JP2012158181A - Active agent composition for hydraulic transfer film - Google Patents

Abstract

An activator composition for activating a printing layer of a hydraulic transfer film, corresponding to various application methods of the activator composition, and maintaining a good state of the printing layer of the hydraulic transfer film, To provide an activator composition for a hydraulic transfer film, in which a good transfer state can be obtained on a transfer medium, and further, the appearance of the transfer medium is improved.
An activator composition for activating a printing layer of a hydraulic transfer film comprising a base film and a printing layer, comprising at least a solvent, the solvent having a boiling point of 70 to 130 ° C. It consists essentially of a high-boiling solvent having a boiling point of 160 to 260 ° C., the low-boiling solvent is at least one selected from alcohols, esters and aliphatic hydrocarbons, and the high-boiling solvents are ethers, esters and ketones The activator composition for a hydraulic transfer film in which the mass ratio of the low boiling point solvent to the high boiling point solvent is in the range of 55:45 to 95: 5.
[Selection figure] None

Description

  The present invention relates to a hydraulic transfer film suitable for forming a transfer layer on the surface of a molded body having mainly three-dimensional surfaces and curved surfaces due to unevenness, and an activator composition for activating the print layer of the film by a spray coating method Related to things.

For automobile interior products, home appliances, OA equipment, etc., molded products having decorations such as wood grain or metallic tone (metallic luster) on the surface are used. Many of these molded articles have a complicated three-dimensional shape, and conventionally, methods for simply applying a highly designed decoration to a molded article having the complicated shape have been studied.
As such a decoration method, a water pressure transfer method using water pressure is known. In this hydraulic transfer method, a transfer film in which a desired decorative layer is printed on a water-soluble or water-swellable base film is prepared, and an activator composition comprising an organic solvent is applied to the decorative layer of the transfer film. Then, at least a part of the decorative layer is dissolved or swollen to be softened (activated). Before or after that, the transfer film is floated on the water surface with the transfer printing layer surface as the upper surface, and then the article to be transferred is pressed onto the transfer film, and the transfer film is transferred by water pressure. After the body is brought into close contact with the surface to be decorated, the base film is removed and the decoration layer is transferred (for example, see Patent Document 1).

By the way, as an activator composition, various things have been proposed so far. For example, an activator composition used in a hydraulic transfer system containing extender pigments such as precipitated barium carbonate (see Patent Document 2), A hydraulic transfer activator composition comprising a resin component comprising a short oil-based alkyd resin and cellulose acetobutyrate, a solvent component comprising butyl cellosolve and butyl carbitol acetate, a plasticizer component comprising dibutyl phthalate, and ultrafine silica (Patent Literature) 3) has been proposed.
The extender pigments and ultrafine silica used in the activator compositions disclosed in Patent Documents 2 and 3 can prevent ink displacement, and can impart extensibility that can follow the deformation of the transfer film accompanying pressing of the transfer target. However, when the activator is applied by spray coating, the extender pigment or fine particle silica closes the nozzle for injecting the activator composition, and the activator composition is not satisfactorily applied. Since the agent composition has too many resin components, the viscosity is high, and even if the air pressure is increased, it is difficult to form a clean mist, and stable spraying may not be possible.

  On the other hand, there is a specific activator having leveling properties, penetrability, curable resin layer dissolution swellability, and decorative layer dissolution swellability, and a method for producing a hydraulic transfer body using the activator (see Patent Document 4). It is disclosed. When this activator is applied by a spray coating method, it enables the production of a good hydraulic transfer body without color unevenness or pattern disturbance, but when applied by other methods such as a roll coating method. In this case, the decorative layer was not sufficiently swollen (not activated), and a good transfer state could not be obtained, so that the design of the hydraulic transfer member was impaired.

In recent years, in the hydraulic transfer system, various methods such as spray coating, roll coating, and gravure coating have been adopted as methods for applying the active agent composition. As described above, there are various active agent compositions. The problem of not being able to cope with the coating method, the activator composition should be prepared by selecting appropriate components each time depending on the type of hydraulic transfer film and the type of ink used in the printing layer However, the conventional activator composition has a problem that the function required for the activator composition cannot always be sufficiently exhibited. Furthermore, since it is necessary to use a large amount of the activator composition for sufficient activation of the decoration layer, etc., the design property (transparency) of the transferred material and the design reproducibility are not sufficient. There was a case.
Thus, further improvements have been desired for the active agent composition to accommodate a wide variety of situations.

JP 54-33115 A JP-A 63-197685 JP-A-8-238898 JP-A-2005-132014

  Under such circumstances, the present invention is an activator composition for activating a printing layer of a hydraulic transfer film, which corresponds to various application methods of the activator composition, and printing of the hydraulic transfer film. It is an object of the present invention to provide an activator composition for a hydraulic transfer film that keeps the state of the layer good, provides a good transfer state on the transfer target, and further improves the appearance of the transfer target.

