TW201303001A - Fluorine water-repellent and oil-repellent agent - Google Patents

Abstract

A fluorine water-repellent and oil-repellent agent is to provide a fluorine-containing copolymer, a hydroxyl-containing cationic surfactant, a polyoxy ether group-containing nonionic surfactant, and a self-synthesized fluorine-containing polyurethane monomer, which is formed into a stabilized water dispersion of the fluorine water-repellent and oil-repellent agent after emulsion polymerization.

Description

Fluorine water and oil repellent

The present invention relates to a surface treatment agent, and more particularly to a fluorine water-repellent oil-repellent agent.

Fluorinated compounds are often used as surface treatment agents and are widely used in the surface treatment of substrates such as textiles, wood, metals, concrete, etc. The substrates that exhibit better results are textiles, and the types include natural fibers. Synthetic fiber and semi-synthetic fiber, the fluorine-containing compound can make the surface of the fiber hydrophobic, prevent moisture from adhering and reduce pollution.

At present, the fiber product has a water-repellent oil-repellent property, and is generally used as a fluoroalkyl acrylate, and an aqueous fluorine-containing water-repellent oil-removing agent obtained by emulsion copolymerization with a copolymerizable monomer.

It is known that in order to improve the linear perfluoroalkyl chain of eight fluorinated carbon atoms, the fluorine compound may degrade under certain conditions to form perfluorooctane carboxylic acid, and accumulate in the living body, so vinyl chloride is added. An olefinic monomer of vinylidine chloride in a mixture of perfluoroalkylethyl methacrylate to replace a linear perfluoroalkyl chain of eight fluorinated carbon atoms. The vinyl chloride/vinylidene chloride has better water repellency and good water resistance in the textile processing fiber, but due to the low boiling point of the olefin, the acryl is often dangerous when the emulsification reaction temperature is increased, and the latter is in the latter stage. When processing textile fibers, problems such as monomer residue are often caused.

In view of the above, the main object of the present invention is to provide a fluorine water-repellent oil-repellent agent, which comprises a self-synthesized fluorine-containing polyurethane monomer, which is stable during the emulsification reaction and processing, and is preferably provided with a substrate. Water and oil effect.

In order to achieve the above object, the fluorinated water-repellent oil-repellent agent provided by the present invention comprises a fluorine-containing polyurethane monomer, and the general formula of the fluorine-containing polyurethane monomer is

Wherein X is an aliphatic, cycloaliphatic or aromatic structure; Y is a reactive functional group; Z is a fluorine-containing alkyl group having a fluoroalkyl group having a carbon number of 4 to 16.

In one embodiment, wherein the fluorourethane monomer is polymerized from the following monomers, comprising: (A) a bisisocyanate monomer having the general formula A-X-B (wherein A and B represents two different reactive isocyanate groups; X is an aliphatic, cycloaliphatic or aromatic structure such as a benzene ring, a naphthalene ring or a cyclohexane), a bisisocyanate monomer Specific examples are Toluene diisocyanate, Isophorne diisocyanate or Hexamethylene diisocyanate.

(B) A reactive monomer having a general formula of Y-OH comprising an acryl group, an oxime group, an aldehyde group, a ketone group, an ether group, a carboxylic acid group or a hydroxyl group.

A specific embodiment of Y-OH is

(C) a fluoroalkyl group having the general formula of H _m CF _n (CF ₂ ) _p C _q X (where m + n = 3, p = 6 to 12, q = 1 to 4, and X is OH).

Specific examples of the fluoroalkyl group are H-(CF ₂ ) ₆ -OH, H-(CF ₂ ) ₈ -OH, H-(CF ₂ ) ₁₀ -OH, H-(CF ₂ ) ₁₂ -OH, H-(CF ₂ ) ₁₄ -OH, H-(CF ₂ ) ₁₆ -OH, H-(CF ₂ ) ₁₈ -OH, H-(CF ₂ ) ₂₀ -OH.

In one embodiment, the fluorocarbon water-repellent agent further comprises a fluorinated copolymer composed of a fluorine-containing alkyl monomer and a monomer copolymerizable therewith.

