Patent Application
20160002516
1. Technical Field
The present invention relates generally to water-repellent and oil-repellent agent, and more particularly to a type of water-repellent and oil-repellent agent which belongs to fluorine-containing polymers.
2. Description of Related Art
Fluorine-containing compounds are widely applied as surface treatment agents for several kinds of materials, such as textiles, wood, metal, concrete, etc. This type of surface treatment agents have better waterproofing and oil-proofing effect on surfaces of textiles, including natural fibers, synthetic fibers, and semi-synthetic fibers.
According to the literature, perfluoroalkyl ethyl acrylate of the formula H2C═C(X)C(═O)—Y—Z—Rf is suitable for manufacturing waterproofing and oil-proofing surface treatment agents if Rf represents fluoroalkyl containing 8 carbon atoms. On the other hand, the waterproofing and oil-proofing effect gets poorer if fluoroalkyl represented by Rf contains only 4 to 6 carbon atoms. In such cases, it has to additionally apply vinyl chloride or vinylidene chloride to enhance the effect. Although the mixtures which are made by adding olefin monomer of vinyl chloride or vinylidene chloride into perfluoroalkyl ethyl acrylate can provide textile fibers with good waterproofing and water tolerance effect, the surface treatment agents may cause adhesion problem on rollers which are used for processing the fibers.
In view of the above, the primary objective of the present invention is to provide a water-repellent and oil-repellent agent, which has good water-repellent and oil-repellent effect, and also eases the adhesion problem happened on rollers.
The water-repellent and oil-repellent agent provided in the present invention includes a fluorine-containing monomer, a non-fluorinated branched monomer, a non-fluorinated crosslinking monomer, and an olefin monomer.
In an embodiment, the fluorine-containing monomer is of the formula
where X is hydrogen atom, monovalent organic group, halogen atom, linear or branched fluoroalkyl with 1 to 21 carbon atoms, or cyano; Y is oxygen atom, sulfur atom, or secondary amine; Z is straight chain alkane, divalent organic group, aromatics or cycloaliphatic of which carbon-number is 6 to 18, or aliphatic groups of which carbon-number is 1 to 10; and Rf is linear or branched fluoroalkyl of which carbon-number is 4 to 6.
In an embodiment, the non-fluorinated branched monomer is of the formula H2C═CACOOA′, where A is hydrogen atom or methyl; A′ is branched primary to tertiary alkyl, and is of the formula CnHm, where n=3˜10, m=7˜30.
In an embodiment, the non-fluorinated branched monomer is selected from at least one member of the group consisting of tert-Butyl methacrylate, iso-butyl methacrylate, 2-ethylhexyl methacrylate, n-nonyl acrylate, isobornyl acrylate, isobornyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, and benzyl acrylate.
In an embodiment, the non-fluorinated crosslinking monomer has two or more reactive functional groups.
In an embodiment, the non-fluorinated crosslinking monomer is selected from at least one member of the group consisting of 3-chloro-2-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, epoxypropyl methacrylate, 2,3-dihydroxypropyl methacrylate, ethylene glycol methyl ether methacrylat, ethyl methacrylate, diacetone acrylamide, 4-hydroxybutyl acrylate, 1,4-cyclohexane dimethanol monoacrylate, and 4-hydroxybutyl acrylate glycidyl ether.
In an embodiment, the olefin monomer is halogenated olefin monomer.
In an embodiment, the olefin monomer is vinyl chloride or vinylidene chloride.
In an embodiment, the fluorine-containing monomer is 45˜80% by weight.
In an embodiment, the non-fluorinated branched monomer is 1˜30% by weight.
In an embodiment, the non-fluorinated crosslinking monomer is 1˜10% by weight.
In an embodiment, the olefin monomer is 10˜50% by weight.
In an embodiment, the water-repellent and oil-repellent agent is applied for processing fiber products.
In an embodiment, the water-repellent and oil-repellent agent is water-based.
None.
The present invention provides several preferred embodiments to synthesize a water-repellent and oil-repellent agent which belongs to fluorine-containing polymers, and the water-repellent and oil-repellent agent is polymerized with a fluorine-containing monomer, a non-fluorinated branched monomer, a non-fluorinated crosslinking monomer, and an olefin monomer.
