WO2009119423A1 - Polymer for leather treatment and leather treatment agent - Google Patents
Polymer for leather treatment and leather treatment agent Download PDFInfo
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- WO2009119423A1 WO2009119423A1 PCT/JP2009/055382 JP2009055382W WO2009119423A1 WO 2009119423 A1 WO2009119423 A1 WO 2009119423A1 JP 2009055382 W JP2009055382 W JP 2009055382W WO 2009119423 A1 WO2009119423 A1 WO 2009119423A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
- C08L51/085—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds on to polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C09D151/085—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds on to polysiloxanes
Abstract
A polymer for leather treatment and a leather treatment agent having excellent properties can be obtained from a fluorine-containing polymer comprising repeating units derived from: (A) a monomer which comprises; (a) a fluorine-containing monomer of the formula: CH2=C(X)COOYRf, wherein X is a hydrogen atom, a monovalent organic group, or a halogen atom, Y is a direct bond or a divalent organic group, and Rf is a fluoroalkyl group having 1 to 21 carbon atoms, wherein the monomer is polymerized in the presence of: (B) a mercapto functional organopolysiloxane.
Description
DESCRIPTION
POLYMERFORLEATHERTREATMENT AND LEATHERTREATMENT AGENT
Cross-reference to related applications
This Application claims benefit under 35 U.S.C. §119(e) of U.S. Provisional Application No. 61/040,209 filed March 28, 2008, incorporated herein by reference in its entirety.
Field of the Invention
The present invention relates to a fluorine-containing polymer for leather treatment and leather treatment agent imparting excellent water and oil repellency, and softness feeling to leather.
Related Art
Fluorocarbon compounds are used to impart water and oil repellency to leather. For example, US-3524760 describes Rf-containing fluoropolymer dispersion. JP-A-2002-155300 describes treatment agent comprising a mixture of fluorine-containing ionic polymer and fluorine-free ionic polymer. JP-A-2003-129380 describes the combination of soil release agent comprising fluorine-containing hydrophilic polymer and water and oil repellent. JP- A-2001-504874 describes amphiphilic fluoropolymer for waterproofhess of leather. WO2005/087826 describes fluorine-containing polymer for waterproofhess of leather.
However, their agents for leather treatment don't have enough property such as water and oil repellency without adversely affecting the appearance, touch, texture,
flexibility, breathability and other desirable properties of the leather and protein fibers. By the way, the fluoroacrylate polymer used as the conventional surface treatment agent needs at least 8 carbon atoms in the fluoroalkyl group so as to give sufficient water- and oil-repellency. Since said fluoroacrylate polymer has high hydrophobicity, in the case of emulsion polymerization, there are necessity that the amount of the used emulsifier is large, the problem that the type of the emulsifier is limited, and the necessity that an aid solvent should be used due to poor compatibility with another fluorine-free monomer. In the case of a solution polymerization, there is the problem that the solubility into a polymerization solvent is decreased for the same reason.
Recent study results (EPA Report "PRELIMINARY RISK ASSESSMENT OF
THE DEVELOPMENTAL TOXICITY ASSOCIATED WITH EXPOSURE TO
PERFLUOROOCTANOIC ACID AND ITS SALTS"
(http://www.epa.gov/opptintr/pfoa/pfoara.pdf)) and the like clarify that a PFOA (perfluorooctanoic acid) doubtfully has a potential risk of environmental load. EPA
(Environmental Protection Agency of USA) announced on April 14, 2003 that the EPA intensifies the scientific investigation.
On the other hand, Federal Register (FR Vol. 68, No. 73/April 16, 2003
[FRL-2303-8]) (http ://www. epa. gov/opptintr/pfoa/pfoafr . pdf), EPA Environmental News for release Monday April, 2003 "EPA INTENSIFIES
SCIENTIFIC INVESTIGATION OF A CHEMICAL PROCESSING AID"
(http ://www. epa. gov/opptintr/pfoa/pfoaprs. pdf), and
EPA OPPT FACT SHEET April 14, 2003
(http://www.epa.gov/opptintr/pfoa/pfoafacts.pdf) announced that a fluorinated "telomer" may metabolize or decompose to PFOA It is also announced that the telomer is used in
a large number of commercial products including fire fighting foams, care products and cleaning products as well as soil, stain and grease resistant coating on carpets, textiles, paper, and leather.
WO2006/121171 describes fluorine- and silicon-containing surface treatment agent, but the main purpose is the application to fabric for textile as shown by the examples, and it is not suitable for the leather treatment.
Means for solving the Problem
The present inventors intensively studied to solve above-mentioned problems, and discovered that a polymer comprising a specified fluoroacrylate having a mercapto silicone can have excellent water and oil repellency for leather and protein fibers without adversely affecting the appearance, touch, texture, flexibility, breathability and other desirable properties of the leather and protein fibers.
The present invention provides a fluorine-containing polymer for leather treatment comprising a fluorine-containing polymer comprising repeating units derived from:
(A) a monomer which comprises;
(a) a fluorine-containing monomer of the formula:
CH2=C(X)COO-Y-Rf, wherein X is a hydrogen atom, a monovalent organic group, or a halogen atom,
Y is a direct bond or a divalent organic group, and Rf is a fluoroalkyl group having 1 to 21 carbon atoms, wherein the monomer is polymerized in the presence of:
(B) a mercapto functional organopolysiloxane.
Detailed Description of the Solving Means
The monomer (A) which forms a fluorine-containing polymer in this invention comprises:
(a) a fluorine-containing monomer, (b) optionally present, a monomer which is free from a fluorine atom, and
(c) optionally present, a crosslinkable monomer.
The fluorine-containing polymer is a homopolymer which consists of one monomer, or it may be a copolymer which consists of two or more monomers.
The homopolymer has the repeat unit derived from a fluorine-containing monomer (a).
The polymer may have the repeat units derived from at least two fluorine-containing monomers (a), or may have the repeat units derived from at least one fluorine-containing monomer (a), the repeat units derived from at least one fluorine-free monomer (b) and optionally at least one crosslinkable monomer (c).
The fluorine-containing polymer can be obtained by polymerizing the monomer (A) in the presence of mercapto group-containing silicone (B).
(A) Monomer (a) Fluorine-containing Monomer
The component (a) of the present invention is a fluorine-containing monomer of the formula:
CH2=C(X)COO-Y-Rf wherein X is a hydrogen atom, an linear or branched alkyl group having 1 to 21 carbon atoms, a halogen atom (such as a fluorine atom, a chlorine atom, a bromine atom, a iodine
atom), a CFX1X2 group (wherein X1 and X2 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or a iodine atom ), a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group, Y is a direct bond or a divalent organic group. Y may be for example a linear or branched alkylene group having 1 to 20 carbon atoms, for example a group of the formula -(CH2)χ- where x is 1 to 10, a group of the formula -SO2N (R^R2- or of the formula -CONCR^R2-, where R1 is an alkyl group having 1 to 10 carbon atoms and R2 is a linear or branched alkylene group having 1 to 10 carbon atoms, or a group of the formula -CH2CH(OR3)CH2- where R3 represents a hydrogen atom or an acyl group having 1 to
10 carbon atoms such as formyl or acetyl, or a group of the formula -Ar-CH2- where Ar is an arylene group optionally having a substituent, and Rf is a linear or branched fluoroalkyl group having 1 to 21 carbon atoms. The alpha-position of the fluorine-containing monomer may be substituted with, for example, a halogen atom. Accordingly, in the formula (I), X may be an linear or branched alkyl group having 2 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, a iodine atom, a CFX1X2 group (wherein X1 and X2 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or a iodine atom.), a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group.
Rf group is preferably a perfluoroalkyl group. The carbon number of the Rf group is from 1 to 21, for example, from 1 to 6, particularly from 4 to 6.
Y is preferably an aliphatic group having 1 to 10 carbon atoms, an aromatic group or cycloaliphatic group having 6 to 10 carbon atoms, a -CH2CH2N(R1) SO2- group
(R1 is an alkyl group having 1 to 4 carbon atoms.) or a -CH2CH(O Y')CH2- group (Y1 is a hydrogen atom or an acetyl group.). The aliphatic group is preferably an alkylene group (particularly the carbon number is from 1 to 4, for example, 1 or 2.). The aromatic group and cycloaliphatic group may be substituted or unsubstituted.
The examples of the fluorine-containing monomer (a) are as follows:
wherein Rf is a linear or branched fluoroalkyl group having, for example, 1 to 21 carbon atoms.
