TW413687B - Fluorourethane additives for water-dispersed coating compositions - Google Patents

Abstract

Fluorourethane additives for water-dispersed coating compositions comprising the product of the reaction of (1) at least one diisocyanate, or polyisocyanate or a mixture of polyisocyanates containing at least three isocyanate groups per molecule, (2) at least one fluorochemical compound containing at least one Zerewitinoff hydrogen in an amount sufficient to react with 5% to 80% of the isocyanate groups in the diisocyanate or polyisocyanate, (3) at least one compound of the formula R10-(R2)k-YH in an amount sufficient ot react with 5% to 80% of the isocyanate groups in the diisocyanate or polyisocyanate and wherein R10 is a C1-C18 alkyl, C2-C18 omega-alkenyl radical, or C2-C18 omega-alkenoyl; R2 is -CnH2n- optionally end-capped with -[OCH2C(R4)H]p-, -[OCH2C(CH2Cl)H]p-, or -C(R5) (R6) (OCH2C[CH2Cl]H)p-, wherein R4, R5, and R6 are the same or different and are H or a C1-C6 alkyl radical, n is 0 to 12, p is 1 to 50; Y is O, S, or N(R7) wherein R7 is H or C1-C6 alkyl; and k is 0 or 1; and optionally (4) water in an amount sufficient to react with 5% to 60% of the isocyanate groups in the diisocyanate or polyisocyanate are disclosed.

Description

No. 85110441 of the Chinese manual for the revision of the year 3 ^ -L ... V. Description of the invention (3) 1 1 1— I * I -....... Clothing--I ____ η fPlease take care ¾ the precautions on the back (Fill in this page) A coating of colloidal silica available in Delaware (D E)) is applied to a dry surface and modified. This method has two disadvantages, it requires coating the surface twice and 2) it removes with the dirt. Preferably, the washability enhancer can be applied in conjunction with the paint and retain its effectiveness after washing. It can provide cost-effective, durable stain resistance and washability to dried water-dispersed coating compositions by adding an aqueous emulsion of these oil-repellent additives to water-dispersed coating compositions used in the industry. Sex, is better. Summary of the Invention Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs The present invention contains a polyfluorourethane compound, which is the product of the reaction of: (1) at least one diisocyanate, and (2) sufficient to interact with diisocyanates 5% to 80% of the isocyanate group is reacted in an amount of at least one fluorochemical compound containing at least one nivolitovin hydrogen, (3) sufficient to be 5% to 80% in diisocyanate Isocyanate-reactive amount of at least one SR10- (R2) k-YH compound (where R1 () is a Ci-Cu gauge group, C2-C18 Miga-dilute radical, or c2-C 丨 8 咢Miga-alkenyl; R2 is based on-[OCH2C (R4) H] p-,-[OCH2C (CH2Cl) H] p-, or -C (R5) (R6) (OCH2C [CH2Cl] H) p-terminated -CnH2n-, wherein R 4, R 5 and R 6 are the same or different and are Η or a C t-C 6 棍 radical, η is 0 to 12, 2 1 to 50; Y is 0, S 'or N (R7), of which 117 is 11 or C₁ 丨 alkyl; and k is 0 or 1); and if necessary (4) is sufficient to be compatible with the diisocyanate 5 to 60% of the amount of isocyanate-reacted water. -6-This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) 413687 A7 B7 V. Description of Invention (T Employee Consumer Cooperation of Central Bureau of Standards, Ministry of Economic Affairs, Du Yinye, etc.) This application claims the benefit of US Provisional Patent Application No. 06 / 004,912, filed on October 6, 1995. Scope of the Invention The present invention relates to substituted diisocyanates that are extended by partial reaction with water. Fluoroalkyl esters or diisocyanates. These compounds are used as additives in water-dispersed coating compositions to reduce the swelling of wood substrates and to provide stain resistance and oil repellency to dried coatings. And improved washability. This issue is a step related to coating compositions containing these additives, and dried coatings generated from such coating compositions. BACKGROUND OF THE INVENTION Water-dispersed coating compositions provide The main benefits over solvent-based paints, such as nonflammability, solvent costs, and environmental concerns over the evaporation of volatile organic compounds during manufacturing and application. Dry, water-dispersed coating compositions utilize a resin, screw, or other film-forming material as an emulsion 'latex, or suspension, as an adhesive, if! L, or film-forming ingredient. For example, in conventional paints A resin is used. Although other film-forming materials that are emulsified or suspended can be used; these resins are usually made from acrylic-ester copolymers (acrylic emulsions and latex paints) or from vinyl acetate, vinyl, or Vinyl butyral poly (I) copolymer (acetic acid emulsion or latex paint) is produced. This raspberry 'D ^.-^ — Temple instinctive formulation is well known to those skilled in the art. Emulsion paint is made by Ordered by w (Morgans) in " Summary of Lacquer Technology ", Third Edition, M. Morgans Hallst Press, 11, I ~~. II (Please read the notes on the back before filling in this page) -4 Each paper size applies Chinese National Standard (CNS) A4 (210X297 mm)

Article 85 〖1044 ΐ4ί Chinese version of the Chinese manual amendment page (8i Feng March 3 ') 5. Description of the invention (4) The present invention also contains a polyethylaminofluoroacetate compound, which is the reaction product of the following substances: ( 1) at least one polyisocyanate containing at least three isocyanate groups per molecule or a mixture of more than one polyisocyanate, (2) sufficient to react with 5% to 33% of the isocyanate group in the polyisocyanate At least one of the number of fluorine chemical compounds containing at least one Nirevidinov hydrogen, (3) at least one formula of an amount sufficient to react with 5% to 80% of isocyanate groups in the polyisocyanate! ? _1 () _ (112;)] 4_YH compound (where R1C) is a Ci-C18 alkyl group, C2-C18 hydrazone-alkenyl radical, or C2-C18 Miga- hydrazone; R_2 is optionally terminated with [OCH2C (R4) H] p-,-[〇CH2C (CH2C1) H] p-, or -C (R5) (R6) (〇CH2C [CH2Cl] H) p- -CnH2n-, where R4, R5, and are the same or different and are Η or a C 丨 -C 6 alkyl radical, η is 0 to 12, and ρ is 1 to 5 0; Υ is 0, S Or N (R 7), in which the 7 is 11 or CrC6 alkyl; and the k is 0 or 1); and (4) is sufficient if necessary to be 5% to 60% of the isocyanate group in the polyisocyanate. The amount of reaction water. The invention further comprises an improved water-dispersed coating composition and a dried coating derived therefrom, an emulsion, latex, or suspension comprising a film-forming material dispersed in an aqueous medium, Wherein the combination containing a polyfluorourethane compound is improved in an aqueous medium, which is the product of the reaction of: (1) at least one diisocyanate, or polyisocyanate or more than one polyisocyanate containing at least three isocyanate groups per molecule A mixture of isocyanates, which is enough to react with 5% to 80% of isocyanate groups in diisocyanate or polyisocyanate. The paper size is in accordance with the China National Standard (CNS) A4 specification (210X297 mm> ^^^ 1 n ^ i ί Hi ^^^ 1 i ^^^ 1 ^ 1. ^ 1 ^^^ 1 ^^^ 1 (Please read the precautions on the back before filling out this page) The Central Bureau of Standards, Ministry of Economic Affairs, Consumer Affairs Cooperation Du Yinzhuang Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 413687 A7 _ B7 V. Description of the Invention (2) (Halstead Press) (John Wiley & Sons,

Inc.) 'New York City, NY (1990) states 0 During coating, water evaporates, leaving pigments and polymer particles that are secondary dispersing cloths. Matrix. The coating system forms a continuous film such as particles agglomerated into a combined pigment. Although these dried, water-dispersible coating compositions have good protection and decorative properties and can provide reasonable water repellency, they have minimal or no oil repellency. This lack of oil repellency can cause problems with staining. In particular, these dried coatings exhibited poor oil repellency during contact angle measurement, dirt cleaning, and they had poor stain resistance. In addition, water-dispersed coatings tend to cause swelling of the wood substrate, which may detract from the properties of the dry topcoat. In U.S. Patent 5,414,111, Kirchner discloses, for example, a polyfluoronitrogen-containing compound formed by reacting an isocyanate trimer with a fluorinated alcohol and then further extending the reaction product with water. These products are coated on fiber substrates to impart water repellency, oil repellency, and soil repellency and / or soil release properties to these substrates. The patent does not disclose the use of these compounds as additives to water-dispersible coating compositions to improve stain resistance and washability. In other places, fluorinated surfactants are used as flow modifiers in paint films, but they are not used as additives to improve the stain resistance and washability of water-dispersed coating compositions. Recently, it has been found that the washability of flat amido = ethyl ester finished products can be obtained by using LUD0x (from Pont de Nemours and Company of DuPont) (Wilmington (Continent), -5- this paper The scale is applicable to the Chinese National Standard (CNS) A4 specification (2χ 297 Gongchu) --------- Installation ------ Order ------ East (Fill in this page again) Patent case No. 85110441 --- Chinese manual revision page (87 ref. March), .l -1 --------------- 1 _ * V. Description of the invention (5) 1 ~~ — (Please read the precautions on the back before filling this page) The amount of at least one fluorochemical compound containing at least one Levivitinol, (3) is sufficient At least one compound of the formula Y10 __ (112) YH in a quantity that reacts with 5% to 80% of the heart isocyanate group in a diisocyanate or polyisocyanate (where R 〖〇 is a Ci_Cis alkyl group, C2-Cm 咢Miga-alkenyl radical, or C2-c 18-miga-alkenyl; R2 is optionally-[〇CH2C (R4) H] p-,-[OCH2C (CH2Cl) H] p •, or _ C (R5) (R6) (〇CH2C [CH2Cl] H) p-capped -CnH2n-, where R4, R5, and R6 are phases Or different and is H or an alkyl radical, from 0 to 12 ′ p is 1 to 50: Y is ◦, S, or n (r7), where R 7 is fluorene or C rc 6: ¾ And k is 0 or J); and (4) if necessary, in an amount sufficient to react with 5% to 60% of the isocyanate groups in the diisocyanate or polyisocyanate. The invention further comprises a method for reducing the swelling of a wood substrate when the wood substrate is coated with an improved water-dispersed coating composition, and a surface on which a coating composition comprising the improved water-dispersed coating described above has been deposited. A method for cleaning and oil repellency of a dry coating composition). Detailed description of the invention Printed by the Consumer Cooperatives of the Central Government Bureau of the Ministry of Economic Affairs This invention contains a polyfluorourethane compound, a water-dispersible coating composition containing a polyfluorourethane compound, and a process derived from these compositions Dry coating. These compounds are formulated as aqueous emulsions and added to conventional water-dispersed coating mixes used on various substrates, such as paints and topcoats. For wood substrates, a water-dispersible coating composition is used. When coated, the compounds reduce the swelling of the wood. The dried coatings from these modified water-dispersible coating compositions provide the surface of the substrate -8-This paper size is based on CNS A Oge (Café Meal)

