JP2002038380A - Antibacterial synthetic leather and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a synthetic leather satisfying the requirements on high antibacterial effect and having high resistance to laundry. SOLUTION: This synthetic leather comprises a textile fabric and a zinc pyrithione complex containing polyurethane resin film provided on at least one side of the fabric. This synthetic leather is obtained by forming a film of a polyurethane resin formulated with a zinc pyrithione complex on at least one side of a textile fabric.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a synthetic leather having bacteriostatic properties and a method for producing the same. The present invention, in particular,
The present invention relates to a synthetic leather having high bacteriostatic performance and improved washing resistance and a method for producing the same.

[0002]

2. Description of the Related Art With the recent trend toward cleanliness and hygiene, various types of fiber fabrics using various antibacterial agents and bacteriostatic agents have been devised. BACKGROUND ART In clothing, bedding materials such as sheets and bedsheets, and miscellaneous goods such as caps and hoods, a technique for imparting higher antibacterial properties and antibacterial properties is required. In addition, because of the desire for cleanliness and hygiene, it is also required to realize a more effective washing method and a high degree of washing resistance capable of coping with severe industrial washing.

[0003] At present, antibacterial agents and bacteriostatic agents are roughly classified into three types, and there are natural, inorganic and organic materials. For example, natural materials include hinokitiol extracted from hinoki, chitosan made from crab shells and the like. Examples of inorganic materials include antibacterial ceramics and antibacterial zeolites prepared by mixing antibacterial metals such as silver, zinc, and copper with ceramics and zeolites.

For example, JP-A-7-67758 discloses an antibacterial sheet material laminated with a polyvinylidene fluoride film containing antibacterial ceramic particles. However, under the current situation where higher antibacterial properties and washing resistance are required, natural and inorganic materials have no immediate effect on antibacterial properties and sufficient washing resistance cannot be obtained.

On the other hand, organic materials have higher antibacterial properties than natural and inorganic materials, and have an immediate effect. For example, Japanese Patent Application Laid-Open No. 2000-119960 discloses a method of treating a fiber cloth, which is immersed in an aqueous dispersion of an organic material (zinc pyrithione, copper pyrithione, etc.) and heat-treated. However, this is a method of immersing or padding a material with an aqueous dispersion, and the obtained fabric has insufficient antibacterial or bacteriostatic effects, and has insufficient washing resistance.

According to the "Science of Antimicrobial Agents" Industrial Research Institute 1996, "antibacterial" refers to "the effect of bacteria that inhabit the living environment is not temporary but is effective for several weeks to several years, and sometimes for several tens of years. It is said that the sterilization level lasts for a year and is below the bacteriostatic and bactericidal levels, and that the microbiological hygiene of the living environment is maintained for a long period of time, and that the relationship of bactericidal ≧ antibacterial holds.

[0007] The Textile Products New Function Evaluation Council (JAF)
According to ET, "antimicrobial means sterilization, sterilization,
It is a very vague term that includes everything such as disinfection and disinfection, and is easily misunderstood to consumers and distribution, and may be regarded as a pharmaceutical term. On the other hand, bacteriostats also specify Staphylococcus aureus, Klebsiella pneumoniae, Escherichia coli, Pseudomonas aeruginosa, and MRSA as bacteria that suppress the growth of the specified bacteria on the fiber. And set it apart from antibacterials. "

[0008]

SUMMARY OF THE INVENTION In view of the above-mentioned state of the art, it is an object of the present invention to provide a synthetic leather which satisfies the demand for higher antibacterial or bacteriostatic properties and has extremely high washing resistance. And More specifically, JAFE
JIS L-1 which was revised and transferred from the unified test method for specific antibacterial products for textile products used in medical institutions and facilities equivalent thereto specified by T
For a textile product that satisfies both the evaluation criterion in the 902 method and the evaluation criterion in the JAFET test method clearly specified for washing resistance and the like, JA
FET <red label> is applied, but the present invention
An object of the present invention is to provide a synthetic leather having a bacteriostatic property and a washing resistance that exceed the criteria for providing the FET <red label>.

