JP7317310B2 - Antifouling clothing and manufacturing method thereof - Google Patents

Description

The present invention relates to stain-resistant and water-repellent clothing in dry gas and hydrophilic in liquid water, and a method for manufacturing the same.

BACKGROUND ART Conventionally, fabrics imparted with antifouling properties and water repellency have been used for clothing, carpets, tablecloths and the like. Patent Document 1 proposes a fluorine compound containing a fluoroalkyl group having 22 or less carbon atoms in order to impart antifouling properties against dry stains. Patent Document 2 discloses a monomer derived from a monomer having a fluoroalkyl group or a fluoroalkenyl group, a monomer having an alkylene oxide group, a monomer having an acetoacetyl group, and a monomer having an acid anion group. A fiber finishing agent having washing durability, oil repellency and stain resistance is proposed using the copolymer obtained.

JP-A-2002-220781 JP 2010-222382 A

However, the fiber finishing agents of the prior art contain fluorine, and are environmentally problematic.
In order to solve the above problems, the present invention provides stain-resistant clothing that is stain-resistant and water-repellent in dry gas and hydrophilic in liquid water without using fluorine, which is harmful to the environment, and its manufacture. provide a way.

The antifouling clothing of the present invention is a garment comprising an antifouling fabric obtained by graft-polymerizing an environmentally responsive water-soluble substance having a radical-bonding group to a fiber base material, wherein the environmentally responsive water-soluble substance comprises: One molecule contains a radical-bonding group, a hydrophilic group and a hydrophobic group , the environmentally responsive water-soluble substance is graft-polymerized to the fabric in an amount of 0.1 to 50% by mass, and the hydrophilic group is It is at least one selected from an amide group, an ether group and an alcohol group, the radical-bonding group is at least one selected from an acryloyl group, a methacryloyl group and a vinyl group, and the antifouling fabric contains a dry gas Inside, it becomes a hydrophobic shrink gel state, has antifouling properties and water repellency , and in liquid water, it becomes a hydrophilic swollen gel state by being compatible with water. It is characterized by having stainability and water repellency, and becoming hydrophilic at the time of home washing so that stains can be removed.

The method for producing the antifouling clothing of the present invention is the above-described method for producing the antifouling clothing , wherein the fiber base material of the fabric constituting the clothing is brought into contact with an environmentally responsive water-soluble substance having a radical bonding group. before or at the same time as the contact, the environment-responsive water-soluble substance is graft-polymerized on the fiber base material, then washed and dried.

The antifouling clothing of the present invention is an antifouling clothing obtained by graft-polymerizing an environmentally responsive water-soluble substance having a radical-bonding group to a fiber base material, and the environmentally responsive water-soluble substance does not contain fluorine. , it is antifouling and water-repellent in dry gas, and hydrophilic in liquid water. As a result, it has antifouling properties and water repellency when used, and becomes hydrophilic in liquid water when washed at home, making it easy to remove stains. Moreover, the production method of the present invention can efficiently graft-polymerize the environment-responsive water-soluble substance to the fiber base material.

FIG. 1A shows the molecular structure of the environmentally responsive water-soluble substance when clothes of one embodiment of the present invention are washed at home, and FIG. 1B shows the molecular structure of the environmentally responsive water-soluble substance when worn.

The present invention is an antifouling fabric obtained by graft-polymerizing an environment-responsive water-soluble substance having a radical-bonding group to a fiber base material. Here, the environmentally responsive water-soluble substance is a compound having a property of forming a hydrophobic shrinking gel state in dry gas, and a hydrophilic swollen gel state with affinity to water in liquid water. The environmentally responsive water-soluble substance maintains its hydrophobicity when dry, for example, when it is worn on clothes, and thus has stain resistance and water repellency. Further, the environmentally responsive water-soluble substance does not contain fluorine. Fluorine compounds are environmentally unfavorable substances, including during synthesis.