No. 85110441 of the Chinese manual for the revision of the year 3 ^ -L ... V. Description of the invention (3) 1 1 1— I * I -....... Clothing--I ____ η fPlease take care ¾ the precautions on the back (Fill in this page) A coating of colloidal silica available in Delaware (D E)) is applied to a dry surface and modified. This method has two disadvantages, it requires coating the surface twice and 2) it removes with the dirt. Preferably, the washability enhancer can be applied in conjunction with the paint and retain its effectiveness after washing. It can provide cost-effective, durable stain resistance and washability to dried water-dispersed coating compositions by adding an aqueous emulsion of these oil-repellent additives to water-dispersed coating compositions used in the industry. Sex, is better. Summary of the Invention Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs The present invention contains a polyfluorourethane compound, which is the product of the reaction of: (1) at least one diisocyanate, and (2) sufficient to interact with diisocyanates 5% to 80% of the isocyanate group is reacted in an amount of at least one fluorochemical compound containing at least one nivolitovin hydrogen, (3) sufficient to be 5% to 80% in diisocyanate Isocyanate-reactive amount of at least one SR10- (R2) k-YH compound (where R1 () is a Ci-Cu gauge group, C2-C18 Miga-dilute radical, or c2-C 丨 8 咢Miga-alkenyl; R2 is based on-[OCH2C (R4) H] p-,-[OCH2C (CH2Cl) H] p-, or -C (R5) (R6) (OCH2C [CH2Cl] H) p-terminated -CnH2n-, wherein R 4, R 5 and R 6 are the same or different and are Η or a C t-C 6 棍 radical, η is 0 to 12, 2 1 to 50; Y is 0, S 'or N (R7), of which 117 is 11 or C₁ 丨 alkyl; and k is 0 or 1); and if necessary (4) is sufficient to be compatible with the diisocyanate 5 to 60% of the amount of isocyanate-reacted water. -6-This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) Patent Application No. S5U0441 Chinese Manual Correction Page (87

Printed by the Consumers' Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs 5. Description of the Invention (18) The system reacts with at least one of these non-fluorinated compounds. For example, the non-fluorinated compound may be represented by the following formula:

R 1 0_ (Chinese 2) k_ YH, where R10 is an alkyl group, a C2-C18 咢 miga-alkenyl radical, or a c2-c18 咢 miga · enemyl group; R2 is capped with the following formula as required A kind of bivalent linear hydrocarbon radical, _ C „H2n- _ r4 ch2ci

i I-(〇CH2CH) p-,-(OCH2CH) p-, or R5

I -C- (OCH2CH) p- I!

Rg CH2C1; wherein R4, R5, and R6 are the same or different and are a type of H or 1 to 6 carbon atoms; η is 0 to 12 and ρ and 1 to 50; Υ is 0 , S, or N (R 7), where R7 is Η or an environment group containing 1 to 6 carbon atoms; and -21-this paper size is applicable to the Chinese and European countries (CMS > Α4 size (2i〇 .X297 公 暖) < Please read the notes on the back before filling in this page), τ

Article 85 〖1044 ΐ4ί Chinese version of the Chinese manual amendment page (8i Feng March 3 ') 5. Description of the invention (4) The present invention also contains a polyethylaminofluoroacetate compound, which is the reaction product of the following substances: ( 1) at least one polyisocyanate containing at least three isocyanate groups per molecule or a mixture of more than one polyisocyanate, (2) sufficient to react with 5% to 33% of the isocyanate group in the polyisocyanate At least one of the number of fluorine chemical compounds containing at least one Nirevidinov hydrogen, (3) at least one formula of an amount sufficient to react with 5% to 80% of isocyanate groups in the polyisocyanate! ? _1 () _ (112;)] 4_YH compound (where R1C) is a Ci-C18 alkyl group, C2-C18 hydrazone-alkenyl radical, or C2-C18 Miga- hydrazone; R_2 is optionally terminated with [OCH2C (R4) H] p-,-[〇CH2C (CH2C1) H] p-, or -C (R5) (R6) (〇CH2C [CH2Cl] H) p- -CnH2n-, where R4, R5, and are the same or different and are Η or a C 丨 -C 6 alkyl radical, η is 0 to 12, and ρ is 1 to 5 0; Υ is 0, S Or N (R 7), in which the 7 is 11 or CrC6 alkyl; and the k is 0 or 1); and (4) is sufficient if necessary to be 5% to 60% of the isocyanate group in the polyisocyanate. The amount of reaction water. The invention further comprises an improved water-dispersed coating composition and a dried coating derived therefrom, an emulsion, latex, or suspension comprising a film-forming material dispersed in an aqueous medium, Wherein the combination containing a polyfluorourethane compound is improved in an aqueous medium, which is the product of the reaction of: (1) at least one diisocyanate, or polyisocyanate or more than one polyisocyanate containing at least three isocyanate groups per molecule A mixture of isocyanates, which is enough to react with 5% to 80% of isocyanate groups in diisocyanate or polyisocyanate. The paper size is in accordance with the China National Standard (CNS) A4 specification (210X297 mm> ^^^ 1 n ^ i ί Hi ^^^ 1 i ^^^ 1 ^ 1. ^ 1 ^^^ 1 ^^^ 1 (Please read the precautions on the back before filling out this page) The Central Bureau of Standards, Ministry of Economic Affairs, Consumer Affairs Cooperation Du Yinzhuang Patent Meeting No. 85110441 --- Chinese Manual Revised Page (87 ref. March), .l -1 --------------- Ί _ * 5 、 Explanation of the invention (5) 1 ~~ — (Please read the notes on the back before filling in this ) An amount of at least one fluorine chemical compound containing at least one Nitrovirudinol, (3) at least one formula in an amount sufficient to react with 5% to 80% of the heart isocyanate group in a diisocyanate or polyisocyanate 111〇_ (112) YH compounds (where R 〖〇 is a Ci_Cis alkyl, C2-Cm 咢 miga-alkenyl radical, or C2-c 18 咢 miga_enalyl group; R2 is as required With-[〇CH2C (R4) H] p-,-[OCH2C (CH2Cl) H] p •, or _C (R5) (R6) (〇CH2C [CH2Cl] H) p-terminated -CnH2n-, Where R4, R5, and R6 are the same or different and are H or an alkyl radical, from 0 to 12 ′ p from 1 to 50: Y is ◦, S, or n (r7), where R 7 Η or C rc 6: ¾; and k is 0 or J); and (4) if necessary, in an amount sufficient to react with 5% to 60% of isocyanate groups in diisocyanate or polyisocyanate The present invention further comprises a method for reducing the swelling of a wood substrate when it is coated with an improved water-dispersed coating composition, and an improved surface on which a coating containing the above-mentioned improved water-dispersed coating has been deposited One of the compositions A method for cleaning and oil repellency of dry coating composition). Detailed description of the invention Detailed description of the invention Printed by the Consumer Cooperative of the Central Economic and Trade Bureau of the Ministry of Economic Affairs The present invention contains a polyfluorourethane compound Water-dispersible coating compositions and dried coatings derived from these compositions. These compounds are formulated as aqueous emulsions and added to conventional water-dispersible coating mixes used on various substrates, Compounds such as paints and finishes D For wood substrates, when coated with a water-dispersible coating composition, the compounds reduce the swelling of the wood. The dried coatings from these modified water-dispersible coating compositions provide -8 to the surface of the substrate-this paper size is based on CNS A Auge (Ministry of Economics, Public Meal and Economics) A7 printed by the Consumer Standards Cooperative of the Central Bureau of Standards _________ £ 1 ____________ 5. Description of the Invention (6) Stain resistance, oil repellency, and improved washability. The polyfluorourethane compound of the present invention (hereinafter referred to as "Polyurethane Additives" or "Polyurethane Compound M) is based on the diisocyanate or polyisocyanate (hereinafter referred to as the" isocyanate "reactant) in their preparation. The use as a reactant is classified as follows: 1) By reacting one or more diisocyanates (isocyanate reactants) in an amount sufficient to react with 5% to 80% of isocyanate groups, one or more lightning arresters are included. A fluorochemical compound of Wei Dinov hydrogen (hereinafter referred to as a fluorine chemical reactant) 丄, a compound of SRI (r (R2) k_YH (hereinafter referred to as a non-fluorinated reactant), and A compound prepared by requiring water; and 2) containing one or more Nitro Vertino by reacting one or more polyisocyanates (isocyanate reactants) in an amount sufficient to react with 5% to 33% of isocyanates A hydrogen chemical compound of hydrogen

RiO- (R2) k_YH is a non-fluorinated reactant, and a compound prepared with water as needed. The polyfluoroamine phosphonate additive used in the improved coating composition and the dried coating composition of the present invention contains two or more polyfluoroamine methyl 'acid ethyl ester compounds plus a compound of another group. This additional group includes a fluorochemical reactant of the formula R10- (R2) k-YH in a quantity sufficient to react with 5% to 80% of the isocyanate group via the reaction of a polyisocyanate isocyanate) A non-fluorinated reactant, and a compound prepared with water as needed. The term "water-dispersed coating composition" If used in this article, the paper size is _ · 9_ This paper size applies to China National Standard (CNS) Α4 size (2 丨 〇_〆 ^^ Binding ¾ (Please read the back first Please note, fill in this page] A7 B7 413687 V. Description of the invention (Planned for the decoration or protection of a substrate, which essentially contains a film-forming material dispersed in an aqueous phase—an emulsion, Latex, or suspension, and if necessary, including surfactants, protected colloids and thickeners, pigments and admixtures, pigments, preservatives, fungicides, freeze-thaw ampoules, defoamers, pH control agents Surface coatings of coalescents, coalescing aids, and other ingredients. Water-dispersible coating compositions are exemplified by, but not limited to, the following: Pigmented coatings such as latex paints, unpigmented coatings such as wood sealer primers 'Colorants and top coats, coating compositions for monuments and cement, and water-based asphalt emulsions. Materials used in emulsion paints and film formation are acrylic esters, acrylic derivatives' vinyl-acrylic derivatives Thing A latex polymer of acetamyl compound, or a mixture thereof. These water-dispersible coating compositions are made by C.R Martens in M emulsion and water-soluble paints and coatings, ( Reinhod Publishing Corporation, New York City, New York, 1965). Conventional air-dried, water-dispersible coating compositions use methyl acrylate and butyl acrylate. Polymers of methacrylic acid in an aqueous solvent (available from RHOPLEX from Rohm & Haas Company (Philadelphia, PA)), ethylene An emulsion of methacrylic acid derivative, methacrylic acid derivative, butyl acrylic acid, and methacrylic acid (-obtained from Rohm and Haas Moss T as rOVACE 9100) or UCAR (from Yongbei Company (Union Carbide) (available in Danbury 'CT) as an adhesive or film-forming ingredient. Partial reaction of diisocyanates or polyisocyanates with water Applicable paper size National Standards (CNS) A4 Specification (2) 〇χ 297mm --------- ¢ ------ ΐτ ------ 1 .Fill in this tile) Printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 413687 Five 'Invention Description (8 is called-extension of isocyanic acid brewing "and the reaction product is called a type of diisocyanate by the extension of God". Procedures for extending diisocyanates are well known in the art. For example, 'U.S. Patent 3,124,605 Wagner describes the reaction for using water with a half mole ratio. 4-Diisocyanic acid extends 1-fluorenylbenzene-2,4 -di to produce tri-minor, 1 ^ _- (3-isocyanoxy-4-fluorenylbenzyl) biuret Isocyanate method. A "Nirevi Dinov Hydrogen" is an active hydrogen that will react with a methyl magnesium sulphide (Grenya reagent) to release methane. The reaction is through the method of Nirevi Dinov and others An organic compound containing an active hydrogen such as -0 Η, -COOH, and the like can be reacted with a methyl magnesium halide to release methane. The volume measurement of methane allows the active hydrogen content of the compound to be reduced. Quantitative estimation. When reacting under cold conditions, the first amines produce 1 mole of pristane, and usually 2 moles when heated (organic chemistry by Paul Karrer, by Ai English translation by Elsever, 1938, p. 135). For the purposes of the present invention, it is assumed that a first amine provides an active hydrogen, such as by Nirevitinov and others Humans have defined a reaction between Nitrovirudinol hydrogen and an isocyanate group to form urethane. The dried water-dispersible coating composition of the present invention comprises 50% relative indoor degree under normal indoor ° conditions; drying duration A coating composition for 7 days, comprising at least one kind of polyfluorourethane additive as defined above. The polyfluorourethane additive of the present invention is from (1) a significant reactant, (2)- Fluorine chemical reactants, (3) —II '" ^ J kinds of non-rolling reactions 11 纸张 paper · size applicable to China National Standard (CNS) A4 specification (210X297 mm) 1 ^ 1 -in IIII Shimin | I— n I; i ^ — »" ^-In (Read the precautions on the back before you fill out this page) Printed by the Staff Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (9) A7 B7- ----- and, if necessary, (4) water preparation. Polyfluorourethane additives are prepared in a suitable solvent, converted into an aqueous emulsion, and sufficient to produce about 100 to about 20,000 micrograms. The amount of a dried coating per gram of fluorine is combined into a water-dispersed coating composition. The dried coating has enhanced stain resistance, increased resistance to repellency, and can be modified by gas. Detergent. Reactants and catalysts used to make polyurethane compounds And emulsification methods, and the use and application of polyurethane additives in water-dispersible coating compositions are described below in succession. For the purpose of the present invention, 'any can be used, any diisocyanate or has three or Polyisocyanate having three or more isocyanate groups is used as the first or isocyanate reactant. For example, diisocyanate hexamethylene ester homopolymers having the following formula can be used: OCN- ( H2C) 6 HN —G: 〇11 11 C (CH) 2y6 NC〇 "

