JP2005262610A - Hydraulic transfer method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain sufficient adhesion and durability of a decorative layer, even when a coating process after transfer is omitted, in a hydraulic transfer method. <P>SOLUTION: In this hydraulic transfer method, (A) as an easy adhesion process for the transfer surface of an object M to which an image is transferred, a modification process (A1) to throw a flame 6 containing not less than one kind of chemical compound containing a silicon atom, a titanium atom or an aluminum atom, is performed, then (B) a hydraulic transfer process to transfer the decorative layer composed of a curable resin of a solid state at a room temperature yet not completely cured to the transfer surface using a hydraulic pressure as a transfer pressure, and (C) a curing process for the curable resin is performed. In the easy adhesion process, an oxidative flame treatment process (A0) which throws an oxidative flame to the transfer surface is preferably performed before the modification process (A1). In addition, preferably the easy adhesion process is applied to the decorative layer surface of a transfer sheet. The hydraulic transfer process includes (B1) a process to prepare the transfer sheet with the decorative layer of a specific curable resin, (B2) an activation process for the decorative layer and (B3) a hydraulic pressure application process to press the object M to which an image is transferred to the transfer sheet on a water surface in the order cited. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a hydraulic transfer method capable of decorating an article having a curved surface or a three-dimensional surface.

  Conventionally, a hydraulic transfer method is known as a method for decorating an article having a non-planar surface such as a curved surface or a three-dimensional surface, and is used for decorating various articles.

(1) If a typical example of such a hydraulic transfer method is shown, a transfer sheet on which a desired decorative layer is printed on a water-soluble or water-swellable support sheet is prepared. After applying an activator to give the decorative layer an adhesive force, the transfer sheet is floated on the water surface with the support sheet side facing the water surface, and then the transfer sheet floated on the water surface. From the step of pressing the article to be transferred onto the transfer sheet and bringing the transfer sheet into close contact with the transfer surface to be decorated by water pressure, and then transferring the decoration layer by removing the support sheet (See Patent Document 1). According to such a water pressure transfer method, even if the transfer surface of the transfer target to be transferred is a curved surface, it is possible to provide a decorative layer made of a pattern by causing the transfer sheet to sufficiently follow the transfer target surface.

  However, the method disclosed in Patent Document 1 has a drawback in that the durability (scratch resistance, chemical resistance, stain resistance, etc.) of the decorative layer is insufficient. That is, since the decorative layer made of ink is exposed, the decorative layer is directly exposed to external force, wear, contamination, and the like. In addition, this method is a method in which the decorative layer is adhered to the transferred body by the adhesive while the decorative layer ink is undried and sticky, so the adhesion between the decorative layer and the transferred body is insufficient. It is. For this reason, the decorative layer is easily peeled off from the transferred body by an external force. In addition, the decorative layer itself has a drawback of being damaged and contaminated.

(2) Then, as a measure for improving the durability problem of the decorative layer as described above, Patent Document 2 proposes the following method. That is, in addition to the above prior art, an activator made of an organic solvent is applied in advance to the decorative layer of the transfer sheet to swell and stick the decorative layer (this is called activation), and then In addition, by transferring, the adhesive force between the decorative layer and the transfer object is reinforced by the adhesive force by applying the activator.
In addition, after the transfer, the surface of the decoration layer on the transfer object is coated and the outside of the decoration layer is protected with a coating film. The coating film itself becomes a protective layer against external force and contamination. In addition to this, the liquid paint penetrates through the decoration layer made up of an aggregate of ink halftone dots and reaches the transfer target, so that the decoration layer can be firmly fixed to the transfer target.

  However, in the method disclosed in Patent Document 2, the coating process causes the solvent and paint to diverge around the mist droplets at the time of application, which is not preferable in terms of environmental hygiene. There was also a problem that the work environment was contaminated. In addition, the painting process requires time and labor for preparations such as paint preparation, dilution, etc., and cleaning and disposal of the remaining paint. Furthermore, the coating process requires a long time (several hours to several days) for drying and curing the coating film. In the case of coating with a liquid paint, it flows until the coating film is dried and solidified. Therefore, in the case of a curved transfer object, the film thickness of the convex part (thinning) and the concave part (thickening) There was a problem of causing non-uniformity.

(3) Therefore, Patent Document 3 proposes a method of omitting the painting process. That is, in the water pressure transfer method as described above, the coating process after transfer is omitted as follows, and sufficient adhesion between the decoration layer and the transfer target and the durability of the decoration layer are improved. It is a method of aiming. Specifically, a solid ionizing radiation curable resin is used as the decoration layer even in an uncured state at room temperature. Then, when the ionizing radiation curable resin of the decoration layer is in an uncured state, the decoration layer (which is uncured and soluble in an organic solvent) is activated with an activator containing an organic solvent and hydraulically transferred. This strengthens the adhesive force between the layer and the transfer target. Further, after the transfer, the decoration layer is irradiated with ionizing radiation such as ultraviolet rays and electron beams to crosslink and cure the decoration layer, thereby imparting durability to the decoration layer itself.

However, in the method disclosed in Patent Document 3, the painting process can be omitted, but when the transfer target is a material having poor chemical adhesion and surface wettability, sufficient adhesion of the decorative layer can be obtained. It was difficult. For example, this is the case when a non-polar resin such as polyolefin resin, metal, ceramics, or the like, for which demand has been increasing in recent years, is selected as the transfer target. Compared with the conventional coating method, the effect of improving the adhesive strength could not be expected for the hardly-adherent transferred article made of these materials. This depends on the adhesive strength of the decorative layer to the transferred object only by the adhesive strength of the activated decorative layer, and the liquid coating penetrates the decorative layer and fixes the decorative layer to the transferred material from the outside. Presumed to be lacking.
Moreover, compared with the conventional coating system, the durability of the coating film was not sufficiently improved. This is because the adhesive force between the coating film and the transfer target is insufficient, so that when the external force or friction is applied, the coating film breaks and falls off.

Japanese Examined Patent Publication No. 52-41682 Japanese Patent Publication No. 60-58718 Japanese Patent Publication No. 7-29084

  That is, the problem of the present invention is to further improve the method of (3) above in the hydraulic transfer method, omit the coating process after transfer, and save time and labor for preparation and cleaning that accompany the coating process. It is omitted, and the drying and curing time of the coating film is shortened, and further, the unevenness of the film thickness between the convex part and the concave part due to the flow of the paint is eliminated. Moreover, even if the coating is omitted, the adhesion between the decorative layer and the transferred material and the durability of the decorative layer on the transferred material can be obtained sufficiently for a wide variety of substrates. is there.

In order to solve the above problems, the first invention related to the hydraulic transfer method of the present invention is:
(A) an easy-adhesion treatment step for easily adhering at least the transfer surface of the transfer object;
(B) a water pressure transfer step of transferring a decorative layer made of a solid curable resin at room temperature that is not completely cured using water pressure as a transfer pressure on the transfer surface;
(C) a curing step for curing the curable resin of the decorative layer;
A hydraulic transfer method in which the steps are performed in this order;
Easy adhesion treatment process (A)
(A1) including a modification step of emitting a flame containing one or more compounds having a silicon atom, a titanium atom, or an aluminum atom on the transfer surface,
The hydraulic transfer process (B)
(B1) preparing a transfer sheet in which a desired decorative layer is formed by printing or coating on a water-soluble or water-swellable support sheet;
(B2) As an activation process for imparting adhesive force to the decorative layer,
(B21) First, an activator for imparting adhesive force to the decorative layer is applied to the decorative layer surface side of the transfer sheet, and then the transfer sheet is placed on the water surface so that the support sheet side faces the water surface side. Float or
(B22) First, the transfer sheet is floated on the water surface so that the support sheet side faces the water surface side, and then an activator for imparting adhesive force to the decorative layer is provided on the decorative layer surface side of the transfer sheet. Either do the coating,
(B3) Next, a water pressure application step of pressing the transfer target onto the transfer sheet on the water surface and bringing the transfer sheet into close contact with the transfer target surface of the transfer target by water pressure is included in this order.
It was set as the hydraulic transfer method of composition.

