TWI290184B - Aqueous composition for rendering fibrous substrates water repellent - Google Patents

Abstract

The present invention provides an aqueous composition comprising: (a) a melamine that is at least partially derivatised with an aliphatic hydrocarbon group having at least 8 carbon atoms; (b) a wax; and (c) at least one component selected from the group consisting of (i) a reaction product of an aliphatic polyisocyanate and an organic compound having one or more groups capable of reacting with an isocyanate, said reaction product having free isocyanate groups and having a molecular weight of at least 350 g/mol and (ii) a blocked aromatic polyisocyanate. The compositions can be used to treat textile to provide good water repellency properties thereto.

Description

1290184 A7 B7 V. INSTRUCTION DESCRIPTION (1) Field of the Invention The present invention relates to an aqueous composition for imparting water repellency to a fibrous substrate. In particular, the invention relates to such compositions which are substantially free of fluorochemical compounds. BACKGROUND OF THE INVENTION The manufacture of substrates, especially compositions of fibrous substrates such as textiles, water repellency is well known in the art for a long time. Generally, commercial compositions which impart water repellency to fabrics include fluorochemical compounds, i.e., the compounds include substantial amounts of fluorine. The fluorochemical compound can be a simple low molecular weight compound as well as an oligomer or a polymer compound. For example, U.S. Patent 3,480,579 discloses the use of a mixture of hydrocarbon-derived melamine and a fluorochemical compound to impart water and oil repellency to the fabric. The composition of US 3,480,579 may contain a wax such as an alkane wax. Melamine derived from a fluorochemical group is disclosed in U.S. Patent No. 4,477,498 and U. WO 98/45345 discloses melamine derived from a hydrocarbyl group and a fluorochemical group. These compositions are used to treat fabrics and impart the same oil and water repellency. A composition for the manufacture of fabric oil repellent and water repellent based on a protected isohydroester component and a fluorochemical compound is further known from U.S. Patent No. 4,834,764 and WO 99/14422. Similarly, US 5,508,370 shows self-emulsified polyisocyanates emulsified in water, and such protected pen isocyanates can be used to impart a water repellency to a substrate such as a fabric, and are generally indicated for use in combination with a fluorochemical compound. Since a fluorine chemical compound is used in the composition, the substrate can be imparted with excellent oil and water repellency. But unfortunately, its application has recently caused environmental problems. Therefore, it is necessary to find another grain substance that does not contain fluorine chemistry.

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Line paper size applies to China National Standard (CNS) A4 size (210 X 297 mm) 1290184 A7 B7 V. Invention description (3) — When reacting at room temperature, it will be obtained at room temperature and usually at room temperature with isoammonium. The compound in which the acid vinegar reacts does not react, but reacts with the isocyanate-reactive compound at a high temperature. Generally, at elevated temperatures, the protecting group is released from the protected aromatic polyisocyanate compound, so that it can again react with the isocyanine reactive group (isocyanate group. The protective agent and its mechanism are detailed). Said, protected isocyanuric acid m: eight, institutions and chemistry,,, D〇uglas wicks and

Zeno W. Wicks Jr., Progress in Organic Coatings, 36 (1999), pp. 14-172 0 The present invention also provides a method of treating a fibrous substrate with a composition, and a substrate treated with the composition. DETAILED DESCRIPTION OF THE INVENTION The present invention <Aqueous composition comprises melamine derived at least in part from an aliphatic hydrocarbon group having at least 8 carbon atoms, preferably 12 carbon atoms. The system has a carbon atom of from 1 to 5 carbon atoms. Melamine can be produced in any known manner. For example, methylolated melamine or its lower (c丨·4) alkoxy derivative can be reacted with a hydroxy compound of the formula:

Rh-(X1)m^ZlH wherein h represents an aliphatic hydrocarbon group having at least 8 carbon atoms; X1 represents a divalent organic bond group; z Η represents a per group, a thiol group, or an acid group such as a cleavage acid; Is 0 or 1.

Rh contains a group having at least 8 carbon atoms, and more preferably 12 carbon atoms. The base is preferably saturated. Preferably, the Rh-group comprises a non-substituted straight chain or branch

1290184 A7 B7

Chain base. Preferably, the alkyl group has 8 to 30 carbon atoms. The Rh- group may also contain a cycloester group such as a cyclohexyl group or a cyclohexyl group. The organic divalent linking group X1 preferably has from 1 to about 2 carbon atoms and may contain a milk-containing, SL or sulfur-containing group or a combination thereof. For example, the organic divalent linking group may be selected from the group consisting of an exoaryl group, an aralkyl group, a sulfonyl group, a poly(alkyleneoxy group), a urethane group, a ureido group, a carbamine group or an alkyl group. Sulfonamide alkylene. The reaction of methylolated melamine or an alkoxy derivative thereof is generally carried out in the presence of an acid catalyst. Strong acid catalysts are generally used as acid catalysts, such as p-toluene acid, decene acid, amberlyst IR-120 and toxin. The dioxyamine is converted to at least a portion of the mercapto or lower alkoxy group, preferably at least 2% by weight of the mercapto or lower alkoxy group. Better, at least 4 0 _ 5 〇 % is converted. Therefore, the melamine of a preferred embodiment of the present invention may be a mixture of melamine compounds represented by the following formula:

