JP2017065166A - Water pressure transfer film and decorative molding using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water pressure transfer film which is excellent in transfer working property to a molding, and can impart excellent gloss-matte design to a decorative molding.SOLUTION: There is provided a water pressure transfer film which has at least a water-soluble film, a partially provided design layer and a primer layer in this order, where the design layer contains a matting agent, the primer layer is formed from a resin composition containing acrylic polymer polyol, and the primer layer is partially provided.SELECTED DRAWING: None

Description

  The present invention relates to a hydraulic transfer film and a decorative molded product using the same.

  For building materials, automobile interior parts, home appliances, office automation equipment, etc., molded products having a surface decorated with wood grain or metallic tone are used. Many of these molded products have a complicated three-dimensional shape, and conventionally, a method of simply applying a highly designed decoration to a molded product having the complicated shape has been studied.

  As such a decoration method, a water pressure transfer method using water pressure is known. In the hydraulic transfer method, a transfer film in which a desired decorative layer is printed on a water-soluble or water-swellable water-soluble film is prepared, and an activator composition composed of an organic solvent is applied to the decorative layer of the transfer film. Swell and stick the decorative layer (this is called activation). Before or after that, the transfer film is floated on the water surface with the decorative layer (printing layer) surface for transfer as the upper surface, and then the article to be transferred is pressed onto the transfer film by water pressure. After the transfer film is brought into close contact with the transfer surface of the transfer object to be decorated, the water-soluble film is removed to transfer the decoration layer.

  Such a water pressure transfer method is an excellent curved surface decoration method in terms of design characteristics such as transfer processing to a three-dimensional surface, "depth" such as a clear paint feeling, and high-quality pattern expression. It has been known. In recent years, an attempt has been made to impart a design that exhibits an excellent three-dimensional effect to a resin molded product using this hydraulic transfer method.

  By the way, for example, when expressing a natural object such as wood grain by printing, it is difficult to reproduce the gloss of the real object by a method using normal ink. For this reason, a technique for expressing a design with a high texture (closer to a natural object) by providing a layer containing a matting agent in synchronization with the pattern of printing is known. For example, in the case of wood grain, a technique for expressing a design with a high texture by providing a low gloss portion at a position corresponding to the pattern of the conduit portion is known.

  In Patent Document 1, in a hydraulic transfer film having a design layer on a water-soluble film, a difference in gloss between 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. Discloses a method of expressing a strong contrast. However, in the technique disclosed in Patent Document 1, the acrylic polymer polyol used in the high gloss portion has a feature of high solvent resistance, and the high gloss portion is the entire surface above the low gloss portion. Therefore, it acts like a barrier layer for the active agent composition. For this reason, dissolution (activation) of the design layer or the like by the activator composition hardly occurs. For example, when transferring to a molded product having a complicated shape, the activator composition having high solubility (for example, patent document) 2), etc. may be necessary, and improvements are required so that processing can be performed under more general conditions.

JP 2013-240976 A Japanese Patent Laying-Open No. 2015-66786

  The present invention provides a hydraulic transfer film that is excellent in transfer processability for a molded product and that can impart an excellent gloss mat design to a decorative molded product, a manufacturing method thereof, and a decorative molded product using the film. This is the issue.

  The inventors of the present invention have made extensive studies to solve the above problems. As a result, in the hydraulic transfer film having at least a water-soluble film, a partially provided design layer, and a primer layer in this order, the design layer includes a matting agent, and the primer layer is an acrylic polymer. It has been found that the transfer processability of a molded product is improved by being formed of a resin composition containing a polyol and further providing the primer layer partially. Furthermore, the present inventors surprisingly have an excellent gloss mat design for a decorative molded product by partially forming a primer layer formed of a resin composition containing an acrylic polymer polyol. I found out that it can be granted. That is, this invention provides the following hydraulic transfer film, its manufacturing method, and a decorative molded product using this film.

Item 1. At least a water-soluble film, a partially provided design layer, and a hydraulic transfer film having a primer layer in this order,
The design layer includes a matting agent,
The primer layer is formed of a resin composition containing an acrylic polymer polyol,
The primer layer is a hydraulic transfer film partially provided.
Item 2. Item 2. The hydraulic transfer film according to Item 1, wherein the resin composition forming the primer layer further contains a urethane resin.
Item 3. Item 3. The hydraulic transfer film according to Item 1 or 2, wherein a portion where the primer layer is formed and a portion where the primer layer is not formed are formed in a pattern on the design layer.
Item 4. Item 4. The hydraulic transfer film according to any one of Items 1 to 3, further comprising a pattern layer on the opposite side of the primer layer from the water-soluble film.
Item 5. Item 5. The hydraulic transfer film according to Item 4, wherein the pattern layer forms a wood grain pattern, and the design layer forms a conduit portion of the wood grain pattern.
Item 6. The manufacturing method of the hydraulic transfer film which has the following processes (A) and (B) in order.
Step (A) Step of partially laminating a design layer containing a matting agent on the surface of a water-soluble film Partially forming a primer layer formed from a resin composition containing an acrylic polymer polyol on the design layer 6. Process for laminating The manufacturing method of the decorative molded product which has the following process (a)-(d) in order.
Step (a) The hydraulic transfer film according to any one of Items 1 to 6 is floated on the water surface so that the water-soluble film side faces downward and faces the water surface side. (B) On the primer layer side of the hydraulic transfer film An activator application step (c) for applying an activator composition. The primer layer is pressed by a hydraulic pressure by pressing a transfer material onto a hydraulic transfer film floating on the water surface after the steps (a) and (b). Step (d) of removing the water-soluble film that is in close contact with the transfer surface of the transfer body (d) At least a decorative molded product having a design layer partially provided on the surface of the molded product and a primer layer in this order,
The design layer includes a matting agent,
The primer layer is formed of a resin composition containing an acrylic polymer polyol,
The primer layer is a decorative molded product that is partially formed.