By adopting the water pressure transfer method having such a configuration, the transfer object is transferred after being subjected to a specific easy adhesion treatment in advance. However, the chemical activity and wettability of the surface to be transferred are improved and are stable over time. Therefore, the adhesiveness between the decorative layer and the transfer object is good. Therefore, the present invention can also be applied to the case where the transfer target is a non-polar resin such as a polyolefin resin, a hardly adhesive article such as a metal or ceramics.
Furthermore, since a specific curable resin is used for the decoration layer and cured after transfer, the mechanical strength of the decoration layer is improved, and the decoration layer is not easily broken or peeled off by an external force, and is chemically inert. Turn into. Therefore, the adhesiveness between the decorative layer and the transfer object is enhanced without depending on the fixing action of the liquid paint. Therefore, even if the coating is omitted, the durability of the decorative layer transferred on the transfer target can be sufficiently obtained. Accordingly, since the painting process after the transfer can be omitted, the time and labor required for pre-preparation and cleanup associated with the painting process are omitted. Also, the time for drying and curing the coating film is not required. Furthermore, there is no environmental pollution caused by mist of solvent and paint. Furthermore, since a liquid paint is used for painting, the film thickness of the convex part and the concave part is not uniform due to the flow of the paint, but this non-uniformity does not occur if the painting is omitted.

The second invention related to the hydraulic transfer method of the present invention is the first invention, wherein the easy adhesion treatment step (A) comprises:
(A0) Oxidation flame treatment process for radiating an oxidation flame to the transfer surface;
(A1) a reforming step of emitting a flame containing one or more compounds having a silicon atom, a titanium atom, or an aluminum atom on the transfer surface;
Were performed in this order.

  By using the hydraulic transfer method having such a configuration, the adhesion between the decoration layer and the transfer object and the durability of the decoration layer on the transfer object can be strengthened and stabilized.

  Further, in the hydraulic transfer method of the present invention, in the first or second invention, the easy adhesion treatment step (A) is further performed on the decorative layer surface side of the transfer sheet (A1s). Prior to (B2), a method including a modifying step of emitting a flame containing one or more compounds having a silicon atom, a titanium atom, or an aluminum atom was employed.

  By using the hydraulic transfer method having such a configuration, the adhesion between the decoration layer and the transfer object and the durability of the decoration layer on the transfer object can be strengthened and stabilized.

Moreover, the hydraulic transfer method of the present invention is the above-described first or second invention, wherein the easy adhesion treatment step (A) further comprises:
(A0s) First, an oxidation flame treatment process for radiating an oxidation flame prior to the activation process (B2) on the decorative layer surface side of the transfer sheet,
(A1s) Next, a modification step of emitting a flame containing one or more compounds having a silicon atom, a titanium atom, or an aluminum atom on the decorative layer surface side of the transfer sheet,
Including a method.

  By using the hydraulic transfer method having such a configuration, the adhesion between the decoration layer and the transfer object and the durability of the decoration layer on the transfer object can be strengthened and stabilized.

(1) According to the hydraulic transfer method of the present invention, the adhesion between the decorative layer and the transferred material and the durability of the decorative layer can be obtained without coating, and the transferred material is a nonpolar resin such as a polyolefin resin. It can also be applied in the case of difficult adhesion such as metal and ceramics. In addition, since painting can be omitted, it saves time and labor for pre-preparation and cleaning, reduces the time for drying and curing the coating, and further reduces the coating thickness between the convex and concave portions due to the flow of the coating. The non-uniformity is also eliminated.
(2) Furthermore, in the easy adhesion treatment step, if the oxidation flame treatment step is also performed before the reforming step, the adhesion and durability of the decorative layer can be strengthened and stabilized.
(3) Also, with respect to the transfer sheet, if the reforming step is performed before the activation step, the adhesiveness and durability of the decorative layer can be strengthened and stabilized.
(4) Alternatively, for the transfer sheet, if the reforming step and the oxidation flame treatment step are performed before the activation step, the adhesion and durability of the decorative layer can be strengthened and stabilized.

  The best mode for carrying out the present invention will be described below with reference to the drawings.

[Transfered material]
In the present water pressure transfer method, the article to be decorated, that is, the material to be transferred is basically not particularly limited, and various materials and shapes can be applied. However, the water pressure transfer method according to the present invention, in particular, the one that exerts its effect is an article that is difficult to obtain adhesiveness as it is and an easy adhesion treatment is desirable.
(I) Polyolefin resin such as polyethylene, polypropylene, polymethylpentene, ionomer, ethylene-propylene copolymer, ethylene-propylene-butene copolymer, olefinic thermoplastic elastomer, polyvinyl fluoride, polyvinylidene fluoride, poly 4 fluorine Wetting tension of 45 mN / wet of fluororesins such as ethylene fluoride, ethylene-tetrafluoroethylene copolymer, polyester resins such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate, silicon resins such as silicone rubber, polycarbonate resins, etc. m or less resin,
(Ii) metals such as aluminum, iron, copper, titanium,
(Iii) Glasses, ceramics, ceramics such as glazes,
Etc.

[Easy adhesion treatment process (A)]
The present invention includes the following two forms (a) and (b) of the target surface to which the easy adhesion treatment is performed in the easy adhesion treatment step (A).
(A) Only the transfer surface of the transfer object (essential).
(B) The transfer surface of the transfer object and the decorative layer surface of the transfer sheet.
Among these, the form (b) is an essential form in the third invention and the fourth invention. In the following description, the surface to be transferred and the decorative layer surface are simply referred to as “treated surface” unless otherwise distinguished.

  In the modification step, the treatment on the transfer surface is the modification step (A1), and the treatment on the decoration layer surface is the modification step (A1s). Similarly, in the oxidation flame treatment process, the treatment on the transfer surface is the oxidation flame treatment process (A0), and the treatment on the decorative layer surface is the oxidation flame treatment process (A0s). In the description, for example, in the reforming process, the description of “modifying processes (A1), (A1s)” is a general description of each processing surface of the transferred surface and the decorative layer surface.

  As the easy adhesion treatment step (A), in the present invention, the treatment surface of the object to be transferred or the decoration layer is modified to emit a flame containing one or more compounds having silicon atoms, titanium atoms, or aluminum atoms. Steps (A1) and (A1s) are performed, and more preferably, before the reforming steps (A1) and (A1s), as another easy-adhesion treatment, an oxidation flame that emits an oxidation flame on the treated surface, respectively. Processing steps (A0) and (A0s) are preferably performed. That is, the oxidation flame treatment step (A0) for emitting an oxidation flame to the treatment surface is performed prior to the modification step (A1). Further, the oxidation flame treatment step (A0s) for radiating the oxidation flame to the treatment surface is performed prior to the modification step (A1s). These oxidation flame treatment steps (A0) and (A0s) and the reforming steps (A1) and (A1s) are disclosed in JP 2002-53982 A and JP 2003-238710 A. Surface modification techniques can be used.

  Oxidized flame treatment steps (A0) and (A0s) are present on the treatment surface and reduce the treatment effect of the reforming steps (A1) and (A1s) or cause variations, This is a process for decomposing and removing organic contaminants such as fats and oils. In the oxidation flame treatment steps (A0) and (A0s), a combustible gas and air are mixed to burn the combustible gas to generate a flame. The mixing ratio of the flammable gas and air and the combustion conditions are adjusted, and the flame is changed to an oxygen flame containing excess oxygen or having an oxidizing action, and this is emitted from the nozzle of the burner to the processing surface. By radiating such an oxidization flame to the treated surface, organic contaminants such as adsorbed moisture and fats and oils on the treated surface are decomposed and removed, and the easy adhesion of the reforming steps (A1) and (A1s) as the subsequent steps In addition to enhancing the expression effect, the effect can be ensured and stabilized.

