JP6420655B2 - Fabric and method for producing the fabric - Google Patents

Description

  TECHNICAL FIELD The present invention relates to a fabric excellent in durability against repeated washing, such as removability of oily dirt and the like and prevention of washing recontamination, and a method for producing the fabric.

  Conventionally, synthetic fiber fabrics that easily adhere to oily stains, such as hydrophobic polyester fiber fabrics, are less likely to have oily stains (Soil guard (SG))) and stain removal properties (the stains can be removed by washing). Various methods have been used to provide the performance (Soil Release (SR) property) that becomes easy.

  For example, a method of forming a coating layer made of a fluoroalkyl acrylate copolymer containing a hydrophilic group on the surface of a cloth made of a synthetic fiber is disclosed (for example, see Patent Document 1). In the fabric described in Patent Document 1, by forming a coating layer containing the copolymer on the surface of the fabric, the synthetic fiber is excellent in oil repellency and hardly gets oily dirt, and the dirt removal property is improved.

  Further, a fiber structure in which a fluororesin fiber treatment agent is bonded to the surface of the fiber structure via a coating layer of a hydrophilic resin processing agent is disclosed (for example, see Patent Document 2). According to the fiber structure, it is described that oil stains are difficult to be attached and performance that is easy to fall off can be imparted simultaneously.

Japanese Patent Laid-Open No. 9-296372 JP 62-141177 A

  However, although the fabric described in Patent Document 1 is excellent in oil repellency and difficult to get oily stains, and the stain removal property is improved, the stain removal property is still not sufficient. In addition, there is a problem that durability against repeated washing is inferior, oily dirt discharged into the liquid at the time of washing adheres to the fiber, blackening or yellowing occurs in the fabric, and washing recontamination is likely to occur.

  Further, the fiber structure described in Patent Document 2 is still not sufficient, although it can hardly give oil stains and can easily provide a performance that easily drops. Furthermore, the fiber structure is inferior in productivity because it requires two steps, a step of forming a coating layer of a hydrophilic resin processing agent and a step of applying a fluororesin fiber treatment agent. There is a problem. Further, although means for applying a low temperature plasma treatment is disclosed as means for forming a coating layer of a hydrophilic resin processing agent, there is also a problem that it is difficult to carry out in a dyeing processing place that does not have a low temperature plasma treatment apparatus. In addition, since the outermost layer of the fiber is covered with a fluorinated fiber treatment agent, the hydrophobic part occupies most of the hydrophilic part, and the removal of dirt is inferior, so it is less than ordinary oils such as lipsticks and foundations. In some cases, however, cosmetic stains with strong adhesiveness may be difficult to remove.

  The present invention solves the above-mentioned problems of the prior art, not only using a special apparatus such as a low-temperature plasma processing apparatus, but also has excellent removability such as oily dirt, and is excellent in prevention of washing recontamination, and oily. It is an object of the present invention to provide a fabric and a method for producing the fabric that are excellent in durability against repeated washing, such as removal of dirt and the like and prevention of washing recontamination.

The present inventor has intensively studied to improve the soil removability (SR property) during washing and durability against repeated washing without impairing the SG property. As a result, the fluoroalkyl containing a hydrophilic group is obtained. By providing a coating layer formed of an acrylate copolymer, a triazine-based compound and / or an isocyanate-based compound cross-linking agent, and a cellulose-based compound, the resulting synthetic fiber fabric can be used as an oily stain even in a one-step treatment. It has been found that not only is the removability excellent, but it is also excellent in preventing washing recontamination. In addition, surprisingly, it has been found that the obtained synthetic fiber fabric is remarkably excellent in the removability of the oily stains and the durability of preventing the washing re-contamination when repeated washing is performed. The inventor has further studied and completed the present invention. That is, the present invention is as follows.

（８）下記（Ｉ）〜（ＩＩＩ）を満足する、請求項１〜７のいずれか１項に記載の布帛。
（Ｉ）家庭洗濯３０回後における口紅除去性能が３．５級以上
（ＩＩ）家庭洗濯３０回後における再汚染防止性が３．５級以上
（ＩＩＩ）家庭洗濯１０回後におけるＪＩＳ Ｌ１９１９ Ｃ法（親油性汚染物質２）による汚れの落ちやすさが３．５級以上
（９）（１）〜（８）のいずれかに記載の布帛の製造方法であって、
布帛に、前記親水性基を含有するフルオロアルキルアクリレート共重合体と、前記架橋剤と、前記セルロース系化合物とを含む液を付着させる工程と、
前記付着させる工程より後に前記布帛を温度１５０〜２００℃で熱処理する熱処理工程とを含む、布帛の製造方法。
（１０）前記付着させる工程より前に、前記布帛を親水性樹脂で被覆する工程を含む、（９）に記載の布帛の製造方法。 (1) A film made of a synthetic fiber, which is formed of a fluoroalkyl acrylate copolymer having a hydrophilic group, a crosslinking agent that is a triazine compound and / or an isocyanate compound, and a cellulose compound. A fabric comprising a layer.
(2) The fabric according to (1), wherein the cellulose compound is one or more compounds selected from the group consisting of hydroxyethylcellulose, carboxymethylcellulose, methylcellulose, hydroxypropylmethylcellulose, and carboxymethylhydroxyethylcellulose.
(3) The fabric according to (1) or (2), wherein at least a part of the synthetic fiber is coated with a hydrophilic resin.
(4) The fabric according to any one of (1) to (3), wherein the mixed ratio of the polyester fiber is 100%, and the crosslinking agent is a triazine compound.
(5) The fabric according to any one of (1) to (3), wherein the fabric includes polyester fibers and cellulosic fibers, and the crosslinking agent is an isocyanate compound.
(6) The fabric according to (5), wherein the mixed ratio of the cellulose fiber fibers is 10 to 70% by mass.
(7) The application rate X _A (mass%) of the fluoroalkyl acrylate copolymer containing the hydrophilic group, the application ratio X _B (mass%) of the cross-linking agent, and the cellulose-based polymer based on the mass of the entire fabric. The fabric according to any one of (1) to (6), wherein the compound application rate X _C (% by mass) satisfies the following formulas (i) to (iii):

