KR20200064592A - Fluorinated Water-repellant surface-treating composition having high water-glinding property and manufacturing method thereof - Google Patents

Abstract

The present invention provides a fluorinated water-repellent surface-treating composition, which includes: a mixture including a perfluoroalkyl group-containing organopolysilane serving as a water repellent ingredient, an arbitrary silicone crosslinking agent, and a reactive silicone polymer solution; one or more compounds selected from the group consisting of N-polyoxyalkylene fatty acid amide or O-alkyl polyglucoside, which serves as a modifier of a water-gliding property; an acid catalyst containing inorganic or organic acid; and an aqueous solvent, a method for preparing the same, and a permeable article and a non-permeable article subject to water repellent treatment using the same. According to the present invention, the fluorinated water-repellent surface-treating composition may be stably and economically prepared, and maintain a colorless and transparent property without a white crystal even in a long-term storage, thereby enhancing stability and a storage property. In addition, a higher adhesion property is represented even in a permeable article such as fabric, and excellent water-repellant and gliding properties may be provided.

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 excellent in rolling properties and a method for manufacturing the same, specifically, a perfluoroalkyl group-containing organopolysilane as a water-repellent component and N-polyoxyalkylene fatty acid amide or O- as a rolling agent. It relates to a fluorine-based water repellent surface treatment composition excellent in rolling properties, including an alkylated polyglucoside, and a method for manufacturing 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 textiles.

Items including windshields, shower booths, veranda windows, car windshields, car side mirrors, ship exteriors, electronics, cell phones, etc. can be exposed to water, resulting from water or contaminants dissolved or mixed with water. The product is contaminated and has a reduced lifespan. In particular, in the case of an article used in automobiles, ships, etc., it is also 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 preventing contamination by coating a thin thickness on the surface of the article is adopted.

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

However, the fluorine-based water-repellent material containing a perfluoroalkyl group-containing organopolysilane and the non-fluorine-based water-repellent material containing a silane polymer are excellent in water repellency, and there is a problem in that cloudiness, which is a property that water droplets roll or slide on the surface, has poor cloudiness. It was difficult to use the required article, and in the case of a permeable article such as a fabric, when water in excess of the water repellency touches the surface or stays for a long time, there is a inconvenience that the surface wetting phenomenon occurs as it permeates into the fabric. In addition, long-term stability is also required in order to have marketability, but long-term stability is often insufficient.

On the other hand, moisture-permeable waterproofing is often required for permeable articles such as fabrics, and water-repellent treatment may be applied for this purpose. In order to impart water repellency without impairing the permeability to a permeable article such as a fabric, not only water repellency, which is a property of water droplets on or off the surface, but also water droplets on the surface of the fabric that remain or stagnate, flow or roll without retention It is also necessary to consider the falling surface cloudiness.

Patent Document 1 (Domestic Publication No. 10-2015-0081177, published date July 13, 2015) includes 2 to 4 million needle-shaped nano structures per 1 mm ^{2 of} area Nano needle-fiber 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 is disclosed, which is characterized by including a coating layer containing a hydrophobic material on a surface including the nanostructures, and a manufacturing method.

In Patent Document 2 (Domestic Publication No. 10-2016-0060913, published date May 31, 2016), a sol-gel dispersion in which nanoparticles are aggregated using a solvent having a dielectric constant of 20 or less is prepared, and the surface thereof is prepared. A method for producing a superhydrophobic surface in which the surface rolling angle converges to 0 degree by coating on and then impregnating with a hydrophobic silane to hydrophobize the surface is disclosed.

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

In general, water and air permeable articles, specifically, liquids such as water and oil, and air and water and gas permeable articles such as water vapor, permeable articles, while maintaining the moisture permeability characteristics of the permeable article while maintaining water repellency It is not easy to give. For example, in order to utilize the fabric as a water-repellent and water-repellent water-repellent fabric, it is required that the surface of the water-repellent fabric has excellent water repellency (or high contact angle) as well as excellent cloudiness (low rolling angle). Wearable fabrics using conductive carbon fibers, sportswear with internal wiring, fire resistant fabrics for firefighters, etc. have high water repellency even during long-term contact with water, yet high rolling properties to avoid long-term contact with water as much as possible. This is required. Therefore, development of a water repellent surface treatment composition having excellent water repellency as well as rolling properties has been desired.