Non-limiting specific examples of the fluorine-containing monomer (a) include the followings:
CF3(CF2)5(CH2)2OCOCH=CH2 CF3(CF2)5(CH2)2OCOC(CH3)=CH2 CF3(CF2)S(CHZ)1OOCOCH=CH2
CF3(CF2)5(CH2)10OCOC(CH3)=CH2 CF3(CF2)4CH2OCOCH=CH2 CF3(CFZ)3CH2OCOCH=CH2 (CF3)zCF(CF2)3(CH2)zOCOCH=CH2
(CF3)2CF(CF2)2(CH2)2OCOCH=CH2
(CF3)2CFCF2(CH2)2OCOCH=CH2
(CF3)2CF(CF2)3(CH2)2OCOC(CH3)=CH2
(CF3)2CF(CF2)2(CH2)2OCOC(CH3)=CH2 (CF3)2CFCF2(CH2)2OCOC(CH3)=CH2
CF3(CF2)2(CH2)2OCOCH=CH2
CF3(CF2)2(CH2)2OCOC(CH3)=CH2
CF3(CH2)2OCOCH=CH2
CF3 (CH2)2OCOC(CH3)=CH2 CF3(CF2)5SO2N(CH3)(CH2)2OCOCH=CH2
CF3(CF2)5SO2N(C2H5)(CH2)2OCOCH=CH2
(CF3)2CF(CF2)3CH2CH(OCOCH3)CH2OCOC(CH3)=CH2
(CF3)2CF(CF2)3CH2CH(OH)CH2OCOCH=CH2
C6F B-O-Ph-CH2OCOCH=CH2 (where Ph represents 1 ,4-phenylene) C5Fn-O-Ph-CH2OCOC(CH3)=CH2
C4F9-O-Ph-COOCH2CH(OH)CH2OCOC(CH3)=CH2
(CF3)2CFOCOC(CH3)=CH2
(CF3)2CF(CH2)2OCOC(CH3)=CH2
CF3(CF2)5SO2N(CH3)(CH2)2OCOC(F)=CH2 CF3(CF2)5SO2N(CH3XCH2)2OCOC(C1)=CH2
CF3(CF2)5SO2N(CH3)(CH2)2OCOC(Br)=CH2
CF3(CF2)5SO2N(CH3)(CH2)2OCOC(I)=CH2
CF3(CF2)5SO2N(CH3)(CH2)2OCOC(CF3)=CH2
CF3(CF2)5SO2N(CH3)(CH2)2OCOC(CN)=CH2 CF3(CF2)5SO2N(CH3)(CH2)2OCOC(C6H5)=CH2
CF3(CF2)5(CH2)2OCOC(F)=CH2 CF3(CF2)5(CH2)2OCOC(C1)=CH2 CF3(CF2)5(CH2)2OCOC(Br)=CH2 CF3(CF2)5(CH2)2OCOC(I)=CH2 CF3(CF2)5(CH2)2OCOC(CF3)=CH2
CF3(CF2)5(CH2)2OCOC(CN)=CH2 CF3(CF2)5(CH2)2OCOC(C6H5)=CH2
Especially, the above-mentioned fluorine-containing monomer (a) is a C4- or C6-(per)fluoroalkyl-ethyl alpha-Cl acrylate or a Ce (per)fluorohexyl-ethyl methacrylate.
(b) Fluorine-free monomer
The fluorine-containing polymer may have the repeating units derived from the fluorine-free monomer (b). The fluorine-free monomer (b) is other than the crosslinkable monomer (c). The monomer (b) is preferably a fluorine-free monomer having a carbon-carbon double bond. The monomer (b) is preferably a vinyl monomer which is free from fluorine. The fluorine-free monomer (b) is generally a compound having one carbon-carbon double bond. Preferable examples of the fluorine-free monomer (b) include, for example, ethylene, vinyl acetate, vinyl halide such as vinyl chloride, vinylidene halide such as vinylidene chloride, acrylonitrile, styrene, polyethyleneglycol (meth)acrylate, polypropyleneglycol (meth)acrylate, methoxypolyethyleneglycol (meth)acrylate, methoxypolypropyleneglycol (meth)acrylate, vinyl alkyl ether and isoprene. The fluorine-free monomer (b) is not limited to these examples. The fluorine-free monomer (b) may contain vinyl halide and/or vinylidene halide.
The fluorine-free monomer (b) may be a (meth)acrylate ester having an alkyl group. The number of carbon atoms of the alkyl group may be from 1 to 30, for example, from 6 to 30, e.g., from 10 to 30. For example, the fluorine-free monomer (b) may be acrylates of the general formula: CH2=CA1COOA2 wherein A1 is a hydrogen atom, a methyl group, or a halogen atom (for example, a chlorine atom, a bromine atom and a iodine atom) other than a fluorine atom, and A2 is an alkyl group represented by CnH2n+ i (n = 1 to 30).
The fluorine-free monomer (b) is preferably a Cwoo-alkyl (meth)acrylate, particularly preferably stearyl acrylate.
(c) Crosslinkable monomer
The fluorine-containing polymer may contain the repeating units derived from the crosslinkable monomer (c). The crosslinkable monomer (c) may be a fluorine-free monomer having at least two reactive groups and/or carbon-carbon double bonds. The crosslinkable monomer (c) 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. Examples of the reactive group include a hydroxyl group, an epoxy group, a chloromethyl group, a blocked isocyanate group, an amino group, an amide group, a carboxyl group, a phosphate group and a sulfonate group. In the case of leather wet end processing, a carboxyl group, a phosphate group and a sulfonate group are preferable at the point of the binding ability to leather.
Examples of the crosslinkable monomer (c) include diacetoneacrylamide, (meth)acrylamide, N-methylolacrylamide, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, N,N-dimethylaminoethyl
(meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, glycerol (meth)acrylate, glycidyl (meth)acrylate, (meth)acrylic acid, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyl phthalic acid, itaconic acid, crotonic acid, 2-(meth)acryloyloxyethyl acid phosphate, acid phosphoxypropyl methacrylate, 2-sulfoethyl (meth)acrylate, butadiene and chloroprene, to which the crosslinkable monomer is not limited.
The crosslinkable monomer (c) is preferably glycerol (meth)acrylate, glycidyl (meth)acrylate and/or (meth)acrylic acid.
The copolymerization of the monomer (b) and/or the monomer (c) with the monomer (a) can optionally improve various properties such as water repellency, oil repellency, softness feeling, binding affinity to leather, durability of repellency, stability of polymer liquid.
In the fluorine-containing polymer, the amount of the fluorine-free monomer (b) may be from 0.1 to 100 parts by weight, for example, from 0.1 to 50 parts by weight, and the amount of the crosslinkable monomer (c) may be at most 50 parts by weight, for example, at most 20 parts by weight, particularly, from 0.1 to 15 parts by weight, based on 100 parts by weight of the fluorine-containing monomer (a). The amount of vinyl halide and vinylidene halide may be from 0 to 90 parts by weight, for example, from 1 to 45 parts by weight, based on 100 parts by weight of the fluorine-containing monomer (a).
The monomer (A) can be polymerized in the presence of the mercapto organopolysiloxane (B). Examples of an olefinically unsaturated co-monomer included in the monomer (A) include alkyl acrylate or methacrylate esters having 1 to 30 carbon atoms in the alkyl group such as butyl acrylate, ethyl acrylate, methyl acrylate, methyl methacrylate or butyl methacrylate. The alkyl acrylate or methacrylate can be used to
adjust the glass transition temperature (Tg) of the resulting polymeric product resulting from the reaction of the fluorine-containing monomer (A) and the mercapto organopolysiloxane (B); for example an acrylate having a long chain alkyl group of 4-20, particularly 8-20 carbon atoms such as stearyl acrylate or methacrylate, octyl acrylate, 2-ethylhexyl acrylate or dodecyl acrylate or methacrylate can be used to form a softer polymer of lower Tg. Copolymers with an alkyl acrylate or methacrylate monomer may improve various properties such as water repellency, oil repellency, softness feeling, binding affinity to leather, durability of repellency, stability of polymer liquid. Other acrylate or methacrylate comonomers which can be used include polyethylene glycol acrylate or methacrylate, polypropylene glycol acrylate or methacrylate, methoxypolyethylene glycol acrylate or methacrylate and methoxypolypropylene glycol acrylate or methacrylate. Other olefinically unsaturated comonomers which can be used include vinyl chloride, vinylidene chloride, styrene, acrylonitrile, methacrylonitrile, ethylene, a vinyl alkyl ether, isoprene or a vinyl ester such as vinyl acetate or vinyl propionate. The olefinically unsaturated comonomer can be used which contains a functional group that may be reactive with other functional groups to give properties such as increased binding ability to leather. Examples of such functional groups are hydroxyl, epoxy, chloromethyl, blocked isocyanate, amino, amide, carboxyl, phosphate and sulfonate, and examples of olefinically unsaturated comonomers containing them are diacetoneacrylamide, (meth)acrylamide, N-methylolacrylamide, hydroxymethyl
(meth)acrylate, hydroxyethyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, N, N-dimethylaminoethyl (meth)acrylate, N, N-diethylaminoethyl (meth)acrylate, glycerol (meth)acrylate, glycidyl (meth)acrylate, (meth)acrylic acid, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyl phthalic acid, itaconic acid, crotonic acid, 2-(meth)acryloyloxyethyl acid phosphate, acid phosphoxypropyl methacrylate and
2-sulfoethyl (meth)acrylate.
