KR102193238B1 - Fluorinated Water-repellant surface-treating composition having high water-glinding property and manufacturing method thereof - Google Patents

Abstract

According to the present invention, a mixture comprising a perfluoroalkyl group-containing organopolysilane, an optional silicone crosslinking agent, and a reactive silicone polymer solution as a water repellent component; At least one compound selected from the group consisting of N-polyoxyalkylenated fatty acid amide polyoxyalkylenated fatty acid amide as the rolling property improving agent; Acidic catalysts containing inorganic or organic acids; And a fluorine-based water-repellent surface treatment composition comprising an aqueous solvent, a method for producing the same, and a water-repellent permeable and impermeable article using the same.
The fluorine-based water-repellent surface treatment composition according to the present invention is stable and economical to manufacture, and can maintain colorless and transparent properties even during long-term storage, so it has high stability and storage properties, as well as high adhesion to permeable articles such as fabrics, and excellent Water repellency and rolling properties can be given.

Description

Fluorinated Water-repellant surface-treating composition having high water-glinding property and manufacturing method thereof

The present invention relates to a fluorine-based water-repellent surface treatment composition having excellent rolling properties and a method for producing the same, and specifically, an organopolysilane containing a perfluoroalkyl group as a water-repellent component, and an N-polyoxyalkylenated fatty acid amide or O- The present invention relates to a fluorine-based water-repellent surface treatment composition containing an alkylated polyglucoside having excellent rolling properties and a method for producing the same. The fluorine-based water repellent surface treatment composition according to the present invention can impart excellent water repellency and rolling properties to permeable articles such as fabrics.

Items including windshields, shower booths, veranda windows, car windshields, car side mirrors, ship exteriors, electronics, mobile phones, etc., may be exposed to water, and contaminants dissolved or mixed in water The product is contaminated and its lifespan is shortened. In particular, in the case of items used in automobiles and ships, there is a problem in safety of operation.

Therefore, it is possible to prevent contamination of the article by using a material exhibiting water repellency. In this case, since the material exhibiting water repellency is relatively expensive, a method of coating the surface of the article with a thin thickness to prevent contamination is adopted.

In general, for articles (hereinafter referred to as permeable articles) that exhibit air, water, and water permeability, such as fibers, knitted fabrics, woven fabrics, and nonwovens, materials with low surface energy such as fluorinated polymers and silane polymers are used as water repellent agents. Or, it imparts water repellency as a hydrophobic agent. Until now, a fluorine-based water-repellent material, which has a chemical structure based on a fluorine molecule, is made by combining a fluorine-based material with an inorganic material or using an organic material containing fluorine has been mainly used. For example, organopolysilane containing a perfluoroalkyl group, which is one of the fluorinated polymers, has a very small surface free energy and has high water repellency, and is excellent in chemical resistance due to the perfluoroalkyl group. In addition, it has good adhesion to substrates such as glass, plastic, and cloth. Recently, a non-fluorine-based water-repellent material having a structure similar to this and based on silicon or long hydrogen bonds has been developed, and now shows relatively low performance compared to fluorine-based materials.

However, fluorine-based water-repellent materials including perfluoroalkyl group-containing organopolysilanes and non-fluorine-based water-repellent materials including silane polymers have excellent water repellency, but there is a problem that the rolling property, which is the property of rolling or sliding of water droplets, is poor. It was difficult to use for required articles, and in a permeable article such as a fabric, there is an inconvenience that water exceeding the water repellency will seep into the fabric and cause surface wetting if it contacts the surface or stays for a long time. In addition, long-term stability is also required to have marketability, but long-term stability is often insufficient.

On the other hand, permeable articles such as fabrics are often required to have moisture-permeable and waterproof properties, and water-repellent treatment can be applied for this. In order to impart water repellency to permeable articles such as fabrics without impairing the permeability, not only water repellency, which is a property of not forming or adhering to water droplets on the surface, but also water droplets on the surface of the fabric flow or roll without staying or stagnating. It is also necessary to consider the surface cloudiness of falling.

Patent Document 1 (Korean Publication No. 10-2015-0081177, publication date July 13, 2015) includes 2 million to 4 million needle-shaped nano structures per 1 mm ^{2 of} area. Nanoacicular-fibers having a surface of 5 to 100 nm in thickness; In addition, a superhydrophobic fiber having a contact angle of 150 degrees or more and a rolling angle of 3 degrees or less and a manufacturing method is disclosed, which is located on a surface including the nanostructures and includes a coating layer containing a hydrophobic material.

In Patent Document 2 (Korean Publication No. 10-2016-0060913, publication date May 31, 2016), a sol-gel dispersion in which nanoparticles were aggregated was prepared using a solvent having a dielectric constant of 20 or less, and the surface And then impregnated with hydrophobic silane to hydrophobize the surface, thereby providing a method for producing a super-water-repellent surface in which the surface rolling angle converges to 0 degrees.

In Patent Document 3 (Korean Registration No. 10-1831380, registration date February 14, 2018), a sol-gel reaction by mixing an organopolysilane containing a perfluoroalkyl group, an alkylamide or alkyl polyglucoside, an acid and a solvent It is disclosed that the water-repellent surface treatment agent excellent in adhesion to the substrate, water repellency, and surface lubricity can be produced by causing this. However, the water-repellent surface treatment agent disclosed in the document is for forming a water-repellent surface having lubricity on the impermeable substrate, and there is no description of water repellency and/or rollability in a permeable article such as a fabric.

In general, in a permeable article through which water and air can permeate, specifically, in a permeable article through which liquids such as water and oil and gases such as air and water vapor can permeate, water repellency is maintained while maintaining the moisture permeability characteristic of the permeable article. It is not easy to give. For example, in order to use the fabric as a water-permeable water-repellent fabric by water-repellent treatment, the surface of the water-repellent-treated fabric is required to have excellent rolling properties (low rolling angle) in addition to excellent water repellency (or high contact angle). Wearable fabrics using conductive carbon fiber, sportswear with internal wiring, and fire-resistant fabrics for firefighters have high water repellency even when in contact with water for a long time, but have high rolling properties that can avoid long-term contact with water as much as possible. Is being demanded. Therefore, development of a water-repellent surface treatment composition excellent in not only water repellency but also rolling property is desired.

Under these circumstances, the present invention was developed to meet the need for a new water-repellent surface treatment composition for imparting high water repellency and excellent surface rollingability to permeable articles such as fabrics.

Domestic Publication No. 10-2015-0081177 (Publication date 2015.07.13.) Domestic Publication No. 10-2016-0060913 (Publication date 2016.05.31) Domestic Registration Gazette No. 10-1831380 (Registration Date 2018.02.14)

The present invention includes a water-repellent component comprising a perfluoroalkyl group-containing organopolysilane, an optional silicone crosslinking agent, and a reactive silicone polymer solution, and a cloudability improving agent comprising an N-polyoxyalkylenated fatty acid amide or an O-alkylated polyglucoside It is intended to provide a water-repellent surface treatment composition having excellent rolling properties and a method for producing the same.

The present invention is also intended to provide a water-repellent article, particularly a permeable article such as a fabric, using the water-repellent surface treatment composition.

