JPH0284530A - Modified sheep wool and modification treatment method thereof - Google Patents

Abstract

PURPOSE:To obtain a modified sheep wool containing an acidic substance consisting of a compound of element of IIA group or IIIA group in the fiber and having excellent wool characteristics and light resistance by subjecting the sheet wool to oxidation and reduction treatment and impregnating the above-mentioned acidic substance into the wool. CONSTITUTION:A sheep wool is subjected to oxidation treatment by hydrogen peroxide and reduction treatment by sodium sulfite to extract and remove a material dissolved by internal denaturated and then an acidic substance consisting of a compound of element of IIA group or IIIA group (preferably an ionic compound of the above- mentioned element absorbing a salt or acid component of the above-mentioned element whose aqueous solution exhibits acidity) is impregnated into the wool to provide the modified sheep wool containing the above-mentioned acidic substance at an amount of 0.01-10wt.% as the above-mentioned element based on the sheep wool and almost free from yellowing by light, embrittlement, etc. Furthermore, when a dicyan based polycondensation product is impregnated into the wool together with the above- mentioned acidic substance, a modified sheep wool further improved in light resistance is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application This invention relates to modified wool that is less likely to yellow or become brittle due to light, and to a method for modifying the same.

BACKGROUND OF THE INVENTION In general, when wool is exposed to sunlight, it yellows and becomes brittle, eventually leading to decomposition. This deterioration phenomenon is largely due to photoradical decomposition of wool proteins by ultraviolet rays in sunlight, and this decomposition reaction tends to be accelerated by heat.

Therefore, as a means to prevent the above-mentioned deterioration, unprocessed wool (greasy wool) has conventionally been used.

Washed wool, 5coured wool
In addition to basic treatments such as oxidation bleaching and reductive bleaching, dyeing agents are added to fabric colors or dyed products for processed wool (so-called anti-shrunk wool such as surface scale treated wool and descaled wool). A method of pre-reducing the degree of yellowing of pale or pastel colors, a method of applying so-called ultraviolet absorbers such as benzophenone type, triazole type, hindered amine type, metal complex type, etc. and a light stabilizer called ultraviolet shielding agent; A method of incorporating antioxidants such as dophenol type, hydrazine type, and phosphorus type has been adopted.

Problems to be Solved by the Invention However, none of the above-mentioned conventional deterioration prevention means has achieved a remarkable effect, and has not been able to sufficiently prevent yellowing and embrittlement caused by sunlight and ultraviolet rays. Particularly, when wool is used in applications where it is exposed to intense sunlight or heat, such as for example as a fiber material for automobile seats, it is subject to significant deterioration, and improving its durability is a major issue.

In addition, dyed fabrics in light or pastel colors are strongly influenced by the yellowing of the wool itself, even if the type of dye and its light resistance are selected, so there is a problem that early discoloration and fading cannot be avoided.

In view of the above circumstances, this invention provides strong light resistance to sunlight and artificial light without impairing the original wool properties.
The object of the present invention is to provide a modified wool that exhibits a significantly lower degree of yellowing and embrittlement caused by light, and a method for modifying the wool.

Means for Solving the Problems In order to achieve the above object, the present invention imparts strong light resistance to wool by incorporating a specific compound or a specific polymer thereof into the inside of the wool fibers, thereby preventing yellowing. This prevents deterioration such as corrosion and embrittlement over a long period of time.

That is, the modified wool according to the present invention has ■A inside the fiber.
It contains an acidic substance consisting of a group element or a compound of an HA group element.

Further, in the wool modification treatment method according to the present invention, the wool is subjected to internal modification treatment by immersion in a bath including reduction treatment and oxidation treatment to extract and remove dissolved substances, and then the wool is treated with II.
It is characterized by impregnation treatment with an acidic substance consisting of a compound of a Group A or Group IIIA element.

