WO2004016584A1 - Compose urethane fluore et utilisation de ce compose - Google Patents

Compose urethane fluore et utilisation de ce compose Download PDF

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Publication number
WO2004016584A1
WO2004016584A1 PCT/JP2003/010242 JP0310242W WO2004016584A1 WO 2004016584 A1 WO2004016584 A1 WO 2004016584A1 JP 0310242 W JP0310242 W JP 0310242W WO 2004016584 A1 WO2004016584 A1 WO 2004016584A1
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group
carbon atoms
fluorine
atom
hydrogen
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Japanese (ja)
Inventor
Ikuo Yamamoto
Kayo Kusumi
Takuya Yoshioka
Fumihiko Yamaguchi
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Daikin Industries Ltd
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Daikin Industries Ltd
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Priority to JP2004528862A priority Critical patent/JPWO2004016584A1/ja
Priority to AU2003255001A priority patent/AU2003255001A1/en
Publication of WO2004016584A1 publication Critical patent/WO2004016584A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
    • C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C323/52—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/30—Only oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3802—Low-molecular-weight compounds having heteroatoms other than oxygen having halogens
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
    • 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
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/402—Amides imides, sulfamic acids
    • D06M13/432—Urea, thiourea or derivatives thereof, e.g. biurets; Urea-inclusion compounds; Dicyanamides; Carbodiimides; Guanidines, e.g. dicyandiamides
    • 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
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • D06M15/576—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them containing fluorine

