KR20220045283A - Non-fluorinated superhydrophobic surface-treating composition, preparation thereof and surface-treated article using the same - Google Patents

Abstract

The present invention provides a non-fluorine-based superhydrophobic surface treatment composition, manufacturing method thereof, and surface-treated article using the same. The non-fluorine-based superhydrophobic surface treatment composition includes: (a) organosilsesquioxane; (b) linear organopolysiloxane; (c) organosilsesquioxane-hybridized linear organopolysiloxane in which the organosilsesquioxane and the linear organopolysiloxane are connected to each other by an ether, amino, ester, or thioether linkage; (d) a rolling improver selected from N-polyoxyalkylenated fatty acid amide or O-alkylated polyglucoside; (e) a silicon-based crosslinking agent selected from tetraalkoxysilane or tetraaryloxysilane; (f) an acidic catalyst selected from an organic or inorganic acid; and (g) an aqueous solvent. According to the non-fluorine-based superhydrophobic surface treatment composition of the present invention, a superhydrophobic surface having excellent water repellency and rolling properties and having improved bonding properties and bonding durability is provided or formed on surfaces of an organic material, an inorganic material, and a metal material, especially surfaces of natural fibers, synthetic fibers, or carbon fibers.

Description

Non-fluorine-based superhydrophobic surface treatment composition, manufacturing method thereof, and article surface-treated using the same

The present invention relates to a non-fluorine-based superhydrophobic surface treatment composition, a method for preparing the same, and an article surface-treated using the same.

Items, including windshields, shower booths, veranda windows, car windshields, car side mirrors, ship exteriors, electronics, mobile phones, etc., can be exposed to water, The article is contaminated and the lifespan is reduced, and in particular, in the case of articles used for automobiles, ships, etc., safety of operation is also a problem.

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 for preventing contamination by coating the surface of the article with a thin thickness is adopted.

Surface properties such as water repellency are classified by the water droplet contact angle. Super hydrophilic when the droplet contact angle is less than 10°, hydrophilic from 10° to 40°, hydrophobic (or water repellent) from 70° to 110°, and 110° to 180°. A number up to ° is called ultra-hydrophobic (or super-repellent).

In general, in articles showing permeability to air, water, and further water (hereinafter referred to as permeable articles) such as fibers, knitted fabrics, woven fabrics and nonwoven fabrics, materials with low surface energy such as fluorinated polymers and silane polymers are used as water repellent agents. Alternatively, water repellency is imparted as a hydrophobizing agent. Until now, a fluorine-based water-repellent material that has a chemical structure based on fluorine molecules and is made by bonding a fluorine-based material to 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 low surface free energy and high water repellency, and has excellent chemical resistance due to the perfluoroalkyl group. In addition, adhesion to substrates such as glass, plastic, and cloth is also good. Recently, non-fluorine-based water-repellent materials having a similar structure and based on silicon or long hydrogen bonds have been developed, and currently exhibit relatively low performance compared to fluorine-based materials.

However, fluorine-based water-repellent materials including perfluoroalkyl group-containing organopolysilane and non-fluorine-based water-repellent materials including silane polymers have excellent water repellency, but have a problem in that the rolling properties, which are properties of water droplets rolling or sliding on the surface, are poor. It is difficult to use for necessary articles, and in permeable articles such as fabrics, when water exceeding water repellency comes into contact with the surface or stays for a long time, it permeates into the fabric and causes surface wetting. In addition, long-term stability is also required to have marketability, but long-term stability is often insufficient.

On the other hand, moisture-permeable waterproofness is often required for permeable articles such as fabrics, and for this purpose, water-repellent treatment may be applied. In order to impart water-repellent functionality to a permeable article such as a fabric without impairing its permeability, in addition to water repellency, which is a property of water droplets forming or not forming on the surface, water droplets on the surface of the fabric flow or roll without staying or stagnant. It is also necessary to consider the falling surface cloudiness.

In Patent Document 1 (Korean Registration Publication No. 10-1831380, published on February 22, 2018), perfluoroalkyl group-containing organopolysilane, alkylamide or alkyl polyglucoside, acid and solvent are mixed to perform a sol-gel reaction. 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 it. However, the water-repellent surface treatment agent disclosed in the above document is for forming a water-repellent surface having lubricity on an impermeable substrate, and there is no description about water-repellent property and/or rolling property in a permeable article such as a fabric, and the bonding strength and bonding durability of the water-repellent component are improved. It needs further improvement.

On the other hand, by the present inventors, in Patent Document 2 (Korean Patent Application Laid-Open No. 10-2020-0064588, published on June 08, 2020), (a) as a water-repellent component, in a mixture of a silicone precursor, a silicone-based crosslinking agent and a solvent Organopolysiloxane sol prepared by adding a reactive silicone polymer solution, (b) at least one compound selected from the group consisting of N-polyoxyalkylenated fatty acid amide or O-alkylated polyglucoside as a cloudiness improving agent, (c) organic acid Or an acid catalyst selected from inorganic acids, and (d) an aqueous solvent, a non-fluorine-based water-repellent surface treatment composition having excellent rolling properties has been developed. The water-repellent surface treatment composition of the above document has a contact angle of approximately 110° and a rolling property of approximately 25°, but there is no description of better bonding properties and bonding durability to a fibrous support, particularly carbon fiber.

In this situation, when superhydrophobic surface treatment of the surface of organic materials, inorganic materials and metallic materials, especially carbon fibers, it is possible to provide or form a superhydrophobic surface with improved bonding properties and bonding durability while excellent water repellency and rolling properties. There is still a need for new non-fluorine-based superhydrophobic surface treatment compositions that can be used.

Domestic Registration Publication No. 10-1831380 (Announced on February 22, 2018) Republic of Korea Patent Publication No. 10-2020-0064588 (published on June 08, 2020)

An object of the present invention is to provide a superhydrophobic surface with improved bonding properties and bonding durability while excellent in water repellency and rolling properties, on the surface of organic materials, inorganic materials and metal materials, in particular on the surface of natural fibers, synthetic fibers or carbon fibers, or It is to provide a novel non-fluorine-based superhydrophobic surface treatment composition or superhydrophobic surface treatment method that can be formed.

