JP2970896B2 - Shrink-proofing method and shrink-proofing agent for animal hair fiber - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for shrink-proofing animal hair fibers and an agent for shrink-proofing animal hair fibers.

[0002]

2. Description of the Related Art Several methods have been proposed for suppressing shrink felt by washing animal hair fibers such as wool. For example, there are a Croy / Harco method, a potassium permanganate method, a Bantian method, a sirolambap method, an enzyme method, and the like. In principle, the scale edge of the animal hair epidermis is scraped off or the scale edge is embedded with a resin material to make it difficult to entangle and give the animal hair fiber a shrink resistance. In many cases, these methods obtain an effect by using the two methods in combination, as compared with a case where these methods are applied alone. These conventional methods are different depending on each of them, but it is difficult to obtain a sufficient shrinkproof effect, the feeling becomes rough and hard, there is a problem of environmental pollution, there is a problem of equipment corrosion, the wool is yellowed, There are drawbacks such as embrittlement and a significant loss of the original texture of wool.

At present, the Kuroi / Harko method is the most effective shrink-prevention treatment method for animal hair fibers in the world. Although this method shows a nearly perfect shrinkage-preventing effect, it has a major drawback that the natural feel of animal hair fibers is significantly impaired. For example, wool has a very high water repellency on the surface, but the one treated with this treatment has no water repellency at all. The feeling is that the voluminous volume of wool disappears and it feels like a filament of synthetic fiber.When washing with a sweater, etc., it stretches in the opposite direction and produces a taratsuki, notorious that there is no place different from acrylic fiber There is also yellowing due to processing. Furthermore, in the case of this method, there is also a problem of environmental pollution since chlorine-based organic substances are discharged.

[0004] According to International Publication No. WO 89/02497 (Japanese Patent Application No. 63-507250), a water-soluble organic phosphine compound is proposed as an animal hair fiber treating agent. This publication describes that when animal hair fibers are treated with a water-soluble organic phosphine compound, a shrinkproof effect can be obtained. However, the shrinkage-preventing effect of animal hair fibers by the organic phosphine compound alone is still insufficient, and in order to obtain a sufficient shrinkage-preventing effect by the organic phosphine compound alone, it is necessary to increase the ratio of use to the animal hair fiber. When the organic phosphine compound is used at such a high usage ratio, animal hair fibers are damaged, and the quality thereof is remarkably deteriorated.

[0005]

DISCLOSURE OF THE INVENTION The present invention provides a method and an agent for shrink-treating animal hair fibers which impart excellent shrink resistance to animal hair fibers without impairing the natural texture of the animal hair. That is the subject.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, after treating animal hair fibers with an organic phosphine compound, whether the animal hair fibers are treated with a specific non-phosphine compound, Alternatively, when treating with a mixture of an organic phosphine compound and a specific non-phosphine compound, it has been found that, with a low amount of the organic phosphine compound, excellent shrinkage resistance can be imparted to animal hair fibers, thereby completing the present invention. Reached.

According to the present invention, a first treatment step of treating animal hair fiber with a first aqueous treatment liquid containing a water-soluble organic phosphine compound, and an animal hair fiber treated in the first treatment step are represented by the following (1): And at least one non-phosphine compound selected from the group B-1 consisting of the compounds of (12) to (12).
A method for shrink-proofing animal hair fibers comprising a second step of treating with an aqueous treatment solution is provided.

According to the present invention, the animal hair fiber contains a water-soluble organic phosphine compound and at least one non-phosphine compound selected from the group B-2 consisting of the following compounds (1) to (8). There is provided a method for shrink-proofing animal hair fibers, wherein the method comprises treating with an aqueous treating solution.

Further, according to the present invention, there is provided an agent A comprising a water-soluble organic phosphine compound and at least one non-phosphine compound selected from the group B-1 comprising the following compounds (1) to (12). And a shrink-proofing agent for animal hair fibers.

Further, according to the present invention, the agent A comprising a water-soluble organic phosphine compound, and the following (1) to (8)
And at least one non-phosphine compound selected from group B-2.

