JP7067542B2 - Decorative molded products and their manufacturing methods - Google Patents

Description

The present invention relates to a decorative molded product and a method for producing the same.

Molded products with wood grain or metallic decoration on the surface are used for building materials, automobile interior products, home appliances, OA equipment, and the like. Many of these molded products have a complicated three-dimensional shape, and conventionally, a method of easily applying a highly-designed decoration to a molded product having the complicated shape has been studied.

As one of such decoration methods, a hydraulic transfer method using hydraulic pressure is known. In the hydraulic transfer method, a transfer film having a desired decorative layer printed on a water-soluble or water-swellable water-soluble film is prepared, and an activator composition composed of an organic solvent is applied to the decorative layer of the transfer film. , The decorative layer is swollen and adhered (this is called activation). Before or after that, the transfer film is suspended 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 surface to be transferred to be decorated, the water-soluble film is removed and the decorative layer is transferred.

Such a hydraulic transfer method is an excellent curved surface decoration method in terms of transfer processability to a three-dimensional surface, "depth" of a clear painter, etc., and designability such as high-quality pattern expression. It has been known. It is known that the decorative molded product obtained by using such a hydraulic transfer method has a design that expresses a high three-dimensional effect with respect to the resin molded product.

For example, in Patent Document 1, a hydraulic transfer film having a design layer on a water-soluble film is used to provide a low-gloss portion containing a binder resin and a matting agent, and a high-gloss portion containing an acrylic polymer polyol or a cured product thereof. It is disclosed that a decorative molded product that expresses a design having a feeling of unevenness can be manufactured by a method of expressing a strong contrast by a difference in gloss.

Japanese Unexamined Patent Publication No. 2013-240976

However, for example, in the method disclosed in Patent Document 1, the transfer processability of the acrylic polymer polyol layer, which is a high-gloss portion, is slightly inferior. Further, in this method, it is necessary to provide two layers, a low gloss portion and a high gloss portion. Therefore, there is a problem that the production cost increases in order to express a high three-dimensional effect in the decorative molded product by the method disclosed in Patent Document 1.
Under such circumstances, it is a main object of the present invention to provide a decorative molded product having a design that expresses a high three-dimensional effect and having a reduced production cost, and a method for producing the same.

The present inventors have conducted extensive research to solve the above problems. As a result, the decorative molded product having the high-gloss-like molded product and the pattern layer provided on a part of the surface of the high-gloss-like molded product has a high three-dimensional effect and the design property changes depending on the observation angle. It has been found that a decorative molded product having a unique design can be obtained, and further, the production cost of the decorative molded product can be reduced. The present invention has been completed by further studies based on such findings.

That is, the present invention provides the inventions of the following aspects.
Item 1. A decorative molded product having a high-gloss-like molded product and a pattern layer provided on a part of the surface of the high-gloss-like molded product.
Item 2. Item 2. The decorative molded product according to Item 1, wherein the high-gloss molded product has a gloss value (60 °) of the surface on the pattern layer side of 70 or more.
Item 3. The high-gloss molded product is a laminate of a base material layer and a high-gloss resin layer.
Item 2. The decorative molded product according to Item 1 or 2, wherein the high-gloss resin layer is laminated on the pattern layer side.
Item 4. Item 3. The decorative molded product according to Item 3, wherein the high-gloss resin layer is formed of a cured product of a resin composition containing an acrylic polymer polyol.
Item 5. Item 2. The decorative molded product according to any one of Items 1 to 4, wherein the pattern layer is formed by a hydraulic transfer method.
Item 6. Item 2. The decorative molded product according to any one of Items 1 to 5, further comprising a top coat layer on the pattern layer.
Item 7. Item 6. The decorative molded product according to Item 6, wherein the top coat layer has a matte tone.
Item 8. A method for manufacturing a decorative molded product, which comprises a high-gloss molded product and a pattern layer provided on a part of the surface of the high-gloss molded product.
A decorative molded product comprising a step of transferring a pattern layer onto a high-gloss-like molded product using a hydraulic transfer film having a water-soluble film and a pattern layer provided on a part of the water-soluble film. Production method.
Item 9. Item 8. The method for manufacturing a decorative molded product according to Item 8, wherein the high-gloss molded product has a surface gloss value (60 °) of 70 or more.
Item 10. The high-gloss molded product is a laminate of a base material layer and a high-gloss resin layer.
Item 8. The method for manufacturing a decorative molded product according to Item 8 or 9, wherein the high-gloss resin layer is laminated on the pattern layer side.

According to the present invention, it has a high three-dimensional effect and a unique design in which the design property changes depending on the observation angle, and further, it is not necessary to provide a design layer having low transfer processability, so that the production cost is high. It is possible to provide a decorative molded product that can also reduce the amount of. Further, according to the present invention, it is also possible to provide a suitable manufacturing method for the decorative molded product.