As a result of intensive studies to achieve the above object, the present inventor has found that the above problem can be solved by mixing and using a specific low boiling point solvent and a high boiling point solvent. The present invention has been completed based on such findings.
That is, the present invention
(1) An activator composition for activating a printing layer of a hydraulic transfer film comprising a base film and a printing layer, comprising at least a solvent, the solvent having a boiling point of 70 to 130 ° C. and a boiling point It consists essentially of a high boiling point solvent at 160 to 260 ° C., the low boiling point solvent is at least one selected from alcohols, esters and aliphatic hydrocarbons, and the high boiling point solvent is from ethers, esters and ketones. An activator composition for a hydraulic transfer film, which is at least one selected, and the mass ratio of the low boiling point solvent to the high boiling point solvent is in the range of 55:45 to 95: 5;
(2) The activator composition for hydraulic transfer film according to (1), further comprising a plasticizer, wherein the plasticizer content is 35% by mass or less. (3) The plasticizer is a phthalate ester. , The activator composition for hydraulic transfer film according to (2), wherein the content is 5 to 35% by mass,
(4) The activator composition for a hydraulic transfer film according to any one of the above (1) to (3), wherein the low boiling point solvent contains at least one of ethyl acetate, butyl acetate and isobutyl acetate,
(5) The activator composition for a hydraulic transfer film according to any one of (1) to (4), which is used for activation by a spray coating method or a roll coating method,
(6) The activator composition for a hydraulic transfer film according to any one of the above (1) to (5), wherein the substrate film is a polyvinyl alcohol-based resin film, and (7) the solvent of the ink used for the printing layer. And at least one selected from ethyl acetate, propyl acetate, butyl acetate, cellosolve, cyclohexanone, ethyl alcohol, isopropyl alcohol, isobutyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, propylene glycol mono-butyl ether, and propylene glycol (1 ) To (6), an activator composition for hydraulic transfer film,
Is to provide.

  According to the present invention, it can be applied to various application methods of the activator composition, and the printing layer of the hydraulic transfer film can be kept in a good state, and a good transfer state can be obtained in the transferred body. It is possible to provide an activator composition for a hydraulic transfer film that has a good appearance.

It is a schematic sectional drawing which shows an example of a structure of a hydraulic transfer film. It is explanatory drawing which shows notionally 1 process at the time of manufacturing a molded article by the hydraulic transfer method.

The activator composition for a hydraulic transfer film of the present invention contains at least a solvent, which essentially consists of a low-boiling solvent having a boiling point of 70 to 130 ° C and a high-boiling solvent having a boiling point of 160 to 260 ° C. It is at least one selected from alcohols, esters and aliphatic hydrocarbons, the high boiling point solvent is at least one selected from ethers, esters and ketones, and a low boiling point solvent and a high boiling point solvent The mass ratio is in the range of 55:45 to 95: 5.
The solvent in the present invention consists essentially of these low-boiling solvent and high-boiling solvent, and other solvents are not contained in principle, but may be contained in a slight amount within a range not impairing the effects of the present invention. Good.

In order to apply the activator composition for the hydraulic transfer film to the transfer printing surface of the printed matter, a gravure offset coat, a gravure coat, a roll coat, a bar coat, a spray coat, or the like can be used. The time from when the activator composition is applied to when the printed matter is transferred to the transfer target is different.
The activator composition has a function of dissolving or swelling at least a part of the printing layer for transfer in the hydraulic transfer film to soften it (hereinafter sometimes referred to simply as activation). Takes some time.
On the other hand, it is important not to evaporate until the process of transferring the printing layer for transfer onto the transfer surface of the transfer object is completed in water. Therefore, it is important to control the type and content of the solvent in the activator composition in order to transfer the print layer to the transfer medium under optimum conditions in various usage situations.

The activator composition for a hydraulic transfer film of the present invention is suitable for activating the printing layer of the hydraulic transfer film by a spray coating method or a roll coating method by taking the above-described configuration. At least a part is dissolved or swollen and softened, and the state can be maintained until the printed material is transferred to the transfer target.
Hereinafter, each component will be described in detail.

