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WO2003035967A1 - Agent pour le traitement de fibre proteique et procede de traitement - Google Patents

Agent pour le traitement de fibre proteique et procede de traitement Download PDF

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Publication number
WO2003035967A1
WO2003035967A1 PCT/JP2002/010815 JP0210815W WO03035967A1 WO 2003035967 A1 WO2003035967 A1 WO 2003035967A1 JP 0210815 W JP0210815 W JP 0210815W WO 03035967 A1 WO03035967 A1 WO 03035967A1
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WO
WIPO (PCT)
Prior art keywords
compound
group
water
monomer
oil
Prior art date
Application number
PCT/JP2002/010815
Other languages
English (en)
Japanese (ja)
Inventor
Masahiko Maeda
Akihiko Ueda
Masashi Nanri
Teruyuki Fukuda
Original Assignee
Daikin Industries, Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Daikin Industries, Ltd. filed Critical Daikin Industries, Ltd.
Publication of WO2003035967A1 publication Critical patent/WO2003035967A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/10—Animal fibres
    • D06M2101/12—Keratin fibres or silk
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/11—Oleophobic properties
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties

Definitions

  • the present invention relates to a treating agent and a treating method for treating a protein fiber product. Related technology
  • tanned leathers for clothing, furniture, shoe uppers, gloves, etc. have not been treated, or tend to be used only slightly.
  • a tanned leather having properties such as natural leather's original appearance, feel, texture, and flexibility can be obtained.
  • WO94 / 24179 Japanese Unexamined Patent Application Publication No. 8-509094 discloses a water- and oil-repellent fluoro (meth) acrylate copolymer. It discloses that it can be applied to leather substrates. However, even when this copolymer is used, heat treatment is required and adversely affects leather.
  • An object of the present invention is to provide a protein fiber with high water and oil repellency while maintaining properties such as protein, product's unique appearance, feel, and flexibility without the need for heat treatment.
  • An object of the present invention is to provide a treating agent and a treating method applied to products.
  • the present invention relates to a method for treating water and oil repellency of a protein fiber product using a fluorine-containing compound, wherein the fluorine-containing compound comprises: (A) a dirt-removing compound (B); A method comprising the combination is provided.
  • the fluorine-containing compound comprises: (A) a dirt-removing compound (B); A method comprising the combination is provided.
  • the soil release compound (A) is a compound used as an active ingredient in a soil release agent generally called “SR agent”.
  • the water and oil repellent compound (B) is a compound used as an active ingredient in a water and oil repellent.
  • the dirt releasing compound (A) is a fluorine-containing polymer or a fluorine-containing low molecular weight compound.
  • the stain release compound (A) preferably has a fluoroalkyl group, for example, a perfluoroalkyl group, particularly a perfluoroalkyl group having 1 to 21 carbon atoms.
  • Component (A) may be a compound (polymer or low molecular weight compound) having a fluoroalkyl group and a hydrophilic group.
  • hydrophilic group examples include an etherene group such as an oxyalkylene group, a hydroxyl group, a carboxyl group, a carbonyl group, a sulfo group (sulfonate group), a sulfonamide group, and a phosphate group.
  • etherene group such as an oxyalkylene group, a hydroxyl group, a carboxyl group, a carbonyl group, a sulfo group (sulfonate group), a sulfonamide group, and a phosphate group.
  • a polymer having a fluoroalkyl group and a hydrophilic group A polymer having a fluoroalkyl group and a hydrophilic group
  • (A-III) It is preferably a polymer having a structural unit derived from a non-fluorinated monomer, which is present as necessary.
  • the structural unit (A-1) may be derived from a (meth) acrylate monomer containing a fluoroalkyl group (A-I).