(B-1) (1) Epoxy compound (2) Ethylene imine compound (3) Urea compound (4) Thiourea compound (5) Alkylene carbonate (6) Unsaturated carboxylic acid and its derivative (7) Saturated nitrile (8) Unsaturated alcohol and its ester (9) Sulfonate having vinyl group (10) Cyanate (11) Alkylene oxide addition type nonionic surfactant and its sulfate ester salt (12) Vinyl group With silane coupling agent

(Group B-2) (1) Glycidyl ether compound (2) Poly [3- (1-aziridinyl) propionate of polyhydric alcohol] (3) Urea compound (4) Thiourea compound (5) Unsaturated alcohol (6) Sulfonate having a vinyl group (7) Cyanate (8) Alkylene oxide-added nonionic surfactant and sulfate thereof

The organic phosphine compound used as the agent A in the present invention may be any compound having a water solubility and a solid or liquid state at room temperature, and any compound can be used. The water-soluble organic phosphine compound contains a hydrophilic group, for example, a hydroxyl group, a carboxyl group, a sulfone group, a hydroxylamino group, a hydroxymethyl group, etc., in the organic group bonded to the phosphorus atom, and shows water solubility as a whole. It is. Such water-soluble organic phosphine compounds are described in detail in International Publication No. WO89 / 02947. Preferred water-soluble organic phosphine compounds used in the present invention are those represented by the following general formula. In the above formula, R ¹ , R ² and R ³ represent an alkylene group or a phenylene group. The alkylene group has 1 to 10 carbon atoms,
Preferably, 1 to 6 alkylene groups are used. Also,
These alkylene groups or phenylene groups may have a substituent such as an alkyl group, an alkoxy group, and an amino group.

Specific examples of the organic phosphine compound used in the present invention include, for example, dimethylhydroxymethylphosphine, dimethylhydroxyethylphosphine, ethylbis (hydroxyethyl) phosphine, ethylbis (hydroxypropyl) phosphine, tris (hydroxymethyl) phosphine, Tris (hydroxyethyl) phosphine, tris (hydroxypropyl) phosphine,
Tris (hydroxyoctyl) phosphine, tris (hydroxycyclohexyl) phosphine, tris (hydroxybutyl) phosphine, tris (hydroxyphenyl) phosphine and the like can be mentioned. In the present invention, an alkylene oxide adduct of the organic phosphine represented by the general formula (I), such as an ethylene oxide adduct, a propylene oxide adduct, or an ethylene oxide / propylene oxide adduct, can be preferably used. In this case, the number of moles of the alkylene oxide adduct is not particularly limited, but is usually in the range of 1 to 20, preferably 1 to 10. Further, in the present invention, a quaternary phosphonium salt obtained by reacting the organic phosphine represented by the general formula (I) with a quaternizing agent can be preferably used. In this case, examples of the quaternizing agent include alkyl halides and alkyl sulfates having an alkyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and aryl halides and the like. The quaternizing agent may have a substituent, for example, a hydroxyl group, a carboxyl group, an amino group and the like. Further, in this case, the anions forming the phosphonium salt are anions of various inorganic acids and organic acids such as sulfate ion, phosphate ion and acetate ion, in addition to halogen atoms such as chlorine, bromine and iodine. be able to.

In the present invention, the agent B composed of a non-phosphine compound used in combination with the agent A composed of an organic phosphine compound is at least one selected from the group B-1 or B-2. The non-phosphine compound of group B-1 is applied to the two-step method, and is used in the second treatment step after the first treatment step using the agent A. On the other hand, B-
The two groups of non-phosphine compounds are applicable to the two-step method and also applicable to the one-step method, and are used in combination with the agent A.

Next, the non-phosphine compound used as the agent B in the present invention will be specifically described. (Epoxy compound) The epoxy compound includes a monoepoxy compound and a polyvalent epoxy compound. Among the epoxy compounds, polyvalent epoxy compounds can be applied to the one-step method. Specific examples of the epoxy compound include the following. (1) Glycerol triglycidyl ether (2) polypropylene glycol diglycidyl ether (3) propylene glycol diglycidyl ether (4) 2,2-bis (bromomethyl) propylene glycol diglycidyl ether (5) Glycidyl ether of lauryl alcohol ethylene oxide adduct (In the formula, n represents 12 to 18.) (6) Sorbitan polyglycidyl ether (7) Neopentyl glycol diglycidyl ether (8) Phenol (C ₂ H ₄ O) n glycidyl ether (where n is 2 (9) epichlorohydrin (10) glycidol (11) propylene oxide Among the epoxy compounds, the compounds of (1) to (8), which are glycidyl ether compounds, can also be applied to the one-step method. .