The inventors,

(a) a mixture comprising a perfluoroalkyl group-containing organopolysilane, an optional silicone crosslinking agent, and a reactive silicone polymer solution as a water repellent component,

(b) at least one compound selected from the group consisting of N-polyoxyalkylenated fatty acid amide or O-alkylated polyglucoside as a rolling property improving agent,

(c) an acidic catalyst selected from organic or inorganic acids, and

(d) aqueous solvent

It was found that the fluorine-based water-repellent surface treatment composition comprising, not only has excellent stability and long-term storage, but also can impart excellent water repellency and high rolling properties to permeable articles such as fabrics, and completed the present invention.

The fluorine-based water-repellent surface treatment composition may be prepared by a method comprising the following steps:

(Step 1) At least one compound selected from the group consisting of a perfluoroalkyl group-containing organopolysilane as a water-repellent component, an N-polyoxyalkylenated fatty acid amide or an O-alkyl polyglucoside as a cloudability improving agent, and an optional silicone crosslinking agent Dissolving or dispersing in an aqueous solvent to prepare a mixture; And

(Step 2) sol-gel reaction by adding an acidic catalyst to the mixture;

(Step 3) During the sol-gel reaction, a reactive silicone polymer solution is added to form an organopolysiloxane sol.

The fluorine-based water-repellent surface treatment composition according to the present invention is stable and economical to manufacture, and can maintain colorless and transparent properties even during long-term storage, so it has high stability and storage properties, as well as high adhesion to permeable articles such as fabrics, and excellent Water repellency and rolling properties can be given.

The first object of the present invention is to provide a fluorine-based water-repellent surface treatment composition comprising the following components:

(a) a mixture comprising a perfluoroalkyl group-containing organopolysilane, an optional silicone crosslinking agent, and a reactive silicone polymer solution as a water repellent component,

(b) at least one compound selected from the group consisting of N-polyoxyalkylenated fatty acid amide or O-alkylated polyglucoside as a rolling property improving agent,

(c) an acidic catalyst selected from organic or inorganic acids, and

(d) an aqueous solvent.

A second object of the present invention is to provide a fluorine-based water-repellent surface treatment composition having excellent rolling properties, and may include the following steps.

(Step 1) At least one compound selected from the group consisting of a perfluoroalkyl group-containing organopolysilane as a water-repellent component, an N-polyoxyalkylenated fatty acid amide or an O-alkyl polyglucoside as a cloudability improving agent, and an optional silicone crosslinking agent Dissolving or dispersing in an aqueous solvent to prepare a mixture; And

(Step 2) sol-gel reaction by adding an acidic catalyst to the mixture;

(Step 3) During the sol-gel reaction, a reactive silicone polymer solution is added to form an organopolysiloxane sol.

A third object of the present invention is to provide a permeable article manufactured using the fluorine-based water-repellent surface treatment composition having excellent rollability and excellent water repellency and rollability, and the permeable article is selected from fibers, knitted fabrics, woven fabrics, or nonwoven fabrics. Can be.

The present invention will be described in more detail below.

(1) Water-repellent surface treatment composition

The water-repellent surface treatment composition according to the present invention may include, as a water-repellent component, an organopolysilane containing a perfluoroalkyl group, an optional silicone crosslinking agent, and a reactive silicone polymer solution.

[Organopolysilane containing perfluoroalkyl group]

In the present invention, the perfluoroalkyl group-containing organopolysilane may be represented by a compound of Formula 1:

[Formula 1]

CF ₃ -(CF ₂ ) _n -R-SiX _p Y _3-p

In the above formula,

n is an integer from 0 to 12,

R is an organic group having 1 to 10 carbon atoms or a group containing a silicon atom and an oxygen atom,

X is H or a monovalent hydrocarbon group having 1 to 4 carbon atoms, or a substituent selected from a derivative of the group,

p is 0, 1 or 2,

Y is a C1-C4 alkoxy group, an acyloxy group, or a halogen atom.

In the above formula, n may be an integer of 3 to 12, for example.

In the above formula, R may be, for example, an alkylene group having 1 to 10 carbon atoms, and specifically, for example, may be a methylene group or an ethylene group.

In the above formula, X is a substituent selected from H or a monovalent hydrocarbon group having 1 to 4 carbon atoms, or a derivative of the group.

Here, the "monovalent hydrocarbon group" may be branched or unbranched, acyclic or cyclic, saturated or unsaturated, or aromatic, and contain 1 to 4 (or 3 or 4 in the case of an aromatic group) carbon atoms. I can.

In the above formula, X may be, for example, an alkyl group, a cycloalkyl group or an allyl group.

At least one hydrogen in R, X, and Y may be substituted with a halogen atom such as fluorine.

Specific examples of the compound of Formula 1 are described below, but are not limited thereto.

C ₆ F ₁₃ CH ₂ CH ₂ Si(OCH ₃ ) ₃ ;

C ₇ F ₁₅ CH ₂ CH ₂ Si(OCH ₃ ) ₃ ;

C ₈ F ₁₇ CH ₂ CH ₂ Si(OCH ₃ ) ₃ ;

C ₉ F ₁₉ CH ₂ CH ₂ Si(OCH ₃ ) ₃ ;

C ₁₀ F ₂₁ CH ₂ CH ₂ Si(OCH ₃ ) ₃ ;

C ₆ F ₁₃ CH ₂ CH ₂ SiCl ₃ ;

C ₇ F ₁₅ CH ₂ CH ₂ SiCl ₃ ;

C ₈ F ₁₇ CH ₂ CH ₂ SiCl ₃ ;

C ₉ F ₁₉ CH ₂ CH ₂ SiCl ₃ ;

C ₁₀ F ₂₁ CH ₂ CH ₂ SiCl ₃ ;

C ₈ F ₁₇ CH ₂ CH ₂ Si(CH ₃ )(OCH ₃ ) ₂ ;

C ₈ F ₁₇ CH ₂ CH ₂ Si(OC ₂ H ₅ ) ₃ ;

C ₆ F ₁₃ CH ₂ CH ₂ Si(OC ₂ H ₅ ) ₃ ;

C ₆ F ₁₃ CH ₂ CH ₂ Si(OCH(CH ₃ ) ₂ ) ₃ ; And

C ₈ F ₁₇ CH ₂ CH ₂ Si(OCOCH ₃ ) ₃ .

[Silicone crosslinking agent]

The water-repellent surface treatment composition according to the present invention may further contain an optional silicone crosslinking agent and/or an optional reactive silicone crosslinking agent in addition to the perfluoroalkyl group-containing organopolysilane as a water repellent component.

As a non-limiting example of the silicone crosslinking agent, methoxysilane, ethoxysilane, propoxysilane, isopropoxysilane, aryloxysilane, tetramethylorthosilicate (TMOS), tetraacetylorthosilicate (TEOS) or tetra Mention may be made of propyl orthosilicate (TPOS). Such a silicone crosslinking agent may be included in an amount of 10 to 300 parts by weight, preferably 50 to 200 parts by weight, more preferably 100 to 150 parts by weight based on 100 parts of the organopolysilane containing a perfluoroalkyl group, but is not limited thereto. . If it falls within the above range, durability is high and high adhesion to a substrate such as fiber can be maintained.

