JP2005132014A - Activator for hydraulic transfer and method for manufacturing hydraulic transfer medium - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an activator for hydraulic transfer which makes it possible to manufacture a hydraulic transfer medium free from color irregularities, a disorderly pattern and creases, in transferring a hydraulic transfer film consisting of a support film formed of a water-soluble or water-swelling resin and a hydrophobic decorative layer soluble in an organic solvent and a curable resin layer with a thickness of not more than 30 μm, formed on the support film as a subject to be solved. <P>SOLUTION: The activator for hydraulic transfer shows leveling properties which spread over a transfer layer for the hydraulic transfer film; permeability into the transfer layer; the solubility/swelling properties of the curable resin layer which dissolves or swells the curable resin layer; and the solubility/swelling properties of the decorative layer which dissolves or swells the decorative layer. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a method for producing a hydraulic transfer member.

  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. However, the method of manufacturing a molded product by the hydraulic transfer method requires spray coating of a curable resin as a protective layer on the decorative layer that has been further hydraulically transferred after the hydraulic transfer. Although it is suitable for the production of varieties, the cost is high, and the molded products manufactured by the hydraulic transfer method are limited to high-quality products and limited products.

  In order to eliminate this complexity and high cost, attempts have been made to transfer a curable resin layer together with a decorative layer to a transfer object by a hydraulic transfer method, and a resin coating layer that is cured by irradiation with ionizing radiation or heat is used. Using the water pressure transfer sheet and the water pressure transfer sheet, after applying the activator by gravure coating or the like, the uncured coating layer and the decorative layer are transferred to the transfer target, and then water-soluble or water-soluble A method for producing a molded article (hydraulic transfer body) having a cured resin layer in which the coating layer is cured with ionizing radiation or heat after removing the swellable support film with water is disclosed (for example, patents) Reference 1).

In the hydraulic transfer method, activation means that the resin constituting the coated transfer layer is not completely dissolved, but is solubilized, and the transfer layer is given flexibility, thereby giving the transfer layer a three-dimensional transfer target. It means improving the followability and adhesion to a curved surface.
The organic solvent used for activation is called an activator.

Conventionally, activation of a hydraulic transfer film having a curable resin layer and a decorative layer has the following problems.
1) It is difficult to uniformly activate the curable resin layer.
2) It is difficult to uniformly activate the curable resin layer without disturbing the pattern of the decorative layer of the transfer layer. At that time, if the curable resin layer became thicker, the difficulty further increased.
In other words, when a printed pattern is applied as a decorative layer in the transfer layer, the pattern must not be destroyed and a curable resin layer having a thickness several times that of the decorative layer can be activated simultaneously and uniformly. Was difficult.

In order to uniformly activate the curable resin layer, increasing the activator makes it easier to break the print pattern of the decorative layer. On the other hand, when the activator is decreased, the curable resin layer is uniformly activated.
An activator having a composition with excellent penetrability, for example, when a droplet such as a spray is applied, the activation state is different between the sprayed part and the non-sprayed part, and the surface of the transferred product is fine. An uneven defect is generated.

Japanese Unexamined Patent Publication No. 64-22378

    The problem to be solved by the present invention is to provide an activator that enables uniform activation of a transfer layer having a curable resin layer and a decorative layer.

  As a result of intensive studies to solve the above problems, the present inventors have used an activator having a specific range of parameters for the activation of the hydraulic transfer film, thereby disturbing the pattern of the decorative layer, It was found that the hydraulic transfer film can be uniformly activated without causing unevenness.

That is, the present invention has a support film made of a water-soluble or water-swellable resin, and a hydrophobic transfer layer that can be dissolved in an organic solvent provided on the support film, and the transfer layer is a decorative layer. A hydraulic transfer film having a curable resin layer curable with at least one of active energy ray irradiation and heating is floated on water with the transfer layer facing up, and the transfer layer activated by an activator The film for water pressure transfer was transferred to the material to be transferred by pressing the material to be transferred, and after removing the support film from the water pressure transfer film transferred to the material to be transferred, the film was transferred by irradiation with active energy rays. The activator used in the production of a hydraulic transfer body for curing a curable resin layer, the activator comprising:
Leveling property that expands to a diameter of 10 mm or more 30 seconds after dropping 10 μL of the activator on the transfer layer of the hydraulic transfer film,
Penetration that the volume reduction rate of the droplets is 5% to 30% 15 seconds after dropping 10 μL of the activator on the transfer layer of the hydraulic transfer film,
Dissolve or swell the dripping part 30 seconds after dropping 10 μL of the activator on the curable resin layer from which the decorative layer is removed from the hydraulic transfer film, and 80% by mass or more can be easily removed. Swelling and
On the decorative layer of the hydraulic transfer film, 10 μL of the activator is dropped 30 seconds after the dropping part is dissolved or swelled, and the decorative layer has a decorative layer dissolving swelling property that can be easily removed by 80% by mass or more. An activator for hydraulic transfer is provided.