  As the combustible gas, a combustible gas such as hydrocarbons such as propane and butane, hydrogen, natural gas, and city gas can be used. The relative speed (line speed) at which the oxidation flame and the processing surface of the transfer target are brought into contact with each other is appropriately adjusted at about 50 to 100 m / min. In addition, when the treatment surface is clean and the required easy adhesion effect is sufficiently obtained by the reforming steps (A1) and (A1s) even without the oxidation flame treatment steps (A0) and (A0s), the oxidation flame is used. Processing steps (A0) and (A0s) can be omitted.

The modification steps (A1) and (A1s) are steps for emitting a flame containing one or more compounds having a silicon atom, a titanium atom, or an aluminum atom on the treated surface. By the modification process, a thin film made of silicon, titanium atoms, or aluminum oxide is formed on the treated surface, the surface wettability is improved, and the decorative layer is dissolved or swollen by the activator during hydraulic transfer. The adhesion between the toner and the transfer medium can be improved.
The flame used in the reforming step is a compound having a silicon atom, a titanium atom, or an aluminum atom (hereinafter referred to as “modified”) in the mixed gas of combustible gas and air described in the above-mentioned oxidation flame. Combustion gas in which one or more kinds are mixed is combusted to form a flame and radiates toward the processing surface. Each gas mixture component excited by heating chemically reacts, and a thin film made of one or more oxides of silicon, titanium, or aluminum is laminated on the treated surface. The thin film has a reactive hydroxyl group (Si—OH, Ti—OH, Al—OH, or the like) on the surface. Further, water molecules in the air are bonded to the hydroxyl group, and the chemical composition becomes SiO _x , TiO _x , or AlO _x (X exceeds 2 and becomes about 2.5). As a result, the wetting tension which is the wettability of the surface can be improved to 40 to 80 mN / m, and the contact angle of water can be improved to about 0.1 to 30 ° (both values at 25 ° C.). Therefore, the easy adhesion effect between the transferred surface and the decorative layer surface is improved.

  As said modifier, what is necessary is just a compound which has any 1 or more types of a silicon atom, a titanium atom, or an aluminum atom. Examples of such modifiers include alkyl silane compounds, alkoxy silane compounds, alkyl titanium compounds, alkoxy titanium compounds, alkyl aluminum compounds, and alkoxy aluminum compounds.

  Moreover, as a modifier, the thing whose boiling point (under atmospheric pressure) is in the range of 10-100 degreeC is more preferable. This is because a modifier having a boiling point of less than 10 ° C. is volatile and may be difficult to handle. On the other hand, when the modifier has a boiling point exceeding 100 ° C., the miscibility with other gases such as combustible gas and carrier gas is remarkably lowered, and the modifier is liable to be incompletely burned. This is because the easy adhesion effect due to modification may vary or the easy adhesion effect may not be sustained for a long time.

  Among the modifiers exemplified above, alkylsilane compounds, alkyltitanium compounds, and alkylaluminum compounds are generally low in boiling point, are easily used as those having a boiling point in the range of 10 to 100 ° C., and are heated. Therefore, it is a desirable modifier because it is easily vaporized and easily mixed with air or the like. Specific examples of such alkylsilane compounds, alkyltitanium compounds, and alkylaluminum compounds include tetramethylsilane, tetramethyltitanium, tetramethylaluminum, tetraethylsilane, tetraethyltitanium, tetraethylaluminum, and 1,2-dichloro. Examples include tetramethylsilane, 1,2-dichlorotetramethyltitanium, 1,2-dichlorotetramethylaluminum, and the like. These can be used individually by 1 type or in combination of 2 or more types.

  The molecular weight of the modifier is preferably within the range of 50 to 1,000 in terms of average molecular weight measured by mass spectrum. If the average molecular weight is less than 50, volatility may be high and handling may be difficult. On the other hand, if the average molecular weight exceeds 1,000, it may be difficult to heat and vaporize and mix with air. This is because there may occur.

The modifier is more preferably one having a density in the liquid state of 0.3 to 0.9 g / cm ³ . This is because if the density is less than 0.3 g / cm ³ , handling may be difficult, or it may be difficult to accommodate in a gas cylinder. On the other hand, when the density exceeds 0.9 g / cm ³ , it is difficult to vaporize, and when stored in a gas cylinder, it may be completely separated from air or the like.

Further, the addition amount of the modifier is preferably in the range of 1 × 10 ⁻¹⁰ to 10 mol% when the total amount of the combustion gas is 100 mol%. If the addition amount is less than 1 × 10 ⁻¹⁰ , the reforming effect may not be obtained. If the addition amount exceeds 10 mol%, the mixing property between the modifier and air decreases, and the modifier becomes Incomplete combustion may occur.

  The combustible gas is mixed with air and burned as a combustion gas. The content of the combustible gas in the combustion gas is 80 to 99.9 mol when the total amount of the combustion gas is 100 mol%. % Range is preferred. If the content is less than 80 mol%, the mixing property between the modifier and air may be reduced, and the modifier may burn incompletely. If the content exceeds 99.9 mol%, the reforming effect This is because it may not be possible.

  In addition, it is also preferable to add a carrier gas to the combustion gas in order to make the mixing of the modifier uniform. Specifically, a modifier and a carrier gas are mixed in advance, and then mixed with a mixed gas in which a combustible gas and air are mixed. As the carrier gas, it is preferable to use the same kind of gas as the flammable gas, for example, air, oxygen, or a hydrocarbon gas such as propane gas or natural gas.

  Further, even when a compound having a boiling point in the range of 10 to 100 ° C. is used as a modifier, a compound having a boiling point exceeding 100 ° C. may be supplementarily used as a modifier (modification aid). good. By using a modification auxiliary having a boiling point exceeding 100 ° C., the easy adhesion effect by surface modification can be further increased. Such a modification auxiliary agent having a boiling point exceeding 100 ° C. is at least one compound selected from the group consisting of alkylsilane compounds, alkoxysilane compounds, alkyltitanium compounds, alkoxytitanium compounds, alkylaluminum compounds, and alkoxyaluminum compounds. Is preferably used. Even if the compound has a slightly higher boiling point, it is possible to reduce the boiling point of the modifier having a boiling point of 100 ° C. or lower by adding a modifying auxiliary similar to the modifier having a boiling point of 100 ° C. or lower such as an alkylsilane compound. It is possible to improve the difficulty in handling the combustion gas due to the low level, and to further improve the easy adhesion effect due to the surface modification. In addition, the addition amount of the modification aid is preferably in the range of 0.01 to 50 mol% when the total amount of the modifier is 100 mol%. If the addition amount is less than 0.01 mol%, the effect of addition may not be obtained, and if it exceeds 50 mol%, incomplete combustion of the combustion gas may occur.

  In addition, the temperature of the flame of the combustion gas radiated | emitted to a process surface has preferable 500-1500 degreeC. If the temperature is less than 500 ° C., incomplete combustion of the modifier is likely to occur. On the other hand, if the temperature exceeds 1,500 ° C., the transfer medium or transfer sheet is thermally deformed or thermally deteriorated. This is because there are severe restrictions on the material of the transfer target and transfer sheet that can be applied. The flame treatment time (radiation time) is preferably 0.1 s to 100 s. If the treatment time is less than 0.1 s, the easy-adhesion effect due to the modifier may not be evenly expressed. On the other hand, if the treatment time is more than 100 s, the transfer medium or transfer sheet may be thermally deformed or heated. This is because the material limit of the material to be transferred and the transfer sheet that can be applied becomes severe.