The environmentally responsive water-soluble substance is preferably graft-polymerized in an amount of 0.1 to 50% by mass, more preferably 1 to 40% by mass, and still more preferably 3 to 35% by mass with respect to the fabric. Within this range, stain resistance and water repellency can be obtained when dry, for example, when clothes are worn, and stains can be easily removed when washed at home.

The environmentally responsive water-soluble substance preferably contains a hydrophilic group and a hydrophobic group in addition to a radical-bonding group in one molecule. Radical bonding groups are useful for grafting onto fabrics. At least one hydrophilic group selected from an amide group, an ether group and an alcohol group is preferred. The hydrophobic group is preferably an alkyl group or a cycloalkyl group, more preferably an n-propyl group, an isopropyl group, a cyclopropyl group, or the like. Hydrophobic groups have antifouling properties and water repellency when clothes are worn, and hydrophilic groups have an affinity for water and become hydrophilic when washed at home, so that stains can be easily removed.

Preferably, the radical-bonding group is at least one selected from an acryloyl group, a methacryloyl group and a vinyl group. These can be graft-polymerized to the fabric by electron beam irradiation.

The temperature at which the environmentally responsive water-soluble substance becomes insoluble in water (Lower Critical Solution Temperature: LCST) is preferably 25 to 80°C, more preferably 28 to 72°C. For example, the LCST of poly-N-isopropylacrylamide is 32°C.

LCST can be measured using a differential scanning calorimeter (DSC), for example, a DSC apparatus "DSC6200" manufactured by Seiko Instruments Inc. As an example of a specific method for measuring the LCST of a polymer that has been graft-polymerized with an environmentally responsive water-soluble substance onto a fabric, a DSC device is applied to a fabric graft-polymerized with an environmentally responsive water-soluble substance. to determine the LCST in water. A cloth sample is cut into small pieces using scissors, and 1 mg is placed in an aluminum pan. After that, 20 μl of water is added to the aluminum pan, the fabric is immersed, and left for 5 minutes. After that, soak up the water with a Kimwipe, seal it up, and place it in the DSC. The temperature is from -5°C to 60°C, and the temperature rise rate is 10°C/min.

Specific examples of the environmentally responsive water-soluble substance include compounds having structures shown in [a] to [d] of the following (Chem. 1) to (Chem. 4). is preferred. The N-substituted acrylamide polymer can be used alone or in combination. In (Chem. 1) to (Chem. 4), R is an alkyl group having 1 to 22 carbon atoms or a cycloalkyl group, and n is a repeating unit (a numerical range to indicate the degree of polymerization of the main chain by electron beam polymerization. cannot be shown).

Compounds having the structure [a] include N-substituted acrylamides, N-ethylacrylamide, N-propylacrylamide, N-isopropylacrylamide: NIPAM, N-cyclopropylacrylamide, N-methyl-N-ethyl Acrylamide, N-ethylmethacrylamide, N-propylmethacrylamide, 2-carboxyisopropylacrylamide, etc.
Compounds having the structure [b] include amides, such as N-vinylpyrrolidone and N-vinylisobutyramide.
Examples of the compound having the structure [c] include ethers such as hydroxypropyl acrylate, vinyl alcohol, ethylene oxide, vinyl methyl ether, oxyethylene vinyl ether, hydroxypropyl methylcellulose, hydroxypropyl cellulose, and methyl cellulose.
Compounds having the structure [d] include oxozaline compounds such as 2-isopropyl-2-oxazoline.

As the solvent, one or more of water, methanol, ethanol, isopropanol, toluene, methyl ethyl ketone and the like can be used. The dispersion may also contain an emulsifier. It may also contain a cross-linking agent, for example, an organic compound having two or more radically polymerizable groups per molecule, such as methylolmelamine, glyoxal, ditrimethylolpropane tetraacrylate, urethane acrylate, polyglycerol acrylate, pentaerythritol tetraacrylate. etc. can be used.