(B) The Mercapto Functional Organopolysiloxane
Component (B) of the present invention is a mercapto functional organopolysiloxane, that is, an organopolysiloxane having a mercapto functional organic group present in the molecule. As used herein, a "mercapto functional organic group" is any organic group containing a sulfur atom.
Mercapto group-containing silicone (B) (that is, the mercapto functional organopolysiloxane (B)) is a siloxane compound which has at least one (for example, 1 to 500, particularly 2 to 50) mercapto group and a silicone moiety having two or more siloxane linkages. The mercapto group-containing silicone (B) functions as a chain transfer agent. In a polymerization reaction, a H radical is generated from a -SH group, and a S atom bonding to the silicone moiety bond to the fluorine-containing polymer.
Organopolysiloxanes are well known in the art and are often designated by the general formula
where the organopolysiloxanes may comprise any number of "M" (mono functional) siloxy units (RsSiOo 5 ), "D" (difunctional) siloxy units (R2SiO), "T" (trifunctional) siloxy units (RSiO1 5), or "Q" siloxy units (SiO2) where R is independently a monovalent organic group. These siloxy units can be combined in various manners to form cyclic, linear, or branched structures. The chemical and physical properties of the resulting polymeric structures can vary. For example organopolysiloxanes can be volatile or low viscosity fluids, high viscosity fluids/gums, elastomers or rubbers, and resins. R is independently a monovalent organic group, alternatively R is a hydrocarbon group containing 1 to 30 carbons, alternatively R is an alkyl group containing 1 to 30 carbon atoms, or alternatively R is methyl. The organopolysiloxanes useful as component (B) in the present invention are
characterized by having at least one of the R groups in the formula RnSiO(4-n)/2 be a mercapto group, or alternatively at least one of the R groups be a mercapto group and one of the R groups be an organofunctional group, or alternatively one of the R groups be an organofunctional group also containing a mercapto group. The organofunctional group and mercapto functional group may be present on any siloxy unit having an R substituent, that is, they may be present on any M, D, or T unit. Typically, the organofunctional groups and mercapto groups are present as a R substituent on a D siloxy unit.
As used herein, "organofunctional group" means an organic group containing any number of carbon atoms, but the group contains at least one atom other than carbon and hydrogen. Representative examples of such organofunctional groups include, hydroxyls, amines, amides, sulfonamides, quaternaries, ethers, epoxy, phenols, esters, carboxyls, ketones, halogen-substituted alkyls and aryls group, to name a few. Alternatively, the organofunctional group is an amino-functional organic group.
When the organofunctional group is an amino-functional organic group, the amino-functional organic group is designated in the formulas herein as RN and is illustrated by groups having the formula: -R1NHR2 , -R1NR2 2 , or -R1NHR1NHR2, wherein each R1 is independently a divalent hydrocarbon group having at least 2 carbon atoms, and R2 is hydrogen or an alkyl group. Each R1 is typically an alkylene group having from 2 to 20 carbon atoms. R1 is illustrated by groups such as; -CH2CH2-, -CH2CH2CH2-, -CH2CHCH3-, -CH2CH2CH2CH2-,
-CH2CH(CH3)CH2-, -CH2CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2CH2-, -CH2CH2CH(CH2CH3)CH2CH2CH2-, -CH2CH2CH2CH2CH2CH2CH2CH2-, and -CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2-. The alkyl groups R2 are as illustrated above for R. When R2 is an alkyl group, it is typically methyl. Some examples of suitable amino-functional hydrocarbon groups are;
-CH2CH2NH2, -CH2CH2CH2NH2, -CH2CHCH3NH, -CH2CH2CH2CH2NH2,
-CH2CH2CH2CH2CH2NH21 -CH2CH2CH2CH2CH2CH2NH2,
-CH2CH2NHCH3, -CH2CH2CH2NHCH3, -CH2(CH3)CHCH2NHCH3,
-CH2CH2CH2CH2NHCH37 -CH2CH2NHCH2CH2NH2, -CH2CH2CH2NHCH2CH2CH2NH2, -CH2CH2CH2CH2NHCH2CH2CH2CH2NH2,
-CH2CH2NHCH2CH2NHCH35 -CH2CH2CH2NHCH2CH2CH2NHCH3,
-CH2CH2CH2CH2NHCH2CH2CH2CH2NHCH3, and
-CH2CH2NHCH2CH2NHCH2CH2CH2CH3. Typically, the amino functional group is
-CH2CH2CH2NH2 . The mercapto-functional organic group is designated in the formulas herein as Rs and is illustrated by groups having the formula: -R1SR2, wherein each R1 and R2 is as defined above. The mercapto-functional group is illustrated by the following formulae;
CH2CH2CH2SH, -CH2CHCH3SH, -CH2CH2CH2CH2SH,
-CH2CH2CH2CH2CH2SH, -CH2CH2CH2CH2CH2CH2SH, -CH2CH2SCH3. Typically, the mercapto functional group is -CH2CH2CH2SH.
In a preferable embodiment, the mercapto functional organopolysiloxane
(designated B') comprises siloxy units having the average formula:
(R2SiO)a(RRNSiO)b(RRsSiO)c where; a is 0-4000, alternatively 1 to 1000, alternatively 2 to 400, b is 1-1000, alternatively 2 to 100, alternatively 3 to 50, c is 1- 1000, alternatively 2 to 100, alternatively 3 to 50;
R each is independently a monovalent organic group, alternatively R each is a hydrocarbon containing 1- 30 carbon atoms, alternatively R each is a monovalent alkyl group containing 1 - 12 carbons, or alternatively R each is a methyl group;
RN each is a monovalent amino functional organic group as defined above, R each is a monovalent mercapto functional organic group as defined above.
The RN group may be RF wherein RF may be a monovalent organofunctional organic group as defined above, such as hydroxyls, amines, amides, sulfonamides, quaternaries, ethers, epoxy, phenols, esters, carboxyls, ketones, halogen-substituted alkyls and aryls group. The mercapto functional organopolysiloxane may comprise siloxy units having the average formula (R2SiO)a(RRFSiO)b(RRsSiO)c wherein the groups and subscripts (that is, a, b and c) are the same define above. Organopolysiloxane (B') may be terminated with a hydrogen atom (resulting in a silanol group on the terminal siloxy unit of the terpolymer), or with an alkyl group containing 1 - 30 carbon atoms (resulting in an alkoxy group on the terminal siloxy unit of the terpolymer). When an alkyl group is used, the alkyl group can be a linear or branched alkyl, containing 1 — 30 carbons, alternatively the alkyl group can be a long chain alkyl group of 4-20, alternatively 8-20 carbon atoms such as stearyl. Alternatively the organopolysiloxane can be terminated with a trimethylsilyl group.
The mercapto group-containing silicone (B) is of, for example, the formula:
R1 R2 R3
R1— 0-(-SiO-) — (-SiO-)- (-SiO-) — R1
A a B b R3 c I I
SH C
wherein R1 is independently a methyl group, a methoxy group, a phenyl group, or a hydroxyl group,
R2 is independently a methyl group, a methoxy group, a phenyl group, or a hydroxyl group,
R3 is independently a methyl group, a methoxy group, a phenyl group, or a hydroxyl group, R' is independently a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, or
Me3Si,
A is independently a divalent saturated hydrocarbon group having 1-10 carbon atoms which may be interrupted with one or two ether linkages,
B is independently a divalent saturated hydrocarbon group having 1-10 carbon atoms which may be interrupted with one or two ether linkages,
C is independently hydroxyls, amines, amides, sulfonamides, quaternaries, ethers, epoxy, phenols, esters, carboxyls, ketones, halogen-substituted alkyls or aryls group, a, b, and c are integers showing the number of repeat units, a is from 1 to 4000, for example, 2 to 2000, b is from 1 to 1000, preferably from 2 to 800 ,and c is from 0 to 1000, preferably from 1 to 800.
