KR20180000238A - Copolymer and hydrophilic coating composition comprising the same - Google Patents

Abstract

The present invention relates to a (co)polymer and a hydrophilic coating composition comprising the same, and More specifically, the present invention relates to a (co)polymer which comprises a repeating unit derived from a (meth)acrylate-based or (meth)acrylamide-based unsaturated monomer having a zwitter ion group in a side chain thereof and having a polyfunctional silane group at a terminal thereof. The present invention also relates to a hydrophilic coating composition comprising the same.

Description

(COPOLYMER AND HYDROPHILIC COATING COMPOSITION COMPRISING THE SAME)

TECHNICAL FIELD The present invention relates to a (co) polymer and a hydrophilic coating composition comprising the same. More particularly, the present invention relates to a (co) polymer having a zwitter ion group in its side chain and a (meth) acrylate or (Co) polymer comprising a repeating unit derived from an unsaturated monomer and containing a polyfunctional silane group at the terminal thereof, and a hydrophilic coating composition comprising the same.

As a method for preventing solid surface contamination such as glass, metal, fiber, etc., hydrophobic surface treatment and hydrophilic surface treatment method for facilitating water repellency are known.

The hydrophobic surface treatment is a method for preventing the water-soluble contaminants from adhering easily by performing surface treatment so as to have water repellency on the solid surface of glass, metal, fiber or the like.

For example, there is a method in which clothing is washed, treated with a softening agent, or sprayed with a water repellent agent to impart a waterproof effect, and a method in which wax is coated on a painted surface of an automobile to impart water repellency.

However, in this method, there is a problem that it is difficult to completely treat the surface of the solid body by hydrophobic, and when the water-soluble contaminant is repeatedly contacted, it is difficult to accumulate on the solid surface .

On the other hand, a method of preventing contamination by hydrophilic surface treatment is to make contact with water or a water-soluble substance easier by lowering the contact angle with respect to water on the solid surface. Even if contaminants adhere to the solid surface after the treatment, It can be easily removed at the time of cleaning using.

In addition, it is possible to prevent the occurrence of fogging or weathering on the surfaces of glass, mirrors, transparent plastics, etc., and it is also possible to obtain a surface antistatic effect.

Examples of such a hydrophilic surface treatment method include a method of treating with a composition containing a positive polymer electrolyte and a method of treating with a composition containing a surfactant and a polymer material having a specific structure of amphoteric ions .

However, such a composition has high hydrophilicity, and it is difficult to secure excellent adhesion on a substrate requiring coating, such as glass, metal, and plastic.

Therefore, there is a need for research on a method capable of imparting hydrophilicity for preventing contamination to the surface of a base material while realizing excellent adhesion to the surface of the base material.

The present invention provides a (co) polymer capable of imparting hydrophilicity to the surface of a base material such as glass, plastic or the like for preventing contamination, and capable of realizing excellent adhesion to a substrate, and a hydrophilic coating composition containing the same.

The present invention relates to a resin composition comprising a repeating unit derived from a (meth) acrylate-based unsaturated monomer or a (meth) acrylamide-based unsaturated monomer having an amphoteric ion group in a side chain thereof; And a (co) polymer comprising a multifunctional silane group at the end.

In this case, the repeating unit may be represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

R1 is hydrogen, deuterium, or a hydrocarbyl group having 1 to 10 carbon atoms,

X1 is oxygen or a divalent amine group (-NR3-), R3 is hydrogen, deuterium, or a hydrocarbyl group having 1 to 10 carbon atoms,

R2 is a zwitter ion group.

The amphoteric ion group may be represented by the following general formula (1-1).

[Formula 1-1]

In Formula 1-1,

R 21 and R 22 are each independently a hydrocarbyl group having 1 to 10 carbon atoms,

 (AA) and (BB) are, independently of each other, the same or different, a hydrocarbylene having 1 to 10 carbon atoms.

According to one embodiment of the present invention, the polyfunctional silane group at the (co) polymer end may be represented by the following formula (2). The silane group of the following formula (2) may be introduced by a silane chain exchanger containing a mercapto group, and this silane chain exchanger may be introduced as a chain exchange reagent to control the molecular weight of the (co) Co-polymer) with a specific type of polyfunctional silane group.