(Ethyleneimine compound) The ethyleneimine compound includes a compound having an ethyleneimine (aziridine) skeleton represented by the following formula.

Embedded image Specific examples of the ethyleneimine compound include, for example, the following compounds. (12) Ethyleneimine (13) 2,2-bishydroxymethylbutanol tris [3- (1-aziridinyl) propionate] (14) Trihydroxypropane-tris [3- (1-
(Aziridinyl) propionate] (15) Propylene glycol-bis [3- (1-aziridinyl) propionate] Among the ethyleneimine compounds, compounds (13) to (13) to which are polyhydric alcohol poly [3- (1-aziridinyl) propionate] (15) can also be applied to the one-step method.

(Urea compound) The urea compound includes a compound having a skeleton represented by the following formula.

Embedded image Specific examples of the urea compound include, for example, the following compounds. (16) urea (17) ethylene urea (18) N-alkyl-N ′, N′-ethylene urea

Embedded image (In the formula, R represents a higher alkyl group or alkenyl group having 12 to 22 carbon atoms.) Each of the urea compounds can be applied to the one-step method.

(Thiourea compound)
Compounds containing a skeleton represented by the following formula are included.

Embedded image Specific examples of the thiourea compound include, for example, the following compounds. (19) Thiourea (20) Ethylenethiourea (21) N-alkyl-N ′, N′-ethylenethiourea

Embedded image (In the formula, R represents a higher alkyl group or an alkenyl group having 12 to 22 carbon atoms.) Each of the thiourea compounds can be applied to a one-step method.

(Alkylene carbonate) Specific examples of the alkylene carbonate include the following. (22) Ethylene carbonate (23) Propylene carbonate

(Unsaturated carboxylic acids and derivatives thereof) The unsaturated carboxylic acids include maleic acid, fumaric acid, crotonic acid, sorbic acid, aconitic acid, acrylic acid, methacrylic acid and the like. The derivatives of unsaturated carboxylic acids include acid anhydrides, amides, imides, esters and the like. Specific examples of the unsaturated carboxylic acids and derivatives thereof include, for example, the following. (24) Maleic acid (25) Fumaric acid (26) Crotonic acid (27) Sorbic acid (28) Aconitic acid (29) Acrylic acid (30) Methacrylic acid (31) Maleic anhydride (32) Methyl acrylate (33) 2-hydroxyethyl methacrylate (34) acrylamide (35) methacrylamide

(Unsaturated nitrile) Examples of the unsaturated nitrile include the following. (36) Acrylonitrile (37) Methacrylonitrile

(Unsaturated alcohol and its ester) Examples of the unsaturated alcohol and its ester include the following. (38) Allyl alcohol (39) Propargyl alcohol (40) Vinyl acetate Compounds (38) and (39) which are unsaturated alcohols
Can also be applied to the one-step method.

(Sulfonate having a vinyl group) The sulfonate having a vinyl group includes aliphatic and aromatic sulfonates. Further, the sulfonate includes sodium sulfonate, potassium sulfonate, ammonium sulfonate and the like. Specific examples of these compounds include, for example, the following. (41) Sodium allyl sulfonate (42) Potassium styrene sulfonate Any of these compounds can be applied to the one-step method.

(Cyanate) Specific examples of the cyanate include the following. (43) Sodium cyanate (44) Potassium cyanate (45) Ammonium cyanate Any of these cyanates can also be applied to the one-step method.

(Alkylene oxide addition type nonionic surfactant and its sulfate ester salt) Specific examples of the alkylene oxide addition type surfactant and its sulfate ester salt include the following. (46) a surfactant represented by the following formula:

Embedded image [Wherein, X _{1 to} X ₄ represent hydrogen, RCOO (R represents a saturated or unsaturated higher aliphatic group) or SO ₃ M (M represents an alkali metal or ammonium), (PO) represents propylene oxide, (EO) represents ethylene oxide, m,
p, r and t are the average number of moles of (PO) added, and
And n, q, s and u are the average number of moles of (EO) added and represent the number of 1 to 160.] In the formula (X), the bonding order of (EO) · (PO) is arbitrary. And may be (PO) (EO). (47) Surfactant represented by the following formula (EO) n (PO) m (EO) p (XI) (wherein (PO) represents propylene oxide, (EO) represents ethylene oxide, and m represents (PO) ) Represents the number of 15 to 35, and n and p represent the average number of added moles of (EO) and represents the number of 2 to 150.) In the formula (XI), (EO) · ( The binding order of (PO) is arbitrary, and may be (PO). (EO). (PO). (48) Ethylene oxide adduct of phenol

