TWI537371B - Water repellent (1) - Google Patents

Description

Water and oil repellent (1)

The invention relates to a water- and water-repellent agent; in particular to a water- and oil-repellent agent with a fluorine-free fluorine-containing mixed polymer.

Fluorinated compounds are often used as surface treatment agents and are widely used for surface treatment of substrates, such as textiles, wood, metals, concrete, etc., and substrates that exhibit better effects are textiles, and their types include natural fibers and synthetic Fiber and semi-synthetic fibers, the fluorinated chemicals provide water and oil repellency to the fiber surface. In the past, water-repellent or oil-repellent components having a perfluoroalkyl group having 8 or more carbon atoms, such as H2C=C(X)C, have been used for the purpose of imparting water repellency or antifouling properties to fiber products. =O)-YZ-Rf refers to a perfluoroalkyl acrylate which is suitable for use in the manufacture of a water repellent and oil repellent surface treatment agent when Rf has a fluoroalkyl group of 8 carbon atoms. When Rf is reduced to a fluoroalkyl group of 4 to 6 carbon atoms, the surface treatment agent has poor water and oil repellency, and it is necessary to use vinyl chloride or vinylidene chloride to improve the effect; however, vinyl chloride or partial dichloride is used. The mixture of ethylene olefin monomers in perfluoroalkyl ethyl methacrylate is effective for the water repellency of textile processing fibers and good water resistance, and there is still a problem of adhesion to the rolls.

In view of the above, an object of the present invention is to provide a water-repellent and oil-repellent agent which has a good water-repellent oil-repellent effect and can improve the adhesion of the roller on the roller, and can reduce the amount of fluorine used to reduce the amount of fluorine. Environmental and human injuries harm.

In order to achieve the above object, the water-repellent and oil-repellent agent provided by the present invention is obtained by mixing at least a fluorine-containing polymer and a fluorine-free polymer, wherein the fluorine-containing polymer is at least a fluorine-containing monomer or a non-fluorinated polymer. a fluorine-chain branched monomer, a non-fluorine crosslinkable monomer, and an olefin monomer, which are at least a non-fluorine non-crosslinkable monomer, a non-fluorine crosslinkable monomer, and The olefin monomer is polymerized.

In one embodiment, the general formula of the fluoromonomer is: Wherein X is a hydrogen atom, a monovalent organic group, a halogen atom, a cyano group, or a linear or branched fluoroalkyl group having 1 to 21 carbon atoms; Y is an oxygen atom, a sulfur atom or a secondary amine; Z is straight An alkane, a divalent organic group, an aliphatic group having a carbon number of 1 to 10, an aromatic or alicyclic group having a carbon number of 6 to 18; and, R _f is a linear having 4 to 6 carbon atoms Or branched fluoroalkyl.

In one embodiment, the non-fluorine non-crosslinkable monomer has the general formula: H ₂ C=CACOOA' wherein A is a hydrogen atom or a methyl group; A' is C _n H _2n+1 (n=3~30) The alkyl group.

In one embodiment, the non-fluorine branched monomer has the general formula: H ₂ C=CACOOA' wherein A is a hydrogen atom or a methyl group; A' is a 1st to 3rd branched alkyl group, and is C _n H _m (n=3~10, m=7~30) alkyl group.

In one embodiment, the non-fluorine branched monosystem is selected from the group consisting of t-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, and 3,5,5-trimethylhexyl. In the group consisting of acrylate, isobornyl acrylate, isobornyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, benzyl acrylate and cyclohexyl methacrylate One less.

In one embodiment, the non-fluorine crosslinkable single system is a crosslinkable monomer having two or more reactive functional groups.

In one embodiment, the non-fluorine crosslinkable single system is selected from the group consisting of 3-chloro-2-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, methacrylic acid. Glycidyl propyl ester, methoxyethyl methacrylate, ethoxyethyl methacrylate, diacetone acrylamide, 4-hydroxybutyl acrylate, 1,4-cyclohexane dimethanol monoacrylate, and 4 At least one of the group consisting of -hydroxybutyl acrylate glycidyl ether.

In one embodiment, the olefinic monomer is a halogenated olefin monomer.

In one embodiment, the olefinic monomer is vinyl chloride or vinylidene chloride.

