JP3209381B2 - Anti-mold transfer material and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transfer material on which a layer having a fungicidal function can be provided on various substrates and a method for producing the same. Moldy plastic is obtained.

[0002]

2. Description of the Related Art Conventionally, an antibacterial agent has been added to various substrates for the purpose of antibacterial and antifungal, thereby imparting antibacterial and antifungal functions to the substrate. For example, Japanese Patent Publication No. 63-54013 discloses a bactericidal zeolite composition in which silver ions are supported on zeolite by ion exchange.
A method for producing a bactericidal polymer composition by adding to a polymer such as nylon or polyester is disclosed. JP-A-63-154746 discloses that a zeolite carrying silver ions by ion exchange is made of polyethylene. An antibacterial film added to such a film is disclosed, and JP-A-1-108230 further discloses a method for producing an antifungal synthetic resin foam to which an organic antifungal agent is added.

[0003]

However, when an antibacterial agent is added to the entire resin as described above, there are adverse effects on the resin such as a decrease in strength, poor dispersion and discoloration. If exposed to high temperatures at the time of incorporation, the fungicide may vaporize and significantly impair the working environment, and only the antibacterial agent in the surface layer of the antibacterial agent kneaded into the resin is effective,
There is a problem that the antibacterial agent inside is completely wasted, leading to an increase in cost. The present invention has been made in view of the above problems, and an object of the present invention is to provide a fungicide transfer material capable of easily imparting a fungicide function to various substrates without adverse effects, and a method for producing the same.

[0004]

Means for Solving the Problems To solve the above-mentioned problems, the antifungal transfer material of the present invention firstly contains an organic antifungal agent on the surface of a base sheet in an amount of 0.01 to 20% by weight. Forming a release layer included therein, secondly forming an adhesive layer on the surface of the release layer, and thirdly forming a pattern layer between the release layer and the adhesive layer, Fourth, the composition is prepared by printing a composition containing 0.01 to 20% by weight of a resin, an organic solvent and an organic fungicide soluble in the organic solvent on the surface of the base sheet. Forming the fifth
A composition containing 0.01 to 20% by weight of a resin, an organic solvent and an organic fungicide having an average particle diameter of 2 μm or less insoluble or hardly soluble in the organic solvent is printed on the surface of the base sheet. It is characterized in that a release layer is formed. The present invention will be described in more detail with reference to the drawings. FIG. 1 is a cross-sectional view showing an embodiment of the mold transfer material according to the present invention. FIG. 2 is a cross-sectional view showing one embodiment in which the antifungal transfer material according to the present invention is applied to a base material. 1 is a base sheet, 2 is a release layer, 3 is an organic fungicide contained in the release layer, 4 is a design layer, 5 is an adhesive layer, 6
Denotes a substrate, and a denotes a transfer layer.

The organic fungicides according to the present invention include chloromethyl-p-tolylsulfone, 2- (4-thiazolyl) benzimidazole, 2-methylcarbonylaminobenzimidazole, 2,4,4 5,6-tetrachloroisophthalonitrile, 2,3,5,6-tetrachloro-
4- (methylsulfonyl) -pyridine, N-fluorodichloromethylthio) sulfamide, bis (2-pyridylthio-1-oxide) zinc, N-dimethyl-N-phenyl- (N-fluorodichloromethylthio) sulfamide, 10-10 ' -Oxybisphenoxyarsine, zinc dimethyldithiocarbamate, 1,2-bis-bromoacetoxyethane, p-chloro-m-xylenol,
p-chloro-m-cresol, 2-n-octyl-4-
Isothiazolin-3-one, 8-oxyquinoline,
(2,2'-dihydroxy-5,5'-dichloro-) diphenylmethane and the like, but are not limited thereto. In addition, since it can be said that fungicides generally have different fungicide spectra, it is more preferable to use two or more kinds of fungicides, and in general, many fungicides are ineffective against bacteria. , Bis (2-pyridylthio-1-
Oxide) zinc and the like have an effect on bacteria, so they may be used in combination or inorganic antibacterial agents such as bactericidal zeolite may be used in combination.