Under these circumstances, the present invention has been developed to meet the need for a new water repellent surface treatment composition to impart high water repellency and good surface rolling properties to permeable articles such as textiles.

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

The present invention includes a perfluoroalkyl group-containing organopolysilane, an optional silicone crosslinking agent, and a water repellent component comprising a reactive silicone polymer solution and a cloudiness improving agent comprising an N-polyoxyalkylene fatty acid amide or an O-alkylated polyglucoside. To provide a water repellent surface treatment composition excellent in rolling properties and a method for manufacturing the same.

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

The present 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-polyoxyalkylene fatty acid amides or O-alkylated polyglucosides as a cloudiness 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 containing, as well as having excellent stability and long-term storage properties, can impart excellent water repellency and high rolling properties to permeable articles such as textiles.

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

(Step 1) One or more compounds selected from the group consisting of a perfluoroalkyl group-containing organopolysilane as a water repellent component, N-polyoxyalkylene fatty acid amide or O-alkyl polyglucoside as a cloudiness improving agent, and any silicone-based 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.

The fluorine-based water-repellent surface treatment composition according to the present invention is stable and economical in production, can maintain white colorless and colorless and transparent properties even during long-term storage, and has high stability and storage, as well as high adhesion to permeable articles such as textiles, and excellent Water repellency and cloudiness can be imparted.

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-polyoxyalkylene fatty acid amides or O-alkylated polyglucosides as a cloudiness improving agent,

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

(d) aqueous solvent.

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

(Step 1) One or more compounds selected from the group consisting of a perfluoroalkyl group-containing organopolysilane as a water repellent component, N-polyoxyalkylene fatty acid amide or O-alkyl polyglucoside as a cloudiness improving agent, and any silicone-based 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.

The third object of the present invention is to provide a permeable article which is manufactured using the fluorine-based water repellent surface treatment composition excellent in cloudiness and excellent in water repellency and cloudiness, wherein 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 a perfluoroalkyl group-containing organopolysilane, an optional silicone crosslinking agent, and a reactive silicone polymer solution as a water repellent component.

[Organopolysilane containing perfluoroalkyl group]

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

[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 derivatives of the above groups,

p is 0, 1 or 2,

Y is an alkoxy group having 1 to 4 carbon atoms, 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, may be, for example, a methylene group or an ethylene group.

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

Here, the "monovalent hydrocarbon group" may be branched or unbranched, acyclic or cyclic, saturated or unsaturated, or aromatic, containing 1 to 4 (or 3 or 4 in the case of aromatic groups) carbon atoms. Can be.

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-based crosslinking agent and/or an optional reactive silicone-based crosslinking agent in addition to the perfluoroalkyl group-containing organopolysilane as the water-repellent component.

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

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 Ethoxysilanes, 3-(trimethoxysilyl)propylmethacrylate, N-[3-(trimethoxysilyl)propyl]-ethylenediamine and 3-glycidoxypropyltrimethoxysilane. The reactive silicone crosslinking agent may be included in an amount of 2 to 30 parts by weight, preferably 5 to 25 parts by weight, and more preferably 10 to 20 parts by weight based on 100 parts by weight of the perfluoroalkyl group-containing organopolysilane. Does not work.

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

[Rollability improver]

According to one embodiment of the present invention, the cloudiness improving agent is a hydrophobic group having 8 to 36 carbon atoms, preferably 12 to 32 long chain alkyl groups and a hydrophilic group, a polyoxyalkylene group or a polyglucoside group bonded with a linker having excellent chemical stability Compound, for example, N-polyoxyalkylene fatty acid amide or O-alkyl polyglucoside.