  According to the present invention, there is provided a hydraulic transfer film that is excellent in transfer processability for a molded product and can impart an excellent gloss mat design to a decorative molded product, a manufacturing method thereof, and a decorative molded product using the film. Can be provided.

It is a schematic sectional drawing which shows an example of a structure of the hydraulic transfer film of this invention. It is a schematic sectional drawing which shows an example of a structure of the hydraulic transfer film of this invention. It is a schematic sectional drawing which shows an example of the decorative molded product obtained by the manufacturing method of the decorative molded product of this invention.

  The hydraulic transfer film of the present invention includes at least a water-soluble film, a partially provided design layer, and a primer layer in this order. The design layer contains a matting agent, and a primer The layer is formed of a resin composition containing an acrylic polymer polyol, and the primer layer is partially formed. Hereinafter, the hydraulic transfer film of the present invention, the production method thereof, and the decorative molded product using the film will be described in detail.

[Hydraulic transfer film]
Hereinafter, the hydraulic transfer film of the present invention will be described with reference to FIGS. FIG.1 and FIG.2 is a schematic sectional drawing which shows an example of a structure of the hydraulic transfer film of this invention. As shown in FIGS. 1 and 2, the hydraulic transfer film 10 of the present invention includes at least a water-soluble film 1, a design layer 2, and a primer layer 3 in this order. The design layer 2 is partially provided on the surface of the water-soluble film 1.

  The design layer 2 contains a matting agent. The design layer 2 constitutes a relatively low-gloss portion on the surface of the water-soluble film 1 relative to the portion where the design layer 2 is not formed. That is, in the hydraulic transfer film 10 of the present invention, the design layer 2 is partially formed on the water-soluble film 1, and the hydraulic transfer film 10 is transferred to the molded product 5. A glossy part is formed.

  In the hydraulic transfer film of the present invention, the primer layer 3 formed of a resin composition containing an acrylic polymer polyol is partially formed. That is, in the hydraulic transfer film 10 of the present invention, the design layer 2 is partially formed on the water-soluble film 1, and the primer layer 3 is partially formed so as to cover the design layer 2. Therefore, the primer layer 3 is partially formed on the design layer 2, and is also partially formed on a portion where the design layer 2 is not formed (for example, on the water-soluble film 1). As will be described later, the partially formed design layer 2 normally forms a low-gloss portion corresponding to the handle, and therefore a portion where the design layer 2 is formed and a portion where the design layer 2 is not formed. However, it is formed in a size that can be visually confirmed. On the other hand, in the partially formed primer layer 3, the portion where the primer layer 3 is formed and the portion where the primer layer 3 is not formed are formed in such a fine size that it cannot be visually confirmed, for example. It is desirable to be a thing. For example, it is preferable that a plurality of portions 3 a where the primer layer is formed and portions 3 b where the primer layer is not formed are formed on the portion where the design layer 2 is formed.

  In the hydraulic transfer film 10 of the present invention, since the primer layer 3 is partially formed, the activator composition easily penetrates through the non-formation part 3b of the primer layer, so that the design layer 2 is easily dissolved and excellent. Transfer processability is demonstrated. In particular, in a conventional hydraulic transfer film, when an acrylic polymer polyol is used for the resin composition forming the primer layer 3, the primer layer is less likely to penetrate the activator composition, and the transfer processability tends to decrease. In the hydraulic transfer film 10 of the present invention, since the area where the primer layer 3 is formed is within the specific range, the activator composition easily penetrates into the primer layer 3 even when an acrylic polymer polyol is used. Excellent transfer processability is exhibited.

  Furthermore, in the hydraulic transfer film 10 of the present invention, the primer layer 3 formed of a resin composition containing an acrylic polymer polyol is partially formed, which is surprisingly superior to decorative molded products. A gloss mat design can be applied. The reason for this can be considered as follows. That is, in the hydraulic transfer film 10, the matting agent in the design layer 2 that constitutes a relatively low gloss portion relative to the surroundings is usually present in an aggregated state, but the activator composition is When applied to the hydraulic transfer film 10, the primer layer 3 is partially formed, so that the activator composition suitably penetrates the primer layer 3 and dissolves the design layer 2. It is thought that the matting agent is dispersed. Resin that forms the topcoat layer 6 by transferring the hydraulic transfer film 10 to a molded product in a state where the matting agent in the design layer 2 is dispersed, and further applying the topcoat layer 6 to the surface of the design layer 2 Easily penetrates into the matting agent, and the surface of the top coat layer 6 where the design layer 2 is present becomes rough. For this reason, since the mat feeling of the surface of the top coat layer 6 of the low gloss part of the decorative molded product is increased by using the hydraulic transfer film 10 of the present invention, it is considered that an excellent gloss mat design is exhibited. It is done.

  The hydraulic transfer film 10 of the present invention may further have a pattern layer 4 on the opposite side of the primer layer 3 from the water-soluble film 1 as necessary. Hereinafter, each layer constituting the hydraulic transfer film of the present invention will be described in detail.

