JP2013000895A - Film for water transfer printing, and method for manufacturing decorative molding using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film for water transfer printing which hardly causes film breaks after being subjected to emboss processing, has a superior transfer property, and gives a to-be-transferred object excellent brightness, and to provide a decorative molding manufactured by using the film.SOLUTION: The film for water transfer printing is provided which includes a water-soluble film, a transfer adjusting layer on the water-soluble film, and a metal thin-film layer on the transfer adjusting layer. A concavo-convex pattern is formed between the transfer adjusting layer and the metal thin-film layer. Heat of transition (ΔH) of the water-soluble film determined in conformity to JIS K 7122-1987 is 1 to 27 J/g. A manufacturing method for the film for water transfer printing and a manufacturing method for the decorative molding using the film are also provided.

Description

  The present invention relates to a hydraulic transfer film suitable for forming a transfer layer on the surface of a molded body having a three-dimensional surface or a curved surface due to unevenness, a method for producing the same, and a method for producing a decorative molded product using the same.

For automobile interior parts, home appliances, office automation equipment, and the like, molded products having decorations such as wood grain or metallic tone (metallic luster) on the surface are used. Many of these molded products have a complicated three-dimensional shape, and conventionally, a method of simply applying a highly designed decoration to a molded product having the complicated shape has been studied.
As such a decoration method, a water pressure transfer method using water pressure is known. In this hydraulic transfer method, a transfer film in which a desired decorative layer is printed on a water-soluble or water-swellable water-soluble film is prepared, and an activator composition made of an organic solvent is applied to the decorative layer of the transfer film. Then, the decorative layer is swollen and adhered (this is called activation). Before or after that, the transfer film is floated on the water surface with the decorative layer (printing layer) surface for transfer as the upper surface, and then the article to be transferred is pressed onto the transfer film by water pressure. After the transfer film is brought into intimate contact with the transfer surface of the transfer object to be decorated, the water-soluble film is removed and the decoration layer is transferred (see, for example, Patent Document 1).

The water pressure transfer method is an excellent curved surface decoration method in terms of “depth” such as a clear paint feeling, adaptability to a three-dimensional surface, and high-quality pattern expression. There was a problem when trying to give a more excellent luxury feeling with the addition of glitter such as “shine”. In other words, the embossed uneven pattern that can express various glitters needs to have a suitable layer thickness in order to incorporate the embossed uneven pattern into the transfer layer. It was considered an unsuitable method.
On the other hand, in Patent Document 2, in order to form a printed pattern layer that exhibits a pearly feeling, glass fiber is added in advance to a synthetic resin molded body that is a transfer target, and water pressure transfer is performed on the surface of the synthetic resin molded body. It has been proposed to transfer the printed pattern layer by the method. However, in this method, the material of the synthetic resin molded body is limited, and the production of the synthetic resin molded body is complicated.

In order to solve the above problems, Patent Document 3 attempts to improve the hydraulic transfer sheet, and comprises a nitrified cotton / alkyd transparent resin layer on a water-soluble film, and a deposited metal layer on the transparent resin layer, There has been proposed a hydraulic transfer sheet in which the transparent resin layer is embossed between a vapor-deposited metal layer and the transparent resin layer.
However, the deposited metal layer has excellent properties such as high glitter, but when the transparent resin layer of the hydraulic transfer sheet is swollen and tackified, it does not extend in the same manner as the transparent resin layer, so the transferability is low. .
Further, in the manufacturing process of the hydraulic transfer sheet, there is a problem that the transfer sheet breaks after embossing.

JP 54-33115 A JP-A-4-107182 JP 2001-328398 A

  Under such circumstances, the present invention is a hydraulic transfer film that hardly causes film breakage after embossing, has good transferability, and imparts excellent glitter to a transfer object, and decoration using the film It is an object to provide a molded product.

