JP2000144577A - Shrink proofing agent for animal hair fiber product or the like and shrink proofing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an agent almost preventing shrinkage, hardening and touch deterioration of animal hair fiber products even treating in water by imparting pilling resistance. SOLUTION: This shrink proofing agent includes a preparation comprising 100 wt.% total shrink proofing components, 20-200 wt.% alkyl nitrogen- containing surfactant, 5-100 wt.% aliphatic aldehyde compound and/or aromatic aldehyde compound and 50-300 wt.% hydroxyalkylphosphine wherein the shrink proofing components comprises 5-80 wt.% polyalkylene oxide polyol having 2-6 functionality, 0.1-20 wt.% aliphatic isocyanate and/or aromatic isocyanate the terminals of which are treated with the 2-6 functional polyalkyleneoxide polyol, 5-94.7 wt.% water-soluble polyurethane and/or water-dispersible polyurethane, 0.1-7 wt.% divalent to tetravalent metal salt and 0.1-20 wt.% surfactant (except a >=6C alkyl nitrogen-containing surfactant) and the alkyl nitrogen- containing surfactant is the >=6C alkyl nitrogen-containing surfactant.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a textile or fur made from wool, animal hair, etc. (hereinafter referred to as animal hair product, etc.).
The present invention relates to a treating agent for preventing animal hair products or the like from being deformed or hardened in a water treatment such as washing and dyeing, and a treating method using the treating agent.

[0002]

2. Description of the Related Art Conventionally, when water treatment such as washing with animal hair products is performed, deformation (shrinkage or elongation), change in appearance (felting,
Crimping, fluff), change in flexibility (hardening, texture)
Therefore, dry cleaning has been performed. Alternatively, animal hair products and the like have been pressed and washed in lukewarm water using a detergent mainly containing a nonionic surfactant such as polyoxyethylene alkyl ether. However, the washing using the detergent has a problem that shrinkage and curing occur even when the washing is performed in lukewarm water. In particular, when animal hair products or the like are immersed in a detergent solution for a long time, shrinkage becomes severe.

Therefore, for water treatment such as washing and dyeing of animal hair products, measures have been taken to prevent shrinkage from the material. Means for preventing shrinkage of animal hair products include an oxidation method, a softening method, and a resin method.

[0004] In the oxidation method, cuticle (scale) existing on the surface of a fiber such as animal hair products is treated with an enzyme or chlorine.

[0005] The softening method is a method of softening animal hair products or the like when wet to prevent entanglement between fibers.
an FTC method, protein method, and the like.

[0006] In the resin method, fibers of animal hair products and the like are bonded to each other with a resin to prevent the movement of the fibers during washing, or to cover the scale with a resin to prevent entanglement of the fibers. And IWS chlorination / resin method, croy resin method, siroran BAP method, DC-109 method and the like.

[0007]

However, in the oxidation method,
Since the cuticle (scale) is removed, the texture changes, and there is a problem that the fibers are easily frayed. Further, the softening method has a drawback that fibers of animal hair products and the like become slippery and the fibers are easily frayed. Further, in the resin method, animal hair products and the like are hardened, the texture is reduced, and the material once shrunk and made into a felt cannot be restored to the original size.

[0008] The present inventor has previously disclosed Patent No. 2525507.
No. 2,561,752, Patent 2,693,790
No. 2,568,329 and JP-A-7-11584, provided a treating agent for fibrous materials. However, these treatment agents are such that crimping and felting progress rapidly under severe conditions such as long-time intense stirring in water and rubbing. In Japanese Patent Application No. 9-341935, the ability to maintain shrink resistance of animal hair products and the like was weak. An object of the present invention is to provide a treating agent and a treating method for preventing shrinkage and hardening of animal hair products and the like in conventional water treatment.

[0009]

Means for Solving the Problems The present inventor has found that crimping and felting are slowed by delaying the invasion of water into animal hair fibers and the rise of cuticles (scales), and thus the present invention. Completed.

[0010] The first invention of the present invention comprises, as a shrink-resisting component,
Component A: 5 to 80% by weight of 2 to 6 functional polyalkylene oxide polyol, Component B: 0.1 to 0.2% of aliphatic isocyanate and / or aromatic isocyanate terminated with 2 to 6 functional polyalkylene oxide polyol.
1 to 20% by weight, component C: water-soluble polyurethane and / or
Or 5 to 94.7% by weight of a water-dispersible polyurethane, D
Component: 0.1 to 7% by weight of divalent metal salt, 0.1 to 20% by weight of E component: 0.1 to 20% by weight of surfactant (excluding nitrogen-containing surfactant having 6 or more carbon atoms in the alkyl group) (The total of the A component + B component + C component + D component + E component is 100% by weight), and the shrinkproof component is 100% by weight.
Component F: 20 to 200% by weight of a nitrogen-containing surfactant having 6 or more carbon atoms in the alkyl group, Component G: aliphatic aldehyde compound and / or aromatic aldehyde compound 5
An antishrinking agent such as a solid or liquid animal hair fiber product containing about 100% by weight.

Further, the second invention of the present invention is characterized in that as the shrink-resisting component, component A: 2 to 6 functional polyalkylene oxide polyol is 5 to 80% by weight, component B: 2 to 6 functional polyalkylene oxide polyol is terminated. 0.1 to 20% by weight of the treated aliphatic isocyanate and / or aromatic isocyanate, C component: 5 to 94.7% by weight of water-soluble polyurethane and / or water-dispersible polyurethane, D component: divalent to tetravalent 0.1 to 7% by weight of the metal salt and 0.1 to 20% by weight of the E component: 0.1 to 20% by weight of the surfactant (excluding the nitrogen-containing surfactant having an alkyl group having 6 or more carbon atoms). (However, the total of the A component + B component + C component + D component + E component is 100% by weight).
0% by weight, F component: 20 to 200% by weight of a nitrogen-containing surfactant having an alkyl group of 6 or more carbon atoms, G component: aliphatic aldehyde compound and / or aromatic compound 5
Felting of the animal hair product or the like is delayed by immersing the animal hair product or the like in a shrink-proofing agent such as a solid or liquid animal hair fiber product containing 100% by weight for a certain period of time. This is a method for shrink-proofing animal hair products.

[0012] The third invention of the present invention relates to an anti-shrinkable component comprising A
Component: 5 to 80% by weight of 2 to 6 functional polyalkylene oxide polyol, B component: 0.1 to 0.1% of aliphatic and / or aromatic isocyanate terminated with 2 to 6 functional polyalkylene oxide polyol
20% by weight, C component: 5 to 94.7% by weight of water-soluble polyurethane and / or water-dispersible polyurethane, D component: 0.1 to 7% by weight of divalent to tetravalent metal salt, E component: surfactant (However, excluding nitrogen-containing surfactants having 6 or more carbon atoms in the alkyl group) are essentially 0.1 to 20% by weight (provided that the total of the A component + B component + C component + D component + E component is 100%). F component: 20 to 200% by weight of a nitrogen-containing surfactant having 6 or more carbon atoms in the alkyl group, and G component: an aliphatic aldehyde compound and / or an aromatic aldehyde compound, based on 100% by weight of the shrinkproof component. 5-1
00% by weight, H component: hydroxyalkylphosphine 5
A solid or liquid animal hair fiber product containing 0 to 300% by weight of a shrinkproofing agent.

