JP2006123392A - Method for manufacturing hydraulic transfer film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydraulic transfer film with a transfer layer which can hardly be affected by temperature and humidity in a hydraulic transfer film manufacturing process and can produce a precise decorative layer or a curable resin layer of excellent surface properties in a hydraulic transfer object. <P>SOLUTION: This method is to manufacture the hydraulic transfer film with a transfer layer which can produce the curable resin layer which can be cured by the irradiation of an activating energy ray and at least one kind of heating, and activated by an organic solvent, and/or can produce a decorative layer which is formed of a printing ink film or a coating material film and dissoluble in an organic solvent, laminated on a support film composed of a water-soluble or a water-swelling resin. (1) The support film composed of a water-soluble or a water-swelling resin is thermally treated, and (2) the transfer layer is formed on the support film. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

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

  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. Recently, a conventional hydraulic transfer method has been developed that does not have a complicated process, such as spraying a curable resin as a protective layer after the decorative layer is hydraulically transferred. A hydraulic transfer film obtained by laminating a transfer layer having a surface on a support film has been developed (for example, see Patent Document 1).

In these hydraulic transfer methods, a hydraulic transfer film is generally floated on water with the support film down, the transfer layer is activated with an organic solvent, the transfer layer is transferred to the transfer target, and the support film is removed. Thereafter, when the transfer layer has a curable resin layer as a surface protective layer, the layer is cured by heat or ultraviolet rays to obtain a hydraulic transfer body.
At this time, since the support film needs to be finally removed with water, a water-soluble or water-swellable resin is usually used.

However, a water-soluble or water-swellable resin tends to sag and shrink under the influence of temperature and humidity. For example, when a decorative layer is provided in a state where the support film itself is slack, the decorative layer lacks precision. In addition, if the film thickness of the support film is partially changed due to sagging or shrinkage, the film thickness of the obtained hydraulic transfer film, in particular, the film thickness of the curable resin layer serving as the surface protective layer is not uniform. The physical properties of the obtained hydraulic transfer product may be affected. For this reason, in the manufacturing process of a hydraulic transfer film, temperature and humidity management was indispensable.
Japanese Unexamined Patent Publication No. 64-22378

  The problem to be solved by the present invention is a transfer that is less susceptible to temperature and humidity in the hydraulic transfer film manufacturing process, and can form a precise decorative layer on a hydraulic transfer body or a cured resin layer with excellent surface properties. It is to provide a hydraulic transfer film having a layer.

  As a result of intensive studies, the present inventors have preliminarily heat-treated a support film for a hydraulic transfer film made of a water-soluble or water-swellable resin, so that “sagging” due to moisture absorption of the support film or the support film itself The above-mentioned problem was solved by removing the “sag”.

That is, the present invention provides a curable resin layer that can be cured with at least one of active energy ray irradiation and heating and can be activated with an organic solvent on a support film made of a water-soluble or water-swellable resin, and / or A method for producing a hydraulic transfer film comprising a transfer layer having a decorative layer that is soluble in an organic solvent comprising a printing ink film or a paint film,
1) After the heat treatment step of heat-treating a support film made of a water-soluble or water-swellable resin,
2) A method for producing a hydraulic transfer film, comprising the step of providing the curable resin layer and / or the decorative layer on the support film.

  According to the present invention, it is possible to produce a hydraulic transfer film in which moisture absorption of the support film and the undulation of the film itself are alleviated, a precise decorative layer is provided, or the film thickness of the curable resin layer is uniform. As a result, the smoothness of the support film can be maintained, and a curable resin layer having a uniform thickness can be obtained. Therefore, the stability of activation in the hydraulic transfer process is improved, and a hydraulic transfer film having excellent adhesion to the transfer target can be obtained.

(Support)
The support film used in the present invention contains a water-soluble or water-swellable resin as a main component.
Examples of the resin include polyvinyl alcohol (PVA), polyvinyl pyrrolidone, acetyl cellulose, polyacrylamide, acetyl butyl cellulose, gelatin, glue, sodium alginate, hydroxyethyl cellulose, carboxymethyl cellulose and the like. Among them, PVA generally used as a hydraulic transfer film is particularly preferable because it is easily dissolved in water, easily available, and has good compatibility with the 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.

