Polyurethane (Polyurethane 2569 made by Arakawa Chemical): 20 parts
Pigment (black): 10 parts
Ethyl acetate / toluene (1/1): 60 parts
Additives such as wax: 10 parts

(Production Example 7: Production of film (b) C1 having a decorative layer containing a flaky pigment)
As a peelable film (b), a biaxially stretched polypropylene film (hereinafter abbreviated as OPP film) having a thickness of 50 μm manufactured by Toyobo Co., Ltd., and ink-3 (black) as a resin coating layer with a microgravure coater, a predetermined dry film thickness (1 μm) and then dried at 60 ° C. for 2 minutes, and then the ink layer and the decorative layer of the metallic decorative film B1 are faced to each other and laminated at 60 ° C. and aged at a temperature of 40 ° C. for 18 hours. Thus, a metallic decorative film C1 was produced. When the peelable film (a) was peeled off from the film C1, the ink layer was transferred to the OPP film side without generating defects such as wrinkles, streaks, and floats that affected the appearance.

(Production Example 8: Production of film (b) C2 having decorative layer containing flake pigment)
A metallic decorative film C2 was obtained in the same manner as in Production Example 7 except that B2 was used instead of the metallic decorative film B1.

(Production Example 9: Production of film (b) C3 having decorative layer containing flake pigment)
A metallic decorative film C3 was obtained in the same manner as in Production Example 7 except that B3 was used instead of the metallic decorative film B1.

(Production Example 10: Production of film (b) C4 having decorative layer containing flake pigment)
As the peelable film (b), a 50 μm-thick unstretched polypropylene film (hereinafter abbreviated as CPP film) manufactured by Toyobo Co., Ltd. was used, and ink-4 (transparent), ink-5 (white), ink- 6 (pearl) is continuously printed in the order of transparent (resin coating layer), white (resin coating layer), pearl (solid), pearl (solid) on a gravure 4-color printing machine, and a pearl tone with a thickness of 3 μm A decorative film C4 was produced.

<Ink-4 transparent>
Polyurethane (Polyurethane 2569 made by Arakawa Chemical): 20 parts
Pigment (precipitated barium sulfate): 10 parts
Ethyl acetate / toluene (1/1): 60 parts
Additives such as wax: 10 parts <Ink-5 white>
Polyurethane (Polyurethane 2569 made by Arakawa Chemical): 20 parts
Pigment (white): 10 parts
Ethyl acetate / toluene (1/1): 60 parts
Additives such as wax: 10 parts <Ink-6 Pearl>
Polyurethane (Polyurethane 2569 made by Arakawa Chemical): 20 parts
Pigment (pearl): 10 parts
Ethyl acetate / toluene (1/1): 60 parts
Additives such as wax: 10 parts

(Example 1: Production of hydraulic transfer film)
The curable resin composition A1 is applied to a 30 μm-thick PVA film manufactured by Aicero Chemical Co., Ltd., which is a support film, with a rod gravure coater so as to have a predetermined dry film thickness (20 μm), and then dried at 60 ° C. for 2 minutes. After that, the curable resin layer and the decorative layer of the decorative film C1 from which the peelable film (a) has been peeled are faced to each other and laminated at 60 ° C., and aged for 18 hours at a temperature of 40 ° C. Produced. When the peelable film (b) is peeled off from the hydraulic transfer film D1, the ink layer is on the PVA film side without causing wrinkles, streaks, defects or the like that affect the hydraulic transfer on the PVA film and the decorative layer. Metastasized.

(Example 2: Production of hydraulic transfer film)
Using A2 as the curable resin composition, a hydraulic transfer film D2 was produced using the decorative film C1 from which the peelable film (a) was peeled off in the same manner as in Example 1. When the peelable film (b) is peeled off from the hydraulic transfer film D2, the ink layer is formed on the PVA film side without causing wrinkles, streaks, defects or the like that affect the hydraulic transfer on the PVA film and the decorative layer. Metastasized.

(Example 3: Production of hydraulic transfer film)
Using A2 as the curable resin composition, a hydraulic transfer film D3 was produced using the decorative film C2 from which the peelable film (a) was peeled off in the same manner as in Example 1. When the peelable film (b) is peeled off from the hydraulic transfer film D3, the ink layer does not generate wrinkles, streaks, defects, etc. that affect the hydraulic transfer on the PVA film and the decorative layer on the PVA film side. Metastasized.

(Example 4: Production of hydraulic transfer film)
Using A2 as the curable resin composition, a hydraulic transfer film D4 was produced using the decorative film C3 from which the peelable film (a) was peeled off in the same manner as in Example 1. When the peelable film (b) is peeled off from the hydraulic transfer film D4, the ink layer is formed on the PVA film side without causing wrinkles, streaks, defects, etc. that affect the hydraulic transfer on the PVA film and the decorative layer. Metastasized.

