JPH07324284A - Wool product - Google Patents

Abstract

PURPOSE:To obtain a wool product excellent in washing resistance and having good heat-insulating effect and light-resistant fastness by removing the cuticle layer on the surface of wool, uniformly applying a specific IR light-irradiating substance to the surface, and subsequently coating the product with a resin in the uniformly substance-distributed state. CONSTITUTION:An ion-modified far IR light-radiating substance, e.g. cation- modified TiO2, SiO2, ZnO2, ZnO, ZrO2, Al2O3 or SnO2, is uniformly bound to the surfaces of wool fibers modified into a good hydrophilic property by removing a part of the cuticle layer by an oxidation treatment using e.g. chlorine. The treated wool is coated with a polyamide epichlorohydrin having an azetidinium cation capable of being bound to the modified wool fibers to obtain the wool product excellent in washing durability not lost even after repeatedly washed, and excellent in heat-insulating effect and light-resistant fastness.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a wool product which has an excellent heat retaining property or, in addition, an excellent light fastness, and these effects are not deteriorated by repeated washing.

[0002]

2. Description of the Related Art Recently, new technologies utilizing far infrared rays have been developed in various fields, and even in the textile industry, clothing made of synthetic fibers or plant fibers with a far infrared radiating substance has a high heat retaining effect. Etc. are known to be obtained. However, if the far-infrared radiation substance is simply attached to the fiber, the far-infrared radiation substance will fall off as the laundry is washed, and the heat retaining effect will fade with time. Therefore, as a method for imparting washing durability to the heat retention effect, a urethane-based, silicone-based, urea-formalin-based suspension or solution containing a far-infrared emitting substance (hereinafter abbreviated as “a far-infrared emitting substance-containing liquid”) is used. Glyoxal-based, acrylic-based, epoxy-based, acetal-based resins, etc. are added and then applied to the fiber, and after dehydration and drying, the resin is crosslinked by the action of a catalyst or heat to form a resin film, and this resin emits far infrared rays. A method of confining a substance has been put into practical use. In this method, the resin used is acrylic, special silicone, polyacrylamide, special polyester, amphoteric surfactant, quaternary ammonium salt, alkyl phosphate, cationic polymer,
By appropriately selecting from water-soluble urethane, ether type nonionic, etc., various levels of washing durability can be obtained.

[0003]

It has been studied to impart the above-mentioned heat retaining effect to the wool fiber. However, wool fibers are naturally more hydrophilic than plant fibers, but their surface is covered with an epicuticle layer that has water repellency, so they have a low affinity for both hydrophilic and hydrophobic chemical substances, and they are water-based. A substance that forms a film on the surface of wool by treatment,
No resin has been found so far.

However, some resins have been found which do not form a film, but which adhere to the surface of the wool in a lump form and partially chemically bond with the wool fibers and which have durability against washing. For example Synthapp
Examples include retBAP (Synthlet BAP, manufactured by Bayer). These are applied only to the cloth, and by adhering to the fiber and drying and then curing, the cross-linking between the resins is promoted and the resin is lumped. This lump resin is used to bond wool fibers to each other, thereby preventing movement of wool fibers and preventing felt shrinkage during washing. It is conceivable to use a far-infrared emitting substance mixed with such a resin, but the resin should be suitable for the special property of wool fiber, which has a poor affinity for both hydrophilic and hydrophobic chemical substances. Since the affinity is imparted by the special structure, when the far-infrared emitting substance is mixed, the affinity is impaired and the durable attachment to the wool fiber is not exhibited. Therefore, this becomes a bottleneck, and one having excellent washing durability cannot be put into practical use.

Further, when the surface of the wool is modified to be hydrophilic, various resins such as water-based silicone, urethane, polyester, etc. can be applied in the same manner as in the case of the synthetic fibers or vegetable fibers, and these can be emitted with far infrared rays. It seems that the far-infrared radiation substance can be fixed to the fiber surface by mixing the substances and applying the mixture to the wool to form a resin film on the fiber surface. However, since wool fibers are weak against alkali and high temperature, it is not possible to set strong queuing conditions like the above synthetic fibers and vegetable fibers, so that the cross-linking of the resin is insufficient and the washing resistance is low. I can only get things.

