JP7052277B2 - Hydraulic transfer film and its manufacturing method - Google Patents

Description

The present invention relates to a hydraulic transfer film suitable for forming a design layer having excellent three-dimensional design on the surface of a decorative molded product, and a method for producing the same.

A hydraulic transfer method using hydraulic pressure is known as a method for easily decorating a molded product having a complicated shape such as an automobile interior product, a home electric appliance, or an OA device with a high design. In the hydraulic transfer method, a hydraulic transfer film having a desired design layer provided on a water-soluble film is prepared, and the design layer of the hydraulic transfer film is placed before or after being suspended on the water surface with the design layer of the hydraulic transfer film facing up. This is a method in which an activator composition is applied to a swelling and adhesiveness of the design layer (this is referred to as activation), and the design layer is transferred to a transferred body by using water pressure (for example, Patent Document 1). And 2).
When activating the design layer, the ink of the design layer having a three-dimensional shape is activated by the activator composition, which may cause a disadvantage that the three-dimensional shape cannot be maintained.
Further, in order to secure physical properties on the surface of the decorative molded product after transfer, it is generally practiced to form a top coat layer using a resin. However, by providing the top coat layer, the surface of the design layer having a three-dimensional shape tends to be visually flat, and it is difficult to express the three-dimensional shape after transfer.

Under such circumstances, a hydraulic transfer film for forming a design layer capable of expressing a three-dimensional design on the surface of a decorative molded body has been studied.
For example, Patent Document 3 discloses a water-soluble transfer film in which an uneven shape is formed on a glittering ink layer laminated on a stretch-suppressing resin layer, and a water-soluble film is provided on the glittering ink layer. ing.
Further, Patent Document 4 discloses a water-soluble transfer film in which a water-soluble film is embossed and then a glittering ink layer is laminated so as to fill the uneven shape.

Japanese Unexamined Patent Publication No. 61-66685 Japanese Unexamined Patent Publication No. 60-165300 Japanese Unexamined Patent Publication No. 2014-193551 Japanese Unexamined Patent Publication No. 2005-238674

In Patent Document 3, the uneven shape can be satisfactorily formed by providing the stretch-suppressing resin layer, and the stretch of the brilliant ink layer can be suppressed to maintain the unevenness even after transfer. However, since the brilliant ink layer is laminated by the gravure coating method, it has a thickness of about 1 μm, and the design of the three-dimensional shape lacks a sense of depth. Further, in Patent Document 4, the thickness of the brilliant ink layer including the convex portion in the hydraulic transfer sheet can be set to about 30 μm. However, since the brilliant ink layer is provided on the entire surface of the hydraulic transfer sheet, the entire surface of the decorative molded body after transfer has the same glossy color tone, and the convex portions are not conspicuous and it is difficult to obtain an impressive three-dimensional effect.
As described above, there is room for improvement in the water-soluble transfer film capable of forming a design layer sufficiently satisfying in the expression of three-dimensional design on the surface of the decorative molded product.

From the above situation, the present invention provides a water-soluble transfer film capable of forming a design layer having excellent three-dimensional design such as an uneven shape on the surface of a decorative molded product and a method for producing the same. Is the subject.

As a result of diligent studies to solve the above problems, the present inventors have conceived the following inventions and found that the problems can be solved.
That is, the present invention is as follows.

[1] A hydraulic transfer film having a design layer on a water-soluble film, a recess is formed on the surface of the water-soluble film having a design layer, and a design layer a constituting the design layer is formed in the recess. A hydraulic transfer film having a non-formed portion of the design layer a on a surface of the water-soluble film having the design layer.
[2] Hydraulic transfer including a step of forming a recess on at least one surface of the water-soluble film, and a step of applying a paint to the surface on which the recess is formed and then performing a wiping treatment to form a design layer a in the recess. How to make a film.

According to the present invention, it is possible to provide a water-soluble transfer film capable of forming a design layer having excellent three-dimensional design such as an uneven shape on the surface of a decorative molded product and a method for producing the same.

It is a schematic diagram which shows the embodiment example of the hydraulic transfer sheet of this invention. It is a schematic diagram which shows the embodiment example of the conventional hydraulic transfer sheet. It is a schematic diagram which shows the embodiment example of the hydraulic transfer sheet of this invention. It is a schematic diagram which shows the embodiment example of the decorative molded article using the hydraulic transfer sheet of this invention. It is a schematic diagram for demonstrating the depth and width of the recess of the hydraulic transfer sheet of this invention.