  By the way, in the modification process or the easy adhesion treatment process in which the oxidation flame treatment process is used in combination as described above, the wet tension (specified in JIS K 6768 (1999) is applied to the treated surface after the easy adhesion treatment. It is preferable that the measurement temperature is 25 to 80 mN / m. That is, if the wetting tension of the treated surface is less than 40 mN / m, the effect of easy adhesion cannot be obtained sufficiently. On the other hand, if the wetting tension exceeds 80 mN / m, the surface treatment is too strong and the heat of the transfer object or transfer sheet is high. This is because deterioration may occur.

  Further, as described above, in the easy adhesion treatment process in which the reforming process or the oxidation flame treatment process is used in combination with this, the treatment surface after the easy adhesion treatment is defined by JIS R 3257, which is measured using water. The contact angle (measurement temperature 25 ° C.) is preferably 0.1 to 30 °. That is, when the contact angle is less than 0.1 °, the surface treatment may cause thermal deterioration of the transfer medium or the transfer sheet. On the other hand, when the contact angle exceeds 30 °, the easy adhesion effect cannot be sufficiently obtained. Because.

[Water pressure transfer process (B)]
The hydraulic transfer step (B) includes at least a step (B1) for preparing a transfer sheet and an activation step (B2) for applying an adhesive force to a decorative layer made of a solid curable resin at room temperature that is not completely cured. ) And a water pressure applying step (B3) in this order. As described above, this hydraulic pressure transfer step after subjecting the transfer target to easy adhesion is a decorative layer made of a solid curable resin at room temperature, where the decorative layer of the transfer sheet is not completely cured, The process by a conventionally well-known hydraulic transfer method can be employ | adopted suitably.

[Step of preparing transfer sheet (B1)]
As a transfer sheet, a transfer layer having a conventionally known configuration in a hydraulic transfer method, except that a decorative layer made of a curable resin that is not completely cured at room temperature is used as a decorative layer of the transfer layer. What is necessary is just to prepare suitably selecting according to a use. Such a transfer sheet uses a water-soluble or water-swellable support sheet on which a decorative layer made of a solid curable resin at room temperature that is not completely cured is formed by printing or coating. be able to.

  First, the water-soluble or water-swellable support sheet may be a water-soluble or water-swellable sheet. Specific examples of the material include polyvinyl alcohol resin, dextrin, gelatin, glue, and casein. , Shellac, gum arabic, starch, protein, polyacrylic acid amide, polyacrylic acid soda, polyvinyl methyl ether, copolymer of methyl vinyl ether and maleic anhydride, copolymer of vinyl acetate and itaconic acid, polyvinyl pyrrolidone, Examples include acetyl cellulose, acetyl butyl cellulose, carboxymethyl cellulose, methyl cellulose, hydroxyl ethyl cellulose, sodium alginate and the like. And a support body sheet | seat will be obtained if 1 type single selected from these, or a 2 or more types of mixture is formed into a film. A sheet often used as a support sheet is a sheet having a thickness of about 20 to 100 μm, which is formed by mixing a saponified polyvinyl alcohol and starch, and further forming a mixture to which rubber or the like is added if necessary.

The decorative layer is formed using a curable resin that is not completely cured and is solid at room temperature. The decoration layer may be either a colored layer containing a colorant or a colorless transparent layer not containing a colorant. Further, any of a pattern layer partially provided in a desired pattern shape or a solid layer continuously provided over the entire surface may be used. For example, as a pattern of the decoration layer, for example, a solid surface, a grain pattern of various tree species, such as a grain pattern or a grain pattern, a stone pattern such as marble or granite, a tiled pattern, a brickwork pattern, a texture pattern, a leather pattern, A satin pattern, a grain pattern, an arabesque pattern, a floral pattern, a stripe pattern, a geometric figure, a character, or a combination of two or more of these is used.
Examples of the method for forming the decorative layer include gravure printing, offset printing, letterpress printing, flexographic printing, silk screen printing, ink jet printing, and electrophotographic printing, or roll coating, gravure roll coating, It can be applied by a coating method such as a bar coat.

As the ink for forming the decoration layer, a binder containing a curable resin that is not completely cured at room temperature and a colorant and, if necessary, various additives are used. As said curable resin used for a binder, curable resins, such as ionizing radiation curable resin and a thermosetting resin, can be used. Typical curing methods (mechanisms and molds) for completing the curing of such a curable resin after transfer are ionizing radiation curing and thermal curing.
The ink constituting the decorative layer needs to be not completely cured before the transfer process in order to ensure followability to the shape of the transfer surface and adhesion imparting by activation. The “not completely cured” state may be “a state where the curing reaction has partially progressed but has not yet been completed” other than the case where “the curing reaction has not progressed at all”. If the decorative layer is prevented from being excessively dissolved or swollen at the time of activation, or if the decorative layer does not become a non-adhesive solid when completely uncured, the decorative layer is partially cured.

As the ionizing radiation curable resin that is not completely cured (in the state) and is solid at room temperature as described above, for example, the following ionizing radiation curable resins (I) and (II) can be used.
Hereinafter, “room temperature” as used in the present invention means the ambient temperature in the room (or outdoors) where the transfer sheet is manufactured and stored, and the support sheet is peeled off. The specific value varies depending on the climate and the working environment, but is usually in the range of 10 to 40 ° C.

(I) Two types of thermoplastic resins (1) or (2) having a radically polymerizable unsaturated group.
(1) A polymer having a glass transition temperature of 0 to 250 ° C. and having a radically polymerizable unsaturated group. More specifically, radically polymerizable unsaturated groups were introduced by the methods (a) to (d) described later to those obtained by polymerizing or copolymerizing the following (1-1) to (1-8). Things can be used. In the following, for example, (meth) acrylate is used in the meaning of acrylate or methacrylate.
(1-1) Monomer having a hydroxyl group: N-methylol (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3 -Phenoxypropyl (meth) acrylate and the like.
(1-2) Monomers having a carboxyl group; (meth) acrylic acid, (meth) acryloyloxyethyl monosuccinate and the like.
(1-3) Monomers having an epoxy group; glycidyl (meth) acrylate and the like.
(1-4) Monomers having an aziridinyl group; 2-aziridinylethyl (meth) acrylate, allyl 2-aziridinylpropionate, and the like.
(1-5) Monomer having an amino group; (meth) acrylamide, diacetone (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and the like.
(1-6) Monomers having a sulfonic group; 2- (meth) acrylamido-2-methylpropane sulfonic acid and the like.
(1-7) Monomer having an isocyanate group; addition of a diisocyanate such as an adduct of 1,4-toluene diisocyanate and 2-hydroxyethyl (meth) acrylate to 1 mol and a radical polymerizable monomer having active hydrogen Things.
(1-8) Monomers other than the above (1-1) to (1-7) which can be copolymerized with the above monomers (1-1) to (1-7); Used as a copolymerization component to adjust the transition temperature and physical properties. For example, methyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, isoamyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl ( (Meth) acrylate and the like.

Next, the polymer or copolymer obtained as described above is reacted by the methods (a) to (d) described below to introduce radically polymerizable unsaturated groups.
(A) In the case of a polymer or copolymer of a monomer having a hydroxyl group, a monomer having a carboxyl group such as (meth) acrylic acid of (1-2)) mentioned above is subjected to a condensation reaction.
(B) In the case of a polymer or copolymer of a monomer having a carboxyl group or a sulfone group, the monomer having a hydroxyl group described in (1-1) is subjected to a condensation reaction.
(C) In the case of a polymer or copolymer of a monomer having an epoxy group, an isocyanate group, or an aziridinyl group, the monomer having the hydroxyl group described in (1-1) or the carboxyl group described in (1-2). The monomer is subjected to an addition reaction.
(D) In the case of a polymer or copolymer of a monomer having a hydroxyl group or a carboxyl group, the monomer having the epoxy group described in the above (1-3), the monomer having the aziridinyl described in the above (1-4), or the above-mentioned (1 A monomer having an isocyanate group, such as an adduct of 1 mol to 1 mol of the diisocyanate compound of -7) and a hydroxyl group-containing acrylate monomer, is subjected to an addition reaction.
In addition, in order to perform the said reaction, it is desirable to add a trace amount polymerization inhibitor, such as hydroquinone, and to carry out, sending dry air.