The present inventors describe (a) an organosilsesquioxane; (b) linear organopolysiloxanes; (c) an organosilsesquioxane-hybridized linear organopolysiloxane, wherein the organosilsesquioxane and the linear organopolysiloxane are linked by ether, amino, ester or thioether linkages; (d) a rolling agent selected from N-polyoxyalkylenated fatty acid amides or O-alkylated polyglucosides; (e) a silicone-based crosslinking agent selected from tetraalkoxysilane or tetraaryloxysilane; (f) an acid catalyst selected from organic acids or inorganic acids; and (g) an aqueous solvent; the non-fluorine-based superhydrophobic surface treatment composition comprising: not only has excellent stability and long-term storage properties, but also organic materials, inorganic materials and metal materials, especially natural fibers, synthetic fibers or carbon fibers. It has been found that when the surface is treated with superhydrophobicity, bonding properties and bonding durability can be improved while having excellent water repellency and rolling properties.

The present inventors also prepared the non-fluorine-based superhydrophobic surface treatment composition from a mixture of (step 1) an epoxy reactive group-containing organodialkoxysilane precursor and an epoxy reactive group-free organodialkoxysilane precursor, (a) linear or preparing ganopolysiloxane; (Step 2) from a mixture of an epoxy group-containing organotrialkoxysilane precursor and an epoxy group-free organotrialkoxysilane precursor, (b) preparing an organosilsesquioxane; (Step 3) mixing the (a) linear organopolysiloxane, (b) organosilsesquioxane, (d) cloudiness improving agent and (e) silicone-based crosslinking agent; (Step 4) heating the mixture resulting in step 3 above to prepare (c) organosilsesquioxane-hybridized linear organopolysiloxane from (a) linear organopolysiloxane and (b) organosilsesquioxane step; and (step 5) to the reaction mixture resulting from step 4, (f) adding an acid catalyst; and by this method, the above-described properties can be exhibited more efficiently found and completed the present invention.

The non-fluorine-based superhydrophobic surface treatment composition according to the present invention provides a superhydrophobic surface with excellent water repellency and rolling properties while improving bonding and bonding durability on the surfaces of organic materials, inorganic materials and metal materials, especially natural fibers, synthetic fibers or carbon It may be provided or formed on the surface of the fiber.

1 is a diagram showing the structure of polysilsesquioxane as organosilsesquioxane, (a) a random structure and (b) a ladder structure, respectively.
2 is a diagram showing the structure of an oligosilsesquioxane as an organosilsesquioxane, (c) a cage (basket) structure, (d) an open cage structure, and (e) a double decker structure, respectively.

A first object of the present invention is to provide a non-fluorine-based superhydrophobic surface treatment composition comprising the following components:

(a) organosilsesquioxane;

(b) linear organopolysiloxanes;

(c) an organosilsesquioxane-hybridized linear organopolysiloxane, wherein the organosilsesquioxane and the linear organopolysiloxane are linked by ether, amino, ester or thioether linkages;

(d) a rolling agent selected from N-polyoxyalkylenated fatty acid amides or O-alkylated polyglucosides;

(e) a silicone-based crosslinking agent selected from tetraalkoxysilane or tetraaryloxysilane;

(f) an acid catalyst selected from organic acids or inorganic acids; and

(g) aqueous solvents.

In the present invention, (a) the organosilsesquioxane is from a mixture comprising 80 to 90 mol% of an epoxy group-free organotrialkoxysilane compound and 10 to 20 mol% of an epoxy group-containing organotrialkoxysilane compound can be prepared, wherein the (b) linear organopolysiloxane is a mixture comprising 90 to 95 mol% of an epoxy reactive group-free organodialkoxysilane compound and 5 to 10 mol% of an epoxy reactive group-containing organodialkoxysilane compound can be prepared from.

In the present invention, the term “reactive group” refers to a functional group capable of reacting with a specific functional group, and the term “functional group” refers to a group that does not have reactivity with any specific reactive group but can exhibit reactivity with other reactive groups. Accordingly, the term “epoxy reactive group” refers to a functional group capable of reacting with an epoxy group, for example, a hydroxyl group, an amino group, a carboxyl group, or a thiol group.

In the present invention, in the (c) organosilsesquioxane-hybridized linear organopolysiloxane, the organosilsesquioxane and the linear organopolysiloxane are linked by an ether, amino, ester or thioether bond, for example, , can be represented by the following formula (1).

In Formula 1,

R ¹ represents, independently of each other, a monovalent hydrocarbon group;

R ² represents a monovalent hydrocarbon group independently of each other, and at least one of R ² is a vinyl group, an acryl group, a methacryl group, an alkylcarbonyloxy group, an alkoxy group, a hydroxyl group, a halogen, a dialkylamino group, an amido group, an alkoxycarbonyl group or a functional group selected from an alkylthiol group;

R ³ has the same meaning as R ¹ or R ² ;

R ⁴ and R ⁵ each independently represent a divalent hydrocarbon group, for example, a straight or branched C _{1 to} C ₁₂ alkylene group or a C ₆ to C ₁₂ arylene group;

X represents -0-, -NH-, -CO ₂ - or -S-;

Y represents a residue derived from the organosylsesquioxane represented by the general formula (R ² SiO _1.5 ) _n ;

p, q, r and s may represent a molar ratio of 1: 0 to 0.10: 0 to 0.10: 0.05 to 0.25.

In the present invention, the linear organopolysiloxane may be prepared from a mixture of an epoxy reactive group-containing organodialkoxysilane and an epoxy reactive group-free organodialkoxysilane, and the ratio thereof is not particularly limited, but an epoxy reactive group It can be used in an amount of 0.05 to 0.25 moles, preferably 0.08 to 0.22 moles, more preferably 0.1 to 0.2 moles of an epoxy reactive group-containing organodialkoxysilane with respect to 1 mole of the -free organodialkoxysilane precursor. The weight average molecular weight of the linear organopolysiloxane may be, for example, selected in the range of 1,000 to 400,000, preferably in the range of 2,000 to 300,000. When applied to a substrate such as fiber, the weight average molecular weight can be selected in the range of 1,000 to 100,000, preferably in the range of 2,000 to 50,000, and when forming a hard coating on the surface of a metal, the weight average molecular weight is 20,000 to It can be selected in the range of 400,000, preferably in the range of 50,000-200,000. The epoxy reactive group may be at least one selected from a carboxyl group, a hydroxyl group, an amino group, or a thiol group.

In one preferred embodiment of the present invention, the linear organopolysiloxane may further include other functional groups that do not react with the epoxy group or have poor reactivity. Specifically, the amount of the epoxy-reactive group-containing organodialkoxysilane is 0.05 to 0.25 mol, preferably 0.08 to 0.22 mol, more preferably 0.1 to 0.2 mol, per 1 mol of the epoxy-reactive group-free organodialkoxysilane can be used as The organodialkoxysilane having other functional groups that do not react with the epoxy group (eg, acryl group, vinyl group, ureido group, epoxy group, etc.) can be used in an amount of 0 to 0.1 mol, preferably 0.01 to 0.1 mol.

