JPH09157989A - Vamp material of cloth shoe - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a vamp material of a cloth shoe having excellent every properties of water repelling property, soil-proofing property, quick-drying property and light fastness. SOLUTION: This vamp material of a cloth shoe is a cloth obtained by containing 0.2-1.0wt.% of a fluorine-based water repellent emulsified and dispersed with an anionic or nonionic surfactant onto the cloth constituted with polyester fibers mixed with 0.01-0.3wt.% of a fluorescent brightener in producing of the fibers and the cloth has <=-15mV; ζ-potential on the surface and >=40% F15 concentration to all elements in an ESCA spectrum on the surface of the cloth. This vamp material can give a cloth shoe having high whiteness keeping property hardly soiled with muddy water in wearing cloth shoes, capable of readily removing dirt particles such as once attached soil or sand with washing and quickly drying.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an upper material for a cloth shoe, and more particularly, to a cloth shoe having a sole made of rubber or synthetic resin, which is water-repellent, stain-proof, quick-drying,
The present invention relates to an upper material having a light resistance function.

[0002]

2. Description of the Related Art In general, a cloth shoe is made by laminating two or more cloths as an upper material, which is sewn in advance to form a shoe main body, and then the shoe sole, that is, the outer sole, is made of rubber. Are bonded together with an adhesive, or a synthetic resin such as polyvinyl chloride resin is injection-molded and integrally joined. in this case,
Although cotton is mainly used as a material for the fabric forming the upper, synthetic fibers such as nylon and polyester fibers have also come to be used.

[0003] Conventionally, cloth shoes have a problem that they are often white and stains are easily noticeable. Particularly, stains containing water such as mud penetrate into the inside of the shoes together with water, and the stains are not easily removed. In addition, there was a drawback that the comfort of the shoes was very poor due to the water that penetrated inside the shoes. For the problem of dirt, in the past, a method of making the upper material hydrophilic to improve the dirt removal property in washing, or a method of applying water repellent treatment to the upper material to prevent dirt by repelling muddy water Is proposed.

However, the former hydrophilic method cannot prevent the infiltration of muddy water into the shoe when the shoe is worn, and on the contrary, it has a drawback that it easily absorbs muddy water and becomes dirty because of its high water absorption. It was On the other hand, the latter method of applying water repellent treatment to the upper material is very effective against mud and has been put to practical use, but it is still insufficient and has various problems. . Specifically, the water-repellent upper material made of cotton has poor water-repellent performance, loses water repellency after washing the shoes several times, and after washing the shoes, There was a fatal drawback that it was difficult to dry. In addition, synthetic resin such as nylon and polyester treated with water-repellent finish has excellent durability and water repellency, and it also has excellent quick-drying properties. Has a problem in light resistance, and has a drawback that it turns yellow in a short period of time and cannot be used for a white material. On the other hand, when polyester adheres to a water-repellent upper material, it is difficult to remove it even by washing. However, there was a drawback that stains remained and darkened.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of such a situation as described above, and has water repellency, antifouling property, quick drying property,
The object is to provide an upper material having excellent light resistance.

[0006]

Means for Solving the Problems In the cleaning action of dirt particles attached to a cloth, the present inventors have focused their attention on the “hetero-aggregation theory”, which is a theory of interaction between different particles, by the F _iS concentration for all elements in the zeta potential and ESCA spectrum of fabric fiber surface which is subjected to carapace material above a particular value, that occupy Yuse combined excellent water repellency and antifouling performance The inventors have found out what can be done and have reached the present invention. That is, according to the present invention, fluorine is obtained by emulsifying and dispersing a cloth made of polyester fiber in which 0.01 to 0.3% by weight of a fluorescent whitening agent is mixed at the time of manufacturing the fiber, with an anionic or nonionic surfactant. A fabric containing a water-repellent agent of 0.2 to 1.0% by weight, the surface zeta potential of which is -15 mv or less,
Further, the gist is the upper material of a cloth shoe, wherein the _FIS concentration for all elements in the ESCA spectrum of the fabric surface is 40% or more.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.
First, as the upper material of the cloth shoe of the present invention, a cloth made of polyester fiber containing 0.01 to 0.3% by weight of a fluorescent whitening agent at the time of manufacturing the fiber is used. The polyester fiber as used in the present invention is a thermoplastic resin obtained by melt-spinning a chain polymer having an aliphatic group or an aromatic group as a main chain structural unit and repeatedly bonding while forming an ester group —COO—. The fiber is, for example, polyethylene terephthalate, polybutylene terephthalate, or the like.