(Example 5: Production of hydraulic transfer film)
A1 was used as the curable resin composition, and a hydraulic transfer film D5 was produced using the decorative film C4 in the same manner as in Example 1. When the peelable film (b) is peeled off from the hydraulic transfer film D5, the ink layer is formed on the PVA film side without causing wrinkles, streaks, defects, etc. that affect the hydraulic transfer on the PVA film and the decorative layer. Metastasized.

(Example 6: Production of hydraulic transfer film)
Using A3 as the curable resin composition, a hydraulic transfer film D6 was produced using the decorative film C1 from which the peelable film (a) was peeled off in the same manner as in Example 1. When the peelable film (b) is peeled off from the hydraulic transfer film D6, the ink layer is formed on the PVA film side without causing wrinkles, streaks, defects, etc. that affect the hydraulic transfer on the PVA film and the decorative layer. Metastasized.

(Comparative Example 1: Production of hydraulic transfer film)
A1 was used as the curable resin composition, and a hydraulic transfer film D7 was produced using the decorative film B1 in the same manner as in Example 1. When the peelable film (a) is peeled off from the hydraulic transfer film D7, the ink layer does not generate wrinkles, streaks, defects, etc. on the PVA film side, and the PVA film and the decorative layer affect the hydraulic transfer. Metastasized.

(Comparative Example 2: Production of film for hydraulic transfer)
In the same manner as in Production Example 5, a metal decorative film B4 was obtained using an unstretched polypropylene film (hereinafter abbreviated as CPP film) as the peelable film (a). Next, a metallic decorative film C5 was produced in the same manner as in Production Example 7. Using the film C5, a hydraulic transfer film D8 was produced in the same manner as in Example 1. However, when the peelable film (a) is peeled off, the metallic decoration layer floats due to zipping, and the metallic decoration layer floats even after the laminating process when producing the hydraulic transfer film D8. The remaining part remained as a defect and appeared as a defect even after the final hydraulic transfer.

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 7) Water pressure transfer Water at 25 ° C was placed in a water tank, and the peelable film (b) of the water pressure transfer film D1 was peeled off, and then floated on the water surface with the PVA side down. Activating agent (xylene / isobutanol / butyl acetate / Solfit acetate / MIBK = 50/20/15/10/5) was sprayed at 25 g / m ² , and after 15 seconds, an A4 size ABS plate was transferred to a hydraulic transfer film. Inserted into the water from the bottom and hydraulically transferred.
PVA was washed away with water and dried at 80 ° C. for 30 minutes. Next, by using a UV irradiation apparatus, UV light of 1200 mJ / cm ² was irradiated to cure the curable resin layer, and a decorative hydraulic transfer body having a polished aluminum tone was obtained. Until the transfer, the orientation of the silver pigment in the metallic decorative layer was not disturbed. The evaluation results are shown in Table 3.

(Example 8) Water pressure transfer A water pressure transfer film D2 was used to obtain a decorative water pressure transfer body having a cut aluminum shape in the same manner as in Example 7. Until the transfer, the orientation of the silver pigment in the metallic decorative layer was not disturbed. The evaluation results are shown in Table 3.

(Example 9) Water pressure transfer A water pressure transfer film D3 was used in the same manner as in Example 7 to obtain a decorative water pressure transfer body having a shaved aluminum tone dyed red. Until the transfer, the orientation of the silver pigment in the metallic decorative layer was not disturbed. The evaluation results are shown in Table 3.

(Example 10) Water pressure transfer Using the water pressure transfer film D4, in the same manner as in Example 7, a decorative water pressure transfer body having a patterned cut-out aluminum tone was obtained. The evaluation results are shown in Table 3. Until the transfer, the orientation of the silver pigment in the metallic decorative layer was not disturbed. The transfer body has a slightly low gloss value, but this is due to the decoration of the mesh-like abstract pattern on the metallic decoration layer.

(Example 11) Water pressure transfer A decorative water pressure transfer body exhibiting a pearl tone was obtained in the same manner as in Example 7 using the water pressure transfer film D5. Until the transfer, the orientation of the silver pigment in the metallic decorative layer was not disturbed. The evaluation results are shown in Table 3.

(Example 12) Water pressure transfer Warm water at 25 ° C was put in a water tank, and the water pressure transfer film D6 from which the peelable film was peeled was floated on the water surface with the PVA side facing down. An activator (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 was inserted into the water from the hydraulic transfer film. Hydraulic transfer was performed. After PVA was washed away with water, the PVA was heated at 80 ° C. for 60 minutes to dry the activator and cure the thermosetting resin layer, thereby obtaining a decorative hydraulic transfer body having a cut aluminum shape. Until the transfer, the orientation of the silver pigment in the metallic decorative layer was not disturbed. The evaluation results are shown in Table 3.

