JPH0726320B2 - Modified wool and its modification treatment method - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a modified wool that is less susceptible to yellowing, embrittlement, and the like due to light, and a method for modifying the same.

BACKGROUND OF THE INVENTION Generally, when wool is exposed to sunlight, it undergoes yellowing and embrittlement, and eventually decomposes. Such a deterioration phenomenon is largely due to photoradical decomposition of wool protein by ultraviolet rays in sunlight, and this decomposition reaction tends to be accelerated by heat.

Therefore, conventionally, as a means for preventing the above deterioration, raw wool (Greasy wool, Wached wool, Scoured wool)
Etc.) and processed wool (so-called shrink-proof processed wool such as surface-scale treated wool and descaled wool), in addition to basic treatments such as oxidative bleaching and reduction bleaching, addition of dye chemicals to fabric color or dye A method of previously reducing the degree of yellowing of light colors or pastel colors, a method of applying a so-called UV absorber such as benzophenone-based, triazole-based, hindered amine-based, metal complex-based, and a light stabilizer called an ultraviolet shielding agent, hindered A method of incorporating a phenol-based, hydrazine-based, phosphorus-based, or other antioxidant is used.

SUMMARY OF THE INVENTION However, none of the above-mentioned conventional deterioration preventing means has achieved a remarkable effect and cannot sufficiently prevent yellowing and embrittlement due to sunlight and ultraviolet rays. In particular, when wool is used in places where it is exposed to intense sunlight or heat such as fiber materials for automobile seats, deterioration is remarkable, and improvement in durability is a major issue. In addition, in light-colored or pastel-colored dyed fabrics, even if the type of dye and its light resistance are selected, the effect of yellowing of the wool itself is strongly exerted, and there is a problem in that early discoloration and fading is inevitable.

In view of the above situation, the present invention imparts strong light resistance to sunlight and artificial light without impairing the original wool properties,
Therefore, it is an object of the present invention to provide a modified wool having a significantly small degree of yellowing and embrittlement due to light and a method for modifying the wool.

Means for Solving the Problems The present invention, in order to achieve the above object, by containing a specific substance inside the wool fiber, imparts strong light resistance and deterioration such as yellowing and embrittlement over a long period of time. To prevent.

That is, the modified wool according to the present invention contains a water-soluble organic acid salt of an alkaline earth element or an aluminum group element, or an ionic compound of an alkaline earth element or an aluminum group element having an organic acid component adsorbed inside the wool fiber. In addition, the method for modifying the wool according to the present invention is characterized in that the wool is subjected to an internal modification treatment by dipping in a bath consisting of two steps of reduction-oxidation or three steps of oxidation-reduction-oxidation. After the solution is extracted and removed by applying, the wool is impregnated with a water-soluble organic acid salt of an alkaline earth element or an aluminum group element or an ionic compound of an alkaline earth element or an aluminum group element adsorbing an organic acid component. It is characterized by that.

In the modified wool of the present invention, the composition containing a cationic polycondensate inside the fiber, a water-soluble organic acid salt of an alkaline earth element or an aluminum group element, or an alkaline earth element adsorbing an organic acid component or The composition in which the content of the ionic compound of the aluminum group element with respect to the wool is 0.01 to 10% by weight as the above element, and the content of the cationic polycondensation with respect to the wool is 0.01 to 2% by weight.
Are the preferred embodiments. Further, in the modification treatment method of the present invention, it is preferable that the ionic polycondensate is impregnated with the water-soluble organic acid salt or the organic acid component-adsorbed ionic compound at the same time.

Specific Structure and Action In the modified wool of the present invention, an alkaline earth group (II A group) element or an aluminum group (III A) element contained inside the fiber is used.
Water-soluble organic acid salts of (A group) elements, or ionic compounds of alkaline earth elements or aluminum group elements that have adsorbed organic acids prevent intrafiber substance such as proteins from being transformed into yellowing / embrittlement substances. It has been confirmed that it acts and imparts high chemical stability to the wool itself. Therefore, this modified wool exhibits excellent fastness to sunlight based on high chemical stability and is less likely to undergo deterioration such as yellowing and embrittlement due to light.

