JP2005205659A - Manufacturing method for film for hydraulic transfer, film for hydraulic transfer, and hydraulic transfer body - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method for a film for hydraulic transfer, whereon a pattern of a decorative layer is printed by an inkjet system, and a hydraulic transfer body using the film manufactured by the manufacturing method. <P>SOLUTION: In this manufacturing method for the film for hydraulic transfer, a film (A) and a film (B) are stuck together in such a manner that a curable resin layer of the film (A) and a printed layer of the film (B) face each other. In the film (A), the curable resin layer, which can be cured by at least either active energy ray irradiation or heating and which can dissolve in an organic solvent, is provided on a substrate film which is composed of a water-soluble or water-swelling resin. In the film (B), the printed layer, where printing is applied by the inkjet system, is provided as the decorative layer on a releasable film. The film for hydraulic transfer is manufactured by the manufacturing method, and the hydraulic transfer body is obtained by hydraulically transferring the obtained film for hydraulic transfer. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention provides a method for producing a hydraulic transfer film capable of simultaneously hydraulically transferring a curable resin-forming layer and a decorative layer having a printed layer printed by an ink jet method onto the surface of a material to be transferred such as various molded articles, and the production method. The present invention relates to a hydraulic transfer film and a hydraulic transfer body produced by hydraulic transfer of the hydraulic transfer film.

  The hydraulic transfer method is known to be a method capable of imparting a decorative layer rich in design to a molded article having a complicated three-dimensional shape (for example, see Patent Document 1). However, the molded article having a complicated three-dimensional shape is known. In order for the hydraulic transfer film to follow the surface of the film, the hydraulic transfer film itself must have sufficient flexibility.

Making the hydraulic transfer film flexible is activation in a so-called hydraulic transfer method.
Activation is to redissolve the transfer layer formed into a film with an organic solvent, but it is important to make it soft without breaking the decorative pattern. When a curable resin layer is provided, a laminated structure composed of a curable resin layer and a decoration layer must also be maintained.

The decorative layer is generally composed by gravure printing, etc., but individuality and differentiation of the design is required. If the existing pattern cannot be used, a new plate must be manufactured, which is suitable for mass production. In the case of gravure printing, there is a problem of plate making cost when a small amount and a large variety are used. Therefore, it is very difficult to cope with the design specified by the consumer.
Japanese Patent Laid-Open No. 4-197699

The problem to be solved by the present invention is to provide a method for producing a hydraulic transfer film capable of printing a pattern or the like of a decorative layer by an ink jet method and transferring an image using a digital image recording device or a computer to a three-dimensional object. The object of the present invention is to provide a hydraulic transfer body using the film for hydraulic transfer according to the production method and capable of dealing with a small variety of products.
Polyvinyl alcohol (PVA) is suitably used as the water-soluble or water-swellable resin for the hydraulic transfer film, and PVA is also used as a receiving layer for water-based inkjet printing. Since it is used as a single film, it is sensitive to temperature and humidity and is difficult to use as it is as an inkjet printing paper.

As a result of intensive studies to solve the above problems, the present inventors can dissolve in an organic solvent curable by at least one of active energy ray irradiation and heating on a support film made of a water-soluble or water-swellable resin. A film for hydraulic transfer having a decorative layer printed by an inkjet method can be produced by laminating a film (A) provided with a curable resin layer and a peelable film (B) provided with a decorative layer. I found.
That is, the present invention
A film (A) provided with a curable resin layer soluble in an organic solvent curable by at least one of active energy ray irradiation and heating on a support film made of a water-soluble or water-swellable resin, and a peelable film A film (B) provided with a printing layer printed by an inkjet method as a decorative layer was bonded to the film so that the curable resin layer of the film (A) and the printing layer of the film (B) face each other. A method for producing a hydraulic transfer film is provided.

  Moreover, the film for hydraulic transfer manufactured by this manufacturing method is provided.