The modified wool of the present invention has a structure in which a cationic polycondensate is contained inside the fiber, a group IIA or nI
A configuration in which the content of an acidic substance consisting of a compound of a group A element in wool is 0.01 to 10% by weight as the above element,
The content of cationic polycondensate in wool is 0.01~
2IrW%, a configuration in which the acidic substance is a group IIA or a salt of a group IIA element that is acidic as an aqueous solution, and a configuration in which the acidic substance is an ionic compound of a group IIA or group IIIA element that has adsorbed an acid component are preferable. It shall be the mode. Furthermore, in the modification treatment method of the present invention, a preferred embodiment is such that the impregnation treatment with the cationic polycondensate is performed simultaneously with the impregnation treatment with the acidic substance.

Specific structure and function IIA contained inside the fiber in the modified wool of this invention
Acidic substances consisting of compounds of Group or IIA elements have the effect of preventing the transformation of white fiber substances such as proteins into yellowing and brittle substances, and impart high chemical stability to the wool itself. This has been confirmed. Therefore, this modified wool exhibits excellent sunlight fastness due to high chemical stability,
It becomes less susceptible to deterioration such as yellowing and embrittlement due to light.

This effect is due to the fact that proteins based on amino acids inside wool fibers are originally stable in an acidic range of pH 4.3 to 4.5, and this stable state is maintained by the acidifying effect of the above acidic substances. , and when wool products are exposed to alkaline components during manufacture and use, the above acidic substances neutralize the alkaline components and prevent the formation of yellowing and brittle substances that are particularly prone to be caused by alkali components. This is thought to be due to the fact that it functions as a barrier to prevent

The above acidic substances include salts of group IIA or group IIIA elements whose aqueous solutions are acidic, and I
Suitable examples include ionic compounds of Group IA or Group IIIA elements.

Examples of the former salt include organic acid salts (including complex salts) such as acetate, formate, and citrate, as well as inorganic acid salts such as sulfate and chloride. All you have to do is select. The latter ionic compounds include hydroxides, oxides, halides, acidic sulfides,
These are sulfides, hydroxides, carbonates, cyanides, etc., which have adsorbed organic acid components such as acetic acid, formic acid, and citric acid, or inorganic acid components such as sulfuric acid and hydrochloric acid.

The content of these acidic substances in the wool is preferably about 0.01 to 10% by weight of the above elements based on the wool.
If the content is too small, the above-mentioned effects will not be fully exhibited, and if the content is too large, the wool properties will deteriorate.

On the other hand, the modified wool of the present invention preferably contains a cationic polycondensate together with the above-mentioned acidic substance inside the fiber.

In other words, the acidic substance gradually dissolves when the wool fiber comes into contact with water, although the degree differs depending on the type, and gradually reduces the effect, whereas the cationic polycondensate acts as a binder inside the fiber. This serves to prevent the above-mentioned elution. In addition, this cationic polycondensate reacts with fiber white substances such as proteins to suppress their chemical and physical activity, and is effective against external substances that cause yellowing and embrittlement and pollutants. It also functions to inhibit reactive addition and adsorption.

Such cationic polycondensates include dicyanide condensates, which are polycondensates of dicyandiamide and formalin, polyamine condensates, which are polyamides, dicyanamides, and alkyl amines, and quaternary ammonium salt polymers. Examples include polycationic polymers such as. The content of this cationic polycondensate is preferably about 0.01 to 2% by weight based on the wool; if it is too small, the above-mentioned effects will not be fully exhibited, and if it is too large, it will become sticky. As a result, the quality of the wool deteriorates, and the fastness also deteriorates.

In addition to the above-mentioned acidic substance and cationic polycondensate, the modified wool of the present invention can be made by adding various existing additives such as antioxidants to prevent yellowing due to heat, if necessary. It may be included.

The means for obtaining such modified wool is not particularly limited, but according to the modification treatment method of the present invention described above, the effects of the acidic substance or the cationic polycondensate thereof can be maximized. be able to.

That is, in the modification treatment method of the present invention, after performing an internal modification treatment including a reduction treatment and an oxidation treatment as a pretreatment, the acidic substance or a cationic polycondensate thereof is introduced into the inside of the fiber by immersion in an acidic bath. This is a method of impregnating it with water.

The wool to which this treatment method is applied may be either the unprocessed wool or processed wool described above, but it is preferable to remove shrimp cuticles, which are hydrophobic proteins on the scale surface, by a general scale treatment method, such as oxidation treatment with chlorine or the like. Pre-treatment to make the surface hydrophilic by denaturing or removing is preferable.