In one embodiment, the proportion of the composition of the fluorocarbon water-repellent and oil-repellent agent is 100-70 parts by weight relative to the fluorine-containing alkyl monomer, and the monomer copolymerizable with the fluorine-containing water-removing agent is 20-70 parts by weight. The polyurethane monomer is from 1 to 100 parts by weight.

The preferred embodiment of the present invention is for forming a fluorine water-repellent oil-repellent agent comprising the following composition: (A) a fluorine-containing copolymer, (B) a cationic surfactant, (C) a nonionic surfactant, and (D) Self-synthesized fluorine-containing polyurethane monomer. Wherein: (A) Fluoropolymer The fluorine-containing copolymer of the present embodiment is obtained by copolymerizing a fluorine-containing alkyl monomer with a fluorine-free monomer.

Fluorinated alkyl monomers are exemplified as follows:

(wherein R _f is a perfluoroalkyl group or a perfluoroalkenyl group having 3 to 20 carbon atoms.)

More specifically, the listable ones are:

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 ) ₇ (CH ₂ ) ₂ OCOCH=CH ₂

CF ₃ (CF ₂ ) ₉ (CH ₂ ) ₂ OCOCH=CH ₂

CF ₃ (CF ₂ ) ₁₁ (CH ₂ ) ₂ OCOCH=CH ₂

CF ₃ (CF ₂ ) ₁₃ (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

CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ OCOC(CH ₃ )=CH ₂

CF ₃ (CF ₂ ) ₉ (CH ₂ ) ₂ OCOC(CH ₃ )=CH ₂

CF ₃ (CF ₂ ) ₁₁ (CH ₂ ) ₂ OCOC(CH ₃ )=CH ₂

CF ₃ (CF ₂ ) ₁₃ (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

F ₂ HC(CF ₂ ) ₇ CH ₂ OCOCH=CH ₂

F ₂ HC(CF ₂ ) ₇ CH ₂ OCOC(CH ₃ )=CH ₂

F ₂ HC(CF ₂ ) ₇ CH ₂ CH ₂ OCOCH=CH ₂

F ₂ HC(CF ₂ ) ₇ CH ₂ CH ₂ OCOCH ₂ (CH)=CH ₂

F ₂ HC(CF ₂ ) ₉ CH ₂ OCOCH=CH ₂

F ₂ HC(CF ₂ ) ₉ CH ₂ OCOC(CH ₃ )=CH ₂

F ₂ HC(CF ₂ ) ₉ CH ₂ CH ₂ OCOCH=CH ₂

F ₂ HC(CF ₂ ) ₉ CH ₂ CH ₂ OCOCH ₂ (CH)=CH ₂

F ₂ HC(CF ₂ ) ₁₁ CH ₂ OCOCH=CH ₂

F ₂ HC(CF ₂ ) ₁₁ CH ₂ OCOC(CH ₃ )=CH ₂

F ₂ HC(CF ₂ ) ₁₁ CH ₂ CH ₂ OCOCH=CH ₂

F ₂ HC(CF ₂ ) ₁₁ CH ₂ CH ₂ OCOCH ₂ (CH)=CH ₂

F ₂ HC(CF ₂ ) ₁₃ CH ₂ OCOCH=CH ₂

F ₂ HC(CF ₂ ) ₁₃ CH ₂ OCOC(CH ₃ )=CH ₂

F ₂ HC(CF ₂ ) ₁₃ CH ₂ CH ₂ OCOCH=CH ₂

F ₂ HC(CF ₂ ) ₁₃ CH ₂ CH ₂ OCOCH ₂ (CH)=CH ₂

The fluorine-free monomer, comprising an acrylic functional group and an acrylamide functional organic group, is exemplified by a specific embodiment of the fluorine-free monomer, wherein: Table 1 is a fluorine-free functional group-containing fluorine-free monomer. Monomer; Table 2 is a fluorine-free monomer containing a acrylamide functional group.

(B) Cationic Emulsifier The cationic emulsifier used in this example is of the formula: (R'4N ⁺ )‧X ^- (wherein R' may be a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, and a carbon number of 2 ~30 alkyl or EO segments, 4 R' may be the same or different configurations; X is a chlorine atom, an ethyl sulfate ion or an acetate ion.)

