TWI698518B - Fluoride-free water repellent - Google Patents

Abstract

A fluorine-free water-repellent water repellent made by polymerizing the following monomers, containing: (A) a linear alkyl (meth)acrylate with a carbon number of 12 to 24, 50 to 89% by weight; (B) Monocyclic, polycyclic or crosslinked alkyl (meth)acrylate with carbon number of 6 to 20, 10 to 20% by weight; (C) Alkyl of reactive groups (hydroxyl, amino, chloro, epoxy) The base (meth)acrylate is 1 to 10% by weight; and (D) the modified polyurethane monomer is 5 to 20% by weight. The fluorine-free water-repellent water repellent of the present invention can improve the water resistance and washing resistance of the fluorine-free superhydrophobic water-repellent.

Description

Fluorine-free water repellent

The present invention relates to a water-repellent agent, in particular to a fluorine-free water-repellent agent.

With the rise of human environmental protection awareness, there are demands for green environment and low-carbon products. Advanced countries such as Europe, America and Japan have even begun to ban and reduce the use of fluorine-based products. As fluoride may be released from end products, As rainwater enters nearby water sources, soil or food, it accumulates in animal bones and shells for a long time. Moderate amounts of fluoride affect teeth, and long-term intake of large amounts of fluoride may cause serious bone problems and become more serious. Brittle and easier to crack.

In order to meet people's continuous requirements for textiles, more and more textiles are given functionality, and waterproof function is an important branch. At present, fluorocarbon water repellents are still widely used, but with the continuous improvement of people's environmental protection requirements, the application of fluorocarbon water repellents is strictly restricted. Although more and more researchers are studying a large number of short-chain fluorocarbon water repellents in recent years, as people's requirements for textile and chemical safety are further improved, environmentally friendly fluorine-free water repellents will increase The more popular. Fluorine-free water-based superhydrophobic water repellent has good initial waterproof performance for pure cotton fabrics, polyester fabrics, and polyester-cotton blended fabrics. Improving the water repellency and washing resistance of fluorine-free superhydrophobic water repellents will be the development trend of environmentally friendly fluorine-free water repellents in the future.

Patent Cooperation Treaty PCT Patent Publication Nos. WO2015080026, WO2015076348, WO2015076347, and WO2015111668 utilize non-fluorine-based polymers containing structural units derived from (meth)acrylate monomers to synthesize non-fluorine-based water repellents. While the present invention uses polyamino acrylate polyur The structure of ethane acrylate and PUA is introduced into the fluorine-free acrylic system to further improve the water resistance and washing resistance of the fluorine-free superhydrophobic water repellent.

The purpose of the present invention is to provide a fluorine-free water-repellent agent, which can improve the water resistance and washing resistance of the fluorine-free superhydrophobic water-repellent agent.

The present invention provides a fluorine-free water-repellent water repellent to achieve the above-mentioned object, which is polymerized by the following monomers and contains: (A) a linear alkyl (meth)acrylate with a carbon number of 12 to 24, 50 to 89 Weight%; (B) monocyclic, polycyclic or cross-linked alkyl (meth)acrylate with carbon number 6 to 20, 10 to 20% by weight; (C) reactive groups (hydroxyl, amino, chloro , Epoxy) alkyl (meth)acrylate is 1 to 10% by weight; and (D) the modified polyurethane monomer is 5 to 20% by weight.

Compared with the conventional non-fluorine water repellent, the present invention has the following advantages:

1. Excellent water repellency and oil repellency.

2. Dry, breathable and comfortable, easy to clean and good stain resistance.

3. Non-toxic, environmentally friendly and free of fluorocarbons.

The fluorine-free water repellent of the present invention is polymerized by the following monomers, including

(A) The content of linear alkyl (meth)acrylate (Methyl propiolate) having a carbon number of 12 to 24 is 50 to 89% by weight.

CH ₃ (CH ₂ ) _n OC(O)CR=CH ₂ where n=an integer from 11 to 21; R=H or CH ₃

(B) Monocyclic, polycyclic or cross-linked alkyl (meth)acrylate with carbon number of 6-20, isobornyl (meth)acrylate, isobornyl acrylate, tert-butyl cyclohexyl methacrylate , Dicyclopentyl (meth)acrylate, styrene, 1,3 chloromethyl styrene, 1,4 chloromethyl styrene and cyclohexyl methacrylate, monocyclic, polycyclic or cross-linked alkyl The content of (meth)acrylate is 10 to 20% by weight;

(C) The alkyl (meth)acrylate of the reactive group (hydroxyl, amino, chloro, epoxy) is 1 to 10% by weight, and the alkyl (meth)acrylate of this reactive group is HOC ₂ H ₄ -OC(O)CR=CH ₂

