JPH11172580A - Agent for treating animal hair, treating bath and treatment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable the impartment of a soft touch, shrinkage resistance and pilling resistance to animal hairs by treating the animal hairs with a treating agent containing a specific hydroxyalkyl phosphine, an alkali and an alkaline protease as active ingredients. SOLUTION: This treating agent comprises 0.1-60 pts.wt. of one or more kinds of a hydroxyalkylphosphine of the formula [R<1> is a 1-10C hydroxyalkyl; R<2> and R<3> are each a 1-10C (hydroxy)alkyl] and its derivatives, preferably hydroxypropyl phosphine, 0.005-1.5 pts.wt. (converted into NaOH) of an alkali and 0.001-15 pts.wt. of an alkaline protease active ingredients. The treating agent is used to prepare a treating bath containing 0.1-60 g/L of the phosphine compound, 0.005-1.5 g/L of the alkali and 0.001-15 g/L of the protease. The top silvers of animal hairs are immersed in the treating bath within a temperature range of from the ordinary temperature to 60 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a treatment agent for animal hair fibers,
The present invention relates to a treatment bath and a treatment method therefor, and more particularly, to impart a soft and unique slimy feel to animal hair fibers and also imparts shrinkage resistance and pilling resistance, so that weight loss due to treatment is small. The present invention relates to a treatment agent, a treatment bath, and a treatment method for animal hair fibers, which can provide a bleaching effect which is less likely to yellow with natural whiteness.

[0002] Further, the processing method of the present invention relates to AOX (Ab
sorbable OrganicHalogens,
It can be carried out in a continuous manner in a non-chlorine system which does not have a problem of an absorbent organic halogen compound), so that fiber treatment can be performed very efficiently.

[0003]

2. Description of the Related Art Currently, ISO-14 is mainly used in Europe.
Environmental regulations are being promoted based on the concept of environmental protection represented by the 000 series. 2. Description of the Related Art Conventionally, for shrinkproofing of animal hair, a method using chlorine or a chlorine-based compound, particularly in a continuous system, has been widely put to practical use worldwide. However, chlorinated shrink-prevention processing causes chlorinated proteins to be discharged from animal hair into waste liquid, and so-called AOX (absorbable organic halogen compound) is generated, which is a factor that has an adverse effect on the environment.

[0004] In the cleaning process of animal hair fibers, in the washing of water-based cleaning, felt shrinks unless shrink-proofing is performed. Therefore, the cleaning is called dry cleaning using a solvent such as trichloroethylene or perchloroethylene. Has been done as the mainstream. Environmental problems have led to restrictions or production bans on these organic halogens due to atmospheric pollution such as ozone depletion.

[0005] Non-polar solvents are also considered as dry cleaning alternatives, but these also have the potential to cause air pollution and are problematic. Therefore, even in animal hair fibers, there is no felt shrinkage or pilling, and AOX
There is a demand for a non-chlorine-based animal hair processing method and a continuous processing system that do not produce any.

[0006] Animal hair represented by wool has been subjected to a number of processing steps before it is used in our daily life as a textile product, starting from a shampooing treatment of cut raw wool. For example, there are steps of chemical treatment such as scouring bleaching and dyeing, and shrink-proof processing.

For example, as reforming by oxidation, cuticles are oxidized using hydrogen peroxide, persulfate, permanganate, hypochlorite, dichloroisocyanurate, chlorine and the like. Have been done. Modification by resin includes polyamide epichlorohydrin resin, batholane SW
(BASF) or the like.
As a modification with an enzyme, there is a method of treating with an alkaline solution containing an alkaline protease and having a pH of 8.5 or more (JP-A-51-99196). There is also a method in which a solution containing a chlorinating agent or a peroxidizing agent is allowed to act on animal hair, and then a proteolytic enzyme is allowed to act thereon (Japanese Patent Application Laid-open No. Sho 57-57).
No. 71474). Furthermore, there is also a method in which an oxidation treatment is performed in advance, and then a protease is used in the presence of salts (Japanese Patent Application Laid-Open No. 58-144105). The modification with trishydroxypropylphosphine is described in Japanese Patent No. 20228268 and US Pat. No. 5,147,409.
No. etc.

These not only provide shrink resistance by modifying the cuticle portion of animal hair, but also improve glossiness and feeling,
Its purpose is to improve pilling resistance and rigidity.

JP-A-5-272057 relates to an animal hair fiber treating agent comprising hydroxyalkylphosphine and a protease as active ingredients. Such a protease has an enzymatic action in an acidic to neutral range.

[0010] Furthermore, a method of continuously treating in a high temperature region using a hydroxyalkylphosphine (Japanese Patent Laid-Open No. Hei 5-
9869, and JP-A-7-207577).

In any of the above methods, animal hair can be imparted with shrinkage resistance, but in order to impart pilling resistance (to prevent pilling), modification with a hydroxypropylphosphine compound is most remarkable. Is effective.

[0012]

However, animal hair products cannot be said to meet the needs of commercial products merely by satisfying the functions of shrinkage resistance and pilling resistance. Animal hair products are required to have shrinkage resistance and pilling resistance, but at the same time, are required to have an extremely sensuous feeling. In addition, it is strongly desired that the weight loss due to the treatment is small by comparing the wool weight before the treatment with the wool weight before the treatment. This is because a decrease in weight leads to a decrease in strength.

[0013] For example, speaking of cashmere-like texture,
The expression "soft" is not sufficient, and "slimy" is extremely subtle and cannot be described with a measuring machine.

The feeling of animal hair varies widely depending on the place of production, growing conditions, parts, and the like, and the feeling is not always the same even for the same type. For example, cashmere, vicuña,
Alpaca, Angola, Mohea, Merino wool, etc. are not the same texture even if they are of the same type.

Good animal hair products are preferred and expensive. Conversely, if the hand is too rigid or does not suit your taste, it will sell poorly, and therefore will have to be inexpensive. In other words, in addition to shrink-proofing and pilling resistance, it is possible to impart a feeling like cashmere to inexpensive animal hair because of its poor texture, and furthermore, the weight loss rate is small, and If the strength is satisfactory, natural resources will be used effectively, which will be beneficial for both processors and consumers.

