JPH0411665B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD This invention relates to modified wool that is less likely to cause yellowing or brittleness due to light, and a modification treatment method thereof. Prior Art 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, we have traditionally used unprocessed wool (Greasy wool, Washed wool).
In addition to basic treatments such as oxidative bleaching and reductive bleaching, dyeing agents are added to the processed wool (so-called anti-shrunk wool, such as surface scale treated wool and descaled wool). Alternatively, a method of reducing the degree of yellowing of pale or pastel colors of dyed products in advance, applying so-called ultraviolet absorbers such as benzophenone type, triazole type, hindered amine type, metal complex type, etc. and light stabilizer called ultraviolet shielding agent. Methods of containing antioxidants such as hindered phenol, hydrazine, and phosphorus antioxidants have been adopted. Problems to be Solved by the Invention However, with the above conventional deterioration prevention means,
None of them had a significant effect and could not 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 deteriorates significantly, 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 early discoloration and fading cannot be avoided. In view of the above-mentioned circumstances, the present invention aims to provide modified wool that has strong light resistance against sunlight and artificial light without impairing its original wool properties, and has significantly reduced yellowing and brittleness caused by light. The purpose is to provide a modification treatment method. Means for Solving the Problems In order to achieve the above object, the present invention imparts strong light resistance to wool by incorporating specific inorganic fine particles or a specific polymer thereof into the inside of the wool fibers. This prevents deterioration such as yellowing and brittleness over a long period of time. That is, the modified wool according to the present invention contains water-insoluble inorganic fine particles having an average particle diameter of 0.2 μm or less that have adsorbed acid components inside the fibers. 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 a non-woven material having acid adsorption properties. It is characterized in that the fine particles having an average particle diameter of 0.2 μm or less are contained inside the fibers by immersing the fibers in an acidic bath in which water-soluble inorganic fine particles are dispersed. The modified wool of the present invention has a structure in which a cationic polycondensate is contained inside the fiber, and the content of water-insoluble inorganic fine particles in the wool is 0.02 to 1.
10% by weight of the cationic polycondensate, the content of the cationic polycondensate relative to wool is 0.01 to 2% by weight, and the water-insoluble inorganic fine particles are at least one kind selected from silicon, group A elements, and group A elements. A configuration consisting of a hydrous complex salt compound containing an oxide of an element is a preferred embodiment. Further, in the modification treatment method of the present invention, a cationic polycondensate is dissolved in an acidic bath in which water-insoluble inorganic fine particles are dispersed, and a dye is dissolved in the same acidic bath, and the fine particles are dissolved in the above-mentioned acidic bath. A preferred embodiment is a configuration in which dyeing is carried out at the same time as the dye is contained inside the fiber. Specific structure and action The water-insoluble inorganic fine particles contained inside the fibers of the modified wool of this invention retain acid components adsorbed in the modification process etc. on the particle surface, and this acid component makes the wool It maintains internal proteins, etc. in a stable acidic range, and when it is affected by alkaline components during the manufacture and use of wool products, the alkaline components are neutralized by the above acid components, and the alkaline components are It acts as a barrier to prevent the formation of yellowing and brittle substances due to the denaturation of proteins and other intrafiber substances. Therefore, this modified wool is
It exhibits excellent sunlight fastness based on high chemical stability, and is resistant to deterioration such as yellowing and embrittlement due to light. The size of the water-insoluble inorganic fine particles mentioned above is an average particle size of 0.2 μm or less, and if the particle size becomes larger than 0.2 μm, the original wool properties will deteriorate and it will be difficult to be stably retained inside the fiber, resulting in shedding. It becomes easier. In addition, the content of the fine particles is 0.02% relative to wool.
A content of about 10% by weight is desirable; if the content is too low, the above-mentioned effects will not be fully exhibited, while if it is too high, the wool properties will deteriorate. Such water-insoluble inorganic fine particles may be any material that has acid adsorption properties and does not adversely affect the quality of wool.For example, it can be used in the medical field as an antacid adsorbent to suppress the effects of acids such as stomach acid. Fine particles of known compounds or similar compounds thereof can also be suitably used. And, as a particularly preferable one,
Examples include fine particles made of a hydrous complex salt compound containing silicon, an oxide of at least one element selected from group A elements, and group A elements. The above-mentioned hydrated complex salt compound is the above-mentioned oxide.