Embedded image (Wherein, R is hydrogen or an alkyl group, (EO) is ethylene oxide, n is the average number of moles of (EO) added,
(49) an ethylene oxide adduct of a higher alcohol R-O- (EO) nH (wherein R is an alkyl or alkenyl group having 12 to 20 carbon atoms, (EO) represents ethylene oxide, n is (E
The average number of added moles of O) is 2 to 20.) The above-mentioned surfactants of the alkylene oxide addition type can be applied to the one-step method.

(Silane Coupling Agent Having Vinyl Group) Specific examples of the silane coupling agent having a vinyl group include the following. (50) vinyltrichlorosilane (51) vinyltris (β-methoxyethoxy) silane (52) vinyltriethoxysilane (53) vinyltrimethoxysilane (54) γ- (methacryloxypropyl) trimethoxysilane

The shrinkproof treatment of animal hair fibers according to the present invention can be carried out by a two-step method or a one-step method. Hereinafter, these methods will be described in detail. (Two-step method) This method comprises a first treatment step in which animal hair fibers are treated with a first aqueous treatment liquid containing agent A (a water-soluble organic phosphine compound), and an animal hair fiber treated in the first treatment step. B
A second treatment step of treating with a second aqueous treatment liquid containing an agent (at least one non-phosphine compound selected from the group B-1). In the first treatment step, the animal hair fiber is first treated.
It can be carried out by immersion in an aqueous treatment liquid. The amount of the A agent in the first aqueous treatment liquid is 0.14 to 3% by weight in terms of phosphorus atom with respect to the animal hair fiber to be treated,
Preferably, it is in the range of 0.5 to 2.3% by weight. The ratio of the B agent to the A agent is 0.2 to 15 times, preferably 1 to 5 times the weight of the phosphorus contained in the A agent. The usage ratio (bath ratio) of the first aqueous treatment liquid is 1 to 100 parts by weight, preferably 5 to 30 parts by weight, based on 1 part by weight of the animal hair fiber to be treated. Processing temperature is 20-10
0 ° C, preferably 30 to 80 ° C. The processing time is 5
It is 60 minutes, preferably 10 to 40 minutes.

The second treatment step can be carried out by immersing the animal hair fibers treated in the first treatment step in a second aqueous treatment liquid containing the agent B. The amount of the B agent in the second aqueous treatment liquid is 0.5 to 1 with respect to the animal hair fiber to be treated.
It is in the range of 5% by weight, preferably 1 to 8% by weight. Second
The usage ratio (bath ratio) of the aqueous treatment liquid is 1 to 100 parts by weight, preferably 5 to 3 parts by weight, based on 1 part by weight of the animal hair fiber to be treated.
0 parts by weight. The processing temperature is 20 to 100 ° C,
Preferably it is 30-80 degreeC. Processing time is 1 to 90
Minutes, preferably 20 to 60 minutes. By the treatment using the agent B, 0.5 to 4% by weight based on the animal hair fiber to be treated
B agent binds.

The two-stage treatment according to the present invention imparts shrink resistance to animal hair fibers. The imparting of the shrinkproof property to the animal hair fiber is achieved by reducing a considerable amount of -SS bonds present in the animal hair fiber into the highly reactive -SH bond in the first treatment step. It is considered to be achieved by reacting the B agent to the -SH bond.

In the present invention, a surfactant or a pH adjuster can be added to the aqueous treatment liquid used in the first treatment step and the second treatment step, if necessary. As the surfactant, an anionic surfactant, a nonionic surfactant and a cationic surfactant can be arbitrarily used. The concentration in the aqueous treatment liquid is 0.05 to 0.5 wt%, preferably 0.1 to 0.3 wt%. As the pH adjusting agent, for example, acidic substances such as formic acid, acetic acid, citric acid, hydrochloric acid, and sulfuric acid, and alkaline substances such as ammonia, sodium carbonate, and disodium phosphate are used. The pH of the aqueous treatment liquid used in the first treatment step is 3 to 7, preferably 4 to
It is good to adjust to the range of 6. The pH of the aqueous solution used in the second treatment step is adjusted to a range of 2 to 12, preferably 2 to 10.