The activator composition for a hydraulic transfer film of the present invention contains at least one low-boiling solvent selected from alcohols, esters and aliphatic hydrocarbons having a boiling point of 70 to 130 ° C.
Alcohols constituting the low boiling point solvent include ethyl alcohol (boiling point 78 ° C.), n-propyl alcohol (boiling point 97 ° C.), isopropyl alcohol (boiling point 82 ° C.), n-butyl alcohol (boiling point 117 ° C.), isobutyl alcohol ( Boiling point 108 ° C.), 2-butyl alcohol (boiling point 99 ° C.), tert-butyl alcohol (boiling point 84 ° C.) and the like. Of these, isopropyl alcohol and isobutyl alcohol are preferred.
The esters constituting the low-boiling solvent are preferably acetates. Specifically, ethyl acetate (boiling point 77 ° C.), propyl acetate (boiling point 102 ° C.), butyl acetate (boiling point 125 ° C.), isobutyl acetate ( Boiling point 118 ° C.), sec-butyl acetate (boiling point 112 ° C.), tert-butyl acetate (boiling point 98 ° C.), and the like. Of these, ethyl acetate, butyl acetate and isobutyl acetate are particularly preferred, and at least one of these is preferred.
Further, the aliphatic hydrocarbons constituting the low boiling point solvent include heptane (boiling point 98 ° C.), 2-methylhexane (boiling point 90 ° C.), 3-methylhexane (boiling point 92 ° C.), 3-ethylpentane (boiling point 94 ° C.). ), Octane (boiling point 126 ° C.), isooctane (boiling point 99 ° C.) and the like. Among these, heptane is preferable.
These low-boiling solvents can be used alone or in combination of two or more.

Next, the activator composition for a hydraulic transfer film of the present invention contains at least one high boiling point solvent selected from ethers, esters and ketones having a boiling point of 160 to 260 ° C.
Examples of ethers constituting the high boiling point solvent include butyl cellosolve (boiling point 171 ° C.), isoamyl cellosolve (boiling point 181 ° C.), and among these, butyl cellosolve is preferable.
Examples of the esters constituting the high boiling point solvent include methoxybutyl acetate (boiling point 172 ° C.), butyl carbitol acetate (boiling point 247 ° C.), and dibutyl oxalate (boiling point 246 ° C.).
Furthermore, examples of the ketones constituting the high boiling point solvent include dibutyl ketone (boiling point 187 ° C.) and diisobutyl ketone (boiling point 168 ° C.).
These high boiling point solvents can be used alone or in combination of two or more.

  The activator composition for a hydraulic transfer film of the present invention comprises a mixture of the above-mentioned low boiling point solvent and high boiling point solvent in a mass ratio of 55:45 to 95: 5. Within this range, when the printing layer is transferred to the transfer target, the printing layer of the hydraulic transfer film is appropriately activated.

The activator composition for a hydraulic transfer film of the present invention preferably contains 35% by mass or less of a plasticizer. The plasticizer is for imparting to the activator composition the function of softening the ink of the printing layer, and when the content is 35% by mass or less, there is no problem that dissolution of a part of the ink is too early, The handle does not flow or distort.
As the plasticizer, a phthalate ester is preferable, and examples of the phthalate ester include dimethyl phthalate, dibutyl phthalate, dioctyl phthalate, diisooctyl phthalate, and the like. Of these, dimethyl phthalate is preferable because it stabilizes the active state and evaporates with other solvents.
Although there is no restriction | limiting in particular about the lower limit of content of a plasticizer, It is preferable that it is 5 mass% or more from the point of an effect. That is, the content of the plasticizer is preferably in the range of 5 to 35% by mass, more preferably 10 to 35% by mass, and further preferably 10 to 20% by mass.

  Moreover, the following resin can be added to the activator composition for hydraulic transfer films of this invention about 1-20 mass% with respect to a solvent, for example. Examples of this resin include vinyl halide polymers such as polyvinyl chloride and polyvinylidene chloride; styrene polymers such as polystyrene and polystyrene derivatives; vinyl ester polymers such as polyvinyl acetate; (meth) acrylic acid, itacon Polymers of ester derivatives of unsaturated carboxylic acids such as acid, crotonic acid, maleic acid or fumaric acid; polymers of nitrile derivatives or acid amide derivatives; N-methylol derivatives of acid amide derivatives of the above unsaturated carboxylic acids And the same N-alkylmethylol ether derivatives, glycidyl (meth) acrylate, allyl glycidyl ether, vinyl isocyanate, allyl isocyanate, 2-hydroxyethyl- (meth) acrylate, 2-hydroxypropyl- (meth) acrylate, ethylene glycol-mono ( A) Thermoplastic resins composed of monomers such as acrylates or copolymers; polyamide resins; polyester resins; phenol resins; melamine resins; urea resins; epoxy resins; diallyl phthalate resins Silicon resin; thermosetting resin such as polyurethane resin or modified resin or initial condensate thereof, natural resin, rosin and derivatives thereof, cellulose derivative such as nitrocellulose, natural or synthetic rubber, petroleum resin, cellulose acetate Examples thereof include cellulose resins such as butyrate (CAB) and nitrocellulose, and alkyd resins.

The hydraulic transfer film to which the activator composition for hydraulic transfer film of the present invention is applied has a base film and a printing layer for transfer.
FIG. 1 is a schematic cross-sectional view showing an example of the configuration of a hydraulic transfer film. The hydraulic transfer film 10 has a first picture layer 2, a second picture layer 3, a third picture layer 4 and a fourth picture layer 5 in order on one surface of the base film 1 by gravure printing. A printing layer 6 is formed.