(8) The fabric according to any one of claims 1 to 7, which satisfies the following (I) to (III).
(I) The lipstick removal performance after 30 home washings is 3.5 or more (II) The anti-recontamination property after 30 home washings is 3.5 or more (III) JIS L1919 C method after 10 home washings The method for producing a fabric according to any one of (9) (1) to (8), wherein the dirt is easily removed by (lipophilic pollutant 2).
Attaching a liquid containing a fluoroalkyl acrylate copolymer containing the hydrophilic group, the crosslinking agent, and the cellulose compound to a fabric;
And a heat treatment step of heat treating the fabric at a temperature of 150 to 200 ° C. after the step of attaching.
(10) The method for producing a fabric according to (9), including a step of coating the fabric with a hydrophilic resin before the attaching step.

  According to the fabric of the present invention, durability against repeated washing, such as removal of oily dirt including lipstick stains and prevention of washing recontamination, even in a one-stage treatment without using a special apparatus such as a low-temperature plasma treatment apparatus. Excellent in properties. Therefore, the fabric can be suitably used for clothing that requires repeated washing, such as an office blouse for women and an apron.

  Hereinafter, the present invention will be described in detail.

  The fabric of the present invention is made of a synthetic fiber, and is formed of a fluoroalkyl acrylate copolymer containing a hydrophilic group on the fabric surface, a crosslinking agent that is a triazine compound and / or an isocyanate compound, and a cellulose compound. A coating layer is provided.

  Examples of the synthetic fibers forming the fabric of the present invention include semi-synthetic fibers such as acetate, polyamide fibers such as nylon 6 and nylon 66, acrylic fibers, polyurethane fibers, polyethylene terephthalate, polybutylene terephthalate, and polypropylene terephthalate. And polyester fibers such as fibers obtained from polylactic acid. Of these, polyester fibers are preferable.

  The fabric of the present invention may be a mixture of fibers other than the above synthetic fibers, for example, cellulosic fibers, animal hair fibers, silk, and the like. As other fibers to be mixed, cellulosic fibers are preferable from the viewpoint of the application to be used. Examples of the cellulose fibers include natural cellulose fibers such as cotton and hemp, regenerated cellulose fibers such as cupra ammonium rayon and viscose rayon, acetate fibers, and purified cellulose fibers represented by lyocell.

  In the fabric of the present invention, the mixing ratio of the synthetic fiber and the other fiber is not particularly limited, but the mixing ratio of the polyester fiber when the synthetic fiber is mixed as the polyester fiber and the other fiber is mixed as the cellulosic fiber is used. From the viewpoint of functionality in use (shrinking due to washing, generation of wrinkles, etc.), for example, 30 to 90% by mass is exemplified, and 50 to 80% by mass is preferably exemplified.

  The method of mixing the synthetic fiber with other fibers is not particularly limited, and examples thereof include knot twisting, blend spinning, blending, knit or knitting. Also, the form of the fabric is not particularly limited, and examples thereof include woven fabric, knitted fabric, and non-woven fabric. In the case of clothing for office blouse or apron, the form of the fabric is preferably woven or knitted.

  The form of the synthetic fiber and other fibers may be either long fibers or short fibers. Moreover, those cross-sectional shapes are not specifically limited, either cross-sectional shape may be sufficient. Furthermore, the synthetic fibers and other fibers may contain titanium dioxide, silicon dioxide, pigments, other inorganic fine particles, and the like as necessary within the range not impairing the effects of the present invention.

  The coating layer of the fabric of the present invention contains a fluoroalkyl acrylate copolymer containing a hydrophilic group as one component.

  Although it does not specifically limit with the said hydrophilic group, Ethylene oxide, a hydroxyl group, a carboxyl group, a sulfonic acid group etc. are mentioned preferably. In particular, ethylenically unsaturated substances such as acrylates, methacrylates, vinyl acetate, vinyl chloride, etc. are modified, and hydrophilic groups such as ethylene oxide, hydroxyl groups, carboxyl groups, sulfonic acid groups, etc. are added to these modified substances. The introduced hydrophilic segment is preferably copolymerized with a fluoroalkyl acrylate. Among the hydrophilic segments, a hydrophilic segment obtained by reacting hydrogen sulfide with polyethylene glycol dimethacrylate is more preferable from the viewpoint of more excellent oil repellency, oily soil removability and washing recontamination prevention property.

  Further, the fluoroalkyl acrylate is not particularly limited, but a fluoroalkyl acrylate containing a perfluoroalkyl group is preferable from the viewpoint of more excellent oil repellency, oily soil removability, and washing recontamination prevention property. Furthermore, as fluoroalkyl acrylates, perfluorooctanoic acid, perfluorooctane sulfonic acid, perfluoroalkanoic acid having 8 or more carbon atoms, and perfluoroalkene having 8 or more carbon atoms are considered in consideration of safety to the living body and environmental load. Perfluorohexanoic acid systems that do not contain acids and precursors that change to these upon decomposition are preferred.