_SiO2 , _{B2O3 , Al2O3} , _{Ga2O3 , In2O3 , BeO} ,
Hydrous composite oxides containing two or more of MgO, CaO, SrO, BaO, etc., oxides of one or more of these oxides and other elements, halides and cyanides of the above elements or other elements, hydroxide,
It may be any hydrous compound containing one or more of sulfides, hydrosulfides, carbonates, hydrogen carbonates, etc., but among these, silicate compounds are particularly preferred. These compounds include synthetic materials obtained by dry methods such as the melting method and various wet methods such as the coprecipitation method, as well as natural minerals such as rocks and clays such as various silicate minerals. It is also possible to use those obtained as In addition, specific examples of the above-mentioned hydrous complex salt compounds include Al ₂ O ₃・9SiO ₂・10H ₂ O 2MgO・Al ₂ O ₃・SiO ₂・6H ₂ O KCa ₄ F(Si ₄ O ₁₀ ) ₂・8H ₂ O (Fisheye) 6MgO・Al ₂ O ₃・CO ₂・12H ₂ O 3Na ₂ O・2CaO・TiO ₂・12H ₂ O Al ₂ O ₃・2NaHCO ₃・3H ₂ O 3MgO・2Al ₂ O ₃・Examples include 9H ₂ O MgO, CaO, Al ₂ O ₃ , 3H ₂ O, and the like. The acid components adsorbed by such water-insoluble inorganic particles having acid adsorption properties are not particularly limited, and include organic acids such as acetic acid, formic acid, and citric acid, as well as sulfuric acid,
An inorganic acid such as hydrochloric acid may also be used. In order to cause the acid component to be adsorbed onto the fine particles, the fine particles may be dispersed and mixed in an aqueous acid solution. On the other hand, for the modified wool of the present invention, it is particularly preferable that the wool contains a cationic polycondensate together with the above-mentioned inorganic fine particles inside the fiber. In other words, cationic polycondensates react and add to substances in fibers such as proteins to suppress their chemical and physical activity, and prevent external substances that cause yellowing and embrittlement and pollutants from reacting with substances in fibers. In addition to preventing addition and adsorption, it also functions as a binder that strengthens the bonds between substances within the fibers, preventing impurities from entering the fibers, and in combination with the action of the inorganic fine particles, improves the sunlight fastness of wool. It significantly improves physical and chemical stability and prevents deterioration such as yellowing and embrittlement caused by light over a long period of time. 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 from 0.01 to wool.
It is preferably about 2% by weight; if it is too small, the above-mentioned effects will not be fully exhibited, and if it is too large, it will become sticky, resulting in poor wool quality and even worse fastness. In addition to the water-insoluble inorganic fine particles and cationic polycondensate mentioned above, the modified wool of the present invention may contain various existing additives such as antioxidants to prevent yellowing due to heat, if necessary. A suitable agent 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 action and effect of the water-insoluble inorganic fine particles or the cationic polycondensate thereof can be maximized. can be demonstrated. That is, in the modification treatment method of the present invention, after carrying out an internal modification treatment including reduction treatment and oxidation treatment as a pretreatment, the inorganic fine particles or a cationic polycondensate thereof are introduced into the inside of the fiber by immersion in an acidic bath. This is a method of carrying out this treatment in which the The wool to which this treatment method is applied may be either the above-mentioned unprocessed wool or processed wool, but it is preferable to remove hydrophobic proteins on the scale surface by a general scale treatment method, for example, by oxidation treatment with chlorine or the like. Preferably, the surface is pretreated to make it hydrophilic by denaturing or removing epicuteicles. The internal transformation treatment consists of a combination of a reduction treatment by immersion in a bath and an oxidation treatment, and preferably a two-stage treatment of reduction → oxidation or a three-stage treatment of oxidation → reduction → oxidation is performed depending on the strength of the preliminary treatment. That is,
Through this internal denaturation treatment, some of the yellowed proteins and residual lipids in the cortex and intercellular packing are decomposed or denatured, and the residual epidermis and cortex of the exocuteicle and endocuteicle in the wool, scale, and residual lipids are decomposed or denatured. As the substances are extracted and removed, the inside of the wool becomes coarse and has strong impregnating properties and chemical reactivity suitable for containing inorganic fine particles or cationic polycondensates with them in the next main treatment. An internally modified wool is provided. Note that this type of internal modification treatment is different in that it is a strong treatment that extends to the inside of the fiber, whereas conventional basic treatments such as general oxidation bleaching and reduction bleaching treat the surface of the wool fiber. It's on. 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 This is carried out by preparing 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. Also,
In the bath, a penetrant consisting of a nonionic surfactant such as polyoxyethylene alkylphenol is added in an amount of about 1.0 to 2.0% by weight based on the weight of the wool, in order to promote and uniformize the penetration of the oxidizing agent into the wool. Add various additives as necessary, such as adding about 0.1 to 1% by weight of a sequestering agent made of a phosphate polymer, etc., for the purpose of preventing the adsorption of metal ions to wool. be able to. Note that 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 oxidation treatment with hydrogen peroxide, 5 to 20 ml/
The treatment time is about 2.5 to 3 hours at a bath ratio of about 1:20 to 50 using hydrogen peroxide.
