JPH1143867A - Fiber materials for jeans - Google Patents

Abstract

(57) [Abstract] [Problem] An aurushi that can be worn in the middle of summer or in the middle of winter while utilizing the characteristics of conventional jeans with good touch and texture, and that does not cause water to splash even when wet with water. -To provide a fiber material for jeans comprising a cellulosic fiber material of the dung type. A JIS-based water repellent is treated by JIS.
-Measurement of water absorption by the L-1096-B method shows that the water absorption ratio of the untreated fiber material is 10 to 90%;
It is 1 based on the measurement of water absorption according to the IS-L-1096-A method.
It is a fiber material for jeans provided with water repellency of 0 seconds or more.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fiber material for jeans, and more particularly, to a girth material which is preferably used for an orgasm type which does not become stuffy in the middle of summer and does not feel cold in the middle of winter. The present invention relates to a fiber material for wine.

[0002]

2. Description of the Related Art Conventionally, fiber materials for jeans include cotton,
Cellulose fiber materials such as rayon are used. For example, indigo blue jeans known as a so-called typical jeans color in which these fiber materials are dyed with an indigo dye or the like are provided.

[0003] However, when these genes are worn in the summer, they become stuffy, sticky, and produce odors due to absorbed sweat.
Since it is cold and poor in heat retention when worn in midwinter, it is often not worn in midsummer and midwinter. In addition, the conventional jeans have a drawback that they are inferior in fashionability as a result of impairing their appearance because they are easily stained when wet with water and hard to dry. Furthermore, in the case of a typical blue-colored gene, conventionally, a normal dyeing hardly produces a bluish blue,
In addition to the above problems, there has been a particular need for a fiber material for jeans having a bluish blue final dyeing because it tends to become reddish blue.

[0004]

SUMMARY OF THE INVENTION Accordingly, the inventions according to the first to third aspects of the present invention have the advantages of the conventional jeans having water absorbency and good touch and texture while utilizing the features of the conventional jeans. Which can be worn in the middle of the summer or in the middle of winter, and dries easily even when wet with water and does not cause stains.
An object of the present invention is to provide a fiber material for lucidity type jeans. In addition to the objects of the invention described in claims 1 to 3, the final dyeing and coloring is bluish blue. Of an all-season type cellulose fiber material having
It is an object of the present invention to provide a fiber material for a lens.

[0005]

To achieve the above object, as a result of intensive studies, it has been found that the disadvantage of wearing jeans in midsummer or midwinter is the water absorption of cellulose fiber material. Attention was paid to the fact that the water repellent treatment, which was not considered to impair the properties of the gene so far, was considered to impair the properties of the cellulose. The present inventors have found that the above-mentioned drawbacks of the jeans can be improved while making use of the features of the conventional jeans having good properties and good touch and texture, and completed the present invention. That is, the invention according to claim 1 of the present invention provides JIS-L-1 by treatment with a fluorine-based water repellent.
According to the measurement of water absorption by the 096-B method, the water absorption of the untreated fiber material was 10% to 90% and JIS-L
This is a fiber material for jeans which has a water repellency of 10 seconds or more as measured by water absorption according to the -1096-A method.
Here, the measurement based on JIS-L-1096-A method (hereinafter, simply referred to as method A) refers to JIS-L-1096-A.
It is not a measurement of the time (seconds) until the water droplets on the test piece no longer undergoes special reflection in the method, but a measurement of the "time (seconds) until the water drops on the test piece are completely absorbed visually." It is.

The fiber material used in the present invention is not particularly limited as long as it is a cellulose fiber material. Here, cellulo
The cellulosic fiber material is meant to include not only a material composed of 100% cellulose fibers but also a material in which cellulose fibers are partially present. Therefore, not only materials consisting of cellulose fibers such as cotton, hemp, rayon, cupra, polynosic, etc., but also these cellulose fibers and other fibers (semi-synthetic fibers such as acetate, synthetic fibers, etc.) )), And fiber products made of a mixed woven fabric by using them for part or all of the warp and weft. As a water repellent,
Paraffin-based, silicon-based, fluorine-based, etc. are known, but paraffin-based has insufficient durability and silicon-based has a slimy feeling and is not suitable, but fluorine-based has no these disadvantages and is suitable. It is.