Definitions

  • the present invention relates to a novel fluorine-containing urethane compound, a composition containing the same, and a treating agent.
  • the fluorine-containing urethane compound of the present invention is suitable for treating (especially, surface treating) various substrates, for example, ⁇ products.
  • Fluorine-containing compounds have the advantage of having excellent properties such as heat resistance, oxidation resistance, and weather resistance. Utilizing the property that the free energy of the fluorine-containing compound is low, that is, the property that it is hard to adhere, the fluorine-containing compound is used, for example, as a water and oil repellent and an antifouling agent.
  • Fluorine-containing compounds that can be used as water- and oil-repellents include, for example,
  • JP-B2-60702, JP-B2-60702, and JP-B-63-45665 examples include, for example, USP 5414111, USP 5565564, EP-A-383365, JP-A-7-505190 (WO 93/17165), WO 91/25308, USP 3547894, JP-T 2001-525010 ( WO 98/51727), JP 2001-525871 Gazette (WO 98/51723), JP 2001-25827
  • JP 525872 (WO 98/51726)
  • JP-T 2001-525874 (WO 98/51724)
  • JP-T 2002-504938 (WO 98/51725).
  • An object of the present invention is to provide a novel fluorine-containing compound that gives high water / oil repellency.
  • I is a group obtained by removing Isoshiana one bets group from polyisocyanate compounds
  • X 1 is a divalent organic residue obtained after active atom and active hydrogen desorbed from the chain transfer agent ,
  • X 2 is a trivalent linear or branched aliphatic group having 2 to 5 carbon atoms
  • Rf 1 is the formula:
  • a 1 is a direct bond or a divalent organic group having 1 to 21 carbon atoms
  • B 11 and B 12 are a hydrogen atom or a methyl / le group
  • B 13 is a hydrogen atom or a chlorine atom
  • B 21 is a hydrogen atom or an R′-A 2 — group (where R ′ is a linear or branched hydrocarbon group having 1 to 21 carbon atoms which may have an oxygen atom; 2 is a direct bond, an oxygen atom or a divalent organic group having 1 to 21 carbon atoms.
  • a is a number from 1 to 20;
  • b and c are numbers from 0 to 20.
  • R 1 and R 2 are a hydrogen atom or an alkyl group having 1 to 20 carbon atoms
  • p is a number from 1 to 20;
  • n is a number from 1 to 15;
  • n is a number from 0 to 14;
  • I is a group obtained by removing an isocyanate group from a polyisocyanate compound.
  • a polyisocyanate compound is a compound having at least two isocyanate groups.
  • the polyisocyanate compound may be an aliphatic polyisocyanate, an aromatic polyisocyanate, or a derivative of these polyisocyanates.
  • aliphatic polyisocyanates especially aliphatic diisocyanates
  • Aromatic polyisocyanates, especially aromatic diisocyanates are Methylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated dihexyl hexylmethane diisocyanate.
  • Ti “1” are 1, Rerange, etc., "Diphenyl methane diisocyanate” (MD I), Trizin diisocyanate, and Naphthalenedi isocyanate.
  • Polyisocyanate compounds include diisocyanate, polymeric MD I (diphenylmethane diisocyanate), modified isocyanate (particularly, trimer of diisocyanate, or adduct of polyhydric alcohol and diisocyanate). ) Is preferable.
  • modified isocyanates include urethane-modified diisocyanate, arophanate-modified diisocyanate, biuret-modified diisocyanate, isocyanurate-modified diisocyanate, carposimid-modified diisocyanate, uretonimine-modified diisocyanate, and uretonimine-modified diisocyanate. It is.
  • X 1 is a divalent organic residue obtained after two atoms of one active atoms and one active hydrogen atom from a chain transfer agent is eliminated.
  • Chain transfer agents are compounds having at least one active atom (eg, a hydrogen atom and a halogen atom (eg, a chlorine atom and a bromine atom)) and at least one active hydrogen atom.
  • chain transfer agents examples include aromatic hydrocarbons (eg, toluene), amine compounds (eg, triethylamine), hydrogenated hydrocarbons (eg, carbon tetrachloride, chloroform, carbon tetrabromide), water, Alcohols (eg, ethanol) which may be halogen-substituted; and thionoles (eg, 2-mercaptoethanol, 2-chloroethanol, 1-butanethiol, laurylmercaptan) which may be halogen-substituted.
  • aromatic hydrocarbons eg, toluene
  • amine compounds eg, triethylamine
  • hydrogenated hydrocarbons eg, carbon tetrachloride, chloroform, carbon tetrabromide
  • Alcohols eg, ethanol
  • thionoles eg, 2-mercaptoethanol, 2-chloroethanol, 1-butanethiol, laurylmercaptan
  • Examples of X 1 is one ⁇ _ one C CD 1 (D 1 2) - (where, D "is a halogen atom, D 1 2 Ha port Gen atom or a hydrogen atom), at least one sulfur atom, a nitrogen atom Or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have an oxygen atom, and an aromatic hydrocarbon group having 6 to 20 carbon atoms.
  • X 2 is a trivalent linear or branched aliphatic group having 2 to 5 carbon atoms. Examples of X 2 are,> CH 2 CH- (rather one CH 2 CH),> CHCH 2 CH. One (-CH 2 CH 2 CH ⁇ ), One C3 ⁇ 4CHC3 ⁇ 4—
  • CHCH 2 CH 2 CH 2 CH 2 CH 2 - is (_CH 2 CH 2 CH 2 CH 2 CH ⁇ ).
  • Rf 1 is the formula:
  • R f is a perfluoroalkyl group having 2 to 21 carbon atoms
  • a 1 is a direct bond or a divalent organic group having 1 to 21 carbon atoms
  • B 11 and B 12 are a hydrogen atom or a methyl group
  • B 13 is a hydrogen atom or a chlorine atom
  • B 21 is hydrogen or R '-A 2 - in group (wherein, R' is a linear or branched hydrocarbon group may carbon number 1 to 21 which have an oxygen atom, A 2 Is a direct bond, an oxygen atom or a divalent organic group having 1 to 21 carbon atoms.)
