KR102492231B1 - Eco-friendly superhydrophobic surface-treating composition utilizing lotus leaf, preparation thereof and surface-treated article using the same - Google Patents

Abstract

The present invention, (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 improver selected from N-polyoxyalkylenated fatty acid amides or O-alkylated polyglucosides; (e) a silicone-based crosslinking agent selected from tetraalkoxysilane or tetraaryloxysilane; (f) lotus leaf powder; (g) an acidic catalyst selected from organic or inorganic acids; And (h) an aqueous solvent; an eco-friendly super-hydrophobic surface treatment composition using lotus leaves containing, a manufacturing method thereof, and a surface-treated article using the same are provided.
The eco-friendly super-hydrophobic surface treatment composition using lotus leaves according to the present invention utilizes natural materials to provide a super-hydrophobic surface that is fluorine-free, eco-friendly, has excellent water repellency and cloudiness, and has improved bonding and bonding durability, using organic and inorganic materials. And it can be provided or formed on the surface of a metal material, especially the surface of natural fiber, synthetic fiber or carbon fiber.

Description

Eco-friendly super-hydrophobic surface treatment composition using lotus leaf, manufacturing method thereof, and surface-treated article using the same

The present invention relates to an eco-friendly super-hydrophobic surface treatment composition using lotus leaves, a manufacturing method thereof, and an article surface-treated using the same.

Superhydrophobic materials are materials that repel water and allow water droplets to roll (roll) to achieve a self-cleaning effect. A surface is said to be superhydrophobic if it exhibits a static water contact angle greater than 150° and a rolling angle (rolling angle) less than 10°.

Superhydrophobic surfaces have been studied in recent years due to their self-cleaning, oil-water separation, corrosion resistance, anti-icing and anti-fogging properties.

In nature, a lotus leaf exhibits a superhydrophobic surface characteristic called “lotus leaf effect”, and has a water contact angle of about 160° and a rolling angle of about 2°. As the scanning electron microscope was developed, it was found that the micron mastoid structure of the surface of the lotus leaf and the waxy material on the surface were the core of the lotus leaf effect, that is, the self-cleaning function. The lotus leaf effect is believed to be caused by a combination of low surface energy materials and micron-sized structures.

In order to impart the lotus leaf effect, which is represented by self-cleaning, to the surface of an object, studies on simulating the surface structure of a lotus leaf and materials with low surface energy have been actively conducted.

As a pioneering study in another direction, a natural material with a lotus leaf effect was applied to the surface of an object.

Patent Document 1 (Korean Patent Publication No. 10-1323146, published on October 30, 2013) powders lotus leaf, a natural material, and forms a micro-nano structure by hybridizing it with silica modified with polymers and phenyl groups A superhydrophobic polymer composite is disclosed.

Patent Document 2 (Korean Patent Publication No. 10-1323144, published on October 30, 2013) is a structurally super-hydrophobic leaf powder obtained from plant leaves and a hydrophobic polymer hybridized to form a micro-nano structure. A superhydrophobic polymer composite is disclosed.

In Patent Documents 1 and 2, by hydrolyzing hydrophobic polymethylhydroxysiloxane and phenyltrialkoxysilane in the presence of natural superhydrophobic leaf powder to prepare a leaf powder / organopolysiloxane composite, the dynamic water contact angle and the static water contact angle are improved However, the rolling angle is low and the cloudiness is not satisfactory, which is believed to be because the cloudability of the organopolysiloxane is low and the compounding of the organopolysiloxane and the leaf powder is not sufficient.

In this situation, there is still a need to develop a leaf powder/organopolysiloxane composite having improved rolling properties as well as a contact angle by combining natural superhydrophobic leaf powder with organopolysiloxane.

Domestic Registered Patent Publication No. 10-1323146 (Announced on October 30, 2013) Domestic Patent Registration No. 10-1323144 (Announced on October 30, 2013)

An object of the present invention is to provide a super-hydrophobic surface that is environmentally friendly, has excellent water repellency and cloudiness, and has improved bonding and bonding durability on the surface of organic materials, inorganic materials, and metal materials, especially natural fibers, synthetic fibers, or carbon fibers. It is to provide a new environmentally friendly superhydrophobic surface treatment composition or a superhydrophobic surface treatment method capable of providing or forming.