(Method for heating support film)
The method for heating the support film in advance may be a known method, and for example, it can be heated using a hot air dryer, a heat roll, a drying furnace or the like. When the support film is a sheet, a hot air dryer or the like is preferable. For example, the support film is applied to a heat-resistant sheet whose surface is subjected to a satin finish to prevent adhesion of the support film. Can be attached and heated in a hot air dryer.
If it is wound in a roll, use a device with a drying furnace, such as a printing machine or a coating machine, and heat it by airing the film without printing or coating anything. Can do. Moreover, it can also heat by making it contact a heat roll. In this case, after the heat treatment, it is possible to immediately enter the process of providing a transfer layer on the next support film, and there is less concern about moisture re-absorption due to the passage of time, producing a hydraulic transfer film. This is more preferable.

  Although the heating temperature depends on the material of the support film, it is preferable that the upper limit of the heating temperature is in a range not exceeding the glass transition point (Tg) of the resin of the support film material plus 50 ° C. Thereby, the “sag” of the support film itself can be alleviated. Moreover, in order to remove the unnecessary water | moisture content which a support body film contains, it is preferable that a minimum is 35 degreeC or more. For example, in a PVA film having a Tg of 75 ° C., the heating is preferably performed in a temperature range of 35 to 125 ° C., more preferably in a temperature range of 40 to 100 ° C., and further in a temperature range of 40 to 70 ° C. Preferably it is performed. If the heating temperature is too high, the film may easily shrink or wrinkle. There is no particular limitation on the heating time, but if it is heated too long, it may cause changes in film properties, etc., so it should be kept within 10 minutes. Usually, the effect of the present invention can be sufficiently obtained by heating for about 2 seconds to 5 minutes. For example, for a PVA film having a Tg of 75 ° C., heating at 60 ° C. for about 3 to 60 seconds is preferable.

On the support film preheated by the above method, it comprises a curable resin layer that can be cured by at least one of active energy ray irradiation and heating and that can be activated by an organic solvent, and / or a printing ink film or a paint film. A transfer layer having a decorative layer that is soluble in an organic solvent is provided to obtain a hydraulic transfer film. As this specific method, for example,
(A) A method of applying or printing a curable resin layer or a decoration layer on a support film (b) A curable resin layer is applied or printed on a support film, and then on the curable resin layer (C) A method of 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 Is mentioned.

When the transfer layer has a decorative layer, the method (b) applies or prints the decorative layer on the curable resin layer provided on the support film, so that the wettability of the surface of the curable resin layer, etc. Appropriateness for painting or printing 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, the method (c) forms a decorative layer on the peelable film, and therefore can be handled by ordinary printing, and the above-described problems do not occur. Therefore, when it has a decoration layer, it laminates | stacks by the dry lamination of the film (A) in which the film (B) which has a decoration layer on the peelable film of (c), and the curable resin layer was formed on the support film. The method is more preferred.

  As an example of the specific method of (c), a support film that has been heat-treated in advance is attached to one feeding roll (first feeding roll) of a dry laminator, and the other feeding roll (second feeding roll). A film (B) in which a decorative layer of a pattern is printed on a peelable film in advance is mounted on the roll). 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 up on a winding roll. By doing so, a hydraulic transfer film can be suitably produced.

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

(Applying or printing method to peelable film)
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).
In the step of bonding the film (A) having a curable resin layer provided on a support film and the film (B) having a decorative layer provided on a peelable film, generally a support film including a PVA film is used. When the film is pasted at a temperature exceeding 130 ° C., the film tends to shrink or the wrinkle of the laminate easily enters. It is preferable to carry out in a temperature range of 120 ° C, and more preferably in a temperature range of 40 to 100 ° C.
Since the hydraulic transfer film obtained by the production method of the present invention can be provided with a curable resin layer in a state where the smoothness of the support film is increased, the film thickness uniformity is improved. Furthermore, it is preferable to use the obtained hydraulic transfer film because the stability of activation in the hydraulic transfer process is improved based on the uniformity of the film thickness, and the physical properties of the final hydraulic transfer product are also stabilized.