The mechanism that causes such an action is not clear, but the protein based on the amino acid in the wool fiber is originally PH4.3-
Since it is in a stable state in an acidic region of about 4.5, the organic acid component of the water-soluble organic acid salt or the organic acid component adsorbed to the ionic compound contributes to maintain the stable state as an acid. In addition, the organic acid component neutralizes the alkaline component when it is subjected to the action of the alkaline component during the production and use of the wool product, and the formation of a yellowing / embrittlement substance which is particularly likely to be caused by the alkaline component. It is thought to be due to the fact that it functions as a barrier to prevent the above.

Examples of the water-soluble organic acid salts include acetates, formates, and citric acids of alkaline earth (IIA) elements such as Be, Mg, and Ca or aluminum group (IIIA) elements such as B, Al, and Ga. A salt of an organic acid having a relatively small number of carbon atoms, such as a salt, which exhibits a certain degree of solubility in water is suitable. As the ionic compound adsorbing the organic acid component, an ionic compound of an alkaline earth element or an aluminum group element similar to the above, for example, a hydroxide, an oxide, a halide,
Acidic sulfides, sulfides, hydroxides, carbonates, cyanides, etc., such as acetic acid, formic acid, and citric acid, which have a relatively small number of carbon atoms are adsorbed on water-soluble or sparingly soluble compounds. Those are preferable.

The content of such a water-soluble organic acid salt or an organic acid-adsorbing ionic compound in wool is 0.01 as the above element for wool.
Approximately 10% by weight is desirable, and if the content is too small, the above-mentioned action and effect are not sufficiently exhibited, and conversely, if it is too large, the wool properties are deteriorated.

On the other hand, in the modified wool of the present invention, it is particularly preferable that the fiber contains a cationic polycondensate together with the water-soluble organic acid salt or the organic acid adsorbing ionic compound inside the fiber.

That is, although the water-soluble organic acid salt and the organic acid component adsorbed on the ionic compound differ to some extent depending on their types, they gradually elute when the wool fiber comes into contact with water and gradually attenuate the above-mentioned effects. However, the cationic polycondensate functions as a binder inside the fiber to prevent the above elution. In addition, this cationic polycondensate reacts and adds to the fiber substance such as protein to suppress its chemical and physical activity, and to the substance inside the fiber which is a factor causing yellowing and embrittlement to the outside and contaminants. It also functions to prevent reaction addition and adsorption.

Examples of such a cationic polycondensate include a dicyan condensate which is a polycondensate of dicyandiamide and formalin, a polyamine condensate which is a polycondensate of polyamide or dicyanamide and an alkylamine, and a quaternary ammonium salt polymer. And polycationic polymers such as
The content of the cationic polycondensate is preferably about 0.0 to 2% by weight with respect to the wool, and if it is too small, the above-mentioned effects cannot be sufficiently exhibited, and if it is too large, stickiness or the like occurs. As the wool quality deteriorates, the fastness also deteriorates.

In addition to the above-mentioned oxidizing substance and cationic polycondensate, the modified wool of the present invention may optionally contain various existing additives such as an antioxidant for preventing yellowing due to heat. It may be contained.

The means for obtaining such modified wool is not particularly limited, but according to the modifying treatment method of the present invention described above, the above-mentioned water-soluble organic acid salt or organic acid adsorbing ionic compound or these and a cationic polycondensate. The effect of can be maximized.

That is, the modification treatment method of the present invention, after performing an internal transformation treatment including a reduction treatment and an oxidation treatment as a pretreatment, then by immersion in an acid bath, the water-soluble organic acid salt or the organic acid-adsorbed ionic compound or This is a method of performing a treatment of impregnating the inside of these fibers with these and a cationic polycondensate.

The wool to which this treatment method is applied may be either unprocessed wool or processed wool described above, but is preferably a general scale treatment method, for example, epicuticle which is a hydrophobic protein on the scale surface by an oxidation treatment with chlorine or the like. It is preferable that the surface is subjected to a pretreatment with hydrophilicity by modifying or removing.