[0013] The fourth invention of the present invention is a method for preparing a shrink-resisting component comprising A
Component: 5 to 80% by weight of 2 to 6 functional polyalkylene oxide polyol, B component: 0.1 to 0.1% of aliphatic and / or aromatic isocyanate terminated with 2 to 6 functional polyalkylene oxide polyol
20% by weight, C component: 5 to 94.7% by weight of water-soluble polyurethane and / or water-dispersible polyurethane, D component: 0.1 to 7% by weight of divalent to tetravalent metal salt, E component: surfactant (However, excluding nitrogen-containing surfactants having 6 or more carbon atoms in the alkyl group) are essentially 0.1 to 20% by weight (provided that the total of the A component + B component + C component + D component + E component is 100%). F component: 20 to 200% by weight of a nitrogen-containing surfactant having 6 or more carbon atoms in the alkyl group, and G component: an aliphatic aldehyde compound and / or an aromatic aldehyde compound, based on 100% by weight of the shrinkproof component. 5-1
00% by weight, H component: hydroxyalkylphosphine 5
Piling of animal hair fiber products, etc. by immersing animal hair products, etc. for a certain period of time in a shrink-preventing agent such as solid or liquid animal hair fiber products containing 0 to 300% by weight and attaching them, This is a method for shrink-proofing animal hair fiber products and the like, characterized in that occurrence is reduced and felting is delayed.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The addition amount of the component A is 5 to 80% by weight.
And preferably 8 to 70% by weight. A component is 5
If the amount is less than 10% by weight, no shrinkage-preventing effect of the animal hair product or the like after washing is exhibited, and even if it is added more than 80% by weight, no further effect can be expected.

The addition amount of the component B is 0.1 to 20% by weight, preferably 0.2 to 15% by weight. If the B component is less than 0.1% by weight, the shrinkproof effect of the animal hair product or the like after water washing will not be exhibited, whereas if it exceeds 20% by weight, the liquid will thicken and become difficult to use.

The addition amount of the component C is 5 to 94.7% by weight, preferably 10 to 70% by weight. C component is 5
If the amount is less than 10% by weight, the shrinkage-preventing effect of the animal hair product or the like after washing is not exhibited, and if the amount exceeds 94.7% by weight, no particular effect is exhibited.

The addition amount of the component D is 0.1 to 7% by weight, preferably 0.2 to 5% by weight. When the D component is 0.
If the amount is less than 1% by weight, the shrinkage-preventing effect of the animal hair product or the like after washing with water will not be exhibited, whereas if it exceeds 7% by weight, the stability of the liquid will also deteriorate, and the texture will decrease.

The addition amount of the component E is 0.1 to 20% by weight. If the component E is less than 0.1% by weight, the stability of the liquid is poor and the effect of penetrating the fiber does not appear. 2
Even if more than 0% by weight is added, the effect of adding only cannot be expected.

In the present invention, the F component is contained in an amount of 20 to 200% by weight, preferably 30 to 200% by weight, based on 100% by weight of the A, B, C, D and E components.
If the component is less than 20% by weight, no shrinkage-preventing effect of delaying the curing and shrinkage due to felting of animal hair products and the like will not be exhibited, and if it exceeds 200% by weight, no further effect will be exhibited.

The shrink-preventing component contains as component A a polyalkylene oxide polyol having 2 to 6 functionalities, preferably 2 to 4 functionalities, and most preferably trifunctional. The molecular weight of such a polyalkylene oxide polyol is
Preferably 600 to 10,000, more preferably 2,
000-6,000. As the alkylene oxide which is a raw material of the polyalkylene oxide polyol, ethylene oxide, propylene oxide, 1,2- or 2-3 butylene oxide, or a combination of two or more thereof may be used.

The polyols used as raw materials for the polyalkylene polyols include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin, 1,4-butanediol,
6-hexanediol, glycerin triol, C ₈ ~
C ₂₄ aliphatic triols, C ₉ -C and which may or may not be ₂₄ aliphatic unsaturated polyhydric alcohols.

The component B can contain aliphatic or aromatic isocyanates terminated with 2 to 6 functionalities, preferably 2 to 4 functionalities, most preferably trifunctional polyalkylene oxide polyols. The component B can be obtained by reacting an aliphatic isocyanate or an aromatic isocyanate with a large excess amount of a 2 to 6-functional polyalkylene oxide polyol, and protecting the terminal isocyanate group with a polyol.

The aliphatic and / or aromatic isocyanates include hydrogenated xylylene diisocyanate, dicyclohexyl methane diisocyanate, isophorone diisocyanate, mono- or poly-hexamethylene diisocyanate, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate,
Examples thereof include phenylene diisocyanate, polymethylene polyphenyl polyisocyanate, and xylene diisocyanate. Among them, polyhexamethylene diisocyanate and isophorone diisocyanate are preferred. On the other hand, as the polyalkylene oxide polyol having 2 to 6 functionalities, the polyol described above as the component A is used.

The water-soluble polyurethane and / or water-dispersible polyurethane of the component C include water-soluble polyurethane (non-reactive type), water-dispersible polyurethane (non-reactive type, forced emulsification type), and water-dispersible polyurethane (non-reactive type). , Self-emulsifying type) and reactive water-soluble or water-dispersible polyurethane (forced emulsifying type, self-emulsifying type).

Among these polyurethanes, water-soluble polyurethane (non-reactive type) and water-dispersible polyurethane (non-reactive type, self-emulsifying type) are preferable in the present invention. Table 1 shows the resin properties of the above polyurethanes.

The above-mentioned polyurethanes may be of any type as long as the physical properties are in the range shown in Table 1, depending on the use of the object, and can be applied according to the purpose of use.

[0027]

[Table 1]

In Table 1, the hardness is JIS-K-721.
It measured using the D durometer prescribed in 5. The 100% modulus and elongation were measured at a temperature of 23 ° C. after preparing a 0.3 mm film. The measurement method is JIS-
K-6301.

The preferred amount of the water-soluble polyurethane or water-dispersible polyurethane is 5 to 94.7% by weight,
More preferably, it is 10 to 70% by weight, and still more preferably 1 to 70% by weight.
5 to 60% by weight. When the blending amount is large, the fibers treated with the treating agent of the present invention are prevented from shrinking even after repeated water treatment or washing with water. If the amount exceeds 94.7% by weight, the texture of animal hair products and the like changes, which is not preferable. If it is less than 5% by weight, dimensional stability does not appear. Two or more of these water-soluble polyurethanes or water-dispersible polyurethanes can be used in combination.

The divalent to tetravalent metal salt of the component D is a metal salt of an inorganic acid or an organic acid, preferably a trivalent to tetravalent metal salt, more preferably a trivalent metal salt. Specifically, divalent metal salts such as copper salts, zinc salts, calcium salts, and magnesium salts; trivalent metal salts such as aluminum salts, chromium salts, iron salts, lanthanum salts, and cerium salts; and zirconium salts , Silicon salts and the like.
Examples of the aluminum salt include sodium aluminate, aluminum sulfate, aluminum ammonium sulfate, aluminum nitrate, aluminum acetate, aluminum fluoride, aluminum chloride, aluminum oxalate, and aluminum lactate. Examples of the zirconium salt include zirconium sulfate. Among them, aluminum sulfate is preferred, and combined use with other metal salts is also preferred.

