JP2014069502A - Water pressure transfer film, decorative molding and method of producing decorative molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water pressure transfer film enabling production of a decorative molding expressing an industrial design having an irregular feeling by a water pressure transfer method and excellent in thermal transfer processing property, and to provide a method of producing a decorative molding using it.SOLUTION: A water pressure transfer film has a design layer on a water-soluble film, and the design layer has a low-glossiness layer formed at least partially. The resin composition composing the low-glossiness layer contains a binder resin and a delustering agent, and the oil absorption of the delustering agent, measured by JIS K 5101-13-1:2004, is 180 mL/100 g or greater. A method of producing a decorative molding using the water pressure transfer film is 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, a decorative molded product using the same, and a method for producing a decorative molded product.

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 close 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 Documents 1 and 2).
This 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. In addition, there is a need for a method that imparts a superior sense of quality.

JP-A 61-66685 JP 60-165300 A

  Under such circumstances, the present invention provides a hydraulic transfer film capable of imparting a design that expresses a texture, particularly a texture of wood, to a decorative molded product by a hydraulic transfer method, a decorative molded product using the same, and a decorative molded product. It is an object to provide a method for producing a decorative molded product.

As a result of intensive studies to solve the above problems, the inventors of the present invention are hydraulic transfer films having a design layer including a low gloss layer on a water-soluble film, and a matting agent specific to the low gloss layer It has been found that the above-mentioned problems can be solved by using. The present invention has been completed based on such findings.
That is, the present invention
[1] A hydraulic transfer film having a design layer on a water-soluble film, wherein the design layer has a low gloss layer provided at least partially, and the resin composition constituting the low gloss layer is a binder A hydraulic transfer film comprising a resin and a matting agent and having an oil absorption of 180 mL / 100 g or more measured according to JIS K 5101-13-1: 2004 of the matting agent;
[2] A decorative molded product obtained by transferring the design layer of the hydraulic transfer film according to [1] to a transfer target, and [3] the hydraulic transfer film according to [1], and the following steps: (A)-(d) are included, The manufacturing method of the decorative molded product characterized by the above-mentioned,
Step (a): A step of floating the hydraulic transfer film on the water surface so that the water-soluble film side faces the water surface.
Step (b): A step of applying the activator composition to the design layer side of the hydraulic transfer film.
Step (c): a step of pressing the transferred body onto the hydraulic transfer film that has undergone the steps (a) and (b), and bringing the design layer into close contact with the transferred surface of the transferred body by hydraulic pressure.
Step (d): a film removal step of removing the water-soluble film from the transfer surface of the transfer object,
Is to provide.

  According to the present invention, a hydraulic transfer film capable of imparting a design that expresses a texture, in particular, a texture of a grain, to a decorative molded product by a hydraulic transfer method, a decorative molded product using the same, and a decorative molded product. A manufacturing method can be provided.

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

Hereinafter, the hydraulic transfer film of the present invention will be described. 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 of the present invention has a design layer 2 on a water-soluble film 1, and the design layer has a low gloss layer 2a provided at least partially. Moreover, the design layer 2 may have the pattern layer 2b in addition to the low gloss layer 2a, and the design layer 2 should have the low gloss layer 2a and the pattern layer 2b in this order from the water-soluble film 1 side. Is preferred.
Usually, like the hydraulic transfer film 10 shown in FIG. 1, the low gloss layer 2a formed in a pattern and the low gloss layer 2a on the water-soluble film 1 are provided while covering the low gloss layer 2a. It is comprised by the pattern layer 2b formed so that the area | region which does not exist may be coat | covered. Thus, the structure in which the pattern layer 2b is formed is preferable in that excessive spreading of the entire hydraulic transfer film can be suppressed.