In one embodiment, the fluorine-free polymer is added in an amount of 30 to 70%.

In one embodiment, the fluorine-containing monomer in the fluoropolymer has a weight percentage of 45 to 80%.

In one embodiment, the non-fluorine-branched monomer in the fluoropolymer has a weight percentage of 1 to 30%.

In one embodiment, the non-fluorine crosslinkable monomer in the fluoropolymer has a weight percentage of from 1 to 10%.

In one embodiment, the olefinic monomer in the fluoropolymer has a weight percentage of 10 to 50%.

In one embodiment, the non-fluorine non-crosslinkable monomer in the non-fluoropolymer is from 45 to 80% by weight.

In one embodiment, the non-fluorine crosslinkable monomer in the non-fluoropolymer is from 1 to 30% by weight.

In one embodiment, the olefinic single in the non-fluoropolymer The weight percentage of the body is 10~50%.

In one embodiment, the water and oil repellency agent is applied to the processing of fiber products.

In one embodiment, the water-repellent oil-repellent agent is an aqueous water-repellent oil-repellent agent.

The preferred embodiment of the present invention is for forming a fluoropolymer water-repellent and oil-repellent agent, which is prepared by mixing a fluoropolymer and a non-fluoropolymer; wherein the fluoropolymer is composed of a fluoromonomer a non-fluorine-branched monomer, a non-fluorine-crosslinkable monomer, and an olefin-based monomer. The non-fluorinated polymer is a non-fluorine non-crosslinkable monomer or a non-fluorine crosslinkable monomer. And the polymerization of olefin monomers. Among them: the general formula of fluorine-containing monomer is: Wherein X is a hydrogen atom, a monovalent organic group, a halogen atom, a cyano group, or a linear or branched fluoroalkyl group having 1 to 21 carbon atoms; Y is an oxygen atom, a sulfur atom or a secondary amine; Z is straight An alkane, an aliphatic group having 1 to 10 carbon atoms, an aromatic or alicyclic group having 6 to 18 carbon atoms; and R _f is a linear or branched fluoroalkyl group having 4 to 6 carbon atoms. For example, but not limited to: CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ OCOCH=CH ₂ CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ OCOCH=CH ₂ CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ OCOC(CH ₃ )=CH ₂ CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ OCOC(CH ₃ )=CH ₂ F ₂ HC(CF ₂ ) ₃ CH ₂ OCOCH=CH ₂ F ₂ HC(CF ₂ ) ₃ CH ₂ OCOC(CH ₃ )=CH ₂ F ₂ HC(CF ₂ ) ₃ CH ₂ CH ₂ OCOCH=CH ₂ F ₂ HC(CF ₂ ) ₃ CH ₂ CH ₂ OCOC(CH ₃ )=CH ₂ F ₂ HC(CF ₂ ) ₅ CH ₂ OCOCH=CH ₂ F ₂ HC(CF ₂ ) ₅ CH ₂ OCOC(CH ₃ )=CH ₂ F ₂ HC(CF ₂ ) ₅ CH ₂ CH ₂ OCOCH=CH ₂ F ₂ HC (CF ₂ ) ₅ CH ₂ CH ₂ OCOCH ₂ (CH)=CH ₂

The non-fluorine non-crosslinkable monomer is represented by the formula: H ₂ C=CACOOA' wherein A is a hydrogen atom or a methyl group; and A' is a C _n H _2n+1 (n=3 to 30) alkyl.

The general formula of the non-fluorine branched monomer is: H ₂ C=CACOOA' wherein A is a hydrogen atom or a methyl group; A' is a 1st to 3th branched alkyl group, and is C _n H _m (n =3~10, m=7~30) alkyl; Table 1 lists functional non-fluorine branched monomers, which may be composed of one or more, for example, but not limited to This: Table 1. Non-fluorinated branched monomers Further, in addition to the monomers listed above, benzyl acrylate and cyclohexyl 2-methacrylate may also be used.

The non-fluorine crosslinkable monomer is a crosslinkable monomer having two or more reactive functional groups. Table 2 exemplifies a plurality of non-fluorine functional crosslinking monomers. The present embodiment may be composed of one or more of them, but is not limited thereto: The olefinic monomer may preferably be a halogenated olefin monomer, and may be, for example, vinyl chloride or vinylidene chloride.

