JPH09296372A - India ink stain-resistant synthetic fiber fabric and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an India ink stain-resistant synthetic fiber fabric excellent in washing durability and abrasion durability and useful for carpets, etc., by impregnating a synthetic fiber fabric with an aqueous solution containing a fluorine-based water and oil repellent, etc., having hydrophilic segments and heat treating under a specific condition. SOLUTION: This India ink stain-resistant synthetic fiber fabric having >=4th grade stain resistance SR to India ink stains judged by a gray scale as the stain in JIS L0805 after 20 times of repeating washing (a method according to JIS L0217-103) and >=4th grade stain resistance SR to India ink stains judged by the ray scale as the stain in JIS L0805 after repeating abrasion (using an abrasion tester II described in JIS L0823, at 3000 times of abrasion under 500g load of an abrasion unit) is obtained by impregnating a synthetic fiber fabric from which adhered impurities are removed by prewashing or prerefining with an aqueous solution containing a fluorine-based water and oil repellent having hydrophilic segments, a nonhydrophilic fluorine-based water and oil repellent, and a crosslinking agent, and heat-treating at 140-180 deg.C under dry heating after drying.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink stain resistant synthetic fiber cloth excellent in SR (Soil Release) stain resistance of ink stain after repeated washing and repeated abrasion, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, various antifouling processing techniques have been proposed as a means for improving the antifouling property of synthetic fibers which easily deposit dirt. For example, when roughly classifying the antifouling processing technology for various oily or aqueous liquid stains, (1) hydrophilic synthetic fibers copolymerized or kneaded with a polyalkylene glycol-based or other hydrophilic compound, or acrylic acid-based hydrophilic by post-processing. Stain removability at the time of washing by making the fiber surface hydrophilic by a method of coating the fiber surface with a graft copolymer or a hydrophilic polymer or a chemical modification, that is, SR (S
(2) Water release or oil repellency by (2) kneading silicon-based or fluorine-based antifouling agent with raw yarn or coating these antifouling compounds on the fiber surface in post-processing. To make it difficult for liquid stains to adhere, that is, to improve SG (Soil guard) properties,
(3) Fluorine-based antifouling agent having a hydrophilic group (JP-A-53-53)
No. 134786, No. 59-204980, No. 61-266487) or a perfluoroalkyl group-containing (meth) acrylate copolymer having a hydrophilic group is applied and dried, and then water repellency in a JIS L1092 spray test is increased. A two-step processing method in which 90 or more fluorine-based water and oil repellents are applied, dried and heat treated (Japanese Patent Laid-Open No. 6-337376).
The method of making stain resistant and easy to remove by washing, that is, improving SGR (Soil Guard & Release) property by (4) benzoxazole-based optical brightener
An antifouling polyester-based synthetic fiber containing 1 to 0.3% by weight and having a zeta potential of -15 mV or less (JP-A-3-17).
No. 4068) is known.

However, all of these antifouling processing techniques have insufficient washing and abrasion durability (SR antifouling property) against washing ink stains. For example, SR at the time of washing against ink stains containing both aqueous and oily components
As a technique for dealing with antifouling property, the method of hydrophilizing the fiber surface of the above (1) is effective, and some antifouling effect can be obtained, but a polyalkylene glycol-based or other hydrophilic compound is copolymerized or kneaded. The method has a drawback that fiber physical properties and light fastness are easily deteriorated, and the method of graft-copolymerizing a hydrophilic monomer is apt to cause fiber physical property deterioration in order to obtain a sufficient effect, and the processing is complicated. There is a drawback that the cost tends to be high, and the method of applying the hydrophilic polymer by post-processing has a drawback that washing and abrasion durability cannot be sufficiently obtained. The method (2) of imparting SG properties makes it difficult to attach the ink stains temporarily, but once attached, it has a drawback that the SR stain-proofing property during washing tends to deteriorate. The method (3) of imparting the SGR property has a drawback that not only the processing cost is high because of the two-step processing method, but also the washing and abrasion durability cannot be sufficiently obtained. The method of controlling the zeta potential of the fiber surface by kneading the fluorescent whitening agent of (4) is excellent in removing dirt on mud stains at the time of washing and preventing re-contamination at washing, but it is effective for preventing SR stains at the time of washing of ink stains. Little effect on dirt. Thus, in the textile products used in the field of interiors such as carpets and upholstered fabrics that are repeatedly washed and repeatedly worn, and in the field of clothing such as uniforms and casual knits, SR stain resistance during washing against ink stain is insufficient. Met.