The internal transformation treatment consists of a combination of a reduction treatment by immersion in a bath and an oxidation treatment, preferably a two-stage treatment of reduction-oxidation or a three-stage treatment of oxidation-reduction monoxidation depending on the strength of the above-mentioned preliminary treatment.
Perform stage processing. In other words, through such internal denaturation treatment, the residual epidermis and cortex of the shrimp cuticle and endocuticle in the wool interior, the scale, and some yellowed proteins and residual lipids in the intercellular filling are decomposed or denatured, and the lysate is dissolved or denatured. is extracted and removed, and as a result, the inside of the wool becomes coarse and has strong impregnating properties and chemical reactivity suitable for containing acidic substances or cationic polycondensates with them in the next impregnation process. Provided with internally modified wool. In addition, this kind of internal metamorphism process is
Unlike conventional basic treatments such as oxidative bleaching and reductive bleaching, which treat the surface of wool fibers, this method differs in that it is a strong treatment that extends to the inside of the fibers.

Oxidation treatment extracts oxidized products and dissolved substances and removes residual reducing agents after reduction treatment in the previous stage. Hydrogen peroxide, bleaching powder, sodium hypochlorite, sodium chlorite, chlorination The process is carried out by creating an oxidizing bath with water and an agent having an oxidizing effect such as cyanurate, and immersing the wool in this bath. In this case, it goes without saying that both the water used and the bath container should be of a type that does not generate metal ions, and the bath solution should be stirred slowly to avoid redeposition of dissociated components and damage to the wool. In addition, in the bath, a penetrant consisting of a nonionic surfactant such as polyoxyethylene alkylphenol is added at a rate of 1.0 to 2% per wool weight, in order to promote and uniformize the penetration of the oxidizing agent into the wool. ．．
Various methods may be used as needed, such as adding approximately 0% by weight, or adding approximately 0.1 to 1% by weight of a sequestering agent made of a phosphate polymer or the like for the purpose of preventing the adsorption of metal ions to wool. Additives can be added as appropriate. In addition,
Processing conditions such as bath ratio, processing temperature, processing time, pH, and amount of oxidizing agent added vary depending on the type of oxidizing agent used.

In the oxidation treatment with hydrogen peroxide, hydrogen peroxide of about 5 to 20 d/ρ is used, and the treatment time is about 2.5 to 3 hours at a bath ratio of about 1:20 to 50. In order to suppress this, the pH is raised stepwise from the initial acidic range of about 4.0 to 465 to a final pH of 7 or an acidic range close to this, and the treatment temperature is also set at a low temperature (normal temperature) at the start. It is preferable to raise the temperature more gradually so that the final temperature is about 80°C. In addition, in order to promote uniform penetration of the oxidizing agent into the wool and dissociation and extraction of dissolved and denatured substances, the wool should be gently removed from the bath at each pH adjustment, during pH maintenance, and after the final pH adjustment. It is recommended that you bathe for about 3 minutes.

In oxidation treatment using a chlorine-based oxidizing agent, the amount of oxidizing agent added is approximately 0.2 to 8% by weight based on the wool weight in terms of available chlorine, and the pH from the start to the end of the treatment is adjusted at a bath ratio of approximately 1:20 to 50. It is preferable to maintain the temperature at about 6.8 to 7°C, the temperature at 15 to 20°C, and perform the treatment for about 5 to 10 hours. In this case, the bath may be drained in the same manner as described above.

After the oxidation treatment is completed, wash with water or hot water several times and drain.

Reduction treatment involves the extraction of reduced denatured products and dissolved substances, as well as the neutralization and fixation of unextracted denatured substances, such as oxides and peroxides, which were obtained through oxidation treatment in the previous stage. A reducing bath is created with water and additives such as the penetrant, and the wool is placed in this bath. Do this by doing A. In this case as well, it goes without saying that water and a bath container that do not generate metal ions are used, and that the bath liquid is stirred slowly.

The reducing agents used include sodium sulfite, sodium hydrogen sulfite, dechlorin [2 mouths (0H) HSO3C
H20), Rongalit C (NaH8O3・CH2O
・2H20), etc., and the amount added is preferably about 1 to 5 weight 26 to the weight of wool.