(2)

In Formula 2,

S is a sulfur atom, N is a nitrogen atom, Si is a silicon atom,

R40 to R42 each independently represent the same or different hydrocarbylene having 1 to 10 carbon atoms,

R43 to R48 each independently represent hydrogen, deuterium, a hydroxy group, a hydrocarbyl group having 1 to 10 carbon atoms, or a hydrocarbyl group.

And, the weight average molecular weight of the copolymer may be about 50,000 g / mol to about 800,000 g / mol.

The present invention also provides a hydrophilic coating composition comprising the (co) polymer.

Such a hydrophilic coating composition may further comprise a surfactant and a polyvalent organic acid.

According to one embodiment of the invention, the hydrophilic coating composition may have a pH of about 1.0 to about 7.0.

And, according to another embodiment, the hydrophilic coating composition may have a stationary contact angle with respect to water when coated on a glass substrate surface of less than about 15 degrees.

The hydrophilic coating composition of the present invention can impart hydrophilicity to the surface of a substrate such as glass, metal and plastic by a (co) polymer having a cation and an anion together, effectively preventing surface contamination, The polyfunctional silane group can provide excellent adhesion to the surface of the substrate.

The terminology used herein is for the purpose of describing exemplary embodiments only and is not intended to be limiting of the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, the terms "comprising," "comprising," or "having ", and the like are intended to specify the presence of stated features, But do not preclude the presence or addition of one or more other features, integers, steps, components, or combinations thereof.

Also in the present invention, when referring to each layer or element being "on" or "on" each layer or element, it is meant that each layer or element is formed directly on each layer or element, Layer or element may be additionally formed between each layer, the object, and the substrate.

While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings and will herein be described in detail. It should be understood, however, that the invention is not intended to be limited to the particular forms disclosed, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.

Throughout the specification, the hydrocarbyl group means a monovalent functional group formed by removing one hydrogen from a linear or branched aliphatic or aromatic hydrocarbon.

The hydrocarbylene means a divalent functional group formed by removing two hydrogen atoms from a linear or branched aliphatic or aromatic hydrocarbon.

Further, (meth) acrylamido means a form in which, in the acrylamide group, the carbonyl alpha carbon is substituted with various hydrocarbyl groups as well as hydrogen or a methyl group.

The (co) polymer includes both a (co) polymer formed by a single monomer and a copolymer formed by polymerization of two or more different monomers.

Hereinafter, the present invention will be described in more detail.

The (co) polymer according to one aspect of the present invention includes a repeating unit derived from a (meth) acrylate-based or (meth) acrylamide-based unsaturated monomer having a zwitter ion group in its side chain , And a polyfunctional silane group at the end.

In the case of the known hydrophilic surface treatment method known in the art, when a polymer substance including a hydrophilic moiety is applied to the surface of a base material, it is difficult to maintain the surface characteristics by dissolving in water, and even when a photocatalyst on a particle is introduced, It is easily peeled off by an external force.

Further, even if a method of introducing a functional group into the end of the hydrophilic polymer material is used in order to secure the adhering force, it is often impossible to introduce the hydrophilic polymer material or terminal functional group depending on the characteristics thereof, and the molecular weight distribution of the polymer to be polymerized is wide, It is difficult to ensure sufficient surface stability on the surface of the substrate.

Another (co) polymer in one aspect of the present invention includes a repeating unit derived from a (meth) acrylate-based or (meth) acrylamide-based unsaturated monomer containing an zwitterion group in the side chain .

(Meth) acrylamide-based unsaturated monomer constitutes a repeating unit to form a main chain of the (co) polymer, and the side chain of each repeating unit is bonded to the side chain through an ester bond or an amide bond, Means a form in which an ionic group is connected.

The (co) polymer according to one aspect of the present invention has a partial charge in many portions due to the amphoteric ion group contained in the side chain in this form, and these partial charges impart hydrophilicity to superhydrophilicity . Therefore, when such (co) polymer is applied onto a substrate, it becomes possible to provide a hydrophilic to superhydrophilic surface.