In addition, animal hair products are required to be matched with well-selling hues, etc., according to the trend of the fashion at that time. When a clear pastel color from white or very light color to light color is required, sufficient bleaching is essential prior to the dyeing process. because,
Animal hair originally has a unique pale cream hue.

In particular, in the shrink-preventing process by the chlorine-based continuous method, yellowing is accompanied, and the yellowing is clearly noticeable. For example, when a clear color tone from a very light color such as pink, light green, beige, or blue is required, if the animal hair is yellowed, it cannot be adjusted to the desired color tone. Therefore, it is necessary to bleach the yellowing animal hair to white.

However, animal hair, once yellowed, is unlikely to have a bleaching effect. For example, animal hair is oxidized and bleached at a high concentration of 30% to 50% owf of 35% hydrogen peroxide, and then reduced and bleached using a sulfur-based reducing agent such as hydrosulfite. It requires time work. Naturally, in such a high-temperature and long-time operation, animal hair must be damaged, and how to minimize the damage has been an issue of the bleaching operation.

In the method disclosed in JP-A-5-272057, when animal hair which has been dyed in advance is treated by a processing method using an acidic to neutral protein enzyme, the irritability on the dyeing (skittle: uneven dyeing) Although the phenomenon (2) does not occur, if the animal hair fibers that have been treated in advance by the processing method are dyed, the irritation problem may occur.

The present invention solves the above-mentioned conventional problems and provides a soft, unique slimy feeling, a shrinkproof property and a pilling resistance, and further reduces the weight loss due to the treatment. An object of the present invention is to provide a treatment agent, a treatment bath, and a treatment method for animal hair fibers that can impart a natural whiteness and a bleaching effect that does not easily yellow to animal hair fibers.

[0021]

Means for Solving the Problems As a result of intensive studies, the present inventors were able to solve the above-mentioned conventional problems. That is, the present invention provides the following general formula (1)

[0022]

Embedded image (Wherein R ¹ represents a hydroxyalkyl group having 1 to 10 carbon atoms, R ² and R ³ represent an alkyl group or a hydroxyalkyl group having 1 to 10 carbon atoms) and one of derivatives thereof. Or two or more,
The present invention relates to an animal hair fiber treating agent comprising an alkali and an alkaline protease as active ingredients.

Preferably, said hydroxyalkylphosphine is trishydroxypropylphosphine.
The animal hair fiber treating agent contains 0.005 to 1.5 parts by weight of alkali (in terms of NaOH) and 0.001 to 15 parts by weight of alkaline protease with respect to 0.1 to 60 parts by weight of hydroxyalkylphosphine. Is preferred.

Further, the present invention provides the following general formula (1)

[0025]

Embedded image (Wherein R ¹ represents a hydroxyalkyl group having 1 to 10 carbon atoms, R ² and R ³ represent an alkyl group or a hydroxyalkyl group having 1 to 10 carbon atoms) and one of derivatives thereof. Or two or more,
The present invention relates to an animal hair fiber treatment bath comprising a solution having an alkaline pH range containing an alkali and an alkaline protease.

Preferably, the hydroxyalkyl phosphine is trishydroxypropyl phosphine.
The animal hair fiber treatment bath contains 0.1 to 60 g / L of hydroxyalkyl phosphine and 0.0 of alkali (in terms of NaOH).
It preferably contains 0.5 to 1.5 g / L and 0.001 to 15 g / L of alkaline protease.

Further, the present invention relates to the following method for treating animal hair fibers. (1) A method for treating animal hair fibers, wherein the animal hair fibers are immersed in the treatment bath described above.
Specifically, there is provided a method for treating animal hair fibers, wherein the animal hair fibers are immersed in a treatment bath in an alkaline pH range containing the treatment agent.

(2) Animal hair fibers are kept at room temperature in the above-mentioned treatment bath.
The present invention relates to a method for treating animal hair fibers, comprising continuously performing a step of maintaining the temperature at a temperature in the range of 60 ° C. for a predetermined time to continuously treat animal hair fibers. Specifically, the animal hair fiber is continuously treated by holding the animal hair fiber sliver in a treatment bath in the alkaline pH range containing the above-mentioned treating agent for 180 seconds or less in a treatment bath within a range of room temperature to 60 ° C. A method for treating animal hair fibers.

(3) A step of immersing animal hair fibers in the above-mentioned treatment bath for a short period of time, then squeezing the hair to an appropriate pickup rate, and further keeping the animal hair in the atmosphere at a temperature in the range of room temperature to 60 ° C. The present invention relates to a method for treating animal hair fibers, which comprises continuously treating animal hair fibers.
Specifically, after the animal hair fiber sliver is immersed continuously for a short period of 30 seconds or less in a treatment bath in the alkaline pH region containing the treatment agent, the sliver is squeezed to a pickup rate of 60 to 160%, Further, a method for treating animal hair fibers, wherein the animal hair fibers are continuously treated while being kept in the atmosphere at room temperature to 60 ° C. for 180 seconds or less. In the above method for treating animal hair fiber, the animal hair fiber is preferably a top sliver.

[0030]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. In this specification, “% owf” means weight% based on the weight of the fiber.

The present invention provides a method of using hydroxyalkylphosphine in combination with an alkali or alkaline protease.
By combining a specific concentration range of the compound, the animal hair fiber is given a delicately soft and unique slimy feeling, and also imparts shrinkage resistance and pilling resistance, and is yellowed with natural whiteness. It also provides bleaching that is difficult to do.

First, the animal hair fiber treating agent of the present invention has the following general formula (1)

[0033]

Embedded image Or one or more of hydroxyalkylphosphines and derivatives thereof represented by the formula (1) and alkali and alkaline proteases as active ingredients.

