JPH0759791B2 - Treatment agent and treatment method for animal hair fibers - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a treating agent and a treating method for animal hair fibers.

More specifically, the present invention relates to a novel agent for treating animal hair fibers that improves the bleaching, dyeing, shrink-proofing, and other processing of animal hair fibers, and also to a rational method for treating animal hair fibers using said agent.

[Background Art] As is well known, animal hair, such as sheep's wool, undergoes many processes before it can be used in our daily lives as a textile product, starting with the washing of the shorn raw wool. In particular, chemical treatments such as scouring, bleaching, dyeing, and shrink-proofing are essential.

For example, conventional bleaching of animal hair fibers involves oxidation bleaching, which is carried out in a bleaching bath containing an oxidizing agent, typically hydrogen peroxide, as the active ingredient, while reduction bleaching, which is carried out in a bleaching bath containing a reducing agent, such as hydrosulfite, as the active ingredient, is also carried out.

In particular, animal hair fibers after the former oxidative bleaching are often subjected to post-treatment in a bath containing a thionic acid reducing agent such as hydrosulfite or thiourea dioxide in order to further improve whiteness.

However, in recent years, many animal hair garments, such as wool, have been sold commercially with decorative plated beads or metal products attached. However, when these animal hair garments are stored in plastic packaging bags or displayed in stores, sulfur-based gases are generated from the reducing agent used in the post-bleaching process, which remains in small amounts in the animal hair garments. This causes problems such as discoloration of pearl-colored beads to a dark black within one to two months.

In addition, due to the characteristics of its fiber structure, animal hair generally shrinks during processing or washing of the processed product.
Shrinkage prevention processing is applied.

For example, shrink-proofing of animal hair fibers has conventionally been carried out by immersing the fibers in a bath of an aqueous solution containing, as an active ingredient, a chemical such as chlorinated isocyanurate, potassium permanganate, or peroxide.

However, when shrink-proofing animal hair using the conventional shrink-proofing agents, it is common to perform the shrink-proofing before dyeing, and it is extremely difficult to perform shrink-proofing on animal hair after dyeing because it can cause discoloration, fading, or bleaching of the dyed product or damage to the animal hair. Therefore, when shrink-proofing is required after dyeing, conventional shrink-proofing treatments cannot be performed.

Furthermore, shrink-proofing using the above chemicals requires very strict processing conditions and bath control is extremely difficult. In particular, it has been extremely difficult to simultaneously impart pilling resistance to animal hair fibers in conventional shrink-proofing processes.

Furthermore, traditionally, dyeing animal hair fibers requires the addition of sulfuric acid to the dye.
A high-temperature dyeing method (boiling-point dyeing method) is commonly used, in which a dyebath adjusted to a weakly acidic or acidic range by adding acids such as acetic acid or formic acid, or salts such as ammonium sulfate or ammonium acetate, or sodium sulfate and a leveling agent, is used, and the temperature is gradually increased from room temperature until it reaches the boiling point, at which point the dye is maintained for about 60 minutes.

On the other hand, since such dyeing methods tend to damage the fiber structure of animal hair, low-temperature dyeing methods, such as the urea method, formic acid method, surfactant method, and organic solvent method, in which dyeing is performed at a low temperature below the boiling point without heating the dye bath to the boiling point, have been studied in order to protect the quality of animal hair. In particular, there has been a report on the use of a bath containing an organic phosphine compound as an active ingredient in an attempt to process a sheep color suitable for low-temperature dyeing (Journal of
The Society of Dyers and Colourists (J.Soc.Dyers & Colourists) Vol.95,396, Australian Journal of Chemistry (Aus
Australian Journal of Biological Sciences (Aust. J. Chem.) Vol. 19, 2347-2360 (1966), Australian Journal of Biological Sciences (Aust. J. Biol. Sci.) Vol. 21, 805-813 (1968). This bath is prepared by dissolving tributylphosphine in an aqueous propanol solution. However, this tributylphosphine is not water-soluble and is therefore different from the water-soluble organic phosphine compound of the present invention.

In the chemical processing of animal hair fibers as described above, the conventional post-treatment of oxidative bleaching cannot prevent discoloration over time of metal or plated items attached to the animal hair product for decorative purposes.

Furthermore, conventional high-temperature dyeing methods inevitably cause damage to animal hair fibers, resulting in embrittlement of the animal hair and deterioration of the handling touch. On the other hand, despite efforts to develop low-temperature dyeing methods, the technology is still incomplete, and the reality is that few methods have been put into industrial use.