The surfactant of the component E (excluding the nitrogen-containing surfactant having an alkyl group having 6 or more carbon atoms) is nonionic.
A surfactant is preferable, and a combination of a nonionic surfactant and an anionic surfactant or a combination of a nonionic surfactant and a cationic surfactant is preferable, and an amphoteric surfactant is also used.

As the nonionic surfactant, an ethylene oxide adduct of an alkyl phenol is preferred. Polyoxyethylene polyoxypropylene alkyl phenyl ether, polyoxyethylene polyoxypropylene alkyl ether, having an average of 6 to 12 alkyl groups and 1 to 20 moles of ethylene oxide, fatty acids having less than 6 carbon atoms in the alkyl group (Mono) dialkylamide or alkylamine, vegetable fatty acid ester, alkyl saccharide, fatty acid glycerin monoester, polyoxyethylene having an alkyl or alkenyl group having an average of 10 to 20 carbon atoms and having 1 to 20 mol ethylene oxide added Examples thereof include alkyl and alkenyl ethers.

The following are examples of the anionic surfactant. (1) Alkali metal salt of higher fatty acid (soap) (2) It has a linear or branched alkyl or alkenyl group having an average of 10 to 20 carbon atoms, and has an average of 0.1 to 1 in one molecule.
An alkyl group or alkenyl sulfate to which 5 to 8 moles of ethylene oxide is added (3) an alkylbenzene sulfonate having an alkyl group having an average carbon number of 10 to 16 (4) an alkyl group or alkenyl group having an average carbon number of 10 to 20 (5) olefin sulfonate having an average of 10 to 20 carbon atoms in one molecule (6) alkane sulfonate having an average of 10 to 20 carbon atoms in one molecule (7) sulfo Sodium succinate (8) Ether carboxylate (9) Ethoxylate of higher alcohol (10) Sulfate of higher alcohol (11) Monoalkyl phosphate (12) Alkyl polyglycoside.

Examples of the cationic surfactant include (1) aliphatic primary, secondary, and tertiary amine salts and aliphatic 4
Quaternary ammonium (2) aromatic quaternary ammonium salt (3) heterocyclic quaternary ammonium salt (4) benzethonium chloride (5) pyridinium salt (6) imidazolinium salt.

The amphoteric surfactants include (1) alkyl betaine type and (2) amido betaine type.

Each of the above nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants may be used in combination of two or more.

Examples of the nitrogen-containing surfactant having 6 or more carbon atoms in the alkyl group of the component F include coconut oil fatty acid diethanolamide, polyoxyethylene coconut oil fatty acid monoethanolamide, lauric acid diethanolamide, and coconut oil fatty acid monoethanolamide. Mono (di) ethanolamide, stearyl acid, isopropanolamide laurate, polyoxyethylene alkylamine, alkylamino oxide and the like. Among them, nonionic surfactants such as water-soluble lauric acid dietalamide and coconut oil fatty acid diethanolamide are preferred.

Examples of the nitrogen-containing surfactant having 6 or more carbon atoms in the alkyl group of the component F include aminopropylethyldimethylammonium ethyl lanolin sulfate, distearylmethylammonium chloride, stearyldimethylbenzylammonium chloride, and alkyltrimethylammonium chloride. , Stearyltrimethylammonium chloride, cetyltrimethylammonium chloride, benzalkonium chloride (R
Is mainly a lauryl group), and the like.

Examples of the nitrogen-containing surfactants having 6 or more carbon atoms in the alkyl group of the F component include coconut oil fatty acid amidopropyl betaine, lauric acid amidopropyl betaine, lauryl dimethylaminoacetic acid betaine, 2-alkyl-N
-Carboxy-N-hydroxyethylimidazolinium betaine, amphoteric surfactants such as sodium N-lauroyl-N'hydroxyethylethylenediamine and sodium β-laurylaminopropionate.

Examples of the F component include the above-mentioned polyamide-based cationic surfactants, nonionic / cationic surfactants, nonionic surfactants, quaternary ammonium salt-type cationic surfactants, amphoteric surfactants and the like. . By changing the type of these surfactants, shrink resistance after treatment,
Texture (flexibility, fluffiness, sliminess, feel, etc.)
Can be changed. Among them, coconut oil fatty acids,
A nitrogen-containing surfactant having a natural fatty acid such as lanolin fatty acid in the alkyl group is desirable. Two or more of these surfactants may be used in combination.

Examples of the aliphatic aldehyde compound as the component G include acetaldehyde, paraacetaldehyde, metaacetaldehyde, butyraldehyde, hydroxybutyraldehyde, glutaraldehyde, crotonaldehyde, margalaldehyde and the like.

Examples of the aromatic aldehyde compound as the component G include benzaldehyde, hydroxybenzaldehyde,
Examples include formaldehyde and cinnamaldehyde.

As the aldehyde compound of the G component, glutaraldehyde and a water-soluble aliphatic aldehyde having little discoloration are desirable.

The amount of the G component (aliphatic aldehyde compound and / or aromatic aldehyde compound) added to 100% by weight of the shrink-resisting component consisting of 100% by weight of the total of the A component + B component + C component + D component + E component. 5.0-10
0% by weight. If the added amount is less than 5.0% by weight, the effect of adding shrinkage-preventing property is not exhibited. Also 100
Even if it is more than the weight%, no particular improvement in shrinkage resistance is observed. Desirable addition amount of the G component is 20 to 70% by weight. Two or more of these aldehyde compounds may be used in combination.

A total of 100% by weight of the shrink-preventing component consisting of 100% by weight of the total of the A component + B component + C component + D component + E component is 20 to 200% by weight of the F component and 5 to 1% of the G component.
The H component: hydroxyalkyl phosphine is further added to 50 to 30 parts per 100% by weight of an antishrinking agent such as animal hair products.
By adding 0% by weight and performing a reduction treatment, an anti-pilling property can be imparted to an animal hair product or the like without impairing the shrinkproof property. This addition amount is A component + B component + C component + D component + E
The shrink-resisting component 100 comprising a total of 100% by weight of the components.
The amount of hydroxyalkylphosphine added is 50 to 300% by weight with respect to% by weight. 50% by weight
If it is less than 30, the anti-pilling effect does not appear remarkably.
If the content exceeds 0% by weight, not only is there no particular effect, but also the price becomes high and the texture decreases. In addition, by previously performing a reduction treatment on hair with sodium sulfite or the like, the anti-pilling effect is further improved.

Component H used in the present invention: Examples of the hydroxyalkylphosphine include dimethylhydroxymethylphosphine, dimethylhydroxyethylphosphine, diethylhydroxypropylphosphine, trishydroxymethylphosphine, trishydroxyethylphosphine, trishydroxypropylphosphine, and the like. Trishydroxybutylphosphine, trishydroxypentylphosphine, trishydroxyhexylphosphine, trishydroxyoctylphosphine, ethylbis (hydroxyethyl) phosphine, ethylbis (hydroxypropyl) phosphine and the like can be exemplified. Among them, trishydroxypropylphosphine is preferred.

As the hydroxyalkylphosphine derivative, for example, an alkylene oxide adduct can also be used. The number of moles of the alkylene oxide adduct of hydroxyalkylphosphine may be in the range of 1 to 7. The above hydroxyalkyl phosphines and their derivatives can be used in combination of two or more.