Comparative Example 1, as shown in Table 3, 75 g of perfluorooctyl methacrylate (6FMA), 15 g of isobornyl acrylate (IBOA), and 2,3-dihydrocarbyl propyl 2-methyl-2-acrylate 2 g of (GLA), 6 g of diacetone acrylamide (DAAM), n-dodecyl mercaptan (0.75 g), 43.5 g of dipropylene glycol methyl ether and 300 g of deionized water were stirred at 50 ° C for 20 minutes, and homogenized at a pressure of 40 MPa. A stable homogeneous emulsion with a UV of greater than 15% T at a wavelength of 650 nm. The high pressure homogeneous emulsion was placed in a 1 L four-neck glass reaction flask, and 0.8 g of 2,2'-azobisisobutylphosphonium dihydrochloride was added, and 45 g of vinylidene chloride (VDC) was added, and the reaction was carried out at 60 ° C for 6 hours. An aqueous dispersion of the acrylic polymer is obtained.

In Comparative Example 2, as shown in Table 3, 15 g of isobornyl acrylate (IBOA), 2 g of 2-methyl-2-acrylic acid-2,3-dihydrocarbyl propyl ester (GLA), and diacetone acrylamide (DAAM) 6 g were used. , n-dodecyl mercaptan (0.75g), dipropylene glycol methyl ether 43.5g and deionized water 300g were stirred at 50 ° C for 20 minutes, high pressure homogenization at a pressure of 40MPa to obtain a stable homogeneous emulsion, using UV at a wavelength of 650nm The penetration needs to be greater than 15% T. The high pressure homogeneous emulsion was placed in a 1 L four-neck glass reaction flask, and 0.8 g of 2,2'-azobisisobutylphosphonium dihydrochloride was added, and 45 g of vinylidene chloride (VDC) was added, and the reaction was carried out at 60 ° C for 6 hours. An aqueous dispersion free of fluoropolymer is obtained.

Comparative Example 3, as shown in Table 3, octadecyl acrylate (SA) 15 g, glycidyl methacrylate (GMA) 2.5 g, diacetone acrylamide (DAAM) 6 g, n-dodecyl mercaptan (0.75 g), dipropylene glycol methyl ether 43.5 g and 300 g of deionized water were stirred at 50 ° C for 20 minutes, and homogenized under high pressure at 40 MPa. The high pressure homogeneous emulsion was placed in a 1 L four-neck glass reaction flask, and 0.8 g of 2,2'-azobisisobutylphosphonium dihydrochloride was added, and 45 g of vinylidene chloride (VDC) was added, and the reaction was carried out at 60 ° C for 6 hours. An aqueous dispersion of a fluorine-free polymer is obtained.

Production Example 1, as shown in Table 3, 15 g of isobornyl acrylate (IBOA), 2 g of 2-methyl-2-acrylic acid-2,3-dihydrocarbyl propyl ester (GLA), and diacetone acrylamide (DAAM) 6 g , n-dodecyl mercaptan (0.75g), dipropylene glycol methyl ether 43.5g and deionized water 300g were stirred at 50 ° C for 20 minutes, high pressure homogenization at a pressure of 40MPa to obtain a stable homogeneous emulsion, using UV at a wavelength of 650nm The penetration needs to be greater than 15% T. The high pressure homogeneous emulsion was placed in a 1 L four-neck glass reaction flask, and 0.8 g of 2,2'-azobisisobutylphosphonium dihydrochloride was added, and 45 g of vinylidene chloride (VDC) was added, and the reaction was carried out at 60 ° C for 6 hours. An aqueous dispersion of a fluorine-free polymer is obtained. The aqueous dispersion of the above fluorine-free polymer was mixed in a ratio of 3 to Comparative Example 1, whereby an aqueous dispersion having a fluorine-free fluorine-mixed polymer was obtained.