'NH ~' ― (ch2) 6——NCO button-up -------- tr ------ Quan (Please read the precautions on the back before filling out this page). Du prints where x is an integer equal to or greater than 1, preferably between 丨 and 8. Due to their marketability, a mixture of these hexamethylene diisocyanate and a 7L polymer is preferred for the purposes of the present invention. It is also an important isotricyanate terpolymer derived from diisocyanate, which can be represented by the following formula: -12 This paper size applies to China National Standard (CNS) A4 specification (210X297mm) 413687 A7 B7 V. Description of the invention (10

Ri 1- —NC〇 〇CN—Rn C R11 ~ 〇

-NCO wherein R i 1 is a divalent hydrocarbon group, preferably aliphatic, cycloaliphatic, aromatic, or paraffin aliphatic. For example, 'R 丨 丨 is 7T methylene'toluene or cyclohexyl, and the former is preferred. For the purpose of the present invention, other polyisocyanates are reacted by the reaction of 1,1,1,3-tris (hydroxymethyl) ethane or 1,1,1-tris (hydroxymethyl) propane. Obtained from toluene isocyanate. Isotricyanate trimer of toluene isocyanate diisocyanate and isotricyanate trimer of 3-isocyanoxymethyl_3,4,4_ trimethylcyclohexyl isocyanate Other examples of polyisocyanates that are useful for the purposes of the present invention are, for example, cylidene-shen- (phenylisocyanate). Also useful for the purposes of the present invention are polyisocyanates having the formula:

OCN (please read the precautions on the back before filling in this page)

H3C

NCO CONH CONH

The suitable diisocyanates of the market are listed below as examples: DESMODUR Η (1,6-hexamethylene diisocyanate; HMDI), DESMODUR W (13- This paper size applies to the Chinese National Standard (CNS) A4 specification ( 210 × 297 mm) 413687 A7 B7

V. Description of the Invention (U.S. Consumer Cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs, Yinfan bis [4-isocyanoxycyclohexyl] methane, PICM), MONDUR TD (toluene diisocyanate isomers (particularly 2, A mixture of 4-diisocyanoxy-1-methylbenzene and 1,3-diisocyanoxy-2-methylbenzene, TDI), 1 ^ € ^ 011 feet from (4,4'- Diisocyanoxydiphenylmethane; 1 ^ 01), and isophorone diisocyanate (5-isocyanoxy-1- (isocyanoxyfluorenyl) -1,3,3- Trimethyl-cyclohexane; IPDI), each available from Aldrich Chemical Co. (Milwaukee, Wisconsin (WI)). Suitable pre-produced market-proven Jingyan J. Diisocyanates are exemplified by the following: DESMODUR 3200 and DESMODUR available from Bayer Corpo.ration (Pittsburgh, Pennsylvania) N-1 00 (hexamethylene diisocyanate homopolymer), both of which are presumed to be prepared by the method described in US Patent No. 3,124,605 to produce mono-, bi-, and gin- , 肆-, and a mixture of higher secondary derivatives. Also suitable are DESMODUR 3 3 00 (a hexamethylene-derived isotricyanate trimer), and from American Cyanamid (Stamford, Connecticut) State) CYTHANE 3 160 (a glycerin-based isocyanate) ° Typical properties of these compounds are as follows: Typical properties DESMODUR N-100 DESMODUR N-3200 average equivalent 191181 NCO content,% 22.0 23.2- 1 I--I--! — 士 " ·--ϋ-κ Τ-I -____________ Good (please read the intent on the back before filling out this page) -14- This paper size applies Chinese National Standard (CNS ) A4 specification (210 × 297 mm) 413687 A7 B7 V. Description of the invention (12

The typical NCO content of Desmodur N-100 is close to that of an SRI International Company Report (Isocyanates No. 1D, July 1983, p. 279). Hexamethylene diisocyanate homopolymer having the following composition Listed: Product composition is heavy, hexamethylene diisocyanate 0.1 single February exhibition 44.5 biuret 17.4 biuret-r. 9.5 diuretic 5.4 higher fractions of derivatives 23.1 NC ◦ Content 21.8 Based on its average equivalent and NCO content, the double, triple, high, and other content compared with DESMODUR N-3200 should be lower than the content of N-100 products. DESMODUR N-3300 is one of the following hexamethylene diisocyanate-derived isotrimeric cyanuric acid terpolymers. The policy of employee consumer cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page)

R12-NCO

I '' I

OCN—Ri〆C —NCO 〇, where R 丨 2 is hexamethylene-15- This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) Printed by the Consumer Cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs 413687 V. Description of the invention (13) As long as each fluorine chemical compound contains at least two carbon atoms and each carbon atom contains at least two fluorine atoms, a wide variety of fluorine chemical compounds can be used as the second or fluorine chemical reactant . For example, a fluorochemical compound can be represented by the following formula:

RfR ^ -XH wherein R f is a monovalent aliphatic group containing at least one carbon atom, each of which contains at least two fluorine atoms;. R is a divalent organic radical; k is 0 or 1; and X is .0, or an N (Ri) _, where R ^ H contains a kind of agile radical or a kind of Rf_Rk_ radical containing carbon atoms. In a more specific embodiment, a fluorochemical compound containing a single functional group may be represented by the following formula:

Rf-Rk-R2-X_H, where R f and k are as defined above; R is a divalent radical; -C H ^ Γ τϊ ς η,

LtnH2mSO-, -CmH2mS〇2-, -S02N (R3)-, or _c〇N (R3) 'wherein the claw is a divalent alkyl group of i to 22 and or 1 to 6 carbon atoms; _ -16- The paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210 ^ 7 ^ 57 nn 1 * 1τI II --- ---- 1 (谇 Please read the precautions on the back before filling in this page) 413687 A7 The Ministry of Internal Affairs and Standards Bureau ’s Anti-Poverty Cooperative, India ’s B7 R 2 is a bivalent linear hydrocarbon radical, -C η H 2 n-, which is terminated with f-base as needed, 'ch2ci-(〇CH2CH} p- ,-(0CH2CH) p-, or r5

I -C- (OCH2CH) p- II ^ R6 CH2C1-where n is 0 to 12 and p is 1 to 50; R4, R5, and R6 are the same or different and are H or contain 1 to 6 A type of carbon atom; X is 0, S, or N (R7), of which 117 is fluorene, a fe group containing 1 to 6 carbon atoms, or an Rf-Rk_R2_ group. More specifically, R f is a perfluorinated linear or branched aliphatic radical of 3 to 20 carbon atoms which can be interrupted via an oxygen atom. In a preferred embodiment, the fluorochemical compound may be represented by the following formula:-',-

Rf- (CH2) qXH 'where X is 0, S, or N (R7), where R7 is Η, contains i to 6 carbon atoms -17- This paper applies the national standard (CNS) A4 specification (2 ] OX297 mm) ^^ 1 —ϋ ^^ 1 ·-1----I— I. *. Ci II-—1 1 f ~ * 5, V5 (Please read the precautions on the back first (Fill in this page) 413687 A7 A / B7 V. Description of the invention (15), an alkyl group, or an Rf-Rk-R2- group,

Rf is a mixture of perfluoroalkyl CF3CF2 (CF2) r, wherein r is 2 to 18; and q is 1, 2 or 3. In a more specific embodiment, 'Rf is a mixture of the perfluoroalkyl group, CF 3 CF 2 (CF 2) r, and r is 2' 4, 6, 8, 10, 12, 14, 16, and 18. In a preferred embodiment, r is mainly 4, 6, and 8. In another preferred embodiment, r is mainly 6 and 8. The preferred embodiment of the former is more convenient for car dealers and therefore less expensive, while the latter can provide improved properties. Representative fluorine-based aliphatic alcohols that can be used for the purpose of the present invention

CgF (2g +) _) (CH2) t-0H., (CF3) 2CFO (CF2CF2) UCH2CH2〇H,

CsF (2s + l) (Rg)-. (CH2) D-OH, CSF < 2s + l J S02N (Rb).-(CH2) t -OH ... -(Please read the notes on the back before filling this page)

CSF (2s + lJ S ° 2n _C (〇CH2CH-) OH-., I ^ R9 (CH2Cliv where s is 3 to 1 4; t is 1 to 12; U is 1 to 5; each of R8 and R9 is H or an alkyl group containing 1 to 6 carbon atoms. -18- This paper adopts the Chinese National Standard (CNS) A4 specification (2 丨 〇 × 297 mm) 413687 5. Description of the invention (16) In a specific embodiment, the fluorine chemical compound may be represented by the following formula:

H (CF2CF2) wCH20H where w is 1-1 0. The latter fluorochemical compound is prepared by reacting tetrafluoroethylene with methanol. Another such compound is 1,1,1,2,2,2-hexafluoroisopropanol of the following formula: CF3 (CF3) GHOH ο has the structure RfCH2CH2OH (where R # is a c2-C20 perfluorocarbon ) Suitable fluorinated alcohols for the second reactant are exemplified below, but not limited to ZONYL BA and BA-N fluorotelomers from DuPont (Wilmington, Delaware) Intermediate marketed perfluoroalkyl ethanol. ZONYL BA and BA-N are included in the form of a mixture of ingredients of the homologous series of the following formula: Aval-fluoro-isomiga- (2-ethylidene) -poly (difluorofluorenylene): —, F (CF2CF2) n (CH2CH2) 〇H, which contains: For η = 2, BA contains 1%-2%, BA-N contains < 1% For η = 3, BA contains 2 7%-3 4 % 'BA-N contains 3%-8% For n = 4, BA contains 29% -34%, BA-N contains 45% -50% -19- This paper size applies the Chinese National Standard (CNS) A4 specification (21 〇Χ 297mm) --------- f.— (谙 First read the notes on the back and then fill out this page) Printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 41S68 < A7 _. __B7_ V. Description of the invention (17) For n = 5, BA contains 17% -21%, BA-N contains 28%-3 3 0 / 〇 For η = 6, BA contains 6%-9%, BA-N contains 8% -1 3% For n = 7, BA contains 2%-5%, BA-N contains 1%-6% For n = 8, 'BA contains 1% -2%, BA-N contains 1% -6 % Structure RfCH2CH2SH (where 1 ^ is a C2-C 2 0 perfluorocarbon of the second reactant) suitable fluorinated thiols It is sold by Ciba-Geigy (Ardsley, NJ)

LODYNE 924 is exemplified. Structure RfSQjNCCt ^ CHdCi ^ Cf ^ OiK, where Rf is a C2-C2G perfluoro group, a suitable fluorinated sulfonamide is obtained from the Minnesota Mining and Manufacturing Company (3M Company) (Minneapolis ), Example of FLUORAD FCM0 available in Minnesota (MN)). Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Consumer Cooperatives (please read the note on the back, and then fill out this page) In another specific embodiment, the water-modified fluorochemical urethanes have been developed by DESMODUR N-100, DESMODUR N-3200, or DESMODUR N-3 3 00 (Hexamethylene diisocyanate homopolymers available from Bayer (Pittsburgh, PA)) or one of them The mixture is prepared with a perfluoroalkyl compound containing a functional group, which is insufficient in stoichiometry, and then reacted with a non-fluorinated reactant as described below, and then reacted with the lotus in water. -. For the third or non-fluorinated reactant used in the preparation of the polyfluoro-based compound of the present invention and the polyurethane additive used in the coating of the present invention ^ ° non-fluorinated organic compounds, It contains a single functional group. Generally, the isocyanate is between about 60% and about 60% of the polyisocyanate. _____ -20- This paper standard is based on ggj alignment (CNS) such as specifications (male thin). Patent application No. S5U0441 Chinese specification correction page (87

Printed by the Consumers' Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs 5. Description of the Invention (18) The system reacts with at least one of these non-fluorinated compounds. For example, the non-fluorinated compound may be represented by the following formula:

R 1 0_ (Chinese 2) k_ YH, where R10 is an alkyl group, a C2-C18 咢 miga-alkenyl radical, or a c2-c18 咢 miga · enemyl group; R2 is capped with the following formula as required A kind of bivalent linear hydrocarbon radical, _ C „H2n- _ r4 ch2ci

i I-(〇CH2CH) p-,-(OCH2CH) p-, or R5

I -C- (OCH2CH) p- I!

Rg CH2C1; wherein R4, R5, and R6 are the same or different and are a type of H or 1 to 6 carbon atoms; η is 0 to 12 and ρ and 1 to 50; Υ is 0 , S, or N (R 7), where R7 is Η or an environment group containing 1 to 6 carbon atoms; and -21-this paper size is applicable to the Chinese and European countries (CMS > Α4 size (2i〇 .X297 public heating) < Please read the notes on the back before filling out this page), τ Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 413687 A7 —___ ___B7 5. Invention Description (19) k is 0 or 1. For example, the non-fluorinated foot compound may be an alkanol or a monooxy or monoalkenyl ether or ester of a polyoxyalkylol. Specific features of these compounds: Examples include monomethyl ether of stearyl alcohol, polyoxyethylene glycol, and mono-allyl ether or mono-methylallyl ether of polyethylenyl alcohol. 'And mono-methacrylate or acrylate of polyoxyethylene glycol. In a specific embodiment, the polyurethane additive used in the coating of the present invention is reacted by: at least one diisocyanate, or polyisocyanate containing at least three isocyanates, or one A mixture of the above isocyanates with (2) to at least one fluorochemical compound (each molecule containing (a) a single functional group having one or more Nirovitinol hydrogen atoms and (b) at least two Carbon atoms, each containing at least two fluorine atoms), and (3) at least one non-fluorinated reactant as described above. The remaining isocyanate groups can then react with water as needed to form one or more urea linkages or can fully react with the second and third reactants previously described to form urea, carbamate, or thiamine Ester linkage. Generally, isocyanate groups between about 40% and about 95% will have reacted before water is reacted with the diisocyanate or polyisocyanate as needed. In other words, the amount of Y water is usually sufficient to react with about 5% to about 60% of the isocyanate groups in the diisocyanate or polyisocyanate. Preferably, the isocyanate group between about 60% and 95% has reacted before water reacts with the diisocyanate or polyisocyanate as needed, and optimally about 8 before the reaction of water. Isocyanate groups between 0% and 90% have reacted. Therefore, in a kind of -22- this paper size applies the Chinese National Standard (CNS) A4 specification (2! OX 297 mm) --------- installation ------ order ------ Dong (Please read the notes on the back of the book before you fill out this page) A7 413687 --------- B7 V. Description of the invention (2〇) ~-(Please read the notes on the back before reading. (Fill in this section) [Preferred embodiment] In the embodiment, the amount of water is sufficient to react with about 5 ° /. To about 35% of the cyanate group, and the best is at 10 ° /. And 20 The cooperation between members of the Central Bureau of Commerce of the Ministry of Economic Affairs and consumer cooperation, and the preparation of Leflurane additives by DuPont are based on the presence of a catalyst in a suitable solvent such as methyl isobutyl ketone solution. A diisocyanate or an extended diisocyanate reacts an alkyl-terminated polyalkylene glycol 'a fluoroalcohol or fluorothiol, and optionally an alcohol, thiol, or amine. Suitable. The catalyst is well known to those skilled in the art. For example, the catalyst is exemplified by dibutyltin dilaurate or tin octoate, a metal organic compound, or trialkylamine, pyridine Ethylmorpholine, l4-diazabicyclo [2.2 · 2] octane (DABCO, Aldrich Chemical Company (Miwokie, Wisconsin)), or 8-diazabicyclo [54〇] 11-carbon_7-association (DBU, Aldrich Chemical Company (Miwokie, Wisconsin)) Example of a third amine = reaction product is further reacted with water as needed to produce methyl isobutyl A kind of polyurethane in methyl ketone. Emulsifies polyurethane in methyl isobutyl ketone in water. In most cases, emulsification occurs easily by mixing. Emulsification is as required Anionic surfactants (eg, alkyl sulfonates) or non-ionic surfactants (eg, 'alcohol ethoxylates' or Alkylphenol ethoxides) are used. Under reduced pressure-the methyl isobutyl ketone solvent is removed to leave an aqueous dispersion. This dispersion is then added to an existing aqueous solution. Disperse the coating composition and mix thoroughly. Apply by standard equipment. A modified water-dispersed coating composition. A suitable solvent for the reaction is a ketone such as fluorenyl isobutyl ketone 'f -23- This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) A7 B7 21 413687 V. Description of the invention (exemplified by pentyl ketone, methyl ethyl ketone, esters such as ethyl acetate, and aromatic solvents such as toluene or xylene. Water-modified Fluorochemical urethanes are usually prepared by first feeding a diisocyanate or polyisocyanate, a perfluoroalkyl compound, and a dry organic solvent such as methyl isobutyl ketone into a reaction vessel. The order of reagent addition is not important. The specific weights of the aliphatic diisocyanates, polyisocyanates' and perfluorochemical compounds added are determined based on their equivalents and based on the working capacity of the reaction vessel, and are adjusted so that all of the third reactants added Responsibility for thunder_Novohydrogen will react with some total NCO groups added between 40% and 100%. The dry solvent weight is usually 15%-30% of the total feed weight. Feed under nitrogen and heat to 40-70 ° C. A catalyst (usually dibutyltin dilaurate itself, or a small amount, for example, 1 to 2 parts per 10,000 parts of diisocyanate or polyisocyanate) As in a solution of methyl isobutyl ketone). After the resulting exothermic reaction, the mixture was stirred at 65 ° C and 10 ° C (between 0 ° C and 20 ° C since the time the catalyst was added), and then the temperature was adjusted to between 55 ° C and 90 ° C. After that, treatment with water itself or with wet isopropyl ketone for an additional I 1 to 20 hours. Production (products are as prepared or stored and / or used after further solvent dilution, or converted into- Emulsion or dispersion. In some cases, the emulsion or dispersion is stabilized with a surfactant. 1 In other cases, it can be prepared-seed emulsion or dispersion without the use of surfactants. Ethyl additives in milk pan pores are formed by continuous reaction of isocyanate-24 paper standard puncture if financial standard (CNS) 格格 (2iGx297 ^^ ~ I—II / J · 衣 I! — Order ( Please read the notes on the back before filling in this page.] Employees ’Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 413687 A7 B7 V. Description of the invention (22) @say, fluorinated 'and non-paragraphized reactants, By reacting with water to further extend the reaction Product 'and finally produced by adding water, emulsifying aid as needed, and removing the remaining organic solvents to prepare an aqueous emulsion. Polyurethane additives in the form of an aqueous emulsion can be sufficient to produce. Concentrations of a dry coating of about 100 to 20,000 micrograms / gram of fluorine and preferably about 500 to 2,000 micrograms / gram of fluorine are conveniently combined into conventional water-dispersible coating compositions. For inclusion in liquid paints of about 45 % To 60% solids, a typical latex paint, the polyurethane additive of the present invention is sufficient to produce; contains about 50 to 100,000 micrograms / gram of fluorine and preferably about 250 to An amount of 1,000 micrograms / gram of fluorine as a coating composition is combined into the coating composition. For other coatings such as wood colorants, tile coatings, asphalt emulsions, and similar compositions, the polyfluoride of the present invention The methyl ethyl acetate additive is combined in an amount sufficient to produce a coating composition containing about 50 to about 10,000 micrograms per gram of fluorine. The additive is adjusted in consideration of the percentage solids of the coating composition. Printed by the Central Bureau of Standards of the Ministry of Economic Affairs and Consumer Cooperatives (read the back of the book first; fill in this matter before filling out this page) Add water-dispersed coating composition per 100 weight units to make the resulting coating composition will be The weight unit of an aqueous emulsion that is dried to a film containing F micrograms per gram of fluorine is the following formula: 100FS / C (104 f_p) where f is in polyfluoroamine The percentage of fluorine in the ethyl formate additive, s is the percentage of solids (non-volatile materials) in the original water-dispersible coating composition, and C is of the polyfluorocarbamate additive in the emulsion Percent concentration. Stirring water-dispersed coating containing polyurethane additives -25- This paper size applies to Chinese National Standards (CNS) M specifications (210X297 Gongchu) 413687 Α7 Β7 Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Description of the invention (23) The material composition to produce a homogeneous mixture. The addition of a dispersion of poly (fluoroamine) ethyl acetate to a pre-formulated coating composition is performed at the time of sale or use, but when the appropriate quality control procedures will be more conveniently available, it is preferably This is carried out at the time of manufacture of the water-dispersible coating composition. The application and drying properties of the water-dispersible coating composition are essentially unaffected by the addition of the melamine acetic acid additive. Alternatively, it is understood that the formulation of the coating composition can be modified when a polyurethane additive is added. Although this publication has described some specific specific embodiments, it should be noted that those skilled in the art can make various changes and modifications without departing from the invention. The present invention & an aqueous emulsion containing a coating composition with a water content "polyurethane additive, when compared with a control coating containing no such additive, is improved from these water-dispersible coating compositions. The dry coating has oil repellency, scour resistance, and washability. When measuring advancing and receding cetane contact angles on dried coatings according to test method π cetane contact angle ratio on dried coatings containing such compounds or additives The corresponding cetane contact angle is larger on a reference coating that does not contain such compounds or additives, so the dried coating has improved oil repellency. When, using the method described below (Test Method 2-Paint Brush Test), a crayon is used to mark the preparation of the stained specimen, the dried 2 coating containing this compound or additive is used before brushing. The marks produced on the surface are visually less obvious than the corresponding marks produced on the control coating without the polyfluorourethane additive, so the dried ^ -26- This paper size applies to the Chinese National Standard (CNS) A4 specifications (2l0x297 mm) --- 1 1 ί {Seed clothing I —. T 1 order I ". 11 line (谙 Please read the precautions on the back before 〆 ·% 'page) 413687 A7 B7 Central Standard of the Ministry of Economic Affairs Bureau employee consumer cooperatives Yin Jia V. Invention Description (24) The layer has improved stain resistance. After brushing in accordance with Test Method 2 and evaluation in accordance with Test Method 3, the percentage of soil removed from a dried coating containing such a compound or additive is less comparable to that of a control coating without such a compound or additive. The percentage of soil is more, so the dried coating has improved washability. The butterfly pen washability test yielded good washability results related to similar tests using other oily soils, including carbon black dispersed in mineral oil and a tomato sauce. Sample preparation i-" ϊ ~ · The compound or additive was added to the test water-dispersed coating composition at the weight percentage indicated in the data sheet and mixed thoroughly with a paint stick. The lacquer is applied at a 6 mil (0.15 mm) wet thickness and 6 inches (15 mm) width to a Mylar sheet (called a drawdown), or at 3 mil (0.076) Mm) wet thickness is applied to a scrubbing plate type R121 -10N from Leneta Corporation (Mahwah, NY), and allowed to be used at room temperature and humidity (about 70 below (2 1 C) and 50% relative humidity) for 7 days. After drying, the water and hexadecane contact angle measurements are made in Test Method 1, the stained and brushed paint film samples are described in Test Method 2, and the washability is evaluated as described in Test Method 3. --Test Method 1-Contact Angle Measurement The contact angle is measured by the Sessile Drop Method, which is based on A.W. Adamson " Physical Chemistry of Surface " (Fifth Edition, Wiley Father and Son Company, New York City, New York State, 1990) Chapter II fully describes -27-k This paper size applies to China's family & standard (0 milk 8 size " d〇X297 mm) installed n ϋ Thread (please read the precautions on the back before ^ .1 page) 413687 A7 B7 V. Description of the invention (25), which is incorporated herein by reference. Additional information on the equipment and procedures needed to measure these contact angles is provided by R. 丹 Dettre and R. E. Johnson Jr. in " Wettability " (Edited by J, C. Berg, Marcel Dekker, 'New York', New York State, 1993) More fully described in Chapter 1, which is incorporated herein by reference. Using a kind of Rame- Hart optical bench to hold the substrate in a horizontal position. The contact angle is measured with a retractable goniometer from the same manufacturer. A drop of test liquid is placed on a surface and in contact with the surface The point accurately measures the tangent line. A forward angle is determined by increasing the size of the droplet, and a receding angle is determined by decreasing the size of the droplet. The data is usually displayed in forward and backward contact angles. The difference between the two angles. The relationship between the contact angle of water and organic liquids and the washability and dirt retention are described in chapters XΠ and XIII of AW Adamson above. In general, the surface The larger the contact angle, the more resistant to dirt or dirt and the more the surface Easy to clean. Test Method 2-Paint brushing test The stained sample is prepared in a Leneta brushing test board (type number P121, 10v) (available from Leneta Corporation (Mawa 'NY)) , Which is one of the 4X17 inch (10-X 43 cm) paint coating samples that have been cured under ambient room conditions for 7 days). One end (2.5 thick meters) is cut off. Then 2 ρ inches (5 Centimeters) increase and apply a blue crayon (CrayOla Co. (Easton, Pennsylvania) mark) in a 2 inch (5 cm) area, Use the following procedure to standardize the coating. A crayon is slightly -28 by rubbing on a piece of sandpaper.- This paper size applies Chinese National Standard (CNS) A4 size ^ 210x297 public envy) [IIi system II order nn line (please Read the ii meanings on the back before reading. \ This page}