As a result of intensive research to solve the above problems, the present inventor solved the above problems by using a specific resin for the transfer adjustment layer and appropriately adjusting the physical properties of the water-soluble film after embossing. I found out that I could do it. The present invention has been completed based on such findings.
That is, the present invention
(1) A hydraulic transfer film having a water-soluble film, a transfer adjustment layer on the water-soluble film, and a metal thin film layer on the transfer adjustment layer, between the transfer adjustment layer and the metal thin film layer The transfer adjustment layer contains a polyvinylpyrrolidone resin, and the transition heat (ΔH) of the water-soluble film obtained in accordance with JIS K 7122-1987 is 1 to 27 J / g. Features hydraulic transfer film,
(2) It has a water-soluble film, a transfer adjustment layer on the water-soluble film, and a metal thin film layer on the transfer adjustment layer, and an uneven pattern is formed between the transfer adjustment layer and the metal thin film layer. A method for producing a hydraulic transfer film,
The step (A) of laminating the transfer adjustment layer containing polyvinylpyrrolidone resin on the water-soluble film, the step (B) of forming the metal thin film layer on the surface of the transfer adjustment layer, and the step (A). And after the step (B) or after the step (B), a step (C) of forming an uneven pattern by embossing, and obtained in accordance with JIS K 7122-1987. The method for producing a hydraulic transfer film, wherein the water-soluble film after embossing has a transition heat (ΔH) of 1 to 27 J / g, and (3) the following steps (a) to (c): A method for producing a decorative molded product,
Step (a): having a water-soluble film, a transfer adjustment layer on the water-soluble film, and a metal thin film layer on the transfer adjustment layer, and a concavo-convex pattern between the transfer adjustment layer and the metal thin film layer The water-soluble transfer film is characterized in that the water-soluble transfer film has a transition heat (ΔH) of 1 to 27 J / g determined according to JIS K 7122-1987. Before or after floating on the water surface facing the side, an activator application step (b) for applying the activator composition to the metal thin film layer: the transferred object on the hydraulic transfer film that has undergone the step (a) Step (c) of pressing and bringing the metal thin film layer into close contact with the transferred surface of the transferred body by water pressure: Defilming process for removing the water-soluble film and transfer adjustment layer that are in close contact with the transferred surface of the transferred body Is to provide.

  According to the present invention, it is possible to provide a hydraulic transfer film that hardly causes film breakage after embossing, has good transferability, and imparts excellent glitter to a transfer target, and a decorative molded product using the film. it can.

It is a schematic sectional drawing which shows an example of a structure of the hydraulic transfer film of this invention.

Hereinafter, the present invention will be described with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing an example of the configuration of the hydraulic transfer film of the present invention.
The hydraulic transfer film 1 of the present invention is a hydraulic transfer film having a water-soluble film 2, a transfer adjustment layer 3 on the water-soluble film 2, and a metal thin film layer 4 on the transfer adjustment layer 3. 3 has a concavo-convex pattern 5 between the metal thin film layer 4 and the transition heat (ΔH) of the water-soluble film 2 obtained in accordance with JIS K 7122-1987 is 1 to 27 J / g. To do.

[Water-soluble film]
The water-soluble film according to the present invention may be any water-soluble or water-swellable film, and can be appropriately selected from water-soluble films generally used as a conventional hydraulic transfer film.
Examples of the resin constituting the water-soluble film include polyvinyl alcohol resin, dextrin, gelatin, glue, casein, shellac, gum arabic, starch, protein, polyacrylic amide, sodium polyacrylate, polyvinyl methyl ether, methyl vinyl ether and anhydrous Various water-soluble polymers such as a copolymer with maleic acid, a copolymer of vinyl acetate and itaconic acid, polyvinylpyrrolidone, acetylcellulose, acetylbutylcellulose, carboxymethylcellulose, methylcellulose, hydroxyethylcellulose, sodium alginate and the like can be mentioned. These resins may be used alone or in combination of two or more. In addition, rubber components, such as mannan, xanthan gum, and guar gum, may be added to the water-soluble film.

Among the above water-soluble films, polyvinyl alcohol (PVA) resin films are particularly preferable from the viewpoints of production stability, solubility in water and economy. In addition, the polyvinyl alcohol-type resin film may contain additives, such as starch and rubber | gum, besides PVA.
When a polyvinyl alcohol-based resin film forms a printing layer for transfer on a water-soluble film by changing the polymerization degree of polyvinyl alcohol, the degree of saponification, and the blending amount of additives such as starch and rubber. Adjust the required mechanical strength, moisture resistance during handling, speed of softening by water absorption after floating on the water surface, time required for spreading or spreading in water, ease of deformation in the transfer process, etc. Can do.