(One-Step Method) This method comprises a step of treating animal hair fibers with an aqueous treatment solution containing the A agent and the B agent. This treatment step is performed by immersing the animal hair fibers in an aqueous treatment liquid containing the A agent and the B agent. As the agent B, a non-phosphine compound selected from the group B-2 is used. The content of the agent A in the aqueous treatment liquid is 0.14 to 3% by weight, preferably 0.1 to 3% by weight in terms of phosphorus atom, based on the animal hair fiber to be treated.
It is in the range of 5 to 2.3% by weight. The content of the agent B in the aqueous treatment liquid is 0.5 to 15 with respect to the animal hair fiber to be treated.
%, Preferably in the range of 1 to 8% by weight. The use ratio of the B agent to the A agent is 0.2 to 15 times by weight, preferably 1 to 5 times, per mole of the phosphorus atom contained in the A agent.
Weight times. The usage ratio (bath ratio) of the aqueous treatment liquid is 1 to 100 parts by weight, preferably 5 to 30 parts by weight, based on 1 part by weight of the animal hair fiber to be treated. Processing temperature is 2
It is 0-100 degreeC, Preferably it is 30-80 degreeC. The processing time is 10 to 90 minutes, preferably 10 to 40 minutes.

As in the case of the two-stage method, a surfactant or a pH adjuster can be added to the aqueous treatment solution used in the one-stage method, if necessary. The pH of the aqueous treatment liquid is preferably set in the range of 3 to 9, preferably 4 to 8.

The animal hair fibers used as a raw material in the present invention include various types such as wool, mohair, cashmere hair, alpaca hair, vicuña hair, guanaco hair, wool hair, camel hair, etc., and are not particularly limited. . The animal hair fiber may be in the form of a woven or knitted fabric. Further, the animal hair fiber may be previously dyed. Dyeing of animal hair fibers can be performed before or after the treatment of the present invention, and can also be performed in an aqueous treatment solution containing the agent A.

[0035]

Next, the present invention will be described in more detail with reference to examples. All the percentages shown below are percentages by weight.

Example 1 After wool yarn was scoured with a nonionic activator at 60 ° C. for 10 minutes, trishydroxypropylphosphine: 2.8% owf, sodium tripolyphosphate: 1% by weight (% owf) based on the wool yarn .5% owf, Migure Girl W
A (manufactured by SENKA CORPORATION, nonionic activator): 1% owf,
Acetic acid (68%): aqueous solution containing 5% owf (pH = 5.
Using 7), the mixture was treated at 75 ° C. for 30 minutes at a bath ratio of 1:15, and then washed with water (first treatment step). Next, the wool yarn obtained in the first treatment step is subjected to epichlorohydrin: 5% ow.
f, Disper VG (a mixture of anionic and nonionic surfactants, manufactured by Meisei Chemical Industry Co., Ltd.): using an aqueous solution (pH = 6.5) containing 5% owf, at a bath ratio of 1:15 and at 30 ° C.
, And then washed with water and dried (second processing step).

Example 2 A first treatment was applied to wool yarn in the same manner as in Example 1 and then an aqueous solution containing ethyleneimine: 5% owf (pH
= 9.2), the mixture was treated at 50 ° C. for 60 minutes at a bath ratio of 1:15, washed with water and dried.

Example 3 After wool yarn was refined with a 60 ° C. aqueous solution containing a nonionic activator, trishydroxypropylphosphine: 2.8%
owf, Migregal WA: 1% owf, sulfuric acid (50 °
Be ′): an aqueous solution (pH = 5.6) containing 0.7% owf and sodium tripolyphosphate: 1.5% owf,
The mixture was treated at a bath ratio of 1:15 at 75 ° C. for 20 minutes, and then washed with water (first treatment step). Next, the wool yarn obtained in the first treatment step is dried without drying in an aqueous solution containing tripropylene glycol diglycidyl ether: 5% owf and sodium carbonate: 3% owf, at a bath ratio of 1:15.
, And then washed with water and dried (second processing step).