Printed by the Shellfish Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 413687 A7 B7 Printed by the Shellfish Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (26) Flattened. The crayon was placed in a holder made from a 12-inch (305 cm) 1 / 2-inch (1.27 cm) non-recorded steel rod and praised at a 90-degree angle to provide a One of the ends (2.54 cm) of the "L" shape. Attach a lab-frame connector to the i-inch (2.54 cm) section to maintain the stylus at a 45-degree angle to the surface. The curved rod is maintained at the opposite end of the stylus assembly, and the weight of the Guxu device provides consistent force to the stylus tip. Rub the tip of the crayon back and forth 50 times to produce a uniform mark on the paint. Usually such grips will apply a force of 100 grams (0.98 Newtons) to the surface. Cut the object and wash it on the test. The rods and connectors are from VWR Co. (South Plainfield, NJ) with catalog numbers 6079_533 and 60079, respectively. -055 is available. Preparation of a brushing machine A water-based 1% TIDE cleaner (Proctor and Gamble Co. (Cincinnati, OH) was dropped for use For cleaning tests, a 丨 pound (〇45 kg) Gardner Abrasion boat (WA-2151, Paul N. Gardner Co.), Popano Beach (P⑽pan 〇Beach), Florida (FL)) 'Fold a 9 "(22.9 cm) wide bundle of double-layer dry 5¾ wrap (grade 20B' Deroya Textiies, Camden (C am den) 'South Carolina (sc)) three times to make a 2.5-pair (6.3 cm) salamander. It is tightly combined with the attrition boat and the milliliter of decomposing liquid is applied. The boat is placed in a scrubber (Gardner DV-10, Paul N. Gardner Company, Popano Beach, Florida) and brushing examples have passed 29. Zhang scales apply the Chinese National Standard (CNS) from the specifications (2⑴χ 297 public Chu --- ------ Seeds ------ 1Τ ------ '!-(Please read the precautions on the back before filling in this page) A7 413687 _______ _B7_ V. Description of the invention (27) The number of brushing strokes indicated in the data sheet. For each test, use a new piece of cheesecloth. The test object is a transparent adhesive tape (for example, supplied from the commercial office of Minnesota Mining and Manufacturing Company The SCOTCH MAGIC TAPE of the Department (St. Paul, Minnesota) is adhered to the center of the scrubbing table so that about 1/2 of the marked surface will be cleaned by the machine. The table should be dry before being adhered. After brushing, 'remove Objects, washed with water and air-dried. The amount removed is visually or through the use of a reflectance scoring scale as described in Test Method 3 to compare with the unwashed surface. Test Method 3-Warp The grade of 样本 -1 on the brushed stained sample indicates that the mark is stained or darker. The grade of 0 indicates no change. The scale of 1 to 10 indicates that 10% to 100% of the dirt has been removed. Used in The numbers shown in Table 1 and the evaluation of the items are as follows: Table 1 The stain resistance and washability of the flat sheet 彳 f removed amount m 〇 0 10 20 30 40 50 60 70 -30- This paper size applies to China country孳 (CNS) A4 size (210x 297 male Chu ------------------ install -------- order -------- Quan (please read the note on the back first) Please fill in this page again) 0 1 Employees' Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs of the People's Republic of China 4 5 6 7 80413687 A7 B7 V. Description of the invention (28 8 9 10 90 95+ It is estimated that the board is' removed after the required number of cycles, washed under running water, and air-dried. A washability scale is created by measuring the reflectance of a stained, unwashed area using a reflectance meter, and assigning a zero washability level. Measure the reflectivity of an uncontaminated area and assign a cleanability rating of 〇. The anisotropy between these reflectivities 値 is divided into 10 equal intervals to produce a washability classification scale. If it is not possible to use a reflectance meter to use the Munsell neutral value scale to assist in the designation of a washable system grade, if the reflectance is measured, the highest value for an unstained area showing 80% A minimum measurement of the measured reflectance and 20% of the stained area can establish a scale, as shown below. Packing ------ Order ------ 涞 (Please read the notes on the back before filling out this page) Printed by the Employees' Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 51 Qin _2_ Washability can be divided into different sizes and can be washed Sex grade% reflectance 10 80 (maximum) 9 74 8 _-68 7 62 6 56 5 50 4 44 -31-This paper size applies to Chinese national standard < CNS > Α4 size (2! 0 × 297 mm) Economy Printed by the Consumer Standards Cooperative of the Ministry of Standards of the People's Republic of China 413687 at __ ____B7_______ V. Description of Invention (29) 3 38 2 32 1 26 '0 20 (minimum) After staining as in Test Method 2 and before brushing, When the intensity of the color on the dried coating of the fluorourethane additive is lower than the corresponding intensity of the color on the control coating without the compound or additive, it is considered that a dried coating has improved stain resistance Sex. A control (untreated paint) is often used to test for better stain resistance of paints with or without the compound or polyurethane additives. After brushing according to Test Method 2 and evaluation according to Test Method 3, the classification number of the dry coating containing the polyfluorourethane additive is higher than the corresponding classification number of the control coating without the polyfluorinated ethyl acetate additive. At the time, a dried coating was considered to have improved washability. A pair of photos (untreated paint) is often used for testing to compare the washability of paints with or without polyfluoroamine additives. Test Method 4-Lubrication of Wood Substrates The swelling of a wood substrate due to the application of a water-dispersed coating composition was measured using a SWellmeter instrument and the method described therein. The polyurethane-gg compound of the present invention is used as a water-dispersed coating composition. It is small and can be added to reduce the moistening of the wood substrate after the coating I of the water-dispersed coating composition, and the dry coating. The layer is useful for providing stain resistance and oil repellent cleaning performance. The present invention containing these additives. '. And σ and the dry coating of the present invention generated from it are for coating each ------------32-Degree encounter ~~~~~ —— __ --------- Installation ------ Order ------ Quan (Please read the notes on the back ^ before filling in this page) 413687 A7 B7 Employees of the Central Standards Bureau of the Ministry of Economic Affairs Printed by a consumer cooperative V. Description of the invention (30) Seed villages such as walls, furniture, wood, bricks and tiles, permanent clay, asphalt, and other surfaces (on which conventional paints are applied, sealing primers, colorants, Topcoats and emulsions) are useful. The coating composition is particularly useful for a surface where stain resistance and easy cleaning are required. Example _Example 1