When the transfer object is decorated using the hydraulic transfer film 10 of FIG. 1, the low-gloss layer 2 a and the pattern layer 2 b existing on the end surface of the design layer 2 are exposed by removing the water-soluble film 1. Thus, the design of gloss mat (gloss difference) appears. Thereby, the portion of the low gloss layer 2a can be seen as a concave portion, and a design with a three-dimensional effect can be imparted to the decorative molded product.
However, since the top coat layer is usually provided on the exposed design layer 2 in order to impart stain resistance and scratch resistance, the above-described gloss mat design is impaired. In contrast, the hydraulic transfer film of the present invention can maintain a good gloss mat design even after the top coat layer is provided by improving the resin composition constituting the low gloss layer 2a. . In addition, due to the interaction between the top coat layer and the low gloss layer, a low gloss area visually recognized as a concave portion is formed immediately above the low gloss layer and in the vicinity thereof. It is formed

Moreover, in the hydraulic transfer film of this invention, as shown in FIG. 2, the design layer 2 may have the high gloss layer 2c other than the low gloss layer 2a, and the design layer 2 is the water-soluble film 1 side. To low gloss layer 2a and high gloss layer 2c in order. Furthermore, the design layer 2 may have the low gloss layer 2a, the high gloss layer 2c, and the pattern layer 2b in order from the water-soluble film 1 side. Thus, in the aspect provided with the high gloss layer 2c, the design given to the decorative molded product has a more three-dimensional effect due to the contrast of the gloss difference between the low gloss layer 2a and the high gloss layer 2c. preferable.
Usually, like the hydraulic transfer film 20 shown in FIG. 2, the low gloss layer 2a formed in a pattern and the low gloss layer 2a on the water-soluble film 1 are provided while covering the low gloss layer 2a. The high gloss layer 2c is formed so as to cover even a non-existing region, and the pattern layer 2b is formed on the high gloss layer. Thus, the structure in which the high gloss layer 2c was formed is preferable at the point which can suppress the excessive expansion | swelling of the whole hydraulic transfer film.

<Water-soluble film>
As the water-soluble film 1 in the present invention, any water-soluble or water-swellable film may be used, and it can be appropriately selected from water-soluble films generally used in conventional hydraulic transfer films.
Examples of the resin constituting the water-soluble film 1 include polyvinyl alcohol resin, dextrin, gelatin, glue, casein, shellac, gum arabic, starch, protein, polyacrylamide, sodium polyacrylate, polyvinyl methyl ether, and methyl vinyl ether. Examples thereof include various water-soluble polymers such as a copolymer with maleic anhydride, a copolymer of vinyl acetate and itaconic acid, polyvinyl pyrrolidone, acetyl cellulose, acetyl butyl cellulose, carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, and sodium alginate. 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 1.

Among the water-soluble films 1, a polyvinyl alcohol (PVA) resin film is particularly preferable from the viewpoints of production stability, solubility in water, and economic efficiency. 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 excessive transfer and deformation of the transfer layers during the hydraulic transfer.

  As thickness of the water-soluble film 1, 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 1 is more preferably in the range of 20 to 60 μm.

  In addition, although said water-soluble film 1 can also be laminated | stacked and used for the base material which has water permeability, such as paper, a nonwoven fabric, cloth, for example, such a water-permeable base material and water-soluble or When the water-swellable film having water swellability is laminated, the water-permeable substrate is separated from the water-soluble or water-swellable film before the hydraulic transfer film floats on the water surface, or the water surface It is preferable that the substrate having water permeability is separated from the water-soluble film having water solubility or water swellability by the action of water after floating on the substrate.

<Design layer>
As described above, the hydraulic transfer film of the present invention has the design layer 2 on the water-soluble film 1, and the low gloss layer 2a is present in the end surface of the design layer 2 on the water-soluble film side. Further, in the embodiment in which the design layer 2 has the low gloss layer 2a and the pattern layer 2b in this order from the water-soluble film 1 side as shown in FIG. 1, the low gloss layer is provided in the end surface of the design layer 2 on the water-soluble film side. 2a and the design layer 2b, and the design layer 2 has the low gloss layer 2a, the high gloss layer 2c, and the design layer 2b in this order from the water-soluble film 1 side as shown in FIG. The low gloss layer 2a and the high gloss layer 2c exist in the end surface of the water-soluble film side.

