JPH09142094A - Transfer material with antibacterial, antifungal, stain decomposition, and antistatic functions - Google Patents

Abstract

(57) 【Abstract】 PROBLEM TO BE SOLVED: By adding titanium dioxide only to a release layer, which is a surface layer of a transfer material, without impairing the physical properties of a base plastic, antibacterial, antifungal, stain decomposition,
It is also an object of the present invention to provide a transfer material that can easily provide an antistatic function. SOLUTION: A peeling layer 2 containing 1 to 95% by weight of titanium dioxide 3 having an average particle diameter in the range of 0.001 to 0.2 μm is formed on a surface of a substrate sheet 1, and then a colored layer 4 and a colored layer 4 are sequentially formed. We propose a transfer material having an antibacterial, antifungal, stain decomposition and antistatic function with the adhesive layer 5 formed.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transfer material which can be provided with a layer having antibacterial, antifungal, stain decomposing, and antistatic functions on various substrates, for example, a plastic molded article or the like. When it is transferred to, the surface of the plastic can be provided with antibacterial, antifungal, stain decomposition, and antistatic functions.

[0002]

2. Description of the Related Art When a semiconductor powder is dispersed in an aqueous solution and irradiated with light having an energy higher than the band gap of the substance, electrons and holes generated by photoexcitation move to the surface of semiconductor particles, and the ionic species in the aqueous solution And acts on molecular species,
Inducing various reactions such as decomposition of water is well known as a semiconductor photocatalytic reaction. Since titanium dioxide has a large band gap of 3 eV, it was thought that only ultraviolet light with large energy could be used, but recently, the activity dramatically increased as the particle size of titanium dioxide became smaller. (Saturation below about 0.2 μm) was found. The reason is that as the particle size decreases,
It is believed that this is because it becomes easier for the electrons and holes generated inside the particles to reach the surface of the particles before they recombine.

By irradiating such fine particles of titanium dioxide with weak light such as fluorescent light or natural light, organic substances (microorganisms, slime by microorganisms, oil stains, malodor, harmful chemical substances, etc.) are rapidly decomposed. By utilizing this, purification in various situations of the living environment becomes possible. For example, prevention of decomposition of harmful substances such as trihalomethane in water, removal of mold odor in tap water, decomposition of toilet odor, decomposition of tobacco odor adhering to office / home room, decomposition of oil stains scattered on kitchen wall, ventilation fan Dissolve oil stains on walls of baths, etc.
Prevents the growth of bacteria and mold on the ceiling, prevents slimming of kitchen and bath products, disintegrates stains on tablecloths, prevents microbes from soiling toilet bowls and tiles, prevents the growth of green algae in tanks, prevents the growth of water moss, and leaks due to marine accidents, etc. Examples include decomposition of crude oil, decomposition of persistent chemical substances such as PCB, prevention of nosocomial infection, and sterilization of bacteria in the air.

Among these applications, in the case of water-related applications such as prevention of decomposition of harmful substances in water, it is difficult to handle finely divided titanium dioxide, and therefore JP-A-6-65012 discloses that
Make titanium dioxide sol from titanium alkoxide,
After coating on a glass substrate by the dip coating method, it is dried and baked, and it is transparent and water resistant and heat resistant.
A titanium dioxide film photocatalyst with excellent durability has been proposed, but it could only be used for inorganic materials with high heat resistance such as glass and ceramics.

[0005]

Plastics and paints have been widely used as everyday life products, and it has been conventionally strong to impart antibacterial, antifungal, deodorant, stain disintegrating, and antistatic functions to them. Was wanted. But,
The dip coating method using titanium dioxide sol cannot be applied to plastics having a low heat resistant temperature. In the method of kneading fine particles of titanium dioxide into plastic for resin molding, or applying a paint containing fine particles of titanium dioxide to the surface of the molded product, only a small amount of kneaded titanium dioxide is present on the surface or near the surface. Therefore, in order to fully exhibit the above-mentioned various functions, it is necessary to knead a large amount of titanium dioxide, which causes a fatal problem that the physical properties of plastics and paints are significantly impaired, and these methods cannot be adopted. It was

The present invention has been made in view of the above problems, and by incorporating titanium dioxide only in the peeling layer which is the surface layer of the transfer material, the physical properties of the base plastic are not impaired and various base materials are used. It is an object of the present invention to provide a transfer material that can easily provide antibacterial, antifungal, stain decomposition, and antistatic functions.

[0007]

In order to solve the above problems, the base sheet 1 has a release layer 2 containing 1 to 95% by weight of titanium dioxide 3 having an average particle size of 0.001 to 0.2 μm. We propose a transfer material having antibacterial, antifungal, stain decomposing, and antistatic functions, which is characterized in that a colored layer 4 and an adhesive layer 5 are sequentially formed after being formed on the surface.

