KR20050100091A - Silicone coating agent with improved antifouling property - Google Patents

Abstract

The present invention relates to a silicone coating agent having excellent antifouling properties, and more particularly, by preparing a coating agent using a certain amount of a methyl hydrogen silicone copolymer having a hydrogen group and a silicone having an alkoxy group, it is easily converted into a hydrophilic liquid during coating itself. The present invention relates to a silicone coating which has improved the antifouling property against aqueous contaminants on the porous tile surface by introducing a coating agent capable of simultaneously presenting both hydrophilic and hydrophobic groups in the coating film.

Description

Silicon coating agent with improved antifouling property}

The present invention relates to a silicone coating agent having excellent antifouling properties, and more particularly, by preparing a coating agent using a certain amount of a methyl hydrogen silicone copolymer having a hydrogen group and a silicone having an alkoxy group, it is easily converted into a hydrophilic liquid during coating itself. The present invention relates to a silicone coating agent having an excellent antifouling property against an aqueous contaminant on the surface of a porous tile by introducing a coating agent having hydrophilic groups and hydrophobic groups simultaneously in a coating film.

In general, since the coating agent protects the surface of the coating material and is most easily exposed to external contamination, the first required function is antifouling function. If the surface to be coated is a tile, in addition to the antifouling function of the coating agent, physical properties such as water repellency, adhesion, and curability are also required.

Therefore, in order to have antifouling properties against general aqueous pollution, the coating agent must have both hydrophilic and hydrophobic groups on the surface. If only a hydrophilic group or a hydrophobic group exists, the contact angle with water is extremely or very small, and thus, a contact angle suitable for antifouling properties cannot be achieved. Therefore, hydrophilic and hydrophobic groups must be located close to each other and form strong bonds with minerals.

In order to improve to have the above characteristics, the following related art has been proposed.

U. S. Patent No. 5,593, 732 discloses a technique for producing room temperature curable silicone coatings using hydroxy silicone polymers, alkyl silicates and curing agents. In particular, a filler (filler) was used as a hydrophilic group, and a hydroxy silicone polymer was used at the sock end as a hydrophobic group to show antifouling properties. This patent is worth noting that a marine coating is not suitable for direct application to tiles, but has applied an antifouling mechanism.

In addition, US Pat. No. 6,337,129 uses titanium oxide as a hydrophilic group and silicon having a fluorine functional group as a hydrophobic group. In the patent, hydrophilic groups and hydrophobic groups were adjacent to each other to exhibit antifouling properties.

However, as can be seen from the above two patents, conventionally, metal oxides or inorganic fillers have been used to represent hydrophilic groups. Since these materials are incompatible with general solvents and exist as solid phases, these solid phases require high cost and relatively difficult technology because the particle size must be controlled to a very fine and constant size.

In order to solve the above problems, the inventors of the present invention have tried to develop a silicone coating agent that can generate its own hydrophilic group in a liquid state without using a solid phase by introducing a hydrophilic group. When a coating agent is prepared using a certain amount of hydrogen silicone copolymer and silicon having an alkoxy group, it can be easily converted into a hydrophilic group during the coating process, and the hydrophilic group and the hydrophobic group in the coating film are present.

Accordingly, an object of the present invention is to provide a silicone coating which has improved the antifouling property against aqueous contaminants on the porous tile surface in an economical and simple manner.

The present invention is a silicone coating agent containing silicone as a main component, a silicone component comprising a methyl hydrogen silicone copolymer (A) having a hydrogen group represented by the following formula (1) and a silicone (B) having an alkoxy group represented by the following formula (2): It is characterized by the silicone coating agent which contains 0.01-2 weight part of catalysts (C) represented by following formula (3) with respect to 100 weight part.

Me ₃ Si- (O-SiMe ₂ ) _m- (O-SiHMe) _n -OSiMe ₃

In Chemical Formula 1; m is 0 ≤ positive number ≤ 80, and n is 0 ≤ positive number ≤ 80.

R ' _a R " _b SiO _{(4- (a + b)) / 2}

In Chemical Formula 2; a and b are 0 <a + b <4 by a positive number, and R 'is an alkyl group with 1-4 carbon atoms, and R ": an alkoxy group with 1-4 carbon atoms.