In addition, using the hydraulic transfer film, the transfer layer is floated on water, and the transfer object is pressed against the transfer layer activated by an organic solvent to transfer the transfer film to the transfer object. Then, after removing the support film from the hydraulic transfer film transferred to the transfer object, the transferred curable resin layer is cured by at least one of irradiation with active energy rays and heating. A hydraulic transfer body is provided.

  According to the method for producing a hydraulic transfer film of the present invention, a hydraulic transfer film capable of simultaneously activating and transferring a decorative layer and a curable resin layer printed by an inkjet method can be produced.

(Support film)
The support film used in the method for producing a 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 (decoration layer, curable resin layer))
Next, the transfer layer (decoration layer, curable resin layer, and swelling suppression layer) provided on the support used in the method for producing a hydraulic transfer film of the present invention will be described. The transfer layer is a composite layer in which a curable resin layer and a decoration layer are laminated. The decoration layer has an ink jet printing ink layer, but it suppresses swelling, which is a resin containing an ink receiving layer for improving the precision printability of ink jet ink and an additive that does not dissolve and swell in the organic solvent used for activation. It may have a layer.

(Decoration layer)
The ink-jet printing is used to form the decorative layer of the hydraulic transfer film of the present invention. As long as it is an inkjet system, the type of ink may be any of solvent-based, water-based, or solventless such as UV curable ink, and the ink colorant may be dye-based or pigment-based.
During activation, the dye-based ink is likely to bleed, and the pigment-based ink is preferable from the viewpoint of pattern reproducibility. In addition, water-based ink is preferable from the viewpoint of versatility of the inkjet printer and environmental considerations.

The decorative layer can be easily formed by printing on a peelable film.
If it is solvent-based or solvent-free inkjet printing, it can print directly on a peelable film. However, when using a hydraulic transfer film, the peelable film is peeled off and used, but the printed layer is formed on a support film made of a water-soluble or water-swellable resin and an organic solvent provided on the support film. It must be transferred to the side of the curable resin layer that can be dissolved. Therefore, a release layer may be provided on the surface of the peelable film in order to transfer without defects. Further, an ink-jet ink receiving layer may be provided in order to form a precise print. These release layer and ink receiving layer may be multi-layered, or one layer may have both functions.
In the case of water-based ink jet printing, it is difficult to print directly on the peelable film, so it is necessary to provide an ink receiving layer. The ink receiving layer is not particularly limited as long as it can be activated, and may be a swelling type or a penetration type, or a swelling / penetration hybrid type. Above all, the penetrating type can absorb and fix ink by containing inorganic filler, resin fine particles, etc., and the fine particles do not dissolve in organic solvents, so the function of stabilizing the swelling behavior by activation Also have. Among these, silica, silica sol, alumina, alumina sol, kaolin, basic magnesium carbonate, cationic acrylic fine particles, cationic urethane fine particles, and the like are preferable because they are excellent in ink absorption and fixing. By using these, the hydrophilicity of the binder resin described later can be reduced, and it can be suitably used in that it does not adversely affect the activation.

The binder resin used for adhering the fine particles is generally a nonionic hydrophilic resin such as polyvinyl alcohol (PVA), an anionic hydrophilic resin such as polyacrylic acid, or a quaternized ammonium-containing vinyl polymer. These cationic hydrophilic resins are used alone or in combination. Many of these resins are insoluble in organic solvents, and if used as they are, they tend to agglomerate and cause defects upon activation. Therefore, it is preferable that the resin is hydrophobicized to such an extent that it does not aggregate with the active agent. For example, cationic acrylic resins, cationic urethane polymers, partially saponified PVA, polyvinyl pyrrolidone and the like can be suitably used.

  In the case of providing a release layer, the release layer can be formed into an ink or paint and printed or applied to a peelable film.

