JP5254756B2 - Cloth - Google Patents

Description

  The present invention relates to a fabric excellent in antibacterial properties, antistatic properties and antifouling properties.

  Conventionally, various attempts have been made to impart antibacterial, antistatic, and antifouling properties to fabrics.

  For example, Patent Document 1 discloses a dyed fabric using a specific amount of polyester fiber containing an inorganic antibacterial agent, and describes that an antibacterial activity value of 2.2 or more can be achieved. Yes. Patent Document 2 discloses a fiber structure in which a resin composition containing a photocatalytic semiconductor is adhered to the surface of an intermediate layer made of an inorganic composition, and has a desired deodorizing effect as well as excellent antifouling properties. It has been described that its properties and antibacterial properties are exhibited.

Furthermore, Patent Document 3 discloses a fiber structure comprising vinyl sulfonic acid and a quaternary ammonium salt on its surface, and exhibits effects such as hygroscopicity, deodorant properties, antibacterial properties, and antistatic properties. It is stated that it will be.
JP 2008-111221 A Japanese Patent Laid-Open No. 2000-119956 JP-A-9-188970

  However, in the fabric described in Patent Document 1, since a predetermined amount of an inorganic compound metal in which metal ions are supported on a polyester fiber is kneaded in order to exhibit antibacterial properties, there is a drawback that the bacterial species that can exhibit antibacterial performance are limited. In addition, the metal ions gradually elute on the fiber surface as they are used, and the fabric is yellowed.

  Moreover, in the fiber structure described in Patent Document 2, a resin layer containing a photocatalytic semiconductor is formed in the outermost layer, and when this photocatalytic semiconductor is excited by ultraviolet rays, a strong oxidizing power is generated. Is obtained. The oxidizing power generated by this photocatalytic semiconductor is much stronger than that of the generally known titanium oxide photocatalyst, and therefore the fiber structure itself may be decomposed and colored. An intermediate layer is provided on the surface as a protective layer.

  However, since the fiber structure described in Patent Document 2 has two layers on the surface, the texture is very hard, and the fiber structure as a whole does not have antistatic properties. Moreover, according to the document, such a fiber structure can be applied to uniform clothing, but is limited to uniform clothing for machine work, and other fields such as food manufacturing field, medical field, precision machine manufacturing field, etc. There is also a problem that it is difficult to apply to uniform clothing used in Japan.

  Furthermore, the fiber structure described in Patent Document 3 is obtained by immersing the fabric in a treatment liquid having a predetermined composition, which is inferior in washing durability and gradually loses its characteristics as it is used. There is a problem of going.

  The present invention eliminates the drawbacks of the prior art as described above, has antibacterial properties, antistatic properties, antifouling properties, and is excellent in washing durability, and also in the medical field and precision machine field. It is an object of the present invention to provide a fabric suitable for uniform clothing.

  The inventors of the present invention have arrived at the present invention as a result of intensive studies in order to solve such problems.

That is, the gist of the present invention is as follows.
(1) A cloth comprising a vinyl polymer containing a hydrophilic polyester and an antibacterial agent on its surface, and after washing 50 times according to JIS L0217 103 method, the bactericidal activity value is greater than 0, and the friction A fabric having a charged voltage of 800 V or less and a recontamination prevention grade of 4 or more.
(2) The vinyl polymer contains a bifunctional vinyl monomer as a structural unit, and is at least one polymer selected from the group consisting of acrylate resins, methacrylate resins, epoxy acrylate resins, and epoxy methacrylate resins. The fabric according to (1) above.
(3) The fabric according to (1) or (2), wherein the antibacterial agent is pyrithione zinc.

  The fabrics of the present invention have antibacterial properties, antistatic properties, and antifouling properties, and are also excellent in washing durability. Therefore, the fabric of the present invention can be applied to uniform clothing and the like, and is particularly suitable for uniform clothing used in the food manufacturing field, medical field, precision machine manufacturing field, and the like.

  The fabric of the present invention is intended for fabrics, knitted fabrics, nonwoven fabrics and the like formed from fibers.

