JP2002013077A - Amino-modified silicone woven fabric - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a woven fabric having excellent washing resistance. SOLUTION: This woven fabric contains an amino-modified silicone and comprises a high-strength functional fiber as at least a part of the woven fabric composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a woven fabric having excellent washing resistance, and more particularly to a woven fabric using a high-performance fiber such as para-aramid having improved washing resistance.

[0002]

2. Description of the Related Art In the field of outdoor sports such as mountain climbing, fishing, and motorcycles, unexpected situations of natural opponents occur, so conventional clothing materials are not satisfactory, and higher functionality such as tear strength is required. Have been. At present, various functional fibers are put on the market, and application to clothing is being attempted. For example, para-aramid fiber,
High-strength functional fibers such as PBO fiber and polyarylate fiber have high tensile strength of 10 cN / dtex (centi-Newton / decitex) or more, and nylon, polyester fiber, and acrylic fiber having a tensile strength of about 4 cN / dtex. It is clearly different from general-purpose fibers such as. When these highly functional fibers and general-purpose fibers are used in combination, improvements in tensile strength, tear strength, abrasion strength and the like are expected.

For example, para-aramid fiber is 20.3 cN
/ Dtex has high tensile strength. A woven fabric partially or entirely using the yarns made of the fiber is used for outdoor shirts, pants, ski wear, snowboard wear, and the like, which have high tear strength and are likely to be torn by a bush or the like. Jeans pants in which high-strength, high-performance fibers are partially woven are also used as rider wear in order to reduce injuries when falling, in addition to the outdoor sports. For example, Japanese Utility Model Publication No. 1-36006 and Japanese Examined Patent Publication No. 62-26900 propose that a 100% para-aramid fiber filament or spun yarn is partially woven. It is stated that this method provides an improvement in tear strength.

In Japanese Patent Application Laid-Open No. 10-130990, a core yarn having an aramid fiber as a core and a light-resistant fiber such as cotton as a sheath is used for the weft, and a warp made of the light-resistant fiber is disposed on the front side of the fabric. A reinforced fabric having excellent light resistance has been proposed, which has a structure in which aramid fibers are substantially concealed by light-resistant fibers, in the form of a fabric having a warp or twill structure in which a weft is arranged on the back side. In this reinforced fabric, since the core yarn having a high strength aramid fiber as a core is arranged on the weft, the tear strength for cutting the weft is greatly improved. However, a woven fabric using a high-strength high-performance fiber has a reduced tear strength due to repeated washing. High-strength high-performance fibers have a high degree of fiber molecule orientation in the fiber axis direction and a high tensile strength in the fiber axis direction, but are weak in friction in the fiber cross-section direction. It is considered that the abrasion of the fiber causes damage to the fiber surface, resulting in a decrease in strength and consequently a decrease in tear strength of the woven fabric.

[0005]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, and has a high tear strength, partially or wholly using a high-strength functional fiber yarn. An object of the present invention is to provide a woven fabric having excellent properties.

[0006]

The gist of the present invention is to provide (1)
A woven fabric containing amino-modified silicon and comprising high-strength functional fibers as at least a part of the fiber composition, (2) characterized by being treated with amino-modified silicon before, simultaneously with or after weaving The woven fabric according to the above (1), (3)
A fabric using a high-strength functional fiber having a tensile strength of a single fiber of 10 cN / dtex (centinewton / decitex) or more contains amino-modified silicon, and after drying, is heated to form a cross-linked amino-modified silicon on the fiber surface. (1) The woven fabric according to (1) or (2), (4) any of (1) to (3), wherein the content of the amino-modified silicon is 0.01 to 10% by weight based on the weight of the woven fabric. (5) The woven fabric according to any of (1) to (4), wherein the woven fabric contains high-strength functional fibers at 3% or more of the entire woven fabric.
(6) The woven fabric according to any one of (1) to (5), wherein the high-strength functional fiber is a para-aramid fiber, and (7) the para-aramid fiber is a polyparaphenylene terephthalamide fiber. And (8) the high-strength functional fiber has a double structure having the high-strength functional fiber itself as a core and a light-resistant fiber as a sheath. The woven fabric according to any one of the above (1) to (7).

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a yarn composed of high-strength functional fibers is used for the whole or a part of a woven fabric. The yarn made of the high-strength functional fiber may be a continuous fiber yarn or a spun yarn obtained by spinning a staple (short fiber) made of the high-strength functional fiber. . Also, a core-sheath yarn obtained by combining a yarn made of these high-strength functional fibers with another general-purpose material, or a yarn mixed with another material by a twisted yarn, a blended yarn, an air, or the like may be used.