Example 4 After the first treatment of wool yarn with the same prescription as in Example 3,
2,2-bishydroxymethylbutanol-tris [3
-(1-aziridinyl) propionate]: 5% owf
In an aqueous solution (pH = 8) containing
After treatment at 60 ° C. for 60 minutes, it was washed with water and dried. The chemical formula of the treatment agent is as follows.

Embedded image

Example 5 A wool yarn was treated in the same manner as in Example 3, and then a dye (Yamada Chrome Black PLW) 4% owf Miggle Girl WA 1% owf acetic acid 4% owf formic acid 1% owf in an aqueous solution containing 1% owf 1:15 at 100 ° C. for 30 minutes and then in an aqueous solution containing sodium dichromate 1.4% owf formic acid 0.5% owf at a bath ratio of 1:15 at 102 ° C. for 30 minutes. To obtain a black dyed product.

Example 6 A scoured wool yarn was immersed in an aqueous solution (pH = 5.6) containing trishydroxypropylphosphine: 4% owf, Miggregal WA: 1% owf, acetic acid: 5% owf, and a bath ratio of 1: At 15, the substrate was treated at 75 ° C. for 20 minutes and washed with water (first treatment step). Next, the substrate was treated in an aqueous solution (pH = 7.3) containing urea: 5% owf at a bath ratio of 1:15 at 50 ° C. for 1 hour, washed with water, and dried (second treatment step).

Example 7 An experiment was conducted in the same manner as in Example 6, except that thiourea was used instead of urea.

Example 8 A scoured wool was immersed in an aqueous solution (pH = 5.7) containing trishydroxypropylphosphine: 4% owf, Miggregal WA: 1% owf, acetic acid: 5% owf, at a bath ratio of 1:15. And then washed with water at 75 ° C. for 60 minutes (first treatment step). Next, after treatment in an aqueous solution (pH = 7.2) containing ethylene urea: 5% owf obtained in the first treatment step at a bath ratio of 1:15 at 80 ° C. for 60 minutes, the mixture was washed with water and dried ( Second processing step).

Example 9 An experiment was conducted in the same manner as in Example 8, except that ethylene thiourea was used instead of ethylene urea.

A knitted fabric is prepared from each of the modified wool yarns obtained as described above as a raw material, and the knitted fabric is washed with a home washing machine under the following conditions. The degree was measured as follows. Table 1 shows the results. Table 1 also shows the measurement results of the untreated wool yarn, the wool yarn treated only in the first treatment step in Example 1, and the wool yarn treated by the conventional Kloi-Harko method.

(Washing conditions) Temperature: 45 to 37 ° C. Time: 1 hour Washing liquid: pH 7 containing 4.5 g / L of monosodium phosphate (anhydrous salt) and 8.0 g / L of disodium phosphate (anhydrous salt) Buffer (felt shrinkage) was calculated by the following equation. Felt shrinkage (%) = (1−A ′ × B ′ / A × B) ×
100 A: Vertical length of untreated knitted fabric B: Horizontal length of untreated knitted fabric A ': Vertical length of treated knitted fabric B': Horizontal length of treated knitted fabric (surface hydrophobicity) Distilled water was dropped on the knitted fabric, and the time until the water droplets permeated the fabric and disappeared was expressed in seconds.

[0047]

[Table 1]

Example 10 After wool yarn was refined with a 60 ° C. aqueous solution containing a nonionic activator, trishydroxypropylphosphine: 2.8%
owf, Migregal WA: 1% owf, sulfuric acid (50 °
Be ′): an aqueous solution (pH = 5.5) containing 0.7% owf and sodium tripolyphosphate: 1.5% owf,
The mixture was treated at a bath ratio of 1:15 at 75 ° C. for 20 minutes, and then washed with water. Next, the wool treated as described above was treated without drying in an aqueous treatment solution containing the agent B at a bath ratio of 1:15 at 70 ° C. for 40 minutes. The knitted fabric shrinkage (%) and surface hydrophobicity (seconds) of the wool thus obtained are described.
And the results are shown in Table 2.