According to a preferred embodiment of the present invention, the linear organopolysiloxane may be represented by the following Chemical Formula 2:

In Formula 2, R ¹ , R ² , R ³ , R ⁴ , X, p, q, r and s have the same meaning as in Formula 1.

As the organodialkoxysilane compound usable in the present invention, for example, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, propylmethyldimethoxysilane, di-n-propyl Dimethoxysilane, di-n-propyldiethoxysilane, di-i-propyldimethoxysilane, di-i-propyldiethoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di -n-pentyldimethoxysilane, di-n-pentyldiethoxysilane, di-n-hexyldimethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyldiethoxysilane, din-octyldimethoxy Silane, di-n-octyldiethoxysilane, di-n-cyclohexyldimethoxysilane, di-n-cyclohexyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, γ-chloropropylmethyldiethoxy Silane, γ-chloropropyldimethyldimethoxysilane, chlorodimethyldiethoxysilane, (p-chloromethyl)phenylmethyldimethoxysilane, γ-bromopropylmethyldimethoxysilane, acetoxymethylmethyldiethoxysilane, acetoxymethyl Methyldimethoxysilane, acetoxypropylmethyldimethoxysilane, benzoyloxypropylmethyldimethoxysilane, 2-(carbomethoxy)ethylmethyldimethoxysilane, phenylmethyldimethoxysilane, phenylethyldiethoxysilane, phenylmethyldipro Poxysilane, hydroxymethylmethyldiethoxysilane, N-(methyldiethoxysilylpropyl)-O-polyethylene oxide urethane, N-(3-methyldiethoxysilylpropyl)-4-hydroxybutylamide, N-(3 -Methyldiethoxysilylpropyl)gluconamide, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinylmethyldibutoxysilane, isopropenylmethyldimethoxysilane, isopropenylmethyldiethoxysilane, isopropenylmethyldibu Toxysilane, vinylmethylbis(2-methoxyethoxy)silane, allylmethyldimethoxysilane, vinyldecylmethyldimethoxysilane, vinyloctylmethyldimethoxysilane, vinylphenylmethyldimethoxysilane, isopropenylphenylmethyldimethoxy Silane, 2-(meth)acryloxyethylmethyldimethoxysilane, 2-(meth)acryloxyethylmethyldiethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropylmethyl Dimethoxysilane, 3-(meth)-acryloxypropylmethyldis(2-methoxyethoxy)silane, 3-[2-(allyloxycarbonyl)phenylcarbonyloxy]propylmethyldimethoxysilane; 3-(vinylphenylamino)propylmethyldimethoxysilane, 3-(vinylphenylamino)propylmethyldiethoxysilane, 3-(vinylbenzylamino)propylmethyldiethoxysilane, 3-(vinylbenzylamino)propylmethyldiethoxy Silane, 3-[2-(N-vinylphenylmethylamino)ethylamino]propylmethyldimethoxysilane, 3-[2-(N-isopropenylphenylmethylamino)ethylamino]propylmethyldimethoxysilane, 2- (vinyloxy)ethylmethyldimethoxysilane, 3-(vinyloxy)propylmethyldimethoxysilane, 4-(vinyloxy)butylmethyldiethoxysilane, 2-(isopropenyloxy)ethylmethyldimethoxysilane, 3- (allyloxy) propylmethyldimethoxysilane, 10-(allyloxycarbonyl)decylmethyldimethoxysilane, 3-(isopropenylmethyloxy)propylmethyldimethoxysilane, 10-(isopropenylmethyloxycarbonyl) Decylmethyldimethoxysilane, 3-[(meth)acryloxypropyl]methyldimethoxysilane, 3-[(meth)acryloxypropyl]methyldiethoxysilane, 3-[(meth)acryloxymethyl]methyldimethoxysilane , 3-[(meth)acryloxymethyl]methyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, N-[3-(meth)acryloxy2-hydroxypropyl]-3-aminopropylmethyldie Toxysilane, O-[(meth)acryloxyethyl]-N-(methyldiethoxysilylpropyl)urethane, γ-glycidoxypropylmethyldiethoxysilane, β-(3,4-epoxycyclohexyl)ethylmethyldime Toxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, 4-aminobutylmethyldiethoxysilane, 11-aminoundecylmethyldiethoxysilane, m-aminophenylmethyldimethoxysilane, p -Aminophenylmethyldimethoxysilane, 3-aminopropylmethyldis(methoxyethoxyethoxy)silane, 2-(4-pyridylethyl)methyldiethoxysilane, 2-(methyldimethoxysilylethyl)pyridine, N -(3-methyldimethoxysilylpropyl)pyrrole, 3-(m-aminophenoxy)propylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2- Aminoethyl)-3-aminopropylmethyldiethoxysilane, N-(6-aminohexyl)aminomethylmethyldiethoxysilane, N-(6-aminohexyl)aminopropylmethyldimethoxysilane, N-(2-aminoethyl) )-11-aminoundecylmethyldimethoxysilane, (aminoethylaminomethyl)phenethylmethyldimethoxysilane , N-3-[(amino(polypropyleneoxy))]aminopropylmethyldimethoxysilane, n-butylaminopropylmethyldimethoxysilane, N-ethylaminoisobutylmethyldimethoxysilane, N-methylaminopropylmethyldime Toxysilane, N-phenylγ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminomethylmethyldiethoxysilane, (cyclohexylaminomethyl)methyldiethoxysilane, N-cyclohexylaminopropylmethyldimethoxysilane, Bis(2-hydroxyethyl)-3-aminopropylmethyldiethoxysilane, diethylaminomethylmethyldiethoxysilane, diethylaminopropylmethyldimethoxysilane, dimethylaminopropylmethyldimethoxysilane, N-3-methyldime Toxysilylpropyl-m-phenylenediamine, N,N-bis[3-(methyldimethoxysilyl)propyl]ethylenediamine, bis(methyldiethoxysilylpropyl)amine, bis(methyldimethoxysilylpropyl)amine, bis [(3-methyldimethoxysilyl)propyl]-ethylenediamine, bis[3-(methyldiethoxysilyl)propyl]urea, bis(methyldimethoxysilylpropyl)urea, N-(3-methyldiethoxysilylpropyl) -4,5-dihydroimidazole, ureidopropylmethyldiethoxysilane, ureidopropylmethyldimethoxysilane, acetamidepropylmethyldimethoxysilane, 2-(2-pyridylethyl)thiopropylmethyldimethoxysilane, 2-(4-pyridylethyl)thiopropylmethyldimethoxysilane, bis[3-(methyldiethoxysilyl)propyl]disulfide, 3-(methyldiethoxysilyl)propylsuccinic anhydride, γ-mercaptopropylmethyldimethyl Toxysilane, γ-mercaptopropylmethyldiethoxysilane, isocyanatopropylmethyldimethoxysilane, isocyanatopropylmethyldiethoxysilane, isocyanatoethylmethyldiethoxysilane, isocyanatomethylmethyldiethoxysilane, carboxy Ethylmethylsilanediol sodium salt, N-(methyldimethoxysilylpropyl)ethylenediamine triacetic acid trisodium salt, 3-(methyldihydroxysilyl)-1-propanesulfonic acid, diethylphosphate ethylmethyldiethoxysilane, 3- Methyldihydroxysilylpropylmethylphosphonate sodium salt, bis(methyldiethoxysilyl)ethane, bis(methyldimethoxysilyl)ethane, bis(methyldiethoxysilyl)methane, 1,6-bis(methyldiethoxysilyl) ) hexane, 1,8-bis(methyldiethoxysilyl)octane, p-bis(methyldimethoxysilylethyl)benzene, p-bis(methyldimethoxysilylmethyl)benzene, 3-methyl Toxypropylmethyldimethoxysilane, 2-[methoxy(polyethyleneoxy)propyl]methyldimethoxysilane, methoxytriethyleneoxypropylmethyldimethoxysilane, tris(3-methyldimethoxysilylpropyl)isocyanurate, [ Hydroxy(polyethyleneoxy)propyl]methyldiethoxysilane, N,N'-bis(hydroxyethyl)-N,N'-bis(methyldimethoxysilylpropyl)ethylenediamine, bis-[3-(methyldiethoxy) mention may be made of silylpropyl)-2-hydroxypropoxy]polyethyleneoxide, bis[N,N'-(methyldiethoxysilylpropyl)aminocarbonyl]polyethyleneoxide, bis(methyldiethoxysilylpropyl)polyethyleneoxide .