And, at the end of such (co) polymer, polyfunctional silane group is included. Such a polyfunctional silane group may form a silane bond or a silanol bond with the substrate surface when the (co) polymer is applied onto the substrate. By such bonding, the (co) polymer can secure an excellent adhesion to various organic or inorganic substrate surfaces.

According to one example, the repeating unit contained in the (co) polymer may be represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

R1 is hydrogen, deuterium, or a hydrocarbyl group having 1 to 10 carbon atoms,

X1 is oxygen or a divalent amine group (-NR3-), R3 is hydrogen, deuterium, or a hydrocarbyl group having 1 to 10 carbon atoms,

R2 is a zwitter ion group.

R1 is a functional group bonded to the carbonyl alpha carbon of acrylamide, which is hydrogen, deuterium, or a hydrocarbyl group having 1 to 10 carbon atoms, preferably hydrogen or a straight or branched alkyl group having 1 to 10 carbon atoms.

The R2 is a zwitter ion group for imparting hydrophilicity to the (co) polymer of the present invention. The cation and the anion may be adjacent to each other (ylide group) and may be separated from each other betaine group, in terms of improving the hydrophilicity of the (co) polymer, the form of betaine spaced apart from one another may be more advantageous.

According to an embodiment of the present invention, the amphoteric ion group may be represented by the following general formula (1-1).

[Formula 1-1]

In Formula 1-1,

R 21 and R 22 are each independently a hydrocarbyl group having 1 to 10 carbon atoms,

 (AA) and (BB) are, independently of each other, the same or different, a hydrocarbylene having 1 to 10 carbon atoms.

That is, the amphoteric ion included in the (co) polymer of the present invention may be in the form of ammonium-sulfonate betaine.

In particular, R21 and R22 each represent a functional group bonded to nitrogen of ammonium, and may be a hydrocarbyl group having 1 to 10 carbon atoms. In order to improve the hydrophilicity, the alkyl group having 1 to 3 carbon atoms , It may be desirable that the nitrogen atom be in the form of quaternary ammonium.

(AA) and (BB) may be hydrocarbylene having 1 to 10 carbon atoms, which may be the same or different and each independently represent a hydrophilic property improving side, a stability of the polymer, and From the viewpoint of ease of polymer formation, alkylene having 1 to 5 carbon atoms or arylene having 6 to 10 carbon atoms may be more preferable.

According to another embodiment of the present invention, the polyfunctional silane group at the (polymer) terminal of the (co) polymer may be represented by the following formula (2). The silane group of the following formula (2) can be introduced by a silane chain exchange agent containing a mercapto group. The silane chain exchange agent is introduced into a chain transfer agent, and the molecular weight of the (co) And may serve to attach a terminal silane group of a specific type of the (co) polymer.

(2)

In Formula 2,

S is a sulfur atom, N is a nitrogen atom, Si is a silicon atom,

R40 to R42 each independently represent the same or different hydrocarbylene having 1 to 10 carbon atoms,

R43 to R48 each independently represent hydrogen, deuterium, a hydroxy group, a hydrocarbyl group having 1 to 10 carbon atoms, or a hydrocarbyl group.

The (co) polymer according to one example of the present invention may have a weight average molecular weight of about 50,000 g / mol to about 800,000 g / mol, which may be advantageous in terms of improvement in hydrophilicity and adhesion to a substrate.

On the other hand, the (co) polymer may be a (meth) acrylate-based or (meth) acrylamide-based unsaturated monomer having a zwitter ion group in its side chain; And polymerizing the silane chain exchanger in the presence of an initiator. For example, the following will be described in detail.

First, the (meth) acrylamide-based unsaturated monomer and the silane chain exchanger are added to a reactor equipped with a nitrogen supplier, a condenser, a stirrer, etc., and stirred for about 10 minutes to about 120 minutes in a solution state, Is uniformly mixed.