[0009]

In order to solve the above-mentioned problems, the present invention provides a synthetic leather comprising a fiber fabric and a polyurethane resin film containing a pyrithione zinc complex provided on at least one surface thereof. The present invention also provides a synthetic leather comprising applying a resin solution containing a polyurethane resin blended with a pyrithione zinc complex to at least one surface of a fiber cloth, coagulating the resin solution in an aqueous solvent, and then removing the solvent and drying. And a method for producing the same.

According to the present invention, further, a resin solution containing a polyurethane-based resin containing a pyrithione zinc complex is coated on a release paper, dried, and then an adhesive layer is provided on the resin layer. Provided is a method for producing synthetic leather, which comprises bonding a resin layer to at least one surface of a fiber fabric via a layer and peeling off release paper on the resin layer.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a zinc pyrithione complex is used as a bacteriostatic agent, and zinc pyrithione is a typical example of such a pyrithione zinc complex. According to the present invention, it has been unexpectedly found that the zinc pyrithione complex is specific as compared with other organic antibacterial agents, inorganic antibacterial agents and the like. That is,
When the zinc pyrithione complex is used in a synthetic leather as a bacteriostatic agent according to the present invention, sufficient bacteriostatic properties can be imparted without lowering the peel strength of the polyurethane resin film, and this bacteriostatic The washing resistance with respect to the properties can be made extremely high.

Further, as a further feature of the synthetic leather of the present invention, the polyurethane resin film has a sublime property,
It has a soft texture and voluminous feel, and its surface feel is smooth. The method for producing synthetic leather according to the present invention is roughly classified into a method based on a wet coating method and a method based on a dry lamination method.

In the wet coating method, a resin solution containing a polyurethane resin containing a pyrithione zinc complex is applied to at least one surface of a fiber cloth, coagulated in an aqueous solvent, then desolvated, and dried. including. At this time, the zinc pyrithione complex is uniformly added to the resin solution containing the polyurethane resin in an amount of 0.0
It is preferably contained in an amount ranging from 06 to 1.2% by weight, more preferably from 0.015 to 0.6% by weight. When the content is less than 0.006%, the bacteriostatic effect of the obtained synthetic leather may be insufficient.

The fiber fabric used in the present invention includes synthetic fibers such as polyamide, polyester and rayon, regenerated fibers or semi-synthetic fibers, natural fibers such as cotton and wool, and woven, knitted and non-woven fabrics made of a mixture thereof. And it is not particularly limited. In the present invention, in order to prevent the urethane-based polymer solution from excessively penetrating into the fiber cloth before forming the polyurethane-based polymer film on the fiber cloth by wet coagulation, the fiber cloth is repelled in advance. Water treatment or calendar treatment may be performed. The water repellent in this case may be a known water repellent such as a fluorine-based water repellent, and the treatment can also be performed using a commonly known method such as a padding method or a spray method. .

In such a coating method, a resin solution containing a polyurethane resin in which a powder of a zinc pyrithione complex is uniformly dispersed is applied to at least one surface of a fiber cloth by a known coating technique. The polyurethane-based resin may be any urethane-based resin such as an ether-based, ester-based, or ether-ester-based resin, and is not particularly limited. The resin solution contains the polyurethane resin as a main component, but may contain a resin other than the polyurethane resin as an inferior component, if desired.

As the organic solvent constituting the solvent of the resin solution, a water-soluble polar organic solvent such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone is preferred from the viewpoint of solubility of the resin, ease of coagulation and desolvation. Selected. The amount of the solvent used is preferably in the range of 300 to 600 parts by weight based on 100 parts by weight of the resin. When the amount is less than 300 parts by weight, the adhesiveness to the fabric is increased, but the bulkiness, the soft texture and the voluminous feel of the obtained resin film may be reduced.

