JPH06506966A - Fluorine-effect oil- and water-repellent compositions - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Fluorine-effect oil- and water-repellent composition Background of the invention Technical field The present invention relates to aqueous compositions containing fluorochemical oils and water repellents. present invention Also, the fluorine effect of fluorochemical oil- and water-repellents (Fluorine The present invention also relates to reagents that enhance The present invention relates to a method for providing oil- and water-repellent properties to materials.

Description of related technology Water-1 oil- and soil-repellent finishes containing fluorochemical reagents or compositions are well Are known. However, a significant drawback of such finishes lies in their high price.

Therefore, so-called "extenders" have been developed to reduce the price. Revised High quality synthetic resins, waxes, paraffin emulsions and MjEl products are used for this purpose. It is used for.

U.S. Pat. No. 3,849,521 (Ktrimoto et al.) discloses that fluoroalkyl Polymers containing monomer units containing le and the following formula % formula % (In the formula, R, , R, and R8 represent a hydrogen atom or a methyl group, and R4bac (represents l-1-alkyl group); and the following formula: %formula% (wherein R2 represents a hydrogen atom or a methyl group) Oil- and water-repellent compositions containing additional copolymers are described.

U.S. Pat. No. 4,834.784 (Deiner et al.) describes The use of blocked incyanate compounds has been described, and The isocyanate is diphenylmethane diiso having a molecular weight of at least 450. Cyanate or isocyanate compound.

Summary of the invention The present invention is a fluorine-effect oil- and water-repellent composition comprising: (A) Fluorocarbon Mikal's oil- and water-repellent; (B) (i) seven months of formula ■ CR+Rt=CRsRa (V) (In the formula, each R+, Rz, Rs and R4 independently represents hydrogen, halogen, or organic groups such as alkyl, carboxyl or acyloxyalkyl (i.e. -CO □A polymerized unit derived from (representing alkyl); (11) Monomer of formula ■ CHz=CRsX (■) (In the formula, R2 represents a hydrogen atom or a methyl group, and X interacts with the fibrous substrate. a polymerized unit derived from a component comprising a functional group that can be used; copolymer extender; and (C-based isocyanate extract) A composition comprising: a tender;

The present invention also provides substrates treated with the fluorine effect compositions described above as well as Fluorochemistry comprising the step of blending a chemical reagent with the above components (B) and (C) This invention relates to a method for enhancing the fluorine effect of Mical's oil- and water-repellents.

The compositions of the invention contain at least one component of each of the two classes of extenders. It consists of members. This combination enhances the fluorine effect of fluorochemical reagents and The price of fluorochemicals can be compared with the individual characteristics of each class of extenders. much lower than would be expected based on gender.

Detailed description of the invention Component (A) in the compositions of the present invention contains a plurality of fluoroaliphatic (!p, Rf) groups. fluorochemical oil- and water-repellent agents. Such reagents are Well-known to the industry and numerous (e.g. 5COTCHCARD) (Trademark) Fabric Protector, 3M) is commercially available as a prepared formulation.

Generally, fluorochemical reagents useful in the present invention are fluorinated, stable and is inert, non-polar, preferably saturated, -valent, and a fluorocarbon compound containing one or more fluoroaliphatic groups R, which are both oleophobic and hydrophobic; e Rf comprising a chemical compound or polymer, preferably at least 3 carbons elementary atoms, more preferably from 3 to about 20 carbon atoms, and most preferably from about 6 to about 20 carbon atoms. Contains about 14 carbon atoms. R, is a straight chain, branched chain or cyclic fluorinated alkali Kylene group or a combination thereof, or with them a straight chain, branched chain or ring Rf is preferably a polymerizable olefin, which may include a combination with an alkylene group such as having systematic unsaturation, and optionally catenary heteroatoms, e.g. oxygen, also divalent or hexavalent sulfur, or nitrogen. Preferably contains fluorine, more preferably about 50 to about 78% by weight of fluorine. The terminal portion of the f group contains a fully fluorinated end group, which end group is at least It is preferable to contain 7 fluorine atoms, for example, CFzChCFz-1 (CF 3) 2CF-1CFgSFs, etc. Perfluorinated fatty acid groups (i.e., formula C, h , 1*+) is the most preferred embodiment of R.

Examples of fluorochemical reagents include, for example, R1-containing urethanes, ureas, esters, etc. , amines (and their salts), amides, acids (and their salts), carbodiimides, guani gin, allophthanate, biuret, and compounds containing two or more of these groups , as well as mixtures and blends thereof.

Useful fluorochemical polymers containing R2 groups include the fluorochemical acrylic ester and/or methacrylate monomer and a copolymerizable monomer such as fluorine. Containing and fluorine-free monomers, such as methyl methacrylate, butyl acrylate , octadecyl methacrylate, poly(oxyalkylene) polyol oligomer - and polymeric acrylate and methacrylate esters, e.g. ethylene) glycol dimethacrylate, glycidyl methacrylate, ethylene vinyl acetate, vinyl chloride, vinylidene chloride, vinylidene fluoride olide, acrylonitrile, vinyl chloroacetate, isoprene, chlorobrane , styrene, butadiene, vinyl pyridine, vinyl alkyl ether, vinyl Alkyl ketones, acrylic and methacrylic acids, 2-hydroxyethyl acrylate salt, N-methylolacrylamide, 2-(N,N,N-)limethylammo copolymers with ethyl methacrylate, etc.