It is a schematic sectional drawing which shows an example of the structure of the decorative molded article of this invention. It is a schematic sectional drawing which shows an example of the structure of the decorative molded article of this invention. It is a schematic sectional drawing which shows an example of the structure of the decorative molded article of this invention. It is a schematic sectional drawing which shows an example of the structure of the hydraulic transfer film used for manufacturing the decorative molded article of this invention.

The decorative molded product of the present invention is characterized by having a high-gloss-like molded product and a pattern layer provided on a part of the surface of the high-gloss-like molded product. Since the decorative molded product of the present invention has such a configuration, it has a high three-dimensional effect, a unique design in which the design changes depending on the observation angle, and further, transfer processability. Since it is not necessary to provide a low design layer, the production cost can be reduced. The decorative molded product of the present invention can be suitably produced by the hydraulic transfer method described later. In the present invention, the "pattern layer provided on a part of the surface of the high-gloss-like molded product" includes a portion provided with the pattern layer and a portion not provided on the entire surface of the high-gloss-like molded product. Aspects formed in a patterned or non-patterned manner are included.

As described above, in the conventional decorative molded product (particularly, the decorative molded product manufactured by the hydraulic transfer method), a pattern layer and a design layer having a low-gloss portion and a high-gloss portion are provided on the molded product. By forming the above, a design that expresses a high three-dimensional effect is given. Such a design is formed, for example, by a hydraulic transfer method using a hydraulic transfer film having the low-gloss portion and the high-gloss portion in order on a water-soluble film. However, such decoration with a hydraulic transfer film does not have sufficient transfer processability because an acrylic polymer polyol is used in the design layer. Further, in this method, it is necessary to provide two layers, a low gloss portion and a high gloss portion. Therefore, there is a problem that the production cost increases in order to give a high three-dimensional effect to the decorative molded product by the conventional method.

On the other hand, in the decorative molded product of the present invention, the surface of the molded product before decoration has a high gloss tone (that is, the surface of the molded product itself has a high gloss tone), and the surface of the molded product has a high gloss tone. By providing the pattern layer 2 on a part of the surface of the above, a design layer having a high three-dimensional effect and a unique design in which the design property changes depending on the observation angle is provided, and the transfer processability is low. Since there is no need, the production cost can be reduced. Hereinafter, the decorative molded product of the present invention will be described in detail with reference to FIGS. 1 to 3.

[Decorative molded products]
1 to 3 are schematic cross-sectional views showing an example of the configuration of the decorative molded product of the present invention. As shown in FIG. 1, the decorative molded product 10 of the present invention has a high-gloss-like molded product 1 and a pattern layer 2. In the high-gloss molded product 1, at least the surface on the pattern layer 2 side has a high-gloss tone.

The pattern layer 2 is provided on a part of the high-gloss-like surface of the high-gloss-like molded product 1. That is, the surface of the high-gloss molded product 1 is composed of a portion provided with the pattern layer 2 and a portion not provided with the pattern layer 2. Therefore, when the decorative molded product 10 of the present invention is viewed from the pattern layer 2 side, the portion provided with the pattern layer 2 and the high gloss tone of the high gloss tone molded product 1 without the pattern layer 2 are provided. The surface is visible. Since the decorative molded product 10 of the present invention has such a configuration, the high-gloss-like molded product 1 without the pattern layer 2 and the pattern layer 2 has a high three-dimensional effect due to the gloss contrast of the high-gloss-like surface. And, it has a unique design whose design changes depending on the observation angle.

Further, as shown in FIG. 2, in the decorative molded product 10 of the present invention, the high-gloss-like molded product 1 is a laminate of the base material layer 1a and the high-gloss resin layer 1b, and the high-gloss resin. The layer 1b may be laminated on the pattern layer 2 side.

Further, as shown in FIG. 3, the decorative molded product 10 of the present invention may further have a top coat layer 3 on the pattern layer 2, if necessary. Hereinafter, each layer constituting the decorative molded product 10 of the present invention will be described in detail.

<High gloss molded product 1>
In the high-gloss molded product 1, at least the surface on the pattern layer 2 side has a high-gloss tone. As described above, in the decorative molded product 10 of the present invention, since a part of the high-gloss-like surface of the high-gloss-like molded product 1 is covered with the pattern layer 2, the decorative molded product 10 is referred to as the pattern layer 2. When viewed from the side, the contrast between the high-gloss tone surface of the high-gloss tone molded product 1 without the pattern layer 2 and the high-gloss tone surface of the pattern layer 2 changes the high three-dimensional appearance and the design depending on the observation angle. It expresses such a unique design.

From the viewpoint of further enhancing the designability of the decorative molded product 10 of the present invention, the gloss value (60 °) of the surface of the high-gloss molded product 1 on the pattern layer 2 side is preferably 70 or more, more preferably 70 or more. 90 or more can be mentioned. The upper limit of the gloss value (60 °) is preferably about 95. In the present invention, the gloss value (60 °) is a gloss value measured using a commercially available gloss meter under the condition of an incident angle of light of 60 ° to the surface of the matte-adjusted molded product, and is any 3 It is the average value of measured points.