The reduction treatment conditions include a bath ratio of about 1:20 to 50, a pH of about 2.5 to 3.0 from start to finish, and a treatment temperature of about 80°C from the low temperature (room temperature) at the start. Raise the temperature stepwise or continuously for a processing time of 0.5~
It may take about 2 hours. Also, during this treatment, it is desirable to drain the bath several times as in the oxidation treatment.

After the reduction treatment, it is slowly cooled, washed with water or hot water several times, and then drained.

In addition, such internal metamorphosis treatment consists of two or three stages of treatment that combines the above-mentioned oxidation treatment and reduction treatment, but in order to achieve a good deterioration prevention effect, it is recommended that the final stage treatment be oxidation treatment. is desirable.

The wool thus subjected to the internal modification treatment is then subjected to a treatment for impregnating the interior of the fiber with the acidic substance or a cationic polycondensate thereof.

As this impregnation treatment, it is possible to adopt either a method of spraying the wool with an acidic substance or an aqueous solution containing the same and a cationic polycondensate, or a method of immersing the wool in the aqueous solution as a bath. The latter immersion method is recommended to ensure that the process is carried out reliably and uniformly.

The above aqueous solution prepared in advance can be used as the treatment bath in the immersion method, but it is easier to first prepare a diluted solution of an organic acid such as acetic acid, formic acid, or citric acid or an inorganic acid such as sulfuric acid or hydrochloric acid, and then dilute this solution. Group IIA or I that can react with the acid or adsorb acid components to produce acidic substances in the diluent
There is a method of adding a Group IIA compound or a cationic polycondensate thereof to form a treatment bath. For example, when magnesium oxide (Mg 2 O) is added to a dilute solution of acetic acid, magnesium acetate, which is an acidic substance, is produced.

It is desirable to maintain the pH of the treatment bath on the acidic side,
For example, when acetic acid is used, it is preferably about 3.5 to 4.5. The treatment involves placing the wool after internal modification treatment in a bath at a bath ratio of 1:
This is done by dipping at about 20-50°C. At this time, it is desirable that the processing temperature be raised stepwise or continuously from an initial low temperature (room temperature) to a final temperature of about 90°C. The processing time varies depending on the intensity of stirring, etc., but it is usually 2.
The duration is approximately 0 to 120 minutes.

After this treatment, it is slowly cooled and then washed with water or hot water several times.

The wool thus obtained has the interior of the fiber impregnated with an acidic substance or a cationic polycondensate thereof, and has very strong resistance to oxidative decomposition by light.

In addition, the wool containing the acidic substance or its cationic polycondensate may, if necessary, be subjected to auxiliary treatment such as treatment to contain an antioxidant to prevent yellowing due to heat. It's okay.

Further, it is possible to incorporate a dyeing process by a conventional method between the pre-treatment internal transformation treatment and the impregnation treatment or simultaneously with the main treatment. To dye at the same time as impregnation,
A dyeing solution and an acid diluted solution containing the acidic substance for impregnation treatment or this and a cationic polycondensate are prepared separately in advance, and the mixture of these two solutions is used as a treatment bath to adjust the pH and temperature and perform internal transformation treatment. All you have to do is soak the wool afterwards. This simultaneous processing greatly simplifies the dyeing and modification processing operations,
It also has the advantage of shortening processing time.

EXAMPLES Hereinafter, the present invention will be specifically explained using examples. In addition, in the following, OWW refers to wool weight, TrL.
Ω/Ω and g/Q are bath concentration.

Example 1 A pile fabric using 2/32 worsted yarn of Comeback wool, whose surface scale has been oxidized with chlorine, as the pile material, was washed with 1% oww of neutral detergent (Score Roll #700 manufactured by Kako Soup Co., Ltd.). Soaping treatment was carried out by immersing the specimen in a bath in which the sample was dissolved at a bath ratio of 1:30 and a treatment temperature of 40° C. for 10 minutes. Next, this wool fabric was subjected to internal modification treatment in the following order.