[0007] The fluorine-based water repellent used in the present invention is not particularly limited as long as it is generally called a fluorine-based water-repellent, but is usually of the general formula (1): CH ₂ = C (R ₁ ). CO
O (R ₂ ) _m R _f (where R _f is a linear or branched polyfluoroalkyl group having 3 to 20 carbon atoms, R ₁ is a hydrogen atom or a methyl group, and R ₂ is a C 1 to C 10 carbon atom) linear or branched alkylene group, m is represented by 0 or 1) acrylate - Tomonoma - or Metaakurire - Tomonoma - of preferably a polymer, in particular the number of carbon atoms of R _f 6 to 1
2, a monomer polymer in which R ₂ has 2 to 4 carbon atoms and m is 1 is preferable. The following are examples of specific monomers.

CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ OCOCH = CH ₂ , CF ₃ (CF ₂ ) ₄ CH ₂ OCO (CH ₃ ) = CH ₂ (CF ₃ ) ₂ CF (CF ₂ ) ₆ (CH ₂ ) ₃ OCOCH
= CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₈ (CH ₂ ) ₃ OCOCH
= CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₁₀ (CH ₂ ) ₃ OCOCH
_{= CH 2, CF 3 (CF} 2) 6 (CH 2) 2 OCOC (CH 3) =
CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₅ (CH ₂ ) ₂ OCOCH
= CH ₂ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₄ OCOCH = CH ₂ , CF ₃ (CF ₂ ) ₆ OCOCH = CH ₂ , H (CF ₂ ) ₁₀ CH ₂ OCOCH = CH ₂

Further, specific examples of monomers containing a polyfluoroalkyl group include the following.

The fluorine-based water repellent used in the present invention comprises these polyfluoroalkyl group-containing monomers, -OH,-
It may be a copolymer with the following monomer containing an active hydrogen group such as NH ₂ or —COOH. For example, the general formula (2); CH ₂ ＣC (R ₁ ) COO— (R ₂ O) _n −
H (where R ₁ is a hydrogen atom or a methyl group, R ₂ is a divalent alkylene group having 2 to 6 carbon atoms, n is 0 or 1
An unsaturated carboxylic acid such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, crotonic acid, or an alkylene oxide adduct of such an unsaturated carboxylic acid; That is, C
H ₂ ＣC (CH ₃ ) COO (CH ₂ CH ₂ O)
_{1 ~ 2 H, CH 2 =} C (CH 3) COO (CH 2 CH 2
_{O) 6 ~ 9 H, CH} 2 = C (CH 3) COO (CH 2 C
H (CH ₃ ) O) ₁₀ H,

General formula (3); CH ₂ ＣC (R ₁ ) CONH
-A-OH (wherein R ₁ is a hydrogen atom or a methyl group, and A is a divalent alkylene group or a phenyl group), and specific examples thereof include N-methylolacrylamide. , OH group-containing acrylamides such as N-ethanolacrylamide,

General formula (4); CH ₂ ＣC (R ₁ ) CONH
-A-NHR ₂ (wherein, R ₁ is a hydrogen atom or a methyl group, A is a divalent alkylene group or a phenyl group, and R ₂ is a hydrogen atom or an alkyl group). As a specific example, CH ₂ ＣＨCHCONHCH ₂ C
H ₂ NHCH ₃ .

The polyfluoroalkyl group-containing monomer and the copolymer of the polyfluoroalkyl group-containing monomer and the active hydrogen group-containing monomer may further include other monomers including the following general monomers:
May be copolymerized. For example, ethylene, vinyl acetate, vinylidene chloride, vinyl fluoride, acrylamide,
Methacrylamide, styrene, α-methylstyrene, p
-Alkyl esters of methyl styrene, acrylic acid or methacrylic acid, benzyl acrylate or methacrylate, vinyl alkyl ether, halogenated alkyl vinyl ether, vinyl alkyl ketone, cyclohexyl acrylate or methacrylate G, maleic anhydride, butadiene, isoprene, chloroprene, general formula
(5); CH ₂ ＣC (R ₁ ) COO- (R ₂ O) _n -R ₃
(However, in the formula, R ₁ and R ₃ represent a hydrogen atom or a methyl group,
₂ is a divalent alkylene group having 2 to 4 carbon atoms, and n is 1 to 5
(An integer of 0).