  As a fluoroalkyl acrylate copolymer containing a hydrophilic group, a hydrophilic segment obtained by reacting hydrogen sulfide with polyethylene glycol dimethacrylate and a fluoroalkyl acrylate as a fluorinated hydrophobic segment are copolymerized. The copolymer obtained is more preferable, and the one represented by the following general formula (1) is more preferable.

  In the general formula (1), n is preferably an integer of 2 to 10, a is preferably an integer of 1 to 10, and b is preferably an integer of 1 to 10. R represents a lower alkyl group, and an alkyl group having 1 to 3 carbon atoms is particularly preferable. Rf represents a perfluoroalkyl group, and among them, a perfluoroalkyl group having 6 or less carbon atoms is preferable.

  In the present invention, as the fluoroalkyl acrylate copolymer containing a hydrophilic group, a commercially available product can be suitably used. Specifically, a product name “Asahi Guard AG-E100” manufactured by Meisei Chemical Co., Ltd., or Ohara Product name “Paragard SRF6000” manufactured by Palladium Co., Ltd. may be mentioned.

  The coating layer of the fabric of the present invention contains a crosslinking agent which is a triazine compound and / or an isocyanate compound as one component.

  The triazine compound is a compound containing a triazine ring, and a compound represented by the following general formula (2) is preferable.

  Among the compounds represented by the general formula (2), trimethylol melamine, hexamethylol melamine, and the like are more preferable.

  The isocyanate compound is a compound containing an isocyanate group in the molecule, and a polyfunctional isocyanate compound containing two or more isocyanate groups in the molecule is preferable. The polyfunctional isocyanate compound is not particularly limited as long as it is an organic compound having two or more isocyanate functional groups in the molecule. Tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane Examples include diisocyanate, triphenyl triisocyanate, xylene resin isocyanate, and dichloromethane diisocyanate. In addition, phenol and malonic acid diethyl ester, which are blocking compounds (compounds that regenerate isocyanate groups by heating to 70 to 200 ° C. together with isocyanate adducts), such as trimethylolpropane tolylene diisocyanate adducts and frucrine tolylene diisocyanate adducts. , Methyl ethyl ketoxime, sodium bisulfite, [epsilon] -caprolactam, and the like can be mentioned. Among these, from the viewpoint of washing durability, among these, a triisocyanate compound, for example, a modified product of hexamethylene diisocyanate such as a modified tris burette of hexamethylene diisocyanate is more preferable.

  When the fibers of the fabric of the present invention are made of only polyester fibers (that is, when the mixing ratio of polyester fibers is 100%), the oil-based soil removability and the oil-based soil removability are durable against repeated washing. From the viewpoint of further improving the property, the cross-linking agent for forming the coating layer is preferably a triazine compound. In addition, when polyester fibers and cellulose fibers are mixed as the fibers constituting the fabric of the present invention, the oil repellent property, oily soil removal property, and washing re-contamination prevention property are more excellent due to repeated washing durability and soft texture. In view of the above, the crosslinking agent for forming the coating layer is preferably an isocyanate compound.

  The coating layer of the fabric of the present invention contains a cellulose compound as one component.

  The cellulose compound is not particularly limited as long as it is a compound having a cellulose skeleton, but a cellulose compound in which a hydrophilic group is copolymerized in a side chain is preferable. Examples of the cellulose compound having a hydrophilic group copolymerized in the side chain include one or more compounds selected from the group consisting of hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, hydroxypropyl methyl cellulose, and carboxymethyl hydroxyethyl cellulose. Among these, hydroxyethyl cellulose is more preferable from the viewpoint of ionicity and hydrophilicity imparting ability.

  Unlike the conventional fabrics, the fabric of the present invention uses, as raw materials, a fluoroalkyl acrylate copolymer containing a hydrophilic group, a crosslinking agent that is a triazine compound and / or an isocyanate compound, and a cellulose compound. Since it is a fabric having a coating layer formed by a one-step treatment, it is more excellent in durability against repeated washing with oily soil removal property and washing recontamination prevention property. Unlike the conventional fabrics, the mechanism of the present invention is not clear of the mechanism of action that is excellent in soil removability (SR property) during washing, durability against repeated washing, etc. without impairing water repellency (SG property). However, it can be estimated as follows, for example.

The fluoroalkyl acrylate copolymer containing a hydrophilic group has a hydrophilic segment and a hydrophobic segment. In general, in the air, the hydrophobic segment in the polymer segregates on the surface in the air to express oil repellency and the like, while in water, the hydrophilic segment and the hydrophobic segment are inverted and the hydrophilic segment is reversed. Shows a so-called flip-flop (reversal) phenomenon that segregates on the surface and exhibits oily soil removal performance. However, for example, in the film composed of a fluoroalkyl acrylate copolymer containing a hydrophilic group and a cross-linking agent disclosed in Patent Document 1, the inversion of the hydrophilic segment and the hydrophobic segment is restricted, and the SR property This is thought to have led to a decline. On the other hand, in the present invention, by adding a cellulose compound as a component to the coating layer and using a specific cross-linking agent, a large amount of the cellulose compound is incorporated into the cross-linked structure and inhibition of inversion of the cross-linked structure is suppressed. it is conceivable that. Furthermore, by including a cellulose compound in the coating layer, the hydrophilicity is improved, so that the soil removal property (SR property) during washing is improved, and in addition, durability against repeated washing can be given. Guessed.