  • the fluoroalkyl group-containing (meth) acrylate ester (A-I) may be represented by the following general formula.
  • R f is a fluoroalkyl group having 3 to 21 carbon atoms
  • R 11 is a hydrogen or methyl group
  • A is a divalent organic group.
  • A is a linear or branched alkylene group having 1 to 20 carbon atoms, one S0 2 N (R 2 R 22 — group or one CH 2 CH (OR 23 ) CH 2 — Groups (where R 21 is an alkyl group having 1 to 10 carbon atoms, R 22 is a linear or branched alkylene group having 1 to 10 carbon atoms, R 23 is a hydrogen atom or 1 It is an acyl group having up to 10 carbon atoms.
  • fluoroalkyl group-containing (meth) acrylate monomer examples include the following.
  • Rf is a fluoroalkyl group having 3 to 21 carbon atoms
  • R 1 is hydrogen or an anoalkyl group having 1 to 10 carbon atoms
  • R 2 is an alkylene group having 1 to 10 carbon atoms
  • R 3 is a hydrogen or methyl group
  • Ar I is an arylene group which may have a substituent
  • n is an integer of 1 to 10.
  • the structural unit having a hydrophilic group (A-II) can be derived from a hydrophilic group-containing monomer (A-II).
  • hydrophilic groups are ether groups such as oxyalkylene groups, hydroxyl groups, hydroxyl groups, carpul groups, sulfo groups (sulfonic acid groups), sulfonamide groups, and phosphoric acid groups.
  • the hydrophilic group-containing monomer (A-II) may have a carbon-carbon double bond and a hydrophilic group.
  • the amount of the monomer (A-I) and the monomer (A-II) is based on 100 parts by weight of the monomer (A-I) having a fluoroalkyl group and the monomer (A-I) having a hydrophilic group.
  • A—II) 1 to 200 parts by weight, for example 5 to 50 parts by weight.
  • the hydrophilic group-containing monomer (A-II) is, for example,
  • R 21 and R 23 represent a hydrogen atom or a methyl group
  • R 22 represents an alkylene group having 2 to 6 carbon atoms
  • n represents an integer of 1 to 50, for example, 3 to 40.
  • the R 22, usually one CH 2 CH.
  • One is preferred, but one CH (CH 3 ) CH 2 —, One CH (C 2 H 5 ) CH 2 — or the like may be used. That is, in the present invention, polyethylene dalicol acrylate or methacrylate in which R 22 is —CH 2 CH 2 — can be particularly preferably used. May also be in the form of a type and n numbers are different a mixture of two or more of R 22.
  • hydrophilic group-containing monomer Specific examples of the hydrophilic group-containing monomer are shown below.
  • CH 2 CHC00 (CH 2 CH ( ⁇ ) 0) ⁇ CH 3
  • CH 2 C (CH 3 ) COO (CH 2 CH 2 0) 5 (CH 2 CH (CH 3 ) 0) 3 H
  • the polymer which is the component (A) contains, in addition to a fluoroalkyl group (R f group) -containing monomer and a hydrophilic group-containing monomer, other structural units (A-III) as necessary. It may contain other monomers (A-III) that form.
  • Examples of other monomers (A-III) are ethylene, vinyl chloride, vinylidene halide, styrene, acrylic acid and its alkyl ester, methacrylic acid and its alkyl ester, penzinole methacrylate, bier alkyl ketone, butyl alkyl ether, Rf groups such as isoprene, chloroprene, maleic anhydride, butadiene, 3-chloro_2-hydroxypropynole (meth) acrylate, glycerol mono (meth) acrylate, and glycidinole (meth) acrylate Contains no monomer.
  • the other monomer (A-III) may be a monomer having neither a fluoroalkyl group nor a hydrophilic group.
  • alkyl (meth) acrylate esters May be The alkyl group may have 1 to 30 carbon atoms, for example, 6 to 30 carbon atoms, for example, 10 to 30 carbon atoms.
  • the monomer (A-III) has the general formula:
  • a 11 is a hydrogen atom or a methyl group
  • the structural unit (A-III) may be formed by a crosslinkable monomer.
  • the crosslinkable monomer may be a fluorine-free butyl monomer having at least two reactive groups.
  • the crosslinkable monomer may be a compound having at least two carbon-carbon double bonds, or a compound having at least one carbon-carbon double bond and at least one reactive group.