We found (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 improver selected from N-polyoxyalkylenated fatty acid amides or O-alkylated polyglucosides; (e) a silicone-based crosslinking agent selected from tetraalkoxysilane or tetraaryloxysilane; (f) lotus leaf powder; (g) an acidic catalyst selected from organic or inorganic acids; And (h) an aqueous solvent; it is possible to provide an eco-friendly super-hydrophobic surface treatment composition using lotus leaves, including, the surface treatment composition using such natural materials is excellent in stability and long-term storage, as well as organic materials , It was found that when the surface of inorganic materials and metal materials, especially natural fibers, synthetic fibers, or carbon fibers, is treated with superhydrophobicity, bonding ability and bonding durability can be improved while excellent water repellency and rolling properties.

The present inventors also found that an environmentally friendly superhydrophobic surface treatment composition using the lotus leaf, (Step 1) from a mixture of an epoxy reactive group-containing organodialkoxysilane precursor and an epoxy reactive group-non-containing organodialkoxysilane precursor, (a ) preparing a linear organopolysiloxane; (Step 2) preparing organosilsesquioxane from a mixture of an epoxy group-containing organotrialkoxysilane precursor and an epoxy group-free organotrialkoxysilane precursor; (Step 3) mixing the (a) linear organopolysiloxane, (b) organosilsesquioxane, (d) cloudiness improving agent, (e) silicone-based crosslinking agent and (f) lotus leaf powder; (Step 4) Heating the mixture resulting from step 3 to prepare (c) organosilsesquioxane-hybridized linear organopolysiloxane from (a) linear organopolysiloxane and (b) organosilsesquioxane step; And (step 5) adding an acidic catalyst to the reaction mixture resulting from step 4, (g). discovered and completed the present invention.

The eco-friendly super-hydrophobic surface treatment composition using lotus leaves according to the present invention utilizes natural materials to provide a super-hydrophobic surface that is fluorine-free, eco-friendly, has excellent water repellency and cloudiness, and has improved bonding and bonding durability, using organic and inorganic materials. And it can be provided or formed on the surface of a metal material, especially the surface of natural fiber, synthetic fiber or carbon fiber.

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

The first object of the present invention is to provide an eco-friendly superhydrophobic surface treatment composition using lotus leaves, including 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 improver selected from N-polyoxyalkylenated fatty acid amides or O-alkylated polyglucosides;

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

(f) lotus leaf powder;

(g) an acidic catalyst selected from organic or inorganic acids; and

(h) aqueous solvents.

In the present invention, the organosilsesquioxane (a) is obtained from a mixture containing 80 to 90 mol% of an epoxy group-free organotrialkoxysilane compound and 10 to 20 mol% of an epoxy group-containing organotrialkoxysilane compound. 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" means a functional group capable of reacting with a certain specific functional group, and the term "functional group" means a group that is not reactive with any specific reactive group but can show reactivity with other reactive groups. Accordingly, the term “epoxy-reactive group” means a functional group capable of reacting with an epoxy group, and may mean, for example, a hydroxyl group, an amino group, a carboxyl group, or a thiol group.

In the present invention, the (c) organosilsesquioxane-hybridized linear organopolysiloxane is an organosilsesquioxane and a linear organopolysiloxane connected by an ether, amino, ester or thioether bond, for example , It can be represented by Formula 1 below.

In Formula 1,

R ¹ independently represents 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, and 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 independently represent a divalent hydrocarbon group, such as a straight-chain or branched-chain C ₁ -C ₁₂ alkylene group or a C ₆ -C ₁₂ arylene group;

