JPH08157900A - Agent for treating leather, fur and natural fiber and fiber product mainly composed of natural fiber and treatment using the same - Google Patents

Abstract

PURPOSE: To obtain a treating agent for leather, fur, natural fibers and natural fiber products, improves their washing resistance, dimensional stability, flexibility, tensile strength, touch or fabric hand, compressing a specific composition. CONSTITUTION: This treating agent comprises (A) a polyoxyalkylene polyol having 2-6 functional groups (preferably having 600-5,000 molecular weight and 3 functional groups), (B) a water-soluble polyurethane and/or a water- dispersible polyurethane, (C) an aromatic (poly)isocyanate and/or an aliphatic (poly)isocyanate and (D) a surfactant (preferably a nonionic surfactant as an ethylene oxide adduct to an alkylphenol. The component B is preferably a non-reactive water-soluble polyurethane obtained by reaction of a polyethylene glycol with tolylene diisocyanate. Preferably, the amounts of component A of 25-70wt.%, component B of 15-60wt.%, component C, of 0.3-3%, and component D of 0.8-15wt.% are blended together.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a treatment agent for imparting water-washing resistance to leather, fur and natural fibers and a textile product mainly composed of the natural fiber, and water-washing resistance using the treatment agent. Treatment method to be imparted, leather imparted with water washing resistance by this treatment method, waterproof treatment method for imparting waterproofness to fur, and leather and fur imparted with water washing resistance by the treatment method with the treatment agent The present invention also relates to an antibacterial treatment method for imparting antibacterial properties to a natural fiber and a fiber product mainly composed of the natural fiber.

More specifically, leather, fur and natural fibers, and textile products based on the natural fibers, even when washed with water and washed,
A treatment agent for obtaining a water-washable treated product which maintains flexibility, has excellent dimensional stability (anti-shrinkage properties) and can increase the water absorption of fibers, and a treatment method using the treatment agent; Leather treated with this treatment agent, leather for imparting excellent waterproofness and water repellency to treated fur, a method for waterproofing fur, and leather, fur and natural fibers treated with the treatment agent, and natural The present invention relates to an antibacterial treatment method for imparting excellent antibacterial properties to a processed product of a fiber product mainly composed of fibers.

[0003] In the present invention, natural fibers refer to animal hair such as wool, natural animal fibers such as silk and feathers, and natural vegetable fibers such as cotton and linen. Refers to woven fabrics, knitted fabrics, nonwoven fabrics, and the like, in which fibers other than natural fibers such as synthetic fibers are blended with the natural fibers or the superior amount of the natural fibers.

[0004]

2. Description of the Related Art Generally, leather and fur have been hardened and shrunk by washing with water, so that washing with water has been considered difficult. In order to make the leather and fur washable with water, a method of re-liming at the stage of the raw hide or performing tanning after sufficiently performing enzyme treatment to grind a sulfated oil or the like has been attempted. These drawbacks could not be eliminated because they harden or shrink in one or several washings with water. Therefore, washing is performed by a dry cleaning method or a powder method, but it is difficult to remove water-soluble contaminants.

On the other hand, the above-mentioned natural fibers and fiber products mainly composed of natural fibers are similarly hardened and shrunk by washing with water. Among them, scales called cuticles exist on the surface of various animal hairs including wool, and there is a problem that these scales are entangled with each other and felt and cannot be restored. Due to this, felting is further promoted during drying after washing with water, and shrinkage occurs. Also, silk, cotton,
Hemp and the like also expand and expand when immersed in water, but have the property of shrinking during drying.

[0006] As a method of preventing such shrinkage, for wool and the like, an enzymatic treatment method or a chlorination treatment is carried out in order to remove the surface scale (the above-mentioned cuticle). The Dylan method, the FTC method, the DCCA method, the protein method, and the like for reducing the number of fibers and preventing entanglement between the fibers have been carried out. However, there is a problem that the fibers are liable to slip and fray easily.

Further, there is a resin method in which fibers are adhered to each other with a specific synthetic resin to cover a scale (cuticle).
WS chlorination method, cloi / resin method, siroran BAP method,
There are a DC-109 method and a laser beam irradiation method. However, according to these methods, the fibers are hardened and the texture is deteriorated. Therefore, for cellulose fibers such as cotton, the form is stabilized by mercerizing, blanching, or the like.

The above-mentioned leathers and furs have no or very weak effect of inhibiting the growth of bacteria and molds such as Trichophyton and Staphylococcus aureus. It is easily detached by friction or water washing by application, and leather is hardened and shrunk when water washing is repeated, and antibacterial properties are reduced. In addition, even if an inorganic antibacterial agent having a particle size of submicron to several microns is generally penetrated into the inner layer of the leather to impart antibacterial properties, it is difficult to fix the antibacterial agent because there are few gaps between the leather fibers. Similarly, water washing could not be repeated while maintaining the antibacterial property.

[0009] In general, as a method for antibacterial treatment of natural fibers, an organic antibacterial agent is attached by a resin serving as a binder, but it is difficult to handle in general households, and the durability of antibacterial property after treatment is poor. The effect of preventing shrinkage of fibers after washing was also poor. In particular, in order to apply resin treatment to animal hair such as wool that has not been subjected to any pretreatment, a resin dissolved in a relatively large amount of organic solvent is attached, but the texture is poor and it becomes hard In many cases, it was difficult to impart antibacterial properties without changing these.

In order to solve these problems, the inventor of the present invention has previously disclosed in Japanese Patent No.
68360) disclosed the invention of pig leather with improved properties. Further, Japanese Patent No. 182516 (Japanese Patent Publication No. 5-28280) proposes various leather treatment agents including the above-mentioned improvement of pig leather.
No. 08170 proposes a treating agent for fibrous materials.

[0011]

DISCLOSURE OF THE INVENTION The present invention further improves on the improvement techniques for leather and fibrous materials such as the above-mentioned Japanese Patent No. 1783854, and mainly uses leather, fur and natural fibers and the natural fibers. For textiles,
A treatment agent capable of expressing a wide range of overall textures such as dimensional stability, water absorbency and flexibility after water washing, slimming, swelling, stiffness, etc., and its treatment method, and the leather and fur obtained by this treatment method are waterproof to fur. As a result of a diligent research test on a waterproofing method for imparting water repellency and an antibacterial treatment method for imparting antibacterial properties to leather, fur and natural fibers, and textile products based on the natural fibers, the present invention was found. It has been completed.

It is an object of the present invention that the conventional leather and fur are hardened or washed out when washed with water, so that they are greatly restricted in various uses such as shoes, bags and clothing. Providing a treatment agent having sufficient durability to wash leather, fur, natural fibers, and fiber products mainly containing natural fibers in ordinary households with water by solving the problems and similar problems such as dimensional shrinkage. It is something you want to do.

Another object of the present invention is to provide a treatment method for treating leather, fur, natural fibers, and fiber products mainly composed of natural fibers with the above-mentioned treating agent so as to enable repeated washing with water. It is assumed that.

Another object of the present invention is to provide a leather, a fur, a natural fiber and a fiber product mainly comprising the natural fiber, which can be washed with water treated by the above-mentioned treatment method, and which have excellent durability. It is intended to provide an antibacterial treatment method for imparting antibacterial properties.

Still another object of the present invention is to provide a waterproofing method for imparting waterproofness and water repellency to leather and fur which can be washed with water treated with the above-mentioned treating agent. It is assumed that.

[0016]

In order to achieve the above-mentioned object, the leather, fur and natural fibers of the present invention and the treatment agents for textile products mainly containing the natural fibers are the following a) to d).
Characterized by comprising the following components: a) Component: polyoxyalkylene polyol having 2 to 6 functional groups b) Component: water-soluble polyurethane and / or water-dispersible polyurethane c) Component: aromatic (poly) isocyanate or / and aliphatic (poly) Isocyanate d) Component: surfactant

The above a), b), and
Each of the components c) and d) is preferably 5 to 94.5% by weight of the component a) 5 to 90% by weight of the component b) 0.1 to 5. 0% by weight and d) component in the range of 0.1 to 20% by weight.

Another invention of the leather, the fur and the natural fiber and the treating agent for the fiber product mainly containing the natural fiber is characterized by containing the following components a) to e). It is a thing. a) Component: polyoxyalkylene polyol having 2 to 6 functional groups b) Component: water-soluble polyurethane and / or water-dispersible polyurethane c) Component: aromatic (poly) isocyanate or / and aliphatic (poly) Isocyanate d) Component: surfactant e) Component: di- to tetravalent metal salt

In the above other invention, the a),
Each of the components b), c), d), and e) is preferably 5 to 94.5% by weight of the component a) 5 to 90% by weight of the component b), relative to 100% by weight in total. 0.1 to 5.0% by weight of component d) is 0.1 to 20% by weight, and e) is 0.01 to 7.0% by weight.