A support film made of a water-soluble or water-swellable resin; and a hydrophobic transfer layer that can be dissolved in an organic solvent provided on the support film. A film for hydraulic transfer having a curable resin layer that can be cured by at least one of irradiation and heating is floated on water with the transfer layer facing up, and is transferred to the transfer layer activated by an activator The film for water pressure transfer is transferred to the transfer body by pressing the substrate, the support film is removed from the water transfer film transferred to the transfer body, and the transferred curable resin is irradiated with active energy rays. A method for producing a hydraulic transfer body for curing a layer, wherein the activator according to any one of claims 1 to 3 is used.

  By using the hydraulic transfer activator of the present invention, it is possible to produce a hydraulic transfer body free of pattern distortion or wrinkles on the decorative layer when transferring a hydraulic transfer film having a curable resin layer and a decorative layer. . In particular, the hydraulic transfer activator of the present invention is effective for uniform activation of a hydraulic transfer film in which the curable resin layer of the transfer layer is 30 μm or less. Furthermore, it is particularly useful for the production of decorated hydraulic transfer bodies such as home appliances, building members, automobile members, and the like that require design and surface strength.

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

(Decoration layer)
The printing ink or paint used for forming the decorative layer of the present invention is a printing ink or paint that can be printed on or applied to a peelable film, has a low peel strength from the peelable film, and is activated by an organic solvent. Thus, it is preferable that sufficient flexibility is obtained when the transfer layer is transferred to the transfer target, and gravure printing ink is particularly preferable. A colored layer having no pattern can also be formed by coating.
Varnish resins used for printing ink or paint are acrylic resin, polyurethane resin, polyamide resin, urea resin, epoxy resin, polyester resin, vinyl resin (vinyl chloride, vinyl acetate copolymer resin), vinylidene resin (vinylidene chloride, vinylidene fluoride) ), Thermoplastic resins such as ethylene-vinyl acetate resin, polyolefin resin, chlorinated olefin resin, ethylene-acrylic resin, petroleum resin, and cellulose derivative resin are preferably used.

(Colorant in the decoration layer)
The colorant in the decorative layer is preferably a pigment, and any of inorganic pigments and organic pigments can be used. It is also possible to use a metallic gloss ink containing a metal fine particle obtained from a paste of metal cutting particles or a deposited metal film as a pigment. As these metals, aluminum, gold, silver, brass, titanium, chromium, nickel, nickel chrome, stainless steel and the like are preferably used. These metal strips may be surface-treated with a cellulose derivative such as an epoxy resin, polyurethane, acrylic resin, or nitrocellulose in order to improve dispersibility, oxidation prevention, and ink layer strength.

(Method for forming decorative layer)
As a method for forming the decoration layer, offset printing, screen printing, ink jet printing, thermal transfer printing, and the like can be used in addition to gravure printing. It is preferable that the dry film thickness of a decoration layer is 0.5-15 micrometers, More preferably, it is 1-7 micrometers.
Unless detrimental to design and spreadability, antifoaming agent, anti-settling agent, pigment dispersant, fluidity modifier, anti-blocking agent, antistatic agent, antioxidant, light stabilizer, UV absorber Various conventional additives such as these 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 activator during hydraulic transfer. Therefore, the curable resin layer must improve the penetrability of the activator and the curable resin layer dissolution swellability 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. In order to balance such contradictory requirements, The thermoplastic resin layer preferably contains a thermoplastic resin.
Since the activator of the present invention has sufficient penetrability and curable resin layer dissolution swellability, it can quickly penetrate into the curable resin layer to facilitate dissolution and swelling of the curable resin layer. In addition, by including a thermoplastic resin, the curable resin layer can be activated more gently, which further causes uneven dissolution of the curable resin layer and cracks in the decorative layer due to rapid activation. Can be suppressed.
That is, the curable resin layer containing a thermoplastic resin has an appropriate resistance to the penetrability of the activator and the curable resin layer dissolution swell, and has a firm self-holding power before curing, By applying the activator of the present invention, 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.

The peelable film (A) on which a decorative layer is coated or printed and the support film (B) on which a curable resin layer is laminated may be bonded together by dry lamination (dry lamination method). it can. 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 transfer layer and the peelable film and select a preferable combination of the peelable film and the transfer layer.
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.

  What is necessary is just to measure the peeling force of the peelable film in the interface of these peelable films and the transfer layer to be used, and to select a preferable combination of the peelable film and the transfer layer. Further, if necessary, it is possible to further reduce the peeling force by further surface-treating the peelable film.