For example, cetyltrimethylammonium chloride (CTAC), octadecyltrimethylammonium chloride (SMTAC), dioctadecyl dimethylammonium chloride (Kao-D86P), double cattle Ester ammonium chloride (Taiwan-CNA90), bis-fatty alkyl ethyl hydroxyethyl methyl ammonium sulfate (REWOQUAT WE-18), and the like.

(C) Nonionic Emulsifier One or more APEO-free nonionic emulsifiers used in this example, the nonionic emulsifier of which is: RX-(EO) _n -(PO) _m -H (where R A linear or branched alkyl group having a carbon number of 8 to 30, comprising an oleic acid group; X can be oxygen or nitrogen; n and m are each an integer of 0 to 50, and the sum of n and m is required to be greater than 3.)

For example, polyoxyethylene (03) lauryl ether (Zhongri Chemical SP1203), polyoxyethylene (09) lauryl ether (Zhongri Chemical SP1209), polyoxyethylene (20) lauryl ether (Zhongri Chemical SP1220), polyoxygen Ethylene (07) stearyl ether (Zhongri Chemical SP1807), polyoxyethylene (30) stearyl ether (Zhongri Chemical SP1830), polyoxyethylene (13) oleate (Zhongri Chemical SP1213), etc.

(D) Self-synthesized fluorine-containing polyurethane monomer

Synthesis and production method

The isocyanate monomer and the catalyst were placed in a three-necked round bottom bottle equipped with a mechanical stirrer, and the reactive monomer Y-OH was added to the round bottom bottle by means of dropping, and the whole temperature control was lower than 40 ° C and reacted for 3 hours. . In the second stage, the fluoroalkyl group Z-OH is further added to the round bottom bottle by dropwise addition, and the whole temperature control is lower than 40 ° C and the reaction is carried out for 4 hours. Upon completion of the reaction, a fluoropolyurethane structural monomer can be obtained which is transparent and colorless. The Y-OH, Z-OH and fluorine-containing polyurethane structural monomers are described as follows:

Y-OH representative description

Y-OH is a reactive functional group such as an acrylic group, an oxime group, an aldehyde group, a ketone group, an ether group, a carboxylic acid group, or a hydroxyl group.

Specifically, Y-OH is:

Z-OH representative instructions:

Z is a fluorine-containing alkyl group, and its general formula may be H _m CF _n (CF ₂ ) _p C _q X (where m+n=3, p=6~12, q=1~4; X=OH) .

Specifically, Z-OH is: H-(CF ₂ ) ₆ -OH, H-(CF ₂ ) ₈ -OH, H-(CF ₂ ) ₁₀ -OH, H-(CF ₂ ) ₁₂ -OH, H -(CF ₂ ) ₁₄ -OH, H-(CF ₂ ) ₁₆ -OH, H-(CF ₂ ) ₁₈ -OH, H-(CF ₂ ) ₂₀ -OH

Fluorinated polyurethane structural monomer

Its general formula is as follows:

Wherein X represents an aliphatic or aromatic structure such as a benzene ring, a naphthalene ring or a cyclohexane; Y represents a reactive functional group such as a vinyl group, an acrylic group or an oxime group; and Z represents a fluorine-containing alkane. The group may have a fluoroalkyl carbon number of 4 to 16. R _f is a linear or branched fluoroalkyl group having 6 to 12 carbon atoms. For example: H-(CF ₂ )6-OH, H-(CF ₂ ) ₈ -OH, H-(CF ₂ ) ₁₀ -OH, H-(CF ₂ ) ₁₂ -OH, H-(CF ₂ ) ₁₄ - Examples of OH, H-(CF ₂ ) ₁₆ -OH, H-(CF ₂ ) ₁₈ -OH, H-(CF ₂ ) ₂₀ -OH, and the like.

The above is the introduction of the monomer used in the formation of the fluorine water-repellent oil-repellent agent in the present embodiment, and then, the synthesis method of the self-synthesized fluorine-containing polyurethane structural monomer is described later, and four synthesis examples are introduced. .