Examples of the fluorescent whitening agent include pyrene-based, oxazole-based, coumarin-based, thiazole-based, imidazole-based, imidazolone-based, pyrazole-based, benzidine-based, diaminocarbazole-based, diaminostilbenedisulfonic acid-based and the like. Among these, oxazole-based optical brighteners are most preferable because they have good whiteness and acid resistance.

The polyester fiber of the present invention is a white colored fiber obtained by kneading a fluorescent whitening agent in a chip in advance and then spinning. The amount of the optical brightener to be kneaded into the fiber must be in the range of 0.01 to 0.3% by weight based on the weight of the fiber, and the amount of kneading should be 0.3% by weight. If it exceeds, yellowing occurs, and if it is less than 0.01% by weight, good whiteness cannot be obtained. The cloth referred to in the present invention is a woven fabric, circular knitting machine, weft knitting machine, weft knitting machine, shuttle knitting machine, dobby weaving machine, jacquard weaving machine, water jet loom, air jet loom, rapier weaving machine, etc. Knitted with a knitting machine, a non-woven fabric having a mat-like structure manufactured by a dry method, a wet method, or a direct method.

The first feature of the present invention is that the upper material of the cloth shoe is composed of polyester fibers which are colored white during the fiber production, and the zeta potential on the surface of the cloth is -15 mv or less. It has a numerical value. The zeta potential (ζ) means an electrokinetic potential, which is a potential difference between electric double layers formed on the surface of a fiber by being charged when the fiber contacts the interface with water. Here, if the zeta potential becomes -15 mv or more or a positive value, the removability of dirt particles deteriorates. In the present invention, 0.2 to 1.0 of a fluorine-based water repellent obtained by emulsifying and dispersing an anionic or nonionic surfactant in a cloth made of polyester fiber in which a fluorescent whitening agent is kneaded at the time of manufacturing the fiber is used. Contains by weight percent.

The term "fluorine-based water repellent" as used herein means a radical-reactive compound capable of copolymerizing with a fluoroalkyl group-containing polymerizable compound such as an acrylic ester or a methacrylic ester containing a perfluoroalkyl group. Emulsion polymerization of an acrylic acid amide derivative having an unsaturated bond or a compound such as vinyl chloride or vinylidene chloride with an anionic or nonionic surfactant and optionally a water-soluble organic solvent as a dispersion aid. A copolymer obtained by the above is dispersed in water.

In the present invention, it is essential that the surfactant in which the fluorine-based water repellent is emulsified and dispersed is an anionic or nonionic surfactant. Examples of the anionic surfactant include alkyl sulfonic acid and its salt, alkylbenzene sulfonic acid and its salt, alkyl carboxylic acid and its salt, and sodium alkoxypolyoxyethylene sulfonate. As the nonionic surfactant, , Polyoxyethylene monooleyl ether, polyoxyethylene monoalkyl ether, polyoxyethylene mono (alkylphenyl) ether, polyoxyethylene monooleyl ester, polyoxyethylene monoalkylcarboxylic acid ester, sorbitan ester, sucrose ester, etc. Can be mentioned. Here, if the surfactant is a cationic type, the zeta potential on the surface of the fabric becomes -15 mv or more, which is unsuitable.

The fluorine-based water repellent must contain the copolymer obtained by emulsion polymerization in an amount of 0.2 to 1.0% by weight based on the weight of the fiber. If the content is less than 0.2% by weight, good water repellency cannot be obtained, while 1.
When the amount exceeds 0% by weight, although good water repellency can be obtained, dirt particles are likely to remain and the antifouling property is greatly reduced, which is not preferable. In the present invention, the method of incorporating the fluorine-based water repellent into the cloth is not particularly limited, but the cloth is impregnated with the treatment liquid, the solution is squeezed with a mangle or the like and then dried, or the treatment liquid is sprayed onto the cloth. After that, it may be performed by a known method such as a method of drying. Also,
If necessary, it may be used together with an appropriate cross-linking agent for curing.