A suitable water-soluble film comprising a polyvinyl alcohol-based resin film is the one described in JP-A-54-92406, for example, 80% by mass of PVA resin, 15% by mass of polymer water-soluble resin. %, 5% by mass starch, and about 3% equilibrium water content is preferred.
The polyvinyl alcohol-based resin film is water-soluble, but preferably remains as a film while being swollen and softened in the water before being dissolved in water. This is because, by performing the hydraulic transfer while the film is still alive, it is possible to prevent an excessive flow and deformation of the printing layer for transfer during the hydraulic transfer.

The transition heat (ΔH) of the water-soluble film 2 provided on the hydraulic transfer film 1 needs to be 1 to 27 J / g. Here, the transition heat (ΔH) is the transition heat (ΔH) determined in accordance with JIS K 7122-1987. More specifically, it is the transition heat (ΔH) obtained from a thermogram obtained by heating from 25 ° C. to 160 ° C. at a heating rate of 10 ° C./min by a differential scanning calorimeter (DSC).
If the transition heat (ΔH) of the water-soluble film 2 exceeds 27 J / g, film breakage may occur in the manufacturing process after embossing or the rod order state becomes unstable. From these viewpoints, the transition heat (ΔH) of the water-soluble film 2 is preferably 4 to 10 J / g.
As thickness of the water-soluble film 2, 10-100 micrometers is preferable. When it is 10 μm or more, the uniformity of the film is good and the production stability is high. On the other hand, when it is 100 μm or less, the solubility in water is moderate and the printability is excellent. From the above viewpoint, the thickness of the water-soluble film is more preferably in the range of 20 to 60 μm.

  The water-soluble film can be used by being laminated with a water-permeable base material such as paper, non-woven fabric, cloth, etc., but such a water-permeable base material and water-soluble or water are used. When laminating a water-soluble film having swellability, the substrate having water permeability is separated from the water-soluble or water-swellable film before the hydraulic transfer film floats on the water surface, It is preferable that the water-permeable substrate is separated from the water-soluble or water-swellable water-soluble film by the action of water after floating.

[Transfer adjustment layer]
The transfer adjustment layer 3 according to the present invention preferably contains a polyvinyl pyrrolidone resin, and any of a polyvinyl pyrrolidone resin alone and a resin composition containing a polyvinyl pyrrolidone resin is preferred.
The polyvinyl pyrrolidone resin is a polymer compound in which N-vinyl-2-pyrrolidone is polymerized, dissolves in water, and has good water swellability. By using this polyvinyl pyrrolidone resin, the transfer adjustment layer 3 swells at an appropriate speed during hydraulic transfer, so that the metal thin film layer 4 is less likely to crack non-uniformly (cracks), and uniform fine cracks (cracks: A width of about 1 to 120 μm). Thereby, since the uneven | corrugated pattern 5 formed between the transcription | transfer adjustment layer 3 and the metal thin film layer 4 is maintained favorably without breaking, transferability becomes favorable and the decorative molded product which is a to-be-transferred object is Excellent glitter can be achieved.
In addition, since the polyvinyl pyrrolidone resin has a water swelling speed that is not too fast, the hydraulic transfer film is floated on the water surface, and then transferred to the transfer target with an appropriate time for the activator application step (a). Can do.
In the resin composition containing the polyvinyl pyrrolidone resin, the water-soluble polymer may be added to the polyvinyl pyrrolidone resin as desired, or a rubber component such as mannan, xanthan gum, guar gum, or the like may be added. . By adding these, the water swelling speed can be adjusted to be optimal for the desired hydraulic transfer process.

  The thickness of the transfer adjustment layer 3 is preferably 0.5 to 20 μm. If it is this range, a fine crack (crack) will generate | occur | produce more uniformly in the metal thin film layer 4, ensuring the more suitable time of an activator application | coating process (a), and transferring to a to-be-transferred body more suitably. Can do. From these viewpoints, 1 to 6 μm is more preferable.