The amount of the organic fungicide according to the present invention is 0.01 to 20% by weight based on the resin of the release layer 2,
Preferably, the content is 0.1 to 5% by weight. If the amount is less than 0.01% by weight, a sufficient antifungal effect cannot be obtained, and if it exceeds 20% by weight, adverse effects such as a decrease in the strength of the release layer 2 are undesirably produced. The release layer 2 according to the present invention is formed by a known printing method such as gravure printing, screen printing, or roll coating using a resin such as a thermoplastic resin, natural rubber, or synthetic rubber. Note that a coloring agent, an antistatic agent, or the like may be added to the release layer 2. The base sheet 1 according to the present invention is made of polyester, polypropylene, polyethylene, cellophane,
Known films such as a resin film such as nylon or a composite film of a resin film and paper or metal foil can be used without limitation.

The adhesive layer 5 according to the present invention has a heat sensitivity suitable for the material of the transfer surface such as a plastic molded product as a base material,
Alternatively, a pressure-sensitive resin is preferably used. For example, in the case of a polypropylene resin, a chlorinated polypropylene resin or an ethylene vinyl acetate resin can be used, and in the case of an ABS resin, an acrylic, vinyl chloride, vinyl acetate resin or the like can be used. The design layer 4 according to the present invention is formed by gravure printing or the like on the release layer 2 formed on the base sheet 1 using a coloring ink containing a dye or a pigment. When no design is required, the design layer 4 can be omitted.

[0008] The fungicide transfer material according to the present invention, when the organic fungicide is soluble in the organic solvent dissolving the resin of the release layer 2,
After mixing a resin, an organic fungicide, and an organic solvent to form a uniform solution, a release layer 2 is formed on the base sheet 1 by gravure printing or the like, and an adhesive layer 5 is formed thereon by gravure printing or the like. Thus, a mold transfer material can be obtained. If necessary, the design layer 4 may be inserted between the release layer 2 and the adhesive layer 5 by gravure printing or the like. Further, when the organic fungicide is insoluble or only slightly soluble in the organic solvent that dissolves the resin of the release layer 2, by wet grinding using an organic solvent such as toluene and methyl ethyl ketone that are familiar with the resin of the release layer 2, Average particle size of organic fungicide is 2μ
m, more preferably a suspension having an average particle diameter of 0.5 μm or less is added to the resin solution of the release layer 2 to form a uniform solution, and then the release layer 2 may be formed in the same manner. If the average particle diameter exceeds 2 μm, the thickness of the release layer 2 is generally several μm or less, and thus the film cannot be used because problems such as a decrease in the strength of the coating film occur.

The wet pulverization performed to obtain a suspension of an organic fungicide is carried out by a known media mill, planetary mill, vibrating ball mill, ball mill, etc., which can be wet-milled using a grinding medium. It can be performed using a wet pulverizer. The diameter of the pulverizing medium used is preferably in the range of 0.1 to 5 mm, and the material of the pulverizing medium may be glass, alumina, zirconia, or the like, but is not limited thereto. In wet grinding, to promote grinding and improve dispersibility, tristyrenated phenol-based, polyethyleneamine-based, alkylamine salt-based, polycarboxylic acid-based, fluorine-based surfactants, silanes, etc. A coupling agent such as a system, a titanate, and an aluminate may be used.

The substrate 6 to which the present invention can be applied is a synthetic resin,
Household goods, home appliances, OA equipment made of wood and metal, and their painted surfaces, woven fabric, nonwoven fabric, towels, glass, paper, etc.
It can deal with containers, furniture, building exterior walls, etc. without any restrictions.
The transfer of the transfer layer a to the substrate 6 can be easily performed by so-called binder transfer by pressing or heating and pressing. In addition, a known method of transferring simultaneously with resin molding can be used without limitation.

[0011]

According to the present invention, by adopting the above solution, a fungicidal function can be easily imparted, so that a design such as a floral pattern can be transferred at the same time without adversely affecting a substrate such as a resin. Household goods such as bowls, balls, kitchen knife handles, trash boxes, toilet brush handles, tableware dryers, refrigerators, vacuum cleaners, air conditioners, etc., polypropylene resin, toilet seats, office automation equipment, telephones Resin molded products such as ABS resin, which are often used for vessels, resin tiles for baths, kitchens and toilets, sanitary ware, building exterior wall materials, dining tables,
It can be widely applied to clothing, bedding, insoles, dental treatment tables, barbers, etc.