In this case, vinyl acetate or the like is copolymerized with a monomer containing a polyfluoroalkyl group, and the resulting copolymer is hydrolyzed.
OH) and a fluorine-based water repellent containing a polyfluoroalkyl group. Further, as the fluorine-based water repellent, although not a polymerizable monomer, the following compounds containing both a polyfluoroalkylene group and an active hydrogen group in the molecule are also employed.

[0015]

Embedded image (Where R _f is a linear or branched polyfluoroalkyl group having 3 to 20 carbon atoms, R ₁ is a linear or branched alkyl group having 1 to 10 carbon atoms, R ₂ is hydrogen or A lower alkyl group, m is 0 or 1, n is an integer of 0 to 50, and R ₃ is an alkylene group having 2 to 6 carbon atoms).

In the present invention, the water absorption is determined by measuring the water absorption by the method B so that the water absorption ratio to the untreated fiber material is 10% to 10%.
90%, preferably 30% to 80%,
More preferably, it is 30% to 60%. 10% water absorption
If it is less than 90%, the characteristics of the jeans, such as the touch and texture, are impaired. If it exceeds 90%, the wearer gets stuffy and sticky in summer, produces an odor due to absorbed sweat, and feels cold in winter. Here, the "untreated fiber material" used as a reference for the water absorption measurement of the present invention refers to a so-called dyed fiber material for a jeans, and the "water absorption ratio to the untreated fiber material" refers to an untreated fiber material. The ratio (%) of the water absorption (mm) by the method B of the fluorine-based water repellent treated fiber material when the water absorption by the method B of the treated fiber material is 100 mm.

In the present invention, the water repellency needs to be at least 10 seconds as measured by the method A, preferably at least 30 seconds, more preferably at least 110 seconds. Water repellency is 1
If the time is less than 0 seconds, if water adheres to the gene, the stain is caused by the water, and it is hard to dry, which impairs the appearance. The upper limit of the water repellency is not limited as long as the water repellency is at least 10 seconds as long as the water absorbency is within the above numerical range.

The fiber material for cellulosic jeans formed in this manner is appropriately controlled in water absorption and exhibits water repellency, so that the feel and feel of the conventional jeans are good. While taking full advantage of this feature, it does not produce odor due to sweat, stickiness and absorbed sweat even when worn in the middle of summer, it does not feel cold even when worn in the middle of winter, it is rich in heat retention, and it is wet with water Can also provide a gene that repels the water well and dries easily so that the part does not stain.

The amount of adhesion of the fluorine-based water repellent may be as defined in claim 2.
As described in the invention described above, 0.01% by weight to
It is preferably 0.60% by weight. This is because the range of the attached amount is preferable for achieving the water absorbency and the water repellency described in claim 1. In addition, more preferably, it is 0.10% by weight to 0.30% by weight.

In order to improve the durability of the water repellent adhered by the treatment with the fluorine-based water repellent and to maintain the water absorption and water repellency in the predetermined range for a long period of time, as in the invention according to claim 3, It is preferable to add a crosslinking agent treatment to the water repellent treatment. Here, the addition only needs to include a crosslinking agent treatment, and includes not only a simultaneous treatment with a water repellent treatment but also a pre-treatment and a post-treatment thereof. In particular, the -OH, -NH _2, -COO
When a fluorine-based water repellent comprising a copolymer with an active hydrogen group-containing monomer such as H is used, suitable crosslinking agents include:
The following can be exemplified.