(Method for producing hydraulic transfer film)
Next, a method for producing the hydraulic transfer film of the present invention will be described.
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 film (A) provided, and the film (B) provided with a hydrophobic decorative layer that can be dissolved in an organic solvent composed of a printing ink film or paint film on the peelable film, are curable resin for the film (A). It is preferable that the layer and the decorative layer of the film (B) are overlapped and bonded together by dry lamination (dry lamination method).

  When the transfer layer does not have a decorative layer and the transfer layer is composed of a curable resin layer, the film (A) having a curable resin layer on the support and the peelable film are converted into a curable film (A). The resin layer and the peelable film are stacked so as to face each other and are bonded together by dry lamination (dry lamination method).

  The production of the hydraulic transfer film of the present invention is preferably carried out using a dry laminator. That is, a film in which a support is attached to one feeding roll (first feeding roll) of a dry laminator, and a decorative layer having a pattern is printed on a peelable film in advance on the other feeding roll (second feeding roll). Wear (B). An organic solvent solution of the curable resin is applied to the surface of the water-soluble or water-swellable resin layer of the support film fed from the first feed roll, and further dried by a drier to be curable resin on the support film. A film (A) in which a layer is formed is obtained. Next, the curable resin layer of this 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 bonded together by a thermocompression-bonding roll and wound up on a winding roll. As a result, the hydraulic transfer film of the present invention is produced.

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

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

On the other hand, when the decoration layer is formed on the release film in advance in (b), it can be dealt with by ordinary printing, and the above problem does not occur. For this reason, the method of laminating | stacking by the dry lamination of the film (A) in which the film (B) which has a decoration layer on the peelable film of (b), and the curable resin layer was formed on the support body film is preferable.

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

  The obtained film for hydraulic transfer of the present invention is wound around a roll and covered with light-shielding paper, and if stored in a dark place such as a warehouse, the curing reaction does not proceed unnecessarily, and the film is blocked during storage. It does not occur, it can be fed out from the roll at the time of water pressure transfer, it can transfer the water of a clear decorative layer, and has sufficient market distribution unless it is actively exposed to ultraviolet rays and sunlight. It is.

(Method for manufacturing molded products)
Next, a method for producing a molded product using the hydraulic transfer film of the present invention having a cured resin layer or a decorative layer and a cured resin layer as a transfer layer will be described.
The method for producing a hydraulic transfer body of the present invention is such that the hydraulic transfer film of the present invention is floated on water with the transfer layer facing up and the support facing down after peeling the peelable film, and curable with an organic solvent. Activate the resin layer or the transfer layer composed of the decorative layer and the curable resin layer (activation may be performed before floating in water), transfer the transfer layer to the transfer target, remove the support, In this method, 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 curable resin layer and the decorative 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 and a decorative layer is obtained.

  The transfer layer having the curable resin layer and the decorative layer needs to be activated by an activator sprayed before being hydraulically transferred and sufficiently solubilized or softened. Activation imparts flexibility to the transfer layer, and the followability and adhesion of the transfer layer to the three-dimensional curved surface of the transfer target can be obtained.

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

(activation)
The activator for hydraulic transfer of the present invention has the following leveling properties, penetrability, curable resin layer dissolution swellability, which is dissolution swellability to the transfer layer (curable resin layer and decoration layer), and decoration layer dissolution: Has swelling properties.

The leveling property referred to in the present invention refers to a property of expanding 10 mm or more, preferably 15 mm or more after 30 seconds when 10 μL of activator is dropped on the transfer layer of the hydraulic transfer film.
The penetrability referred to in the present invention refers to a characteristic that the volume reduction rate of the droplet is 5% to 30% 15 seconds after 10 μL of the activator is dropped on the transfer layer of the hydraulic transfer film.
This value can be calculated by subtracting the volume shrinkage due to evaporation from the volume reduction rate of the droplet using a contact angle measuring device or the like.

The curable resin layer dissolution swellability referred to in the present invention means that the portion where the dripping spreads dissolves or swells 30 seconds after 10 μL of the activator is dropped on the curable resin layer having no hydraulic transfer film decoration layer. , 80% by mass or more of the characteristics that can be easily removed.
This value can be calculated by pressing the filter paper against the curable resin layer with a force of 10 N for 10 seconds after dropping the activator, removing the filter paper, and measuring the weight loss of the curable resin layer. it can.

Examples of the organic solvent satisfying the swellability of the curable resin layer according to the present invention vary depending on the composition of the curable resin layer. For example, toluene, xylene, ethyl acetate, butyl acetate, isobutyl acetate, 3-methyl-3-methoxy Examples include butyl acetate, ethyl cellosolve, butyl cellosolve, diacetone alcohol, methyl ethyl ketone, and methyl isobutyl ketone.