<Hydraulic transfer film>
The hydraulic transfer film of the present invention is a hydraulic transfer film having a design layer on the water-soluble film, and recesses are formed on the surface of the water-soluble film having the design layer, and the design layer a constituting the design layer a. Is formed in the recess, and has a non-formed portion of the design layer a on the surface of the water-soluble film having the design layer.
As will be described in detail later, by forming the design layer a constituting the design layer in the recesses of the water-soluble film, the design layer a can give a feeling of depth and enhance the three-dimensional design. Further, since the non-formed portion of the design layer a is provided on the surface of the water-soluble film having the design layer, the entire surface of the decorative molded product after transfer is not covered with the design layer a, so that the film is partially present. The design layer a is enhanced and a more three-dimensionally superior impression can be given.
Hereinafter, each configuration of the hydraulic transfer film of the present invention will be described.

[Design layer]
(Design layer a)
The hydraulic transfer film of the present invention has a design layer for transfer. At least the design layer a is included as a layer constituting the design layer. The design layer a is formed mainly in the recesses of the water-soluble film described later, and schematic views of FIGS. 1A to 1C are shown as examples of aspects of the hydraulic transfer film of the present invention.
As shown in FIG. 1A, the design layer a constituting the design layer 11 may be formed in the entire recess 12 of the water-soluble film 10, and in FIGS. 1B and 1C. It may be formed in a part of the recess 12 as shown.

Further, the above-mentioned "having a non-formed portion of the design layer a on the surface having the design layer of the water-soluble film" means the entire convex portion 13 on the surface having the design layer of the water-soluble film shown in FIG. It means that the design layer a is not partially formed.
Here, in an example of the conventional hydraulic transfer film as disclosed in Patent Document 4, which is shown in FIG. 2, the design layer 21 is the entire concave and convex portions of the water-soluble film 20, that is, the design layer of the water-soluble film. The same design layer is formed on the entire surface having the above. Therefore, the entire surface of the decorative molded product after transfer is covered with the same design layer, which makes it easy to see a visually flat design and the expression of three-dimensional design is insufficient. On the other hand, the hydraulic transfer film of the present invention has a non-formed portion of the design layer a on the convex portion peak 13 on the surface of the water-soluble film having the design layer, and is shown in the schematic diagram of FIG. 4 (G). Since the formed portion and the non-formed portion of the design layer a are provided on the surface of the decorative molded product after the transfer, the design layer a can be enhanced to give a more three-dimensionally superior impression.

On the surface of the water-soluble film having the design layer, the area ratio of the formed portion and the non-formed portion of the design layer a on the plane may be appropriately determined from the pattern formed by the uneven shape, but cannot be unconditionally determined. From the viewpoint of enhancing the three-dimensional design, [design layer a formed partial area] / [design layer a non-formed partial area] is usually about 1/10 to 10/1, preferably 1/1 to 10 /. It is 1.

The non-formed portion can be provided by forming the design layer a on the convex portion peak 13 by a wiping treatment or the like in the method for manufacturing a hydraulic transfer film described later. From the viewpoint of enhancing the design layer a and giving a three-dimensional effect, it is particularly preferable that the non-formed portion of the design layer a is all the convex peak portions.

The paint used to form the design layer a is, for example, transparent, opaque, transparent colored, or opaque colored, as long as the design layer a can exhibit the design property in the post-transcriptional decorative molded product. May be good. Even when the design layer a is formed of a paint containing no colorant using a transparent resin or the like, the design layer a after transfer is partially formed on the surface of the decorative molded product, so that light is emitted. A three-dimensional design can be expressed by adjusting the amount of light and viewing angle.
The paint may contain a colorant, various additives, a solvent and the like, in addition to a resin generally used as a binder resin in the field of hydraulic transfer film.

<Binder resin>
Examples of the binder resin include thermoplastic resins, and specific examples thereof include polyester resins such as acrylic resins, acrylic polyol resins, and alkyd resins; unsaturated polyester resins, urethane resins (for example, polyester urethane resins), and polycarbonate resins. Examples thereof include vinyl chloride-vinyl acetate copolymer resin, polyvinyl acetal resin such as polyvinyl butyral (butyral resin); nitrocellulose resin such as vitrified cotton, and these can be used alone or in combination of two or more.