Production Example 2, as shown in Table 3, 15 g of octadecyl acrylate (SA), 2.5 g of glycidyl methacrylate (GMA), 6 g of diacetone acrylamide (DAAM), n-dodecyl mercaptan (0.75 g) 43.5 g of dipropylene glycol methyl ether and 300 g of deionized water were stirred at 50 ° C for 20 minutes, and homogenized under high pressure at 40 MPa. The high pressure homogeneous emulsion was placed in a 1 L four-neck glass reaction flask, and 0.8 g of 2,2'-azobisisobutylphosphonium dihydrochloride was added, and 45 g of vinylidene chloride (VDC) was added, and the reaction was carried out at 60 ° C for 6 hours. An aqueous dispersion of a fluorine-free polymer is obtained. The aqueous dispersion of the above fluorine-free polymer was mixed in a ratio of 3 to Comparative Example 1, whereby an aqueous dispersion having a fluorine-free fluorine-mixed polymer was obtained.

Production Example 3, as shown in Table 3, 75 g of perfluorooctyl methacrylate (6FMA), 15 g of isobornyl acrylate (IBOA), 2.5 g of glycidyl methacrylate (GMA), and diacetone acrylamide. (DAAM) 6g, n-dodecane sulfur 0.75 g of alcohol, 43.5 g of dipropylene glycol methyl ether and 300 g of deionized water were stirred at 50 ° C for 20 minutes, and homogenized under high pressure at 40 MPa. The high pressure homogeneous emulsion was placed in a 1 L four-neck glass reaction flask, and 0.8 g of 2,2'-azobisisobutylphosphonium dihydrochloride was added, and 28 g of vinylidene chloride (VDC) was added, and the reaction was carried out at 60 ° C for 6 hours. An aqueous dispersion of the acrylic polymer is obtained. Comparative Example 2 was mixed in an amount of 3 parts to the aqueous dispersion of the above acrylic polymer to obtain an aqueous dispersion having a fluorine-free fluorine-mixed polymer.

Production Example 4, as shown in Table 3, 75 g of perfluorooctyl methacrylate (6FMA), 24 g of isobornyl acrylate (IBOA), 2.5 g of glycidyl methacrylate (GMA), and diacetone acrylamide. (DAAM) 6 g, n-dodecyl mercaptan (0.75 g), dipropylene glycol methyl ether 43.5 g and 300 g of deionized water were stirred at 50 ° C for 20 minutes, and homogenized under high pressure at 40 MPa. The high pressure homogeneous emulsion was placed in a 1 L four-neck glass reaction flask, and 0.8 g of 2,2'-azobisisobutylphosphonium dihydrochloride was added, and 45 g of vinylidene chloride (VDC) was added, and the reaction was carried out at 60 ° C for 6 hours. An aqueous dispersion of the acrylic polymer is obtained. Comparative Example 2 was mixed in an amount of 3 parts to the aqueous dispersion of the above acrylic polymer to obtain an aqueous dispersion having a fluorine-free fluorine-mixed polymer.

Production Example 5, as shown in Table 3, 100 g of perfluorooctyl methacrylate (6FMA), 15 g of isobornyl acrylate (IBOA), 2.5 g of glycidyl methacrylate (GMA), and diacetone acrylamide. (DAAM) 6 g, n-dodecyl mercaptan (0.75 g), dipropylene glycol methyl ether 43.5 g and 300 g of deionized water were stirred at 50 ° C for 20 minutes, and homogenized under high pressure at 40 MPa. The high pressure homogeneous emulsion was placed in a 1 L four-neck glass reaction flask, and 0.8 g of 2,2'-azobisisobutylphosphonium dihydrochloride was added, and 45 g of vinylidene chloride (VDC) was added, and the reaction was carried out at 60 ° C for 6 hours. An aqueous dispersion of the acrylic polymer is obtained. Comparative Example 2 was mixed in an amount of 3 parts to the aqueous dispersion of the above acrylic polymer to obtain an aqueous dispersion having a fluorine-free fluorine-mixed polymer.

Production Example 6, as shown in Table 3, perfluorooctyl methacrylate 100 g of acid ester (6FMA), 15 g of isobornyl acrylate (IBOA), 21.5 g of 2-ethylhexyl methacrylate (EHMA), 8.5 g of diacetone acrylamide (DAAM), n-dodecyl mercaptan (0.75 g) 43.5 g of dipropylene glycol methyl ether and 350 g of deionized water were stirred at 50 ° C for 20 minutes, and homogenized under high pressure at 40 MPa. The high pressure homogeneous emulsion was placed in a 1 L four-neck glass reaction flask, and 1 g of 2,2'-azobisisobutylphosphonium dihydrochloride was added, and 30 g of vinylidene chloride (VDC) was reacted at 60 ° C for 6 hours. An aqueous dispersion of an acrylic polymer. Comparative Example 2 was mixed in an amount of 3 parts to the aqueous dispersion of the above acrylic polymer to obtain an aqueous dispersion having a fluorine-free fluorine-mixed polymer.