Certain fluorochemical reagents include US Pat. No. 2,803,615 (Ahlbrecht et al.), No. 2,934,450 (Brown), No. 3.068.187 (Bolstad et al.), No. 3.09 No. 4,547 (Heine), No. 3,329,661 (Smith et al.), No. 3 ．． No. 341,497 (Sherman et al.), No. 3.398,182 (Guen thner et al.), No. 3,458,571 (Tokoli), No. 3.462.2 No. 96 (Reynolds et al.), No. 3,574,791 C5berman et al. ), No. 3.728.151 (Sherman et al.), No. 3.896.251 ( Landucc i), No. 3.916,053 (Sherman et al.), No. 4, No. 013,627 (Temple), No. 4,024,178 (Landucc. i), No. 4,029,585 (Detter), No. 4,034,964 (S. Herman et al.), No. 4,144,367 (Landucci), No. 4,16 No. 0.777 (Loudas), No. 4.165.338 CKatsushim a et al.), No. 4,190,545 (Marshall), No. 4.215,205 No. (Landucci), No. 4,264,484 (Patel), No. 4,32 No. 5,857 (Chaspaneria et al. No. 4,340,749 (Pate) l), No. 4,401,780 (Steel), No. 4,426,476 ( Chaog), No. 4,525,305 (Patel), No. 4,525,4 No. 23 (Lynn et al.), No. 4,529,658 (Schwartz et al.), No. No. 4.540.479 (Chang et al.), No. 4.560.487 (Brink ley), No. 4,564,366 (Patel), No. 4.565.641 (Chang et al.), No. 4,566.981 (Homells), No. 4.57 No. 9,924 (Schwartz et al.), No. 4,582.882 (Lynn et al.), No. 4,606,737 (Stern), No. 4,668.406 (C Hang), No. 4,668,726 (Flowells), Agent Case No. No. 4434811 SASA (assigned together with and issued on the same day III) Includes those that have been

Component (B) in the composition of the present invention is (i) 2V's Seven Tsuma CR+Rt=CR+R4(V) (In the formula, each of R, , R, , R, and R4 is independently hydrogen, halogen, or a polymerized unit derived from (representing a machine group); and a monomer of formula (11) CHz-CRsX　(■〕 (wherein R3 is hydrogen or methyl and X is capable of interacting with the fibrous substrate a polymerized unit derived from a component comprising a functional group; A copolymer extender comprising:

Examples of monomers of formula ■ include ethylene compounds capable of free radical polymerization, e.g. lower olefinic hydrocarbons (optionally degenerated), e.g. Tylene, propylene, isobutyne, 3-chloro-2-isobutyne, butadiene, Isoprene, chloro and dichlorobutadiene, fluoro and difluorobutadiene 2,5-dimethyl-1,5-hexadiene; vinyl, allyl or vinylidene halides, such as vinyl or vinylidene chloride, vinyl or vinylidene ph fluoride, allylpromide, allyl chloride, methallyl chloride; styrene and its derivatives, such as vinyltoluene, α-methylstyrene, α-cyanomethylstyrene; tyrene, divinylbenene, N-vinylcarbazole; vinyl esters, e.g. Vinyl acetate, vinyl propionate, vinyl isobutyrate, vinyl sulfate cinate, vinyl stearate, divinyl carbonate; allyl ester, e.g. Allyl acetate and allyl heptanoate; alkyl vinyl or alkyl Lylethers such as cetyl vinyl ether, dodecyl vinyl ether, isobutyl ether, Chill vinyl ether Chill vinyl ether, 2-chloroethyl vinyl ether, Te triallyloxyethane; vinyl alkyl ketones, such as vinyl methyl ketone; Unsaturated acids such as acrylic acid, α-chloroacrylic acid, α-dimethyl maleate acid, ethyl crotonate, acid methyl maleate, acid butyl itaconate, and Vinyl, allyl, methyl, ethyl, butyl, isobutyl, hexyl, 2-ethyl hexyl, chlorohexyl, octyl, lauryl or stearyl acrylate and and methacrylates; olefinic silanes such as vinyltrichlorosilane, vinyl rutrimethoxysilane, vinyltriethoxysilane and methacryloyloxyp Lopyltrimethoxysilane; nitriles such as acrylonitrile, methacrylate Tolyl, 2-chloroacrylonitrile, 2-cyanoethyl acrylate, methylene geltalonitrile, vinylidene cyanide, alkyl cyanoacrylate, e.g. Isopropyl cyanoacrylate: (tris)-acryloyl-hexahydro -S-+-riazine; special acrylates, e.g. butanediol dimethacrylate dicyclopentenyl acrylate, ethoxylated bisphenol A dimeta Acrylates, isobornyl acrylates and methacrylates, trimethylolp Ropane triacrylate, allyl methacrylate; acrylamide and methacrylate amide; mono- or di(meth)acrylic acid of glycol or polyalkylene glycol rylates, e.g. ethylene glycol dimethacrylate, triethylene glycol acrylates, methoxypolyethylene glycols and polyethylene glycols of various molecular weights Mono-, di- and polyacrylates and methacrylates of lene glycol (CARB (available as OWAX [trademark]); endcapped with hydroxy groups Block copolymer of ethylene oxide and propylene oxide (PLUI?O available as NIC E trademark), tetramethylene oxide glycol (TER ATHANE [trade mark]), amino- or diamino-terminated polyether (available as JEpp+vrNE [Commercial 1]); siloxane mono-, or mono-, di- and polyacrylates and methacrylates of polyols, e.g. ．． 3-bis(4-hydroxybutyl)tetramethyldisiloxane (Petrar ch Systems, Bristol, PA); VP-1610 Shiroki Sandiol (Wacker-Germany); Q4-3667 Siloxa Corning diol (now Corning); Q4-3557 siloxane diol (Dow Corning); Siloxane mono-, di- or polyamide acrylic amides and methacrylamides, such as 1.3 bis(y-aminopropyl)tetra Methyldisoloxane (Petrarch 5ystes+s); DC-53 1 Siloxane polyamine (Dow Corning); DC-536 Siloxa Polyamines (Dow Corning); No. 4,728,571 (Clemens), which incorporates This includes things in general.