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

Y represents a residue derived from organosilsesquioxane 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, the ratio of which is not particularly limited, but the epoxy reactive group It may be used in an amount of 0.05 to 0.25 mol, preferably 0.08 to 0.22 mol, more preferably 0.1 to 0.2 mol of the epoxy reactive group-containing organodialkoxysilane relative to 1 mol of the non-containing organodialkoxysilane precursor. The weight average molecular weight of the linear organopolysiloxane can be selected, for example, in the range of 1,000 to 400,000, preferably in the range of 2,000 to 300,000. When applied to substrates such as fibers, 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 in the case of forming a hard coating on the surface of metal or the like, 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 to 200,000. The epoxy reactive group may be one or more 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 epoxy groups or have poor reactivity. Specifically, the amount of the epoxy reactive group-containing organodialkoxysilane is 0.05 to 0.25 moles, preferably 0.08 to 0.22 moles, more preferably 0.1 to 0.2 moles, relative to 1 mole of the epoxy reactive group-free organodialkoxysilane. can be used as An organodialkoxysilane having another functional group that does not react with an epoxy group (eg, an acryl group, a vinyl group, a ureido group, an epoxy group, etc.) can be used in an amount of 0 to 0.1 mole, preferably 0.01 to 0.1 mole.

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

In Formula 2, R ¹ , R ² , R ³ , R ⁴ , X, p, q, r and s represent 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-aminopropylmethyldieter Toxysilane, O-[(meth)acryloxyethyl]-N-(methyldiethoxysilylpropyl)urethane, γ-glycidoxypropylmethyldiethoxysilane, β-(3,4-epoxycyclohexyl)ethylmethyldimethyne 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-methylaminopropylmethyldimethoxysilane Toxysilane, N-phenylγ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminomethylmethyldiethoxysilane, (cyclohexylaminomethyl)methyldiethoxysilane, N-cyclohexylaminopropylmethyldimethoxysilane, Bis(2-hydroxyethyl)-3-aminopropylmethyldiethoxysilane, diethylaminomethylmethyldiethoxysilane, diethylaminopropylmethyldimethoxysilane, dimethylaminopropylmethyldimethoxysilane, N-3-methyldimethoxysilane 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-mercaptopropylmethyldimethyne Toxysilane, γ-mercaptopropylmethyldiethoxysilane, isocyanatopropylmethyldimethoxysilane, isocyanatopropylmethyldiethoxysilane, isocyanatoethylmethyldiethoxysilane, isocyanatomethylmethyldiethoxysilane, carboxy Ethylmethylsilanediol sodium salt, N-(methyldimethoxysilylpropyl)ethylenediaminetriacetic acid trisodium salt, 3-(methyldihydroxysilyl)-1-propanesulfonic acid, diethylphosphateethylmethyldiethoxysilane, 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) Silylpropyl)-2-hydroxypropoxy]polyethylene oxide, bis[N,N'-(methyldiethoxysilylpropyl)aminocarbonyl]polyethyleneoxide, bis(methyldiethoxysilylpropyl)polyethyleneoxide may be mentioned. .

Among the organodialkoxysilane compounds described above, reactive group-containing organodialkoxysilanes, reactive group-free organodialkoxysilanes, epoxy group-containing organodialkoxysilanes and/or epoxy group-containing organodialkoxysilanes are selected as necessary. and can be used.

In the present invention, organosilsesquioxane may have various structures depending on the preparation method, reaction conditions, and monomer ratio, and, 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 ) , 10-mer (T ₁₀ ) and 12-mer (T ₁₂ ) may be represented.

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

In Formula 3,

Each R 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.), and the substituent may be selected from the group consisting of halogen, hydroxy, amino, mercapto, epoxy, isocyanato, (meth)acryl or vinyl.

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

Examples of the epoxy group-containing or epoxy group-free organotrialkoxysilane precursor include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, and n-propyltriene. 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, vinyltributoxyl 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 -Aminundecyltriethoxysilane, m-aminophenyltrimethoxysilane, p-aminophenyltrimethoxysilane, 3-aminopropyltris (methoxyethoxysilane) 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, carboxyethylsilanetriol sodium salt, N-(trimethoxysilylpropyl)ethylenedia Mineral triacetic acid trisodium salt, 3-(trihydroxysilyl)-1-propanesulfonic acid, diethyl phosphate 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'-(triethoxysilylpropyl) propyl) aminocarbonyl] polyethylene oxide, bis(triethoxysilylpropyl) polyethylene oxide and mixtures thereof. However, it is preferable that the organotrialkoxysilane precursor does not have a functional group (eg, amino, hydroxy, mercapto, isocyanato, etc.) capable of reacting with an epoxy group.