It is also possible to use copolymers, for example, N-isopropylacrylamide (NIPAM), N,N-dimethylacrylamide as a hydrophilic group, N-n-butylacrylamide as a hydrophobic group, butyl methacrylate, etc. can polymerize. When a hydrophilic group is copolymerized, the LCST can be shifted to the high temperature side, and when a hydrophobic group is copolymerized, the LCST can be shifted to the low temperature side, so that the balance between hydrophilicity and hydrophobicity can be controlled.

The antifouling fabric of the present invention is preferably at least one selected from woven fabrics, knitted fabrics and non-woven fabrics. The fiber base material constituting the antifouling fabric is preferably polyester, nylon (polyamide), acrylic, modacrylic, polyolefin such as polypropylene, aramid, rayon, acetate, cupra, cotton, wool, hemp, silk, and the like.

Next, a manufacturing method will be described. In the method for producing the antifouling fabric of the present invention, a fiber base material constituting the fabric is irradiated with radiation such as electron beams, gamma rays, or ultraviolet rays, and then brought into contact with an environmentally responsive water-soluble substance having a radical-bonding group. Then, the environmentally responsive water-soluble substance is graft-polymerized on the fiber base material (pre-irradiation method), or the environmentally responsive water-soluble substance is contacted with the fiber base material, and then irradiated with electron beams, gamma rays, or Radiation such as ultraviolet rays is applied to graft polymerize the environmentally responsive water-soluble substance onto the fiber base material (simultaneous irradiation method), followed by washing and drying. As for the irradiation method, it is preferable to employ an electron beam from the viewpoint of ease of handling, safety, and effective generation of radicals.

Electron beam irradiation is usually performed at a dose of 1 to 200 kGy, preferably 5 to 100 kGy, more preferably 10 to 50 kGy. As for the atmospheric conditions, the irradiation is performed in a nitrogen atmosphere. Further, since the electron beam has penetrating power, it is sufficient to irradiate only one side of the fiber base material. Commercially available electron beam irradiation devices can be used. ), EPS300 (manufactured by NHV Corporation), etc. can be used.

After electron beam irradiation, unreacted components are usually removed by washing with water, followed by drying. Drying is achieved, for example, by holding the fibrous substrate at 20-90° C. for 0.5-24 hours.

Description will be made below with reference to the drawings. FIG. 1A shows the molecular structure of the environmentally responsive water-soluble substance when clothes of one embodiment of the present invention are washed at home, and FIG. 1B shows the molecular structure of the environmentally responsive water-soluble substance when worn. This environmentally responsive water-soluble substance becomes a hydrophobic shrinking gel state in dry gas as shown in FIG. 1B, and becomes a hydrophilic swollen gel state in liquid water as shown in FIG. 1A by affinity with water. Therefore, it maintains its hydrophobicity when worn, and thus has antifouling and water-repellent properties, and becomes hydrophilic when washed at home, so that stains can be easily removed.

EXAMPLES The present invention will be described in more detail with reference to the following examples. It should be noted that the present invention is not limited to the following examples.
(Example 1)
<Adhesion of environmentally responsive water-soluble substance>
A fabric of 35 mass% cotton/65 mass% polyester (mass 114 g/m ² ) was treated at room temperature (20 ± 5 ° C.) with N-isopropylacrylamide (manufactured by Wako Pure Chemical Industries, Ltd., molecular weight 113, hereinafter simply referred to as “NIPAM “. Squeeze with a mangle until it becomes 50% by weight, and one side of the fabric is irradiated with an area beam type electron beam irradiation device (Curetron; manufactured by NHV Corporation) under a nitrogen gas atmosphere at an acceleration voltage of 250 kV and an irradiation dose of 200 kGy. The electron beam was irradiated under the conditions of The electron-beam-irradiated fabric was reacted in a dryer at 80° C. for 3 hours. Thereafter, the fabric was washed with shaking in methanol and distilled water for 30 minutes each and dried in a drier at 70° C. to obtain a fabric to which the environmentally responsive water-soluble substance (NIPAM homopolymer) was fixed. Assuming that the fabric is 100% by mass, the adhered amount of the environmentally responsive water-soluble substance was 25.0% by mass. Electron beam irradiation causes N-isopropylacrylamide to polymerize with each other and to covalently bond with the cotton (cellulose fiber) and polyester fibers that make up the fabric. When the fabric containing the environmentally responsive water-soluble substance was measured through a polyester film (thickness 25 μm) with a spectrophotometer (CM-600d; manufactured by Konica Minolta Japan Co., Ltd.), the chromaticity a* indicating hue and saturation was -0.7, b* was 3.9 (a* indicates red direction, -a* indicates green direction, b* indicates yellow direction, -b* indicates blue direction).