M (X) _y

In Formula 3, M is Tin, Co, Zn, Ti, X is a hydrocarbon compound capable of coordinating bond to the metal M and having an aromatic or aliphatic, y is an integer of 2 to 6.

Generally, there are various kinds of hydrocarbon compounds having aromatic or aliphatic compounds such as pentane, hexane, heptane, and the like.

Referring to the present invention in more detail as follows.

The present invention relates to a silicone coating agent having excellent antifouling properties by having a hydrophilic group and a hydrophobic group in the coating film by converting into a hydrophilic group in the composition by reacting with moisture in the air during coating using a methyl hydrogen silicone copolymer and silicone having an alkoxy group. .

In particular, the present invention uses a methyl hydrogen silicone copolymer represented by the formula (1), which can be changed from hydrophobic groups to hydrophilic groups on its own, without using a solid phase such as metals or inorganic fillers for introducing hydrophilic groups into the coating, Silicone having a copolymer and an alkoxy group represented by the formula (2) is used. Reactive alkoxy groups or hydrogen groups react with hydroxy groups through hydrolysis at room temperature with water in the air to form siloxane bonds through condensation of the reacted hydroxy groups. To form a bond. In addition, the unreacted hydrogen group is affected by the air surface of the tile, so that the orientation of the hydrophobic group is directed to the air surface. Thus, the hydrogen group formed in this direction reacts slowly with the moisture in the air to change into a hydroxyl group, thereby changing the hydrophilic group to Is switched to. Therefore, the hydrophobic alkyl group and the hydrophilic group coexist in close proximity to have antifouling performance against aqueous contaminants.

Referring to the components constituting the silicone coating agent according to the present invention having the above characteristics in more detail as follows.

The methyl hydrogen silicone copolymer represented by Chemical Formula 1, which is component A, is prepared by hydrolyzing dichloromethylsilane and chlorotrimethylsilane to form a methyl hydrogen polymer, and adding and reacting dimethylcyclic silane thereto. At this time, by adding a variety of dimethyl cyclic silane and hexamethyldisilonic acid as a terminal bond can be prepared a methyl hydrogen silicone copolymer of various m value and n value. In the present invention, it is preferable to use a copolymer having a degree of polymerization of 1000 or less among various methyl hydrogen silicone copolymers. If the degree of polymerization of the polymer is 1000 or more, the curing rate after coating is slow and the water repellency is poor, and the surface hardness after curing is weak. The phenomenon occurs.

Silicone having an alkoxy group represented by Formula 2, which is component B, may be prepared by inducing partial condensation using water after alcoholation of chlorosilane with methanol or ethanol or partial condensation of alkoxy silane. Chlorosilane can be used alone or mixed with methyl trichlorosilane and dimethyldichlorosilane to prepare a silicone compound having an alkoxy group. The alkoxy group should be 30 to 70 parts by weight based on 100 parts by weight of the silicone compound to induce strong bonds, and the hydrophobicity should be 10 to 50 parts by weight of an alkyl group which is a hydrophobic group. The quantity can be made by using 0 mol or more and 0.5 mol or less in the number of moles of the chlorine group which may be substituted with an alkoxy group.

The usage-amount of the said component A and B is preferable to mix and use 0.1-0.5 mol of hydrogen groups and 0.1-1 mol of alkoxy groups which are hydrophilic groups based on 1 mol of methyl groups which are hydrophobic groups. The weight part of component A is then determined by the molar ratio of the product components.

Meanwhile, the catalyst represented by Chemical Formula 3, which is component C, is a metal catalyst capable of reacting at room temperature to induce a bond between a silicon having an alkoxy group and a methyl hydrogen silicone copolymer and a bond between these copolymers and a hydrophilic group of a tile. Use Reactive alkoxy groups or hydrogen groups are reacted with hydroxy groups through hydrolysis at room temperature with water in the air to induce condensation of hydroxy groups to cure. A metal catalyst is used to speed up the series of processes, and since the metal catalyst affects the shelf life, 0.01 to 2 parts by weight is used for 100 parts by weight of the component A and B mixture.