The base film preferably has water solubility or water swellability, and can be appropriately selected from films generally used as conventional hydraulic transfer films.
Examples of the resin constituting the water-soluble or water-swellable film include polyvinyl alcohol resin, dextrin, gelatin, glue, casein, shellac, gum arabic, starch, protein, polyacrylamide, sodium polyacrylate, polyvinylmethyl. Examples include ether, a copolymer of methyl vinyl ether and maleic anhydride, a copolymer of vinyl acetate and itaconic acid, polyvinyl pyrrolidone, acetyl cellulose, acetyl butyl cellulose, carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, sodium alginate and the like. 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 base film.

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

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

  As thickness of the base film which has water solubility or water swelling property, 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 base film is further preferably in the range of 20 to 60 μm.

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

  The hydraulic transfer film used in the present invention has a printing layer for transfer, and as the printing ink for forming the printing layer, conventionally known ones can be appropriately selected and used. For example, titanium white, antimony Inorganic pigments such as white, lead white, iron black, yellow lead, titanium yellow, vermilion, cadmium red, ultramarine, cobalt blue, pearl pigments, silver pigments such as aluminum paste; carbo black (black ink), benzidine yellow, isoindian Organic pigments such as linone yellow, polyazo red, quinacridone red, indanthrene blue, and phthalocyanine blue can be used.

  The vehicle contained in the printing ink is not particularly limited, and examples thereof include various oils such as linseed oil, soybean oil, and synthetic drying oil; natural resins such as rosin, hardened rosin, rosin ester, and polymerized rosin; phenol Synthetic resins such as resin, rosin-modified phenolic resin, maleic acid resin, alkyd resin, petroleum resin, vinyl resin, acrylic resin, polyamide resin, epoxy resin, aminoalkyd resin, fluororesin; nitrocellulose, cellulose acetate buty Examples thereof include fiber derivatives such as rate resin and ethyl cellulose; rubber derivatives such as chlorinated rubber and cyclized rubber; and other caseins, dextrins, and zeins.

Moreover, it is preferable to add an ultraviolet absorber or a light stabilizer to the printing ink, and the weather resistance of the printing layer transferred to the transfer surface of the transfer target can be improved.
Examples of the ultraviolet absorber include organic compounds such as benzotriazole, benzophenone, and salicylic acid ester, and inorganic compounds such as fine particle zinc oxide and cerium oxide having a particle size of 0.2 μm or less. Examples thereof include hindered amine radical scavengers such as bis- (2,2,6,6-tetramethyl-4-piperidinyl) sebacate and radical scavengers such as piperidine radical scavengers.
In addition, content of these ultraviolet absorbers and light stabilizers is about 0.5-10 mass%, respectively.

  Next, the solvent for the printing ink used in the present invention is not particularly limited, and is aliphatic such as pentane, hexane, heptane, octane, etc., or a mixture thereof such as gasoline, petroleum, benzine, mineral spirit, petroleum naphtha. Hydrocarbons; aromatic hydrocarbons such as benzene, toluene, xylene, cyclohexane, and ethylbenzene; halogenated hydrocarbons such as trichloroethylene, perchlorethylene, chloroform, and carbon tetrachloride; methyl alcohol, ethyl alcohol, and n-propyl Monohydric alcohols such as alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, amyl alcohol, benzyl alcohol, diacetone alcohol; polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin; Ketones such as seton, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methylcyclohexanone, isophorone; ethyl ether, isopropyl ether, ethylene glycol mono-methyl ether, ethylene glycol mono-ethyl ether, diethylene glycol mono-methyl ether, diethylene glycol, Ethers such as mono-ethyl ether, diethylene glycol mono-butyl ether, diethylene glycol di-butyl ether, propylene glycol mono-butyl ether; ethyl acetate, propyl acetate, butyl acetate, ethylene glycol mono-methyl ether acetate, ethylene glycol Mono / Ethyl ether / Acetate, Diethylene glycol / Mono / Methyl ether / A Acetates such as tate, diethylene glycol mono-ethyl ether acetate, diethylene glycol mono-butyl ether acetate, esters such as butyric acid ester, cellosolve, nitrohydrocarbons, nitriles, amines, other acetals, acids; Examples include furans. Among these, in consideration of the environment, it is preferable not to use aromatic hydrocarbons such as benzene, toluene, xylene, etc., and ethyl acetate, propyl acetate, butyl acetate, cellosolve, cyclohexanone, ethyl alcohol, isopropyl alcohol, isobutyl alcohol, Methyl ethyl ketone, methyl isobutyl ketone, propylene glycol mono-butyl ether, propylene glycol, and the like are preferably used from the viewpoint of solubility with the activator composition of the present invention. In addition, these solvents can be used individually by 1 type or in mixture of 2 or more types.