[0008]

The present invention will be described in more detail with reference to the drawings. FIG. 1 is a sectional view showing an embodiment of the present invention. FIG. 2 is a cross-sectional view showing an example in which the transfer material of the present invention is applied to a base material. FIG. 3 is an explanatory view showing the peeling layer portion of FIG. 2 in an enlarged manner. FIG. 4 is a sectional view showing a comparative example in which a coating material containing titanium dioxide is directly applied to the surface of a base material. As shown in FIGS. 1 to 3, the transfer material according to the present invention is used by peeling off the base sheet 1 after transferring to the base material 6, so that the titanium dioxide 3 is uniformly present on the surface and in the vicinity of the surface. On the other hand, when the coating material containing titanium dioxide is directly applied to the base material 6, a transparent layer 7 containing no titanium dioxide 3 is formed on the surface as shown in FIG. 4 showing a comparative example. However, it becomes a barrier, and it becomes difficult to exhibit antibacterial, antifungal, stain decomposition, and antistatic functions.

The titanium dioxide according to the present invention may be in the crystal form of anatase and rutile having an average particle size in the range of 0.001 to 0.2 μm. A smaller particle size is more desirable because it can cover a large area with a small amount and is excellent in transparency. If the average particle size is less than 0.001 μm, the photocatalytic effect is lost, and if the average particle size exceeds 0.2 μm, the activity is poor and the printability is deteriorated. Further, in order to disperse titanium dioxide in the peelable paint, it is possible to add it afterwards by dispersing it in an organic solvent such as toluene, methyl acetate or methyl ethyl ketone, which is well compatible with the paint. At this time, in order to facilitate dispersion, tristyrenated phenol type, polyethylene amine type,
Alkylamine salt-based, polycarboxylic acid-based, fluorine-based surfactants, silane-based, titanate-based, aluminate-based coupling agents and the like may be used without limitation.

The substrate sheet 1 according to the present invention is a polyester film such as polyethylene terephthalate, polybutylene terephthalate, polyethylene terephthalate-isophthalate copolymer, polytetrafluoroethylene, polytetrafluorovinyl, polyvinylidene fluoride, ethylene-.
Polyfluoroethylene resin film such as tetrafluoroethylene copolymer, polyolefin film such as polyethylene, polypropylene and polymethylpentene, nylon film such as 6 nylon and 6.6 nylon, polyvinyl chloride film, polyvinylidene chloride film, Polyvinyl alcohol film, ethylene-vinyl acetate copolymer film, ethylene-vinyl alcohol copolymer film, polystyrene film, polycarbonate film, resin film such as cellophane, thin paper, sulfuric acid paper, paper such as kraft paper, metal foil such as aluminum Alternatively, a known film such as a composite film obtained by combining the above base sheet can be used without limitation.

The release layer 2 according to the present invention is the base sheet 1
It is formed on the surface of the base material sheet in order to enhance the peeling property between the transfer layer a and the transfer layer a, and mainly comprises a vehicle, a plasticizer, a stabilizer,
Dispersant, extender pigment, colorant, antistatic agent, silicone,
Wax, gravure printing, a gravure offset printing, flexo printing, flat plate offset printing, letterpress printing, intaglio printing, screen printing, electrostatic printing, gravure coating, a peelable coating formed by adding a solvent and a diluent as necessary.
It can be formed by a known coating method such as roll coating, air knife coating, and kiss coating.

Vehicles used in the peelable coating include polystyrene, styrene resins such as poly-α-methylstyrene and styrene copolymer resins, acrylic or methacrylic resins such as polymethylmethacrylate, polyethylmethacrylate and polybutylacrylate. Homogeneous or copolymer resin, rosin resin, rosin-modified maleic acid resin, rosin-modified phenolic resin, rosin ester resin such as polymerized rosin, ethyl cellulose, ethyl hydroxyethyl cellulose, cellulose acetate propionate, cellulose derivative such as cellulose acetate, polyvinyl acetate resin,
Coumarone resin, vinyl toluene resin, vinyl chloride resin,
At least one of polyester resin, polyurethane resin, butyral resin, polyamide resin, vinyl chloride-vinyl acetate copolymer resin and the like can be used.

The peeling layer 2 has a film thickness of 0.5 to 5 μm, and more preferably 1 to 2 μm in order to exhibit antibacterial, antifungal, stain decomposition and antistatic functions. It may be applied twice or more to give a predetermined film thickness. Known antibacterial agents and antifungal agents may be added to the above-mentioned peelable paint for the purpose of antibacterial and antifungal when there is no light irradiation such as at night.