In particular, since the acrylic polyol resin has excellent solvent resistance, the shape of the design layer a is maintained even when the activator composition is applied during the transfer process, and a delicate three-dimensional design can be expressed even after the transfer. Therefore, it is preferable to use an acrylic polyol resin as the binder resin. That is, the design layer a is preferably a layer formed of at least one of a resin composition containing an acrylic polyol resin and a cured product thereof.
The cured product may be in a semi-cured state or a completely cured state, but is preferably in a semi-cured state in consideration of transfer processability and the like. Further, a state in which a resin composition containing an acrylic polyol resin and a cured product thereof are mixed is also a preferable embodiment.

The acrylic polyol resin preferably has a weight average molecular weight of 1,000 to 100,000, preferably 5,000 to 80,000, as determined by the gel permeation chromatography (GPC) method, in terms of standard polystyrene. More preferably, it is more preferably 20,000 to 50,000. When the molecular weight of the acrylic polyol resin is 1,000 or more, the solvent resistance to the solvent contained in the activator composition is remarkably improved. If it is 100,000 or less, the viscosity is lowered or gelation is less likely to occur when the ink is formed, so that workability is improved.

The acrylic polyol resin 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. When the hydroxyl value of the acrylic polyol resin is 30 mgKOH / g or more, excessive spreading of the entire hydraulic transfer film can be suppressed. When it is 130 mgKOH / g or less, the flexibility of the design layer a is good, and problems such as cracks do not occur. The hydroxyl value can be measured by an acetylation method using acetic anhydride.

Further, the paint may further contain isocyanate in addition to the acrylic polyol resin. Isocyanate is a curing agent for an acrylic polyol resin, and by containing isocyanate, at least a part of the resin composition containing the acrylic polyol resin can be in a completely cured state or a semi-cured state. This makes it possible to further enhance the resistance to the solvent contained in the activator composition.
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.

When an acrylic polyol resin and another resin are used in combination as a binder resin, the mass ratio of the acrylic polyol resin: other resin is 95: 5 to 50: from the viewpoint of the balance between the solvent resistance of the acrylic polyol resin and the transfer processability. It is preferably 50, more preferably 90:10 to 60:40, and even more preferably 85:15 to 70:30.

<Colorant>
The paint is preferably used as a coloring ink containing a colorant. By using colored ink, it is possible to give more depth to the design. Further, since the design layer a is formed in the above-mentioned recesses, it is preferable that the colorant contained in the coloring ink has an average particle size smaller than the depth of the recesses. That is, the design layer a preferably contains a colorant having an average particle size smaller than the depth of the recess.

As the colorant, conventionally known ones can be appropriately selected and used. For example, pearl luster (pearl) composed of metal pigments such as aluminum and brass, and scaly foil pieces such as titanium dioxide-coated mica and basic lead carbonate. ) Bright pigments such as pigments; titanium white, antimony white, white lead, iron black, yellow lead, titanium yellow, vermilion, cadmium red, ultramarine and cobalt blue inorganic pigments; benzidine yellow, isoindolinone yellow, polyazored, quinacridone Organic pigments such as red, induslen blue, phthalocyanine blue, disazo yellow and insoluble azo (red) can be used. These colorants can be used alone or in combination of two or more. Among these, it is preferable to use a bright pigment as a colorant from the viewpoint of making the design more three-dimensionally superior. That is, the design layer a is preferably a brilliant ink layer.

The average particle size of the brilliant pigment is not particularly limited as long as it is smaller than the depth of the recess as described above, but is preferably 1 to 20 μm, more preferably 3 to 15 μm.
Here, the average particle size is a volume-based average particle size (μm) measured using a laser diffraction / scattering type particle size distribution measuring device.
The content of the brilliant pigment is preferably 1 to 800 parts by mass, more preferably 3 to 500 parts by mass with respect to 100 parts by mass of the binder resin. If it is 1 part by mass or more, sufficient metallic luster can be obtained and the three-dimensional design can be enhanced. If it is 800 parts by mass or less, the binding property with the binder resin is guaranteed and the transferability is ensured.

<Additive>
Further, to the above-mentioned paint, a plasticizer, a dispersant, a surfactant, an antistatic agent, a viscosity modifier, a defoaming agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a matting agent, a slip agent and the like are added. The agent may be contained. A matting agent and a slip agent are preferable from the viewpoint of design.