Y Υ eight of the Y groups may be the same or different, and each Y group represents CH2 OH, CH2OR, and alkyl, or CHaZ^X^-Rh, and z, the paper scale applies to the Chinese National Standard (CNS) Α 4 specification (210 X 297 mm) 1290184 A7 B7 V. Description of invention (6)

The organic compound reacts. The organic compound is generally reacted with a lipid polycyanate in the presence of a catalyst such as an organotin compound under the reaction conditions generally employed. The amount of organic compound is selected so that the desired amount of unreacted isocyanate groups is left behind. The resulting reaction mixture can be used to prepare the aqueous composition of the present invention, and generally does not contain any unreacted low molecular weight aliphatic polyisocyanate, or its content is preferably less than 1% by weight, more preferably less than 5% by weight. . The organic compound preferably has one or two functional groups which can react with the isocyanate group. The functional group contains a hydroxyl group, an amine group, and a thiol group. Examples of the organic compound include an alkanediol such as ethylene glycol, a mono-alkanol having at least 6 carbon atoms, a lipid ester-resistant diol, a polyester diol, an alkylenediamine, and a dimer diol. According to a preferred embodiment, the organic compound will contain one or more water-soluble groups or groups which form a water-soluble group, and thus a reaction product which is self-emulsified in water can be obtained. Suitable water-soluble groups include cationic, anionic and zwitterionic groups, as well as nonionic water-soluble groups. Examples of the ionic water-soluble group include an ammonium group, a rust group, a thio group, a treate group, a sulfonate group, a phosphate group, a phosphite group or a phosphonate group. Examples of water-soluble groups which can form water in water include groups which may be protonated in water, such as amine groups, especially tertiary amine groups. The organic compound which is most preferably reacted with the aliphatic polyisocyanate is an organic compound having only one or two functional groups which can react with the NC0-group, and further contains a nonionic water-based group. A nonionic water-soluble group contains a polyoxyalkylene group. Preferred polyoxyalkylene groups include those having from 丨 to 4 carbon atoms, such as polyoxyethylene, polyoxytetramethylene, and copolymers thereof, such as polymers having an ethyloxy group and an oxypropyl group. . The polyoxyalkylene-containing organic compound may contain one or two functional groups such as a hydroxyl group or an amine group. Polyoxyethylene-containing ethyl compound -9- This paper scale applies to Chinese National Standard (CNS) A4 specification (210 X 297 mm)

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1290184 A7 B7 V. INSTRUCTION DESCRIPTION (7) Examples include monoalkyl ethers of polyglycols such as monomethyl or ethyl ether of polyethylene glycol, random or block of ethylene oxide or propylene oxide The base-terminated methyl or ethyl ether of the copolymer, the amine-terminated methyl or ethyl ether of polyethylene oxide, polyethylene glycol, polypropylene glycol, and the hydroxyl group of ethylene oxide and propylene oxide Blocked copolymers (including block copolymers), diamine terminated poly(ethylene oxides) such as JeffaminesTM ED, JeffamineTM EDR-148 and poly(oxygen-based) thiols. 0 Commercially available lipids used herein. The reaction product of the polyisocyanate and the organic compound comprises BaygardTM VP SP 23012, RucoguardTM EPF 1421 and TubicoatTM Fix ICB. In addition to the above reaction product, the composition may comprise a polyisocyanate component of the protected aromatic polyisocyanate. The protected polyisocyanate is generally a protected aryl di- or triisocyanate or a mixture thereof, and can be prepared by reacting an aromatic polyisocyanate with a protecting agent having at least one functional group reactive with an isocyanate group. Preferably, the aromatic polyisocyanate is protected from an isocyanate-reactive group at a temperature below 150 ° C, preferably at a high temperature to deprotect the protective agent. Preferred protecting agents include aryl alcohols such as phenols, decylamines such as c-caprolactam, J-valeroguanamine, 7*-butylidene, such as formaldehyde oxime, acetaldoxime, methyl ethyl ketone oxime, Cyclohexanone oxime, acetophenone oxime, benzophenone monthly loss, 2-butanone oxime, or diethylglyoxime. Other suitable protecting groups include bisulfite and three bites. The amount of aromatics of the protected aromatic polyisocyanate is preferably at least 350 g/mole. According to a particular specific particle of the invention, the protected aromatic polyisocyanate may comprise an aromatic polyisocyanate (for example a di- or tri-isocyanate), a protective oxime and a deprotecting agent and one or more isocyanate groups. Hydroxyl, Amine or -10- This paper scale applies to Chinese National Standard (CNS) Α4 size (210 X 297 mm)

