JP6601715B2 - Water pressure transfer method and water pressure transfer decorative article - Google Patents

Description

  The present invention relates to a water pressure transfer method and a water pressure transfer decorative article.

  A hydraulic transfer method is known as a method for transferring a printed pattern or the like to a transfer target having a three-dimensional surface.

  Patent Document 1 describes a hydraulic transfer film in which a support layer made of a water-soluble or water-swellable resin, a transfer layer soluble in an organic solvent, and a dissociable film are laminated on a peelable film. ing. Patent Document 2 discloses that after a hydraulic transfer film is suspended on the surface of the water, an activator is sprayed onto the transfer layer of the hydraulic transfer film to activate the transfer layer, and then on the transfer layer of the hydraulic transfer film. Describes a water pressure transfer method in which a transfer material is pressed to transfer a transfer layer in close contact with the transfer material by water pressure.

JP 2004-291439 A JP 2003-145997 A

  Since the hydraulic transfer method can transfer a printed pattern or the like to a transfer target having a three-dimensional surface, transfer to various compositions is expected. For example, nonpolar polymers such as polyethylene and polypropylene have a weak binding force due to intermolecular force, and materials having a close surface such as ceramics and glassy materials such as glazes have a low mechanical binding force, and these have poor adhesion. Therefore, in order to bring the transfer layer of the hydraulic transfer film into close contact with them, it is required to improve the adhesion of the transfer layer to the transfer target.

  However, the hydraulic transfer method uses a dry film in order to prevent color bleeding and swelling due to water during the hydraulic transfer. Due to the dry condition, the raw materials that can be used are limited, and it is difficult to improve the adhesion of the transfer layer to the transfer target.

  The present invention provides a water pressure transfer method and a water pressure transfer decorative article that enable water pressure transfer even if the surface to be transferred is a glassy or nonpolar polymer having poor adhesion. .

  In the hydraulic transfer method of the present invention, the hydraulic transfer film is floated on the surface of the water, the transferred body is pressed from the transfer layer on the surface of the hydraulic transfer film, and the transferred layer is transferred to the transferred body by hydraulic pressure. In the transfer method, a transfer surface of the transfer object is formed of a glassy material or a nonpolar polymer, and the surface to be transferred is subjected to a surface modification treatment with an organic-inorganic composite compound as a pretreatment of the hydraulic transfer. It is said.

  In the hydraulic transfer method of the present invention, the glassy material or nonpolar polymer inferior in adherence as the surface to be transferred is subjected to a surface modification treatment with an organic-inorganic composite compound, thereby improving the adherence. It becomes possible to perform water pressure transfer on the transfer surface.

  In addition to the above effects, the organic-inorganic composite compound is a silane coupling agent, so that the hydraulic transfer decorative article has excellent durability such as water resistance and alkali resistance due to the condensability of the silane coupling agent. It becomes.

  In addition to the above-described effects, the surface modification treatment is any one of electrostatic painting treatment, pressure painting treatment, and combustion painting treatment. Energy consumption can be reduced.

  In addition, the hydraulic transfer decorative article is obtained by the above-described hydraulic transfer method, so that even if the transfer target is a glassy material or a nonpolar polymer, the printed pattern or the like is transferred cleanly by the surface modification treatment. Can be a decorated item.

It is explanatory drawing which shows the concept of the hydraulic transfer method in this invention.

  An embodiment of a hydraulic transfer method according to the present invention will be described with reference to the drawings. The water pressure transfer method of the present invention is not limited to this configuration. That is, various design changes can be made without departing from the gist of the present invention.

  In the present invention, the hydraulic transfer film 10 is floated on the surface of the water, the transferred body 30 is pressed from above the surface transfer layer 12 of the hydraulic transfer film 10, and the transfer layer 12 is transferred to the transferred body 30 by hydraulic pressure. In the transfer method, the transfer surface 30A of the transfer target 30 is formed of a glassy material or a nonpolar polymer, and the surface to be transferred 30A is subjected to a surface modification treatment with an organic-inorganic composite compound as a pretreatment for hydraulic transfer. It is characterized by.