[Metal thin film layer]
As a material of the metal thin film layer 4 according to the present invention, for example, a metal such as aluminum, chromium, nickel, cobalt, copper, gold, silver, tin, zinc, brass, stainless steel, an alloy, a metal oxide, or the like is used. Can do. Examples of the metal oxide include aluminum oxide and silicon dioxide. Of these, aluminum is preferable from the viewpoint of uniformly generating cracks. The thickness of the metal thin film layer 4 is usually preferably 100 to 800 mm, and more preferably 200 to 600 mm. When the thickness of the metal thin film layer 4 is within the above range, a fine crack having a crack width of 1 to 120 μm can be uniformly generated.

[Picture printing layer]
In the present invention, a pattern printing layer (not shown) can be provided between the transfer adjustment layer 3 and the metal thin film layer 4 as desired. It is preferable to use the same resin as the transfer adjustment layer 3 as the binder resin of the pattern printing layer. As the colorant, those conventionally used are used.

[Uneven pattern]
The concavo-convex pattern 5 according to the present invention is not particularly limited as long as it corresponds to the glitter design expression. For example, line groove, wood grain conduit groove, wood grain annual ring pattern, sand grain pattern, stone pattern, metal crystal surface pattern, cloth pattern, satin pattern, leather pattern, matte surface pattern, hairline pattern, spin tone pattern, character , Symbols, geometric figures and the like. The depth of the concavo-convex pattern is preferably 3 to 50 μm from the viewpoint of being able to uniformly generate cracks (cracks) and obtaining a molded article with good design properties having high glitter. Moreover, from the same viewpoint, it is more preferably 10 to 40 μm, and further preferably 20 to 40 μm. Here, in the present invention, the depth of the concavo-convex pattern 5 is the depth of the concave portion of the concavo-convex pattern. Here, the depth of the concave portion is the maximum value of the depth from the straight line when the interface between the transfer adjustment layer and the metal thin film layer is regarded as a substantially straight line.

10-100 micrometers is preferable and, as for the periodic width (pitch) of the uneven | corrugated pattern 5, More preferably, it is 20-40 micrometers. When the period width (pitch) of the uneven pattern 5 is within the above range, a fine crack (crack) of 1 to 120 μm can be uniformly generated as the crack (crack) width. Here, in the present invention, the period width (pitch) of the concavo-convex pattern 5 is a separation distance between adjacent convex portions.
Moreover, 10-100 micrometers is preferable and, as for the width | variety of the uneven | corrugated pattern 5, More preferably, it is 20-40 micrometers. When the width of the concavo-convex pattern 5 is within the above range, a fine crack (crack) of 1 to 120 μm can be uniformly generated as a crack (crack) width. Here, in this invention, the width | variety of the uneven | corrugated pattern 5 is a width | variety of convex part itself.
Moreover, the uneven | corrugated pattern 5 can be provided suitably by embossing.

[Method for producing hydraulic transfer film]
The method for producing a hydraulic transfer film 1 of the present invention includes a water-soluble film 2, a transfer adjustment layer 3 on the water-soluble film 2, and a metal thin film layer 4 on the transfer adjustment layer 3. A method for manufacturing a hydraulic transfer film in which a concavo-convex pattern 5 is formed between a metal thin film layer 4 and a step (A) of laminating a transfer adjustment layer 3 on a water-soluble film 2, and a transfer adjustment layer 3 A step (B) of forming the metal thin film layer 4 on the surface, and after the step (A) and before the step (B), or after the step (B), embossing is performed to form an uneven pattern. And having a step (C), the transition heat (ΔH) of the water-soluble film after embossing determined according to JIS K 7122-1987 is 1 to 27 J / g. For the reasons described above, the heat of transition (ΔH) of the water-soluble film 2 after embossing is preferably 4 to 10 J / g.