R-(OC ₂ H ₄ ) _m -OC(O)CR=CH ₂

R-(OC ₃ H ₆ ) _m -OC(O)CR=CH ₂

NH ₂ -C(O)CR=CH ₂

HOC ₂ H ₄ -NH-C(O)CR=CH ₂

C ₂ H ₆ NC ₂ H ₄ -OC(O)CR=CH ₂

^{_{C 3 H 9 N + (Cl}} -) C 2 H 4 -OC (O) CR = CH 2

ClH ₂ CH(OH)CH ₂ OC(O)CR=CH ₂

式中R=H或CH₃ m=2至50的整數；以及

Where R=H or CH ₃ m=an integer from 2 to 50; and

其中X為脂肪族、環脂肪族或芳香族結構；Y為具反應性的(甲基)丙烯酸官能基；Z為肟基或碳數為12至22烷基醇，此聚氨酯單體，由下列單體聚合而成，通式為Y-X-Z；Y=HO(CH2)_n-OC(O)CR=CH₂；式中R=H或CH₃、n=2至4的整數；X=雙異氰酸酯單體，可以是甲苯二異氰酸酯(Toluenediisocyanate，TDI)、異佛爾酮二異氰酸酯(Isophoronediisocyanate，IPDI)、二環己基甲烷二異氰酸酯(hexamethylene diisocyanate,HDI)或二苯基甲烷二異氰酸酯(Methylenediphenyl Diisocyanate，MDI)；Z=封鎖劑或烷基醇；封鎖劑，可以是甲基乙基酮肟(methylethyl ketoxime,MEKO)、己內醯胺(caprolactam,E-cap)、3,5-二甲基吡唑(3,5-dimethyl pyrazole,DMP)烷基醇為H-(CH2)_n-OH，式中n=12至22的整數。 (D) The modified polyurethane (Polyurethane) monomer is 5 to 20% by weight, and the above modified polyurethane monomer (polyurethane acrylate, PUA) is

Where X is an aliphatic, cycloaliphatic or aromatic structure; Y is a reactive (meth)acrylic functional group; Z is an oxime group or an alkyl alcohol with a carbon number of 12 to 22. This polyurethane monomer is composed of It is formed by polymerization of monomers, the general formula is YXZ; Y=HO(CH2) _n -OC(O)CR=CH ₂ ; where R=H or CH ₃ , n=an integer from 2 to 4; X=diisocyanate mono The body can be toluenediisocyanate (TDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI) or Methylenediphenyl diisocyanate (MDI) ; Z=blocking agent or alkyl alcohol; blocking agent, can be methyl ethyl ketoxime (MEKO), caprolactam (caprolactam, E-cap), 3,5-dimethylpyrazole ( 3,5-dimethyl pyrazole, DMP) alkyl alcohol is H-(CH2) _n -OH, where n=an integer from 12 to 22.

The fluorine-free water-repellent water repellent of the present invention can be used in polymerization methods, including solution polymerization, suspension polymerization and emulsion polymerization. In the fluorine-free water-repellent polymer of the present invention, the emulsifier used includes nonionic emulsifiers, reactive nonionic emulsifiers, and cationic emulsifiers used alone or in combination to perform emulsification copolymerization. The nonionic emulsifier used is the following formula: R-X-(EO)n- (PO)mH (where R is a linear or branched alkyl group having 8 to 30 carbons, including oleic acid group; X is oxygen or nitrogen; n and m are integers from 0 to 50, respectively, and n and m are The sum must be greater than 3.). Non-ionic emulsifiers are polyoxyethylene (03) lauryl ether (China-Japan Chemical SP1203), polyoxyethylene (09) lauryl ether (China-Japan Chemical SP1209), polyoxyethylene (20) lauryl ether (China-Japan Chemical SP1220), Polyoxyethylene (07) stearyl ether (Chinichi Chemical SP1807), polyoxyethylene (30) stearyl ether (Chinichi Chemical SP1830) or polyoxyethylene (13) oleic ether (Chinichi Chemical SP1213). The cationic emulsifier used is the following formula: (R'4N+)‧X- (where R'may be a hydrogen atom, an alkyl group with 1 to 30 carbons, a chain alkyl group with 2 to 30 carbons or an EO chain In section, the 4 R's can be the same or different configurations; X is a chlorine atom, ethyl sulfate ion or acetate ion). Cationic emulsifiers are cetyl trimethyl ammonium chloride (CTAC), octadecyl trimethyl ammonium chloride (SMTAC), dioctadecyl dimethyl ammonium chloride (Kao-D86P), double Tallow ester ammonium chloride (Taijie-CNA90) or double fatty alkyl carboethoxyethyl methyl ammonium methyl sulfate (REWOQUAT WE-18). The zwitterionic emulsifiers used in the present invention include acidic amphoteric surfactants, polyolamine sulfates, and alkylamine sulfonates. The cationic functional groups are ammonium and quaternary ammonium salts, and the anionic functional groups are carboxyl. Acid salts, sulfates and sulfonates.