The base resin used for the release layer is 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 fluorinate), ethylene-vinyl acetate resin, polyolefin resin, chlorinated olefin resin, ethylene-acrylic resin, petroleum resin, cellulose derivative resin, and other thermoplastic resins are 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 used for the resin used in the release layer 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, Those having a molecular weight of 2,500 or more and 40,000 or less are preferable because they have solubility in an organic solvent and appropriate adhesion to a peelable film. When the number average molecular weight of the polyurethane resin is smaller than 2,000, the weather resistance is lowered, and when the number average molecular weight is larger than 60,000, the glass transition temperature is increased, and the adhesion or fluidity of the ink or paint is increased. Pigment dispersibility and transferability are reduced. In addition, the glass transition temperature of the polyurethane resin is preferably −5 ° C. or more and 70 ° C. or less from the viewpoint of solubility in an organic solvent and appropriate adhesion to a transfer object.

  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 number average molecular weight of the polyester resin used for the resin used in the release layer is preferably 2,000 to 8,000 in order to have appropriate adhesion to the peelable film, more preferably 2500 to 8,000. 7,500, most preferably 2,500 to 7,000. When the number average molecular weight is less than 2,000, the flexibility and elongation at break are lowered, the followability to the transferred material at the time of transfer is lowered, and the image quality of the decorative layer formed on the obtained hydraulic transfer body is improved. descend. If the number average molecular weight is larger than 8,000, the polyester resin molecules tend to become large molecules due to hydrogen bonding or the like, the glass transition temperature becomes high, and the transferability decreases. Moreover, it is preferable that the glass transition temperature of the polyester resin used for printing ink or a coating material is -5 degreeC or more and 70 degrees C or less from having moderate adhesiveness with a to-be-transferred material.

  The resin used for the release layer, that is, the polyester resin used for printing ink or paint is preferably a polyester having a small hydroxyl group, and 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 be lowered. When other resins are blended and the glass transition temperature of ink or paint is prepared to be low, it is preferable to use the above polyurethane resin as a resin other than the polyester resin.

In order to adjust the peeling force between the decorative layer and the peelable film, the release 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 an inking or paint release layer. However, it is preferable to use a fluorine-based compound or a silicone-based compound, and it is easy to control the molecular weight and chemical structure. Compounds are particularly preferred. Among silicone compounds, polyether-modified polysiloxanes and polysiloxane-polyether block copolymers can be suitably used.

  The content of the silicone compound in the printing ink or paint is preferably 0.01% by mass or more and 6.0% by mass or less, more preferably 0.05% by mass or more and 4.0% by mass or less in the nonvolatile content. It is. When the amount is less than 0.01% by mass, the effect of the release agent is insufficient. When the amount exceeds 6.0% by mass, when the hydraulic transfer film of the present invention is used, the release layer and the ink receiving layer or the curable resin layer It becomes easy to cause peeling between.

The release layer is a balance with the design, and may be colorless or colored, the base may be transparent, or the base may be concealed.
If it is transparent to white, it can be used for general purposes. Examples of the colorant include lime carbonate powder, precipitated calcium carbonate, gypsum, clay (China Clay), silica powder, diatomaceous earth, talc, kaolin, Alumina white, basic magnesium carbonate, barite powder, abrasive powder, titanium white, etc. can be used. These fine particles may be used alone or in combination.

  In the case of coloring, pigments (azo pigments, phthalocyanine pigments, selenium pigments, quinacridone pigments, phosphorescent pigments, etc.) and dyes (azo dyes, fluorescent dyes, etc.) used in printing inks and paints can be used.

The resin used for the release layer may contain a plasticizer, a surfactant, an antioxidant, an ultraviolet absorber, a solvent, and the like as necessary.
When the release layer also has a function as a receiving layer for ink jet printing, silica, silica sol, alumina, alumina sol, kaolin, basic magnesium carbonate, cationic acrylic fine particles, cationic urethane fine particles, etc., fine particles used in the ink jet receiving layer Can be added. These fine particles may be used alone or in combination.