In step (A), the transfer adjustment layer 3 is laminated on the water-soluble film 2 by laminating a known coating method or printing method, co-extrusion method with a water-soluble film, or resin film on the water-soluble film 2. Is done.
Known coating methods include gravure coating, reverse coating and the like, and known printing methods include gravure printing and the like.
In the step (B), the metal thin film layer 4 is a known metal vapor deposition method such as vacuum vapor deposition, sputtering, or ion plating, or a metal containing a metal powder of a metal species that forms the metal thin film layer 4 and a binder resin. It can be formed by applying a paste and drying. In the present invention, it is preferably formed by a metal vapor deposition method.
In the step (C), in the case after the step (A) and before the step (B), the embossing is performed on the surface of the transfer adjustment layer 3 or the surface of the picture printing layer provided as desired. Further, in the case after the step (B), it is applied to the surface of the metal thin film layer 4.
The embossing is usually performed by an embossing apparatus at a temperature of 80 to 125 ° C. and applying a pressure of 20 to 100 ton / m ² , preferably 20 to 60 ton / m ² , to form a desired uneven pattern 5. When embossing is performed at 100 ° C. or higher, it is easy to mold, and when it is performed at a temperature of 115 ° C. or lower, the transition heat (ΔH) of the water-soluble film can be easily within the range of 1 to 27 J / g. It is more preferable because a film break does not occur later.
From the viewpoint of ease of processing, embossing is preferably performed on the surface of the transfer adjustment layer 3 after the step (A) and before the step (B).
In addition, when providing a pattern printing layer depending on necessity, embossing is performed after providing a pattern printing layer.

[Method of manufacturing decorative molded product]
The method for producing a decorative molded product of the present invention is such that the hydraulic transfer film 1 of the present invention having the water-soluble film 2, the transfer adjusting layer 3, and the metal thin film layer 4 is so that the water-soluble film 2 side faces the water surface. A method of transferring the metal thin film layer 4 to a transfer medium, wherein the activator composition is applied to the metal thin film layer 4 before or after the hydraulic transfer film 1 is floated on the water surface. An agent coating step (a), a step of pressing the transferred body onto the hydraulic transfer film 1 that has undergone the step (a), and bringing the metal thin film layer 4 into close contact with the transferred surface of the transferred body (step (b) )), And a film removal step (c) for removing the water-soluble film 2 and the transfer adjustment layer 3 which are in close contact with the transfer surface of the transfer body.

<Activator application process (a)>
The activator application step (a) is a step of applying the activator composition to the metal thin film layer 4 before or after the hydraulic transfer film 1 is floated on the water surface. By applying the activator to the metal thin film layer 4 in this step, the surface of the metal thin film layer 4 is roughened, and it becomes easy to adhere to the transfer target. It floats on the water surface so that the water-soluble film 2 side of the hydraulic transfer film 1 faces the water surface side. In order to float the hydraulic transfer film 1 on the surface of the water, it is possible to float the printed matter one by one. Alternatively, the water is flowed in one direction, and a continuous belt-like hydraulic transfer film is continuously supplied on the surface of the water. And may be suspended.

(Activator composition)
The activator composition is not particularly limited as long as it is a composition that can roughen the metal thin film layer 4 for transfer in the hydraulic transfer film 1 and has a function of dissolving the surface of the transfer target described later, It is preferable that the metal thin film layer 4 does not evaporate until the metal thin film layer 4 is transferred to the transfer surface of the transfer target. As such an activator composition, the composition containing ester, acetylene glycol, ethers, and resin is mentioned preferably, for example.
Preferred examples of esters include ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, tert-butyl acetate, dibutyl oxalate, dibutyl phthalate, dimethyl phthalate, dioctyl phthalate, and diisooctyl phthalate. It is done.
Preferred examples of acetylene glycols include methoxybutyl acetate, ethoxybutyl acetate, ethyl carbitol acetate, propyl carbitol acetate, and butyl carbitol acetate.
Preferred examples of ethers include methyl cellosolve, butyl cellosolve, and isoamyl cellosolve.
In addition, as resins, thermoplastic resins such as acrylate monomers alone or copolymers, polyamide resins, polyester resins, phenol resins, melamine resins, urea resins, epoxy resins, alkyd phthalate resins, diallyl phthalates Preferred examples include thermosetting resins such as resins, alkyd resins, and polyurethane resins, and among these, thermosetting resins are preferred.
The content of each preferable composition of the activator composition used in the present invention is 5 to 40% by mass for esters, 40 to 80% by mass for acetylene glycols, 5 to 30% by mass for ethers, and 1 for resin. About 20% by mass.

The activator composition may be applied by spray coating or the like, and the application amount is usually 1 to 50 g / m ² , preferably 3 to 30 g / m ² , more preferably 10 to ²⁰ g / m ^{2. 2} .