The decorative layer dissolution swellability referred to in the present invention means that the portion where the dripping spreads dissolves or swells 30 seconds after 10 μL of the activator is dropped on the decorative layer of the hydraulic transfer film, and 80% by mass or more easily. A characteristic that can be removed.

This value can be calculated by pressing the filter paper against the decorative layer for 5 seconds with a force of 1 N 30 seconds after dropping the activator, and then removing the filter paper and measuring the removed area of the decorative layer.
The organic solvent satisfying the decoration layer dissolution swellability referred to in the present invention varies depending on the composition of the decoration layer. For example, ethyl acetate, butyl acetate, 3-methyl-3-methoxybutyl acetate, diacetone alcohol, methyl ethyl ketone, methyl isobutyl Examples include ketones.

By mixing an organic solvent having each of the above characteristics required for the activator, an activator that satisfies the above characteristics can be obtained.
In particular,
1) The organic solvent satisfying the leveling property referred to in the present invention varies depending on the transfer layer of the hydraulic transfer film. For example, toluene, xylene, isobutyl acetate, isobutanol, 2-propanol, ethyl cellosolve, butyl cellosolve, Cyclohexane can be mentioned as an organic solvent having these characteristics.
2) Examples of the organic solvent having permeability according to the present invention include toluene, xylene, isobutanol, 2-propanol, and isobutyl acetate, although the permeability varies depending on the transfer layer of the hydraulic transfer film.
3) As an organic solvent satisfying the swellability of the curable resin layer referred to in the present invention, for example, toluene, xylene, ethyl acetate, butyl acetate, isobutyl acetate, 3-methyl-3, although it varies depending on the composition of the curable resin layer. -Methoxybutyl acetate, ethyl cellosolve, butyl cellosolve, diacetone alcohol, methyl ethyl ketone, methyl isobutyl ketone and the like.
4) The organic solvent satisfying the decoration layer dissolution swellability referred to in the present invention varies depending on the composition of the decoration layer. For example, ethyl acetate, butyl acetate, 3-methyl-3-methoxybutyl acetate, diacetone alcohol, methyl ethyl ketone, And methyl isobutyl ketone.

  Organic solvent having leveling properties, organic solvent having permeability, curable resin layer having swelling or solubility of transfer layer (curable resin layer and decoration layer), organic solvent having dissolution swelling property and decoration layer dissolving swelling The organic solvents having the properties may be different from each other, and one kind of organic solvent may be responsible for a plurality of performances.

  In the case of the hydraulic transfer film having the transfer layer of the present invention, the activator first lands on the decorative layer and then penetrates to activate the curable resin layer. For this reason, if the activator has low permeability to the curable resin layer and the decoration layer has high solubility, the pattern of the decoration layer tends to collapse, and conversely, the activator penetrates the curable resin layer. If the solubility of the decorative layer is low and the curable resin layer is activated, the handle tends to break. Therefore, the activator balances the penetrability into the curable resin layer and the solubility of the decorative layer, so that the activation of the curable resin layer and the activation of the decorative layer proceed simultaneously, and the water pressure with excellent appearance is achieved. It becomes possible to obtain a transcript.

Accordingly, as an activator suitable for a hydraulic transfer film in which the transfer layer of the present invention has a curable resin layer and a decorative layer,
1) Leveling property when landing on a decorative layer to lead uniform activation,
2) Permeability from the decorative layer to the curable resin layer,
3) solubility of the curable resin layer,
4) Solubility of the decorative layer,
Is required, and the balance between these is important. Furthermore, it is preferable that the hydraulic transfer film has a drying resistance for maintaining flexibility to follow the curved surface well.

  The activator of the present invention preferably has a leveling property that expands to a diameter of 13 mm or more 30 seconds after 10 μL of the activator is dropped on the transfer layer of the hydraulic transfer film. In the case of a plurality of organic solvents, it is preferable to contain 30% by mass or more of a component having leveling properties that expands to a diameter of 15 mm or more.

  It is preferable that 10 μL of activator is dropped on the transfer layer of the hydraulic transfer film, and the volume reduction rate of the droplets due to penetration after 15 seconds is 8% to 23%. When composed of a plurality of organic solvents, 10 μL is dropped on the transfer layer of the hydraulic transfer film, and a penetrating component having a volume reduction rate of 30% or more due to penetration after 15 seconds is 20% by mass or more. It is preferable to contain. Furthermore, in order to control to a desired permeability, it is preferable to contain 10% by mass or more of an osmotic component in which the volume reduction rate of the droplets by osmosis after 15 seconds is 10% or less.

10 μL of activator is dropped on the transfer layer of the hydraulic transfer film, and after 30 seconds, the decorative layer becomes soft but does not dissolve, but the components that swell or dissolve the curable resin layer, such as toluene, xylene, ethyl It is preferable to contain 50% by mass or more of cellosolve, butyl cellosolve, and the like.