Gradually raise the pH from the acidic range of about 4.0 to 4.5 to reach an acidic range of 7 or close to this,
Further, it is preferable to adjust the treatment temperature so that the temperature is gradually raised from a low temperature (room temperature) at the start to a final temperature of about 80°C. In addition, in order to uniformly penetrate the oxidizing agent into the wool and promote the 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 0.2 to 8% of the wool weight in terms of effective chlorine amount.
% by weight, bath ratio of about 1:20 to 50, pH of about 6.8 to 7 from start to finish of treatment, temperature of 15 to 20℃.
It is best to maintain the temperature at a constant temperature 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 prepared using additives such as the above-mentioned dipping agent and water, and the wool is immersed in this 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 that the bath liquid is stirred slowly. The reducing agent used is sodium sulfite,
Sodium bisulfite, dechlorin [Zn(OH)
HSO ₂ CH ₂ O], Rongarit C (NaHSO ₃
CH ₂ O.2H ₂ O), etc., and the amount added is preferably about 1 to 5% by weight based on the weight of wool. The reduction treatment conditions include a bath ratio of about 1:20 to 50;
The pH from start to finish is about 2.5 to 3.0, and the treatment temperature is raised stepwise or continuously from the low temperature at the start (room temperature) to the final temperature of about 80℃, and the treatment time is about 0.5 to 2 hours. And it is sufficient. 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 main treatment in which the above-mentioned inorganic fine particles or a cationic polycondensate thereof are incorporated into the fibers by immersion in an acidic bath. The treatment bath is made into an acidic bath by adding a diluted solution of an acid such as acetic acid to an aqueous dispersion of inorganic fine particles. As a result, the acid component is adsorbed and retained on the particle surface of the fine particles. Here, it is necessary to select the particle size of the above-mentioned inorganic fine particles to have an average particle size of 0.2 μm or less,
In addition to selecting the particle size in advance, a simple method is to add powder containing coarse particles to water, stir it, and then let it stand.
There is a method in which coarse particles are precipitated, a supernatant liquid is collected, an acid is added to this supernatant liquid to adjust the pH, and if necessary, a cationic polycondensate is added, the mixture is thoroughly dispersed and stirred, and then left to stand still. In other words, by standing still, some of the precipitate settles to the bottom, and the liquid itself becomes a very uniform and stable dispersed colloidal solution in which colloidal fine particles with an average particle size of 0.2 μm or less, usually 0.1 μm or less are dispersed. Therefore, this solution may be used as a treatment bath. For example, when using acetic acid, the pH of the processing solution is 3.5 to 4.5.