A particularly preferred class of monomers of formula V are acrylate monomers of formula ■ CRbCRq = CI? 5COORq (IX) (where R&, R? and 8 independently represent a hydrogen atom or a methyl group, and R9 is an alkyl group of C+-+S. (represents a kill group).

Preferred within this class are alkyl crotonates, alkyl acrylates and and alkyl methacrylates, such as methyl acrylate, methyl methacrylate , propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, isoamyl acrylate, isoamyl methacrylate, 2- Ethyl hequinyl acrylate, 2-ethylexyl methacrylate, octylmethacrylate Tacrylate, lauryl acrylate, lauryl methacrylate, cetyl acrylate cetyl methacrylate or cetyl methacrylate.

The copolymer extender further comprises polymerized units derived from monomers of formula It consists of 2. Suitable monomers include those that have a fibrous structure, such as through physical entanglement, with the fibrous substrate. This copolymer via nucleolytic groups, electrophilic groups, ionic groups, free radicals, etc. Functions that can interact by covalent bonding by reaction with substrate or by ionic bonding. Examples include those containing a functional group. Various wool, leather, paper, cotton and nylon , hydroxyl, amino, carboxyl and carboxamide groups.

For purposes of this specification and claims, a "functional group capable of interacting with a fibrous substrate" means a group capable of interacting with the fabric via any of the mechanisms listed above. . The darning group is a slanting group that is attached to certain fibrous substrates that are intended to be treated with the compositions of the present invention. can be easily selected by a person skilled in the art. a suitable group to interact with the substrate; Representative examples include polymerizable olefins, olefins that can undergo hydrolysis reactions, and edoxylic olefins. , ami-octahydroxy, halo, haloformyl, aziridino, acidic groups, e.g. xy, sulfo, sulfino, sulfeno, dihydroxyphosphofinyl and hydro Roxyphosphinylidene, their alkali metal and alkaline earth metal salts, their Amine salts, quaternary ammonium salts thereof, or amino and quaternary ammonium groups, and their salts with acids of the above-mentioned species.

Examples of suitable functionalized monomers include N-methylolacrylamide; methacrylamide; aziridinyl acrylate and methacrylate; diacetate acrylamide and methacrylamide; methylolated diacetone acrylamide and methacrylamide; 2-hydroxy-3-chloropropyl acrylate and and methacrylate; hydroxy (CZ-C,)alkyl acrylate and methacrylate; rylate; maleic anhydride; butadiene; isoprene; chlorobrene; allylua alcohol; allyl glycolate; isobutynediol; allyloxyethanol ;0-allylphenol;divinylcarbinol;glycerol α-allyl ether ter, acrylamide; methacrylamide; maleamide; maleimide; N-sia Noethylacrylamide; N-isopropylacrylamide; Glyoxalbis - Acrylamide; metal salts of acrylic acid and methacrylic acid; vinyl sulfonic acid and and styrene p-sulfonic acid and their metal salts: monoallylamine; Lysine; n-vinylpyrrolidone; 2-acrylamido-2-methylpropanesul Fonic acid (AMPS) and its salts, vinyl azlactone; glycidyl acrylate and methacrylate; allyl grindyl ether; acrolein; N,N-dime Thylaminoethyl acrylate and methacrylate; N-tert-butylaminoethyl Tyl methacrylate; Allyl methacrylate; Diallyl maleate; Vinyltri Includes ethoxysilane; vinyltrichlorosilane, etc.

Preferred functionalization agents of formula (1) include 2XICHz=CRsCON)Ic) Those of OH(XI) (in the formula, R1 represents a hydrogen atom or a methyl group) are mentioned. Ru. Copolymers comprising such heptamers are described in US Pat. No. 3,849,521 (Kirimoto et al.).

Other suitable copolymers can be prepared by methods familiar to those skilled in the art.

Component (C) in the composition of the present invention is a blocked isocyanate. of use Suitable isocyanates (before bronking) include aromatic diisocyanates. For example, 4,4'-methylene diphenyl diisocyanate, 4,6-di( trifluoromethyl)-1,3-benzenediisocyanate, 2,4-) toluene Diisocyanate, 2,6-toluene diisocyanate, o, m and p-xylene diisocyanate, 4,4-diisocyanatodiphenyl ether, 3,3'- Dichloro-4,4'-diisocyanatodiphenylmethane, 4,5'-diphenyl Diisocyanate, 4,4'-diisocyanatodiphenyl, 3,3'-dimeth xy-4,4'-diisocyanatodiphenyl, 3,3'-dimethyl-4,4'- Diisocyanatodiphenyl, 2,2. -dichloro-5,5,-dimethoxy-4° 4'-dicyanatodiphenyl, ■, 3-diisocyanatobenzene, 1,2-naph ethylene diisocyanate, 4-chloro-1,2-naphthylene diisocyanate, 1.3-naphthylene diisocyanate and 1,8-dinitro-2,7-naphthylene Cycloaliphatic diisocyanates, such as 3-isocyanatomethyl -3,5,5-trimethylcyclohexyl isocyanate i aliphatic diisocyanate such as methylene diisocyanate, 1,6-hexamethylene diisocyanate 2,2,4-)dimethyl-1,6-hexamethylene diisocyanate and 1.2-ethylene diisocyanate; aliphatic triisocyanates, e.g. 1,3 ．． 6-hexamethylene triisocyanate; aromatic polyisocyanates, e.g. Polymethylene polyphenylisocyanate (PAPI); and cyclic diisocyanate Mention may be made of anates such as isophorone diisocyanate (IPDI).