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

In the present invention, the cloudiness improving agent (d) may be selected from N-polyoxyalkylenated fatty acid amides or O-alkylated polyglucosides, specifically, N-polyoxyalkylenated fatty acid amides of the following formula 4, 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 acid, 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 present invention, (f) lotus leaf powder can be prepared by collecting and washing lotus leaves, first removing thick leaf veins, and then drying and grinding the remaining soft parts. If necessary, the leaf veins and soft parts may be separated by wet grinding and/or ultrasonic grinding, and the soft parts may be dried and ground. The drying is preferably carried out to the extent that the powder does not agglomerate, for example, the moisture content may be 3% by weight or less, preferably 1% by weight or less, more preferably 0.5% by weight or less. The dried lotus leaf is ground to have a particle size of about 500 microns or less, preferably about 300 microns or less, more preferably about 200 microns or less, and an average particle size of 0.1 to 300 microns, preferably 1 to 200 microns It is best to crush it as much as possible.

In the surface treatment composition according to the present invention, the composition ratio of the components is not strictly limited, but preferably, (c) organosilsesquioxane-hybridized linear organopolysiloxane 100 parts by weight, (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 cloudiness improving agent, (e) 5 to 20 parts by weight of a silicone-based crosslinking agent, and (f) lotus leaf 1 to 25 parts by weight of powder (based on dry weight), preferably 2 to 20 parts by weight, more preferably 3 to 15 parts by weight. When the surface to be treated does not have a surface reactive group such as a metal, 10 to 100 parts by weight of linear organopolysiloxane may be additionally added, and when a surface hydroxyl group exists, such as an inorganic material, the amount of linear organopolysiloxane 10 to 100 parts by weight of organosilsesquioxane may be additionally added.

The surface treatment composition according to the present invention may be prepared in a two-component type, and, for example, an acidic catalyst and components unreactive to the acidic catalyst may be separately provided.

A second object of the present invention is to provide a method for producing an environmentally friendly superhydrophobic surface treatment composition using lotus leaves comprising the following steps:

(Step 1) From a mixture of an organodialkoxysilane precursor containing an epoxy reactive group and an organodialkoxysilane precursor without an epoxy reactive group, (a) preparing a linear organopolysiloxane;

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

(Step 3) mixing the (a) linear organopolysiloxane, (b) organosilsesquioxane, (d) cloudability improving agent, (e) silicone-based crosslinking agent, and (f) lotus leaf powder;

(Step 4) Heating the mixture resulting from step 3 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, (g) adding an acidic 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-described monomers. For example, the following silane precursors:

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

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

- As dialkyldialkoxysilanes containing an epoxy reactive group, γ-hydroxypropylmethyldiethoxysilane, 4-hydroxybutylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, 4-aminobutylmethyldiethoxysilane or 0.05 to 0.25 mol of mixtures thereof;

A linear organopolysiloxane sol may 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.

Preferably, the linear organopolysiloxane sol described above has a viscosity of 700 to 1500 cps. If the viscosity is less than 700cps, it is not possible to form a hybrid organopolysiloxane sol having a desired molecular weight, and thus the durability of the three-dimensional network structure of the organopolysilonic acid crosslinked product may decrease, and the water repellency may also decrease due to a decrease in density. . If the viscosity exceeds 1500cps, the texture of the coated surface is significantly lowered, and in the case of water-repellent coating on permeable articles such as fibers or fabrics, their flexibility is lowered, resulting in very poor tactile feel and drapability of the fabric. There are problems that can get worse.

In step 2 of the present invention, organosilsesquioxane may be prepared according to a method commonly known in the art by selecting the type and composition of the above-described monomers. For example, a 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 organosyl Sesquioxanes can be prepared, which patent documents are incorporated herein by reference.

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

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

In step 4 of the present invention, 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. At this time, it is preferable to adjust the reaction so that both (a) linear organopolysiloxane and (b) organosilsesquioxane do not react and some remain unreacted, and the ratio of unreacted precursors is 50% or less, It is preferably 40% or less, more preferably 30% or less, and can be specifically selected from 10 to 30%. When the amount of the unreacted precursor is less than the above range due to excessive progress of the reaction, it may be additionally added or supplemented up to an amount within the above range.