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1290184 A7 _____B7 I. V. Inventive Note (9) "~~' - The polyisocyanate compound is generally added to the aqueous treatment composition only immediately before the treatment of the fibrous substrate because of the freeness contained in the composition. The cyanate vine group reacts slowly with water and thus disappears, resulting in no: reacting with the groups on the fibrous substrate. Moreover, even if the polyisocyanate component contains a reaction product free of isocyanate groups, it has been found that the aqueous composition can be effectively used for from i hours to about 12 hours. If the polyisocyanate contains only the protected aromatic polyisocyanate, the aqueous composition will have a substantially longer stability of typically weeks or months. The aqueous treatment composition generally contains melamine in an amount of from 2% by weight to 15% by weight, preferably from 0.5% by weight to 10% by weight. The content of the wax is generally from 〇2% by weight to 15% by weight, preferably from 5% by weight to 10,000% by weight, and the content of the polyisocyanate component is generally from 0.01% by weight to 5% by weight, preferably 〇·〇5 From % by weight to about 2% by weight. The aqueous treatment composition can contain other additives used in conventional fiber treatment compositions. However, the aqueous compositions of the present invention are generally free of fluorochemical compounds, or levels thereof generally less than 〇〇5 by weight, more preferably less than 〇.〇1% by weight. The fibrous substrate treated with the present invention comprises, inter alia, a fabric. The fibrous substrate may be mainly composed of synthetic fibers such as polyester fibers, or natural fibers such as cellulose fibers and mixtures thereof. When the fibrous substrate is substantially composed of a polyester fiber, the base is preferably treated with an aqueous composition comprising a reaction product of a lipid polyisocyanate and an organic compound. In order to impart water repellency to the fibrous substrate, an effective amount of the aqueous composition is applied to the substrate. The amount of the aqueous composition applied to the substrate is selected to impart a sufficiently high degree of desired properties to the surface of the substrate. The amount is generally based on the weight of the substrate, 0 3 to 5% by weight, preferably 丨 to 3% by weight of the paper size of the standard (CNS) A4 specification (21 〇 X 297 mm) - 12- 1290184 A7 B7 V. INSTRUCTIONS (1Q) The composition is present on a treated substrate. The amount imparted to the desired properties can be determined empirically and can be adjusted as needed or desired. In order to affect the treatment of the textile substrate, the substrate can be immersed in the diluted emulsion. The soaked substrate can then be operated through a blade/drum to remove excess aqueous composition, dried and hardened in an oven that is sufficiently temperature and time to obtain a hardened substrate. The hardening process is generally carried out at a temperature of from about 110 ° C to about 190 ° C depending on the particular system and coating method employed. Generally, a suitable temperature is from about 120 ° C to about 170 ° C, especially from about 150 ° C to about 170 ° C for from about 20 seconds to 10 minutes, preferably from 30 seconds to 5 minutes. The invention is further illustrated by reference to the following non-limiting examples. EXAMPLES Dispensing and Handling Procedures The required amount of melamine, wax and polyisocyanate are formulated in an aqueous treatment tank. The test substrate was treated with a mat to obtain a concentration of 0.5 to 3% (based on the weight of the fiber, and SOF (solid on fiber), and the sample was dried and hardened at 160 ° C for 2 minutes. The present invention The substrate used for the evaluation was commercially available and listed below: 100% cotton (khaki): style no. 1511.1, available from Utexbel NV, Ronse, Belgium. PES/CO 65/35 (white): style no. 2681, Available from Utexbel NV, Ronse, Belgium 100% PESp (椋色): style no. 6145, available from Sofinal, Belgium. After drying, the substrate was tested for water repellency. The water repellency shown in the examples and comparative examples The data is subject to the following measurement and evaluation criteria. Spray test (SR) -13- This paper scale applies to China National Standard (CNS) A4 specification (210X 297 mm) 1290184 A7 B7 V. Invention description (11) The blasting evaluation of the substrate shows the dynamic water repellency data of the treated substrate on the water sprayed on the treated substrate. The water repellency is published in the American Fabric Chemistry and Color (AATCC) 1985 Technical Manual and the Annual Manual. Standard test number 22 is measured and sprayed on the test substrate According to the rating, the spray rating is obtained by spraying 250 ml of water onto the substrate from a height of 15 cm. Visually evaluating the type of wetting: using 0 to 100 aliquots, where 0 means complete Wetting, 100 means completely non-wetting.

Bundesmann test The Bundesmann Test Method (DIN 53888) was used to determine the wetting of rainwater on treated substrates. In this test, the treated substrate simulates raining while wiping the back side of the substrate. The appearance of the exposed surface was visually inspected after 1.5 and 10 minutes, and was evaluated between 1 (complete surface wetting) and 5 (no water left on the surface). The Bundesmann test was carried out only on substrates with a initial spray rating of 100. Washing Procedure The following procedure was used to prepare a substrate sample referred to as "5 Home Launderings Ironing (5HL IR)" in the following samples. A 230 gram sample of a treated substrate sheet of typically 400 cm2 to about 900 cm2 square. The sample with the fold (1.9 kg of 8 oz square folded 8100 cm2 piece of fabric) was placed in the washing machine. A commercially available detergent (''S apt on", 46 grams of Henkeb from West Germany) was added, and the washing machine was filled with hot water (40 ° C + -3 ° C) to a high water level. The substrate and the folding load were washed five times using a 12-minute general wash cycle, followed by five washes and centrifugation. The sample does not dry between repeated cycles. Hang the substrate on the support frame and dry it at room temperature (about 20 °C)-14- The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) 1290184 A7 B7 V. Invention Description (12) 24 hours. After drying, the sample is passed through an electric iron at a temperature set by the substrate fibers. The washing process was then tested as in the spray test. Abbreviation The following abbreviations and brand names are used in the examples and comparative examples. IN SR: Initial spray rating PESa: Polyester microfiber PES/CO: Polyester/cotton FreepelTM 1225 · Melamine/alkane emulsion, purchased from BF Goodrich RepearlTM MF: Protected aromatic polyisocyanate available from Mitsubishi CerolTM EWL: melamine/alkane emulsion available from Clariant BaygardTM EDW: anionic protected aromatic polyisocyanate dispersion from Bayer BaygardTM VP SP23012: aliphatic isocyanate , purchased from Bayer TubicoatTM Fix ICB: a fatty isocyanate available from CHT RucoguardTM EPF1421: a fatty isocyanate available from Rudolf Co GmBH MPEG 350: poly(ethylene glycol) monodecyl ether, molecular weight 350, available from Aldrich DBTDL : Dibutyltin dilaurate DESN : Desmodui: TM N100: aliphatic polyisocyanate, available from Bayer PMAc: methoxypropanol acetate from Merck HMMM: hexamethoxymethyl melamine, available from Dyno Cyanamid, trade name For CymelTM 303 DMAE: dimethylaminoethanol, available from Merck