[0004]

The present invention was devised in order to solve the drawbacks of the prior art, and its purpose is to provide a fluorine-based water and oil repellent agent having a hydrophilic segment and a non-hydrophilic fluorine-based agent. By optimizing the antifouling component including the water and oil repellent and the crosslinking agent, and uniformly coating the fiber surface,
It is an object of the present invention to provide an ink stain resistant synthetic fiber cloth which greatly improves SR stain resistance during washing against ink stain after repeated washing and repeated abrasion, and a method for producing the same.

[0005]

Means for Solving the Problems As a result of intensive studies for achieving the above object, the present inventors have found that a fluorine-based water / oil repellent agent having a hydrophilic segment, a non-hydrophilic fluorine-based water / oil repellent agent, and crosslinking It was found that the SR antifouling property at the time of washing against ink stain after the repeated washing and repeated abrasion is further improved by compounding and using the antifouling component including the agent in a specific ratio, and uniformly covering the fiber surface, The present invention has completed the ink stain resistant synthetic fiber cloth and the method for producing the same.

That is, according to the present invention, a synthetic fiber in which the surface of a fiber is uniformly coated with an antifouling component containing a fluorine-based water / oil repellent having a hydrophilic segment, a non-hydrophilic fluorine-based water / oil repellent and a crosslinking agent. A synthetic fiber cloth which is resistant to ink stain and is characterized by having the following characteristics: (1) Repeated washing (JIS L0217-103 method) 2
Ink stain SR property after 0 times is grade 4 or higher according to JIS L0805 contamination gray scale judgment. (2) The ink smear SR property after repeated wear (wearing the friction tester II specified by JIS L0823 for 3000 times under a load of 500 g under a friction tester II) is grade 4 or higher according to the gray scale judgment for JIS L0805 contamination. Here, the SR stain resistance of India ink means India ink (manufactured by Fuze Paste Industry Co., Ltd .:
1 drop of standard stain (ink ink) is dropped using a spoid, a polyethylene (PE) film is placed on the sample, a glass plate is placed, and the stain is pressure-bonded for 30 minutes under a load of 2 kg, and then the weight is removed for 3 hours. After leaving it, JIS L0217-1
The stain removal property after washing once with method 03 is JIS L
Graded 1 to 5 according to 0805 gray scale for contamination.

In the present invention, a synthetic fiber cloth which has been washed or scoured beforehand to remove adhered impurities is provided with a fluorine-based water / oil repellent agent having a hydrophilic segment, a non-hydrophilic fluorine-based water / oil repellent agent and a crosslinking agent. It is a method for producing a synthetic fiber cloth resistant to ink stains, which comprises impregnating an aqueous solution containing the same, drying, and then heat-treating at 140 ° C. to 180 ° C. under dry heat.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The fluorine-based water and oil repellent having a hydrophilic segment used in the present invention is a perfluoroalkyl group-containing (meth) acrylate copolymer represented by the following general formula (I). There is no particular limitation as long as it is a fluorine-based water and oil repellent having SR properties.

Embedded image In the formula, R represents a lower alkyl group, n, a, and b each represent an integer of 1 or more, and Rf represents a perfluoroalkyl group or a group containing a perfluoroalkylene glycol.