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

The ink receiving layer and release layer are formed by gravure printing, offset printing, screen printing, inkjet printing, slit reverse coater, die coater, comma coater, bar coater, knife coater, gravure coater, gravure reverse coater, rod gravure. Gravure printing, rod gravure coater coating, and comma coater coating are preferred because they can be carried out by a coater, flexo coater, blanket coater, roll coater, air knife coater, etc. and are easy to mass-produce. The dry film thickness of the ink receiving layer and the release layer is preferably 0.5 to 20 μm, and more preferably 1 to 15 μm in order to enable good decoration and activation during hydraulic transfer. .
As long as the design and spreadability are not hindered, an antifoaming agent, an anti-settling agent, a pigment dispersant, a fluidity modifier, an antiblocking agent, an antistatic agent, an antioxidant, Various conventional additives such as a light stabilizer and an ultraviolet absorber may be added.

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

The curable resin layer contains a resin that can be cured by at least one of active energy ray irradiation and heating, and specific examples thereof 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.

Further, in the above (1) to (6), as long as the designability and curability are not impaired, an antifoaming agent, an antisettling agent, a pigment dispersant, a fluidity modifier, an antiblocking agent, an antistatic agent, an oxidation agent Various conventional additives such as an inhibitor, a light stabilizer, and an ultraviolet absorber 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 Examples include acrylic (meth) acrylate, epoxy (meth) acrylate, polyalkylene glycol poly (meth) acrylate, polyether (meth) acrylate, and polyurethane (meth) acrylate, polyester (meth) acrylate, and epoxy (meth) acrylate. Is preferably used.

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

  The curable resin layer containing these active energy ray-curable resins may contain a conventional photopolymerization initiator or photosensitizer as necessary. Typical photopolymerization initiators include acetophenone compounds such as diethoxyacetophenone and 1-hydroxycyclohexyl-phenyl ketone; benzoin compounds such as benzoin and benzoin isopropyl ether; 2,4,6-trimethylbenzoin diphenylphosphine. Acyl phosphine oxide compounds such as oxides; benzophenone, o-benzoylbenzoic acid methyl-4-phenylbenzophenone compounds such as benzophenone compounds; thioxanthone compounds such as 2,4-dimethylthioxanthone; amino compounds such as 4,4'-diethylaminobenzophenone Examples thereof include benzophenone compounds; polyether maleimide carboxylic acid ester compounds, and the like, and these can be used in combination.

  The usage-amount of a photoinitiator is 0.1-15 mass% normally with respect to the active energy ray curable resin to be used, Preferably it is 0.5-8 mass%. Examples of the photosensitizer include amines such as triethanolamine and ethyl 4-dimethylaminobenzoate. Furthermore, onium salts such as benzylsulfonium salt, benzylpyridinium salt, and arylsulfonium salt are known as photocationic initiators, and these initiators can also be used, and are used in combination with the above photopolymerization initiators. You can also

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

  The thermoplastic resin is compatible with the active energy ray curable resin to be used, and specific examples include polymethacrylate, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, and polyester. These may be a homopolymer or a copolymer of a plurality of monomers. The thermoplastic resin is preferably non-polymerizable.

  Among them, polystyrene and polymethacrylate are preferable because they have high Tg and are suitable for reducing the adhesiveness of the curable resin layer, and in particular, polymethacrylate mainly composed of polymethyl methacrylate is transparent, solvent resistant, and It is preferable at the point which is excellent in abrasion resistance.

  Further, the molecular weight and Tg of the thermoplastic resin have a great influence on the film-forming ability. In order to suppress the fluidity of the curable resin and facilitate activation of the curable resin layer with an organic solvent, the mass average molecular weight of the thermoplastic resin is preferably 3,000 to 400,000, more preferably 10,000. The Tg is preferably 35 ° C to 200 ° C, more preferably 35 ° C to 150 ° C. When using a thermoplastic resin having a relatively low Tg of around 35 ° C., the mass average molecular weight of the thermoplastic resin is preferably 100,000 or more.

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

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

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

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

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

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

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

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

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

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

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

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

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

The curable resin layer must be able to be activated by an 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, It is preferable that the curable resin layer contains a thermoplastic resin.
In the activation according to the present invention, since the activator lands on the transfer layer with pressure, the activator can permeate quickly and easily dissolve (activate) the curable resin layer. In addition, by including a thermoplastic resin, the curable resin layer can be activated more gently, thereby suppressing uneven dissolution of the curable resin layer and cracking of the decorative layer due to rapid activation. can do.