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Line -15- This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1290184 A7 ___B7_ V. Invention description (13)

ArquadTM 2HT/75 : Dimethyldihydrogenated tallow ammonium chloride, purchased from AKZO

TweenTM 81: Polyoxyethylene ethyl (5) sorbitol monooleate, available from Uniqema All parts, percentages, etc. in the following examples are by weight unless otherwise indicated. Synthesis of Fatty Isocyanate 1·Acid Isocyanate DESN/MPEG 350 1/0.25 (Morby) Synthesis 57.3 g 5€5111〇 (1111^ 00 and 19 g methoxypropanol acetate injection device machinery Add a 0.017 g DBTDL to the 500 ml 3-neck reaction flask with a stirrer, temperature control, dropping funnel, condenser and nitrogen input and output, and slowly increase the temperature to 70 ° C. Add 8.75 g MPEG 350 via the dropping funnel. 2 5 g of PMAc. The reaction was carried out at 70 ° C for 16 hours to obtain a clear, thick 60% solution for use in the treatment tank. 2. Lipid isocyanate DESN/DMAE 1/0.25 (Morbi) and Synthesis of DESN/DMAE 1/0.5 (Morby) The above procedure was repeated to prepare the lipid isocyanates DESN/DMAE 1/0.25 and DES/DMAE 1/0.5, but DBTDL was not added, and the reaction was in 70% solids. 3 hours at 70 ° C. Synthesis of melamine derivative HMMM / stearyl alcohol (mole ratio 1/4) 108 g of stearyl alcohol and 39 g of JHMMM were added to the device mechanical stirrer, thermometer, Dean cold Stark condenser and heating mantle in a 500 ml three-neck reaction flask. Stir the reaction mixture and flow in a stream of nitrogen Heat to 80 ° C until the reaction mixture became clear. Then add 0,294 g of p-toluene acid catalyst. The reaction was carried out at 95 ° C under a nitrogen stream for 2.5 hours _ while at the Dean Stark -16- paper scale Applicable to Chinese National Standard (CNS) A4 Specification (210 X 297 mm) 1290184 A7 B7 V. Description of Invention (15 ) Table 1: Water repellency of cotton, treated with melamine, wax and protected isocyanate example number composition (% SOF) IN SR Bundesmann 5HLIR SR Γ 5, 10, 1 FreepelTM 1225 (0.5) + RepearlTM MF (0.16) 100 2 2 1 0 C-1 FreepelTM 1225 (0.5) 90 0 2 FreepelTM 1225 (1) + RepearlTM MF (0.16) 100 3 3 2 0 C-2 FreepelTM 1225 (1) 100 1 1 1 0 3 FreepelTM 1225 (2) + RepearlTM MF (0.16) 100 3 3 2 70 C-3 FreepelTM 1225 (2) 100 3 1 1 0 4 CerolTM EWL (0.5) + BaygardTM EDW (0.15) 50 0 C-4 CerolTM EWL (0.5) 0 0 5 CerolTM EWL (1) + BaygardTM EDW (0.15) 100 2 1 1 80 C-5 CerolTM EWL (1) 80 0 6 CerolTM EWL (2) + BaygardTM EDW (0.15) 100 2 2 1 80 C-6 CerolTM EWL (2) 90 0