Examples of the high-strength functional fiber include functional fibers such as para-aramid fiber, polyparaphenylene benzobisoxazole (PBO) fiber, polyarylate fiber, and ultrahigh molecular weight polyethylene fiber. More specifically, the para-aramid fiber is a para-based wholly aromatic polyamide fiber, and specific examples thereof include polyparaphenylene terephthalamide and copolyparaphenylene-3,4'-oxydiphenylene terephthalamide. Above all, polyparaphenylene terephthalamide fiber is preferred in that it has high strength, flexibility, and high flame retardancy (limit oxygen index 29). Single fiber strength of high strength functional fiber is 10c
N / dtex or more, preferably 15c
Those having N / dtex or more are preferable. Single fiber strength 10c
If it is less than N / dtex, the improvement of the tear strength of the woven fabric is not sufficient.

Ultrahigh molecular weight polyethylene fibers are excellent in light resistance among these functional fibers, but are inferior in heat resistance and are easily melted by tobacco fire or frictional heat. Further, para-aramid fibers and the like discolor when exposed to light including ultraviolet rays, and may be deteriorated by strong direct sunlight. These problems can be solved by using a two-layer structure yarn in which high-performance fibers are arranged in the core and light-resistant fibers such as cotton are arranged in the sheath. The form of the functional fiber constituting the core of the two-layer structure yarn as the reinforcing yarn is
It may be an aggregate, for example, with or without twist. A spun yarn, a drawn-off spun yarn, an air entangled yarn, a filament or the like can be used, but a spun yarn is preferable in terms of feeling and strength. A multifilament, a short fiber, or a spun yarn can be used for the sheath.

[0010] Further, by weaving the reinforcing yarn comprising the two-layer structure yarn as a warp and / or a weft different from the basic structure on the back side of the basic woven fabric comprising the light-resistant fiber, the functional fibers in the reinforcing yarn are substantially reduced. Since light is covered twice, light resistance can be improved. Here, examples of the light-resistant fiber used for the sheath portion and the basic fabric include cotton, wool, hemp, polyester, nylon, and acrylic fiber, and cotton is particularly preferable. Cotton not only has excellent light fastness in terms of physical properties, but also has no heat-fusing property like many functional fibers, and it is carbonized without melting when exposed to high temperatures. Less risk of burns.

The amino-modified silicon used in the present invention is, for example,

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[0012]

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[0013]

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[0014]

Embedded image

(Where n and m are integers of 1 or more, and X is-
RNH ₂ or RNHR′NH ₂ , wherein R and R ′ are alkylene groups. ) Etc. That is, the amino-modified silicon of the present invention refers to a compound having a siloxane bond as a repeating unit, but an amino group is added to a linear polydimethylsiloxane molecular chain. Those substituted with an alkyl group, allyl group, or phenyl group, or those having a branched or cross-linked polydimethylsiloxane molecular chain can also be used.
The amino group may be added to the side chain and / or the terminal of the molecular chain. Further, the amino group may be an amino group to which an amine such as a primary amine, a secondary amine, a monoamine, and a diamine is derived. Both are effective. Preferably, it is an amino-modified silicon represented by the general formulas (1) to (4).

The amino group equivalent (g / eq) of the amino-modified silicon used in the present invention corresponds to the molecular weight of siloxane per amino group. The smaller the amino group equivalent, the larger the amount of amino group in the molecule. Represents. The amino-modified silicon used in the present invention has an amino group equivalent (g / e).
q) is preferably 3,000 or less, more preferably 10
00 or less.

The amino-modified silicon used in the present invention has the formula (5)

Embedded image (However, m is an integer of 1 or more, and R ¹ and R ^{2 each} have 1 to 1 carbon atoms.)
And 0 represents an alkyl group or an aryl group. ) May be used.

Furthermore, the amino-modified silicon used in the present invention has the formula (6)

Embedded image May be used.

Further, in the present invention, TK SET W (manufactured by Takamatsu Yushi Co., Ltd., special silicone resin), Crosil® (Crosil R) (manufactured by Crossfield Textile Co.), Ultra Latex E
SU (Ultratex) (manufactured by Avantis), amino-modified silicon KF-861 (manufactured by Shin-Etsu Chemical Co., Ltd.),
SF-8417 (manufactured by Dow Corning Toray),
IM137 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and the like.