That is, the curable resin layer containing a thermoplastic resin has an appropriate resistance against the penetration of the activator and a firm self-holding power before curing, and the activator is applied as the pressure liquid of the present invention. By doing so, a synergistic effect is exhibited.

  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 satisfy the function as a protective layer and the design properties, the thickness is preferably 5 to 30 μm.

To the above (1) to (6), an inorganic / metal compound or an inorganic / metal compound subjected to organic treatment can also be added.
There are no restrictions on these compounds that can be added, and for example, organic treatments such as silica gel, silica sol, montmorillonite, mica, alumina, titanium oxide, glass beads, and other inorganic / metal compounds, organosilica sol, acrylic-modified silica, and closite are performed. Inorganic / metal compounds prepared can be used.

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

a) Release film (A)
In addition to direct ink jet printing,
The release layer and the ink receiving layer are formed on the peelable film (A).
b) Peelable film (A) / Peelable layer c) Peelable film (A) / Peelable layer / ink receiving layer d) Peelable film (A) / Peelable layer / ink receiving layer The decorative layer is formed by performing inkjet printing on the coated or printed peelable film (A). In that case, it is necessary that the decorative layer is fixed on the peelable film with such a peeling force that the decorative layer is not peeled off by the work or handling such as film feeding. The peelable film (A) on which the decorative layer is formed can be produced by attaching the curable resin layer so as to face the curable resin layer of the support film (B) on which the curable resin layer is laminated, thereby producing a hydraulic transfer film. it can. Among these, dry lamination (dry lamination method) is preferable because the amount of the remaining organic solvent in the hydraulic transfer film can be reduced as much as possible. The residual solvent in the hydraulic transfer film makes the peelable film peel heavy, and the decorative layer on which ink jet printing has been performed becomes difficult to transfer to the support film (B) side on which the curable resin layer is laminated. In that case, it is necessary that the decorative layer is fixed on the peelable film with such a peeling force that the decorative layer is not peeled off by the work or handling such as film feeding.

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

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

(Method for producing hydraulic transfer film)
Next, an example of the manufacturing method of the hydraulic transfer film of the present invention is shown below.
In the method for producing a hydraulic transfer film of the present invention, a curable resin layer that is soluble in an organic solvent that can be cured by at least one of active energy ray irradiation and heating is formed on a support made of a water-soluble or water-swellable resin. The provided film (A) and the film (B) provided with a pattern such as an image printed by the inkjet method as a decorative layer on the peelable film, the curable resin layer of the film (A) and the film (B It is preferable that the printed surfaces are laminated so as to face each other and are bonded by dry lamination (dry lamination method).

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

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

  In addition, by using a support laminated on a peelable film, the coating or printing substrate is hardly affected by sagging and has good dimensional stability. The film thickness can be precisely controlled.

  The production of the film (B) having a decorative layer on the peelable film is performed by ink jet printing. However, since residual solvent or residual moisture in the decorative layer in the hydraulic transfer affects the transfer behavior, it is removed after printing. It is preferable to dry. The drying temperature is preferably 80 ° C. or lower in consideration of the heat resistance of the peelable film.

  The obtained film for hydraulic transfer of the present invention is often used immediately after production due to its properties, but if it is stored in a dark place such as a warehouse in a moisture-proof, light-shielded state, the curing reaction does not proceed unnecessarily. In addition, the water pressure transfer of a clear decorative layer is possible.

(Method for manufacturing molded products)
Next, a method for producing a molded article using the hydraulic transfer film of the present invention having a decorative layer provided with a pattern such as an image printed by an inkjet method as a transfer layer and a cured resin layer will be described.
The method for producing a hydraulic transfer body of the present invention comprises the steps of peeling off the peelable film from the film for hydraulic transfer of the present invention, then floating the transfer layer up, floating the support in water, and decorating the organic layer with an organic solvent. And the transfer layer composed of the cured resin layer is activated (the activation may be performed before floating in water), the transfer layer is transferred to the transfer object, the support is removed, and then the curable resin layer of the transfer layer Is cured by at least one of active energy ray irradiation and heating.
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. The outline of the manufacturing method of the hydraulic transfer body using these hydraulic transfer films is as follows.