Specific examples of the matting agent include inorganic fillers such as silica, clay, heavy calcium carbonate, light calcium carbonate, precipitated barium sulfate, calcium silicate, synthetic silicate, and fine powder of silicic acid, and acrylic resins. Examples thereof include organic fillers such as urethane resin, nylon resin, polypropylene resin, and urea-based resin, and these can be used alone or in combination of two or more. For example, by containing silica having a high oil absorption amount, the design layer a expresses a gloss mat design in which the region where the design layer a is formed is low-gloss and the region where the design layer a is not formed is high-gloss. Can give depth to the design. The oil absorption amount of silica contained in the design layer a is preferably 180 to 400 mL / 100 g, and more preferably 230 to 300 mL / 100 g.
Specific examples of the slip agent include aluminum stearate, calcium stearate, silicone, polyethylene wax and the like, and these can be used alone or in combination of two or more. Since the design layer a contains a slip agent, even if a top coat is applied on the design layer after transfer, the three-dimensional design property can be maintained due to the repelling effect.

<solvent>
Further, the paint may contain a solvent for adjusting the viscosity and the like.
The solvent is not particularly limited, and is not particularly limited, and is limited to aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, alcohols, polyhydric alcohols, ketones, ethers, esters, nitrohydrocarbons, and nitriles. Classes, amines, other acetals, acids, furans and the like. These solvents can be used alone or in combination of two or more.

(Design layer b)
The design layer may be composed of a layer including the design layer a and the design layer b. When the hydraulic transfer film has the design layer b, it is preferable to have the water-soluble film, the design layer a, and the design layer b in this order.
The design layer b is not particularly limited as long as it is not the same as the design layer a, and may be a layer formed by using a paint different from the design layer a. The "different paint" includes, for example, colored inks containing different colorants, as well as colored inks containing the same colorant but having different contents.
As the paint of the design layer b, the binder resin, the colorant and the like exemplified in the above-mentioned design layer a can be used. The content of the colorant is not particularly limited as long as it does not impair the coatability. Further, the design layer b may be either a solid printing layer or a pattern layer, or may be composed of one layer or two or more layers of the same type or different types.
When the design layer b has a pattern layer, the pattern may be appropriately selected according to the combination with the recess formed on the water-soluble film.

When the design layer is composed of the design layer a and the design layer b, schematic views (D) to (F) of FIGS. 3 are shown as an example of the aspect of the hydraulic transfer film of the present invention.
In the aspect shown in FIG. 3D, both the design layer a and the design layer b constituting the design layer 11 are formed in the recesses. For example, when the design layer a is a brilliant ink layer and the design layer b is a colored solid printing layer other than the brilliant ink layer, the brilliant design and the colored color are combined, and the design layer after transfer is partially. Because it is formed in, the three-dimensional design can be made more prominent.

The design layer b may be formed on the entire surface of the water-soluble film having the design layer a without being formed in the recesses, as shown in the aspect shown in FIG. 3 (E). Further, the design layer b may be formed on the entire surface having the recess on the design layer a and the design layer a of the water-soluble film, as shown in FIG. 3 (F). According to the embodiments shown in FIGS. 3 (E) and 3 (F), the surface of the decorative molded product after transfer has different design properties as shown in the schematic views of FIGS. 4 (H) and (I). Since the design layer a and the design layer b are formed, it is possible to enhance the three-dimensional design property of the design layer a which becomes a convex portion after transfer.
Therefore, if the non-formed portion of the design layer a is present on the surface of the water-soluble film having the design layer, the design layer b is partially on the surface of the water-soluble film having the design layer as described in (D) above. It may be formed, or may be formed on the entire surface of the water-soluble film having the design layer as described in (E) and (F) above.

Further, the design layer b is preferably formed on at least a part of the non-formed portion of the design layer a on the surface of the water-soluble film having the design layer. By forming the design layer b in this way, the design layer b can be easily visually recognized through the non-formed portion of the design layer a, and an excellent design by the combination of the design layer a and the design layer b can be expressed. Can be done.

(Thickness of design layer)
When the design layer is composed of only the design layer a, the thickness of the design layer can be 5 to 100 μm, which is about the same as the depth of the recess described later. Further, when the design layer is composed of the design layer a and the design layer b, the design layer having a thickness thicker than the depth of the recess is formed by the embodiment shown in FIGS. 3 (E) and 3 (F) above. It becomes possible.
From the viewpoint of designability and shapeability, the thickness of the design layer in the hydraulic transfer film is preferably 5 to 110 μm at the maximum including the recesses, and more preferably 10 to 100 μm.

[Water-soluble film]
(Depth of recess)
A recess is formed on the surface of the water-soluble film having the design layer. From the viewpoint of sterically improving the design, the average depth of the recesses is preferably 5 to 100 μm, more preferably 10 to 70 μm, and even more preferably 20 to 60 μm. If it is 5 μm or more, a three-dimensional design can be exhibited. When it is 100 μm or less, the water-soluble film is not damaged and the shapeability is good. By adjusting the depth of the recess, it is possible to give a good sense of depth to the three-dimensional design.