<Step (b)>
The step (b) is a step of pressing the transferred body onto the hydraulic transfer film 1 that has undergone the step (a) and bringing the metal thin film layer 4 into close contact with the transferred surface of the transferred body by water pressure.
The water for applying the floating water pressure to the hydraulic transfer film 1 should be adjusted to an appropriate water temperature according to the type of the water-soluble film 2 of the hydraulic transfer film 1, and preferably about 25 to 50 ° C. Preferably it is 25-35 degreeC.
The transfer time between the hydraulic transfer film 1 of the present invention and the transfer target is preferably about 20 to 120 seconds, more preferably about 30 to 60 seconds. In order to widen the crack width, the application amount may be increased, the water temperature may be increased, and the transfer time may be increased. Here, the transfer time is the time from when the transfer film 1 of the present invention is suspended in water until the transfer to the transfer target is completed.

(Transfer material)
Examples of the transfer object used in the present invention include polystyrene resin, acrylonitrile-butadiene-styrene copolymer (ABS resin), polycarbonate resin, melamine resin, phenol resin, urea resin, fiber resin, polyethylene, and polypropylene. In addition to a resin or a resin obtained by mixing these, a structure made of a material such as a metal such as iron, aluminum, or copper, ceramics such as ceramics, glass, or wood, or wood can be used.
In addition, the shape of the transfer surface may be a two-dimensional shape that is a planar shape, or may be a three-dimensional shape such as an uneven shape or a curved shape. Of these, resin structures are usually used frequently. In the resin structure, a mold release agent adheres at the time of molding, and dust and fat may also adhere. In order to transfer the printing layer of the hydraulic transfer film with good adhesion, the resin structure is previously coated with a degreasing liquid. It is preferable to clean the transfer surface.

  In the step (b), the activator composition applied on the metal thin film layer 4 is in contact with the transferred body, and the surface of the transferred body is dissolved, so that the transfer film 1 of the present invention and the transferred body are adhered. The property is good.

<Film removal step (c)>
The film removal step (c) is a step of removing the water-soluble film 2 and the transfer adjustment layer 3 of the printed material that are in close contact with the transfer surface of the transfer target.
The removal of the water-soluble film 2 and the transfer adjusting layer 3 can be performed by, for example, shower cleaning using water. By this step (C), the water-soluble film 2 and the transfer adjustment layer 3 attached to the transfer surface are removed. The shower cleaning conditions vary depending on the material for forming the water-soluble film 2 and the transfer adjustment layer 3, but usually a water temperature of about 15 to 60 ° C. and a cleaning time of about 10 seconds to 5 minutes are preferable. Then, after the step (c), if the transferred body is sufficiently dried and moisture is evaporated, the resin molded product to which a desired design is given by the metal thin film layer 14 transferred to the transferred surface of the transferred body. Is obtained.

<Step (d)>
Step (d) is a step of forming a protective film on the metal thin film layer transferred as desired.
In step (d), the metal thin film layer transferred to the transfer surface of the transfer target in step (c) is coated as necessary for surface strength improvement, surface protection, surface gloss adjustment, and the like. And a protective film can be formed. The protective film is formed of a resin composition containing, for example, a thermoplastic resin, a thermosetting resin, an ultraviolet curable resin, specifically, a urethane resin, an epoxy resin, an acrylic resin, a fluororesin, a silicon resin, or the like. Are preferred.

  The protective film can be formed by coating and curing these resin compositions. As a coating method, known methods such as spray coating, electrostatic coating, brush coating, and dip coating can be used. In addition, the curing method may be appropriately selected depending on the resin composition to be used. If a thermoplastic resin is used, it may be cured for several days. If a thermosetting resin is used, heat treatment may be performed. In the case of using a functional resin, it may be performed by irradiating with an appropriate ultraviolet ray.

The decorative molded product thus obtained has excellent glitter since it has a fine crack (crack) of 1 to 120 μm as a crack (crack) width on the surface, that is, the metal thin film layer.
In order to uniformly generate a fine crack (crack) of 1 to 120 μm as a crack (crack) width at the time of transfer, it is most important that the depth of the concavo-convex pattern 5 is 3 to 50 μm. The adjustment of the crack (crack) width includes the depth of the uneven pattern 5, for example, the selection of the period width (pitch) and width of the uneven pattern 5, the selection of the resin forming the transfer adjustment layer 3, and the thickness thereof, This can be done by selecting the thickness of the metal thin film layer 4 or the like. For example, if the depth of the concavo-convex pattern 5 is made deeper, the crack width tends to be widened, and if it is desired to increase the crack width, the period width (pitch) and width of the concavo-convex pattern 5 may be increased. The thickness of the metal thin film layer 4 may be increased, and the thickness of the transfer adjustment layer 3 may be increased.