Further, among the far infrared emitting materials,
There are some such as ZnO ₂ , ZnO, and Al ₂ O ₃ which are used in cosmetics because they reflect ultraviolet rays and help prevent sunburn. Therefore, in particular, if a far-infrared radiation substance and a substance having a high ultraviolet reflection effect can be applied to the fiber surface of wool, the light fastness, which is a weak point of wool, is improved, and the fading of the dye and the yellow of the fiber itself are improved. It is expected that the color change can be prevented and bright colors and pastel colors can be realized. However, this has not been put to practical use for the same reason as above.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a wool product which is excellent in heat retention property or, in addition, light fastness and fastness, and which is excellent in washing resistance. To do.

[0008]

In order to achieve the above-mentioned object, the wool product of the present invention has a surface of wool fiber from which at least a part of the cuticle layer on the surface has been removed, and an ion-modified far-infrared radiation substance The resin is coated in a distributed state.

[0009]

In other words, the inventors of the present invention have conducted research from various directions on a method of imparting a durable heat-retaining effect to wool fibers, and as a result, damaged or removed the cuticle layer on the fiber surface of wool to When the number of active anion groups is increased, and the cation-modified far-infrared emitting substance is fixed thereto by ionic bond, and further, it is coated with a polyamide epichlorohydrin resin capable of covalently bonding with wool fiber, the cation-modified far-infrared emitting substance is Far-infrared radiation because it is ionically bonded to the anionic groups of the wool fiber in a state of being uniformly dispersed on the fiber surface and directly fixed, and in that state is covered with a polyamide epichlorohydrin resin film that is firmly bound to the wool fiber by covalent bonding. It was found that the substance does not fall off the fiber surface and exhibits excellent wash resistance, It has been reached. Further, among the above far-infrared radiation materials, it is found that when a material having a particularly high ultraviolet reflection effect is used, a wool product excellent not only in heat retention but also in light fastness is obtained, and its application is expanded. I understood.

Next, the present invention will be described in detail.

The wool product to which the present invention is applied refers to various forms of fiber products such as sliver, loose fibers, yarns, woven fabrics and knitted fabrics formed from wool fibers.

The wool product of the present invention is obtained by processing the fiber surface of the above-mentioned wool fiber product in the following steps (1) to (3), for example, to which a far-infrared emitting substance is applied.

(1) Modification of wool fiber surface

Oxidation of chlorine or oxygen produces anions and / or cations on the surface of the wool fiber to impart hydrophilicity. That is, the outermost layer of the wool fiber surface epicuticle layer is damaged or eluted to remove the water repellency of the wool fiber surface, and the intermediate layer exoicle layer is also damaged to give anion to the wool fiber surface. , Generates cations and makes the surface hydrophilic to the same extent as the innermost layer, the endicle layer. Usually, the exoicle layer is less hydrophilic than the endocuticle layer, and the bimetal action resulting from this difference causes the cuticle layer to curl up in water and entangle the fibers, resulting in a felting phenomenon. Therefore, if the hydrophilicity of both layers is set to the same level as described above, the above-described felting is eliminated and the wettability of the fiber surface is significantly improved.

As a method of performing the above chlorine or oxygen oxidation, for example, a method of performing chlorine oxidation (usually referred to as "chlorination") using a known Chloe processing machine can be mentioned. This method uses chlorine gas or hypochlorous acid (Na
OCl) and the like to destroy cystine and peptide bonds on the surface scale of wool fiber to generate ions,
It is well known as a shrink-proofing method for wool products. In the present invention, when performing the above-mentioned chlorine oxidation, it is preferable to set the effective chlorine amount to 1 to 6% owf (weight relative to fiber weight, the same applies hereinafter). The chemical changes on the surface of the wool fiber caused by such an oxidation reaction will be described.

Oxidation of cystine

[0017]

[Chemical 1]

Cleavage of peptide bonds

[0019]

[Chemical 2]

Degradation of cystine by sulfite

[0021]

[Chemical 3]

By such a modification treatment, an anion group and a cation group are generated on the surface of the wool fiber, the ionic binding ability is increased, and the wettability is improved. By the way,
The critical surface tension of ordinary wool fiber is 40 to 45 dyne / cm, but the critical surface tension is 55 dyne / cm by the above modification.
It can be increased to above. Therefore, in the present invention, when a resin film described below is formed, a special resin having a critical surface tension of the above value or less is used, and the resin is sufficiently diffused on the wool surface to form a uniform and strong resin film. This is a major feature of the present invention.

The modification treatment can be applied to any form of wool product such as sliver, loose wool, yarn, woven fabric, and knitted fabric.