As a non-limiting example of the reactive silicone crosslinking agent, [3-(trimethoxysilyl)propyl]-octadecyldimethylammonium chloride, (3-triethoxysilylpropyl)-5,5-dimethylhydantoin, potassium trimethyl Silanolate, triisopropylsilanol, methoxydimethyloctylsilane, (3-chloropropyl)triethoxysilane, (3-chloropropyl)dimethoxymethylsilane, octadecyltrimethoxysilane, 3-aminopropyltri Ethoxysilane, 3-(trimethoxysilyl)propylmethacrylate, N-[3-(trimethoxysilyl)propyl]-ethylenediamine and 3-glycidoxypropyltrimethoxysilane may be mentioned. Such a reactive silicone crosslinking agent may be included in an amount of 2 to 30 parts by weight, preferably 5 to 25 parts by weight, more preferably 10 to 20 parts by weight, based on 100 parts by weight of the organopolysilane containing a perfluoroalkyl group, but limited thereto. It doesn't work.

The reactive silicone crosslinking agent can increase the molecular weight of the organopolysiloxane sol in step 2), thereby helping to form a water-repellent coating layer having a stable three-dimensional network structure on the surface of the fiber, and improving the density of the water-repellent coating layer. Therefore, it is possible to prevent the water-repellent coating layer from being easily peeled off by impact and to improve durability.

[Cloudy improvement agent]

According to one embodiment of the present invention, the cloudability improving agent is a hydrophobic group having a long-chain alkyl group having 8 to 36 carbon atoms, preferably 12 to 32, and a polyoxyalkylene group or a polyglucoside group having excellent chemical stability as a hydrophilic group. Compounds, for example N-polyoxyalkylenated fatty acid amides or O-alkyl polyglucosides.

In the present invention, the N-polyoxyalkylenated fatty acid amide is an amide derivative of a long-chain fatty acid in the range of 8 to 36 carbon atoms, and in the nitrogen atom of the amide group, 3 to 20 oxyalkylene groups, preferably 4 to It may be a compound substituted with 14 oxyalkylene groups, more preferably 5 to 10 oxyalkylene groups.

The long-chain fatty acids are tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, eicosanoic acid, hencosanoic acid, decosanoic acid, tetracosanoic acid , Pentacosanoic acid, tricosanoic acid, hexacosanoic acid, triacontanoic acid, dotriacontanoic acid, tetratriacontanoic acid, gentriacontanoic acid, pentatriacontanoic acid, hexatriacontanoic acid, Myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid and hexatriisocontanoic (C36) acid, oleic acid, palmitoleic acid, linolenic acid and cetoleic acid, and analogs thereof may be selected from the group consisting of.

The alkylene group of the polyoxyalkylene group may be selected from the group consisting of ethylene, propylene, isopropylene, butylene, isobutylene, and mixtures thereof, preferably ethylene or propylene.

A typical example of an N-polyoxyalkylenated fatty acid amide may be a compound represented by Formula 2:

[Formula 2]

RC0NH(A0) _n H or RCON[(A0) _n H] ₂

In the above formula,

R represents a substituted or unsubstituted alkyl group having 8 to 36 carbon atoms,

(A0) _n represents polyoxyethylene, polyoxypropylene or polyoxyethylene/polyoxypropylene block copolymer,

n represents an integer of 3 to 20, preferably 4 to 14, more preferably 5 to 10.

Non-limiting examples of the N-polyoxyalkylenated fatty acid amide represented by Formula 2 include polyoxyethylene lauramide, polyoxyethylene stearamide, polyoxyethylene cocamide, polyoxypropylene cocamide, and polypropylene glycol 2-hydro Mention may be made of oxyethyl isostearamide and polypropylene glycol 2-hydroxyethyl cocamide. They can be prepared by polyalkoxylation of fatty acid monoalkanolamides (eg, addition of ethylene oxide or propylene oxide), or by fatty acid amidation with polyalkylene glycols.

In the present invention, the O-alkyl polyglucoside is a compound in which an alkyl group is bonded to at least one of the hydroxy groups (OH) of the polyclucoside by ether linkage, for example, O-alkyl polyglucoside represented by the following formula (3). It can be represented by glucosides:

[Formula 3]

In the above formula,

y is 0 to 6, preferably 1 to 4,

R is an alkyl group having 8 to 36 carbon atoms, preferably 12 to 32 carbon atoms.

In the present invention, the content of the rolling property improving agent is 0.001 to 20 parts by weight, preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight based on 100 parts by weight of the perfluoroalkyl group-containing organopolysilane. Can be included in quantity. When the rolling property improving agent is used in an amount included in the above range, the water-repellent surface treatment composition can provide a transparent coating while exhibiting desired rolling properties, and a flat coating surface can be obtained.

When both N-polyoxyalkylenated fatty acid amide and O-alkyl polyglucoside are used as the cloudability improving agent, the mixing ratio thereof is 100:0.1 to 0.1:100, preferably 100:1 to 1:100 by weight. , More preferably, it may be selected from the range of 100:10 to 10:100. When used in a proportion included in the above range, the water-repellent surface treatment composition can provide a water-repellent surface having high rolling properties as well as excellent washing durability.

In the present invention, the N-polyoxyalkylenated fatty acid amide and O-alkyl polyglucoside are materials generally used as nonionic surfactants or slip agents, and are mainly located at the interface between the gas and the solid on the water repellent surface. As a result, it is understood that the long-chain alkyl group protrudes from the water-repellent surface, thereby pushing or rolling the water droplets formed or adhering to the water-repellent surface, thereby imparting or further improving the rolling properties.

In the present invention, the rolling angle is formed by slightly dropping 0.2cc of water on a sample to be measured on a flat surface installed on a horizontal plate to form a water drop, and the flat plate is slightly inclined at a constant speed, so that the formed water drop starts to roll. Means angle. When the sample to be measured is a permeable article such as a fabric, since the central portion may be drooped down by gravity or the like, it may be necessary to support a flat plate underneath to maintain the flat surface.

The water-repellent surface treatment composition according to the present invention can provide a rolling angle of 20 degrees or less, preferably 15 degrees or less, more preferably 10 degrees or less, and particularly preferably 5 degrees or less.

[Acid catalyst]

According to the present invention, the water-repellent surface treatment composition may include an acidic catalyst selected from inorganic acids or organic acids as a gelling catalyst and a pH adjusting agent. As the usable acidic catalyst, at least one acid selected from hydrochloric acid, acetic acid, nitric acid, sulfuric acid and phosphoric acid may be included. The acid may be an aqueous solution having a concentration of 0.001 to 1 N. If it falls within the above concentration range, the reaction time for preparing the surface treatment composition may proceed within a few days to several days.

The acidic catalyst may be used in an amount of 0.001 to 50 parts by weight, preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the perfluoroalkyl group-containing organopolysilane. If it falls within the above range, not only can the speed and particle size of the sol-gel reaction be adjusted to an appropriate level, but also cloudiness or precipitation of the composition can be prevented.