  • a is a number from 1 to 20,
  • b and c are numbers from 0 to 20. ]
  • Rf 1 group - (- CH 2 - ( Rf-A 1 -) C (_B U) -) a - group, one (- CH 2 - (B 21 _) C (- B 12) -) b - group Contact and - (-CH 2 -C (-CI) (-B 13) -) c - the order of the groups Nakuteyore were as display.
  • each group may be a random shape, even proc shaped yo les.
  • R f is a number from 2 to 21 per full O b alkyl group carbon.
  • the carbon number of R f may be, for example, from 3 to 12, especially from 4 to 8.
  • a 1 is a direct bond or a divalent organic group having 1 to 21 carbon atoms.
  • An example of one A group is of the formula:
  • R 11 is hydrogen or an alkyl group having 1 to 20 carbon atoms
  • R 12 is an alkylene group having 1 to 20 carbon atoms
  • R 13 is hydrogen or a methizole group
  • Ar is an arylene group (for example, having 6 to 20 carbon atoms) which may have a substituent, and p is :! It is an integer of ⁇ 10. ]
  • the A 1 group may in particular be an alkylene group having 1 to 5 carbon atoms.
  • B 11 and B 12 are a hydrogen atom or a methyl group.
  • B 13 is a hydrogen atom or a chlorine atom.
  • B 21 is hydrogen or R '-A 2 - is a radical.
  • the R 'group is a linear or branched alkyl group having 1 to 21 carbon atoms and a (poly) oxyalkyl group which may have an oxygen atom.
  • the number of carbon atoms of the R ′ group may be, for example, from 3 to 12, especially from 4 to 8.
  • a is a number from 1 to 20.
  • a is, for example, 1 to 1 °, particularly 1 to 5.
  • b and c are numbers from 0 to 20.
  • b and c may for example be from 0 to 10, especially from 0 to 5.
  • R 1 and R 2 are a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
  • the alkyl group may have, for example, 1 to 10 carbon atoms.
  • ⁇ is a number from 1 to 20.
  • p may for example be 1 to 10, especially 1 to 5.
  • m is a number from 1 to 15.
  • m is, for example, 1 to 10, particularly 1 to 5.
  • n is a number from 0 to 14.
  • n can be, for example, 0-10, especially 0-5.
  • the sum of m and n is 2 to 15.
  • the sum of m and n may be, for example, from 2 to 10, in particular from 2 to 5.
  • fluorine-containing urethane compound (1) of the present invention are as follows.
  • the fluorine-containing urethane compound (1) of the present invention is, for example, a polyisocyanate compound,
  • the total number of moles of the fluorinated alcohol (i) and the chlorinated ether alcohol (ii) relative to 1 mole of the isocyanate group of the polyisocyanate compound is 0.5 to 2.0, particularly 0. It is preferably from 8 to 1.5 mol.
  • Hydrochloride ether alcohol (ii) is a component that may or may not be used. This reaction is preferably performed in the presence of a solvent at a temperature of 0 to 150 ° C. for 0.1 to: L 0 hours.
  • Solvents are organic solvents that are inert to isocyanates.
  • solvents examples include hydrocarbons, ketones, halogenated hydrocarbons (eg, chlorinated hydrocarbons).
  • the amount of the solvent may be 20 to 500 parts by weight, for example 100 to 300 parts by weight, based on 100 parts by weight of the reactants.
  • catalysts include amines (eg, monoamine, diamine, triamine, alcoholamine, etheramine), organic metals (eg, metal salts of organic acids (eg, di-n-butyltin dilaurate)). It is.
  • the amount of catalyst may be from 0.001 to 0.5 parts by weight, for example from 0.01 to 0.3 parts by weight, based on 100 parts by weight of the reactants.
  • the fluorinated alcohol (i) has, for example, the formula:
  • a chlorine-containing monomer represented by the formula (I) can be obtained by polymerizing a chlorine-containing monomer represented by the formula (I) with a chain transfer agent (ie, a compound having X 1 and an active atom and an active hydrogen atom).
  • a chain transfer agent ie, a compound having X 1 and an active atom and an active hydrogen atom.
  • Rf, A ⁇ B u, B 12, B 13, B 21 is as defined above.
  • fluorine-containing monomer is a fluoroalkyl group-containing (meth) acrylate represented by the following general formula.
  • R is a fluoroalkyl group having 2 to 21 carbon atoms
  • B 11 is hydrogen or a methynole group
  • a 11 is a divalent organic group.
  • a 11 is 1-2 0 straight-chain or branched alkylene group having carbon atoms, -3 0 2 ⁇ (1 21) 1 22 -? Group or - ⁇ ⁇ 1 2 ⁇ ⁇ (01 23 ) ⁇ ? 1 2 — group
  • 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 an asinole group having from 10 to 10 carbon atoms.
  • fluoroalkyl group-containing (meth) acrylate examples include the following.
  • Rf is a fluoroalkyl group having 2 to 21 carbon atoms
  • R 1 is hydrogen or an alkyl group having 1 to 10 carbon atoms
  • R 2 is an alkylene group having 1 to 10 carbon atoms
  • R 3 is hydrogen or A tyl group
  • Ar is an arylene group which may have a substituent
  • n is an integer of 1 to L0.
  • fluorine-containing monomer examples include as follows.
  • Non-fluorinated monomers are fluorine-containing unsaturated unsaturated monomers.
  • the non-fluorinated monomer include ethylene, vinyl acetate, acrylonitrile, styrene, polyethylene glycol mono (meth) acrylate, polypropylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, and methoxy polypropylene Examples include, but are not limited to, recall (meth) acrylate, bier alkyl ether, isoprene, and the like.
  • the non-fluorinated monomer may be a (meth) acrylate containing an alkynole group.