(Water-soluble film)
The water-soluble film has a role of a substrate in the hydraulic transfer film of the present invention, and is removed when obtaining a decorative molded product after the hydraulic transfer. Any water-soluble film may be used as long as it has water-solubility or water-swellability, and can be appropriately selected from water-soluble films that have been conventionally used as a hydraulic transfer film.

  Examples of the resin constituting the water-soluble film include polyvinyl alcohol resin, dextrin, gelatin, glue, casein, shellac, gum arabic, starch, protein, polyacrylic amide, sodium polyacrylate, polyvinyl methyl ether, methyl vinyl ether and anhydrous Various water-soluble polymers such as copolymers with maleic acid, copolymers of vinyl acetate and itaconic acid, polyvinylpyrrolidone, acetylcellulose, acetylbutylcellulose, carboxymethylcellulose, methylcellulose, hydroxyethylcellulose, sodium alginate and the like can be mentioned. These resins may be used alone or in combination of two or more. In addition, rubber components, such as mannan, xanthan gum, and guar gum, may be added to the water-soluble film.

  Among the above water-soluble films, a polyvinyl alcohol (PVA) resin film is 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.

  Polyvinyl alcohol resin film is necessary when forming a printing layer for transfer on a water-soluble film by changing the degree of polymerization of polyvinyl alcohol, the degree of saponification, and the amount of additives such as starch and rubber. The mechanical strength, moisture resistance during handling, speed of softening due to 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. it can.

  A suitable water-soluble film comprising a polyvinyl alcohol resin film is as described in JP-A-54-92406, for example, 80% by mass of PVA resin, 15% by mass of polymer water-soluble resin. A composition having a mixed composition of 5% by mass of starch and having an equilibrium water content of about 3% is preferable.

  Further, although the polyvinyl alcohol resin film is water-soluble, it is preferable that the film remains as a film while being swollen and softened in water at a stage before being dissolved in water. This is because, by performing the hydraulic transfer while the film is still alive, it is possible to prevent an excessive flow and deformation of the printing layer for transfer during the hydraulic transfer.

  As thickness of a water-soluble film, 10-100 micrometers is preferable. When it is 10 μm or more, the uniformity of the film is good and the production stability is high. On the other hand, when it is 100 μm or less, the solubility in water is moderate and the printability is excellent. From the above viewpoint, the thickness of the water-soluble film is more preferably in the range of 20 to 60 μm.

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

<Design layer>
The design layer includes a matting agent to form a low gloss portion. For example, as shown in FIGS. 1 and 2, in the hydraulic transfer film 10, the design layer 2 constituting the low gloss portion is partially formed, and the design layer 2 is formed on the surface of the water-soluble film 1. The part which has and the part which does not have the design layer 2 exist. Since the design layer 2 usually forms a low-gloss portion corresponding to the handle, the portion where the design layer 2 is formed and the portion where the design layer 2 is not formed are formed in a size that can be visually confirmed. ing. In the case where a decorative molded product is manufactured using the hydraulic transfer film 10 of the present invention, in the upper part or the upper part of the low gloss part and the vicinity thereof (hereinafter sometimes simply referred to as “the upper part and the vicinity thereof”). A low gloss region is formed. That is, the low gloss portion has a function of expressing low gloss on a part of the decorative molded product (immediately above and near the low gloss portion).

  The gloss mat design of a decorative molded product obtained by using the hydraulic transfer film 10 of the present invention has a low gloss region in a low gloss portion and a high gloss region around it (directly above or directly above the high gloss portion and the vicinity thereof). This is due to the difference in glossiness between the two. The low-gloss area in the low-gloss part is visually recognized as a concave part, and the high-gloss area in the high-gloss part is recognized as a convex part. Be recognized.

  The design layer can be formed of a resin composition containing a matting agent. Examples of the binder resin contained in the design layer include thermoplastic resins. Specific examples include acrylic resins, polyester resins such as alkyds, unsaturated polyester resins, urethane resins (for example, polyester urethane resins), polycarbonate resins, and chlorides. Examples thereof include vinyl-vinyl acetate copolymers, polyvinyl acetals (butyral resins) such as polyvinyl butyral, and nitrocellulose resins such as nitrified cotton. If necessary, one or more of these resins may be mixed in order to adjust the degree of expression of the low gloss region and the contrast of the gloss difference between the low gloss region and the high gloss region. It is not a thing. As the binder resin, a resin similar to a resin that can be used for a primer layer described later (which constitutes a high gloss portion in a portion where the design layer is not formed), that is, an acrylic polymer polyol described later is a main component. Resin can also be used. However, the content of such a resin is preferably small. This is because a higher gloss difference can be generated by using different resin systems for the high gloss portion by the primer layer and the low gloss portion by the design layer. Specifically, the ratio of the resin used in the high gloss portion to the binder resin is 5% by mass or less, more preferably 3% by mass or less, and most preferably 1% by mass or less. If it is this grade, the effect of this invention will not be inhibited significantly.

  Moreover, in order to improve the physical properties of the binder resin, an ionizing radiation curable resin, a thermosetting resin, or a curing agent thereof (isocyanate or the like) is further added as necessary to the extent that the moldability is not impaired. Can do.

(Matting agent)
In the design layer, a known matting agent can be used. Specific examples of matting agents include inorganic fillers selected from silica, clay, heavy calcium carbonate, light calcium carbonate, precipitated barium sulfate, calcium silicate, synthetic silicate, and fine silicate powder, acrylic Examples include organic fillers or resin beads selected from resins, urethane resins, nylon resins, polypropylene resins, or urea resins, and any one of them may be used, or two or more may be used in combination.