  By using the water pressure transfer method of the present embodiment, the transfer target 30 is processed in the order of surface modification treatment, undercoat material coating, water pressure transfer, top coat material coating, and becomes a water pressure transfer decorative article.

(Transfer)
The transfer target 30 is decorated with the hydraulic transfer film 10. And the composition is not particularly limited, but in the present invention, as a special ground for which it is difficult to make the transfer layer 12 of the hydraulic transfer film 10 in close contact, a glassy material, a nonpolar polymer The thing that consists of.

“Vitreous” means an amorphous oxide, but it is assumed to be vitreous even if a part thereof is crystallized, as is common technical knowledge. In general, the vitreous material has a dense surface structure in which a metal oxide such as SiO ₂ , Al ₂ O ₃ , ZrO _2, etc. is heated to a temperature range of 700 to 1300 ° C. and then cooled and vitrified. It is supposed to be. Due to the dense surface structure, the vitreous material has a weak mechanical bonding force and it is difficult to adhere the transfer layer 12 of the hydraulic transfer film 10. Examples of the glassy material include amorphous solid (glass), ceramics, sanitary ware, and jars.

  Sanitary ware is ceramic appliances used in architectural sanitary facilities, including basins, toilets, and sinks. In sanitary ware, for example, a bowl portion of a toilet bowl is a portion where the surface of the sanitary ware needs to be vitreous having a weak mechanical bonding force in order to prevent contamination due to adhesion of foreign matter or the like. However, as other parts, for example, the outer part of the toilet is a part that is desired to be decorated by the transfer layer 12 of the hydraulic transfer film 10. And by using a general-purpose masking tape etc., it can be divided into a decoration part and a non-decoration part according to these parts.

  Nonpolar polymers are polymeric substances that do not have permanent dipoles, even if they contain permanent dipoles derived from normal impurities or additives that are usually added as common technical knowledge. It is considered as a functional polymer Examples of nonpolar polymers include polyethylene resin, polypropylene resin, and tetrafluoroethylene resin. Nonpolar polymers have a low intermolecular force because they are not polar, and it is difficult to make the transfer layer 12 of the hydraulic transfer film 10 adhere to them.

(Surface modification treatment)
The surface modification treatment is a treatment for modifying the surface of the transfer target 30 and uniformly coats the transfer surface 30A of the transfer target 30 with an organic-inorganic composite compound described later. Before the surface modification treatment, it is preferable that impurities such as fat are removed from the transfer target 30 by degreasing with ethanol or the like.

  As surface modification treatment methods, electrostatic painting treatment, pressure painting treatment, combustion painting treatment, plasma treatment, corona discharge treatment, ultraviolet irradiation treatment, ozone treatment, laser irradiation treatment, electron beam irradiation treatment, etc. are used. be able to. Among these surface modification treatment methods, electrostatic coating treatment, pressure coating treatment, and combustion coating treatment are more preferable because they consume less energy than other surface treatments. Further, electrostatic coating processing and combustion coating processing, which require a small amount of the organic-inorganic composite compound, are more preferable.

  In general, the electrostatic coating treatment is performed by charging a surface modification agent to a negative polarity, spraying it toward the grounded transfer target 30, and inducing it by electric lines of force of an electrostatic field. 30 is a coating process for coating 30. The coating process can be performed using a general-purpose electrostatic coating machine.

  The pressure coating process is a so-called air coating, in which a surface modifying treatment agent and a diluent are uniformly mixed, and sprayed toward the transfer target 30 with the force of pressurized air. This is a coating process in which the modifying agent is uniformly applied to the transfer target 30. It can be painted using a general-purpose air coating machine.

  The combustion coating process is a process in which a surface modification treatment agent and a combustion agent are uniformly mixed and burned, and the burned flame is jetted toward the transfer body 30 to transfer the surface modification treatment agent to the transfer body. 30 is a coating process that uniformly coats 30. The combustion coating process is also called a frame coating process or a flame coating process. It can be painted using a general-purpose combustion coating machine.

(Organic inorganic composite compound)
In this specification, an organic-inorganic composite compound is a compound in which one or more organic groups are bonded to a metal atom, a semiconductor atom, or a non-metal atom, and the surface of a glassy or nonpolar polymer that is the transfer target 30 It improves the adherence of the.