The method for making the surface of the high-gloss molded product 1 high-gloss is not particularly limited, but a laminate of the base material layer 1a and the high-gloss resin layer 1b is preferable. In the high-gloss-like molded product 1 made of the laminated body, the surface of the high-gloss-like molded product 1 can be made high-gloss by laminating the high-gloss resin layer 1b on the pattern layer 1a side.

The material constituting the high-gloss resin layer 1b is not particularly limited as long as it is a material capable of making the surface of the high-gloss-like molded product 1 high-gloss, but the designability of the decorative molded product 10 of the present invention is further improved. From the viewpoint of further enhancing, a cured product of a resin composition containing an acrylic polymer polyol is preferable. The cured product may be completely cured or may be in a semi-cured state. Further, the resin composition containing the acrylic polymer polyol and the cured product of the resin composition may be in a mixed state. Further, the resin composition forming the high-gloss molded product 1 may further contain isocyanate in addition to the acrylic polymer polyol. Isocyanate is a curing agent for an acrylic polymer polyol, and by containing isocyanate, at least a part of the resin composition is put into a cured state or a semi-cured state.

(Acrylic polymer polyol)
The acrylic polymer polyol preferably has a weight average molecular weight of 1,000 to 100,000 converted to standard polystyrene, which is determined by a gel permeation chromatography (GPC) method, and is preferably 5,000 to 80,000. It is more preferably 20,000 to 50,000, and particularly preferably 20,000 to 50,000.

The acrylic polymer polyol preferably has a hydroxyl value of 30 to 130 mgKOH / g, more preferably 50 to 130 mgKOH / g, and even more preferably 60 to 120 mgKOH / g.

(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 (or or) such as 1,6-hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), methylene diisocyanate (MDI), hydrogenated tolylene diisocyanate, and hydrogenated diphenylmethane diisocyanate. Polyisocyanate such as alicyclic) isocyanate is used.

Further, if necessary, blocked isocyanate may be used in which the isocyanate group is protected with an appropriate blocking agent and inactivated, and the isocyanate group is regenerated by heating. As the blocking agent, known blocking agents such as phenol, alcohol, active methylene such as dimethyl malonate and ethyl acetoacetate, and oxime may be used.

By using blocked isocyanate, high glossability can be imparted to the high-gloss resin layer 1b, and after molding into a desired shape, the molded product is heat-treated to regenerate the isocyanate group, react with the polyol, and cure. , Good adhesion to the pattern layer 2 can be exhibited.

The resin composition constituting the high gloss resin layer 1b includes urethane resin, (meth) acrylic resin, (meth) acrylic / urethane copolymer resin, vinyl chloride-vinyl acetate copolymer, polyester resin, butyral resin, and the like. It may contain chlorinated polypropylene, chlorinated polyethylene and the like. Of these, urethane resin is particularly preferable because it has high compatibility with acrylic polymer polyol.

Further, a colorant may be added to the high gloss resin layer 1b as long as the effect of the present invention is not impaired. As the colorant, the same colorant as that used in the pattern layer described later can be used.

(Urethane resin)
As the urethane resin, a non-crosslinked type, that is, a thermoplastic resin having a linear molecular structure rather than a three-dimensionally crosslinked one having a network-like three-dimensional molecular structure is selected. Is preferable. As such a non-crosslinked urethane resin, a polyester polyol, a polyether polyol, a polycarbonate polyol, a polycaprolactone polyol, a polyethylene glycol, a polypropylene glycol or the like is used as a main component as a polyol component, and the non-crosslinked urethane resin is reacted with isocyanate. A type urethane resin can be used, and one synthesized by a combination of a polyester polyol and an isocyanate such as hexamethylene diisocyanate is particularly preferable from the viewpoints of moldability, heat resistance, weather resistance, adhesion to the pattern layer 2, and the like. Normally, the number of hydroxyl groups in one molecule of polyol and the number of isocyanate groups in one molecule of isocyanate are 2 on average.

Further, as the urethane resin, a urethane urea resin synthesized from a combination of a polyol component, a polyamine component and an isocyanate is preferably used, and as the polyol component and an isocyanate, the above-mentioned ones can be used.

The urethane resin preferably has a glass transition point of 100 ° C. or lower, and more preferably 20 to 100 ° C. When the glass transition point of the urethane resin is 100 ° C. or lower, the flexibility of the high-glossy portion 2b at room temperature is excellent, and when it is 20 ° C. or higher, the cohesive force is significantly reduced by heating, or the high-gloss resin layer 1b has a water pressure. It is preferable because it does not dissolve in water during transfer.

The ratio of the total amount of isocyanate added to the acrylic polymer polyol or the acrylic polymer polyol as needed in the resin composition constituting the high gloss resin layer 1b to the urethane resin is usually 99: 1 to 50:50 in terms of mass ratio. It is preferably 95: 5 to 50:50, more preferably 90:10 to 60:40, and particularly preferably 80:20 to 68:32.