[Low gloss layer]
The low gloss layer 2a includes a binder resin and a matting agent described below.
(Binder resin)
Examples of the binder resin contained in the low gloss layer 2a include thermoplastic resins. Specific examples include acrylic resins, polyester resins such as alkyds, unsaturated polyester resins, urethane resins (for example, polyester urethane resins), polycarbonate resins. , Vinyl chloride-vinyl acetate copolymer, polyvinyl acetal (butyral resin) such as polyvinyl butyral, and nitrocellulose resin such as nitrified cotton. If necessary, one or more of these resins may be mixed in order to adjust the degree of expression of the low gloss region and the contrast of the gloss difference between the low gloss region and other regions, and the above is limited to the above. It is not a thing.

Moreover, in order to improve the physical properties of the binder resin, an ionizing radiation curable resin, a thermosetting resin, or a curing agent thereof (isocyanate or the like) is further added as necessary to the extent that the moldability is not impaired. Can do.
For example, if the low gloss layer 2a is intended to express a wood grain pattern by the pattern layer 2b described later, a pattern in which the conduit portion is visually depressed due to the gloss difference is obtained by synchronizing with the wood grain conduit portion. It is done.

(Matting agent)
Specific examples of matting agents include inorganic fillers selected from silica, clay, heavy calcium carbonate, light calcium carbonate, precipitated barium sulfate, calcium silicate, synthetic silicate, and fine silicate powder, acrylic An organic filler selected from a resin, a urethane resin, a nylon resin, a polypropylene resin, or a urea resin may be used, and any one of them may be used, or two or more may be used in combination. Of these, silica, which is a material having a high degree of freedom in material design such as oil absorption, particle size, pore volume, etc., and excellent in designability, whiteness, and coating stability as an ink, is preferable. Silica is preferred.

In the present invention, it is important that the oil absorption measured in accordance with JIS K 5101-13-1: 2004, a matting agent, is 180 mL / 100 g or more. When the oil absorption is 180 mL / 100 g or more, obstruction of the matting effect by the topcoat layer is eliminated, and interaction with the topcoat layer is caused to obtain the above low gloss region. From the above viewpoint, the oil absorption is preferably 230 mL / 100 g or more.
The upper limit of the oil absorption amount is not particularly limited as long as the effect of the present invention is achieved, but is 400 mL / 100 g or less from the viewpoint of maintaining appropriate thixotropy and not impairing coating suitability. Preferably there is. From the balance between the effect as the matting agent and the coating suitability, the oil absorption amount of the matting agent is more preferably 250 to 300 mL / 100 g.

Next, the volume average particle diameter of the matting agent is not particularly limited, but is preferably 1 to 8 μm, more preferably 4 to 8 μm. When the particle size is 1 μm or more, the effect as a matting agent is sufficiently obtained. On the other hand, when the average particle size is 8 μm or less, the stress at the time of processing diffuses due to an increase in the interfacial area, and voids and the like generated at the interface absorb energy, or the interparticle distance becomes small, Alternatively, plastic deformation occurs between the voids, and whitening during expansion can be suppressed. That is, good transfer processability can be ensured.
The volume average particle size referred to here is the particle size at an integrated value of 50% in the particle size distribution determined by the laser diffraction-scattering method.

  Further, the content of the matting agent in the resin composition constituting the low gloss layer 2a is preferably 0.5 to 80% by mass from the viewpoint of the balance between the gloss matte effect and the moldability, More preferably, it is 75 mass%, and it is further more preferable that it is 25-70 mass%.

  In addition, by surface-treating the matting agent, the adhesion between the binder resin and the matting agent can be improved, and a tough coating film can be formed when cured. Such a surface treatment is preferable because cracks and whitening during molding can be suppressed. The treatment method is not particularly limited as long as the above effects are obtained, and may be a surface treatment with an organic material or a surface treatment with an inorganic material. Particularly preferred is a silane coupling treatment.

  Moreover, a coloring agent can be added to the low gloss layer 2a as desired for the purpose of improving the design. There is no restriction | limiting in particular as a coloring agent, The coloring agent used for a hydraulic transfer method can be used. Specifically, those similar to those used in the pattern layer described later can be used.

  The thickness of the low gloss layer 2a is preferably 0.5 to 30 μm, more preferably 1 to 20 μm, and even more preferably 1 to 10 μm.