[0012]

【Example】

1. Preparation of a fungicide solution [Example 1] To 99 g of toluene, 1 g of diiodomethyl-p-tolylsulfonetoluene (Yotol DP95, manufactured by Mitsui Toatsu Chemicals, solubility in toluene: 43 g / l) was added, and a solution (hereinafter referred to as "solution") was added. "Solution 1"). Example 2 To 99 g of toluene was added 1 g of (2,2'-dihydroxy-5,5'-dichloro-) diphenylmethane (Priventl GD, manufactured by Bayer, solubility in toluenei: 12 g / l), and the mixture was melted (hereinafter referred to as ""). Solution 2 ").

2. Preparation of a fungicide suspension [Example 3] 30 g of 2- (4-thiazolyl) benzimidazole (San-Isol 100, Sanai Petroleum, almost insoluble in toluene) in 2.97 kg of toluene and a polycarboxylic acid-based interface Activator (E-503, Chukyo Yushi, solid content 10
%), Dispersed and mixed with a homogenizer for 10 minutes, and then mixed with a medium mill (1 l par mill PMIRL-V).
(Made by Ashizawa). 2 mm ¢ alumina pulverized bead (V-celax; manufactured by Shinto Kogyo) 11
Using 50 g, 1 pass at a processing speed of 500 ml / min.
By performing 0 passes, a suspension (hereinafter referred to as “suspension 1”) was obtained. The average particle size observed with a scanning electron microscope is about 0.2μ
m.

Example 4 2-methylcarbonylaminobenzimidazole (SK-BC) was added to 2.97 kg of toluene.
M, almost insoluble in Sanai Petroleum, and toluene) and 1 g of a polycarboxylic acid-based surfactant (E-503, manufactured by Chukyo Yushi, solid content 10%), and dispersed and mixed with a homogenizer for 10 minutes. Mill (1 liter par mill PMIR)
(LV type, manufactured by Ashizawa). 2mm ¢
Using 1150 g of a pulverized bead made of alumina (V CELLAX; manufactured by Shinto Kogyo Co., Ltd.), a suspension (hereinafter referred to as "suspension 2") was performed by performing 10 passes at a processing speed of 500 ml / min per pass. Obtained. The average particle size observed with a scanning electron microscope was about 0.15 μm.

Comparative Example 1 Toluene was added to 2.97 kg of toluene.
-(4-Thiazolyl) benzimidazole (San-Isol 100, almost insoluble in Sanai Petroleum, toluene) 30
g and a polycarboxylic acid-based surfactant (E-503, manufactured by Chukyo Yushi Co., Ltd., solid content: 10%) were added, and the mixture was dispersed and mixed with a homogenizer for 10 minutes to obtain a suspension (hereinafter referred to as “Suspension 1”). "
). The average particle size observed with a scanning electron microscope was about 1
It was 5 μm. This suspension had a problem that it settled immediately after being placed in a container and allowed to stand.

3. Preparation of anti-mold transfer material [Example 5] "Solution 1", "Solution 2", "Suspension 1", "Suspension 2" obtained in Examples 1, 2, 3, 4 and Comparative Example 1 And 20 parts by weight of the polymethyl methacrylate resin and 60 parts by weight of toluene, respectively, to obtain a composition containing 1% by weight of an antifungal agent (hereinafter referred to as "the suspension"). "Composition 1", "Composition 2", "Composition 3",
"Composition 4" and "Composition 5"). Next, compositions 1, 2, 3, 4, and 5 were gravure-printed on polyester films (25 μm in thickness) to form release layers. When the composition 5 is allowed to stand, the antifungal particles settle out, so that it is necessary to stir again immediately before use, and gravure printing itself cannot be performed because the antifungal particles are too large.
Next, 10 parts by weight of chlorinated polypropylene and 90 parts of toluene
The composition consisting of parts by weight was further subjected to gravure printing to form an adhesive layer, whereby an antifungal transfer material (the antifungal transfer material using the compositions 1, 2, 3, and 4 for the release layer, was sequentially referred to as "antifungal transfer material"). Transfer material 1 "," mold transfer material 2 "," mold transfer material 3 "and" mold transfer material 4 "). Separately, after forming a release layer using a composition containing no fungicide, which is a mixture of 20 parts by weight of polymethyl methacrylate resin and 80 parts by weight of toluene, 10 parts by weight of chlorinated polypropylene and 90 parts by weight of toluene are used. The composition was further subjected to gravure printing to form an adhesive layer, thereby obtaining a blank transfer material (hereinafter referred to as "blank transfer material 1").