The initiator is added thereto and stirred for about 1 hour to about 5 hours under a nitrogen atmosphere to remove oxygen in the reactor. At this time, a complex or a salt capable of maintaining the charge balance may be further added to improve the solubility of the (meth) acrylamide-based unsaturated monomer.

The polymerization reaction can be carried out for about 2 hours to about 8 hours while the inside temperature of the reactor is raised to about 50 ° C to about 90 ° C, and as a result, the above-mentioned (co) polymer can be obtained as a solution mixture .

At this time, the unsaturated monomer is for forming a (meth) acrylamide-based repeating unit containing an amphoteric ion group in the (co) polymer described above, and specifically can be represented by the following formula (1a).

[Formula 1a]

In formula (1a)

R1 is hydrogen, deuterium, or a hydrocarbyl group having 1 to 10 carbon atoms,

X1 is a divalent amine group (-NR3-), R3 is hydrogen, deuterium, or a hydrocarbyl group having 1 to 10 carbon atoms,

R2 is a zwitter ion group.

It is to be noted that the amphoteric ion group can be represented by the following formula (1-1).

[Formula 1-1]

In the above formula (1a-1)

R 21 and R 22 are each independently a hydrocarbyl group having 1 to 10 carbon atoms,

 (AA) and (BB) are, independently of each other, the same or different, a hydrocarbylene having 1 to 10 carbon atoms.

On the other hand, the present invention provides a hydrophilic coating composition comprising the (co) polymer.

According to one example, the hydrophilic coating composition may further include a surfactant and a polyvalent organic acid, and may include one or more (co) polymers.

And, the (co) polymer may be contained at about 1 wt% or more, more preferably about 5 wt% to about 30 wt%, based on the total weight of the hydrophilic coating composition. When the (co) polymer is contained in an amount less than the above range, it may be difficult to impart sufficient hydrophilicity to the target substrate, and if it exceeds the above range, the viscosity becomes high and it becomes difficult to produce a uniform composition, The hydrophilic property may be lowered.

The surfactant can further improve the hydrophilicity of the composition and facilitate the application to the substrate surface. When a surfactant is included, the hydrophilic coating composition can be easily dispersed on the solid surface, thereby making it possible to achieve uniform coating and further improve the hydrophilicity. In particular, hydrophobic contaminants are present on the target substrate surface , The contaminants can be easily removed by the surfactant, so that the hydrophilicity can be further improved.

Such a surfactant may be from about 0.01 wt% to about 1 wt%, more preferably from about 0.05 wt% to about 0.5 wt%, based on the total weight of the hydrophilic coating composition.

As the surfactant, a surfactant generally used in a liquid detergent can be used without particular limitation, and an anionic surfactant, a nonionic surfactant, a cationic surfactant, and a positive surfactant can be used.

As the anionic surfactant, one or two or more selected from a sulfuric acid ester salt, a sulfonic acid salt, a carboxylate salt, a phosphoric acid ester salt, and an amino acid salt may be preferably used.

Specific examples thereof include sulfuric acid ester salts such as alkyl sulfate, alkenyl sulfate, polyoxyalkylene alkyl ether sulfate, polyoxyalkylene alkenyl ether sulfate, and polyoxyalkylene alkyl phenyl ether sulfate;

Sulfonic acid salts such as sulfo succinic acid alkyl ester salts, polyoxyalkylene sulfosuccinic acid alkyl ester salts, alkane sulfonic acid salts, internal olefin sulfonic acid salts, acyl isethionate and acylmethyl taurate;

Carboxylic acid salts such as higher fatty acid salts and polyoxyalkylene alkyl ether acetate having 8 to 16 carbon atoms;

Phosphoric acid ester salts such as alkyl phosphates and polyoxyalkylene alkyl ether phosphates;

Acyl glutamate, alanine derivatives, glycine derivatives, arginine derivatives and the like.

Particularly, in order to improve the hydrophilicity, polyoxyethylene alkyl ether sulfate or higher fatty acid salt may be more preferable.