The fluorine-containing monomer is of the formula
where X is hydrogen atom, monovalent organic group, halogen atom, linear or branched fluoroalkyl with 1 to 21 carbon atoms, or cyano; Y oxygen atom, sulfur atom, or secondary amine; Z is straight chain alkane, divalent organic group, aromatics or cycloaliphatic of which carbon-number is 6 to 18, or aliphatic groups of which carbon-number is 1 to 10; Rf is linear or branched fluoroalkyl of which carbon-number is 4 to 6. Here are some examples of Rf listed below, but please be noted that they are not limitations of the present invention:
The non-fluorinated branched monomer is of the formula H2C═CACOOA′, where A is hydrogen atom or methyl; A′ is branched primary to tertiary alkyl, and is of the formula CnHm, where n=3˜10, m=7˜30. There are several functional non-fluorinated branched monomers listed in Table 1, and they can be synthesized by one or more compounds mentioned above. Please be noted that what are listed in Table 1 is not a limitation of the present invention.
In addition to the monomers listed in Table 1, benzyl acrylate and cyclohexyl methacrylate can be selected too.
The non-fluorinated crosslinking monomer has two or more reactive functional groups. There are several functional non-fluorinated crosslinking monomers listed in Table 2, and they can be synthesized by one or more compounds mentioned above. Please be noted that what are listed in Table 2 is not a limitation of the present invention.
The non-fluorinated crosslinking monomer is preferably to be halogenated olefin monomer. For example, it can be vinyl chloride or vinylidene chloride.
As shown in Table 3, blend 75 g of 6FMA, 15 g of IBOA, 2 g of GLA, 6 g of DAAM, 0.75 g of 1-dodecanethiol, 43.5 g of dipropylene glycol monomethyl ether, and 300 g of deionized water under 50° C. for 20 minutes; evenly apply 40 MPa of pressure to produce a stable homogeneous emulsion, of which penetrability has to be larger than 15% under test with UV of wavelength 650 nm; pour the homogeneous emulsion into a 1 liter four-necked glass reaction flask, and add in 0.8 g of 2,2′-azobis(-amidinopropane)dihydrochloride and 45 g of VDC for reaction under 60° C. for 6 hours. An aqueous dispersion of acrylic polymer is then obtained.
As shown in Table 3, blend 75 g of 6FMA, 15 g of IBOA, 2.5 g of GMA, 6 g of DAAM, 0.75 g of 1-dodecanethiol, 43.5 g of dipropylene glycol monomethyl ether, and 300 g of deionized water under 50° C. for 20 minutes; evenly apply 40 MPa of pressure to produce a stable homogeneous emulsion; pour the homogeneous emulsion into a 1 liter four-necked glass reaction flask, and add in 0.8 g of 2,2′-azobis(-amidinopropane)dihydrochloride and 45 g of VDC for reaction under 60° C. for 6 hours. An aqueous dispersion of acrylic polymer is then obtained.
As shown in Table 3, blend 75 g of 6FMA, 15 g of IBOA, 2.5 g of GMA, 6 g of DAAM, 0.75 g of 1-dodecanethiol, 43.5 g of dipropylene glycol monomethyl ether, and 300 g of deionized water under 50° C. for 20 minutes; evenly apply 40 MPa of pressure to produce a stable homogeneous emulsion; pour the homogeneous emulsion into a 1 liter four-necked glass reaction flask, and add in 0.8 g of 2,2′-azobis(-amidinopropane)dihydrochloride and 28 g of VDC for reaction under 60° C. for 6 hours. An aqueous dispersion of acrylic polymer is then obtained.
As shown in Table 3, blend 75 g of 6FMA, 24 g of IBOA, 2.5 g of GMA, 6 g of DAAM, 0.75 g of 1-dodecanethiol, 43.5 g of dipropylene glycol monomethyl ether, and 300 g of deionized water under 50° C. for 20 minutes; evenly apply 40 MPa of pressure to produce a stable homogeneous emulsion; pour the homogeneous emulsion into a 1 liter four-necked glass reaction flask, and add in 0.8 g of 2,2′-azobis(-amidinopropane)dihydrochloride and 45 g of VDC for reaction under 60° C. for 6 hours. An aqueous dispersion of acrylic polymer is then obtained.