The example of mercapto group-containing silicone (B) is as follows.
R1 R2 R3
R3 3Si— 0-(-SiO-)- fSiO-H-SiO-)— SiR3 3
A a B b R3 c I I
SH C
wherein the groups such as the R1 group and the subscripts are defined as the same as above-mentioned.
The functional group C is particularly preferably an amino group (that is, the
mercapto group-containing silicone (B) is an amino mercapto silicone). The amino group has the effect of remarkably improving the affinity with other materials constituting the cosmetic and with a human body skin.
The organopolysiloxane (B') of the above-mentioned preferable embodiment can be represented by the following average formula for example;
(CH2)3SH
R1O(SiMe2O)3(SiMeO)I5(SiMeO)0R1
I (CH2J3NH2
where; a is 0-4000, alternatively 1 to 1000, alternatively 2 to 400, b is 1-1000, alternatively 2 to 100, alternatively 3 to 50, c is 1- 1000, alternatively 2 to 100, alternatively 3 to 50; and R' is independently H, an alkyl group having 1 to 40 carbon atoms, or MesSi. The amino-mercapto functional organopolysiloxane terpolymers of this preferable embodiment (B') can be prepared by any technique known in the art for preparation of organopolysiloxane terpolymers containing amino and/or mercapto functional groups. Typically, the organopolysiloxanes (B') are prepared via a condensation polymerization reaction of an amino functional alkoxy silane, a mercapto functional silane monomer, and organopolysiloxane having alkoxy or silanol termination as illustrated by the following general reaction scheme.
HO(SiMe2O)nH (CH2J3SH
+ ROH I
(MeO)2SiMe(CH2)3NH2 ^ RO(SiMe2O)a(SiMeO)b(SiMeO)cR
+ Catalyst (EtO)2Si(CH2)3SH (CH2J3NH2
Condensation organopolysiloxanes are well known in the art and are typically catalyzed by the addition of a strong base, such as an alkaline metal hydroxide or a tin compound. Alternatively co-polymerization of the fiinctionalized cyclosiloxanes could be used.
The fluorine-containing polymer may have a weight-average molecular weight of 2,000 to 5,000,000, particularly 3,000 to 5,000,000, especially 10,000 to 1,000,000. The weight-average molecular weight (in terms of polystyrene) of the fluorine-containing polymer can be determined by GPC (Gel Permeation Chromatography). The fluorine-containing polymer of the present invention can be produced by any polymerization method. The polymerization method includes, for example, bulk polymerization, solution polymerization and emulsion polymerization.
In the bulk polymerization, a method is adopted in which a mixture of the monomers and the mercapto silicone is purged by nitrogen, a polymerization initiator is then added, and the mixture is stirred in the range of from 30 to 80°C for several (2 to 15) hours to be polymerized. Examples of the polymerization initiator include azobisisobutyronitrile, benzoyl peroxide, di-teit-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate and diisopropyl peroxydicarbonate. The polymerization initiator may be used in the amount within the range from 0.01 to 20 parts by weight, for example, from 0.01 to 10 parts by weight, based on 100 parts by weight of the monomers.
In the case of the solution polymerization, the mixture of the monomers and the mercapto silicone is dissolved in a suitable organic solvent in which these can dissolve and to which these are inert, and then polymerized in the same manner as described earlier. Examples of the organic solvent include a hydrocarbon-based solvent, an
ester-based solvent, a ketone-based solvent, an alcohol-based solvent, a silicone-based solvent, and a fluorine-containing solvent. The organic solvent is inert to the monomer and dissolves the monomer, and examples thereof include acetone, chloroform, HCFC225, isopropyl alcohol, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane and trichlorotrifluoroethane. The organic solvent may be used in the amount within the range from 50 to 2,000 parts by weight, for example, from 50 to 1,000 parts by weight, based on 100 parts by weight of total of the monomers.
In the solution polymerization, there can be used a method of dissolving the monomer(s) into an organic solvent in the presence of a polymerization initiator, replacing the atmosphere by nitrogen, and stirring the mixture with heating, for example, at the temperature within the range from 30 degrees C to 120 degrees C for 1 hour to 10 hours.
In the case of the emulsion polymerization, the polymerization is carried out in the same manner as described above after emulsifying a mixture of the monomers and the mercapto silicone in water using a proper emulsifier. In some combinations of the monomers (a) to (c) and the mercapto silicone, a poor compatibility of the monomers and the mercapto silicone in water results in a poor copolymerizability. In such a case, a method in which a proper auxiliary solvent such as glycols and alcohols and/or a low molecular weight monomer is added to improve the compatibility of the mixture is adopted. A hydrophobic group in the emulsifier to be used in the emulsion polymerization may be any of hydrocarbon type, silicon-containing type and fluorine-containing type. As for the ionicity of a hydrophilic group, any of nonionic one,
anionic one, cationic one and amphoteric one may be used. In the case of leather wet end processing, an anionic emulsifier is preferable in view of the binding ability to leather.
In the present invention, the polymerization is generally a radical polymerization which uses a radical polymerization initiator. As the polymerization initiator for solution polymerization, for example, oil-soluble initiators (e.g., azobisisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, lauryl peroxide, t-butyl peroxybenzoate, cumene hydroperoxide, t-butyl peroxypivalate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxy- propionyl peroxide, acetyl peroxide and diisopropyl peroxydicarbonate) are used. As the polymerization initiator for emulsion polymerization, for example, water-soluble initiators (e.g., azobisisobutylamidine dihydrochloride, sodium peroxide, potassium persulfate and ammonium persulfate) are used. The radical polymerization initiator is preferably a peroxide compound which generates an anionic group after a peroxide decomposition, in view of the binding ability to leather. Examples of the preferable peroxide compound include potassium persulfate and ammonium persulfate. The polymerization initiator may be used in the amount within the range from 0.01 to 10 parts by weight based on 100 parts by weight of the monomers.
In the emulsion polymerization, there can be used a method of emulsifying monomers in water in the presence of a polymerization initiator and an emulsifying agent, replacing the atmosphere by nitrogen, and polymerizing with stirring, for example, at the temperature within the range from 30 degrees C to 120 degrees C, for example, from 50 degrees C to 80 degrees C, for 1 hour to 10 hours.
When the monomers are not completely compatibilized, a compatibilizing agent capable of sufficiently compatibilizing them (e.g., a water-soluble organic solvent and a low-molecular weight monomer) is preferably added to these monomers. By the
addition of the compatibilizing agent, the emulsifiability and polymerizability can be improved.
Examples of the water-soluble organic solvent include acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol and ethanol. The water-soluble organic solvent may be used in the amount within the range from 1 to 50 parts by weight, e.g., from 10 to 40 parts by weight, based on 100 parts by weight of water. Examples of the low-molecular weight monomer are methyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate. The low-molecular weight monomer may be used in the amount within the range from 1 to 50 parts by weight, e.g., from 10 to 40 parts by weight, based on 100 parts by weight of total of monomers.
As the emulsifier, various emulsifiers such as an anionic emulsifier, a cationic emulsifier and a nonionic emulsifier can be used in the amount within the range from 0.5 to 20 parts by weight based on 100 parts by weight of the monomers. The emulsifier used in the emulsion polymerization may have a hydrophobic group which may be a hydrocarbon, a silicone or a fluorine-containing compound, and hydrophilic group which may be nonionic, anionic, cationic or amphoteric. In the case of leather wet end processing, anionic emulsifier is preferable in view of the binding ability to leather. A combination of the anionic emulsifier and the nonionic emulsifier is preferable in order to obtain both the stability of the emulsion and the binding ability to leather. The amount of the anionic emulsifier is from 5 to 80 % by weight, preferably from 10 to 60 % by weight, based on the total of the anionic emulsifier and the nonionic emulsifier. Preferably, the anionic emulsifier is polyoxyethylene alkyl (preferably C1 to C30 alkyl) ether sulfate salt and alfa-olefin sulfonate salt, and the nonionic emulsifier is fatty acid sorbitan ester, polyoxyethylene fatty acid sorbitan ester, polyoxyethylene hydrogenated
castor oil, polyoxyethylene fatty acid sorbit ester, polyoxyethylene alkylether and/or polyoxyalkylene derivative.