The internal conversion treatment is composed of a combination of a reduction treatment by immersion in a bath and an oxidation treatment, and a two-step treatment of reduction → oxidation or a three-step treatment of oxidation → reduction → oxidation is performed depending on the strength of the above-mentioned pretreatment. That is, by such an internal denaturing treatment, some yellowing proteins and residual lipids of the residual epidermis and cortex of the exocuticle and endocuticle of the inside of wool, that is, the intercellular packing are decomposed or denatured, and the lysate is dissolved. However, when the wool is extracted and removed, the inside of the wool becomes coarse, which is suitable for containing a water-soluble organic acid salt or an organic acid-adsorbed ionic compound in the next impregnation treatment or a cationic polycondensate thereof. An internally modified wool having a strong impregnating and nominal chemical reactivity is provided.
It should be noted that such an internal denaturing treatment is different from the conventional basic treatment such as oxidative bleaching and reduction bleaching in that it is a treatment on the surface of the wool fiber, whereas it is a strong treatment that extends to the inside of the fiber. ing.

Oxidation treatment involves the extraction of oxidative metabolites and dissolved substances and removal of residual reducing agent after the reduction treatment in the previous stage. Hydrogen peroxide, bleaching powder, sodium hypochlorite, sodium chlorite, chlorination It is carried out by forming an oxidizing bath with a chemical having an oxidizing action such as cyanurate and water and immersing the wool in the bath. In this case, it goes without saying that both the water used and the bath container do not generate metal ions, and the stirring of the bath liquid is performed gently to avoid reattachment of dissociated components and damage to the wool. Further, in the bath, a dipping agent composed of a nonionic surfactant such as polyoxyethylene alkylphenol is used for the purpose of promoting and uniformizing the penetration of the oxidizing agent into the wool, and 1.0 to 2.0% by weight based on the weight of the wool. Various additives as necessary, such as adding about 0.1 to 1% by weight of a metal-sequestering agent made of a phosphate-based polymer for the purpose of preventing the adsorption of metal ions to wool. Can be added. The treatment conditions such as bath ratio, treatment temperature, treatment time, PH, and amount of oxidizing agent added vary depending on the type of oxidizing agent used.

For oxidation treatment with hydrogen peroxide, use hydrogen peroxide of about 5 to 20 ml /, and treatment time at a bath ratio of about 1:20 to 50
It takes about 2.5 to 3 hours, but in order to suppress excess damage to wool, PH is gradually increased from the acidic range of about 4.0 to 4.5 at the beginning to PH7 or an acidic range close to this. Further, it is preferable that the treatment temperature is gradually raised from the low temperature (normal temperature) at the start and finally adjusted to about 80 ° C. In order to uniformly permeate the oxidant into the wool and to promote dissociation and extraction of dissolved substances and denatured products, gently remove the wool from the bath during each PH adjustment, while maintaining the PH, and after the final PH adjustment. It is recommended to cut the bath for about 2 to 3 minutes.

In the oxidation treatment with a chlorine-based oxidant, the oxidant addition amount is about 0.2 to 8% by weight based on the effective chlorine amount based on the weight of wool, and the bath ratio is about 1:20 to 50 and the PH from the start to the end of the treatment is 6%. .
It is preferable to maintain the temperature at 8 to 7 and the temperature at 15 to 20 ° C. and the treatment time to be 5 to 10 hours. In this case, the bath may be removed in the same manner as described above.

After completion of the oxidation treatment, washing with water or washing with hot water several times is performed to drain water.

The reduction treatment involves the extraction of reduction metabolites and lysates, and the neutralization and fixation of non-extracted modified substances, i.e. oxides and peroxides, which have undergone the oxidation treatment in the previous stage. A reducing bath is prepared by using the above-mentioned additives such as a penetrant and water and immersing the wool in the bath. In this case as well, it goes without saying that water and a bath container that do not generate metal ions are used and the bath solution is gently stirred.

Examples of the reducing agent used include sodium sulfite, sodium hydrogen sulfite, dechlorin [Zn (OH) HSO ₂ CH ₂ O], Rongalit C (NaHSO ₃ · CH ₂ O · 2H ₂ O), etc. It is preferable that the amount is about 1 to 5% by weight based on the weight of wool.

As the reduction treatment conditions, a bath ratio of 1:20 to 50, a pH of 2.5 to 3.0 from the start to the end, and the treatment temperature is gradually changed from the low temperature (normal temperature) at the start to about 80 ° C. Alternatively, the temperature may be continuously raised and the treatment time may be about 0.5 to 2 hours. Further, during this treatment, it is desirable that the bath be removed several times as in the oxidation treatment.

After the reduction treatment, after cooling, the product is washed with water or hot water several times to drain water.