The gas charging results show that a substrate having a high water repellency can be obtained when treated with an aqueous mixture of melamine, wax and protected isocyanate. In particular, an improved initial dynamic water repellency can be obtained as compared to samples treated only with melamine and wax. Moreover, the durability is significantly improved, especially at high addition levels. Examples 7-12 and Comparative Examples C7-C12 In Examples 7 - 2, cotton fibers were treated with melamine, chain wax and aliphatic isocyanate (the amounts are listed in Table 2). Comparative Example C-7-C-12 was carried out in the same manner, but no aliphatic isocyanate was added. The sample was treated in a crucible to give a concentration (% SOF) on the fiber as shown in Table 2. After processing, the fiber is dried at 160 ° C. 2 -18- This paper scale is applicable to China National Standard (CNS) A4 specification (210X297 mm) 1290184 A7 B7 V. Invention description (16) minutes. Record the initial spray rating and Bundesmann test results. After washing according to the general procedure, the test sample is evaluated for the spray. The results are shown in Table 2. Table 2: Water repellency of cotton, treated with melamine, wax and aliphatic isocyanate Example number composition (% SOF;) IN SR Bundesmann 5HLIR SR 1, 5, 10, 7 FreepelTM 1225 (0.5) + TubicoatTM Fix ICB (0.13) 100 3 1 1 95 C-7 FreepelTM 1225 (0.5) 90 0 8 FreepelTM 1225 (1) + TubicoatTM Fix ICB (0.13) 100 1 1 1 85 C-8 FreepelTM 1225 (1) 100 1 1 1 0 9 FreepelTM 1225 (2) + TubicoatTM Fix ICB (0.13) 100 4 3 3 80 C-9 FreepelTM 1225 (2) 100 3 1 1 0 10 CerolTM EWL (0.5) + TubicoatTM Fix ICB ( 0.13) 90 80 C-10 CerolTM EWL (0.5) 0 0 11 CerolTM EWL (1) + TubicoatTM Fix ICB (0.13) 100 3 3 3 80 C-I1 CerolTM EWL (1) 80 0 12 CerolTM EWL (2) + TubicoatTM Fix ICB (0.13) 100 3 3 2 90 CM2 CerolTM EWL (2) 90 0 The results show that compared with samples treated with melamine and wax alone, trimeric amines, bond burns and lipids The substrate treated with the isocyanate mixture exhibits a comparable improvement in initial dynamic water repellency and durability. Examples 1 3 to 18 and Comparative Examples C - 1 3 to C - 1 8 In Examples 1 3 - 1 8 and Comparative Examples C-13 to C-18, Examples 1- 12 were repeated with white polyester/cotton fibers. Comparative Examples C-1 to C-12 were tested in the same class. The treated compositions and water repellency results are listed in Table 3. Table 3 ·························· - Example number composition (%SOF) IN SR Bundesmann 5HLIR SR 1, 5, 10, 13 FreepelTM 1225 (0.5) + RepearlTM MF (0.16) 100 2 1 1 80 C-13 FreepelTM 1225 (0.5) 90 50 14 FreepelTM 1225 (1) + RepearlTM MF (0.16) 100 4 2 2 90 C-14 FreepelTM 1225 (1) 100 2 1 1 50 15 FreepelTM 1225 (2) + RepearlTM MF (0.16) 100 4 2 2 90 C-15 FreepelTM 1225 (2) 100 3 1 1 50 16 CerolTM EWL (0.5) + BaygardTM EDW (0.15) 70 0 C-16 CerolTM EWL (0.5) 50 0 17 CerolTM EWL (1) + BaygardTM EDW (0.15) 100 4 3 3 90 C-17 CerolTM EWL (I) 100 1 1 1 50 18 CerolTM EWL (2) + BaygardTM EDW (0.15) 100 4 3 3 90 C-18 CerolTM EWL (2) 100 3 1 1 50

For the same polyester/cotton fiber, it should be noted that the treated substrate has a higher initial dynamic water repellency and higher durability than a substrate treated only with melamine and wax. Examples 1 9 to 24 and Comparative Examples C - 1 9 to C - 24 In Examples 19 to 24 and Comparative Examples C-19 to C-24, Examples 7 - 1 2 and Comparative Examples were repeated with white polyester/cotton fibers. Experiments of the same class of C-7 to C-1. The treated compositions and water repellency results are listed in Table 4. Table 4: Water repellency of PES/CO, treated with melamine, wax and aliphatic isocyanate -20- This paper scale is applicable to China National Standard (CNS) A4 specification (210 X 297 mm)