In view of the above-mentioned problems, the present inventors have conducted extensive research into the processing of animal hair fibers in order to solve these problems. As a result, they have discovered that by using a chemical containing a water-soluble tris(3-hydroxypropyl)phosphine compound as an active ingredient, significant improvements can be achieved, and in particular, good quality animal hair processed products with improved pilling resistance can be obtained after any processing operation, and have thus completed the present invention.

[Disclosure of the Invention] In other words, the present invention relates to an animal hair fiber treatment agent characterized by being composed of an aqueous solution (with a concentration of 0.005 to 3% owm in terms of P and a pH range of 2 _to 7) in which tris(3-hydroxypropyl)phosphine represented by the following general formula: PR3 [wherein R represents a 3-hydroxypropyl group] and one or more auxiliaries selected from acidifying agents, pH adjusters, surfactants, or leveling agents are dissolved as active ingredients.

Furthermore, the second invention of the present invention is a method for treating animal hair fibers by immersing the animal hair fibers in the agent for treating animal hair fibers at a bath ratio of 1:1 to 100:1 at a temperature of 0.5 to 3°C.
The present invention relates to a method for treating animal hair fibers, characterized in that the temperature is raised at a rate of 100°C/min and then held at a maximum temperature of 100°C for 5 seconds to 60 minutes.

The first object of the present invention is to impart significant pilling resistance to animal hair fiber products.

The second object of the present invention is to preserve the quality of metal-attached parts such as decorative beads and to impart light resistance to animal hair fibers by using a post-treatment instead of the conventional oxidative or reductive bleaching post-treatment.

The third object of the present invention is to enable low-temperature dyeing and, at the same time, shrink-proofing in one bath.
Moreover, it is also possible to provide easy and safe processing.

Furthermore, a fourth object of the present invention is to apply shrink-proofing treatment to animal hair fibers at any processing stage, whether before or after the dyeing treatment of the animal hair fibers, without adversely affecting the dyeing treatment at all.

The present invention will be described in detail below.

One of the features of the animal hair treating agent according to the present invention is the use of the specific tris(3-hydroxypropyl)phosphine (hereinafter referred to as "THPP") as described above.

If necessary, the THPP may be used as an adduct of ethylene oxide or propylene oxide.

This adduct can be easily obtained by reacting THPP with ethylene oxide or propylene oxide. The addition reaction of alkylene oxide to this hydroxyalkyl group is obvious to those skilled in the art. The function of these adducts in animal fiber treatment agents is not substantially different from that of THPP.

The number of moles added may be up to 5 at most.

THPP is easily soluble in water because it has three -OH hydrophilic groups, and because it is a trivalent organic phosphorus compound, even a small amount will produce a strongly reducing aqueous solution. The content of THPP in animal hair fiber treatment agents is usually 0.00 in terms of P in the compound.
The desired range is 5 to 3.0% owm, and preferably 0.02 to 2.0% owm. The reason is that if the owm is less than 0.005% owm, there is no fiber treatment effect, and if the owm is more than 3.0%, the effect does not increase and there is no economic meaning. In this invention, the unit of % owm means weight % of the fiber material to be treated.

Another feature of the animal hair fiber treatment agent of the present invention is that it is composed of an aqueous solution in which the above-mentioned THPP and one or more auxiliaries selected from an acidifying surfactant, a pH adjuster, or a leveling agent (dye) are dissolved.

The acidifying substance is a compound that adjusts the pH of the treatment bath to neutral or weakly acidic, and is a weak acid that does not form a phosphonium addition salt. Examples of such a weak acid include carboxylic acids such as formic acid, acetic acid, propionic acid, citric acid, and oxalic acid, as well as phosphonic acids and sulfonic acids, with carboxylic acids such as acetic acid being preferred.

The pH adjuster is a compound that has a pH moderating effect on the treatment solution, and examples thereof include alkali monohydrogen phosphate, alkali dihydrogen phosphate, alkali pyrophosphate, alkali tripolyphosphate, alkali borate, and alkali acetate.

Surfactants have been commonly used in the treatment of animal hair fibers for a long time. Examples include anionic surfactants based on carboxylates, sulfonates, sulfates, or phosphates; cationic surfactants such as alkylamines; zwitterionic surfactants based on carboxybetaines, aminocarboxylates, or imidazolinium betaines; nonionic surfactants based on ethers, ether esters, esters, or nitrogen-containing types; and fluorine-based surfactants.