(1) Oxidation treatment After adding 0.10 to 0.15 d/fl of 90% acetic acid to room temperature soft water to adjust the pH to 4.0 to 4.5, add a polyoxyethylene alkylphenol penetrant (Meisei Chemical Industry Co., Ltd.) Meiselin H-170) 1.5% OWW and 1% OWW of a metal sequestering agent made of a phosphate polymer (Mynex 5P, manufactured by Kasei Kagaku Kogyo Co., Ltd.) were added, and 15 d/w of 35% hydrogen peroxide solution was added. An oxidation bath was prepared by adding Ω.

The wool fabric was immersed in this oxidation bath at a bath ratio of 1:30, and the treatment was started at room temperature (30°C) or below with gentle stirring, and 0.5% ammonia water was added in 5 portions. P
As H was raised stepwise to a final temperature of 6.8, the treatment temperature was gradually raised to a final temperature of 80°C for 2 hours and 30 minutes.
The process was completed in 3 hours. During this process, the bath was drained for 2 to 3 minutes each time, 5 times at each pH adjustment and 5 other times. The final treatment at pH 6.8 and temperature 80.degree. C. was carried out for 20 minutes, during which time the bath was drained.

(2) Washing with water It was carried out twice at 20-30°C.

(3) Reduction treatment Add 3~4a2/Ω of 88% formic acid to room temperature soft water and adjust the pH to 2.
．． Adjust to 5 to 3,0 and add the penetrant Meycellin H-170 (
A reducing bath was prepared by adding 1% OWW (mentioned above) and 5 g/ρ of dechlorin.

The above-mentioned oxidized wool fabric was immersed in this reducing bath at room temperature at a bath ratio of 1:30, gently stirred, and gradually raised to 60°C. After draining the bath and maintaining it at 60°C for 15 minutes, the temperature was further increased.
The temperature was maintained at 80°C for 30 minutes, and then slowly cooled to 30°C to complete the treatment.

(4) Hot water washing The test was carried out twice at 60°C.

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

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

(7) Hot water washing The test was carried out twice at 60°C.

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

The wool fabric that had undergone this internal modification treatment was subjected to an impregnation treatment as follows.

First, a 5% diluted solution of acetic acid (90%) in water is gradually added to a colloidal dispersion of aluminum oxide (AQz 03 ) sol in several portions while stirring until the pH of the solution is stabilized at 4.0. Added to.

As a result, the above dispersion became a completely transparent aqueous solution.

Next, a quaternary ammonium salt water-soluble polycondensate (Neofix RP-70 manufactured by NICCA Chemical Industry Co., Ltd.) was added to
% and stirred thoroughly.

Wool that had previously been subjected to an internal modification treatment was put into this bath (solution) at a bath ratio of 1:30 to start the modification treatment. The treatment was carried out with thorough stirring, paying attention to uniformity, and maintained at room temperature for 10 minutes at the start of treatment, then heated to 50°C over 20 minutes, maintained at this temperature for 15 minutes, and then for 20 minutes. At 9
Raise the temperature to 0℃, maintain it at this temperature for 15 minutes, and finally
The treatment was completed under temperature and time conditions of slowly cooling to room temperature in 5 minutes.

After this treatment, it was washed with water at room temperature twice, dehydrated, and dried to obtain a modified wool fabric. And furthermore, this wool fabric has 1
Antioxidant at a concentration of 0 to 20% (AF manufactured by Kasei Kagaku Kogyo Co., Ltd.)
Pick-U by padding an aqueous solution containing -24)
Treated with p25-50% and dried. The obtained wool is
Approximately 0°052% by weight of an aluminum compound (considered to be a hydroxide) that adsorbs acetic acid as an acidic substance (AQ)
, contains about 0.2 to 0.4% by weight of a cationic polycondensate, and the content of cationic polymer is 1.3% by weight, which shows a remarkable prevention effect against yellowing and embrittlement caused by sunlight. Ta.

Example 2 Worsted yarn of Merino wool with a count of 2/48 whose surface scale was oxidized with chlorine at the wool top stage was made into a skein, and this was soaped in the same manner as in Example 1 at a bath ratio of 1:40. did.

Next, this worsted yarn was subjected to an internal modification treatment in the following order.