  • crosslinkable monomer examples include diacetone acrylamide, (meth) acrylamide, N-methylol acrylamide, hydroxymethyl (meth) acrylate, hydroxyxetinole (meth) acrylate, and 3-chloro-2-hydroxy Examples include droxypropinole (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, butadiene, chloroprene, and glycidyl (meth) acrylate. However, it is not limited to these. By copolymerizing these monomers, various properties such as water repellency and antifouling properties and clean-up resistance, washing resistance, solubility in solvents, hardness, feel, etc. of these properties can be obtained as required. Can be improved.
  • the stain release compound (A) may be a fluorine-containing low molecular weight compound having a hydroxyl group.
  • the fluorine-containing low molecular weight compound having a hydroxyl group include a fluoroalkyl group-containing maleate or fumarate, a fluoroalkyl group-containing ester, and a fluoroalkyl group-containing urethane.
  • fluoroalkynole group-containing maleate or fumarate examples include:
  • R f is a perfluoroalkyl group having 3 to 21 carbon atoms.
  • R f is a perfluoroalkyl group having 3 to 21 carbon atoms.
  • the fluoroalkyl group-containing ester may be an aliphatic ester obtained by reacting a fluoroalkyl group-containing aliphatic alcohol with a fatty acid.
  • Fluoroalkyl-containing aliphatic alcohols are compounds having a fluoralkyl group and a hydroxyl group.
  • the number of hydroxyl groups may be one or more.
  • the fluoroalkyl group and the hydroxyl group may be bonded by a direct bond or an alkylene group (for example, having 1 to L0 carbon atoms).
  • the fatty acid preferably has at least one or two or more (eg, three) unsaturated bonds (polymerizable carbon-carbon double bonds).
  • fatty acids are flax oil fatty acids, linolenic acid, oleostearic acid, ricinoleic acid, oleic acid, linoleic acid, sorbic acid, and dimeric acids (such as maleic acid, fumaric acid, adipic acid).
  • fluoroalkyl group-containing aliphatic alcohol has at least one hydroxyl group
  • examples of the fluoroalkyl group-containing aliphatic alcohol include monoesters of dimer acid (having a hydroxyl group at one end), Ethylene oxide adducts of esters are mentioned.
  • Urethanes containing fluoroalkyl groups have at least two terminal segments and
  • a urethane compound comprising one intermediate segment, at least one terminal segment comprising a fluoroalkyl group, and the intermediate segment comprising a urethane compound comprising at least two mono-C0NH-bonding groups.
  • the fluoroalkyl group-containing polyurethane is an OH group-containing fluoroalkyl group-containing polyurethane further having at least one hydroxyl group.
  • OH-containing fluoroalkyl group-containing urethanes are:
  • R f is a fluoroalkyl group having 3 to 21 carbon atoms, in particular, a perfluoroalkyl group, and n is an integer of 1 to 20, for example, 1 to 5, particularly 1 to 3. ].
  • the water- and oil-repellent compound (B) is a fluorinated polymer or a fluorinated low molecular weight compound.
  • Component (B) preferably has a fluoroalkyl group, for example, a perfluoroalkyl group, particularly a perfluoroalkyl group having 1 to 21 carbon atoms.
  • Component (B) may be a compound having a fluoroalkyl group and no hydrophilic group.
  • the component (B) is a polymer, it may be a homopolymer or a copolymer of a fluorine-containing monomer.
  • Examples of the fluorine-containing monomer constituting the component (B) which is a polymer include a (meth) acrylate monomer containing a fluoroalkyl group, a maleate or fumarate monomer containing a fluoroalkyl group, a perethane or perylene bond, or a fluoroalkyl.
  • Examples include a monomer having a group.
  • component (B) which is a polymer examples include:
  • (B-1) a polymer having a structural unit derived from a (meth) acrylate polymer containing a fluoroalkyl group
  • (B-3) a polymer having a constitutional unit derived from a monomer having a urethane or perrea bond and a fluoroalkynole group
  • the polymer (B-1) having a structural unit derived from a fluoroalkyl group-containing (meth) acrylate ester monomer is a homopolymer or a copolymer of a fluoroalkyl group-containing (meth) acrylate ester monomer.
  • Examples of the (meth) acrylate monomer containing a fluoroalkynole group in the polymer (B-1) are the same as those described for the structural unit (A-1) in the component (A). is there.
  • the polymer (B-2) is a homopolymer or a copolymer of a monomer having a urethane or perylene bond and a fluoroalkyl group.