[Aqueous solvent]

As the aqueous solvent that can be used in the present invention, water, an organic solvent compatible with the water, or a mixture thereof may be mentioned. The organic solvent having compatibility with water may be a water-soluble, water-miscible and/or water-soluble organic solvent, preferably an alcohol having 1 to 10 carbon atoms, more preferably methanol, ethanol, propanol, isopropanol, butanol, iso It may be selected at least one type from the group consisting of butanol, sec-butanol, ethylene glycol and propylene glycol.

The content of the aqueous solvent may be selected from 10 to 300 parts by weight, preferably 50 to 200 parts by weight, more preferably 100 to 150 parts by weight, based on 100 parts by weight of the perfluoroalkyl group-containing organopolysilane, It is not limited to this. If it falls within the above range, the sol-gel reaction rate is appropriate, and adhesion with a substrate such as fiber can be maintained.

When a mixture of water and an organic solvent is used as the aqueous solvent, the mixing ratio thereof is 1:100 to 100:1, preferably 10:100 to 100:10, more preferably 50:100 to 100: It may be selected from the range of 50, but is not limited thereto. If it falls within the above range, it is possible to maintain adhesion with a substrate such as a fiber, and can provide excellent water repellency and transparency.

[Reactive silicone polymer]

In the present invention, the reactive silicone polymer may be a silicone oil containing a reactive functional group at least one of a carboxyl group, a hydroxy group and an azo group or an amino group at the end of the polymer main chain or the end of the side chain, preferably containing an amino group as a reactive functional group. It can be chosen from silicone oils. As a silicone oil that can be used as the reactive silicone polymer, mention may be made of polydimethylsilane (PDMS), preferably a polydimethylsilane containing an amino group or an azo group as a reactive functional group.

The reactive silicone polymer may be used in an amount of 10 to 50 parts by weight, more preferably 15 to 25 parts by weight, based on 100 parts by weight of a perfluoroalkyl group-containing organopolysilane. If the reactive silicone polymer is contained in less than 10 parts by weight, it is difficult to form a crosslinked product of organopolysiloxane having a highly durable and highly water-repellent three-dimensional network structure.If the reactive silicone polymer is contained in more than 50 parts by weight, it is unreacted. There may be a problem of insignificant improvement in physical properties and an increase in cost due to a large number of reactive silicone polymers.

The reactive silicone polymer that can be used in the present invention preferably has a viscosity of 700 to 1500 cps. If the viscosity is less than 700 cps, it is not possible to form an organopolysiloxane sol having a molecular weight of the desired level, and thus durability of the crosslinked organopolysiloxane of a three-dimensional network structure decreases, and water repellency may decrease due to a decrease in density. If the viscosity exceeds 1500 cps, the touch of the water-repellent coated surface is markedly deteriorated, and in the case of water-repellent coating of permeable articles such as fibers or fabrics, the touch and drape properties of the fabricated fabric decrease as their flexibility decreases. There is a problem that can get very bad.

The reactive silicone polymer is further improved durability through reaction with the organopolysiloxane primary sol formed in step 2), for example, through thermal curing with a silicon precursor such as 3-glycidoxypropyltrimethoxysilane. A crosslinked product of organopolysilonic acid having a three-dimensional network structure having high water repellency can be formed.

It is preferable to use the reactive silicone polymer in the form of a solution containing a solvent to dissolve it. The solvent may be used without limitation in the case of a known solvent suitable for dissolving a known reactive silicone polymer, and a non-limiting example thereof may include isopropyl alcohol, and 100 parts by weight of the reactive silicone polymer It can be used in ~150 parts by weight.

(2) Method for preparing a water-repellent surface treatment composition

According to one embodiment of the present invention, the water-repellent surface treatment composition of the present invention,

(Step 1) At least one compound selected from the group consisting of a perfluoroalkyl group-containing organopolysilane as a water-repellent component, an N-polyoxyalkylenated fatty acid amide or an O-alkyl polyglucoside as a cloudability improving agent, and an optional silicone crosslinking agent Dissolving or dispersing in an aqueous solvent to prepare a mixture; And

(Step 2) sol-gel reaction by adding an acidic catalyst to the mixture;

(Step 3) during the sol-gel reaction, adding a reactive silicone polymer solution to form an organopolysiloxane sol;

It can be manufactured according to a manufacturing method comprising a.

In the manufacturing method of the present invention, step 1) may be performed at a temperature of 10 to 40° C., preferably at room temperature, using a reactor, kneader or mixer equipped with a stirring device and a thermometer. The order and method of addition of the constituents in step 1), and the mixing method and conditions are not particularly limited and may be performed according to what is commonly used in the art. For example, the constituents may be administered sequentially or simultaneously in a reactor at a temperature of, for example, 10 to 40° C., preferably room temperature, and stirred or kneaded.

In the manufacturing method of the present invention, the step 2) is a sol-gel reaction for 30 to 80 minutes, preferably 40 to 60 minutes at a temperature of 50 to 70°C, preferably 55 to 60°C by adding an acidic catalyst. It can be done by If the temperature is less than 50°C, the reaction time may be delayed or the sol may not be formed smoothly. If the temperature exceeds 70°C, there may be problems such as decomposition reaction in the sol-type reaction product. In addition, the sol-gel reaction of step 2) is preferably carried out until the solution becomes transparent.

In step 2), by adding an acidic catalyst in the form of an acid or an acidic solution to adjust the pH of the reaction mixture to an appropriate range, for example, pH 3 to 6, preferably in the range of pH 4.5 to 5.0, smooth formation of sol is achieved. Can be promoted. Acids that can be used include, without limitation, hydrochloric acid, nitric acid, sulfuric acid or acetic acid. The concentration and amount of the acid or acid solution are not particularly limited in the present invention as long as the pH of the mixture satisfies the above range. Preferably, acetic acid can be added in an amount of 0.5 to 10 parts by weight, more preferably 1.5 to 3 parts by weight, based on 100 parts by weight of the silicone-based crosslinking agent. In order to produce a more smooth sol, it may be added dropwise or added gradually or gradually while checking the pH of the reaction mixture from time to time.

In the manufacturing method of the present invention, the step 3) is 25 to 45° C., preferably 30 to 40° C., while adding or adding a reactive silicone polymer solution to the organopolysiloxane primary sol solution obtained in step 2). It can be carried out by reacting for 30 to 120 minutes, preferably 40 to 80 minutes at a temperature of °C, but the reaction temperature and time are not limited thereto.

In step 3), the reactive silicone polymer reacts with an unreacted silicone-based crosslinking agent to form an organopolysiloxane secondary sol.

Therefore, after the step 2) is finished, before the reactive silicone polymer solution is added, the organopolysiloxane primary sol solution is cooled to a temperature range of 25 to 45°C, preferably 30 to 40°C, and then reactive It is preferable to add a silicone polymer solution. In order to increase the temperature according to the reaction and/or for a homogeneous reaction, the reactive silicone polymer solution is preferably added slowly. If the reaction temperature is less than 25°C, the reaction time may be delayed or the formation of the organopolysiloxane secondary sol solution may not be smooth.If the temperature exceeds 45°C, a decomposition reaction of the reactive silicone polymer or gelation may occur rapidly. There may be problems such as progress.