(Transfer layer (curable resin layer, decorative layer))
The transfer layer has a curable resin layer that can be cured by at least one of active energy ray irradiation and heating and can be activated by an organic solvent. In many cases, it has the said curable resin layer and the decoration layer which can be melt | dissolved in the organic solvent which consists of a printing ink membrane | film | coat or a coating film. These layers may be a composite layer in which a plurality of layers are overlapped.

(Curable resin layer)
The curable resin layer curable by at least one of active energy ray irradiation and heating is preferably transparent because the design of the decorative layer of the resulting hydraulic transfer body can be expressed well. Due to the design. Basically, it is sufficient that the color and pattern of the decorative layer of the hydraulic transfer body obtained can be seen through, and it is not necessary to be completely transparent. That is, from transparent to translucent ones are included. Moreover, it may be colored.
Specific examples of the curable resin layer include the following configurations (1) to (6).
(1) A curable resin layer containing an active energy ray-curable resin.
(2) A curable resin layer containing an active energy ray-curable resin and a thermoplastic resin.
(3) A curable resin layer containing a thermosetting resin.
(4) A curable resin layer containing a thermosetting resin and a thermoplastic resin.
(5) A curable resin layer containing an active energy ray curable resin and a thermosetting resin.
(6) A curable resin layer containing an active energy ray curable resin, a thermosetting resin, and a thermoplastic resin.

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

Next, the specific configurations (1) to (6) of the curable resin layer will be described.
(1) Curable resin layer containing active energy ray-curable resin The active energy ray-curable resin is an oligomer and a polymer having a polymerizable group or a structural unit curable by active energy rays in one molecule. The active energy rays referred to here are ultraviolet rays and electron rays, and both oligomers and polymers that are cured by these can be used, but ultraviolet curable resins are particularly suitable.

  As the ultraviolet ray source, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like is used.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The curable resin layer containing the fine particles can resist the swelling of the resin due to the fine particles becoming resistant to the swelling of the resin, and the swelling of the adjacent decorative layer due to the restrained swelling state thereof. Therefore, it is preferable that the fine particles do not dissolve or swell in an organic solvent for activation, a resin used for the curable resin layer, or the like.
Further, since the fine particles impart thixotropic properties to the activated curable resin layer, if the curable resin layer contains the fine particles, the transferred material can be transferred to the obtained hydraulic transfer film at a low speed. When pressing, resistance is generated against the shearing stress applied to the hydraulic transfer film. Accordingly, it is possible to suppress a decrease in design of the transfer layer in the transfer process, and it is easy to follow and adhere to a three-dimensional curved surface.

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

  Examples of the organic fine particles include organic coloring pigments, organic crystals, and polymer fine particles. Examples of organic coloring pigments include general-purpose pigments such as azo pigments, phthalocyanine pigments, selenium pigments, and quinacridone pigments. Depending on the particle size and amount of addition, the organic color pigment has a concealing effect on the base layer (transfer base material) in the case where the decorative layer in the transfer layer or the decorative layer is not provided, depending on the particle size and addition amount. What is necessary is just to control a particle size and addition amount.

Examples of the organic crystal include crystalline polyurea, crystalline polyurethane, crystalline polyamide, crystalline amino acid, crystalline polypeptide, crystalline organometallic complex, and the like.
Examples of the polymer particles include crosslinked acrylic particles, crosslinked polystyrene resin particles, crosslinked urethane particles, phenol resin particles, silicone resin particles, polyethylene particles, fluorine particles, melamine particles, polycarbonate particles, and phenol particles. .