The non-hydrophilic fluorine-based water and oil repellent used in the present invention is a non-hydrophilic fluorine-based oil repellent which does not contain a polyalkylene glycol unit such as a polyethylene glycol unit represented by the formula (I) or a sulfonic acid group. A water repellent,
Examples thereof include perfluoroacrylate-based polymers, perfluorosulfonamide acrylate-based polymers, perfluoroalkyl polyethers, low-molecular-weight perfluoroalkyl urethane-based oligomers and perfluoroalkyl aromatic ester-based compounds. Among these, perfluoroacrylate-based polymers and perfluorosulfonamide acrylate-based polymers having a fluorine atom content of 20% or more in the polymer are particularly preferable.

The cross-linking agent used in the present invention is a methylol melamine type containing N-methylol group or a blocked isocyanate (TDI / trimethylol propane adduct ME).
K oxime adduct), which is used by optimizing the amount of adhesion by using the above-mentioned fluorine-based water- and oil-repellent agent having a hydrophilic segment and non-hydrophilic fluorine-based water and oil-repellent agent in a specific compounding ratio. It is possible to exhibit an antifouling effect (an effect of removing liquid stains at the time of washing or wiping) which is excellent in abrasion durability, which is not present. In order to obtain such an effect, the weight ratio of the fluorine-based water and oil repellent agent having a hydrophilic segment to the non-hydrophilic fluorine-based water and oil repellent agent and the cross-linking agent is 5
It is preferably from 0 to 80/49 to 10/1 to 10, and the amount of the antifouling component attached is preferably 1% by weight or more based on the fiber weight. When the blending ratio of the fluorine-based water and oil repellent having a hydrophilic segment is less than 50, the SR stain resistance of ink stains during washing tends to be lowered, and the blending ratio of the non-hydrophilic fluorine-based water and oil repellent is 10%. If it is less than 1 or the cross-linking agent is less than 1, the washing durability and the abrasion durability are likely to decrease. Further, if the amount of the antifouling component attached is less than 1%, the sufficient SR antifouling property of the ink stain during washing is not exhibited.

The synthetic fiber cloth in the present invention means polyethylene terephthalate type polyester fiber, copolymerized polyester fiber with isophthalic acid or 5-sulfoisophthalic acid, acrylic fiber such as cation dyeable acrylic or acid dyeable acrylic, A sheet-like material such as a knitted woven fabric or a non-woven fabric composed of synthetic fibers such as protein-acrylonitrile graft copolymer and synthetic fibers such as cotton, hemp, rayon and polynosic fibers, and the fineness of the constituent fibers. , Cross-sectional shape, amount of dull agent added,
The presence or absence of various polymer stabilizers and the structure, basis weight and density of the fabric are not particularly limited.

Next, a method for manufacturing the ink stain resistant synthetic fiber cloth of the present invention will be described. A fluorine-based water and oil repellent having a hydrophilic segment, a non-hydrophilic fluorine-based water and oil repellent, and an antifouling component containing a cross-linking agent are mixed and used in a specific ratio,
As a manufacturing method for effectively expressing SR antifouling property at the time of washing against excellent ink stain even after repeated washing and repeated abrasion by uniformly coating the surface of the fiber with a certain amount,
The following methods may be mentioned: (1) A synthetic fiber cloth which has been washed or scoured beforehand to remove adhered impurities is provided with a fluorine-based water and oil repellent agent having a hydrophilic segment, and a non-hydrophilic fluorine-based water and oil repellent agent and a crosslinking agent. A method for producing an ink stain resistant synthetic fiber cloth, which comprises impregnating an aqueous solution containing the same, drying and heat-treating at 140 ° C. to 180 ° C. under dry heat. (2) A synthetic fiber cloth is impregnated with an aqueous solution containing a fluorine-based water and oil repellent agent having a hydrophilic segment, a non-hydrophilic fluorine-based water and oil repellent agent and a cross-linking agent, and after drying, 140 ° C. to 18 ° C.
After heat treatment under dry heat at 0 ° C., further washing with water, drying, 1
A method for producing a synthetic fiber cloth resistant to ink stains, which comprises performing a dry heat treatment at 30 ° C. or higher.