In order to obtain a polymer dispersion in water, which has a high polymer solid content and which has very fine and stable particles, it is desirable that the mixture of the monomers and the mercapto silicone is dispersed in water by using an emulsifying device capable of applying a strong shearing energy (e.g., a high-pressure homogenizer and an ultrasonic homogenizer) to prepare the fine particles of the mixture, and then the polymerization is conducted.
In the polymerization, a chain transfer agent other than the mercapto silicone or a pH modifier may be added, if necessary. The weight average molecular weight
(measured by GPC) of the fluorine-containing polymer obtained after the polymerization is from 10,000 to 1,000,000, preferably from 20,000 to 300,000.
The fluorosilicone reaction product of the fluorine-containing monomer (A) and the mercapto organopolysiloxane (B) may be prepared by any reaction process known in the art to effect polymerisation of such monomers. Preferably, the fluorosilicone may be prepared according to the process of the present invention comprising; I) reacting,
(A) a monomer comprising a fluorine-containing monomer of the formula:
CH2=C(X)COOYRf, X is a hydrogen atom, a monovalent organic group, or a halogen atom,
Y is a direct bond or a divalent organic group having 1 to 20 carbon atoms, and
Rf is a fluoroalkyl group having 1 to 21 carbon atoms, in the presence of (B) a mercapto functional organopolysiloxane,
via a polymerization reaction, preferably a free radical polymerisation reaction.
Components (A) and (B) in the process are the same as described above.
The process may also be conducted in the presence of a polar organic solvent. The polar organic solvent can be one or more alcohol, ketone or ester solvents selected from butanol, t-butanol, isopropanol, butoxyethanol, methyl isobutyl ketone, methyl ethyl ketone, butyl acetate or ethyl acetate and/or an aromatic hydrocarbon such as xylene, toluene or trimethylbenzene a blend of one or more of these.
The initiator for the free radical polymerisation reaction can be any compound known in the art for initiating free radical reactions, such as organic peroxides or azo compounds. Representative, non-limiting examples are; azo compounds such as azobisisobutyronitrile or azobisisovaleronitrile (ATVN), peroxides such as benzoyl peroxide. The polymerisation temperature typically ranges 50-120°C.
Alternatively the polymeric reaction product can be obtained using the technique of emulsion polymerisation, where all the components are polymerised in the presence of water, surfactants and polymerisation initiator.
The fluorosilicone reaction product can contain various ratios of the fluorine-containing monomer (A) and the mercapto organopolysiloxane (B), as controlled by the amount of each of components (A) and (B). The fluorosilicone may contain 5 to 99.9% by weight, preferably 10 to 95% by weight of the monomer (A), and 0.1 to 95% by weight, preferably 5 to 90% by weight of the mercapto organopolysiloxane (B) with the proviso that sum of the wt % of (A) and (B) equals 100%. A fluorosilicone product having a high proportion of mercapto organopolysiloxane may provide greater substantivity to leather or softness of handle of the treated leather. A polymeric product having a high proportion of fluorine-containing monomer may provide maximum hydrophobicity and oleophobicity.
A fluorine-containing polymer prepared by solution polymerization or emulsion polymerization may be blended directly in the form of a reaction liquid into the liquid for application to leather. Alternatively, the polymer may be dissolved (or dispersed) in solvents (or water) after the isolation of only the polymers. Although the fluorine-containing polymer may be an isolated polymer, it is preferable that the polymer is supplied as a raw material of leather application in the form dissolved or dispersed in water or at least one of hydrocarbon-based solvents, alcohol-based solvents, ester-based solvents, ketone-based solvents, silicone-based solvents and fluorine-containing solvents. The fluorine-containing polymer may be contained in an amount of from 1 to 60% by weight, preferably from 2 to 50% by weight, more preferably from 3 to 40% by weight relative to the total amount [the fluorine-containing polymer plus (water or a solvent)]. When it is from 1 to 60% by weight, the amount of the fluorine-containing polymer in the liquid for application to leather is sufficient for imparting insufficient water and oil repellency. The leather treatment agent with the fluorine-containing polymer of the present invention may optionally contain various additives. Examples of the additive include, an other type of water and/or oil repellent agent (fluorine-containing compound, silicon-containing compound and/or hydrocarbon compound), a fluorine-containing oil, a silicon-containing oil, a hydrocarbon oil, a fluorine-containing wax, a silicon-containing wax, a hydrocarbon wax, a fluorine-containing resin, a silicon-containing resin, a hydrocarbon resin, a fluorine-containing rubber, a silicon-containing rubber, a hydrocarbon rubber, an antifoaming agent, a pH adjuster, an antifreezing agent, an antigelling agent, a coalescent agent, a film-forming agent, a viscosity adjusting agent, a crosslinker, an antioxidation agent, a surfactant, a solvent, a penetrating agent, a leveling agent, an ultraviolet absorbing agent, a dyestuff, a level dyeing agent, a pigment, a
pigment dispersing agent , a fatliquor, a retanning agent, a touch modifier, a softener, an antistatic agent, an antibacterial agent, an antiseptic agent, a moth proofing agent, an aromatic substance and a flame retardant.
Examples of the fluorine-containing oil include a perfluoropolyether comprising repeating units of the formula : -(CF(CF3)CF2O)-,
-(CF(CF3)CF2O)p-(CF2O)q-(CF(CF3)O)r- wherein p, q and r are integers a sum of which is not smaller than 2 and not larger than 200,
-(CH2CF2CF2θ)a-(CHClCF2CF2O)b-(CCl2CF2CF2O)c-(CHFCF2CF2θ)d-(CFClCF2CF2O)e -(CF2CF2CF2OV wherein a, b, c, d, e and fare 0 or positive integers and satisfy the range (a+b+c+d+e+f) equal or over 2 to equal or under 200 and (a+c+d+f) equal or over 1, and a compound comprising repeating units of the formula : -(CF2CFCl)-. The molecular end may be modified with for example, a carboxyl, a hydroxyl, a phosphate or a silane group.
Examples of the silicon-containing oil are any of a straight silicone oil and a modified silicon oil, and include dimethyl silicone, methylphenyl silicone, methylhydrogen silicone, cyclic polydimethylsiloxane, alkyl-modified silicone, alcohol-modified silicone, amino-modified silicone, fluoroalkyl-modified silicone, chloroalkyl-modified silicone, and other organic modified silicones. Non-limiting specific examples of the silicone oil include the followings:
CH3 CH3 CH3 H2NR-SiO (SiO )x— Si-RNH2 CH3 CH3 CH3
CH3 CH3 CH3 CH3 CK3SiO ( SiO )„-( SiO )y-SiCH3 CH3 CH3 R-Rf CH3
wherein R is an alkylene group having at least one carbon atom, PA is a polyalkylene oxide, Rf is a perfluoroalkyl group containing an alkyl group having 1 to 20 carbon atoms, x is an integer of 0 or at least 1, and y is an integer of at least 1. The polymer can be applied to leather from aqueous solution or emulsion at various stages of leather processing, for example during leather wet end processing or during leather finishing, to render the leather hydrophobic and oleophobic.
The fluorine-containing polymer of the present invention can be applied to leather and protein fibers. Examples of the leather include a natural leather originated from the animal such as an ox, a sheep, a goat, a pig, a horse, a kangaroo and a deer, and the leather-like material such as an artificial leather, a synthetic leather and a vinyl leather which texture are, for example, suede, nubuck and grain type. The protein fibers products include a fiber itself, a yarn-like material formed from the fiber, a fabric-like material. Examples of the protein fibers other than natural leather include cashmere fibers, wool, silk and feathers.
In the case of wet end processing of natural leather and protein fibers, generally, after the substrate is tanned by a metal salt, vegetable tannin, aldehyde or the like, the substrate is treated with a treatment agent of the present invention (that is, a treatment liquid). The treatment with the treatment agent of the present invention is performed before, during or after a fatliquoring process. Treatment with a fluorine-free agent such as a hydrocarbon fatliquoring agent, a synthetic tannin, and a dye can be performed before or after, or simultaneously with the treatment with the treatment agent of the present invention. After the treatment with the fluorine-free agent, it is preferable to
treat the substrate with the treatment agent of the present invention.
The "treatment" means that a treatment agent is applied to the substrate by immersion, spraying, coating or the like. The treatment gives the result that a fluorine-containing polymer which is an active component of the treatment agent is penetrated into the internal parts of the substrate and/or adhered to surfaces of the substrate.