However, since there are fluctuations due to the above-mentioned adsorption of acetic acid, it is best to repeat the addition of acetic acid and the PH measurement at small intervals. The treatment is carried out by immersing the wool after the internal modification treatment in the above dispersed colloidal solution as a bath at a bath ratio of about 1:20 to 50. 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 20
It takes about 120 minutes. After this treatment, it is slowly cooled and then washed with water or hot water several times. The wool obtained in this way contains the above-mentioned inorganic fine particles with acid components adsorbed on the particle surface or a cationic polycondensate of these particles inside the fibers, and has extremely strong resistance to oxidative decomposition by light. . Furthermore, if necessary, the wool containing inorganic fine particles or a cationic polycondensate thereof may be further subjected to auxiliary treatment such as treatment to contain an antioxidant to prevent yellowing due to heat. Good too. Further, it is possible to incorporate a dyeing process by a conventional method between the pretreatment internal metamorphosis treatment and the main treatment or simultaneously with the main treatment. To carry out staining at the same time as the main treatment, prepare the dyeing solution and the above-mentioned dispersed colloid solution for the main treatment separately in advance, and use the mixed solution of these two solutions as a treatment bath, adjusting the pH and temperature. Just soak the wool. This simultaneous treatment has the advantage of greatly simplifying the dyeing and modification treatment operations and shortening the treatment time. EXAMPLES The present invention will be specifically described below with reference to Examples. In addition, in the following, oww is the wool weight, and ml/ and g/ are the bath concentration. Example 1 A pile fabric made of 2/32 worsted Camback wool yarn whose surface scale had been previously oxidized with chlorine was washed with 1% OWW neutral detergent (Score Roll #700 manufactured by Kao Soap Co., Ltd.). Soaping treatment was carried out by immersing the specimen in a bath containing 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 adjusting the pH to 4.0 to 4.5 by adding 0.10 to 0.15 ml of 90% acetic acid to soft water at room temperature, a polyoxyethylene alkylphenol type penetrant (Meiselin H-170 manufactured by Meisei Chemical Industry Co., Ltd.) 1.5 % oww and 1% oww of a metal sequestering agent (Meinex SP manufactured by Meisei Kagaku Kogyo Co., Ltd.) consisting of a phosphate polymer.
Further, 15 ml of 35% hydrogen peroxide solution was added to prepare an oxidation bath. 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 while gently stirring.
Add 0.5% ammonia water in 5 times to adjust the pH.
Increasing it step by step to a final value of 6.8,
The treatment temperature was gradually raised to a final temperature of 80° C., and the treatment was completed in 2 hours and 30 minutes to 3 hours. During this process, 5 times for each PH adjustment and 2 times for each other 5 times.
I took a bath for ~3 minutes. Also final PH6.8,
The treatment at a temperature of 80°C was for 20 minutes, during which time the bath was drained. (2) Washing with water was carried out twice at 20 to 30°C. (3) Reduction treatment: Add 3-4ml of 88% formic acid to soft water at room temperature to adjust the pH.
was adjusted to 5.5 to 3.0, and the penetrating agent Meiselin H-
A reduction bath was prepared by adding 170 (supra) 1% oww and 5 g/dechlorin. The wool fabric after the oxidation treatment was immersed in this reducing bath at room temperature at a bath ratio of 1:30, and gradually heated to 60°C while stirring gently.
At the same time, during this time, the bath was drained five times, and the temperature was maintained at 60℃ for 15 minutes, then the temperature was further increased, maintained at 80℃ for 30 minutes, and then slowly cooled to 30℃. Finished processing. (4) Hot water washing was carried out twice at 60℃. (5) Washing with water Washed once at room temperature. (6) Oxidation treatment Oxidation treatment was performed in exactly the same manner as in (1). (7) Hot water washing was carried out twice at 60℃. (8) Washing with water Washed once at room temperature. The wool fabric that had undergone this internal modification treatment was subjected to the main treatment using inorganic fine particles and a cationic polycondensate as described below. That is, first, the chemical formula Al ₂ O ₃・9SiO ₂・10H ₂ O
10 g of synthetic aluminum silicate (light) powder and 990 ml of soft water were placed in a container, stirred, and allowed to stand for about 10 hours. Larger particles were precipitated and removed, and the supernatant liquid was taken out. The particle size in this supernatant is
It became less than 1.5μm. In this solution (supernatant liquid), disperse 0.45 to 0.50 ml of a 5% diluted solution of acetic acid (90%) in water while stirring.