In the fabric of the present invention, the application rate X _A (mass%) of the fluoroalkyl acrylate copolymer containing the hydrophilic group, the application rate X _B (mass%) of the crosslinking agent, and the mass of the entire fabric, and The application rate X _C (mass%) of the cellulose compound is represented by the following formulas from the viewpoint of achieving both oil repellency excellent in durability against repeated washing, soil removability, and washing re-contamination prevention property and soft texture. It is preferable that (i) to (iii) are satisfied. Furthermore, the application rate X _C (mass%) of the cellulose compound is more preferably 0.1 to 1.5 (mass%), still more preferably 0.3 to 1.2 (mass%), 0.5 -1.0 (mass%) is particularly preferable.

The application rate X _T (% by mass) of the coating layer formed on the fabric surface is a viewpoint that achieves both a soft texture and oil repellency excellent in durability against repeated washing, soil removability, and washing recontamination prevention property. Therefore, 0.5 to 6.0 mass% is preferable and 1.0 to 3.0 mass% is more preferable with respect to the mass of the entire fabric. In this case, _{X A} (wt%), _{X B} (wt%), _{X C} ratio (mass%) as the _{(X A:: X B X} C), X A ( wt%) is to 10, X More preferably, _B (mass%) is 1 to 3 and X _C (mass%) is 1 to 3.

However, the application rate _XT (mass%) of the coating layer formed on the fabric surface is in accordance with the following formula (iv), and X _A (mass%), X _B (mass%), and X _C (mass%). Is calculated according to the following formulas (v) to (vii).

  The fabric of the present invention comprises a coating layer formed of a fluoroalkyl acrylate copolymer containing a hydrophilic group, a triazine compound and / or a crosslinking agent which is an isocyanate compound, and a cellulose compound, as well as synthesis. At least a part of the fibers may be covered with a hydrophilic resin. As a result, durability against repeated washing of washing recontamination prevention and washing recontamination prevention tends to be further improved.

  In the present invention, the hydrophilic resin means a resin having excellent hydrophilicity other than the cellulose compound, and among them, a polyester polyether block copolymer is preferable. As the polyester polyether block copolymer, a commercially available product can be used. For example, trade names “SR1000” manufactured by Ohara Palladium Chemical Co., Ltd. and trade names “SR1000” manufactured by Takamatsu Yushi Co., Ltd. Can be used. As the application rate of the hydrophilic resin, from the viewpoint of further improving durability against repeated washing of washing recontamination prevention and washing recontamination prevention, 0.01 to 5 relative to the mass of the entire fabric obtained. % By mass is preferable, and 0.05 to 3% by mass is more preferable.

Since the fabric of the present invention is provided with a specific coating layer on the fabric surface, it is excellent in durability against repeated washing, such as the ability to remove oily stains including stains due to lipstick and the prevention of washing recontamination. As the oily soil removal property, particularly the soil removal property by lipstick and the durability against repeated washing of the removal property, the fabric of the present invention preferably specifically satisfies the following (I). As durability with respect to repeated washing of washing recontamination prevention and washing recontamination prevention provided in the fabric of the present invention, it is preferable that the following (II) is specifically satisfied. It is preferable that the fabric of the present invention specifically satisfies the following (III) as the removability of oily soil and the durability of the removability to repeated washing. Furthermore, the fabric of the present invention more preferably satisfies the following (I) to (III).
(I) Lipstick removability after 30 home washings is 3.5 or higher (II) Recontamination prevention after 30 home washings is 3.5 or higher (III) JIS L1919 C method after 10 home washings Easily to remove dirt due to (Lipophilic Pollutant 2)

  In the above (I), the lipstick removability at the initial stage is more preferably 4.5 grade or higher, and the lipstick removability after 30 home washings is more preferably 4.0 grade or higher. In the above (II), the recontamination preventing property at the initial stage is more preferably 4.5 grade or higher, and the recontamination preventing property after 30 washings at home is more preferably 4.0 grade or higher. Further, in the above (III), the ease of removal of dirt by the JIS L1919 C method (lipophilic pollutant 2) in the initial stage is preferably 4.5 or higher, and the JIS L1919 C method (lipophilic contamination) after 10 home washings. The ease of removal of dirt by the substance 2) is more preferably 4.0 grade or higher.

  In the present invention, the lipstick removability at the initial stage is evaluated as follows. First, the fabric of the present invention is cut into 10 cm × 10 cm. Next, draw a circle with a diameter of 1.5 cm on the surface of a PP film (product number F-780-A4 manufactured by KOKUYO Co., Ltd.) on which a circle with a diameter of 1.5 cm is drawn, and fill the circle uniformly. Apply 0.03 g of lipstick (trade name Media Creamy Lasting Grip A DR-03, manufactured by Kanebo Cosmetics Co., Ltd.). Then, the cut fabric of the present invention is pressed against the surface of the film coated with lipstick with a cylindrical natural rubber block having a diameter of 25 mm and a height of 35 mm for 10 seconds at a pressure of 10 kg. Thereafter, washing is performed once in accordance with method 103 of JIS L 0217, and the degree of soiling after hanging and drying is determined using a gray scale for contamination according to JIS L 0805 to obtain initial lipstick removability.

  In the present invention, the lipstick removability after 30 home washings is evaluated as follows. First, the fabric of the present invention is cut into 10 cm × 10 cm, and washing is repeated 30 times in accordance with JIS L 0217 method 103. Then, the cloth of the present invention subjected to the above-described repeated washing on the film surface coated with lipstick in the same manner as the evaluation of lipstick removability in the initial stage was formed into a cylindrical shape (rubber block shape, weight, etc.) having a diameter of 25 mm and a height of 35 mm (Instead, the product name is OK) Press with a pressure of 10kg from the top for 10 seconds. Thereafter, washing is performed 30 times in accordance with method 103 of JIS L 0217, the degree of soiling after hanging and drying is determined with a gray scale for contamination according to JIS L 0805, and lipstick removal after 30 home washings Sexually.