(2) Binding of cation-modified far-infrared emitting material to the surface of wool fiber

Ion-modified, for example, cation-modified far-infrared emitting material is supplied to the wool modified as described above, and the cation-modified far-infrared emitting material is ionically bonded to the anion groups on the surface of the wool fiber. As a result, the cation-modified far infrared ray emitting substance is directly and firmly fixed to the fiber surface. Moreover, since the far-infrared-emitting substance is bonded in a state where the far-infrared emitting substance is uniformly dispersed where the anionic groups are present on the fiber surface, the distribution of the bonded silica particles is not biased.
This is a great feature of the present invention. This binding reaction
For example, it can be carried out by reacting a cation-modified far-infrared emitting substance-containing liquid in the same manner as dyeing a wool product such as a sliver with a package. The cation-modified far-infrared emitting substance-containing liquid is a dispersion liquid or an aqueous solution in which the cation-modified far-infrared emitting substance is dispersed in a dispersion medium such as water in a suspended state or a sol state. As such a cation-modified far-infrared emitting substance-containing liquid,
Examples thereof include commercially available cation-modified zirconia oxide solution (PCY-1, manufactured by Nikko Chemical Research Co., Ltd.) and cation-modified aluminum oxide solution (PCY-2, manufactured by Nikko Chemical Research Co., Ltd.). The cation-modified far-infrared radiation material means TiO ₂ , SiO ₂ , ZnO ₂ , ZnO, Zr.
A far-infrared emitting substance such as O ₂ , Al ₂ O ₃ , and SnO ₂ is cation-modified, and in particular, when it is desired to improve the light fastness of the product, ZnO ₂ and ZnO having a high ultraviolet reflection effect among them are used. , ZrO _{2 and the} like are preferably used. These may be used alone or in combination of two or more. Further, different types of cation-modified far infrared ray emitting substance-containing liquids themselves may be mixed and used.

However, the particle size of the far-infrared emitting material used is 100 mμ (millimicron) or less, particularly 5 to 50 m.
It is preferable to set it to about μ. That is, if the particle size is too small, there is a problem in the stability of adsorption to the wool, and conversely, if the particle size is greater than 50 mμ, the feeling of coarse and rigid becomes strong and the far-infrared radiation substance tends to easily separate from the wool fiber surface. Because it will be done. In addition, the blending amount of far-infrared radiation material with respect to wool fiber is 0.1 to 3.0% owf,
In particular, it is optimal to set 0.4 to 2.0% owf. Within this range, a particularly preferable heat retention effect or excellent light fastness can be obtained.

(3) Packing and fixing of cation-modified far-infrared radiation substance by resin

Polyamide epichlorohydrin resin capable of covalently bonding to the hydrophilic modified wool fiber is supplied to the wool to which the cation-modified far infrared emitting material is bound as described above, and the far infrared emitting material together with the wool fiber. A resin film for coating the surface is formed to coat the outside of the far-infrared radiation substance and fix it on the surface of the wool fiber. Since the resin film is strongly integrated with the fiber surface by the covalent bond, the far-infrared radiation substance is firmly fixed. The thickness of the resin film to be formed is preferably 15 to 150 mμ, particularly about 100 mμ. In order to achieve the above thickness, the content of the polyamide epichlorohydrin resin used is 0.3 to 3.0% owf, especially 0.6.
It is preferable to set to ˜2.0% owf.

The polyamide epichlorohydrin resin has an azetidinium cation and is water-swellable.

The azetidinium cation is a quaternary ammonium cation as shown below, and has a structure that easily forms a covalent bond with an anion group.

[0031]

[Chemical 4]

As a polyamide epichlorohydrin resin having such an azetidinium cation and having water swelling property, Hercoset 57 (manufactured by Dick Hercules, molecular weight 6000 to 10000), POLAMIN E-125, POLAMIN 300XC (both are available). Toho Kagaku KK, molecular weight 8000 to 11000) and the like.
The critical surface tension of these resins is about 50 to 54 dyne / cm, and the modified wool fiber (having a critical surface tension of 55
Good compatibility with dyne / cm or more). Then, the azetidinium cation present in the structure of these resins forms a strong covalent bond with the sulfonic acid group, the carboxyl group, etc. of the modified wool fiber shown below to form a highly durable resin film. Form.

[0033]

[Chemical 5]

[0034]

[Chemical 6]

Therefore, the cation-modified far-infrared emitting material is not wrapped in the resin film and is not easily dropped from the surface of the wool fiber, and its characteristics do not change even after repeated washing. Furthermore, since the resin itself is highly water-swellable, the resin absorbs water and swells during washing, and the wool fiber becomes sufficiently flexible in an aqueous system. Therefore, an unreasonable load is not applied to the fixed portion of the far infrared radiation material.