[High gloss layer]
In the present invention, the high gloss layer 2c can be provided on the low gloss layer 2a if desired. For the high gloss layer 2c, it is preferable to use a resin composition containing an acrylic polymer polyol or a cured product thereof from the viewpoint of enhancing the three-dimensional effect of the design by increasing the gloss difference with the low gloss layer 2a. The cured product may be completely cured, but is preferably in a semi-cured state in consideration of transfer processability and the like. Moreover, the thing with the resin composition containing an acrylic polymer polyol and the hardened | cured material of this resin composition is also a preferable aspect.
In addition to the acrylic polymer polyol, the resin composition forming the high gloss layer 2c may further contain an isocyanate. Isocyanate is a curing agent for acrylic polymer polyol, and by containing isocyanate, at least a part of the resin composition is brought into a cured state or a semi-cured state. Thereby, it is possible to suppress excessive spreading that is likely to occur due to dissolution or swelling of the hydraulic transfer film in the process of floating the hydraulic transfer film on the water surface during the production of the decorative molded product.

(Acrylic polymer polyol)
The acrylic polymer polyol preferably has a weight average molecular weight calculated by a gel permeation chromatography (GPC) method in terms of standard polystyrene of 1,000 to 100,000, preferably 5,000 to 80,000. More preferably, it is particularly preferably 20,000 to 50,000. When the molecular weight of the acrylic polymer polyol is 1,000 or more, the solvent resistance is improved, and when the pattern layer 2b is formed, problems such as dissolution of the high gloss layer 2c are less likely to occur, and it is 100,000 or less. When it is made into an ink, the viscosity is lowered or it becomes difficult to gel, so workability is improved.

  The acrylic polymer polyol preferably has a hydroxyl value of 30 to 130 mgKOH / g, more preferably 50 to 130 mgKOH / g, and still more preferably 60 to 120 mgKOH / g. When the hydroxyl value of the acrylic polymer polyol is 30 mgKOH / g or more, it is preferable in that excessive stretching of the entire hydraulic transfer film can be suppressed, and when it is 130 mgKOH / g or less, the flexibility of the high gloss layer 2c is high. It becomes good and does not cause defects such as cracks. The hydroxyl value can be measured by an acetylation method using acetic anhydride.

(Isocyanate)
The isocyanate may be a polyvalent isocyanate having two or more isocyanate groups in the molecule. For example, 2,4-tolylene diisocyanate (TDI), xylene diisocyanate (XDI), naphthalene diisocyanate, 4,4′- Aromatic isocyanates such as diphenylmethane diisocyanate or aliphatics such as 1,6-hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), methylene diisocyanate (MDI), hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate Polyisocyanates such as (alicyclic) isocyanates are used.

If necessary, a blocked isocyanate in which the isocyanate group is protected by an appropriate blocking agent to be inactivated and the isocyanate group is regenerated by heating may be used. As the blocking agent, for example, a known blocking agent such as active methylene such as phenol, alcohol, dimethyl malonate, ethyl acetoacetate, or oxime may be used.
By using a blocked isocyanate, it is possible to impart high moldability to the high gloss layer 2c, and heat-treat the molded product after molding into a desired shape, regenerate the isocyanate group, react with the polyol, and cure, Good adhesion to the low gloss layer 2a and the pattern layer 2b can be exhibited.

The resin composition constituting the high gloss layer 2c includes urethane resin, (meth) acrylic resin, (meth) acrylic / urethane copolymer resin, vinyl chloride-vinyl acetate copolymer, polyester resin, butyral resin, chlorine It is preferable to contain chlorinated polypropylene, chlorinated polyethylene or the like. This is because the high gloss layer 2c can be made flexible and transfer processability at the time of manufacturing a decorative molded product can be improved. Here, “(meth) acryl” means acryl or methacryl.
Of these, urethane resins are particularly preferred because of their high compatibility with acrylic polymer polyols.
Moreover, you may add a coloring agent to the said high gloss layer 2c in the range which does not inhibit the effect of this invention. As the colorant, the same colorants as those used in the pattern layer described later can be used.