10 μL of activator is dropped on the transfer layer of the hydraulic transfer film, and an organic solvent having a solubility that disturbs the pattern or layer structure of the printing ink film or paint film of the decoration layer after 30 seconds, that is, the decoration layer It is preferable to contain 45% by mass or less of an organic solvent having dissolution swellability.

  Furthermore, it is preferable that the activator is appropriately present on the hydraulic transfer film within the time until the transfer is completed. As the activator permeates and dries due to volatilization, the surface of the hydraulic transfer film becomes hard and wrinkles are likely to occur. As the drying further progresses and the surface tackiness decreases, the adhesion to the substrate to be transferred tends to decrease. Therefore, it is necessary to maintain the wet state with the organic solvent during the transfer process. For this purpose, an organic solvent component having penetrability in which 10 μL is dropped onto the transfer layer of the hydraulic transfer film and the volume reduction rate of the droplets by penetration after 15 seconds is 10% or less, and It is preferable to contain 10% by mass or more of an organic solvent having a vapor pressure at 25 ° C. of 1.6 kPa or less.

Various additives such as an antifoaming agent, a fluidity modifier, an antistatic agent, an antioxidant, a light stabilizer, and an ultraviolet absorber may be added to the activator as long as the activation performance is not impaired.
Furthermore, in order to improve the adhesiveness of printing ink or a coating material and a molded article in this activator, you may include some resin components. For example, adhesion may be increased by including 1 to 10% of an ink binder having a similar structure such as polyurethane, acrylic resin, or epoxy resin.

  Examples of the application method of the activator include a method of applying or spraying. Specifically, there is no limitation as long as the activator can be applied to the film, and a roll coater, a die coater, a curtain coater, a spray nozzle, an inkjet nozzle, or the like can be used.

In activating the hydraulic rolling film, there is also a method of improving the permeability by spraying the activator so that pressure is applied to the hydraulic transfer film,
If the landing pressure of the activator is too strong, physical damage such as undulation of the film due to undulation of the water surface is likely to occur, and the activator permeates excessively and the appearance of the hydraulic transfer body is impaired.

  The pressure applied to the film is the pressure calculated from the load when the activator is applied to or sprayed on a 2 cm deep, 23.5 cm square container filled with the activator on the electronic balance. (Hereinafter referred to as landing pressure) is preferably less than 2 Pa, more preferably 1 Pa or less.

In the present invention, the hydraulic transfer film can be activated even by spray landing of a mild activator of less than 2 Pa by increasing the permeability and dissolution swellability of the activator to the hydraulic transfer film.

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

(Primer layer)
It is preferable that the curable resin layer and the decoration layer are sufficiently adhered to the surface of the transferred body, and a primer layer is provided on the surface of the transferred body as necessary. As the resin forming the primer layer, a conventional resin can be used as the primer layer without particular limitation, and examples thereof include a urethane resin, an epoxy resin, and an acrylic resin. In addition, primer treatment is not required for a transfer medium comprising a resin component having high solvent absorbability such as ABS resin or SBS rubber having good adhesion. The material of the transferred material may be any of metal, plastic, wood, pulp mold, glass, etc., as long as it has a waterproof property so that its shape does not collapse even if it is submerged in water by applying a waterproof process. There is no particular limitation.

(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. The measurement method and determination method used are described below.

(Landing pressure)
Measures the landing pressure as the pressure calculated from the load when the activator is applied or sprayed on a container filled with activator in a 2 cm depth, 23.5 cm long and horizontal container placed on an electronic balance. did.

(Leveling)
Spreading is measured 30 seconds after 10 μL of activator or organic solvent is dropped on the transfer layer of the hydraulic transfer film.
A measured value having a diameter of 10 mm or more was regarded as having leveling properties.

(Penetration)
15 seconds after 10 μL of the activator or organic solvent was dropped on the transfer layer of the hydraulic transfer film, the volume reduction rate of the droplets was measured with a contact angle measuring device.
The characteristic that the measured volume reduction rate was 5% to 30% was determined to have penetrability suitable for activation.

(Curable resin layer dissolution swelling)
A hydraulic transfer film having no decorative layer was prepared, and 10 μL of activator or organic solvent was dropped on the curable resin layer, and 30 seconds after the activator or organic solvent spread, the filter paper was applied at a pressure of 10 N. Press evenly and weigh the portion where a portion of the curable resin layer has been transferred to the filter paper and removed.
The case where the removed part was 80% by mass or more of the dropped part was regarded as having a curable resin layer dissolution swelling property.