In the present invention, besides amino-modified silicon, mineral-modified fine particles such as polyester-modified silicon, polyether-modified silicon, polyorganosiloxane, mineral oil, talc, silica, colloidal alumina, magnesium stearate, calcium stearate, etc. Various kinds of waxes such as solid wax at normal temperature such as higher fatty acid metal salt powder, higher aliphatic carboxylic acid, higher aliphatic alcohol, and paraffin polyethylene may be used in combination.

The above amino-modified silicon is dissolved in an organic solvent such as chloroform, for example, or before or at the same time as weaving, before weaving the fabric with an emulsion in which amino-modified silicon is dispersed in water using a surfactant. By treating the fibers of the woven fabric after weaving, the fabric of the present invention is produced.

Hereinafter, preferred embodiments of the present invention will be described. According to the present invention, a woven fabric using the high-strength functional fiber as a whole or a part thereof is dipped in an emulsion of amino-modified silicon having a purity of about 3%, and lightly squeezed with a mangle (rubber roll) to a weight of about 80%. ~ 100% emulsion pick-up, dried at 100 ° C for 3-5 minutes,
Subsequently, it is obtained by heating at 150 ° C. for 2 to 3 minutes to cross-link and cure the resin to form cross-linked amino-modified silicon on the fiber surface. The ratio of the high-strength functional fibers to the entire woven fabric is preferably 3% or more, more preferably 4% or more. When the proportion of the high-strength functional fiber is 3% or less, the improvement of the physical properties of the woven fabric such as tear strength is not remarkable. A woven fabric that uses such high-performance fibers partially or wholly has a reduced tear strength even after repeated washing and retains its initial functionality, so it can be used for climbing, fishing, motorcycles, etc. It is suitable as a material used for clothing in the field of outdoor sports.

The pure content of amino-modified silicon to be applied to the weight of the fabric is about 0.1 to 10% by weight. It is preferably about 0.5 to 5% by weight, more preferably about 1 to 4% by weight. When the content is less than 0.1% by weight, the effect is small. When the content is more than 10% by weight, slip between yarns constituting the fabric is liable to occur, and a slimy feeling peculiar to silicon occurs, which is not preferable for clothing.

The processing of the present invention may be applied to a woven fabric,
It may be applied in the state of the yarn at the previous stage, or may be applied to the fiber at the previous stage, for example, staples. It may be applied to clothing products such as shirts and pants after sewing. As the amino-modified silicon, a reactive amino silicon emulsion is preferable, and specific examples include, for example, 1M137 (trade name of Daiichi Kogyo Seiyaku). In order to improve abrasion resistance, a polyethylene emulsion may be added to the emulsion.

[0025]

The present invention will be described below in detail with reference to examples. The physical property test method of the woven fabric was based on the following method.

[Washing and drying] The following washing and drying steps were defined as one washing. Washing was performed according to JIS L 0217 103 method. That is, a standard washing capacity with a centrifugal squeezing device conforming to the standard of JIS C 9606 (electric washing machine) is used as a test device, and a household electric washing machine with a standard water volume is used. Water at a temperature of 40 ° C. is added, and a synthetic detergent for clothing is added and dissolved at a ratio of 2 g per liter of water to prepare a washing liquid. The operation is started by inputting materials and, if necessary, load cloth into the washing machine so that the bath ratio becomes 1:30. After processing for 5 minutes, the operation is stopped, and the material and the load cloth are dehydrated with a dehydrator.
Next, the washing liquid is replaced with fresh water at room temperature, and rinsing is performed for 2 minutes at the same bath ratio. After rinsing for 2 minutes, the operation is stopped, the sample and the load cloth are dehydrated, rinsed again for 2 minutes, and dehydrated. Drying: Drying was performed according to the tumble drying method described in JIS L 1042 6.9.2 I-2 method (high-temperature tumble drying method). That is, after entanglement of the test piece and the load cloth after centrifugal dehydration, the test piece and the load cloth are put into a tumble dryer, and the test piece and the load cloth are sufficiently dried at a temperature not exceeding 80 ° C. I do.

[Tear strength] JIS L 1096.
The tear strength was determined by the D method (Pendulum method) specified in 6.15.5. In addition, a woven fabric having a high proportion of high-performance fibers which cannot be measured by the pendulum method because of high tear strength is JIS L 1096. 6.
The tear strength specified in 15.2 was measured by the A-1 method (single tongue method).