(Urethane resin)
As the urethane resin, select a non-cross-linked type, that is, a resin having a linear molecular structure instead of a three-dimensionally cross-linked three-dimensional molecular structure. It is preferable. As such a non-crosslinked urethane resin, as a polyol component, a polyol such as polyester polyol, polyether polyol, polycarbonate polyol, polycaprolactone polyol, polyethylene glycol, polypropylene glycol, etc. is used as a main ingredient, and is non-crosslinked by reacting with isocyanate. Type urethane resins can be used, and those synthesized by a combination of a polyester polyol and an isocyanate such as hexamethylene diisocyanate are particularly preferred from the viewpoints of moldability, heat resistance, weather resistance, adhesion to the low gloss layer 2a, etc. . Usually, the number of hydroxyl groups in one molecule of polyol and the number of isocyanate groups in one molecule of isocyanate are two on average.
Moreover, as a urethane resin, the urethane urea resin synthesize | combined from the combination of a polyol component, a polyamine component, and isocyanate is used preferably, and what was mentioned above can be used as a polyol component and isocyanate.

  The urethane resin preferably has a glass transition point of 100 ° C. or lower, and more preferably 20 to 100 ° C. If the glass transition point of the urethane resin is 100 ° C. or lower, the high gloss layer 2c is excellent in flexibility at room temperature. If it is 20 ° C. or higher, the cohesive force is remarkably lowered by heating, or the high gloss layer 2c is hydraulically transferred. Sometimes it is preferred because it does not dissolve in water.

  The ratio of the total amount of isocyanate added to the acrylic polymer polyol or the acrylic polymer polyol as necessary in the resin composition constituting the high gloss layer 2c and the urethane resin is 99: 1 to 50:50 by mass ratio. It is preferably 90:10 to 60:40, more preferably 90:10 to 68:32. When the ratio of the urethane resin is high, the transfer processability is improved, but when the ratio is too high, the designability may be inferior. In particular, when the isocyanate content is high, it is preferable from the viewpoint of transfer processability to increase the ratio of the urethane resin.

  The high gloss layer 2c is formed by applying a coating solution obtained by dissolving the above-described acrylic polymer polyol, isocyanate, urethane resin, and other resins in a solvent by a known method, and drying and curing as necessary. be able to. About the thickness of the high gloss layer 2c, it is about 0.5-20 micrometers normally, Preferably, it is the range of 1-5 micrometers.

[Picture layer]
In the present invention, the pattern layer 2b can be provided on the low gloss layer 2a or the high gloss layer 2c as desired. The picture layer 2b usually contains a binder resin and a colorant. Examples of the binder resin for the picture layer 2b include the same binder resins used for the low gloss layer 2a.
Colorants include carbon black (black), iron black, titanium white, antimony white, yellow lead, titanium yellow, petal, cadmium red, ultramarine, cobalt blue and other inorganic pigments, quinacridone red, isoindolinone yellow, phthalocyanine Organic pigments or dyes such as blue, metal pigments made of scaly foil pieces such as aluminum and brass, pearlescent pigments made of scaly foil pieces such as titanium dioxide-coated mica and basic lead carbonate, and the like are used.

  About the thickness of a pattern layer, it is about 1-10 micrometers normally, Preferably it is about 2-5 micrometers.

<Method for producing hydraulic transfer film>
The hydraulic transfer film 10 of the present invention shown in FIG. 1 includes, for example, a step (A) of forming a low gloss layer 2a in a pattern on a water soluble film 1, a water soluble film 1 while coating the low gloss layer 2a. It can be manufactured by the step (B) in which the design layer 2 is formed by forming the pattern layer 2b so as to cover the region where the upper low gloss layer 2a is not provided.
In the step (A), the low gloss layer 2a can be formed into a pattern by a known printing method, for example, using a gravure plate material having a cell shape of a columnar recess and ink containing a binder resin and a matting agent. , Gravure printing, preferably gravure offset printing.
In the step (B), the pattern layer 2b can be formed by a known coating method or printing method, or can be formed by laminating a resin film on the low gloss layer 2a. Examples of the application method include gravure coating and reverse coating, and examples of the printing method include gravure printing. Further, the pattern layer 2b may be full-surface printing.
When the hydraulic transfer film 20 of the present invention shown in FIG. 2 is manufactured, the high gloss layer 2c is formed by a known coating method or printing method prior to forming the pattern layer 2b in the above step (B). That's fine.