  The crack width is also adjusted by various conditions of the hydraulic transfer method, for example, the coating amount of the activator composition, the temperature of the water in which the hydraulic transfer film 1 is suspended, the transfer time between the film 1 and the transfer target. Can do.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
In addition, the performance evaluation shown below was performed about the hydraulic transfer film obtained in each case, and the decorative molded product using the same.
(1) Measurement of transition heat (ΔH) of water-soluble film Using a differential scanning calorimeter (DSC) (trade name “DSC 8230L2” manufactured by Rigaku Corporation) in accordance with JIS K 7122-1987 The temperature was obtained from a thermogram obtained by heating from 25 ° C. to 160 ° C. at a heating rate of 10 ° C./min at 4 mmg.
(2) Existence of film break after embossing A film (8 mm width) after embossing of a hydraulic transfer film is subjected to a tensile test at a chucking distance of 80 mm and a tensile speed of 50 m / min using a tensile tester (Tensilon). The presence or absence of film breakage at a breaking point load of 30 N was evaluated.

(3) Transferability 3 g / m ² of the activator composition having the following composition is applied to the surface of the metal thin film layer of the hydraulic transfer film, and the activator composition is made uniform with a smoothing roll. After passing through the activator application step (a) of 4, the film to be transferred is passed through the step (b) of pressing the transferred body against the hydraulic transfer film and bringing the metal thin film layer into close contact with the transferred surface of the transferred body by water pressure. The surface state of the decorative molded product obtained after (c) was visually observed and evaluated according to the following criteria.
(Composition of activator composition)
Phthalic acid-based alkyd resin 6 parts by weight Microsilica (pigment) 2 parts by weight Dibutyl phthalate 17 parts by weight Solvent (butyl carbitol acetate) 60 parts by weight Solvent (butyl cellosolve) 15 parts by weight (evaluation criteria)
○: The uneven pattern is uniformly transferred, and there is no distortion of the pattern.
Δ: Pattern distortion occurred in a part of the transferred concavo-convex pattern.
X: Most of the transferred concavo-convex pattern had pattern distortion. Alternatively, the metal thin film layer did not extend and could not be transferred.

Example 1
As a water-soluble film, a PVA film (thickness 30 μm) was used, and a polyvinyl pyrrolidone resin was gravure-coated at a coating amount of 3 g / m ² on one side to provide a transfer adjustment layer having a thickness of 2 μm. Next, using a embossing apparatus, embossing was performed from the surface side of the transfer adjustment layer at a pressure of 50 ton / m ² and a temperature of 110 ° C. to form a concavo-convex pattern having a depth of 20 to 40 μm. Next, an aluminum metal thin metal film layer having a thickness of 350 mm was formed on the concavo-convex pattern of the transfer adjustment layer by a vacuum deposition method. Table 1 shows the heat of transition of the water-soluble film before and after embossing. The film breakage after embossing of the hydraulic transfer film and the transferability of the obtained hydraulic transfer film were evaluated by the above methods. The results are shown in Table 1.

Example 2
A hydraulic transfer film was obtained in the same manner as in Example 1 except that the embossing step (C) was performed after the step (B) of forming the metal thin film layer. Table 1 shows the heat of transition of the water-soluble film before and after embossing. The film breakage after embossing of the hydraulic transfer film and the transferability of the obtained hydraulic transfer film were evaluated by the above methods. The results are shown in Table 1.

Comparative Example 1
A hydraulic transfer film was obtained in the same manner as in Example 1 except that the water-soluble film was changed to the water-soluble film B. Table 1 shows the heat of transition of the water-soluble film before and after embossing. The film breakage after embossing of the hydraulic transfer film and the transferability of the obtained hydraulic transfer film were evaluated by the above methods. The results are shown in Table 1.