(1) Sodium hypochlorite 4% OW with 12% effective chlorine for oxidation treated soft water
W and a penetrating agent Meiselin H-170 (described above) 1% OWW were added and mixed to create an oxidation bath with a pH of 6.7 to 8.0. The above worsted yarn was immersed in this bath at a bath ratio of 1:30, and the treatment temperature was 15 to 20°C with gentle stirring.
Time processed.

(2) Washing with water After doing this three times at room temperature, it was drained.

(3) Acid treatment The worsted wool yarn after washing with water is soaked in soft water at room temperature with 88% formic acid and 3% ow.
A bath with a bath ratio of 1:
Soak at 30°C, and with gentle stirring at 25°C for 30°C.
Processed for minutes.

(4) Washing with water The test was carried out twice at room temperature.

(5) Reduction treatment room temperature soft water with 68% sulfuric acid 0.1% oww, penetrating agent Meiselin H-170 (mentioned above) 1% oww and Rongalit C 4%
o w w were added and mixed to create a reduction bath with a pH of 4.5 to 5.0.

The oxidized worsted yarn was immersed 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 The test was carried out twice at room temperature.

(7) Acid treatment The worsted wool yarn after washing with water is soaked in soft water at room temperature with 68% sulfuric acid and 0.2%.
In a bath with pH 2 to 3 by adding oww, the bath ratio was 1:3.
An immersion treatment was performed for 1 to 2 minutes at room temperature.

(8) Washing with water This was done twice at room temperature.

(9) Oxidation treatment The oxidation treatment in Example 1 (1) was carried out in exactly the same manner.

(10) Washing with water This was done twice at room temperature.

For the worsted yarn that has undergone this internal metamorphosis treatment, gallium oxide (2Ga203.3H2) is used instead of aluminum oxide sol.
0) 10g of powder #! When used in the proportion of
Impregnation treatment with an antacid adsorbent and a cationic polymer was performed in the same manner as in Example 1 except that 3% OWW (Levogen WN) manufactured by Bayer was used.

After this treatment, after washing with water at room temperature twice, Example 1
Antioxidant treatment was carried out in the same manner as above.

The obtained worsted yarn contains a gallium compound (considered to be a hydroxide) that has adsorbed acetic acid as an acidic substance, and has a concentration of about 0% Ga.
．． 081% by weight, about 0.4 to 0% of the cationic polycondensate,
Contains 6% by weight, has excellent resistance to yellowing and embrittlement due to sunlight, and has a tensile strength of about 10% compared to before treatment.
% improved.

Example 3 A pile fabric using 2/48 worsted yarn of merino wool, which is pre-surface-treated shrink-proof wool, was subjected to internal transformation treatment in the same manner as in Example 1 as the pile material, and then subjected to the following process. dyeing method, and then replace the aluminum oxide sol with magnesium oxide (Mg O) powder at 1.5 g/Ω.
The impregnation treatment was carried out in the same manner as in Example 1, except that the proportion was used, and the same antioxidant treatment as in Example 1 was further carried out.

Ac1dol Gray MG (manufactured by BaSF)
:0.120% Ac1dol Bor-duex MB (same as above)
: 0.006% Uniperol 5E-5 (same as above): 2% Eulysin S (same as above) 2 0.5% Ammonium sulfate: 3% B at a bath ratio of 1:30 at each bath concentration above
Oil (boiling) - 30 minute staining was performed. This dyed product has a beautiful light gray color, and the standard density is (STANDA).
RD DEPTH 1/4].

In addition, the finally obtained dyed product contains about 0.046% by weight of magnesium acetate as Mg and about 0.4 to 0.6% by weight of cationic polycondensate as acidic substances, and has a light color. However, it was extremely durable against sunlight and resistant to discoloration and fading.

Example 4 A 2/48 merino worsted yarn, which is a shrink-proof wool that has been scale-treated in advance at the wool top stage, was reduced in a linear state in the same manner as in (3) to (8) of Example 1. After performing a two-stage internal transformation treatment of oxidation, impregnation treatment and dyeing were performed simultaneously as described below.