  Examples of fibers that can constitute the fabric of the present invention include polyester fibers such as polyethylene terephthalate, polybutylene terephthalate, polypropylene terephthalate, and polylactic acid, polyamide fibers such as nylon 6 and nylon 66, acrylic fibers, and polyurethane fibers. Natural fibers such as cotton, wool, silk, hemp and bamboo, recycled fibers such as viscose rayon, copper ammonia rayon, solvent-spun cellulose fiber, semi-synthetic fibers such as acetate, etc. , Mixed spinning, mixed fiber, union, knitting, and the like.

  The form of the fiber may be either a long fiber or a short fiber, and the cross-sectional shape is not particularly limited. Further, the fiber may contain titanium dioxide, silicon dioxide, pigment, etc. depending on the purpose.

  In the present invention, a vinyl polymer is used. The use of a vinyl polymer greatly contributes to the improvement of washing durability.

  As the vinyl polymer in the present invention, any polymer can be used as long as it is a polymer mainly composed of a vinyl monomer as a structural unit. Examples of the vinyl monomer include acrylic acid, methacrylic acid, maleic acid, itaconic acid, butenetricarboxylic acid, fumaric acid, ctronic acid, vinylpropionic acid, methylvinylsulfonic acid, styrenesulfonic acid, α-methylstyrenesulfonic acid, sulfone. Propyl acrylate, sulfopropyl methacrylate, 2-hydroxy-3-acryloyloxypropane sulfonic acid, 2-hydroxy-3-methacryloyloxypropane sulfonic acid, 2-acryloyloxyethane sulfonic acid, 2-methacryloyloxyethane sulfonic acid Allylsulfonic acid, methallylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamide-2-methylpropanesulfonic acid, 3-acrylamido-2-hydroxypropanesulfonic acid, 3 Methacrylamide-2-hydroxypropane sulfonic acid, t- butyl acrylamide sulfonic acid, such as allyl sulfosuccinic acid, or derivatives thereof. In the present invention, vinyl monomers are used alone or in combination.

  In the present invention, as the vinyl polymer, a bifunctional vinyl monomer is preferably used from the viewpoint of antistatic properties and antifouling properties. As the bifunctional vinyl monomer, diacrylate is preferable, and specifically, polyethylene glycol diacrylate, polypropylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, polyethylene glycol epoxy diacrylate, polypropylene glycol epoxy diacrylate, Examples include polyethylene glycol epoxy dimethacrylate and polypropylene glycol epoxy dimethacrylate. And when using the acrylate quoted here, as a repeating number of polyethyleneglycol or polypropylene glycol which is a repeating unit, 1-23 are preferable, and this is equivalent to 100-1000 when converted into the molecular weight of only a repeating unit.

  Here, as a structural formula of diacrylate, the following formula (1) represents an acrylate-based general formula, and formula (2) represents an epoxy acrylate-based general formula.

  As the vinyl monomer in the present invention, it is preferable to use a bifunctional vinyl monomer as described above. When this is included in a constituent unit in the molecule, the vinyl polymer is an acrylate resin, a methacrylate resin, an epoxy acrylate resin, or an epoxy. It becomes at least one polymer selected from the group consisting of methacrylate resins.

  In the present invention, the vinyl polymer as described above is used, but in the present invention, it is not used alone, but from the viewpoint of bactericidal properties, antistatic properties, and antifouling properties, hydrophilic polyester, bactericidal agent, Is used.

  Examples of the hydrophilic polyester include condensation polymers of polyalkylene glycols such as polyethylene glycol and polypropylene glycol and dicarboxylic acid compounds such as terephthalic acid and sulfoisophthalic acid. The molecular weight of the hydrophilic polyester is preferably 100 to 10,000.

  The use amount of the hydrophilic polyester is 1 to 100 parts by mass of the vinyl polymer alone (hereinafter, the vinyl polymer alone refers to a vinyl polymer in a state not containing the hydrophilic polyester and the antibacterial agent described below). It is preferable to set it as 100 mass parts, and 5-50 mass parts is more preferable. If the amount of the hydrophilic polyester used is less than 1 part by mass, the antistatic property and antifouling property tend not to be improved, which is not preferable. On the other hand, if it exceeds 100 parts by mass, the dyeing fastness tends to decrease, which is not preferable.