Synthesis Example 1--Fluorine-containing urethane structural monomer (D-V1)

In a three-necked round bottom bottle equipped with a mechanical stirrer, 100 g of IPDI monomer and 0.03 g of catalyst ES 100Ag catalyst were placed, and 55.6 g of HEMA (2-hydroxyethyl methacrylate) was added to the round bottom bottle. The temperature control was below 40 ° C and the reaction was carried out for 3 hours. In the second step, 163 grams of dodecafluoroheptanol (2,2,3,3,4,4,5,5,6,6,7,7-dodecafluorooctan-1-ol) was added to the circle. In the bottom bottle, the whole temperature control is lower than 40 ° C and reacted for 4 hours. The reaction was completed to obtain a transparent colorless mucus of 318.6 g.

Synthesis Example 2--Fluorine-containing urethane structural monomer (D-V2)

In a three-neck round bottom bottle equipped with a mechanical stirrer, 100 g of IPDI monomer and 0.03 g of catalyst ES 100Ag catalyst were placed, and 55.6 g of 2-hydroxypropyl methacrylate was added to the round bottom bottle. The whole temperature control was low. The reaction was carried out at 40 ° C for 3 hours. In the second step, 156.6 grams of dodecafluoroheptanol (2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptan-1-ol) was added to the circle. In the bottom bottle, the whole temperature control is lower than 40 ° C and reacted for 4 hours. The reaction was completed to obtain a transparent colorless mucus of 312.2 g.

Synthesis Example 3 - Fluorinated urethane structural monomer (D-V3)

100 DI of IPDI monomer and 0.03 g of catalyst ES 100Ag catalyst, 149.4 g of dodecafluoroheptanol (2, 2, 3, 3, 4, 4, 5) in a three-neck round bottom bottle equipped with a mechanical stirrer , 5,6,6,7,7-dodecafluorooctan-1-ol) was added to the round bottom bottle by the method of dropping and dropping, and the whole temperature control was lower than 40 ° C and reacted for 3 hours. In the second step, 41.2 grams of methyl ethyl ketone oxime (MEKO) was added to the round bottom bottle by way of dropwise addition. The whole temperature control was lower than 40 ° C and the reaction was carried out for 4 hours. The reaction was completed to obtain a transparent colorless mucus of 290.6 g.

Synthesis Example 4--Fluoro-Polyurethane Structural Monomer (D-V4)

100 psi IPDI monomer and catalyst ES 100Ag catalyst 0.03 g, 157.5 g decafluoroheptanol (2, 2, 3, 3, 4, 4, 5) in a three-neck round bottom bottle equipped with a mechanical stirrer , 5,6,6,7,7,7-tridecafluorooctan-1-ol) was added to the round bottom bottle by the method of dropping and dropping, and the whole temperature control was lower than 40 ° C and reacted for 3 hours. In the second step, 41.2 grams of methyl ethyl ketone oxime (MEKO) was added to the round bottom bottle by way of dropwise addition. The whole temperature control was lower than 40 ° C and the reaction was carried out for 4 hours. The reaction was completed to obtain a transparent colorless mucus of 298.7 g.

The above is an example of the self-synthesis of the fluorine-containing polyurethane structural monomer of the preferred embodiment, and then the method for producing the copolymer of the fluorine water-repellent and oil-repellent agent of the present embodiment is as follows: the water-dispersion type of the present embodiment The method for producing a copolymer of a fluorine water-repellent and oil-repellent agent is preferably an emulsion polymerization method. For example, in the presence of an emulsifier, water or a solvent is used as a medium to emulsify a fluorine-containing alkyl monomer, a fluorine-free monomer, and a fluorine-containing polyurethane structural monomer, and an initiator and a chain transfer agent are added to the emulsion. And polymerization is carried out to obtain an aqueous solution or a dispersion of the copolymer. The polymer is assumed to be 100 parts by weight with respect to the fluorine-containing alkyl monomer, and the amount of the fluorine-free monomer is 20 to 70 parts by weight, more preferably 40 to 60 parts by weight, and the relative weight of the fluorine-containing polyurethane structural monomer. The serving is 1 to 100 parts by weight.

In this embodiment, in order to control the molecular weight distribution, a chain transfer agent is used, which comprises an aromatic compound, a mercapto alcohol, and a mercaptan, and is a linear dimer of carbon tetrachloride, mercaptoethanol, and α-methylstyrene. 2,4-Diphenyl-4-methyl-1-pentene, octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, and the like.