Examples of the nonionic surfactant include polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbit fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyoxyethylene fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, poly A polyethylene glycol type nonionic surfactant such as an oxyalkylene (hardened) castor oil and a polyhydric alcohol type nonionic surfactant such as a sucrose fatty acid ester, a polyglycerin alkyl ether, a polyglycerin fatty acid ester, an alkyl glucoside, and a fatty acid alkanolamide, .

In particular, polyoxyethylene alkyl ethers or alkyl glucosides may be more preferred.

Examples of the cationic surfactant include a quaternary ammonium salt, a pyridinium salt or a tertiary amine organic acid salt having a hydrocarbon group having 12 to 20 carbon atoms and containing an amide group, an ester group or an ether group.

Specific examples include trimethylammonium salts such as cetyltrimethylammonium salt, stearyltrimethylammonium salt and biphenyltrimethylammonium salt;

Long-chain alkyldimethylbenzylammonium salts such as stearyldimethylbenzylammonium salt;

Dialkyldimethylammonium salts such as distearyldimethylammonium salt and diisotetradecyldimethylammonium salt;

And mono long-chain alkyldimethylamine salts such as stearyldimethylamine, biphenyldimethylammonium, and acid salts of ocadadecyloxypropylmethylamine.

In particular, long-chain alkyldimethylbenzylammonium salts may be preferred.

Examples of the amphoteric surfactant include betaine surfactants such as imidazoline betaine, alkyldimethylaminoacetic acid betaine, fatty acid amidepropylbetaine and sulfobetaine, and amine oxide type surfactants such as alkyldimethylamine oxide. .

Particularly, fatty acid amide propyl betaine such as amidopropyl l, N, N-dimethyl-acetic acid betaine may be more preferable.

The hydrophilic coating composition may further include a polyvalent organic acid having two or more acidic groups such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group in the molecule.

For example, there may be mentioned oxalic acid, maleic acid, citric acid, adipic acid, sebacic acid, malic acid, EDTA, nitrilo-3-acetic acid, polyacrylic acid, polymethacrylic acid, Methylpropanesulfonic acid, polystyrenesulfonic acid, and the like.

Such a polyvalent organic acid may be contained in the form of a salt. Specifically, the polyvalent organic acid may be in the form of an alkali metal salt, an alkali rare earth metal salt, an ammonium salt, or an amine salt, and may be an alkali metal salt or an ammonium salt for improving hydrophilicity.

The hydrophilic coating composition of the present invention may contain a lower alcohol such as ethyl alcohol, isopropyl alcohol and the like; Solvents such as toluene sulfonate, xylene sulfonate and urea; Viscosity modifiers; Water insoluble abrasive; Humectants such as glycerin and sorbitol; Other pigments may be added.

Such a hydrophilic coating composition can be obtained by further adding to the above-mentioned (co) polymer and water, if necessary, the above-mentioned surfactant or other components such as polyvalent organic acid and the like, for example, homogenizer, ultrasonic disperser, Followed by stirring and mixing by the method described in "

The pH of the obtained hydrophilic coating composition may be preferably about 1.0 to about 7.0 from the viewpoints of handling safety, prevention of damage to the solid surface and improvement in hydrophilicity. To this end, the above-mentioned additives, pH adjusters, .

The hydrophilic coating composition of the present invention can impart hydrophilicity to the surface of the substrate by the following method. The substrate to be used is not particularly limited and can be applied to surfaces of glass, ceramics, ceramics, metals, polymer resins, natural fibers and the like. Particularly in glass, ceramics, A hydrophobic hard surface of at least 30 degrees is suitable.

The method of applying the hydrophilic coating composition is not particularly limited. For example, by immersing the target substrate in a hydrophilic coating composition, or spraying a hydrophilic coating composition onto the surface of the substrate. Preferably, the surface of the substrate is subjected to plasma treatment to lower the surface energy of the substrate surface, to improve the wetting of the coating liquid, to increase the reactivity of the silanol group or the hydroxyl group, to coat the coating composition, You can proceed.

The amount of application may vary depending on the properties of the substrate or the concentration of the hydrophilic coating composition, but may be applied, for example, from about 0.01 g to about 0.2 g per unit area of 10 cm ² , based on the (co) polymer weight .