Note that such an internal shift treatment is a two-stage or three-stage process in which the above-described oxidation process and reduction process are combined, but the final stage process is an oxidation process in order to exert the deterioration preventing effect satisfactorily.

The wool thus subjected to the internal modification treatment is then subjected to a treatment for impregnating the inside of the fiber with the water-soluble organic acid salt, the organic acid-adsorbing ionic compound or the above and the cationic polycondensate. In this impregnation treatment, a water-soluble organic acid salt or an organic acid adsorbing ionic compound or a cation polycondensate thereof with a cation polycondensate is formed in a void inside the fiber generated by removing a part of the internal constituents in the previous internal modification treatment. It will get in.

As the impregnation treatment means, a method of spraying an aqueous solution containing a water-soluble organic acid salt or an organic acid-adsorbing ionic compound or a cationic polycondensate thereof with a spray or the like,
Any of the methods of immersing wool using the aqueous solution as a bath can be adopted, but the latter immersing method is recommended to ensure reliable and uniform impregnation.

Although the above-mentioned aqueous solution prepared in advance can be used in the treatment bath in the dipping method, simply, a diluted solution of an organic acid such as acetic acid, formic acid, and citric acid is first prepared, and the acid is reacted with the diluted solution in the diluted solution. Alternatively, there is a means for adding a compound of an alkaline earth group or an aluminum group capable of adsorbing an acid component or a compound thereof and a cationic polycondensate to prepare a treatment bath. For example, adding magnesium oxide (MgO) to a dilute solution of acetic acid produces magnesium acetate.

It is desirable to maintain the pH of the treatment bath on the acidic side, and for example, when acetic acid is used, it is about 3.5 to 4.5. The treatment is carried out by immersing the wool after the internal modification treatment in the bath at a bath ratio of about 1:20 to 50. At this time, it is desirable that the treatment temperature is gradually or continuously raised from the initial low temperature (normal temperature) and finally raised to about 90 ° C. The treatment time varies depending on the strength of stirring and the like, but is usually about 20 to 120 minutes.

After this treatment, it is cooled and then washed with water or hot water several times.
The wool thus obtained has the above-mentioned water-soluble organic acid salt or organic acid-adsorbing ionic compound, or these and a cationic polycondensate replaced with a part of the constituent substances such as proteins in the original fiber, and is exposed to light. Very resistant to oxidative degradation.

Thus, the wool containing the water-soluble organic acid salt or the organic acid-adsorbing ionic compound or the cationic polycondensate with these, if necessary, further contains an antioxidant in order to prevent yellowing due to heat. You may perform auxiliary processing, such as processing to make it contain.

Further, it is possible to incorporate a dyeing step by an ordinary method between the internal conversion treatment of the pretreatment and the impregnation treatment or simultaneously with the main treatment. To dye at the same time as the impregnation treatment,
The dyeing solution and the water-soluble organic acid salt or organic acid adsorbing ionic compound for impregnation treatment or an acid diluting solution containing the same and a cationic polycondensate are separately prepared in advance, and the mixed solution of these two solutions is used as a treatment bath. The temperature may be adjusted and the wool after the internal modification treatment may be dipped. This simultaneous processing has the advantage that the processing operations of dyeing and modification are greatly simplified and the processing time is shortened.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples. In the following, oww is the weight of wool, and ml / and g / are the concentrations of bath.

Example 1 A pile woven fabric in which the number 2/32 worsted yarn of comeback type wool whose surface scale was previously oxidized with chlorine was used as a pile material was used as a 1% oww neutral detergent (Scoreroll # 700, manufactured by Kao Soap Co., Ltd.). In a bath that dissolves 1: 1 at a bath ratio of 1:30 and a treatment temperature of 40 ° C.
Soaking was performed by immersing for 0 minutes. Next, this woolen fabric was internally modified in the following order.

