JP5114946B2 - Fiber structure - Google Patents

Description

  The present invention relates to a fiber structure having a durable antifouling property.

  Conventionally, the request | requirement which improves the antifouling property of a fiber structure is high, and various methods to improve are proposed. From the viewpoint of a processing agent, a fluororesin containing a hydrophilic group (Patent Documents 1 and 2) has been developed in order to impart performance that is less likely to cause aqueous stains or oily stains and is easily removed. Further, after the fiber surface is coated with a hydrophilic resin, a fiber structure (Patent Document 3) that forms a layer of a water- and oil-repellent resin having a hydrophilic group, a film made of a fluoropolymer and a hydrophilic, antistatic polymer A fiber product to be formed (Patent Document 4) has been proposed.

However, the water / oil repellent having a hydrophilic group is fixed to the fiber surface even if a crosslinking agent or a catalyst is used in combination, the washing durability is insufficient. What forms a layer of a water- and oil-repellent resin having a hydrophilic group on a hydrophilic resin coating has properties that conflict with hydrophilic and water-repellent properties, but the adhesion of the resin is weak and it is difficult to obtain sufficient durability It requires a two-step process of forming a water- and oil-repellent layer after the formation of the hydrophilic layer, and also involves economic problems. The method of forming a film comprising a fluorinated polymer and a hydrophilic, antistatic polymer is intended to impart high water repellency with the fluorinated polymer. Although there is no description about antifouling property, the performance that dirt does not spread easily is expected. Since the fluoropolymer does not have a hydrophilic component, oily dirt is particularly strongly bonded, and the attached dirt is difficult to be removed by washing or the like.
JP-A-3-70757 JP-A 61-266487 Japanese Patent No. 3748592 JP-A-55-148281

  In view of the background of such prior art, the present invention is intended to provide a fiber structure having an antifouling property against aqueous dirt and oily dirt excellent in durability.

In order to solve the above problems, the present invention employs the following means.
1. A monofilament surface has a resin film containing a triazine ring-containing polymerizable monomer as a polymerization component, and the film contains a fluorine-based water / oil repellent resin having a hydrophilic component. A fiber structure having a water repellency of 3 or less.
2. 3. The fiber structure according to 1 above, wherein the water / oil repellent resin is at least one compound represented by the following formula 1 or 2.

3. 3. The fiber structure according to 1 or 2 above, wherein the lipstick antifouling property when measured by the following measurement method is 4th or higher.
(Measuring method)
0.006 g of lipstick RS366 made by Shiseido Co., Ltd. is evenly applied to the surface of a 25φ rubber plug, pressed against the cloth, and the rubber plug is rotated 45 ° to contaminate the lipstick with the cloth. The contaminated cloth is allowed to stand for 24 hours, and then washed according to the method defined in JIS L0217-103, and the degree of contamination is determined (grade) on the contamination gray scale.
4). 4. The fiber structure according to any one of the above 1 to 3, wherein the foundation antifouling property is 4th or higher when measured by the following measurement method.
(Measuring method)
0.006 g of foundation ocher 30 manufactured by Shiseido Co., Ltd. is uniformly applied to the surface of a 25φ rubber plug, pressed against the cloth, and the rubber plug is rotated 45 ° to contaminate the foundation with the cloth. The contaminated cloth is allowed to stand for 24 hours, and then washed according to the method defined in JIS L0217-103, and the degree of contamination is determined (grade) on the contamination gray scale.
5. 5. The fiber structure according to any one of 1 to 4 above, wherein the antifouling property of sebum contamination when measured by the following measurement method is 4 or more.
(Measuring method)
Apply 0.006 g of the cortical fouling agent described in the Journal of Japanese Society of Home Economics Vol. 46 No 3 265-269 (1995) uniformly to the surface of a 25φ rubber plug, press it against the fabric, rotate the rubber plug by 45 °, and cortex Contaminate the fabric with a contaminant. The contaminated cloth is allowed to stand for 24 hours, and then washed according to the method defined in JIS L0217-103, and the degree of contamination is determined (grade) on the contamination gray scale.
6). The fiber structure according to any one of the above 1 to 5, wherein the antifouling property when measured by the following measurement method is 4th or higher.
(Measuring method)
Red jade soil / black soil / water is collected at a 1/1/1 weight ratio, placed in a mortar and pulverized and mixed to prepare a mud for contamination. 20 g of the stain is applied to a 10 cm × 10 cm fabric surface with a knife coater and left for 24 hours, and then washed according to the method defined in the JIS L0217-103 method. Grade).
7). Clothing which uses the fiber structure in any one of said 1-6.