The hydroxyalkylphosphine usable in the present invention is represented by the above general formula (1), wherein R ¹ is a hydroxyalkyl group having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms. Represents R ² , R ³
Represents an alkyl group or a hydroxyalkyl group having 1 to 10, preferably 1 to 3 carbon atoms. The groups R ¹ , R ² and R ³ may be the same or different.

Specific examples of the hydroxyalkylphosphine which can be used in the present invention include, for example, dimethylhydroxymethylphosphine, dimethylhydroxyethylphosphine, diethylhydroxypropylphosphine, ethylbis (hydroxyethyl) phosphine, ethylbis (hydroxypropyl) phosphine, trishydroxymethyl Examples include phosphine, trishydroxyethylphosphine, trishydroxypropylphosphine, trishydroxybutylphosphine, trishydroxypentylphosphine, trishydroxyhexylphosphine, trishydroxyoctylphosphine, and the like. Among them, trishydroxypropylphosphine is preferred.

As the hydroxyalkylphosphine derivative, for example, an alkylene oxide adduct can be used. It is an alkylene oxide adduct of hydroxyalkylphosphine, and the number of moles added is in the range of 1 to 5. The above hydroxyalkylphosphines and derivatives thereof may be used alone or in combination of two or more.

The alkaline protease used in the present invention may be crude or purified, but is not particularly limited. The alkaline proteolytic enzyme is preferably an enzyme whose useable pH range is pH 8 to 13, preferably pH 8 to 12. They are preferably, for example, endoproteases, for example those belonging to the Bacillus Alcalophilus system, such as Streptomyces griseus variety alkaline filass. 33 proteases and the like. As a specific example,
Enzyin 2GE (Chiyoda Corporation), Bacillus
Alkali filasu and the like can be mentioned. Further, the amount of the active ingredient of the alkaline protease means the amount of the purified active ingredient.

The alkali used in the present invention does not need to be particularly limited.
Anything can be maintained as long as it can be maintained. Specifically, for example, sodium carbonate, potassium carbonate, sodium silicate, potassium silicate, caustic soda, caustic potassium, lithium hydroxide, sodium 2 phosphate, 3 sodium phosphate, 3 potassium phosphate, 4 sodium pyrophosphate, Water soluble lithium salts such as sodium tripolyphosphate, sodium metaborate, potassium metaborate, sodium metasilicate, potassium metasilicate, lithium carbonate, lithium phosphate, or caustic soda and sodium phosphate, caustic soda and borax, caustic potassium and tetraborate It may be potassium acid, soda ash and sodium bicarbonate, or a combination thereof.

The animal hair treating agent of the present invention comprises one or more of the hydroxyalkylphosphines represented by the general formula (1) and derivatives thereof and an alkali and alkaline protease, preferably Hydroxyalkylphosphine 0.1 to 60 parts by weight Alkali (as NaOH) 0.005 to 1.5 parts by weight Alkaline proteinase 0.001 to 15 parts by weight. When used beyond such a range, the damage to the animal hair is increased, and the commercial value of the animal hair is impaired.

The amount of alkali in terms of NaOH is a value obtained by converting the amount of alkali liberated in an aqueous solution of an alkali salt into NaOH. For example, in the case of NaOH, the amount used is an alkali amount in terms of NaOH. In the case of a sodium salt, for example, sodium phosphate 3
(G) If used, the following formula

[0041]

Embedded image A × [40 (molecular weight of NaOH) / 272 (N
a ₃ PO ₄ .6H ₂ O molecular weight)] = A × 0.147
(G) is the alkali amount in terms of NaOH.

In the case of KOH, for example,
(G) When used, B × [40 (molecular weight of NaOH) / 56 (molecular weight of KOH)] = B × 0.71 (g)
Is the amount of alkali in terms of NaOH. In the case of a potassium salt, KO is obtained in the same manner as described above.
The amount of H is determined, and the amount of KOH
The amount of alkali is determined by H conversion.

In the case of LiOH, for example, when LiOH is used in C (g), C × [40 (molecular weight of NaOH) / 24 (molecular weight of LiOH)] = C × 1.667.
(G) is the alkali amount in terms of NaOH.

In the case of a lithium salt, the amount of LiOH is obtained by the same method as described above, and the amount of LiOH is converted to NaOH by the same method as above to obtain the alkali amount. For example, when D (g) of LiOH.H ₂ O is used, the following formula is used.

[0045]

Embedded image From the formula, D × [24 (molecular weight of LiOH) / 42 (molecular weight of LiOH · H ₂ O)] = D × 0.571... 0.571D × [40 (molecular weight of NaOH) / 24 (molecular weight of LiOH)] = D × 0.952 (g).

[0046] Further, when the _Li 2 CO ₃ was used E (g), the following equation

[0047]

Embedded image From the formula, E × [24 (molecular weight of LiOH) × 2/74 (molecular weight of Li ₂ CO ₃ )] = E × 0.650... 0.650 E × [40 (molecular weight of NaOH) ) / 24 (molecular weight of LiOH)] = E × 1.083 (g).

The agent for treating animal hair fibers of the present invention may be applied to any animal hair, but typically includes, for example, wool, goat wool, rabbit hair, camel hair and the like. Or a blend thereof. Further, not only the animal hair fiber but also a mixture of animal hair and other fibers can be included in the category if the animal hair fiber is at least about 20%. The animal hair fibers include, without limitation, raw wool, top sliver, yarn obtained by processing the same, skein yarn, cheese, woven fabric, knitted fabric, and various processed products thereof.

It is preferable to appropriately use auxiliary agents such as a surfactant, a penetrating agent and a chelating agent in this treating agent in order to enhance the treating effect of the animal hair fibers to be treated. As the surfactant, those known in the art of treating animal hair fibers can be used. For example, carboxylate type, sulfonate type, sulfate ester type or phosphate ester type anionic surfactant, cationic surfactant such as alkylamine type, carboxybetaine type, aminocarboxylate type,
Examples include imidazolinium betaine-based zwitterionic surfactants, ether-type, ether-ester-type, ester-type, nitrogen-containing nonionic surfactants, and other fluorine-based surfactants. The amount used is not particularly limited, but is usually 0.1 to 10 parts by weight based on 0.1 to 60 parts by weight of hydroxyalkylphosphine.