Jr is made of MPEG-3 50 polyurethane additive. 256 g of N-163D (DESMODUR N-100 (from Bayer, Pittsburgh, Pennsylvania)) Butyl ketone solution), 42 grams of ZON YL BA fluorotelomer intermediate (from DuPont (Wilmington, Delaware)), and 235 grams of MPEG-350 (from Evergreen Corporation (Danbury, Connecticut) Nadick)), placed in a 1000-ml round-bottomed flask equipped with a mechanical stirrer, condenser, and nitrogen inlet and heated with a controlled heating head. Heat the contents to 55 ° C. 20 grams of a solution containing 0.040 grams of monobutyl laurate methyl isobutyl ketone was added and the exothermic reaction was raised to 90 ° C over a period of 20 minutes, followed by heating to maintain the tank temperature at 90 ° ° C lasted another 3 hours. After 3 hours of maintenance ', the organic reaction mass was added to a 2 liter stirred (15 rpm') flask containing 40 grams of water and 100 grams of methyl isobutyl ketone over a half hour period, and at After the addition was completed, it was maintained at 7 5 for 2 hours. Turn off the stirrer and add 600 g of water at 75 ° C over a period of 30 minutes. The mixture was stirred for 1 hour, after which a steam trap, condenser, and vacuum extraction device were connected to the flask and vacuum was applied to remove methyl isobutyl at a temperature of about 55 ° C and a pressure of 13 kPa. Ketone / water azeotrope. Allow the flask to cool 33- This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) --------- ^ ------_ ΐτ ------. ^ (Poetry Read the precautions on the back before you read this page. / · This page) Employee Consumer Cooperatives, Central Standards Bureau, Ministry of Economic Affairs, Yinfan 413687 A7 ΑΊ ________ B7 V. Description of the invention (31) to 5 0 C, and then maintain this temperature at 1 3 kPa Until the tank material has a flash point above 9 3 t (200 ° F). The retort contained 914 grams of a solution with 445% solids. Dilute this solution with water to a solid content of 33%, and add the additive to the percentage of the product required in the treated coating (as shown in Table 4, usually 2 ° /. And 5%). In a water-dispersible coating composition. The coating composition was thoroughly mixed by stirring. Samples were prepared for staining, brushing, and evaluation of coatings using Test Methods 2 and 3. The results are shown in Table 4. The contact angle system is measured in accordance with Test Method 1 and the L. Cai fruit system is shown in Table 3. Table 3 Contact angle measurement of Example 1 | Contact angle water sixteen burned samples forward, backward, forward, backward Reverse control coating without polyurethane additive 78 0 0 0 Including the polyurethane additive of Example 1 Coating 16 0 74 46 *,-. Table-4 Mutual it: Measurement of washability and anti-fouling properties Commercially available coatings prepared using a 3% solid solution of the polyurethane additive as prepared in Example 1 The composition prepares a coated sample. Commercial lacquers are marked with the letters A to V. -34- This paper size is applicable to China National Standard (CNS) A4 specification (210X297mm) --------- installation ------- order ------ line (please read first Note on the back again \ This page) A7 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 413687 B7 V. Invention Description (32) A Β If you buy 2% additives 5% Add if you buy 2% additives 5% Additive brushing cycle 0 0 0 0 0 0 (if stained) 25 0 0 9 5 10 10 50 2 1 10 8 10 10 100 4 5 9 10 10 200 7 7 10 10 10 10 CD if purchased 2% additives 5% additives if purchased 1 2% additive 5% additive brushing cycle 0 (if stained) 0 0 0 0 0 0 25 3 7 9 7 8 10 50 5 9 10 9 10 10 eye 7-10. 10 ^ 10 10 10 200 8 10 10 10 10 10 --------- Installation ------ Order -------- East (Please read the precautions on the back before filling out this page) -35- This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) 413687 V. Description of invention (33) A7 B7 Printed by EF of the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, such as buying 2% additives, 5% additives such as gambling 2% Thai additive 5% Additive brushing cycle 0 (if stained) 0 0 0 0 0 0 25 5 7 10 3 6 9 50 8 9 10 5 9 10 100 10 10 8 10 10 200 10 10 Γ0… 10 10 10 G Η If you buy 2% additive 5% Add if you buy 2% Additive 5% Additive brushing cycle 0 (if stained) 0 0 0 0 0 25 3 5 8 5 9 8 50 7 9 10 9 10 10 100 10 10 10 10 10 10 200, 10. 10. 10. 10 ^ 10 10 10 --------- install --------- order --------- (Please read the note on the back first Matters re-fill this page) -36- This paper size applies to China National Standards (CNS) A4 specifications (210X29 ^ mm) A7 Printed by the Central Consumer Bureau of the Ministry of Economic Affairs Consumer Cooperatives 413687 B7 V. Description of invention (34) IJ If you buy 2% Additive 5% Additive If you buy 2% Paint Additive 5% Additive Brushing cycle 0 (if stained) 0 0 0 0 0 25 1 5 7 2 8 9 50 3 9 8 5 9 10 100 7 10 10 9 10 10 200 9 10 1 ^ 10 10 10 KL if purchased 2% additive 5% additive if purchased 2% additive 5% additive brushing cycle 0 (if stained) 0 0 0 0 0 0 25 2 2 9 0 1 9 50 4 6 10 1 5 10 100 7 8 10 3 9 10 200, 8 10 10 _ 9 10 10 --------- install -------- order ------ 泉 (# 先 读Remarks on it on the back-fill in this page) -37- This paper size applies to China National Standards (CNS) A4 (210X 297 mm) 413687 Employees' Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 Imprint of the invention (35) Μ Ν If you buy 2% Additive 5% Additive If you buy 2% Additive 5% Additive Brushing cycle 0 (if stained) 0 0 0 0 0 0 25 2 4 10 1 2 7 50 9 9 5 5 9 9 100 10 10 10 8 9 10 200 10 10 1Ό, -9 10 10 0 Ρ if purchased 2% additive 5% additive if purchased 2% additive 5% additive brushing cycle 0 (if stained) 0 0 0 0 0 0 25 2 9 9 8 8 9 50 7 10 10 9 9 100 9 10 10 10 10 10 200, 10 10 ^ 10 _ 10 10 10 --------- install ------ order-- --- 涞 (Please read the precautions on the back before filling in this I) -38- The paper size is applicable to Chinese standards {CNS) A4 specification (2 丨 〇 X 297 mm) 413G87 A7 B7 V. Description of the invention ( 36) _Q_ 2% 5% If you purchase additives, brushing cycle 0 (If contaminated) 0 0 0 25 0 1 8 50 3 3 9 100 5 7 10 200 7 9 10 Employee Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs of the PRC will print RS if they buy 2% additives 5% additives if buy 2% additives 5% additive brushing cycle 0 (if stained) 0 0 0 0 0 0 25 9 10 10 8 8 8 50 10 10 10 9 9 9 100 10 10 10 10 10 10 200, 10 10-10 _ 10 10 10- -------- Installation ------ Order ------ Quan {谙 Read the precautions on the back before filling in this page) -39- The standard of this paper is applicable to Chinese standards (CNS ) A4 specification (2.0 × 297 mm) 413687 A7 B7 V. Description of the invention (37) TU if purchased 2% additive 5% additive if purchased 2% additive 5% additive brushing cycle 0 (if stained) 0 0 0 0 0 0 25 6 6 9 2 1 7 50 9 9 10 6 8 9 100 10 10 10 9 10 10 200 10 10 itr 10 10 10 (Please read the precautions on the back before filling this page) V Brushing cycle as Buy 2% Additive 5% Additive 0 (if contaminated) 0 0 0 25 2 8 8 50 7 9 10 100 9 10 10 200, 10. 1 10 10 Printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 2 65 grams of A-147 (DESMODUR N-100 (from Pitt-40-this paper size applies the Chinese National Standard (CNS) A4 specification (210X2) ? 7 mm) 413687 China ’s Husband-like Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperation Du Yin 袈 Α7 B7 V. Description of the Invention (38, Fort, Pennsylvania)) a 60% fluorenyl isobutyl ketone Solution) and 200 grams of methyl isobutyl ketone were placed in a 1000 ml round bottom flask equipped with a mechanical stirrer, condenser, and nitrogen inlet and heated with a controlled heating stove. 10 grams of ZONYL BA fluorotelomer intermediate (from DuPont (Wilminton, Delaware)) and 120 grams of polyethylene glycol monomethyl acid with an average molecular weight of 750 (from Yongbei Company) (Danbury, Connecticut) available MPEG-750), and 0.05 grams of dibutyltin dilaurate were added, and the flask was heated to raise the temperature of the contents to 80 ° C. The contents were stirred at 80 ° C for 2 hours. Then add 1 «water and continue heating for another 2 hours. The organic solution was then added to 400 grams of water and blended in a SilverSon mixer for 30 seconds. The resulting emulsion was freed from the solvent at about 50 ° C and a pressure of 13 kPa to leave 4 12 g of a clear liquid dispersion. 6 weight percent of this solution was added to a formulated white latex paint (Rohm and Haas Company (Philadelphia, Pennsylvania)) to produce 1,000 micrograms per gram of fluorine in the modified latex paint. Apply 5 mils of lacquer (polyester film ’DuPont (Wilmin, Delaware)) and dry under ambient conditions for 2 to 4 hours. The dried film contained about 2,000 micrograms per gram of fluorine. Example 3 Preparation of Polyurethane Additive with MPEG-3 50 Equivalent Molar Ratio Gas Chemical Alcohol Ratio Polyethylene Monomethyl Ether Add 256 grams of DESMODUR_N-100 (from Bayer, Pittsburgh, Pennsylvania Sivania) a 60 ω / 〇 methyl isobutyl ketone solution, 18 grams of ZONYL Βα fluorotelomer intermediate (from DuPont (Wilminton, -41-this paper music scale applies to China) Standards (CNS) M specifications (210X297 mm) (please read the back of the page; the meaning of the matter, then this page) " * 413687 A7 B7 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. Lava)), and 126 grams of polyethylene glycol monomethyl ether having an average molecular weight of 3 50 (350 from Evergreen Corporation (Danbury, Connecticut)), placed with a mechanical stirrer A 1000 ml round bottom flask was equipped with a condenser, condenser, and nitrogen inlet and heated with a controlled exhaust heating burner. Heat the internal product to 55 ° C. Add 20 grams of a solution containing 0.040 grams of dibutyltin dilaurate in methylhexyl butyl ketone and exothermic reaction to raise the temperature to 90 °. [, Maintaining this temperature for another 3 hours. After 3 hours of maintenance, 8 grams of water was added and the contents were stirred for another 1 hour. Then, the inner two substances were added to a 2 liter flask containing 900 g of 75 ° C water and 100 g of methyl isobutyl ketone with stirring over a period of 10 minutes. This type of flask is equipped with a steaming head, condenser, and empty extraction joint and receiver. The mixture was stirred for 15 minutes and vented to remove the methyl isobutyl ketone / water azeotrope at a temperature of 5500C and a pressure of 13 kPa. Allow the flask to cool to 50 ° C and then maintain this temperature at 1 3 kPa until the tank mass has a temperature above 93.为止 (200 F) until the flash point. The full tank contained 914 grams of a solution with 44.5% solids. This solution was diluted with water to 33% solids, added to the paint at a weight ratio of 6%, and evaluated as described previously. Example 4 is based on perfluorooctyl mercaptan (Lodyne 924) and MPEG-350 · ^ acetaminophen ethyl ester additive-preparation--except for the reaction system of 130 grams of DESMODUR N-100 (from Bayer Corporation (Pittsburgh , Pennsylvania)) a 60% methyl isobutyl ketone solution, 53 grams (0.10 mol) of 3,3,4,4,5,5,6,6,7,7, 8,8,9,9,10,10,10 -Heptadecafluoro-1-decanethiol (L0DYNE 924 (from Ciba Jiaji Company, -42 private paper size applies Chinese National Standard (CNS) A4 specifications (210X297 mm) --------- Seed coat ------ 1T ------ ^ (Please read the precautions on the back before filling in this page) 413687 A7 B7 V. Description of the Invention (40) Addesley, New York) and 91 grams of polyethylene glycol monomethyl ether having an average molecular weight of 35 (from Yongby Corporation (Danbury, Connecticut)) (M PEG-3 50) was prepared as in Example 3. After the beer has been raised above 93 °, (200 τ.), The steamer tank contains 734 grams of 34% 2% solids. Luo liquid. Dilute the falling liquid with water to 33% solids content, add it to the paint at a weight ratio of}%, and Evaluation is as described previously. Example 5 Poor_N-ethyl-N- (2-Hydroxyethyloctane Sulfamine MPEG-3 50 Polyurethane Addition Jianxiong)] Prepare 130 g of reactant system DESMODUR N-100 (from Bayer, Pittsburgh, California) a 60% fluorenyl isobutyl ketone solution '54 g (0.10 mole) of N-ethyl-1,1 , 2,2,3,3,4,4,5,5,6,6,7,7, 8,8,8-heptadecafluoro-1 \ 1- (2-hydroxyethyl) -1-octane Sulfasalazine ({7 (^ 1〇 (Minnesota Mining and Manufacturing Company, Minneapolis, Minnesota and 91 grams of polyethylene glycol monomethyl acid with an average molecular weight of 350 (Berry, Connecticut) except for MPEG-3 50), the preparation was performed as in Example 3. After the flash point has been raised to above 93 ° C (200T), the 'distillation tank contains 568 grams of 37.3% solids Solution. Dilute the solution to 33% solids with water, add it to the paint at 1% by weight, and evaluate as described previously. ·--Example 6 Ethyl ethane perfluoroalkane Preparation of Polyurethane Additive for MPEG-350 except Reactant System 130 DESMODUR Nl00 (from Bayer (-43- this paper music scale applies Chinese National Standard (Cns) A4 specifications (210X297 mm) ----------------- order --- --- 溧 (Please read the notes on the back before filling in this page) M Printed by the Consumers Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 413687 A7 B7 V. Invention Description (41 Pittsburgh, Pennsylvania) 60% methyl isobutyl ketone solution, 75 g (0.10 mol) of ZONYL FSO-100 (a fluorotelomer monoether with polyethylene glycol, CAS No. 122525-99-9 (from DuPont, Wilmington, Delaware) and 91 grams of MPEG-350 (from Evergreen (Danbury, Connecticut)) were prepared as in Example 3. After the flash point has been raised above 93 ° C (200 T), the retort contains 622 grams of a solution with 3 6.1% solids. The solution was diluted with water to 33% solids, added to the paint at 1% by weight and evaluated as described previously. Example 7: Polyurethanes based on latex can be cleaned. Evaluation of ketones. Examples 3-6 of perfluoroalkyl polyfluorourethanes as cleanable agents. The system consists of 1% by weight. The substance was evaluated by adding it to a commercial flat latex paint. The paint was sampled as previously described and the film was allowed to cure at ambient temperature for 7 days. The cleanability of the film was evaluated as described in Test Methods 2 and 3. For the blue crayon, the following results were obtained. Table 4: A kind of perfluoroalkane polyamine Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs The number of scrubbing cycles Example 3 Example 4 Example 5 Example 6 Does not contain detergent