[0048]

Water treatment of animal hair products and the like with the treatment agent of the present invention,
The effect of delaying crimping and felting during water washing and imparting the fiber with shrink resistance is presumed to be as follows.
The fiber of animal hair products is keratin consisting of the accumulation of spindle-shaped cortical cells (cortex cells: CX) that constitute the main body and the intussusception of flat flaky epidermal cells (cutyl cells: CU) that surround the cells in a protective manner. As a main component.

Cortical cells have two sets of bonded structures, orthocortex and paracortex, which have different crosslink densities, have bimetallic properties, and have different extensibility due to moisture absorption. The crimp causes crimping, and the crimp causes expansion and contraction in response to humidity, and is a source of a unique bulky property (bulky property).

The epidermal cells (cuticle scale) are such that the outermost layer hardly swells from endoctyl, which is easily swelled on the cortex side of the hair body, which shows hydrophilicity, to exooctyl, and epicutyl, which shows water repellency, is attached in a bimetallic form. It is composed of thin-walled bag-like cells. The scale edge rises by the action of an aqueous solution such as acid or alkali, and water permeates through the intercellular packing having water conductivity, so that the fibers are easily entangled, so-called felting. A phenomenon occurs, and the fiber bundle and the knitted fabric shrink irreversibly.

Intercellular junction region: Between each of the cortex cells and cuticle cells, a cell membrane complex (Cell Menbran
Complex: CMC) exists as a cell-cell junctional substance.
In CMC, a component having hydrophobicity, poor water solubility, and enzyme resistance protects a component having hydrophilicity, and the whole is stabilized. The end cuticle and the CMC, which constitute the innermost cuticle, are directly connected to each other to form a canal, and exhibit a water pipe function by being connected to the components in the cortex. Orthocortex and paracortex are crimped due to the difference in elongation rate due to water intrusion.

An aliphatic aldehyde compound and / or an aromatic aldehyde compound of component F and G such as higher fatty acid dialkanolamide, which is a nitrogen-containing surfactant having 6 or more carbon atoms in the alkyl group, is combined with component A + component B + component C + D In addition to the shrinkproof component of the fiber composed of component + E component,
When animal hair or wool fiber is treated, it adheres to the amino acid residues of CMC existing between cuticles and the cuticle, and the alkyl group in the treatment agent shows hydrophobicity, preventing water from entering the inside of the hair. It is presumed that the rise of cuticle was suppressed and the crimping and felting were delayed.

The hair may be reduced in advance with an aqueous solution of trishydroxypropylphosphine, sodium carbonate, sodium sulfite, sodium thiosulfate, ammonium thioglycolate, sodium acetate, sodium metasilicate, etc., having a pH of 12 or less, or If the hair is oxidized with an aqueous solution of hydrochloric acid, monooxyphthalic acid, monopersulfuric acid, or the like, or the above-mentioned polyvalent metal salt solution is added to the above solution, the crimping or felting of the hair is further delayed. it can. This means that the hydrophobicity of the epicuticle in the outermost layer of the cuticle is reduced and oxidized even slightly to make it hydrophilic.
By improving the adhesiveness of the composition of the treatment agent to soften the hair to suppress the rising of the cuticle, and to inhibit crimping and felting by inhibiting the intrusion of water into the hair. Guessed. In addition, the expression of the shrinkage-preventing effect is promoted in a recycled fiber cloth such as rayon.

It is presumed that the divalent or tetravalent metal salt, which is the D component, also has a function of enhancing the binding to amino acid residues or keratin moieties, and thus delays crimping and felting. When the treated cloth is immersed in a 6% by weight aqueous solution of aluminum sulfate, the effect of delaying the felting is also observed.

The shrink-preventing component consisting of the A component + B component + C component + D component + E component has flexibility and elasticity, and after being attached to animal hair, wool, etc., exhibits a form that is just glued. When it is applied, it expands and contracts easily, but when no force is applied, it is restored to its original size and the dimensions are stabilized. Since the shrink-preventing component is soft, the change in texture is small, and in many cases, it is improved. In addition, since the shrink-resistant component has thermoplasticity, it can be plastically deformed by heating such as steam spraying or ironing, and then cooled to room temperature to set it to the desired shape and dimensions, and is insoluble in water. Therefore, even if the fiber is immersed in water, it does not fall off from the fiber, and can withstand repeated water treatment and washing with water. Moreover, the shrink-resisting component is capable of imparting shrink-resisting properties to natural fibers such as silk, cotton, hemp and the like, as well as to fiber products mainly composed of the natural fibers.

In the case of regenerated fibers, particularly fibrous materials obtained by blending rayon and rayon with other fibers, and twisted yarn produced by blending animal hair, wool and animal hair, and blending wool with other natural fibers or chemical fibers, When immersed in water, relaxation stress acts and contracts. For this reason, woven fabrics and knits using strong twisted yarns shrink and deform when subjected to water treatment and washing with water, and are difficult to handle. These fibrous substances can also be immersed in a dilute aqueous solution of the treating agent of the present invention, relaxed in stress, and then dried while being stretched in a wet state to significantly reduce shrinkage to produce a product. This is due to the shrink-prevention property of the treatment agent due to the gluing effect.

The components A to E and the nitrogen-containing surfactant having 6 or more carbon atoms in the alkyl group of the F component and the aliphatic aldehyde compound and / or the aromatic aldehyde compound of the G component are blended as follows. Is done. First, a 2- to 6-functional polyalkylene oxide polyol as the component A and B
A predetermined amount of an aliphatic polyisocyanate and / or an aromatic isocyanate as a component and a surfactant as an E component is blended, and the mixture is stirred at a temperature of 60 to 85 ° C. for a predetermined time,
An aqueous solution of a divalent or tetravalent metal salt as the component D is added thereto.
Next, a nitrogen-containing surfactant having an alkyl group having 6 or more carbon atoms as an F component and an aliphatic aldehyde compound and / or an aromatic aldehyde compound as a G component are added. Then C
It can be obtained by adding a water-soluble polyurethane and / or a water-dispersible polyurethane emulsion as components and stirring for a predetermined time. In addition, a component having a modulus according to the purpose of use can be added at the time of use without adding the component C and the component F. The C component, the F component, and the G component can also be added to a dilute aqueous solution of the shrink-preventing component consisting of the above A to E components. Furthermore, PH adjusters, antibacterial agents, coloring agents,
Auxiliary components such as fragrances and defoamers can be contained in appropriate amounts.

Next, a method for treating animal hair products and the like using the treating agent of the present invention will be described. A necessary amount of each component of the present treatment agent is added by owf per weight of animal hair such as wool, wool, woven fabric, knitted fabric, non-woven fabric and fur and diluted with water, and a treatment liquid having a bath ratio of 3 to 60 times. Use as The fiber to be treated is put into the treatment liquid, immersed for a required time, and rinsed with water for 1 minute or twice for 2 minutes to remove the liquid if necessary. If the fibers are less than a predetermined size when in a wet state, they are pulled to a predetermined size and dried. After drying, the shrink-preventing component of the present treatment agent firmly adheres to the fibers to form a paste. It is set after drying and the dimensions are stabilized. Iron at the proper temperature of the fiber and correct wrinkles and stretched parts.
When the acid treatment or the reduction treatment is performed, a prescribed amount of an acid or a reducing agent is added to the shrink-prevention treatment or the treatment liquid. However, in the case of using a fiber which has been subjected to a polyvalent metal salt treatment, an acid treatment or a reduction treatment in advance, it is not necessary to add an oxidizing agent or a reducing agent. In addition, when reduction treatment with hydroxyalkylphosphine is performed, pilling resistance is improved.