In the present invention, the technical point for accurately exhibiting the antifouling effect which is excellent in washing durability and abrasion durability is that spinning or spinning oil agents, weaving sizing agents, dispersants, and soothing agents that tend to remain in the synthetic fiber cloth in a trace amount. After cleaning and removing as much as possible the dyeing agent, the dyeing aid such as the softening agent in the bath or the cationic fixing agent, the antistatic agent used for the yarn-dyed yarn, the pre-dyeing oil agent containing the softening agent and the leveling agent as the main component, The point is that the antifouling component according to the present invention is uniformly applied in a fixed amount. In particular, if a synthetic fiber cloth in which a trace amount of water-soluble hydrophilic impurities remains is used as it is, the original initial water / oil repellent and antifouling durability after abrasion cannot be obtained. As a solution to these problems, the manufacturing method described in (1) or (2) above is effective.

As a method of applying the antifouling component according to the present invention, a usual pad dry cure method is suitable, and after uniformly adhering to the surface of the cloth, it is dried by a conventional method and then 140 ° C to 180 ° C.
A uniform film of an antifouling component is formed on the fiber surface by a method of dry heat setting at 30 ° C for 3 seconds to 3 minutes. Superior SR of the present invention
It is possible to mix conductive fibers and to use with other functional agents such as antistatic agents, flame retardants, antibacterial agents, antifungal agents and deodorants, as long as the antifouling effect is not impaired.

The mechanism of the SR antifouling effect which is excellent in washing durability and abrasion durability in the present invention is unknown, but a specific ratio of "fluorine-based water / oil repellent having a hydrophilic segment and non-hydrophilic fluorine-based agent" is used. Water and oil repellent and crosslinker "
The SR antifouling effect is achieved by applying a predetermined amount of the antifouling component of (1) to a clean synthetic fiber cloth. Therefore, (1) strong adhesion between the fiber surface and the compounded antifouling component, (2) washing It is considered that this is due to the formation of a uniform SR antifouling film that is resistant to dry abrasion.

[0016]

The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited to these examples.
The percentages in Examples and Comparative Examples are on a weight basis unless otherwise specified.

The evaluation methods of the antifouling fiber cloths of Examples and Comparative Examples are as follows. (1) Repeated washing test: Wash 20 times according to JIS L0217-103 method. (2) Repeated wear test: 3000 with a friction load of 500 g under a friction tester II specified by JIS L0823.
Wears once. As the friction cloth, a cotton gold cloth is used, and a wear test is performed by replacing the friction cloth with a new one every 1000 times of wear.

(3) Soil Release SR
Properties: For the samples before and after the repeated washing or repeated abrasion test, one drop each of standard stains of India ink (manufactured by Fuze Paste Industry Co., Ltd .: Sumai) was dropped onto each of the samples, and PE was placed on the samples.
Cover with a film and put a glass plate on it under a load of 2 kg.
After pressing dirt for minutes, remove the weight and leave for 3 hours, then JISL
The stain removal property after washing once by the method of 0217-103 is determined by JI
S L0805 Staining gray scale determines 1 to 5 grades.

Example 1 Polyester textured yarn knitted fabric (150d-48f-SD round cross-section yarn using M type false twisted textured yarn, 30φ-22G smooth knitted fabric, basis weight 160 g / m ² ) was scoured and preset by a conventional method. Then, high-pressure fluorescent dyeing with a jet dyeing machine (Dyeing with Hoechst fluorescent dye Hostalux ERC 1.2% at 130 ° C x 40 minutes)
Then, after reduction washing and water washing and drying, the compounded antifouling component of the following formulation is uniformly applied at a squeezing ratio of 80% WPU (wet pickup) by a normal padding method, dried at 120 ° C, and then 160 ° C x 60 A dry heat set for 2 seconds was performed. Table 1 shows the SR properties of the obtained polyester knitted fabric with stain resistance to ink stains. (Formulation for antifouling treatment) Fluorine-based water and oil repellent having hydrophilic segment (20% aqueous dispersion) (Asahi Guard GS-1 manufactured by Meisei Chemical Co., Ltd.) 7.0% Non-hydrophilic fluorine and water repellent (20% aqueous dispersion) (Asahi Guard AG970 manufactured by Meisei Chemical Co., Ltd.) 3.0% Crosslinking agent (solid content concentration 60%) (Sumitex Resin M3 manufactured by Sumitomo Chemical Co., Ltd.) 0.3% Catalyst (Sumitomo Chemical Co., Ltd.) Sumitex Accelerater ACX) 0.2%