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

  The transfer layer composed of the decorative layer and the cured resin layer needs to be activated with an organic solvent sprayed before being hydraulically transferred and sufficiently solubilized or softened. The activation mentioned here means that the resin constituting the transfer layer is solubilized without being completely dissolved by applying or spraying an organic solvent to the transfer layer, and transferred from a hydrophilic support film during hydraulic transfer. This means that the layer can be easily peeled and the transfer layer can be made flexible to improve the followability and adhesion of the transfer layer to the three-dimensional curved surface of the transfer target. This activation may be performed to such an extent that when the transfer layer is transferred from the hydraulic transfer film to the transfer target, these transfer layers are softened and can sufficiently follow the three-dimensional curved surface of the transfer target.

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

  The activator used in the present invention is an organic solvent that solubilizes the cured resin layer, the decorative layer stabilizing layer, and the decorative layer. As the activator used in the present invention, the same activator used for general hydraulic transfer can be used. Specifically, toluene, xylene, butyl cellosolve, butyl carbitol acetate, carbitol, carbitol acetate , Cellosolve acetate, methyl isobutyl ketone, ethyl acetate, isobutyl acetate, isobutyl alcohol, isopropyl alcohol, n-butanol, solfit acetate, and the like, and mixtures thereof.

  In order to improve the adhesion between the printing ink or paint and the molded product, this activator may contain some resin components. For example, adhesion may be increased by including 1 to 10% of an ink binder having a similar structure such as polyurethane, acrylic resin, or epoxy resin.

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

  It is preferable that a transfer layer composed of a decorative layer and a cured resin layer is sufficiently adhered to the surface of the transfer target, and a primer layer is provided on the surface of the transfer target as required. 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 with reference to examples. Unless otherwise specified, “part” and “%” are based on mass.

<Testing method for hydraulic transfer film>
The hydraulic transfer bodies obtained in Examples and Comparative Examples were evaluated by the following tests.

(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.

<Manufacture of curable resin composition>
(Production Example 1: Production of curable resin composition A1)
60 parts of urethane acrylate (UA1) obtained by reacting 2 molar equivalents of pentaerythritol, 7 molar equivalents of hexamethylene diisocyanate and 6 molar equivalents of hydroxyethyl methacrylate at 60 ° C. (average number of acryloyl groups in one molecule: 6, weight average molecular weight: 890) ) And 40 parts of Rohm and Haas acrylic resin trade name Paraloid A-11 (Tg 100 ° C., weight average molecular weight 125,000) are dissolved in a mixed solvent of ethyl acetate and methyl ethyl ketone (mixing ratio 1: 1). -3 parts of a photopolymerization initiator trade name “Irgacure 184” manufactured by Specialty Chemicals was added and stirred to produce a curable resin composition A1 having a resin solid content of 42%.

(Production Example 2: Production of curable resin composition A2)
Acrylic polyol (a) obtained by copolymerizing hydroxyethyl methacrylate, methyl methacrylate, ethyl acrylate, butyl acrylate and styrene at a molar ratio of 20: 30: 15: 15: 20 was added to 81 parts of acrylic polyol. 19 parts of a mixture of a hexamethylene diisocyanate phenol adduct having an isocyanate value 1.1 times equivalent to the hydroxyl value and a trimer phenol adduct of hexamethylene diisocyanate was mixed with toluene and ethyl acetate (1: 1). Was added and stirred to produce a curable resin composition A2 having a resin solid content of 35%.

<Ink B1 composition for release layer, white>
Polyurethane (Dainippon Ink Co., Ltd., Bernock EZL676): 35 parts by mass, pigment (titanium oxide): 10 parts by mass, ethyl acetate / toluene (1/1): 50 parts by mass, and additives such as wax: 5 parts by mass.