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1290184 A7 B7 V. INSTRUCTIONS (18) f EXAMPLE NUMBER COMPOSITION (% S0F) IN SR Bundesmann 5HLIR SR 1, 5, 10, 19 FreepelTM 1225 (0.5) + TubicoatTM Fix ICB (0.13) 100 4 3 2 90 C-19 FreepelTM 1225 (0.5) 90 50 20 FreepelTM 1225 (1) + TubicoatTM Fix ICB (0.13) 100 3 3 2 90 020 FreepelTM 1225 (1) 100 2 1 1 50 21 FreepelTM 1225 (2 + TubicoatTM Fix ICB (0.13) 100 4 4 3 90 C-21 FreepelTM 1225 (2) 100 3 1 1 50 22 CerolTM EWL (0.5) + TubicoatTM Fix ICB (0.13) 100 3 1 1 80 022 Cerol TM EWL (0.5) 50 0 23 CerolTM EWL (1) + TubicoatTM Fix ICB (0.13) 100 4 4 4 100 C-23 CerolTM EWL (1) 100 1 1 1 50 24 CerolTM EWL (2) + Tubicoat TM Fix ICB (0.13) 100 4 4 4 100 C-24 CerolTM EWL (2) 100 3 1 1 50 In this set of experiments, the effect of adding a fatty isocyanate to a mixture of melamine and wax was quite clear. It has a relatively high dynamic water repellency (and low % ABS) and high durability (SR100 after 5 washes). Improvements are also quite noticeable even at low additions. Example 2 5 to 2 7 and Comparative Example C25 In Examples 2 to 2 7, an aqueous mixture of melamine, wax and various aliphatic isocyanates listed in Table 5 was prepared. The mixture was treated with polyester/cotton fibers according to the general procedure described above. Comparative Example C-25 used only a mixture of melamine and wax. The compositions of the samples and the water repellency of the substrates treated there are listed in Table 5. Table 5: Water repellency of PES/CO, treated with melamine, wax and aliphatic isocyanate-21 - This paper scale applies to Chinese National Standard (CNS) A4 specification (210X297 mm) 1290184 A7 B7 V. Invention description (19) Example No. Composition (%SOF) IN SR Bundesmann 5HLIR SR 1, 5, 10, 25 FreepelTM 1225 (1) + TubicoatTM Fix ICB (0.13) 100 3 2 2 80 26 FreepelTM 1225 (1) + BaygardTM VP SP 23012 (0.16) 100 4 3 2 100 27 FreepelTM 1225 (1) + RucoguardTM EPF 1421 (0.13) 100 4 3 3 100 C-25 FreepelTM 1225 (1) 100 2 1 1 50 Results shown in melamine and wax The addition of various lipid isocyanates significantly increases the water repellency and durability of the PES/CO substrate treated therewith. In addition, it also has a high spray uniformity after washing. Example 28-3 2 and Comparative Example 〇26-〇30 In Example 2 8 - 3 2, polyester microfibers were treated with an aqueous mixture of melamine, alkane wax and a fatty isocyanate (the amounts listed in Table 6). Comparative Example 26-C - 3 0 was carried out in the same manner, but no aliphatic isocyanate was added. The sample was processed in a crucible according to the general method. The results of the initial spray rating, Bundesmann test and spray evaluation are listed in Table 6. Table 6: Water repellency of PES a, treated with melamine, wax and aliphatic isocyanate-22- This paper scale applies to Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1290184 A7 B7 V. Description of invention (2. ) _Example Number Composition (%SOF) IN SR Bundesmann 5HLIR SR 1, 5, 10, 28 FreepelTM 1225 (0.5) + TubicoatTM Fix ICB (0.13) 90 80 C-26 FreepelTM 1225 (0.5) 90 50 29 FreepelTM 1225 (1) + TubicoatTM Fix ICB (0.13) 100 2 2 2 80 C-27 FreepelTM 1225 (1) 100 2 2 2 70 30 FreepelTM 1225 (2) + TubicoatTM Fix ICB (0.13) 100 3 3 ' 3 90 C-28 FreepelTM 1225 (2) 100 2 2 2 70 31 CerolTM EWL (1) + TubicoatTM Fix ICB (0.13) 80 70 C-29 CerolTM EWL (1) 70 50 32 CerolTM EWL (2) + TubicoatTM Fix ICB (0.13) 100 4 3 2 80 C-30 CerolTM EWL (2) 80 70 As can be seen from the table, the composition of the present invention provides improved durability. Example 3 3 to 40 and Comparative Example C-3 1 to C-32 The water-soluble treatment tank of Example 3 to 3 8 was prepared by mixing FreepelTM 1225 with a lipid polyisocyanate as shown in Table 7. To prepare the stabilizing treatment tanks for Examples 3, 3, 3, 3 and 40, 2 g/liter of 60 acetic acid aqueous solution was added to FreepelTM 1225 prior to the addition of the aliphatic isocyanate. The cotton or PES/CO substrate was coated to give a concentration of 1.85% SOF FreepelTM 1225 and 0.15% SOF isocyanate. Comparative Examples C-31 and C-32 were carried out only with FreepelTM 1225 aqueous solution. The treated substrate is hardened according to the general method. The results of the initial spray rating, Bundesmann test and spray evaluation are listed in Table 7. 0 Table 7 · Water repellency of substrates treated with FreepelTM 1225 and lipid isocyanate-23- This paper scale applies to Chinese national standards ( CNS) A4 size (210X 297 mm) 1290184 A7 B7 V. Description of invention (21) Example number isocyanate IN SR Bundesmann 5HLIR SR V 5, 10, Substrate : Cotton 33 TubicoatTM Fix ICB 100 4 4 3 90 34 DESN/MPEG 350 1/0.25 100 4 4 3 90 35 DESN/DMAE 1/0.25 100 4 4 3 90 36 DESN/DMAE 1/0.5 100 4 4 3 80 C-31 / 100 3 2 1 50 Substrate : PES/CO 37 TubicoatTM Fix ICB 100 3 2 2 80 38 DESN/MPEG 350 1/0.25 100 3 2 2 80 39 DESN/DMAE 1/0.25 100 4 3 2 90 40 DESN/DMAE 1/0.5 100 4 3 2 90 C-32 / 100 3 2 2 50 The results show that substrates treated with a combination of Fi: eepelTM 1225 and different lipid isocyanates exhibit higher dynamic water repellency and better durability than substrates treated with only Fi* eepelTM 1225. . Real life J 4 1 to 4 2 and t匕 compared to C 3 3 and C - 3 6 Examples and 42, cotton and PES/CO melamine-derived HMMM/4 stearyl alcohol (1/4), fat system Treatment of an aqueous mixture of isocyanate DESN/MPEG 350 (1/0.25) and paraffin wax (listed in Table 8). Comparative Examples C - 33 to C - 36 were carried out by treating the substrate only with an aqueous solution of melamine or with an aqueous mixture of melamine and a fatty isocyanate but without the addition of an alkane wax. The treated substrate was run at 160 ° C for 2 minutes. The spray test results are listed in Table 8. , -24- The paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 1290184 A7 B7 V. Invention description (22) Table 8: Spray test for treating substrate with water melamine mixture No. % SOF Melamine % SOF DESN/MPEG 350 % S OF Sewing Tiger Substrate IN SR 41 0.92 0.15 0,92 PES/C0 80 C-33 1.85 0.15 / PES/C0 60 C-34 2 / / PES/C0 0 42 0.92 0.15 0.92 Cotton 80 C-35 1.85 0.15 / Cotton 70 C-36 2 / / Cotton 50 Compared to substrates treated with melamine alone, the base can be found when the substrate is treated with a mixture of melamine and a fatty isocyanate. The initial water repellency of the material increases. The spray rating can also be further increased by using a key burn sample. Various modifications and alterations of the present invention will be apparent to those skilled in the art. -25- This paper size is applicable to China National Standard (CNS) A4 specification (210X 297 mm)