A method for forming a printing layer for transfer is not particularly limited, but it is often formed by gravure printing.
In the gravure printing method, overprinting is performed by gravure printing on one surface of a substrate to form a printing layer having two or more picture layers. In this overprinting, for example, when printing a color photograph or the like, the overprinting is generally performed 3 to 7 times. In four-color printing, for example, C (cyan), M (magenta), Y (yellow), and K (black) are generally used.

Although there is no restriction | limiting in particular in the thickness of each pattern layer, Usually, about 0.1-10 micrometers, Preferably it is 0.5-5 micrometers.
The amount of ink applied to each pattern layer is not particularly limited as long as the thickness of each pattern layer is within the above range, but is preferably 0.5 to 1.5 g / m ^2. More preferably, it is 7 to 1.4 g / m ² .

The activator composition for a hydraulic transfer film of the present invention is for activating the printing layer of the hydraulic transfer film, and before floating on the water surface so that the base film side of the hydraulic transfer film faces the water surface side. Alternatively, the activator composition is applied to the printed layer later. Hereinafter, a method for producing a molded product will be described.
The molded article is preferably an activation step in which the activator composition is applied to the printing layer of the hydraulic transfer film in step (A), and at least a part of the printing layer is dissolved or swollen to soften the step (B) A step of pressing the transferred body against the hydraulic transfer film that has undergone the activation step, and causing the printed matter to adhere to the transferred surface of the transferred body by water pressure; Manufacturing by a hydraulic transfer method having a film removal step of completely removing the material film and transferring only the print layer, and a step (D) forming a protective film as necessary on the transferred print layer. Can do.

[Step (A)]
Step (A) is an activation step in which the activator composition of the present invention is applied to the printing layer of the hydraulic transfer film, and at least a part of the printing layer is dissolved or swollen to soften the activator composition. The object is applied before or after the hydraulic transfer film is floated on the water surface.
A hydraulic transfer film composed of a base film and a printing layer is floated on the water surface so that the base film side faces the water surface. In order to float the hydraulic transfer film on the surface of the water, it is possible to float one sheet of printed matter at a time, or to flow water in one direction and continuously supply a continuous belt-like hydraulic transfer film on the surface of the water. May be suspended.
As the method for applying the activator composition of the present invention to the printing layer of the hydraulic transfer film, as described above, methods such as gravure offset coating, gravure coating, roll coating, bar coating, spray coating, etc. can be used. From the viewpoint of obtaining sufficient activity of the printing layer, the spray coating method and the roll coating method are preferable.
In addition, the coating amount of the activator of the present invention is usually about 1 to 50 g / m ² , preferably 3 to 30 g / m ² , and more preferably 10 to 25 g / m ² .

[Step (B)]
The step (B) is a step of pressing the transferred body onto the hydraulic transfer film that has undergone the activation step, and bringing the hydraulic transfer film into close contact with the transferred surface of the transferred body by water pressure.
FIG. 2 is an explanatory diagram conceptually showing the step (B). That is, in the step (B), the transferred object 7 is lowered from above the hydraulic transfer film 10 ′ suspended on the water surface W so that the transferred surface 8 faces downward, and the transferred object is transferred. By pushing the body 7 into the water, the hydraulic transfer film 10 ′ is stretched and deformed along the shape of the transfer surface 8, and the hydraulic transfer film 10 ′ is brought into close contact with the transfer surface 8 by water pressure. When the hydraulic transfer film 10 ′ is floated on the water surface W and the base film 1 ′ is in contact with water, the base film 1 ′ swells when it is water-swellable and dissolves when it is water-soluble. . Therefore, when the base film 1 ′ is water-swellable, the base film 1 ′ is in close contact with the transfer surface 8 together with the printing layer 6 ′. On the other hand, when the base film 1 ′ is water-soluble, the base film 1 ′ is completely dissolved in water and only the print layer 6 ′ is floated on the water surface, and a part of the base film 1 ′ is dissolved and a part remains. There are cases. When only the former print layer 6 ′ floats on the water surface, only the print layer 6 ′ is in close contact with the transfer target 7.

  The water for applying the floating water pressure to the hydraulic transfer film 10 ′ is adjusted to an appropriate water temperature according to the type of the base film 1 ′ of the hydraulic transfer film 10 ′ (for example, difference in water solubility or water swellability). Good to do. For example, when the substrate film 1 ′ is a starch film, the water temperature is preferably 25 to 50 ° C. Further, an additive that promotes the removal of the base film 1 'may be added. For example, in the case of a starch film, it is preferable to add amylase or the like.