In the present invention, the N-polyoxyalkylene fatty acid amide is an amide derivative of a long chain fatty acid in the range of 8 to 36 carbon atoms, and is 3 to 20 oxyalkylene groups on the nitrogen atom of the amide group, 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, octadeanoic acid, nonadecanoic acid, eicosanoic acid, hencosanoic acid, decosanoic acid, tetracosanoic acid , Pentacosanoic acid, tricosanoic acid, hexacosanoic acid, triacantanoic acid, dotriaconanoic acid, tetratriaconanoic acid, hentriaconanoic acid, pentatriaconanoic acid, hexatriaconanoic acid, Myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid and hexatriisocontanic acid (C36) acid, oleic acid, palmitoleic acid, linolenic acid and cetoleic acid and analogs thereof.

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 N-polyoxyalkylene fatty acid amide may be a compound represented by 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/polyoxy propylene block copolymer,

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

Non-limiting examples of the N-polyoxyalkylene fatty acid amide represented by Formula 2 include polyoxyethylene lauramide, polyoxyethylene stearamide, polyoxyethylene cocamide, polyoxypropylene cocamide, polypropylene glycol 2-hydr Hydroxyethyl isostearamide and polypropylene glycol 2-hydroxyethyl cocamide. These 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 attached to at least one of the hydroxyl groups (OH) of the polyclocoside by an ether linkage, for example, an O-alkyl poly represented by the following formula (3) It can be represented as glucoside:

[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 cloudiness 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. It can be included in a quantity. When the rolling improver 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 obtain a flat coating surface.

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

In the present invention, the N-polyoxyalkylene fatty acid amide and O-alkyl polyglucosides are materials that are generally used as nonionic surfactants or slip agents, and are mainly located at the interface between a gas and a solid on a water repellent surface. , Thereby protruding the long-chain alkyl group on the water-repellent surface, by pushing or rolling the water droplets formed or adhered to the water-repellent surface, it is understood to act to impart or improve the rolling properties.

In the present invention, the rolling angle is formed by dropping 0.2 cc of water into a sample to be measured on a flat surface installed on a horizontal plate to form water droplets, and tilting the plate slightly at a constant speed, when the formed water droplets begin to roll. Mean angle. When the sample to be measured is a permeable article such as a fabric, it may be necessary to hold the flat plate underneath and maintain a flat surface, since the central portion may sag due to gravity or the like.

The water-repellent surface treatment composition according to the present invention may 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 an inorganic acid or an organic acid as a gelling catalyst and a pH adjusting agent. Usable acidic catalysts may include one or more acids selected from hydrochloric acid, acetic acid, nitric acid, sulfuric acid and phosphoric acid. The acid may be an aqueous solution having a concentration of 0.001 to 1 N. If it falls within the concentration range, the reaction time for the preparation of the surface treatment composition can be carried out within minutes 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, and 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, it is possible to control the speed and particle size of the sol-gel reaction to an appropriate level, and to prevent turbidity or precipitation of the composition.

[Aqueous solvent]

As the aqueous solvent that can be used in the present invention, water, or an organic solvent having compatibility with the water, or a mixture thereof can be mentioned. The organic solvent having compatibility with the 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 One or more types may be selected 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 by weight, 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 to provide excellent water repellency and transparency.

[Reactive silicone polymer]

In the present invention, the reactive silicone polymer may be a silicone oil containing at least one of a carboxyl group, a hydroxy group and an azo group or an amino group reactive functional group at the terminal or side of the polymer main chain, and preferably includes an amino group as the reactive functional group. Silicone oil. As a silicone oil that can be used as a reactive silicone polymer, polydimethylsilane (PDMS), preferably polydimethylsilane containing an amino group or an azo group as a reactive functional group, can be mentioned.

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 organopolysiloxane having a high durability and high water repellency, and if the reactive silicone polymer is contained in excess of 50 parts by weight, unreacted There may be a problem in that the number of reactive silicone polymers to be increased increases the physical properties and increases the cost.