Among the organodialkoxysilane compounds described above, a reactive group-containing organodialkoxysilane, a reactive group-free organodialkoxysilane, an epoxy group-containing organodialkoxysilane and/or an epoxy group-containing organodialkoxysilane is selected as needed can be used by

In the present invention, the organosilsesquioxane may have various structures depending on the preparation method, reaction conditions, and monomer ratio, for example, as shown in FIGS. 1 and 2, (a) a random structure, (b ) ladder structure, (c) cage (basket) structure, (d) open cage structure and (e) double decker structure, and the cage (basket) structure is hexamer (T ₆ ), octamer (T ₈ ) , a decamer (T ₁₀ ) and a dodecimer (T ₁₂ ).

In the present invention, an organosilsesquioxane having a cage structure represented by the following formula (3) can be preferably used:

In the above formula,

R each independently represents a monovalent hydrocarbon group which may have a substituent, for example, a C _1-12 alkyl group or a cycloalkyl group (eg, methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, octyl, cyclohexyl, cycloheptyl, etc.), or a C _6-12 aryl group (eg phenyl, tolyl, naphthyl, etc.) or a C _7-12 alkylaryl group (eg benzyl, phenethyl, propylphenyl, etc.), may be selected from the group consisting of halogen, hydroxy, amino, mercapto, epoxy, isocyanato, (meth)acrylic or vinyl.

According to a preferred embodiment of the present invention, the organosilsesquioxane can be prepared from a mixture of 80-90 mol% of an organotrialkoxysilane precursor and 10-20 mol% of an epoxy group-containing organotrialkoxysilane precursor, preferably Alternatively, it can be prepared from a mixture of 80-90 mol% of an epoxy group-free organotrialkoxysilane precursor and 10-20 mol% of an epoxy group-containing organotrialkoxysilane precursor.