Production Example 7, as shown in Table 3, 100 g of perfluorooctyl methacrylate (6FMA), 15 g of isobornyl acrylate (IBOA), 8.5 g of diacetone acrylamide (DAAM), n-dodecyl mercaptan ( 0.75 g), 43.5 g of dipropylene glycol methyl ether and 350 g of deionized water were stirred at 50 ° C for 20 minutes, and homogenized under high pressure at 40 MPa. The high pressure homogeneous emulsion was placed in a 1 L four-neck glass reaction flask, and 1 g of 2,2'-azobisisobutylphosphonium dihydrochloride was added, and 30 g of vinylidene chloride (VDC) was reacted at 60 ° C for 6 hours. An aqueous dispersion of an acrylic polymer. Comparative Example 2 was mixed in an amount of 3 parts to the aqueous dispersion of the above acrylic polymer to obtain an aqueous dispersion having a fluorine-free fluorine-mixed polymer.

Production Example 8, as shown in Table 3, 75 g of perfluorooctyl methacrylate (6FMA), 24 g of isobornyl acrylate (IBOA), 3.5 g of glycidyl methacrylate (GMA), and methacrylate 2.2 g of ester (CHMA), 6.5 g of diacetone acrylamide (DAAM), 0.75 g of n-dodecyl mercaptan, 43.5 g of dipropylene glycol methyl ether and 350 g of deionized water were stirred at 50 ° C for 20 minutes, and the pressure was high at a pressure of 40 MPa. Homogeneous. The high pressure homogeneous emulsion was placed in a 1 L four-neck glass reaction flask, and 1 g of 2,2'-azobisisobutylphosphonium dihydrochloride was added, and 28 g of vinylidene chloride (VDC) was added, and the reaction was carried out at 60 ° C for 6 hours to obtain An aqueous dispersion of an acrylic polymer. Comparative Example 2 was mixed in an amount of 3 parts to the aqueous dispersion of the above acrylic polymer to obtain an aqueous fraction of a fluorine-free fluorine-containing mixed polymer. Loose liquid.

Production Example 9, as shown in Table 3, 75 g of perfluorooctyl methacrylate (6FMA), 24 g of isobornyl acrylate (IBOA), 2.5 g of glycidyl methacrylate (GMA), and diacetone acrylamide. (DAAM) 6 g, n-dodecyl mercaptan (0.75 g), dipropylene glycol methyl ether 43.5 g and 300 g of deionized water were stirred at 50 ° C for 20 minutes, and homogenized under high pressure at 40 MPa. The high pressure homogeneous emulsion was placed in a 1 L four-neck glass reaction flask, and 0.8 g of 2,2'-azobisisobutylphosphonium dihydrochloride was added, and 45 g of vinylidene chloride (VDC) was added, and the reaction was carried out at 60 ° C for 6 hours. An aqueous dispersion of the acrylic polymer is obtained. Comparative Example 3 was mixed in an amount of 3 parts to the aqueous dispersion of the above acrylic polymer to obtain an aqueous dispersion having a fluorine-free fluorine-mixed polymer.

Production Example 10, as shown in Table 3, 100 g of perfluorooctyl methacrylate (6FMA), 15 g of isobornyl acrylate (IBOA), 21.5 g of 2-ethylhexyl methacrylate (EHMA), and diacetone 8.5 g of acrylamide (DAAM), n-dodecyl mercaptan (0.75 g), 43.5 g of dipropylene glycol methyl ether and 350 g of deionized water were stirred at 50 ° C for 20 minutes, and homogenized under high pressure at 40 MPa. The high pressure homogeneous emulsion was placed in a 1 L four-neck glass reaction flask, and 1 g of 2,2'-azobisisobutylphosphonium dihydrochloride was added, and 30 g of vinylidene chloride (VDC) was reacted at 60 ° C for 6 hours. An aqueous dispersion of an acrylic polymer. Comparative Example 3 was mixed in an amount of 3 parts to the aqueous dispersion of the above acrylic polymer to obtain an aqueous dispersion having a fluorine-free fluorine-mixed polymer.