(1) Oxidation treatment 90% acetic acid 0.10 to 0.15 ml / added to normal temperature soft water to add PH 4.0
After adjusting to 4.5, polyoxyethylene alkylphenol type penetrant (Meiserin H-17 manufactured by Meisei Chemical Industry Co., Ltd.)
0) Add 1% oww of a sequestering agent consisting of 1.5% oww and a phosphate polymer (Mynex SP manufactured by Meiseikagaku Kogyo Co., Ltd.),
Further, 35% hydrogen peroxide water was added so as to be 15 ml / to form an oxidation bath. Immerse the woolen dough in this oxidation bath at a bath ratio of 1:30, start the treatment at room temperature (30 ° C) or less with gentle stirring, and add 0.5% ammonia water in 5 batches to add PH. If you step up to the final 6.8,
Gradually raise the treatment temperature to 80 ° C for 2 hours and 30 minutes
The process was completed in 3 hours. In addition, during this treatment, the bath was cut 5 times for each pH adjustment and 5 times other than that for 2 to 3 minutes each.
The final treatment at pH 6.8 and a temperature of 80 ° C was for 20 minutes, and the bath was cut during this time.

(2) Washing with water Two times at 20 to 30 ° C.

(3) Reduction treatment Adjust the pH to 2.5-3.0 by adding 3-4 ml / 88% formic acid to room temperature soft water, and add the dipping agent Meiserine H-170 (described above) 1% oww and dechlorin 5g / to make a reducing bath. Created. Immerse in the reducing bath at room temperature at a ratio of 1:30 for the wool material after the above-mentioned oxidation treatment, gently stir, and then gradually raise the temperature to 60 ° C. The bath was removed, the temperature was maintained at 60 ° C. for 15 minutes, the temperature was further raised, the temperature was maintained at 80 ° C. for 30 minutes, and then the mixture was cooled to 30 ° C. to complete the treatment.

(4) Washing with hot water Two times at 60 ° C.

(5) Washing with water It was performed once at room temperature.

(6) Oxidation treatment Oxidation treatment was performed in exactly the same manner as (1).

(7) Washing with hot water Two times at 60 ° C.

(8) Washing with water It was performed once at room temperature.

The wool material that had been subjected to this internal modification treatment was impregnated as follows.

First, a 5% aqueous solution of acetic acid (90%) in a colloidal dispersion of aluminum oxide (Al ₂ O ₃ ) sol is stirred and gradually and divided into several times to stabilize the pH of the solution at 4.0. Added by. As a result, the above dispersion became a completely transparent aqueous solution.

Then, a water-soluble polycondensate of a quaternary ammonium salt (Neofix RP-70 manufactured by Nichika Kagaku Kogyo Co., Ltd.) was added in an amount of 3% by weight of the wool and the mixture was stirred well.

To this bath (solution), the wool which had been subjected to the internal modification treatment was introduced at a bath ratio of 1:30 to start the modification treatment. The treatment should be carried out with good agitation, keeping it at room temperature for 10 minutes at the start of treatment, followed by heating to 50 ° C for 20 minutes and keeping at this temperature for 15 minutes, then for 20 minutes. At 90 ° C., the temperature was raised to 90 ° C. and maintained at this temperature for 15 minutes.

After this treatment, washing with water at room temperature was performed twice, dehydration and drying to obtain a modified woolen fabric. And 10 more on this woolen fabric
Antioxidant with a concentration of up to 20% (AF-24 manufactured by Meisei Chemical Industry Co., Ltd.)
Aqueous solution containing was treated by padding with 25-50% Pick-Up and dried. About the obtained wool, the aluminum compound that adsorbed acetic acid (probably a hydroxide) was used as Al.
0.052% by weight, about 0.2-0.4% by weight of cationic polycondensate
The content of the cationic polymer was 1.3% by weight, which showed a remarkable effect of preventing yellowing and embrittlement due to sunlight.

Example 2 A merino wool type 2/48 worsted yarn whose surface scale was oxidized by chlorine at the stage of the wool top was made into a knotted state,
This was subjected to soaping treatment in the same manner as in Example 1 with a bath ratio of 1:40. Next, the worsted yarn was internally modified in the following order.

(1) Oxidation treatment Soft water was mixed with 4% oww of sodium hypochlorite containing 12% of effective chlorine and 1% oww of penetrant Meiserine H-170 (described above) to prepare an oxidation bath of PH 6.7 to 8.0. did. The above carded yarn was immersed in this bath at a bath ratio of 1:30 and treated at a treatment temperature of 15 to 20 ° C. for 10 hours with gentle stirring.

(2) Washing with water After washing three times at room temperature, the water was drained.

(3) Acid treatment The worsted yarn after washing with water is dipped in a bath having a pH of 2.8 to 3.3 by adding 88% formic acid 3% oww to normal temperature soft water at a bath ratio of 1:30 and gently agitated. It was treated at 25 ° C for 30 minutes.