  • Monomers having a perethane or perea bond and a fluoroalkyl group are represented by the general formula:
  • Rf 1 is a fluoroalkyl group having 4 to 16 carbon atoms
  • X 1 is one R 1 —, one C ⁇ N (R 2 ) —Q 1 —, or one S0 2 N (R 2 ) —Q 1 —, R 1 is an alkylene group, R 2 is a hydrogen atom, or A lower alkyl group, Q 1 is an alkylene group,
  • a 1 is one O—, one S—, or —N (R 2 ) —;
  • R 2 is a hydrogen atom or a lower alkyl group;
  • Y 1 is a residue excluding an aromatic or alicyclic diisocyanate
  • a 2 is a divalent organic group having 2 to 9 carbon atoms and capable of containing one or more oxygen atoms
  • R 3 represents a hydrogen atom or a methyl group.
  • a monomer having a urethane or perea bond and forming a structural unit having a fluoroalkyl group is
  • Examples of compound (a) are as follows.
  • Compound (a) is preferably diisocyanate. However, triisocyanates and polyisocyanates can also be used in the reaction.
  • a dimer of diisocyanate, polymeric MDI (diphenylmetadiisocynate), and an adduct of diisocyanate with a polyhydric alcohol such as trimethylolpropane, trimethylolethane, or glycerin can be used.
  • triisocyanates and polyisocyanates are as follows.
  • Compound (b) has, for example, the formula
  • CH 2 CH-CH 2 -OH
  • R 1 is a hydrogen atom or a methyl group.
  • An example of X is as follows.
  • n and n are numbers from 1 to 300.
  • Compound (c) has the formula:
  • R f represents a fluoroalkyl group having 1 to 22 carbon atoms.
  • R 2 represents an alkylene group having 1 to 1 ° carbon atoms and may include a hetero atom. ] It may be the compound shown by these.
  • Examples of compound (c) are CF 3 CH 2 OH
  • the polymer (B-3) is a homopolymer or copolymer of a fluoroalkyl group-containing maleate or fumarate.
  • fluoroalkyl group-containing maleate or fumarate constituting the polymer (B-3) examples include, for example,
  • R f is a perfluoroalkyl group having 3 to 21 carbon atoms.
  • OH-containing fluorinated maleate represented by the formula:
  • R f is a perfluoroalkyl group having 3 to 21 carbon atoms.
  • OH-containing fluorinated fumarate represented by the formula:
  • R f is a perfluoroalkyl group having 3 to 21 carbon atoms
  • A is an alkylene group having 1 to 4 carbon atoms
  • R 1 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R 2 is an alkylene group having 1 to 4 carbon atoms.
  • R f is a perfluoroalkyl group having 3 to 21 carbon atoms
  • A is an alkylene group having 1 to 4 carbon atoms
  • R 1 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R 2 is an ⁇ / alkylene group having 1 to 4 carbon atoms.
  • fluorinated maleate and the fluorinated fumarate include the following.
  • R f is a perfluoroalkynole group having 3 to 21 carbon atoms.
  • Component (B) may be (B-4) a polyester having a fluoroalkyl group.
  • Polyester (B-4) is a polyester of a divalent or higher valent acid and a divalent or higher valent alcohol. It is preferred that the dihydric or higher alcohol has a fluoroalkyl group.
  • polyesters (B-4) are phenolic alkynole group-containing polyesters of dimer acid and Z or trimer acid.
  • a copolymer (B-1) containing a fluoroalkyl group-containing (meth) acrylate monomer is a phthalolealkynole group-containing (meth) acrylate monomer, and has a general formula: CH ⁇ CA 1 1 CO OA 1 2
  • a 11 is a hydrogen atom or a methyl group
  • the amount of the fluorine-containing monomer is 30% by weight of the polymer. / 0 or more, for example, 50% by weight or more.
  • Examples of the fluorine-containing low molecular weight compound used as the component (B) are a fluoroalkyl group-containing maleate or fumarate, a fluoroalkyl group-containing ester and a fluoroalkyl group-containing urethane.
  • Examples of a fluoroalkyl group-containing maleate or fumarate include the polymers described above.
  • the fluoroalkyl group-containing ester may be an aliphatic ester obtained by reacting a fluoroalkyl group-containing aliphatic alcohol with a fatty acid.
  • the fluoroalkyl group-containing aliphatic alcohol is a compound having a fluoroalkyl group and a hydroxyl group.
  • the number of hydroxyl groups may be one or more.