  In the present invention, the anti-recontamination property at the initial stage is evaluated as follows. First, the fabric of the present invention is cut into 10 cm × 10 cm. Next, B heavy oil (the second kind of heavy oil described in JIS K 2205) and a surfactant (trade name Actinol R100 manufactured by Matsumoto Yushi Co., Ltd.) are used. The concentration of B heavy oil is 0.3 g / L. In addition to hot water at a temperature of 80 ° C. so that the surfactant concentration is 0.3 g / L, the mixture is stirred and mixed with a glass rod as an emulsifying means to prepare a test solution. The amount of the test solution obtained was adjusted so that the bath ratio (fabric: test solution) to the cut fabric of the present invention was 1: 100, and the cut fabric of the present invention was added to the adjusted test solution, Stir at 80 ° C. for 10 minutes. Next, it is washed with running water using 60 ° C hot water, washed with running water at room temperature, dehydrated, suspended and dried, and then used to determine the residual contamination level using a gray scale for contamination according to JIS L0805. Early recontamination prevention.

  In the present invention, the recontamination prevention property after 30 home washings is evaluated as follows. First, the fabric of the present invention is cut into 10 cm × 10 cm, and washing is repeated 30 times in accordance with JIS L 0217 method 103. Then, the fabric of the present invention that has been repeatedly washed is added to the test solution prepared in the same manner as the above-described anti-recontamination property, and stirred at 80 ° C. for 10 minutes. Next, it is washed with running water using 60 ° C hot water, washed with running water at room temperature, dehydrated, suspended and dried, and then used to determine the residual contamination level using a gray scale for contamination according to JIS L0805. The anti-recontamination property after 30 home washings.

  In the present invention, the easy removal of dirt by the JIS L 1919 C method (lipophilic pollutant 2) in the initial stage is based on the JIS L 1919 C method, and the lipophilic pollutant 2 specified by the JIS L 1919 C method is used. Use to evaluate. In addition, the ease of removal of dirt by the JIS L 1919 C method (lipophilic pollutant 2) after 10 home washings is based on the JIS L 1919 C method, and washing is performed 10 times in accordance with JIS L 0217 103 method. Using the repeated fabric, evaluation is performed using the lipophilic pollutant 2 defined by the JIS L 1919 C method.

  Means for allowing the fabric of the present invention to satisfy the above (I) to (III) is, for example, formed of a fluoroalkyl acrylate copolymer containing a hydrophilic group, a crosslinking agent, and a cellulose compound. In addition to the coating layer, the coating rate is adjusted, the ratio of the fluoroalkyl acrylate copolymer containing a hydrophilic group, the crosslinking agent and the cellulose compound is adjusted. Preferably it is formed.

  The durability of the fabric of the present invention with respect to oil repellency and oil repellency repeated washing is preferably such that the oil repellency after 30 home washings is 3.5 or higher, preferably 4 or higher. More preferred.

  The initial method for evaluating oil repellency is to cut the obtained fabric into 10 cm × 10 cm and perform the test in accordance with AATCC-TM118-1998. A few drops are dropped at about 4 mm in diameter, and the highest grade of the test solution that does not penetrate both drops after 30 seconds is defined as the initial oil repellency.

  Further, the oil repellency after 30 home washings is evaluated as follows. That is, the obtained fabric is cut into 10 cm × 10 cm, and washing is repeated 30 times in accordance with JIS L 0217 method 103. Then, according to AATCC-TM118-1998, several drops of the test solution shown in Table 1 were dripped so that the diameter was about 4 mm at two locations on the sample cloth, and the fabric after repeated washing was 30 seconds later. The highest grade of the test solution that does not penetrate into two drops is defined as oil repellency after 30 home washings.

  Next, an example is given and demonstrated about the manufacturing method of the fabric of this invention.

  The fabric in the present invention uses synthetic fibers or synthetic fibers and other fibers and is made into a fabric such as a woven fabric or a knitted fabric by a known method. The obtained fabric can be subjected to treatment such as scouring, presetting, and dyeing.

(Adhesion process)
In the production method of the present invention, a step of adhering a liquid containing a fluoroalkyl acrylate copolymer containing a hydrophilic group, the crosslinking agent, and the cellulose compound to the fabric obtained as described above. It is preferable to contain. Examples of the step include a padding treatment step in which padding treatment is performed using the above-described liquid, a step of applying the above-described liquid, and the like, and a padding treatment step is preferable from the viewpoint of simplicity. In the padding treatment step, mangle or the like can be used in the drawing treatment, and the drawing rate is from the viewpoint of making it easier to adjust the coating layer application rate to be 0.5 to 6.0% by mass. For example, it is preferably 50 to 90%. As the conditions for the heat treatment step after impregnation and drawing in the padding treatment, from the viewpoint of making the coating layer stronger and making it easier to improve the adhesion to the fibers, a tenter is used, and the drying temperature is 130 to 200. ° C and 150 to 200 ° C are preferable, and 170 to 190 ° C is more preferable. The drying time is preferably 30 seconds to 2 minutes.