  The volume average particle size of the matting agent is preferably 0.5 to 25 μm, more preferably 1 to 15 μm, and further preferably 3 to 10 μm. If the volume average particle size of the matting agent is 25 μm or less, the interfacial area increases, the stress during processing diffuses, and voids generated at the interface absorb energy or reduce the interparticle distance. Can cause plastic deformation between particles or voids, and can suppress whitening during stretching. Moreover, it is preferable from a viewpoint of a matting effect that the volume average particle diameter of a matting agent is 0.5 micrometer or more. The volume average particle size referred to here is the particle size at an integrated value of 50% in the particle size distribution determined by the laser diffraction-scattering method.

  The content of the matting agent in the design layer is preferably 0.5 to 50% by mass, and preferably 10 to 50% by mass, from the viewpoint of the balance between the gloss mat design expressed in the decorative molded product and the transfer processability. %, More preferably 25 to 50% by mass.

  The oil absorption measured in accordance with JIS K 5101-13-1: 2004 for matting agent is 230 mL / 100 g or more, preferably 230 to 400 mL / 100 g, more preferably 230 to 350 mL / 100 g. 230-300 mL / 100 g is more preferable. It is preferable to use a matting agent having an oil absorption amount of 230 mL / 100 g or more from the viewpoint of a matting effect, and using a matting agent having an oil absorption amount of 400 mL / 100 g or less can maintain a suitable thixotropy. From the viewpoint of not impairing the coating suitability at the time of forming.

  The matting agent may be surface-treated. The surface treatment method is not particularly limited, and may be a surface treatment with an organic material or a surface treatment with an inorganic material. Particularly preferred is a silane coupling treatment.

  The design layer can be formed by applying a coating solution prepared by dissolving the above-described binder resin and matting agent in a solvent by a known method, and drying and curing as necessary. About the thickness of a design layer, it is about 0.5-20 micrometers normally, Preferably, it is the range of 1-5 micrometers.

<Primer layer>
The primer layer is partially formed from above the design layer. That is, as shown in FIGS. 1 and 2, in the hydraulic transfer film 10 of the present invention, the design layer 2 is partially formed on the water-soluble film 1, and the primer layer covers the design layer 2. 3 is partially formed. In the partially formed primer layer 3, the portion where the primer layer 3 is formed and the portion where the primer layer 3 is not formed may be formed in such a fine size that it cannot be visually confirmed, for example. desirable. For example, it is preferable that a plurality of portions 3 a where the primer layer is formed and portions 3 b where the primer layer is not formed are formed on the portion where the design layer 2 is formed.

  In the hydraulic transfer film of the present invention, the primer layer only needs to be partially formed. As a ratio of the portion 3a where the primer layer is formed, the area of the surface of the water-soluble film 1 on the design layer 2 side is as follows. Of these, the range is preferably 60 to 95%, and more preferably 80 to 90%. That is, as shown in FIGS. 1 and 2, in the hydraulic transfer film 10 of the present invention, the total area of the primer layer forming portion 3 a and the primer layer non-forming portion 3 b is equal to the design layer 2 side of the water-soluble film 1. It is preferable that the ratio of the total area of the primer layer forming portion 3a is within these ranges out of the total area of 100%.

  The area ratio of the primer layer is a value calculated by calculating one cell area using the gravure printing plate cell calculation software and integrating the number of cells per unit area. The ratio of the total area of the recesses on the printing surface of the plate substantially matches the area ratio of the primer layer formed by printing. In addition, when the primer layer forming portion 3a and the primer layer non-forming portion 3b are formed in a certain pattern (for example, when the primer layer is viewed from the thickness direction, the primer having the same shape and size) For example, when the layer forming portions are arranged at equal intervals, the area ratio can be estimated from the cross section in the thickness direction of the hydraulic transfer film 10.

  In the hydraulic transfer film 10 of the present invention, the primer layer 3 is usually formed in the same manner as a portion positioned on the design layer 2 and a portion not positioned. Therefore, the ratio of the area of the portion where the primer layer 3 is formed in the portion positioned on the design layer 2 and the portion not positioned is usually the same.

  The primer layer is formed of a resin composition containing an acrylic polymer polyol. In addition to the acrylic polymer polyol, the resin contained in the resin composition further forming the primer layer is not particularly limited, and examples thereof include the thermoplastic resins described above. Examples of the thermoplastic resin include polyester resins such as acrylic resins and alkyds, unsaturated polyester resins, urethane resins (for example, polyester urethane resins), polycarbonate resins, vinyl chloride-vinyl acetate copolymers, and polyvinyl acetals such as polyvinyl butyral. (Butyral resin) and nitrocellulose resins such as nitrified cotton. These resins may be used alone or in combination of two or more. The acrylic polymer polyol forming the primer layer may be used in the form of a cured product reacted with a curing agent such as isocyanate. The cured product may be completely cured, but transfer processability is considered. Then, it may be in a semi-cured state. From the viewpoint of improving transfer processability, it is preferable that the acrylic polymer polyol is not cured, that is, used while maintaining the properties as a thermoplastic resin.

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

  The acrylic polymer polyol preferably has a hydroxyl value of 30 to 130 mgKOH / g, more preferably 50 to 130 mgKOH / g, and still more preferably 60 to 120 mgKOH / g. When the hydroxyl value of the acrylic polymer polyol is 30 mgKOH / g or more, it is preferable in that excessive stretching of the entire hydraulic transfer film can be suppressed, and when it is 130 mgKOH / g or less, the flexibility of the primer layer becomes good. No defects such as cracks occur. The hydroxyl value can be measured by an acetylation method using acetic anhydride.