The high-gloss resin layer 1b is a known method using a coating liquid in which a resin composition (for example, the above-mentioned acrylic polymer polyol, isocyanate, urethane resin, and other resins) constituting the high-gloss resin layer 1b is dissolved in a solvent. It can be applied with, dried if necessary, and cured to form. The thickness of the high-gloss resin layer 1b is preferably about 1 to 25 μm, and more preferably in the range of 1 to 15.

Examples of the material constituting the base material layer 1a 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 resins or resins in which these are mixed, structures made of metals such as iron, aluminum and copper, ceramics such as ceramics, glass and amber, and materials such as wood can be used. Further, the shape of the base material layer 1a is not particularly limited, and may be a two-dimensional shape that is a planar shape, or a three-dimensional shape such as an uneven shape or a curved surface shape. As the high-gloss molded product 1, a resin structure is often used.

Further, in the present invention, the high-gloss molded product 1 may be formed from a cured product of a resin composition containing an acrylic polymer polyol in the same manner as the above-mentioned high-gloss resin layer 1a. In this case, the shape of the high-gloss-like molded product 1 is not particularly limited, and may be a two-dimensional shape that is a planar shape, or a three-dimensional shape such as an uneven shape or a curved surface shape. As the high-gloss molded product 1, a resin structure is often used. The high-gloss molded product 1 can be manufactured by a known molding method using, for example, the above-mentioned materials.

<Picture layer 2>
The pattern layer 2 is a layer that imparts decorativeness to the decorative molded product 10. The pattern formed by the pattern layer 2 is not particularly limited, and for example, a stone pattern imitating the surface of rock such as a wood grain pattern, a marble pattern, and a marble pattern (for example, a travertin marble pattern), a cloth pattern, or a cloth-like pattern can be used. Examples include imitated fabric patterns, tiled patterns, and brickwork patterns, as well as patterns such as parquet and patchwork that combine these patterns.

In the decorative molded product 10 of the present invention, the pattern layer 2 is provided on a part of the surface of the high-gloss-like molded product 1 and has a missing portion where the pattern layer 2 is not provided. For example, in the wood grain pattern, the conduit portion is missing from the pattern, and the pattern is provided in the other portion. Due to such a structure of the pattern layer, the decorative molded product 10 of the present invention has a high-gloss-like surface of the high-gloss-like molded product 1 which is a missing portion where the pattern layer 2 is not provided, and the gloss of the pattern layer 2. It has a design that expresses a high three-dimensional effect due to the contrast of. Furthermore, it expresses a unique design whose design changes depending on the observation angle.

When the high-gloss molded product 1 is composed of the above-mentioned base material layer 1a and the high-gloss resin layer 1b, the pattern layer 2 is a part of the surface of the high-gloss resin layer 1b as shown in FIG. It will be provided.

The pattern layer 2 usually contains a binder resin and a colorant. Examples of the binder resin of the pattern layer 2 include a thermoplastic resin, and specific examples thereof include acrylic resin, polyester resin such as alkyd, unsaturated polyester resin, urethane resin (for example, polyester urethane resin), polycarbonate resin, and vinyl chloride. -Vinyl acetate copolymer, polyvinyl acetal (butyral resin) such as polyvinyl butyral, and nitrocellulose resin such as nitrified cotton can be mentioned. One type of binder resin may be used alone, or two or more types may be used in combination.

Coloring agents include carbon black (black), iron black, titanium white, antimony white, yellow lead, titanium yellow, petals, 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, titanium dioxide-coated mica, and pearl gloss pigments made of scaly foil pieces such as basic lead carbonate are used.

The pattern layer 2 can be formed by a known method such as a hydraulic transfer method. In particular, the pattern layer 2 is formed by the hydraulic transfer method in that a design expressing a unique design whose design changes depending on the observation angle can be imparted to the decorative molded product 10 with a high three-dimensional effect. Is preferable.

The thickness of the pattern layer 2 is not particularly limited, but from the viewpoint of imparting a high three-dimensional effect and a design expressing a unique design whose design changes depending on the observation angle to the decorative molded product 10. It is preferably about 1 to 25 μm, and more preferably about 1 to 15 μm.

The hydraulic transfer method is a method of decorating a molded product using the hydraulic transfer film 20. The hydraulic transfer film 20 is preferably a water-soluble film 4 and a film in which the pattern layer 2 is provided on the water-soluble film 4. The pattern layer 2 of the decorative molded product 10 of the present invention is preferably formed by transferring the pattern layer 2 of the hydraulic transfer film onto the high-gloss molded product 1.

FIG. 4 shows a schematic cross-sectional view of an example of a hydraulic transfer film. As shown in FIG. 4, the hydraulic transfer film 20 is provided with a pattern layer 2 on a water-soluble film 4.

Examples of the resin constituting the water-soluble film 4 include polyvinyl alcohol resin, dextrin, gelatin, sardine, casein, cellac, gum arabic, starch, protein, polyacrylic acid amide, sodium polyacrylic acid, polyvinyl methyl ether, and methyl vinyl ether. Examples thereof include a copolymer with maleic anhydride, a copolymer of vinyl acetate and itaconic acid, and various water-soluble polymers such as polyvinylpyrrolidone, 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. A rubber component such as mannan, xanthan gum, or guar gum may be added to the water-soluble film 4.