The method for treating leather, fur and natural fibers and textile products based on the natural fibers according to the present invention comprises:
Fur and natural fiber and a fiber product mainly comprising the natural fiber are treated with a treating agent comprising the above components a) to d) or a treating agent comprising the above a) to e). is there.

The method for waterproofing leather and fur according to the present invention is directed to a leather, fur and a leather obtained after treating with a treating agent comprising the above components a) to d) or a treating agent comprising the above a) to e). For a leather or fur in which the freeness of the fibers of the mesh layer in contact with the subcutaneous tissue layer is 580 ml or more, the fatliquoring agent consisting of a monoalkyl phosphate having an alkyl group having 8 to 22 carbon atoms is used for the leather and the fur. It is characterized by impregnating leather and fur in the range of 5 to 25% by weight.

The antibacterial treatment method for leather, fur and natural fibers of the present invention and textile products mainly comprising the natural fibers is preferably a treating agent comprising the above components a) to d) or a treatment agent comprising the above components a) to d).
Inorganic fine powder having an antibacterial property of 0.05 to 8.0% by weight with respect to leather, fur and natural fibers treated with the treatment agent comprising each component of e) and fiber products mainly containing the natural fibers. Alternatively, it is characterized by impregnating or adhering an antibacterial treatment agent comprising 0.02 to 5.0% by weight of an organic preservative.

In another aspect of the present invention, there is provided a method for antibacterial treatment of leather, fur and natural fibers, and a textile product comprising the natural fiber as a main component.
One or more binder resins selected from water-soluble polyurethane, water-dispersible polyurethane, water-soluble acrylic copolymer and water-dispersible acrylic copolymer are added to the antibacterial component in an amount of 0.5 to 40. % By weight.

Hereinafter, the agent for treating leather, fur and natural fibers of the present invention and textile products mainly comprising the natural fibers (hereinafter referred to as "the present agent"), and various treatment methods using the agents will be described in detail.

The present treating agent The components a) to e) constituting the present treating agent are as follows. (1) Component a) of the present treating agent The polyoxyalkylene polyol having 2 to 6 functional groups of the component a) of the present treating agent preferably has a molecular weight of 30.
0 to 10,000, more preferably 400 to 8,000.
0, more preferably 600 to 5,000, and among them, 3 to 4 functional polyoxyalkylene polyols, in particular, trifunctional polyoxyalkylene polyols are more preferably used.

The alkylene oxide as a raw material of the polyoxyalkylene polyol having 2 to 6 functional groups is preferably an alkylene oxide having 2 to 4 carbon atoms, and examples of such alkylene oxide include ethylene oxide, propylene oxide, 1, 2-butylene oxide,
2,3-butylene oxide and the like and combinations thereof are used. Examples of such a) component polyoxyalkylene polyol include polyethers such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol, polypropylene oxide-trimethylolpropane triol, polypropylene oxide-
Hexanetriol triol, polypropylene oxide-glycerin triol, random or block copolymerized propylene oxide / ethylene oxide-glycerin triol, random or block copolymerized ethylene oxide / propylene oxide-ethylenediamine.
Tetraol, propylene oxide-sorbitol hexaol, etc. can be mentioned.

The preferred amount of these compounds is 5 to 94.5.
%, More preferably 15 to 90% by weight, even more preferably 25 to 70% by weight. This amount is 94.
If the content exceeds 5% by weight, no particular effect is obtained, and if the content is less than 5% by weight, the flexibility of the processed product is lost. Two or more of these polyoxyalkylene polyols having 2 to 6 functional groups may be used in combination.

(2) Component b) of the present treatment agent The water-soluble polyurethane and / or water-dispersible polyurethane of component b) may be used alone or in combination of two or more of the various embodiments of the polyurethane obtained by the following production method. It was done.

1) Water-Soluble Polyurethane (Non-Reactive Type) A polyurethane obtained by reacting a polyol containing a large amount of ethylene oxide as a polyol with diisocyanate is water-soluble, for example, polyethylene glycol and tolylene diisocyanate ( TDI) is reacted and dissolved in water.

2) Water-dispersed (emulsion) polyurethane (non-reactive type, forced emulsification type) A polyurethane solution prepared by dissolving a polyurethane obtained by reacting a polyol with a diisocyanate in an organic solvent, or by reacting the polyol with the diisocyanate in an organic solvent,
If necessary, a solution of the polyurethane diluted with an organic solvent is gradually added to water or a mixture of water and a surfactant to perform phase inversion emulsification. Emulsifiers (surfactants) include anionic (such as sodium alkyl benzene sulfonate),
Cationic (such as a quaternary ammonium salt) or nonionic (such as an ethylene oxide adduct of a long-chain alcohol) is used, and gelatin, sodium carboxymethyl cellulose, polyvinyl alcohol, or the like is used in combination as an emulsion stabilizer.

3) Water-dispersed (emulsion) polyurethane (non-reactive type, self-emulsifying type) A diisocyanate and a diol and a diol having a carboxyl group or a diamine having a carboxyl group are subjected to a urethane reaction to prepare a prepolymer. This prepolymer can be used to form a self-emulsifying emulsion by the following two methods. During the production of the prepolymer, N
Tertiary amine compounds such as alkyl dialkanolamines are used as chain extenders; This is diluted with the above solvent, and the tertiary amine moiety is quaternized (hydrophilized) using an aqueous acid solution or a quaternizing agent such as diethylsulfate or methyl iodide.

4) Anion type polyurethane can be obtained by reacting the end of the prepolymer with dimethylpropionic acid or the like with some isocyanate remaining and adding a basic aqueous solution. Since these can have a hydrophilic group in the molecule of the polyurethane, a water-dispersed polyurethane having a feature not using a low-molecular-weight emulsifier in combination, such as a forced emulsification type, can be obtained.

5) Reactive water-soluble or water-dispersible polyurethane (forced emulsification type, self-emulsification type) The isocyanate group is temporarily bonded when reacted with a specific active hydrogen-containing compound, and heat is applied to the compound. The original isocyanate is released when the conditions such as are changed. The carbamoyl sulfonate reacted with an isocyanate and sodium bisulfite becomes a strong hydrophilic group, and the polyurethane can be a water-soluble or water-dispersible type without using an emulsifier. Among these polyurethanes of 1) to 5), 1) water-soluble polyurethane (non-reactive type) and 3) water-dispersible (emulsion) polyurethane (non-reactive type, self-emulsifying type) are preferably used. The polyurethane produced by the above-mentioned methods 1) to 5) may be produced by any method as long as its physical properties fall within the range shown in Table 1, depending on the use of the object such as leather. Can be applied.

[0034]

[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. by forming a 0.3 mm film. (Measurement method is J
(Based on IS-6301)

The amount of such a water-soluble polyurethane and / or water-dispersible polyurethane blended is preferably 5 to 90% by weight, more preferably 10 to 70% by weight, and further preferably 15 to 60% by weight. If the amount is more than 90% by weight, the flexibility of the treated product is undesirably reduced, and if it is less than 5% by weight, the dimensional stability is undesirably reduced.

(3) Component c) of the present treating agent The aromatic (poly) isocyanate or / and the aliphatic (poly) isocyanate of the component c) is tolylene diisocyanate (2,4 or 2,6-isomer). Mixing ratio 8
0:20), 4,4 diphenylmethane diisocyanate (including crude, purified and modified), m
-Aromatic diisocyanates such as phenylene diisocyanate, xylylene diisocyanate, naphthalene 1,5 diisocyanate, polymethylene polyphenyl polyisocyanate, tolylene diisocyanate adduct to trimethylolpropane, tetramethylene diisocyanate, hexamethylene diisocyanate, 1,4-cyclohexylene Examples thereof include aliphatic isocyanates such as diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and tetramethylene diisocyanate.

The preferred compounding amount is 0.1 to 5.0% by weight, more preferably 0.2 to 3.5% by weight, further preferably 0.3 to 3.0% by weight. If the amount is more than 5.0% by weight, it is difficult to handle the solution because the viscosity of the solution is large. If the amount is less than 0.1% by weight, the washing resistance against water is deteriorated. As the component (c), two or more kinds thereof may be used in combination.

(4) Component d) of the present treatment agent The surfactant of component d) is preferably a nonionic surfactant, or a combination of a nonionic surfactant and an anionic surfactant or a nonionic surfactant. A combination use of a surfactant and a cationic surfactant is also preferable, and an amphoteric surfactant is also used.

As the nonionic surfactant, an ethylene oxide adduct of an alkyl phenol is particularly preferred.
Polyoxyethylene alkyl phenyl ether having an average carbon number of 6 to 12 and having 1 to 20 mol of ethylene oxide added thereto, polyoxypropylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, higher fatty acid alkanolamide or ethylene thereof. Oxide adduct, Sucrose fatty acid ester, Alkyl succaloid, Fatty acid glycerin monoester,
Examples thereof include polyoxyethyne alkyl or alkenyl ether having an alkyl group or alkenyl group having an average carbon number of 10 to 20, and having 1 to 20 moles of ethylene oxide added thereto.