JiAiL is an evaluation of washable tinctures ^ --_ 100. Washability etc. --------------------------------- (Please read the back Note again. Fill out this page) 2 '4 2 2 2 -44-8 8 8 7 3 9 10 9 9 This paper size applies to China National Standard Soap (CNS) A4 specifications (2I0X29? Employees of the Central Standards Bureau of the Ministry of Economy Consumer Cooperative India Pei 413687 A7 ______B7 V. Description of the Invention (42) Example 8 An ethyl ester additive as an anti-swelling agent for wood is diluted with water from a sample of 200 grams to 200 grams of the substance described in Example 3. As described Test, method 4 (ASTM D-4446-84) treated a piece of wood, and air-dried under the surrounding repairs for 7 days. Then it was placed in a wood swellometer and tested by the ASTM procedure. The treated wood swelled 3 5% and 46% lower than the untreated control sample. Example 9 Details of an ethyl formate additive as an oil repellent on hard surfaces jk_ Diluted with water. The substance described in Example 3 became 5% solids. Content and use—paint on the surface shown below. Measure oil and water contact angles, and describe in the table below Table 6 Control samples of oil-repellent and water-repellent concrete on hard surfaces. Perpetual contact angle advances. * Cetane contacts fish forward and backwards. * Treated concrete 127 34 Stele control sample Ψ 氺% treated stele 63 〇111 38 Terracotta control sample ψ * * * Treated terracotta 86 86 〇128 0 -45- Paper size _ ^ ®iii? {&Quot; cNs) --------- pack ---- --Order ------ ¾ (Please read the notes on the back before filling in this page) 413687 A7B7 V. Description of the invention (43) Slate control sample 0 0 * Fortunately treated slate 62 0 95 43 Granite control sample 51 16 12 0 Treated granite name 42 0 80 56 Marble control sample 52 0 12 0 Treated marble 46 0 84 55 Wood control sample ψ * * * Treated wood 133 0 137 0 Limestone Control sample + —V ·?-* Treated limestone umbrella-** ** Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs * Absorbed into the surface by the flow system * * The surface is too rough to measure the contact angle Example 1 0 Evaluation of Polyfluorocarbamate Additive as an Oil Repellent for Asphalt It is estimated that the substance described in Example 3 diluted with water becomes 5% solids content. Coat a piece of asphalt with this solution and allow it to dry overnight. Drops of hexadecane and water were placed on the surface, and it was found that they formed beads relative to the untreated control sample. --------- Installation ------ 1T ------ tt (Please read the precautions on the back before filling in this page) -46-This paper size applies to Chinese National Standards (CMS ) A4 size (210X297 mm)

Claims (1)