Next, the animal hair fiber treatment bath of the present invention is a treatment bath containing the above-mentioned animal hair fiber treatment agent and comprising a solution having an alkaline pH range. Specifically, the animal hair fiber treatment bath of the present invention contains one or more of hydroxyalkylphosphine and its derivative represented by the general formula (1), an alkali and an alkaline protease, Range, hydroxyalkyl phosphine 0.1 to 60 g / L Alkali (as NaOH) 0.005 to 1.5 g / L Alkaline proteinase 0.001 to 15 g / L is preferable.

When used outside of these ranges, damage to the animal hair is increased and the commercial value of the animal hair is impaired. Further, it is preferable to appropriately use an auxiliary agent such as a surfactant in the animal hair fiber treatment bath. The amount of the auxiliary agent is not particularly limited, but is usually 0.1 to 10 g / L.

For the animal hair fiber treating bath of the present invention, a solution having an alkaline pH range obtained by dissolving an animal hair fiber treating agent containing the above components in water is used. The pH of the solution is pH 8 to 1 in a pH range suitable for use of alkaline protease.
3, preferably in the range of pH 8-12.

Next, the method for treating animal hair fibers of the present invention will be described. The method of treating animal hair fibers used in the present invention may be appropriately changed depending on the type of animal hair fibers, the main purpose of processing, and the like.

Such a treatment system includes a batch system and a continuous system. For example, raw cotton, skein, cheese, knitted fabric,
Textiles and the like are processed in a batch mode, and top slivers and the like are processed in a continuous mode.

(1) In the batch method, animal hair fibers are immersed in a treatment solution.
The processing time should be at least 10 minutes or more, and preferably 20 to 30 minutes for the purpose of process control.

(2) In the continuous system, any device may be used as long as the main reaction can be completed within an extremely short time in units of seconds. is there. The first method is a so-called parallel padder (precision style) or cloi style, in which both animal hair fibers are instantaneously immersed in a device having a treatment bath in an alkaline pH range for a short time, and then squeezed by an appropriate amount. The fiber is subjected to a processing reaction in the atmosphere.

The feature of this method is that it is immersed for a short time. FIG. 1 is an explanatory diagram showing an example of a specific method for treating animal hair fibers (parallel padder). In the figure, a parallel padder (precision style) specifically has a top sliver of animal hair fiber 1 in an apparatus having two rolls 3a and 3b and a treatment bath 2 between the rolls. After being immersed continuously in a short time of 30 seconds or less from the top, then squeezed to a pickup rate of 60 to 160%, and further kept at room temperature to 60 ° C, preferably 20 to 55 ° C,
This is a method of continuously treating animal hair fibers for a period of 180 seconds or less, preferably 20 to 90 seconds.

FIG. 2 is an explanatory view showing another processing method (cloi style) of animal hair fiber. In the Croi style, the top sliver of the animal hair fiber 1 is instantaneously immersed in the treatment bath 2 for a short time of 30 seconds or less, and thereafter, the same operation as the parallel padder is performed. In any case, in the case of such a treatment method, the contact time between the animal hair fiber top sliver and the treatment agent is extremely short, which is an industrially preferable method.

The second method is called milling style. Specifically, a top hair sliver of animal hair is placed in a treatment bath in an alkaline pH region containing an agent for treating animal hair within a temperature range from room temperature to 60 ° C. In the treatment bath for 180 seconds or less, preferably for 20 to 90 seconds to continuously treat animal hair fibers. FIG. 3 is an explanatory view showing an example of a specific method for treating animal hair fibers (milling style), in which animal hair fibers 1 are continuously treated in a treatment bath 2 provided with a plurality of rolls 3. Is the way.

The above-mentioned method of treating animal hair fibers differs in whether the processing into fibers is performed in the air or in a processing bath. The amount of each active ingredient in the above-mentioned treatment bath needs to be determined in consideration of the following depending on the form of the animal hair to be processed and the processing method (batch method or continuous method).

That is, hydroxyalkylphosphine (A), alkali (B), and alkaline protease (C), which are constituents of the animal hair fiber treating agent, are used in the batch system (1) and the continuous system (2)-, In each of the above methods, treatment can be performed with a composition within the above numerical range, but it is more preferable to treat with a composition within the following numerical range.

(1) Batch method Hydroxyalkylphosphine 0.1 to 10 g / L (0.2 to 5 g / L) Alkali (in terms of NaOH) 0.005 to 1.5 g / L (0.02 to 0 g) .2 g / L) Alkaline proteolytic enzyme 0.001-1 g / L (0.01-0.5 g / L)

(2) Method of Continuous Method Hydroxyalkylphosphine 3 to 60 g / L (6 to 30 g / L) Alkali (in terms of NaOH) 0.005 to 1.5 g / L (0.02 to 1 g / L) L) Alkaline proteinase 0.05 to 15 g / L (0.1 to 10 g / L)

Hydroxyalkylphosphine 1 to 40 g / L (2 to 30 g / L) Alkali (as NaOH) 0.005 to 1.5 g / L (0.02 to 1 g / L) Alkaline protein degradation Enzyme 0.01 to 10 g / L (0.05 to 5 g / L) However, the range in parentheses is a more preferable range.

The alkali used in the above method is preferably NaOH, KOH or LiOH.H ₂ O in the continuous method, and Na ₃ PO ₄ .6H ₂ O in the batch method.
Buffered alkalinity such as is preferred.

In the treatment method of the present invention, the hydroxyalkylphosphine (A), the alkali (B), and the alkaline protease (C) have a quantitative relationship as described above.
It generally has the following relationship. (1) When using A more, B is less (2) When using A less, B is slightly more (3) When using more C, A and B are less (4) C When using a little, A and B are slightly more

In this treatment method, the treatment temperature is naturally determined from the relationship between the treatment time and the alkaline protease, but in the case of the present invention, the same effect can be obtained by treating at normal temperature or at a high temperature.