Examples of the transfer object used in the present invention include polystyrene resin, acrylonitrile-butadiene-styrene copolymer (ABS resin), polycarbonate resin, melamine resin, phenol resin, urea resin, fiber resin, polyethylene, polypropylene, and the like. In addition to a resin or a resin in which these are mixed, 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. The shape of the transfer surface may be a two-dimensional shape that is a planar shape, or a three-dimensional shape such as an uneven shape or a curved shape. Of these, resin structures are usually used frequently. In the resin structure, a mold release agent adheres at the time of molding, and dust and fat may also adhere. In order to transfer the printed layer of the hydraulic transfer film with good adhesion, the resin structure is previously coated with a degreasing liquid. It is preferable to clean the transfer surface.
As the degreasing liquid, a surfactant-free material such as an alkaline degreasing agent is used. For example, a surfactant-free potassium / phosphate weak alkaline liquid can be used. Since such a potassium / phosphate-based solution does not contain a surfactant, it can repel water from the surface of the transfer target. In this way, by suppressing the familiarity with water on the surface of the transfer object, it is possible to prevent water from entering between the transfer object and the printing layer of the hydraulic transfer film. The printed layer can be directly and reliably attached to the surface.
In addition, a primer layer may be formed in advance on the transfer surface of the transfer body in order to improve the adhesion between the surface of the hydraulic transfer film and the printing layer surface.

[Step (C)]
This step is a step in which only the printing layer is transferred by completely removing the base film of the hydraulic transfer film in close contact with the transfer surface of the transfer target.
In the step (C), when the base film is also pressed against the transferred body together with the printing layer and is in close contact with the transferred body, the base film is removed by dissolution or washing, and only the printed layer is placed on the transferred body. Therefore, this step (C) is not necessary when only the print layer is floating on the water surface when the object to be transferred is pushed into water and water pressure is applied. That is, in the step (C), when at least a part of the base film of the hydraulic transfer film is not dissolved but remains on the transferred body, the printed layer transferred to the transferred surface of the transferred body is This is a step of removing the base film after sufficiently adhering.
The removal of the base film can be performed, for example, by shower cleaning using water. By this step (C), the substrate film adhering to the transfer surface is completely removed. In addition, although the conditions of shower washing differ with kinds etc. of a base film, the water temperature of about 15-60 degreeC and the washing | cleaning time of about 10 second-about 5 minutes are preferable normally. And after a process (C) or when a process (C) is abbreviate | omitted, if a to-be-transferred body is fully dried and a water | moisture content is evaporated after the said process (B), the to-be-transferred object of a to-be-transferred body will be obtained. A molded product to which a desired design is imparted is obtained by the printed layer transferred to the surface.

[Step (D)]
Step (D) is a step of forming a protective film on the transferred printing layer as necessary.
In the step (D), the printed layer transferred to the transfer surface of the transfer target in the step (C) is coated as necessary for surface strength improvement, surface protection, surface gloss adjustment, and the like. To form a transparent protective film. As this transparent protective film, for example, a thermoplastic resin, a thermosetting resin, an ultraviolet curable resin, or the like, specifically, a urethane resin, an epoxy resin, an acrylic resin, a fluorine resin, a silicon resin, or the like is used. As a coating method, known methods such as spray coating, electrostatic coating, brush coating, and dip coating can be used.
Molded articles decorated with the activator composition for hydraulic transfer films of the present invention are suitably used as automobile interior materials, building materials, furniture, electrical appliance housings and the like that require particularly high design properties.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
In addition, the performance evaluation shown below was performed about the printed matter for transfer and the hydraulic transfer molded product obtained in each example.
(1) State after activation of hydraulic transfer film The activator composition prepared in each Example and Comparative Example was applied to the printing layer of the hydraulic transfer film, and the state of the pattern was visually evaluated. The evaluation criteria are as follows.
○: The pattern extends uniformly and there is no distortion or blurring of the pattern.
(Triangle | delta); A crack or a crack generate | occur | produces in part and it becomes partial expansion | extension.
X: The design is broken by cracking the design as a whole.

(2) Transfer state The transfer state of the pattern after the activated pattern was transferred to the transfer target was visually evaluated. The evaluation criteria are as follows.
○: The pattern is uniformly transferred and there is no bending of the pattern.
Δ: Some patterns are bent.
×: A part of the base material has a part to which a pattern due to repelling or the like is not transferred.

(3) Initial adhesion In the initial state where the pattern was transferred to the transfer target, the state of the pattern when water pressure was applied by a shower was evaluated visually. The evaluation criteria are as follows.
○: The pattern is not damaged by the water pressure, and the transferred state is maintained.
Δ: There is a portion where the pattern is slightly broken.
X: The pattern is broken and the designability is impaired.

(4) Pinholes Air was blown during transfer and washing, pinholes due to solvent volatilization were observed, and whether or not the pattern was transferred and the substrate was visible was evaluated visually. The evaluation criteria are as follows.
○: No pinhole.
Δ: Some pinholes were observed, but there was no problem in practical use.
X: Pinholes occurred in the entire pattern.