  (2) A compound having a melting point of 20 ° C. to 250 ° C. and having a radically polymerizable unsaturated group. Specific examples include triazine (meth) acrylate, stearyl (meth) acrylate, triacryl isocyanurate, cyclohexanediol di (meth) acrylate, spiroglycol diacrylate, and spiroglycol (meth) acrylate.

Also, the above (1) and (2) can be mixed and used.
Furthermore, a radically polymerizable monomer can also be added as a reactive diluent to the above (1) or (2) or a mixture of (1) and (2). This radically polymerizable monomer increases the crosslink density by irradiation with ionizing radiation and improves heat resistance. Examples of the monomer include, in addition to the monomers (1-1) to (1-8) described above, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, Trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) Acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, polyethylene glycol diglycidyl ether di (meth) acrylate, propylene glycol diglycidyl ether di (meth) Acrylate, polypropylene glycol diglycidyl ether di (meth) acrylate, and sorbitol tetraglycidyl ether tetra (meth) acrylate can be used. The blending amount is preferably 0.1 to 100 parts by mass with respect to 100 parts by mass of the resin of the above (1) or (2) alone or as a mixture.
In addition, a non-crosslinked resin described later (b) can be added.

(II) An ionizing radiation curable resin obtained by mixing an ionizing radiation curable resin that is liquid at normal temperature with a non-crosslinked resin that is a thermoplastic solid at normal temperature.
(A) An ionizing radiation curable resin that is liquid at room temperature; a composition comprising a single polymer or a mixture of prepolymers or monomers having radically polymerizable unsaturated groups in the molecule. Alternatively, it is a composition comprising a prepolymer or a monomer having a cationically polymerizable functional group.
Examples of the prepolymer having a radical polymerizable unsaturated group include polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, and melamine (meth) acrylate.
Examples of the monomer having a radical polymerizable unsaturated group include, as monofunctional monomers, methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenoxyethyl (meth) acrylate, and the like. In addition, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate as polyfunctional monomers Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.
Examples of the prepolymer having a cationic polymerizable functional group include a prepolymer of an epoxy resin such as a bisphenol type epoxy resin or a novolac type epoxy compound, or a vinyl ether resin such as a fatty acid vinyl ether or an aromatic vinyl ether.

(B) Non-crosslinked resin is a room-temperature solid thermoplastic resin that does not contribute to the crosslinking and curing reaction caused by ionizing radiation. For example, acrylic resin, cellulose resin, polyester resin, vinyl acetate resin, vinyl chloride Vinyl resins such as vinyl acetate copolymer and butyral resin.
For example, acrylic resin is used as the monomer,
(Meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid-n-propyl, (meth) acrylic acid isopropyl, (meth) acrylic acid-n-butyl, (meth) (Meth) acrylic acid alkyl esters such as isobutyl acrylate, (meth) acrylic acid-n-amyl, (meth) acrylic acid-n-hexyl, (meth) acrylic acid-n-octyl, (meth) acrylic acid lauryl,
(Meth) acrylic acid alkyl halides such as (meth) acrylic acid-2-chloroethyl and (meth) acrylic acid-3-chloropropyl,
(Meth) acrylic acid ester having a hydroxyl group such as (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl,
halogenated (meth) acrylic acid esters such as methyl α-chloro (meth) acrylate and ethyl α-chloro (meth) acrylate,
Α-alkyl (meth) acrylic acid ester having a hydroxyl group such as (meth) acrylic acid-1-chloro-2-hydroxyethyl,
And a homopolymer or copolymer composed of one or more of (meth) acrylic monomers such as glycidyl (meth) acrylate.
These acrylic resins preferably have an average molecular weight of 50,000 to 600,000 and a glass transition temperature of 50 to 130 ° C. If the average molecular weight and glass transition temperature are both within these numerical ranges, the effect of losing the fluidity of the ionizing radiation curable resin that is liquid at room temperature at room temperature, high durability of the adhesive, high final adhesion, and adhesion All the flexibility of the agent layer can be provided, which is preferable.

In addition, when making it harden | cure with an ultraviolet-ray or visible light, a photoinitiator is further added to the ionizing radiation-curable resin of said (I) or (II). In the case of a resin system having a radically polymerizable unsaturated group, acetophenones, benzophenones, thioxanthones, benzoin, and benzoin methyl ethers can be used alone or in combination as a photopolymerization initiator. In the case of a resin system having a cationic polymerizable functional group, an aromatic diazonium salt, an aromatic sulfonium salt, an aromatic iodonium salt, a metallocene compound, a benzoin sulfonic acid ester or the like is used alone or as a mixture as a photopolymerization initiator. be able to. In addition, as addition amount of these photoinitiators, it is about 0.1-10 mass parts with respect to 100 mass parts of ionizing radiation curable resin.
As the ionizing radiation, electromagnetic waves or charged particles having energy capable of crosslinking the molecules in the adhesive are used. Usually used are ultraviolet rays or electron beams, but in addition, visible light, X-rays, ion rays and the like can also be used. As the ultraviolet light source, a light source such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light, a metal halide lamp or the like is used. As a wavelength of ultraviolet rays, a wavelength range of 190 to 380 nm is mainly used. As the electron beam source, various electron beam accelerators such as a cockcroft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, a high frequency type, etc. are used, preferably 100 to 1000 keV, preferably That irradiates electrons having energy of 100 to 300 keV is used.

  Moreover, various additives can also be added to the ionizing radiation curable resin as necessary. Examples of these additives include extender pigments (fillers) made of fine powders such as calcium carbonate, barium sulfate, silica, and alumina.

  The thermosetting resin includes a self-crosslinking acrylic resin, a melamine cross-linking acrylic resin, a blocked isocyanate curable acrylic resin, a self-crosslinking polyester resin, a melamine cross-linking polyester resin, a blocked isocyanate curable polyester resin, and esterification. A composition such as a polyester resin with incomplete reaction can be used.

  In addition, as the thermosetting resin, it is possible to use a polyurethane resin containing an isocyanate and an active hydrogen-containing compound that reacts with the isocyanate, and is a solid and thermoplastic urethane uncured product at room temperature. As the isocyanate and the active hydrogen-containing compound that reacts with the isocyanate, for example, the following compounds can be used.

  As the isocyanate, a divalent or higher aliphatic or aromatic isocyanate can be used. For example, divalent isocyanate such as 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, 1,5-naphthalenediisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylene diisocyanate, or the like , Trisocyanate such as Desmosur R (Bayer, trade name of tolylene diisocyanate adduct), Desmosur L (Bayer, trade name of tolylene diisocyanate adduct), Tri Examples thereof include tetravalent or higher isocyanatoates such as diisocyanate trimer polymers.

In addition, the above isocyanate may be used alone, but the following blocking agent is added to the isocyanate group, and is used in a form in which the blocking is released by appropriately heating together with a dissociation catalyst at the time of crosslinking and curing. It may be used. Moreover, even if it is an isocyanate simple substance even if it is a normal temperature liquid, it can also be solidified and used. By using as a blocked isocyanate, in particular, in the present invention, the isocyanate is preferably converted to a blocked isocyanate in order to prevent unnecessary reaction with water during the transfer because of the transfer by hydraulic transfer. This also prevents cross-linking curing before transfer.
Examples of the blocking agent include phenol, cresol, xylenol, p-ethylphenol, o-isopropylphenol, p-tert-butylphenol, p-tert-octylphenol, thymol, p-naphthol, p-nitrophenol, and p-chlorophenol. Phenolic blocking agents such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, phenyl cellosolve, furfuryl alcohol, cyclohexanol and other alcohol blocking agents, dimethyl malonate, Active methylenes such as diethyl malonate and ethyl acetoacetate, and mer such as butyl mercaptan, thiophenol and tert-dodecyl mercaptan Butane-based blocking agents, acid-amide-based blocking agents such as acetanilide, acetanisidide, acetic acid amide, benzamide, imide-based blocking agents such as succinimide, maleic acid imide, amine-based blocking agents such as diphenylamine, phenylnaphthylamine, aniline, carbazole, Imidazole-based blocking agents such as imidazole and 2-ethylimidazole, urea-based blocking agents such as urea, thiourea, and ethyleneurea, carbamate-based blocking agents such as phenyl N-phenylcarbamate and 2-oxazolidone, and ethyleneimine Imine blocking agents, formaldehyde oximes, acetoald oximes, oxime blocking agents such as methyl ethyl ketoxime, cyclohexanone oxime, sodium bisulfite, bisulfite Sulfurous acid blocking agents such as potassium gluconate.