The treatment of the substrate with the fluorine-free agent and the treatment agent of the present invention can be performed by immersing the substrate into the these agents at the temperature of 0-80°C, particularly 20-50°C for 0.5 minutes to 24 hours, particularly 20 minutes to 120 minutes. The treatment can be performed also by spraying, coating, etc. The method of the present invention can be performed even at a high temperature of 80-1200C. It is preferable to adjust the pH of treatment liquid to at most 4.
In the processing of a cashmere or wool textile, generally, the treatment with the treatment agent of the present invention is performed after or before a final finishing step
(a feeling adjustment step). The cashmere or wool textile is immersed into an aqueous bath containing the treatment agent of the present invention at the temperature of 0-80°C, particularly 20-500C for 0.5 minutes to 24 hours, particularly 5 to 50 minutes. It is preferable to adjust the pH of treatment liquid to an acidic value (pH 2.5 or less). After applying the treatment agent, the fluid medium (such as water and/or organic solvent) existing in the treatment agent is removed from the leather or protein fiber.
In the case of finish processing of leather and protein fibers, the polymer may be in the form of an aqueous dispersion, a non-aqueous dispersion or an organic solvent composition. In the case of aqueous dispersion, the polymer may be dispersed in water or water/aqueous solvent mixture. Examples of a solvent used in the organic solvent
composition include esters such as ethyl acetate, butyl acetate, isopropyl acetate, isobutyl acetate, cellosolve acetate, propyleneglycol methyl ether acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; cyclic ethers such as tetrahydrofuran and dioxane; amides such as N,N-dimethyl formamide and N,N-dimethyl acetamide; aromatic hydrocarbons such as toluene and xylene; alcohols such as isopropyl alcohol, propyleneglycol methyl ether, dipropyleneglycohol methyl ether; hydrocarbons such as hexane and heptane; a mixture solvent thereof. The concentration of solid components in the organic solvent composition is from 1 to 20 % by weight, preferably from 3 to 10 % by weight. The treated leather of the present invention treated with the polymer can be prepared by treating the polymer composition on the leather with/without the other agents such as dyestuff, and then drying and curing. The treating amount (solid content) of the polymer may be at least 1 g/m2 , for example, from 2 to 20 g/m2 . The polymer puts on the surface of the treated leather. The treating method is not limited, and a spray coating, a brush coating, a curtain coating, a roll coating and the like can be used. The treated leather can be dried and cured usually at 0 to 2000C for 2 or 3 seconds to 10 days. The drying and curing method vary depending on a treating amount and type of leather and the like. Examples of said drying and curing method include (1) a method of keeping standing at room temperature for at least one day, (2) a method of keeping standing in 5O0C hot air dryer for at least 30 seconds, (3) a method of heating by an infrared heating machine for at least 10 seconds and (4) a method of keeping in toggling machine.
The leather treated with the fluorine-containing polymer of the present invention has excellent water and oil repellency and softness. The leather treated with the fluorine-containing polymer of the present invention can be processed to give various leather products. Examples of the leather products are leather shoes such as boots,
pumps, business shoes, sports shoes and hard shoes; leather bags such as a school child's satchel, a handbag, a shoulder bag, a porch, a Boston bag and rucksack; leather clothes such as a skirt, a coat, pants, a jacket, a rider suit, a ski wear, a glove and a cap; leather accessories such as a purse, a belt, a watch band, a pocket diary, a harness and a book cover; interiors of building constructions; interiors of vehicles such as a seat, headrest, armrest, steering, door interior and ceiling interior of an automobile, a seat or interior of an aircraft, a seat of a rail way vehicle, and a seat of a ship; leather furniture items such as a sofa, a living chair, a dining chair and a table; and a raw material for handicrafts. The leather product can be prepared by cutting and sewing the treated leather of the present invention or by shaping the leather in the form of the leather product and then treating the shaped leather.
Examples
The following Examples further illustrate the present invention in detail but are not to be construed to limit the scope thereof.
Synthetic Example 1
Preparation of aminomercaptosilicone:
Into a three necked round bottomed flask fitted with a condenser, overhead stirrer and thermocouple were charged a silanol terminated polydimethylsiloxane (323g
Mn ~ 900 and 380g Mn ~ 300), mercaptopropylmethyldimethoxysilane (230g), aminopropylmethyldiethoxysilane (27g), trimethylethoxysilane (42g), barium hydroxide (0.62g) and sodium orthophosphate (0.25g). The reaction mixture was heated to 75°C and held at this temperature for three hours after which volatile removal was carried out at 75°C and a reduced pressure of 200mbar for four hours to give an amino mercapto
silicone polymer. The resulting polymer had an Mn of 4396, viscosity of 74Cts, % N of -0.26 w/w and % SH of ~4.1w/w, and 9% of the end groups were SiMe3 and the remainder was a mixture of SiOH and SiOMe/SiOEt.
Preparative Example 1
Into a 300 cc flask, CF3CF2-(CF2CF2^-CH2CH2OCOC(CHB)=CH2 (9.2 g), stearyl acrylate (1.15 g), glycerol methacrylate (0.22 g), glycidyl methacrylate (0.07 g), aminomercaptosilicone prepared in Synthetic Example 1 (1.42 g), pure water (23.3 g), dipropylene glycol (4.25 g), sodium polyoxyethylene laurylether sulfate (0.76 g), sorbitan monopalmitate (0.13 g), polyoxyethylene hydrogenated castor oil (0.635 g) were charged and emulsified by ultrasonic wave at 60°C for 15 minutes with stirring. The atmosphere of the autoclave was replaced with nitrogen, and then vinyl chloride (3.36 g) was injected. Ammonium persulfate (0.20 g) and sodium pyrosulfite (0.10 g) were added and the reaction was conducted at 60°C for 5 hours to give an aqueous dispersion of a polymer.
Preparative Example 2
Into a 300 cc flask, CF3CF2-(CF2CF2)2-CH2CH2OCOC(CH3)=CH2 (9.2 g), stearyl acrylate (2.25 g), lauryl acrylate (2.25 g), glycerol methacrylate (0.22 g), glycidyl methacrylate (0.07 g), aminomercaptosilicone prepared in Synthetic Example 1 (1.42 g), pure water (23.3 g), tripropylene glycol (4.25 g), sodium polyoxyethylene laurylether sulfate (0.76 g), sorbitan monopalmitate (0.13 g), polyoxyethylene hydrogenated castor oil (0.635 g) were charged and emulsified by ultrasonic wave at 600C for 15 minutes with stirring. The atmosphere of the autoclave was replaced with nitrogen. Ammonium persulfate (0.20 g) and sodium pyrosulfite (0.10 g) were added and the reaction was conducted at 60°C for 5 hours to give an aqueous dispersion of a polymer.
Preparative Example 3
Into a 300 cc flask, CF3CF2-(CF2CF2)2-CH2CH2OCOC(CH3)=CH2 (20.5 g), stearyl acrylate (2.6 g), glycerol methacrylate (0.48 g), glycidyl methacrylate (0.16 g), aminomercaptosilicone prepared in Synthetic Example 1 (3.2 g), pure water (50.5 g), dipropyleneglycol monomethylether (8.8 g), sodium alfa-olefin sulfonate (1.0 g), polyoxyethylene laurylether (1.0 g), polyoxyalkylene derivative (1.0 g) were charged and emulsified by ultrasonic wave at 60°C for 15 minutes with stirring. The atmosphere of the autoclave was replaced with nitrogen, and then vinyl chloride (7.5 g) was injected. Ammonium persulfate (0.45 g) and sodium pyrosulfite (0.23 g) were added and the reaction was conducted at 60°C for 5 hours to give an aqueous dispersion of a polymer.
Preparative Example 4
The procedure of Preparative Example 3 was repeated except that in place of sodium alfa-olefin sulfonate and polyoxyethylene laurylether, polyoxyethylene laurylether (2.0 g) was used.
Preparative Example 5
The procedure of Preparative Example 3 was repeated except that in place of glycidyl methacrylate, methacrylic acid was used.
Preparative Example 6
The procedure of Preparative Example 1 was repeated except that in place of sodium alfa-olefin sulfonate, dialkyldimethyl ammonium chloride was used, and in place of ammonium persulfate and sodium pyrosulfite, 2,2'-azobis (2-amidinopropane)
dihydrochloride (0.12 g) was used.
Comparative Preparative Example 1
The procedure of Preparative Example 1 was repeated except that in place of the aminomercaptosilicone, n-dodecyl mercaptan (0.23 g) was used.
Comparative Preparative Examples 2
The procedure of Preparative Example 2 was repeated except that in place of the aminomercaptosilicone, n-dodecyl mercaptan (0.23 g) was used.