In step 4, the (d) cloudability improving agent, (e) silicone-based crosslinking agent, and (f) lotus leaf powder present in the reaction mixture do not substantially participate in the epoxy ring opening reaction, but the reaction product (c) organosilses. The quioxane-hybridized linear organopolysiloxane not only forms a mixed sol with the cloudability improver and (e) silicone-based crosslinking agent, but also the mixed sol thus formed is physically closely linked to (f) lotus leaf powder, This is understood to be the basis for improving bonding strength and bonding durability when the surface treatment composition is applied to the target article.

On the other hand, after step 4 is completed, (a) linear organopolysiloxane and (b) organosilsesquioxane may be further added to the reaction mixture to increase the proportion of unreacted precursors, but in order to obtain a homogeneous reaction mixture For this, vigorous stirring is required, and vigorous stirring may disturb the intimate mixing state of the various components formed in the reaction mixture, which may be rather undesirable.

In step 5 of the present invention, (g) an acidic catalyst may be added to the reaction mixture resulting from step 4 above. As the acidic catalyst that can be used, inorganic or organic acids such as hydrochloric acid, acetic acid, nitric acid, sulfuric acid, phosphoric acid, or mixed acids thereof can be mentioned. The acidic 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. there is.

In the present invention, the acidic catalyst can act as a gelling catalyst and/or a pH adjusting agent, and can be used in Steps 1 and 2 as well as Step 5. 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 within minutes to days.

Meanwhile, the acidic catalyst may be used in an amount of 0.001 to 10 parts by weight, preferably 0.005 to 5 parts by weight, and more preferably 0.01 to 1 part by weight, based on 100 parts by weight of the precursor used in Steps 1 and 2. When it is within the above range, it is possible to control the speed and particle size of the sol-gel reaction to an appropriate level, and also to prevent cloudiness or precipitation of the composition.

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

In the present invention, the lotus leaf powder is characterized in that it is complexed twice with the organosilicon component and the cloudiness improving component including organopolysiloxane.

That is, in step 4, a ring-opening reaction is performed in the presence of (d) a cloudiness improving agent, (e) a silicone-based crosslinking agent, and (f) lotus leaf powder to prepare (c) organosilsesquioxane-hybridized linear organopolysiloxane. By doing so, (c) organosilsesquioxane-hybridized linear organopolysiloxane and (f) lotus leaf powder are characterized in that they are primarily complexed.

Also in step 5, by performing a gelation reaction in the presence of (d) a cloudiness improver and (f) lotus leaf powder, (c) organosilsesquioxane-hybridized linear organopolysiloxane and (f) lotus leaf powder (e ) characterized in that it is secondarily complexed by a silicone-based crosslinking agent.

In the present invention, the lotus leaf powder is physically/chemically closely bonded to the organosilicon component and the cloudiness improving component by the above-described primary and secondary compounding, so that it can exhibit excellent bonding, durability and water repellency.

A third object of the present invention is to provide an article surface-treated with a surface treatment composition containing the organosilsesquioxane-hybridized linear organopolysiloxane described above. There is no particular limitation on 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 and the surface treatment method using the same according to the present invention is that organosilsesquioxane and linear organopolysiloxane, particularly organosilsesquioxane, are used, and the surface treatment composition containing them has very high It has surface hardness, excellent transparency, scratch resistance, water repellency, antifouling, fingerprint resistance, heat stability and gloss characteristics, excellent adhesion to metal, inorganic 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 have water repellency, oil repellency and/or cloudiness, especially for fibrous materials such as natural fibers, synthetic fibers, or woven fabrics, nonwoven fabrics, knitted fabrics, etc. made of natural fibers, synthetic fibers, or carbon fibers. can be granted

Another advantage of the surface treatment composition and the surface treatment method using the same according to the present invention is that it contains an organosilsesquioxane-hybridized linear organopolysiloxane, so that the characteristics of the organosilsesquioxane can be sufficiently expressed, Separation of organosilsesquioxane is prevented, adhesion to the treated surface can be further improved, and the above-mentioned advantages (sufficient expression of properties, prevention of detachment, 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 intended 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 may be appropriately modified or 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 ( 9.6 g (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 heated to 60 °C while maintaining pH 5.0±0.2 with acetic acid. It was stirred for 2 hours at °C. 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 Registration No. 10-1249798, an epoxy group-containing organosilsesquioxane was prepared as follows.