(Isocyanate)
Isocyanate is a curing agent for acrylic polymer polyol, and by containing isocyanate, at least a part of the resin composition is brought into a cured state or a semi-cured state. The isocyanate may be a polyvalent isocyanate having two or more isocyanate groups in the molecule. For example, 2,4-tolylene diisocyanate (TDI), xylene diisocyanate (XDI), naphthalene diisocyanate, 4,4′- Aromatic isocyanates such as diphenylmethane diisocyanate or aliphatics such as 1,6-hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), methylene diisocyanate (MDI), hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate Polyisocyanates such as (alicyclic) isocyanates are used.

  If necessary, a blocked isocyanate in which the isocyanate group is protected by an appropriate blocking agent to be inactivated and the isocyanate group is regenerated by heating may be used. As the blocking agent, for example, a known blocking agent such as active methylene such as phenol, alcohol, dimethyl malonate, ethyl acetoacetate, or oxime may be used.

  By using blocked isocyanate, it is possible to impart high moldability to the design layer, and after molding into a desired shape, the molded product is heat-treated, the isocyanate group is regenerated, reacted with polyol, and cured, thereby the design layer. Alternatively, it can exhibit good adhesion with a pattern layer provided as necessary.

  The content of the acrylic polymer polyol in the primer layer is not particularly limited, but it is preferably 50 to 100% by mass of the resin component constituting the primer layer from the viewpoint of expressing a high three-dimensional effect on the decorative molded product. From the viewpoint of improving transfer processability, the content is more preferably 50 to 90% by mass.

  In addition to acrylic polymer polyol, the resin composition constituting the primer layer includes urethane resin, (meth) acrylic resin, (meth) acrylic / urethane copolymer resin, nitrocellulose-based resin such as nitrified cotton, and alkyd resin. It is preferable to contain a vinyl chloride-vinyl acetate copolymer, a polyester resin, a butyral resin, a chlorinated polypropylene, a chlorinated polyethylene, or the like. This is because the primer layer can be made flexible and the transfer processability during the production of a decorative molded product can be improved.

(Urethane resin)
As the urethane resin, select a non-cross-linked type, that is, a resin having a linear molecular structure instead of a three-dimensionally cross-linked three-dimensional molecular structure. It is preferable. As such a non-crosslinked urethane resin, as a polyol component, a polyol such as polyester polyol, polyether polyol, polycarbonate polyol, polycaprolactone polyol, polyethylene glycol, polypropylene glycol and the like is a non-crosslinked product obtained by reacting with isocyanate. A type urethane resin can be used, and those synthesized by a combination of a polyester polyol and an isocyanate such as hexamethylene diisocyanate are particularly preferred from the viewpoints of moldability, heat resistance, weather resistance, adhesion to a pattern layer, and the like. Usually, the number of hydroxyl groups in one molecule of polyol and the number of isocyanate groups in one molecule of isocyanate are two on average.

  Moreover, as a urethane resin, the urethane urea resin synthesize | combined from the combination of a polyol component, a polyamine component, and isocyanate is used preferably, and what was mentioned above can be used as a polyol component and isocyanate.

  The urethane resin preferably has a glass transition point of 100 ° C. or lower, and more preferably 20 to 100 ° C. When the glass transition point of the urethane resin is 100 ° C. or lower, the design layer is excellent in flexibility at room temperature, and when it is 20 ° C. or higher, the cohesive force is remarkably reduced by heating, or the primer layer dissolves in water during hydraulic transfer. This is preferable.

  The ratio between the acrylic polymer polyol in the resin composition constituting the primer layer (or the total amount of acrylic polymer polyol and isocyanate added as necessary) and the urethane resin is usually 99: 1 to 50: mass ratio. 50, preferably 95: 5 to 50:50, more preferably 90:10 to 60:40, and particularly preferably 80:20 to 68:32. In particular, when the isocyanate content is high, it is preferable from the viewpoint of transfer processability to increase the ratio of the urethane resin.

  The primer layer can be formed so as to have the above-mentioned area ratio by applying a coating solution obtained by dissolving the above resin in a solvent by a known method. On the design layer, it is preferable that the portion 3a where the primer layer is formed and the portion 3b where the primer layer is not formed are formed in a pattern. For example, when the primer layer 3 is viewed from the thickness direction, the primer layer forming portions 3a having the same shape and the same size are equally spaced (between adjacent primer layer forming portions 3a constitute the primer layer non-forming portion 3b). It is preferable that they are arranged. Since the primer layer forming portion 3a and the primer layer non-forming portion 3b are formed in such a constant pattern, activation by the activator composition can be performed uniformly.

  Although it does not restrict | limit especially as thickness of a primer layer, Preferably it is about 0.5-20 micrometers, More preferably, about 0.5-5 micrometers is mentioned. In addition, the thickness of a primer layer means the thickness of the part located on a design layer.

<Pattern layer>
The pattern layer is provided on the opposite side of the primer layer from the water-soluble film, if necessary, for the purpose of imparting decorativeness to the decorative molded product. The pattern layer is formed by printing various patterns using ink and a printing machine. The pattern formed by the pattern layer is not particularly limited. For example, a grain pattern imitating the surface of a rock such as a wood grain pattern, a marble pattern (for example, a travertine marble pattern), or a fabric pattern imitating a texture or cloth pattern Tiled patterns, brickwork patterns, etc., and patterns such as parquets, patchwork, etc. that combine these. These patterns can be formed by multicolor printing with normal yellow, red, blue and black process colors, or by multicolor printing with special colors prepared by preparing individual color plates constituting the pattern. It is formed. Moreover, the dark color part in a pattern layer will not be specifically limited if it is a color whose brightness is relatively lower than another part, However, It is especially preferable to set it as black.