The resin solution can be coated by a known coating method, for example, using a pipe coater, a knife coater, a comma coater, a reverse coater, etc., whereby the resin solution is applied to at least one surface of the fiber cloth. , Coagulate, desolvate and dry.
The coating amount of the resin solution is 0.08 to 5 mm on the fiber cloth.
It is preferable that the thickness is more preferably 0.1 to
The thickness is in the range of 0.2 mm. Thereby, a bacteriostatic synthetic leather having a microporous polyurethane-based resin film containing a zinc pyrithione complex on a fiber cloth can be obtained.

Coagulation and desolvation may be performed by a known wet coagulation method. For the coagulation bath, an aqueous solution or water of an organic solvent used as a resin solvent is preferably used. The solidification temperature is preferably in the range of 5 to 40C from the viewpoint of adjusting the diameter of the microporous pores formed in the resin film to an appropriate range. The desolvation is preferably performed using water, and the temperature of the desolvation is 5-8.
Preferably it is in the range of 0 ° C.

The solvent-free cloth is then dried by a conventional method, and the drying temperature is preferably 90 to 140 ° C. In the present invention, after desolvation and drying, a water-repellent treatment can be performed to impart durable waterproofness. A known water repellent can be used for the water repellent treatment, and it is preferable to further perform a finishing set from the viewpoint of improving the quality of the product.

In the resin solution, as other additives,
A cell conditioner, a crosslinking agent, a white pigment, and the like can be added. On the other hand, in the method by a dry lamination method, a resin solution containing a polyurethane-based resin containing a pyrithione zinc complex is applied to release paper, dried, and then an adhesive layer is provided on the resin layer. Adhering the resin layer to at least one surface of the fiber fabric via the layer, and peeling off the release paper on the resin layer. For example, an organic solvent solution of a resin containing a polyurethane resin mixed with a pyrithione zinc complex is applied to the entire surface of a release paper, dried, and then an adhesive is applied to the obtained resin film surface and dried. Next, this is bonded to a fiber cloth, wound up, aged, and the release paper is peeled off. Thereby, a bacteriostatic synthetic leather having a nonporous polyurethane-based resin film containing a zinc pyrithione complex on a fiber cloth can be obtained. The thickness of the obtained nonporous membrane is preferably 3 to 20 μm. 3 μm thick
When it is less than the above, a uniform film surface and thickness may not be obtained. If it is 20 μm or more, the washing resistance may be significantly reduced.

The amount of the zinc pyrithione complex in the polyurethane resin solution is the same as in the case described above for the wet coating method. The application of the resin solution can be performed by a known means such as a knife over roll coater. In addition, as the adhesive used for bonding the fiber cloth and the polyurethane resin film, a known adhesive can be used, and as long as the adhesiveness is not reduced, a pyrithione zinc complex is added to this. Is also good. The application of the adhesive can be performed by a known method using a knife over roll coater, a gravure roll coater, or the like, and the adhesive may be applied over the entire surface, or may be applied in a dotted or linear manner.

Drying of the resin on the release paper is 100%.
The drying is preferably performed at a temperature of 100 ° C to 160 ° C, and the drying after the application of the adhesive is preferably performed at a temperature of 100 ° C to 160 ° C using an air oven or the like. The lamination with the fiber cloth is preferably performed at a temperature of 100 to 160 ° C. and a pressure of 1 to 5 kg / m ² , and the aging time is preferably about 20 hours.

The structure of the fiber cloth is the same as that described above for the wet coating method. After the aging, the release paper is peeled from the laminated fabric to obtain a synthetic leather, and the obtained laminated fabric is further subjected to thermocompression bonding with a wet-coated fabric having a microporous film as described above. And a moisture-permeable coated fabric. The bonding surface at this time is the non-porous membrane surface of the laminated fabric and the microporous membrane surface of the wet-coated fabric, and the crimping conditions are appropriately selected depending on the physical properties of the fiber fabric and the non-porous membrane.
It is preferably carried out at a temperature of 00 to 160 ° C. and a pressure of 1 to 5 kg / m ² .