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, the organopolysiloxane sol having the desired molecular weight cannot be formed, and thus the durability of the crosslinked organopolysiloxane of the three-dimensional network structure is lowered, and water repellency may also be lowered due to lower density. If the viscosity exceeds 1500 cps, the feel of the water-repellent coated surface is significantly reduced, and when water-repellent coating of a permeable article such as fibers or fabrics, the softness and drape of the fabrics produced as their flexibility decreases There is a problem that can be very bad.

The reactive silicone polymer is further improved in durability and durability through reaction with the organopolysiloxane primary sol formed in step 2), for example, through thermal curing with a silicone precursor such as 3-glycidoxypropyltrimethoxysilane. It is possible to form an organopolysilonic acid crosslinked product having a high water-repellent three-dimensional network structure.

The reactive silicone polymer is preferably used 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 as a non-limiting example, isopropyl alcohol may be mentioned, 100 to 100 parts by weight of the reactive silicone polymer It can be used in ∼150 parts by weight.

(2) Manufacturing method of 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) One or more compounds selected from the group consisting of a perfluoroalkyl group-containing organopolysilane as a water repellent component, N-polyoxyalkylene fatty acid amide or O-alkyl polyglucoside as a cloudiness improving agent, and any silicone-based 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 may be manufactured according to a manufacturing method comprising a.

In the manufacturing method of the present invention, the step 1) may be performed at a temperature of 10 to 40° C., preferably at room temperature, using a reactor equipped with a stirring device and a thermometer, a kneader or a mixer. The order and method of adding the components in step 1), and the mixing method and conditions are not particularly limited and may be performed as conventionally used in the art. For example, the components 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 production method of the present invention, step 2) is performed by adding an acidic catalyst to the sol-gel reaction at a temperature of 50 to 70°C, preferably 55 to 60°C for 30 to 80 minutes, preferably 40 to 60 minutes. Can be carried out. If the temperature is less than 50°C, the reaction time may be delayed or the formation of the sol may not be smooth. If the temperature exceeds 70°C, there may be problems such as decomposition reaction in the sol-type reaction product. In addition, it is preferable to perform the sol-gel reaction of step 2) until the solution becomes transparent.

In step 2), an acidic catalyst in the form of an acid or acidic solution is added to adjust the pH of the reaction mixture to an appropriate range, for example, pH 3 to 6, preferably pH 4.5 to 5.0, thereby smoothly generating the sol. Can promote. Acids that can be used include, but are not limited to, hydrochloric acid, nitric acid, sulfuric acid or acetic acid. The concentration and the amount of the acid or acidic solution is not particularly limited in the present invention if the pH of the mixture satisfies the above range. Preferably, acetic acid can be added in a range 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. For smoother sol production, the pH of the reaction mixture can be added dropwise or slowly little by little or slowly while frequently checking the pH.

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

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

Therefore, after the step 2) is completed, 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. For the temperature rise and/or homogeneous reaction according to the reaction, it is preferable to add the reactive silicone polymer solution 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, decomposition of the reactive silicone polymer may occur or gelation may be rapid. There may be problems such as progress.

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

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 fiber, polymer, plastic, glass, carbon, ceramic or metal.

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 a liquid such as water and oil, and a permeable article through which gas such as air and water vapor can permeate. And excellent water repellency (low rolling angle). Non-limiting examples of the permeable article may refer to water repellency and rolling properties on the surfaces of fibers, knitted fabrics, woven fabrics, and nonwoven fabrics.

The most representative examples of the permeable article, fibers and fabrics, may be known natural fibers or synthetic fibers, or fabrics made of them. The water-repellent composition for textiles according to the present invention contains an organopolysiloxane sol solution having excellent adhesion to or coating to fibers, and is therefore very limited in the material of fibers or fabrics, since the coating properties of fibers or adhesives are very excellent. It can be applied universally without receiving. Therefore, the conventional water-repellent coating agent is a type of fiber, that is, while the coating property is excellent for the polyester-based fiber, the problem that the coating property for the fiber of another material is significantly reduced can be solved.

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

Further, the fabric may be a fabric or fabric comprising 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 woven fabric or fabric using honseom yarn according to the present invention as one or more of warp and weft yarns.