Further, the width of the frontage of the recess cannot be unconditionally specified because it differs depending on the pattern of the recess, but the average value is usually about 30 to 1000 μm.
Here, the depth of the recess means the vertical distance h from the valley bottom of the recess 12 to the surface of the water-soluble film (convex peak 13) as shown in FIG. The width of the frontage of the recess 12 is indicated by W in FIG.
Since the water-soluble film in the present invention has elasticity, it is possible to make the depth of the recess deeper than the thickness of the water-soluble film, as shown in the schematic diagram of FIG. 1 (C). Is.

(Pattern of recess)
The patterns formed in the entire recess include a perforated pattern, a wood grain conduit pattern, a wood grain annual ring pattern, a sand grain pattern, a stone grain pattern, a metal crystal surface pattern, a cloth grain pattern, a satin finish pattern, a skin squeezing pattern, and a matte surface pattern. Hairline patterns, spin-like patterns, characters, symbols, geometric diagrams and the like can be mentioned, and among them, a perimeter pattern and a hairline pattern are preferable from the viewpoint of wiping processing.

(Water-soluble film)
The water-soluble film is not particularly limited as long as it is water-soluble or has water swelling property, and can be appropriately selected and used from the films generally used as a conventional hydraulic transfer film.
Examples of the resin constituting the water-soluble film include polyvinyl alcohol, dextrin, gelatin, sardine, casein, cellac, gum arabic, starch, protein, polyacrylic acid amide, sodium polyacrylate, polyvinyl methyl ether, methyl vinyl ether and anhydrous maleine. Examples thereof include copolymers with acids, copolymers of vinyl acetate and itaconic acid, and various water-soluble resins such as polyvinylpyrrolidone, acetyl cellulose, acetylbutyl cellulose, carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, and sodium alginate.
These resins can 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.

Of these, polyvinyl alcohol (PVA) film is particularly preferable because it has good film-forming stability, stable swellability and solubility in water, and versatility. The polyvinyl alcohol film may contain additives such as starch and rubber in addition to PVA.
The polyvinyl alcohol film is necessary for forming a design layer for transfer on a water-soluble film by changing the degree of polymerization and saponification of polyvinyl alcohol, the blending amount of additives such as starch and rubber, and the like. The mechanical strength, moisture resistance during handling, the rate of softening by water absorption after floating on the water surface, the time required for spreading or diffusion in water, the ease of deformation in the transfer process, etc. can be appropriately adjusted. ..

Suitable as a water-soluble film made of a polyvinyl alcohol film is as described in Japanese Patent Application Laid-Open No. 54-92406, for example, 80% by mass of PVA resin, 15% by mass of polymer water-soluble resin, and the like. It is preferably composed of a mixed composition of 5% by mass of starch and having an equilibrium water content of about 3%.
Although the polyvinyl alcohol film is water-soluble, it is preferable that the polyvinyl alcohol 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 design 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 is preferably 10 to 100 μm, more preferably 20 to 60 μm, still more preferably 30 to 50 μm. When it is 10 μm or more, the uniformity of the film is good and the production stability is high. When it is 100 μm or less, the solubility in water is appropriate and the printability of the design layer is excellent.

The water-soluble film may be used by laminating it with a water-permeable base material such as paper, non-woven fabric, or cloth (hereinafter referred to as "water-permeable base material"). Is configured to separate the water-permeable base material from the water-soluble film before floating the laminated sheet on the water surface, or to separate the water-permeable base material by the action of water after floating on the water surface. Is preferable.

[Manufacturing method of hydraulic transfer film]
The method for producing a hydraulic transfer film of the present invention is a step of forming a recess on at least one surface of a water-soluble film, applying a paint to the surface on which the recess is formed, and then wiping the recess to form a design layer a in the recess. Has a step of forming.
(Recess forming process)
In the step of forming the recesses on at least one surface of the water-soluble film, the recesses can be formed by embossing by heating and pressurizing using an embossing plate or an embossing roll having a desired depth of the recesses.
In the embossing by heating and pressurizing, the surface of the water-soluble film is usually heated at about 80 to 180 ° C., and the embossed plate is usually pressed at about 5 to 50 kg / cm ² to shape the uneven shape of the embossed plate. , Can be cooled and fixed. Further, a known single-wafer type or rotary type embossing machine can be used.