In the case of a knitted fabric that requires processing order and shrinking, shrinking processing is first performed on the knitted fabric. Thereafter, a reduction / oxidation treatment is performed to cleave the disulfide bonds in the cuticle (scale) portion on the hair surface and the C, M, and C portions to convert the -SS- bonds into -SH. After that, it is washed with water and moves to a shrink-proofing step.

Next, a shrink-proofing process is performed. First, A ~
The object to be treated is put into a solution in which the shrink-preventing component composed of the E component, the F component, and the G component are dissolved, and the mixture is slowly stirred to perform the treatment. When the texture adjustment is required, a part of the F component and a part of the G component are added and processed after the above processing. afterwards,
Wash with water and finish the process.

The shrinkproof component of the treating agent of the present invention is dispersed in water in the form of a fine hydrogel or micelle. During the immersion or at the wet stage, some of the shrink-resistant components adhere strongly to the fibers, but some only adhere to the fibers.
The strong adhesion to the fiber occurs after the water evaporates, the fine gels and micelles are destroyed, and a part of the active ingredient of the treating agent of the present invention is precipitated and adheres to the water-swelling fiber. . Therefore, if strong centrifugal dehydration is performed at the time of dehydration or if the water content is reduced to 20% by weight or less due to excessive squeezing, the shrink-preventing component flows out together with water, and the expression of the shrink-preventing effect is weak.

Next, the water treatment and the washing method of the fiber after the shrink-proof treatment will be described. Usually, animal hair fibers such as wool are
Under strong friction such as hand massage in an aqueous solution containing a clothing detergent such as sodium dodecylbenbensulfonate, 10
A crimping and felting phenomenon occurs in about 60 seconds. In addition, when a household washing machine is used even when a yarn washing detergent for fibers having a dry-cleaning sign and containing a polyethylene alkyl ether-based nonionic surfactant as a main component is used, washing is performed for 3 to 5 minutes. It is described that the water washing is completed by rinsing for a minute.

The animal products such as wool treated with the treating agent of the present invention exhibit resistance of 10 minutes or more even under severe friction such as hand rubbing in a solution containing the above-mentioned detergent for clothing, and furthermore, oxidized. -When subjected to a reduction treatment, it exhibits resistance of 15 minutes or more. In an untreated blank, curing starts around 15 seconds, and felting occurs. In addition, even if the treated cloth is washed with a household washing machine and washed with a sodium dodecylbenzenesulfonate-based detergent for clothes, the treated cloth has a resistance of 60 minutes or more,
Has shrink resistance.

The effect of using the nitrogen-containing surfactant alone having 6 or more carbon atoms in the alkyl group of the F component is as follows. Palm oil fatty acid diethanolamide, lauric acid diethanolamide, ethyl lanolin sulfate fatty acid aminopropylethyldimethylammonium, distearyldimethylammonium chloride, polyoxyethylene lauryl ether triethanolamine sulfate, alkyl (11,13,15)
Triethanolamine sulfate and coconut oil fatty acid amide propyl betaine solution were used, but no shrinkproof effect was produced. However, the effect of delaying the felting is slightly recognized, and shows a resistance of about 45 seconds even under severe friction such as hand massage described below. In addition, the alkyl group having 6 or more carbon atoms of the F component attached thereto by using in combination with the A to E components and the G component of the present invention shows hydrophobicity, and prevents the intrusion of water into the hair, whereby the shrinkage-preventing effect is improved. It seems to have been accepted.

The aliphatic aldehyde compound of the component G and / or
The effect of using the aromatic aldehyde compound alone is as follows. Glutaraldehyde, a water-soluble aliphatic aldehyde with little discoloration (BASF, Germany, trade name: Relugan) was used, but no shrinkage-preventing effect was observed. However, effects were observed when used in combination with the components A to E of the present invention. This is presumed to be due to the fact that the A to F and H components are prevented from falling off the fibers by crosslinking with the treating agent component.

The effects of using the oxidizing agent and the reducing agent alone are as follows. Monooxyphthalic acid and monopersulfate were used at pH 3-4 as oxidizing agents, and sodium metasilicate, sodium carbonate, sodium thiosulfate, and sodium sulfite were used at pH 8-12 as reducing agents. I was not able to admit. When trishydroxypropylphosphine is used alone as a reducing agent anti-pilling agent, the treated cloth is hardened and the texture is lowered, but the shrink resistance is recognized immediately after the treatment. However, when water washing was repeated, the shrink resistance was considerably reduced. The anti-pilling effect is
It increased as the amount of addition increased. However, when used in combination with the treating agent of the present invention, effects of improving texture, maintaining shrinkage resistance and anti-pilling properties were observed. When trishydroxypropylphosphine was used in combination with an enzyme (protease), the same anti-pilling property was exhibited even when the amount used was reduced.
However, the amount of the enzyme (protease) alone was small, and no anti-pilling effect was exhibited. If the amount of the enzyme added is increased, it is difficult to control the work process, and it is expensive. It is presumed that these weakened the water repellency / hydrophobicity of the animal hair surface, increased the amount of the animal hair attached to and adhered to the fiber surface, and reduced the rising of cuticle (scale).

The method for simultaneously carrying out the shrinkproof treatment and the washing with one liquid is as follows. When the method for washing a test cloth described below is performed, a specified amount of the shrinkproofing agents A to G of the present invention is simultaneously injected with a detergent and washed. The fiber product shrunk by wearing can be extended and restored to the new length.

[0068]

EXAMPLES The present invention will be described more specifically below with reference to examples and comparative examples. Various test methods performed in the examples and comparative examples are as follows.

繊 維 Fiber shrinkage: JIS-L-1042
Method and shrinkage test method of the woven fabric.

○ Shrinkage of knitted fabric: JIS-L-108
1. 1990, Knitted fabric test method 6.30G method (home electric washing machine method). This was based on JIS-L-1057, an iron shrinkage test method for woven and knitted fabrics, and a B-1 method (steaming iron method). The length of the measurement section before treatment and before washing, which is the basis of the treatment with the shrinkproofing agent of the present invention, and the calculation of the shrinkage rate when water washing and water washing are repeated, the fiber cloth is treated with this treating agent. Calculated using the values before The calculation of the shrinkage rate was based on the following equation. Shrinkage rate = (length of measurement section before processing−length of measurement section after processing) / length of measurement section before processing × 100 When the shrinkage rate is negative, it indicates elongation.

Washing test: In accordance with JIS-L-0217, display symbols related to the handling of textile products and their display methods, test methods according to the different symbols, numbers 103 and 105.

○ Pilling test: JIS-L-1076,
The method was based on the pilling test method A of a woven or knitted fabric (method using an ICI type testing machine).

風 Handle: When the unprocessed product is set to “no change”, the touch of each processed product is evaluated in five stages (reduced, slightly reduced,
No change, slight improvement, improvement).