  Titanium, aluminum, silicon, etc. are mentioned as a metal atom contained in an organic inorganic composite compound. By including these metal atoms, the organic-inorganic composite compound is easily adhered to the transfer target 30.

  Examples of the organic group contained in the organic-inorganic composite compound include an alkyl group and an alkoxy group. By containing these organic groups, the transfer layer 12 is easily adhered to the organic-inorganic composite compound (transfer object 30).

  Examples of the organic-inorganic composite compound containing an alkyl group include tetramethyl titanium, tetramethyl aluminum, tetramethyl silane, tetraethyl titanium, tetraethyl aluminum, tetraethyl silane, 1,2-dichlorotetramethyl titanium, 1,2-dichlorotetramethyl aluminum, 1 1,2-dichlorotetramethylsilane, 1,2-dichlorotetraethyltitanium, 1,2-dichlorotetraethylaluminum, 1,2-dichlorotetraethylsilane, hexamethyldisiloxane, hexamethyldisilazane, and the like can be used.

A silane coupling agent can also be used as the organic-inorganic composite compound containing an alkoxy group. A silane coupling agent is a compound containing an organic functional group and a group (alkoxy group) having hydrolyzability and condensability. For example, the general formula: R ¹ — (CH ₂ ) _n —Si (OR ² ) It is represented by _m . R ¹ is an organic functional group, R ² is a methyl group or an ethyl group, n is an integer of 1 to 3, and m is an integer of 1 to 3. By using a silane coupling agent, the adhesiveness to the transfer target 30 is improved, and the condensation property of the silane coupling agent allows the water pressure transfer decorative article to have durability such as water resistance and alkali resistance. It will be excellent.

  As silane coupling agents, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxy Silane, 3-aminopropyltrimeth Sisilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane or the like can be used.

  The organic-inorganic composite compound is used for the surface modification treatment by adding components usually required for the respective surface modification treatments. Ingredients usually required for surface modification treatment include water as a solvent for electrostatic coating treatment, water, diluent such as ethanol and butanol for pressure coating treatment, and combustion agent such as ethanol and butanol for combustion coating treatment Examples of the plasma treatment include argon, and examples of the ozone treatment include oxygen and ozone.

(Primer coating)
After the surface modification treatment, it is preferable to apply a primer to the transfer body 30. This is because the adhesiveness of the hydraulic transfer film 10 is further improved. As the primer, a general-purpose synthetic resin-based primer is used, and a urethane-based or acrylic-based synthetic resin primer can be suitably used. Either a thermosetting type or a room temperature curable type can be used. Moreover, it can be used even if it is a water-system paint or solvent-type paint by the difference in a diluent. For example, Neo Paint Urethane # 7000AB (urethane-based, room-temperature curing type, solvent-based, manufactured by Asia Industry Co., Ltd.), Kikusui Primer Van Nou S (acrylic system, room-temperature-curing type, solvent-based, manufactured by Kikusui Chemical Co., Ltd.) ) Etc. can be used.

  The primer coating can be performed using a general-purpose air coating machine. For diluents, etc., follow the coating specifications for each primer.

(Hydraulic transfer film)
The hydraulic transfer film 10 is a film that performs hydraulic transfer, and includes a support layer 11 having water solubility or water peelability, and a transfer layer 12 on which a printing pattern or the like transferred to the transfer target 30 is applied. It is a laminated film.

  For the support layer 11, a water-soluble or water-removable vinyl alcohol resin or the like is used. For the transfer layer 12, an acrylic resin, a silicon resin, or the like that is excellent in water resistance (water-insoluble and water-swellable) is used. The transfer layer 12 can be printed by inkjet printing. This eliminates the need for a cylinder (plate cylinder) for each printed pattern unlike gravure printing, which is general printing, and is suitable for hydraulic transfer from a small quantity. For the ink used for inkjet printing, a highly weather-resistant pigment and a synthetic resin are used.