The second feature of the present invention is that F for all elements in the ESCA spectrum of the obtained fabric surface is
_{The IS} concentration is 40% or more. ESCA is an electron spectroscopy method for analyzing constituent elements of a solid surface and their chemical bonding states, and ESCA spectra are X-rays on a solid sample surface.
It is the photoelectron spectrum of photoelectrons emitted from excited atoms when they are irradiated with a line.

The F _IS concentrations for all elements in the ESCA spectrum are obtained from the following equations (1) and (2), and show the abundance ratio of fluorine element on the fabric surface. In other words, the F _IS concentration is obtained by selecting the photoelectrons emitted from the sample by irradiating X-rays with an analyzer, detecting and amplifying the photoelectron peak areas S of the respective elements recorded in the XY recorder from the following formula (1). It is obtained by calculating and then obtaining the F concentration from the equation (2). Peak area S = S _A × (1 / X) × (Y / 100) (1) (where S _A is the peak area recorded on the chart, X
Is the relative intensity of the photoelectron peak, and Y is the measurement sensitivity. ) F _IS concentration (%) = peak area of F / total peak area of detected elements x 100 (2)

In the present invention, the _FIS concentration must be 40% or more, and if it is less than 40%, good water repellency cannot be obtained. The present invention has the above configuration.

[0017]

The function of the present invention is not clear as to why a shoe upper material having excellent water repellency, antifouling property, quick-drying property and light resistance can be obtained. I'm guessing.

Usually, the adhesion and desorption phenomena between the fibers and the dirt particles in the cleaning liquid are discussed by the "heteroaggregation theory" of the theory of interaction between different particles, and the potential energy of attractive force generated between the particles and the fibers. Contamination removability is affected by the potential energy of total interaction, which is the sum of the potential energy of repulsive force, and the greater the potential energy of total interaction, the better the contamination removability. The zeta potential is a factor that greatly contributes to the potential energy of all interactions, and dirt particles such as soil and sand are negatively charged during cleaning. We have:
As a result of research focusing on the above points, it was found that excellent antifouling property can be obtained by setting the zeta potential of the polyester fiber surface to -15 mv or less.

Like the upper material of the cloth for shoes of the present invention, when polyester fibers are mixed with 0.01 to 0.3% by weight of a fluorescent whitening agent at the time of fiber production, negative zeta on the fiber surface at the time of dyeing. Compared with polyester fiber that lowers the potential to increase the dyeability and dyes and fluorescent whitens, it has excellent light resistance and has a zeta potential of -15 mv or less, thus removing dirt particles such as soil and sand. The properties are greatly improved and the antifouling property is excellent. 0.2 to 1.0 of a fluorine-based water repellent obtained by emulsifying and dispersing an anionic or nonionic surfactant in such an instep material.
And the additional inclusion wt%, when leaving the F _IS concentration more than 40% for all elements in the ESCA spectrum of the fiber surface, the zeta potential of the polyester fiber surface -15
The water repellency can be imparted without being changed more positively than mv, and the excellent water repellency can be imparted without deteriorating the antifouling property.

[0020]

EXAMPLES Next, the present invention will be described in more detail with reference to Examples. Measurement and evaluation of the performance of the fabrics in Examples were carried out by the following methods.

(1) Soil removability by washing A. Test method with synthetic pollutant 0.75g of synthetic pollutant mixed with oily pollutant and dry pollutant shown below in a ratio of 3: 1, sodium tripolyphosphate 5
g, and 5 g of sodium laurylbenzene sulfonate were dispersed and prepared to 1 liter with distilled water to prepare a contaminated liquid.