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 group or alkenyl group having an average carbon number of 10 to 20, and has an average of 0.5 in one molecule.
Alkyl or alkenyl sulfate to which 8 to 8 moles of ethylene oxide is added 3) alkylbenzene sulfonate having an alkyl group having an average of 10 to 16 carbon atoms 4) alkyl or alkenyl group having an average of 10 to 20 carbon atoms or Alkenyl sulfate 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) Sulfosuccinate sodium salt 8) Ether carboxylate 9) Acyl-N-methyl taurate sulfonic acid sodium salt 10) Sarcosinate sodium salt 11) N-acyl glutamate 12) Alkyl ether sulfate 13) Alkyl polyglucoside 14) Monoalkyl phosphate 15) Fatty acid alkanoate Lamide 16) Ethoxylate of higher alcohol 17) Sulfate of higher alcohol.

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

Examples of the amphoteric surfactant 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. The amount of this surfactant is preferably 0.1 to 20% by weight, more preferably 0.5 to 18% by weight, still more preferably 0.8 to 20% by weight.
15% by weight. If the amount exceeds 20% by weight, there is no particular effect, and if the amount is less than 0.1% by weight, the permeability is inferior and the stability of the treating agent is also reduced, so neither is preferable.

(5) Component e) of the present treating agent The divalent to tetravalent metal salt of component e) is added as necessary to components a) to d). The valent metal salt 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, copper salts, zinc salts, calcium salts,
Trivalent metal salts such as divalent metal salts such as magnesium salts, aluminum salts, chromium salts, iron salts, lanthanum salts, and cerium salts;
Examples thereof include salts of tetravalent metals such as zirconium salts and silicon salts. Aluminum salts include sodium aluminate, aluminum sulfate, aluminum ammonium sulfate, potassium aluminum sulfate, aluminum nitrate, aluminum acetate, aluminum fluoride, aluminum chloride, aluminum oxalate, aluminum lactate, etc. Zirconium salts such as zirconium sulfate, chromium salts Examples thereof include chromium sulfate and basic chromium sulfate. Among them, aluminum sulfate and zirconium sulfate are preferred, and combination with other metal salts is also preferred.

The content of the component e) which is a divalent to tetravalent metal salt is 0.01 to 7.0% by weight, more preferably the total amount including the components a) to d). 0.2 ~
5.0% by weight, more preferably 0.5 to 4.0% by weight
Is. If the amount exceeds 7.0% by weight, the stability of the liquid is poor and precipitates are generated, and if it is less than 0.01% by weight, the adhesion to leather or fibers is deteriorated, which is not preferable.

The e-component, a divalent to tetravalent metal salt, is a poly (alcohol) having 2 to 6 functional groups of the a) component that binds to collagen of leather and fur. It is necessary to prevent the oxyalkylene polyol from falling off and exert a tanning function to enhance its binding, and also to bind to natural fibers such as wool and feathers to enhance the binding with the cortex of the keratinous base. However, there is a case where the effect is exhibited even if it is not particularly added to fibers such as silk and cotton.

Each of the components a) to d) or a) to
Each component of e) is compounded as follows. First, a)
A component which is a polyoxyalkylene polyol having 2 to 6 functional groups, an aromatic (poly) isocyanate or / and an aliphatic (poly) isocyanate which is a component c) and a surfactant which is a component d). To obtain the present treatment agent by adding a fixed amount and stirring at a temperature of 60 ° C. for a predetermined time, and then adding a predetermined amount of the water-soluble polyurethane or / and the water-dispersible polyurethane as the component b) and stirring for a predetermined time. You can In addition, this treating agent contains an appropriate amount of auxiliary components such as a detergent, a water repellent, a crosslinking agent, an organic solvent, an ultraviolet absorber, a fragrance, a coloring agent, an antifoaming agent, and a foaming agent. be able to.

[Treatment Method with This Treatment Agent] The raw material leather to be treated in the case of treating leather or fur with this treatment agent to exhibit water-washing resistance is the raw material leather used in the tanning industry, cowhide, Aquatic animal skins such as sheep skin, horse skin, goat skin, pig skin, deer skin, kangaroo skin and crocodile skin, and lizard skin, and these fur can be mentioned, among which cow skin, sheep skin, goat skin, pig skin It can be processed appropriately.

There are no particular restrictions on the form of these leathers and furs, and it is preferable to use raw leather, naked skin, acid-skinned leather, tanned leather, dyed leather, and oiled leather. Among them, tanned leather, dyed leather and oiled leather are preferable. Can be processed more suitably, and other knitted products, sewn products, drawn products, and the like can be processed, and can be easily and sufficiently processed even in ordinary households.

In addition to the above-mentioned leather and fur, animal and vegetable natural fibers (animal hair such as wool,
Water-resistant washing resistance can be imparted to woven fabrics, knitted fabrics, non-woven fabrics and the like obtained by blending silk, hemp, cotton, etc.) and synthetic fibers mainly composed of the natural fibers.

The method of treating the leather, fur, natural fibers, and fiber products mainly containing the natural fibers (hereinafter referred to as “objects to be treated”) with the treating agent is described in detail below. A predetermined amount of treatment agent (usually,
(Approximately 0.5 to 5% by weight based on the weight of the object)
Is diluted with water to form a treatment liquid, leather is put into the liquid, and the mixture is stirred and immersed for a predetermined time to be treated. After that, the leather is pulled up from the liquid, washed with water, hung up and dried with dehydration (containing about 50% moisture), and then dried, and then rubbed (staking) (mainly in the case of leather and fur) ) Or ironing at the appropriate temperature (for textiles). The treatment agent effectively functions as a fixing binder for a coloring agent, a fragrance, a waterproofing agent, a water repellent, an antibacterial agent, and the like.

[Method of Waterproofing Leather and Fur Treated with this Treatment Agent] Leather and fur treated as described above with this treatment agent have high water absorption, and are particularly useful for applications such as leather for filtration, sound absorbing materials, and underwear. Although useful, it is necessary to waterproof the outer wear and the like that require waterproofing and water repellency as conventional leather and fur applications. In this waterproofing treatment, if a monoalkyl phosphate ester-based reactive greasing agent having an alkyl group with 8 to 22 carbon atoms is greased during leathermaking, it will bond with the chromic acid in the chrome tanning agent in the leather and wash with water. It does not come off even after repeated use, and the waterproof / water-repellent effect can be maintained.

When the alkyl group of the monoalkyl phosphate ester-based reactive fatliquor has less than 8 carbon atoms, the waterproofing and water repellency effects are weak, and when the number of carbon atoms exceeds 22, the treatment liquid becomes solid and handling becomes difficult. It will be difficult. Preferred alkyl groups have 12 to 18 carbon atoms. For example, the alkyl group has 14 carbon atoms.
Leather treated with the monoalkyl phosphate ester-based reactive fatliquor does not permeate even when subjected to a bending resistance test several thousand times. The impregnation amount for the leather is 5 to 25% by weight, preferably 10 to 20% by weight.

[Antibacterial treatment method for leather, fur and natural fibers treated with this treating agent and textile products mainly composed of natural fibers] The antibacterial treating agent used in this antibacterial treating method is inorganic fine powder having antibacterial properties. And / or an antiseptic organic preservative.

As the inorganic fine powder having antibacterial properties, a phosphoric acid compound carrying silver ions, for example, an antibacterial agent represented by the general formula 1 shown below is used.

[0057]

[Chemical formula 1] M ¹ aAbM ² c (P0 ₄ ) d · nH ₂ O

In the formula 1, M ¹ is at least one selected from silver, copper, zinc, tin, mercury, lead, iron, cobalt, nickel, manganese, arsenic, antimony, bismuth, barium, cadmium, or chromium. Seed metal,
A is at least one ion selected from an alkali metal ion, an alkaline earth metal ion, an ammonium ion and a hydrogen ion, M ² is a tetravalent metal, and n is
It is a number that satisfies 0 ≦ n ≦ 6. a and b are both positive numbers, and c and d are c = 2 and d = 3 when la + mb = 1.
Then, when la + mb = 2, c = 1 and d = 2. Here, 1 is the valence of M ¹ and m is the valence of A.

Examples of these compounds include tricalcium phosphate carrying silver ions [ceramics obtained by firing a mixture of tricalcium phosphate and a silver compound at a temperature of 1000 ° C. or higher (for example, “Apacider” manufactured by Sangi Co., Ltd.); Zirconium phosphate ceramic powder carrying silver ions (average particle size 0.5 μm) (“NOVALON” manufactured by Toagosei Co., Ltd.), and metal ions such as zinc, silver, copper, etc., as inorganic carriers (zeolites, porous ceramics,
Montmornite, glass, etc.), an inorganic metal-based antibacterial agent, copper fine powder, zinc white, and the like.