Also useful are isocyanates containing internal isocyanate-derived components, such as M From obay, DESMONDUR (commercial [)] can be done manually as N-100. Biuret-containing - tri-isocyanate, Huls AC, IPD from Germany Isocyanurate-containing triisocyanates such as available as I-1890 and Bayer as DESMONDUR(TM) TT. azetidinedione-containing diisocyanate. Furthermore, triisocyanate , for example tri(4-isocyanatophenyl)-methane (DES from Bayor) A0NDtll? (trademark) R) is suitable.

Another suitable class of isocyanates is isocyanate-functionalized low molecular weight polyurethanes. It is. These polyurethanes may be polyvalent, aliphatic, cycloaliphatic, araliphatic or is an aromatic polyisocyanate, such as hexamethylene-1,6-diisocyanate. various isomers of toluene diisocyanate, diphenylmethane diisocyanate ester, isophorone diisocyanate, etc., and at least two, preferably at least two, Both can be produced by reaction with a low molecular weight polyol containing three hydroxyl groups. Ru. Suitable low molecular weight polyols include trimethylolpropane, 1,3,5-h Xantriol, glycerol, pentaerythritol, propylene glycol ole, hexylene glycol and diethylene glycol. even more appropriate are other low molecular weight polyhydroxy compounds, such as triethanolamine. be.

These low molecular weight polyurethanes allow the polyol to react with excess polyisocyanate. It can be manufactured by reacting. Hydroxyl vs. Isocyanate in Reactions The equivalent ratio of the groups is at least 1:1.3, more preferably t:t, S~2.5 is preferred.

The above-mentioned isocyanates are "blocked isocyanates" in the composition of the present invention, In other words, it is used in the form of a reaction product of insia fuite and a blocking agent. , where the blocking agent is a compound containing this blocked isocyanate group. The isocyanate is subjected to thermal conditions such as those used in curing the treated substrate. can be removed from Commonly used isocyanate blocking agents include polyalcohols. (e.g. phenol, cresol, nitrophenol, 〇- and p-chlorophene) alcohol, naphthol, 4-hydroxybiphenyl); C2 to C8 alkanone oximes (e.g. acetone oxime, butanone oxime); arylthiols (e.g. thiophenol); organic active hydrogen compounds (e.g. diethylmalonate, acetate); tylacetone, ethyl acetoacetate, ethyl acetate, E-caprola lactam); sodium bisulfite; and hydroxylamine. especially Preferred blocked isocyanates include those blocked with 02-C8 alkanone oximes. Locked ones, especially butanone oxime. Such block-type isocyanates For example, a composition comprising this blocked isocyanate may be processed at a relatively low temperature. may be deblocked during the process of curing the treated substrate.

Some of the above blocked isocyanates are listed in US Pat. No. 4,834,764 (Delner et al.).

Others can be prepared by methods well known to those skilled in the art.

The compositions of the present invention are useful in imparting repellent properties to fibrous substrates to be treated with the compositions. comprising an effective amount of a fluorochemical reagent. This fluoroconstitute constitutes an effective amount. The amount of chemical reagent to be used can be readily determined by one of ordinary skill in the art. Certain fluorochemical reagents and copolymers and blocked isocyria used Depends on the amount of nate extender.

the copolymer extender and the blocked isocyanate extender, present in a combined amount effective to enhance the fluorine effect of the fluorochemical reagent . Each extender is preferably provided by either extender alone. is present in such an amount that the enhancement of the fluorine effect is superior to that produced by the fluorine.

As used herein, "improvement of fluorine effect" refers to of repulsive properties conferred by a fluorochemical reagent per unit weight of fluorine. It means an improvement in the quality of life. This repulsion property is measured using the test procedure below. . In other words, if a composition containing a fluorochemical reagent at the same or lower temperature If the performance is improved by including this (multiple) extenders in , this extender (or combination of extenders) contains certain fluorochemicals. This means that the fluorine effect of Cal reagent has been improved.

Generally, the extender is about 1:20 to about 20:1, preferably about 1=4 to about 4 :1, more preferably about 2:1 to about 1:2, and most preferably about 1:1. Exists in opposite quantities. Generally, the fluorochemical reagent is combined with a copolymer. from about 20 to about 2, based on 100 parts by weight of block isocyanate extender. 000, preferably from 40 to about 900, and most preferably from about 100 to about 400 It is present in an amount of .

Treating a fibrous substrate, such as a fabric intended for use in clothing, with the composition of the invention When applied to the treated substrate, based on the weight of the untreated substrate, the weight of the treated substrate is about 0.1 Preferably, it comprises from about 0.6% by weight of the fluorochemical reagent. Furthermore, Treated substrates based on untreated substrates, fluorochemical reagents, copolymer extracts From about 0.1 to about 1% by weight of tender and block type isocyanate extenders Preferably, it comprises a total combined amount of.

The amount of compound intended to be included on the substrate, the impregnation rate of the substrate, and the mass of the substrate. It will be appreciated that the compositions of the present invention can be applied to a substrate by any suitable method. Wear. For example, preparing the composition in the form of an aqueous dispersion and treating the substrate therein can do. Dispersions are generally used in water to impart repellent properties to the substrate to be treated. composition in an effective amount and in an amount effective to stabilize the dispersion. It will contain an emulsifying agent. The water is preferably based on 100 parts by weight of the composition of the invention. present in an amount of about 70 to about 900 parts by weight. Emulsifying agents are preferably those of the present invention. From about 1 to about 25 parts by weight, preferably from about 5 to about 1 part by weight, based on 100 parts by weight of the composition. Preferably, it is present in an amount of 50%. Commonly used cationic, nonionic, anionic Ionic and zwitterionic emulsions are suitable.