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

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

c) A water-containing solution was prepared by dissolving potassium carbonate (0.2 g) as a catalyst in prepared distilled water in advance and uniformly stirring with tetrahydrofuran for 20 minutes.

d) When propyltrimethoxysilane (0.4mol) and glycidylpropyltrimethoxysilane (0.06mol) were added dropwise to the hydrous solution and stirred, and the increase in molecular weight stopped by GPC measurement and the molecular weight was maintained for 10 hours or longer The reaction was terminated. Total reaction time was approximately 70 hours. Purification was performed by fractional distillation using an organic solvent (eg, chloroform, methylene chloride, toluene, xylene, etc.) capable of dissolving polysilsesquioxane-based materials among water-immiscible organic solvents.

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

Preparation Example 3: Preparation of lotus leaf powder

Dried lotus leaf powder was prepared with reference to Korean Patent Registration No. 10-1323146.

Fresh lotus leaves were collected together with the stems, dust on the lotus leaves was removed with water, the thick veins between the leaves were removed, and the remaining leaves were washed once again with distilled water and dried at room temperature (25 ° C). The dried leaves were pulverized with a blender, and only those pulverized smaller than 45 μm were collected using a sieve and dried for 24 hours at room temperature (25° C.) in a vacuum oven to prepare lotus leaf powder.

Example 1: Preparation of Organosilsesquioxane-Hybridized Linear Organopolysiloxanes

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, 0.2 g of alkyl polyglucoside (trade name: Milcoside 100; manufacturer: LG Household & Health Care), 1.5 g of N-polyoxyethylene cocamide (trade name: NINOL 1301; manufacturer: Stepan), 0.2 g of tetraethoxysilane, and 1 g of lotus leaf powder obtained in Preparation Example 3 were added and homogenized by vigorous stirring, followed by epoxy ring opening reaction A catalyst was added followed by reaction at approximately 70° C. for 2 hours to prepare an organosilsesquioxane-hybridized linear organopolysiloxane.

Example 2: Preparation of Organosilsesquioxane-Hybridized Linear Organopolysiloxanes

Instead of the organosilsesquioxane obtained in Preparation Example 2, epoxy group-containing organosilsesquioxane (mw 931.63) of the following formula 8 (Sigma-Aldrich) 0.5g 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% by weight to the reaction mixture obtained in Examples 1 and 2, and used as a surface treatment composition.

The surface treatment composition was applied to polypropylene nonwoven fabric, carbon fiber woven fabric and cotton fabric in an amount of 0.1 g/m ² , respectively, and dried to impart superhydrophobic surface properties.

The surface-treated polypropylene nonwoven fabric, carbon fiber woven fabric, and cotton fabric exhibited excellent water repellency and rolling properties, and had excellent durability against washing.

Although specific embodiments according to the present invention have been described so far, it is obvious that various modifications are possible within the limits that do not deviate from the scope of the present invention.

Therefore, the scope of the present invention should not be limited to the described embodiments and should not be defined, and should be defined by not only the claims to be described later, but also those equivalent to these claims.

That is, it should be understood that the above-described embodiments are 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 and All changes or modified forms derived from the equivalent concept 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 rolling improver selected from N-polyoxyalkylenated fatty acid amides or O-alkylated polyglucosides;
(e) a silicone-based crosslinking agent selected from tetraalkoxysilane or tetraaryloxysilane; and
(f) lotus leaf powder;
(g) an acidic catalyst selected from organic or inorganic acids; and
(h) an aqueous solvent;
Eco-friendly super-hydrophobic surface treatment composition using lotus leaf.
According to claim 1,
The (a) organosilsesquioxane,
Characterized in that it is prepared from a mixture containing 80 to 90 mol% of an epoxy group-free organotrialkoxysilane compound and 10 to 20 mol% of an epoxy group-containing organotrialkoxysilane compound,
Eco-friendly super-hydrophobic surface treatment composition using lotus leaf.
According to claim 1,
The (a) organosilsesquioxane,
Characterized in that it is selected from organosilsesquioxanes having a cage structure of the following formula (3),
Eco-friendly super-hydrophobic surface treatment composition using lotus leaf.
[Formula 3]