Example 2 Acrylic fiber (manufactured by Japan Exlan Industrial Co., Ltd.) 2/52's
The cationic dye pre-dyed jacquard fabric used is scoured, washed with water and dried, and then the processing liquid having the same antifouling processing formulation as in Example 1 is applied to WPU (wet pickup) by a normal padding method.
Apply evenly with a squeezing ratio of 80%, and after drying at 110 ° C, 1
A dry heat set at 40 ° C. for 60 seconds was performed. The SR properties of the obtained ink-jet stain-resistant dyed jacquard fabrics are summarized in Table 1.

Example 3 Promix fiber consisting of protein-polyacrylonitrile graft copolymer: Sinone (manufactured by Toyobo Co., Ltd.) 100d-
After de-sizing and refining a plain fabric using 48f by a conventional method, it is pale blue dyed with an acid dye, soaped, washed with water, dried, and then mixed with an antifouling ingredient of the following formulation by a normal padding method to WPU.
(Wet pickup) It was uniformly applied at a squeezing ratio of 80%, dried at 100 ° C., and then dry heat set at 140 ° C. for 30 seconds. Table 1 shows the SR properties of the obtained ink mix stain resistance promix fiber knitted fabric. (Formulation for antifouling treatment) Fluorine-based water and oil repellent having hydrophilic segment (20% water dispersion) (Asahi Guard GS-1 manufactured by Meisei Chemical Co., Ltd.) 6.0% Non-hydrophilic fluorine and water repellent (20% aqueous dispersion) (Asahi Guard AG970 manufactured by Meisei Chemical Co., Ltd.) 2.0% Crosslinking agent (solid content concentration 60%) (Sumitex Resin M3 manufactured by Sumitomo Chemical Co., Ltd.) 0.1% Catalyst (Sumitomo Chemical Co., Ltd.) Sumitex Accelerater ACX) 0.1%

Comparative Example 1 Among the antifouling treatment formulation of Example 1, a fluorine-based water and oil repellent having a hydrophilic segment (Asahi Guard GS-
Processing was performed under exactly the same sample and under the same conditions except that 1) was not used. SR of the obtained polyester yarn knitted fabric
The sex is summarized in Table 1.

Comparative Example 2 The same sample and processing as in Example 1 except that the non-hydrophilic fluorine-based water and oil repellent (Asahi Guard AG970) was not used in the antifouling treatment formulation of Example 1. Was carried out. The SR properties of the obtained polyester textured knitted fabric are summarized in Table 1.

Comparative Example 3 Processing was carried out under the same conditions and conditions as in Example 2, except that the antifouling treatment formulation of Example 2 was changed to the following formulation. The SR properties of the resulting dyed jacquard fabric are summarized in Table 1. (Formulation for antifouling treatment) Fluorine-based water and oil repellent having hydrophilic segment (20% water dispersion) (Asahi Guard GS-1 manufactured by Meisei Chemical Co., Ltd.) 3.0% Non-hydrophilic fluorine and water repellent (20% aqueous dispersion) (Asahi Guard AG970 manufactured by Meisei Chemical Co., Ltd.) 2.0% Crosslinking agent (solid content concentration 60%) (Sumitex Resin M3 manufactured by Sumitomo Chemical Co., Ltd.) 0.3% Catalyst (Sumitomo Chemical Co., Ltd.) Sumitex Accelerater ACX) 0.2%

Comparative Example 4 Processing was carried out under exactly the same sample and under the same conditions as in Example 1 except that the crosslinking agent and the catalyst were not used in the antifouling composition formulation of Example 2. The SR properties of the resulting dyed jacquard fabric are summarized in Table 1.