In the emulsion polymerization reaction of the present invention, the reactant is divided into an oil phase and an aqueous phase, and the oil phase comprises a fluorine-containing alkyl monomer, a fluorine-free monomer, a fluorine-containing polyurethane structural monomer, a chain transfer agent and an emulsifier; The phase contains water, acid, and solvent.

In the present invention, by using a radical polymerization reaction, it is necessary to carry out an initiation reaction using an initiator, which comprises a photoinitiator, an ion initiator and a radical initiator, and is preferably a radical initiator, a radical initiator. The agent comprises a peroxide initiator and an azo initiator, and is preferably an azo initiator, and the polymerization temperature is preferably 40 to 100 ° C.

The invention adopts one or more nonionic emulsifiers and cationic emulsifiers in the preparation and polymerization process; before the reaction, the oil phase and the water phase are preheated and dispersed at a high speed, and then uniformly dispersed by a high pressure homogenizer to obtain stable After the uniform pre-emulsion, the pre-emulsion is further subjected to emulsion polymerization in a continuous or batch manner.

The above is an overview of the manufacturing method of the present invention, and then the manufacturing conditions and the surface treating agent of the present invention will be described in detail in the examples, and the parts exemplified in the examples are based on the weight percentage, unless otherwise specified, all tests. The evaluation was carried out at 25 °C.

Comparative Example 1 (as shown in Table 3)

In a four-neck glass reaction flask with a thermometer and a stirrer and circulated with nitrogen, FMA (65g), SMA (28.2g), Topolene-M (4g), nonionic emulsifier C (6g), cationic emulsifier B (6.6 g), TPG (42.5 g), acetic acid (0.5 g), n-dodecyl mercaptan (0.3 g), deionized water (195.5 g). A milky white emulsion was obtained using a high pressure homogenizer at a temperature not exceeding 40 ° C and a pressure of 40 MPa. 2,2'-Azodiisobutylphosphonium dihydrochloride (0.75g) was added, and the initial polymerization reaction was carried out at 75 ° C for 7.5 hours, and then cooled to 40 ° C or lower to obtain a solid content of about 30.2%. Aqueous acrylic emulsion.

ratio Comparative example 2 (as shown in Table 3)

In a four-neck glass reaction flask with a thermometer and a stirrer and circulated with nitrogen, FMA (35g), D-V4 (30g), SMA (28.2g), Topolene-M (4g), nonionic emulsifier C ( 6 g), cationic emulsifier B (6.6 g), TPG (42.5 g), acetic acid (0.5 g), n-dodecyl mercaptan (0.3 g), deionized water (195.5 g). A milky white emulsion was obtained using a high pressure homogenizer at a temperature not exceeding 40 ° C and a pressure of 40 MPa. 2,2'-Azodiisobutylphosphonium dihydrochloride (0.75g) was added, and the initial polymerization reaction was carried out at 75 ° C for 7.5 hours, and then cooled to 40 ° C or lower to obtain a solid content of about 27.8%. Aqueous acrylic emulsion.

Examples 1 to 6 (as shown in Table 3)

The four-neck glass reaction flask with a thermometer and a stirrer was circulated with nitrogen gas, and the raw materials listed in Table 3 were subjected to a high pressure homogenizer at a temperature of not more than 40 ° C and a pressure of 40 MPa to obtain a milky white emulsion. 2,2'-Azodiisobutylphosphonium dihydrochloride (0.75 g) was added, and the initial polymerization reaction was carried out at 75 ° C for 7.5 hours, and then cooled to 40 ° C or lower to obtain a product.

(Note)

FMA: CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ OCOCH ₃ =CH ₂ perfluorooctyl methacrylate

SMA: stearyl methacrylate octadecyl methacrylate Topoliene-M: 3-chloro-2-hydroxy-propyl methacrylate 3-chloro-2-hydroxypropyl methacrylate

TPG: tripropylene glycol tripropylene glycol

B: stearyltrimethylammonium chloride hard ester chlorinated quaternary ammonium salt surfactant

C: polyoxyethylene alkly ether polyoxyethylene alkyl nonionic surfactant

The above is a description of specific embodiments of the present invention, followed by an illustration of an applicative evaluation test for an embodiment of the present invention.

Water reclamation evaluation of water repellent composition of fluorine-containing organic copolymer

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, and more preferably at 150 to 200 ° C for 60 to 90 seconds to generate a dial. Water-based.