  • the alkyl group may have 1 to 30, for example, 6 to 30, for example, 10 to 30 carbon atoms.
  • non-fluorine monomers have the general formula:
  • a 21 is a hydrogen atom or a methyl group
  • May be an acrylate represented by An example of a non-fluorinated monomer is stearyl alcohol.
  • chlorine-containing monomers examples include vinyl chloride vinylidene and vinylidene chloride.
  • Examples of the fluorinated alcohol (i) include (a) a homopolymer of a fluoroalkyl group-containing acrylate, (b) a copolymer of a fluoroalkyl group-containing acrylate and stearyl acrylate, and (c) a fluoroalkyl-containing acrylate. (D) a copolymer of vinylidene chloride or vinylidene chloride; and (d) a copolymer of a fluoroalkyl group-containing atalylate, stearyl atalylate, and salted vinyl or salted vinylidene.
  • Non-fluorine monomer and chlorine-containing monomer in fluorinated alcohol (i) May be, for example, from 0.1 to 1.0 mol, especially from 0.2 to 0.5, per mol of the fluorinated monomer.
  • the chlorine-containing ether alcohol (i i) has, for example, the formula:
  • a chlorine-containing cyclic ether compound represented by An example of a chlorinated cyclic ether compound is epichlorohydrin.
  • Examples of the chlorine-containing ether alcohol (ii) is, H (- 0CH 2 C ( CH 2 C1) H -) p - 0CH a 3 [p is a number from 1 to 2 0. ].
  • the fluorine-containing urethane of the present invention may be contained in a composition.
  • the composition may be in the form of a solution or an emulsion.
  • the solution-type composition comprises a fluorinated urethane compound and a solvent.
  • the solvent especially, organic solvent
  • the emulsion-type composition contains a fluorine-containing urethane compound, an emulsifier, and water.
  • the emulsion-type yarn composition may further contain an organic solvent, particularly an organic solvent that dissolves the fluorine-containing urethane compound.
  • the emulsifier may be nonionic or ionic (eg, cationic, anionic, amphoteric).
  • the amount of the fluorine-containing urethane compound may be 0.1 to 70% by weight, for example, 5 to 30% by weight.
  • the amount of the emulsifier is 0.1 to 30 parts by weight, for example, 2 to 10 parts by weight, and the amount of water is 3 to 100 parts by weight of the fluorine-containing polyurethane compound.
  • the amount of the organic solvent may be 0 to 99.9 parts by weight, for example 70 to 95 parts by weight, and the amount of the organic solvent may be 10 to 200 parts by weight, for example 50 to 100 parts by weight.
  • the fluorinated urethane compound of the present invention can be used as a surface treatment agent for treating the surface of various articles, and modifies the surface of the article to provide, for example, water / oil repellency.
  • the fluorine-containing urethane compound of the present invention has excellent water and oil repellency and is molecularly stable High durability and high durability. Therefore, when the treatment is performed using the fluorinated urethane compound, the treated material can maintain excellent texture for a long period of time.
  • an arbitrary method is adopted according to the form of the surface treatment agent.
  • a method of attaching a treatment liquid to at least the surface of the object to be treated by a method such as dip coating and drying is used.
  • the emulsion type it is desirable to carry out curing after drying for the purpose of continuity of the fine particles of the treatment agent, welding to the agent to be treated, and penetration.
  • great water and oil repellency can be expected.
  • the solvent type has an advantage that a sufficiently large water and oil repellency can be expected without performing curing or cleaning since a film is formed on the object to be processed by drying.
  • drying temperature can be selected arbitrarily, but in the case of an emulsion type, it may be room temperature, and drying with hot air at 50 to 120 ° C is efficient. In the case of a solvent type, drying at a temperature of about 50 to 150 ° C is appropriate.
  • Examples of the object to be treated with the surface treatment agent of the present invention include various objects.
  • Examples of objects to be treated are textiles, glass, paper, wood, leather, fur, asbestos, bricks, cement, metals and oxides, ceramic products, plastics, painted surfaces and plasters.
  • the article to be treated is preferably a textile, such as a carpet.
  • a textile such as a carpet.
  • fiber products animal and plant natural fibers such as cotton, hemp, wool, and silk; polyamide, polyester, poly.vier alcohol, synthetic fibers such as polyacrylonitrile, polychlorinated vinyl, polypropylene, etc .; semi-synthetic fibers such as rayon and acetate; and glass fibers.
  • inorganic fibers such as carbon fibers and asbestos fibers, or mixed fibers thereof.
  • the textile product may be in any form of fiber, yarn, cloth and the like.
  • the carpet When treating a carpet according to the method of the present invention, the carpet may be formed after treating the fibers or yarns, or the formed carpet may be treated.
  • Surface treatment agent, a fluorine-containing urethane compound 0. 0 2 3 0 wt 0/0, preferably 0. 0 can be contained in a state diluted 2 to 1 0% by weight.