Generally, curing catalysts include tin, dibutyltin dilaurate, tetrabutyltin, tetrabutyltin, 2-ethylhexoate, and stenous. Stanolous oleate, dibutyltin diacetate, dibutyltin bis (2-ethylhexoate), and other metals are Zn, Co, Ti Zinc octoate, zinc naphthenate, cobalt octoate, cobalt naphthenate, titanium ethoxide, tetrabutyl titanium There are several types, such as tetrabutyl titanate and tetra (tert-butyl) orthotitanate.

Looking briefly at the method for producing a silicone coating agent using the above components, the prepared methyl hydrogen silicone copolymer and the silicone having an alkoxy group is a hydrocarbon-based boiling point of 70 ~ 150 ℃ that can be evaporated at room temperature after mixing A catalyst, which is component C capable of curing at room temperature after dilution of the solid content to 10 to 50% with a solvent, is prepared by mixing 0.01 to 2 parts by weight with respect to 100 parts by weight of components A and B.

As described above, the coating agent according to the present invention may be particularly useful as a tile coating agent because the anti-fouling property is greatly improved and the water repellency, adhesiveness and curability are improved by using a specific component of a silicone component and using a specific catalyst.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by Examples.

Example 1

5.5 parts by weight of hexamethyldisiloxane in 94.5 parts by weight of methyl hydrogen copolymer Me ₃ Si- (O-SiMe ₂ ) _m- (O-SiHMe) _n -OSiMe ₃ (m = 20, n = 20, molecular weight = 2800) Part was added and reacted under acidic clay to prepare a low molecular weight methyl hydrogen silicone copolymer (A) having m = 10, n = 10 and molecular weight = 1429.

Silicone having an alkoxy group was prepared by mixing 28.7 parts by weight of methyl triclosilane, 27.3 parts by weight of dimethyldichlorosilane, 41.3 parts by weight of ethanol, and 2.7 parts by weight of water to prepare a silicone having an alkoxy group having a molar ratio of methyl and ethoxy groups of 1: 1. It was.

The two materials prepared above were mixed with 60 parts by weight of methyl hydrogen silicone copolymer (A) and 40 parts by weight of silicon (B) having an alkoxy group [0.3 moles of hydrogen group, 0.3 moles of alkoxy group, based on 1 mole of methyl group], and then a hydrocarbon-based compound. Dilution with a solvent (Hansol-Korea Petrochemical Co., Ltd. HYDROCARBON SOLVENT) in a solid content of 10-50%, and then a tin catalyst called 0.01- 2 parts by weight of dibutyltin dilaurate (DBTDL) is added to 100 parts by weight of components A and B. A room temperature curable coating agent was prepared.

Examples 2 to 10 and Comparative Examples 1 to 4

Next, the silicone coating was prepared in the same manner as in Example 1 using the contents shown in Table 1.

division Methyl Hydrogen Silicone Copolymer (A) Silicone (B) having an alkoxy group (molar ratio) A mixture of A and B (molar ratio) Catalyst (C) Example 1 m, n = 10 Me: OR = 1: 1 Me: H: OR = 1: 0.3: 0.3 DBTDL Example 2 m, n = 10 Me: OR = 1: 1 Me: H: OR = 1: 0.3: 0.3 Zn Octoate Example 3 m, n = 20 Me: OR = 1: 1 Me: H: OR = 1: 0.25: 0.25 DBTDL Example 4 m, n = 20 Me: OR = 1: 1 Me: H: OR = 1: 0.25: 0.25 Ti Ethoxide Example 5 m, n = 10 Me: OR = 1: 0.5 Me: H: OR = 1: 0.3: 0.25 DBTDL Example 6 m, n = 10 Me: OR = 0.5: 1 Me: H: OR = 1: 0.25: 0.3 DBTDL Example 7 m, n = 10 Me: OR = 1: 0.3 Me: H: OR = 1: 0.3: 0.1 DBTDL Example 8 m, n = 5 Me: OR = 1: 1 Me: H: OR = 1: 0.5: 0.3 DBTDL Example 9 m, n = 5 Me: OR = 1: 0.5 Me: H: OR = 1: 0.3: 0.2 DBTDL Example 10 m, n = 5 Me: OR = 1: 0.3 Me: H: OR = 1: 0.3: 0.3 DBTDL Comparative Example 1 m, n = 10 - Me: H: OR = 1: 0.9 DBTDL Comparative Example 2 - Me: OR = 1: 1 Me: OR = 1: 1 DBTDL Comparative Example 3 m, n = 10 Me: OR = 1: 1 Me: H: OR = 1: 0.3: 0.3 - Comparative Example 4 Terminal OH-silicone poymer silica gel Me: OR = 1: 0.3 DBTDL