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

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

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

  In particular, among the fine particles, lime carbonate powder, precipitated calcium carbonate, gypsum, clay (China Clay), silica powder, diatomaceous earth, talc, kaolin, alumina white, barium sulfate, aluminum stearate, magnesium carbonate, barite powder, Organic extender pigments such as abrasive powders, crosslinked acrylic particles, crosslinked polystyrene resin particles, crosslinked urethane particles, phenol resin particles, silicone resin particles, polyethylene particles, fluorine particles, melamine particles, polycarbonate particles and phenol particles These are used as matting agents, and by using these, it is possible to obtain a hydraulic transfer body that is excellent in surface properties and has a matte tone that gives a high-class design feeling. Among them, silica powder is preferable because a high matting effect can be obtained with a small amount of addition.

  The matting agent may have a spherical shape or an indefinite shape, but preferably has a spherical shape or a shape close thereto. Further, the size of the fine powder is preferably 0.05 to 30 μm from the viewpoint of dispersibility in paint, matteness of efficiency, and surface smoothness. Of course, the range of the optimum particle diameter varies depending on the film thickness, but for example, in the case of a film thickness of about 20 μm, it is preferably 0.5 to 10 μm.

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

  The refractive index of the fine particles when used as a matting agent can scatter light more efficiently, so it is preferable that the difference from the refractive index of the coating resin is large, but the hydraulic transfer film according to the present invention is used. Since the matte property can be efficiently exhibited by the hydraulic transfer, it is not necessary to provide any particular limitation. Rather, fine particles having a small difference in refractive index can be used so as to make full use of the pattern and color of the base.

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

  The above-described curable resin layer has a greater surface protection effect of the obtained hydraulic transfer body as the dry film thickness is thicker, and has a greater effect of absorbing irregularities of the decorative layer, so that the molded product has an excellent gloss. This is preferable. Therefore, in order to satisfy the function as the protective layer and the effect of absorbing the irregularities of the decorative layer, the dry film thickness of the curable resin layer is preferably 3 to 200 μm, and the uncured curable resin layer is stored. From the viewpoint of stability, it is preferably 100 μm or less. However, if the dry film thickness is too thick, activation (solubilization) of the curable resin layer by the organic solvent tends to be insufficient. Therefore, in order to sufficiently activate the curable resin layer with an organic solvent and to satisfy the function as a protective layer and the designability, the thickness is preferably 5 to 30 μm.

(Decoration layer)
The printing ink or paint used for forming the decorative layer used in the present invention is preferably activated with an organic solvent so that sufficient flexibility can be obtained when transferring the transfer layer to the transfer target. It is preferable to form with gravure printing ink from a viewpoint that it is easy to obtain. A colored layer having no pattern can also be formed by coating.

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

  The polyurethane resin used for the base resin has a number average molecular weight (measured by GPC using a polystyrene calibration curve) of 2,000 to 60,000, more preferably 2,500 to 56,000, and even more preferably 2. , 500 or more and 40,000 or less is preferable because it has 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 adhesiveness and fluidity of the printing ink or paint are increased. , Pigment dispersibility and transferability are reduced. In addition, the glass transition temperature of the polyurethane resin is preferably −5 ° C. or more and 70 ° C. or less because it has solubility in an organic solvent and appropriate adhesion to a transfer target.

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

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

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

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

  Examples of the colorant include carbon black as a black pigment; yellow lead, yellow lead, anthraquinone yellow, mineral fast yellow, titanium yellow; red pigments such as Bengala, cadmium red, quinacridone red, permanent red 4R, risol red, and pyrazolone. Red, Watching Red Calcium Salt, Lake Red D, Brilliant Carmine 6B, Eosin Lake; Blue Pigment, Bitumen, Cobalt Blue, Alkaline Blue Lake, Victoria Blue Lake, Phthalocyanine Blue, Metal-free Phthalocyanine Blue; Green Pigment, Chrome Green , Chromium oxide, pigment green B, malachite green lake; titanium white or the like can be used as a white pigment.

  The resin used for the decorative layer, that is, the printing ink or paint, may contain a plasticizer, a surfactant, an antioxidant, an ultraviolet absorber, a matting agent, a solvent, or the like, if necessary.