  • Fluorine-containing acrylate monomer CH 2 CHCOOCH 2 CH 2 C 8 F 17 144.7 g (275 mmol), 2-mercaptoethanol 7.8 g (200 mmol), methyl isobutyl ketone 176.2 g Stirring rod, thermometer, nitrogen inlet tube Then, the mixture was placed in a 500 ml square flask equipped with a cooling tube, stirred, and heated to 70 ° C. Thereafter, 0.154 g of 2,2'-azobisisobutyronitrile was injected and reacted for 5 hours. It was confirmed by gas chromatography that 17FA reacted 98.1%. The reaction was performed under a nitrogen stream.
  • Hexamethylene diisocyanate adduct to the same trimethylolpropane used in Production Example 3 (Sumijur HT, manufactured by Sumika Bayeno Perethane Co., Ltd., isocyanate content is 13%) 18 g (55.7 mmol), di- n-butyl tin dilate
  • the water repellency was evaluated based on the maximum value of the isopropyl alcohol (IPA) content (vol%) of the test solution that passed, and was evaluated as Fail, 0, 1, 2, 3 from poor water repellency to a good level. , 4, 5, 6, 7, 8, 9, and 10 are evaluated on a 12-point scale.
  • test was performed according to AATCC Test Method 123-1989.
  • the antifouling property was evaluated using a gray scale for discoloration and fading, and compared with the cartilage sample before the antifouling test, from a level of significant discoloration to a level of no discoloration. Evaluate in 9 levels of 2, 2-3, 3, 3-4, 4, 4-5 and 5.
  • Example 1 the fluorinated urethane compound (2) synthesized in Production Example 2 was emulsified. 97.5 g of water was added to 2.5 g of this milk solution to make a total amount of 100 g, which was used as a treatment liquid. A carpet was treated with a repellent according to Example 1.
  • Example 1 the fluorine-containing urethane compound (3) synthesized in Production Example 3 was subjected to milking. 97.5 g of water was added to 2.5 g of this emulsion to make a total amount of 100 g, which was used as a treatment liquid.
  • Implementation ⁇ Power according to column 1 ⁇ . was treated with a repellent. Next, a water repellency test, an oil repellency test, and an antifouling tt test were performed. Table 3 shows the results. Comparative Example 1
  • Example 1 the fluorinated urethane compound (C 3) synthesized in Comparative Production Example 3 was emulsified. 97.5 g of water was added to 2.5 g of this emulsion to make a total amount of 100 g, which was used as a treatment liquid. A carpet was treated with a repellent according to Example 1.
  • This emulsified liquid lg and a stin block agent (a mixture of a phenol / formaldehyde condensate and polymethacrylic acid at a weight ratio of 50:50) (hereinafter referred to as “stin block agent A”) 5 g and water Diluted to 1000 g.
  • stin block agent A a mixture of a phenol / formaldehyde condensate and polymethacrylic acid at a weight ratio of 50:50
  • the pH of this A treatment liquid was obtained by adding a 10% aqueous solution of sulfamic acid to 1.5.
  • Example 4 the fluorinated urethane compound (2) synthesized in Production Example 2 was emulsified. 1 g of this emulsion, 5 g of stin block agent A and water were added to dilute the mixture to a total volume of 1000 g. A 10% aqueous solution of sulfamic acid was added to adjust the pH to 1.5 to obtain a treatment solution. A carpet was treated with a repellent according to Example 4.
  • Example 4 the fluorinated urethane compound (3) synthesized in Production Example 3 was emulsified. 1 g of this milky drier, 5 g of stimplock agent A and water were added to dilute so that the total amount would be 1000 g. A treatment solution was obtained by adding a 10% aqueous solution of sulfamic acid so that the pH of the solution became 1.5. A carpet was treated with a repellent according to Example 4.
  • Example 4 the fluorinated urethane compound (C 1) synthesized in Comparative Production Example 1 was emulsified. 1 g of this emulsion, 5 g of stin blocker A and water were added to dilute the mixture so that the total amount was I000 g. 10% sulfamine so that its pH is 1.5 An aqueous acid solution was added to obtain a treatment liquid. C then water repellency test were processed Bachizai car pets preparative analogously to Example 4, the oil repellency test were conducted antifouling property test. Table 4 shows the results. Comparative Example 4
  • Example 4 the fluorinated urethane compound (C 2) synthesized in Comparative Production Example 2 was emulsified. 1 g of this emulsified solution, 5 g of stin block agent A and water were added to dilute so that the total amount was 1000 g. A 10% sulfamic acid solution was added to adjust the pH to 1.5 to obtain a treatment solution. A carpet was treated with a repellent according to Example 4. Next, a water repellency test, an oil repellency test, and an antifouling test were performed. Table 4 shows the results. Comparative Example 5
  • Example 4 the fluorinated urethane compound (C 3) synthesized in Comparative Production Example 3 was emulsified. 1 g of this emulsion, 5 g of stin block agent A and water were added to dilute so that the total amount was 1000 g. A 10% aqueous solution of sulfinic acid was added to adjust the pH to 1.5 to obtain a treatment solution. A carpet was treated with a repellent according to Example 4. Next, a water repellency test, an oil repellency test, and an antifouling test were performed. Table 4 shows the results. Comparative Example 6
  • the fluorine-containing urethane compound of the present invention imparts various excellent properties to an object to be treated as a component of a surface treatment agent.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Combustion & Propulsion (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