In the polymerization reaction, the reactants are divided into an oil phase and a water phase. The oil phase contains monomers (A), monomers (B), monomers (C), monomers (D) and emulsifiers; the water phase contains Water, acid, solvent. In the preparation and polymerization process, one or more nonionic emulsifiers, cationic emulsifiers and zwitterionic emulsifiers are used; the oil phase and water phase are preheated and dispersed at a high speed before the reaction, and then uniformly dispersed by a high-pressure homogenizer. After obtaining a stable uniform pre-emulsion, the pre-emulsion is then subjected to emulsion polymerization in a continuous or batch manner.

In order to control the potential distribution of the micelles dispersed in the emulsion, in addition to emulsifiers, it is also necessary to use acids and salts to control the appropriate potential range. Commonly used acids are organic and inorganic acids and their salts, preferably hydrochloric acid, phosphoric acid, Sulfuric acid, acetic acid, citric acid, malic acid and their salts.

The water repellent composed of the fluorine-free polymer of the present invention can be coated on the fiber surface of a fabric or fabric blend, and the processing method can be sprayed, impregnated or impregnated together with other types of additives. The method is to coat the surface of the fiber, and then heat it at 100~200℃ for 30~180 seconds for curing to achieve the effect of water repellency.

In the water repellency evaluation of the water-based water repellent composed of the fluorine-free polymer of the present invention, the polymer solution or emulsion can be applied to textile man-made synthetic fiber substrates by using general textile processing methods. For example, it can be 0.5 to 25% by weight, or 1 to 10% by weight, more preferably 1 to 5% by weight. For the substrate of the textile, the fabric can be immersed in the solution first, or the solution can be pressed out by pressing dye. The substrate drying process of the textile can be processed by heating and drying procedures, heating at 100 to 200°C for 60 to 90 seconds, and better conditions are heating at 150 to 200°C for 60 to 90 seconds to produce water repellency .

The water-based water-repellent agent composed of the fluorine-free polymer of the present invention can be processed and applied as synthetic synthetic fiber woven fabrics, including knitted fabrics, non-woven fabrics, various garments, woven fabrics and blankets in the form of outer clothing, and can also be used It is an intermediate textile product of fiber or yarn, cotton sliver and roving. Textile products can be man-made synthetic fibers, packaging polyester, polyamide or acrylic series synthetic fibers. It can also be a fiber mixture of natural and synthetic fibers. The present invention is particularly hydrophobic in synthetic fiber fabrics used in nylon or polyester. Compared with untreated woven fabrics, the copolymerized product of the present invention treated woven fabrics can improve the water repellency of the fabrics and optimize the touch at the same time.

Claims (4)

A fluorine-free water-repellent water repellent made by polymerizing the following monomers, containing: (A) a linear alkyl (meth)acrylate with a carbon number of 12 to 24, 50 to 89% by weight; (B) Monocyclic, polycyclic or crosslinked alkyl (meth)acrylate with carbon number of 6 to 20, 10 to 20% by weight; (C) Alkyl of reactive groups (hydroxyl, amino, chloro, epoxy) Base (meth)acrylate is 1 to 10% by weight; and (D) the modified polyurethane monomer is 5 to 20% by weight; wherein the (D) modified polyurethane monomer is

Where X is one of the following, aliphatic, cycloaliphatic and aromatic structures; Y is a reactive (meth)acrylic functional group; Z is an oxime group or an alkyl alcohol with a carbon number of 12 to 22, this polyurethane monomer Formed by the polymerization of the following monomers, the general formula is YXZ; Y=HO(CH2) _n -OC(O)CR=CH ₂ ; where R=H or CH ₃ , n=an integer from 2 to 4; X =Diisocyanate monomer, one of the following, toluenediisocyanate (TDI), isophorone diisocyanate (Isophoronediisocyanate, IPDI), dicyclohexylmethane diisocyanate (hexamethylene diisocyanate, HDI) and diphenylmethane Isocyanate (Methylenediphenyl Diisocyanate, MDI); Z=blocking agent or alkyl alcohol; blocking agent, one of the following, methyl ethyl ketoxime (MEKO), caprolactam (E-cap), And 3,5-dimethyl pyrazole (DMP), the alkyl alcohol is H-(CH2) _n -OH, where n=an integer from 12 to 22. The fluorine-free water-repellent agent as described in claim 1 further includes the use of nonionic emulsifiers, reactive nonionic emulsifiers, and cationic emulsifiers alone or in combination for emulsification and copolymerization. The fluorine-free water-repellent agent according to claim 2, wherein the cationic emulsifier is one of the following: dioctadecyl dimethyl ammonium chloride, bis-tallow ester ammonium chloride, and di-fatty alkyl ethoxylate Hydroxyethyl methyl ammonium methyl sulfate. The non-fluorine water-repellent water repellent described in claims 1 to 3 is used in the processing and application of fiber products.