In the padding treatment step, the ratio B (parts by mass) of the crosslinking agent and the ratio C (parts by mass) of the cellulose compound with respect to 100 parts by mass of the fluoroalkyl acrylate copolymer containing a hydrophilic group satisfy the following formulas, respectively. It is preferable to do.
5 ≦ B (parts by mass) ≦ 100
5 ≦ C (parts by mass) ≦ 100
Moreover, it is more preferable to satisfy the following formula.
10 ≦ B (parts by mass) ≦ 50
10 ≦ C (parts by mass) ≦ 40

  The production method of the present invention preferably includes a step of washing the fabric with hot water and drying after the heat treatment step. Thereby, the unreacted cellulose compound is more easily removed, and the resulting fabric is likely to have a softer texture. As conditions for hot water washing, for example, washing in a bath at a temperature of 60 to 100 ° C. for about 10 minutes can be mentioned. Moreover, from a viewpoint of productivity, you may wash | clean continuously using an open soaper.

  The drying condition is not particularly limited as long as the fabric dries. For example, a tenter is used and the temperature is 130 to 190 ° C. and the time is 30 to 120 seconds.

  The method for producing a fabric of the present invention may include a step of coating the fabric with a hydrophilic resin before the padding step. As a result, the fabric of the present invention is likely to be even more excellent in durability against repeated washing of washing recontamination prevention and washing recontamination prevention.

  As the step of coating with a hydrophilic resin, for example, a method of putting a fabric in a bath containing a hydrophilic resin, treating it at a temperature of 100 to 135 ° C. for 15 to 60 minutes, and exhausting the hydrophilic resin to the fiber (bath Medium exhaustion method), or after dyeing the fabric, immersing it in a bath containing a hydrophilic resin and taking it out, then squeezing with mangle and drying at a temperature of 160-190 ° C. for 0.5-3 minutes These methods can be performed alone or in combination. The bath exhaustion treatment method is preferable from the viewpoint of further improving the durability against repeated washing of washing recontamination prevention and washing recontamination prevention and dyeing fastness. From the viewpoint of simplification of the process, it is preferable that in the bath exhaustion treatment method, a dye is also contained in the bath and the dye and the hydrophilic resin are exhausted simultaneously.

  In the bath exhaustion treatment method, when the dye is also contained in the bath and the dye and the hydrophilic resin are exhausted simultaneously, the temperature condition of the bath containing the hydrophilic resin and the dye is 100 to 120 ° C. It is more preferable. As a result, the hydrolysis of the hydrophilic resin can be more easily suppressed, the occurrence of uneven dyeing due to the aggregation of the dye can be further suppressed, and the durability against repeated washing for preventing washing recontamination can be improved. It becomes easier to become even better.

  In the production method of the present invention, a step of attaching the liquid containing the fluoroalkyl acrylate copolymer containing the hydrophilic group, the crosslinking agent, and the cellulose compound to the fabric, and the step of attaching the fabric. And a heat treatment step of heat treating the fabric at a temperature of 130 to 200 ° C. later, the coating layer formed by the fiber treatment agent of the present invention on the fabric surface can be made stronger and the adhesion to the fibers can be improved. The resulting fabric can be further improved in oil repellency, oily soil removability, and laundry recontamination prevention properties, which are excellent in durability against repeated washing.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. In addition, the evaluation method in an Example and a comparative example is as follows.

1. Oil repellency at the initial stage and after 30 home washings was evaluated according to the method described above. A grade 3 or higher was considered acceptable.

2. Lipstick removability at the initial stage and after 30 home washings was evaluated according to the method described above. A grade 3 or higher was considered acceptable.

3. Prevention of recontamination at the initial stage and after 30 home washings Evaluation was made according to the method described above. A grade 3 or higher was considered acceptable.

4). Ease of soil removal by JIS L1919 C method (lipophilic pollutant 2) at the initial stage and after 10 home washings was evaluated according to the method described above. A grade 3 or higher was considered acceptable.

5. The texture of the fabric The sensory evaluation by the monitor of five persons was performed about the texture (flexibility) of the obtained fabric. Each sample had a good texture (soft) with a maximum score of 5 and was evaluated in 5 stages of 1 to 5 points, and the average value of 5 people was calculated and evaluated. In Examples (Examples 1 to 4 and Comparative Examples 1 to 3 and 6) in which the mixing ratio of polyester fibers is 100%, the fabric of Example 3 was used as a reference fabric, and polyester fibers and cotton were mixed. In Examples 5 to 8 and Comparative Examples 4, 5, and 7), the fabric of Example 7 was used as a reference fabric.
5 points: A softer texture than the reference fabric.
4 points: A slightly softer texture than the reference fabric.
3 points: A texture comparable to that of the reference fabric.
2 points: A slightly harder texture than the reference fabric.
1 point: Compared to the reference fabric, the texture was harder.

6). Evaluation of free formaldehyde JIS L-1096 was evaluated by the acetylacetone method.

Example 1
A twill fabric (warp density of 128 yarns / 2.54 cm, using a false twisted single yarn (167 dtex / 48f) made of polyethylene terephthalate as a warp and a false twisted double yarn ((334 dtex / 96f) made of polyethylene terephthalate as a weft. A weft density of 58 yarns / 2.54 cm) was obtained, and scouring was relaxed and preset by a conventional method.