(3) Water-repellent treatment method and water-repellent products

The water-repellent surface treatment composition according to the present invention can be applied to both organic, inorganic and metallic surfaces. Non-limiting examples of these may include fibers, polymers, plastics, glass, carbon, ceramics or metals.

The water-repellent surface treatment composition according to the present invention has high water repellency (high contact angle) to a permeable article through which water and air can permeate, specifically to a permeable article through which liquids such as water and oil and gases such as air and water vapor can permeate. And it is possible to provide a water-repellent surface having excellent rolling properties (low rolling angle). Non-limiting examples of such permeable articles may mention water repellency and rollability on the surfaces of fibers, knitted fabrics, woven fabrics and nonwovens.

Fibers and fabrics, which are the most representative examples of the permeable article, may be known natural fibers or synthetic fibers, or fabrics made of them. The water-repellent composition for fibers according to the present invention contains an organopolysiloxane sol solution having excellent adhesion or coatability to fibers, and has excellent fiber or adhesion coating properties, so it is largely limited to the material of fibers or fabrics. It can be applied universally without receiving it. Therefore, while the conventional water-repellent coating agent is excellent in coating properties for the type of fiber, that is, polyester-based fibers, the problem of remarkably deteriorating coating properties for fibers of other materials can be solved.

As a non-limiting example of the fiber, as natural fiber, cellulose fiber, protein fiber such as wool or silk fiber, mineral fiber may be used, and as synthetic fiber, polyamide fiber, polyester fiber, polyurethane fiber, acrylic fiber, olefin fiber , Polyvinyl alcohol fibers, polyvinyl chloride fibers, polyvinylidene chloride fibers, polyvinylidene dinitrile fibers, and polytetrafluoride ethylene fibers may be used. In addition, it can be applied to special fibers such as carbon fiber and aramid fiber.

In addition, the fabric may be a fabric or fabric including known natural or synthetic fibers. The term used in the present invention, the fabric or fabric is meant to include all fabrics or knitted fabrics. The fabric may be a fabric or fabric that is woven using at least one of warp and weft yarns according to the present invention.

The weaving may be made by any one method selected from the group consisting of plain weave, twill weave, weave and double weave. When these plain weave, twill weave, and weave are referred to as three-way fabrics, the specific weaving method of each three-way fabric is based on a conventional weaving method, and it may be a fabric that changes by modifying the structure or combining several fabrics based on the three-way fabric. For example, there are changeable plain weaves such as tuduk weave and basket weaves, and changeable twill weaves include new twill weaves, par twill weaves, non-twill weaves, mountain twill weaves, etc. There is this. The double weave is a method of weaving a fabric in which either one of the warp or weft is doubled or both are doubled, and a specific method may be a conventional double weaving method.

However, it is not limited to the substrate of the fabric structure, and the density of warp yarns in weaving is not particularly limited.

In addition, the fabric may be a knitted fabric including honseom yarn as a yarn. The knitting may be performed by a weft knitting or warp knitting method, and the specific method of the weft knitting and warp knitting may be by a conventional weft knitting or warp knitting method.

According to one advantage of the present invention, the water-repellent surface treatment composition of the present invention has excellent water repellency and rolling properties, is stable and economical to manufacture, and can maintain colorless and transparent properties without being cloudy during long-term storage, so it has high storage properties. In addition, excellent water repellency and rolling properties can be imparted to permeable articles such as fabrics.

According to another advantage of the present invention, the water-repellent surface treatment composition of the present invention contains at least one compound selected from the group consisting of N-polyoxyalkylenated fatty acid amide and O-alkyl polyglucoside as a rolling property improving agent, Long-term storage stability can be provided to organopolysiloxane sols formed from phosphorus perfluoroalkyl group-containing organopolysilanes, optional silicone crosslinking agents, and reactive silicone polymer solutions, so that they can be stored for a long time even if they are not stored separately from acids and solvents. Do.

According to another advantage of the present invention, it is possible to stably and economically prepare a water-repellent surface treatment composition, excellent adhesion to the substrate and water repellency, excellent surface rolling properties, and colorless and transparent surface treatment without cloudiness during long-term storage. The composition can be prepared.

The present invention will be described in more detail through the following examples, but the scope of the present invention is not limited thereto.

<Reference Example 1>

Preparation of surface treatment composition

As described in Example 2 of Patent Document 3, 5.68 g of FAS-17 (trade name: TSL-8233; manufacturer: Momentive Japan) of heptadecafluor decyl trimethoxysilane called 0.006 g of alkyl polyglucoside (trade name: Milcoside 100; manufacturer: LG Household & Health Care). Then, the mixture was added to a 7.56 ml of isopropanol solvent, and 0.18 g of a 0.1N aqueous hydrochloric acid solution was added thereto, followed by a sol-gel reaction to prepare a surface treatment composition.

Articles treated with surface treatment composition

Slide glass and PET film were used as the article substrate, and the slide glass was immersed in 10% by weight of NaOH aqueous solution for 5 minutes and washed with distilled water in order to improve adhesion to the surface treatment composition. Then, it was used after drying with nitrogen gas. In the case of a PET film, plasma pretreatment was performed to improve the adhesion of the surface of the PET film. The surface treatment composition prepared above was diluted to 0.05 wt% (solid content) in HFE-7200 (Ethoxy-nonafluorobutane; manufacturer: 3M) solvent to prepare a surface treatment composition dilution, and then to a slide glass dried with the nitrogen gas. The diluent of the surface treatment composition was spin-coated at 1000 rpm and then put in an oven and cured at 50° C. for 3 hours. In addition, the pretreatment PET film was dip-coated in the diluent of the surface treatment composition diluted to 0.05% by weight for 1 minute and then put in an oven and cured at 50° C. for 3 hours.

Water repellency and rolling test

The water repellency was evaluated by the average contact angle obtained by measuring at a total of 50 water contact angle measurement points of five samples coated on a slide glass with a contact angle measuring device (GSA-X; manufacturer: STK Korea).

Rolling property uses a rolling angle measuring machine (manufactured by TFJ Global), placing an A4-size PET film coated with a surface treatment composition on a flat plate, adding 0.2 cc of water to the PET film, and tilting the flat plate little by little, The angle at which the water droplets slide was measured and averaged 10 times, and evaluated as the average cloud angle.

The measured average water contact angle was 110°, and the average cloud angle was 38°.

Test for cloudiness (opacity) during long-term storage

When the surface treatment composition stock solution and the surface treatment composition diluted solution diluted to 20% by weight (solid content) in a solvent of HFE-7200 (manufacturer: 3M) were stored at room temperature for three to four months, cloudiness (opacity) did not occur.

Durability test of surface-treated articles

After dry rubbing the slide glass surface-treated with the surface treatment composition with a double-sided multipurpose scrubber (product name: Scotch Bright; manufacturer: 3M) 10 times, a total of 15 water contact angle measurement points were measured to obtain an average value, and the rolling angle was 10 times. It was measured and the average value was calculated|required.