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

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

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

(Peelable film)
As the peelable film used in the present invention, for example, a film made of a material such as polypropylene, polyethylene, polyester, nylon, or polyvinyl chloride can be used, and the thickness is preferably 20 μm to 250 μm.
In the present invention, at the time of hydraulic transfer, the curable resin layer and the decorative layer laminated on the peelable film must be easily peelable from the peelable film. Accordingly, the peelable film used for the hydraulic transfer film is preferably a film having a weak peel force at the transfer layer interface, which is an interface with the curable resin layer or the decorative layer. On the other hand, when a peelable film with a decorative layer coated or printed thereon and a support film provided with a curable resin layer are bonded together by dry lamination (dry lamination method), film feeding, etc. It is necessary for the decorative layer to be fixed on the peelable film with such a peeling force that the decorative layer does not peel off during the above work and handling. Therefore, the peelable film may control the peeling force by surface treatment as necessary.

(Method for manufacturing molded products)
Next, a method for producing a hydraulic transfer body using the hydraulic transfer film obtained in the present invention will be described.
The method for producing a hydraulic transfer body of the present invention is such that the hydraulic transfer film obtained by the present invention is floated on water with the support facing down after peeling the peelable film, and cured with an organic solvent and the curable resin layer or decorative layer. A method of activating a transfer layer made of a photosensitive resin layer, transferring the transfer layer to a transfer target, removing the support, and then curing the curable resin layer of the transfer layer by at least one of active energy ray irradiation and heating. is there.
After the peelable film is peeled from the hydraulic transfer film of the present invention, the hydraulic transfer can be performed by the same method as the hydraulic transfer of the conventional hydraulic transfer film. Specifically, it is as shown below.
(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 or the curable resin layer and the decoration 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 pressing the transfer material against the transfer layer, the transfer material and the hydraulic transfer film are submerged in water, and the transfer layer is brought into close contact with the transfer material 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 curable resin layer or the curable resin layer and the decoration 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 the transfer layer is transferred with flexibility. It means to improve the followability and adhesion of the layer to the transferred body of the three-dimensional curved surface. 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 brings the curable resin layer of the hydraulic transfer film or the curable resin layer and the decorative layer into close contact with the three-dimensional curved surface of the transfer object when transferring the transfer layer. The body film swells or dissolves. Specifically, water such as tap water, distilled water, and ion exchange water may be used. Depending on the support film used, 10% of an inorganic salt such as boric acid may be added to the water. The alcohols may be dissolved below 50% or less.

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

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.
In the present invention, since the curable resin layer is uncured at the transfer stage, it is easy to activate the curable resin layer of the hydraulic transfer film, and further, at least one of active energy ray irradiation and heating after the transfer. It is cured by the above and exhibits sufficient surface protection performance and gloss.

  Primer treatment is not necessary when the transfer target is made of a resin component with high solvent absorption such as ABS resin or SBS rubber with good adhesion, but there is sufficient curable resin layer or decoration layer on the surface of the transfer target. In order to make it adhere, a primer layer can be provided on the surface of the transferred material 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. The material of the transferred material may be any of metal, plastic, wood, pulp mold, glass, etc., as long as it is waterproof 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 by way of examples. Unless otherwise specified, “part” and “%” are based on mass. The measurement method and determination method used are described below.

(Method for measuring adhesion of hydraulic transfer body)
The ink adhesion of the hydraulic transfer body that was hydraulically transferred to an ABS resin plate (flat plate: A4 size, thickness 3 mm) was evaluated based on a cross-cut tape method (JIS K5400) 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.

(Production Example 1) Production of active energy ray-curable resin A1 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 60 parts (mass average molecular weight 890), 40 parts by Rohm and Haas acrylic resin Paraloid A-11 (Tg 100 ° C., mass average molecular weight 125,000), 3 parts photopolymerization initiator Irgacure 184, ethyl acetate, A mixed solvent of methyl ethyl ketone (mixing ratio 1/1) was mixed to produce an active energy ray-curable resin A1 having a solid content of 42%.