  Examples of the antibacterial agent include organic antibacterial agents such as quaternary ammonium salt type, biguanide and imidazole, and natural organic antibacterial agents such as hinokitiol and chitosan. Especially, it is preferable to use the pyrithione zinc shown by following (3) Formula from a viewpoint of exhibiting the stable antimicrobial property with respect to many microbial species.

  As a usage-amount of an antibacterial agent, it is preferable to set it as 0.1-50 mass parts with respect to 100 mass parts of vinyl polymer single, and 1-30 mass parts is more preferable. If the amount of the antibacterial agent used is less than 0.1 parts by mass, the desired antibacterial property tends to be difficult to obtain. On the other hand, if it exceeds 50 parts by mass, the dyeing fastness may be reduced or colored. Therefore, neither is preferable.

  In the present invention, a vinyl polymer containing the above hydrophilic polyester and an antibacterial agent is used and used as provided on the surface of the fabric. At this time, the vinyl polymer is preferably attached in an amount of 1 to 30% by mass, more preferably 1 to 20% by mass with respect to the mass of the fiber fabric (fabric before processing). When the adhesion amount of the vinyl polymer is less than 1% by mass, desired antibacterial properties, antistatic properties and antifouling properties tend to be difficult to obtain, whereas when it exceeds 30% by mass, the texture tends to become coarse and hard. Both are not preferred.

  The fabrics of the present invention have antibacterial properties, antistatic properties, and antifouling properties, and are also excellent in washing durability. “Excellent washing durability” means “JAFET standard detergent” (polyoxyethylene alkyl ether) specified in the antibacterial processed fiber product certification standard (JEC S301) issued by the Japan Fiber Evaluation Technology Council. This means that the effect can be maintained even after washing 50 times according to JIS L0217 103 method.

  In the present invention, as an index of antibacterial properties, it is necessary that the bactericidal activity value after washing 50 times according to the JIS L0217 103 method is greater than zero. By setting the bactericidal activity value within this range, the growth of bacteria attached to the fabric can be suppressed.

The bactericidal activity value shall be measured in accordance with JIS L1902 (antibacterial test method / antibacterial effect of textile products) bacterial liquid absorption method with the test target bacteria as pneumoniae (ATCC4352). After the measurement, the obtained measured value is substituted into the following formula for calculation.

  Setting the bactericidal activity value in the above range can be achieved by including a predetermined amount of an antibacterial agent in the vinyl polymer and then attaching the polymer to the surface of the fiber fabric by a predetermined amount.

  In addition, as an index of antistatic property, the frictional voltage after washing 50 times according to JIS L0217 103 method needs to be 800 V or less. If it exceeds 800V, it will become charged during wearing and adsorb dirt particles in the air, making it easy to get dirty, making it impossible to apply to uniform clothing used in the food manufacturing field.

  Note that the frictional voltage is measured according to JIS L1094B method.

  Setting the frictional voltage within the above range can be achieved by including a predetermined amount of hydrophilic polyester in the vinyl polymer and then attaching a predetermined amount of polymer to the surface of the fiber fabric.

  Further, as an index of antifouling property, the recontamination preventing property class after washing 50 times according to JIS L0217 103 method is required to be 4th or higher. When the re-contamination prevention grade is less than 4th grade, dirt tends to remain even after washing, which is not preferable. The re-contamination prevention grade refers to 0.2 ml of B heavy oil dropped on the fabric, left for 30 minutes, washed once according to JIS L0217 103 method, dried, and judged according to JIS L0805 contamination gray scale. Refers to the residual contamination level. This re-contamination prevention grade is rated at grade 5, with grade 1 being the worst and grade 5 being the best. The B heavy oil corresponds to the second type heavy oil described in JIS K2205.