Among these, zirconium phosphate carrying silver ions, tricalcium phosphate carrying silver ions,
Inorganic metal-based antibacterial agents carrying silver and copper ions, copper fine powder, and the like are preferable, and it is also preferable to use two or more of them. The preferable particle size of these is 5 μm or less, and more preferably 2 μm or less.

The suitable amount of the inorganic fine powder having antibacterial properties is at least 0.05% by weight, more preferably 0.05 to 8.0% by weight, and even more preferably 0.1% by weight, based on the weight of the treated leather. 2 to 5.0% by weight.

As the organic preservative having an antibacterial component, those which are effective against molds and have low toxicity to the human body are desirable, and the following organic preservatives can be mentioned. These organic preservatives can be used in combination of two or more thereof. 1) Diiodomethyl-p-toluylsulfone (Di-i
odomethyl p-tolylsulfon
e), 2) Mixed phenolic
ic), heterocyclic compound (Heter)
3) p-chloro-m-cresol (p-Chioro-)
m-cresol), 4) 2,4-dichlorobenzyl alcohol (2,4-D
ichlorobenzyl alcohol 5) 2- (Tricyanomethylthio) benzothiazole (2- (Thio cyanomethylthio))
Benzothiazol): [TCMTB] 6) 2-hydroxyethyl 2,3-dibromopropionate (2-hydroxyethyl 2,3-di)
bromopropionate) 7) 2-bromo-4-hydroxyacetophenone (2-bromo-4-hydroxyacetophenone)
Bromo-4-hydroxyacetophen
one) 8) Methylenebisthiocyanate (Methylene)
bis thiocyanate) 9) Sodium orthophenylphenate (Sodiu)
m orthophenylphenate) 10) Chlorinated aliphatic amino compound (Chlorinat)
edaliphaticamino compoun
d) 11) β-naphthol trichlorophenol (β-N
aphol trichlorophenol 12) 2-n-octyl-4-isothiazolin-3-one (2-n octyl-4-isothazolin-
3-one) 13) Dichlorophene 14) Methylenebisthiocyanate (Methylne)
bis thiocyanate) and the like.

Among these, 2- (tricyanomethylthio) benzothiazole [TCMTB], which is an organic nitrogen-sulfur compound, is most preferable in consideration of the safety of oral toxicity. Organic preservatives may cause bacterial resistance and the preservative effect may decrease with time, and diiodomethyl-p-toluylsulfone or 2-noctyl-4-isothiazoline, which hardly produces such resistance. -3-One (9% in propylene glycol) is preferably used.

The suitable amount of such an organic preservative is at least 0.02% by weight, more preferably 0.05 to 5% by weight, even more preferably 0.2 to 5% by weight, based on the weight of the processed product.
It is 3.0% by weight, more preferably 0.5 to 3.0% by weight. It is also preferable to use an inorganic fine powder having these antibacterial properties and an organic preservative together, and when the inorganic fine powder / organic preservative is added in a weight ratio range of 1/6 to 6/1, the total amount is Addition of 0.7% by weight or more shows a desirable antibacterial effect.

When such an inorganic fine powder and an organic preservative are applied to leather, fur and natural fibers treated with the present treatment agent and textile products mainly containing the natural fibers, the adhesiveness is increased and the water-resistant washing is performed. It is desirable to use a binder resin in combination to improve the properties. As such a binder resin, the above-mentioned treating agent may be used, and a water-soluble polyurethane, a water-dispersible polyurethane, and a water-soluble acrylic component of the component (b), which is a component of the above-mentioned treating agent, may be used. One or more selected from polymers and water-dispersible acrylic polymers can be used, and the amount of these added is 0.5 to 40% by weight, more preferably 1.
It is 0 to 10% by weight.

Specific examples of the preferred composition of the binder resin and the amount thereof are as follows. 1) 50 to 20% by weight of a carboxyl group-containing vinyl monomer such as (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid, etc. 2) The following vinyl monomer copolymerizable with the above carboxyl group-containing vinyl monomer The compound of the above 2) includes, for example, a compound represented by the following general formula 2, vinyl acetate, styrene, acrylonitrile, butadiene rubber and the like.

[0067]

Embedded image CH ₂ ＣＲCR ¹ —COOR ²

In the above formula 2, R ¹ ＨH or CH ₃ , R ² = an alkyl group having 1 to 22 carbon atoms, which may be linear or branched.

This binder resin, after being impregnated or adhered to the object to be treated together with the antibacterial component, coagulates or precipitates by changing the pH, and thus has a function of strongly bonding the antibacterial agent to the object to be treated. Have.

[0070]

The action of the present treatment to impart the water-washing resistance of the article to be treated is presumed to be as follows. For leather (as well as fur), mucoid and fat in the leather are, for example,
It is also effectively removed as much as 1.0% by weight or less, preferably 0.1% by weight or less. Due to the removal of the mucoid, etc., the impurities in the net-like layer are almost removed and do not exist.
The pores are large, there is no off-flavor, and the freeness of the leather fibers of the net-like layer is 580 ml or more (according to the Canadian standard form specified in JIS-P-8121), and the water absorption is dramatically improved.

In the water-containing state after the leather has been treated with the present treating agent, it is presumed that the components of the present treating agent are weakly adhered to the leather fibers and are not in a firmly adhered state, and thus work as a slip agent. This results in extensibility that allows deep drawing. In addition, when the leather is pulled in a water-containing state and dried with a toggle dryer, the contraction of the leather caused by drying of the conventional manufacturing leather is inhibited, and the area increases by elongation. The percentage increases on average over about 5% over untreated leather. The components of this treatment agent that have permeated into the leather mesh layer during the treatment are firmly adhered to the leather fibers in the drying stage to form a three-dimensional structure.
The contraction is prevented, and the sewing machine can be sewn even with a household sewing machine.

On the other hand, the leather which has been dried after being treated with the present treating agent does not become hard even when the leather containing a large amount of water after washing with water or the like is dried by exposing it to sunlight, is soft and has dimensional stability, and has water absorption. It is highly resistant, hard to slip, and does not lose weight.
That is, it is possible to repeatedly wash with water by promoting various excellent properties as leather (feel, texture, tensile strength, tear strength, bending resistance, extensibility, etc.). Due to the above advantages, the leather treated with this treatment agent is useful for clothing, upper leather, backskin leather, gloves, shoes, bags, bags, boxes, hats, rugs, slippers, sandals, etc. In addition to drawn products made of leather, leather paper with excellent dimensional accuracy and bending resistance, even when fibers of leather are loosened and pulverized into pulp, they are evenly dispersed in water, making it easy to fabricate by a wet method. A washable leather paper can be made. Also,
This can be combined with a binder to provide a water-resistant washing product such as a plate-like leather board, a mat-like product, and a leather cloth. Further, by applying the waterproofing treatment method according to the present invention to the treated leather, waterproofness and water repellency can be imparted, and antibacterial properties can be imparted by the antibacterial treatment method of the present invention.

The treatment of natural fibers or fiber products mainly composed of the natural fibers with the present treating agent works in the same manner as in the case of leather and fur, but in the treating agent liquid diluted with water. When the natural fiber and the fiber product mainly composed of the natural fiber are dipped in, the natural fiber swells with water and expands, and the minute hydrous gel or micelle of the treatment agent component adheres to the expanded fiber. At the wet stage, it is considered that the water content is merely adhered. However, when the water content is considerably reduced due to strong centrifugal dehydration or water squeezing, the fiber is peeled off from the natural fibers and the effect of preventing shrinkage is weak. However, when this is dried, fine water-containing gels and micelles are destroyed as the water evaporates, and the components of the present treatment agent precipitate, and strongly adhere to the water-containing swelling and extending fibers.

The hydrated fiber products (woven fabric,
When knitting, non-woven fabric, etc.) are stretched while stretching wrinkles, the fiber product shrunk by wearing can be stretched and restored to its original length. The effect of preventing the fiber from shrinking is that the treatment agent component adhered to the fiber has three effects.
It has a three-dimensional structure, and untreated conventional fibers are dehydrated,
It is believed that the treatment agent inhibits the shrinkage that occurs during drying. Further, when the treatment agent is made cationic, the bond with the OH group or the like of the natural fiber is accelerated, but the treatment agent component adhered to the fiber is a flexible resin, and does not impair the feel of the fiber. By treating the thus obtained treated product with an antibacterial treatment agent in the same manner as described above, a treated product having excellent antibacterial properties can be obtained.

[0075]

EXAMPLES The present invention will be described in more detail below with reference to Examples and Comparative Examples. Various test methods used in Examples and Comparative Examples are as follows: Example 45, Comparative Example 12 and Example 46. The following is except for Comparative Example 13.