(4) Washing with water It was performed twice at room temperature.

(5) Reduction treatment 68% sulfuric acid 0.1% oww and penetrant Meiserine H-17 in normal temperature soft water
0% (supra) 1% oww and Rongalit C4% oww were added and mixed to form a reducing bath having a pH of 4.5 to 5.0. The carded yarn after the oxidation treatment was dipped in this bath at a bath ratio of 1:30 and treated at 20 to 25 ° C for 2 hours with gentle stirring.

(6) Washing with water It was performed twice at room temperature.

(7) Acid treatment The worsted yarn after washing with water is adjusted to PH2 to 3 by adding 68% sulfuric acid 0.2% oww to normal temperature soft water, and the bath ratio is 1:30 under normal temperature 1
Immersion treatment for 2 minutes was performed.

(8) Washing with water It was performed twice at room temperature.

(9) Oxidation treatment The same oxidation treatment as in (1) of Example 1 was performed.

(10) Washing with water It was performed twice at room temperature.

Regarding the worsted yarn that has undergone this internal modification treatment, gallium oxide (2Ga ₂ O ₃ · 3H ₂ O) powder is used instead of aluminum oxide sol.
The organic acid was used in the same manner as in Example 1 except that 3% oww of a quaternary polyammonium salt condensate (Rebogen FWN manufactured by Bayer Co.) was used as the cationic polycondensate when used at a rate of 10 g /. An impregnation treatment with an adsorbed ionic compound and a cationic polymer was performed.

After this treatment, washing with water at room temperature was performed twice, and then Example 1 was performed.
The same treatment with the antioxidant was performed.

The obtained worsted yarn contains about 0.081% by weight of a gallium compound (which is considered to be a hydroxide) adsorbing acetic acid as Ga and about 0.4 to 0.6% by weight of a cationic polycondensate, which causes yellowing due to sunlight. The resistance to brittleness and brittleness was excellent, and the tensile strength of the yarn was improved by about 10% compared with that before the treatment.

Example 3 As a pile material, a pile woven fabric using merino type wool count 2/48 worsted yarn which is a shrink-resistant wool which has been surface-treated in advance was subjected to an internal modification treatment in the same manner as in Example 1 and then Impregnation was performed in the same manner as in Example 1 except that magnesium oxide (MgO) powder was used instead of aluminum oxide sol at a rate of 1.5 g /, and the same oxidation prevention as in Example 1 was applied. The agent was treated.

Acidol Gray MG (manufactured by BaSF): 0.120% Acidol BorduexMB (same as above): 0.006% UniperolSE-S (same as above): 2% EulysinS (same as above): 0.5% Ammonium sulphate: 3% Recipe at the concentration of each bath above gives a bath ratio of 1 At 30 Boil
(Boiling) Dyeing was carried out for 30 minutes. This dyed product is a light gray color and the standard density is [STANDARD DEPTH 1/4].
Met.

The finally obtained dyed product contains magnesium acetate.
About 0.046 wt% as Mg, about 0.4-
It contained 0.6% by weight, and although it was a light color, it was extremely fast against sunlight and was resistant to discoloration.

Example 4 A 1/48 worsted merino-type worsted yarn, which is a non-shrinkage wool that has been prescaled at the stage of the wool top, is in a drape state.
In the same manner as (3) to (8) above, after performing two-stage internal conversion treatment of reduction → oxidation, impregnation treatment and dyeing were simultaneously performed as follows.

(1) Dyeing and impregnation Anthrasol Blue IBC: 0.20% 〃 Yellow IRK: 0.04% 〃 Red IFBB: 0.09% Eganal UN: 1% (above, manufactured by Hoechst) Albegal B (manufactured by CIBA-GEIGY): 1.5% acetic acid Ammonium: 4% An aqueous solution for dyeing having each of the above concentration compositions and an aqueous solution for impregnation treatment prepared in the same manner as in Example 1 except that PH 6.5 to 6.8 were mixed at a mixing polymerization ratio of 2: 1, Immerse the worsted yarn after the internal conversion treatment in this mixed solution at a bath ratio of 1:30, maintain it at room temperature for 20 minutes, then raise it to 98 ° C in 45 minutes and add acetic acid at the time of 10 minutes. Then, the pH was adjusted to pH 4.0 to 4.5, and the treatment was completed by boiling for 30 minutes.