  Setting the re-contamination prevention grade within the above range can be achieved by including a predetermined amount of hydrophilic polyester in the vinyl polymer and adhering a predetermined amount of polymer to the fiber fabric surface.

  Next, a method for producing the fabric of the present invention will be described.

  The fabric of the present invention is prepared by first preparing a fiber fabric composed of the above-mentioned fibers, and then applying an aqueous solution containing a vinyl monomer, a hydrophilic polyester and an antibacterial agent to the fiber fabric, and then polymerizing the monomer. Can be obtained.

  The fiber fabric may be scoured, alkali-reduced and dyed in advance.

  Moreover, it does not specifically limit as a method of providing aqueous solution to a fiber fabric, Well-known methods, such as a padding method, a spray method, a kiss roll coater method, and a slit coater method, can be employ | adopted suitably.

  Arbitrary means can be adopted as means for polymerizing the vinyl monomer, and after application of the aqueous solution, first air drying or preliminary drying by heating, followed by low temperature plasma treatment, dry heat treatment, steam heat treatment, cold batch treatment or ultraviolet treatment, etc. It is possible to adopt a means to do so. Of these, low temperature plasma treatment and steam heat treatment are preferred from the viewpoint of polymerization efficiency and stability.

  Similarly, from the viewpoint of polymerization efficiency and stability, the aqueous solution preferably contains a polymerization initiator. Examples of the polymerization initiator include ammonium persulfate, potassium persulfate, cerium ammonium nitrate, hydrogen peroxide. Inorganic polymerization initiators such as 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis (N, N′-dimethyleneisobutyramide) dihydrochloride, 2- A radical initiator such as an organic radical initiator such as (carbamoylazo) isobutyronitrile is generally used, but a so-called redox initiator using a peroxide and a reducing substance in combination can also be used. Examples of the redox initiator include peroxides such as ammonium persulfate and potassium persulfate, and examples of the reducing substance include a reaction product of sodium sulfoxylate and formalin, hydrosulfite, and the like.

  The amount of the polymerization initiator used is preferably 0.1 to 15.0 parts by mass with respect to the mass of the vinyl monomer alone.

  Furthermore, the aqueous solution may contain a polymerization inhibitor. By using a polymerization inhibitor in combination, polymerization in a low temperature region can be suppressed, and a vinyl polymer having a desired degree of polymerization can be obtained. Polymerization inhibitors include quinones such as benzoquinone, hydroquinone and methoxyphenol, polyoxy compounds such as tert-butylcatechol, organic sulfur compounds such as sodium dimethyldithiocarbamate and diethylhydroxylamine, nitro compounds, diethylhydroxylamine and isopropylhydroxyl. And amino compounds such as amines.

  As a usage-amount of a polymerization inhibitor, 0.01-2.00 mass% is preferable with respect to the mass of a vinyl-type monomer independent.

  As described above, low temperature plasma treatment and steam heat treatment are preferable as means for polymerizing the vinyl monomer after applying the above aqueous solution to the fiber fabric. Specifically, when the low temperature plasma treatment is employed, the vinyl monomer can be polymerized by placing the fiber fabric in the plasma atmosphere for a certain period of time. Low-temperature plasma is generated as a result of excitation of oxygen molecules by applying high-frequency energy to oxygen or a mixed gas containing oxygen in a reduced pressure state.

The oxygen or mixed gas containing oxygen in the present invention is a gas obtained by mixing 100% oxygen or oxygen and another gas. Examples of other gases include inert gases such as helium and argon, nitrogen, water vapor, and carbon dioxide. Further, the frequency of the high frequency energy is not particularly limited as long as it is a frequency that can generate low temperature plasma, and can be used in the range of 1 to 3000 MHz. However, in practical use, it is preferable to use any of 13.56 MHz, 27.12 MHz, 40.68 MHz, 915 MHz, and 2450 MHz according to regulations such as the Radio Law. The power of the high frequency energy (high frequency power) is preferably 0.1 to 10.0 W / cm ² . Further, the degree of vacuum at the time of processing is not particularly limited as long as low temperature plasma is generated, but in practice, 13 to 2670 Pa is preferable, and 40 to 1330 Pa is more preferable. The processing time is not particularly limited, but is preferably in the range of 1 to 240 seconds.