The specific contents of the agent B shown in Table 2 are as follows. B (11): maleic acid B (12): allyl alcohol B (13): Pluronic TR represented by the following structural formula
704 (made by Asahi Denka)

Embedded image (Molecular weight: 7000, EO content: 40% by weight) B (14): sodium cyanate B (15): acrylic acid B (16): 2-hydroxyethyl methacrylate B (17): methacrylamide B (18): Acrylonitrile B (19): Vinyl acetate B (20): Sodium allyl sulfonate B (21): Sodium styrene sulfonate B (22): Ethylene carbonate B (23): 7 mol (EO) adduct of nonylphenol B (24) ): Nonionic surfactant represented by the following structural formula (EO) n (PO) m (EO) p (molecular weight: 3700, (EO) content: 40% by weight) B (25): vinyltrimethoxysilane

[0050]

[Table 2]

Example 26 A wool yarn was washed with a 60 ° C. aqueous solution containing a nonionic surfactant, and then tetrakishydroxymethylphosphonium sulfate: 4% owf, sodium carbonate: 2% owf
In an aqueous solution (pH: 6.6) containing 80 at a bath ratio of 1:15.
After treatment at 20 ° C. for 20 minutes, washing with water was performed, followed by treatment with an aqueous solution containing maleic acid: 5% owf at a bath ratio of 1:15 at 80 ° C. for 20 minutes, followed by washing with water and drying. The wool yarn thus obtained exhibited a shrinkage of 13% and a hydrophobicity of 300 seconds or more.

Example 27 After wool yarn was scoured with a nonionic activator at 60 ° C. for 10 minutes, trishydroxypropylphosphine: 3.2% o
wf, sulfuric acid 1.0% owf, sun salt 7000 (Nika Chemical Industry Co., Ltd., anionic surfactant) 7% ow
f (pH = 2.9) and a bath ratio of 1:15
, And then washed with water and dried. The felt shrinkage of the wool yarn thus obtained was 9%.

The structural formula of the sun salt 7000 is as follows.

Embedded image

Example 28 A wool yarn was washed with a 60 ° C. aqueous solution containing a nonionic surfactant, and then trishydroxypropylphosphine as an agent A: 2.8% owf, sulfuric acid (50 ° Be ′): 0.1%.
7% owf, tripropylene glycol diglycidyl ether as agent B: aqueous solution containing 5% owf (pH =
4.6), the mixture was treated at a bath ratio of 1:15 at 75 ° C for 40 minutes, washed with water and dried.

Example 29 An experiment was carried out in the same manner as in Example 28 except that 2,2-bishydroxymethylbutanol [3- (1-aziridinyl) propionate]: 5% owf was used as the B agent.

Example 30 An experiment was carried out in the same manner as in Example 28 except that Pluronic TR704: 5% owf shown in Example 13 was used as the B agent.

Example 31 In Example 28, as the B agent, thiourea: 5% ow
f, Pluronic TR704: An experiment was performed in the same manner except that 2% owf was used.

Example 32 A commercial wool sweater was prepared using nonionic surfactant 60
After washing with an aqueous solution at a temperature of 5 ° C., an aqueous solution containing trishydroxypropylphosphine: 2.8% owf and 2,2-bishydroxymethylbutanol-tris [3- (1-aziridinyl) propionate]: 5% owf (pH: 8) .
8) After immersion in room temperature for 15 hours, it was washed with water and dried.

Example 33 A wool yarn was washed with a 60 ° C. aqueous solution containing a nonionic surfactant, and then tetrakishydroxymethylphosphonium sulfate: 3.5% owf, 2,2-bishydroxymethylbutanol-tris [3- (1-aziridinyl) propionate]: aqueous solution containing 5% owf (p
H: 6.6) at a bath ratio of 1:15 at 75 ° C. for 40 minutes, then washed with water and dried.

Example 34 A wool yarn was washed with a 60 ° C. aqueous solution containing a nonionic surfactant, and then trishydroxypropylphosphine:
Aqueous solution containing 2% owf, sodium cyanate: 4% owf, sulfuric acid (50 ° Be ′): 6% owf (pH:
In 3.3), the mixture was treated at 80 ° C. for 20 minutes at a bath ratio of 1:15, washed with water and dried.

Example 35 An experiment was conducted in the same manner as in Example 28 except that urea: 5% owf was used as the B agent.

Example 36 In Example 28, the agent B was changed to ethylenethiourea:
The experiment was performed in the same manner except that 5% owf was used.

Example 37 In Example 28, as the B agent, sodium allyl sulfonate: 4% owf and B represented by the above formula (XIV)
(13): An experiment was conducted in the same manner except that 2% owf was used.