(Decoration and swelling of decorative layer)
On the decorative layer of the hydraulic transfer film, 10 μL of activator or organic solvent was dropped, and 30 seconds after the activator or organic solvent spread, the filter paper was pressed evenly with a pressure of 1 N, and a part of the decorative layer was The portion transferred and removed to the filter paper side is weighed. However, since direct weighing has a large error, the area of the removed portion is calculated, and the weighing is performed indirectly by converting using the specific gravity of the ink film.
The case where the portion removed by the above treatment was 80% by mass or more of the dripping portion was regarded as having a decorative layer dissolution swelling property.

(Drying suppression)
When a hydraulic transfer film is floated on water, an activator or an organic solvent is sprayed on the decorative layer under the same conditions as the hydraulic transfer, and after 30 seconds, a 1/2 inch sphere is pressed to the depth of the radius. Those that were transferred without any problems and easily trimmed by removing the residue were regarded as having drying-inhibiting properties.

(Appearance evaluation)
(Wrinkle)
○: Wrinkles are not visually observed.
Δ: Wrinkles only at the periphery or small wrinkles that can be partially repaired are observed.
X: Wrinkles are observed as a whole.

(Decoration of decorative layer)
○: No disorder (blurring) of the pattern is visually observed.
Δ: Slightly disturbed pattern (blurring) is observed.
X: Both pattern distortion (blur) and cracks are observed.

(Method for measuring adhesion of hydraulic transfer body)
The ink adhesion of the hydraulic transfer body that was hydraulically transferred to a primer-treated galvanized steel sheet (flat plate: 100 mm x 100 mm x 0.5 mm) was 1 x 1 mm with a cutter on the transfer layer according to the cross-cut tape method (JIS K5400). After making 100 grids and applying an adhesive tape to the part, this adhesive tape was peeled off rapidly, the peeling state of the coating film was observed visually, and the ink adhesion was evaluated with a maximum of 10 points.

(Measurement method of scratch resistance of hydraulic transfer body)
The scratch resistance of the hydraulic transfer body was measured according to JIS K5401 “Pencil scratch tester for coating film”. The length of the core used was 3 mm, the angle with the coating surface was 45 degrees, the load was 1 kg, the scratching speed was 0.5 mm / min, the scratching length was 3 mm, and the pencil used was Mitsubishi Uni.

(Method for measuring surface gloss of hydraulic transfer body)
The 60-degree specular gloss (JIS K5400) of the hydraulic transfer member was measured.

(Method for measuring wear resistance of hydraulic transfer bodies)
A hydraulic transfer body, which has been hydraulically transferred to a primer-treated galvanized steel sheet (flat plate: 100 mm × 100 mm × 0.5 mm), is wiped dry with a rubbing tester (load 500 g) with a normal cotton canvas # 10 (20 mm × 20 mm) 1000 reciprocations (30 After reciprocation / min), it was visually observed, and a 60 degree gloss was measured with a gloss meter, and the gloss retention was calculated.

Production Example 1 Production of Curable Resin A1 60 parts of an average hexafunctional urethane acrylate (UA1) obtained by reacting 2 molar equivalents of pentaerythritol, 7 molar equivalents of hexamethylene diisocyanate and 6 molar equivalents of hydroxyethyl methacrylate at 60 ° C. The weight average molecular weight 890), Rohm and Haas acrylic resin paraloid A-11 (Tg 100 ° C., mass average molecular weight 125,000) 40 parts, and a mixed solvent of ethyl acetate and methyl ethyl ketone (mixing ratio 1/1) A 50% curable resin A1 was produced.
(Production Example 2) Production of Curable Resin Layer A2 100 parts of curable resin A1 shown in Production Example 1 with 5 parts of Silicia 350D (Tg 100 ° C., mass average molecular weight 125,000) manufactured by Fuji Silysia, and acetic acid 5 parts of ethyl was added and dispersed using an edged turbine blade for 2 hours to produce a curable resin A2.

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

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

(Production Example 4) Production of hydraulic transfer film C1 As a support film, the curable resin A1 of Production Example 1 is applied to the glossy surface of PVA (film thickness 30 μm, width 360 mm) manufactured by Aisero Chemical Co., Ltd. with a comma coater and the solid content film thickness 20 μm And then dried at 60 ° C. for 2 minutes to produce a film (A). The curable resin layer of this film (A) and the ink layer of the film (B) B1 having a decorative layer are laminated at 60 ° C., and the laminated film is wound up as it is and the film C1 for hydraulic transfer. Manufactured.

(Production Example 5) Manufacture of hydraulic transfer film C2 In the same manner as in Production Example 4, curable resin A2 is used, and curable resin layer of film (A) and film (B) B1 ink layer having a decorative layer Were laminated so as to face each other, to produce a hydraulic transfer film C2.

Table 1 summarizes the film specifications and production conditions of the hydraulic transfer films C1 and C2 obtained in Production Examples 4 to 5.

(Activator)
Table 2 shows the composition (mass%) of the activator used in Examples and Comparative Examples. The numerical values shown in parentheses in the table are a preferred range.