(Production Example 2) Production of thermosetting resin 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 (mass (Average molecular weight 25,000) 81 parts,
19 parts of a mixture of hexamethylene diisocyanate phenol adduct and hexamethylene diisocyanate trimer phenol adduct (having an isocyanate value 1.1 times equivalent to the hydroxyl value of acrylic polyol (a)) and toluene A mixed solvent of ethyl acetate (1/1) was mixed to produce thermosetting resin A2 having a solid content of 35%.

(Production Example 3)
(Production of film B1 having a decorative layer)
Using a comma coater on a 50 μm thick unstretched polypropylene film (hereinafter abbreviated as “PP film”) manufactured by Toyobo Co., Ltd., the ink for the release layer and ink receiving layer is applied to a dry film thickness of 10 μm. A film was obtained. The film is cut into A3 size, a photographic image is inkjet-printed with pigment-based ink using Hewlett-Packard Design Jet 2000CP, and dried at 40 ° C. for 30 minutes to form a decorative layer, and decorative film B1 Got.

(Reception layer ink)
Polyurethane (Dainippon Ink Co., Ltd., Burnock EZL676): 23 parts by mass
Silica (manufactured by Fuji Silysia, Silicia 350D): 30 parts by mass
Pigment (cationic urethane fine particles): 12 parts by mass
Ethyl acetate / toluene (1/1): 30 parts by mass
Additive: 5 parts by mass

(Production Example 4)
(Production of film B2 having a decorative layer)
As the peelable film, a 50 μm thick unstretched polypropylene film (hereinafter abbreviated as “PP film”) manufactured by Toyobo Co., Ltd. was used, and urethane ink (trade name: Univia A) was applied to the film with a gravure 4-color printing machine. A decorative layer was formed by printing a 3 μm wood grain pattern to produce a decorative film B2.

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

(Example 1: Production of hydraulic transfer film C1)
After a 30 μm thick PVA film (Tg: 73 ° C.) made by Aicero Chemical Co., Ltd., which is a support film, is cut out to 300 mm × 400 mm and attached to a 2 mm thick, B4 size aluminum plate so that the end wraps around the back side Heat treatment was performed in a hot air dryer at 60 ° C. for 1 minute. Take out from the hot air dryer, and apply the active energy ray-curable resin composition A1 to the surface of the PVA. Using 542-AB, it was applied with a bar coater to a predetermined dry film thickness (20 μm), then dried at 60 ° C. for 2 minutes, and then the curable resin layer and the decorative layer of the decorative film B1 were faced to face each other. The hydraulic transfer film C1 was produced by laminating at 60 ° C. Since the coating was performed in a state where the waviness of the film was almost alleviated by the heat treatment, the fluctuation of the film thickness of the curable resin layer was within 1%. When the peelable film was peeled off from the hydraulic transfer film C1, the ink layer was transferred to the PVA film side without causing wrinkles, streaks, defects or the like that affected the hydraulic transfer on the PVA film and the decorative layer.

(Example 2: Production of hydraulic transfer film C2)
A PVA film roll (Tg: 73 ° C.) made by Aicero Chemical Co., Ltd., which is a support film, was attached to the film unwinding part of the comma coater, and was evacuated at a rate of staying in a drying furnace at 60 ° C. for 1 minute. Then, it was wound up on a paper tube. The PVA film roll was printed with a 3 μm thick grain pattern with a gravure four-color printing machine to produce a hydraulic transfer film C2. Since the coating was performed in a state where the waviness of the film was almost alleviated by the heat treatment, a hydraulic transfer film free from printing pattern loss and fading was obtained.