<Ink C1 composition for ink receiving layer>
Dainippon Ink Co., Ltd., Pateracol IJ-150 was used as it was.

<Ink D1 composition for release layer and ink receiving layer>
Polyurethane (Dainippon Ink, Vernock EZL676): 23 parts by mass, silica (Fuji Silysia, Silicia 350D): 30 parts, pigment (cationic urethane fine particles): 12 parts by mass, ethyl acetate / toluene (1/1 ): 30 parts by mass, and additive: 5 parts by mass.

(Production Example 3: Decorative film E1 having a release layer and an ink receiving layer)
Using a solid plate at a printing speed of 20 m / min on a non-stretched polypropylene film (hereinafter abbreviated as PP film) having a thickness of 50 μm manufactured by Toyobo Co., Ltd., the ink B1 for the release layer has a dry film thickness of 1 μm. Printed with settings. On the resulting release layer, a comma coater was used to apply the ink receiving layer ink C1 to a dry film thickness of 10 μm to obtain a decorative layer film. The film was cut into A3 size, a photographic image was printed with a pigment-based ink using Hewlett-Packard Design Jet 2000CP, and dried at 40 ° C. for 30 minutes to obtain a decorative film E1.
(Production Example 4: Decorative film E2 having a release layer and ink receiving layer)
Using a comma coater on a PP film having a thickness of 50 μm manufactured by Toyobo Co., Ltd., the ink D1 for the release layer / ink receiving layer was applied to a dry film thickness of 10 μm to obtain a film for a decorative layer. The film was cut into A3 size, a photographic image was printed with a pigment-based ink using Hewlett-Packard Design Jet 2000CP, and dried at 40 ° C. for 30 minutes to obtain a decorative film E2.

(Example 1: Production of hydraulic transfer film)
The curable resin composition A1 was applied to a 30 μm thick PVA film manufactured by Aicero Chemical Co., Ltd., which is a support film, with a comma coater so as to have a predetermined dry film thickness (20 μm), and then dried at 60 ° C. for 2 minutes. Later, the curable resin layer and the decorative layer of the decorative film E1 were faced to each other and laminated at 60 ° C. to prepare a hydraulic transfer film F1.

(Example 2: Production of hydraulic transfer film)
A hydraulic transfer film F2 was prepared in the same manner as in Example 1 except that E2 was used as the decorative film.

(Example 3: Production of hydraulic transfer film)
A hydraulic transfer film F3 was prepared in the same manner as in Example 1 except that A2 was used as the curable resin composition.

(Example 4: Production of hydraulic transfer body)
Hot water of 25 ° C. was put in a water tank, and after the PP film of the hydraulic transfer film F1 was peeled off, the hydraulic transfer film F1 was floated on the water surface with the PVA side down. An activator (toluene / butyl acetate / ethyl cellosolve / 3-methyl 3-methoxybutyl acetate / isobutanol = 50/15/15/10/10) was sprayed at 20 g / m ² , and after 15 seconds, an ABS mobile phone was made. The telephone mold was inserted into the water and transferred by hydraulic pressure. After PVA was washed away with water, it was dried at 80 ° C. for 30 minutes. Next, by using a UV irradiation apparatus, UV light of 2400 mJ / cm ² is irradiated to cure the curable resin layer, thereby obtaining a hydraulic transfer body P1 having excellent surface gloss and a clear photographic image by ink jet printing. It was.

(Example 5: Production of hydraulic transfer body)
A hydraulic transfer member P2 having an excellent surface gloss and a clear photographic image by inkjet printing was obtained in the same manner as in Example 4 except that the hydraulic transfer film F2 was used.