Amend Amendment to Patent No. 0441 "3687 ft Patent Scope Amendment ^ (10,88 3, A8 B8 C8 D8 Main Tau f. Cooperative cooperative policy 6. Scope of patent application --------- 1. A polyfluorourethane compound that can be used as an additive in water-dispersed coating compositions for coating hard surfaces, which are the following substances Product of the reaction: (1) at least one diisocyanate, (2) at least one of an amount sufficient to react with 5% to 80% of the isocyanate groups in the diisocyanate, and at least one of Fluorochemical compound, (3) at least one compound of the formula R10- (R2) k_YH (where R10 is a Ci-Cw alkyl group) in an amount sufficient to react with 5% to 80% of the isocyanate groups in the diisocyanate , C2-C18 咢 miga-fluorenyl radical, or C 2 -C 1 8 咢 miga-alkenyl; R 2 is based on-[OCH2C (R4) H] p-,-[〇CH2C ( CH2Cl) H] p-, or -C (R5) (R6) (〇CH2C [CH2Cl] H) p-terminated-CnH2n-, where R 4, R 5 and R 6 are the same or different and Η or A C! -C 6 alkyl radical, η is 0 to 12 and p is 1 to 50; Y is 0, S, or n (r7), wherein r7sh or (: 丨-(: 6 alkyl; And k is 0 or 1); and (4) if necessary, an amount of water sufficient to react with 5% to 60% of the isocyanate groups in the diisocyanate. 2. A kind of coating which can be used as a coating on hard surfaces Polyfluorourethane compounds as additives to water-dispersible coating compositions, which are the reaction products of: (1) at least one polyisocyanate containing at least three isocyanate groups per molecule or a mixture of more than one polyisocyanate, (2) at least one fluorinated chemical compound containing at least one nivolitovin hydrogen in an amount sufficient to react with 5% to 33% of isocyanate groups in the polyisocyanate, (3) sufficient to react with Polyisocyanate in the amount of 5% to 800/0 of the number of isocyanate group reaction at least one formula R10_ (R2) k_YH This paper size applies Chinese National Standard (CNS) A4 specifications (210X297 public epidemic) I n. Ni I line (Please read the notes on the back before filling this page) Amendment to Patent No. 0441 "3687 ft Patent Scope Amendment ^ (10,88 3, A8 B8 C8 D8 Main Tau f. Cooperative cooperative policy 6. Scope of patent application --------- 1. A polyfluorourethane compound that can be used as an additive in water-dispersed coating compositions for coating hard surfaces, which are the following substances Product of the reaction: (1) at least one diisocyanate, (2) at least one of an amount sufficient to react with 5% to 80% of the isocyanate groups in the diisocyanate, and at least one of Fluorochemical compound, (3) at least one compound of the formula R10- (R2) k_YH (where R10 is a Ci-Cw alkyl group) in an amount sufficient to react with 5% to 80% of the isocyanate groups in the diisocyanate , C2-C18 咢 miga-fluorenyl radical, or C 2 -C 1 8 咢 miga-alkenyl; R 2 is based on-[OCH2C (R4) H] p-,-[〇CH2C ( CH2Cl) H] p-, or -C (R5) (R6) (〇CH2C [CH2Cl] H) p-terminated-CnH2n-, where R 4, R 5 and R 6 are the same or different and Η or A C! -C 6 alkyl radical, η is 0 to 12 and p is 1 to 50; Y is 0, S, or n (r7), wherein r7sh or (: 丨-(: 6 alkyl; And k is 0 or 1); and (4) if necessary, an amount of water sufficient to react with 5% to 60% of the isocyanate groups in the diisocyanate. 2. A kind of coating which can be used as a coating on hard surfaces Polyfluorourethane compounds as additives to water-dispersible coating compositions, which are the reaction products of: (1) at least one polyisocyanate containing at least three isocyanate groups per molecule or a mixture of more than one polyisocyanate, (2) at least one fluorinated chemical compound containing at least one nivolitovin hydrogen in an amount sufficient to react with 5% to 33% of isocyanate groups in the polyisocyanate, (3) sufficient to react with Polyisocyanate in the amount of 5% to 800/0 of the number of isocyanate group reaction at least one formula R10_ (R2) k_YH This paper size applies Chinese National Standard (CNS) A4 specifications (210X297 public epidemic) I n. Ni I line (Please read the notes on the back before filling this page) 8888 ABCD 41S687 Patented compounds (where R10 is an alkyl group, C2-C18 gomiga-alkenyl radical, or C 2 -C 丨 8 咢 miga-enolyl group; R 2 is based on-[0CH2C ( R4) H] P-,-[〇CH2C (CH2Cl) H] p ·, or -C (R5) (R6) (OCH2C [CH2Cl] H) p-terminated -cnH2n-, where R4 'R5, and R6 is the same or different and is Η or a C 丨 -C 6 alkyl radical, η is 0 to 12 and p is 1 to 50; Y is 0, S, or N (R7), of which 117 Η or <: "(: (; alkyl; and k is 0 or 1); and (4) if necessary, water in an amount sufficient to react with 5% to 60% of the isocyanate groups in the polyisocyanate . 3.-An improved water-dispersible coating composition comprising an emulsion, latex, or suspension of a film-forming material dispersed in an aqueous medium, wherein the modification comprises a polyfluorourethane compound The combination into an aqueous medium is the product of the reaction of: (1) at least one diisocyanate, or a polyisocyanate containing at least three isocyanate groups per molecule or a mixture of more than one polyisocyanate, (2 ) At least one fluorinated chemical compound containing at least one Nirewetinov hydrogen in an amount sufficient to react with 5% to 80% of isocyanate groups in a diisocyanate or polyisocyanate, (3) is sufficient to react with Diisocyanate or polyisocyanate in the amount of 5% to 80% of isocyanate groups reacted in at least one compound of the formula R10- (R2) k-YH (where R_10 is a calcined group, C〗 -Ci8 Gomiga- A radical, or c 1-c 丨 8miga-alkenyl; R 2 is optionally-[〇ch2C (R4) H] p-, • [〇CH2C (CH2C1) H] P-, Or -C (R5) (R6) (OCH2C [CH2Cl] H) p-terminated -C η Η 2 η-, where R 4, R 5, and R 6 are the same or different and are Η or -2- This paper standard is applicable to China National Standards (CNS) A4 rule (2tOX297 mm) --- ------ ^ ------ ir ------ 0 (#First read the notes on the back before filling in this card) Yin Yang, Ministry of Economic Affairs Printed by the Central Bureau of the Ministry of Economic Affairs Printed by the Bureau's Consumer Cooperative Cooperative 412687 it C8 D8 Six. Patent application scope A C 丨 -C 6 alkyl radical, π is 0 to 12 and p is i to 50; γ is 0, S, or N (R7 ) 'Wherein R7 # H or C〗 -C6 alkyl; and k is 0 or 1); and if necessary (4) sufficient to react with 5% to 60% of the isocyanate group in the diisocyanate or polyisocyanate The amount of water. 4. Composition according to item 3 of the scope of patent application 'wherein the material forming the film is a latex selected from the group consisting of acrylate, acrylic derivative, vinyl-acrylic derivative', ethylene derivative, or a mixture thereof polymer. 5. The composition according to item 3 of the scope of patent application, wherein the fluorochemical compound is a perfluoro gauge group in an amount sufficient to react with at least 40% of the isocyanate group and its formula R 丨 〇 (R2) k-YH The compound is a polyethylene glycol methyl ether in an amount sufficient to react with at least 30% of the isocyanate groups. 6. A dry coating composition comprising a thin film incorporating a polyfluorocarbamate compound: an emulsion, latex or suspension forming a substance, the polyfluorocarbamate compound is a reaction product of the following substances : (1) at least one diisocyanate, or a polyisocyanate containing at least three isocyanate groups per molecule or a mixture of more than one polyisocyanate, (2) sufficient to interact with diisocyanate or polyisocyanate Of 5 / 0 to 80% of the isocyanic acid group in the amount of at least one fluorine chemical compound containing at least one Nirewetinov hydrogen, (3) is sufficient to be 5% of the diisocyanate or polyisocyanate Up to 80% of the isocyanate-reacted amount of at least one compound of the formula R10- (R2) k_YH (wherein Ri0 is a Ci-Cu alkyl group, Cl-C18 咢 miga-alkenyl radical 'or C 1 -C 丨 8 咢 miga-enyl group; R 2 is based on-[〇CH2C (R4) H] p_, -3- This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm)- -------- ¾ ------ Order ------ line (please read the notes on the back before filling in this page) AB, CD 413687 6. Scope of patent application-[OCH2C ( CH2a) H] p- 'or -C (R5) (R6) (〇CH2C [CH2Cl] H) p-terminated -cn Η 2 n-, where R 4, R 5, and r6 are the same or different And Η or a kind of C 丨 -C 6 alkyl radical, η is 0 to 12 and ρ is 1 to 50; Υ is 0, S, or N (R7), where R7 is Η or C 丨-(: 6 alkyl group; and k is 0 or 1); and (4) if necessary, it is sufficient to be 5% to 60% of isocyanate in diisocyanate or polyisocyanate Amount of water for ester-based reaction. 7. A method for improving the cleanability of a surface on which a dry coating composition has been deposited, comprising a polyurethane which is the product of the following reaction before drying The ethyl ester compound is added to the coating composition: (1) at least one diisocyanate, or a polyisocyanate containing at least three isocyanate groups per molecule or a mixture of more than one polyisocyanate, (2) sufficient to be compatible with the diisocyanate or polyisocyanate 5% to 80% of the isocyanate groups in the isocyanate are reacted in an amount of at least one fluorine chemical compound containing at least one Nirewetinov hydrogen, (3) sufficient to be compatible with 5 to 5% of the diisocyanate or polyisocyanate 80% of the isocyanate-reacted amount of at least one compound of the formula R10- (R2) k-YH (wherein R10 is a C ^ -Cu alkyl group, C2-Ci8? Miga-alkenyl radical, or C2 -C18 and other mika-bound coolers; r2 is based on-[◦CH2C (R4) H] p-,-[〇CH2C (CH2C1) H] p-, or -C (R5) (R6) (OCH2C [CH2Cl] H) p-terminated-CnH2n- 'where R4, R5, and R6 are the same or different And Η or a C 丨-(: 6 alkyl radical, η is 0 to 12 and p is 1 to 50; Y is 0, S, or N (R 7) 'wherein R 7 is Η or C丨 -C 6 alkyl; and k is 0 or 1); and if necessary (4) is sufficient to be 5% of the diisocyanate or polyisocyanate -4-This paper applies the China National Standard (CNS) A4 ^ (210X297 mm) --------- I ------ ^ ------- ^ (Read the notes on the back of the book before you fill in this page) Central Bureau of Standards, Ministry of Economic Affairs Employee consumer cooperative printing 8 8 88 ABCD 413687 6. Apply for patents ranging from 60% of the amount of isocyanate-reactive water. 8. A method for improving the oil repellency of a surface on which a dry coating composition has been deposited, comprising adding a polyurethane compound, a product of the following reaction, to the coating composition before drying: (1) at least one diisocyanate, or a polyisocyanate or a mixture of more than one polyisocyanate containing at least three isocyanate groups per molecule, (2) sufficient to be 5% to 80% of the diisocyanate or polyisocyanate At least one of the isocyanate-reactive amounts of the fluorochemical compound containing at least one nirevitivum hydrogen (3) is sufficient to react with 5% to 80% of the isocyanate groups in the diisocyanate or polyisocyanate The amount of at least one compound of the formula R1 ()-(R2) k_YH (where R10 is an alkyl group, a C2-Cls 咢 miga-alkenyl radical, or a C 2 -C 1 8 咢 miga-alkenyl group ; R 2 is terminated with-[0CH2C (R4) H] P-,-[0CH2C (CH2C1) H] P-, or -C (R5) (R6) (0CH2C [CH2C1] H) P- -cnH2n-, where R4, R5, and ruler 6 are the same or different and are Η or a Ci-Ce From the group, η is 0 to 12, and p is 1 to 50; Y is 0, S, or N (R7), where 117 is only C or C6 alkyl; and k is 0 or 1); and (4) Water is required in an amount sufficient to react with 5% to 60% of the isocyanate groups in the diisocyanate or polyisocyanate. 9. A coating for reducing the application of a water-dispersible coating composition at A method for swelling in wood, comprising adding a polyurethane compound, a product of the following reaction, to a coating composition before coating: (1) at least one diisocyanate 'or at least three iso- 5- The paper scale is applicable to Chinese National Standard (CNS) A4 (2t〇X297mm) --------- ^ ------ 1T ------ ii (Please first (Please read the notes on the back and fill in this page again.) Printed by the Central Bureau of Standards of the Ministry of Economic Affairs of the Department of Shellfish Consumer Cooperation Du printed 413687 A8 BS C8 D8 6. Apply for a patent range of polyisocyanate or a mixture of more than one polyisocyanate, ( 2) at least one of an amount sufficient to react with 5% to 80% of the isocyanate group in the diisocyanate or polyisocyanate Fluorine chemical compound containing at least one Nitrovirudin hydrogen, (3) at least one formula of the number R1Q_ (R2) k sufficient to react with 5% to 80% of isocyanate groups in a diisocyanate or polyisocyanate -YH compounds (where R10 is a kind of <: 丨-(: 18 alkyl, C2-C18, etc. Miga · alkenyl radicals' or C 2 -C 丨 s, etc. Miga-alkenyl groups; r 2 series If necessary, [OCH2C (R4) H] p- '-[0CH2C (CH2C1) H] P-, or C (R5) (R6) (0CH2C [CH2Cl] H) p-terminated-CnH2n-, where R 4. R 5 and R 6 are the same or different and are Η or a C i -C 6 alkyl radical, η is 0 to 12 and p is 1 to 50; Y is 0, S, or N (R 7), wherein R 7 is fluorene or C 丨 -C 6 alkyl; and k is 0 or 1); and (4) is sufficient to be as high as 5% to 6 in diisocyanate or polyisocyanate. 0% of the amount of isocyanate reacted water. --------- ^ ------ 1T ------. ^ (Please read the notes on the back before filling out this page) Printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs L This paper size applies to China National Standard (CNS) A4 specifications (2 丨 〇 > < 297 mm)