Comparative Example 5 Processing was carried out under the same conditions and conditions as in Example 2, except that the scouring, washing and drying before the antifouling process were carried out. The SR properties of the resulting dyed jacquard fabric are shown in Table 1.
Summarized in The pre-processed yarn-dyed jacquard fabric had a cationic softener having an antistatic property attached thereto in an amount of 0.3% per fiber weight.

Comparative Example 6 Processing was carried out under the same conditions and conditions as in Example 1 except that the formulation for antifouling treatment in Example 1 was changed to the following formulation. The SR properties of the obtained polyester textured knitted fabric are summarized in Table 1. (Antifouling processing formulation) Polyester resin having hydrophilic segment (20% aqueous dispersion) (SR-1000 manufactured by Takamatsu Yushi Co., Ltd.) 3.0% Cross-linking agent (solid content concentration 60%) (Sumitomo Chemical Co., Ltd.) Sumitex Resin M3) 0.3% Catalyst (Sumitex Chemical Industries Sumitex Accelerater ACX) 0.2%

Comparative Example 7 The SR properties of the polyester processed yarn knitted fabric before the antifouling process in Example 1 are summarized in Table 1.

[0029]

[Table 1]

[0030]

As described above in detail, the ink stain resistant synthetic fiber of the present invention comprises a fluorine-based water and oil repellent agent having a hydrophilic segment, a non-hydrophilic fluorine-based water and oil repellent agent and a cross-linking agent in a specific ratio. A uniform amount of the antifouling component blended in (3) is adhered evenly to a clean synthetic fiber cloth that does not contain impure residual components that hinder the adhesion between the fiber surface and the antifouling component to form a strong antifouling film. Therefore, SR (Soil R) at the time of washing against excellent ink stain even after repeated washing and repeated wear
elease) Shows antifouling effect. In particular, according to the present invention, carpet, chair upholstery, table cloth and uniforms, clothing for casual knits, which are susceptible to repeated washing and repeated wear, clothes for calligraphy / painting classrooms and school applications where ink stains are easily encountered It is possible to effectively provide an SR antifouling synthetic fiber cloth having excellent properties.

Front page continued (72) Inventor Hiroyuki Morii 2-8 Dojimahama, Kita-ku, Osaka Toyobo Co., Ltd.

Claims (4)

[Claims] 1. A synthetic fiber cloth in which a fiber surface is uniformly coated with an antifouling component containing a fluorine-based water and oil repellent agent having a hydrophilic segment, a non-hydrophilic fluorine-based water and oil repellent agent and a crosslinking agent. Ink-resistant stain resistant synthetic fiber cloth having the following characteristics: (1) Repeated washing (JIS L0217-103 method) 2
Ink stain SR property after 0 times is grade 4 or higher according to JIS L0805 contamination gray scale judgment. (2) The ink smear SR property after repeated wear (wearing the friction tester II specified by JIS L0823 for 3000 times under a load of 500 g under a friction tester II) is grade 4 or higher according to the gray scale judgment for JIS L0805 contamination. 2. An antifouling composition in which the weight ratio of the fluorine-based water and oil repellent agent having a hydrophilic segment to the non-hydrophilic fluorine-based water and oil repellent agent and the crosslinking agent is 50 to 80/49 to 10 to 1 to 10. The synthetic fiber cloth according to claim 1, characterized in that 1% by weight or more of the organic component is attached to the weight of the fiber. 3. The ink stain resistant synthetic fiber fabric according to claim 1, wherein the synthetic fiber fabric is an acrylic fiber knitted fabric and a polyester fiber knitted fabric. 4. A synthetic fiber cloth, which has been washed or scoured in advance to remove adhered impurities, is made into an aqueous solution containing a fluorine-based water and oil repellent agent having a hydrophilic segment and a non-hydrophilic fluorine-based water and oil repellent agent and a crosslinking agent. After impregnation and drying, 140 ℃ ~
A method for producing a synthetic fiber cloth resistant to ink stains, which comprises heat-treating at 180 ° C. under dry heat.