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 include: natural fibers, animal or vegetable fibers, such as cotton, hemp, wool and silk; synthetic fibers, for example, nylon, polyester, polyamide, polyvinyl alcohol, poly Acrylonitrile, 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. Spray water repellency is indicated by the spray dial water number, as explained below.

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 sprayer was placed at the center, and 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 wetness of the test pieces 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 (as shown in Table 4).

The water repellency test of the present invention is the measured average result of three test pieces. As shown in Table 5.

Durable water wash test (AATCC-22)

Choose the washing conditions and drying methods and record them, or select the appropriate Xicheng according to the manufacturer's offer.

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

Put 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.

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

The durable water wash test of the present invention is a measured average result of three test pieces. As shown in Table 6.

Mechanical stability

The finished product was diluted with water to a solvent of 200 g of a 0.5% solid solution, and stirred by a homogenizer at 2000 rpm for 30 minutes, and then filtered with a cotton cloth to judge impurities adhering to the cotton cloth.

○: completely free of impurities

△: a small amount of impurities

╳: A large amount of impurities

Storage stability

The finished product was stored in a 45-degree constant temperature oven to observe the emulsion precipitation at different times.

○: no precipitation at all

△: a small amount of precipitation

╳: a large amount of precipitation

The mechanical stability and storage stability of the present invention are the measured average results of three test pieces. As shown in Table 7.

The fluorinated water-repellent oil-removing agent provided by the invention comprises a self-synthesized fluorine-containing polyurethane monomer, which is extremely stable in the emulsification reaction and processing, and has no monomer residue, and is subjected to a water repellency test, a durable water washing test, and a mechanical The results of the stability test and the storage stability test show that the fluorine water-repellent oil-repellent agent fully imparts a better water-repellent effect to the substrate.

The above is only a preferred embodiment of the present invention, and variations in the composition and manufacturing method of the present invention and the scope of the patent application are intended to be included in the scope of the present invention.

Claims (7)

A fluorine water-repellent oil-repellent agent comprising a fluorine-containing polyurethane monomer, wherein the general formula is Wherein X is an aliphatic, cycloaliphatic or aromatic structure; Y is a reactive functional group; Z is a fluorine-containing alkyl group having a fluoroalkyl group having a carbon number of 4 to 16. The fluorocarbon water-repellent oil-removing agent according to claim 1, wherein the fluorourethane monomer is polymerized by the following monomers, comprising: (A) a bisisocyanate monomer, wherein the general formula is A ─X-B wherein A and B represent two different reactive isocyanate groups, X is an aliphatic, cycloaliphatic or aromatic structure; (B) a reactive monomer, which is generally Y-OH, containing acryl, oxime, aldehyde, ketone, ether, carboxylic acid or hydroxyl; (C) fluoroalkyl group, the general formula is H _m CF _n (CF ₂ ) _p C _q X where m+n=3, p=6~12, q=1~4, and X is OH. The fluorocarbon water-repellent oil-removing agent according to claim 2, wherein the bis-isocyanate monomer is Toluene diisocyanate, Isophorne diisocyanate or 1,6-hexan Diisocyanate (Hexamethylene diisocyanate). The fluorocarbon water-repellent oil-removing agent according to claim 2, wherein the reactive monomer is The fluorocarbon water-repellent oil-removing agent according to claim 2, wherein the fluoroalkyl group is H-(CF ₂ ) ₆ -OH, H-(CF ₂ ) ₈ -OH, H-(CF ₂ ) ₁₀ - OH, H-(CF ₂ ) ₁₂ -OH, H-(CF ₂ ) ₁₄ -OH, H-(CF ₂ ) ₁₆ -OH, H-(CF ₂ ) ₁₈ -OH or H-(CF ₂ ) ₂₀ - OH. The fluorinated water-repellent oil-repellent agent according to claim 1, further comprising a fluorinated copolymer which is composed of a fluorine-containing alkyl monomer and a monomer copolymerizable therewith. The fluorine water-repellent oil-repellent agent according to claim 6, wherein the monomer copolymerizable with the fluorine-containing urethane monomer is 20 to 70 parts by weight based on 100 parts by weight of the fluorine-containing alkyl monomer, and the fluorine-containing urethane monomer is 1 to 100 parts by weight.