  Of the formed product of the hydraulic transfer film 10, the transfer layer 12 is transferred to the transfer target 30. And in order to prevent the bleeding and swelling of the color by the water at the time of a hydraulic transfer, these are the films of the dry state. Since the dry condition is limited, the usable raw materials are limited, and there is a difficulty in improving the adhesion to the transfer target 30.

  Commercially available products can be used as the hydraulic transfer film 10. For example, Aquatransa (manufactured by DIC Corporation), Curl Fit (manufactured by Dai Nippon Printing Co., Ltd.), hydraulic transfer film for ink-jet paper decoration (manufactured by Plus Corporation). ), Water transfer paper for inkjet (manufactured by Ishikawa from Washi Co., Ltd.) and the like.

(Water pressure transfer)
The hydraulic transfer is a method in which a printing pattern or the like is transferred and printed on the surface of the transfer target 30 by the hydraulic pressure using the hydraulic transfer film 10. Hydraulic transfer has the advantage that transfer printing is possible not only for planar shapes but also for three-dimensional shapes.

  An example of the transfer method is described below. The hydraulic transfer film 10 is floated on the water surface in a water tank 20 containing warm water 21 at 28 to 32 ° C. with the water-soluble or water-peelable support layer 11 side down. In order to prevent the generation of wrinkles, the hydraulic transfer film 10 is appropriately fixed by the mold 22. Since it is water-soluble, the support layer 11 is dissolved in water or peeled off from the transfer layer 12. As the support layer 11 is melted or peeled off, the transfer layer 12 is released to the water surface.

  If necessary, the activator 25 can be sprayed onto the transfer layer 12 using the activator applicator 26. The activator 25 is an agent that dissolves or swells part of the transfer layer 12 to increase the adhesion to the transfer target 30. As activator 25, butyl cellosolve acetate, butyl carbitol acetate, dibutyl phthalate or mixtures thereof can be used.

  The transferred object 30 is pressed against the transfer layer 12 on the water surface, and the transferred layer 12 is transferred to the transferred object 30 by water pressure. A fixing jig 31 is attached to the transfer target 30 to prevent the transfer target 30 from falling.

(Coating material coating)
The top coating material is applied onto the transfer target 30 that has been subjected to hydraulic transfer, and imparts weather resistance and water resistance. A general-purpose synthetic resin-based topcoat material is used for the topcoat material, and acrylic, urethane-based, silicon-based, and fluorine-based synthetic resin topcoat materials can be suitably used. Both thermosetting and room temperature curing types are available. Can be used. Moreover, it can be used even if it is a water-system paint or a solvent-type paint. For example, Super Lac Eco (acrylic, thermosetting, solvent-based, manufactured by Nippon Paint Co., Ltd.), Urethane Clear UC-810F (urethane-based, room temperature curable, solvent-based, manufactured by Asia Industrial Co., Ltd.), silicon Clear SC-310PE (silicon-based, room-temperature curable, solvent-based, manufactured by Asia Kogyo Co., Ltd.), clean mild fluorine (fluorine-based, room-temperature curable, solvent-based, manufactured by SK Kaken Co., Ltd.), and the like can be used. .

  The top coating material can be applied using a general-purpose air coating machine. For diluents, etc., follow the coating specifications for each topcoat material.

  Hereinafter, the present invention will be described in more detail with reference to examples.

(Transfer)
As the transfer target 30, transfer target A: sanitary ware (glassy), transfer target B: polypropylene container (nonpolar polymer) was used. The transferred object 30 was degreased with ethanol to remove fat. A toilet bowl was used as sanitary ware, and the bowl portion, which is a portion through which water flows, was covered with a curing tape so that it was not decorated with the hydraulic transfer film 10.

(Surface modification treatment)
The surface modification treatment agent and surface modification treatment described in Table 1 were performed. In the electrostatic coating treatment, a general-purpose aqueous electrostatic coating machine was used and the output voltage was DC 30 KV. In the pressure coating process, a general-purpose air spray gun was used and the air pressure was 0.2 MPa. In the combustion coating treatment, a general-purpose combustion coating machine was used and the total flow rate of the organic-inorganic composite compound and the combustion agent was 1 g / min.