The binding of the cation-modified far infrared ray emitting substance and the filling and fixing of the far infrared ray emitting substance by the polyamide epichlorohydrin resin may be carried out in separate steps as described above, but may be carried out simultaneously.

The wool product thus obtained has a heat retaining effect which cannot be obtained by a usual wool product by fixing the far infrared ray emitting substance, and the heat retaining effect is not impaired even after repeated washing. Has features. Therefore, although wool products were originally unsuitable for washing with water, this wool product can be washed with water and is easy to handle. Further, when a far-infrared emitting substance having a high ultraviolet reflection effect is used, not only the above-mentioned heat retaining property is added, but also an excellent light fastness which is not obtained by conventional wool products is imparted. In other words, the dyed processed products of conventional wool products have light fastness standard 3 for bright colors and pastel colors.
Although there was a limit to securing the grade, ZnO ₂ , ZnO, ZrO ₂
And the like are added by the method of the present invention, the light fastness is improved, and the fastness standard 4 can be secured. Therefore, a brighter color can be maintained for a long period of time, and the outer garment can be highly fashionable.

Next, examples will be described together with comparative examples.

[0039]

Example 1 First, a wool sliver was subjected to chlorine treatment under the following conditions.

Effective chlorine amount: 2% owf processing machine: Chloy processing machine Processing temperature: 10 ° C

The properties of the wool sliver obtained by the above treatment were modified as shown in Table 1 below, before the treatment.

[0042]

[Table 1] *: Thread (2/48) and cover factor 0.41
The knitted knit was made into a plain cloth. Then, the washing shrinkage rate of this knit fabric was measured according to IWS Test Method TM185.

Next, the wool sliver is spun into 2
After making a / 48 worsted yarn, the usual package dyeing was performed. Then, using the package dyeing machine used for dyeing, subsequently, a cation-modified far-infrared emitting substance was bound to the surface of the wool fiber under the following conditions, and at the same time, a resin film was formed.

Treatment liquid: cation-modified zirconia oxide solution (PCY-1, manufactured by Nikko Chemical Laboratory) 2.0% owf polyamide epichlorohydrin resin solution (Harcoset 57, manufactured by Dick Hercules) Solid content converted 1. 0% owf Silicone-based softener 0.5% owf in terms of solid content Treatment temperature: 20 to 25 ° C. Treatment time: 20 minutes pH: Starting with weak acidity (pH 5.5 to 5.8) and finally neutrality ~ Finished with weak alkaline (pH 7.0-7.5)

After completion of the above treatment, blower dehydration was performed, and then a hot air dryer was used (90 ° C., 60 minutes) to obtain the target worsted yarn.

[0046]

Example 2 As a cation-modified far-infrared emitting material solution, a cation-modified aluminum oxide solution (PCY-2,
Using Nikko Chemical Laboratory's solid content conversion 2.0% owf),
The polyamide epichlorohydrin-based resin liquid was replaced with one having a solid content of 1.5% owf. And centrifugal dehydration (45
In the drying process after (00 rpm, 1 minute), a high frequency vacuum dryer (65 ° C., 45 minutes) was used instead of the hot air dryer. Except for this, the target worsted yarn was obtained in the same manner as in Example 1.

Using the two kinds of woolen worsted yarns thus obtained and untreated wool yarns (wool count 2/48), each knitted fabric (texture: double-sided) having the same specifications on the same knitting machine Smooth, basis weight: 350 g / m ² ) Then, a practical washing test (JIS 0217, 104 method) was performed on these, and the heat retention effect and texture after practical washing were evaluated. The heat insulation effect evaluation test was performed as follows.

<Heat-retaining effect test> The power consumption of the heater was measured by using Thermolabo Model 2 (manufactured by Kato Iron Works Co., Ltd.) while keeping the plate temperature at 36.5 ° C. Environment is 20 ℃ × 65% RH,
It was made calm. Therefore, the higher the heat retaining effect, the smaller the value.

The zircon content of the knitted fabric of Example 1 was measured by the atomic absorption method before and after the practical washing test.

On the other hand, each of the above worsted yarns was knitted into a plain cloth with a cover factor of 0.41, and IWS TM 1
The washing shrinkage rate was measured according to the 85 method (180 minutes, acceptance criterion: less than 10%).

The results are shown in Table 2 below.