<Manufacturing method of decorative molded product>
Using the hydraulic transfer films 10 and 20 of the present invention, a decorative molded product can be produced by the following steps (a) to (d).
Step (a): A step of floating the hydraulic transfer film 10 or 20 on the water surface so that the water-soluble film 1 side faces the water surface.
Step (b): A step of applying an activator composition to the design layer 2 side of the hydraulic transfer film 10 or 20.
Step (c): a step of pressing the transfer body onto the hydraulic transfer film 10 or 20 that has undergone the steps (a) and (b), and bringing the design layer 2 into close contact with the transfer surface of the transfer body by water pressure.
Step (d): a film removal step of removing the water-soluble film 1 from the transfer surface of the transfer object.
Moreover, you may provide the following process (e) following said process (d).
Step (e): A step of forming a topcoat layer on the transfer surface of the transfer object.

[Step (a)]
Step (a) can be performed before or after step (b). The hydraulic transfer films 10 and 20 are suspended on the water surface so that the water-soluble film 1 side faces the water surface side. In order to float the hydraulic transfer films 10 and 20 on the surface of the water, the printed sheets may be floated one by one, or water is allowed to flow in one direction, and the continuous belt-shaped hydraulic transfer film 10 or 20 is placed on the water surface. , May be continuously supplied and floated.

[Step (b)]
A process (b) can be performed before or after a process (a), and is a process of apply | coating an activator composition to the design layer 2 side. By applying the activator composition in this step, at least a part of the design layer 2 dissolves or swells and softens (activates), and becomes easy to adhere to the transfer target.

(Activator composition)
The activator composition is not particularly limited as long as it is a composition having a function of activating the design layer 2 or the pattern layer 2b and transferring the design layer 2 or the image layer 2b to the transfer surface of the transfer object. It is preferable that the layer does not evaporate until each layer is transferred. 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 preferred 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 resins. About 20% by mass.

Coating of the active agent composition may be performed by gravure printing, spray coating method, the coating amount is usually 1 to 50 g / m ^2, preferably from 3 to 30 g / m ^2, more preferably 10 to 20 g / m ² .

[Step (c)]
In the step (c), the transferred body is pressed onto the hydraulic transfer films 10 and 20 that have undergone the steps (a) and (b), and at least the design layer 2 is brought into close contact with the transferred surface of the transferred body by the hydraulic pressure. It is.
The water for applying the floating water pressure to the hydraulic transfer films 10 and 20 should be adjusted to an appropriate water temperature according to the type of the water-soluble film 1 of the hydraulic transfer films 10 and 20, and preferably 25 to 50. It is about 25 degreeC, More preferably, it is 25-35 degreeC.
Further, the transfer time between the hydraulic transfer films 10 and 20 of the present invention and the transfer target is preferably about 20 to 120 seconds, more preferably about 30 to 60 seconds.

(Transfer)
Examples of the material to be transferred include polystyrene resin, acrylonitrile-butadiene-styrene copolymer (ABS resin), polycarbonate resin, melamine resin, phenol resin, urea resin, fiber resin, polyethylene, polypropylene, and the like. In addition to the mixed resin, 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. This resin structure may have a release agent attached at the time of molding, and dust and fat may also adhere. In order to transfer each layer of the hydraulic transfer film with good adhesion, it is transferred in advance with a degreasing solution. It is preferable to clean the surface.

  In the step (c), the activator composition applied to the design layer 2 side is in contact with the transferred body, and the surface of the transferred body is dissolved, whereby the hydraulic transfer film 10 or 20 of the present invention and the transferred body The adhesion can be further improved.

[Film removal step (d)]
The film removal step (d) is performed after the step (c), and is a step of removing the water-soluble film 1 from the transfer surface of the transfer target.
Removal of the water-soluble film 1 adhering to the transfer surface of the transfer object can be performed, for example, by shower cleaning using water. In addition, although the conditions of shower washing differ with materials etc. which form the water-soluble film 1, a water temperature of about 15 to 60 ° C. and a washing time of about 10 seconds to 5 minutes are usually preferable. After the step (d), if the transfer body is sufficiently dried and moisture is evaporated, the gloss matte is caused by the difference in gloss between the low gloss layer 2a transferred to the transfer surface of the transfer body and other portions. A resin molded product to which the design is applied is obtained.