[Test method for leather] Tensile strength: Implemented in accordance with JIS-K-6552 Clothing leather test method Elongation: Implemented in accordance with JIS-K-6552 Clothing leather test method Minutes): Implemented in accordance with JIS-K-6550 Leather Test Method

Freeness; JIS-P-8121 Pulp freeness test method Performed in accordance with Canadian standard form. (Note) Untreated leather of Comparative Example floats on the water surface in the form of cotton.
The dispersibility in water is extremely poor.
It was dispersed in water (000 rpm × 25 minutes) and used for the test immediately.

Washing method: JIS-L-0217, N
o. Perform the washing operation in accordance with the 104 method and follow JIS-C
A home-use electric washing machine with a standard washing capacity and a standard amount of water with a centrifugal squeezing device conforming to the standard of -9606 (electric washing machine) was used.

Water-proof washing resistance: When leather is repeatedly washed by the above-mentioned method, the initial softness is lost and a hard feeling starts to appear, or the number of times of washing until a dimensional change (area) of 10% or more occurs is shown. .

Penetration and dispersibility of leather fiber in water; leather crushed by a crusher and loosened to 1 to 3 mm 3
150 gr of water was placed in a beaker of 300 cc, and the gr was added to the upper portion of the magnetic stirrer that was slowly stirred at 30 rpm to be completely submerged in water.

Dimensional stability after washing; 15 cm × 15 cm
Using the leather of No. 5, the dimensional change after washing was repeated 5 times was calculated by the following equation 1. Here, in the formula, L indicates a value before washing, and L 'indicates a value after washing.

[0082]

(Equation 1)

Elongation of tsubo: After treating leather (wet blue) with this treatment, the change in area after drying was calculated by the following formula 2 by a conventional method. However, the M in the formula the area before treatment (cm ^2), M'represents an area after treatment (cm ^2).

[0084]

(Equation 2)

Water resistance (water repellency): 0.3 cc of water droplets was dropped by a syringe on the silver side and the flesh side of the leather, and the time required for evaporation was shown. Average value of n = 3

Dynamic water resistance (water permeation time, water absorption during water permeation): Conforms to the IPU-10 method, a dynamic waterproof test for boots and shoe uppers. BALLY PENET
Using ROMETER; the meat surface was immersed in water. Leather piece shrinkage 10%, flexing frequency 53 times / min

[Test Method for Natural Fiber (Related to Table 5, Table 7 and Table 8)] Washing Method Washing Machine; JIS-L-1042-1986 and JIS
-L-0217-1976-No. 104 method (however, cotton is No. 105 method). Hand washing: JIS-L-1042-1986 and JIS
-L-0217-1976-No. It was based on method 106.

Test cloth: JIS-L-1042-1986
According to the washing shrinkage rate test E method of 25 cm x 25 cm
(Width × length), and three test pieces were used. After the operation, the test piece was put into a standard state and then placed on a flat table to remove unnatural wrinkles and tensions, and the lengths (mm) of three measurement sections in each of the warp yarn direction and the weft yarn direction were measured. (Measured to whole number).

Calculation of shrinkage ratio: The average value of the lengths of the three measurement sections in the warp yarn direction and the weft yarn direction is determined, and the shrinkage ratio is calculated by the following equation. The average value of the sheets was obtained and calculated by the following equation 3 (calculated to one decimal place).

[0090]

(Equation 3)

In the above formula 3, L represents the length (mm) of the measuring section before the treatment (Note 1), and L ′ represents the length (mm) of the measuring section after the treatment. The case shows elongation. (Note 1) The length of the measurement section before washing, which is the basis for calculating the shrinkage ratio when water washing is repeated, was calculated using the value before treating the fiber cloth with this treating agent.

Calculation of rate of change: The change in length caused by treating the fiber cloth with this treatment agent was expressed as the rate of change. This calculation method was based on the test cloth of the shrinkage test method.

Tensile strength and elongation test: JIS-
L-1096-1990 General fabric test method 6, 12, a (A) method (strip method), using a constant-speed extension type testing machine, pulling speed 20 cm / min, test width 5 cm, gripping interval 20 cm bending test Use of KES-FB2 pure bending tester, S
ENS 2 × 1 test size 20 cm × 20 cm, direction length × width compression test; KES-FB3 compression tester used, SE
NS 2 × 5 Lowering speed of pressure plate 1 mm / 50 sec, area of pressure plate 2
cm ² (circular) Maximum deformation 5 mm Texture judgment: Depends on touch feeling. Good texture was shown in the order of excellent>good> poor.

[Washing test of knitting and sewing products (related to Table 6)] Sweaters, suit tops and bottoms, blankets, T-shirts, Y-shirts, wool and animal products such as pajamas, and blended products such as wool and synthetic fibers. I washed with water.

[Antibacterial Test (Related to Tables 3 and 7)] (1) Trichophyton; Trichophyton Menta
grophytes (IFO-6202) Evaluation method: JI in which antibacterial activity is determined by width (mm) of growth inhibition
It conformed to S-L1902. Hello test method.

(2) Staphylococcus aureus Staphlo
coccus aurens ATCC 6538P (I
FO-12732) Evaluation method: 1 g of a sample was weighed and finely cut into a square of about 1 to 2 cm to obtain a test sample. The test sample was placed in 15 ml of a phosphate buffer solution in an Erlenmeyer flask, and the bacterial solution was further added so as to give about 105 cells / ml of Budo yellow staphylococci. After shaking at a temperature of 270 ° C. for 1 hour, 1 ml of the test solution was collected, and the number of viable cells was measured by a pour plate method using a standard agar medium (temperature: 36 ° C., 1 day).

(3) Mold resistance; JIS-Z-291
Complies with 1, 6, 2, 2 (wet method). One week after the start of the test, judgment was made based on the following levels 1 to 3. (Note) The sample was used for the test without any pretreatment. Judgment-1: Growth of mycelia exceeding 1/3 was observed on the sample surface. Judgment-2: Growth of hyphae on the sample surface within 1/3. Judgment-3: No growth was observed on the sample surface. Molds: Aspergillus niger (FER
MS-1) Penicillium citrinum (FERM
S-5) Mythotheium, Verrucaria (FE
RMS-13) Chaetomium Globosum (FERM
S-11)

[Example 1 (Water-resistant washing resistance treatment)] 1) Preparation of test leather According to a conventional method, the raw hide (cow / sheep / pork) is washed with water → degreased → washed with water → depilated → limbed → demineralized → washed with water → pickled → Chrome tanning (chromium amount 5% per bare skin weight) → neutralization → wet-washing step to obtain wet blue, which was used as test leather. This test leather was cut from the head to the tail and divided into two equal parts, one of which was used for testing the treatment agent for the example, and the other was used as a test piece for the comparative example. In addition, in order to avoid the difference according to the site | part (shoulder, torso, belly, buttocks) of the leather, the test piece of the Example and the comparative example used the substantially same site | part.

2) Preparation of the present treating agent a) Polyoxyethylene / polypropylene triol (product code FA manufactured by Sanyo Chemical Industries, Ltd.) 40.0 as the component
% By weight and 0.5% by weight of a nitrogen-containing special polyol (product code CA manufactured by Sanyo Chemical Industry Co., Ltd.) and 4,4 ′ of component c)
Diphenylmethane diisocyanate (PMDI)
0% by weight and polyoxyethylene nonyl phenyl ether of component (d) (ethylene oxide adduct 9 mol)
3.0% by weight was added, and the mixture was stirred at a temperature of 60 ° C. for about 2 hours. Subsequently, 26.0% by weight of aluminum sulfate (added as a 10% aqueous solution) as the component e) was added, and the mixture was stirred in the same manner for about 2 hours. 1.5% by weight of nitrogen-containing special polyol (a) (manufactured by Sanyo Chemical Industries, product code CA)
Is added and stirred, and the water-dispersible polyurethane (b) of component b) (product code UE, anionic emulsion manufactured by Toagosei Co., Ltd.) is converted to NV (non-volatile component; the same applies hereinafter) = 100% to 41.4% by weight. And 10.0% by weight of polyoxyethylene nonylphenyl ether as the component (d) were added, and the mixture was stirred for 2 hours and then taken out as the present treatment agent.

3) Treatment of leather with this treating agent The treating agent of each example was 3% by weight based on the weight of the leather and water was 3 times the weight of the leather (wet blue (anhydrous equivalent amount)). The test leather was put into a leather treatment liquid obtained by adding and stirring the mixture, and the mixture was rotated for 15 minutes and stopped for 45 minutes. This was repeated four times, and immersion treatment was performed for 4 hours.
After this immersion treatment, the solution was drained, washed with running water for 10 minutes, taken out, horse-drawn and dehydrated, stretched and dried, and toggle-dried. Further, staking was carried out to knead and loosen the leather fibers, and then net tension was applied, and various tests according to the above-mentioned leather test method were carried out. The leather used for the test was 0.6 thick
mm wet pig blue.