To effect treatment of the substrate, the substrate is immersed in the dispersion and until saturated. Continue stirring. This saturated substrate is then run through a budder/roller to remove excess dispersion. the dispersion medium in an oven at a relatively low temperature (e.g. 70°C). 1 t (e.g. water, ethylene glycol or mixtures thereof) temperature and time sufficient to dry for a period of time and then impart a cured substrate. Allow to harden over time. This curing process can vary up to 40% depending on the particular composition utilized. It may be carried out at temperatures from 0.degree. C. to about 200.degree. Generally, at a temperature of about 150°C, about 10 minutes time is appropriate. This cured substrate is cooled to room temperature and used to create clothing, e.g. It can be used as desired, such as being included in rain gear or shaped. .

In order to improve the fixation of the fluorinated compounds of the invention to the substrate, It also promotes interaction with certain additives, polymers, thermal condensable products, and substrates. It is sometimes advantageous to include a catalyst that can be used. These are urea or A condensate or precondensate of lamin and formaldehyde (in this specification, an amino resin ).

Other auxiliary extenders can be used alone or in combination with each other. Ru. Suitable auxiliary extenders include: paraffins; condensates with urea derivatives (e.g. For example, the product obtained by the reaction of stearic acid with hexamethoxymethylmelamine condensates of fatty acids and polyamines (e.g. stearic acid and diethylene triamine); and its shrimp chlorohydrin adduct. Furthermore, Salts of inorganic or organic acids, e.g. aluminum stearate, zirconium acetate zirconium oxychloride or Werner R form, e.g. For example, it is possible to utilize chrome stearachloride.

Improving the flexibility or "hand" of a substrate treated with the composition of the present invention When desired, flexible preforms, e.g. certain polyethylene, polydimethylsiloxane , modified hydrogen alkyl polysiloxane, or other materials known to those skilled in the art. It is possible to

The compositions of the invention may also contain auxiliary products, such as polyglycols, colloids, such as starch. dextrin, casein, sizing agent, fixing or detaining agent, stain resistance, cleaning agent. Substances that increase heat resistance, fire resistance or electrical resistance properties, buffering agents, fungicides, optical bleaches, sealants. Can also be used with chaining agents, mineral salts, surfactants or swelling agents to increase permeability. It is Noh. Specific suitable adjunct products and their amounts can be readily determined by those skilled in the art. Wear.

In addition to imparting oil- and water-repellent properties to the substrate, the compositions of the present invention impart anti-fouling properties. It can also be used to protect the substrate from solvents or certain clumping chemicals. Wear. These have properties such as stain resistance, sewage resistance, sewage removability and decontamination properties. Can be used to decorate fabric, paper or leather. These have specific properties, e.g. It can also be used to obtain anti-fouling, anti-fouling, anti-malt, anti-corrosion or antifouling properties. Wear.

Substrates treated with the compositions of the present invention were tested according to the test method described below.

Water spray test (-R) The resistance of the treated substrate to wetting by water is determined by ionof Textile Chemists and Co1orists AAT described in Technical Manual, 1977.53°245 It was measured using CC Test Method 224977 r Water Repellency Nispray Test. sun The pull is equal to the pull on a scale of 0 to 100, where 0 is the completeness of the top and bottom surfaces of the substrate. 100 indicates no wetness.

Leprosy test (OR) The oil repellency of the substrate treated with the compound of the present invention was determined by AATCC Technical M AATCC test method 118-197 as described in annual, 1977.53.223 5 rm Oiliness: Measured using "Hydrocarbon Resistance Test". This test is performed on a certain surface. The resistance of a substrate to wetting by a series of hydrocarbon liquids under tension is determined. So Values are reported in the range 0 (least repellent) to 8 (maximum repellent).

washing instructions The following procedure uses treated substrate samples designated as "r5X washing" in the examples. It is used for preparation.

Sample 2 of treated substrate, generally square, 400 cm to approximately 900 cm sheet 30g of ballast sample (generally square, edge-sewn 8100c+w” sheet) 1.9 kg of 802 fabric (in the form of 100 g) was placed in the washing machine.

Add a regular washing machine (rTIDEJ, 46g) and set this washing machine to high Fill to the water mark with warm water (49°C ± 3°C). This base and ballast charge was washed five times using a standard 12 minute wash cycle, then the substrate and ballast I dried it for about 45 minutes using a regular clothes dryer on the rheaJ setting. This dry Use a hand iron set to heat the substrate to the recommended temperature for the specific substrate fabric. I pressed it at the desired setting.

dry cleaning instructions Substrate samples referred to as "dry cleaned" in the examples below. The pull was processed as described in AATCC Test Method 7-1975, Note 8.1. .

The following is a description of the extenders and fluorochemicals used in the examples. Describe the preparation of reagents. Furthermore, some commercially available materials used in the examples. The available fluorochemical reagents are described below.

Intermediate A 2-phthanone oxime (26.1g, 0.3mol, 5ervo Co 5pany, 5ERVOXIl from the Netherlands? E (trademark) as Y-250 PAPI (40.8 g, 0.3 eq., polyphenylpolyisocyanate) Upjohn, equivalent weight 136, has the following chemical formula: CI, CHHz NCONCOr NCO average n=0.7) over about 30 minutes at room temperature.

The reaction temperature was increased to 60°C and maintained for 2 hours. This reaction mixture was then mixed with about 8 Using 6g of ethyl acetate, the solid content in ethyl acetate is 40%. diluted as follows. A clear and brown organic solution (obtained).

In a separate flask, add MARLOjlET (trademark) 5401 cationic emulsion. Agent I (5.7g 10% by weight based on total solids, Hils, Germany) and Deionized water (171 g, 300% by weight of total solids) was charged. Approximately 40% of this solution Warm the organic solution (also about 40 °C) to 40 °C and then mix very vigorously. added to. A milky pre-emulsion is obtained, which is MANTON-GAULIN TM emulsion machine three times at approximately 40°C and a pressure of 300 bar. Depressurize the solvent It was removed under. A brown dispersion was obtained. This dispersion is reduced to 20% solids. Diluted, then filtered and stored.