4. Mold resistance test [Example 6] The anti-mold transfer materials 1, 2 obtained in Example 5
3, 4 and the blank transfer material were transferred to a polypropylene resin plate (5
0 × 50 × 20 mm) and transferred to test pieces (hereinafter “test piece 1”, “test piece 2”, “test piece 3”, “test piece 4”).
And "Test piece 0"). These test pieces 1
The test pieces 2, 3, 4 and 0 were subjected to a mold resistance test. A potato dextrose agar medium that had been sterilized in advance was solidified in a Petri dish, and a test piece was placed thereon. Next, one platinum loop of Alternaria alternata (IFO31188) separately cultured was taken in 10 ml of a 0.005% aqueous solution of dioctyl sodium sulfosuccinate, and spores were dispersed in 10 ml of physiological saline by centrifugation to obtain a spore suspension. Was. This spore suspension was sprayed onto the test piece of the dish and agar previously prepared, and cultured in an incubator at 25 ° C. for 30 days. From the results (Table 1), the test piece to which the antifungal transfer material according to the present invention was transferred showed not only a remarkable mold resistance but also a remarkable halo on the agar.

[0018]

[Table 1]

[0019]

According to the present invention, as is apparent from the above description, an organic antibacterial agent soluble in an organic solvent or an average particle diameter of 2 μm insoluble or hardly soluble in an organic solvent is used as a release layer on a base sheet.
m, the composition containing 0.01 to 20% by weight of an organic anti-sunscreen agent is printed, so that a mold transfer material having excellent transparency can be obtained, and various base materials can be easily prepared. The mold can be provided with a fungicidal function, and the design such as a flower pattern can be transferred at the same time without adversely affecting the base material such as resin, and the handle of a basin, a ball, a kitchen knife, a trash can and a toilet brush. Such as household goods, tableware dryers, refrigerators, vacuum cleaners, polypropylene resins that are often used in household appliances such as air conditioners,
Resin molded products such as ABS resin which are often used for toilet seats, office automation equipment, telephones, etc., resin tiles for baths, kitchens, toilets, etc., sanitary ware, building exterior wall materials, dining tables, clothing, bedding, shoe insoles, dental Can be widely used for treatment tables and barbers.

[Brief description of the drawings]

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

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

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 base sheet 2 release layer 3 organic fungicide 4 design layer 5 adhesive layer 6 base material a transfer layer

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-6-346029 (JP, A) JP-A 1-2212558 (JP, A) JP-A-6-263611 (JP, A) JP-A-6-263611 218029 (JP, A) JP-A-7-138116 (JP, A) JP-A-3-45902 (JP, U) (58) Fields investigated (Int. Cl. ⁷ , DB name) A01N 25/18 A01N 25 / 10 A01N 25/34

Claims (5)

(57) [Claims] 1. An antifungal transfer material, characterized in that a release layer 2 containing 0.01 to 20% by weight of an organic fungicide is formed on the surface of a base sheet 1. 2. An anti-mold transfer material according to claim 1, wherein an adhesive layer is formed on the surface of said release layer. 3. The anti-mold transfer material according to claim 2, wherein a pattern layer 4 is formed between the release layer 2 and the adhesive layer 5. 4. A release layer formed by printing a composition containing 0.01 to 20% by weight of a resin, an organic solvent and an organic fungicide soluble in an organic solvent on the surface of the base sheet 1. 2. A method for producing an anti-mold transfer material, characterized by forming 5. A composition comprising 0.01 to 20% by weight of a surface of a base sheet 1 containing a resin, an organic solvent and an organic fungicide having an average particle diameter of 2 μm or less insoluble or hardly soluble in an organic solvent. A method for producing a fungicidal transfer material, characterized in that a material is printed to form a release layer 2.