When the hydrophilic coating composition of the present invention is coated on the surface of a glass substrate to impart hydrophilicity to the glass surface, the stationary contact angle with respect to water is less than about 15 degrees, preferably less than about 10 degrees, or from about 0.1 degrees to about 10 degrees .

By such hydrophilicity, it is possible to effectively prevent contamination of the surface of the substrate or effectively remove contaminants.

Best Mode for Carrying Out the Invention Hereinafter, the function and effect of the present invention will be described in more detail through specific examples of the present invention. It is to be understood, however, that these embodiments are merely illustrative of the invention and are not intended to limit the scope of the invention.

< Example >

Multifunctional Silane system  Chain exchange agent synthesis

[Preparation Example 1]

15.7 g of bis (3-triethyoxysilylpropyl) amine, 20 ml of toluene and 6 ml of ethylene sulfide were charged into a 100 ml reactor equipped with a stirrer, a condenser and a nitrogen gas introducing tube, and the reaction was carried out at 60 ° C for 24 hours with stirring.

The reactor temperature was lowered to room temperature, and the reaction solvent and residual ethylene sulfide were removed using a rotary evaporator.

And purified through column chromatography to synthesize a multifunctional silane-based chain exchange agent represented by the following formula.

_{^{1 H NMR (CDCl 3):}} 0.55 (4H, t, J = 8.0Hz), 1.47 (4H, m), 1.69 (1H, s), 2.35 (4, t, J = 7.6Hz), 2.49 (2H, t), 2.56 (2H, m), 3.54 (18H, s)

_{^{13 C NMR (CDCl 3):}} d = 6.6, 20.3, 22.9, 50.5, 56.8, 57.1

Copolymer polymerization

[Example 1]

20 g of [2- (Methacryloyloxy) ethyl] dimethyl- (3-sulfopropyl) ammonium hydroxide (inner salt) was added to a 500 ml reactor equipped with a stirrer, a condenser and a nitrogen gas introducing tube, , And 180 g of distilled water were added thereto, and the mixture was stirred for 30 minutes.

Thereafter, 0.17 g of sodium persulfate was added, and the mixture was stirred for 2 hours under a nitrogen atmosphere to remove oxygen in the reactor.

The temperature of the reactor was raised to 70 占 폚 in a nitrogen atmosphere and the reaction was carried out for 6 hours to obtain 200 g of a superhydrophilic polymer (co) polymer aqueous solution (polymer solid content: 10%).

Weight average molecular weight = 120,000 g / mol, PDI = 1.84 (measured by GPC at room temperature, 0.5 M NaCl (aq)

[Comparative Example 1]

20 g of [2- (Methacryloyloxy) ethyl] dimethyl- (3-sulfopropyl) ammonium hydroxide (inner salt), 0.04 g of (3-Mercaptopropyl) trimethoxysilane and 180 g of distilled water were placed in a 500 ml reactor equipped with a stirrer, And the mixture was stirred for 30 minutes.

Thereafter, 0.17 g of sodium persulfate was added, and the mixture was stirred for 2 hours under a nitrogen atmosphere to remove oxygen in the reactor.

The temperature of the reactor was raised to 70 占 폚 in a nitrogen atmosphere and the reaction was carried out for 6 hours to obtain 200 g of a superhydrophilic polymer (co) polymer aqueous solution (polymer solid content: 10%).

Weight average molecular weight = 130,000 g / mol, PDI = 1.71 (measured by GPC at room temperature, 0.5 M NaCl (aq)

Preparation of coating compositions

To 100 g of each superhydrophilic polymer solution obtained in the above example, 100 g of distilled water was added and stirred for 30 minutes to prepare a coating composition.

< Experimental Example >

Coating on glass substrates

Glass substrate: Glass for LCD 75 * 50 * 0.7mm, Manufacturer: SM Tech

The glass substrate surface was firstly washed with primary distilled water and immersed in a 2N NaOH aqueous solution for 10 minutes to activate the silanol groups on the glass substrate surface.