In Formula 3,
Each R independently represents a monovalent hydrocarbon group which may have a substituent, and the monovalent hydrocarbon group is any selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, octyl, cyclohexyl, and cycloheptyl. one C _1-12 alkyl group or cycloalkyl group; any one C _6-12 aryl selected from the group consisting of phenyl, tolyl, and naphthyl; Or any one C _7-12 alkylaryl group selected from the group consisting of benzyl, phenethyl, and propylphenyl, and the substituent is halogen, hydroxy, amino, mercapto, epoxy, isocyanato, (meth) acryl And it may be any one selected from the group consisting of vinyl.
According to claim 1,
The (b) linear organopolysiloxane,
Characterized in that it is prepared from a mixture containing 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,
Eco-friendly super-hydrophobic surface treatment composition using lotus leaf.
According to claim 1,
The (c) organosilsesquioxane-hybridized linear organopolysiloxane is characterized in that represented by the following formula (1),
Eco-friendly super-hydrophobic surface treatment composition using lotus leaf:
[Formula 1]

In Formula 1,
R ¹ independently represents 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, and 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 represent an independent divalent hydrocarbon group, and the divalent hydrocarbon group is a straight-chain or branched-chain C _1- C ₁₂ alkylene group or a C _6- C ₁₂ arylene group;
X represents -0-, -NH-, -CO ₂ - or -S-;
Y represents a residue derived from an organosilsesquioxane represented by the general formula (R ² SiO _1.5 ) _n , wherein n represents a number greater than or equal to 1;
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.
According to claim 1,
Characterized in that the (d) cloudiness improver is selected from N-polyoxyalkylenated fatty acid amides of the following formula 4, O-alkylated polyglucosides of the following formula 5, or mixtures thereof,
Eco-friendly super-hydrophobic surface treatment composition using lotus leaf.
[Formula 4]

In Formula 4,
R represents a substituted or unsubstituted alkyl group having 8 to 36 carbon atoms,
(A0) _n represents polyoxyethylene, polyoxypropylene or polyoxyethylene/polyoxypropylene block copolymer;
Said n represents the number of 3-20.
[Formula 5]

In Formula 5,
R represents a substituted or unsubstituted alkyl group having 8 to 36 carbon atoms,
Said y represents the number of 0-6.
According to 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,
Eco-friendly super-hydrophobic surface treatment composition using lotus leaf.
According to claim 1,
Based on 100 parts by weight of (c) organosilsesquioxane-hybridized linear organopolysiloxane, (a) 10 to 100 parts by weight of organosilsesquioxane, (b) 10 to 100 parts by weight of linear organopolysiloxane, ( d) 0.01 to 5 parts by weight of a cloudiness improving agent, (e) 5 to 20 parts by weight of a silicone-based crosslinking agent, and (f) 2 to 20 parts by weight of lotus leaf powder,
Eco-friendly super-hydrophobic surface treatment composition using lotus leaf.
(Step 1) From a mixture of an organodialkoxysilane precursor containing an epoxy reactive group and an organodialkoxysilane precursor without an epoxy reactive group, (a) preparing a linear organopolysiloxane;
(Step 2) preparing organosilsesquioxane from a mixture of an epoxy group-containing organotrialkoxysilane precursor and an epoxy group-free organotrialkoxysilane precursor;
(Step 3) mixing the (a) linear organopolysiloxane, (b) organosilsesquioxane, (d) cloudiness improving agent, (e) silicone-based crosslinking agent and (f) lotus leaf powder;
(Step 4) heating the resulting mixture in step 3 to prepare a composite of (c) organosilsesquioxane-hybridized linear organopolysiloxane and (f) lotus leaf powder; and
(Step 5) To the reaction mixture resulting from step 4, (g) adding an acidic catalyst;
Manufacturing method of eco-friendly super-hydrophobic surface treatment composition using lotus leaf.
An article surface-treated with the eco-friendly super-hydrophobic surface treatment composition using the lotus leaf according to claim 1.

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