(Example 3: Production of hydraulic transfer film C3)
A PVA film roll (Tg: 73 ° C.) made by Aicero Chemical Co., Ltd., which is a support film, was attached to the film unwinding part of the comma coater, and was passed through at a rate of staying in a drying furnace at 60 ° C. for 1 minute. Then, it was wound up on a paper tube. The PVA film roll is again attached to the comma coater, and the active energy ray-curable resin composition A1 is applied so as to have a predetermined dry film thickness (20 μm), and then dried at 60 ° C. for 2 minutes. The layer and the decorative layer of the decorative film B2 were faced and laminated at 60 ° C., and aged at 40 ° C. for 18 hours to prepare a hydraulic transfer film C3. Since the coating was performed in a state where the waviness of the film was almost alleviated by the heat treatment, the fluctuation of the film thickness of the curable resin layer was within 1%. When the peelable film was peeled off from the hydraulic transfer film C3, the ink layer was transferred to the PVA film side without causing wrinkles, streaks, defects or the like that affected the hydraulic transfer on the PVA film and the decorative layer.

(Example 4: Production of hydraulic transfer film C4)
A PVA film (Tg: 73 ° C) made by Aicero Chemical Co., which is a support film, is attached to the film unwinding part of the rod gravure coater, installed between the unwinding part and the coating part, and heated to 60 ° C. The resulting heat roll is brought into contact with the heat roll for 6 seconds, and then the active energy ray-curable resin composition A1 is applied so as to have a predetermined dry film thickness (20 μm) at the coating portion, and then at 60 ° C. After drying for 2 minutes, the curable resin layer and the decorative layer of the decorative film B2 were faced and laminated at 60 ° C. and aged at 40 ° C. for 18 hours to prepare a hydraulic transfer film C4. Since the coating was performed in a state where the undulation of the film was almost alleviated by the heat treatment, the fluctuation of the film thickness of the curable resin layer was within 1%. When the peelable film was peeled off from the hydraulic transfer film C4, the ink layer was transferred to the PVA film side without causing wrinkles, streaks, defects or the like that would affect the hydraulic transfer on the PVA film and the decorative layer.

(Example 5: Production of hydraulic transfer film C5)
A hydraulic transfer film C5 having a decorative layer was produced in the same manner as in Example 4 except that the thermosetting resin A2 was used as the curable resin. Since the coating was performed in a state where the undulation of the film was almost alleviated by the heat treatment, the fluctuation of the film thickness of the curable resin layer was within 1%. When the peelable film was peeled from the hydraulic transfer film C5, the ink layer was transferred to the PVA film side without any defects.

(Comparative Example 1: Production of hydraulic transfer film C6)
A hydraulic transfer film C6 was produced in the same manner as in Example 3 except that the PVA film was heat-treated. The distance between the coater blade and the film was the same as in Example 2. When the peelable film was peeled off from the hydraulic transfer film C6, the ink layer was transferred to the PVA film side without generating wrinkles, streaks, defects or the like that affected the hydraulic transfer on the PVA film and the decorative layer. However, since the film was applied in a wavy state, a portion that was not sufficiently adhered to the roll of the coating portion was generated, and a portion having a considerably thin film thickness of the curable resin layer was generated.

(Application example 1) Water pressure transfer Water at 25 ° C was put into a water tank, and the release film of the water pressure transfer film C1 was peeled off. An activator (xylene: MIBK: butyl acetate: isopropanol, 5: 2: 2: 1) was sprayed at 25 g / m ^2, and an A4 size ABS plate was inserted into the water from the surface of the decorative layer to perform hydraulic transfer. After PVA was washed away with water, it was dried at 80 ° C. for 30 minutes, and UV irradiation was performed at an irradiation amount of 1200 mJ / cm ² to completely cure the curable resin layer. As a result, a decorative hydraulic transfer body provided with a cured resin layer having excellent surface gloss was obtained.

Application Example 2 Water Pressure Transfer Water at 25 ° C. was put in a water tank, and the water pressure transfer film C2 was floated on the water surface with the PVA side of the water pressure transfer film C2 facing down. An activator (xylene: MIBK: butyl acetate: 3-methoxybutyl acetate, 5: 2: 2: 1) was sprayed at 15 g / m ^2, and an A4 size ABS plate was inserted into the water from the surface of the decorative layer to perform hydraulic transfer. . After removing PVA by washing with water, the PVA was dried at 80 ° C. for 30 minutes to obtain a decorative hydraulic transfer body free from pattern removal or fading.