(2) Color development Ammonium thiocyanate: 1.2% oww Potassium dichromate: 1.0% oww Sulfuric acid (66 ° Be): 10 ml / A bath having the above-mentioned component concentrations was prepared, and the woolen yarn after the dyeing and the main treatment was made in this bath. Is immersed in a bath ratio of 1:30 and the treatment temperature is gradually raised from room temperature to a final temperature of 85 to 90 ° C.
After maintaining for 30 minutes, the mixture was cooled and washed sufficiently with water to complete color development.

(3) Neutralization In a weak alkaline bath adjusted to pH 7.3 to 7.8 with diluted ammonia water, the carded yarn after the above color development is used at a bath ratio of 1:30 at room temperature for 10
Neutralization was carried out by soaking for a minute.

(4) Bleaching To remove the yellowing of the wool during dyeing and coloring,
A bleaching treatment with hydrogen peroxide is carried out by a conventional method with a bath ratio of 1:
I went to 30.

After passing through each of the above treatments, the worsted yarn obtained by washing with water, dehydration and drying was spray-treated with a 10% aqueous solution of the antioxidant AF-24 (described above), and dried to obtain an ultralight gray standard concentration. A carded yarn dyed product of [STANDARD DEPTH 1/8] was obtained.

Although this dyed product is a very light color, it retains extremely strong fastness to sunlight and has a significantly strong inhibitory action against yellowing and embrittlement.
Discoloration, fading and strong deterioration due to sunlight were extremely small. The content of the aluminum compound that adsorbed acetic acid in the dyed product was about 0.016% by weight as Al, and the content of the cationic polycondensate was about 0.01 to 0.15% by weight.

Example 5 A modified wool fabric was obtained in the same manner as in Example 1 except that the cationic polycondensate was not used in the impregnation treatment.

Example 6 Wool after internal modification treatment in Example was sprayed with an aqueous solution in which 1.0% concentration of magnesium acetate and 5.0% concentration of cationic polycondensate (the same as in Example 1) were sprayed and sufficiently impregnated. Then, it was washed with water, dehydrated and dried to obtain a modified wool fabric. Then, the same treatment with an antioxidant as in Example 1 was performed.

The obtained woolen fabric has magnesium acetate as Mg of about 0.
It contained 048% by weight and about 0.2 to 0.3% by weight of a cationic polycondensate.

Example 7 A modified worsted yarn was obtained in the same manner as in Example 2 except that the same amount of beryllium carbonate (BeCO ₃ ) powder was used instead of the gallium oxide powder in the impregnation treatment. In this worsted yarn, basic beryllium acetate [Be ₄ O (CH ₃ CO ₂ ) ₆ ] was used as Be in an amount of 0.
It was contained at 016% by weight.

Example 8 A wool fabric was obtained in the same manner as in Example 3, except that the dyeing treatment in Example 3 was omitted, and a 2.0% aqueous solution of formic acid was used in place of the acetic acid water dilution solution in the impregnation treatment. This woolen fabric contained a magnesium formic acid compound as Mg in an amount of about 0.046% by weight.

Evaluation of Examples The wool fabrics of Examples 1, 3, 5, 6, and 8 and the wool yarns of Examples 2, 4, and 7 thus obtained were evaluated and measured for the degree of prevention of yellowing and embrittlement.

In addition, with respect to the dyed products of Examples 3 and 4, the degree of discoloration and fading and the degree of prevention of discoloration and fading and embrittlement inhibition were evaluated and measured, respectively.

And each was compared with what was processed by the conventional method (processing method which contains a benzophenone-type light stabilizer).

[Yellowness evaluation]

A black panel temperature (B / P / T) was set to a high temperature of 85 degrees with an ultraviolet carbon arc fade odometer, and a 10 mm thick slab urethane was placed on the back of the fabric samples of Examples 1, 3, 5, 6 and 8 above. And was irradiated with light for 200 hours.

After light irradiation, the yellowing degree of the irradiated part was also compared with that of the unirradiated sample.
In addition, for the purpose of reference comparison, the conventional method sample was also evaluated and measured at the same time. As the conventional method sample, a sample to which only the ultraviolet absorber was added was used.

A spectrophotometer "colorimeter Macbeth 2020" was used for yellowing measurement. The light source is a D light source.