The average water contact angle was 107°, which was a little less than before friction, and the average rolling angle was 38°, almost unchanged from before friction.

<Example 1>

Preparation of surface treatment composition

5.68g of FAS-17 (trade name: TSL-8233; manufacturer: Momentive Japan), called heptadecafluorodecyl trimethoxysilane, is mixed with 0.006g of alkyl polyglucoside (brand name: Milcoside 100; manufacturer: LG Household & Health Care). . Thereafter, the mixture was added to 7.656 ml of isopropanol solvent, and 0.18 g of 0.1N hydrochloric acid aqueous solution was further added to proceed with the sol-gel reaction.

The resulting reaction mixture was cooled to room temperature, and a PDMS-aminopropyl-terminated silicone oil having a viscosity of 1000 cps was dissolved in isopropyl alcohol in a ratio of 1: 1 by weight, and 40 parts by weight of the reactive silicone polymer solution was slowly added while slowly adding 40 parts by weight of the reactive silicone polymer solution at approximately 30° C. for 65 minutes. During the reaction to prepare a surface treatment composition.

Articles treated with surface treatment composition

A slide glass and a polyethylene terephthalate (hereinafter referred to as PET) film are used as the article substrate, and the slide glass is added to a 10% by weight sodium hydroxide (NaOH) aqueous solution for 5 minutes to improve adhesion to the surface treatment composition. After immersion, it was washed with distilled water. Then, it was used after drying with nitrogen gas. In the case of a PET film, plasma pretreatment was performed to improve the adhesion of the surface of the PET film. The surface treatment composition prepared above was diluted to 0.05% by weight (solid content) in HFE-7200 (Ethoxynonafluorobutane; manufacturer: 3M) solvent to prepare a dilution of the surface treatment composition, and then the surface was applied to the slide glass dried with the nitrogen gas. The diluent of the treatment composition was spin-coated at 1000 rpm and then put in an oven and cured at 50° C. for 3 hours. In addition, the pretreatment PET film was dip-coated in the diluent of the surface treatment composition diluted to 0.05% by weight for 1 minute and then put in an oven and cured at 50° C. for 3 hours.

Water repellency and rolling test

Water repellency is evaluated by the average contact angle obtained by measuring at a total of 50 water contact angle measurement points of 5 samples coated on a slide glass with a contact angle measuring device (GSA-X; manufacturer: STK Korea).

Rolling property uses a rolling angle measuring machine (manufactured by TFJ Global), placing an A4-size PET film coated with a surface treatment composition on a flat plate, adding 0.2 cc of water to the PET film, and tilting the flat plate little by little, The angle at which the water droplet slides down is measured and averaged 10 times and evaluated as the average cloud angle.

The measured average water contact angle is 116° and the average cloud angle is 25°.

Test for cloudiness (opacity) during long-term storage

When the surface treatment composition stock solution and the surface treatment composition diluted solution diluted to 20% by weight (solid content) in a solvent of HFE-7200 (manufacturer: 3M) are stored at room temperature for 3 to 4 months, white turbidity (opacity) does not occur.

Durability test of surface-treated articles

After dry rubbing the slide glass surface-treated with the surface treatment composition with a double-sided multipurpose scrubber (product name: Scotch Bright; manufacturer: 3M) 10 times, a total of 15 water contact angle measurement points were measured to obtain an average value, and the rolling angle was 10 times. Measure and get the average value.

The average water contact angle is 116°, almost unchanged from before friction, and the average rolling angle increases slightly to 26°.

<Example 2>

Preparation of surface treatment composition

5.68 g of FAS-17 (trade name: TSL-8233; manufacturer: Momentive Japan), called heptadecafluorodecyl trimethoxysilane, is mixed with 0.1 g of N-polyoxyethylene cocamide (NINOL 1301 supplied by Stepan). . Then, the mixture was added to 7.656 ml of isopropanol solvent, and 0.18 g of 0.1N hydrochloric acid aqueous solution was further added, followed by sol-gel process.

The resulting reaction mixture was cooled to room temperature, and a PDMS-aminopropyl-terminated silicone oil having a viscosity of 1000 cps was dissolved in isopropyl alcohol in a ratio of 1: 1 by weight, and 40 parts by weight of the reactive silicone polymer solution was slowly added while slowly adding 40 parts by weight of the reactive silicone polymer solution at approximately 30° C. for 65 minutes. During the reaction to prepare a surface treatment composition.

Articles treated with surface treatment composition

As the article substrate, slide glass and PET film are used, and the slide glass is immersed in 10 wt% NaOH aqueous solution for 5 minutes and washed with distilled water in order to improve adhesion to the surface treatment composition. Then, it is used after drying with nitrogen gas. In the case of a PET film, plasma pretreatment is performed to improve the adhesion of the surface of the PET film. The surface treatment composition prepared above was diluted to 0.05 wt% (solid content) in HFE-7200 (Ethoxy-nonafluorobutane; manufacturer: 3M) solvent to prepare a surface treatment composition dilution, and then to a slide glass dried with the nitrogen gas. After spin-coating the diluent of the surface treatment composition at 1000 rpm, it was put in an oven and cured at 50° C. for 3 hours. In addition, after dip-coating the pre-treated PET film in the diluent of the surface treatment composition diluted to 0.05% by weight for 1 minute, put in an oven and cured at 50° C. for 3 hours.

Water repellency and rolling test

Water repellency is evaluated by the average contact angle obtained by measuring at a total of 50 water contact angle measurement points of 5 samples coated on a slide glass with a contact angle measuring device (GSA-X; manufacturer: STK Korea).

Rolling property uses a rolling angle measuring machine (manufactured by TFJ Global), placing an A4-size PET film coated with a surface treatment composition on a flat plate, adding 0.2 cc of water to the PET film, and tilting the flat plate little by little, The angle at which the water droplet slides down is measured and averaged 10 times and evaluated as the average cloud angle.

The measured average water contact angle is 112° and the average cloud angle is 26°.

Test for cloudiness (opacity) during long-term storage

When the surface treatment composition stock solution and the surface treatment composition diluted solution diluted to 20% by weight (solid content) in a solvent of HFE-7200 (manufacturer: 3M) were stored at room temperature for three to four months, cloudiness (opacity) did not occur.

Durability test of surface-treated articles

After dry rubbing the slide glass surface-treated with the surface treatment composition with a double-sided multipurpose scrubber (product name: Scotch Bright; manufacturer: 3M) 10 times, a total of 15 water contact angle measurement points were measured to obtain an average value, and the rolling angle was 10 times. Measure and get the average value.

The average water contact angle and rolling angle were 112° and 25°, respectively, and there was little change from before friction.

<Example 3>

A water-repellent surface treatment composition was prepared in the same manner as in Example 2, except that polyoxyethylene lauramide (NINOL L-5 supplied by Stepan) was used.

Water repellency (contact angle) and rolling property (cloud angle) are 113° and 26°, respectively, and durability is also excellent.