Intermediate B 2-ethylhexyl methacrylate Tyrol acrylamide (1.5g, 0.014aol), ETHO DA D (trademark) 18/25 cationic emulsifier (AK20, Netherlands, 3g, total solids) (approximately 5% by weight of total solids), tertiary dodecyl mercaptan (0.15g, approximately 0.0% of total solids). 25% by weight) and V-50 (Common 1) starting side ([2.2'-Aso'bis[2-methythyl] [Lupropanimidamide]-dihydrochloride, Wako, Japan] 0.12 g, total solids content approximately 0 ．． 62.2% by weight) and deionized water (140 g). Degas this mixture , then heated to 75°C for 16 hours. Transparent dispersion strength (obtained).

Intermediate C As described in U.S. Pat. No. 3,068,187 (301stad et al., Example 5) including graft copolymers of fluorinated monomers and fluorine-free comonomers, such as I made a dispersion.

Intermediate D N-ethyl perfluorooctyl sulfonamide ethanol (ETFOSE).

40,8 g, 0.3 eq.), dry ethyl acetate (100 g) and 4 drops of The dibutyltin dilaurate mixture was heated at reflux (approximately 78'C) for 4 hours.

Next, add 2-ethylhexanol (13 g, O. 1 mol), and The reaction was continued at reflux for an additional 6 hours. A clear brown solution was obtained. This reaction mixture was emulsified according to the procedure described for Intermediate A above. A light brown dispersion is obtained, This was diluted to 20% solids with water, filtered and stored.

Intermediate E was prepared using the same synthetic procedure and emulsion method.

PAPI (40.8g, 0.3eq), N-methylperfluorooctylsulfate Honamidoethanol (44.7g, 0.1 equivalent) and 2-butanone oxime ( 17.4g, 0.2so1) to form a blocked isocyanate group. A fluorochemical urethane composition containing the following was obtained.

Intermediate F LODYNE (trademark) 921C (149 g, 0.24 mol, The following formula CnFz-ICHzCHzSH (where n = 6. 8, 10. 12. 14..., and the average of n is about 10) (available from Ciba-Geigy), 2-Fin-1.4-dio (l1 g. 0.13 fog 01) and hexafluoroxylene (100 g) Combined. The mixture was warmed to 62 °C and the Log νOZO(TM) 52 initiator [(2,2'-azobis-(2,4-dimethylbase) A solution of 5 g, DuPont)] was added over 4 hours. ．． The reaction was continued for 4 hours at 70°C. A cloudy, pale yellow reaction mixture formed. de Lyethyl acetate (100 g) and trimethylhexamethylene diisothi Anate (22g, 0.1+mol.

TMDI, Baysr) was added and the reaction mixture was heated to 80°C.

Dibutyltin dilaurate catalyst (0.2 g) was added. This reaction was carried out at 95°C for 8 It lasted for hours. DD [(51 g, 0.08 ol, dimer diisocyanate, H enkel) and methyljetanolamine (6 g, 0.05 ■ ol). I got it. The reaction continued for 4 hours at 90°C. A clear brown solution was obtained. this To 200 g of solution, 101 g of butyl acetate, 3.5 g of acetic acid and 87 g of Added ethylene glycol. You can get it! The solution was warmed to 75°C.

In a separate flask, 5.2 g MARLOIdET in 463 g deionized water. (Trademark) 5401 surfactant (approx. 5% by weight total solids) solution heated to 75°C. The aqueous solution was added to the organic solution while stirring vigorously.

MANTON-GAULIN (trademark) in which the resulting blur emulsion was preheated. It was passed through an emulsion machine five times at about 70-75°C and a pressure of 300 bar. Microemulsion obtained It was done. Remove all solvent (at 50°C and vacuum approximately 5 mmHg), light brown color The dispersion was filtered and stored.

Intermediate G N-methyl perfluorooctyl sulfonamide ethyl acrylate) (61,1 g, 0.1 ol), 2-mercaptoethanol (1.95 g, 0.025 -ol), 40 g of ethyl acetate and AIBN (0.12 g, total solids content: 0. ．． 2% by weight) were mixed, degassed and then heated at reflux (approximately 80° C.) for 16 hours.

The reaction mixture was cooled to room temperature. PAPI (10.2g, 0.075 equivalent) was added along with 2 drops of dibutyltin dilaurate catalyst. Reflux this reaction mixture It was heated for 5 hours. The reactants were then cooled to about 60"C and 4.35g of 2 -Butanone oxime (0,05a+ol) was added. This reaction was carried out at 70″C for 2 hours. It continued for a while. The reaction product was emulsified at 70°C using the procedure described for Intermediate A. . A light brown dispersion was obtained, filtered and stored.

Intermediate H FC-217, a fluorochemical acrylate copolymer available from 3M Company.

Intermediate■ FC-352, a fluorochemical carbodiimide-containing composition commercially available from 3M Company.

Intermediate J FC-353, a fluorochemical-containing ester commercially available from 3M Company.

Intermediate K N-allyl perfluorooctyl sulfonamide (54 g, 0.1 eq.), polymer Chyl hydrogen siloxane (12 g, 0.2 eq., BAYSILON B-6L (trademark) )MH15 silicone, Bayer, expressed by the following formula; (CHs)xsiO[( CTo)(H)SiO]-5j(CL)s here n-40)), and butyl acetate Cetate (60g) was combined. Heat this mixture to 110"C and 2- A solution 1IIi of 1%) IzPtza in butanone was added. 30 minutes later, Monir Vinyl ester (2g + o, otmol, V [10RA (trademark)) 10. 5 hell) and 0.3 d of 1% catalyst solution were added. This reactant was heated to 126°C. I heated it for 1 hour. A light brown solution was obtained.