  In addition, when the steam heat treatment is adopted, any of the treatment based on the normal pressure steam method and the treatment based on the high pressure steam method can be adopted, but the one based on the normal pressure steam method is preferable from the viewpoint of cost. As temperature of a steam heat processing, 80-180 degreeC is preferable and 98-150 degreeC is more preferable. Further, the time for the steam heat treatment is preferably 1 to 20 minutes.

  After the vinyl monomer is polymerized into a vinyl polymer, the fabric may be subjected to a softening treatment, a water repellent treatment, a flame retardant treatment, or the like, if necessary.

  Next, the present invention will be specifically described with reference to examples.

Example 1
Polyester multifilament processed yarn 167dtex48f is used as the warp and polyester multifilament processed yarn 334dtex96f is used as the weft. A twill weave with a warp density of 128 / 2.54cm and a weft density of 58 / 2.54cm is woven and scoured in the usual manner did.

  Next, this twill fabric was impregnated with an aqueous solution having the composition shown in Formula 1 below, then drawn with a mangle at a drawing rate of 80% by mass, and preliminarily dried at 130 ° C. for 60 seconds.

<< Prescription 1 >>
Vinyl monomer (polyethylene glycol 400 epoxy dimethacrylate) 60g / L
Hydrophilic polyester (“SR6200 (trade name)” manufactured by Takamatsu Yushi Co., Ltd.) 30 g / L
Antibacterial agent containing zinc pyrithione (Osaka Kasei Co., Ltd. “Marcaside YP-DP (trade name)”) 20 g / L

Thereafter, the twill fabric was subjected to low-temperature plasma treatment under the conditions of air as the gas species, 133 Pa as the degree of vacuum, 13.56 MHz as the frequency, 1.0 W / cm ² as the high frequency power, and 60 seconds as the treatment time, to obtain the fabric of the present invention. It was.

  At this time, the adhesion amount with respect to the fiber fabric (fabric before processing) of the vinyl-type polymer containing hydrophilic polyester and an antibacterial agent was 5.5 mass%. Moreover, the usage-amount of hydrophilic polyester and an antibacterial agent was 10 mass parts and 5 mass parts, respectively with respect to 100 mass parts of vinyl polymer single.

(Example 2)
A fabric of the present invention was obtained in the same manner as in Example 1 except that an aqueous solution having the composition shown in Formula 2 below was used instead of Formulation 1.

  In the obtained fabric, the adhesion amount of the vinyl polymer containing the hydrophilic polyester and the antibacterial agent to the fiber fabric is 8.7% by mass, and the use amount of the hydrophilic polyester and the antibacterial agent is vinyl. The amount was 6 parts by mass and 3 parts by mass, respectively, based on 100 parts by mass of the single polymer.

<< Prescription 2 >>
Vinyl monomer (polypropylene glycol 200 epoxy dimethacrylate) 100g / L
Hydrophilic polyester (“Nice Pole PR-99 (trade name)” manufactured by Nikka Chemical Co., Ltd.) 30 g / L
Antibacterial agent containing zinc pyrithione (Osaka Kasei Co., Ltd. “Marcaside YP-DP (trade name)”) 20 g / L

( Reference Example 1 )
Weaving a plain fabric with a warp density of 66 / 2.54 cm and a weft density of 56 / 2.54 cm using polyester multifilament processed yarn 334dtex96f as warp and polyester cotton blended yarn 45-number double yarn as weft. Scouring, bleaching and mercerizing.

  Next, this plain woven fabric was impregnated with an aqueous solution having the composition shown in Formula 3 below, then squeezed with a mangle at a squeezing rate of 80% by mass, and preliminarily dried at 130 ° C. for 60 seconds.