The surface of the glass substrate was washed with primary distilled water, and water was removed from the glass surface through an air blowing process.

The coating compositions prepared in the above Examples and Comparative Examples were sprayed so as to be applied in an amount of 0.1 mm ³ per 10 mm ² (width: 75 mm, length: 50 mm, 3.75 mm ³ ) After drying in the oven for 30 minutes, water was removed from the glass surface by washing with primary distilled water and air blowing to form a coating layer of less than about 10 nm.

Initial water Contact angle  Evaluation experiment

Water contact angles of the surfaces of the glass substrates of Examples and Comparative Examples which had undergone the coating process were measured using a contact angle meter.

Abrasion resistance evaluation experiment

The surfaces of the glass substrates of the examples and comparative examples that had undergone the coating process were rubbed 100 to 400 times with a cotton canvas (JIS L 3102. # 10) under a load of 500 g, and the water contact angle was again measured.

The above experimental results are summarized in Table 1 below.

Initial water contact angle
(Degree) After abrasion resistance evaluation
Water contact angle
(100 times, Degree) After abrasion resistance evaluation
Water contact angle
(200 times, Degree) After abrasion resistance evaluation
Water contact angle
(300 times, Degree) After abrasion resistance evaluation
Water contact angle
(400 times, Degree) Example 1 3.5 5.7 6.4 7.3 8.4 Comparative Example 1 3.4 5.7 7.6 11.2 16.2

Referring to Table 1, it can be confirmed that when the hydrophilic coating composition of the present application is applied on a glass substrate, the surface of the substrate is modified to have a superhydrophilic property.

Particularly, in the case of the comparative example, after the evaluation of abrasion resistance, the water contact angle becomes very large and the surface hydrophilicity is lowered. In contrast, in the case of the present embodiment, the water contact angle is about 10 &Lt; / RTI &gt;

That is, in the case of the hydrophilic coating composition of the present application, the adhesion to the surface of the substrate is very excellent and the abrasion resistance is also excellent, and it is expected that the hydrophilicity of the surface can be maintained for a long time, .

Claims (9)

A repeating unit derived from a (meth) acrylate-based unsaturated monomer or a (meth) acrylamide-based unsaturated monomer containing an amphoteric ion group in a side chain; And
(Co) polymer comprising a polyfunctional silane group at the end.
The method according to claim 1,
Wherein the repeating unit is represented by the following formula (1):
[Chemical Formula 1]

In Formula 1,
R1 is hydrogen, deuterium, or a hydrocarbyl group having 1 to 10 carbon atoms,
X1 is oxygen or a divalent amine group (-NR3-), R3 is hydrogen, deuterium, or a hydrocarbyl group having 1 to 10 carbon atoms,
R2 is a zwitter ion group.
3. The method of claim 2,
Wherein the amphoteric ion group is represented by the following formula (1-1): (co) polymer:
[Formula 1-1]

In Formula 1-1,
R 21 and R 22 are each independently a hydrocarbyl group having 1 to 10 carbon atoms,
(AA) and (BB) are, independently of each other, the same or different, a hydrocarbylene having 1 to 10 carbon atoms.
The method according to claim 1,
Wherein the polyfunctional silane group is a (co) polymer represented by the following formula (2):
(2)

In Formula 2,
S is a sulfur atom, N is a nitrogen atom, Si is a silicon atom,
R40 to R42 each independently represent the same or different hydrocarbylene having 1 to 10 carbon atoms,
R43 to R48 each independently represent hydrogen, deuterium, a hydroxy group, a hydrocarbyl group having 1 to 10 carbon atoms, or a hydrocarbyl group.
The method according to claim 1,
(Co) polymer having a weight average molecular weight of 50,000 to 800,000 g / mol.
A hydrophilic coating composition comprising a (co) polymer according to any one of claims 1 to 5.
The method according to claim 6,
&Lt; / RTI &gt; further comprising a surfactant and a polyvalent organic acid.
The method according to claim 6,
and a pH of 1.0 to 7.0.
The method according to claim 6,
Wherein the stationary contact angle to water when coated on the glass substrate surface is less than 15 degrees.