<Example 4>

Preparation of surface treatment composition

5.68 g of FAS-17 (trade name: TSL-8233; manufacturer: Momentive Japan) was mixed with heptadecafluorodecyl trimethoxysilane and 0.006 g of alkyl polyglucoside (brand name: Milcoside 100; manufacturer: LG Household & Health Care) , Next, it is mixed with 0.1 g of N-polyoxyethylene cocamide (NINOL 1301 supplied by Stepan). Thereafter, the mixture was added to 7.656 ml of isopropanol solvent, and 0.18 g of 0.1N hydrochloric acid aqueous solution was further added to proceed with the sol-gel reaction.

The resulting reaction mixture was cooled to room temperature, and a PDMS-aminopropyl-terminated silicone oil having a viscosity of 1000 cps was dissolved in isopropyl alcohol in a ratio of 1: 1 by weight, and 40 parts by weight of the reactive silicone polymer solution was slowly added while slowly adding 40 parts by weight of the reactive silicone polymer solution at approximately 30° C. for 65 minutes React during To the resulting reaction mixture, an additive Bluelogy ^TM Solution PE 2018 (available from TFA Global Co., Ltd.) is added in an amount of approximately 5% by weight (solid content) based on the reaction mixture to prepare a water-repellent surface treatment composition.

Articles treated with surface treatment composition

A slide glass and a polyethylene terephthalate (hereinafter referred to as PET) film are used as the article substrate, and the slide glass is added to a 10% by weight sodium hydroxide (NaOH) aqueous solution for 5 minutes to improve adhesion to the surface treatment composition. After immersion, it was washed with distilled water. Then, it was used after drying with nitrogen gas. In the case of a PET film, plasma pretreatment was performed to improve the adhesion of the surface of the PET film. The surface treatment composition prepared above was diluted to 0.05% by weight (solid content) in HFE-7200 (Ethoxynonafluorobutane; manufacturer: 3M) solvent to prepare a dilution of the surface treatment composition, and then the surface was applied to the slide glass dried with the nitrogen gas. The diluent of the treatment composition was spin-coated at 1000 rpm and then put in an oven and cured at 50° C. for 3 hours. In addition, the pretreatment PET film was dip-coated in the diluent of the surface treatment composition diluted to 0.05% by weight for 1 minute and then put in an oven and cured at 50° C. for 3 hours.

Water repellency and rolling test

Water repellency is evaluated by the average contact angle obtained by measuring at a total of 50 water contact angle measurement points of 5 samples coated on a slide glass with a contact angle measuring device (GSA-X; manufacturer: STK Korea).

Rolling property uses a rolling angle measuring machine (manufactured by TFJ Global), placing an A4-size PET film coated with a surface treatment composition on a flat plate, adding 0.2 cc of water to the PET film, and tilting the flat plate little by little, The angle at which the water droplet slides down is measured and averaged 10 times and evaluated as the average cloud angle.

The measured average water contact angle is 121° and the average cloud angle is 21°.

Test for cloudiness (opacity) during long-term storage

When the surface treatment composition stock solution and the surface treatment composition diluted solution diluted to 20% by weight (solid content) in a solvent of HFE-7200 (manufacturer: 3M) are stored at room temperature for 3 to 4 months, white turbidity (opacity) does not occur.

Durability test of surface-treated articles

After dry rubbing the slide glass surface-treated with the surface treatment composition with a double-sided multipurpose scrubber (product name: Scotch Bright; manufacturer: 3M) 10 times, a total of 15 water contact angle measurement points were measured to obtain an average value, and the rolling angle was 10 times. Measure and get the average value.

The average water contact angle is 121°, almost unchanged from before friction, and the average rolling angle increases slightly to 22°.

<Comparative Example 1>

Preparation of surface treatment composition

5.68 g of FAS-17 (trade name: TSL-8233; manufacturer: Momentive Japan) was added to 7.656 ml of heptadecafluorodecyl trimethoxysilane, followed by adding 0.72 g of 0.1N hydrochloric acid aqueous solution to a sol-gel Reaction to prepare a surface treatment composition.

Articles treated with surface treatment composition

Slide glass and PET film were used as article substrates, and the slide glass was immersed in 10% by weight of NaOH aqueous solution for 5 minutes and washed with distilled water in order to improve adhesion to the surface treatment composition. Then, it was used after drying with nitrogen gas. In the case of a PET film, plasma pretreatment was performed to improve the adhesion of the surface of the PET film. The surface treatment composition prepared above was diluted to 0.05 wt% (solid content) in HFE-7200 (Ethoxy-nonafluorobutane; manufacturer: 3M) solvent to prepare a surface treatment composition dilution, and then to a slide glass dried with the nitrogen gas. The diluent of the surface treatment composition was spin-coated at 1000 rpm and then put in an oven and cured at 50° C. for 3 hours. In addition, the pretreatment PET film was dip-coated in the diluent of the surface treatment composition diluted to 0.05% by weight for 1 minute and then put in an oven and cured at 50° C. for 3 hours.

Water repellency and rolling test

The water repellency was evaluated by the average contact angle obtained by measuring at a total of 50 water contact angle measurement points of five samples coated on a slide glass with a contact angle measuring device (GSA-X; manufacturer: STK Korea).

Rolling property uses a rolling angle measuring machine (manufactured by TFJ Global), placing an A4-size PET film coated with a surface treatment composition on a flat plate, adding 0.2 cc of water to the PET film, and tilting the flat plate little by little, The angle at which the water droplet slides down is measured and averaged 10 times and evaluated as the average cloud angle.

The measured average water contact angle was 110°, and the average cloud angle was 36°.

Test for cloudiness (opacity) during long-term storage

When the surface treatment composition stock solution and the surface treatment composition diluted solution diluted to 20% by weight (solid content) in HFE-7200 (manufacturer: 3M) solvent were stored at room temperature for three to four months, cloudiness (opacity) occurred.

Durability test of surface-treated articles

The slide glass surface-treated with the surface treatment composition was subjected to dry rubbing with a double-sided multipurpose scrubber (product name: Scotch Bright; manufacturer: 3M) 10 times, and then a total of 15 water contact angle measurement points were measured to obtain an average value.

The average water contact angle was 100°, which was much lower than before friction.

Durability test of surface-treated articles

After dry rubbing the slide glass surface-treated with the surface treatment composition with a double-sided multipurpose scrubber (product name: Scotch Bright; manufacturer: 3M) 10 times, a total of 15 water contact angle measurement points were measured to obtain an average value, and the rolling angle was 10 Measure twice and get the average value.

The average water contact angle was 110°, almost unchanged from before friction, and the average rolling angle was 35°, which increased slightly compared to before friction.

Table 1 below shows the water repellency (water contact angle), rolling property (dynamic coefficient of friction), long-term storage (transparent or opaque) and articles of articles coated with the surface treatment compositions prepared in Examples 1 to 3 and Comparative Example 1. This is the test result of durability (measurement of water contact angle after rubbing with a scrubber).