The twill fabric subjected to the scouring relaxation and presetting was put into a bath having the following prescription 1, and then squeezed with mangle (squeezing rate: 80% by mass) and pre-dried at 130 ° C. for 60 seconds. The pre-dried twill fabric was heat treated at 170 ° C. for 60 seconds, washed with hot water at 60 ° C. for 10 minutes, and dried at 130 ° C. for 2 minutes to obtain the fabric of the present invention.
<Prescription 1>
Fluoroalkyl acrylate copolymer containing hydrophilic group (Ohara Palladium Co., Ltd., trade name “Paragard SRF6000”, solid content 20%): 75 g / L
Hydroxyethyl cellulose (trade name “SP400” manufactured by Daicel Finechem Co., Ltd.): 10 g / L
Triazine compound (trimethylolmelamine solid content 80%): 3 g / L
Organic amine catalyst: 3 g / L

(Example 2)
A twill fabric (warp density of 128 yarns / 2.54 cm, using a false twisted single yarn (167 dtex / 48f) made of polyethylene terephthalate as a warp and a false twisted double yarn ((334 dtex / 96f) made of polyethylene terephthalate as a weft. A weft density of 58 yarns / 2.54 cm) was obtained, and scouring was relaxed and preset by a conventional method.

The twill fabric subjected to the scouring relaxation and presetting was put into a bath having the following prescription 2 (bath ratio 1:20), and exhausted in the bath at 120 ° C. for 30 minutes.
<Prescription 2>
Hydrophilic resin (made by Ohara Palladium Chemical Co., Ltd., trade name “Parasolv PET2”, solid content 12%): 4% owf

  Thereafter, it was dehydrated and dried, impregnated in a bath comprising the above-mentioned formulation 1, and then pre-dried under the conditions of squeezing with a mangle (squeezing rate: 80% by mass) and 130 ° C. for 60 seconds. The twill fabric was heat-treated at 170 ° C. for 60 seconds, washed with hot water at 60 ° C. for 10 minutes, and dried at 130 ° C. for 2 minutes to obtain the fabric of the present invention.

(Example 3)
Except having changed the said prescription 1 into the following prescription 3, it carried out similarly to Example 1 and obtained the fabric of this invention.
<Prescription 3>
Fluoroalkyl acrylate copolymer containing a hydrophilic group (Ohara Palladium Chemical Co., Ltd., trade name “Paragard SRF6000”): 75 g / L
Hydroxyethyl cellulose (trade name “SP400” manufactured by Daicel Finechem Co., Ltd.): 10 g / L
Isocyanate-based crosslinking agent (manufactured by Nikka Chemical Co., Ltd., trade name “NK Assist V” solid content 40%): 10 g / L

Example 4
Except having changed the said prescription 1 into the said prescription 3, it carried out similarly to Example 2 and obtained the fabric of this invention.

(Example 5)
Both warp and weft are twilled using a 34th blend yarn of 65% polyester and 35% cotton (warp density 132 / 2.54 cm, weft density 63 / 2.54 cm) and scoured in the usual manner. Bleaching, mercerizing and pre-setting were performed.

  The twill fabric subjected to the scouring, bleaching, mercerization, and presetting was put into the bath having the above formulation 1, and then squeezed with mangle (squeezing rate: 80% by mass) and pre-dried at 130 ° C. for 60 seconds. . The pre-dried twill fabric was heat treated at 170 ° C. for 60 seconds, washed with hot water at 60 ° C. for 10 minutes, and dried at 130 ° C. for 2 minutes to obtain the fabric of the present invention.

(Example 6)
Both warp and weft are twilled using a 34th blend yarn of 65% polyester and 35% cotton (warp density 132 / 2.54 cm, weft density 63 / 2.54 cm) and scoured in the usual manner. Bleaching, mercerizing and pre-setting were performed.

  The twill fabric subjected to the scouring, bleaching, mercerization and presetting was put into the bath having the above formulation 2 (bath ratio 1:20), and exhausted in the bath at 120 ° C. for 30 minutes.

  Thereafter, it was dehydrated and dried, impregnated in a bath comprising the above-mentioned formulation 1, and then pre-dried under the conditions of squeezing with a mangle (squeezing rate: 80% by mass) and 130 ° C. for 60 seconds. The twill fabric was heat-treated at 170 ° C. for 60 seconds, washed with hot water at 60 ° C. for 10 minutes, and dried at 130 ° C. for 2 minutes to obtain the fabric of the present invention.

(Example 7)
Except having changed the said prescription 1 into the said prescription 3, it carried out similarly to Example 5 and obtained the fabric of this invention.

(Example 8)
Except having changed the said prescription 1 into the said prescription 3, it carried out similarly to Example 6 and obtained the fabric of this invention.

(Comparative Example 1)
A fabric of Comparative Example 1 was obtained in the same manner as in Example 1 except that trimethylolmelamine and the organic amine catalyst were omitted in Formulation 1.

(Comparative Example 2)
A fabric of Comparative Example 2 was obtained in the same manner as in Example 1 except that the following formulation 4 was used instead of the above formulation 1.
<Prescription 4>
Fluoroalkyl acrylate copolymer containing no hydrophilic group (manufactured by Nikka Chemical Co., Ltd., trade name “NK Guard S09”, solid content 20%): 75 g / L
Triazine compound (trimethylolmelamine): 3 g / L
Organic amine catalyst: 3 g / L

(Comparative Example 3)
A fabric of Comparative Example 3 was obtained in the same manner as in Example 3 except that the following formulation 5 was used instead of the above formulation 3.
<Prescription 5>
Fluoroalkyl acrylate copolymer containing no hydrophilic group (manufactured by Nikka Chemical Co., Ltd., trade name “NK Guard S09”): 75 g / L
Isocyanate-based crosslinking agent (trade name “NK Assist V” manufactured by Nikka Chemical Co., Ltd.): 10 g / L

(Comparative Example 4)
A fabric of Comparative Example 4 was obtained in the same manner as in Example 5 except that trimethylolmelamine and the organic amine catalyst were omitted in Formulation 1.