<< Prescription 3 >>
Vinyl monomer (polyethylene glycol 1000 dimethacrylate) 100g / L
Hydrophilic polyester (“Nice Pole PR-99 (trade name)” manufactured by Nikka Chemical Co., Ltd.) 30 g / L
Antibacterial agent containing zinc pyrithione (Osaka Kasei Co., Ltd. “Marcaside YP-DP (trade name)”) 20 g / L
Polymerization initiator (ammonium persulfate) 10 g / L

Thereafter, this plain fabric was steam-heated at 99 ° C. for 5 minutes based on the atmospheric steam method to obtain a fabric of Reference Example .

  At this time, the adhesion amount with respect to the fiber fabric of the vinyl polymer containing hydrophilic polyester and antibacterial agent was 8.7 mass%. Moreover, the usage-amounts of hydrophilic polyester and an antibacterial agent were 6 mass parts and 3 mass parts, respectively with respect to 100 mass parts of vinyl polymer single.

(Comparative Example 1)
The twill fabric after scouring used in Example 1 was exhausted at 130 ° C. for 30 minutes using an aqueous solution having the composition shown in Formula 4 below to obtain a comparative fabric.

<< Prescription 4 >>
Hydrophilic polyester (“Parasolve PET-2 (trade name)” manufactured by Ohara Palladium Co., Ltd.) 3% owf
Antibacterial agent containing pyrithione zinc (Osaka Kasei Co., Ltd. “Marcaside YP-DP (trade name)”) 2% owf

(Comparative Example 2)
The mercerized plain fabric used in Reference Example 1 was impregnated with an aqueous solution having the composition shown in Formula 5 below, then drawn with a mangle at a drawing rate of 80% by mass, and pre-dried at 130 ° C. for 60 seconds.

<< Prescription 5 >>
Acrylic polymer-based binder (“Light Epoch AX-30 (trade name)” manufactured by Kitahiro Chemical Co., Ltd.) 40 g / L
Hydrophilic polyester (“SR6200 (trade name)” manufactured by Takamatsu Yushi Co., Ltd.) 30 g / L
Catalyst for hydrophilic polyester (“SR-CA-1 (trade name)” manufactured by Takamatsu Yushi Co., Ltd.) 10 g / L
Organic carboxylic acid compound antibacterial agent (“Amorden MTS (trade name)” manufactured by Daiwa Chemical Industry Co., Ltd.) 20 g / L

  Thereafter, this plain woven fabric was dry heat-treated at 170 ° C. for 1 minute to obtain a comparative fabric.

The bactericidal activity value, the friction band voltage, and the recontamination prevention grade before and after washing of the fabrics according to Examples 1 and 2, Reference Example 1 and Comparative Examples 1 and 2 obtained as described above are shown below. Table 1 shows.

As is apparent from Table 1, the fabrics according to Examples 1 and 2 were excellent in antibacterial properties, antistatic properties and antifouling properties even after 50 washings. Therefore, the obtained fabric is suitable for various uniform garments, particularly uniform garments used in the food manufacturing field, the medical field, the precision machine manufacturing field, and the like. On the other hand, the fabrics according to Comparative Examples 1 and 2 were inferior in washing durability because vinyl polymers were not used unlike the Examples. Therefore, although it can be used for uniform clothing, its application range is limited.

Claims (3)

A cloth comprising a vinyl-based polymer containing a hydrophilic polyester and an antibacterial agent on the surface and satisfying the following (1) to (4), after being washed 50 times according to the JIS L0217 103 method, A fabric having an activity value greater than 0, a frictional voltage of 400 V or less , and a recontamination prevention grade of 4 or more.
(1) The vinyl polymer contains a bifunctional vinyl monomer as a structural unit, and at least one selected from the group consisting of epoxy acrylate resins and epoxy methacrylate resins.
(2) The content of the hydrophilic polyester is 6 to 10 parts by mass with respect to 100 parts by mass of the vinyl polymer.
(3) The content of the antibacterial agent is 3 to 5 parts by mass with respect to 100 parts by mass of the vinyl polymer.
(4) The adhesion amount of the vinyl polymer is 5.5 to 30% by mass. The fabric according to claim 1, wherein the antibacterial agent is pyrithione zinc. The fabric according to claim 1 or 2, wherein the bactericidal activity value exceeds 2.0.