It was gradually added and adsorbed, and the pH of the solution was adjusted to 4.0. Since pH adjustment depends on the adsorption amount, the adjustment was carried out by repeating the addition of acetic acid and the pH measurement several times after a while. Adjustment is completed when acetic acid is adsorbed on the surface of aluminum silicate particles and the pH becomes stable. In this case, the amount of diluted acetic acid solution added was 9 to 10 ml. Next, 3% of the weight of the wool was added with a water-soluble condensation product of quaternary ammonium salt (Neofix RP-70, manufactured by NICCA CHEMICAL INDUSTRIES, INC.), and the mixture was thoroughly dispersed and stirred. When this solution was allowed to stand for about 5 hours or more, some of the precipitates settled on the bottom, and the solution itself became a very uniform and stable dispersed colloidal solution. The particle size of colloid is
Aluminum silicate fine particles with a diameter of 0.1 μm or less and even smaller up to 50 Å are dispersed. 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 good stirring, paying attention to uniformity, and maintained at room temperature for 10 minutes at the start of treatment, then raised to 50℃ over 20 minutes, maintained at this temperature for 15 minutes, and then for 20 minutes. The treatment was completed under temperature and time conditions in which the temperature was raised to 90°C, maintained at this temperature for 15 minutes, and finally cooled down to room temperature for 15 minutes. After this treatment, rinse with water at room temperature twice, dehydrate,
After drying, a modified wool fabric was obtained. Further, this wool fabric was treated with an aqueous solution containing an antioxidant (AF-24 manufactured by Meisei Kagaku Kogyo Co., Ltd.) at a concentration of 10 to 20% by padding with a Pick-Up of 25 to 50%, and dried.
The obtained wool had an inorganic fine particle content of about 0.16% by weight and a cationic polymer content of about 0.2 to 0.3% by weight, and showed a remarkable effect in preventing yellowing and brittleness caused by sunlight. 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) Oxidation treatment For soft water, use 4% OWW of sodium hypochlorite with 12% effective chlorine and penetrant Meiselin H-170 (mentioned above)
It was added and mixed with 1% oww to create an oxidation bath with a pH of 6.7 to 8.0. In this bath, add the above worsted yarn in a bath ratio of 1:
The sample was immersed at 30° C. and treated for 10 hours at a treatment temperature of 15 to 20° C. with gentle stirring. (2) Washing with water After washing three times at room temperature, the water was drained. (3) Acid treatment The above-washed worsted yarn was immersed in a bath at a bath ratio of 1:30 by adding 3% OWW of 88% formic acid to room temperature soft water at a bath ratio of 1:30, and gently stirred. Tsu25
It was treated at ℃ for 30 minutes. (4) Washing with water was carried out twice at room temperature. (5) Reduction treatment A reduction bath with a pH of 4.5 to 5.0 was prepared by adding and mixing 68% sulfuric acid 0.1% oww, penetrating agents Meiselin H-170 (mentioned above) 1% oww, and Rongarit C 4% oww to soft water at room temperature. 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) Water washing was carried out twice at room temperature. (7) Acid treatment The worsted wool yarn after washing is soaked in room temperature soft water with 68% sulfuric acid.
In a bath with the addition of 0.2% oww to a pH of 2 to 3,
Immersion treatment was performed at room temperature for 1 to 2 minutes at a bath ratio of 1:30. (8) Water washing was carried out twice at room temperature. (9) Oxidation treatment The oxidation treatment (1) in Example 1 was carried out in exactly the same manner. (10) Washing with water was carried out twice at room temperature. The worsted yarn that has undergone this internal metamorphosis treatment has the chemical formula 2MgO・Al ₂ O ₃・SiO ₂・
_6H2O Magnesium Aluminum Silicate Powder 10
An antacid was prepared in the same manner as in Example 1, except that 3% oww of quaternary polyammonium salt condensate (Levogen FWN manufactured by Bayer) was used as the cationic polycondensate. This treatment was performed using an adsorbent and a cationic polymer. After this treatment, after washing with water at room temperature twice,
The same antioxidant treatment as in Example 1 was performed. The obtained worsted yarn has a content of inorganic fine particles of approximately
0.75% by weight, cationic polycondensate content approximately 0.4