-HU V. INSTRUCTIONS (2 compounds' and still in the composition of the substrate, especially the fabric. Producing water and water repellency, although the commercially available water-repellent composition - is generally the main type, but it is known that there is still The water repellent composition containing the compound is 3,5 〇M61 teaches a hydrocarbon derivative which imparts water repellency to the fabric. For example, the water repellency achieved by the ruthenium is not good. ', these groups Therefore, it is desirable to find another composition which imparts water repellency to the fibrous substrate and which is free of fluorine-containing chemical compounds. Preferably, the composition can be: water repellency, and preferably water repellency and fluorine-containing chemical compound: group The stone is the same. SUMMARY OF THE INVENTION The present invention provides an aqueous composition comprising: (a) at least a portion of a fatty hydrocarbon derived melamine having at least 8 carbon atoms; (b) a wax; and (c) at least one selected from the group consisting of Containing (i) a fatty polyisocyanate and a reaction product having one or more organic compounds reactive with isocyanate, the reaction product having a free isocyanate group and having a molecular weight of at least 35 g/m [') Gathering The composition of the acid ester. It has been found that when such a composition is used for the treatment of a fibrous substrate, it can be used in some methods in combination with a fluorine chemical composition. The high level of water repellency of water. Further, the composition is generally presented. Good durability and detergency. The term "protected aromatic polyisocyanate" means the isocyanate group and the protective reaction of the aromatic polyisocyanate. The isocyanate protectant is the isocyanate-5- paper scale Affordable 0 National Standard (CNS) A4 Specification (2ι () 297 297 public) 12901 meal ^ 90126605 Patent Application _ ^ Description of the manual replacement page (February 93) Aip >^ I" η V, invention description (5) ...... (X) m-Rh is as defined above, and wherein at least 2%, preferably at least 8%, of the Y group is. The other component of the aqueous composition is a wax. Suitable waxes include inorganic waxes, Synthetic sacrificial natural waxes. Natural waxes include vegetable waxes such as palm wax and candilla wax, dense wax or wax derived from animal sources. Examples of synthetic waxes include petroleum waxes such as paraffin waxes and microcrystalline or semi-fine Crystalline wax. Inorganic waxes include montan wax and mud wax. The melting temperature of the wax is at least 35 I. The preferred wax used in the present composition is an alkane. The composition is commercially available and comprises a mixture of a melamine component and a wax. The commercially available mixture comprises, for example, CerolTM EWL from Clariant, and purchased. Freepel 1225 from BF Goodrich, and can be used to prepare aqueous compositions. The aqueous composition comprises the reaction product of at least one aliphatic polyisocyanate with an organic compound having one or more groups reactive with an isocyanate or protected isocyanate compound. The reaction product of the aliphatic polyisocyanate with the organic compound should have a free isocyanate group and should further have a molecular weight of at least 350 g / mol', preferably at least 450 g / mol, to ensure that the reaction product has a vapor pressure low enough. The amount of the isohydroester groups is generally at least 5% by weight based on the total weight of the reaction product, preferably at least 1% by weight. Suitable lipid isocyanates comprise an isogastric acid ester; triisocyanate S and mixtures thereof. Examples include hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate and isophorone diisocyanate, cyclohexylmethane 4,4,-diisocyanate and lipid It is a triisocyanate such as a trimer of 1,3,6-hexamethyl-triisocyanate, a biuret of hexamethylene dihydrogenate and a trimer of hexamethylene diisocyanate. a lipid compound having one or more groups reactive with an isohydroester