The form of the treatment bath is preferably the same bath system. The same bath system means that the hydroxyalkylphosphine and the alkali and alkaline proteases are used in the same bath with the auxiliary substances such as the above-mentioned surfactants, that is, in one bath.

This bath system is characterized in that hydroxyalkyl phosphine and an alkali or alkaline protease are used together in an alkaline pH range, for example, pH 8 to 13. This makes it possible to achieve the above object effectively in a short time.

The temperature at the time of immersion varies depending on the type of animal hair, but is usually from room temperature to 60 ° C., preferably from 20 to 55 ° C.

After completion of the treatment in the treatment bath as described above, post-treatments such as washing with water and drying can be carried out by a conventional method. However, after washing with water, the product is immediately neutralized with a strong acid capable of forming a phosphonium salt. It is desirable to perform post-processing. In particular, it is preferable to carry out post-treatment with sulfuric acid or a bisulfate aqueous solution such as sodium bisulfate and potassium bisulfate. The purpose of this post-treatment is to remove a small amount of the phosphine compound remaining in the fiber and to inactivate the protease used in the treatment, and in that sense, may be an oxidizing agent. However, the use of a strong acid, particularly sulfuric acid or alkali bisulfate, not only does not impair the fiber, but also helps to achieve a good hand. The processing conditions at this time are:
The acid or salt concentration is 0.1 to 2% owf,
The immersion time may be 5 to 60 minutes, and the bath ratio may be about 5: 1 to 50: 1. By performing such a post-treatment, it is possible to eliminate the reducing power remaining in the treated animal hair fiber of the hydroxyalkylphosphine and to inactivate the protease used in the treatment.

The weight loss by the subsequent treatment was 1%
Or less, preferably 0.5% or less.
Next, the animal hair fibers are washed and dried in a conventional manner to complete the treatment of the animal hair fibers. Drying is also performed at 80 to 90 to deactivate the enzyme.
C., preferably 5 to 10 minutes. In addition, if necessary, after the processing according to the present invention, there is no problem in performing a flexible processing by an ordinary method.

Next, the working mechanism of the present invention will be considered. Animal hair has CMC between cortex and between epidermal cells and cortex.
(Cell membrane complex).
That is, it is said to have a so-called "block cement" structure in which blocks of cells are bonded with cement of CMC.

The details of the action mechanism according to the present invention are unknown, but are presumed to be roughly as follows. The shrinkage resistance and pilling resistance are considered mainly due to the action of hydroxyalkylphosphine. It is considered that fine adjustment can be obtained by adjusting the feeling and improving the whiteness by the action of the alkaline protease used in combination.

The surface of animal hair is repellent (hydrophobic).
In general, at room temperature, there is a property that the action of a drug hardly reaches the inside of animal hair even in a drug aqueous solution. However, once the drug enters the animal hair, it readily penetrates to the cortex portion constituting the animal hair fiber itself and acts on the inside. If the inside of animal hair is affected by chemicals and suffers damage such as dissolution, it may turn yellow, become less powerful,
The texture becomes gross.

The modification of animal hair by chemical treatment is achieved by dissolving and removing the surface cuticle portion (particularly the edge portion) while minimizing damage inside the animal hair.
Edge parts are caught on each other, remove the cause of felt shrinkage of the phenomenon of entanglement, smooth the animal hair epidermis surface,
The aim is to obtain a soft texture and whiteness without yellowing.

The point of the chemical treatment is to control the extent to which the action of the chemical treatment is exerted on the animal hair and to limit where it can be stopped. That is, there is a need for a method of limiting the operation. The reason for using an alkali is that the epidermal epicuticle that maintains water repellency (hydrophobicity) has a lipid substance firmly and covalently bonded to serine or threonine side chains in the outermost layer. This keeps the animal hair surface strongly hydrophobic. This part is generally called an F layer.

Among the chemical treatments for the F layer, an attempt at treatment with an alkali is described in Textile Research J.
own 41, 215-218, 1971; Jo
urnal of the Society of D
yers and Colorists 101,11
~ 16, 1985; Proceedings ofth
e 7th International Wool
Textile Research Conference
e, Tokyo 1985, vol. 4,312-32
It has been reported that when the lipid substance in the F layer is removed by treatment with an alkali, particularly an alcoholic alkali, a hydrophilic group rich in polarity and reactivity is formed, which leads to functionalities such as shrink resistance. .

However, in the alkali treatment,
It is not possible to dissolve and remove the epicuticle part with an alkali alone or an aqueous solution of an alkali and a surfactant.
It is dissolved from the inside of the animal hair, and the animal hair itself dissolves and disappears depending on the amount of alkali used.

In the case of an alcoholic alkali, in particular, t-
In the case of butanol alkali using butanol, t-butanol has a bulky molecular structure, so that permeation into fibers is hindered, and it is suitable for chemically treating only the surface of animal hair.

The combined use of hydroxyalkylphosphine and an alkali achieves the purpose of chemical treatment of epicuticles in a very short amount of seconds, even at room temperature, with an extremely small amount of alkali (1/10 or less that of an alcoholic alkali). Can be.

Hydroxyalkylphosphine has the function of making the hydrophobic part of animal hair hydrophilic by cleaving the —SS— bond of the cystine group to form —SH. When used for the chemical treatment of animal hair, it reaches the interior of the animal hair via the CMC site and has a -SS- bond or a part of a part of microfibrils (intermediate filaments) having a relatively low cystine content. It selectively reduces and cleaves the -SS- bonds existing between the embedded matrix and the microfibrils or the -SS- bonds existing in the matrix. Due to the cleavage of the cystine group in a specific area inside the animal hair, the inside of the animal hair is partially hollowed out and an internal depression occurs. The internal depression has the effect of softening the animal hair fibers themselves. The internal depression, as a phenomenon seen from the surface, shows an appearance as if the epidermal scale had disappeared. This is a so-called scale-off phenomenon. This leads to prevention of felt shrinkage caused by entanglement between the edges of the epicuticle.