[Example] Para-aramid fiber (trade name: Kevlar (R)) staple 1.7 manufactured by Toray DuPont
dtex-51mm (single fiber strength 20.3cN / dte
x, tensile modulus 490 cN / dtex, elongation 3.8
% 177 dtex (cotton count 30)
886 dte with s / 1) as the core and cotton fiber as the sheath
An x (cotton count 6 s / 1) two-layer structure yarn a was prepared by a standard method using a ring spinning machine. That is, a cotton roving is supplied to a front roller while being stretched between a pair of rollers, and is flattened. A spun yarn 177 dtex of para-aramid fiber supplied from another direction is provided at the center thereof (cotton count 3).
0s / 1). When twisting is applied downstream by a ring method, the flattened cotton fiber is wrapped around the spun yarn of para-aramid fiber, and when this is wound up, a two-layer structure yarn is obtained. Table 1 shows the yarn physical properties.

[0029]

[Table 1]

Commercially available 100% cotton spun yarn b for indigo dyeing by yarn dyeing, and commercially available 100% cotton for weft yarn
A spun yarn c was prepared. Table 2 shows the contents.

[Table 2]

Using these, a density of 72 × 52 (lines / 25 m
m), 3/1 twill woven fabric was woven. Fabric A
A warp yarn b (100% cotton) and a weft yarn a (para-aramid core-sheath yarn) were used. The proportion of para-aramid in the whole fabric is 10%. The warp yarn of the woven fabric B is the same as the woven fabric A, and the weft yarns are a (aramid core-sheath yarn) and c (100% cotton)
Are alternately used, and the proportion of para-aramid fibers in the entire woven fabric is 4.5%. The woven fabric C has a warp yarn b,
Because we used c for weft, warp, weft both cotton 100%
It is.

Comparing the tear strength of these woven fabrics, warp yarns are all made of cotton, so that the woven fabrics A, B, C
There is no difference between them, but the tear strength of the weft is 100% cotton
The woven fabrics A and B are about 2.5
And the effect of improving the tear strength by using para-aramid is remarkable. Further, as can be seen from the woven fabrics A and B, even when the para-aramid core-sheath yarn and the cotton yarn are used alternately, the ratio of the effect of improving the tear strength is almost equal. Table 3 shows the contents of the woven fabrics A, B, and C.

[0033]

[Table 3]

The amino-modified silicone emulsion treatment of the fabric was performed as follows. Reactive amino-modified silicone emulsion manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
-1397) to prepare an emulsion having a pure content of 3%, and the woven fabric was immersed in the emulsion and lightly squeezed with a mangle (rubber roll) to obtain an emulsion pickup amount of about 95% of the weight of the woven fabric. Next, transfer this fabric to a tenter,
Was dried with a hot air for 5 minutes, and then heated in a similar tenter with a hot air at 150 ° C. for 3 minutes to crosslink and cure the resin. The fabric (treated fabric) thus treated with the reactive amino-modified silicone emulsion and the fabric (untreated fabric) before the treatment are washed by the above method,
The tear strength was measured. As a detergent, a weak alkaline detergent (Attack manufactured by Kao Corporation) was used.

Example 1, Comparative Example 1 Table 4 shows the results of measuring the tear strength of the woven fabric A (unit: N = Newton).
(): Tearing strength retention rate against 0 washes (%)
Is shown.

[Table 4]

Focusing on a weft thread cutter having a high tear strength due to the use of para-aramid, the amino-modified silicone untreated cloth of Comparative Example 1 has a tear strength retention rate of 63.7% after 10 washes. On the other hand, the amino-modified silicon-treated cloth of Example 1 has a high tear strength retention rate of 83.8% after washing 10 times, and the effect of the amino-modified silicon treatment is remarkable.

Example 2, Comparative Example 2 The results of measuring the tear strength of the woven fabric B (unit N = Newton) are shown in Table 5.
(): Tearing strength retention rate against 0 washes (%)
Is shown.

[Table 5]

The amino-modified silicone untreated cloth of the woven fabric B of Comparative Example 2 has a tear strength retention rate of 51.0 after washing 10 times.
On the other hand, the amino-modified silicone-treated cloth of Example 2 has a tear strength retention rate of 66.5 after 10 washes, whereas 0%.
%, The tear strength after washing is higher than that of the untreated cloth, and the effect of the amino-modified silicon treatment is remarkable.

Comparative Examples 3 and 4 Results of measuring the tear strength of the woven fabric C (unit: N = Newton).
The tear strength retention rate (%) with respect to the number of times is shown.