If desired, a water-repellent treatment is applied to the laminated fabric or the moisture-permeable coated fabric obtained by press-bonding the laminated fabric and the wet-coated fabric in order to impart durable waterproofness. You can also. A known water repellent can be used for the water repellent treatment, and it is preferable to further perform a finishing set from the viewpoint of improving the quality of the product. If necessary, a paper treatment or the like may be performed after the water-repellent treatment.

The synthetic fabric of the present invention obtained as described above has a bacteriostatic property which can be widely applied to clothing, bedding materials, sanitary materials, miscellaneous goods, interior goods, etc., and has excellent durability against severe industrial washing. Has performance.

[0026]

The present invention will be described below with reference to examples and comparative examples. In addition, in an example, a part shows a weight part. The quality evaluation shown in the following examples was performed by the following method. Quality evaluation method 1) Washing method JAFET standard washing detergent (polyoxyethylene alkyl ether, sodium alpha-olein sulfonate) is used, and washing is repeated 50 times by JAFET's prescribed high-temperature accelerated washing method.

2) Bacteriostatic processing test method Staphylococcus aureus, Klebsiella pneumoniae, Escherichia coli, Pseudomonas aeruginosa, MRSA
(Methicillin-resistant Staphylococcus aureus)
The test is performed according to the method of L-1902, and the bacteriostatic evaluation is performed before and after the washing test described above. The evaluation strains used here were MRSA IID1677, Staphylococcus aureus ATCC 653
8P, Klebsiella pneumoniae ATCC 4352, Escherichia
coli IFO 3301 and Pseudomonase areuginosa IFO 30
80.

3) Application of JAFET <red label> If both the test evaluations 1) and 2) and the safety evaluation for JAFET <red label> are passed, JAF is applied.
Authorize ET <red label> grant. Example 1 (Wet coating method) A plain polyamide fabric (having a basis weight of 150 g / m ² ) was dyed gray by an ordinary method using an acid dye.

Next, the fabric is impregnated with a 5% aqueous solution of Asahigard AG710 (a water repellent manufactured by Asahi Glass Co., Ltd.),
After squeezing with a mangle and drying, it was heat-treated at 150 ° C. for 30 seconds. A resin solution having the following composition was prepared for coating. Composition of resin solution for coating 100 parts of polyester urethane resin CR8006 (solid content 30%, solvent dimethylformamide, manufactured by Dainippon Ink Co., Ltd.) 30 parts of dimethylformamide zinc pyrithione powder Nicanon ZP 0.2 part (manufactured by Nichika Chemical Co., Ltd.) White Pigment L5733 2 parts (manufactured by Dainippon Ink Co., Ltd.) Crosslinking agent Coronate HL 1 part (manufactured by Nippon Polyurethane Co., Ltd.) Using a pipe coater, apply this resin solution to one surface of the above-mentioned dyed and water-repellent woven fabric. 0.14-0.16
mm.

After this is introduced into water and solidified for 2 minutes,
The plate was washed with warm water at 50 ° C. for 5 minutes, and further dried using a tenter. Table 1 shows the results regarding the initial bacteriostatic properties of the synthetic leather obtained by the wet coating, the bacteriostatic properties after 50 washings under the specified conditions, and the possibility of adding JAFET <red label>.

Comparative Example 1 (Wet coating method) The procedure of Example 1 was repeated, except that the composition of the coating resin solution was changed as follows. Composition of resin solution for coating Polyester urethane resin CR8006 100 parts Dimethylformamide 30 parts White pigment L5733 2 parts Crosslinking agent Coronate HL 1 part The results are shown in Table 1.

Comparative Example 2 (Wet coating method) The procedure of Example 1 was repeated, except that a powder of calcium phosphate carrying metal silver (Apacider AW, manufactured by Sangi Co., Ltd.) was used in place of the zinc pyrithione powder (Nicanon ZP). . Table 1 shows the results.