Comparative Preparative Examples 3
The procedure of Preparative Example 6 was repeated except that in place of the aminomercaptosilicone, n-dodecyl mercaptan (0.23 g) was used.
Wet end Processing 1
A wet shaved chromium-tanned leather was treated according to the following steps: i) washing with water and drain ii) neutralization iii) washing with water and drain iv) dyeing, fatliquoring, pH adjustment and drain v) washing with water and drain vi) metal retanning and drain vii) washing with water and drain viii) fluorine-containing polymer treatment, pH adjustment and drain
ix) washing with water and drain
The treatment or processing of the leather with the leather modifier of the present invention can be carried out by the conventional method except that the leather modifier of the present invention is added to a wet processing drum in the wet processing step. That is, in the above treatment procedures, the steps were carried out in a rotating drum.
In the washing steps i), v) and ix), water in an amount of 3 times of the weight of the leather was added to the drum, the drum was rotated at 30°C for 10 minutes, and the bath liquid was drained. In the washing steps iii) and vii), the similar processing was carried out except that the temperature was 500C. In the neutralization step ii), an aqueous solution of at least one neutralizing agent was added to the drum in about 1.5 times amount of the weight of the leather, and the drum was rotated at about 30°C for about 60 minutes to adjust pH of the bath at 6.0 to 6.5. The neutralizing agents were sodium formate and sodium bicarbonate. After neutralization, the bath liquid was drained, and the neutralized leather was washed by water.
In the step iv), 500C water in about twice amount of the weight of the leather, acid dyestuff (Sella Fast Brown CR: TFL) in an amount of 3% and fatliquor (Sincolin L: Nippon Fine Chemical) in an amount of 8% of the weight of the leather were added to the drum, and the drum was rotated at 500C for 60 minutes while keeping pH at 5.5 to 6.5. And then formic acid in an amount of 1 to 2% of the weight of the leather was added to the drum and the drum was rotated more for 30 minutes to adjust pH of the bath at 3.3 to 3.7, and the bath liquid was drained.
In the step vi), 30°C water in about twice amount of the weight of the leather and metal retanning agent (Chromosal B: LANXESS) in an amount of 3% of the weight of the leather were added to the drum and the drum was rotated at 300C for 40 minutes, and
the bath liquid was drained.
In the step viii), 50°C water in about twice amount of the weight of the leather and the aqueous dispersion of the fluorine-containing polymer mentioned in the preparative examples (30 mass% concentration) in an amount of 6% of the weight of the leather were added to the drum and the drum was rotated at 50°C for 30 minutes. And then formic acid in an amount of 0.5 to 1% of the weight of the leather was added to the drum and the drum was rotated for 15 minutes to adjust pH of the bath at 3.3 to 3.7, and the bath liquid was drained.
After the final step ix), the leather was washed with flowing water and dried by air drying in a room. After drying, staking and toggling at 60°C according to the general procedure for leather making, the treated leather was subjected to the property tests.
Wet end Processing 2
A dry buffed chromium-tanned crust leather was treated according to the same steps i) to ix) as Wet end Processing 1.
In the washing steps i) and iii), water in an amount of about 6 times of the weight of the leather was added to the drum, the drum was rotated at 50°C for 10 minutes, and the bath liquid was drained. In the washing steps v) and vii), the similar processing was carried out except that the temperature was 40°C. In the washing step ix), the similar processing was carried out except that the temperature was 30°C.
In the neutralization step ii), ammonia water was added to the drum to adjust pH of the bath at 6.0 to 6.5 and the drum was rotated at 500C for about 60 minutes. After neutralization, the bath liquid was drained, and the neutralized leather was washed by water. In the step iv), 50°C water in about 3 times of the weight of the leather, synthetic
resin retanning agent in an amount of 10%, acid dyestuff (Sella Fast Brown CR : TFL) in an amount of 5%, waterproofing fat liquor (Leukotan NS3: LANXESS) in an amount of 8% and neat foot oil in an amount of 1% of the weight of the leather were added to the drum, and the drum was rotated at 50°C for 60 minutes while keeping pH at 5.5 to 6.5. And then formic acid in an amount of 3 to 4% of the weight of the leather was added to the drum and the drum was rotated more for 30 minutes to adjust pH of the bath at 3.3 to 3.7, and the bath liquid was drained.
In the step vi), 40°C water in about 3 times amount of the weight of the leather and metal retanning agent (Chromosal B : LANXESS) in an amount of 6% of the weight of the leather were added to the drum and the drum was rotated at 40°C for 60 minutes, and the bath liquid was drained.
In the step viii), 40°C water in about 4 times amount of the weight of the leather and the aqueous dispersion of the fluorine-containing polymer mentioned in the preparative examples (30 mass% concentration) in an amount of 12% of the weight of the leather were added to the drum and the drum was rotated at 40°C for 20 minutes. And then formic acid in an amount of 1.0 to 1.5% of the weight of the leather was added to the drum and the drum was rotated for 15 minutes to adjust pH of the bath at 3.3 to 3.7, and the bath liquid was drained. After the final step ix), the leather was washed with flowing water and dried by air drying in a room. After drying, staking and toggling at 60°C according to the general procedure for leather making, the treated leather was subjected to the property tests.
Wet end Processing 3
A wet shaved chromium-tanned leather was treated according to the steps i) to v) of Wet end Processing 1, and the following steps:
vi) fluorine-containing polymer treatment and drain vii) washing with water and drain
In the step vi), 50°C water in about twice amount of the weight of the leather and the aqueous dispersion of the fluorine-containing polymer mentioned in the preparative examples (30 mass% concentration) in an amount of 6% of the weight of the leather were added to the drum and the drum was rotated at 500C for 30 minutes, and then the bath liquid was drained.
After the final step vii), the leather was washed with flowing water and dried by air drying in a room. After drying, staking and toggling at 60°C according to the general procedure for leather making, the treated leather was subjected to the property tests.
Finishing Processing 1
The aqueous dispersion of the fluorine-containing polymer mentioned in the preparative examples was diluted with water to prepare the test solution for finishing processing which solid concentration was 3 mass%. The diluted solution (200 g) was sprayed by a spray gun to a suede leather (1 m2). The sprayed leather was heated in 60°C air for 2 minutes and followed by air drying in a room. After drying for 24 hours, the dried leather was subjected to the property tests.
Property tests of the treated leather
1. Feeling
The feeling of the treated leather was evaluated by hand touch for smoothness of surface and softness according to the following criteria
A : Soft (Good) , B : Medium , C : Stiff (Poor)
2. Water repellency
Water repellency of the treated leather was evaluated according to JIS L 1092. The wet test piece was compared with a wet comparison standard to grade 0, 50, 70, 80, 90 and 100 points in order of poor water repellency to excellent water repellency. At the case of middle between the grades, the middle of grades like as 75 between 70 and 80 points is given.
Table 1. Water repellency
Water repellency State
___No.
100 No wet or water droplets adhesion on surface
90 No wet but small water droplets adhesion on surface
80 Separate small water droplets-like wet on surface
70 Wet on half of surface and separate small wet which penetrates
50 Wet on whole surface 0 Wet on front and back whole surfaces
3. Oil repellency (According to AATCC Test Method 118-1992)
The oil repellency was expressed by a maximum point of the test liquid which passed the test. The oil repellency was evaluated as nine levels which were 0, 1, 2, 3, 4, 5, 6, 7 and 8 in order of a bad level to an excellent level. At the case of middle between the levels, the middle of levels like as 2-3 between 2 and 3 point is given.
Table 2. Oil repellency test liquid
The treated leathers were subjected to the property tests. (Table 3 to 6)
Table 3. Cow suede treated by Wet end processing 1
Table 6. Sheep suede treated by Finishing processing 1
Claims
1. A fluorine-containing polymer for leather treatment comprising a fluorine-containing polymer comprising repeating units derived from: (A) a monomer which comprises;
(a) a fluorine-containing monomer of the formula:
CH2=C(X)COO-Y-Rf, wherein X is a hydrogen atom, a monovalent organic group, or a halogen atom,
Y is a direct bond or a divalent organic group, and Rf is a fluoroalkyl group having 1 to 21 carbon atoms, wherein the monomer is polymerized in the presence of: (B) a mercapto functional organopolysiloxane.
2. The fluorine-containing polymer according to claim 1, wherein the monomer (A) comprises:
(b) optionally present, a monomer which does not contain a fluorine atom, and
(c) optionally present, a crosslinkable monomer, in addition to the fluorine-containing monomer (a).