手 Hand massage washing test After the washing cloth was put into an aqueous solution containing a detergent (Kao, the standard amount of attack: 20 g per 30 liters of water), the washing cloth was rolled in both hands, and then The cloth was turned in the hand with strong compression, rubbed vigorously and quickly, and rubbed and washed. After rubbing and washing, take out every 20 seconds, gently pull on the crumple cloth, correct the part that is deformed by wrinkling, and measure the vertical and horizontal dimensions. This is repeated to perform hand-rubbing washing for 180 seconds. In untreated knitted fabrics, sharp shrinkage is usually seen in 10 to 60 seconds. Fully felted after 40 seconds on a fabric that shrinks heavily. 60-80 knitted treatment cloth
After 10 seconds, use a home electric washing machine to wash the net
The shrinkage is approximately the same as the shrinkage rate after repeating about once. The knitted cloth used was 10 × 10 (cm). In a normal knitted fabric, when immersed in water, a relaxation stress acts to cause a shrinkage of 2 to 10%. Or, the shrinkage differs depending on the length and width (wale course) and it deforms. If the shrinkage of the knitted fiber is less than 6% in each of the longitudinal and lateral length directions, it can be easily restored by pulling it for elongating wrinkles. 6-10%
The contraction can be restored by pulling with a little force. With a shrinkage of 10 to 19%, it can be restored to almost the original size by pulling by applying force, but if the shrinkage exceeds 25%, felting occurs and restoration is difficult. The degree of shrinkage (easiness) can be determined in a short time by this hand massage washing test. As a result of the hand massage test, those having a small shrinkage were subjected to an electric washing machine washing to determine the chemicals used, the amount added, and the resistance to washing with water. If the elongation is large, it can be easily restored to the original size by spraying steam and leaving it to cool.

A to E of shrink-preventing agents used for testing the test cloth
Table 2 shows the compounding ratios of the F component, the G component, the H component, the reducing agent, etc., with the components being 100% by weight.

[0076]

[Table 2]

The details of the components in Table 2 are as follows. A component: Polyoxyethylene polyoxypropylene triol (Sanyo Chemical Industries FA) B component: The above A component terminated with hexamethylene diisocyanate C component: Water-dispersible polyurethane (Toagosei Neotan) D component: Aluminum sulfate (used as an aqueous solution) E component: polyoxyethylene nonyl phenyl ether (ethylene oxide addition 11 mol) F component: coconut oil fatty acid diethanolamide (Sanyo Chemical Industrial Prophan): quaternary ammonium salt type cationic surfactant (Sanyo Chemical Industrial Safanol) G Ingredients: water-soluble aliphatic aldehyde aqueous solution (Germany, BAS
F, Relugan)

The H component used: The details of the reducing agent and the reducing agent are as follows. Reducing agent: a mixture of 4 parts of sodium sulfite, 2 parts of sodium thiosulfate, and 1 part of sodium carbonate Reducing agent: trishydroxypropylphosphine (Nippon Kagaku Kogyo, Pirgon PP-40) anti-pilling agent Reducing agent: enzymes, O, W, F , 0.3% added (Nippon Kagaku Kogyo Co., Enzyin WS; main protease type) (Note) The enzyme was used because the anti-pilling effect was observed even when the amount of trishydroxypropylphosphine was reduced. Shrinking agent: Kao Corporation Emar 40 Shrinking agent: Sanyo Chemical Industries, Ltd. Sandet ADX

The shrinkproof treatment of the test cloth is as follows. . Order of treatment Shrinking treatment (implemented for knitting that requires shrinking) Reduction treatment (implemented for those that require reduction treatment) Those requiring anti-pilling properties were treated with trishydroxypropylphosphine . Shrink-proof treatment (using A to G components)

[Sprinkling treatment] Into the treatment tank, hot water at 50 ° C. in a prescribed amount: bath ratio (multiple of the amount of dilution water per weight of the material to be treated, the same applies hereinafter) was injected into the treatment tank.
6-8% of O, W, and F (the same amount of the added agent (%) or less per weight of the material to be treated) and 1% of a synthetic detergent (Kao Attack) were added to the homogenizer to form a uniform solution. An object to be treated was put into this liquid, immersed for 20 to 30 minutes, stirred slowly, then drained, and washed with water.

[Reduction treatment] The treatment was performed on an object to be treated which had not been previously subjected to oxidation / reduction treatment. Table 2 shows three tests: one treated with a reducing agent alone, one treated with a reducing agent and then treated with a reducing agent (partially with an enzyme indicated by the reducing agent), and one treated with only a reducing agent. The results were compared mainly for anti-pilling properties.

Hot water at 50 ° C. was injected into the treatment tank at a bath ratio of 1:30, and the reducing agents shown in Table 2 were added in O, W, and F in an amount of 4 to 6% to form a uniform liquid. An object to be treated is put into this liquid, and 2
After immersion for 0 to 30 minutes and slow stirring, the solution was drained and washed with water.

[Improvement of anti-pilling property] Tests were carried out for the case where trishydroxypropylphosphine was treated alone and the case where an enzyme was used in combination. The result is an enzyme (main component protease)
The same effect was obtained when using in combination with a small amount of trishydroxypropylphosphine. The enzyme alone did not show any improvement in anti-pilling properties. Table 3 shows the compounding ratio of the drug and the anti-pilling property when using trishydroxypropylphosphine and the enzyme. The treated cloth used was cashmere knitting.

[0084]

[Table 3]

Description of Tables Examples 37 to 40, Comparative Example 10 Hot water at 50 ° C. was added to the treatment tank at a bath ratio of 1:30.
Was added to obtain a homogeneous solution. Cashmere knitting was charged, immersed for 30 minutes, stirred slowly, and washed with water after draining. When an enzyme was added, an organic acid having a pH of 3 or less was added to deactivate the enzyme, and then the solution was removed and washed with water. Then, after performing a shrink-proof treatment, the pilling property was tested.

[Shrink-proof treatment] Hot water at 40 ° C was injected into the treatment tank at a bath ratio of 1 to 30. The components A to E in Table 2 are represented by O,
Add 6% of W and F, 4% of coconut oil fatty acid diethanolamide of F component, and 2% of G component to make a uniform solution. The object to be treated was charged, and the mixture was slowly stirred. After 10 minutes, 2% of a quaternary ammonium salt type cationic surfactant of the F component was added. After 10 minutes, the solution was drained and washed with water. It was dehydrated by a centrifuge to a water content of about 30%. In a wet and wet state, the size of the object to be treated was compared with the dimension of the object measured in advance. Alternatively, the shape was corrected while steam was blown after drying to make the fibers soft.

Tables 4 and 5 show the shrinkage ratio of the cashmere knitted product after the treatment with the present treating agent and rinsing with water.