In the present invention in which animal hair is immersed in an aqueous solution containing hydroxyalkylphosphine, alkali and alkaline protease as active ingredients,
Depending on the processing purpose and the machine used, it can be controlled within the allowable range of each of the three to obtain the hydrophilizing effect of the hydrophobic epidermal lipid portion and also the softening effect inside the animal hair. Is obtained. Particularly, there is a remarkable effect in a continuous processing in which the effect must be obtained within a very short time of the order of seconds.

In the case of continuous processing in which the effect must be obtained within a very short time of the order of seconds, the desired effect can be obtained even if any of the three members of hydroxyalkylphosphine, alkali and alkaline protease is missing. Absent. It can be said that the management of the processing is very easy and only the management of the active ingredient in the immersion liquid.

[0085]

The present invention will be described below with reference to examples.

Example 1 The following trishydroxypropylphosphine 12 g / L (manufactured by Nippon Chemical Industry Co., Ltd.) Caustic soda 0.28 g / L chelating agent 3 g / L (coicarin LCL-3320, manufactured by Koizumi Chemical Co., Ltd.) Alkaline protease 3g / L (Enzyne 2GE, Chiyoda Trading Co., Ltd.) A 50 ° C aqueous solution (pH = 10.4) containing 1 g / L (Despol 300, one-sided Yushi Yushi Kogyo Co., Ltd.) containing penetrant was added to Precision Processes Textile Limited. According to the parallel padder method, a 100% wool top sliver preliminarily heated to 50 ° C. was immersed for 5 seconds, and immediately squeezed with a mangle for 2 seconds.

Squeezing rate (Wet Pick Up%)
100%. It took 7 seconds from dipping to squeezing. Further, the top sliver was kept in the atmosphere at 50 ° C. for 40 seconds. Then, it is washed with water and sodium bisulfate (N
aHSO _{4 (} manufactured by Nippon Chemical Industry Co., Ltd.) 1% owf, a bath ratio of 1:50, a normal temperature of 5 minutes, a post-treatment, dehydration without softening treatment, and drying at 85 ° C. for 10 minutes.

The obtained wool top sliver has a soft and smooth texture with excellent gloss and whiteness, has the same strength as before processing, and has excellent spinnability. there were.

FIG. 4 shows an electron micrograph (× 1000) of the wool top before processing, and FIG. 5 shows an electron micrograph (× 1000) of the wool top after processing. In FIG. 4 (before processing), the epidermal epicuticle is clearly distinguished, but in FIG. 5 (after processing), a so-called scale-off state in which the epidermal epicuticle is removed is observed.

The processed wool top was spun into a knitted fabric, and the shrink resistance and pilling resistance were compared with those of a knitted fabric spun from the wool top before processing. Table 1 shows the results
Shown in The shrink resistance test method (I) is based on IWS TM-31.
(5A × 2), the pilling resistance test method is JIS-L1
076A method.

Example 2 Trishydroxypropyl phosphine 24 g / L (manufactured by Nippon Chemical Industry Co., Ltd.) Caustic soda 0.05 g / L chelating agent 1 g / L (coicarin LCL-3320, manufactured by Koizumi Chemical Co., Ltd.) Alkaline protease 3 g / L L (Enzyne 2GE, manufactured by Chiyoda Corporation) Penetrant 1g / L (Despohl 300, manufactured by YAS & CO., LTD.) To room temperature aqueous solution (pH = 9.3) Accordingly, the same wool top sliver as in Example 1 was immersed for 60 seconds while maintaining a bath ratio of 1:30 (sliver in bath: bath) and swimming in an aqueous solution, and then immediately squeezed (Wet Pick U).
p%). Further, the top sliver was kept in the atmosphere for 60 seconds, and then washed with water and post-treated with sodium bisulfate in the same manner as in Example 1. Dehydration was performed without performing softening treatment, and drying was performed at 85 ° C. for 10 minutes.

The obtained wool top sliver has a soft and smooth texture with excellent gloss and whiteness, has the same strength as before the processing, and has excellent spinnability. there were.

The processed wool top was spun into a knitted fabric, and the shrink resistance and pilling resistance were compared with those of a knitted fabric spun from the wool top before processing. The shrink-proof test method (I) is IWS TM-31 (5A x 2),
The pilling resistance test method was based on JIS-L1076A method. Table 1 shows the results.

The yellowing of the wool knitted fabric obtained in Example 2 and the wool knitted fabric obtained from a wool top sliver obtained by chlorine-based continuous shrink-proofing were compared. For comparison, use a colorimeter (N
The b value was determined using D-101DP type (manufactured by Nippon Denshoku Industries Co., Ltd.). Table 2 shows the results.

The chlorine-based continuous shrink-prevention processing was performed by a method of dipping in an aqueous solution of acidic hypochlorous acid for 5 seconds by the Croy method (Kroy Unshrinkable).

[0096]

[Table 1]

[0097]

[Table 2] (Note) The b value indicates that the larger the numerical value, the greater the yellowness.

Example 3 Tris-hydroxybutylphosphine 3 g / L (manufactured by Nippon Chemical Industry Co., Ltd.) of the following: worsted knitted sweater of greige was padded with a paddle dyeing machine at a bath ratio of 1:20 (sweater: bath). 3 Soda 6 hydrate 0.69 g / L (Koizumi Chemical Co., Ltd.) (NaOH equivalent concentration = 0.1 g / L) Alkaline proteinase 0.15 g / L (Enzyne 2GE, Chiyoda Corporation) Penetrant 1 g / L (despol 300, on the other hand, manufactured by YAS & CO., LTD.) For 20 minutes in an aqueous solution (pH = 8.5) at room temperature.

After washing with water and post-treatment with sodium bisulfate as in Example 1, the following dyeing treatment was carried out.