Example 2 (Dry lamination method) A resin solution having the following composition was prepared for coating. Resin composition for coating Ether ester urethane resin KB-X 100 parts (solid content 30%, solvent methyl ethyl ketone and dimethylformamide, manufactured by Dainippon Ink Co., Ltd.) Methylethylketone 20 parts Dimethylformamide 10 parts Pigment Black 1311K 8 parts (Dainippon Ink 0.2 part of zinc pyrithione powder Nicanon ZP 0.2 g of this resin solution was applied to a full-duplex release paper (EV130TPD, manufactured by Lintec Corporation) using a knife over roll coater. The resin on the release paper was dried at 100 ° C. using an air oven to form a nonporous film having a thickness of 10 μm.

Next, an adhesive solution having the following composition was prepared. Adhesive liquid composition Two-part polyurethane resin UZ5 100 parts (solid content 60%, solvent toluene, methyl ethyl ketone and dimethylformamide, manufactured by Dainippon Ink and Chemicals, Inc.) Dimethylformamide 20 parts Crosslinking agent N5 6 parts (manufactured by Negami Industry Co., Ltd.) Crosslinking Agent Coronate HL 6 parts (manufactured by Nippon Polyurethane Co., Ltd.) Catalyst HI215 1 part (manufactured by Dainichi Seika Co., Ltd.) This was applied to the above-mentioned non-porous membrane in the form of dots using a gravure roll coater, and then 100 parts. C. and then pre-heated to 100.degree.
50 g / m ² ) and a pressure of 4 kg / cm ² at 120 ° C.
Thermocompression bonding. Next, after aging this for 20 hours, the release paper was peeled off, and the finishing set was performed at 150 ° C.

Initial bacteriostatic property of synthetic leather by the obtained dry laminate, bactericidal property after washing 50 times under specified conditions,
Further, Table 1 shows the results regarding the availability of JAFET <red label>. Comparative Example 3 (Dry lamination method) The operation of Example 2 was repeated, except that the composition of the coating resin solution was changed as described below.

Composition of Resin Liquid for Coating Ether ester-based urethane resin KB-X 100 parts Methyl ethyl ketone 20 parts Dimethylformamide 10 parts Pigment Black 1311K 8 parts The results are shown in Table 1.

Comparative Example 4 (Dry Lamination Method) The procedure of Example 2 was repeated, except that the zinc pyrithione powder (Nicanon ZP) was replaced by a powder of calcium phosphate carrying metal silver (Apacider AW). Table 1 shows the results.

[0038]

[Table 1] From the above results, it can be seen that the synthetic leather according to the present invention has excellent bacteriostatic properties and sufficient washing resistance, and has a performance compatible with JAFET's <red mark> addition.

[0039]

According to the present invention, excellent bacteriostatic properties can be obtained without lowering the peel strength of the polyurethane film.
A synthetic leather exhibiting extremely high washing resistance can be provided. Moreover, this synthetic leather has a sublimeness, has a soft texture and a voluminous feel, and has a smooth surface feel. Therefore, according to the present invention, not only clothing, bedding, and interior goods, but also so-called special-purpose white coats, surgical gowns, nursing gowns, aprons, bedspreads, covers, hoods, and chairs, which are used especially in medical institutions and facilities equivalent thereto. It is possible to provide various products compatible with the <red mark> of JAFET that can be used for tensioning or the like.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) D06M 15/564 D06M 15/564

Claims (3)

[Claims] 1. Synthetic leather comprising a fiber fabric and a polyurethane resin film containing a zinc pyrithione complex provided on at least one surface thereof. 2. A synthetic leather comprising applying a resin solution containing a polyurethane resin blended with a pyrithione zinc complex to at least one surface of a fiber cloth, coagulating the resin solution in an aqueous solvent, and then removing the solvent and drying. Production method. 3. A resin solution containing a polyurethane resin blended with a pyrithione zinc complex is applied to release paper, dried, and then an adhesive layer is provided on the resin layer, and then through the adhesive layer. A method for producing synthetic leather, comprising bonding a resin to at least one surface of a fiber cloth and peeling off release paper on the resin layer.