[0088]

[Table 4]

Description of Table 4 Test of cashmere knitting, blanks in Examples 1 to 13 and Comparative Example 1 (untreated) Test cloth: 100% cashmere, a cloth immediately after knitting by a flat knitting machine was used. 2. Shrinkage ratio JIS-L-1081G method, value after washing 10 times, according to the report of Tokyo Textile Industry Laboratory. Hand massage washing test: Calculated by the average value of shrinkage in the wale direction and the course direction. Using a household electric washing machine, JIS-L-02177.1
In accordance with Method 05, the laundry was put into a washing net, the washing time was extended, washing was performed, and “rinsing” was performed every 30 minutes, and the dimensions were measured. It was repeated three times. JIS- after washing for 90 minutes
L-1057. The treatment was carried out in accordance with the B-1 method, measured, and calculated by the average value of the shrinkage in the wale direction and the course direction. 3. Pilling test: Test values based on the results of Tokyo Metropolitan Textile Industry Laboratory, Wool Product Inspection Association, Japan Chemical Fiber Inspection Association, and Japan Spinning Inspection Association were used. 4. (Drug used): Kind of vulcanizing agent, combination of reducing agents, A
The chemicals shown in the component description of Table 2 were used for the types of the H components.

[0090]

[Table 5]

Description of Table 5 Cashmere knit washing shrinkage
Example 14 Test cloth: The test cloth of Example 5 was used. Drug used: The same as in Example 5. Test method: JIS-L-1018-1990 Knitted fabric test method 6.30G method (household electric washing machine method) However, separate tables and symbols of JIS-L-0217 (signs for handling textile products and methods for indicating their dimensions) According to another test method (1), a test method specified in washing method No. 105. Drying: screen drying. Detergent: Neutral Akron was used. The test was "wash, dry, measure" for the same material.
The repetition was performed 0 times, and the contraction rate was calculated each time based on the initial length. (Note) Test values based on the report of Tokyo Metropolitan Textile Industry Laboratory were used.

[0092]

[Table 6]

Description of Table 6 Examples 15 to 19 and Comparative Example 2
Is blank (untreated). 1. Test cloth: 100% wool, worsted yarn knit, flat knitted cloth 2. Shrinkage rate Hand massage washing test: Calculated by the average value of shrinkage rates in the wale direction and the course direction. Using a household electric washing machine, JIS-L-0217,1
In accordance with the 05 method, washing was performed by extending the washing time by putting the washing net, and "rinsing" was performed every 30 minutes, and the dimensions were measured. It was repeated three times. After washing for 90 minutes, J
Processing was carried out in accordance with IS-L-1057, B-1 and measured and calculated by the average value of shrinkage in the wale direction and the course direction. 3. (Drug used): For the combination of A to H components, the drugs shown in the component specification of Table 2 were used.

[0094]

[Table 7]

Description of Table 7 Examples 20 to 26, Comparative Example 3
Is blank (untreated). 1. 1. Test cloth: Thick knitted cloth with twill knitting using wool mixed with wool and Angola. Shrinkage: Hand-rubbing washing test Household electric washing machine test The test method and calculation method for shrinkage in Table 6 were the same. 3. (Drug used): For the combination of A to H components, the drugs shown in the component description of Table 2 were used.

[0096]

[Table 8]

(Explanation of Table 8) Knit (knitted) products used for testing Shrinkage after washing of knitted (knitted) products Knit: 100% cashmere flat knit sweater Weight 250g Knit: 100% wool worsted yarn sweater 480g Knit: 100% wool sweater using 100% wool 280 g knit: 80% wool 20% mohair 20% woolen sweater Weight 675 g

2. Chemicals used in test products and treatment method The treatments in Examples 27 to 30 were the same as the chemicals used in Example 13 and the treatment method.

3. Washing method (1) In accordance with JIS-L-0217-105 method (electric washing machine washing, using a washing net). (2) For the second washing, use the product sweater after the first washing, in accordance with JIS-L-0217-105 method (using a washing net), extend only the washing time and carry out continuous washing for 30 minutes did. (3) In the third washing, continuous washing was performed for 30 minutes in the same manner as in the second washing, using the product sweater after the second washing. (4) The product sweater shrinks and has many wrinkles after washing and rinsing and dehydration. Therefore, when it is wet after dehydration, it is stretched by wrinkling and stretching, and then folded in two.
Hanging and drying was performed.

4. Shrinkage (1) For the product sweater after washing and drying, the length, width (upper and lower armpits), width (lower / hem), sleeve length, and sleeve width were measured and recorded. (2) Dimensions before washing were recorded by measuring dimensions after shrink-proofing and drying. (3) The dimensions before the treatment were recorded by measuring the dimensions of the product sweater before the shrink-proof treatment. (4) Finished dimensions are measured by spraying steam and hot air onto the sweater whose dimensions have been measured after washing and drying for the third time (60 minutes), then cooling, and then measuring the dimensions. I filled it out. (Note) The sweater after washing for 60 minutes is easily stretched when pulled because the felting has not progressed. In addition, when steam was blown, the size could be modified more easily.

[0101]

[Table 9] Description of Table 9 Shrinkage of the woven fabric after washing Used woven fabric The test was conducted mainly on a fabric that is easily stretchable when pulled like a knitted fabric while being a woven fabric, and shrinks and deforms when immersed in water. (1) Normal dimension: A value measured in a normal state (when left at room temperature, the same applies hereinafter) was taken as a “normal dimension” as a standard for easily expanding and contracting. (2) Normal tensile size: Measured in a state of being stretched and stretched in a normal state, and defined as “normal tensile size”. (3) Dimension before washing (after treatment): The test cloth contracted due to relaxation stress. In the comparative example: dimensions were measured and filled in after immersion in only 35 ° C. warm water for 15 minutes, followed by drying. In the embodiment: Shrink-proofing is performed using an untreated cloth that is not immersed in water,
After drying, the dimensions were measured and recorded.

(4) Types of Test Cloth Cloth-1: 100% wool strong twisted yarn (1600 times / m) Stretchable thin cloth coarse woven cloth manufactured by Hanari Toshi Fabric-2: 100% wool strong twisted yarn (1600 times / m m) Stretchable thin dense cloth Woven fabric made by Toshi Hanai Co., Ltd. Fabric-3: Wool strong twisted yarn, elastic heavy cloth coarse woven cloth Fabric made by Toshi Hanai Cloth-4: Wool 90% nylon 10% Rassaori thick fabric
Fabric-5: 100% wool striped twill fabric Fabricated by Toshi Hanai

2. Chemicals used for treatment of test cloth and treatment method Comparative Examples 4 to 7 were used as blanks, and cloths immersed only in the above-mentioned warm water were used, and no chemical treatment was performed. Examples 31 to 3
5 was the same as the chemical used and the treatment method of Example 13.

3. Washing method (1) Based on JIS-L-0217-105 method (electric machine washing). (2) For the second wash, use the cloth after the first wash,
According to the SL-0217-105 method, only the washing time was extended, and washing was continuously performed for 30 minutes. (3) In the third washing, continuous washing was performed for 30 minutes in the same manner as in the second washing, using the cloth after the second washing.

4. Shrinkage (1) Using the cloth after washing and rinsing and drying, dimensions in the vertical and horizontal directions were measured and calculated from the difference between normal dimensions. (2) Because the cloth tested this time has elasticity,
Some fabrics had less shrinkage in the next round than in the previous round,
The tendency of the shrinkage-preventing effect was obtained from the measured values of the comparative example and the example.

[0106]

[Table 10]

(Description of Table 10) Shrinkage after fur (mouton) washing Test fur: wool 23 mm long mouton (chrome tanned) 20 cm x 20 cm (70 g) x 2 pieces

2. Type of treatment agent a. Table 2 Shrinkage-preventing components consisting of AE of composition 3 (100
%). B. Table 2 125% F component was used. C. Table 2 33% of the G component was used. D. Table 2 133% of the H component reducing agent and the anti-pilling agent were used. (Note) In Comparative Example-9, a blank was used and no treatment was performed.