Production Example 11, as shown in Table 3, 75 g of perfluorooctyl methacrylate (6FMA), 24 g of isobornyl acrylate (IBOA), 3.5 g of glycidyl methacrylate (GMA), and methacrylate 2.2 g of ester (CHMA), 6.5 g of diacetone acrylamide (DAAM), 0.75 g of n-dodecyl mercaptan, 43.5 g of dipropylene glycol methyl ether and 350 g of deionized water were stirred at 50 ° C for 20 minutes, and the pressure was high at a pressure of 40 MPa. Homogeneous. The high pressure homogeneous emulsion was placed in a 1 L four-neck glass reaction flask, and 2,2'-azobisisobutylphosphonium dihydrochloride 1 g, vinylidene chloride was added. (VDC) 28 g, and reacted at 60 ° C for 6 hours to obtain an aqueous dispersion of an acrylic polymer. Comparative Example 3 was mixed in an amount of 3 parts to the aqueous dispersion of the above acrylic polymer to obtain an aqueous dispersion having a fluorine-free fluorine-mixed polymer. Although the above examples are all mixed at a ratio of 3, preferably, they may be mixed at a ratio of 3 to 70%, in other words, the ratio of addition of the fluorine-free polymer may be 30 to 70%.

The monomer composition weights are shown in the table below.

However, it is not limited to the above. In other embodiments, the weight percentage of the fluorine-containing monomer in the fluoropolymer is preferably from 45 to 80%, and the weight percentage of the non-fluorine-branched monomer is preferably. The weight percentage of the non-fluorine crosslinkable monomer may preferably be from 1 to 10%, and the weight percentage of the olefin monomer may preferably be from 10 to 50%. Moreover, the weight percentage of the non-fluorine non-crosslinkable monomer in the non-fluoropolymer is preferably from 45 to 80%, and the weight percentage of the non-fluorine crosslinkable monomer is preferably from 1 to 30%. The weight percentage of the olefin monomer may preferably be from 10 to 50%.

Water withdrawal assessment of water repellent composition:

The solution or emulsion of the fluorine-containing acrylic short-chain copolymer can be applied to a synthetic synthetic fiber substrate such as a textile using the usual habit of treating textiles. For example, it may be from 0.5 to 25% by weight, or from 1 to 10% by weight, more preferably from 1 to 5% by weight. For the substrate of the textile, the fabric may be first dipped in a solution, or the solution may be pressed out by pressure dyeing. The substrate drying process of the textile can be processed by a heating and drying process, for example, heating at 100 to 200 ° C for 60 to 90 seconds, more preferably at 150 to 200 ° C. Heat for 60 to 90 seconds to produce water repellency.

Typically, the treatable textiles are synthetic synthetic fiber woven fabrics, including woven fabrics, knitted fabrics and non-woven fabrics, woven fabrics and felts in the form of various ready-to-wear and outer garments, and may also be fibers or yarn or cotton or roving. Intermediate textile products. The textile product may be a synthetic synthetic fiber such as a polyester, polyamide or acrylic synthetic fiber, or may be a mixture of fibers such as a mixture of natural and synthetic fibers. This product is particularly effective in the use of a synthetic fiber woven fabric such as nylon or polyester which is hydrophobic. Treating the woven fabric with the copolymerized product of the present invention will impart water repellency to the woven fabric and at the same time improve the feel compared to the untreated woven fabric.

Alternatively, the fibrous substrate is paper. The copolymer product can be applied to pre-formed paper or applied at different stages, such as during paper drying.

The surface treatment agent of the present invention preferably exhibits a solution form. The surface treatment agent mostly contains a fluoropolymer and a medium (for example, an organic solvent or water). The concentration of the fluoropolymer in the surface treatment agent may be from 0.1 to 50% by weight, preferably from 5 to 30% by weight. This surface treatment agent can be carried out by means of immersion. Generally, the surface treatment agent is diluted with an organic solvent or water, adhered to the surface of the substrate by, for example, immersion, and dried by heating. If necessary, an anti-caries agent, a softener, an antibacterial agent, a flame retardant, an antistatic agent, a fixing agent, an anti-caries agent, or the like may be added to the surface treatment agent to the surface treatment agent according to the product requirements.