(Design layer a forming process)
The step of applying the paint to the surface on which the recess is formed and then performing the wiping treatment to form the design layer a in the recess is, for example, after coating the surface of the water-soluble film including the recess with a roll coat or a knife coat or the like. , It can be performed by a wiping process of scraping off the paint coated on the convex portion using a doctor blade or the like. The wiping process may be repeated a plurality of times, and if necessary, a wiping cloth may be used to further remove the paint remaining on the convex portion. Further, the thickness of the doctor blade and the angle at which it is used may be appropriately adjusted.
By the above step, the concave portion of the water-soluble film can be filled with the paint to form the design layer a, and the non-formed portion of the design layer a can be formed in the whole or a part of the convex portion.

The viscosity of the paint used for forming the design layer a is usually about 10 to 2000 cpoise, and is preferably 50 to 1000 cpoise from the viewpoint of wiping treatment and filling the recesses with the paint. The viscosity can be measured using a CS100 rheometer manufactured by CarryMed in the range of a measurement temperature of 20 ° C. and a measurement shear rate of 0.01 to 200 / sec.

(Design layer b forming process)
Further, when the design layer has the design layer b as a constituent layer, the step of forming the design layer b may be performed after the above-mentioned step of forming the design layer a.
When the design layer b is a solid printing layer, the solid printing layer can be formed by a known method such as a gravure printing method. When the design layer b is a pattern layer, the pattern layer is formed by a known method such as inkjet printing, intaglio printing method, lithographic printing method, letterpress printing method, screen printing method, brush coating, spatula coating, and spray coating. be able to.

[Manufacturing method of decorative molded products]
Using the hydraulic transfer film of the present invention, a decorative molded product can be produced by the following steps (a) to (d).
Step (a): A step of suspending the hydraulic transfer film 1 on the water surface so that the water-soluble film 10 side faces the water surface side.
Step (b): A step of applying the activator composition to the design layer 11 side of the hydraulic transfer film 1.
Step (c): A step of pressing the transferred body onto the hydraulic transfer film 1 that has undergone the steps (a) and (b), and bringing the design layer 11 into close contact with the transferred surface of the transferred body by hydraulic pressure.
Step (d): A film removing step of removing the water-soluble film 10 from the surface to be transferred of the transferred body.
Further, the following step (e) may be provided following the above step (d).
Step (e): A step of forming a top coat layer on the transfer surface of the transfer target.

<Step (a)>
Step (a) can be performed before or after step (b). The hydraulic transfer film 1 is suspended on the water surface so that the water-soluble film 10 side faces the water surface side. In order to suspend the hydraulic transfer film 1 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 1 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 design layer 11. By applying the activator composition in this step, at least a part of the design layer 11 is dissolved or swollen and softened (activated), and it becomes easy to adhere to the transferred body.

(Activator composition)
The activator composition is not particularly limited as long as it is a composition having a function of activating the design layer 11 and transferring it to the transferred surface of the transferred body, and each layer is transferred to the transferred surface of the transferred body. It is preferable that it has a property that it does not evaporate until it is allowed to evaporate. 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 phthalate, dibutyl phthalate, dimethyl phthalate, dioctyl phthalate, and diisooctyl phthalate. Be done.
Preferred examples of the 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, isoamyl cellosolve and the like.
The resin includes 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. Heat-curable resins such as resins, alkyd resins, and polyurethane resins are preferably mentioned, and among them, thermo-curable resins are preferable.
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)>
The step (c) is a step of pressing the transferred body onto the hydraulic transfer film 1 that has undergone the steps (a) and (b), and bringing the design layer 11 into close contact with the transferred surface of the transferred body by hydraulic pressure.
The water for floating the hydraulic transfer film 1 and applying the hydraulic pressure is preferably adjusted to an appropriate water temperature according to the type of the water-soluble film 10 of the hydraulic transfer film 1, preferably about 25 to 50 ° C. More preferably, it is 25 to 35 ° C.
The transfer time between the hydraulic transfer film 1 of the present invention and the transferred body is preferably about 20 to 120 seconds, more preferably about 30 to 60 seconds.

(Transfered body)
Examples of the transferred material include polystyrene resin, acrylonitrile-butadiene-styrene copolymer (ABS resin), polycarbonate resin, melamine resin, phenol resin, urea resin, fiber resin, polyethylene, polypropylene and other resins, or these. In addition to the mixed resin, a structure made of a metal such as iron, aluminum and copper, ceramics such as ceramics, glass and amber, and a material such as wood can be used.
Further, the shape of the surface to be transferred may be a two-dimensional shape which is a planar shape, or a three-dimensional shape such as an uneven shape or a curved surface shape. Of these, resin structures are usually often used. This resin structure has a mold release agent attached to it during molding, and dust, oils, etc. may also adhere to it. 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 keep the surface clean.