Example 2 In Example 1, 55.0% by weight of component a) b) 30.0% by weight of component c converted to NV = 100% c) 0.3% by weight of component d) 14.6% by weight of component e) Tested in the same manner as in Example 1 except that 10% aqueous solution of component e was 1.0% by weight.

Example 3 In Example 1, a) component was 70.0% by weight, b) component was 15.0% by weight in terms of NV = 100%, c) component was 2.0% by weight d) Component was 9.0% by weight e) The test was conducted in the same manner as in Example 1 except that the component was changed to 40.0% by weight as a 10% aqueous solution.

Example 4 In Example 1, a) component was 90.0% by weight, b) component was 5.0% by weight, converted to NV = 100%, c) component was 3.0% by weight d) 0.8% by weight of component e) Test was conducted in the same manner as in Example 1 except that the component was changed to 12.0% by weight as a 10% aqueous solution.

[Example 5] In Example 1, a) component was 5.0% by weight b) component was 90.0% by weight in terms of NV = 100% c) component was 0.1% by weight d) 4.4% by weight of component e) Tested in the same manner as in Example 1 except that 10% aqueous solution of component e was 5.0% by weight.

Example 6 In Example 1, a) component was 25.0% by weight b) Component was 55.0% by weight calculated as NV = 100% c) Component was 0.3% by weight d) 19.6% by weight of component e) Aluminum sulfate of component 10% of zirconium sulfate
The same procedure as in Example 1 was carried out except that 1.0% by weight was used in place of the aqueous solution.

Example 7 In Example 1, a) component was 42.0% by weight, b) component was 41.4% by weight in terms of NV = 100%, c) component was 1.0% by weight d) The components were 6.5% by weight of polyoxyethylene nonylphenyl ether and 6.5% by weight of an anionic surfactant (alkylbenzene sulfonate).
It was the same as Example 1 except that the content was 6.0% by weight.

Example 8 In Example 1, water-dispersible polyurethane (Sanyo Chemical Industries UC-20 cationic emulsion) was used in place of the water-dispersible polyurethane (a) of component a) (Toa Gosei UE anionic emulsion). NV =
The procedure was the same as in Example 1 except that it was converted to 100% and 42.0% by weight.

[Comparative Example 1] A test was conducted in the same manner as in Example 1 except that the same pork wet blue having a thickness of 0.6 mm was used, and only the water was used without adding this treating agent. is there. Table 2 shows the test results of Examples 1 to 8 and Comparative Example 1. In the table, Δ indicates elongation.

[0109]

[Table 2]

[Example 9 (Water-Resistant Washing Treatment + Antibacterial Treatment]] Using the treated pig leather treated in Example 1, the treated leather was drained, washed with running water for 10 minutes, taken out, and not dried. Use leather that has undergone water-resistant washing treatment, put it in a treatment tank, and preferably 0.5 to the weight of the leather.
Water of about 3.0 times weight, more preferably 0.8 to 1.5 times weight was injected, and the antibacterial treating agent prepared as described below was put therein.

The antibacterial treating agent was composed of 0.5% by weight of calcium phosphate ceramics (Sangi Co., Ltd., Apacider) carrying silver ions, and an organic sulfur compound [2- (Thiocy).
anmethylthio) benzothiaz
ole: TCMTB] of 0.2 wt% and a binder resin of 3 wt% of the treating agent of Example 1 were added, and the mixture was stirred and the pH of the concentrate was adjusted to 5.5 to 7.5. Ammonia water or alkali such as sodium bicarbonate was added so that the antibacterial treatment agent was adjusted.

The antibacterial treatment agent was charged into the treatment tank containing the leather to be treated, and was stirred and rotated for 60 to 90 minutes to allow the binder resin to penetrate into the leather net-like layer together with the antibacterial component.
Then, an aqueous solution of a divalent or tetravalent metal salt having an antibacterial property and a small amount of an organic acid or an inorganic acid such as formic acid are added, and the p
H was reduced to 4 or less and stirred for about 30 minutes to precipitate or agglomerate the antibacterial component and the binder resin and fix them inside the leather. After draining this, washing with running water was performed for 10 minutes.
The leather was taken out, horse-rided, hung dry, and blanked according to a conventional method, and subjected to a test. The preferable addition amount of the aqueous solution of the divalent or tetravalent metal salt is 2 to 9% by weight of the divalent or tetravalent metal salt having antibacterial activity per 100% by weight of the leather to be treated.
It is the ratio that becomes.

Example 10 (Water-Resistant Washing Treatment + Water-Repellent Treatment) In Example 1, except that isophorone diisocyanate was used instead of the 4,4′-diphenylmethane diisocyanate of the component d). Processed as in Example 1. However, the water-proof and water-repellent treatments were successively performed without performing the treatments after the drying, and the treatments were performed as follows. That is, twice the weight of 30 ℃ in the treatment tank
Warm water and sodium bicarbonate were added little by little, and the leather to be treated was put in, rotated for 30 minutes to confirm the pH of the solution was 6.5, drained, washed with running water for 5 minutes, and taken out.

Next, double weight of 50 ° C. hot water and 18% by weight of a monoalkyl phosphate ester reactive fatliquor (Asai Bussan, Reactor No. 1014-40) were added to the treatment tank, and after rotation, the leather to be treated was added. And rotated for 90 minutes. Formic acid was added to adjust the pH of the solution to 3.8, and the solution was rotated for 10 minutes and then drained. After washing with running water for 10 minutes, the leather was taken out and used for the test through the steps after drying as in Example 1.

Comparative Example 2 A half piece of untreated leather used in Example 10 was treated with water only without adding a water-resistant laundry treatment agent or an antibacterial treatment agent.

Example 11 (Water-resistant washing treatment + dyeing + waterproof / water-repellent treatment + antibacterial treatment) The pig-treated leather of Example 1 was used. However, in the above-described water-resistant washing treatment, antibacterial treatment was performed after dyeing, grease-waterproofing, and water-repellent treatment without performing treatment after drying.

That is, the temperature 5
After injecting twice the weight of hot water at 0 ° C. into the treatment tank, 1.5% by weight of aqueous ammonia was added and stirred. The leather to be treated was put into the container and rotated for 30 minutes. Then, 3% by weight of an alkyl monophosphate dye (manufactured by Asai Bussan; Reactad RCR Brown No. 21) was added for dyeing, and the mixture was rotated for 90 minutes.
After adding a small amount of formic acid to adjust the pH to 3.9, it was drained and washed with running water. Next, a chrome tanning agent for leather (33% saponification) 1.
5% by weight and 0.5% by weight of formic acid were added, and retanning was carried out in a conventional manner, and then sodium bicarbonate was added.
After being adjusted to 6.5, it was taken out.

As a waterproof / water-repellent fat, monoalkyl phosphate ester-based reactive fat fat (Asai Bussan; Reactol N)
o. 1014-40) and twice the weight of hot water at 50 ° C. were added thereto, and the leather to be treated was charged and rotated for 90 minutes.
Thereafter, a small amount of formic acid was added to adjust the pH to 3.8, followed by stirring for 10 minutes, followed by deliquoring and washing with running water.

Next, for antibacterial treatment, 1.5 liters were placed in the treatment tank.
Double weight of water and antibacterial treatment agent [acrylic ester copolymer emulsion as binder resin (Nippon Pure Chemicals; LF
-103) 2.0% by weight, zirconium phosphate ceramics fine powder supporting silver ions (average particle size 0.5 μm: Toagosei; Novalon) 1.0% by weight, nonionic surfactant (nonylphenyl ether) 0. 2% by weight aqueous dispersion] was added, and the leather to be treated was put thereinto,
Spin for 0 minutes. Then, the pH was adjusted to 3.9 by adding formic acid, and the mixture was rotated for 30 minutes. After draining, the leather was washed with running water for 10 minutes, and then the leather was taken out.

[Example 12 (Water-Resistant Washability Treatment + Cowhide / Water Repellent Treatment with Cowhide)] In Example 10, the test leather pig wet blue was treated in place of the cowwet blue thickness of 1.2 mm and subjected to the test. did.

[Comparative Example 3] The same test leather as in Example 12 was used.
Using leather of a wet blue cow, water-washing resistance treatment was carried out in the same manner as in Example 12, and the leather obtained after drying was treated in the same manner as in Example 12 without waterproofing and water-repellent treatment. It was submitted to the test.

[Example 13 (Water-resistant washing treatment with sheep leather)] A test was carried out in Example 1 except that the pig leather of the test leather was replaced with a sheep wet blue having a thickness of 1.2 mm.

[Comparative Example 4] The same treatment as in Example 13 was carried out using the same test leather and half sheep of sheep's wet blue as described in Example 13, but without adding a water-resistant washing-resistance treating agent, using only water.