  As the active hydrogen-containing compound that reacts with isocyanate, a compound containing a hydroxyl group, a carboxyl group, or the like in the molecule is used, and among them, a polyol having two or more hydroxyl groups in the molecule is typical. In order to form a curable resin that is not completely cured at room temperature, a polyol that is solid at room temperature is preferably used. For example, poly (ethylene adipate), poly (butylene adipate), poly (neopentyl adipate), poly (hexamethylene adipate), poly (butylene azelate), poly (butylene sebacate), polyester polyols such as polycaprolactone, polyethylene Examples thereof include polyether polyols such as oxide, polypropylene oxide and poly (tetramethylene ether), and polycarbonate polyols such as poly (butylene carbonate) and poly (hexamethylene carbonate). The number average molecular weight of these polyols is preferably in the range of 600 to 5,000. In the present invention, the resin of the decorative layer at the time of hydraulic transfer is formed as a solid curable resin at room temperature that is not completely cured. Therefore, the above isocyanate and polyol are used in such a combination that they become solid in a mixed uncured state. For this purpose, at least one of them should be solid at room temperature.

  In addition, the polyurethane resin containing the isocyanate and the active hydrogen-containing compound is a metal soap or amine for lowering the dissociation temperature when a curing catalyst such as a metal salt or a blocking agent is used as in the case of a conventionally known adhesive. A dissociation catalyst such as Furthermore, various additives can be added as necessary. Examples of these additives include extender pigments (fillers) made of fine powders such as calcium carbonate, barium sulfate, silica, and alumina.

  In addition, as a coloring agent used for coloring the decorative layer, a known one may be used as appropriate. For example, titanium white, antimony white, lead white, carbon black (black), iron black, chrome lead, titanium yellow, vermilion, Inorganic pigments such as cadmium red, ultramarine and cobalt blue, organic pigments (or dyes) such as benzidine yellow, isoindolinone yellow, polyazo red, quinacridone red, indanthrene blue, and phthalocyanine blue, and scaly foils of metals such as aluminum and brass A metallic pigment made of a piece, a pearlescent pigment made of a scaly foil piece such as titanium dioxide-coated mica, basic lead carbonate, or the like is used. Examples of the additive include extender pigments, ultraviolet absorbers, plasticizers, heat stabilizers, light stabilizers, and surfactants.

  In the present invention, in addition to a layer made of a curable resin that is not completely cured at room temperature (also referred to as a specific curable resin layer), the decorative layer is further normal (completely cured). There may also be a layer (usually called an ink layer) made of an ink (or paint) made of a resin (other than a curable resin that is solid at room temperature).

Here, as a typical form (combination) of both the specific curable resin layer and the normal ink layer,
(I) Support sheet / [transparent solid layer of specific curable resin / colored solid layer of normal ink layer]
(Ii) Support sheet / [transparent solid layer of specific curable resin / colored pattern layer of normal ink layer]
(Iii) Support sheet / [colored pattern layer of specific curable resin / colored pattern layer of normal ink layer]
(Iv) Support sheet / [transparent solid layer of specific curable resin / colored pattern layer of specific curable resin]
(V) Support sheet / [transparent solid layer of specific curable resin / colored solid layer of specific curable resin]
(Vi) Support sheet / [transparent solid layer of specific curable resin / colored pattern layer of normal ink layer / colored solid layer of specific curable resin]
(Vii) Support sheet / [transparent solid layer of specific curable resin / colored pattern layer of specific curable resin / colored solid layer of specific curable resin]
Etc. Here, the inside of [] is a decoration layer.
In order to ensure the durability of the decorative layer, at least the outermost surface layer after transfer (the layer closest to the support sheet) is preferably formed from a layer of a specific curable resin.

[Activation step (B2)]
In the activation step (B2), the prepared transfer sheet as described above is subjected to the easy adhesion treatment step (A0s), or (A0s) and (A1s) with or without these steps. In this step, at least a part of the decorative layer is dissolved or swollen so as to easily adhere to the transfer target, thereby providing an adhesive force. For this purpose, in the activation step, a solvent capable of dissolving or swelling the binder component of the decorative layer is used as an activator. Examples of the solvent include pentane, hexane, heptane, octane, etc., or a mixture thereof such as gasoline, petroleum, benzine, toluene, xylene, cyclohexane, ethylbenzene, and other aromatic hydrocarbons, trichloroethylene, Halogenated hydrocarbons such as lorethylene, chloroform and carbon tetrachloride, monohydric alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol and amyl alcohol, and polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin , Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl ether, isopropyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Ethers such as ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dibutyl ether, ethyl acetate, ethylene glycol monoethyl ether acetate, acetate esters such as diethylene glycol monoethyl ether acetate, esters such as butyric acid ester, Are used alone or as a mixed solvent.

  In the activation step, there are typically the following two forms of applying the activator to the decorative layer surface side of the transfer sheet, and either form may be used. That is, (B21) First, after the activator is applied to the decorative layer surface side of the transfer sheet, the transfer sheet is floated on the water surface with the support sheet side facing the water surface side. The sheet is floated on the water surface with the support sheet side facing the water surface side, and then the activator is applied to the decorative layer surface side of the transfer sheet. In order to float the transfer sheet on the water surface, a single sheet of transfer sheet is floated one by one, or a continuous belt-shaped transfer sheet is continuously supplied and floated on the water surface in which water is flowed from one direction. .

  Note that only the solvent may be used as the activator, but the activator evaporates until the water pressure application process in which the decorative layer contacts and adheres to the transfer surface is completed on the water surface. A material that does not erode and does not erode the surface to be transferred is preferable. As such an activator, the swelling liquid (composition) which added about 5-60 mass% of following resins with respect to the solvent further in the solvent, for example is mentioned. According to the swelling liquid, it is easy to adjust the viscosity of the activator, and it is possible to select a wide range of means for applying the activator coating liquid, and more stable adhesion can be achieved even when the hydraulic pressure application process takes time. can get. Examples of the resin added to the swelling liquid include, for example, vinyl halide polymers such as polyvinyl chloride and polyvinylidene chloride, styrene polymers such as polystyrene and styrene derivatives, vinyl ester polymers such as polyvinyl acetate, Polymers of ester derivatives of unsaturated carboxylic acids such as (meth) acrylic acid, itaconic acid, crotonic acid, maleic acid or fumaric acid, polymers of the same nitrile derivatives or acid amide derivatives, or the above unsaturated carboxylic acids N-methylol derivatives and N-alkylmethylol ether derivatives, glycidyl (meth) acrylate, acrylic glycidyl ether, vinyl isocyanate, allyl isocyanate, 2-hydroxyethyl- (meth) acrylate, 2-hydroxypropyl- ( (Meth) acrylate, Thermoplastic resins or initial condensates of monomers such as ethylene, ethylene glycol-mono (meth) acrylate, or copolymers, or natural resins, rosin and derivatives thereof, cellulose derivatives, natural or synthetic Examples of the resin include rubber and petroleum resin.