The weaving may be made by any one method selected from the group consisting of plain weave, twill weave, double weave and double weave. When these plain weave, twill weave, and embroidery weave are called ternary tissues, the specific weaving method of each ternary tissue is based on the normal weaving method. There are, for example, two-sided jobs, basket jobs, etc. as changeable plain jobs, new talents, talented jobs, non-performance jobs, mountain-type jobs, etc. as changeable jobs, anomalous jobs, mid-career jobs, extended jobs, and training jobs. There is this. The double weaving is a method of weaving a fabric in which either one of the warp yarns or weft yarns is doubled or both are double, and a specific method may be a conventional double weaving method.

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

Further, the fabric may be a knitted fabric including a blended yarn as a yarn. The knitting may be by a method of knitting or warp knitting, and the specific method of knitting and warp knitting may be by a conventional knitting or knitting method.

According to one advantage of the present invention, the water-repellent surface treatment composition of the present invention is excellent in water repellency and cloudiness, is stable and economical in production, and can maintain colorless and transparent properties without cloudiness during long-term storage, thereby providing high storage. In addition, it is possible to impart excellent water repellency and rolling properties to permeable articles such as textiles.

According to another advantage of the present invention, the water repellent surface treatment composition of the present invention is a water repellent component by containing at least one compound selected from the group consisting of N-polyoxyalkylene fatty acid amide and O-alkyl polyglucoside as a cloudiness improving agent. Organopolysilane containing phosphorus perfluoroalkyl group, any silicone crosslinking agent, and organopolysiloxane sol formed from a reactive silicone polymer solution can provide long-term storage stability, 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 prepare a water-repellent surface treatment composition stably and economically, excellent adhesion to a substrate and excellent water repellency, excellent surface cloudiness, and colorless and transparent surface treatment without cloudiness during long-term storage Compositions 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, heptadecafluor decyl trimethoxysilane called 5.68 g of FAS-17 (trade name: TSL-8233; manufacturer: Momentive Japan) is 0.006 g of alkyl polyglucoside (trade name: Milcoside 100; manufacturer: LG H&H). Then, after adding the mixture to 7.656 ml of isopropanol solvent, an additional 0.18 g of 0.1N hydrochloric acid solution was added to sol-gel to prepare a surface treatment composition.

Articles treated with surface treatment compositions

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

Water repellency and rolling test

The water repellency was measured at a total of 50 water contact angle measurement points of 5 samples coated on a slide glass with a contact angle meter (measured by GSA-X; manufacturer: STK Korea), and evaluated by the average contact angle obtained by averaging.

The rolling properties were measured using a rolling angle meter (manufactured by TFJ Global), placing a PET film of A4 size coated with a surface treatment composition on a flat plate, adding 0.2 cc of water to the PET film, and gradually inclining the flat plate. The angle at which the water droplets slide down was measured 10 times and averaged to evaluate the average rolling angle.

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

Test for cloudiness (opacity) during long-term storage

When the surface treatment composition diluent diluted with 20% by weight (solid content) of the surface treatment composition stock solution and HFE-7200 (manufacturer: 3M) solvent was stored at room temperature for 3 to 4 months, no cloudiness (opacity) occurred.

Durability test of surface-treated articles

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

The average water contact angle was 107°, which decreased slightly before friction, and the average rolling angle was 38°, which was almost unchanged from before friction.

<Example 1>

Preparation of surface treatment composition

Heptadecafluor decyl trimethoxysilane called 5.68 g of FAS-17 (trade name: TSL-8233; manufacturer: Momentive Japan) is mixed with 0.006 g of alkyl polyglucoside (trade name: Milcoside 100; manufacturer: LG H&H) . Then, after adding the mixture to 7.656 ml of isopropanol solvent, 0.18 g of 0.1N hydrochloric acid aqueous solution was further added to advance the sol-gel reaction.