As the epoxy group-containing or epoxy group-free organotrialkoxysilane precursor, for example, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltri Methoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxy Silane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxy Silane, γ-chloropropyltriethoxysilane, γ-chloropropyltrimethoxysilane, chloromethyltriethoxysilane, 3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyl Triethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-hydroxypropyltriethoxysilane, 3-hydroxypropyl Trimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltrie Toxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3 -Glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl Triethoxysilane, (p-chloromethyl)phenyltrimethoxysilane, γ-bromopropyltrimethoxysilane, acetoxymethyltriethoxysilane, acetoxymethyltrimethoxysilane, acetoxypropyltrimethoxysilane , benzoyloxypropyltrimethoxysilane, 2-(carbomethoxy)ethyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, N-(triethoxysilylpropyl)- O-polyethylene oxide urethane, N-(3-triethoxysilylpropyl)-4-hydroxybutylamide, N-(3-triethoxysilylpropyl)gluconamide, vinyltrimethoxysilane, vinyltriethoxy Silane, vinyltributoxysil Lan, isopropenyltrimethoxysilane, isopropenyltriethoxysilane, isopropenyltributoxysilane, vinyltris(2-methoxyethoxy)silane, allyltrimethoxysilane, vinyldecyltrimethoxysilane , vinyloctyltrimethoxysilane, vinylphenyltrimethoxysilane, isopropenylphenyltrimethoxysilane, 2-(meth)acryloxyethyltrimethoxysilane, 2-(meth)acryloxyethyltriethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)-acryloxypropyltris(2-methoxyethoxy)silane, 3-[2 -(Allyloxycarbonyl)phenylcarbonyloxy]propyltrimethoxysilane, 3-(vinylphenylamino)propyltrimethoxysilane, 3-(vinylphenylamino)propyltriethoxysilane, 3-(vinylbenzylamino) ) Propyltriethoxysilane, 3-(vinylbenzylamino)propyltriethoxysilane, 3-[2-(N-vinylphenylmethylamino)ethylamino]propyltrimethoxysilane, 3-[2-(N-) Isopropenylphenylmethylamino)ethylamino]propyltrimethoxysilane, 2-(vinyloxy)ethyltrimethoxysilane, 3-(vinyloxy)propyltrimethoxysilane, 4-(vinyloxy)butyltriethoxy Silane, 2-(isopropenyloxy)ethyltrimethoxysilane, 3-(allyloxy)propyltrimethoxysilane, 10-(allyloxycarbonyl)decyltrimethoxysilane, 3-(isopropenylmethyloxy ) propyltrimethoxysilane, 10-(isopropenylmethyloxycarbonyl)decyltrimethoxysilane, 3-[(meth)acryloxypropyl]trimethoxysilane, 3-[(meth)acryloxypropyl]tri Ethoxysilane, 3-[(meth)acryloxymethyl]trimethoxysilane, 3-[(meth)acryloxymethyl]triethoxysilane, γ-glycidoxypropyltrimethoxysilane, N-[3- (meth)acryloxy-2-hydroxypropyl]-3-aminopropyltriethoxysilane, O-[(meth)acryloxyethyl]-N-(triethoxysilylpropyl)urethane, γ-glycidoxypropyl Triethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, 4-aminobutyltriethoxysilane, 11 -Aminoundecyltriethoxysilane, m-aminophenyltrimethoxysilane, p-aminophenyltrimethoxysilane, 3-aminopropyltris(methoxyethoxy) Ethoxy)silane, 2-(4-pyridylethyl)triethoxysilane, 2-(trimethoxysilylethyl)pyridine, N-(3-trimethoxysilylpropyl)pyrrole, 3-(m-amino Phenoxy) propyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-(6- Aminohexyl)aminomethyltriethoxysilane, N-(6-aminohexyl)aminopropyltrimethoxysilane, N-(2-aminoethyl)-11-aminoundecyltrimethoxysilane, (aminoethylaminomethyl) Phenethyltrimethoxysilane, N-3-[(amino(polypropyleneoxy))]aminopropyltrimethoxysilane, n-butylaminopropyltrimethoxysilane, N-ethylaminoisobutyltrimethoxysilane, N- Methylaminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminomethyltriethoxysilane, (cyclohexylaminomethyl)triethoxysilane, N-cyclohexylamino propyltrimethoxysilane, bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, diethylaminomethyltriethoxysilane, diethylaminopropyltrimethoxysilane, dimethylaminopropyltrimethoxysilane, N-3-trimethoxysilylpropyl-m-phenylenediamine, N,N-bis[3-(trimethoxysilyl)propyl]ethylenediamine, bis(triethoxysilylpropyl)amine, bis(trimethoxy Silylpropyl)amine, bis[(3-trimethoxysilyl)propyl]-ethylenediamine, bis[3-(triethoxysilyl)propyl]urea, bis(trimethoxysilylpropyl)urea, N-(3- Triethoxysilylpropyl)-4,5-dihydroimidazole, ureidopropyltriethoxysilane, ureidopropyltrimethoxysilane, acetamidepropyltrimethoxysilane, 2-(2-pyridylethyl)thio Propyltrimethoxysilane, 2-(4-pyridylethyl)thiopropyltrimethoxysilane, bis[3-(triethoxysilyl)propyl]disulfide, 3-(triethoxysilyl)propylsuccinic anhydride, γ -Mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, isocyanatopropyltrimethoxysilane, isocyanatopropyltriethoxysilane, isocyanatoethyltriethoxysilane, isocyanatomethyl Triethoxysilane, carboxyethylsilane triol sodium salt, N-(trimethoxysilylpropyl)ethylenedia Mintriacetic acid trisodium salt, 3-(trihydroxysilyl)-1-propanesulfonic acid, diethylphosphate ethyltriethoxysilane, 3-trihydroxysilylpropylmethylphosphonate sodium salt, bis(triethoxysilyl )ethane, bis(trimethoxysilyl)ethane, bis(triethoxysilyl)methane, 1,6-bis(triethoxysilyl)hexane, 1,8-bis(triethoxysilyl)octane, p-bis (trimethoxysilylethyl)benzene, p-bis(trimethoxysilylmethyl)benzene, 3-methoxypropyltrimethoxysilane, 2-[methoxy(polyethyleneoxy)propyl]trimethoxysilane, methoxytri Ethyleneoxypropyltrimethoxysilane, tris(3-trimethoxysilylpropyl)isocyanurate, [hydroxy(polyethyleneoxy)propyl]triethoxysilane, N,N'-bis(hydroxyethyl)-N ,N'-bis(trimethoxysilylpropyl)ethylenediamine, bis-[3-(triethoxysilylpropyl)-2-hydroxypropoxy]polyethylene oxide, bis[N,N'-(triethoxysilyl) propyl)aminocarbonyl]polyethyleneoxide, bis(triethoxysilylpropyl)polyethyleneoxide and mixtures thereof may be mentioned. However, it is preferable that the organotrialkoxysilane precursor does not have a functional group capable of reacting with an epoxy group (eg, amino, hydroxy, mercapto, isocyanato, etc.).

Among the aforementioned organotrialkoxysilanes, the epoxy group-containing organotrialkoxysilane precursors include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 2-(3,4-epoxy). cyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane and mixtures thereof may be mentioned.

In the present invention, the (d) cloudiness improving agent may be selected from N-polyoxyalkylenated fatty acid amide or O-alkylated polyglucoside, and specifically, N-polyoxyalkylenated fatty acid amide of Formula 4 below; It may be selected from O-alkylated polyglucosides of Formula 5 below, or mixtures thereof.

In Formula 4,

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

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

x represents a number from 3 to 20.

In Formula 5,

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

y represents a number from 0 to 6.

In the present invention, the (e) silicone-based crosslinking agent may be selected from tetraalkoxysilane or tetraaryloxy cinic acid, and specifically, tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), tetrapropoxy It may be at least one selected from the group consisting of silane (TPOS), tetraisopropoxysilane, and tetraphenoxysilane.

In the surface treatment composition according to the present invention, the composition ratio of the components is not strictly limited, but preferably, (c) with respect to 100 parts by weight of the organosilsesquioxane-hybridized linear organopolysiloxane, (a) organosyl 10 to 100 parts by weight of sesquioxane, (b) 10 to 100 parts by weight of linear organopolysiloxane, (d) 0.01 to 5 parts by weight of a rolling property improving agent, and (e) 5 to 20 parts by weight of a silicone-based crosslinking agent may be contained. If the surface to be treated does not have a surface reactive group such as a metal, 10 to 100 parts by weight of the linear organopolysiloxane may be additionally added. can be reduced and additionally 10 to 100 parts by weight of organosilsesquioxane can be added.

The surface treatment composition according to the present invention may be prepared as a two-component type, for example, an acid catalyst and components that are non-reactive to the acid catalyst may be separately provided.