The colored layer 4 according to the present invention is the base sheet 1
Gravure printing method for any coloring or pattern using an ink formed by mixing a pigment or dye, a plasticizer, an additive such as a stabilizer, a solvent or a diluent on the release layer 2 formed on the vehicle, It can be formed by a known printing method such as an offset gravure printing method, a silk screen printing method, an offset printing method, an electrostatic printing method, a jet printing method.
Vehicles used for this purpose include homopolymers or copolymer resins of acrylic acid-based monomers or methacrylic acid-based monomers such as polymethylmethacrylate, polyethylmethacrylate and polybutylacrylate, styrene resins such as polystyrene and poly-α-methylstyrene. Further, alcohol-insoluble resins such as styrene copolymer resin, cellulose acetate, vinyl chloride resin, and polyester resin are desirable, and at least one or more of them can be used. . In addition, a hiding layer may be provided on the colored layer 4 for the purpose of hiding the base material 6. The coloring layer 4 can be omitted when coloring or a pattern is not required. In this case, it is also possible to use a metal vapor deposition film of aluminum or the like.

For the adhesive layer 5 according to the present invention, it is preferable to use a heat-sensitive or pressure-sensitive resin suitable for the material of the transfer surface such as the plastic molded article which is the base material 6. For example, in the case of polypropylene resin, chlorinated polypropylene resin or ethylene vinyl acetate resin can be used, and in the case of ABS resin, acrylic resin, vinyl chloride resin, vinyl acetate resin, etc. can be used. The adhesive layer 5 can be formed by a known coating method similar to that for the peeling layer 2.

The base material 6 according to the present invention is made of synthetic resin, wood or metal, its coated surface, woven fabric, non-woven fabric, tile, glass, paper, etc. for household use, household appliances, containers, furniture,
It can be applied to outer wall materials of buildings. In addition, the transfer layer a is used as the base material 6.
The transfer can be easily performed by so-called binder transfer under pressure or heat and pressure. Further, a known method of transferring simultaneously with resin molding may be used.

[0017]

[Advantageous Effects] The present invention adopts the above-described constitution to prevent bacteria and prevent bacteria by the photocatalytic action of titanium dioxide existing on the surface of the transfer material and in the vicinity of the surface, simply and without adversely affecting the substrate such as resin. A layer having fungi, stain decomposition, and antistatic function can be provided on various substrates, and designs such as floral patterns can be transferred at the same time.

[0018]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below based on embodiments. [Example 1] To 750 g of toluene, 250 g of titanium dioxide (P25, manufactured by Degussa, average particle size 21 nm) and 2.5 g of a titanate coupling agent (manufactured by Ajinomoto Co., Inc., product number KR TTS) were added, and the mixture was dispersed for 10 minutes with a homogenizer. A titanium dioxide dispersion containing 25% by weight of titanium dioxide was mixed to obtain a release coating composition having the following composition. Polymethylmethacrylic acid resin 20 parts by weight Toluene 60 parts by weight Titanium dioxide dispersion 20 parts by weight This release coating is gravure-printed on a polyester film (film thickness 25 μm) and dried, and then the following composition is further gravure-printed. A transfer material according to the present invention was obtained. Chlorinated polypropylene 10 parts by weight Toluene 90 parts by weight Using the transfer material obtained above, a polypropylene resin plate (250 x
A test piece 1 transferred to 250 × 2 mm was obtained. A test piece 0 was obtained in the same manner by using a release coating containing no titanium dioxide.

Comparative Example 1 A release coating made of polymethylmethacrylic acid resin containing no titanium dioxide was directly applied to a polyester sheet (250 × 250 × thickness 0.1 m).
Gravure printing was performed on m) in the same manner as in Example 1 and then dried to obtain a test piece 2.