The leveling agent (dye) used in the present invention may be any dye that can be used to dye animal hair, and examples thereof include acid dyes such as leveling dyes, milling dyes, and super milling dyes, 1:1 type metal complex acid dyes,
Examples include metal complex acid dyes such as 1:2 type metal complex acid dyes, reactive dyes, and chrome dyes.
From the viewpoint of fastness, reactive dyes are particularly preferred.

The animal hair fiber treatment agent according to the present invention is an aqueous solution composed of the above-mentioned chemicals. The specific composition and pH of the agent are determined depending on the type of animal hair fiber and the purpose of processing, but it is recommended to adjust the pH in advance to a range of 2 to 7, preferably a weakly acidic range of 3 to 6 at the end of the bath, which is generally optimal for animal hair.

The animal hair fiber treatment bath according to the present invention has a major feature in that it can dye and prevent shrinkage at the same time when used in combination with a dyeing agent.

In addition, in many conventional dyeing methods, dyeing is performed at the temperature of the boiling point of the bath, that is, boiling point dyeing. However, when dyeing is performed using the treatment agent of the present invention, the temperature is set to between room temperature and 80°C.
It is possible to dye at low temperatures up to 100°C. However, if necessary, it is also possible to dye at higher temperatures up to 100°C. The ability to dye at such low temperatures is a very desirable advantage in that it does not damage the structure of the animal hair fibers.

Furthermore, when shrinkage prevention is the objective of animal hair fibers, the treatment may be carried out after dyeing, or conversely, dyeing may be carried out after shrinkage prevention treatment. Furthermore, as a post-treatment of the conventional oxidation bleaching treatment,
It can be effectively applied.

In any of the processing methods, a common feature is that when the processing bath of the present invention is used, it is possible to impart pilling resistance to the animal hair fibers.

The pilling resistance is a well-known property in the field of animal hair fiber processing, and refers to the property of animal hair that is resistant to pilling due to external friction, etc. Processing animal hair to impart this pilling resistance has been a long-standing challenge in the industry, but no successful examples have been found to date. However, according to the present invention, this pilling resistance can be imparted to animal hair in a surprisingly remarkable manner.

The method for processing animal hair fibers using the animal hair fiber treatment bath according to the present invention has the practical advantage that it can be carried out extremely safely and simply, as will be described below.

That is, the animal hair fiber product to be treated is immersed in the animal hair fiber treatment bath according to the present invention. The weight ratio of the bath to the treated fiber product, i.e., the liquor ratio, is desirably 1:1 to 100:1, preferably 5:1 to 60:1. The bath temperature during immersion may be room temperature.

Next, although it varies depending on the type of animal hair, it is usually kept at room temperature or
The animal hair fiber treatment bath is immersed at 80°C, or up to 100°C if necessary. In this case, the temperature of the animal hair fiber treatment bath is raised at a rate of about 0.5 to 3°C per minute to prevent a sudden reaction. The treatment bath is heated in this way and maintained at a constant temperature. There is no particular restriction on the holding time, but
The time at the highest temperature is generally in the range of 5 seconds to 60 minutes, preferably 20 to 40 minutes.

When immersion treatment is carried out as described above, THPP is oxidized and the pH of the bath gradually decreases, but the decrease in pH is usually about 0.
Since the pH ranges from 0.4 to 0.6, it is easy to set the pH in advance and control the bath. Therefore, for example, if the initial bath is set to pH 5.0, the final bath will have a pH of 4.4 to 4.6, which is optimal for animal hair fibers. Therefore, by controlling the pH, processing can be terminated after the desired time has elapsed when the pH drop has stabilized.

After this processing, the fibers can be washed and dried in the usual manner, but it is preferable to immediately neutralize them with a strong acid capable of forming a phosphonium salt. In the present invention, it is particularly preferable to perform the post-treatment with an aqueous solution of sulfuric acid or an alkali bisulfate such as sodium bisulfate or potassium bisulfate. The purpose of this post-treatment is to remove small amounts of phosphine compounds remaining on the fibers. In this sense, an oxidizing agent may be used, but with a strong acid, particularly sulfuric acid or alkali bisulfate,
Not only does this not damage the fibers, but it also results in a good handling touch.

The treatment conditions at this time, i.e., bath ratio, bath concentration, bath temperature, etc., may be roughly the same as those described above.

By carrying out such post-treatment, it is possible to eliminate the reducing power remaining in the animal hair fibers treated with THPP.

The animal hair fibers are then washed and dried in a conventional manner to complete the processing of the animal hair fibers according to the present invention. If necessary, a conventional softening process may be carried out after the processing according to the present invention.