Of the water-soluble films 4, polyvinyl alcohol (PVA) resin films are particularly preferable from the viewpoints of production stability, solubility in water, and economy. The polyvinyl alcohol resin film may contain additives such as starch and rubber in addition to PVA.

The polyvinyl alcohol resin film has a printing layer (picture layer 2) for transfer to the water-soluble film 4 by changing the degree of polymerization of polyvinyl alcohol, the degree of saponification, and the blending amount of additives such as starch and rubber. Mechanical strength required for forming, moisture resistance during handling, speed of softening by water absorption after floating on the water surface, time required for spreading or diffusion in water, ease of deformation in the transfer process, etc. Can be adjusted as appropriate.

A suitable water-soluble film 4 made of a polyvinyl alcohol resin film is as described in Japanese Patent Application Laid-Open No. 54-92406, for example, 80% by mass of PVA resin and 15% by mass of polymer water-soluble resin. % And 5% by mass of starch, and the one having an equilibrium water content of about 3% is preferable.

Although the polyvinyl alcohol resin film is water-soluble, it is preferable that the polyvinyl alcohol resin film remains as a film while swelling and softening in water before it is dissolved in water. This is because it is possible to prevent excessive flow and deformation of the print layer for transfer during hydraulic transfer by performing hydraulic transfer while the film is in a state of being alive.

The thickness of the water-soluble film 4 is preferably 10 to 100 μm. 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 appropriate 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 4 can be used by laminating it with a water-permeable base material such as paper, non-woven fabric, or cloth, but it is water-soluble or water-swelling with such a water-permeable base material. When laminated with the water-soluble film 4 having properties, the water-permeable substrate is separated from the water-soluble or water-swellable water-soluble film 4 or separated from the water-soluble film 4 before floating the hydraulic transfer film 20 on the water surface. It is preferable that the base material having water permeability is separated from the water-soluble film 4 having water-soluble or water-swelling property by the action of water after floating on the water surface.

The structure of the pattern layer 2 of the hydraulic transfer film 20 is preferably the same as that of the pattern layer 2 of the decorative molded product 10 of the present invention.

The hydraulic transfer film 20 forms the pattern layer 2 on the water-soluble film 4 by a known coating method or printing method using the coating liquid constituting the pattern layer 2, or by laminating a resin film. , Can be manufactured. Examples of the coating method include gravure coating and reverse coating, and examples of the printing method include gravure printing.

A specific method for forming the pattern layer 2 using the hydraulic transfer film 20 will be described later in the section of the method for manufacturing a decorative molded product of the present invention.

<Top coat layer 3>
The decorative molded product 10 of the present invention may further have a top coat layer 3 on the pattern layer 2. By having the top coat layer 3, it is possible to protect the pattern layer 2, increase the surface strength, and adjust the gloss of the surface.

FIG. 3 is a schematic cross-sectional view showing an example of the configuration of the decorative molded product 10 of the present invention, which has the top coat layer 3 on the pattern layer 2.

As the material for forming the top coat layer 3, for example, a thermoplastic resin, a thermosetting resin, an ultraviolet curable resin, or the like is selected, and specifically, a urethane resin, an epoxy resin, an acrylic resin, a fluororesin, or the like is selected. , Silicon-based resin and the like.

The top coat layer 3 can be formed by a known coating method such as spray coating, electrostatic coating, brush coating, dip coating, etc., using a coating material obtained by dissolving the above-mentioned resin in a known organic solvent. ..

The top coat layer 3 may have a matte tone. When the top coat layer 3 has a matte tone, it is preferable that the top coat layer 3 contains a matting agent.

As the matting agent, for example, an inorganic filler selected from silica, clay, heavy calcium carbonate, light calcium carbonate, precipitated barium sulfate, calcium silicate, synthetic silicate, and fine powder of silicate, and an acrylic resin. , Urethane resin, nylon resin, polypropylene resin, or urea-based resin, organic fillers or resin beads may be used, and any one of them may be used, or two or more of them may be used in combination. Among these, silica, calcium carbonate, and sedimentary barium are preferable from the viewpoint of imparting a high three-dimensional effect and a unique design whose design changes depending on the observation angle to the decorative molded product 10. More preferably, silica is mentioned.

The volume average particle size of the matting agent is preferably 0.5 to 25 μm, more preferably 1 to 15 μm, still more preferably 1 to 10 μm, still more preferably 1 to 5 μm, and particularly preferably 1 to 3 μm. .. If the volume average particle size of the matting agent is 25 μm or less, the stress during processing is diffused due to the increase in the boundary area, the voids generated at the interface absorb energy, and the distance between particles becomes small. Causes plastic deformation between particles or voids, and whitening during stretching can be suppressed. Further, it is preferable that the volume average particle size of the matting agent is 0.5 μm or more from the viewpoint of the matting effect. The volume average particle size referred to here is the particle size at an integrated value of 50% in the particle size distribution obtained by the laser diffraction-scattering method.