  ADVANTAGE OF THE INVENTION According to this invention, the textile structure which has stain resistance with washing durability can be supplied stably.

The present invention, as a result of intensive studies on the above-mentioned problem, that is, imparting an antifouling function excellent in washing durability, is a fluorine-based polymer having a polymer composed of a triazine ring-containing monomer and a hydrophilic component on the surface of a single fiber The present inventors have investigated that this problem can be solved all at once by forming a film in which a water / oil repellent is mixed.
The triazine ring-containing compound of the present invention is a compound containing a triazine ring and having at least two polymerizable functional groups, and examples thereof include those represented by the following formula 3.

In the present invention, in addition to those represented by the above general formula, ethylene urea copolymer compounds, dimethylol urea copolymer compounds, dimethylol thiourea copolymer compounds, acid colloid compounds, and the like of the above compounds can also be used.

  As the fluorine-based water / oil repellent of the present invention, those having a water repellency of 3 or less are used. Specifically, a fluorine-based water / oil-repellent resin having a hydrophilic component is preferably used, and a fluorine-based water / oil-repellent resin having a hydrophilic group and / or a hydrophilic segment as part of the resin skeleton is preferably used. It is done. Examples of those having a hydrophilic group include those represented by the following formula 1, and examples of those having a hydrophilic segment include those represented by the following formula 2, but are not limited thereto.

  In the mixing of the monomer of the present invention and the fluorine-based water / oil repellent resin, the weight of the fluorine-based water / oil repellent solid content is 10 to 200, preferably 20 to 100, based on the solid content weight 100 of the monomer. is there. The mixture is preferably deposited in an amount of 0.1 to 10% by weight per fiber weight.