(Example 6: Production of hydraulic transfer body)
Hot water at 25 ° C. was poured into the water tank, and after the PP film of the hydraulic transfer film F3 was peeled off, the hydraulic transfer film F3 was floated on the water surface with the PVA side down. Activating agent (xylene / methyl isobutyl ketone / 3-methyl 3-methoxybutyl acetate / butyl acetate = 50/25/15/10) is sprayed at 20 g / m ² , and 15 seconds later, an ABS mobile phone mold Was inserted into the water and hydraulically transferred. After the PVA was washed away with water, the curable resin layer was cured by drying at 80 ° C. for 60 minutes to obtain a hydraulic transfer body P3 having excellent surface gloss and a clear photographic image by ink jet printing.

(Comparative Example 1)
The curable resin composition A1 was applied to a 30 μm thick PVA film manufactured by Aicero Chemical Co., Ltd., which is a support film, with a comma coater so as to have a predetermined dry film thickness (20 μm), and then dried at 60 ° C. for 2 minutes. Later, the obtained film was cut into A3 size, a photographic image was printed with a pigment-based ink using Hewlett-Packard Design Jet 2000CP, and dried at 40 ° C. for 30 minutes, whereby a hydraulic transfer film F4. It was created. Since the ink absorption was too slow, the image was corrupted at the printing stage. Moreover, the curable resin layer was whitened by the water contained in the ink, and did not return to transparent even when dried.

  As is clear from Table 1, the hydraulic transfer body obtained by using the hydraulic transfer film produced by the lamination method with the decorative layer formed by ink jet printing of the present invention had a clear image. On the other hand, as shown in the comparative example, when printing was directly performed on the curable resin layer, a decorative layer having a clear image could not be formed. A method of adding ink-absorbing fine particles or resin to the curable resin layer is also conceivable, but in this case, the function of the curable resin layer as a protective layer is impaired, so that it is difficult to employ.

  The hydraulic transfer film of the present invention can be individually formed with a decoration layer and a curable resin layer by a lamination method, and can be transferred without deteriorating the high-definition design of the decoration layer by the ink jet method. It is. Furthermore, it becomes possible to deal with a small variety of products.

It is sectional drawing of the film for hydraulic transfer used as the object of the manufacturing method of this invention. 4 and 5 may be an ink receiving layer and a release layer, which may be a single layer. It is a schematic diagram for demonstrating the method of bonding a film (A) and a film (B) together by lamination.

Explanation of symbols

1 Hydraulic transfer film 2 Support 3 Topcoat layer (curable resin layer)
4 Print layer by inkjet method 5 Peeling layer 6 Peelable film 7 Film (A)
8 Film (B)

Claims (8)

A film (A) provided with a curable resin layer soluble in an organic solvent curable by at least one of active energy ray irradiation and heating on a support film made of a water-soluble or water-swellable resin, and a peelable film A film (B) provided with a printing layer printed by an inkjet method as a decorative layer was bonded to the film so that the curable resin layer of the film (A) and the printing layer of the film (B) face each other. A method for producing a hydraulic transfer film. The method for producing a film for hydraulic transfer according to claim 1, wherein the film (B) is produced by printing by an ink jet method on an ink receiving layer provided on a peelable film to provide a printing layer. The manufacturing method of the film for hydraulic transfer of Claim 1 or 2 with which the decoration layer of the said film (B) is laminated | stacked in order of the peeling layer / ink receiving layer. The method for producing a hydraulic transfer film according to claim 1, wherein the ink jet printing is performed using a pigment-based ink. The method for producing a hydraulic transfer film according to claim 1, wherein printing by the inkjet method is performed using water-based ink. The method for producing a hydraulic transfer film according to any one of claims 1 to 5, wherein the method of bonding the film (A) and the film (B) is dry lamination. A hydraulic transfer film produced by the method for producing a hydraulic transfer film according to claim 1. The hydraulic transfer film according to claim 7 is floated on water with the transfer layer facing upward, and the transfer object is pressed against the transfer layer activated by an organic solvent, thereby the hydraulic transfer film is applied to the transfer object. After transferring and removing the support film from the hydraulic transfer film transferred to the transfer target, the transferred curable resin layer is cured by at least one of irradiation with active energy rays and heating. Hydraulic transfer body to do.

Images