3. Order and dimensions of chemical treatment (1) A to E components: O, W, F 3%, bath ratio 1:30, 3
The mouton was immersed in a 0 ° C. bath, stirred for 10 minutes, stopped for 50 minutes, and immersed for a total of 5 hours. (2) H component reducing agent 2, anti-pilling agent: O, W, F10
%, Dibasic sodium phosphate heptahydrate 2 g / l, nonionic surfactant 1%, bath ratio 1:30, after immersing Mouton in the solution for 30 minutes, draining and washing with water. (3) O, W, F: 2% of G component, 6% of F component, 3% of A to E component, bath ratio of 1:30, after immersion in a 30 ° C. liquid for 30 minutes,
It was drained and washed with water.

4. Washing method (Electric washing machine washing) (1) Based on JIS-L-0217-105 method (using a washing net) (2) The second time uses fur (mouton) after the first washing, JIS-L-0217 According to the -105 method, only the washing time was extended, and continuous washing for 30 minutes was performed. (3) In the third washing, the fur (mouton) after the second washing was used to carry out continuous washing for 30 minutes in the same manner as in the second washing.

5. Shrinkage (1) Using fur (mouton) after washing, rinsing and drying, dimensions in the vertical and horizontal directions were measured and calculated from the difference from the dimension before the treatment. (2) Change rate: A change in dimension due to treatment with a shrinkproofing agent. (3) The dimensions before the treatment were used as the dimensions on which the shrinkage rate and the change rate were based.

[0112]

As described above, according to the present invention,
Even if the water treatment time is extended or the number of times of washing with water is increased for animal hair products or the like, the shrink-preventing effect can be maintained, and the anti-pilling property can be obtained. Therefore, the animal hair product or the like treated in the present invention has a feature that dimensional stability, flexibility, and texture are improved because crimping and felting are delayed even after repeated water treatment and washing. ,
In addition, the shrinkage rate can be reduced even for a product such as a knitted fabric having a coarse stitch or a woven fabric of a strong twisted yarn which is easily shrunk only by immersion in water. Further, the animal hair products and the like treated according to the present invention have less fluff, less change in appearance, less flexibility, and dimensional stability even if detergent is added to tap water and repeatedly washed and dried by exposing to direct sunlight. Not only is not lost, but also has the excellent effect that the properties such as pilling resistance, mechanical strength, bending resistance, abrasion resistance, moderate heat retention, moisture retention, air permeability, moisture absorption / desorption, etc. do not change. Can play.

Claims (5)

[Claims] (1) As a shrinkproof component, component A: 5 to 80% by weight of a 2 to 6 functional polyalkylene oxide polyol;
Component B: 0.1 to 20% by weight of aliphatic isocyanate and / or aromatic isocyanate terminated with 2 to 6-functional polyalkylene oxide polyol; Component C: 5 to 5 parts of water-soluble polyurethane and / or water-dispersible polyurethane ９４94.7% by weight, D component: 0.1 to 7% by weight of a divalent to tetravalent metal salt, E component: a surfactant (excluding a nitrogen-containing surfactant having an alkyl group having 6 or more carbon atoms) From 0.1 to 20% by weight (provided that the total of the A component + B component + C component + D component + E component is 100% by weight). Nitrogen-containing surfactant having 6 or more carbon atoms of 20 to 2
00% by weight, G component: aliphatic aldehyde compound and / or
Or an antishrinking agent such as a solid or liquid animal hair fiber product containing 5 to 100% by weight of an aromatic aldehyde compound. 2. As the shrink-preventing component, A component: 5 to 80% by weight of a 2-6 functional polyalkylene oxide polyol;
Component B: 0.1 to 20% by weight of aliphatic isocyanate and / or aromatic isocyanate terminated with 2 to 6-functional polyalkylene oxide polyol; Component C: 5 to 5 parts of water-soluble polyurethane and / or water-dispersible polyurethane ９４94.7% by weight, D component: 0.1 to 7% by weight of divalent metal salt E component: Surfactant (excluding nitrogen-containing surfactant having 6 or more carbon atoms in the alkyl group) 0.1 to 20% by weight, wherein the total of component A + component B + component C + component D + component E is 100% by weight. Nitrogen-containing surfactant having 6 or more carbon atoms 20 to 2
00% by weight, G component: aliphatic aldehyde compound and / or
Alternatively, by dipping the animal hair fiber product or the like in a solid or liquid shrink-proofing agent such as a animal hair fiber product containing 5 to 100% by weight of an aromatic aldehyde compound for a certain period of time,
A method for shrink-proofing animal hair products and the like, which comprises delaying felting of animal hair fiber products and the like. 3. A component as a shrink-preventing component: 5 to 80% by weight of a 2-6 functional polyalkylene oxide polyol;
Component B: 0.1 to 20% by weight of aliphatic isocyanate and / or aromatic isocyanate terminated with 2 to 6-functional polyalkylene oxide polyol; Component C: 5 to 5 parts of water-soluble polyurethane and / or water-dispersible polyurethane ９４94.7% by weight, D component: 0.1 to 7% by weight of divalent metal salt, E component: surfactant (excluding nitrogen-containing surfactant having an alkyl group having 6 or more carbon atoms) )
Is essentially 0.1 to 20% by weight (provided that the total of component A + component B + component C + component D + component E is 100% by weight). Number 6 or more nitrogen-containing surfactants 20 to 20
0% by weight, G component: 5 to 100% by weight of aliphatic aldehyde compound and / or aromatic aldehyde compound, H component: 50 to 300% by weight of hydroxyalkylphosphine
An antishrinking agent for solid or liquid animal hair fiber products or the like, comprising: 4. A component as a shrinkproof component: 5 to 80% by weight of a 2-6 functional polyalkylene oxide polyol;
Component B: 0.1 to 20% by weight of aliphatic isocyanate and / or aromatic isocyanate terminated with 2 to 6-functional polyalkylene oxide polyol; Component C: 5 to 5 parts of water-soluble polyurethane and / or water-dispersible polyurethane ９４94.7% by weight, D component: 0.1 to 7% by weight of divalent metal salt, E component: surfactant (excluding nitrogen-containing surfactant having an alkyl group having 6 or more carbon atoms) )
Is essentially 0.1 to 20% by weight (provided that the total of component A + component B + component C + component D + component E is 100% by weight). Number 6 or more nitrogen-containing surfactants 20 to 20
0% by weight, G component: 5 to 100% by weight of aliphatic aldehyde compound and / or aromatic aldehyde compound, H component: 50 to 300% by weight of hydroxyalkylphosphine
The animal hair fiber product etc. is immersed for a certain period of time in a shrinkproofing agent such as a solid or liquid animal hair fiber product etc. containing A method for preventing shrinkage of animal hair fiber products and the like, which is characterized by delaying the formation. 5. An animal which has been oxidized or reduced by adding an oxidizing agent or a reducing agent during the above-mentioned treatment step, or has been previously treated with a polyvalent metal salt or oxidized and reduced. 5. The method for shrink-proofing animal hair fiber products according to claim 2, wherein a hair product or the like is used.