Example 38 An experiment was conducted in the same manner as in Example 27 except that sodium styrenesulfonate: 4% owf was used as the B agent.

Example 39 In Example 28, as the agent B,
Nonionic surfactant indicated as (24): 5% owf
The experiment was performed in the same manner except that was used.

With respect to the modified wool yarns obtained in the above Examples 28 to 39, the shrinkage (%) and the hydrophobicity (second) were examined, and the results are shown in Table 3.

[0066]

[Table 3]

[0067]

As described above, the modified animal hair fiber obtained by the treatment of the present invention is one in which the contractility is remarkably suppressed and the original feeling of the animal hair fiber is well maintained. is there. Moreover, the modified animal hair fibers obtained by the present invention are improved in light resistance and alkali resistance, and can be effectively discolored to yellow even under sunlight irradiation or contact with an alkaline aqueous solution. It was prevented.

Claims (8)

(57) [Claims] 1. A first step in which animal hair fibers are treated with a first aqueous treatment liquid containing a water-soluble organic phosphine compound, and the animal hair obtained in the first step is prepared from the following compounds (1) to (12): A method for shrinkproofing animal hair comprising a second step of treating with a second aqueous treatment solution containing at least one non-phosphine compound selected from the group B-1. (Group B-1) (1) epoxy compound (2) ethyleneimine compound (3) urea compound (4) thiourea compound (5) alkylene carbonate (6) unsaturated carboxylic acid and its derivative (7) unsaturated nitrile ( 8) Unsaturated alcohol and its ester (9) Sulfonate having a vinyl group (10) Cyanate (11) Alkylene oxide-added nonionic surfactant and its sulfate ester (12) Silane having a vinyl group Coupling agent 2. The amount of the organic phosphine compound contained in the first aqueous treatment liquid used in the first step is 0.14 to 3% by weight in terms of phosphorus atom, based on the animal hair fiber to be treated.
The method of claim 1, wherein 3. The amount of the non-phosphine compound contained in the second aqueous treatment liquid used in the second step is in the range of 0.5 to 15% by weight based on the animal hair fiber to be treated. Or the method of 2. 4. An animal hair fiber is treated with an aqueous treatment liquid containing a water-soluble organic phosphine compound and at least one non-phosphine compound selected from the group B-2 consisting of the following compounds (1) to (8). A method for shrink-proofing animal hair. (Group B-2) (1) Glycidyl ether compound (2) Poly [3- (1-aziridinyl) propionate of polyhydric alcohol] (3) Urea compound (4) Thiourea compound (5) Unsaturated alcohol (6) Sulfonate having a vinyl group (7) Cyanate (8) Alkylene oxide-added nonionic surfactant and its sulfate 5. The method according to claim 4, wherein the amount of the organic phosphine compound contained in the aqueous treatment liquid is in the range of 0.14 to 3% by weight, in terms of phosphorus atom, based on the animal hair fiber to be treated. Method. 6. The method according to claim 4, wherein the amount of the non-phosphine compound contained in the aqueous treatment liquid is in the range of 0.5 to 15% by weight based on the animal hair fiber. 7. A comprising a water-soluble organic phosphine compound
An animal hair fiber anti-shrinking agent comprising an agent and an agent B comprising at least one non-phosphine compound selected from the group B-1 comprising the following compounds (1) to (12). (Group B-1) (1) epoxy compound (2) ethyleneimine compound (3) urea compound (4) thiourea compound (5) alkylene carbonate (6) unsaturated carboxylic acid and its derivative (7) unsaturated nitrile ( 8) Unsaturated alcohol and its ester (9) Sulfonate having a vinyl group (10) Cyanate (11) Alkylene oxide addition type nonionic surfactant and its sulfate ester (12) Silane having a vinyl group Coupling agent 8. A comprising a water-soluble organic phosphine compound
An animal hair fiber antishrinking agent comprising an agent and an agent B comprising at least one non-phosphine compound selected from the group B-2 consisting of the following compounds (1) to (8). (Group B-2) (1) Glycidyl ether compound (2) Poly [3- (1-aziridinyl) propionate of polyhydric alcohol] (3) Urea compound (4) Thiourea compound (5) Unsaturated alcohol (6) Sulfonate having a vinyl group (7) Cyanate (8) Alkylene oxide-added nonionic surfactant and its sulfate