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

Articles treated with surface treatment compositions

As the article base, a slide glass and a polyethylene terephthalate (hereinafter referred to as PET) film are used, and the slide glass is placed in a 10% by weight aqueous sodium hydroxide (NaOH) solution for 5 minutes in order to improve adhesion with 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 pre-treatment was performed to enhance the adhesion of the PET film surface. After diluting the surface treatment composition prepared in the above with HFE-7200 (Ethoxynonafluorobutane; manufacturer: 3M) to 0.05% by weight (solid content) in a solvent to prepare a diluent for the surface treatment composition, the surface of the slide glass was dried with nitrogen gas. After diluting the treatment composition dilution at 1000 rpm, it was placed in an oven and cured at 50° C. for 3 hours. Further, the pre-treated PET film was dip-coated for 1 minute in the diluent of the surface treatment composition diluted to 0.05% by weight, placed in an oven, and cured at 50°C for 3 hours.

Water repellency and rolling test

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

The rolling properties were measured using a rolling angle meter (manufactured by TFJ Global), placing a PET film of A4 size coated with a surface treatment composition on a flat plate, adding 0.2 cc of water to the PET film, and gradually inclining the flat plate. The angle at which the water droplets slide down is measured 10 times and averaged to evaluate the average cloud angle.

The measured average water contact angle was 116° and the average rolling angle was 25°.

Test for cloudiness (opacity) during long-term storage

When the surface treatment composition diluent diluted with 20% by weight (solid content) of the surface treatment composition stock solution and HFE-7200 (manufacturer: 3M) solvent is stored at room temperature for 3 to 4 months, no cloudiness (opacity) occurs.

Durability test of surface-treated articles

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

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

<Example 2>

Preparation of surface treatment composition

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

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

Articles treated with surface treatment compositions

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

Water repellency and rolling test

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

The rolling properties were measured using a rolling angle meter (manufactured by TFJ Global), placing a PET film of A4 size coated with a surface treatment composition on a flat plate, adding 0.2 cc of water to the PET film, and gradually inclining the flat plate. The angle at which the water droplets slide down is measured 10 times and averaged to evaluate the average cloud angle.

The measured average water contact angle was 112° and the average rolling angle was 26°.

Test for cloudiness (opacity) during long-term storage

When the surface treatment composition diluent diluted with 20% by weight (solid content) of the surface treatment composition stock solution and HFE-7200 (manufacturer: 3M) solvent was stored at room temperature for 3 to 4 months, no cloudiness (opacity) occurred.

Durability test of surface-treated articles

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

The average water contact angle and rolling angle are 112° and 25°, respectively, and there is little change before and after 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 (rolling angle) are 113° and 26°, respectively, and durability is excellent.

<Example 4>

Preparation of surface treatment composition

Heptadecafluor decyl trimethoxysilane called 5.68 g of FAS-17 (trade name: TSL-8233; manufacturer: Momentive Japan) was mixed with 0.006 g of alkyl polyglucoside (trade name: Milcoside 100; manufacturer: LG H&H) , Next, mix with 0.1 g of N-polyoxyethylene cocamide (NINOL 1301 supplied by Stepan). Then, after adding the mixture to 7.656 ml of isopropanol solvent, 0.18 g of 0.1N hydrochloric acid aqueous solution was further added to advance the sol-gel reaction.

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

Articles treated with surface treatment compositions

As the article base, a slide glass and a polyethylene terephthalate (hereinafter referred to as PET) film are used, and the slide glass is placed in a 10% by weight aqueous sodium hydroxide (NaOH) solution for 5 minutes in order to improve adhesion with 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 pre-treatment was performed to enhance the adhesion of the PET film surface. After diluting the surface treatment composition prepared in the above with HFE-7200 (Ethoxynonafluorobutane; manufacturer: 3M) to 0.05% by weight (solid content) in a solvent to prepare a diluent for the surface treatment composition, the surface of the slide glass was dried with nitrogen gas. After diluting the treatment composition dilution at 1000 rpm, it was placed in an oven and cured at 50° C. for 3 hours. Further, the pre-treated PET film was dip-coated for 1 minute in the diluent of the surface treatment composition diluted to 0.05% by weight, placed in an oven, and cured at 50°C for 3 hours.