(Comparative Example 5)
A fabric of Comparative Example 5 was obtained in the same manner as in Example 7 except that the following formulation 6 was used instead of the above formulation 1.
<Prescription 6>
Fluoroalkyl acrylate copolymer containing a hydrophilic group (Ohara Palladium Chemical Co., Ltd., trade name “Paragard SRF6000”): 75 g / L
Hydroxyethyl cellulose (trade name “SP400” manufactured by Daicel Finechem Co., Ltd.): 10 g / L
Glioxar resin (Miki Riken Kogyo Co., Ltd., trade name “RIKEN RESIN RG-83”, solid content 50%): 50 g / L
Metal salt catalyst (Miki Riken Kogyo Co., Ltd., trade name “Riken Fixer MX27”, solid content 42%): 15 g / L

(Comparative Example 6)
The same procedure as in Example 1 was carried out except that hydroxyethylcellulose was not added and the step of washing with hot water at 60 ° C. for 10 minutes and drying at 130 ° C. for 2 minutes was omitted to obtain the fabric of the present invention. .

(Comparative Example 7)
A fabric of the present invention was obtained in the same manner as in Example 1, except that hydroxyethylcellulose was not added and the steps of washing with hot water at 60 ° C. for 10 minutes and drying at 130 ° C. for 2 minutes were omitted.

  The evaluation results of the obtained fabric are shown in Table 2.

  The fabrics obtained in Examples 1 to 8 are formed of a fluoroalkyl acrylate copolymer containing a hydrophilic group, a crosslinking agent that is a triazine compound and / or an isocyanate compound, and a cellulose compound. Since it was provided with a coating layer, it had excellent durability against repeated washing, oil repellency, oily soil removal property including lipstick stains, and washing recontamination prevention property.

  Among Examples 1 to 4 consisting only of polyester fibers, Examples 1 and 2 in which the crosslinking agent is a triazine compound are oily soil removing properties including lipstick stains and oily soil removing properties including lipstick stains. The durability against repeated washing was further improved.

  Among Examples 5 to 8 in which polyester fiber and cellulose fiber are mixed, Examples 7 and 8 in which the crosslinking agent is an isocyanate compound are oil repellency, oily soil removal property including lipstick stains, washing recontamination preventing property, The durability against repeated washing, soft texture, and free formaldehyde suppression were even better.

  On the other hand, since Comparative Examples 1 and 4 did not contain a cross-linking agent, they were inferior in durability to repeated washing, such as oil repellency, oily soil removability including lipstick stains, and washing recontamination prevention properties. It was.

  In Comparative Examples 2 and 3, since the fluororesin fiber treatment agent was a fluoroalkyl acrylate copolymer containing no hydrophilic group, oily soil removability including lipstick stains both at the initial stage and after repeated washing, and It was inferior in washing re-contamination prevention property.

  In Comparative Example 5, since the crosslinking agent was other than the triazine compound and / or the isocyanate compound, the oil-repellent property, oily soil including lipstick soil, washing re-contamination preventing property, and durability against repeated washing are inferior. It was a thing.

Since Comparative Examples 6 and 7 did not contain a cellulosic compound, they were inferior in durability to repeated washing of oily soil removing property including lipstick soil and washing recontamination preventing property.

Claims (10)

  A fabric comprising a synthetic fiber, comprising a coating layer formed by a fluoroalkyl acrylate copolymer having a hydrophilic group, a crosslinking agent that is a triazine compound and / or an isocyanate compound, and a cellulose compound. A fabric characterized by the above.   The fabric according to claim 1, wherein the cellulose compound is one or more compounds selected from the group consisting of hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, hydroxypropyl methyl cellulose, and carboxymethyl hydroxyethyl cellulose.   The fabric according to claim 1 or 2, wherein at least a part of the synthetic fiber is coated with a hydrophilic resin.   The cloth according to any one of claims 1 to 3, wherein the cloth has a polyester fiber mixing ratio of 100%, and the crosslinking agent is a triazine compound.   The fabric according to any one of claims 1 to 3, wherein the fabric includes polyester fibers and cellulosic fibers, and the crosslinking agent is an isocyanate compound.   The fabric according to claim 5, wherein the mixed ratio of the cellulose fiber fibers is 10 to 70% by mass. Application rate X _A (mass%) of the fluoroalkyl acrylate copolymer containing the hydrophilic group, application ratio X _B (mass%) of the cross-linking agent, and application of the cellulose-based compound with respect to the mass of the entire fabric. The fabric according to any one of claims 1 to 6, wherein the rate X _C (% by mass) satisfies the following formulas (i) to (iii), respectively.

The fabric according to any one of claims 1 to 7, which satisfies the following (I) to (III).
(I) The lipstick removal performance after 30 home washings is 3.5 or more (II) The anti-recontamination property after 30 home washings is 3.5 or more (III) JIS L1919 C method after 10 home washings Easily to remove dirt due to (Lipophilic Pollutant 2) It is a manufacturing method of the cloth given in any 1 paragraph of Claims 1-8,
Attaching a liquid containing a fluoroalkyl acrylate copolymer containing the hydrophilic group, the crosslinking agent, and the cellulose compound to a fabric;
And a heat treatment step of heat treating the fabric at a temperature of 150 to 200 ° C. after the step of attaching. The manufacturing method of the fabric of Claim 9 including the process of coat | covering the said fabric with hydrophilic resin before the said process to attach.