As shown in Table 3, blend 100 g of 6FMA, 15 g of IBOA, 2.5 g of GMA, 6 g of DAAM, 0.75 g of 1-dodecanethiol, 43.5 g of dipropylene glycol monomethyl ether, and 300 g of deionized water under 50° C. for 20 minutes; evenly apply 40 MPa of pressure to produce a stable homogeneous emulsion; pour the homogeneous emulsion into a 1 liter four-necked glass reaction flask, and add in 0.8 g of 2,2′-azobis(-amidinopropane)dihydrochloride and 45 g of VDC for reaction under 60° C. for 6 hours. An aqueous dispersion of acrylic polymer is then obtained.
As shown in Table 3, blend 100 g of 6FMA, 15 g of IBOA, 21.5 g of EHMA, 8.5 g of DAAM, 0.75 g of 1-dodecanethiol, 43.5 g of dipropylene glycol monomethyl ether, and 350 g of deionized water under 50° C. for 20 minutes; evenly apply 40 MPa of pressure to produce a stable homogeneous emulsion; pour the homogeneous emulsion into a 1 liter four-necked glass reaction flask, and add in 1 g of 2,2′-azobis(-amidinopropane)dihydrochloride and 30 g of VDC for reaction under 60° C. for 6 hours. An aqueous dispersion of acrylic polymer is then obtained.
As shown in Table 3, blend 100 g of 6FMA, 15 g of IBOA, 8.5 g of DAAM, 0.75 g of 1-dodecanethiol, 43.5 g of dipropylene glycol monomethyl ether, and 350 g of deionized water under 50° C. for 20 minutes; evenly apply 40 MPa of pressure to produce a stable homogeneous emulsion; pour the homogeneous emulsion into a 1 liter four-necked glass reaction flask, and add in 1 g of 2,2′-azobis(-amidinopropane)dihydrochloride and 30 g of VDC for reaction under 60° C. for 6 hours. An aqueous dispersion of acrylic polymer is then obtained.
As shown in Table 3, blend 75 g of 6FMA, 24 g of IBOA, 3.5 g of GMA, 2.2 g of CHMA, 6.5 g of DAAM, 0.75 g of 1-dodecanethiol, 43.5 g of dipropylene glycol monomethyl ether, and 350 g of deionized water under 50° C. for 20 minutes; evenly apply 40 MPa of pressure to produce a stable homogeneous emulsion; pour the homogeneous emulsion into a 1 liter four-necked glass reaction flask, and add in 1 g of 2,2′-azobis(-amidinopropane)dihydrochloride and 28 g of VDC for reaction under 60° C. for 6 hours. An aqueous dispersion of acrylic polymer is then obtained.
However, what is listed in Table 3 is not a limitation of the present invention. In other embodiments, the fluorine-containing monomer is preferably to be between 45% and 80% by weight, the non-fluorinated branched monomer is preferably to be between 1% and 30% by weight, the non-fluorinated crosslinking monomer is preferably to be between 1% and 10% by weight, and the olefin monomer is preferably to be between 10% and 50% by weight.
<Evaluation of Water-Repellent Effect of Water-Repellent Agents>
An aqueous dispersion of acrylic polymer can be applied on synthetic fibers with a conventional method of processing textiles. For example, percentage thereof can be between 0.5% and 25% by weight, or between 1% and 10% by weight, or, preferably, between 1% and 5%. The fibers can be immersed in the aqueous dispersion in advance, or can be pad dyed to press out the aqueous dispersion. The fibers can be dried by heating under, as an example, the condition between 100° C. and 200° C. for 60 to 90 seconds, wherein the condition is preferably to be between 150° C. and 200° C. for 60 to 90 seconds. The water-repellent effect can be provided in this way.