This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) A7 B7 129〇4 _1266. Replacement page of Chinese manual for patent application No. 5 (July 1993) V. Description of invention (8 thiol group a condensation product of an organic compound. Examples of the organic compound include the above. The most preferred is a protected aromatic polyisocyanate having self-emulsification ability in water. Therefore, in order to obtain the polyisocyanate compound, an aromatic polyisocyanate, a protective agent, and an organic compound having a water-soluble group or a water-soluble group in water are allowed to react with each other under the general conditions for reacting the isocyanate component. Suitable organic compounds which comprise the water-soluble group or which form a water-soluble agent are described above. Examples of the aromatic polyisocyanate for preparing the protected aromatic polyisocyanate include di- or triisocyanate, and a mixed pentane thereof. Particular examples are aryl diisocyanates such as 4,4,-methyldiphenyl diisocyanate, 4,6-(trifluoromethyl)-1,3-benzene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, o-, m-, and p-xylylene diisocyanate, 4,4,diisocyanate diphenyl ether, 3,3,-di-gas-4,4,-diisocyanate Diphenyl pit, 4,5'-diphenyl diisocyanate, 4,4,-diisocyanate dibenzyl, 3,3,-dimethoxy-4,4, diisocyanate diphenyl, 3,3,_Dimethyl-4,4·-diisocyanate diphenyl, 2,2,-dichloro-5,5,-dimethoxy-4,4, monoisocyanate diphenyl 1 , 3 - diisocyanate benzene, hydrazine, 2 - trial diisocyanate 4-chloro-1,2-mercapto diisocyanate, ι, 3 -tea diisocyanate and 1,8-dinitro-2 7-decane diisocyanate and aryl tri-isocyanate, such as polymethylene-extension-based isocyanic acid. Commercially available protected aromatic polyisocyanates include BaygardTM EDW sold by Bayer Corp. and HydrophobolTM XAN hydrophobic compositions sold by Ciba-Geigy., optionally in the presence of an emulsifier adjuvant, by triammine, The wax and polyisocyanate components are prepared by dispersing or emulsifying in water. When the polyisocyanate component contains a lipid polyisocyanate and an organic compound, the reaction production line 11 12901, Q12_5 Patent Application A7 B7 Chinese Manual Replacement Page (February 93) V. Invention Description (14) Distillation of methanol in the condenser . The reaction is then allowed to proceed at i4. His Majesty is operating at 2 · 5 hours. After the reaction mixture was cooled to 10 ° C, 220.5 g of ethyl acetate was added to the mixture to afford ethyl acetate. 6 gram of this solution was added with 0.96 g of an aqueous solution containing 3% Arquad 2HT/75. The mixture was heated to 65 ° C and 9 6 g of deionized water was added and preheated to 65 t while stirring. The pre-emulsion was then formed by dipping an ultrasonic probe (Branson 450-D Sonifier) for 6 minutes (cycle 10 at 50-60 ° C, operation -5, terminating). Evaporation was carried out using water jet at 5 5 ° C, and ethyl acetate was evaporated by rotary evaporation. A stable milky emulsion of about 20% solids was obtained. Emulsification of paraffin wax 20 g of alkane (cure point 52-54 t, purchased from Merck) was mixed with 8 g of deionized water and 0.4 g of TweenTM 81 and 0.8 g of ArquadTM 2HT/75 (75%) were added. The mixture was heated to 6 〇 - 65 t while stirring. The pre-emulsion formed by immersing the ultrasonic probe (Branson 450-D Sonifier) for 4 minutes (in the next cycle of 10 0-60. (the next cycle of 10 Μ operation - 5 fl) was obtained. About 2 〇% solid content was obtained. A stable emulsion emulsion. Examples 1 - 6 and Comparative Examples C - 1 to (% 6 Males 1 to 6 were treated with melamine, chain hydrazine and protected isocyanate (the amounts are listed in Table 1). Comparative Examples C-1 to c-6 were carried out in the same manner, but no protected isocyanate was added. The sample was treated in a crucible to obtain a concentration (% S0F) on the fiber as shown in Table 1. After the treatment, the fibers were subjected to}^^ Dry for 2 minutes. Record the initial spray rating and Bundesmani^<test results. After washing according to the general procedure, evaluate the test samples for the spray. The results are listed in Table i 0 -17-

Claims (1)

An aqueous composition comprising: (a) a melamine derived at least in part from an aliphatic hydrocarbon group having 8 to 5 carbon atoms; (b) a wax; and (c) at least one selected from the group consisting of a reaction product of a polyisocyanate and an organic compound having one or more groups reactive with isocyanate. The reaction product has a free isocyanate and a molecular weight of at least 350 g/mole, and (π) protected a component of the group consisting of aryl polyisocyanates, wherein the content of the component (a) is between 5% and 10% by weight, and the content of the component (b) is between 5% and 5% by weight. And the content of the component (c) is between 0.05% by weight and 2% by weight. 2 · The aqueous composition of the first aspect of the patent application includes an emulsifier. 3 · The water-based combination of claim 1 A substance which is substantially free of a chemical compound. 4. A method of treating a fibrous substrate comprising the step of applying a composition as claimed in claim J to a fibrous substrate. Method of the fiber The substrate is heat-treated at a temperature of from 1 Torr to 190 ° C to cure the composition. The method of claim 4, wherein the composition is based on the weight of the fibrous substrate. Applying at least 1% by weight solids on the fibrous substrate. 74599-960704.DOC . j . This paper scale applies to National Standard (CNS) A4 (210X297 mm) ^~~~ --- -