Tables 3 and 4 summarize the characteristics of D1 to D6 and the solvents used.
○ means having each characteristic, and x means not having each characteristic.

Ｄ６に関して装飾層膨潤溶解性が過剰であるとは、装飾層上に活性化剤を滴下した３０秒後には滴下部分の柄が崩れ、硬化樹脂層と混濁してしまうほどの溶解性を示す。

Excessive decoration layer swelling solubility with respect to D6 indicates solubility enough to cause the pattern of the dropping portion to collapse and become turbid with the cured resin layer 30 seconds after the activator was dropped onto the decoration layer.

表３において、浸透性の低い（体積減少率≦１０％）である有機溶剤としては、エチルセロソルブ、ブチルセロソルブ、３−メチル−３−メトキシブチルアセテート、ダイアセトンアルコールが挙げられる。

In Table 3, examples of the organic solvent having low permeability (volume reduction rate ≦ 10%) include ethyl cellosolve, butyl cellosolve, 3-methyl-3-methoxybutyl acetate, and diacetone alcohol.

(Example 1)
Water at 25 ° C. was put into a water tank, and the peelable film of the hydraulic transfer film C1 was peeled off. Then, the hydraulic transfer film C1 was floated on the water surface with the PVA side facing down. Using a one-fluid flat spray nozzle, the activator D1 is sprayed at 22 g / m ² at a discharge pressure of 0.4 MPa and a landing pressure of 0.6 Pa, and after 15 seconds, a 10 cm × 30 cm sized steel plate with a primer is curable resin Inserted into the water from the layer surface and hydraulically transferred. After PVA was washed away with water, it was dried at 90 ° C. for 30 minutes. As a result, a decorative hydraulic transfer body having a cured resin layer having a thickness of 20 μm was obtained.

(Example 2)
A decorative hydraulic transfer body having a cured resin layer with a thickness of 20 μm was obtained in the same manner as in Example 2 except that the activator D2 was used.

(Example 3)
A decorative hydraulic transfer body having a cured resin layer having a thickness of 20 μm was obtained in the same manner as in Example 2 except that the activator D3 was used.

Example 4
Matte decorative water pressure with a cured resin layer having a thickness of 20 μm in the same manner as in Example 2 except that C2 is used instead of the hydraulic transfer film C1 and the activator D4 is sprayed at 25 g / m ^2. A transcript was obtained.

  As shown in the present example, it can be seen that a decorative hydraulic transfer body having a protective layer (curable resin layer) having a film thickness comparable to that obtained by spray coating can be obtained. Table 5 shows the transfer conditions and the physical properties of the transfer.

(Comparative Example 1)
Except for the use of activating agent D5, hydraulic transfer was carried out in the same manner as in Example 1. As a result, a transfer body in which the ink was dissolved and the pattern collapsed was obtained.

(Comparative Example 2)
The pattern was not broken as a result of hydraulic transfer performed in the same manner as in Comparative Example 1 except that the activator D5 was sprayed at 18 g / m ² , but the hydraulic transfer was insufficient due to insufficient activation of the curable resin layer. A transfer body with a hard film and many defects due to wrinkles and air bites was obtained.

(Comparative Example 3)
As a result of performing hydraulic transfer in the same manner as in Example 1 except that the activating agent D6 was used, a transfer body in which the ink was dissolved, the pattern collapsed, and the cocoon skin of the curable resin layer was conspicuous was obtained.

(Comparative Example 4)
Except that the activator D6 was sprayed at 18 g / m ² , hydraulic transfer was carried out in the same manner as in Comparative Example 3, and as a result, fish-eye-like irregularities were observed in the curable resin layer. This is considered to be caused by uneven activation of the curable resin layer due to insufficient leveling component and penetrating component, and was not improved even when the transfer timing was delayed until 30 seconds later.
Comparative Examples 1 to 4 are summarized in Table 6.

  It can be applied to a hydraulic transfer method capable of imparting a decorative layer rich in design to a molded article having a complicated three-dimensional shape.

It is sectional drawing of the hydraulic transfer film used as the object of the manufacturing method of this invention. It is sectional drawing of the hydraulic transfer film used as the object of the manufacturing method of this invention, and is a figure explaining the case where a transfer layer consists of a curable resin layer (topcoat layer) and a decoration layer. It is sectional drawing of the hydraulic transfer film used as the object of the manufacturing method of this invention, and film (A) (film which laminated | stacked the peelable film (1), the support body, and the curable resin layer (topcoat layer) in this order) and It is a figure explaining the case where the hydraulic transfer film of this invention is manufactured by bonding together a film (B) (film which laminated | stacked the decoration layer on the peelable film (2)) by dry lamination.