As the fluorine-based water / oil repellent that does not contain a hydrophilic component, a polymer that is generally used as a water repellent and is preferably a polymer having a (meth) acrylic acid ester polymerization unit having a fluoroalkyl group as an essential component. And may be a copolymer. The polymer having a polymerization unit of (meth) acrylic acid ester having a fluoroalkyl group as an essential component is a compound in which a fluoroalkyl group is present in the alcohol residue part of (meth) acrylic acid ester. Such a fluoroalkyl group refers to a group in which two or more hydrogen atoms of an alkyl group are substituted with fluorine atoms. 1-20 are preferable and, as for carbon number of a fluoroalkyl group, 6-16 are especially preferable. The fluoroalkyl group is preferably a linear or branched group. In the case of a branched group, it is preferable that the branched portion is present at the terminal portion of the fluoroalkyl group and is a short chain having about 1 to 4 carbon atoms. Further, the fluoroalkyl group is preferably a group in which all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms (that is, a perfluoroalkyl group) or a group having a perfluoroalkyl group at the terminal portion. In the case of a perfluoroalkyl group, the carbon number is preferably 1-20, and particularly preferably 4-16. When the number of carbon atoms is less than 4, the water repellency of the processing agent composition tends to decrease. When the number is more than 16, the copolymer becomes solid at room temperature, has high sublimation properties, and is difficult to handle. There is a fear. The polymer essentially including a polymer unit of (meth) acrylic acid ester having such a fluoroalkyl group may contain one or more of such polymer units. The mixing amount of the fluorine-based water- and oil-repellent resin not containing such a hydrophilic component is contained at a ratio of 0.1 to 50 with respect to the weight 100 of the fluorine-based water- and oil-repellent resin containing the hydrophilic component. It is preferably 0.5 to 20, and is mixed within a range that does not impair the intended antifouling performance.
Fine particles can be mixed in the film of the present invention. The fine particles may be either inorganic fine particles or organic fine particles. Examples of the inorganic fine particles include aluminum oxide, silicon oxide, titanium oxide, kaolin, bentonite, talc, calcium carbonate, calcium silicate, magnesium oxide, and the like. It is preferably used as a body. Of these, silicon oxide is preferably used. The number average particle diameter of the particles is preferably 5 to 500 nm, more preferably 10 to 100 nm. Examples of the organic fine particles include acrylic resins, urethane resins, melamine resins and copolymers thereof, and the number average particle diameter of the particles is preferably 5 to 2000 nm, more preferably 10 to 300 nm. And is preferably used as an aqueous dispersion. These inorganic fine particles and organic fine particles can be used alone or in admixture of two or more. By the addition of the particles, the formability of the antistatic resin film is improved, and it becomes a tough film and the durability can be enhanced. Furthermore, since fine irregularities are formed on the surface of the resin film by the particles, it is possible to further enhance the adhesion preventing property and drop-off property of solid contaminants. In the present invention, the mixing amount of the fine particles is 1 to 100, preferably 10 to 50 with respect to the mixture weight 100 of the monomer and the fluorine-based water and oil repellent resin.
The resin film of the present invention may contain a polyfunctional isocyanate compound. The polyfunctional isocyanate-based compound is not particularly limited as long as it is an organic compound containing two or more isocyanate functional groups in the molecule. Tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diisocyanate. Examples include phenyl methane diisocyanate, triphenyl triisocyanate, xylene resin isocyanate, dichloromethane diisocyanate, and the like. In addition, phenol and diethyl malonate, which are blocking compounds (compounds that regenerate isocyanate groups by heating to 70-200 ° C. together with isocyanate adducts), such as trimethylolpropane tolylene diisocyanate adducts and frucrine tolylene diisocyanate adducts Examples thereof include polyfunctional block isocyanate urethane resins obtained by reacting an ester, methyl ethyl ketoxime, sodium bisulfite, ε-caprolactam and the like. As the dissociation catalyst used for promoting the improvement of the thermal separation rate of the blocked isocyanate and the reduction of the thermal dissociation temperature, dibutyltin diolate, dibutyltin stearate, stearyl zinc and organic amine compounds are preferred. The mixing of such a mixture has an effect of enhancing the durability of the fluorine-based water / oil repellent and may be mixed with the treatment liquid at a concentration of 0.01 to 1%.

  In the present invention, after a catalyst is mixed with an aqueous liquid in which a polymerizable monomer and a fluorine-based water- and oil-repellent resin having a hydrophilic component are blended, heat treatment is performed to form a polymer film. Examples of such catalysts include acetic acid, formic acid, acrylic acid, malic acid, tartaric acid, maleic acid, phthalic acid, sulfuric acid, persulfuric acid, hydrochloric acid, phosphoric acid and the like, and ammonium salts, sodium salts, potassium salts, magnesium salts thereof and the like. Yes, one or more of these can be used. Of these, ammonium persulfate and potassium persulfate can be preferably used. Such a catalyst is preferably used in a proportion of 0.1 to 20% by weight based on the amount of the polymerizable monomer used.

  The heat treatment for the polymerization is preferably a dry heat treatment or a steam heat treatment at a temperature of 50 to 180 ° C. for 0.1 to 30 minutes. The steam heat treatment forms a uniform film on the fiber surface. Easy, high film strength and flexible texture. For steaming, saturated steam or superheated steam at 80 to 160 ° C. is preferably used. More preferable saturated water vapor is 90 to 130 ° C., and superheated water vapor is 110 to 160 ° C., both of which perform treatment for several seconds to several minutes. After such steaming and heat treatment, in order to remove unreacted monomers and catalysts, and to ensure fastness to dyeing, washing with hot water at a temperature of 50 to 95 ° C., nonionic surfactant, sodium carbonate, hydrosal It is preferable to perform cleaning using a fight or the like.