Representative examples of animal hair that can be used in the animal hair fiber treatment agent of the present invention include sheep's hair, goat's hair, rabbit's hair, camel's hair, etc., and may also be a mixture of these. Furthermore, animal hair fibers include, but are not limited to, raw hair before spinning, as well as processed yarns, woven fabrics, knitted fabrics, and various processed fiber products such as clothing.

[Action] Although the details of the mechanism of action of the animal hair fiber treatment agent of the present invention on animal hair fibers are unknown, it is believed that water-soluble phosphorus with reducing power reacts with the -SS of cystine, which is one of the protein structures of animal hair fibers.
Cleavage of the -bond appears to result in effective processing.

For example, when dyeing is carried out in a bath using the treatment agent according to the present invention, THPP is oxidized as the -SS- bond is cleaved, and the pH of the bath
The dye absorption is slow at first and then progresses gradually. Therefore, there is no chippy dyeing, where the dyeing of the tip of the animal hair differs from that of the whole hair, or the flickering feeling caused by a lack of harmony in the component colors, and uniform dyeing can be achieved. In addition, uniform dyeing can be achieved without uneven dyeing.

Furthermore, since the water-soluble THPP of the present invention is a reducing agent as described above, it can be used as a post-treatment bath following the conventional oxidative bleaching treatment, and also as a shrink-proofing bath.

The common effect of such treatment baths is thought to be the cleavage of -SS- bonds without causing any damage to the animal hair fibers, which is thought to result in the animal hair fibers being endowed with remarkable pilling resistance and improvement thereof.

EXAMPLES Next, the present invention will be described in more detail with reference to examples and comparative examples.

Example 1. Animal Hair Fiber Treatment Agent (Dyeing Treatment Bath) Prepare a dyeing treatment bath consisting of an aqueous solution of the following composition.

CI Acid Yellow 121 (CI Acid Yellow
121) [ICI] 1.0% owm CI Acid Red 359
(CI Corporation) 1.0% owm CI Acid Black 188 (CI Acid Black 1
88) (manufactured by ICI Co., Ltd.) 1.0% owm 90% acetic acid 1.35cc / disodium dihydrogen pyrophosphate 0.9g / trisodium monohydrogen pyrophosphate 0.1g / leveling agent [Unisol WL (manufactured by ICI Co., Ltd.)] 2.35% o.
wm Tris(3-hydroxypropyl)phosphine P( _C3H6OH ) _{3 4.73} % owm (P equivalent: 0.70% owm) Comparative Examples 1. Animal hair fiber treatment agent (conventional dyeing treatment bath) A dyeing bath consisting of an aqueous solution of the following composition corresponding to Example 1 is prepared.

C.I. Acid Yellow 121 1.0% o.w.m. C.I. Acid Red 359 1.0% o.w.m. C.I. Acid Black 188 1.0% o.w.m. 90% Acetic Acid 0.8 cc/ml Disodium Dihydrogen Pyrophosphate 2.25 g/ml Trisodium Monohydrogen Pyrophosphate 0.25 g/ml Leveling Agent [Unisol WL] 2.35% o.w.m. Example 2. Dyeing Bath Prepare a dyeing bath consisting of an aqueous solution of the following composition:

C.I. Reactive Yellow 39 (CIReative
Yellow 39) (Ciba-Geigy) 1.0% owm CI Reactiv Red 84 (CI Reactiv Re
d 84) (manufactured by Ciba-Geigy) 1.0% owm CI Reactiv Blue 69 (CI Reactiv Bl
ue 69) (manufactured by Ciba-Geigy) 1.0% owm 90% acetic acid 1.35 cc/ disodium dihydrogen pyrophosphate 0.9 g/ trisodium monohydrogen pyrophosphate 0.1 g/ leveling agent [Unisol WL] 2.35% owm Tris(3- _{hydroxypropyl} )phosphine P( _C3H6OH ) ₃ 4.73% o.wm (P equivalent: 0.70% owm) Comparative Example 2. A conventional dyeing treatment bath is prepared consisting of an aqueous solution of the following composition corresponding to Example 2.