A second object of the present invention is to provide a method for preparing a non-fluorine-based superhydrophobic surface treatment composition comprising the steps of:

(Step 1) from a mixture of an epoxy reactive group-containing organodialkoxysilane precursor and an epoxy reactive group-free organodialkoxysilane precursor, (a) preparing a linear organopolysiloxane;

(Step 2) from a mixture of an epoxy group-containing organotrialkoxysilane precursor and an epoxy group-free organotrialkoxysilane precursor, (b) preparing an organosilsesquioxane;

(Step 3) mixing the (a) linear organopolysiloxane, (b) organosilsesquioxane, (d) cloudiness improving agent and (e) silicone-based crosslinking agent;

(Step 4) heating the mixture resulting in step 3 above to prepare (c) organosilsesquioxane-hybridized linear organopolysiloxane from (a) linear organopolysiloxane and (b) organosilsesquioxane step; and

(Step 5) To the reaction mixture obtained in Step 4, (f) adding an acid catalyst.

In step 1 of the present invention, the linear organopolysiloxane may be prepared according to a method commonly known in the art by selecting the type and composition of the above-mentioned monomers. For example, the following silane precursors:

- 1 mole of dipropyldiethoxysilane, diphenyldiethoxysilane, propylphenyldiethoxysilane or mixtures thereof as non-reactive dialkyldialkoxysilane;

- 0 to 0.10 moles of 2-acryloxyethylmethyldiethoxysilane, allylmethyldimethoxysilane, vinyldecylmethyldimethoxysilane, or a mixture thereof as a dialkyldialkoxysilane containing a reactive group; and

-Dialkyldialkoxysilane containing an epoxy reactive group, γ-hydroxypropylmethyldiethoxysilane, 4-hydroxybutylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, 4-aminobutylmethyldiethoxysilane or 0.05-0.25 moles of a mixture thereof;

A linear organopolysiloxane sol can be prepared by mixing in an aqueous solvent, adding an acidic catalyst, and reacting at a temperature of 20 to 60° C. for 10 minutes to 6 hours.

The above-mentioned linear organopolysiloxane sol preferably has a viscosity of 700 to 1500 cps. If the viscosity is less than 700 cps, a hybrid organopolysiloxane sol having a desired level of molecular weight cannot be formed, so the durability of the cross-linked organopolysiloxane product having a three-dimensional network structure is reduced, and water repellency may also be reduced due to a decrease in density. . If the viscosity exceeds 1500 cps, the feel of the coated surface is significantly reduced, and when a water-repellent coating is applied to a permeable article such as a fiber or fabric, the softness of the fabric is reduced, so the feel and drape of the fabric are very poor. There are problems that can make things worse.

In step 2 of the present invention, the organosilsesquioxane may be performed according to a method commonly known in the art by selecting the type and composition of the above-mentioned monomers. For example, polysilsesquioxane whose structure is selectively controlled by a method according to Patent Document 1 (Korean Patent Publication No. 10-2012-0017133, published on February 28, 2012), preferably a cage-type organosil Sesquioxane may be prepared, which patent document is incorporated herein by reference.

In the present invention, the organosilsesquioxane containing an epoxy group is commercially available, for example, an epoxy group-containing organosilsesquioxane represented by the following Chemical Formulas 6 and 7 (where to purchase: Sigma-Aldrich):

In step 3 of the present invention, the (a) linear organopolysiloxane, (b) organosilsesquioxane, (d) cloudiness improving agent and (e) silicone-based crosslinking agent may be mixed.

In step 4 of the present invention, (a) linear organopolysiloxane and (b) by adding a catalyst to the mixture and reacting for 1 to 10 hours at a temperature of, for example, 50 to 100° C. to perform an epoxy ring opening reaction (c) organosilsesquioxane-hybridized linear organopolysiloxanes can be prepared from organosilsesquioxanes. At this time, (a) the linear organopolysiloxane and (b) the organosilsesquioxane are not all reacted and some are preferably left unreacted, and the proportion of the unreacted precursor is 50% or less, preferably 40% or less , more preferably 30% or less, specifically 10 to 30%. If the amount of the unreacted precursor is less than the above range due to excessive reaction, it may be further added or supplemented up to the amount within the above range.

In step 4, the (d) cloudiness improving agent and (e) silicone-based crosslinking agent present together in the reaction mixture do not substantially participate in the epoxy ring opening reaction, but the reaction product (c) organosilsesquioxane-hybridized linear It is understood that the organopolysiloxane forms a mixed sol with the (d) rolling property improving agent and (e) silicone-based crosslinking agent, thereby improving bonding strength and bonding durability when the surface treatment composition is applied to a target article.

On the other hand, after the completion of step 4, (a) linear organopolysiloxane and (b) organosilsesquioxane may be further added to the resulting reaction mixture to increase the proportion of unreacted precursor, but a homogeneous reaction mixture Vigorous stirring is required to obtain , and vigorous stirring may disturb the intimate mixing state or mixed sol of various components formed in the reaction mixture resulting in step 4, which may be rather undesirable.

In step 5 of the present invention, (f) an acidic catalyst may be added to the reaction mixture obtained in step 4 above. As acidic catalysts that can be used, mention may be made of inorganic acids or organic acids, for example hydrochloric acid, acetic acid, nitric acid, sulfuric acid, phosphoric acid or mixed acids thereof. The acid catalyst used in step 5 may be used in an amount of 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight, more preferably 0.1 to 5 parts by weight based on 100 parts by weight of the silicone-based crosslinking agent used in step 3 above. there is.

In the present invention, the acidic catalyst may act as a gelation catalyst and/or a pH adjusting agent, and may be used not only in step 5 but also in steps 1 and 2 . The acidic catalyst can be used in the form of an aqueous solution having a concentration of 0.001 to 1 N. In this concentration range, each reaction can proceed from several minutes to several days.

On the other hand, the acid catalyst may be used in an amount of 0.001 to 10 parts by weight, preferably 0.005 to 5 parts by weight, more preferably 0.01 to 1 parts by weight, based on 100 parts by weight of the precursor used in Steps 1 and 2. When 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, as well as prevent cloudiness or precipitation of the composition.

According to one modified embodiment of the present invention, an epoxy group-containing linear organopolysiloxane is reacted with an organosilsesquioxane having a reactive group capable of reacting with an epoxy group to prepare an organosilsesquioxane-hybridized linear organopolysiloxane can do. The epoxy group-containing linear organopolysiloxane and organosilsesquioxane having a reactive group capable of reacting with an epoxy group may be prepared according to a method known in the art.