The oil absorption measured in accordance with JIS K 5101-13-1: 2004 of the matting agent is 230 mL / 100 g or more, preferably 230 to 400 mL / 100 g, and more preferably 230 to 350 mL / 100 g. , 230-300 mL / 100 g, more preferably. It is preferable to use a matting agent having an oil absorption amount of 230 mL / 100 g or more from the viewpoint of the matting effect, and it is preferable to use a matting agent having an oil absorption amount of 400 mL / 100 g or less to apply the matting agent to the coating liquid. In this case, it is preferable from the viewpoint of maintaining an appropriate thixotropic property and not impairing the coating suitability.

The matting agent may be surface-treated. Such surface treatment is preferable because it can suppress cracks and whitening during molding. The treatment method is not particularly limited as long as it exhibits the above effects, and may be a surface treatment using an organic material or a surface treatment using an inorganic material. In particular, a silane coupling treatment or the like is preferably mentioned.

When the top coat layer 3 contains a matting agent, the content of the matting agent in the top coat layer 4 is preferably about 1 to 40% by mass, more preferably about 20 to 40% by mass.

The thickness of the top coat layer 3 is not particularly limited, and is preferably 1 to 25 μm, more preferably 1 to 15 μm.

[Manufacturing method of decorative molded products]
The method for producing the decorative molded product of the present invention is not particularly limited, but a high gloss tone is used by using a water-soluble film and a hydraulic transfer film having a pattern layer provided on a part of the water-soluble film. A hydraulic transfer method including a step of transferring a pattern layer onto a molded product is suitable.

The hydraulic transfer film 20 having the water-soluble film 4 and the pattern layer 2 provided on a part of the water-soluble film 4 is as described above.

Specifically, the step of transferring the pattern layer 2 onto the high-gloss-like molded product 1 using the hydraulic transfer film 20 includes the following steps (a) to (d).
That is, the decorative molded product 10 of the present invention can be suitably manufactured by a method including the following steps (a) to (d).
Step (a) A step of suspending the hydraulic transfer film on the water surface so that the water-soluble film side faces downward and the water surface side. Step (b) An activator coating step of applying the active agent composition to the pattern layer side of the hydraulic transfer film. Step (c) The high-gloss-like molded product is pressed onto the hydraulic transfer film floating on the water surface after the steps (a) and (b), and the pattern layer is subjected to the high-gloss-like molded product by water pressure. Step to make it adhere to the toned surface Step (d) Defilming step to remove the water-soluble film that adheres to the toned surface of the high-gloss-like molded product

Further, following the above step (d), the following step (e) may be provided.
Step (e): A step of forming a top coat layer on a pattern layer formed on a high-gloss molded product.

<Step (a)>
Step (a) can be performed before or after step (b). In the step (a), the hydraulic transfer film 20 is suspended on the water surface so that the water-soluble film 4 side faces downward and faces the water surface side. In order to suspend the hydraulic transfer film 20 on the water surface, the sheet-fed printed matter may be suspended one by one, or water is allowed to flow in one direction, and a continuous band-shaped hydraulic transfer film 20 is continuously formed on the water surface. It may be supplied and floated.

<Step (b)>
The step (b) can be performed before or after the step (a), and is a step of applying the activator composition to the pattern layer 2 side of the hydraulic transfer film 20. By applying the activator composition in this step, at least a part of the pattern layer 2 is dissolved or swollen and softened (activated), and it becomes easy to adhere to the high-gloss-like molded product 1 which is the transferred product.

(Activator composition)
The activator composition applied to the pattern layer 2 has a function of activating the pattern layer 2 and transferring it to the transferred surface (that is, the highly glossy surface) of the transferred body (that is, the high gloss tone molded product 1). The composition is not particularly limited as long as it has, and it is preferable that the composition has a property that it does not evaporate until each layer is transferred to the surface to be transferred. Preferred examples of such an activator composition include compositions containing esters, acetylene glycols, ethers, and resins.

Preferred examples of the esters include ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, tert-butyl acetate, dibutyl acetate, dibutyl phthalate, dimethyl phthalate, dioctyl phthalate, and diisooctyl phthalate. Be 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.

Further, as the resin, a thermoplastic resin such as an acrylate-based monomer alone or a copolymer, a polyamide resin, a polyester resin, a phenol resin, a melamine resin, a urea resin, an epoxy resin, an alkyd phthalate resin, and a diallyl phthalate are used. Thermally curable resins such as resins, alkyd resins, and polyurethane resins are preferred, with thermocurable resins being 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 resins. It is about 20% by mass.

The activator composition may be applied by gravure printing, a spray coating method, or the like, and the amount of the activator composition is usually 1 to 50 g / m ² , preferably 3 to 30 g / m ² , and more preferably 10 to 10. It is 20 g / m ² .