(1) Polyfunctional isocyanate compound The polyfunctional isocyanate compound is not particularly limited as long as it has two or more functional groups. For example, aromatic isocyanates such as 2,4-tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, tolidine isocyanate and dianisidine diisocyanate, 2-methylcyclohexane Alicyclic diisocyanates such as -1,4-diisocyanate, isophorone diisocyanate and hydrogenated MDI, and aliphatic isocyanates such as hexamethylene diisocyanate and decamethylene diisocyanate
And bifunctional isocyanate compounds such as

[0022]

Embedded image

The bifunctional isocyanate compound is represented by the general formula OC
If represented by NY-NCO, OCN-Y-NHC obtained by reacting OCN-Y-NCOs with each other in the presence of water
Dimers such as OY-NCO are also included in the bifunctional isocyanate compounds. In addition to difunctional, polyfunctional isocyanate such as trifunctional, tetrafunctional or pentafunctional may be used. The dimer OCN-Y-NHCO-Y-NCO and the monomer OCN
Trifunctional trimers obtained by reacting with -Y-NCO and trifunctional tetramers obtained by reacting dimers with each other are also suitable crosslinking agents. Other trifunctional isocyanate compounds include

Embedded image is exemplified. These crosslinking agents may be so-called blocked isocyanates blocked with compounds such as sodium acid sulfite, dimethyl malonate, and methyl ethyl ketone oxime, as long as they regenerate isocyanate groups upon heating. No problem.

(2) Ethyleneimine compound

Embedded image A compound having two or more functional groups represented by
For example, the following are exemplified.

[0025]

Embedded image

When such a treatment with a cross-linking agent is added, the fluorine-based water repellent having an active hydrogen group and the OH group of cellulose are strongly bonded via the cross-linking agent. It is possible to improve the washing resistance of the prepared fiber material for jeans, and it is possible to sufficiently maintain the water absorption and water repellency in the above-mentioned predetermined range even after several tens of selections.

A reddish-blue dyed fiber material for jeans has a bluish blue final dyeing color.
In order to easily obtain a fiber material for a lens, the water-repellent agent treatment according to claims 1 and 2 or the water-repellent agent / crosslinking agent treatment according to claim 3 requires copper-containing. Fixing agent treatment may be added. Here, the addition means that the copper-containing fixing agent treatment is added to the water-repellent agent treatment according to claims 1 and 2 or the water-repellent agent / crosslinking agent treatment according to claim 3. 3 includes, of course, pre-processing and post-processing of these processes.

Examples of dyes for dyeing the cellulose-based fiber material for reddish blue include indigo dyes, direct dyes, and reactive dyes. The copper-containing fixing agent is not particularly limited as long as it is generally called a copper-containing fixing agent, and examples thereof include a copper-containing polyamine condensate (polyethylene polyamine type).
By forming in this manner, the fixing agent binds the dye or the fluorine-based water repellent to the fiber material through the fixing agent, and the blue copper ions act to cure the reddish blue dye. The fiber material is dyed bluish blue.

[0029]

BEST MODE FOR CARRYING OUT THE INVENTION A twill fabric for jeans made of cellulose fibers such as cotton, hemp, rayon, cupra, polynosic, etc. is immersed in a fluorine-based water repellent solution or The solution is sprayed or padded onto the woven fabric, and a fluorine-based water repellent of 0.1% to 0.3% by weight in terms of solid content is attached. The amount of the water repellent adhered in this range can be obtained by a known method of adjusting the amount of the treated agent by adjusting the solution concentration of the treating agent and / or the immersion time, the spray amount or the pad amount. As the water repellent, a copolymer of the fluoroalkyl group-containing monomer is preferably used. The solution is preferably a dispersion or emulsion using water as a medium, and the concentration of the water repellent is not particularly limited, but is usually 10% to 30%. The solvent need not be limited to the above aqueous system, but may be acetone, toluene, 1, 1, 1
-It may be a solvent such as trichloroethane.

The water-repellent-treated fabric obtained in this manner has a water absorption ratio of 30% to 80% with respect to the untreated fiber material in the water absorption measured by the method B and a water absorption measured by the method A. Shows water repellency of 30 seconds or more. As a result, the gene made of this material is moderately controlled in water absorbency, so that it does not humid in summer and does not feel cold in winter without impairing the characteristics of conventional jeans. −
Dung type. Further, since water repellency is imparted, even if a part is wet with water, the part does not stain.