  • the fluoroalkyl group and the hydroxyl group may be bonded by a direct bond or an alkylene group (for example, having 1 to 10 carbon atoms).
  • the fatty acid preferably has at least one or two or more (eg, three) unsaturated bonds (polymerizable carbon-carbon double bonds).
  • fatty acids are linoleic fatty acids, linolenic acid, oleostearic acid, ricinoleic acid, oleic acid, linoleic acid, sorbic acid, and dimeric acids (such as maleic acid, fumaric acid, adipic acid).
  • a fluoroalkyl group-containing urethane is a urethane compound consisting of at least two terminal segments and one intermediate segment, each terminal segment containing at least one fluoroalkyl group, and the intermediate segment having at least two mono-COH-bonding groups. Containing urethane compounds. Examples of the urethane containing a fluoroalkyl group are as follows.
  • R f is a fluoroalkyl group having 3 to 21 carbon atoms, in particular, a perfluoroalkyl group. It is a kill group.
  • the fluoropolymer (ie, components (A) and (B)) in the present invention can be produced by any conventional polymerization method, and the conditions for the polymerization reaction can be arbitrarily selected.
  • Such polymerization methods include solution polymerization and emulsion polymerization.
  • milk zirconia polymerization is preferred.
  • solution polymerization a monomer is dissolved in an organic solvent in the presence of a polymerization initiator, and after nitrogen replacement, for example, in the range of 50 to 120 ° C; A method of heating and stirring for up to 10 hours is employed.
  • polymerization initiators for example, azobisisobutyronitrile, benzoyl peroxide, di-t-ptinoleperoxide, laurinole peroxide, tamenhydride peroxide, t-butyl peroxypivalate, diisopropyl And peroxy dicarbonate.
  • the polymerization initiator is used in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the monomer.
  • Organic solvents are those which are inactive in monomers and dissolve them.
  • the organic solvent is used in an amount of from 50 to 100 parts by weight based on 100 parts by weight of the total of the monomers.
  • emulsion polymerization in the presence of a polymerization initiator and an emulsifier, a monomer is emulsified in water, replaced with nitrogen, and then copolymerized by stirring at, for example, 50 to 80 ° C for 1 to 10 hours.
  • Polymerization initiators include benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclyl hexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, and azobisisobutylamidi.
  • Water-soluble substances such as dihydrochloride, azobisisobutyronitrile, sodium peroxide, persulfuric acid rim, and ammonium persulfate azobisisobutyronitrile, benzoinoleperoxide
  • Oil-soluble ones such as t-ptinoleperoxide, laurinoleperoxide, tamenhydroperoxide, t-butyl peroxybivalate, and diisopropyl peroxydicarbonate are used.
  • Single polymerization initiator It is used in the range of 0.01 to 5 parts by weight based on 100 parts by weight of the body.
  • the monomer is finely divided into water using an emulsifying device such as a high-pressure homogenizer or ultrasonic homogenizer that can apply strong crushing energy. It is desirable to carry out the polymerization using a reactive polymerization initiator.
  • an emulsifier various cationic, anionic and nonionic emulsifiers can be used.
  • the emulsifier is used in an amount of 0.5 to 10 parts by weight based on 100 parts by weight of the monomer. It is preferable to use a cationic emulsifier as the emulsifier.
  • a compatibilizing agent that makes the monomers sufficiently compatible with each other, for example, a water-soluble organic solvent or a low-molecular-weight monomer.
  • the weight average molecular weight of the polymer is 5,000 to 5,000, measured by GPC, for example, 1 0, 0000 to 1, 0000, 0000.
  • a compound having a molecular weight lower than 500, such as an oligomer may be used.
  • the low molecular weight compound may have a molecular weight of 2,000 or less, especially 1, 000.
  • a protein sickle product is treated with the treating agent of the present invention.
  • the protein fiber product includes the fiber itself, a thread formed from fibers, or a cloth.