  The pattern layer usually contains a binder resin and a colorant. Examples of the binder resin for the pattern layer include thermoplastic resins. Specific examples include acrylic resins, polyester resins such as alkyds, unsaturated polyester resins, urethane resins (for example, polyester urethane resins), polycarbonate resins, and vinyl chlorides. Examples thereof include vinyl acetate copolymers, polyvinyl acetals (butyral resins) such as polyvinyl butyral, and nitrocellulose resins such as nitrified cotton. Binder resin may be used individually by 1 type and may be used in combination of 2 or more types.

  Colorants include carbon black (black), iron black, titanium white, antimony white, yellow lead, titanium yellow, petal, cadmium red, ultramarine, cobalt blue and other inorganic pigments, quinacridone red, isoindolinone yellow, phthalocyanine Organic pigments or dyes such as blue, metal pigments made of scaly foil pieces such as aluminum and brass, pearlescent pigments made of scaly foil pieces such as titanium dioxide-coated mica and basic lead carbonate, and the like are used.

  In this invention, the design which has a higher three-dimensional effect can be expressed by synchronizing the position of the design layer which comprises a low gloss part, and the pattern of a design layer. For example, the decorative layered product has an excellent wood grain design because the pattern layer forms a wood grain pattern, and the low gloss part of the design layer forms a wood grain conduit part. Can be expressed.

[Method for producing hydraulic transfer film]
The hydraulic transfer film 10 of the present invention having at least a water-soluble film 1, a partially provided design layer 2, and a primer layer 3 in this order as shown in FIGS. Step (A) of partially laminating a design layer 2 containing a matting agent on the surface of the conductive film 1 and a primer layer 3 formed from above the design layer 2 by a resin composition containing an acrylic polymer polyol Can be manufactured by a manufacturing method including a step (B) of partially stacking layers.

  In the step (A), the design layer can be formed by a known printing method, for example, gravure printing, preferably using a resin composition that forms the design layer and a gravure plate material having a columnar recess cell shape. Can be formed by gravure offset printing.

  The primer layer in the step (B) can be formed by a known coating method or printing method using a resin composition containing an acrylic polymer polyol. Examples of the application method include gravure coating and reverse coating, and examples of the printing method include gravure printing.

  In addition, when manufacturing the hydraulic transfer film further provided with the pattern layer 4 as shown in FIG. 2, a step of laminating the pattern layer is performed after the step (B). The pattern layer 4 can be formed by laminating a known coating method or printing method or a resin film on the design layer. Examples of the application method include gravure coating and reverse coating, and examples of the printing method include gravure printing. The pattern layer 4 may be full-surface printing.

[Method of manufacturing decorative molded product]
Using the hydraulic transfer film of the present invention, a decorative molded product can be produced by the following steps (a) to (d). In addition, the decorative molded product 20 manufactured using the hydraulic transfer film 10 shown in FIG. 2 corresponds to FIG.

Step (a) Step of floating a water pressure transfer film on the water surface so that the water-soluble film side faces downward and the water surface side Step (c) The transferred object is pressed onto the hydraulic transfer film floating on the water surface after the steps (a) and (b), and the primer layer is brought into close contact with the transferred surface of the transferred object by water pressure. Process step (d) film removal step for removing the water-soluble film adhered to the transfer surface of the transfer object

Further, following the step (d), the following step (e) may be provided.
Step (e): A step of forming a topcoat layer on the transfer surface of the transfer object.

<Process (a)>
Step (a) can be performed before or after step (b). The hydraulic transfer film 10 is floated on the water surface such that the water-soluble film 1 side faces downward and faces the water surface. In order to float the water pressure transfer film 10 on the surface of the water, the printed sheets may be floated one by one, or water is allowed to flow in one direction, and the continuous water pressure transfer film 10 is continuously formed on the water surface. It may be supplied and floated.

<Step (b)>
Step (b) can be performed before or after step (a), and is a step of applying the activator composition to the primer layer side of the hydraulic transfer film. By applying the activator composition in this step, the primer layer side dissolves or swells and softens (activates), making it easy to adhere to the transfer target.

(Activator composition)
The activator composition applied to the primer layer side is not particularly limited as long as it is a composition having a function of activating the primer layer side layer and transferring it to the transfer surface of the transfer object. It is preferable that the material does not evaporate until each layer is transferred to the transfer surface. As such an activator composition, the composition containing ester, acetylene glycol, ethers, and resin is mentioned preferably, for example.

  Preferred examples of esters include ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, tert-butyl acetate, dibutyl oxalate, dibutyl phthalate, dimethyl phthalate, dioctyl phthalate, and diisooctyl phthalate. It is done. Preferred examples of acetylene glycols include methoxybutyl acetate, ethoxybutyl acetate, ethyl carbitol acetate, propyl carbitol acetate, and butyl carbitol acetate. Preferred examples of ethers include methyl cellosolve, butyl cellosolve, and isoamyl cellosolve.

  In addition, as resins, thermoplastic resins such as acrylate monomers alone or copolymers, polyamide resins, polyester resins, phenol resins, melamine resins, urea resins, epoxy resins, alkyd phthalate resins, diallyl phthalates Preferred examples include thermosetting resins such as resins, alkyd resins, and polyurethane resins, and among these, thermosetting resins are preferred.