<Adhesion of water-based dirt>
Using a micropipette, 50 μl of red wine (“Antioxidant-free delicious wine”; manufactured by Suntory Holdings Ltd.) was dropped onto the fabric containing the environmentally responsive water-soluble substance, and after 10 seconds, a filter paper was placed thereon. A load of 100 g was applied to the sample and left for 60 seconds. After that, it was dried in a heat dryer at 30°C for 15 minutes, and the stained part was measured through a polyester film (thickness 25 µm) with a spectrophotometer (CM-600d; manufactured by Konica Minolta Japan Co., Ltd.). The chromaticity a* indicating is -0.7 before dropping, but shifted to 1.7 after dropping in the red direction.

<Washing water-based dirt>
The fabric containing the environmentally responsive water-soluble substance, which was stained with red wine, was washed with an ultrasonic cleaner (AS52GTU; manufactured by AS ONE) at a water temperature of 10-20°C (bath ratio 1:600) for 15 minutes. After that, it was dried at 70°C. When the stained part was measured through a polyester film (thickness 25 μm) with a spectrophotometer (CM-600d; manufactured by Konica Minolta Japan Co., Ltd.), the chromaticity a*, which indicates hue and saturation, was 1.7 before washing. On the other hand, after washing, it shifted to -0.2 in the green direction.

<Adhesion of oil-based dirt>
Using a micropipette, one drop of chili oil (“spicy oil”; manufactured by SB Foods Co., Ltd.) was dropped onto the fabric containing the environmentally responsive water-soluble substance. Left for 60 seconds. After that, it was dried in a heat dryer at 30°C for 15 minutes, and the stained part was measured through a polyester film (thickness 25 µm) with a spectrophotometer (CM-600d; manufactured by Konica Minolta Japan Co., Ltd.). The chromaticity b*, which indicates , shifted toward yellow from 3.9 before dropping to 15.4 after dropping.

<Cleaning of oil-based dirt>
The fabric containing the environmentally responsive water-soluble substance stained with chili oil was washed with an ultrasonic cleaner (AS52GTU; manufactured by AS ONE) at a water temperature of 10 to 20°C (bath ratio 1:600) for 15 minutes. After that, it was dried at 70°C. When the stained part was measured through a polyester film (thickness 25 μm) with a spectrophotometer (CM-600d; manufactured by Konica Minolta Japan Co., Ltd.), the chromaticity b*, which indicates hue and saturation, was 15.4 before washing. On the other hand, after washing, it shifted to 11.0 in the blue direction.

(Example 2)
<Adhesion of environmentally responsive water-soluble substance>
It was produced in the same manner as in Example 1, except that the concentration of the N-isopropylacrylamide solution was changed to 35% by weight. The fixed amount of the environmentally responsive water-soluble substance was 10.5% by mass.
The chromaticity a* indicating the hue and chroma of the fabric containing this environmentally responsive water-soluble substance was -0.8, and the b* was 3.5.
<Adhesion of water-based dirt>
When the stained part after dropping red wine was measured in the same manner as in Example 1, the chromaticity a*, which indicates hue and saturation, was -0.8 before dropping, and 5.9 after dropping, shifting in the red direction. bottom.
<Washing water-based dirt>
When the stained area after washing was measured in the same manner as in Example 1, the chromaticity a*, which indicates hue and saturation, shifted from 5.9 before washing to 1.9 after washing in the direction of green. .
<Adhesion of oil-based dirt>
When the stained part after dropping the chili oil was measured in the same manner as in Example 1, the chromaticity b*, which indicates hue and saturation, was 3.5 before dropping, and shifted to 20.4 after dropping, in the yellow direction. bottom.
<Cleaning of oil-based dirt>
When the stained area after washing was measured in the same manner as in Example 1, the chromaticity b*, which indicates hue and saturation, was 20.4 before washing, and shifted to 8.7 after washing in the blue direction. .