C.I. Reactive Yellow 39 1.0% o.w.m. C.I. Reactive Red 84 1.0% o.w.m. C.I. Reactive Blue 69 1.0% o.w.m. 90% Acetic Acid 0.8 cc/ml Sodium Dihydrogen Pyrophosphate 2.25 g/ml Trisodium Monohydrogen Pyrophosphate 0.25 g/ml Leveling Agent [Unisol WL] 2.35% o.w.m. Example 3. Prepare a dyeing bath consisting of an aqueous solution of the following composition:

C.I. Acid Yellow 127 (Nippon Kayaku Co., Ltd.)
1.0% owm C.I. Acid Red 138 (Nippon Kayaku Co., Ltd.)
1.0% owm C.I. Acid Blue 138 (Nippon Kayaku Co., Ltd.)
[Manufactured by] 1.0% owm 90% acetic acid 1.35cc/ disodium dihydrogen pyrophosphate 0.9g/ trisodium monohydrogen pyrophosphate 0.1g/ leveling agent [Unisol WL] 2.35% owm Tris(3- _{hydroxypropyl} )phosphine P( _C3H6OH ) ₃ 4.73% owm (P equivalent: 0.70% owm) Comparative Example 3. A conventional dyeing treatment bath is prepared consisting of an aqueous solution of the following composition corresponding to Example 3.

C.I. Acid Yellow 127 1.0% o.w.m. C.I. Acid Red 138 1.0% o.w.m. C.I. Acid Blue 138 1.0% o.w.m. 90% Acetic Acid 0.8 cc/ml Sodium Dihydrogen Pyrophosphate 2.25 g/ml Trisodium Monohydrogen Pyrophosphate 0.25 g/ml Leveling Agent [Unisol WL] 2.35% o.w.m. Example 4. A dyeing bath consisting of an aqueous solution of the following composition is prepared.

C.I. Acid Yellow 121 1.0% owm C.I. Acid Red 359 1.0% owm C.I. Acid Black 188 1.0% owm 90% acetic acid 1.35 cc / disodium dihydrogen pyrophosphate 0.9 g / trisodium monohydrogen pyrophosphate 0.1 g / leveling agent [Unisol WL] 2.35% owm P( _C3H6OH ) ₃ 16.79% owm (P equivalent: 0.71% owm) 1) Dyeing method of Examples 1 _to 4 Wool yarn (50% lamb, 50% merino) (hereinafter referred to as wool yarn) was added to the dyeing treatment agent prepared in Examples 1 to 4 so that the bath ratio was 20:1. The bath temperature at this time was room temperature.
After the wool yarn was added, the bath temperature was increased at a rate of 1°C/min, stopped at 70°C, and held at 70°C for 35 minutes.
The pH values of the initial and final baths are shown in Table 1.

After dyeing, 10 wt% sodium bisulfate 2% owm
The wool yarn was subjected to an acid treatment at 60°C for 20 minutes using a bath containing the above in a bath ratio of 20:1.

After the acid treatment, the sample was washed with a bath containing 2 g of detergent (nonionic anionic FWA-260, manufactured by Ipposha Oil & Fat Industries Co., Ltd.) at a bath ratio of 20:
In step 1, the wool yarn was soaped by keeping it at 60°C for 20 minutes, and then washed twice with water. After washing, the wool yarn was dehydrated and dried to obtain a product.

2) Dyeing treatment method for Comparative Examples 1 to 3 Wool yarns consisting of 50% lamb and 50% merino wool were immersed in a shrink-proofing bath of the following composition, neutralized by adding acetic acid, at a bath ratio of 20:1.
The treated product is washed with water and then added to a 10% oem solution of anhydrous sodium sulfite.
The pieces are then immersed in a bath adjusted to pH 5.5 with acetic acid at a bath ratio of 20:1 and treated at room temperature for 30 minutes. After treatment, the pieces are rinsed with water, hot water, and water again.

Shrinkage prevention bath detergent (nonionic anionic FWA-260, Ipposha Oil & Fat Industries Co., Ltd.)
[Manufactured by] 0.5% owm Leveling agent [Unisol WL] 1% owm Chlorinated potassium isocyanurate 4% owm Potassium permanganate 2% owm Anhydrous sodium sulfate 10 g/l The shrink-proofed wool was then added at room temperature to the dyeing baths prepared in Comparative Examples 1 to 3 so that the bath ratio was 20:1. After adding the wool yarn, the bath temperature was raised at a rate of 1°C/min, and after boiling, the bath was maintained for 45 minutes. The pH of the initial and final baths was as shown in Table 1.

After dyeing, the wool yarn was soaped in a bath containing 2 g of detergent (nonionic anionic FWA-260, manufactured by Ipposha Yushi Kogyo Co., Ltd.) at a bath ratio of 20:1 at 60°C for 20 minutes, and then washed twice with water. After washing, the wool yarn was dehydrated and dried to obtain a product.