In the present invention, the rolling property improvement component is characterized in that it is complexed twice with the organosilicon component including the organopolysiloxane.

That is, in step 4, (d) performing a ring opening reaction in the presence of a rolling agent and (e) a silicone-based crosslinking agent (c) to prepare an organosilsesquioxane-hybridized linear organopolysiloxane, (c) an organ It is characterized in that the nosilsesquioxane-hybridized linear organopolysiloxane and (d) the rolling property improving agent are primarily complexed.

Also in step 5, (d) performing a gelation reaction in the presence of a rolling agent, (c) an organosilsesquioxane-hybridized linear organopolysiloxane and (d) a rolling property improving agent by (e) a silicone-based crosslinking agent It is characterized in that it is secondarily complexed.

In the present invention, as well as excellent water repellency and rolling properties, as well as excellent bonding and durability by being physically/chemically closely coupled with the organosilicon component and the rolling property improvement components by the above-described primary and secondary complexing. it is shown

A third object of the present invention is to provide an article surface-treated with a surface treatment composition containing the aforementioned organosilsesquioxane-hybridized linear organopolysiloxane. There is no particular limitation on the articles or surfaces that can be treated with the surface treatment composition according to the present invention, and it can be applied to all metal materials, inorganic materials and organic materials.

One advantage of the surface treatment composition according to the present invention and the method for surface treatment using the same is that organosilsesquioxane and linear organopolysiloxane, particularly organosilsesquioxane, are used, and the surface treatment composition containing them is very high. It has surface hardness, excellent transparency, scratch resistance, water repellency, antifouling properties, anti-fingerprint, thermal stability and gloss properties, excellent adhesion to metal materials, inorganic materials and organic materials, and high compatibility with pigments. is that it is easy to color.

In particular, the surface treatment composition according to the present invention and the surface treatment method using the same are particularly suitable for fibrous materials, for example, natural fibers, synthetic fibers or carbon fibers, especially for woven fabrics, non-woven fabrics, and knitted fabrics made of carbon fiber, etc. Alternatively, cloudiness may be imparted.

Another advantage of the surface treatment composition according to the present invention and the surface treatment method using the same is that it contains an organosilsesquioxane-hybridized linear organopolysiloxane, so that the properties of the organosilsesquioxane can be sufficiently expressed, Desorption of the organosilsesquioxane is prevented, adhesion to the treated surface can be further improved, and the above-mentioned advantages (sufficient characteristic expression, detachment prevention, and excellent adhesion) can be maintained for a long period of time.

Hereinafter, the present invention will be described in more detail through examples. However, the following examples are provided to explain the present invention in more detail, and the scope of the present invention is not limited by the following examples. The following examples can be appropriately modified and changed by those skilled in the art within the scope of the present invention.

Preparation Example 1: Preparation of linear organopolysiloxane

In a reactor equipped with a stirrer and a thermometer, 200 ml of water and 200 ml of isopropanol were introduced, and 14.8 g (0.1 mol) of diethyl (dimethoxy) silane (mw 180.27), 3-hydroxypropyl (diethoxy) methylsilane ( 0.05 mol of mw 192.31) and 1.91 g (0.01 mol) of 3-aminopropyl (diethoxy)methylsilane (mw 191.34) were added and mixed, and the resulting mixture was maintained at a pH of 5.0±0.2 with acetic acid at 60° C. for 2 hours stirred for a while. When the reaction mixture became clear, the temperature was cooled to approximately 30° C. to obtain a linear organopolysiloxane sol solution.

Preparation Example 2: Preparation of organosilsesquioxane

According to the method described in Korean Patent Publication No. 10-1249798, an epoxy group-containing organosilsesquioxane was prepared as follows.

a) As an organotrialkoxysilane precursor, propyltrimethoxysilane (0.4 mol) was prepared, and HPLC-grade tetrahydrofuran (40 g) and distilled water (24 g) were prepared to prepare an aqueous mixed solvent.

b) As an epoxy group-containing organotrialkoxysilane precursor, glycidylpropyltrimethoxysilane (0.06 mol) was prepared as in a) above.

c) Potassium carbonate (0.2 g), a catalyst, was previously dissolved in prepared distilled water and uniformly stirred with tetrahydrofuran for 20 minutes to prepare an aqueous solution.

d) Propyltrimethoxysilane (0.4mol) and glycidylpropyltrimethoxysilane (0.06mol) are added dropwise to the aqueous solution and stirred, and the molecular weight increases by GPC measurement and the molecular weight is maintained for more than 10 hours The reaction was terminated. The total reaction time was approximately 70 hours. In an organic solvent that is immiscible with water, an organic solvent capable of dissolving the polysilsesquioxane-based material (eg, chloroform, methylene chloride, toluene, xylene, etc.) was used for purification by fractional distillation.

e) The organosilsesquioxane obtained in d) was recrystallized from a 9:1 mixture of methylene chloride and ethanol to obtain cage-type silsesquioxane. The cage-type silsesquioxane purified by recrystallization was T12-POSS, and the molecular weight was approximately 2,300.

Example 1 Preparation of Organosilsesquioxane-Hybridized Linear Organopolysiloxane

In the linear organopolysiloxane sol solution obtained in Preparation Example 1, 1 g of cage-type epoxy group-containing organosilsesquioxane prepared in Preparation Example 2, alkyl polyglucoside (trade name: Milcoside 100; Manufacturer: LG Household & Health Care) 0.2 g, 1.5 g of N-polyoxyethylene cocamide (trade name: NINOL 1301; manufacturer: Stepan) and 0.2 g of tetraethoxysilane were added and homogenized by vigorous stirring, and then an epoxy ring opening reaction catalyst was added, followed by 2 at approximately 70 ° C. By reacting for a period of time, the organosilsesquioxane-hybridized linear organopolysiloxane was prepared.

Example 2: Preparation of organosilsesquioxane-hybridized linear organopolysiloxane

Instead of the organosilsesquioxane obtained in Preparation Example 2, an epoxy group-containing organosilsesquioxane of the following formula (8) (mw 931.63) (Sigma-Aldrich) 0.5 g was used, except that 0.5 g was used as in Example 1 Proceeding similarly, organosilsesquioxane-hybridized linear organopolysiloxanes were prepared.

Test Example 1

An acidic catalyst was added in a catalytic amount of 0.1 wt% to the reaction mixtures obtained in Examples 1 and 2, and used as a surface treatment composition.

The surface treatment composition was applied to the fabric made of carbon fiber in an amount of 0.1 g/m ² and dried to impart superhydrophobic surface properties.