Example 14 (Washing resistance treatment with sheep leather +
Antibacterial treatment)] The sheep water-resistant washing-treated leather obtained in Example 13 was used. However, in the water-resistant laundry treatment, the following antibacterial treatment was performed without performing the treatment after drying. That is,
Instead of the silver ion-supported tricalcium phosphate ceramic of Example 9, copper fine powder (3.0% by weight) and zinc white (3.0%) were used.
% By weight, 0.2% by weight of OiTZO in place of TCMTB, and a polyurethane emulsion resin (Toa Gosei Co., Ltd .: Neotan UE-2102, NV) as a binder resin.
= 40% by weight), except that 10% by weight of an antimicrobial treating agent was added.

[Example 15 (Water-proof washing resistance of sheep fur)] Treated fur: Sheep (mouton) of chrome-tanned sheep is cut from the head to the tail, divided into two equal parts, and one piece thereof is used. Was. Treatment method: water of 3 times the weight of fur in the treatment tank and Example 3
Was added and 4.0% by weight of the present treatment agent was added. By rotating for 5 minutes and resting for 55 minutes,
This was repeated six times, and immersion and treatment were performed for 6 hours.

After the immersion treatment, the mixture was drained, washed with running water for 10 minutes, taken out, dehydrated by horseback, exposed to the sun, and hung to dry. After drying, the hair surface was brushed and used for the test.

Comparative Example 5 A half piece of sheep's fur (mouton) used in Example 15 was immersed in a washing liquid of a neutral detergent without being subjected to a water-resistant washing treatment, and used for a test after washing with water. Table 3 shows the test results of Examples 9 to 15 and Comparative Examples 2 to 5.

[0128]

[Table 3]

Example 16 (Water-resistant washing resistance to fiber cloth and prevention of expansion and contraction) 1) The treating agent used was the treating agent of Example 1. 2) A 100% wool Georgette terrestrial machine was used for the test cloth. 3) The treatment method of the test cloth was implemented as follows. That is, the dough was cut into a large size and dimension marks were drawn so that the JIS-L-1042-1986G method could be measured as it was without stretching or shrinking the fabric. Add 3% by weight of this treatment agent to the weight of the fabric and add warm water (about 4%).
(0 ° C.) was added to make a treating agent solution having a concentration of about 2.0%, and the liquid temperature was adjusted to 35 to 40 ° C., and the treating agent solution was put into a household electric washing machine together with the treated fabric to start the operation. The treatment was performed at a low speed for 5 minutes in a stationary immersion for 15 minutes. After draining, replace with fresh water at room temperature, rinse for 2 minutes and lightly dehydrate (about 50
% Water) and hang to dry.
Dry iron finishing was performed at an appropriate temperature of the fiber. The amount of the treatment agent is usually 0.5 to the weight of the fibrous material.
Used at up to 5% by weight. The adhesion amount of this treatment agent to the fiber cloth is 0.2 gr / m unless otherwise specified.
^Two or more were used for the test.

Comparative Example 6 The test method was the same as that of Example 16 except that the same woven cloth as the test cloth used in Example 16 was treated similarly with only hot water (30 ° C.).

Example 17 The procedure was the same as in Example 16 except that the treating agent used in Example 2 was used.

Example 18 Example 3 was used as a treating agent.
Except for using the present treating agent used in the above, all treatments were carried out in the same manner as in Example 16.

Example 19 Example 4 was used as a treating agent.
Except that this treating agent was used, the treatment was carried out in the same manner as in Example 16.

Example 20 Example 5 was used as a treating agent.
Except that this treating agent was used, the treatment was carried out in the same manner as in Example 16.

Example 21 Example 6 as a treating agent used
Except that this treating agent was used, all the procedures were the same as in Example 16.

Example 22 Example 7 used as a treating agent
Except that this treating agent was used, all the procedures were the same as in Example 16.

Example 23 Example 8 was used as a treating agent.
Except that this treating agent was used, all the procedures were the same as in Example 16. Table 4 shows the results of Examples 16 to 23 and Comparative Example 6.

[0138]

[Table 4]

Example 24 Example 16 was repeated except that (100% wool, knitted knitted cloth) was used in place of the test cloth (100% wool georgette terrestrial machine) used in Example 16.
The same process was carried out.

Comparative Example 7 A knitted fabric of the same material as the test cloth used in Example 24 was used in the same manner as in Example 24 except that only water was used without adding this treating agent. .

Example 25 Instead of the test cloth (100% wool tweed greige machine) used in Example 16, (cotton 10
0%, # 40 double yarn, knitted fabric greige machine) was used in the same manner as in Example 16.

Comparative Example 8 The test method was the same as that of Example 25 except that the cotton fabric of the same material as the test cloth used in Example 25 was treated using only water without adding this treating agent.
The same procedure was followed.

Example 26 All the treatment methods were used except that the test cloth (100% cotton, 40th yarn, knitted cloth) used in Example 25 was replaced with a cotton knitting machine (Tetron 30 / cotton 70). Treated as in Example 25.

[Comparative Example 9] A cotton knit fabric of the same material as that of the test cloth used in Example 26 was treated in the same manner as in Example 26 except that water was used without adding this treating agent. Processed.

Example 27 The test cloth (cotton knitted greige) used in Example 26 was bleached with cotton knit (Tetron 30 /
All the treatments were the same as in Example 26, except that the cotton 70) was used instead.

Comparative Example 10 The same procedure as in Example 27 was carried out except that the cotton knitted fabric of the same material as the test cloth used in Example 27 was treated using only water without adding this treating agent. . The results of Examples 24 to 27 and Comparative Examples 7 to 10 are shown in Table 5 above. In the table, Δ indicates elongation.

[0147]

[Table 5]

Example 28 (Washing resistance treatment for knitted and sewn products) 1) The present treatment agent of Example 1 was used as the treatment agent used. 2) Washing was performed using a wool 100% cashmere knitted sweater. 3) The processing method is as follows. In other words, weigh the sewing products and knitting to be processed,
3% by weight and approximately the same amount of a synthetic detergent for clothing were mixed and added to the product weight to obtain an aqueous solution having a concentration of about 1.0% by weight (around 40 ° C.). The product to be washed was pushed down to the extent that it was hidden below the surface of the water in the container, gently rubbed and washed (in the case of a washing machine, put in a net and rotated for 5 minutes), and then left immersed for 15 minutes. After dewatering, it was rinsed twice for 1 minute, dehydrated and hung up so that the water content was about 30 to 50%, and then immediately pulled lightly to extend wrinkles and the like and dried in the sun. Thereafter, iron finishing was performed at an appropriate temperature of the fiber. The dimensions before and after the treatment were measured and recorded each time.

Example 29 The same treatment as in Example 28 was performed using 100% wool suit.

[Example 30] [0150] A wool-polyester blended wool cloth was used and treated in the same manner as in Example 28.

Example 31 A woven blanket of 100% wool was treated in the same manner as in Example 28.

Example 32 A treatment was performed in the same manner as in Example 28, except that a T-shirt (knitted knit) made of 100% cotton was used.

Example 33 A treatment was carried out in the same manner as in Example 28, using a 100% silk fabric and a tie.

Example 34 A treatment was performed in the same manner as in Example 28 except that a Y-shirt made of 100% silk was used.

Example 35 A Y-shirt made of 100% hemp fabric was treated in the same manner as in Example 28.

Example 36 The same process as in Example 28 was carried out using a cashmere muffler. Examples 28-
Table 6 shows the results of the 36.

[Example 37 (Water-resistant washing resistance and antibacterial property to fiber cloth and knitting)] The fiber cloth used in Example 16 was used. The water-washable (shrinkage-preventing) treatment agent of Example 16
The antibacterial treating agent of Example 11 was added, and the wool fabric was treated in the same manner as in Example 16. The processing method is as follows. The treatment method of the above-mentioned fiber cloth, sewing products,
It was the same as the method of washing the knitted fabric. However, a binder resin and an antibacterial agent were added in addition to this treatment agent.
(Note that, after washing, the process of changing the pH which was performed during the antibacterial treatment of the leather was not performed.) In addition, the amount of the pure substance to be treated was 0.4 gr / m ² or more. It was processed to become.

Example 38 The procedure of Example 37 was repeated except that the fiber cloth of Example 37 was changed to 100% cotton of Example 25, a # 40 double yarn and a knitted cloth.

[Example 39] An inorganic fine powder having an antibacterial property as an antibacterial agent in place of the antibacterial treatment agent of Example 11 in the water-proof washing resistance (shrinkage prevention) treatment agent of Example 16 in Example 38. Example 38 was carried out in the same manner as in Example 38 except that 0.05% by weight of fine powder of zirconium phosphate ceramics carrying silver ions and 0.1% by weight of nonionic surfactant (nonylphenyl ether) were mixed.

Example 40 In Example 38, the treating agent of Example 10 was used in place of the treating agent of Example 16 as the water-resistant laundry (shrinkage prevention) treating agent. The procedure was the same as that of Example 38 except that the antibacterial treating agent of Example 9 was used. Table 7 shows the test results of these Examples 37 to 40.