  The content of each preferred composition of the activator composition used in the present invention is 5 to 40% by mass for esters, 40 to 80% by mass for acetylene glycols, 5 to 30% by mass for ethers, and 1 for resins. About 20% by mass.

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

<Step (c)>
In the step (c), the transferred body is pressed onto the hydraulic transfer film floating on the water surface after the steps (a) and (b), and the primer layer side is transferred to the transferred surface of the transferred body by the water pressure. It is the process of making it adhere. The water for applying the floating water pressure to the hydraulic transfer film should be adjusted to an appropriate water temperature according to the type of water-soluble film of the hydraulic transfer film, preferably about 25 to 50 ° C., more preferably 25. ~ 35 ° C.

  The transfer time between the hydraulic transfer film of the present invention and the transfer target is preferably about 20 to 120 seconds, more preferably about 30 to 60 seconds.

(Transfer material)
Examples of the material to be transferred include polystyrene resin, acrylonitrile-butadiene-styrene copolymer (ABS resin), polycarbonate resin, melamine resin, phenol resin, urea resin, fiber resin, polyethylene, polypropylene, and the like. In addition to the mixed resin, a structure made of a material such as a metal such as iron, aluminum, or copper, ceramics such as ceramics, glass, or wood, or wood can be used.

  In addition, the shape of the transfer surface may be a two-dimensional shape that is a planar shape, or may be a three-dimensional shape such as an uneven shape or a curved shape. Of these, resin structures are usually used frequently. This resin structure may have a release agent attached at the time of molding, and dust and fat may also adhere. In order to transfer each layer of the hydraulic transfer film with good adhesion, it is transferred in advance with a degreasing solution. It is preferable to clean the surface.

  In the step (c), the activator composition applied to the primer layer side is in contact with the member to be transferred and dissolves the surface of the member to be transferred, thereby improving the adhesion between the hydraulic transfer film of the present invention and the member to be transferred. It can be made even better.

<Film removal step (d)>
The film removal step (d) is a step that is performed after the step (c) and removes the water-soluble film adhered to the transferred surface of the transferred body. Removal of the water-soluble film 1 adhering to the transfer surface of the transfer object can be performed, for example, by shower cleaning using water. In addition, although the conditions of shower washing differ with materials etc. which form the water-soluble film 1, a water temperature of about 15 to 60 ° C. and a washing time of about 10 seconds to 5 minutes are usually preferable. And after a process (d), a to-be-transferred body is fully dried and a water | moisture content is evaporated.

  Through the above steps (a) to (d), a high three-dimensional appearance is expressed with respect to the resin molded product, and further, the decorative molded product of the present invention whose design can be changed depending on the angle to be observed is obtained.

<Process (e)>
Step (e) is a step of forming a topcoat layer as necessary on the transfer surface of the transfer object. When the step (e) is performed, in the step (e), the design layer is coated as necessary for the purpose of improving the surface strength, protecting the surface, adjusting the gloss of the surface, etc. A coat layer is formed.

  For example, a thermoplastic resin, a thermosetting resin, an ultraviolet curable resin, or the like is selected as a material for forming the topcoat layer. Specifically, a urethane resin, an epoxy resin, an acrylic resin, a fluorine resin, silicon System resin or the like is used. The top coat layer can be formed by a known coating method such as spray coating, electrostatic coating, brush coating, or dip coating, using a paint obtained by dissolving the above resin in a known organic solvent. Moreover, the thickness of the topcoat layer is preferably 1 to 40 μm, more preferably 10 to 30 μm.

[Decorative products]
As shown in FIG. 3, the decorative molded product 20 of the present invention includes at least a design layer 2 and a primer layer 3 that are partially provided on the surface of the molded product (transfer object 5). Have in order. In the decorative molded product 20, the design layer 2 constitutes a low gloss portion including a matting agent, and a primer layer is formed in the portion. In addition, as shown in FIG. 3, the decorative molded product 20 of the present invention has a pattern layer 4 between the primer layer 3 and the transfer target 5 when a hydraulic transfer film having the pattern layer 4 is used. When the above step (e) is performed, the top coat layer 6 is provided on the design layer 2. About the structure of each layer of a decorative molded product, it is as having demonstrated in the item of the above-mentioned [hydraulic transfer film] and [the manufacturing method of a decorative molded product].

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.

<Example 1-4 and Comparative Example 1>
As a water-soluble film, a polyvinyl alcohol (PVA) film (thickness 40 μm) is used, and the design layer (application amount 1 g / m ² , thickness 3 μm) is partially applied by gravure printing on one side using the following ink. Formed. At this time, the position where the design layer is formed is adjusted so that the synchronization between the design layer and the pattern layer is as follows, and the portion where the design layer is formed on the surface of the water-soluble film And formed. Next, gravure printing was carried out from above the design layer using the following inks so as to have the area ratios shown in Table 1 (the surface area of the water-soluble film on the design layer side was 100%). Thus, a primer layer (2 μm) was formed. Next, a pattern layer (3 μm) having a grain pattern is formed on the primer layer by gravure printing using the following ink containing nitrified cotton and alkyd resin in a mass ratio of 80:20, and is water-soluble. A hydraulic transfer film in which a film / design layer / primer layer / design layer was laminated was obtained. The wood grain pattern of the pattern layer is formed by using three types of ink, black ink, dark brown ink, and light brown ink, in this order, and printing the light brown ink on the entire surface with black ink and dark brown ink as a pattern. The conduit portion was expressed with black ink. In addition, the shape of the concave portion (portion where the ink is transferred) in the plate used for printing the primer layer is a substantially rhombus, and the printing shape of the primer layer by this plate is a shape in which a large number of the rhombus are arranged at equal intervals. . The ratio of the total area of the recesses on the printing surface of each plate substantially matched the area ratio of the primer layer described in Table 1.