The surface-treated carbon fiber fabric exhibited very good durability against washing using water and organic solvents.

Although specific embodiments according to the present invention have been described so far, it is apparent that various implementation modifications are possible without departing from the scope of the present invention.

Therefore, the scope of the present invention should not be limited to the described embodiments, and should be defined by the following claims as well as the claims and equivalents.

That is, it should be understood that the above-described embodiment is illustrative in all respects and not restrictive, and the scope of the present invention is indicated by the claims to be described later rather than the detailed description, and the meaning and scope of the claims; All changes or modifications derived from the concept of equivalents should be construed as being included in the scope of the present invention.

Claims (10)

(a) organosilsesquioxane;
(b) linear organopolysiloxanes; and
(c) an organosilsesquioxane-hybridized linear organopolysiloxane, wherein the organosilsesquioxane and the linear organopolysiloxane are linked by ether, amino, ester or thioether linkages;
(d) a cloudiness improving agent selected from N-polyoxyalkylenated fatty acid amides or O-alkylated polyglucosides;
(e) a silicone-based crosslinking agent selected from tetraalkoxysilane or tetraaryloxysilane;
(f) an acid catalyst selected from organic acids or inorganic acids; and
(g) an aqueous solvent; comprising;
A non-fluorine-based superhydrophobic surface treatment composition.
The method of claim 1,
The (a) organosilsesquioxane is,
characterized in that it is prepared from a mixture comprising 80 to 90 mol% of an epoxy group-free organotrialkoxysilane compound and 10 to 20 mol% of an epoxy group-containing organotrialkoxysilane compound,
A non-fluorine-based superhydrophobic surface treatment composition.
The method of claim 1,
The (a) organosilsesquioxane is,
Characterized in that it is selected from the organosilsesquioxane of the cage structure of Formula 3 below,
A non-fluorine-based superhydrophobic surface treatment composition.
[Formula 3]

In Formula 3,
R each independently represents a monovalent hydrocarbon group which may have a substituent, for example, a C _1-12 alkyl group or a cycloalkyl group (eg, methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, octyl, cyclohexyl, cycloheptyl, etc.), or a C _6-12 aryl group (eg phenyl, tolyl, naphthyl, etc.) or a C _7-12 alkylaryl group (eg benzyl, phenethyl, propylphenyl, etc.), may be selected from the group consisting of halogen, hydroxy, amino, mercapto, epoxy, isocyanato, (meth)acrylic or vinyl.
The method of claim 1,
The (b) linear organopolysiloxane is
characterized in that it is prepared from a mixture comprising 90 to 95 mol% of an epoxy reactive group-free organodialkoxysilane compound and 5 to 10 mol% of an epoxy reactive group-containing organodialkoxysilane compound,
A non-fluorine-based superhydrophobic surface treatment composition.
The method of claim 1,
The (c) organosilsesquioxane-hybridized linear organopolysiloxane is characterized in that it is represented by the following formula (1),
Non-fluorine-based superhydrophobic surface treatment composition:
[Formula 1]

In Formula 1,
R ¹ represents, independently of each other, a monovalent hydrocarbon group;
R ² represents a monovalent hydrocarbon group independently of each other, and at least one of R ² is a vinyl group, an acryl group, a methacryl group, an alkylcarbonyloxy group, an alkoxy group, a hydroxyl group, a halogen, a dialkylamino group, an amido group, an alkoxycarbonyl group or a functional group selected from an alkylthiol group;
R ³ has the same meaning as R ¹ or R ² ;
R ⁴ and R ⁵ each independently represent a divalent hydrocarbon group, for example, a straight or branched C _{1 to} C ₁₂ alkylene group or a C ₆ to C ₁₂ arylene group;
X represents -0-, -NH-, -CO ₂ - or -S-;
Y represents a residue derived from the organosylsesquioxane represented by the general formula (R ² SiO _1.5 ) _n ;
p, q, r and s may represent a molar ratio of 1: 0 to 0.10: 0 to 0.10: 0.05 to 0.25.
The method of claim 1,
The (d) cloudiness improving agent is characterized in that it is selected from N-polyoxyalkylenated fatty acid amide of Formula 4, O-alkylated polyglucoside of Formula 5, or a mixture thereof,
A non-fluorine-based superhydrophobic surface treatment composition.
[Formula 4]

In Formula 4,
R represents a substituted or unsubstituted alkyl group having 8 to 36 carbon atoms,
(A0) _x represents polyoxyethylene, polyoxypropylene or polyoxyethylene/polyoxypropylene block copolymer,
x represents a number from 3 to 20.
[Formula 5]

In Formula 5,
R represents a substituted or unsubstituted alkyl group having 8 to 36 carbon atoms,
y represents a number from 0 to 6.
The method of claim 1,
The (e) silicone-based crosslinking agent,
characterized in that at least one selected from the group consisting of tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), tetrapropoxysilane (TPOS), tetraisopropoxysilane and tetraphenoxysilane,
A non-fluorine-based superhydrophobic surface treatment composition.
The method of claim 1,
(c) based on 100 parts by weight of the organosilsesquioxane-hybridized linear organopolysiloxane, (a) 10 to 100 parts by weight of the organosilsesquioxane, (b) 10 to 100 parts by weight of the linear organopolysiloxane, ( d) 0.01 to 5 parts by weight of a rolling property improving agent, and (e) 5 to 20 parts by weight of a silicone-based crosslinking agent,
A non-fluorine-based superhydrophobic surface treatment composition.
(Step 1) from a mixture of an epoxy reactive group-containing organodialkoxysilane precursor and an epoxy reactive group-free organodialkoxysilane precursor, (a) preparing a linear organopolysiloxane;
(Step 2) from a mixture of an epoxy group-containing organotrialkoxysilane precursor and an epoxy group-free organotrialkoxysilane precursor, (b) preparing an organosilsesquioxane;
(Step 3) mixing the (a) linear organopolysiloxane, (b) organosilsesquioxane, (d) cloudiness improving agent and (e) silicone-based crosslinking agent;
(Step 4) heating the mixture resulting from step 3 above to prepare (c) organosilsesquioxane-hybridized linear organopolysiloxane from (a) linear organopolysiloxane and (b) organosilsesquioxane step; and
(Step 5) to the reaction mixture resulting in step 4, (f) adding an acidic catalyst;
A method for preparing a non-fluorine-based superhydrophobic surface treatment composition.
An article surface-treated with the non-fluorine-based superhydrophobic surface treatment composition according to claim 1 .

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