[0052]

[Table 2]

From the above results, it can be seen that the product of Example has neither shrinkage nor texture even after repeated washing, and has a heat retention effect and washing durability.

[0054]

Example 3 First, a wool sliver was subjected to chlorine treatment under the following conditions.

Effective chlorine treatment amount: 5% owf treatment machine: Chloy processing machine Treatment temperature: 10 ° C

The properties of the wool sliver obtained by the above treatment were modified as shown in Table 3 below before the treatment.

[0057]

[Table 3] *: The measurement was performed in the same manner as in Table 1.

Next, the above wool sliver was spun, and package dyeing was carried out in the same manner as in Example 1. And
Using the package dyeing machine used for dyeing, the cation-modified far-infrared emitting material was subsequently bound to the surface of the wool fiber under the following conditions.

Treatment liquid: Cation-modified zirconia oxide solution (PCY-1, manufactured by Nikko Chemical Laboratories) Solid content conversion 2.0% owf 80% by weight formic acid 1.0% owf Treatment condition: 30 ° C. × 20 minutes

Next, resin processing was performed under the following conditions.

Treatment liquid: Polyamide epichlorohydrin-based resin liquid (Hercoset 57, manufactured by Dick Hercules) 2.0% owf in terms of solid content Treatment conditions: pH 5.5 to 5.8 at 30 ° C. for 20 minutes, pH adjustment The pH was adjusted to 7.0 to 7.5, and the treatment was continued at 30 ° C. for 15 minutes.

After the above treatment was completed, blower dehydration was carried out, and then a hot air dryer was used (90 ° C., 60 minutes) to obtain the target worsted yarn.

[0063]

[Example 4] The amount of effective chlorine in the chlorine treatment was set to 2% owf. Except for this, the target worsted yarn was obtained in the same manner as in Example 3 above. In this example, the degree of modification of the wool sliver at the stage of chlorine treatment is as shown in Table 4 below.

[0064]

[Table 4] *: The measurement was performed in the same manner as in Table 1.

[0065]

Comparative Example 1 A wool sliver was modified in the same manner as in Example 3 above, and resin processing was carried out in the same manner as in Example 3 without adding a cation-modified far infrared ray emitting substance.

[0066]

Comparative Example 2 The wool sliver was modified in the same manner as in Example 4 above, and the resin processing was carried out in the same manner as in Example 3 without adding the cation-modified far infrared radiation substance.

Products of Examples 3 and 4 and Comparative Examples 1 and 2
A blank dyed product and a dyed product dyed in red and blue were used by using an untreated product which was neither given a far-infrared emitting substance nor resin-processed.

Red: Lanasol Red 3G 0.05
% Owf Blue: Polar Brill.Blue GAW 0.05% owf (above, manufactured by Ciba Geigy)

The light fastness of these dyed products was measured according to JIS L0
It was measured according to the 842 method. In addition, the IWS test method T
Based on M185 (180 minutes), the felt shrinkage during washing was determined. The results are summarized in Table 5 below.

[0070]

[Table 5]

From the above results, the Example product is superior in light fastness to the Comparative Example product and the untreated product, and in the vivid hues of red and blue, it is difficult to achieve the level 4 in the conventional wool products. Has achieved light fastness.

[0072]

INDUSTRIAL APPLICABILITY As described above, in the wool product produced by the method of the present invention, the cation-modified far-infrared radiation substance is bound by the ionic bond on the surface of the wool fiber modified to have a critical surface tension of 55 dyne / cm or more. The critical surface tension is less than or equal to the value of the wool fiber, good compatibility with the fiber, and is fixed and covered with a special resin that is firmly integrated with the fiber by covalent bonding, so that it does not fall off by washing. . Therefore, even if washing is repeated, an excellent heat retention effect derived from the far-infrared radiation substance or an excellent light fastness derived from the ultraviolet ray reflection property is maintained for a long time, which is an effect that has not been realized in the past. .

Claims (3)

[Claims] 1. A wool product characterized in that the surface of a wool fiber from which at least a part of the cuticle layer on the surface has been removed is coated with a resin in a state in which an ion-modified far-infrared emitting substance is distributed. 2. The wool product according to claim 1, wherein the resin is a polyamide epichlorohydrin resin. 3. The far-infrared emitting material is TiO ₂ , SiO
₂ , ZnO ₂ , ZnO, ZrO ₂ , Al ₂ O ₃ and S
The wool product according to claim 1 or 2, which is at least one substance selected from the group consisting of nO ₂ .