In order to apply the activator as described above to the decorative layer side of the transfer sheet, a known coating method may be used. Examples of the coating method include gravure offset coating, gravure coating, roll coating, bar coating, spray coating, and the like. The coating amount of the activator is about ² to 30 g / m ² , preferably about 3 to 15 g / m ² .

[Water pressure application step (B3)]
In the water pressure application step (B3), the transfer body is pressed from above against the transfer sheet on the water surface after the activation step, and the transfer sheet is brought into close contact with the transfer body by water pressure, and the decoration layer Is closely attached to the transfer surface of the transfer object. FIG. 2 is an explanatory view conceptually showing this step. That is, in the water pressure application step, the transfer body M is lowered from above the transfer sheet S suspended on the water surface W so that the transfer surface Mf to be decorated is downward, and the transfer body is moved underwater. , The transfer sheet is stretched and deformed along the shape of the transfer surface, and the transfer sheet is brought into close contact with the transfer surface by water pressure. When the transfer sheet S floats on the water surface W and the support sheet Sb comes into contact with water, the transfer sheet S swells when it is water-swellable and dissolves when it is water-soluble. Therefore, when the support sheet is water-swellable, the support sheet Sb is in close contact with the transfer surface Mf integrally with the decorative layer Sp. On the other hand, when the support sheet is water-soluble, there are a case where the support sheet is completely dissolved in water and only the decorative layer floats on the water surface, and a case where a part of the support sheet is dissolved and a part remains. When only the former decorative layer floats on the water surface, only the decorative layer is in close contact with the transfer target.

  Note that the water temperature for floating the transfer sheet and applying the water pressure is appropriately adjusted according to the type of the support sheet of the transfer sheet (for example, difference in water solubility or water swellability). For example, when the support sheet is a starch-based sheet, the water temperature is preferably 40 to 50 ° C. Further, an additive for promoting the removal of the support sheet may be added. For example, in the case of a starch-based sheet, amylase or the like is added.

[Film removal step (B4)]
In the water pressure transfer process, a film removal process is appropriately performed after the water pressure application process. In this film removal step (B4), when the support sheet is also pressed against the transferred body together with the decorative layer in the water pressure applying step, the support sheet is removed by dissolution or washing, In this step, only the decorative layer is left on the transfer target. Accordingly, when only the decorative layer is floating on the water surface when the transfer target is pushed into the water and the water pressure is applied, this film removal step is unnecessary. In other words, the film removal step is performed after the decoration layer is sufficiently adhered to the transfer surface of the transfer object when at least a part of the support sheet of the transfer sheet remains on the transfer object without being dissolved. And removing the support sheet. The support sheet is removed by, for example, shower cleaning using water. The support sheet adhering to the transfer surface is completely removed by the film removal process. In addition, although the conditions of shower washing differ with the kind of support body sheet | seat, etc., the water temperature of 15-60 degreeC and the washing | cleaning time 10s-5min (300s) "are preferable normally. Then, after the film removal step or when the film removal step is omitted, after the water pressure application step and at the end of the water pressure transfer step (B), if the transferred material is sufficiently dried to evaporate the water, A transfer article provided with a desired design is obtained by the decorative layer transferred to the transfer surface of the body.

[Curing process]
The curing step (C) is a step of completely curing a curable resin that is not completely cured at the time of hydraulic transfer. The curing method (mechanism, mold) depends on the curable resin used, and ionizing radiation curing and heat curing are typical.
And the timing of completion of hardening is preferable after completion | finish of a hydraulic transfer process. In particular, in the case of ionizing radiation curing, if moisture is contained in the decorative layer, it may inhibit the curing of the ionizing radiation curable resin, so that it is possible to irradiate ionizing radiation after sufficiently drying the moisture during transfer. preferable.
On the other hand, if it is cured before hydraulic transfer, the decorative layer is cured and becomes brittle, so that it is difficult to follow the shape of the surface to be transferred of the transfer target. Moreover, if it is made to follow forcibly, a crack and a fracture | rupture will be produced in a decoration layer. In addition, the decoration layer loses swelling and solubility due to the organic solvent. For this reason, it is not preferable to complete the curing before the hydraulic transfer because, for example, it becomes impossible to impart (activate) the adhesion of the decorative layer with the activator.

[Auxiliary process: painting process]
In the present invention, one of the major features is that the painting process can be omitted. However, depending on the demand for a transfer product that requires a very thick feeling of coating, it is not possible to completely eliminate the last painting. Absent. For the coating, conventionally known materials and methods will be appropriately employed.
For example, the surface of the obtained transfer article can be further subjected to a coating step (D) for applying a coating and forming a protective film for surface strength improvement, surface protection, surface gloss adjustment and the like. As the protective film, for example, a resin such as a urethane resin, an epoxy resin, an acrylic resin, a fluororesin, or a silicon resin is used. For example, as the urethane resin, the same resins as those listed above for the binder resin of the decorative layer can be used. As a coating method, known coating (coating) methods such as spray coating, electrostatic coating, brush coating, and immersion are used.

[Example 1]
As the transfer object M, an injection-molded product having a shape as shown in FIG. 3 made of polypropylene was prepared. The wetting tension (25 ° C.) of the surface of the transferred material is 33 mN / m. The dimensions are height H = 15 mm, width W = 60 mm, length L = 100 mm, side surface tilt angle Φ = 70 °, and corner radius of curvature R = 10 mm.

  Next, as an oxidation flame treatment step (A0) of the easy adhesion treatment step (A), an oxidation flame treatment was performed using the apparatus as shown in FIG. . That is, the transfer target M was placed on the belt conveyor (mounting table) B so that the transfer target surface Mf faces upward. Then, propane gas as combustible gas is supplied from the combustible gas tank 2 via the valve 3A, air is supplied from the air compressor 1 via the valve 3B, and both are supplied as mixed gas via the valve 3C. Then, it was supplied to the burner 5 via the pipe 4. The burner 5 has nozzles 5A arranged in a straight line, and an oxidization flame obtained by burning the mixed gas from the nozzles is used as a flame 6 to radiate toward the transfer surface Mf of the transfer target M, while being a belt conveyor. B was moved to expose the entire surface of the transfer surface Mf to the oxidation flame for 1 second.

Next, as a modification step (A1) of the easy adhesion treatment step (A), the transfer target M subjected to the oxidation flame treatment was placed on the belt conveyor B again using the apparatus of FIG. This time, in addition to the combustible gas and air, tetramethylsilane (modifier) having a boiling point of 27 ° C. is supplied from the modifier tank 7 via the valves 3D and 3C. 0.00001 mol% of tetramethoxysilane (reforming aid) having a boiling point of 122 ° C. with respect to the total amount is supplied in an amount of 0.00001 mol%, and burner via a pipe 4 as a combustion gas composed of these four mixed gases. The flame 6 containing a compound having a silicon atom was emitted from the nozzle 5A toward the transfer surface Mf of the transfer target M, which is the processing surface, and the transfer surface was exposed for 1 second. In this way, a thin film having a thickness of 20 nm made of oxygen-excess silicon oxide Si0 _2.7 is formed on the transfer surface Mf of the transfer object M by a flame pyrolysis reaction, and subjected to a modification process to facilitate an easy adhesion process. It was.

  Subsequently, as a step (B1) of preparing a transfer sheet in the hydraulic transfer step (B), a water-swellable sheet having a thickness of 40 μm mainly composed of saponified polyvinyl alcohol and starch is used as a support sheet Sb. Then, using a gravure printing machine, a transfer sheet S was manufactured by first printing a colorless and transparent whole surface solid layer and then a wood grain pattern layer thereon to form a decorative layer Sp (see FIG. 2). The binder resin used as the binder for the printing ink of the decoration layer is a solid in an uncured state even at room temperature, in which 1-hydroxycyclohexyl phenyl ketone is added as a photoinitiator to a triazine acrylate prepolymer having a melting temperature of 115 ° C. Of the ionizing radiation curable resin (specifically, an ultraviolet curable resin). The ink for the entire solid layer consists only of the binder resin, and the ink for the grain pattern layer is an ink mainly composed of carbon black, petal, and chrome lead, and phthalocyanine blue and titanium white as colorants. It was used.