Explanation of symbols

1 Hydraulic transfer film 2 Peelable film (1)
3 Peelable film (2)
4 Support 5 Transfer Layer 6 Topcoat Layer (Curable Resin Layer)
7 Decorative layer 10 Laminated film (A)
11 Laminated film (B)

Claims (14)

A support film made of a water-soluble or water-swellable resin, and a hydrophobic transfer layer that can be dissolved in an organic solvent provided on the support film. The transfer layer is a decorative layer, and is irradiated with active energy rays. And a hydraulic transfer film having a curable resin layer that can be cured by at least one kind of heating, floated on water with the transfer layer facing up, and pressed the transferred object against the transfer layer activated by an activator The film for hydraulic transfer is transferred to the transfer body, and the support film is removed from the hydraulic transfer film transferred to the transfer body, and then the active energy ray is irradiated to transfer the transferred curable resin layer. The activator used for producing a hydraulic transfer body to be cured, the activator comprising:
Leveling property that expands to a diameter of 10 mm or more 30 seconds after dropping 10 μL of the activator on the transfer layer of the hydraulic transfer film,
Penetration that the volume reduction rate of the droplets is 5% to 30% 15 seconds after dropping 10 μL of the activator on the transfer layer of the hydraulic transfer film,
Dissolve or swell the dripping part 30 seconds after dropping 10 μL of the activator on the curable resin layer from which the decorative layer is removed from the hydraulic transfer film, and 80% by mass or more can be easily removed. Swelling and
On the decorative layer of the hydraulic transfer film, 10 μL of the activator is dropped 30 seconds after the dropping part is dissolved or swelled, and the decorative layer has a decorative layer dissolving swelling property that can be easily removed by 80% by mass or more. An activator for hydraulic transfer characterized by the above. 2. The activator for hydraulic transfer according to claim 1, wherein the activator for hydraulic transfer is used for producing a hydraulic transfer body having a pressure for landing the activator on the transfer layer of less than 2 Pa. The activator for hydraulic transfer according to claim 1 or 2, wherein the curable resin layer is an activator for a hydraulic transfer film having a film thickness of 5 to 30 µm. The activator for hydraulic transfer according to any one of claims 1 to 3, comprising an organic solvent having a leveling property that expands to a diameter of 15 mm or more after 30 seconds of dropping 10 μL onto the transfer layer of the hydraulic transfer film. . The activator for hydraulic transfer according to claim 3, comprising 30% by mass or more of an organic solvent having a leveling property that expands to a diameter of 15 mm or more 30 seconds after 10 µL is dropped on the transfer layer of the hydraulic transfer film. The organic solvent which has the permeability | transmittance whose volume reduction rate of the droplet by the penetration | infiltration 15 seconds after dripping 10 microliters on the transfer layer of the said hydraulic transfer film is 5%-30% is contained. The activator for hydraulic transfer according to claim 1. The organic solvent having a penetrability containing 20% by mass or more of a penetrating organic solvent having a volume reduction rate of 30% or more due to permeation after 15 seconds when 10 μL is dropped on the transfer layer of the hydraulic transfer film. The activator for hydraulic transfer according to any one of claims. The organic solvent having 10% by mass or more of a penetrating organic solvent having a volume reduction rate of 10% or less due to permeation after 15 seconds when 10 μL is dropped on the transfer layer of the hydraulic transfer film. The activator for hydraulic transfer according to any one of claims. The activator for hydraulic transfer according to any one of claims 1 to 3, wherein the activator for hydraulic transfer does not have the decorative layer dissolution swellability but contains an organic solvent having the curable resin layer dissolution swellability. The activator for hydraulic transfer according to any one of claims 1 to 3, comprising 50% by mass or more of the organic solvent having the curable resin layer dissolution swellability. The activator for hydraulic transfer according to any one of claims 1 to 3, comprising 45% by mass or less of the organic solvent having the decoration layer dissolution swellability. The activator for hydraulic transfer according to any one of claims 1 to 3, comprising 10% by mass or more of an organic solvent having a vapor pressure at 25 ° C of 1.6 kPa or less. A support film made of a water-soluble or water-swellable resin, and a hydrophobic transfer layer that can be dissolved in an organic solvent provided on the support film. The transfer layer is a decorative layer, and is irradiated with active energy rays. And a hydraulic transfer film having a curable resin layer that can be cured by at least one kind of heating, floated on water with the transfer layer facing up, and pressed the transferred object against the transfer layer activated by an activator The film for hydraulic transfer is transferred to the transfer body, and the support film is removed from the hydraulic transfer film transferred to the transfer body, and then the active energy ray is irradiated to transfer the transferred curable resin layer. A method for producing a hydraulic transfer body to be cured, wherein the activator according to any one of claims 1 to 3 is used. The method for producing a hydraulic transfer body according to claim 13, wherein the state when the activator lands on the transfer layer is in the form of droplets.

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