(Application Example 3) Water Pressure Transfer A water pressure transfer film C3 was used to perform water pressure transfer in the same manner as in Application Example 1 to obtain a decorative water pressure transfer body having a cured resin layer having excellent surface gloss.

(Application Example 4) Water Pressure Transfer A water pressure transfer film C4 was used to perform water pressure transfer in the same manner as in Application Example 1, thereby obtaining a decorative water pressure transfer body having a cured resin layer having excellent surface gloss.

(Application example 5) Water pressure transfer Water at 25 ° C was put in a water tank, and the release film of the water pressure transfer film C5 was peeled off, and then the water pressure transfer film C4 was floated on the water surface with the PVA side down. An activator (xylene: MIBK: butyl acetate: isopropanol, 5: 2: 2: 1) was sprayed at 25 g / m ^2, and an A4 size ABS plate was inserted into the water from the surface of the decorative layer to perform hydraulic transfer. After the PVA was washed away with water, it was heated at 120 ° C. for 60 minutes to dry the activator and cure the thermosetting resin layer. As a result, a decorative hydraulic transfer body provided with a cured resin layer having excellent surface gloss was obtained.

(Application Comparative Example 1) Water Pressure Transfer Water pressure transfer was performed in the same manner as in Application Example 1 using the water pressure transfer film C6. However, since the film thickness of the curable resin layer is not uniform, the uniformly sprayed activator becomes excessive especially in the thin film thickness part, and unevenness is generated on the surface of the curable resin layer. . Furthermore, the defect that the ink of a decoration layer also melt | dissolved or cracked in such a part generate | occur | produced.

  As shown in this example and application example, the thickness of the curable resin layer is obtained by applying heat treatment to the PVA film to reduce moisture absorption and undulation of the film itself. It can be seen that uniform precision coating can be performed. Further, it can be seen that a decorative hydraulic pressure transfer body having excellent gloss can be obtained from the obtained hydraulic transfer film. The transfer conditions and physical properties of the transcript are shown in the table.

Claims (6)

On a support film made of a water-soluble or water-swellable resin, a curable resin layer that can be cured by at least one of active energy ray irradiation and heating and can be activated by an organic solvent, and / or a printing ink film or A method for producing a hydraulic transfer film comprising a transfer layer having a decorative layer soluble in an organic solvent comprising a paint film,
1) After the heat treatment step of heat-treating a support film made of a water-soluble or water-swellable resin,
2) A method for producing a hydraulic transfer film, comprising a step of providing the curable resin layer and / or the decorative layer on the support film. The method for producing a hydraulic transfer film according to claim 1, wherein the transfer layer includes the curable resin layer and the decoration layer. A film (A) provided with a curable resin layer which can be cured by at least one of active energy ray irradiation and heating and can be activated with an organic solvent on a support film made of a water-soluble or water-swellable resin; A film (B) provided with a decorative layer soluble in an organic solvent comprising a printing ink film or a paint film on a peelable film, a curable resin layer of the film (A), and a decoration of the film (B) The method for producing a hydraulic transfer film according to claim 2, wherein the layers are laminated so as to face each other and bonded together by dry lamination,
1) After the heat treatment step of heat-treating a support film made of a water-soluble or water-swellable resin,
2) The method for producing a hydraulic transfer film according to claim 2, further comprising a step of providing the curable resin layer on the support film. The method for producing a hydraulic transfer film according to any one of claims 1 to 3, wherein the lower limit of the heating temperature to the support film is 35 ° C, and the upper limit is a plus 50 ° C of the glass transition temperature of the support film. . The manufacturing method of the hydraulic transfer film in any one of Claims 1-4 whose said support body film is a film which has polyvinyl alcohol as a main component, and the heating temperature to this film is 35 to 125 degreeC. The production of a hydraulic transfer film according to any one of claims 1 to 5, wherein the heat treatment step of the support film and the step of providing the curable resin layer and / or the decorative layer are continuously performed in-line. Method.