L'invention concerne un composé uréthane fluoré représenté par la formule générale I[-NHC(=O)O-X1-Rf1-R1)]m[-NHC(=O)O-(X2(-CH2Cl)O)p-R2]n (1), dans laquelle I est un groupe formé par suppression d'un groupe isocyanate d'un composé polyisocyanate, X1 est un résidu organique divalent obtenu par élimination d'un atome actif et d'un hydrogène actif d'un agent de transfert de chaînes, X2 est un groupe aliphatique trivalent C2-5 linéaire ou ramifié, Rf1 est un groupe divalent représenté par la formule -(-CH2-(Rf-A1-)C(-B11)-)a-(-CH2-(B21-)C(-B12)-)b-(-CH2-C(-Cl)(-B13)-)c- et R1 et R2 représentent chacun un atome d'hydrogène ou un groupe alkyle C1-20. Ce composé confère un bon caractère hydrofuge et oléofuge.
PCT/JP2003/010242 2002-08-13 2003-08-12 Compose urethane fluore et utilisation de ce compose Ceased WO2004016584A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2004528862A JPWO2004016584A1 (ja) 2002-08-13 2003-08-12 含フッ素ウレタン化合物およびその用途
AU2003255001A AU2003255001A1 (en) 2002-08-13 2003-08-12 Fluorinated urethane compound and use thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2002/235683 2002-08-13
JP2002235683 2002-08-13