A twill woven fabric for cellulose comprising cellulose fibers is prepared by mixing a copolymer of the fluoroalkyl group-containing monomer and the active hydrogen group-containing monomer with the polyfunctional isocyanate compound as a crosslinking agent. (A blending ratio of the copolymer and the polyfunctional isocyanate compound is usually 45/55 to 99/1, preferably 80/20 to 90 by weight ratio.)
/ 10. If, after the treatment such as the immersion and drying described above is carried out and the heating treatment is further performed, the water repellent is firmly bonded to the fibers by the crosslinking agent. As a result, the washing resistance of the water repellent is improved.

The copper-containing fixing agent is treated with an indigo dye,
Direct dyes, dyed reddish blue with a reactive dye, a cellulose twill woven fabric for jeans, obtained by mixing the fluoroalkyl group-containing monomer copolymer with the copper-containing polyamine condensate After the treatment such as immersion with the mixed aqueous dispersion, heating and drying may be performed. In this case, the mixing ratio of the copolymer and the copper-containing polyamine condensate is a molar ratio,
Usually 20/80 to 90/10, preferably 40/80
60-80 / 20. In this way, a bluish blue can be realized from a reddish blue.

[0033]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples. The present invention is not limited to these. Example 1 Cotton denim was placed in a 1% aqueous solution of a copolymer of a fluoroalkyl group-containing monomer (Asahigard AG-710, manufactured by Meisei Chemical Industry Co., Ltd., solid content concentration: 30%) at room temperature for 5 minutes. After soaking, squeezing with a mangle and draining, 140
Dry at 5 ° C. for 5 minutes. In this case, the adhesion amount of the water repellent to the cotton denim was 0.14% by weight in terms of solid content.

Example 2 Cotton denim was dispersed in a 0.5% aqueous dispersion of a copolymer of a fluoroalkyl group-containing monomer and a crosslinking agent (Aquaplay K manufactured by YAS & Co., Ltd., solid content: 28 %) At room temperature for 5 minutes, squeezed with a mangle to remove liquid, and dried at 140 ° C. for 5 minutes. in this case,
The amount of the water repellent attached to the cotton denim was 0.14% by weight in terms of solid content. Aqua Play K is (CF ₃ ) _{2
CF (CF 2) 6 CH 2} CH (OCOCH 3) OCOC
(CH ₃ ) = CH ₂ and CH ₂ ＣC (CH ₃ ) COOCH
₂ CH ₂ OH and terpolymers and tolylene diisocyanate with butyl esters of acrylic acid - DOO acidic sulfite source -
This is an aqueous dispersion mainly containing an adduct.

Example 3 A cotton yarn dyed on an indigo dye on a warp, a cotton denim woven using a bleached yarn on a weft, washed by a conventional method, and treated with a fluoroalkyl group-containing monomer. Aqueous dispersion of a polymer and a crosslinking agent (Aquaplay K, manufactured by YAS & Co., Ltd., solid content concentration: 1.
0%) and a water-dispersing agent of a copper-containing polyamine condensate (manufactured by Meisei Chemical Industry Co., Ltd., Capramine 700, solid content concentration: 1%) at 20 ° C. for 2 minutes and squeezed with a mangle. After draining, it was dried at 100 ° C. for 2 minutes. In this case, the adhesion amount of the water repellent to the cotton denim is 0.2% in terms of solid content.
7% by weight.

Comparative Example 1 The same cotton denim as used in Example 1 was dispersed in a 5% aqueous dispersion of a copolymer of a fluoroalkyl group-containing monomer and a crosslinking agent (Aqua, manufactured by YAS & Co., Ltd. (Prey K, solid content: 28%) at room temperature for 5 minutes, squeezed with a mangle to remove liquid, and dried at 140 ° C for 5 minutes. In this case, the adhesion amount of the water repellent to the cotton denim was 1.4% by weight in terms of solid content.