The degree of yellowing was represented by YI (Yellowness Index) [YI = (128X−106Z) / Y]. Note that X,
Y and Z are tristimulus values.

The yellowing evaluation results are shown in Table 1 below.

[Evaluation of embrittlement] The wool yarn samples of Examples 2, 4, and 6 were irradiated with light for 200 hours and 300 hours, respectively, in the same manner as in the yellowing evaluation method, and then the yarn tensile strength was measured to obtain unirradiated samples. The ratio of to the tensile strength of the yarn was evaluated as the strength retention expressed as a percentage. The results are shown in Table 2.

[Discoloration and Discoloration Evaluation] Similar to the yellowing evaluation method, discoloration and discoloration after UV irradiation for 20 hours and 300 hours after filling with Bmm / P / T temperature 85 ° C, 10 mm urethane with an ultraviolet carbo arc fade odometer The evaluation was made based on a 5-level gray scale judgment.

The results are shown in Table 3. In the conventional example in this case, the same dyeing treatment as in Example 3 was performed.

EFFECTS OF THE INVENTION The modified wool of the present invention contains a specific water-soluble organic acid salt or an organic acid-adsorbing ionic compound inside the fiber, and therefore has extremely strong light resistance and yellowing or brittleness over a long period of time. Deterioration such as deterioration does not occur, and even in light-colored and pastel-colored dyed fabrics, it exhibits extremely excellent resistance to deterioration in that it does not easily discolor or fade.

In addition, the structure in which the cationic polycondensate is contained in the fiber together with the water-soluble organic acid salt or the organic acid-adsorbing ionic compound has an advantage that the deterioration resistance performance is further improved. Further, the content of the water-soluble organic acid salt or the organic acid-adsorbing ionic compound is 0.01 to 10% by weight as the above element relative to wool, and the content of the cationic polycondensate is 0.01 to 2% by weight. With such a constitution, each action is sufficiently exerted without deteriorating the original wool characteristics.

On the other hand, according to the modification treatment method of the present invention, since the treatment for impregnating the water-soluble organic acid salt or the organic acid-adsorbed ionic compound is performed after the specific pretreatment for performing the internal transformation, the coarse treatment is performed by the pretreatment. The water-soluble organic acid salt or organic acid-adsorbing ionic compound described above is efficiently contained in the voids inside the modified fiber in the form of substituting it with the original constituents, so that its action and effect are maximized, and In the treatment step, the yellowing / embrittlement substance inside the fiber is denatured and dissolved and removed to obtain the modified wool of the present invention having the most ideal deterioration resistance performance.

Then, by impregnating the cationic polycondensate with the water-soluble organic acid salt or the organic acid-adsorbing ionic compound at the same time, the polycondensate is impregnated inside the fiber together with the organic acid salt or the ionic compound. The modified wool of the present invention can be easily obtained.

Claims (6)

[Claims] 1. A modified wool comprising a wool fiber containing a water-soluble organic acid salt of an alkaline earth element or an aluminum group element, or an ionic compound of an alkaline earth element or an aluminum group element adsorbing an organic acid component. . 2. The modified wool according to claim 1, wherein the inside of the fiber contains a cationic polycondensate. 3. A water-soluble organic acid salt of an alkaline earth element or an aluminum group element, or an ionic compound of an alkaline earth element or an aluminum group element having an organic acid component adsorbed therein is contained in an amount of 0.01 to 10% by weight of wool as the above element. The modified wool according to claim 1, which is 4. The cationic polycondensate is 0.01 to 0.01 to the wool.
The modified wool according to claim (2) or (3), which comprises 2% by weight. 5. Wool reduction-oxidation two-step treatment or oxidation-
After subjecting the wool to internal removal treatment by immersion in a bath consisting of three steps of reduction-oxidation to remove the dissolved matter,
A method for modifying a wool, which comprises impregnating a water-soluble organic acid salt of an alkaline earth element or an aluminum group element or an ionic compound of an alkaline earth element or an aluminum group element having an organic acid component adsorbed thereon. 6. A water-soluble organic acid salt of an alkaline earth element or an aluminum group element, or an ionic compound of an alkaline earth element or an aluminum group element having an organic acid component adsorbed thereon, and at the same time, an impregnation treatment of a cationic polycondensate. The method for modifying wool according to claim 5, which is performed.