This material was emulsified at 30°C using the procedure, ingredients and amounts described for Intermediate H.

A light brown dispersion was obtained, the pH was adjusted to 7 and the emulsion was filtered, then Saved with.

Intermediate L FC-247, fluorochemical ester, fluorochemical, commercially available from 3M Company Composition comprising a blend of urethane and fluorochemical acrylate copolymer .

Intermediate M FC-214, fluorochemical urethane and fluorochemical commercially available from 3M Company A composition comprising a blend of calcopolymers.

Intermediate N Fluorochemical carbodiimide and fluorochemical carbodiimide, commercially available from FC-270, 3M Company. A composition comprising a blend of chemical acrylate copolymers.

Intermediate O In the polymerization bottle, add N-methyl perfluorooctyl sulfonamide ethyl acetate. Lylate (30.6g, approx. 0.05■ol, MeFOSEA), 2-ethyl Hexyl acrylate (8,1, approx. 0.044+5ol), 2-hydroxyethyl Thyl acrylate (0.7 g, approx. 0.006 mol), 2 g ETI (OQ AD (trademark) 18/25 emulsion (Ak20, Netherlands), tertiary dodecyl Lucaptan (0.2 g, 0.5% by weight of total), 'l-50 (trademark) started agent (2,2'-azobis[2-methylpropanimidamide], 0.08g, sum Hikari, Japan), acetone (15 g) and deionized water (78 g) were added.

The reaction mixture was degassed, then the polymerization bottle was capped and Placed in a washing machine (Landeroseter) at 0°C for 16 hours. can get The nearly clear dispersion was filtered and stored.

Intermediate P Following the procedure for Intermediate O, MeFOSEA in a molar ratio of 80 to 15 to 5.

Octadecyl methacrylate and polydimethylsiloxane monomethacrylate ( (molecular weight approximately 2000) was reacted. A transparent dispersion was obtained.

Intermediate Q Hexamethoxymethylmelamine (39g, 0.1sof, CYMEL ( Trademark) 303+ American Cyanaa+id), following formula C, Fzn - Fluorochemical mercaptan with +C1hCHzSH (232g, 0 ．． 4■ol, average n is about 10. The average molecular weight is 1J580, ^toches+ , France) and para-toluenesulfone M (0,42 g), and Cooled to 0'C. Methanol evolved and was removed by distillation. 2 hours The temperature was further increased to 180°C over time and maintained at this temperature for 4 hours. about After cooling to 80°C, add hexafluoroxylene solvent to dissolve 40% solids. A solution was made (a total of 348 g of hexafluoroxylene was used). to intermediate F A dispersion of this solution was made according to the procedure described. This dispersion is filtered and stored. It existed.

The above intermediates were tested on their own and with one extender according to the test method described above. It was tested in combination with an extender or in combination with two extenders. General moves below The formulations were prepared and the fabrics were treated accordingly.

Formulation and processing procedures Make the fluorochemical reagents described in Intermediates C-Q above and add the desired amount of each appropriate suitable fluorochemical reagents, the copolymer extender, and blocked isochemicals. Formulated in a treatment bath containing Anate Extender, this treatment is fabric based. This can be done by badge coating at the percentage solids specified. After processing, this The substrate was dried and cured for 10 minutes at 150°C.

The objects and advantages of the invention are further illustrated by the following examples. In these examples The specific materials and amounts described, as well as other conditions and details, do not limit the invention. It should not be considered as something that

Examples 1 to 24 and Comparative Examples C-1 to C-45 fluorochemical reagents were Formulated with a combination of stenders and extenders to achieve a total solids content of 0.0% based on the fabric. A 50150 polyester/cotton fabric was treated at 4%.

The results are shown in Table 1 below, where FC represents the fluorochemical reagent and The weight percentage of the fluorochemical reagent and the extender or extenders is Based on combined weight.

Fluoromical: IIC Fluoromical: IID Fluorochemical: E fluorochemical Fluoromical: GG Steal-”-mouth LLL Fluoromical: YoH Fluorochemical: I■ Fluoromical: liJ Fluorochemical = IIK Fluorochemical: IIL Fluorochemical: Yo M Table-”-mouth 1E le Fluoromical 20N Fluoromical: T#10 Fluorochemical: gP Fluoromical 2g The results in Table ■ show that any of a wide variety of fluorochemical reagents can be The composition of the invention comprises in combination with each member of the class of tenders: Provides superior results compared to comparative compositions comprising only one extender. suggested that it be provided. Excellent oil and water repellency is obtained and therefore the fluorine effect is comparable. Improved compared to comparative example.

Examples 25 to 42 and Comparative Examples C-46 to C-72 Related to Examples 1 to 24 above The formulation was prepared as described above and had a total solids content of 0.6% based on the fabric. It was used to treat 100% cotton fabric.

Pig-e Fluoromical: IIC Fluoromical: Day D Fluorochemical IIIF Fluorochemical; Lu G l-”20LE and Fu J Reolo Mical 2nd H Fluorochemical: 11■ Fluoromical: Yo J Fluoromical: gO Fluoromical: Day Provide superior results and increased fluorine efficiency compared to comparable compositions of comparative examples. It suggests that.

It will be understood by those skilled in the art that various improvements and modifications of the present invention may be made without departing from the scope of the invention. It is understood that this invention is not to be limited to the embodiments set forth herein. There will be.

International Investigation Report DrT/IIs 92100592 Front page continuation (51) Int, C1,5 identification code Internal reference number C08G 18/80 NFM 8620-4JCO8L 33100 LHT 7921-4J751 04 NGG 8620-4J CO9K 3/18 103 8318-4HD06M 15/256 D218 19/24 7199-3B (72) Inventor: Mae, Christopher Se.