(Example 3)
<Adhesion of environmentally responsive water-soluble substance>
It was prepared in the same manner as in Example 1, except that the concentration of the N-isopropylacrylamide solution was changed to 9% by weight. The fixed amount of the environmentally responsive water-soluble substance was 2.7% by mass.
The chromaticity a* indicating the hue and saturation of the fabric containing this environmentally responsive water-soluble substance was -0.8, and the b* was 4.1.
<Adhesion of water-based dirt>
When the stained part after the red wine was dropped was measured in the same manner as in Example 1, the chromaticity a*, which indicates hue and saturation, was -0.8 before dropping, and 6.6 after dropping, shifting in the red direction. bottom.
<Washing water-based dirt>
When the stained area after washing was measured in the same manner as in Example 1, the chromaticity a*, which indicates hue and saturation, was 6.6 before washing, and shifted to 2.0 after washing in the direction of green. .
<Adhesion of oil-based dirt>
When the stained part after dropping the chili oil was measured in the same manner as in Example 1, the chromaticity b*, which indicates the hue and saturation, was 4.1 before dropping, and shifted to 24.6 after dropping in the yellow direction. bottom.
<Cleaning of oil-based dirt>
When the stained part after washing was measured in the same manner as in Example 1, the chromaticity b*, which indicates hue and saturation, was 24.6 before washing, and shifted to 10.5 after washing in the blue direction. .

(Example 4)
<Adhesion of environmentally responsive water-soluble substance>
Environmentally responsive water-soluble The fixed amount of the substance (copolymer of NIPAM and DA) was 20.5% by mass.
The chromaticity a* indicating the hue and saturation of the fabric containing this environmentally responsive water-soluble substance was -0.7, and the b* was 3.7.
<Adhesion of water-based dirt>
When the stained part after dropping red wine was measured in the same manner as in Example 1, the chromaticity a*, which indicates hue and saturation, was -0.7 before dropping and -0.2 after dropping in the red direction. migrated.
<Washing water-based dirt>
When the stained area after washing was measured in the same manner as in Example 1, the chromaticity a*, which indicates hue and saturation, was -0.2 before washing and -0.6 after washing in the green direction. migrated.
<Adhesion of oil-based dirt>
When the stained part after dropping the chili oil was measured in the same manner as in Example 1, the chromaticity b*, which indicates hue and saturation, was 3.7 before dropping, and shifted to 20.0 after dropping, in the yellow direction. bottom.
<Cleaning of oil-based dirt>
When the stained area after washing was measured in the same manner as in Example 1, the chromaticity b*, which indicates hue and saturation, shifted from 20.0 before washing to 14.0 after washing in the blue direction. .

(Comparative example 1)
An environmentally responsive water-soluble substance adhered in the same manner as in Example 1, except that an aqueous solution consisting of 80% methanol and 20% distilled water was used instead of the N-isopropylacrylamide solution, and the electron beam irradiation step was omitted. I got a fabric that wasn't done. Chromaticity a* indicating hue and chroma of this fabric was -0.5 and b* was 1.6. In addition, except that the fabric was used, water-based stains were attached and washed in the same manner as in Example 1, and the stained part was measured with a spectrophotometer (CM-600d; manufactured by Konica Minolta Japan Co., Ltd.) with a polyester film (thickness 25 μm), a* shifted in the red direction from −0.5 before dropping to 8.2 after dropping. Thereafter, before and after washing in the same manner as in Example 1, a* changed from 8.2 before washing to 3.7 after washing.
In addition, oil-based stains were attached and washed in the same manner as in Example 1, and the stained area was measured through a polyester film (thickness 25 μm) with a spectrophotometer (CM-600d; manufactured by Konica Minolta Japan Co., Ltd.). , b* shifted in the yellow direction from 1.6 before dropping to 29.3 after dropping. Thereafter, before and after washing in the same manner as in Example 1, b* shifted in the blue direction from 29.3 before washing to 21.0 after washing.