(5) Pattern uniformity After transferring the pattern onto the transfer object, the uniformity of the pattern extension was evaluated. The evaluation criteria are as follows.
○: The extension of the pattern is uniform.
Δ: Pattern extension is partially uneven.
X: The pattern is transferred unevenly as a whole.

(6) Throwing property It was visually evaluated whether or not the pattern was transferred along the curved surface in the curved surface portion of the transfer object. The evaluation criteria are as follows.
○: The pattern is not cut and is transferred along the curved surface.
Δ: The elongation of the pattern is slightly non-uniform, but there is no problem in practical use.
X: There is a crack in the pattern, which impairs the design.

(7) Yuzu skin, surface irregularity The smoothness of the surface after transferring to a transfer object and drying was evaluated by visual and tactile sensation. The evaluation criteria are as follows.
○: Mirror surface and smooth surface.
Δ: Partially matte and slightly uneven, but practically no problem.
X: The entire surface is uneven and rough.

(8) Appearance The design of the transferred object after being transferred to the transferred object, dried, and provided with a transparent protective layer was visually evaluated in consideration of the design and elongation. The evaluation criteria are as follows.
○: Good designability.
Δ: There are some defects in design.
X: The design property is impaired as a whole.

Example 1
(1) Production of hydraulic transfer film As a water-soluble film, a PVA film [manufactured by Tosero Co., Ltd., “Toslon”, thickness of 30 μm] was used, and gravure ink (Dainippon Ink) on one side with an electric gravure printer. Chemical Industry Co., Ltd., “GT Color”) is used to create a printing layer (wood grain pattern) having a thickness of 2 μm comprising a first pattern layer to a fourth pattern layer as shown in FIG. A transfer film was prepared.

(2) Preparation of activator composition The components shown in Table 1 were mixed so as to have the contents shown in Table 1 to prepare an activator composition.

(3) Manufacture of hydraulic transfer molded product The hydraulic transfer film obtained in (1) above is printed on the water surface W at a water temperature of 30 ° C. with the printed material for transfer 10 ′ on the substrate film 1 ′ side on the water surface side as shown in FIG. It floated so that it might face. After 2 minutes, the activator composition prepared in (2) was sprayed at 15 g / m ² by spray coating. After the lapse of 15 seconds, after the base film 1 ′ is in a swollen state, the transferred object 7 of the ABS resin molded body is pushed in from above the hydraulic transfer film 10 ′, and the transferred surface 8 of the transferred object 7 is transferred. The hydraulic transfer film 10 ′ was spread and adhered to. Thereafter, the transferred object, which was spread and adhered to the surface of the hydraulic transfer film, was drawn out of the water. Next, as a step of removing the substrate film (step (C) above), a 40 ° C. hot water shower is sprayed on the transferred body for 1 minute, and then a fresh water shower is further sprayed to adhere to the transferred body. The substrate film of the hydraulic transfer film was removed. Next, the transfer object was dried to obtain a transfer article having the printing layer transferred to the transfer object.
Next, an acrylic resin layer having a thickness of 10 μm was formed as a transparent protective layer on the surface of the printing layer of the transfer article to produce a hydraulic transfer molded product.
The results of evaluation by the above method are shown in Table 2.

Examples 2-5, Comparative Examples 1 and 2
Except that the activator composition shown in Table 1 was applied by the application method shown in Table 1, a hydraulic transfer molded article was prepared in the same manner as in Example 1 and evaluated by the above method. The results of evaluation are shown in Table 2.

Example 6
A hydraulic transfer film was produced by the following method. As a water-soluble film, a PVA film [manufactured by Nippon Synthetic Chemical Industry Co., Ltd., “Hi-Selon C-300”, thickness 40 μm] was used, and gravure ink (The Inktech ( Co., Ltd., “KLCF”), a hydraulic transfer film is produced by providing a printing layer (wood grain pattern) having a thickness of 2 μm consisting of a first pattern layer to a fourth pattern layer by overprinting as shown in FIG. did.
Using the obtained hydraulic transfer film, the activator composition as shown in Table 1 was prepared in the same manner as in Example 1 except that it was applied by the application method shown in Table 1. Evaluation was performed by the above method. The results of evaluation are shown in Table 2.

Examples 7-18, Comparative Examples 3 and 4
A hydraulic transfer molded article was prepared in the same manner as in Example 6 except that the activator composition shown in Table 1 was applied by the application method shown in Table 1, and evaluated by the above method. The results of evaluation are shown in Table 2.

  According to the present invention, an activator composition for activating a printing layer of a hydraulic transfer film, which corresponds to various application methods of the activator composition and has a good state of the printing layer of the hydraulic transfer film. Therefore, it is possible to provide an activator composition for a hydraulic transfer film in which a good transfer state can be obtained on the transferred material and the appearance of the transferred material is improved.