Publications (1)

Publication Number Publication Date
WO2004016584A1 true WO2004016584A1 (fr) 2004-02-26

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PCT/JP2003/010242 Ceased WO2004016584A1 (fr) 2002-08-13 2003-08-12 Compose urethane fluore et utilisation de ce compose

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Country Link
JP (1) JPWO2004016584A1 (fr)
AU (1) AU2003255001A1 (fr)
WO (1) WO2004016584A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3197865A1 (fr) * 2014-09-26 2017-08-02 The Chemours Company FC, LLC Uréthanes sulfonés fluorés, non fluorés ou partiellement fluorés
JP2024125204A (ja) * 2023-03-03 2024-09-13 ダイキン工業株式会社 含フッ素化合物

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4486391A (en) * 1981-08-25 1984-12-04 Dainippon Ink And Chemicals, Inc. Separation and recovery of ionic substances by fluorine-containing compound
JPS63245492A (ja) * 1987-03-31 1988-10-12 Hitachi Maxell Ltd 潤滑剤とこれを用いた磁気記録媒体
JPH0693234A (ja) * 1992-09-14 1994-04-05 Dainippon Ink & Chem Inc 水性艶出し組成物
EP0919576A1 (fr) * 1996-06-13 1999-06-02 Daikin Industries, Limited Nouveau copolymere, son procede de preparation et son utilisation

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4486391A (en) * 1981-08-25 1984-12-04 Dainippon Ink And Chemicals, Inc. Separation and recovery of ionic substances by fluorine-containing compound
JPS63245492A (ja) * 1987-03-31 1988-10-12 Hitachi Maxell Ltd 潤滑剤とこれを用いた磁気記録媒体
JPH0693234A (ja) * 1992-09-14 1994-04-05 Dainippon Ink & Chem Inc 水性艶出し組成物
EP0919576A1 (fr) * 1996-06-13 1999-06-02 Daikin Industries, Limited Nouveau copolymere, son procede de preparation et son utilisation

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
KIM, DOMG-KWON ET AL: "Synthesis of Urethane Graft Copolymers with Perfluoroalkyl and Silicone-Containing Side Chains and their Surface Properties.", JOURNAL OF APPLIED POLYMER SCIENCE, vol. 74, no. 8, 1999, pages 2029 - 2038, XP002974966 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3197865A1 (fr) * 2014-09-26 2017-08-02 The Chemours Company FC, LLC Uréthanes sulfonés fluorés, non fluorés ou partiellement fluorés
JP2024125204A (ja) * 2023-03-03 2024-09-13 ダイキン工業株式会社 含フッ素化合物
JP7671014B2 (ja) 2023-03-03 2025-05-01 ダイキン工業株式会社 含フッ素化合物
JP2025111538A (ja) * 2023-03-03 2025-07-30 ダイキン工業株式会社 含フッ素化合物

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AU2003255001A1 (en) 2004-03-03
JPWO2004016584A1 (ja) 2005-12-02

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