Glass water repellent treatment Contact angle Cloud angle Long-term storage Product durability
(Contact angle: cloud angle) Example 1 116° 25° transparent 116°; 26° Example 2 112° 26° transparent 112°; 25° Example 3 113° 26° transparent 113°; 26° Example 4 121° 22° transparent 121°; 21° Comparative Example 1 110° 36° Cloudy 110°; 35° Reference Example 1 110° (38°) transparent 107°; (38°)

As shown in Table 1, it can be seen that the article coated with the water-repellent surface treatment composition according to the present invention has excellent water repellency, excellent rolling properties and long-term storage, as well as excellent durability.

Examples 1 to 3 satisfying all four factors of water repellency, rolling property, long-term storage, and durability of the article.Comparative Example 1 generates cloudiness in long-term storage, so even though there is some degree of water repellency before friction This falls. In addition, in Comparative Example 1, the article durability is also inferior to some extent.

<Experimental Example 1> Water repellency and rolling properties of permeable articles subjected to water repellency surface treatment

Polyester fibers and cotton fibers woven in a ratio of 8:2 (basis weight 200 g/cm2) immersed and dehydrated in the water-repellent surface treatment composition for fabrics prepared in the above Examples and Comparative Examples, and gradually dried in a dryer Simultaneously, heat treatment at 165±5° C. for about 5 minutes to form a water-repellent coating layer.

In the same manner as in the above Examples and Comparative Examples, the average contact angle, average rolling angle, and durability on the surface of the water-repellent fabric were measured, and the results are shown in Table 2.

Fabric water repellent treatment Contact angle Cloud angle Product durability
(Contact angle: cloud angle) Example 1 118° 26° 118°; 27° Example 2 114° 27° 114°; 26° Example 3 115° 27° 115°; 27° Example 4 123° 23° 123°; 22° Comparative Example 1 112° 37° 112°; 36° Reference Example 1 112° (39°) 109°; (39°)

As can be seen from Table 2, even when a permeable article such as a fabric is treated with a water-repellent water-repellent surface treatment composition according to the present invention, it can be seen that not only excellent water repellency and rolling property, but also excellent durability.

In the above, preferred embodiments according to the present invention have been described with reference to the drawings and embodiments, but these are only exemplary, and various modifications and other equivalent embodiments are possible from those of ordinary skill in the art. You will be able to understand. Therefore, the scope of protection of the present invention should be determined by the appended claims.

Claims (10)

(a) a mixture comprising a perfluoroalkyl group-containing organopolysilane, a silicone crosslinking agent, and a reactive silicone polymer solution as a water repellent component,
(b) as a cloudability improving agent, an N-polyoxyalkylenated fatty acid amide compound alone or a mixture of an N-polyoxyalkylenated fatty acid amide and an O-alkylated polyglucoside,
(c) an acidic catalyst selected from organic or inorganic acids, and
(d) aqueous solvent
A fluorine-based water-repellent surface treatment composition having excellent rolling properties.
The method of claim 1,
The perfluoroalkyl group-containing organopolysilane is a fluorine-based water-repellent surface treatment composition having excellent rolling properties, characterized in that it contains a compound of the following formula (1):
[Formula 1]
CF ₃ -(CF ₂ ) _n -R-SiX _p Y _3-p
In the above formula, n is an integer from 0 to 12,
R is an organic group having 1 to 10 carbon atoms, or a group containing a silicon atom and an oxygen atom,
X is H or a monovalent hydrocarbon group having 1 to 4 carbon atoms, or a substituent selected from a derivative of the group,
p is 0, 1 or 2,
Y is a C1-C4 alkoxy group, an acyloxy group, or a halogen atom.
The method of claim 1,
The N-polyoxyalkylenated fatty acid amide is a fluorine-based water-repellent surface treatment composition having excellent rolling properties, characterized in that it contains a compound of the following formula (2):
[Formula 2]
RC0NH(A0) _n H or RCON[(A0) _n H] ₂
In the above formula,
R represents a substituted or unsubstituted alkyl group having 8 to 36 carbon atoms,
(A0) _n represents polyoxyethylene, polyoxypropylene or polyoxyethylene/polyoxypropylene block copolymer,
n represents a number from 3 to 20.
The method of claim 1,
The O-alkylated polyglucoside is a fluorine-based water-repellent surface treatment composition having excellent cloudability, comprising a compound of the following formula (3).
[Formula 3]

In the above formula, y is 0 to 6, and R is an alkyl group having 8 to 36 carbon atoms.
The method of claim 1,
The reactive silicone polymer is a fluorine-based water-repellent surface treatment composition having excellent rolling properties, characterized in that it is selected from silicone oils containing at least one reactive functional group among carboxyl groups, hydroxy groups, and azo groups or amino groups at the ends of the polymer main chain or side chain .
The method of claim 1,
0.001 to 20 parts by weight of a rollability improving agent, 10 to 300 parts by weight of a silicone crosslinking agent, 2 to 30 parts by weight of a reactive silicone crosslinking agent, 0.001 to 50 parts by weight of an acidic catalyst, and an aqueous solvent based on 100 parts by weight of the perfluoroalkyl group-containing organopolysilane. A fluorine-based water-repellent surface treatment composition having excellent rolling properties, containing 10 to 300 parts by weight as a gong.
A method for preparing a fluorine-based water-repellent surface treatment composition according to claim 1, comprising the following steps:
(Step 1) preparing a mixture by dissolving or dispersing an organopolysilane containing a perfluoroalkyl group as a water repellent component, a cloudability improving agent, and a silicone-based crosslinking agent in an aqueous solvent, wherein the cloudability improving agent is N-polyoxyalkylenated Selected from a fatty acid amide compound alone or a mixture of an N-polyoxyalkylenated fatty acid amide and an O-alkyl polyglucoside;
(Step 2) sol-gel reaction by adding an acidic catalyst to the mixture; And
(Step 3) During the sol-gel reaction, a reactive silicone polymer solution is added to form an organopolysiloxane sol.
The method for preparing a fluorine-based water-repellent surface treatment composition having excellent rolling properties according to claim 7, comprising the following steps:
(Step 1) A water-repellent component selected from perfluoroalkyl group-containing organopolysilanes, an N-polyoxyalkylenated fatty acid amide compound alone, or a cloudability improving agent selected from a mixture of N-polyoxyalkylene fatty acid amide and O-alkyl polyglucoside , Preparing a mixture by dissolving or dispersing a silicone-based crosslinking agent in an aqueous solvent at a temperature of 10 to 40°C;
(Step 2) adding an acidic catalyst to the mixture to perform a sol-gel reaction at a temperature of 3 to 6 and 50 to 70°C; And
(Step 3) After the sol-gel reaction, a reactive silicone polymer solution is added to the reaction mixture at a temperature of 25 to 45° C., and reacted for 30 to 120 minutes to form an organopolysiloxane sol.
A permeable article having excellent water repellency and rollability, selected from the group consisting of fibers, knitted fabrics, woven fabrics or nonwoven fabrics, and treated with the fluorine-based water repellent surface treatment composition having excellent rolling properties according to claim 1.
An article having excellent water repellency and rolling properties, selected from the group consisting of solar cells, smartphones, touch panels, secondary batteries, displays, or automobiles, and treated with the fluorine-based water repellent surface treatment composition having excellent rolling properties according to claim 1.