In the above examples and comparative examples, the adhesion amount of the environmentally responsive water-soluble substance, the degree of adhesion of water-based stains and oil-based stains due to dripping were determined from the amount of change in chromaticity a* and b* before and after dripping, and from the amount of change in chromaticity a* and b* before and after dripping. The degree of removal of stains was calculated from the amount of change in chromaticity a* and b* before and after washing using the following formulas (1) to (5).
Content of environmentally responsive water-soluble substance (% by weight) = (W1-W0)/W0 x 100 (1)
In the above formula (1), W1 is the weight of the fabric to which the environmentally responsive water-soluble substance is adhered, and W0 is the weight of the fabric before being immersed in the solution containing N-isopropylacrylamide.
Degree of adhesion of dirt (red direction) = A1 - A0 (2)
In the above equation (2), A0 is the value of a* before dirt dripping, and A1 is after dirt dripping.
Degree of adhesion of dirt (yellow direction) = B1 - B0 (3)
In the above equation (3), B0 is the value of b* before dirt is dropped, and B1 is the value of b* after dirt is dropped.
Degree of purification by washing (red direction) = (A1-A2)/(A1-A0) x 100 (4)
In Equation (4) above, A2 is the value of a* after washing.
Degree of purification by washing (yellow direction) = (B1-B2)/(B1-B0) x 100 (5)
In equation (5) above, B2 is the value of b* after washing. Changes in red wine staining were evaluated using the a* value, and changes in chili oil staining were evaluated using the b* value.
The above results are summarized in Tables 1 and 2.

As is clear from Tables 1 and 2, it was confirmed that the products of Examples 1 to 4 are less likely to become dirty, and even if they become dirty, they can be easily cleaned by washing. In addition, in Example 1 and Comparative Example 1, the ultrasonic cleaner was used for washing, but the same applies to household washing.

The antifouling fabric of the present invention can be used in a variety of clothing such as underwear, innerwear, outerwear, outerwear, lowerwear, socks, gloves, mufflers, scarves, and hats, sheets, duvet covers, pillowcases, tablecloths, and carpets. It is useful for various fields.

Claims (3)

A garment comprising an antifouling fabric obtained by graft-polymerizing an environmentally responsive water-soluble substance having a radical-bonding group on a fiber base material,
The environmentally responsive water-soluble substance contains a radical bonding group, a hydrophilic group and a hydrophobic group in one molecule,
0.1 to 50% by mass of the environmentally responsive water-soluble substance is graft-polymerized with respect to the fabric,
the hydrophilic group is at least one selected from an amide group, an ether group and an alcohol group;
The radical-bonding group is at least one selected from an acryloyl group, a methacryloyl group and a vinyl group,
The antifouling fabric becomes a hydrophobic shrinking gel state in dry gas, has antifouling properties and water repellency, and becomes a hydrophilic swollen gel state with affinity to water in liquid water,
The antifouling clothing is characterized in that the clothing maintains hydrophobicity when worn and has stain resistance and water repellency, and becomes hydrophilic when washed at home so that stains can be removed. The antifouling clothing according to claim 1, wherein the temperature at which the environmentally responsive water-soluble substance becomes insoluble in water (Lower Critical Solution Temperature: LCST) is 25°C to 80°C. A method for manufacturing the antifouling clothing according to claim 1 or 2 ,
The environmentally responsive water-soluble substance having a radical bonding group is brought into contact with the fiber base material of the fabric constituting the clothing, and an electron beam is irradiated before or simultaneously with the contact to remove the environmentally responsive water-soluble substance from the fiber base. A method for producing stain-resistant clothing, which comprises graft polymerizing onto a material, then washing and drying.