As the resin film of the present invention, a film having a thickness of 5 to 100 nm when observed using a transmission electron microscope (TEM) at a magnification of 100000 times is preferably used. If the thickness is less than 5 nm, a continuous uniform film may not be formed. If the thickness exceeds 100 nm, the texture may become coarse and hard. The fiber structure of the present invention has a lipstick antifouling property of 4 when measured by the following measurement method. It is preferable that it is a grade or more. The detachment effect of the fluorine-based water and oil repellent having a hydrophilic component promotes the falling off property in washing.
(Measuring method)
0.006 g of lipstick RS366 made by Shiseido Co., Ltd. is evenly applied to the surface of a 25φ rubber plug, pressed against the cloth, and the rubber plug is rotated 45 ° to contaminate the lipstick with the cloth. The contaminated cloth is allowed to stand for 24 hours, and then washed according to the method defined in JIS L0217-103, and the degree of contamination is determined (grade) on the contamination gray scale.
The fiber structure of the present invention preferably has a foundation antifouling property of 4th grade or higher when measured by the following measurement method. The detachment effect of the fluorine-based water and oil repellent having a hydrophilic component promotes the falling off property in washing.
(Measuring method)
0.006 g of foundation ocher 30 manufactured by Shiseido Co., Ltd. is uniformly applied to the surface of a 25φ rubber plug, pressed against the cloth, and the rubber plug is rotated 45 ° to contaminate the foundation with the cloth. The contaminated cloth is allowed to stand for 24 hours, and then washed according to the method defined in JIS L0217-103, and the degree of contamination is determined (grade) on the contamination gray scale.
The fiber structure of the present invention preferably has an antifouling property against sebum contamination as measured by the following measurement method of grade 4 or higher. The detachment effect of the fluorine-based water / oil repellent having a hydrophilic component promotes the detachability in washing.
(Measuring method)
Apply 0.006 g of the cortical fouling agent described in the Journal of Japanese Society of Home Economics Vol. 46 No 3 265-269 (1995) uniformly to the surface of a 25φ rubber plug, press it against the fabric, rotate the rubber plug by 45 °, and cortex Contaminate the fabric with a contaminant. The contaminated cloth is allowed to stand for 24 hours, and then washed according to the method specified in the JIS L0217-103 method, and the degree of contamination is determined (grade) on the contamination gray scale.
The fiber structure of the present invention preferably has a mud antifouling property of 4th grade or higher when measured by the following measurement method. The detachment effect of the fluorinated water and oil repellent promotes the ability to fall off in washing.
(Measuring method)
Red jade soil / black soil / water is collected at a 1/1/1 weight ratio, placed in a mortar and pulverized and mixed to prepare a mud for contamination. 20 g of the stain is applied to a 10 cm × 10 cm fabric surface with a knife coater and left for 24 hours, and then washed according to the method defined in the JIS L0217-103 method. Grade).

  The fiber material used in the fiber structure of the present invention is not particularly limited, but is an aromatic polyester fiber such as polyethylene terephthalate, polypropylene terephthalate and polybutylene terephthalate, and a third component such as isophthalic acid, isophthalic acid. Aromatic polyester fiber copolymerized or blended with acid sulfonate, adipic acid and polyethylene glycol, aliphatic polyester fiber represented by L-lactic acid as a main component, polyamide fiber such as nylon 6 and nylon 66 , Acrylic fibers based on polyacrylonitrile, polyolefin fibers such as polyethylene and polypropylene, synthetic fibers such as polyvinyl chloride fibers, semi-synthetic fibers such as acetate and rayon, cotton, hemp, silk and And natural fibers such as wool, and the like. In the present invention, these fibers can be used singly or as a mixture of two or more. However, fibers mainly composed of polyester fibers and polyamide fibers are preferably used.

  The fibers used in the present invention may be flat yarns such as false twisted yarns, strong twisted yarns, taslan yarns, thick yarns and mixed yarns in addition to normal flat yarns, and staple fibers, tows, or spinning yarns. Various forms of fibers such as yarn may be used.

  The fiber structure of the present invention includes a knitted fabric using the fibers, a fabric-like material such as a woven fabric or a non-woven fabric, or a string-like material.

  Since the fiber structure of the present invention has antistatic and antifouling properties, clothes and bedding, specifically, coats, blousons, windbreakers, blouses, dress shirts, skirts, slacks, gloves, hats, It is suitably used for applications such as apparel products, industrial materials, and the like, such as futon side areas, futon drying covers, curtains, and tents.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these. Moreover, the quality evaluation in an Example was implemented with the following method.