[Table 6]

The amino-modified silicone untreated cloth of the woven fabric C of Comparative Example 3 had a tear strength retention of 88.times. After 10 washes.
At 2%, the amino-modified silicone-treated cloth of Comparative Example 4 had a tear strength retention of 95.0% after 10 washes.
The percentage of improvement in tear strength after washing is lower than that of untreated cloth. In Comparative Example 4, the tear strength retention rate after 10 washes was as high as 95% by weft cutting, but the tear strength was 5%.
It is only 4.9N.

The woven fabric C used in Comparative Examples 3 and 4 uses 100% cotton yarn having a lower tensile strength than the Kevlar core-sheath yarn as the weft yarn, and originally has a low tear strength even though no para-aramid fiber is used. There is no point in treating amino-modified silicon. On the other hand, in Examples 1 and 2, the Kevlar core-sheath yarn having a high tensile strength was used for the weft yarn, so that the tear strength (weft cut) after washing 10 times was 122.5 (N), respectively.
It is as high as 97.1 (N). As in Comparative Example 1, no significance can be found even when amino-modified silicon treatment is applied to a fabric originally having low tensile strength.

Examples 3 and 4 Para-aramid fiber (trade name: Kevlar (R) 29) manufactured by Dupont Toray 100%
Table 7 shows the woven structure of the filament woven fabric D and the spun yarn woven fabric E.

[Table 7] However, the 295 (dtex) double yarn is a combination of two 295 (dtex) yarns.

These fabrics were treated with amino-modified silicone emulsion in the same procedure as in Example 1, and then washed. The detergent was dried using a weak alkaline detergent (New beads manufactured by Kao Corporation), and then the tear strength of the woven fabric was measured. Since the woven fabrics D and E are 100% para-aramid woven fabrics and have high tear strength, JIS L 1096.
The tear strength specified in 6.15.2 was measured by the A-1 method (single tongue method). Table 8 shows the results of measuring the tear strength of the amino-modified silicone untreated cloth of Comparative Example 5 para-aramid filament woven fabric D before and after washing.
Fig. 7 shows the results of measuring the tear strength of the amino-modified silicon-treated cloth of the filament fabric D before and after washing.

Table 9 shows the results of measuring the tear strength of the amino-modified silicone untreated cloth of Comparative Example 6 para-aramid spun yarn fabric E before and after washing, and Example 4 shows the results of the amino-modified silicon-treated cloth of the same spun yarn fabric E. 4 shows the results of measuring the tear strength before and after washing. In both cases, the tear strength retention of the para-aramid fabric after the amino-modified silicone emulsion treatment after washing was higher than the tear strength retention of the untreated fabric after washing, and a remarkable improvement in tear strength was observed. .

[0045]

[Table 8]

[0046]

[Table 9]

[0047]

Industrial Applicability According to the present invention, a high-performance fiber woven fabric having improved washing resistance can be industrially easily produced.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Takeshi Hatano 3-4-1-18 Nakanoshima, Kita-ku, Osaka-shi, Osaka Toray Dupont Co., Ltd. Osaka Head Office (72) Inventor Yasuji Morikawa Shinichi-machi Tote, Ashiya-gun, Hiroshima Prefecture 886-1 Morikawa Twist Yarn Co., Ltd. (72) Inventor Yoshiyuki Nojima 2-24-26 Minamitejo-cho, Fukuyama-shi, Hiroshima F-term (reference) 4L033 AA08 AB01 AB02 AB05 AC15 CA64

Claims (8)

[Claims] 1. A woven fabric comprising amino-modified silicon and comprising high-strength functional fibers as at least a part of the fiber composition. 2. The woven fabric according to claim 1, wherein the woven fabric is treated with amino-modified silicone before, simultaneously with or after weaving. 3. A single fiber tensile strength of 10 cN / dtex.
(Centinewton / Decitex) The amino-modified silicon is added to the fabric using high-strength functional fiber,
The woven fabric according to claim 1 or 2, wherein after drying, the fabric is heated to form a crosslinked amino-modified silicon on the fiber surface. 4. The method according to claim 1, wherein the content of the amino-modified silicon is 0.01 to 10% by weight based on the weight of the woven fabric.
The woven fabric according to any one of the above. 5. The woven fabric according to claim 1, comprising 3% or more of the high-strength functional fiber in the entire woven fabric. 6. The woven fabric according to claim 1, wherein the high-strength functional fiber is a para-aramid fiber. 7. The woven fabric according to claim 1, wherein the para-aramid fiber is a polyparaphenylene terephthalamide fiber. 8. The high-strength functional fiber has a double structure in which the high-strength functional fiber itself is a core and the light-resistant fiber is a sheath. The woven fabric according to item 1.