In the surface treatment agent and the fiber woven substrate or the leather substrate or the glass substrate, the working liquid in contact with the substrate, the concentration of the fluorine-containing compound, based on the treatment liquid, may be 0.01 to 20% by weight. For example, 0.05 to 10% by weight, more preferably 0.05 to 5% by weight.

The preferred substrate to be treated with the hydrophobic water repellent of the surface treating agent of the present invention is a textile. Textiles include different types, textiles The classes include: natural fibers, animal or vegetable fibers, such as cotton, hemp, wool and silk; synthetic fibers such as nylon, polyester, polyamide, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and Polypropylene; semi-synthetic fibers such as hydrazine and acetate; inorganic fibers such as glass fibers, carbon fibers and asbestos fibers; and mixtures of the above fibers.

Spray water repellency test (AATCC-22):

The shower water repellency test was carried out according to AATCC-22. The spray water repellency is indicated by the spray dialing water number, as explained below, and please refer to Table 4.

Prepare a nozzle with a 250 ml volume plastic funnel and spray 250 ml volume of water for a continuous spray time of 20 to 30 seconds. The test piece rack on which the test substrate was placed was a circular test piece holder having a diameter of 15 cm. Three test pieces of about 20 cm × 20 cm in size of the test piece to be tested are prepared, and the fiber woven fabric substrate is cut into a size of 20 cm × 20 cm. And the test piece was fixed on the test piece holder, and the test piece was finished so that the test piece was not wrinkled. The sprinkler was placed at the center of the test piece, and 25 ° C room temperature water (250 ml) was poured into the nozzle-equipped plastic funnel and sprayed on the test piece for 20 to 30 seconds. After spraying, remove the test piece from the table and gently tap the test piece to drop the water drop. The degree of wetting of the test piece was compared, and the scores of 100, 90, 80, 70, 50, and 0 were respectively given in the order of water-repellent excellentness to poor water-repellency. What is obtained is the measured average result of the three test pieces.

1. Select the washing conditions and drying methods and record them, or follow the manufacturer's preference to choose the appropriate Xicheng.

2. Inlet water to a certain water level (18gal is about 68L), adjust the water temperature.

3. Put in the standard cleaner 66±1g (model 1993AATCC, or the same grade), and test the piece and wash the weight of the cloth to a total weight of 1.8 ± 0.1Kg into the washing machine for washing.

4. The sample is washed and dried, placed in a standard temperature and humidity environment of 20 ± 2 ° C, 65 ± 2% R. H. for more than 4 hours.

Stick roller state test:

The finished product was weighed 4 g in a 250 ml beaker, and after mixing 196 g of deionized water at 25 ° C, the textile substrate was immersed in the solution, and the solution was extruded through a press machine having a pressure of 3 kg. When the textile substrate is dyed In the process of the machine, the state of the adhesive roller between the textile substrate and the roller of the press machine is judged.

○: completely non-stick roller

△: small area adhesive roller

×: large area adhesive roller

This test is the result of a sticking roll condition test on three textile substrates.

It can be seen from the above that the water- and oil-repellent agent of the embodiment of the present invention is obtained by permeating a mixed fluoropolymer with a fluorine-free polymer, and the fluoropolymer is composed of a fluorine-containing monomer, a non-fluorine-branched monomer, and a non-fluorine. a cross-linking monomer obtained by polymerizing a non-fluorine non-crosslinkable monomer, a non-fluorine crosslinkable monomer, and an olefin monomer; This can achieve a good dial The water-repellent effect can improve the adhesion of the roller on the roller, and can reduce the amount of fluorine used to reduce the damage to the environment and the human body.

The above is only a preferred embodiment of the present invention, and equivalent changes to the scope of the present invention and the scope of the patent application are intended to be included in the scope of the present invention.