(Water repellency)
Evaluation was made by the spray method according to the method specified in JIS L 1092 “Test method for waterproofness of textile products” (1998), and the grade was determined.
(Anti-fouling property a: Lipstick anti-fouling property)
0.006 g of lipstick RS366 made by Shiseido Co., Ltd. is evenly applied to the surface of a 25φ rubber plug, pressed against the cloth, and the rubber plug is rotated 45 ° to contaminate the lipstick with the cloth. The contaminated fabric was allowed to stand for 24 hours, and then washed according to the method defined in JIS L0217-103, and the degree of contamination was determined (grade) on the contamination gray scale.
(Anti-fouling b: Foundation anti-fouling property)
0.006 g of foundation ocher 30 manufactured by Shiseido Co., Ltd. is uniformly applied to the surface of a 25φ rubber plug, pressed against the cloth, and the rubber plug is rotated 45 ° to contaminate the foundation with the cloth. The contaminated fabric was allowed to stand for 24 hours, and then washed according to the method defined in JIS L0217-103, and the degree of contamination was determined (grade) on the contamination gray scale.
(Anti-fouling property c: Sebum stain anti-fouling property)
The following pollutants described in Journal of Japan Society of Home Economics Vol.46 No3 265-269 (1995) were prepared, 0.006 g of the pollutant was uniformly applied to the surface of a 25φ rubber plug, and pressed against the fabric to plug the rubber plug. Is rotated 45 ° to contaminate the fabric with sebum stains. The contaminated fabric was allowed to stand for 24 hours, and then washed according to the method defined in JIS L0217-103, and the degree of contamination was determined (grade) on the contamination gray scale.
<Sebum dirt pollutant>
(1) Contaminant component and quantity (A) Organic component
(A) Oily soil component oleic acid 14.2 g
Trio Rain 7.8g
Cholesterol oleate 6.1g
Liquid paraffin 1.3g
Squalene 1.3g
Cholesterol 0.8g
(B) Protein
Gelatin 3.5g
(B) Inorganic component
Red yellow soil 15.0g
Carbon black 0.25g
(2) How to make a contaminated liquid Gelatin is put into 850 mL of water having a water quality hardness of 80 mg / L or less in a 1000 mL beaker and dissolved at a temperature not exceeding 45 ° C. Thereafter, carbon black is added and stirred with a homogenizer (stirrer) until the carbon black is sufficiently dispersed, and then allowed to stand for 12 to 72 hours. Then, after stirring for 3 minutes with a homogenizer, red yellow soil is added and stirred for about 30 minutes with a homogenizer. The oily soil component is then added and stirred for about 2 minutes.
(Anti-fouling d: Mud-fouling antifouling)
Red jade soil / ordinary soil / water is collected at a 1/1/1 weight ratio, placed in a mortar and pulverized and mixed to prepare the mud for contamination. 20 g of the stain is applied to a 10 cm × 10 cm fabric surface with a knife coater and left for 24 hours, and then washed according to the method defined in the JIS L0217-103 method. Grade).

(Washing durability)
A weak alkaline synthetic detergent specified in JIS K 337 is dissolved in an automatic inversion swirl electric washing machine to a concentration of 0.2%, a bath ratio of 1:50, and a temperature of 40 ± 2 ° C. under strong conditions. Was washed for 10 minutes, then drained and washed with overflow water for 10 minutes × 2 times, and this was repeated 20 times, followed by air drying. The washing cloth was measured for antifouling property by the method described above, and the washing durability performance was evaluated.

(Examples 1-9, Comparative Examples 1-4)
After weaving a plain fabric using 84 dtex, 72 filament false twisted yarn made of polyethylene terephthalate as warp yarn and weft yarn, the fabric is scoured at a temperature of 95 ° C. according to a conventional method using a continuous scourer. It was washed with water, then dried at 130 ° C. and pinter set at 180 ° C. Next, it is dyed fluorescent white at a temperature of 130 ° C. using a liquid dyeing machine, washed by a conventional method, washed with hot water, dried and pinter set at 170 ° C., and the vertical / horizontal density 140/88 / 2.54 cm. The woven fabric was made.