3) Evaluation method of dyeing: To evaluate the dyed wool samples obtained by dyeing treatment, a colorimeter (ND-101DP type manufactured by Nippon Denshoku Industries Co., Ltd.) was used to determine the L value, a value, b value and Hunter whiteness index.
The color difference was then determined, and the results are shown in Tables 2 and 3.

As is clear from the above results, when processing is performed using the dyebath of the present invention, low-temperature dyeing becomes possible with a dyeing effect that is in no way inferior to that of conventional boiling point dyeing processing.
When the dyed fibers were evaluated, it was clearly confirmed that the fibers had excellent shrink resistance and pilling resistance at the same time. In other words, it became possible to process the fibers in a single bath.

In order to specifically clarify this point, the following example was carried out.

Example 5. Animal hair fiber treatment agent (animal hair fiber shrink-proof bath) (Preparation of animal hair fiber shrink-proof bath) A pH 5 animal hair fiber shrink-proof bath was prepared from an aqueous solution containing: tris( ₃ -hydroxypropyl)phosphine P( _C3H6OH ) ₃ 7.5% owm (P equivalent: 1.11% owm) leveling agent [Unisol WL] 2.35% owm trisodium monohydrogen pyrophosphate 0.1 g disodium dihydrogen pyrophosphate 0.9 g 90% acetic acid 1.8 g

(Shrink-proofing method) This method uses shrink-proofing after dyeing.

Specifically, a 100% wool knit was immersed in a dyebath containing the following composition: CI Reactive Yellow 39 0.3% owm, CI Reactive Red 84 0.3% owm, CI Reactive Blue 69 0.3% owm, ammonium sulfate 4% owm, Alvegal B (Ciba-Geigy) 1.5% owm, and 90% acetic acid 1 cc/ml at a bath ratio of 30:1. The immersion was carried out at room temperature. The temperature was then raised to 90°C at a rate of 1°C/min over approximately 60 minutes, and the fabric was then held at 90°C for approximately 40 minutes to complete the dyeing.

After dyeing, the fabric is treated with an aqueous solution containing 5% ammonia water and 2% owm at a bath ratio of 30:1 at 40°C for 10 minutes.
Washing with water was carried out.

The dyed wool was then immersed in the animal hair fiber shrink-proof bath prepared above at a bath ratio of 30:1 at room temperature. The temperature was raised to 75°C at a rate of 1°C/min over approximately 45 minutes, and then maintained at 75°C for approximately 20 minutes to complete the shrink-proofing process. After completion of the shrink-proofing process, the wool was immersed in an aqueous solution containing 3% sodium bisulfate at a bath ratio of 30:1.
After treating at 40°C for 10 minutes at a ratio of 0:1, the product was obtained by drying.

Comparative Example 4 (Preparation of Conventional Shrink-Proof Bath for Animal Hair Fibers) A shrink-proof bath for animal hair fibers was prepared from an aqueous solution containing 4% owm of chlorinated potassium isocyanurate, 2% owm of potassium permanganate, 0.5% owm of a nonionic surfactant, 1% owm of an anionic surfactant, and 20% owm of anhydrous sodium sulfate, and the pH of the bath was made neutral by adding acetic acid.

(Shrink-proof and dyeing process) Immerse 100% wool knitted fabric in the shrink-proof bath at a bath ratio of 30:1.
The fabric was then kept at 5-18°C for 40 minutes to prevent shrinkage. Then, it was washed with water and diluted with 10% sodium bisulfite, which was made weakly acidic with acetic acid.
The fabric was immersed in an aqueous solution containing the compound at a bath ratio of 30:1 and left at room temperature for 30 minutes.The fabric was then rinsed with water and hot water and dried again.

The above shrink-proofed wool was dyed in the same bath and in the same manner as in Example 5 to give a product.

(Evaluation method for processed fibers) i) Dyeing evaluation is performed using a colorimeter.

ii) Washing fastness is evaluated according to JIS L0844 A-2.

iii) Light fastness is evaluated according to the third exposure method of JIS L0842.

iv) Shrinkage test is evaluated according to IWS TM31 (ISO 5A and 7A cycle 2).

v) Pilling resistance is evaluated according to JIS L1076, ICI type method for 5 hours.

The properties of the shrink-proof products of Example 5 and Comparative Example 4 based on the above evaluation methods are shown in Table 4.

As is clear from the above table, the treatment agent of the present invention provides outstanding shrink and pilling resistance to wool.