Typically, the fibers can be those of synthetic fiber cloth, which includes weaving fabric, knitted fabric, and nonwoven fabric, all kinds of clothes, blankets, or intermediate textile products. The textile products can be synthetic fibers, such as polyester, polyamide, or synthetic fibers of the kinds of acrylic acid, or can be textile mixtures of natural and synthetic fibers. The present invention provides particular high effective water-repellent effect if it is applied on synthetic fibers cloth such as Nylon or polyester. Compared to untreated cloth, the fiber cloth that is treated with the water-repellent and oil-repellent agent of the present invention has good water-repellent effect, and the tactile impression is improved as well.
In practice, the fibers can be those of the kinds of paper, which means, the water-repellent and oil-repellent agent of the present invention can be applied on papers that are going through different processing stages, such as preformed or drying stages.
The surface treatment agent of the present invention is preferably to be in solution form. Conventional surface treatment agents typically contain fluorine-containing polymers and substrate mediums such as organic solvents or water. The surface treatment agents provided in the present invention have 0.1% to 50% of fluorine-containing polymers by weight, wherein 5% to 30% is preferable. The surface treatment agents provided in the present invention can be applied by immersing materials within. Generally, before immersing materials and having the materials dried by heating, surface treatment agents are diluted with organic solvents or water. If necessary, a manufacturer can further add mothproofing agent, softening agent, antibacterial agent, flame resisting agent, antistatic agent, colorant fixing agent, anticorrosive agent etc. in surface treatment agents.
To apply the surface treatment agents provided in the present invention on fiber cloth materials, leather materials, or glass materials, fluorine-containing polymers of the solution in which the materials immersed can be 0.01% to 20% by weight, wherein 0.05% to 5% is preferable. As in the examples provided in the present invention, it is 0.05% to 10% by weight.
The surface treatment agents provided in the present invention provides better water-repellent effect on textiles, which include natural fibers (animal fibers or vegetative fibers, such as cotton, hemp, wool, or silk), synthetic fibers (such as nylon, polyester, polyamide, polyvinyl alcohol, polyacrylonitrile, polyvinylchloride, and polypropylene), semi-synthetic fibers (such as rayon and acetate ester), inorganic fibers (such as glass fiber, carbon fiber, and asbestos fiber), and mixtures of the aforementioned fibers.
<Shower Water-Repellency Test (AATCC-22)>
Prepare a 250 ml plastic funnel which has a nozzle capable of spraying 250 ml of water for 20 to 30 seconds; prepare three 20 cm×20 cm specimens of materials which are going to be tested; place one of the specimens on a round specimen holder which has 15 cm diameter, and the specimen should have no wrinkling; place a sprayer at the center, and pour 250 ml water of room temperature into the plastic funnel; spray water on the specimen for 20 to 30 seconds; remove the specimen, and gently flip the specimen to shake off water drops; test another two specimens in the same way. Each specimen is scored from 0 to 100 according to its wetness, and the scoring standard is shown in Table 4. The test result is an average score of all three specimens.
<Washing Durability Test (AATCC-22)>
Select and record a washing condition and drying method, or follow the washing instructions provided by manufacturers;
Pour water into a washing machine to a predetermined level (about 68 L), and adjust the water temperature;
<Test of Adhesive Status on the Rollers>
Place 4 g of surface treatment agent in a 250 ml beaker, and blend with 196 g of deionized water under 25° C. to form a solution; immerse textile materials into the solution; press out the solution with a padding machine which provides 3 kg pressure; judge the adhesion status on rollers of the padding machine during the textile materials are passing through.
◯: completely clean on the rollers
Δ: adhered with little area on the rollers
x: adhered with large area on the rollers
The test is proceed with three specimens of textile materials.
As we can see, the water-repellent and oil-repellent agent of the present invention, which is polymerized by at least a fluorine-containing monomer, a non-fluorinated branched monomer, a non-fluorinated crosslinking monomer, and an olefin monomer, is able to provide good water-repellent and oil-repellent effect. Furthermore, the adhesion problem on the rollers can be eases as well. It must be pointed out that the embodiments described above are only some preferred embodiments of the present invention. All equivalent formulas which employ the concepts disclosed in this specification and the appended claims should fall within the scope of the present invention.