  • the protein fibers processed include leather (eg, cowhide, pigskin, sheep leather, goatskin, horseskin, suede leather), cashmere sickle, wool, silk, feathers, and the like.
  • the leather When treating leather, the leather is generally tanned with a metal salt, vegetable tannin, aldehyde, or the like, and then treated with the treating agent of the present invention. Before, during or after the greasing step, the treatment with the treating agent of the present invention is performed.
  • the treatment with a non-fluorinated chemical such as a hydrocarbon vulcanizing agent, a synthetic tannin, or a dye can be performed before or after the treatment with the fluorinated chemical, or simultaneously. It is preferable to treat the leather with a fluorine-containing agent after the treatment with a non-fluorine agent.
  • the treatment of leather with non-fluorinated or fluorinated agents can be achieved, for example, by treating the leather with these agents at a temperature of 0-8 ° C, in particular 20-50 ° C, for 0.5 minutes to 24 hours, in particular 20 to This can be done by soaking for 50 minutes.
  • the treatment can also be performed by spraying or applying a treatment liquid.
  • the method of the present invention can be performed even at a high temperature of, for example, 80 to 120 ° C.
  • Component (A) and component (B) may be treated as separate treatment baths, or may be treated in a treatment bath containing both component (A) and component (B).
  • the weight ratio of the component (A) to the component (B) is 5:95 to 95: 5, for example, 20:80 to 80. : May be 20.
  • Protein fiber products processed according to the present invention for example, tanned leather, can be used to make or manufacture tanned leather products such as clothing, furniture, shoes, gloves, etc., regardless of the material of the tanned leather. can do.
  • the treatment with the treatment agent of the present invention is generally performed after or before the uppermost step (texture adjusting step).
  • Cashmere and wool fiber products can be placed in a water bath containing a fluorine-containing agent at a temperature of 0 to 80 ° C, especially 2O to 50 ° C.
  • It can be performed by immersion for 0.5 to 24 hours, especially for 5 to 50 minutes.
  • Tests were conducted according to the JIS L 1 0 9 2 1 9 7 7 method to evaluate the water repellency of leather and cashmere » ⁇ products.
  • IPA isopropyl alcohol
  • Example 1 (Tanned leather treatment ⁇ Evaluation)
  • the aqueous dispersions obtained in Production Examples 1 and 2 were mixed at a solid content ratio of 0: 100, 20:80, 40:60, 60:40, 80:20, 100: 0, and water-repellent. An oil repellent was obtained. The water / oil repellents of each mixing ratio were treated in the following manner, and the performance was evaluated.
  • the processing of the tanning leather according to the present invention was performed by a wet processing drum in combination with a normal post-tanning treatment and a wet operation. That is, the processing was performed in the order shown in Table A.
  • Rinsing and draining Rinsing process ⁇ was to add about 10 times the amount of dry weight of the leather to the drum, and then the drum was rotated at 30 ° C for about 10 minutes and then drained.
  • Rinsing step I was the same as rinsing step III except that the temperature was 50.
  • Table B shows the results of the performance tests.
  • Production Example 1 and Production Example 2 in the resulting aqueous dispersion having a solid content ratio, 0: 100, 3 0 were mixed in pairs 70, 50 to 50, 70 vs. 30, 100 to a rate of 0, the water and oil repellent Obtained.
  • the water / oil repellents of each mixing ratio were treated by the method shown below, and the performance was evaluated.
  • the processing with the cashmere knitted fabric product of the present invention was performed on the fabric whose texture was adjusted.
  • a water bath water temperature 30 ° C
  • 3.3% (ow w 3.3%) of the water and oil repellent was dissolved.
  • the pH of the treatment solution was adjusted to 2.2 using a 10% aqueous solution of sulfamic acid, and the fabric for which the texture was adjusted was immersed for 15 minutes.
  • Table C shows the results of the performance tests. Table C