The white woven fabric was treated by the following method to form an antifouling resin film. The results of evaluating the performance of the obtained fabric are shown in Table 1. All of them had durable antistatic and antifouling properties and a soft texture.
<Anti-fouling resin>
The following polymerizable monomers were mixed in the proportions shown in Table 1, and ammonium persulfate was mixed as a polymerization catalyst at a concentration of 3 g / L to prepare a treatment solution. The fabric was immersed in the treatment liquid, adjusted so that the amount of the treatment liquid adhered was 100% by weight, squeezed with mangle, and treated in a saturated water vapor atmosphere at 105 ° C. for 5 minutes. Subsequently, it was washed for 1 minute in a 60 ° C. aqueous solution containing 1 g / L of a nonionic surfactant and 1 g / L of sodium carbonate, washed with water, dried at 130 ° C., and pinter set at a temperature of 170 ° C. The anti-fouling property of the finished product of the processed fabric and the laundry product that was washed 20 times were measured.
(Polymerizable monomer)
A: Becamine M3 (Dainippon Ink Chemical Co., Ltd., trimethylol melamine, solid content 00%). (Fluorine-based water and oil repellent)
B: Asahi Guard AG1100 (manufactured by Meisei Chemical Co., Ltd., hydrophilic fluorine-based water / oil repellent, solid content 20%)
C: Asahi Guard AG780 (manufactured by Meisei Chemical Co., Ltd., hydrophilic fluorine-based water / oil repellent, solid content 20%)
D: NK Guard SR-108 (manufactured by Nikka Chemical Co., Ltd., hydrophilic fluorine-based water / oil repellent, solid content 20%)
E: F470 (manufactured by Kyo Silk Chemical Co., Ltd., fluorine-based water and oil repellent, solid content 20%))

Claims (7)

A monofilament surface has a resin film containing a triazine ring-containing polymerizable monomer as a polymerization component, and the film contains a fluorine-based water / oil repellent resin having a hydrophilic component. A fiber structure having a water repellency of 3 or less. The fiber structure according to claim 1, wherein the water / oil repellent resin is at least one compound represented by the following formula 1 or 2.

The fiber structure according to claim 1 or 2, which has a lipstick antifouling property of 4th grade or higher when measured by the following measurement method.
(Measuring method)
0.006 g of lipstick RS366 made by Shiseido Co., Ltd. is evenly applied to the surface of a 25φ rubber plug, pressed against the cloth, and the rubber plug is rotated 45 ° to contaminate the lipstick with the cloth. The contaminated cloth is allowed to stand for 24 hours, and then washed according to the method defined in JIS L0217-103, and the degree of contamination is determined (grade) on the contamination gray scale. The fiber structure according to any one of claims 1 to 3, which has a foundation antifouling property of 4th grade or higher when measured by the following measurement method.
(Measuring method)
0.006 g of foundation ocher 30 manufactured by Shiseido Co., Ltd. is uniformly applied to the surface of a 25φ rubber plug, pressed against the cloth, and the rubber plug is rotated 45 ° to contaminate the foundation with the cloth. The contaminated cloth is allowed to stand for 24 hours, and then washed according to the method defined in JIS L0217-103, and the degree of contamination is determined (grade) on the contamination gray scale. The fiber structure according to any one of claims 1 to 4, wherein the antifouling property of sebum contamination when measured by the following measurement method is quaternary or higher.
(Measuring method)
Apply 0.006 g of the cortical fouling agent described in the Journal of Japanese Society of Home Economics Vol. 46 No 3 265-269 (1995) uniformly to the surface of a 25φ rubber plug, press it against the fabric, rotate the rubber plug by 45 °, and cortex Contaminate the fabric with a contaminant. The contaminated cloth is allowed to stand for 24 hours, and then washed according to the method defined in JIS L0217-103, and the degree of contamination is determined (grade) on the contamination gray scale. The fiber structure according to any one of claims 1 to 5, which has a mud antifouling property of 4th grade or higher when measured by the following measurement method.
(Measuring method)
Red jade soil / black soil / water is collected at a 1/1/1 weight ratio, placed in a mortar and pulverized and mixed to prepare a mud for contamination. 20 g of the stain is applied to a 10 cm × 10 cm fabric surface with a knife coater and left for 24 hours, and then washed according to the method defined in the JIS L0217-103 method. Grade). The clothing using the fiber structure in any one of Claims 1-6.