[Physical Property Test of Fiber Cloth Treated with Shrinkage Prevention] [Example 41] 100% wool as the fiber woven fabric used in the test
Gabardine ground plane was used. The treatment agent of Example 1 was used as the treatment agent used for the shrinkage prevention treatment. The shrinkage prevention treatment method was the same as in Example 16.

Example 42 The procedure of Example 41 was repeated, except that the treating agent of Example 2 was used.

Example 43 The procedure of Example 41 was repeated, except that the treating agent of Example 3 was used.

Example 44 Example 41 was repeated, except that the treating agent of Example 5 was used as the treating agent.
Same as.

Comparative Example 11 The fiber fabric used in Example 41 was used without any treatment. These Examples 41 to 4
Table 8 shows the test results of Comparative Example 4 and Comparative Example 11.

[0166]

[Table 8]

Example 45 and Comparative Example 12 Wool 10
0% of the woven fabric was treated in the same manner as in Example 1 using the treating agent prepared in Example 1, and its properties were compared with those of the untreated woven fabric of Comparative Example 12. The results are shown in Table 9.

[0168]

[Table 9]

[Example 46 and Comparative Example 13] Wool 10
0% of the knitted fabric was treated according to Example 1 using the treating agent prepared in Example 1 and its properties were compared with the untreated knitted fabric of Comparative Example 12. The results are shown in Table 10.

[0170]

[Table 10]

Table 11 shows the results of the performance tests of Examples 45 and 46 and Comparative Examples 12 and 13 in which the shrinkage after washing and other performance tests were performed.

[0172]

[Table 11]

Table 12 is a summary of the reference items for judging the characteristic values shown in Tables 9 and 10.

[0174]

[Table 12]

The test methods in Tables 9 to 11 are based on the following. Tensile: Using a tensile / shear tester (KES-FB1), the test width was 20 cm, and the number of tests was three. Bending: Using a pure bending tester (KES-FB2),
Test width: 20 cm, the number of tests was 3 times. Shearing: Using a tensile / shear tester (KES-FB1), the test width was 20 cm, and the number of tests was 3 times. Surface: Using a surface tester (KES-FB4), the test width was 20 cm, and the number of tests was three. Compression: A compression tester (KES-FB3) was used, and the number of tests was three. Texture value; KES Men's winter jacket fabric texture formula (K
N-101-WINTER). Total texture value: Calculated by the texture formula (KN-301-JACKET) of KES men's winter jacket fabric. Shrinkage (after washing once); JIS-L-0217-197
6 Indication symbols related to the handling of textile products and the indication method (106 method), neutral detergent: Akron. Shrinkage rate (after washing 2 or 3 times); JIS-L-0217-1
976 Display symbols and handling methods for textile products (Method 104). Pilling; JIS-L-1076-1992 Piling test method 6.1A method for woven and knitted fabric, using ICI type testing machine. Tensile strength and elongation; JIS-L-1096-1990 General textile test method 6.12.1 (1) A method (strip method),
Uses a constant speed extension type testing machine.

[0176]

The treatment agent for treating leather, fur and natural fibers of the present invention and textile products mainly comprising the natural fibers comprises: a) a polyoxy group having 2 to 6 functional groups as a component; Alkylene polyol b) water-soluble polyurethane or / and water-dispersible polyurethane as component c) aromatic (poly) isocyanate or /
A mixture of a surfactant and an aliphatic (poly) isocyanate as the d) component and, if necessary, a predetermined amount of a divalent to tetravalent metal salt as the e) component. By treating fibers and fiber products mainly composed of the natural fibers with this treating agent, not only the tensile strength is improved and the flexibility is increased, but also the dimensional stability (anti-shrinkage property) is obtained even after repeated washing with water. Various excellent properties such as high water absorption and improved texture (sliminess, swelling, and stiffness) can be imparted without being impaired.

The method for treating leather, fur and natural fibers and textile products based on the natural fibers according to the present invention comprises:
For fur, the treatment agent can drastically improve the freeness and water absorbency of the leather and the reticulated layer of the fur, whereby the tensile strength, flexibility, water-washability and dimensional stability are improved. Properties (anti-shrinkage property) and various properties such as texture can be improved.

The leather and fur treated with this treatment are
Effective use of work-in-process products such as floor scraps, blue floor scraps, punching scraps, shaving scraps, trimming scraps, cutting scraps, semi-finished products and product scraps due to improved freeness and water absorption of the net-like layer Is possible. Therefore, these leather scraps are loosened with a machine or a chemical to form a pulp, which is manufactured as a paper-, plate-, or mat-like product by a wet papermaking method or a manufacturing method similar to a non-woven fabric. It can be applied to many uses such as a moisture release material, a filter material, a cushioning material, a leather board, a leather paper, and a wall material.

The method for waterproofing leather and fur according to the present invention relates to a method for treating leather and fur treated with the above-mentioned agent.
When it is necessary to impart waterproofness or water repellency depending on the application, by treating with a waterproofing treatment agent comprising a specific monoalkyl phosphate, in addition to the properties imparted by the present treatment agent, waterproofing, Water repellency can be reliably provided over a long period of time.

The antibacterial treatment method for the leather, fur and natural fibers of the present invention and the fiber product mainly comprising the natural fibers is mainly composed of the leather, the fur and the natural fibers treated with the treating agent and the natural fibers. By treating a textile product with a specific antibacterial treatment agent comprising an inorganic fine powder having antibacterial properties and / or an organic preservative, in addition to the properties imparted by the present treatment agent, Trichophyton, yellow It is possible to impart long-lasting excellent antibacterial properties capable of sustaining growth inhibition of bacteria such as staphylococcus and molds for a long period of time.

[Table 6]

[Table 7]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location D06M 13/17 13/395 15/564

Claims (8)

[Claims] 1. A treatment agent for leather, fur and natural fibers, and a textile product mainly containing the natural fibers, which comprises the following components a) to d). a) Component: polyoxyalkylene polyol having 2 to 6 functional groups b) Component: water-soluble polyurethane and / or water-dispersible polyurethane c) Component: aromatic (poly) isocyanate or / and aliphatic (poly) Isocyanate d) Component: surfactant 2. The components (a), (b), (c) and (d) are based on the total amount of the components: a) 5 to 94.5% by weight of component a) b) 5 to 90% by weight of component c 2. The composition according to claim 1, wherein component (d) is added in the range of 0.1 to 5.0% by weight and component (d) is added in the range of 0.1 to 20% by weight.
A treating agent for the leather, fur and natural fibers according to the above, and a fiber product mainly comprising the natural fibers. 3. A treating agent for leather, fur and natural fibers and a fiber product mainly comprising said natural fibers, characterized by containing the following components a) to e). a) Component: polyoxyalkylene polyol having 2 to 6 functional groups b) Component: water-soluble polyurethane and / or water-dispersible polyurethane c) Component: aromatic (poly) isocyanate or / and aliphatic (poly) Isocyanate d) Component: surfactant e) Component: di- to tetravalent metal salt 4. The components a), b), c), d) and e) are each based on the total amount of the components: a) from 5 to 94.5% by weight; % By weight of component c) 0.1 to 5.0% by weight d) 0.1 to 20% by weight of component and e) Component of 0.01 to 7.0% by weight. Claim 3
A treating agent for the leather, fur and natural fibers according to the above, and a fiber product mainly comprising the natural fibers. 5. A leather, a fur and a natural fiber, and a textile product mainly composed of the natural fiber are treated with the treatment agent according to any one of claims 1 to 4, and a leather, a fur and a natural fiber, and A method for treating a fiber product mainly comprising the natural fiber. 6. A leather or a fur which has been treated with the treatment agent according to any one of claims 1 to 4 and has a freeness of 580 ml or more in fibers of a reticulated layer in contact with the subcutaneous tissue layer. The leather and the fur are impregnated with a greasing agent comprising a monoalkyl phosphate having an alkyl group having 8 to 22 carbon atoms in an amount of 5 to 25% by weight. Processing method. 7. An antibacterial agent in an amount of 0.05 to 8.0% by weight based on the leather, fur and natural fibers treated with the treatment agent according to any one of claims 1 to 4 and a fiber product mainly composed of the natural fibers. Inorganic fine powder having properties and / or impregnating or adhering an antibacterial treatment agent comprising 0.02 to 5.0% by weight of an organic preservative, leather, fur and natural fiber, and the natural fiber A method for antibacterial treatment of mainly textile products. 8. The antibacterial treatment agent comprises one or more binder resins selected from water-soluble polyurethane, water-dispersible polyurethane, water-soluble acrylic copolymer and water-dispersible acrylic copolymer. 8. The method for antibacterial treatment of leather, fur and natural fiber according to claim 7, and a fiber product mainly composed of the natural fiber, wherein the antibacterial component is contained in an amount of 0.5 to 40% by weight.