Example 6 (Preparation of shrink-proof bath for animal hair fibers) P _{[C3H6O ( C2H4O} ) _4H ] _{3 25.18} % owm (P conversion: 1.07% owm) Leveling agent [Unisol WL manufactured by ICI] 2.3
An animal hair fiber shrink-proofing bath having a pH of 5 was prepared, consisting of an aqueous solution containing 5% owm trisodium monohydrogen pyrophosphate 0.1 g/disodium dihydrogen pyrophosphate 0.9 g/90% acetic acid 1.35 cc/.

(Dyeing and shrink-proofing processing) The following dyeing ingredients: C.I. Mordant Black 11 (CIMordant Bl
ack 11) 3% owm C.I. Mordant Black 7 (CI Mordant Bl
ack 7) 3% owm leveling agent [Unisol WL] 1% owm 90% acetic acid 1cc/ A 100% wool knitted fabric was dyed in a dye bath containing 1 cc/L at a bath ratio of 30:1.
The sample was immersed at room temperature, then heated to 95°C at a rate of 1°C/min over a period of about 65 minutes, and then maintained at 95°C for about 40 minutes.

After cooling to 80°C, 1% ow of 90% acetic acid was added.
m., potassium dichromate 1% owm, added, and heated to 80°C for 5
After holding for 1 minute, the temperature was increased to 95°C at 1°C/minute, and then heated at 95°C for 20 minutes.
Hold for 1 minute, add 1% lactic acid, and keep at the same temperature.
The staining was completed after a 10 minute hold.

Next, the sample was immersed in a bath of an aqueous solution containing 1 g of a nonionic surfactant (Dianol 45, manufactured by Shin-Nakamura Chemical Co., Ltd.) and 1 g of an anionic surfactant (Persoft SL, manufactured by Nippon Oil & Fats Co., Ltd.) at a bath ratio of 30:1, and heated to 60°C for 10 minutes.
After keeping for 1 minute, it was washed with water.

The wool dyed in this manner was then immersed in the animal fiber shrink-proof bath prepared above at a bath ratio of 30:1 at room temperature.

The temperature is raised to 75°C at 1°C/min over approximately 45 minutes, and then the
The fabric was left in this state for 20 minutes to complete the shrinkage and pilling resistance treatment.

After the shrink-proofing treatment, the fabric was treated with an aqueous solution containing 2% sodium bisulfate at a bath ratio of 30:1 at 40°C for 10 minutes, and then dried to obtain a product.
As shown in the table.

Comparative Example 5. The 100% wool knitted fabric used in Example 6 was subjected to shrink-proofing in the same manner as in Comparative Example 4. The product was then dyed in the same manner as in Example 6, and the properties of the product are shown in Table 5.

Example 7. (Preparation of shrink-proof bath for animal hair fibers) A shrink-proof bath for animal hair fibers having a pH of ₅ was prepared from an aqueous solution containing: tris(hydroxypropyl)phosphine P( _C3H6OH ) ₃ 7.5% owm (P equivalent: 1.11% owm), leveling agent [Unisol WL] 2.35% owm, trisodium monohydrogen pyrophosphate 0.1 g, disodium dihydrogen pyrophosphate 0.9 g, and 90% acetic acid 1.8 g.

(Shrinkage prevention and dyeing processing) A knitted fabric made of 100% wool was immersed in the animal hair fiber shrinkage prevention bath prepared above at a bath ratio of 30:1 at room temperature.

The temperature is raised to 75°C at 1°C/min over approximately 45 minutes, and then the
The fabric was left to stand for 20 minutes to complete the shrink-proofing treatment. After completion of the shrink-proofing treatment, the fabric was post-treated at 40°C for 10 minutes using an aqueous solution containing 3% sodium bisulfate in a bath ratio of 30:1.
The product was dyed in the same manner as in Example 5 to obtain a product.

The various properties of the obtained product are shown in Table 6 in comparison with those of Comparative Example 4.

Example 8. Animal hair was bleached by the following method.

(Bleaching procedure) (1) Target fiber: 100% wool knitted fabric (2) Bleaching bath: 35% hydrogen peroxide, 40% owm, 1-hydroxyethylidene-1,1-diphosphonic acid trisodium salt 1.6g, urea 5g, nonionic anionic surfactant 2g, trisodium monohydrogen pyrophosphate 0.25g, disodium dihydrogen pyrophosphate 1g, disodium phosphate heptahydrate 2.5g (3) Bleaching conditions: Bath ratio 20:1, temperature and time: Raise the temperature from room temperature to 60°C at 1°C/min, and at 60°C,
It was held for 120 minutes.