(Priming material)
The following were used as the primer. Undercoat material P (Neopaint urethane # 7000AB (manufactured by Asia)).

(Water pressure transfer)
Hydraulic transfer was performed using the equipment shown in FIG. 1 and the hydraulic transfer film 10 and conditions shown in Table 2. As the activator 25, a mixed solution of butyl cellosolve acetate, butyl carbitol acetate, and dibutyl phthalate was used.

(Coating material)
The following materials were used as the top coating material. Topcoat material T (urethane clear UC-810F (manufactured by Asia Industries Co., Ltd.)).

(Test example)
In accordance with the test examples described in Tables 3 and 4, water transfer was performed on a glassy or nonpolar polymer as the transfer target 30, and adhesion and alkali resistance were tested as a performance confirmation test. Test examples 1 to 7 and 9 to 15 are examples, and test examples 8 and 16 are comparative examples.

(Adhesion)
Adhesive strength is based on adhesion (JIS K 5600-6-6: 1999 (Paint General Test Method-Part 5: Mechanical Properties of Coating Film-Section 6: Adhesion (Cross Cut Method))) It was measured. The test results were evaluated according to classification 0 (the edge of the cut was completely smooth and there was no peeling in any lattice eye) to 5 (the peeling area exceeded 35%).

(Alkali resistance)
The alkali resistance was measured according to JIS A 6909: 2014 (finishing coating material for construction) 7.16 alkali resistance test A method. However, as the test substrate, a substrate to be coated was cut to a size of approximately 150 × 50 × 4 mm. Then, evaluation was made with ○ indicating that there was no occurrence of peeling and blistering (hereinafter referred to as having no abnormality), Δ indicating that blistering occurred, and × indicating that there was blistering and peeling.

(Test Examples 1-8)
In Test Examples 1 to 8, as shown in Table 3, water pressure transfer was performed on a glassy sanitary ware as the transfer target 30. In Test Examples 1 to 6 in which surface modification treatment and primer coating were performed, the adhesion was a classification 0 (the edges of the cut were completely smooth and there was no peeling to the eyes of any lattice), and the alkali resistance was There was no abnormality. In Test Example 7 in which surface modification treatment was performed and no primer coating was performed, the adhesion was classified as 2 (the area of peeling exceeded 5% but never exceeded 15%), but the alkali resistance was There was no abnormality. In Test Example 8 in which the primer coating was performed without performing the surface modification treatment, the adhesion was classified as 5 (the peeling area exceeded 35%), and the alkali resistance was confirmed to be swollen and peeled.

(Test Examples 9 to 16)
In Test Examples 9 to 16, as shown in Table 4, hydraulic transfer was performed on a nonpolar polymer polypropylene container as the transfer target 30. In Test Examples 9 to 14 in which the surface modification treatment and the primer coating were performed, the adhesion was classified as 0 (the edge of the cut was completely smooth and there was no peeling in any lattice eye), and the alkali resistance was There was no abnormality. Test Example 15 in which the surface modification treatment was performed and the primer coating was not performed is classified as adhesion 2 (exfoliation area exceeds 5% but does not exceed 15%), but alkali resistance is not. There was no abnormality. In Test Example 16 in which the primer coating was performed without performing the surface modification treatment, the adhesion was classified as 5 (exfoliation area exceeded 35%), and the alkali resistance was confirmed to be swollen and exfoliated.

10 Hydraulic transfer film 11 Support layer 12 Transfer layer

Claims (2)

In the hydraulic transfer method, the hydraulic transfer film is floated on the water surface, the transferred body is pressed from above the transfer layer on the surface of the hydraulic transfer film, and the transferred layer is transferred to the transferred body by water pressure.
The transfer surface of the transfer object is formed of glassy or nonpolar polymer,
As a pretreatment of the water pressure transfer, no line surface modification treatment with an organic-inorganic composite compound in the transferred surface,
The hydraulic transfer method, wherein the organic-inorganic composite compound is 3-aminopropyltrimethoxysilane or 3-aminopropyltriethoxysilane . The water pressure transfer method according to claim 1 , wherein the surface modification process is a process of performing any one of an electrostatic coating process, a pressure coating process, and a combustion coating process.

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