(Dye) Sea Reactive Yellow 39 1% owf Sea Reactive Red 84 1% owf Sea Reactive Blue 69 1% owf

(Auxiliary agent) Koikarin OKA-50 (manufactured by Koizumi Chemical) 1 g / L Koikarin PHL-535 (manufactured by Koizumi Chemical) 1 g / L Albegar B (manufactured by Ciba Geigy) 1% owf Unisol WL (manufactured by ICI) 1% owf 90% acetic acid 1.5% owf

In the above-mentioned dyeing treatment bath, a bath ratio of 1:20, 90
It was dyed at 60 ° C. for 60 minutes, washed with hot water, washed with water, dehydrated and dried.

The obtained worsted knit sweater had an excellent texture and no irritability (skitty) on dyeing. The shrink resistance and pilling resistance were compared with the setter before processing. Regarding the shrink resistance, IWS TM-31 (5A ×
2) Regarding pilling resistance, JIS-L1076A method was used. Table 3 shows the results.

[0104]

[Table 3]

Comparative Example 1 Alkaline protease (Enzyin 2GE, Chiyoda Shoji Co., Ltd.) was prepared by using soda ash and soda bicarbonate to obtain a pH of 11.4.
An aqueous solution containing g / L and 1 g / L of a penetrant (Deathball 300, manufactured by YAS & Co., Ltd.) was prepared and used as an immersion bath.

The wool top sliver was immersed in an immersion bath at room temperature, and further squeezed (WetPick Up%) 1.
00%. It took 5 seconds from the immersion to the end of squeezing, and was kept in the atmosphere at room temperature for 40 seconds.

Next, it was washed with water, dehydrated without performing a softening treatment, and dried at 85 ° C. for 10 minutes. The processed wool top was spun into a knitted fabric, and the shrink resistance and pilling resistance were compared with those of a knitted fabric spun from the wool top before processing. The shrink resistance test method (I) is based on IWS ™
-31 (5A x 2), pilling resistance test method is JIS-
According to the L1076A method. Table 1 shows the results.

Example 4 Trishydroxypropylphosphine 12 g / L (manufactured by Nippon Chemical Industry Co., Ltd.) Caustic potassium (KOH 90%) 0.2 g / L (NaOH conversion concentration = 0.13 g / L) Chelating agent 1 g / L ( Room temperature aqueous solution containing 3 g / L of alkaline proteolytic enzyme (Enzyne 2GE, manufactured by Chiyoda Corporation) and 1 g / L of penetrant (Despol 300, manufactured by Yushi Yushi Kogyo Co., Ltd.) After immersing the wool top sliver for 60 seconds in the same manner as in Example 2 (pH = 10.1), the squeezing rate (Wet Pick Up%) is 10 immediately.
It was reduced to 0%. Further, the top sliver was kept in the atmosphere for 60 seconds, and then washed with water and post-treated with sodium bisulfate in the same manner as in Example 1. Dehydration was performed without performing softening treatment, and drying was performed at 85 ° C. for 10 minutes.

Example 5 Trishydroxypropylphosphine 4 g / L (manufactured by Nippon Chemical Industry Co., Ltd.) Lithium hydroxide 0.28 g / L (manufactured by Nippon Chemical Industry Co., Ltd., 99% LiOH / H ₂ O) (NaOH conversion concentration = 0) .26 g / L) Chelating agent 3 g / L (koikarin LCL-3320, manufactured by Koizumi Chemical Co., Ltd.) Alkaline proteinase 3 g / L (Enzyin 2GE, manufactured by Chiyoda Corporation) Penetrant 1 g / L (Despol 300, Ichisha) Example 1 was added to a 50 ° C. aqueous solution (pH = 10.3) containing
The same wool top sliver as used in Example 1 was heated to 50 ° C. in advance, immersed for 10 seconds in accordance with the parallel padder method of Precision Processes Textiles Limited, and immediately squeezed for 2 seconds using a mangle. The squeezing rate (Wet Pick Up%) was set to 100%. Thereafter, the same operation as in Example 1 was performed.

Example 6 Trishydroxypropylphosphine 16 g / L (manufactured by Nippon Chemical Industry Co., Ltd.) Caustic soda 0.28 g / L chelating agent 3 g / L (coicarin LCL-3320, manufactured by Koizumi Chemical Co., Ltd.) Alkaline protease 3 g / L L (Enzyin 2GE, manufactured by Chiyoda Shoji Co., Ltd.) Into an aqueous solution (pH = 11.1) containing 1 g / L (Despol 300, on the other hand, manufactured by Yushi Kogyo Co., Ltd.) Immediately after soaking the wool top sliver for 30 seconds, the squeezing rate (Wet Pick Up%) is 10
It was reduced to 0%. Further, the top sliver was kept in the atmosphere for 60 seconds, and then washed with water and post-treated with sodium bisulfate in the same manner as in Example 1. Dehydration was performed without performing softening treatment, and drying was performed at 85 ° C. for 10 minutes.

Comparative Example 2 The same treatment as in Example 2 was performed except for 24 g / L of trishydroxypropylphosphine (manufactured by Nippon Chemical Industry Co., Ltd.).

Comparative Example 3 The same treatment as in Example 4 was carried out except for 3 g / L of alkaline protease (Enzyin 2GE, manufactured by Chiyoda Corporation).

Comparative Example 4 Trishydroxypropylphosphine (manufactured by Nippon Chemical Industry Co., Ltd.) 12 g / L and alkaline protease (Enzain 2GE, Chiyoda Corporation) 3 g / L
Except for the above, the same processing as in Example 4 was performed.

Comparative Example 5 The same treatment as in Example 5 was carried out except for 4 g / L of trishydroxypropylphosphine (manufactured by Nippon Chemical Industry Co., Ltd.).

Comparative Example 6 The same treatment as in Example 5 was carried out except for 3 g / L of alkaline protease (Enzyne 2GE, manufactured by Chiyoda Corporation).

Comparative Example 7 Trishydroxypropylphosphine (manufactured by Nippon Chemical Industry Co., Ltd.) 4 g / L and alkaline protease (Enzain 2GE, Chiyoda Corporation) 3 g / L
Except for the above, the same processing as in Example 5 was performed.

The wool top sliver after the above-mentioned processing was evaluated for shrink resistance by the following test method.