In the step (c), the activator composition applied to the design layer 11 side is in contact with the transferred body, and the surface of the transferred body is dissolved to bring the hydraulic transfer film 1 of the present invention into close contact with the transferred body. The sex can be further improved.

<Membrane removal step (d)>
The film removal step (d) is performed after the step (c) and is a step of removing the water-soluble film 10 from the surface to be transferred of the transferred body.
The water-soluble film 10 adhering to the surface to be transferred can be removed by, for example, shower washing with water. The conditions for shower washing vary depending on the material forming the water-soluble film 10, 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), if the transferred body is sufficiently dried to evaporate the water content, a three-dimensionally excellent design pattern of the design layer transferred to the transferred surface of the transferred body is imparted. A decorative molded product can be obtained.

<Step (e)>
The step (e) is a step of forming a top coat layer on the surface to be transferred of the transferred body, if necessary.
In the step (e), the design layer transferred to the surface to be transferred in the step (d) is coated as necessary for improving the surface strength, protecting the surface, adjusting the surface gloss, and the like. Apply to form a transparent or translucent topcoat layer. Examples of the material forming the top coat layer include a thermoplastic resin, a thermosetting resin, an ionizing radiation curable resin (ultraviolet curable resin, an electron beam curable resin), and specifically, a urethane resin and an epoxy resin. , Acrylic resin, fluororesin, silicon resin and the like are used. The top coat layer 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 not particularly limited, but is preferably 1 to 25 μm, and more preferably 1 to 10 μm.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

[Example 1]
(1) Manufacture of hydraulic transfer film Polyvinyl alcohol film (thickness 40 μm) Using an embossed plate with a hairline pattern on one side, heating and heating under the conditions of a sheet temperature of 120 to 160 ° C and a pressure of 10 to 40 kg / cm ² . Pressurization was performed and embossing was performed to form a recess. The depth of the recesses formed in the film was 50 μm on average, and the width of the frontage was 200 μm on average.
A colored ink (viscosity 100 cpoise) having the following composition is applied to the surface of the film on which the concave portion is formed by a roll coat, the concave portion of the film is filled with the colored ink, and the film is 90 ° to the film using a doctor blade having a thickness of about 3 mm. The colored ink adhering to the convex portion at an angle was removed by a wiping treatment.
A bright ink layer (maximum thickness of 15 μm) is formed in the concave portion of the film by filling the concave portion of the film with colored ink, and the convex portion of the film is used as a non-forming portion of the bright ink layer by wiping treatment. The hydraulic transfer film shown in the schematic diagram of FIG. 1 (B) was manufactured.
In the manufactured hydraulic transfer film, the area ratio on the plane of the surface of the polyvinyl alcohol film having the glitter ink layer [the area where the glitter ink layer is formed] / [the area where the glitter ink layer is not formed] is 2/1. there were.
<Colored ink composition>
・ Binder resin: 100 parts by mass of a mixture of vitrified cotton and alkyd resin (5: 2) ・ Glittering pigment: 20 parts by mass of aluminum flakes (average particle size 10 μm) ・ Solvent: Mixed solvent of ethyl acetate, butyl acetate and isopropyl alcohol 700 Mass part

(2) Manufacture of decorative molded product 10 g / m ² of the activator composition having the following composition is applied to the surface of the hydraulic transfer film produced as described above having the design layer (brilliant ink layer) to make it water-soluble. After floating on the water surface so that the film side faces the water surface side, the transferred object is pressed onto the hydraulic transfer film, and a transfer step is performed in which the design layer is brought into close contact with the transferred surface of the transferred object by water pressure, and the transfer is performed. A demembrane step was performed to remove the water-soluble film from the surface to be transferred of the body. Further, a two-component curable urethane resin was spray-coated on the surface to be transferred to form a top coat layer having a thickness of 10 μm.
(Composition of activator composition)
・ 6 parts by mass of phthalic acid-based alkyd resin ・ 2 parts by mass of microsilica (pigment) ・ 17 parts by mass of dibutyl phthalate ・ 60 parts by mass of solvent (butyl carbitol acetate) ・ 15 parts by mass of solvent (butyl cellosolve) (3) Design evaluation Even if the top coat layer is formed, the obtained decorative molded product can be recognized as having a convex shape of a metallic hairline pattern on the surface of the decorative molded product, and has a three-dimensional design. A decorative molded product having excellent properties was obtained.