(Comparative example 3) Water pressure transfer The water pressure transfer body was obtained by the method similar to Example 7 using the film D7 for water pressure transfer. After spraying the activator and before transfer, the orientation of the silver pigment in the metallic decorative layer was disturbed, and a gray hydraulic transfer body with a poor metallic tone was obtained. The evaluation results are shown in Table 3.

  From the above results, the design expressed by the orientation of the flake pigment is well reproduced, and the surface gloss value is high regardless of the surface state of the curable resin layer. It is clear that the provision of the resin coating layer has the effect of suppressing the disorder of the orientation of the flake pigment.

It is sectional drawing of the film for hydraulic transfer which concerns on embodiment in this invention. Nine patterns or solid layers can be provided as necessary. It is an example of the method of manufacturing the peelable film (b) which laminated | stacked the decoration layer for manufacturing the film for hydraulic transfer in this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Support film 2 Transfer layer 3 Curable resin layer (topcoat layer)
4 Decorative layer A '
5 Decorative layer containing flaky pigment (Decorative layer A)
6 Peelable film (a)
7 Resin coating layer 8 Peelable film (b)
9 Pattern layer, color clear layer

Claims (12)

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, wherein the transfer layer is at least active on the support film A hydraulic transfer film, wherein a curable resin layer curable by at least one of energy ray irradiation and heating, a decorative layer containing a flaky pigment, and a resin coating layer are laminated in this order. The hydraulic transfer film according to claim 1, wherein the flaky pigment is a metal foil pigment or a metal-deposited foil pigment. The hydraulic transfer film according to claim 1 or 2, wherein the resin coating layer contains 30% by mass or more of inorganic fine particles or organic fine particles. The hydraulic transfer film according to claim 1, wherein the resin coating layer is composed of a plurality of layers, and at least a surface facing the decoration layer A is black. The hydraulic transfer film according to claim 1, wherein the curable resin layer contains 1% by mass or more of the inorganic fine particles or the organic fine particles. The hydraulic transfer layer according to any one of claims 1 to 5, wherein the curable resin layer contains a matting agent comprising inorganic fine particles or organic fine particles, and the curable resin layer exhibits a matte tone after hydraulic transfer. the film. 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. The hydraulic transfer film according to claim 1, wherein a mass ratio P: (mass sum of radical polymerizable compounds) / (mass sum of thermoplastic resin) is 45/55 or more and 75/25 or less. The hydraulic transfer film according to any one of claims 1 to 7, further comprising a peelable film that can be peeled at an interface with the transfer layer on the transfer layer. A method for producing a hydraulic transfer film according to any one of claims 1 to 8,
(1) A peelable film (a) having a decorative layer containing a flaky pigment and a peelable film (b) having a resin coating layer are arranged so that the decorative layer and the resin coating layer face each other. After laminating, peeling the peelable film (a), forming the decorative layer on the resin coating layer on the peelable film (b),
(2) A support film on which a curable resin layer is formed, and a peelable film (b) produced in the step (1), in which a decorative layer is formed on the resin coating layer, and the curable resin layer Laminating so that the decorative layer is opposite,
A method for producing a hydraulic transfer film, comprising: A method for producing a hydraulic transfer film according to any one of claims 1 to 8,
(1 ′) A peelable film (a ′) in which a decorative layer containing a flaky pigment is formed on a resin coating layer or a pattern layer, and a peelable film (b) in which a resin coating layer is formed, and the decorative layer After laminating so as to face the resin coating layer, the peelable film (a ′) is peeled off, and the decorative layer and the resin coating layer or the pattern are formed on the resin coating layer on the peelable film (b). Forming layers in order,
(2 ′) A support film on which a curable resin layer is formed, and a peelable film (b) in which a decorative layer and a resin coating layer or a pattern layer are sequentially formed on the resin coating layer produced in the step (1 ′). And laminating the curable resin layer and the resin coating layer or the pattern layer so as to face each other,
And a method for producing a hydraulic transfer film. The method for producing a film for hydraulic transfer according to claim 9 or 10, wherein the laminating method is a dry laminating method. The hydraulic transfer film according to any one of claims 1 to 8, wherein the support film is floated on water, the transfer layer is activated with an organic solvent, and the transfer layer is transferred to a transfer target, A hydraulic transfer body, wherein the support film is removed, and then the transfer layer is cured by at least one of active energy ray irradiation and heating.

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