After bleaching in this manner, the fabric was washed with hot water and then with water, and then subjected to the following post-treatment procedures.

(Post-treatment Procedure) Preparation of Post-treatment Bath Prepare a bleaching post-treatment bath consisting of an aqueous solution of the following composition.

Tris(3-hydroxypropyl)phosphine P( _C3H6OH ) _{3 8.0} % owm (P equivalent: 1.18% owm) Leveling agent [Unisol WL] 2.35% owm Trisodium monohydrogen pyrophosphate 0.1g / Disodium dihydrogen pyrophosphate 0.9g / 90% acetic acid 1.8g / pH 5.0 Post-treatment conditions Bath ratio 20:1 Temperature/time Raise temperature from room temperature to 75°C at 1°C/min, and then
The temperature was maintained at 40°C for 20 minutes.

After the treatment, a new solution containing 2% sodium bisulfate was used in a bath ratio of 20:1.
The mixture was treated at 40°C for 10 minutes and then dried.

Comparative Example 6 After the bleaching operation was carried out in the same manner as in Example 8, post-bleaching treatment was carried out using the following post-treatment using hydrosulfite.

(Post-treatment operation) Preparation of bleaching post-treatment bath Hydrosulfite 5g / 90% acetic acid 0.5g / disodium dihydrogen pyrophosphate 1g / pH 4.5 Post-treatment conditions Bath ratio 20:1 Temperature / time Raise the temperature from 50 to 60°C at 1°C/min, and at 60°C
It was held for 20 minutes.

After the post-treatment was carried out as described above, the product was washed with hot water, then with water, and then dried.

The two treated wools obtained were evaluated, and the seventh
The results in the table were obtained.

EFFECTS OF THE INVENTION When fibers are processed using the animal hair fiber processing agent according to the present invention, the following distinctive advantages can be obtained.

1. The treatment bath containing the dyeing composition together with the animal hair fiber treatment agent of the present invention enables low-temperature dyeing processing at room temperature to 80°C, which causes less damage to the animal hair than conventional boiling point dyeing methods, and also reduces the embrittlement and deterioration of the feel of the animal hair. In addition, it is possible to achieve uniform dyeing without unevenness, chippy dyeing, or unevenness.

Furthermore, the control of the treatment bath and the reproducibility of dyeing are also improved.

2. It can impart remarkable shrink resistance to animal hair fibers, and this treatment can be carried out either before or after dyeing. In this respect, there is a great degree of freedom in the use of treatment baths, considering that conventional shrink resistance treatments were limited to before dyeing.

3. It provides outstanding pilling resistance to animal hair fibers regardless of the type of treatment bath used.

This effect is completely surprising and not found in conventional animal hair fiber treatment agents.

4. By using the animal hair fiber treating agent of the present invention as a treatment bath after bleaching, the animal hair fiber is given light fastness.

──────────────────────────────────────────────────── Continued from the front page (72) Inventor: Yoshifusa Hara 9-33-2-314 Kameido, Koto-ku, Tokyo (72) Inventor: Kunio Kako 6-9-13 Baba, Tsurumi-ku, Yokohama, Kanagawa (72) Inventor: Akira Saito 5-6-5 Kamikitazawa, Setagaya-ku, Tokyo (56) References: Patent Publication No. 1970-23635 (JP, B1) Patent Publication No. 1966-22321 (JP, B1)

Claims (3)

[Claims] Claim 1: A compound comprising tris(3-hydroxypropyl)phosphine represented by the following general formula: PR ₃ [wherein R represents a 3-hydroxypropyl group] or an ethylene oxide or propylene oxide adduct thereof, and one or two selected from the group consisting of an acidifying agent, a pH adjuster, a surfactant, and a leveling agent.
An animal hair fiber treatment agent characterized by being composed of an aqueous solution (with a concentration of 0.005 to 3% owm in terms of P and a pH range of 2 to 7) in which one or more auxiliary agents are dissolved as active ingredients. 2. The animal hair fibers immersed in the animal hair fiber treatment agent according to claim 1 in a bath ratio of 1:1 to 100:1 are washed with water for 0.5 to 3 minutes.
A method for treating animal hair fibers, characterized by heating at a rate of 100°C/min and then holding the temperature at a maximum of 100°C for 5 seconds to 60 minutes. 3. The method for treating animal hair fibers according to claim 2, wherein after the animal hair fibers have been immersed, they are post-treated by immersing them in an acidic aqueous solution of sulfuric acid.