[Example 2]
(1) Manufacture of hydraulic transfer film and decorative molded product The same procedure as in Example 1 was performed except that the colored ink having the following composition was used. The hydraulic transfer film and decorative molded product shown in the schematic diagram of FIG. 1 (B). Manufactured.
<Colored ink composition>
-Binder resin: A mixture of acrylic polyol resin (weight average molecular weight: 30,000, hydroxyl value: 80 mgKOH / g) and vinyl chloride-vinyl acetate copolymer (4: 1) 100 parts by mass-Glowing pigment: Aluminum flakes ( Average particle size 10 μm) 100 parts by mass ・ Solvent: 700 parts by mass of mixed solvent of ethyl acetate, butyl acetate and isopropyl alcohol (2) Design evaluation The obtained decorative molded product is added even if a top coat layer is formed. It can be recognized that the surface of the decorative molded product has a convex shape of a metallic hairline pattern, and the convex shape is equivalent to the shape of the glittering ink layer (concave shape) in the hydraulic transfer film. A decorative molded product having a more three-dimensional design than that of Example 1 was obtained.

[Example 3]
(1) Manufacture of Hydraulic Transfer Film and Decorative Molded Product After the wiping treatment of Example 1, a colored ink having the following composition is applied to the entire surface of the polyvinyl alcohol film on the side where the glittering ink layer is formed by a gravure printing method. In the same manner as in Example 1 except that the solid printing layer was formed, the hydraulic transfer film (maximum total thickness of the design layer is 51 μm) and the decorative molded product shown in the schematic diagram of FIG. 3 (F) were used. Manufactured.
<Colored ink composition>
-Binder resin: 100 parts by mass of a mixture of vitrified cotton and alkyd resin (5: 2) -Colorant: 50 parts by mass of carbon black, quinacridone, isoindolinone-Solvent: 1000 parts by mass of mixed solvent of ethyl acetate, butyl acetate and isopropyl alcohol Part (2) Evaluation of design It should be recognized that the obtained decorative molded product has a convex shape with a metallic hairline pattern on the surface of the decorative molded product even if the top coat layer is formed. A decorative molded product with excellent three-dimensional design was obtained. Further, the obtained decorative molded product had excellent designability due to the combination with the solid printing layer visually recognized in the gap of the hairline pattern.

According to the hydraulic transfer film of the present invention, a design layer having excellent three-dimensional design such as an uneven shape can be formed on the surface of a decorative molded product. Therefore, the hydraulic transfer film of the present invention is used for automobile interior products and home appliances. Suitable for decoration of products or OA equipment.

1. 1. Hydraulic transfer film of the present invention 2. Conventional hydraulic transfer film 3. Decorative molded products 10. Water-soluble film 11. Design layer 12. Recess 13. Convex mountain peak 30. Transferred body a. Design layer a
b. Design layer b

Claims (9)

A hydraulic transfer film having a design layer on a water-soluble film, in which recesses are formed on the surface of the water-soluble film having a design layer, and the design layer a constituting the design layer is formed in all the recesses. A hydraulic transfer film having a non-formed portion of the design layer a on the surface of the water-soluble film having the design layer. The hydraulic transfer film according to claim 1, wherein the depth of the recess is 5 to 100 μm. The hydraulic transfer film according to claim 1 or 2, wherein the design layer a contains a colorant having an average particle size smaller than the depth of the recess. The hydraulic transfer film according to any one of claims 1 to 3, wherein the design layer a is a layer formed of at least one of a resin composition containing an acrylic polyol resin and a cured product thereof. The hydraulic transfer film according to any one of claims 1 to 4, wherein the design layer a is a brilliant ink layer. Any of claims 1 to 5, wherein the design layer is composed of a layer including the design layer a and the design layer b, and has the water-soluble film, the design layer a, and the design layer b in this order. The hydraulic transfer film described in. The hydraulic transfer film according to claim 6, wherein the design layer b is provided in at least a part of the non-formed portion of the design layer a. The hydraulic transfer film according to any one of claims 1 to 7, which has a convex peak between the concave portions, and all the convex peaks are non-formed portions of the design layer a. Production of a hydraulic transfer film having a step of forming a recess on at least one surface of a water-soluble film and a step of applying a paint to the surface on which the recess is formed and then performing a wiping treatment to form a design layer a in the recess. Method.

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