Example 2 The test pieces obtained in Example 1 and Comparative Example 1 were cut into 30 mm × 30 mm and an antibacterial activity test was conducted. As a test bacterium, Staphylococcus aureus (IFO 12732), which is highly resistant to dryness, was transplanted to an ordinary agar medium, and the bacterium that had been cultured (precultured) at 35 ± 1 ° C for 16 to 24 hours was transferred to a normal broth medium with 1 platinum loop.
Incubate at ± 1 ° C for 16 to 20 hours. After mixing 0.5 ml of this statically cultivated bacterial solution with 50 ml of normal agar medium, pour it into a sterile petri dish to solidify it into a flat plate, and keep it at 35 ± 1 ℃ for 16-20
Incubate for hours. Next, place a sterilized velvet cloth (diameter 28 mm) on the medium surface of the inoculum, and immediately place a weight (about 30 g) on it.
A silicon plug) is put on and the weight is instantly removed to attach the bacteria to the velvet cloth. Place the velvet cloth with the bacteria on the test piece (30 mm x 30 mm) placed in a sterile petri dish, and put a weight on it to transfer the bacteria to the test piece. After performing these operations, the test piece was placed at 10 cm under a fluorescent lamp (100 W) at room temperature and irradiated for 6 hours. For the test pieces after 6 hours, the bacteria adhering to the test pieces were separated by SCDLP medium 10
The cells were thoroughly washed out in a sterile petri dish using ml, and the number of viable bacteria in the washed-out solution was measured by the agar plate culture method (culturing at 35 to 37 ° C for 48 hours) using a standard agar medium. From the results (Table 1), the test piece made of the transfer material of the present invention was found to have remarkable antibacterial properties.

[0021]

[Table 1]

[Example 3] The test pieces obtained in Example 1 and Comparative Example 1 were cut into 50 mm x 50 mm and a mold resistance test was conducted. Pre-sterilized agar was placed in a petri dish to solidify. A test piece was placed in the center of the agar. 0.005
% Alternaria altanata (IFO 31188) separately cultured in 10 ml of dioctyl sodium sulfosuccinate solution
Take 1 platinum loop and separate spores by centrifugation. A bacterial solution containing the spores in 10 ml of GPLP was sprayed on a test piece of a Petri dish and irradiated with a fluorescent lamp (100 W) at room temperature for 14 days. From the results (Table 2), the test piece of the transfer material according to the present invention was
Remarkable mold resistance was recognized.

[0023]

[Table 2]

Example 4 The test pieces obtained in Example 1 and Comparative Example 1 were cut into 50 mm × 50 mm and a soil decomposition test was conducted. Each test piece is blown with cigarette smoke until it becomes brown, and then the test piece is kept at room temperature under fluorescent light (100W) for 10 days.
It was placed in cm and irradiated for 10 days. From the results (Table 3),
The test piece of the transfer material according to the present invention showed remarkable stain decomposition.

[0025]

[Table 3]

[Example 5] The test pieces obtained in Example 1 and Comparative Example 1 were cut into 100 mm x 200 mm and an antistatic test was conducted. Rub the surface of each test piece with silk cloth, place the test piece at 5 cm under a fluorescent lamp (100 W) at room temperature and irradiate for 1 hour, then immediately sprinkle the cigarette ash on the test piece to see if the ash is sucked. I looked at the presence or absence of electrification. Results (Table 4)
From the above, the test piece of the transfer material according to the present invention was confirmed to have a remarkable antistatic effect.

[0027]

[Table 4]

[0028]

[Effects of the Invention] It is possible to provide a layer having various functions of antibacterial, antifungal, stain-degrading, and antistatic functions on various base materials easily and without adversely affecting the base materials such as resins. Since it can be transferred at the same time, household miscellaneous goods such as washbasins, balls, kitchen knife patterns, trash cans, toilet brush patterns, etc., polypropylene resin often used for household appliances such as tableware dryers, refrigerators, vacuum cleaners, toilet seats and telephones Resin molded products such as ABS resin, which are often used in, such as resin tiles for baths, kitchens, toilets, sanitary ware, building exterior wall materials, dining tables, clothing, etc.
It can be widely applied to bedding, insoles, dental treatment tables, barbers, etc.

[Brief description of the drawings]

FIG. 1 is a sectional view showing an embodiment of the present invention.

FIG. 2 is a cross-sectional view showing an example in which the transfer material of the present invention is applied to a base material.

FIG. 3 is an explanatory view showing a peeling layer portion of FIG. 2 in an enlarged manner.

FIG. 4 is a cross-sectional view showing a comparative example in which a coating material containing titanium dioxide is directly applied to the surface of a base material.

[Explanation of symbols]

 1 Base Sheet 2 Release Layer 3 Titanium Dioxide 4 Coloring Layer 5 Adhesive Layer 6 Base Material 7 Transparent Layer 8 Coating Film a Transfer Layer

Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location B32B 7/06 B32B 7/06 27/00 27/00 Z 27/20 27/20 Z C09K 3/00 C09K 3 / 00 S 3/16 101 3/16 101A 102 102H

Claims (1)

[Claims] 1. A release layer 2 containing 1 to 95% by weight of titanium dioxide 3 having an average particle size in the range of 0.001 to 0.2 μm is formed on the surface of a base sheet 1, and then a colored layer 4 and an adhesive layer 5 are successively formed. Transfer material having antibacterial, antifungal, stain decomposition, and antistatic functions