Comparative Example 2 The same cotton denim as used in Example 1 was dispersed in a 0.5% aqueous dispersion of a paraffinic water repellent (Neuzebran R-260, manufactured by YAS & Co., Ltd., solid (Concentration: 32%) at room temperature for 5 minutes, squeezed with a mangle to remove liquid, and dried at 140 ° C for 5 minutes. In this case, the adhesion amount of the water repellent to the cotton denim was 0.1% in terms of solid content.
It was 6% by weight.

In Examples 1 to 3 and Comparative Examples 1 and 2, including those after washing (L _O : no washing, L ₁₀ : number of washings: 10)
Times, L _30: Washing times 30 times), the results of the water repellency was measured by the measurement water-absorbing and A method by B method, be shown in Table 1. Here, the washing was performed according to the JIS-L-0217-103 method.

[0039]

[Table 1]

In the try-on tests of Examples 1 to 3 in which the water absorption was within a predetermined range (Table 1), in all of the fitting tests, the stuffiness in the middle of summer was not felt, and the stuff was felt warm even in the middle of winter. In this case, the characteristics of the cotton, such as the touch and the good feel, are maintained without being impaired. The water repellency was above a predetermined value, and even if a part of the film was wet with water, it was repelled and did not stain and did not impair fashionability. Comparative Example 1
Has a large amount of water repellent attached, so it is satisfactory in water repellency,
It was poor in water absorbency, the characteristics of cotton were impaired, and the feel and texture were poor. Further, as shown in Table 1, Example 2
Since a cross-linking agent is used in combination, the water-repellent agent is firmly bonded to the cotton, so that the washing resistance is improved as compared with Example 1 having no cross-linking agent. As shown in Comparative Example 2, the paraffin-based water repellent was remarkably inferior in washing resistance, and it was found that water absorption and
The water repellency was almost the same as that of untreated cotton denim (dyed). Furthermore, the cotton denim of Example 3 treated with the copper-containing fixing agent changed from reddish blue to bluish blue, which is generally preferred, and was close to the color tone of a dyed fabric dyed with natural indigo.

[0041]

As described above, the fiber materials for cellulose-based jeans according to the first to third aspects of the present invention are appropriately controlled in water absorption and exhibit water repellency.
While taking full advantage of the good feel and texture of conventional jeans, they do not produce odors due to stuffiness, stickiness and absorbed sweat even when worn in the middle of summer, and can feel cold even when worn in the middle of winter. It is possible to provide a gene which is highly heat-insulating and has good water repellency even when it gets wet and easily dries, because it is easy to dry. In particular, in the invention according to claim 3, since a treatment with a crosslinking agent is added, in addition to these effects, the fluorinated water repellent having an active hydrogen group and the OH group of cellulose are linked via the crosslinking agent. Because of the strong bonding, the washing resistance of the fiber material for jeans that has been treated with a fluorine-based water repellent can be improved.

According to the fourth aspect of the present invention, since the copper-containing fixing agent is added, the fixing agent acts, and in addition to the effects of the first to third aspects, a dye or a fluorine-based repellent is added. The liquid agent is fixed to the fiber material, and the blue copper ions act to dye the fiber material for jeans dyed reddish blue to bluish blue.

Claims (4)

[Claims] 1. JI by treatment with a fluorine-based water repellent
In the measurement of the water absorption by the SL-1096-B method, the water absorption ratio of the untreated fiber material was 10% to 90%, and the water absorption by the JIS-L-1096-A method was 10 seconds. A fiber material for jeans provided with the above water repellency. 2. The amount of the fluorinated water repellent adhered by the treatment with the fluorinated water repellent is 0.01% by weight to 0.60% by weight in terms of solid content.
The fiber material for jeans according to the above. 3. The fiber material for jeans according to claim 1, wherein a treatment with a crosslinking agent is added to the treatment with the fluorine-based water repellent. 4. A fiber material for jeans obtained by adding a copper-containing fixing agent treatment to the treatment according to claim 1, 2 or 3 for the fiber material for jeans dyed reddish blue.