(1) Dyeing and impregnation treatment Anthrasol BlueBC: 0.20% Ye 11 ow RK: 0.04% ed FBB: 0.09% Eganal UN: 1%
(All of the above are manufactured by Hoechst) Albegal B (manufactured by CIBA-GEIGY): 1.5% Ammonium acetate: 4% Same as Example 1 except for the dyeing aqueous solution having the above concentration composition and pH 65 to 6,8. and the aqueous solution for impregnation treatment prepared as above at a mixing polymerization ratio of 2:1, and the worsted yarn after internal modification treatment was immersed in this mixture at a bath ratio of 1:30, and maintained at room temperature for 20 minutes. Then, the temperature was raised to 98℃ for 45 minutes, and after 10 minutes, acetic acid was added to adjust the pH to 4.0-4.
．． 5 and boiled for an additional 30 minutes to complete the treatment.

(2) Color-forming ammonium thiocyanate = 1.2% potassium dichromate: 1.0% sulfuric acid (66°Be
): 10ml/Q A bath with the above component concentration was prepared, and the worsted yarn after the dyeing and main treatment was immersed in this bath at a bath ratio of 1.30, and the treatment temperature was changed from normal temperature to a final temperature of 85-9.
The temperature was gradually raised to 0° C., maintained at this final temperature for 30 minutes, and then slowly cooled and thoroughly washed with water to complete color development.

(3) Add the above colored worsted yarn to a slightly alkaline bath adjusted to pH 7.3 to 7.8 with neutralized diluted ammonia water at a bath ratio of 1:30.
Neutralization was performed by immersing the sample at room temperature for 10 minutes.

(4) To remove wool yellowing during bleaching, dyeing, and color processing,
Bleach with hydrogen peroxide in a bath ratio of 1 by the usual method.
I went at :30.

After each of the above treatments, the worsted yarn obtained by washing, dehydrating, and drying was treated with 10% of the antioxidant AF-24 (mentioned above).
% aqueous solution and dried to obtain a dyed worsted yarn of very light gray standard density (STANDARD DEPTH 1/8).

Although this dyed product is very light in color, it retains extremely strong sunlight fastness and has an extremely strong inhibitory effect against yellowing and brittleness.
Discoloration, fading, and strength deterioration due to sunlight were extremely small. The content of acidic substances (aluminum compounds that have adsorbed acetic acid) in the dyed material is approximately 0.0161 as 8Ω.
%, the content of the cationic polycondensate is about 0.01-0.
It was 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 An aqueous solution containing 1.0% magnesium acetate and 5.0% cationic polycondensate (same as in Example 1) was sprayed onto the wool after the internal modification treatment in Example 6. After thorough spray impregnation, washing, dehydration, and drying, a modified wool fabric was obtained. Then, the same treatment as in Example 1 with an antioxidant was performed.

The obtained wool fabric contained about 0.048% by weight of an acidic substance (magnesium acetate) as Mg 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 (Be CO3) powder was used in place of the gallium oxide powder in the impregnation treatment. In this worsted yarn, basic beryllium acetate (Be 40
(CH3C02)6] is 0.016% by weight as Be
It was contained.

Example 8 Wool fabric was obtained in the same manner as in Example 3, except that the dyeing process in Example 3 was omitted and a 2.0% aqueous solution of formic acid was used in place of the acetic acid diluted in water in the impregnation process. . This wool fabric contained about 0.046% by weight of magnesium formic acid compound as an acidic substance.

Evaluation of Examples The thus obtained wool fabrics of Examples 1.3.5.6.8 and wool yarns of Examples 2.4.7 were evaluated and measured for the degree of suppression of yellowing and brittleness.

Furthermore, the dyed products of Examples 3 and 4 were evaluated and measured for the degree of discoloration and fading, and the degree of suppression and prevention of discoloration and fading and embrittlement.

Then, each was compared with that treated by a conventional method (a treatment method containing a benzophenone light stabilizer).

[Yellowing evaluation]

The black panel temperature (B-P-T) was set at a high temperature of 85 degrees using an ultraviolet carbon arc fade-o-meter, and a 10 m thick slab of urethane was placed on the back of the fabric sample of Example 1.3.5.6.8. was filled and irradiated with light for 200 hours.

After light irradiation, the degree of yellowing of the irradiated area was compared with that of the unirradiated sample.

For reference comparison, conventional method samples were also evaluated and measured at the same time. In addition, as the conventional method sample, one that was only subjected to the addition treatment of an ultraviolet absorber was used.