[Step (e)]
Step (e) is a step of forming a topcoat layer on the transfer surface of the transfer object.
In the step (e), the design layer transferred to the transfer surface of the transfer object in the step (d) is necessary for improving the surface strength, protecting the surface, adjusting the gloss of the surface, etc. Paint to form a transparent or translucent topcoat layer.
For example, a thermoplastic resin, a thermosetting resin, an ultraviolet curable resin, or the like is selected as a material for forming the topcoat layer. Specifically, a urethane resin, an epoxy resin, an acrylic resin, a fluorine resin, silicon System resin or the like is used. The top coat layer can be formed by a known coating method such as spray coating, electrostatic coating, brush coating, or dip coating, using a paint obtained by dissolving the above resin in a known organic solvent. Further, the thickness of the top coat layer is preferably 1 to 25 μm, more preferably 1 to 10 μm.

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 decorative molded product using the hydraulic transfer film obtained in each case.
(1) Designability (gross matte effect)
The design of the surface was visually evaluated. The evaluation criteria are as follows.
A: The conduit part was recognized as a concave part, close to the real eye, and extremely high in design.
B: The conduit part was recognized as a recessed part, and the design property was high.
C: Although slightly inferior in design, there is no practical problem.
D: The design was flat and extremely inferior in design.

(2) Transfer processability The surface state of the decorative molded product was visually observed and evaluated according to the following criteria.
(Evaluation criteria)
A: The extensibility was good and the followability to a complicated shape part was good.
B: The followability to a complex shape portion was insufficient, but the followability to other portions was good.
C: Slight cracks were observed when transferred, but there is no practical problem.
D: Many cracks were generated when transferred, and the design was impaired.

Example 1
(Manufacture of hydraulic transfer film)
A PVA film (thickness: 40 μm) was used as the water-soluble film, and a low gloss layer having a pattern synchronized with a later-described wood grain pattern conduit was formed by gravure printing on a part of one side. For the formation of the low gloss layer, a mixed resin of nitrified cotton and alkyd resin, which is a binder resin (mass ratio of nitrified cotton and alkyd, 5: 2) is used, and silica (volume average particle diameter) is used as a matting agent. : 3 μm, oil absorption: 200 mL / 100 g) at a mass ratio of 1: 1 was used. The thickness of the low gloss layer was 1 μm.
Next, on the low gloss layer, a wood grain pattern layer was formed by gravure printing so as to synchronize with the low gloss portion of the wood grain conduit portion to obtain a hydraulic transfer film. The pattern layer uses a mixed resin of nitrified cotton and alkyd resin (mass ratio of nitrified cotton and alkyd 5: 2) as a binder resin, and is colored using a petrol and carbon black as a colorant at a predetermined blending ratio. Ink was used.

(Manufacture of decorative molded products)
After applying 3 g / m ² of the activator composition having the following composition to the surface of the pattern layer of the hydraulic transfer film obtained as described above, and floating on the water surface so that the water-soluble film side faces the water surface side, the hydraulic transfer is performed. The transfer object is pressed onto the film and subjected to a transfer process in which a design layer composed of a low gloss layer and a pattern layer is brought into close contact with the transfer surface of the transfer object by water pressure, and then the water-soluble surface of the transfer object is more water-soluble. A film removal process for removing the film was performed. The decorative molded product thus obtained was such that a design layer composed of a low gloss layer and a pattern layer was exposed on the outermost surface.
A topcoat layer was formed on the design layer using a urethane-based two-component curable resin. The thickness of the top coat layer was 10 μm. The design property and transfer processability of the obtained decorative molded product were evaluated by the above methods. The results are shown in Table 1.
(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

Example 2
In Example 1, a hydraulic transfer film was produced in the same manner as in Example 1 except that silica (volume average particle size: 3 μm) having an oil absorption of 250 mL / 100 g was used as a matting agent. Was used to obtain a decorative molded product, and the design and transfer processability were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 3
In Example 2, a hydraulic transfer film was produced in the same manner as in Example 2 except that the particle size of silica as a matting agent was 5 μm, and a decorative molded product was obtained using the hydraulic transfer film. It was. Table 1 shows the results of evaluating the designability and transfer processability in the same manner as in Example 1.