[Oil Contaminating Agent] Stearic acid 12.5 wt% Oleic acid 12.5 〃 Hardened oil 12.5 〃 Olive oil 12.5 〃 Cetyl alcohol 8.5 〃 Solid paraffin 21.5 〃 Cholesterol 5.0 〃 Carbon black 15.0 〃 total 100.0% by weight

[Dry Pollutant] Clay 55.0% by weight Portland cement 17.0〃 ferric oxide 0.5〃 γ-decane 8.75〃 carbon black 1.75〃 silica gel 17.0〃 total 100 0.0% by weight

Next, using a rounder meter tester used for the wash fastness test method of JIS-L-0844, 200 ml of the recontamination liquid and 10 steel balls used for the wash fastness test method were put into a test bottle. , 5
Four pieces of white cloth of a test piece cut into cm × 5 cm were put and hermetically sealed, and a treatment was performed at 40 ± 2 ° C. for 1 hour. After that, the test cloth is taken out, rinsed with running water, further washed with 100 ml of water at 40 ° C. for 10 minutes with a round meter, then the test piece is taken out, rinsed with running water, and again 2 times.
After washing with 100 ml of water at 5 ° C. for 10 minutes with a round meter, rinsing with running water was repeated twice, dehydration, and drying with a tumbler. After drying, it was graded using the gray scale for contamination. Judgment is made in 5 steps, and 5
The grade 1 indicates that there was no pollution at all, and the grade 1 indicated that there was significant pollution (darkening).

B. Test method by earth and sand pollution source Cut a sample into 20 cm x 20 cm, and use two samples and JIS
-Z-8901 (Kanto loam layer fine particles) sand 3g was enclosed in a plastic bag, put in a test box of a pilling tester for 1 hour, then taken out from the plastic bag, using a spiral fully automatic washing machine, It was washed with 0.5 g of Rapid-Acting Top (Lion Co., Ltd.) at 40 ° C. for 10 minutes, rinsed at room temperature for 5 minutes, dehydrated and dried. After drying, 5 grades were judged using a contamination gray scale. 5
The class shows the state where the sand is completely removed, and the class 1 shows the state where the soil is not removed at all.

(2) Water repellency JIS-L-1092 Spray method before and after washing 10
The measurement was performed on the sample after the washing (washing method: JIS-L-0217, 103 method line dry). (3) Quick-drying The sample was soaked in water with a moisture content of 50% and then left in a constant temperature and humidity chamber at a temperature of 25 ° C and a humidity of 60% to measure the change with time of the moisture content.

(4) Light resistance Measured by the third exposure method using a JIS-L-0842 carbon arc fade meter. (5) Zeta potential Shimadzu Corporation streaming potential measuring device ZP-10B
The shape was measured. (6) ESCA ULVAC-PHI ESCA56 manufactured by Shimadzu Corporation
Measured at 00.

Example 1 Yeast Bright OB-1 (produced by Eastman Kodak Co., oxazole type optical brightener) was mixed at 0.1% with respect to the weight of polyethylene terephthalate, melt-spun, and stretched at 150 d / chip. 36f of white spun yarn was obtained.
Next, false twisting (processing conditions: twist number 2470 T / M, first heater temperature 190 ° C, second heater temperature 210 ° C)
After making the false twist crimped bulky processed yarn, the warp of the woven fabric,
Used for wefts, warp density 1 with a water jet loom
02 yarns / inch, weft density is twin yarns 53 yarns / inch 2
A woven fabric having a / 2 twill structure was woven into a white polyester woven fabric.

Next, NaOH 1 g / liter, Sunmor FL (Nika Kagaku Co., Ltd., nonionic surfactant) 1
Relax in a bath containing g / l for 10 minutes at 80 ° C, scouring, dehydration, and drying, then dip in a treatment bath of the following formulation 1 and impregnate with a mangle at a squeezing rate of 100%, and then dry. Heat treatment was carried out at 180 ° C. for 30 seconds to obtain the upper material for cloth of the present invention.

Prescription 1 Asahi Guard LS-317 30 g / liter (Asahi Glass Co., Ltd., nonionic fluorine water repellent, solid content 20%) Sumitex Resin M-3 1 g / liter (Sumitomo Chemical Co., Ltd., melamine resin) ) Sumitex Accelerator ACX 1g / liter (Sumitomo Chemical Co., Ltd., catalyst for melamine resin)

For the purpose of comparison with the present invention, a raw yarn was produced without using the fluorescent whitening agent used in the production of the white garment cloth in the present embodiment, and the temporary yarn was prepared under the same conditions as in the first embodiment. After twisting, weaving, relaxing, scouring, dehydrating and drying,
Using a high-pressure jet dyeing machine, Ubitex EBF (Nippon Ciba Geigy Co., Ltd., fluorescent whitening agent for post-dyeing) 1% owf
It was dyed at 130 ° C. for 15 minutes to obtain a white cloth.
Subsequently, this white cloth was put into a treatment bath of Formulation 1 of this example, impregnated, dried, and heat-treated under the same conditions as in Example 1 to obtain the upper material for the shoes for comparison (Comparative Example 1). ) Got.