(Ink for forming the design layer)
In Example 1, the design layer was formed using an ink containing nitrified cotton and alkyd resin in a mass ratio of 5: 2 and further containing silica (volume average particle size 5 μm) as a matting agent. The mass ratio of the total mass of nitrified cotton and alkyd resin to silica was 1: 1.

(Ink forming the primer layer)
Ink comprising a resin composition comprising an acrylic polymer polyol (weight average molecular weight 30,000, hydroxyl value 80 mg KOH / g) and urethane urea resin (glass transition point 40 ° C.) in a mass ratio of 8: 2.

(Ink forming the pattern layer)
Colored ink containing nitrified cotton and alkyd resin in a mass ratio of 80:20 and using a petrol and carbon black as a colorant at a predetermined blending ratio

(Synchronization of design layer and design layer)
In the design layer and the design layer, the low-gloss portion constituting the design layer was synchronized with the wood grain pattern conduit portion (dark color portion) constituting the design layer.

<Manufacture of decorative molded products>
An activator composition having the following composition is applied to the pattern layer of each hydraulic transfer film obtained above at 10 g / m ² , and the activator composition is made uniform with a smoothing roll. ), A transferred object (a cylindrical member having a diameter of 35 mm and a length of 250 mm is used as the transferred object) is pressed against a hydraulic transfer film floating on the water surface, and the pattern layer is transferred to the transferred object by water pressure. A step (c) for closely adhering to the surface to be transferred, a film removal step (d) by washing with water, and a step (e) for forming a topcoat layer having a thickness of 20 μm by spray coating a paint of a two-component curing type urethane resin. After that, a decorative molded product was obtained.

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

(Design evaluation)
The design of the surface of each decorative molded product obtained by manufacturing the above-described decorative molded product was visually evaluated. The evaluation criteria are as follows.
A: The difference in gloss between the conduit portion and other portions was extremely large, the conduit portion was clearly recognized as a concave portion, and the design properties based on the gloss matte effect were extremely high.
B: The difference in gloss between the conduit portion and other portions was large, the conduit portion was recognized as a recess, and the designability based on the gloss matte effect was sufficiently high.
C: There was a sufficient difference in gloss between the conduit portion and other portions, and the gloss matte effect was felt as a design.
D: The difference in gloss between the conduit portion and other portions was small, and the design due to the gloss matte effect was slightly weak.
E: There was almost no gloss difference between the conduit portion and other portions, and a gloss matte effect could not be obtained.

(Transfer processability evaluation)
In the production of the decorative molded product described above, the transfer processability (followability) of the hydraulic transfer film when the hydraulic transfer film was transferred was evaluated based on the following criteria by visual observation.
A: A decorative molded product was obtained that satisfactorily followed the transfer target and did not cause any cracks.
B: Although cracking occurred slightly, transfer processing could be performed with little influence on the design.
C: Although cracking was slightly conspicuous, transfer processing could be performed without significantly affecting the design properties.
D: The crack was conspicuous and the designability was somewhat impaired.
E: It became a decorative molded product with remarkable cracks. Alternatively, it could not be transferred to the transfer target.

DESCRIPTION OF SYMBOLS 1 Water-soluble film 2 Design layer 3 Primer layer 3a Primer layer formation part 3b Primer layer non-formation part 4 Picture layer 5 Transfer object 6 Topcoat layer 10 Hydraulic transfer film 20 Decorative molded product

Claims (8)

At least a water-soluble film, a partially provided design layer, and a hydraulic transfer film having a primer layer in this order,
The design layer includes a matting agent,
The primer layer is formed of a resin composition containing an acrylic polymer polyol,
The primer layer is a hydraulic transfer film partially provided.   The hydraulic transfer film according to claim 1, wherein the resin composition forming the primer layer further contains a urethane resin.   The hydraulic transfer film according to claim 1 or 2, wherein a portion where the primer layer is formed and a portion where the primer layer is not formed are formed in a pattern on the design layer.   The hydraulic transfer film according to claim 1, further comprising a pattern layer on the opposite side of the primer layer from the water-soluble film.   The hydraulic transfer film according to claim 4, wherein the pattern layer forms a wood grain pattern, and the design layer forms a conduit portion of the wood grain pattern. The manufacturing method of the hydraulic transfer film which has the following processes (A) and (B) in order.
Step (A) Step of partially laminating a design layer containing a matting agent on the surface of a water-soluble film Partially forming a primer layer formed from a resin composition containing an acrylic polymer polyol on the design layer Laminating process The manufacturing method of the decorative molded product which has the following process (a)-(d) in order.
Step (a) The step of floating the hydraulic transfer film according to any one of claims 1 to 6 on the water surface such that the water-soluble film side faces downward and faces the water surface side (b) The primer layer side of the hydraulic transfer film The activator application step (c) for applying the activator composition to (c) The primer is pressed by water pressure by pressing the transferred material onto the hydraulic transfer film floating on the water surface after the steps (a) and (b). Step (d) for removing the water-soluble film adhered to the transfer surface of the transfer body (d) At least a decorative molded product having a design layer partially provided on the surface of the molded product and a primer layer in this order,
The design layer includes a matting agent,
The primer layer is formed of a resin composition containing an acrylic polymer polyol,
The primer layer is a decorative molded product that is partially formed.