Claims (20)

A water-repellent oil-repellent agent obtained by mixing at least a fluorine-containing polymer and a fluorine-free polymer, wherein the fluorine-containing polymer is at least a fluorine-containing monomer, a non-fluorine-branched monomer, and a non-fluorine The crosslinkable monomer and the olefin monomer are polymerized, and the non-fluorinated polymer is polymerized by at least a non-fluorine non-crosslinkable monomer, a non-fluorine crosslinkable monomer, and an olefin monomer. The water-repellent oil-repellent agent according to claim 1, wherein the general formula of the fluorine-containing monomer is: Wherein X is a hydrogen atom, a monovalent organic group, a halogen atom, a cyano group, or a linear or branched fluoroalkyl group having 1 to 21 carbon atoms; Y is an oxygen atom, a sulfur atom or a secondary amine; Z is straight An alkane, a divalent organic group, an aliphatic group having 1 to 10 carbon atoms, an aromatic or alicyclic group having 6 to 18 carbon atoms; and R _f is a linear or 4 to 6 carbon atoms Branched fluoroalkyl. The water-repellent oil-repellent agent according to claim 1, wherein the non-fluorine non-crosslinkable monomer has a general formula of: H ₂ C=CACOOA' wherein A is a hydrogen atom or a methyl group; and A' is C _n H _{2n +1} (n=3~30) alkyl group. The water- and oil-repellent agent according to claim 1, wherein the non-fluorine-branched monomer has a general formula of: H ₂ C=CACOOA' wherein A is a hydrogen atom or a methyl group; and A' is a grade 1 to 3 A branched alkyl group and an alkyl group of C _n H _m (n = 3 to 10, m = 7 to 30). The water-repellent oil-repellent agent according to claim 4, wherein the non-fluorine-branched single system is selected from the group consisting of t-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, and 3. 5,5-trimethylhexyl acrylate, isobornyl acrylate, isobornyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, benzyl acrylate and cyclohexyl 2-methacrylate At least one of the group consisting of. The water-repellent oil-repellent agent according to claim 1, wherein the non-fluorine crosslinkable single system is a crosslinkable monomer having two or more reactive functional groups. The water-repellent oil-repellent agent according to claim 6, wherein the non-fluorine cross-linking single system is selected from the group consisting of 3-chloro-2-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate, and methyl group. Hydroxypropyl acrylate, glycidyl methacrylate, methoxyethyl methacrylate, ethoxyethyl methacrylate, diacetone acrylamide, 4-hydroxybutyl acrylate, 1,4-cyclohexane At least one of the group consisting of alkane dimethanol monoacrylate and 4-hydroxybutyl acrylate glycidyl ether. The water- and oil-repellent agent according to claim 1, wherein the olefin monomer is a halogenated olefin monomer. The water- and oil-repellent agent according to claim 8, wherein the olefin monomer is vinyl chloride or vinylidene chloride. The water-repellent oil-repellent agent according to claim 1, wherein the non-fluoropolymer is added in an amount of 30 to 70%. The water-repellent oil-repellent agent according to claim 1, wherein the fluorine-containing monomer in the fluoropolymer has a weight percentage of 45 to 80%. The water-repellent oil-repellent agent according to claim 1, wherein the non-fluorine-branched monomer in the fluoropolymer has a weight percentage of 1 to 30%. The water- and oil-repellent agent according to claim 1, wherein the non-fluorine-crosslinkable monomer in the fluoropolymer has a weight percentage of 1 to 10%. The water-repellent oil-repellent agent according to claim 1, wherein the olefin monomer in the fluoropolymer has a weight percentage of 10 to 50%. The water-repellent oil-repellent agent according to claim 1, wherein the non-fluorine non-crosslinkable monomer in the non-fluoropolymer has a weight percentage of 45 to 80%. The water- and oil-repellent agent according to claim 1, wherein the non-fluorine-crosslinkable monomer in the non-fluoropolymer is from 1 to 30% by weight. The water-repellent oil-repellent agent according to claim 1, wherein the weight percentage of the olefin monomer in the fluorine-free polymer is 10 to 50%. A use of the water- and oil-repellent agent as claimed in items 1 to 17 for the processing of fibrous products. The water-repellent oil-repellent agent as claimed in item 1 is an aqueous water-repellent oil-repellent agent. A use of the water- and oil-repellent agent as claimed in claim 19 for the processing of fibrous products.