<Step (c)>
In the step (c), the high-gloss-like molded product 1 to be transferred is pressed onto the hydraulic transfer film 20 floating on the water surface after the steps (a) and (b), and the hydraulic transfer film is subjected to hydraulic pressure. This is a step of bringing the pattern layer 2 of 20 into close contact with the high-gloss surface of the high-gloss molded product 1. When the high-gloss molded product 1 has the high-gloss resin layer 1b, the surface to be transferred is the surface of the high-gloss resin layer 1b. The water for floating the hydraulic transfer film 20 and applying the hydraulic pressure is preferably adjusted to an appropriate water temperature according to the type of the water-soluble film 4 of the hydraulic transfer film 20, preferably about 25 to 50 ° C., and more. It is preferably 25 to 35 ° C.

The transfer time between the hydraulic transfer film 20 of the present invention and the high-gloss molded product 1 is preferably about 20 to 120 seconds, more preferably about 30 to 60 seconds.

In the step (c), the activator composition applied to the pattern layer 2 is in contact with the high-gloss-like molded product 1 and the surface of the high-gloss-like molded product 1 is dissolved to dissolve the hydraulic transfer film 20 and the high-gloss-like molding. The adhesion with the product 1 can be further improved.

<Step (d)>
The step (d) is performed after the step (c) and is a step of removing the water-soluble film 4 in close contact with the transferred surface (high gloss tone surface) of the high gloss tone molded product 1. The water-soluble film 4 adhering to the surface to be transferred of the high-gloss molded product 1 can be removed by, for example, shower washing with water. The conditions for shower cleaning vary depending on the material forming the water-soluble film 4, but usually the water temperature is preferably about 15 to 60 ° C. and the washing time is preferably about 10 seconds to 5 minutes. Then, after the step (d), the transferred body is sufficiently dried to evaporate the water content.

By the above steps (a) to (d), the decorative molded product 10 of the present invention can be manufactured.

<Step (e)>
The step (e) is a step of forming the top coat layer 3 on the pattern layer 2 formed on the high-gloss molded product 1 as needed. When the step (e) is performed, in the step (e), the pattern layer 2 is coated as necessary for improving the surface strength, protecting the surface, adjusting the gloss of the surface, etc., and is transparent or translucent. The top coat layer 3 is formed.

As a material for forming the top coat layer 3, for example, a thermoplastic resin, a thermosetting resin, an ultraviolet curable resin or the like is selected, and specifically, a urethane resin, an epoxy resin, an acrylic resin, a fluororesin, etc. Silicon-based resin or the like is used. The top coat layer 3 can be formed by a known coating method such as spray coating, electrostatic coating, brush coating, dip coating, etc., using a coating material obtained by dissolving the above resin in a known organic solvent. .. The thickness of the top coat layer is preferably 1 to 25 μm, more preferably 1 to 10 μm.

Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. The gloss value (60 °) measured in Examples and Comparative Examples is a gloss value measured using a commercially available gloss meter under the condition that the angle of incidence of light on the surface of the matte molded product is 60 °. , Is the average value measured at any three points.

<Manufacturing example of hydraulic transfer film>
A polyvinyl alcohol (PVA) film (thickness 40 μm) is used as the water-soluble film, and the following ink containing vitrified cotton and alkyd resin in a mass ratio of 80:20 is used on one side thereof, and the conduit is subjected to gravure printing. A pattern layer (thickness 3 μm) having a wood grain pattern in which the portion was missing and the other portion was a pattern was formed, and a water-soluble film / pattern layer was laminated to obtain a hydraulic transfer film.
(Ink that forms the pattern layer)
A colored ink containing nitrocellulose and alkyd resin in a mass ratio of 80:20, and using a valve handle and carbon black as a coloring agent in a predetermined blending ratio.

<Manufacturing of high-gloss molded product A>
Acrylic polymer polyol (weight average molecular weight: 30,000, hydroxyl value: 80 mgKOH / g) and urethane urea resin on an ABS resin plate (thickness 2 mm, surface gloss value (60 °) is 60) as a base material layer. An ink containing a mixed resin having a mass ratio of 8: 2 with (glass transition point: 40 ° C., hydroxyl value: less than 1 mgKOH / g) was applied to form a high gloss resin layer having a thickness of 15 μm. The gloss value (60 °) on the surface of the obtained high-gloss molded product A was 90.

<Manufacturing of high-gloss molded product B>
In the production of the high-gloss-like molded product A, the high-gloss-like molded product B was prepared in the same manner as in the production of the high-gloss-like molded product A, except that the thickness of the high-gloss resin layer was 10 μm. The gloss value (60 °) on the surface of the obtained high-gloss molded product B was 80.

<Manufacturing of high-gloss molded product C>
In the production of the high-gloss-like molded product A, the high-gloss-like molded product C was prepared in the same manner as in the production of the high-gloss-like molded product A, except that the thickness of the high-gloss resin layer was set to 5 μm. The gloss value (60 °) on the surface of the obtained high-gloss molded product C was 70.

<Molded product D>
As the molded product D, the above ABS resin plate (thickness 2 mm, surface gloss value (60 °) is 60) was used as it was.