For comparison with the present invention, a nylon 6 chip having the same concentration of the fluorescent whitening agent used in this example was melt-spun and stretched to obtain a 150d / 36f nylon 6 white-dyed yarn. did. Then, after false-twisting into a false-twisted yarn, it is woven, relaxed, scoured, dehydrated and dried under the same conditions as in Example 1, and put into a treatment bath of formulation 1 of this example to give a book. After impregnation and drying under the same conditions as in Example 1, 170 ° C.,
Heat treatment was carried out for 30 seconds to obtain a shoe upper material for comparison (Comparative Example 2).

Further, for comparison with the present invention, a cotton yarn of 30 count is used, a warp density of 95 yarns / inch, and a weft density of 50 yarns / inch is 2/2 in an air jet loom with a design of 2 yarns / inch.
After weaving a twill fabric, fluff, desizing, scouring,
It was bleached, fluorescently whitened under the conditions of 60 ° C. for 30 minutes by a Wins dyeing machine according to the following formulation 2, and then dried. Prescription 2 Ubitex 2B (200%) 0.5% owf (Nippon Ciba Geigy KK, fluorescent whitening agent for cotton) Anhydrous mirabilite 3.0 g / liter

Subsequently, the material was put into a treatment bath having the following formulation 3 and impregnated, dried and heat-treated under the same conditions as in Example 1 to obtain a shoe upper material for comparison (Comparative Example 3). Prescription 3 Asahi Guard LS-317 30 g / liter (Asahi Glass Co., Ltd., nonionic fluorine water repellent, solid content 20%) Meikanate MF 10 g / liter (Meissei Chemical Co., Ltd., blocked isocyanate compound)

The performance was measured and evaluated for the upper materials of the present invention and the comparative cloth shoes, and the results are also shown in Table 1.

[0036]

[Table 1]

As is clear from Table 1, the upper material of the cloth for shoes of the present invention had excellent water repellency, antifouling property, quick drying property and light resistance.

Examples 2 and 3 Polyester white original dyed false twisted yarn 1 obtained in Example 1
After 50d / 36f is twisted to 300d / 72f, the warp density is 55 threads / inch and weft density is 40 with a rapier loom.
A woven fabric with a flat design was woven by the book / inch design to give a polyester white sown cloth. Next, after relaxing, scouring, dehydrating, and drying under the same conditions as in Example 1, the treatment baths under the five conditions shown in Table 2 were prepared, and impregnation, drying, and heat treatment were performed under the same conditions as in Example 1, respectively. The upper materials of the invention and Comparative Examples 4 to 6 were obtained.

[0039]

[Table 2]

The performance of the upper materials of the present invention and the comparative cloth shoes was measured and evaluated, and the results are also shown in Table 3.

[0041]

[Table 3]

As is clear from Table 3, the upper material of the cloth of the present invention was excellent in all of water repellency, antifouling property, quick drying property and light resistance.

[0043]

The upper material for cloth shoes of the present invention has excellent properties such as water repellency, antifouling property, quick drying property and light resistance. When cloth shoes using such upper materials are worn, they are resistant to dirt with muddy water, and dirt particles such as soil and sand that have once adhered can be easily removed by washing, and they can be quickly dried for a long term whiteness. The cloth shoes are kept.

Claims (1)

[Claims] 1. An optical brightener is added in the range of 0.01-0.
A fabric made of polyester fiber containing 3% by weight of a fluorine-containing water repellent emulsified and dispersed with an anionic or nonionic surfactant in an amount of 0.2 to 1.0% by weight. , zeta potential of the surface of the fabric is not more than -15 mV, and the carapace material cloth shoes, characterized in that F _iS concentration for all elements in the ESCA spectrum of the fabric surface is 40% or more.