3. The fluorine-containing polymer according to claim 1 or 2, wherein the fluorine-containing monomer (a) is a compound of the formula: CH2 =C (-X) -C (=0) -0-Y-Rf ( I ) wherein X is a hydrogen atom, an linear or branched alkyl group having 1 to 21 carbon atoms, a halogen atom, a CFX1X2 group (wherein X1 and X2 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or a iodine atom ), a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group, Y is a direct bond, an aliphatic group having 1 to 10 carbon atoms, an aromatic or cycloaliphatic group having 6 to 10 carbon atoms, a -CH2CH2N(R1)SO2- group (wherein R1 is an alkyl group having 1 to 4 carbon atoms.) or -CH2CH(O YX)CH2- group (wherein
Y1 is a hydrogen atom or an acetyl group.), and Rf is a linear or branched fluoroalkyl group having 1 to 21 carbon atoms.
4. The fluorine-containing polymer according to anyone of claims 1 to 3, wherein the fluorine-free monomer (b) is acrylates of the general formula:
CH2=CA1COOA2 wherein A1 is a hydrogen atom, a methyl group, or a halogen atom (for example, a chlorine atom, a bromine atom and a iodine atom) other than a fluorine atom, and A2 is an alkyl group represented by CnH2n+1 (n = 1 to 30).
5. The fluorine-containing polymer according to anyone of claims 1 to 3, wherein the crosslinkable monomer (c) is a fluorine-free monomer having at least two reactive groups and/or carbon-carbon double bonds.
6. The fluorine-containing polymer according to anyone of claims 1 to 5, wherein the mercapto functional organopolysiloxane (designated B') comprises siloxy units having the average formula:
(R2SiO)a(RRFSiO)b(RRsSiO)c where; a is 0-4000, b is 1-1000, c is 1- 1000,
R is independently a monovalent organic group, RF is a monovalent functional organic group, Rs is a monovalent mercapto functional organic group.
7. The fluorine-containing polymer according to claims 6, wherein RF is an amino functional organic group (RN).
8. The fluorine-containing polymer according to anyone of claims 1 to 7, wherein the mercapto group-containing silicone (B) is of the formula:
R1 R2 R3
R1— 0-(-SiO-)- (-SiO-JH-SiO-) — R1
A a B b R3 C I I
SH C
wherein R1 is a methyl group, a methoxy group, a phenyl group, or a hydroxyl group,
R2 is a methyl group, a methoxy group, a phenyl group, or a hydroxyl group, R3 is a methyl group, a methoxy group, a phenyl group, or a hydroxyl group,
R1 is a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, or Me3Si,
A is a divalent saturated hydrocarbon group having 1-10 carbon atoms which may be interrupted with one or two ether linkages,
B is a divalent saturated hydrocarbon group having 1-10 carbon atoms which may be interrupted with one or two ether linkages,
C is hydroxyls, amines, amides, sulfonamides, quaternaries, ethers, epoxy, phenols, esters, carboxyls, ketones, halogen-substituted alkyls or aryls, a, b, and c are integers showing the number of repeat units, a is from 0 to 4000, b is from 1 to 1000, , and c is from 0 to 1000.
9. The fluorine-containing polymer according to anyone of claims 1 to 8, wherein (A) the monomer which comprises;
(a) the fluorine-containing monomer of the formula:
CH2=C(X)COOYRf, wherein X is a hydrogen atom, a monovalent organic group, or a halogen atom,
Y is a direct bond or a divalent organic group, and Rf is a fluoroalkyl group having 1 to 21 carbon atoms, and
(b) a Cio-30-alkyl (meth)acrylate, and is emulsion-polymerized in water in the presence of: (B) the mercapto functional organopolysiloxane, to give the fluorine-containing polymer.
10. The fluorine-containing polymer according to any of claims 1 to 9, which has an anion group resulting from a polymerization initiator, and/or an anion group resulting from an anionic monomer.
11. The fluorine-containing polymer according to claim 10, wherein the anion group is at least one group selected from the group consisting of a carboxyl group, a phosphate group, a sulfonate group and a sulfate group.
12. The fluorine-containing polymer according to any of claims 1 to 11, wherein the Rf is a linear or branched fluoroalkyl group having 1 to 6 carbon atoms.
13. A treatment agent for leather, which comprises (1) the fluorine-containing polymer according to anyone of claims 1 to 12, and (2) a liquid medium.
14. The treatment agent according to claim 13, the liquid medium (2) is water and/or an organic solvent.
15. The treatment agent for leather according to anyone of claims 1 to 12, wherein the fluorine-containing polymer is dispersed in water in the presence of an anionic emulsifier.
16. The treatment agent for leather according to anyone of claims 1 to 12, wherein the fluorine-containing polymer is dispersed in water because of the anion group contained in a fluorine-containing polymer, and/or the anionic emulsifier.
17. A method of treating the leather, which comprises treating a leather with the treatment agent according to anyone of claims 13 to 16.
18. The method according to claim 17 which comprises applying the treatment agent containing a liquid medium to the leather and then removing the liquid medium.
19. A leather treated by the method according to claim 17 or 18.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US4020908P | 2008-03-28 | 2008-03-28 | |
| US61/040,209 | 2008-03-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2009119423A1 true WO2009119423A1 (en) | 2009-10-01 |
Family
ID=40591904
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2009/055382 WO2009119423A1 (en) | 2008-03-28 | 2009-03-12 | Polymer for leather treatment and leather treatment agent |
Country Status (2)
| Country | Link |
|---|---|
| TW (1) | TW200948973A (en) |
| WO (1) | WO2009119423A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010030041A1 (en) * | 2008-09-15 | 2010-03-18 | Daikin Industries, Ltd. | Fluorosilicones and surface treatment agent |
| WO2010044479A1 (en) * | 2008-10-13 | 2010-04-22 | Daikin Industries, Ltd. | Fluorine- and silicon-containing treatment agent for concretes |
| CN102676710A (en) * | 2012-05-29 | 2012-09-19 | 济南鲁日钧达皮革有限公司 | Method for preparing cleaned three-proofing cow split leather and prepared cleaned three-proofing cow split leather |
| WO2012146741A1 (en) * | 2011-04-28 | 2012-11-01 | Rhodia Operations | Copolymerised fatty body, preparation method thereof and uses of same |
| US9534343B2 (en) | 2012-10-18 | 2017-01-03 | The Chemours Company Fc, Llc | Partially fluorinated copolymer emulsions containing fatty acids and esters |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116444737B (en) * | 2023-04-26 | 2023-10-10 | 四川大学 | Cationic acrylic resin retanning agent and preparation method thereof |
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| WO2005087826A1 (en) * | 2004-03-12 | 2005-09-22 | Daikin Industries, Ltd. | Polymer and treatment agent for treating leather and protein fiber |
| WO2006121171A1 (en) * | 2005-05-09 | 2006-11-16 | Daikin Industries, Ltd. | Fluorosilicones and fluorine- and silicon-containing surface treatment agent |
| WO2008014239A2 (en) * | 2006-07-27 | 2008-01-31 | Dow Corning Corporation | Greaseproof paper |
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| WO2005087826A1 (en) * | 2004-03-12 | 2005-09-22 | Daikin Industries, Ltd. | Polymer and treatment agent for treating leather and protein fiber |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010030041A1 (en) * | 2008-09-15 | 2010-03-18 | Daikin Industries, Ltd. | Fluorosilicones and surface treatment agent |
| WO2010044479A1 (en) * | 2008-10-13 | 2010-04-22 | Daikin Industries, Ltd. | Fluorine- and silicon-containing treatment agent for concretes |
| WO2012146741A1 (en) * | 2011-04-28 | 2012-11-01 | Rhodia Operations | Copolymerised fatty body, preparation method thereof and uses of same |
| US20140057956A1 (en) * | 2011-04-28 | 2014-02-27 | Rhodia Operations | Copolymerised fatty body, preparation method thereof and uses of same |
| CN102676710A (en) * | 2012-05-29 | 2012-09-19 | 济南鲁日钧达皮革有限公司 | Method for preparing cleaned three-proofing cow split leather and prepared cleaned three-proofing cow split leather |
| CN102676710B (en) * | 2012-05-29 | 2015-03-25 | 济南鲁日钧达皮革有限公司 | Method for preparing cleaned three-proofing cow split leather and prepared cleaned three-proofing cow split leather |
| US9534343B2 (en) | 2012-10-18 | 2017-01-03 | The Chemours Company Fc, Llc | Partially fluorinated copolymer emulsions containing fatty acids and esters |
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|---|---|
| TW200948973A (en) | 2009-12-01 |
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