It was ~0.6% by weight, and had excellent resistance to yellowing and embrittlement due to sunlight, and the yarn tensile strength was also improved by about 10% compared to before treatment. Example 3 As a pile material, 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, and then subjected to the following process. After dyeing using the same method as in Example 1, the material was treated with inorganic fine particles and a cationic polycondensate in the same manner as in Example 1, and further treated with an antioxidant in the same manner as in Example 1. Acidol Gray MG (manufactured by BaSF): 120% Acidol Borduex MB (same as above): 0.006% Uniperol SE-S (same as above): 2% Eulysin S (same as above): 0.5% Ammonium sulfate: 3% Recipe with the above concentrations in each bath Dyeing was carried out at a bath ratio of 1:30 for 30 minutes at a boil. This dyed product was a beautiful light gray color and had a standard density [STANDARD DEPTH 1/4]. Furthermore, the final dyed product has a content of inorganic fine particles of about 0.30% by weight and a content of cationic polycondensates of about 0.4-0.6% by weight, and although it is light in color, it is resistant to sunlight. However, it was very durable and resistant to discoloration and fading. Example 4 Merino type worsted yarn of 2/48 count, which is a shrink-proof wool that has been scaled in advance at the wool top stage, was reduced in the same manner as in (3) to (8) of Example 1 →
After carrying out two-stage internal modification treatment of oxidation, the main treatment with inorganic fine particles and cationic polycondensate and dyeing were carried out simultaneously as described below. (1) Staining and main treatment Anthrasol Blue IBC: 0.20% Yellow IRK: 0.04% Red IFBB: 0.09% Eganal UN (manufactured by Hoechst): 1% Albegal B (manufactured by CIBA-GEIGY): 1.5% Ammonium acetate : 4% Prepared in the same manner as in Example 1, except that the dyeing aqueous solution with the above concentration composition and magnesium aluminosilicate powder (same as in Example 2) was used as the inorganic fine particles, and the pH was adjusted to 6.5 to 6.8. The modified dispersed colloidal solution was mixed 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, maintained at room temperature for 20 minutes, and then The temperature was raised to 98°C in 45 minutes, and after 10 minutes, acetic acid was added to adjust the pH to 4.0 to 4.5, and the treatment was completed by boiling for another 30 minutes. (2) Color development Ammonium thiocyanate: 1.2%oww Potassium dichromate: 1.0%oww Sulfuric acid (66°Be): 10ml/Create a bath with the above component concentrations, and place the combed yarn after the dyeing and main treatment in this bath. was immersed in a bath ratio of 1:30, the treatment temperature was gradually raised from room temperature to a final temperature of 85-90°C, maintained at this final temperature for 30 minutes, then slowly cooled, and thoroughly washed with water to complete color development. . (3) Neutralization Neutralization was carried out by immersing the colored combed yarn in a slightly alkaline bath adjusted to pH 7.3 to 7.8 with diluted ammonium water at a bath ratio of 1:30 for 10 minutes at room temperature. . (4) Bleaching treatment In order to remove the yellowing of the wool during dyeing and coloring processing, bleaching treatment with hydrogen peroxide was carried out in a bath ratio of 1:30 using a conventional method. After each of the above treatments, the worsted yarn obtained by washing, dehydrating, and drying is sprayed with a 10% aqueous solution of the antioxidant AF-24 (mentioned above) and dried to a very light gray standard density. [STANDARD DEPTH
A dyed worsted yarn with a weight of 1/8] was obtained. Although this dyed product was very light in color, it maintained extremely strong sunlight fastness, had a very strong inhibitory effect against yellowing and brittleness, and was extremely resistant to discoloration, fading, and strength deterioration due to sunlight. The content of the inorganic fine particles in the dyed product was about 0.18% by weight, and the content of the cationic polymer was about 0.1 to 0.15% by weight. Example 5 A modified wool fabric was obtained in the same manner as in Example 1, except that no cationic polycondensate was used in this treatment. Example 6 In this treatment, chemical formula as inorganic fine particles
A modified worsted yarn was obtained in the same manner as in Example 2, except that the same amount of Al ₂ O ₃ .2NaHCO ₃ .3H ₂ O powder was used. In this case, the content of inorganic fine particles was 0.18% by weight. Evaluation of Examples The woven fabrics of Examples 1, 3, and 5 and the wool yarns of Examples 2, 4, and 6 thus obtained were evaluated and measured for the degree of suppression of yellowing and embrittlement. 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-based light stabilizer). [Yellowing evaluation] The black panel temperature (B/P/T) was set to a high temperature of 85 degrees using an ultraviolet carbon arc fade meter, and a 10 mm thick slab was placed on the back of the fabric samples of Examples 1, 3, and 5. It was filled with urethane and exposed to 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 conventional method samples,
A sample that had only been treated with an ultraviolet absorber was used. A spectrophotometer (colorimeter) is used to measure yellowing.
Macbeth 2020” was used. The light source is a D light source. The degree of yellowing was expressed as a yellowness index (YI): YI = (128X-106Z)/Y. In addition,
X, Y, Z are tristimulus values. The yellowing evaluation results are shown in Table 1 below.