Comparative Example 2
A hydraulic transfer film was obtained in the same manner as in Example 1 except that the water-soluble film was changed to the water-soluble film C. Table 1 shows the heat of transition of the water-soluble film before and after embossing. The film breakage after embossing of the hydraulic transfer film and the transferability of the obtained hydraulic transfer film were evaluated by the above methods. The results are shown in Table 1.

Comparative Example 3
A hydraulic transfer film was obtained in the same manner as in Example 1 except that the water-soluble film was changed to the water-soluble film D. Table 1 shows the heat of transition of the water-soluble film before and after embossing. The film breakage after embossing of the hydraulic transfer film and the transferability of the obtained hydraulic transfer film were evaluated by the above methods. The results are shown in Table 1.

Comparative Example 4
A hydraulic transfer film was obtained in the same manner as in Example 1 except that the heating temperature in embossing was changed to 130 ° C. Table 1 shows the heat of transition of the water-soluble film before and after embossing. The film breakage after embossing of the hydraulic transfer film and the transferability of the obtained hydraulic transfer film were evaluated by the above methods. The results are shown in Table 1.

[note]
Water-soluble film A: PVA film (Transition heat: 5.0 J / g, thickness 30 μm)
Water-soluble film B: PVA film (Transition heat: 22.9 J / g, thickness 40 μm)
Water-soluble film C: PVA film (Transition heat: 34.1 J / g, thickness 30 μm)

  The hydraulic transfer film of the present invention can provide a decorative molded product that does not cause film breakage during production, has high productivity, has good transferability, and has high glitter and excellent design. . The obtained decorative molded product can be suitably used as an automobile interior material, building material, furniture, a housing for an electric product, or the like.

DESCRIPTION OF SYMBOLS 1 Hydraulic transfer film 2 Water-soluble film 3 Transfer adjustment layer 4 Metal thin film layer 5 Uneven pattern

Claims (6)

  A hydraulic transfer film having a water-soluble film, a transfer adjustment layer on the water-soluble film, and a metal thin film layer on the transfer adjustment layer, and a concavo-convex pattern between the transfer adjustment layer and the metal thin film layer A water pressure transfer film, wherein the water-soluble film has a transition heat (ΔH) of 1 to 27 J / g determined in accordance with JIS K 7122-1987.   The hydraulic transfer film according to claim 1, wherein the transfer adjustment layer contains a polyvinylpyrrolidone resin. It has a water-soluble film, a transfer adjustment layer on the water-soluble film, and a metal thin film layer on the transfer adjustment layer, and an uneven pattern is formed between the transfer adjustment layer and the metal thin film layer. A method for producing a hydraulic transfer film, comprising:
Laminating the transfer adjustment layer on the water-soluble film (A);
A step (B) of forming the metal thin film layer on the surface of the transfer adjustment layer;
A step (C) of embossing to form a concavo-convex pattern after the step (A) and before the step (B) or after the step (B),
A method for producing a hydraulic transfer film, wherein the water-soluble film after embossing obtained according to JIS K 7122-1987 has a transition heat (ΔH) of 1 to 27 J / g.   The method for producing a hydraulic transfer film according to claim 3, wherein the transfer adjustment layer contains a polyvinylpyrrolidone resin. The manufacturing method of the decorative molded product which has the following process (a)-(c) in order.
Step (a): having a water-soluble film, a transfer adjustment layer on the water-soluble film, and a metal thin film layer on the transfer adjustment layer, and a concavo-convex pattern between the transfer adjustment layer and the metal thin film layer The water-soluble transfer film is characterized in that the water-soluble transfer film has a transition heat (ΔH) of 1 to 27 J / g determined according to JIS K 7122-1987. Before or after floating on the water surface facing the side, an activator application step (b) for applying the activator composition to the metal thin film layer: the transferred object on the hydraulic transfer film that has undergone the step (a) Step (c) of pressing and bringing the metal thin film layer into close contact with the transferred surface of the transferred body by water pressure: Defilming process for removing the water-soluble film and transfer adjustment layer that are in close contact with the transferred surface of the transferred body The manufacturing method of the decorative molded product of Claim 5 which has the following process (d) further after a process (c).
Step (d): forming a protective film on the metal thin film layer

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