DESCRIPTION OF SYMBOLS 1 Base film 1 'Base film 2 1st pattern layer 3 2nd pattern layer 4 3rd pattern layer 5 4th pattern layer 6 Print layer 6' Activator containing printing layer 7 Transfer object 8 Transfer object Surface 10 Printed matter 10 'Transfer printed matter (hydraulic transfer film)
W Water surface

As a result of intensive studies to achieve the above object, the present inventor has found that the above problem can be solved by mixing and using a specific low boiling point solvent and a high boiling point solvent. The present invention has been completed based on such findings.
That is, the present invention
(1) An activator composition for activating a printing layer of a hydraulic transfer film comprising a base film and a printing layer, comprising at least a solvent, the solvent having a boiling point of 70 to 130 ° C. and a boiling point made of a high boiling solvent 160 to 260 ° C., low-boiling solvent is an alcohol, at least one selected from esters and aliphatic hydrocarbons is at least one high-boiling solvent is selected from ketones, lower An activator composition for a hydraulic transfer film, wherein the mass ratio of the boiling solvent to the high boiling solvent is in the range of 55:45 to 95: 5;
(2) The activator composition for hydraulic transfer film according to (1), further comprising a plasticizer, wherein the plasticizer content is 35% by mass or less. (3) The plasticizer is a phthalate ester. , The activator composition for hydraulic transfer film according to (2), wherein the content is 5 to 35% by mass,
(4) The activator composition for a hydraulic transfer film according to any one of the above (1) to (3), wherein the low boiling point solvent contains at least one of ethyl acetate, butyl acetate and isobutyl acetate,
(5) The activator composition for a hydraulic transfer film according to any one of (1) to (4), wherein the ketones contain at least one of diisobutyl ketone and dibutyl ketone,
( 6 ) The activator composition for a hydraulic transfer film according to any one of (1) to (5) , which is used for activation by a spray coating method or a roll coating method,
( 7 ) The activator composition for a hydraulic transfer film according to any one of (1) to (6) , wherein the base film is a polyvinyl alcohol-based resin film ,
(8) The ink solvent used for the printing layer is selected from ethyl acetate, propyl acetate, butyl acetate, cellosolve, cyclohexanone, ethyl alcohol, isopropyl alcohol, isobutyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, propylene glycol monobutyl ether , and propylene glycol. The activator composition for a hydraulic transfer film according to any one of the above (1) to (7) , which is at least one selected from the above, and
(9) A method for producing a molded article having the following steps (A) to (C) in order,
Step (A) The hydraulic transfer film activator composition according to any one of the above (1) to (8) is applied to a printing layer of a hydraulic transfer film comprising a base film and a printing layer, and the printing layer An activation process in which at least a part is dissolved or swollen and softened
Step (B) A step of pressing the transferred body against the hydraulic transfer film that has undergone the activation step, and bringing the printed material into close contact with the transferred surface of the transferred body by water pressure
Step (C) A film removal step of removing the base film of the printed material that is in close contact with the transfer surface of the transfer target and transferring the print layer is provided.

Examples 7-11, Reference Examples 1-7, Comparative Examples 3 and 4
A hydraulic transfer molded article was prepared in the same manner as in Example 6 except that the activator composition shown in Table 1 was applied by the application method shown in Table 1, and evaluated by the above method. The results of evaluation are shown in Table 2.

Claims (7)

  An activator composition for activating a printing layer of a hydraulic transfer film comprising a substrate film and a printing layer, comprising at least a solvent, the solvent having a boiling point of 70 to 130 ° C and a boiling point of 160 to 260 At least one selected from alcohols, esters, and aliphatic hydrocarbons, and the high-boiling solvent is at least selected from ethers, esters, and ketones. An activator composition for a hydraulic transfer film, which is one type and has a mass ratio of a low-boiling solvent and a high-boiling solvent in a range of 55:45 to 95: 5.   The activator composition for a hydraulic transfer film according to claim 1, further comprising a plasticizer, wherein the content of the plasticizer is 35% by mass or less.   The activator composition for a hydraulic transfer film according to claim 2, wherein the plasticizer is a phthalate ester and the content thereof is 5 to 35% by mass.   The activator composition for hydraulic transfer films according to any one of claims 1 to 3, wherein the low boiling point solvent contains at least one of ethyl acetate, butyl acetate and isobutyl acetate.   The activator composition for hydraulic transfer films according to any one of claims 1 to 4, which is used for activation by a spray coating method or a roll coating method.   The activator composition for a hydraulic transfer film according to any one of claims 1 to 5, wherein the base film is a polyvinyl alcohol resin film.   The ink solvent used for the printing layer is selected from ethyl acetate, propyl acetate, butyl acetate, cellosolve, cyclohexanone, ethyl alcohol, isopropyl alcohol, isobutyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, propylene glycol mono-butyl ether, and propylene glycol. The activator composition for a hydraulic transfer film according to claim 1, wherein the activator composition is at least one kind.

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