[Embrittlement evaluation]

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

[Discoloration and fading evaluation]

Same as yellowing evaluation method, B/P/T temperature 85℃, 10mm using ultraviolet carbon arc fade-o-meter.
After filling with urethane and irradiating with light for 20 hours and 300 hours, evaluation was made on a 5-level grayscale scale of discoloration and fading. The results are shown in Table 3. In this case, the conventional example was the same dyeing process as in Example 3.

[Table] On the other hand, FIG. 1 shows fiber cross-sectional views of the wool before the treatment used in Example 2, and FIG. 2 shows the fiber cross-sections of the wool after the treatment of Example 2, taken by electron micrographs. A comparison between the two figures shows that the wool of the present invention has a denser cross-section than the untreated wool, and has inorganic fine particles and cationic condensates added to the intercellular regions. Effects of the Invention The modified wool of this invention contains specific water-insoluble inorganic fine particles inside the fiber, so it has extremely strong light resistance and does not cause deterioration such as yellowing or brittleness over a long period of time. It exhibits excellent deterioration resistance and is resistant to discoloration and fading even on dyed fabrics in light and pastel colors. Further, in a structure in which the cationic polycondensate is contained together with the inorganic fine particles inside the fiber, there is an advantage that the above-mentioned deterioration resistance performance is further improved. In addition, in a configuration in which the content of the above-mentioned inorganic fine particles is 0.02 to 10% by weight based on the wool, and in a configuration in which the content of the cationic polycondensate is 0.01 to 2% by weight, each effect has an inherent characteristic of wool. It is fully demonstrated without reducing the performance. Furthermore, as inorganic fine particles,
By using a hydrous composite salt compound containing silicon, an oxide of at least one element selected from group A elements, and group A elements, the above-mentioned deterioration resistance performance becomes particularly good. On the other hand, according to the modification treatment method of the present invention, the main treatment of containing the inorganic fine particles in an acidic bath is performed after a specific pretreatment for internal transformation, so that the fine particles can maximize their action and effect. The modified material of this invention is efficiently contained inside the fiber in a state where it can exhibit the desired properties, and the yellowing and brittle substances inside the fiber are denatured and dissolved and removed in the pretreatment stage, resulting in the most ideal deterioration resistance performance. Obtains wool. By dissolving the cationic polycondensate in the acidic bath, the modified wool of the present invention containing the polycondensate together with the inorganic fine particles inside the fiber can be easily obtained. Further, by dissolving the dye in the acidic bath, the modification treatment and dyeing can be performed simultaneously, which simplifies the process and enables labor saving and shortening of processing time.

[Brief explanation of drawings]

FIG. 1 is an electron micrograph at a magnification of 1500 times showing the fiber cross-sectional shape of untreated wool used in Example 2 of the present invention, and FIG. This is a magnified electron micrograph.

Claims (1)

[Claims] 1. Average particle diameter of 0.2μ with acid component adsorbed inside the fiber.
Modified wool containing water-insoluble inorganic fine particles of less than m. 2. The modified wool according to claim 1, which contains a cationic polycondensate together with water-insoluble inorganic fine particles. 3 Water-insoluble inorganic fine particles are 0.02 to wool
The modified wool according to claim 1 or 2, containing 10% by weight. 4 The cationic polycondensate is 0.01 to 2
The modified wool according to claim 2 or 3, wherein the modified wool contains % by weight. 5. The modified wool according to any one of claims 1 to 4, wherein the water-insoluble inorganic fine particles are composed of a hydrous complex salt compound containing silicon, an oxide of at least one element selected from group A elements, and group A elements. . 6 After 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, the wool is immersed in an acidic bath in which water-insoluble inorganic fine particles having acid adsorption properties are dispersed. A method for modifying wool, characterized in that the above-mentioned fine particles having an average particle diameter of 0.2 μm or less are contained inside the fibers by doing so. 7. Claim 6, wherein the cationic polycondensate is dissolved in an acidic bath in which water-insoluble inorganic fine particles are dispersed.
The described wool modification treatment method. 8. The method for modifying wool according to claim 6 or 7, wherein the dye is dissolved in an acidic bath in which water-insoluble inorganic fine particles are dispersed, and dyeing is carried out at the same time as the fine particles are contained inside the fiber.