[Test Method for Shrinkage Resistance (II)] A sample (about 2.4 g) of the processing agent was subjected to I.P. W. S After immersion in a 0.5% w / w% detergent solution for washing fastness test at room temperature for 30 seconds, the squeezing rate (Wet Pick Up%) is reduced to 100%. This sample is placed in a plastic bag (20.5 cm × 28.5 cm), and air is blown to inflate the bag. Grab the mouth of the plastic bag with one hand and shake it up and down for 10 minutes. Vibration width is up and down 10c
The m-th order and the number of times of shaking are 240 times / minute.

(Judgment Criteria) A wool top sliver to which no shrinkage resistance has been imparted is felted 2 to 3 minutes after the start of the test, and forms a hard sphere from a eyeball to a golf ball. Wool top slivers with good shrinkage resistance do not form a felt, are in a crushed state, and are not spherical. The shrink-prevention degree in the middle is such that the diameter of the sphere is large and the sphere is soft.

On the basis of the shrinkage resistance test method (II), Examples 1, 2, 4, 5, 6 and Comparative Examples 2, 3,
4, 5, 6, and 7 tests were performed. The results are shown in FIGS. FIG. 6 is a photograph showing the structure of the fiber of the wool top sliver after the processing in Example 2 after the shrinkage resistance test. FIG. 7 is a photograph showing the structure of the fiber of the wool top sliver after the processing in Comparative Example 2 after the shrinkproof test.

The results of the shrinkage resistance tests of Examples 1, 4, 5, and 6 were similar to those of Example 2. Comparative Example 3,
The results of the shrinkage resistance tests of 4, 5, 6, and 7 were the same as those of Comparative Example 2.

From the results of the above shrinkage resistance test, Example 1,
Comparative Examples 2, 3, 4, 5, 6, and 7 were all extremely hard oyster-shaped spheres (major axis: about 45 mm, minor axis: about 2, 4, 5, 6, 7). 30m
m).

[0123]

Industrial Applicability According to the present invention, a non-chlorine-based material which does not cause AOX pollution problem, and which is delicately soft and has a unique slimy feeling, and also has shrinkproofness and pilling resistance, and is further natural It is possible to provide an animal hair fiber treating agent capable of providing animal hair fibers with whiteness and bleaching resistance to yellowing. Further, it is possible to provide a continuous system capable of improving the effect of preventing and reducing pilling of animal hair fibers within an extremely short time in seconds.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram showing an example of a method (parallel padder) for treating animal hair fibers of the present invention.

FIG. 2 is an explanatory view showing another method (cloi style) of animal hair fiber of the present invention.

FIG. 3 is an explanatory view showing an example of a method for treating animal hair fibers (milling style) of the present invention.

FIG. 4 is an electron micrograph (× 1000) of a wool top before processing in Example 1.

FIG. 5 is an electron micrograph (× 1000) of a wool top after processing in Example 1.

FIG. 6 is a photograph showing a structure of a fiber after a shrinkage resistance test of a wool top sliver after processing in Example 2.

FIG. 7 is a photograph showing a structure of a fiber after a shrinkproof test of a wool top sliver after a processing treatment of Comparative Example 2.

[Explanation of symbols]

 1 animal hair fiber 2 treatment bath 3, 3a, 3b roll

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Seiji Shimura 9-11-1, Kameido, Koto-ku, Tokyo Nippon Kagaku Kogyo Co., Ltd. Research and Development Headquarters (72) Inventor Kunio Kako 6 Baba, Tsurumi-ku, Yokohama-shi, Kanagawa Chome 9-13 (72) Inventor Asahi Saito 5-6-15 Kamikitazawa, Setagaya-ku, Tokyo

Claims (10)

[Claims] 1. The following general formula (1): (Wherein R ¹ represents a hydroxyalkyl group having 1 to 10 carbon atoms, R ² and R ³ represent an alkyl group or a hydroxyalkyl group having 1 to 10 carbon atoms) and one of derivatives thereof. Or two or more,
An animal hair fiber treating agent comprising an alkali and an alkaline protease as active ingredients. 2. The animal hair treatment agent according to claim 1, wherein the hydroxyalkylphosphine is trishydroxypropylphosphine. 3. The method of claim 1, wherein said hydroxyalkyl phosphine is 0.1.
Alkali (NaOH equivalent) for 1 to 60 parts by weight
2. The animal hair fiber treating agent according to claim 1, comprising 0.005 to 1.5 parts by weight and 0.001 to 15 parts by weight of an alkaline protease. 4. The following general formula (1): (Wherein R ¹ represents a hydroxyalkyl group having 1 to 10 carbon atoms, R ² and R ³ represent an alkyl group or a hydroxyalkyl group having 1 to 10 carbon atoms) and one of derivatives thereof. Or two or more,
An animal hair fiber treatment bath comprising a solution having an alkaline pH range, containing an alkali and an alkaline protease. 5. The animal hair fiber treatment bath according to claim 4, wherein the hydroxyalkylphosphine is trishydroxypropylphosphine. 6. The method of claim 1, wherein said hydroxyalkylphosphine is 0.1.
1 to 60 g / L, alkali (as NaOH) 0.005
~ 1.5 g / L and alkaline protease 0.0
The animal hair fiber treatment bath according to claim 4, which contains 01 to 15 g / L. 7. A method for treating animal hair fibers, comprising immersing animal hair fibers in the treatment bath according to claim 4. 8. A process in which the animal hair fibers are continuously treated in the treatment bath according to claim 4 at a temperature in a range of from room temperature to 60 ° C. for a predetermined time to continuously treat the animal hair fibers. Animal hair fiber treatment method. 9. An animal hair fiber is immersed in the treatment bath according to claim 4 for a short period of time, then squeezed to an appropriate pickup rate, and further kept in the atmosphere at a temperature in a range of room temperature to 60 ° C. A method for treating animal hair fibers, comprising continuously performing the step of performing animal hair fibers. 10. The method for treating animal hair fiber according to claim 7, wherein the animal hair fiber is a top sliver.