To measure the degree of yellowing, a spectrophotometer [Macbeth
2020J was used. The light source is a D light source.

The degree of yellowing is the yellowness index Y, 1. (Yell.

wness Index) Y, 1. - Expressed as (128X-106Z)/Y.

Note that X5Y12 are tristimulus values.

The yellowing evaluation results are shown in Table 1 below.

Table 1 (yellowing degree suppression effect) I valued it. The results are shown in Table 2.

Table 2 (Evaluation of embrittlement) [Evaluation of embrittlement] After irradiating the wool yarn sample of Example 2.4.6 with light for 200 hours and 300 hours in the same manner as the yellowing evaluation method, The yarn tensile strength was measured and evaluated by expressing the ratio to the yarn tensile strength of the unirradiated sample as a percentage as the strength retention rate.
Discoloration and fading evaluation] Similar to the yellowing evaluation method, the B-p-T temperature was 85℃ using an ultraviolet carboarc fade-o-meter, and after filling with 10 m of urethane and irradiating for 20 hours and 300 hours, the color changed to fading gray. Evaluation was made on a 5-step scale.

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

Table 3 (Discoloration and fading suppression effect) Effects of the invention The modified wool of this invention has extremely strong light resistance and long-term durability because the modified wool of this invention contains an acidic substance made of a compound of a specific element inside the fiber. It exhibits excellent deterioration resistance, without causing deterioration such as yellowing or brittleness over time, and is resistant to discoloration and fading even on dyed fabrics in pale or pastel colors.

Further, in a structure in which a cationic polycondensate is contained together with the acidic substance inside the fiber, there is an advantage that the above-mentioned deterioration resistance performance is further improved. In addition, the content of the acidic substance is 0.01 to 10% by weight as the element based on the wool, and the content of the cationic polycondensate is 0.01 to 10% by weight.
With a composition of 2% by weight, each effect is fully exhibited without deteriorating the original wool properties. Further, as the acidic substance, IIA group or HA whose aqueous solution is acidic
In a structure using a salt of a group element or an ionic compound of a similar element that has adsorbed an acid component, the above-mentioned deterioration resistance performance is particularly good.

On the other hand, according to the modification treatment method of the present invention, since the process of impregnating the acidic substance is performed after performing a specific pretreatment for internal modification, the acidic substance can maximize its effects. The modified wool of this invention is efficiently contained inside the fibers in a state in which the yellowing and brittle substances inside the fibers are denatured and dissolved and removed in the pretreatment stage, and the modified wool has the most ideal deterioration resistance performance. .

By performing the impregnation treatment with the cationic polycondensate at the same time as the impregnation treatment with the acidic substance, the above-mentioned modified wool of the present invention in which the inside of the fiber is impregnated with the polycondensate together with the acidic substance can be easily obtained. .

that's all

Claims (8)

[Claims] (1) Modified wool whose fibers are impregnated with an acidic substance consisting of a compound of a group IIA or group IIIA element. (2) The modified wool according to claim (1), wherein the fiber contains a cationic polycondensate. (3) The modified wool according to claim 1, wherein the acidic substance consisting of a compound of a group IIA or group IIIA element is contained in an amount of 0.01 to 10% by weight as said element based on the wool. (4) The cationic polycondensate is 0.01 to 2% of the wool
The modified wool according to claim 2 or 3, wherein the modified wool contains % by weight. (5) Acidic substances are group IIA or III whose aqueous solution is acidic.
The modified wool according to any one of claims (1) to (4), which is a salt of a group A element. (6) Acidic substances are group IIA or IIIA that have adsorbed acid components.
The modified wool according to any one of claims (1) to (4), which is an ionic compound of group elements. (7) After subjecting the wool to internal transformation treatment by immersion in a bath, including reduction treatment and oxidation treatment, and extracting and removing dissolved substances,
A method for modifying wool, which comprises impregnating the wool with an acidic substance comprising a compound of a group IIA or group IIIA element. (8) The method for modifying wool according to claim (7), wherein the impregnation treatment with a cationic polycondensate is carried out simultaneously with the impregnation treatment with an acidic substance.