Water repellency and rolling test

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

The rolling properties were measured using a rolling angle meter (manufactured by TFJ Global), placing a PET film of A4 size coated with a surface treatment composition on a flat plate, adding 0.2 cc of water to the PET film, and gradually inclining the flat plate. The angle at which the water droplets slide down is measured 10 times and averaged to evaluate the average cloud angle.

The measured average water contact angle was 121° and the average rolling angle was 21°.

Test for cloudiness (opacity) during long-term storage

When the surface treatment composition diluent diluted with 20% by weight (solid content) of the surface treatment composition stock solution and HFE-7200 (manufacturer: 3M) solvent is stored at room temperature for 3 to 4 months, no cloudiness (opacity) occurs.

Durability test of surface-treated articles

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

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

<Comparative Example 1>

Preparation of surface treatment composition

Heptadecafluor decyl trimethoxysilane called 5.68 g of FAS-17 (trade name: TSL-8233; manufacturer: Momentive Japan) was added to 7.656 ml of isopropanol solvent, and 0.72 g of 0.1N hydrochloric acid aqueous solution was added to the sol-gel. The surface treatment composition was prepared by reacting.

Articles treated with surface treatment compositions

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

Water repellency and rolling test

The water repellency was measured at a total of 50 water contact angle measurement points of 5 samples coated on a slide glass with a contact angle meter (measured by GSA-X; manufacturer: STK Korea), and evaluated by the average contact angle obtained by averaging.

The rolling properties were measured using a rolling angle meter (manufactured by TFJ Global), placing a PET film of A4 size coated with a surface treatment composition on a flat plate, adding 0.2 cc of water to the PET film, and gradually inclining the flat plate. The angle at which the water droplets slide down is measured 10 times and averaged to evaluate the average cloud angle.

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

Test for cloudiness (opacity) during long-term storage

When the surface treatment composition diluent diluted with 20% by weight (solid content) in the surface treatment composition stock solution and HFE-7200 (manufacturer: 3M) solvent was stored at room temperature for 3 to 4 months, cloudiness (opacity) occurred.

Durability test of surface-treated articles

The slide glass surface-treated with the surface treatment composition was dry rubbed 10 times with a double-sided multi-purpose scrubber (product name: Scotch Bright; manufacturer: 3M), and 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 less than before friction.

Durability test of surface-treated articles

The slide glass surface-treated with the surface treatment composition was dry rubbed 10 times with a double-sided multi-purpose scrubber (product name: Scotch Bright; manufacturer: 3M), and then a total of 15 water contact angle measurement points were measured to obtain an average value and a rolling angle of 10. Measure the number of times to obtain 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 properties (dynamic friction coefficient), long-term storage properties (whether transparent or opaque) and the articles coated with the surface treatment compositions prepared in Examples 1 to 3 and Comparative Example 1 This is the result of the durability (water contact angle measurement after scrubbing friction).

Glass water repellent Contact angle Cloud Angle Long-term storage Product durability
(Contact angle: rolling 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° Cloudiness 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 cloudiness and long-term storage, and also excellent durability.

Satisfying all four factors of water repellency, rolling properties, long-term storage properties, and product durability are Examples 1 to 3, and Comparative Example 1 exhibits cloudiness in long-term storage properties, even though there is some water repellency before friction. Falls. In addition, in Comparative Example 1, the durability of the article was somewhat deteriorated.

<Experimental Example 1> Water repellency and rolling properties of the water-repellent surface-treated permeable article

Fabrics woven of polyester fibers and cotton fibers in a ratio of 8:2 (basis weight 200 g/cm 2) were immersed and dehydrated in a water-repellent surface treatment composition for fabrics prepared in Examples and Comparative Examples, and dried slowly in a dryer. Simultaneously with heat treatment, heat treatment was performed at 165±5° C. for about 5 minutes to form a water repellent coating layer.

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 Contact angle Cloud Angle Product durability
(Contact angle: rolling 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, the water repellent surface treatment composition according to the present invention, even when the water-repellent article, such as a fabric, water repellency and cloudiness, as well as excellent durability.