<Example 1> Production of decorative molded product A 10 g / m ² of the activator composition having the following composition is applied to the surface of the pattern layer of the hydraulic transfer film obtained above, and the activator composition is applied by a smoothing roll. After making the film uniform, the hydraulic transfer film was suspended on the water surface so that the water-soluble film side was facing downward and the water surface side was facing. Next, the above-mentioned high-gloss-like molded product A is pressed against the floating hydraulic transfer film so that the high-gloss resin layer is on the water surface side, and the pattern layer is pressed by water pressure on the high-gloss resin layer surface of the high-gloss-like molded product 1. A step of bringing the film into close contact with the film and a step of removing the water-soluble film by washing with water were performed. Next, a two-component curing type urethane resin paint (containing 20% by mass of silica) was spray-coated on the pattern layer to form a top coat layer having a thickness of 15 μm, and a decorative molded product A was obtained.

(Composition of activator composition)
Phthalic acid-based alkyd resin 6 parts by mass Micro silica (pigment) 2 parts by mass Dibutyl phthalate 17 parts by mass Solvent (butyl carbitol acetate) 60 parts by mass Solvent (butyl cellosolve) 15 parts by mass

<Example 2> Production of decorative molded product B The decorative molded product is the same as in Example 1 except that the high-gloss-like molded product B is used instead of the high-gloss-like molded product A in Example 1. B was obtained.

<Example 3> Production of decorative molded product C The decorative molded product is the same as in Example 1 except that the high-gloss-like molded product C is used instead of the high-gloss-like molded product A in Example 1. C was obtained.

<Comparative Example 1> Production of Decorative Molded Product D A decorative molded product D is obtained in the same manner as in Example 1 except that the molded product D is used instead of the high gloss-like molded product A in Example 1. rice field.

Design evaluation 1
The decorative molded product obtained above was visually observed and its design was evaluated according to the following criteria. The results are shown in Table 1.
⊚: The overall design is matte and the conduit part is glossier than the pattern part, which gives a high three-dimensional effect and a deep design.
◯: The overall design is matte and the conduit part is glossier than the pattern part, which strongly expresses a high three-dimensional effect and a deep design.
Δ: The overall design is matte and the conduit part is glossier than the pattern part, which gives a high three-dimensional effect and a deep design.
X: The overall design is matte and the conduit part is glossier than the pattern part, which does not express a high three-dimensional effect and a deep design.

Design evaluation 2
The decorative molded product obtained above was visually observed and its design was evaluated according to the following criteria. The results are shown in Table 1.
⊚: When the decorative molded product is observed from the horizontal direction, the 45 degree direction, and the vertical direction, there is a change in the design at each angle.
〇: There is a change in the design only when the decorative molded product is observed from the horizontal direction and when it is observed from the 45 degree direction and the vertical direction.
Δ: There is a slight change in the design only when the decorative molded product is observed from the horizontal direction and when it is observed from the 45 degree direction and the vertical direction.
X: When the decorative molded product is observed from the horizontal direction, the 45 degree direction, and the vertical direction, there is no change in the design at each angle.

1 High-gloss molded product 1a Base material layer 1b High-gloss resin layer 2 Picture layer 10 Decorative molded product 3 Top coat layer 20 Hydraulic transfer film 4 Water-soluble film

Claims (7)

It has a high-gloss-like molded product and a pattern layer provided on the surface of the high-gloss-like molded product.
The pattern layer is provided on a part of the surface of the high-gloss molded product, and has a missing portion where the pattern layer is not provided.
The high-gloss molded product is a laminate of a base material layer and a high-gloss resin layer.
The base material layer is made of resin and is made of resin.
The high-gloss molded product is a decorative molded product in which the gloss value (60 °) of the surface on the pattern layer side is 70 or more and 95 or less. The decorative molded product according to claim 1, wherein the high-gloss resin layer is laminated on the pattern layer side. The decorative molded product according to claim 2, wherein the high-gloss resin layer is formed of a cured product of a resin composition containing an acrylic polymer polyol. The decorative molded product according to any one of claims 1 to 3, further comprising a top coat layer on the pattern layer. The decorative molded product according to claim 4, wherein the top coat layer has a matte tone. A method for manufacturing a decorative molded product, which has a high-gloss-like molded product and a pattern layer provided on the surface of the high-gloss-like molded product.
The pattern layer is provided on a part of the surface of the high-gloss molded product, and has a missing portion where the pattern layer is not provided.
The high-gloss molded product is a laminate of a base material layer and a high-gloss resin layer.
The base material layer is made of resin and is made of resin.
The high-gloss molded product has a gloss value (60 °) of the surface on the pattern layer side of 70 or more and 95 or less.
A decorative molded product comprising a step of transferring a pattern layer onto a high-gloss-like molded product using a hydraulic transfer film having a water-soluble film and a pattern layer provided on a part of the water-soluble film. Production method. The method for manufacturing a decorative molded product according to claim 6, wherein the high-gloss resin layer is laminated on the pattern layer side.

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