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)

Abstract

Une fibre protéique est soumise à un traitement destiné à lui conférer un caractère hydrofuge et oléofuge à l'aide de composés de fluor comprenant une combinaison (A) d'un composé supprimant les salissures et (B) d'un composé hydrofuge et oléofuge. Ainsi, un caractère hautement hydrofuge et oléofuge est conféré au produit à base de fibre protéique sans qu'il soit nécessaire de chauffer, alors que les propriétés inhérentes audit produit, telles que l'aspect, le toucher, la douceur et le soyeux, sont conservées.
PCT/JP2002/010815 2001-10-19 2002-10-18 Agent pour le traitement de fibre proteique et procede de traitement WO2003035967A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2001321980A JP2003129380A (ja) 2001-10-19 2001-10-19 蛋白質繊維の処理剤および処理方法
JP2001-321980 2001-10-19

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WO2003035967A1 true WO2003035967A1 (fr) 2003-05-01

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Publication number Priority date Publication date Assignee Title
WO2006038493A1 (fr) * 2004-10-06 2006-04-13 Daikin Industries, Ltd. Composition hydrofuge et oléorésistante contenant du fluor
CN101193620A (zh) * 2005-04-21 2008-06-04 西斯姆工业股份公司 制作气味抑制纺织品的方法和组合物以及由此制作的纺织品服装
JP4590587B2 (ja) * 2006-02-21 2010-12-01 株式会社アイ．エス．テイ 多孔性羊毛繊維およびその製造方法、ならびに綿、混紡繊維、複合化繊維および布帛

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EP0743349A1 (fr) * 1993-12-29 1996-11-20 Daikin Industries, Ltd. Emulsion d'huile/eau fluoree et composition de traitement de surface
JPH09296372A (ja) * 1996-04-30 1997-11-18 Toyobo Co Ltd 耐墨汁汚れ性合成繊維布帛及びその製造方法
US6274060B1 (en) * 1999-02-04 2001-08-14 Daikin Industries, Ltd. Water- and oil-repellent

Patent Citations (3)

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Publication number Priority date Publication date Assignee Title
EP0743349A1 (fr) * 1993-12-29 1996-11-20 Daikin Industries, Ltd. Emulsion d'huile/eau fluoree et composition de traitement de surface
JPH09296372A (ja) * 1996-04-30 1997-11-18 Toyobo Co Ltd 耐墨汁汚れ性合成繊維布帛及びその製造方法
US6274060B1 (en) * 1999-02-04 2001-08-14 Daikin Industries, Ltd. Water- and oil-repellent

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