In the above, a preferred embodiment according to the present invention has been described with reference to the drawings and examples, but this is merely exemplary, and various modifications and equivalent other implementations are possible from those skilled in the art. Will be able to understand. Therefore, the protection scope of the present invention should be defined by the appended claims.

Claims (10)

(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-polyoxyalkylene fatty acid amide or O-alkylated polyglucoside as a cloudiness improver,
(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.
According to claim 1,
The perfluoroalkyl group-containing organopolysilane is characterized in that it comprises a compound of Formula 1, fluorine-based water repellent surface treatment composition excellent in rolling properties:
[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 derivatives of the above groups,
p is 0, 1 or 2,
Y is an alkoxy group having 1 to 4 carbon atoms, an acyloxy group, or a halogen atom.
According to claim 1,
The N-polyoxyalkylene fatty acid amide, characterized in that it comprises a compound of Formula 2, fluorine-based water repellent surface treatment composition excellent in rolling properties:
[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/polyoxy propylene block copolymer,
n represents an integer of 3 to 20, preferably 4 to 14, and more preferably 5 to 10.
According to claim 1,
The O-alkylated polyglucoside comprises a compound of Formula 3, Fluorine-based water repellent surface treatment composition excellent in rolling properties.
[Formula 3]

In the above formula, y is 0 to 6, and R is an alkyl group having 8 to 36 carbon atoms.
According to 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 any one or more reactive functional groups of a carboxyl group, a hydroxyl group, and an azo group or an amino group at the end of the polymer main chain or the end of a side chain. .
According to claim 1,
The perfluoroalkyl group-containing organopolysilane 100 parts by weight of 0.001 to 20 parts by weight of the cloudiness improving agent, 10 to 300 parts by weight of an optional silicone crosslinking agent, 2 to 30 parts by weight of an optional reactive silicone crosslinking agent, 0.001 to 50 parts by weight of an acidic catalyst A fluorine-based water-repellent surface treatment composition having excellent rolling properties, which contains a part and an aqueous solvent of 10 to 300 parts by weight.
A method for producing a fluorine-based water repellent surface treatment composition according to claim 1, characterized in that it comprises the following steps:
(Step 1) One or more compounds selected from the group consisting of a perfluoroalkyl group-containing organopolysilane as a water repellent component, N-polyoxyalkylene fatty acid amide or O-alkyl polyglucoside as a cloudiness improving agent, and any silicone-based crosslinking agent Dissolving or dispersing in an aqueous solvent to prepare a mixture;
(Step 2) sol-gel reaction by adding an acidic catalyst to the mixture; And
(Step 3) During the sol-gel reaction, adding a reactive silicone polymer solution to form an organopolysiloxane sol.
According to claim 7, characterized in that it comprises the following steps, a method for producing a fluorine-based water repellent surface treatment composition excellent in rolling properties:
(Step 1) Water-repellent component selected from organopolysilane containing perfluoroalkyl group, cloudiness improving agent selected from N-polyoxyalkylene fatty acid amide or O-alkyl polyglucoside, and any silicone-based crosslinking agent at a temperature of 10-40°C Dissolving or dispersing in an aqueous solvent to prepare a mixture; And
(Step 2) step of sol-gel reaction at a temperature of pH 3-6 and 50-70° C. by adding an acidic catalyst to the mixture;
(Step 3) After the sol-gel reaction, adding the reactive silicone polymer solution to the reaction mixture at a temperature of 25 to 45° C. and reacting for 30 to 120 minutes to form an organopolysiloxane sol.
A water-repellent and excellent cloud-permeable article selected from the group consisting of fibers, knitted fabrics, woven fabrics, or non-woven fabrics, treated with the fluorine-based water-repellent surface treatment composition according to claim 1.
An article selected from the group consisting of a solar cell, a smart phone, a touch panel, a secondary battery, a display, or an automobile, treated with the fluorine-based water-repellent surface treatment composition having excellent cloudability according to claim 1, and having excellent water-repellency and cloudability.