Belgium, Belgian-1200 Brussels, Pourbard de la Wallou 106I D06M 15/256

Claims (1)

[Claims] 1. A fluorine-effect oil- and water-repellent composition comprising: (A) a fluorochemical; (B) (i) a monomer of the following formula: CR1R2=CR3R4 (In the formula, each R1, R2, R3 and R4 is independently hydrogen, halogen, or an organic group (ii) a monomer of the following formula; CH2=CR5X (In the formula, R5 represents a hydrogen atom or a methyl group, and X interacts with the fibrous substrate. a polymerized unit derived from a component comprising a functional group that can be used; copolymer extender; and (C) block type isocyanate extender; comprising: wherein the fluorochemical reagent imparts repellent properties to the fibrous substrate treated with the composition. and where this copolymer extract is present in an amount effective to confer Stenders and blocked isocyanate extenders are present in a combined amount effective to enhance the fluorine effectiveness of the Cal reagent. , and each extender has the benefit of either extender alone. present in an amount that provides a greater enhancement of the fluorine effect than the are doing, Composition. 2. The copolymer extender comprises: (i) a monomer of the following formula: CR6CR7=CR8COOR9 (In the formula, R6, R7 and R8 independently represent a hydrogen atom or a methyl group, and R9 represents a C1-18 alkyl group); (ii) Monomer of the following formula CH2=CR5CONHCH2OH (in the formula, R5 represents a hydrogen atom or a methyl group); The composition according to claim 1, comprising: 3. The copolymer extender is: (i) an alkyl crotonate, an alkyl Derived from monomers selected from the group consisting of acrylates and alkyl methacrylates. a polymerized unit that comes; (ii) Monomer of the following formula CH2=CR5CONHCH2OH (in the formula, R5 represents a hydrogen atom or a methyl group); The composition according to claim 2, comprising: 4. The block type isocyanate extender is a block type isocyanate. The composition of claim 1, which is a functionalized low molecular weight polyurethane. 5. The block type isocyanate extender is a block type aromatic isocyanate extender. 2. The composition of claim 1, which is an anate. 6. The blocked isocyanate extender is 2-butanone oxime. The composition of claim 1, which is a blocked polyphenyl polyisocyanate. thing. 7. The copolymer extender is derived from 2-ethylhexyl methacrylate. containing polymerized units derived from N-methylolacrylamide and polymerized units derived from N-methylolacrylamide. The composition according to claim 1, comprising: 8. the extender is present in a relative amount of about 1:20 to about 20:1; A composition according to claim 1. 9. 4. The extender is present in a relative amount of about 1:4 to about 4:1. 1. The composition according to 1. 10. The extender is present in a relative amount of about 2:1 to about 1:2. The composition according to claim 1. 11. 2. The extender of claim 1, wherein the extender is present in a relative amount of about 1:1. composition. 12. The fluorochemical reagent interacts with the copolymer and the blocked isocyanate. About 20 to about 2,000 parts by weight, based on 100 parts by weight including the nate extender A composition according to claim 1, wherein the composition is present in an amount of parts by weight. 13. The fluorochemical reagent interacts with the copolymer and the blocked isocyanate. About 40 to about 900 parts by weight based on 100 parts by weight including nate extender A composition according to claim 1, wherein the composition is present in an amount of parts of parts. 14. The fluorochemical reagent interacts with the copolymer and the blocked isocyanate. About 100 to about 400 parts by weight, based on 100 parts by weight including the nate extender A composition according to claim 1, wherein the composition is present in an amount of parts by weight. 15. a substrate having oil- and water-repellent properties, on the surface of which the substrate has oil- and water-repellent properties; comprising an effective amount of the composition of claim 1 to impart oil- and water-repellent properties. A substrate comprising a fibrous substrate. 16. The substrate is paper, nonwoven fabric, cotton, polyester/cotton blend, nylon or leather. 16. The substrate of claim 15. 17. The fluorochemical reagent has an amount of about 0.1 to 16. The substrate of claim 15, wherein the substrate is present in an amount of about 0.6% by weight. 18. the fluorochemical reagent, the copolymer extender and the block The isocyanate extender is approximately 0.0% based on the weight of the untreated substrate. 16. The substrate of claim 15, present in a total amount of 1 to about 1% by weight. 19. an aqueous dispersion, which imparts repellent properties to water and the substrate to be treated; and an effective amount of the composition of claim 1 to stabilize the dispersion. A dispersion comprising an effective amount of an emulsifying agent. 20. Water is present in an amount of about 70 to about 900 parts by weight based on 100 parts by weight of the composition. and in an amount of about 1 to about 25 parts by weight based on 100 parts by weight of the composition. 20. Aqueous dispersion according to claim 19, wherein an emulsifying agent is present. 21. Water is present in an amount of about 70 to about 900 parts by weight based on 100 parts by weight of the composition. and in an amount of about 5 to about 10 parts by weight based on 100 parts by weight of the composition. 20. Aqueous dispersion according to claim 19, wherein an emulsifying agent is present. 22. A method for imparting oil and water repellency properties to a fibrous substrate material, the method comprising: Process: (1) Effective for imparting oil and water repellency properties to the surface layer of a fibrous substrate material. (2) applying the treatment from step (1) in an amount of the composition of claim 1; heating the treated substrate to a temperature and time sufficient to cure the treated substrate. A method comprising; 23. A method for improving the fluorine effect of fluorochemical reagents, Luorochemical reagents: (a) (i) Monomer of the following formula CR1R2=CR3R4 (In the formula, each of R1, R2, R3 and R4 is independently hydrogen, halogen or (ii) a monomer of the following formula; CH2=CR5X (In the formula, R5 represents a hydrogen atom or a methyl group, and X interacts with the fibrous substrate. a polymerized unit derived from a component comprising a functional group that can be used; copolymer extender; and (b) blocked isocyanate extender. A method comprising the step of blending with a powder.