Next, as an activation step (B21) of the hydraulic transfer step (B), after applying 13 g / m ^{2 of} an activator having the following composition on the decorative layer of the transfer sheet, the water surface at a water temperature of 30 ° C. as shown in FIG. The transfer sheet S was floated on W with the support sheet Sb side facing the water surface. Then, after 1 minute has passed and the support sheet is in a swollen state, the transfer body M that has undergone the above-described easy adhesion treatment process is pushed in from above the transfer sheet, and the transfer sheet is spread on the transfer surface of the transfer body. It was made to adhere. Thereafter, the transferred material, which was spread and adhered to the surface of the transfer sheet, was drawn out of the water. Next, as a film removal step (B4), a hot water shower at 40 ° C. is sprayed on the transferred body for 30 seconds, and then a fresh water shower is further sprayed to support the transfer sheet attached on the transferred body. The sheet was removed. Next, the transfer object was dried to obtain a transfer article having the decorative layer transferred to the transfer object.

Active agent composition:
Butyl cellosolve acetate 26 parts by weight Butyl carbitol acetate 26 parts by weight Butyl methacrylate polymer 8 parts by weight Dibutyl phthalate 20 parts by weight Barium sulfate 20 parts by weight

  Next, as a curing step (C), using a UV irradiation device composed of a high-pressure mercury lamp, the decoration layer on the surface of the transfer object was irradiated with UV to crosslink and cure. As described above, a desired transfer product having a surface decorated by hydraulic transfer was obtained.

[Example 2]
Example 1 was the same as Example 1 except that the oxidation flame treatment step (A0) was omitted.

Example 3
In Example 1, the same procedure as in Example 1 was followed, except that the modifier used in the modifying step (A1) was replaced with tetramethyltitanium and the modifier was omitted.

Example 4
In Example 1, the same procedure as in Example 1 was followed, except that the modifier used in the reforming step (A1) was replaced with tetramethylaluminum and the modifier was omitted.

Example 5
In Example 1, the adhesive layer side of the transfer sheet was subjected to the easy adhesion treatment process under the same conditions as those for the transfer target, that is, the easy adhesion treatment processes (A0s) and (A1s), and then the hydraulic transfer. The procedure was the same as Example 1 except that the step (B) was performed.

Example 6
In Example 2, on the decorative layer surface side of the transfer sheet, the easy adhesion treatment process under the same conditions as those for the transfer target, that is, the easy adhesion treatment process (A1s), is performed, followed by the hydraulic transfer process (B). The procedure was the same as in Example 2 except that

[Comparative Example 1]
In Example 1, it was the same as Example 1 except that the easy adhesion treatment process (A) (process A0 and process A1) was omitted.

[Comparative Example 2]
In Example 1, the easy adhesion treatment step (A) (step A0 and step A1) is omitted, the binder resin of the decoration layer ink is changed to a mixture of nitrified cotton and alkyd resin, and further a curing step Same as Example 1 except that (C) was also omitted.

[Evaluation]
In each of the examples and comparative examples, wetting tension immediately after the easy adhesion treatment step (in Comparative Example 1 and Comparative Example 2, there is no easy adhesion treatment step, which is the untreated surface of the transferred body itself). JIS K 6768 (1999) regulation) (at 25 ° C.) was measured. Further, for each of the obtained transfer articles, the adhesion between the decorative layer and the transfer target was evaluated. Adhesion is achieved by applying a cellophane adhesive tape (made by Nichiban Co., Ltd., trade name “Cellotape (registered trademark)”, width 25 mm) on the decorative layer and then peeling off at room temperature of 25 ° C., and there is no peeling of the decorative layer Those with good (◯), those with partial peeling were evaluated as slightly good (Δ), and those with peeling over the entire surface of the tape were evaluated as poor (×). The evaluation results are shown in Table 1.
In addition, the evaluation of scratch resistance was good (◯) when the surface of the decorative layer on the transferred body was rubbed 3 times with steel wool (product number 0000) and then visually observed, and no scratch was observed. Those with slight scratches were evaluated as slightly good (Δ), and those with clear scratches were evaluated as poor (×).

As shown in Table 1, each of the examples in which the reforming process was performed and the specific curable resin was used for the decoration layer, Comparative Example 1 and Comparative Example 2 without the reforming process, regardless of the presence or absence of the oxidation treatment process. Compared with, wetting tension increased and adhesion improved. However, in Example 2 in which the oxidation flame treatment step was omitted, the increase in wetting tension was slightly less than that in the other examples, resulting in variations, and the adhesion was slightly reduced.
In addition, each example was clearly better in scratch resistance than Comparative Example 2 in which a specific curable resin was not used for the decorative layer.

Explanatory drawing which shows notionally the apparatus structural example which performs a modification | reformation process and an oxidation flame treatment process. Explanatory drawing which illustrates a hydraulic pressure transfer process notionally. Explanatory drawing explaining the example of a shape of a to-be-transferred body with a perspective view (A) and sectional drawing (B).

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Air compressor 2 Flammable gas tank 3A-3D valve 4 Piping 5 Burner 5A Nozzle 6 Flame 7 Modifier tank B Station (belt conveyor)
M Transfer object Mf Transfer surface S Transfer sheet Sb Support sheet Sp Decoration layer W Water surface

Claims (4)

(A) an easy-adhesion treatment step for easily adhering at least the transfer surface of the transfer object;
(B) a water pressure transfer step of transferring a decorative layer made of a solid curable resin at room temperature that is not completely cured using water pressure as a transfer pressure on the transfer surface;
(C) a curing step for curing the curable resin of the decorative layer;
A hydraulic transfer method in which the steps are performed in this order;
Easy adhesion treatment process (A)
(A1) including a modification step of emitting a flame containing one or more compounds having a silicon atom, a titanium atom, or an aluminum atom on the transfer surface,
The hydraulic transfer process (B)
(B1) preparing a transfer sheet in which a desired decorative layer is formed by printing or coating on a water-soluble or water-swellable support sheet;
(B2) As an activation process for imparting adhesive force to the decorative layer,
(B21) First, an activator for imparting adhesive force to the decorative layer is applied to the decorative layer surface side of the transfer sheet, and then the transfer sheet is placed on the water surface so that the support sheet side faces the water surface side. Float or
(B22) First, the transfer sheet is floated on the water surface so that the support sheet side faces the water surface side, and then an activator for imparting adhesive force to the decorative layer is provided on the decorative layer surface side of the transfer sheet. Either do the coating,
(B3) Next, a water pressure application step of pressing the transfer target onto the transfer sheet on the water surface and bringing the transfer sheet into close contact with the transfer target surface of the transfer target by water pressure is included in this order.
Hydraulic transfer method. Easy adhesion treatment process (A)
(A0) Oxidation flame treatment process for radiating an oxidation flame to the transfer surface;
(A1) a reforming step of emitting a flame containing one or more compounds having a silicon atom, a titanium atom, or an aluminum atom on the transfer surface;
The hydraulic transfer method according to claim 1, wherein the steps are performed in this order. The easy adhesion treatment step (A)
(A1s) The modification | reformation process of radiating | emitting the flame containing 1 or more types of a compound which has a silicon atom, a titanium atom, or an aluminum atom is included in the decoration layer surface side of a transfer sheet prior to an activation process (B2). Alternatively, the hydraulic transfer method according to claim 2. The easy adhesion treatment step (A)
(A0s) First, an oxidation flame treatment process for radiating an oxidation flame prior to the activation process (B2) on the decorative layer surface side of the transfer sheet,
(A1s) Next, a modification step of emitting a flame containing one or more compounds having a silicon atom, a titanium atom, or an aluminum atom on the decorative layer surface side of the transfer sheet,
The hydraulic transfer method according to claim 1 or 2, comprising:

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