Example 4
In Example 2, a hydraulic transfer film was produced in the same manner as in Example 2 except that the particle size of the matte silica was 10 μm, and a decorative molded product was obtained using the hydraulic transfer film. It was. Table 1 shows the results of evaluating the designability and transfer processability in the same manner as in Example 1.

Example 5
In Example 2, a hydraulic transfer film was produced in the same manner as in Example 2 except that the particle size of the matting silica was 15 μm, and a decorative molded product was obtained using the hydraulic transfer film. It was. Table 1 shows the results of evaluating the designability and transfer processability in the same manner as in Example 1.

Comparative Example 1
In Example 1, a hydraulic transfer film was produced in the same manner as in Example 1 except that the matting agent was not blended, and a decorative molded product was obtained using the hydraulic transfer film. Table 1 shows the results of evaluating the designability and transfer processability in the same manner as in Example 1.

Comparative Example 2
In Comparative Example 1, a hydraulic transfer film was produced in the same manner as Comparative Example 1 except that titanium oxide was blended as a pigment, and a decorative molded product was obtained using the hydraulic transfer film. Table 1 shows the results of evaluating the designability and transfer processability in the same manner as in Example 1.

Comparative Example 3
In Example 1, a hydraulic transfer film was produced in the same manner as in Example 1 except that silica having an oil absorption of 150 mL / 100 g was used as a matting agent, and a decorative molded product was produced using the hydraulic transfer film. Obtained. Table 1 shows the results of evaluating the designability and transfer processability in the same manner as in Example 1.

  As described above, the decorative molded products obtained in Examples 1 to 5 show a good gloss mat design, and there is no practical problem with respect to transfer processability. On the other hand, the decorative molded product obtained in Comparative Examples 1 to 3 was inferior in design.

  The hydraulic transfer film of the present invention can provide a decorative molded product having an excellent gloss mat 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 Water-soluble film 2 Design layer 2a Low gloss layer 2b Picture layer 2c High gloss layer 10 Hydraulic transfer film 20 Hydraulic transfer film

Claims (11)

  A hydraulic transfer film having a design layer on a water-soluble film, wherein the design layer has a low gloss layer provided at least partially, and the resin composition constituting the low gloss layer is a binder resin and a gloss layer. A hydraulic transfer film comprising an eraser and having an oil absorption of 180 mL / 100 g or more measured according to JIS K 5101-13-1: 2004 of the matting agent.   The hydraulic transfer film according to claim 1, wherein the matting agent is silica.   The hydraulic transfer film according to claim 1 or 2, wherein the matting agent has a particle size of 1 to 8 µm.   The hydraulic transfer film according to claim 1, wherein the matting agent has an oil absorption of 230 mL / 100 g or more.   The hydraulic transfer film according to any one of claims 1 to 4, wherein a blending amount of the matting agent in the resin composition constituting the low gloss layer is 0.5 to 80% by mass.   The binder resin in the resin composition constituting the low gloss layer is at least one selected from acrylic resin, polyester resin, urethane resin, polycarbonate resin, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral resin, and nitrified cotton. The hydraulic transfer film according to claim 1, which is a seed.   The hydraulic transfer film according to claim 1, wherein the design layer has a low-gloss layer and a pattern layer in this order from the water-soluble film side.   The decorative molded product which transcribe | transferred the design layer of the hydraulic transfer film in any one of Claims 1-7 to a to-be-transferred body.   The decorative molded product according to claim 8, further comprising a topcoat layer on the transfer layer obtained by the transfer. A method for producing a decorative molded product, comprising using the hydraulic transfer film according to claim 1 and comprising the following steps (a) to (d).
Step (a): A step of floating the hydraulic transfer film on the water surface so that the water-soluble film side faces the water surface.
Step (b): A step of applying the activator composition to the design layer side of the hydraulic transfer film.
Step (c): a step of pressing the transferred body onto the hydraulic transfer film that has undergone the steps (a) and (b), and bringing the design layer into close contact with the transferred surface of the transferred body by hydraulic pressure.
Step (d): a film removal step of removing the water-soluble film from the transfer surface of the transfer object.   The manufacturing method of the decorative molded product of Claim 10 which has a process (e) further after the said process (d).

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