Test Example

The silicone coating agents of Examples 1 to 10 and Comparative Examples 1 to 4 prepared above were cured for 1 to 5 days after coating on the surface of the porous tile. When the curing was completed, the soil was stained with an aqueous ink and then stained with a tissue or cotton to test for stain resistance. The results are shown in Table 2 below.

The phenomenon in which the contamination was completely removed was expressed as 10, and the state in which the contamination remained completely was expressed as 0.

division Curing time Water repellency Antifouling BLACK CARBONICBLACK BLUE BLUEBLACK Example 1 1 day Good 9.5 9.5 9.5 9 Example 2 1 day Good 10 10 9.5 9.5 Example 3 2 days Good 10 9.5 9 9 Example 4 2 days Good 9 8 9 9 Example 5 1 day Good 10 9.5 9.5 9.5 Example 6 1 day Good 10 9.5 9.5 9.5 Example 7 1 day Good 9.5 9.5 9 9 Example 8 1 day Good 9 9 9 8.5 Example 9 1 day Good 10 10 9 9 Example 10 1 day Good 9.5 9.5 9.5 9.5 Comparative Example 1 1 day Bad 8 5 6 6 Comparative Example 2 1 day Good 8 7 7 7 Comparative Example 3 5 days Good 6.5 5 5.5 5 Comparative Example 4 5 days Bad 8 7 6 6

As shown in Table 2, it was confirmed that the silicone coating agent according to the embodiment of the present invention is excellent in antifouling properties without using a solid phase such as metals or inorganic fillers to introduce a hydrophilic group.

As described above, the silicone coating agent according to the present invention does not use a solid phase such as metals or inorganic fillers to introduce a hydrophilic group, and uses silicone having a silicone hydrogen group and an alkoxy group which can be changed from a hydrophobic group to a hydrophilic group itself. It can be easily converted into hydrophilic groups so that both hydrophilic and hydrophobic groups in the coating can be simultaneously maximized antifouling properties against aqueous contaminants on the tile, and it becomes liquid and can be easily coated without a series of operations. In particular, the present invention is a natural affinity in that the air emitting materials (HYDROCARBON-SOLVENT, ETHANOL, etc.) is not toxic, so there is an advantageous effect in use.

Claims (3)

0.01 to Catalyst (C) represented by the following formula (3) to 100 parts by weight of the methyl hydrogen silicone copolymer (A) having a hydrogen group represented by the following formula (1) and the silicone (B) having the alkoxy group represented by the following formula (2) Silicone coating agent comprising 2 parts by weight. [Formula 1] Me ₃ Si- (O-SiMe ₂ ) _m- (O-SiHMe) _n -OSiMe ₃ In Chemical Formula 1; m is 0 ≤ positive number ≤ 80, and n is 0 ≤ positive number ≤ 80. [Formula 2] R ' _a R " _b SiO _{(4- (a + b)) / 2} In Chemical Formula 2; a and b are 0 <a + b <4 by a positive number, R 'is an alkyl group of 1-4 carbon atoms, and R ": an alkoxy group of 1-4 carbon atoms. [Formula 3] M (X) _y In Formula 3, M is Tin, Co, Zn, Ti, X is a hydrocarbon compound capable of coordinating bond to the metal M and having an aromatic or aliphatic, y is an integer of 2 to 6. The silicone coating agent according to claim 1, wherein the content of component A and component B is 0.1 to 0.5 mol of hydrogen group and 0.1 to 1 mol of alkoxy group based on 1 mol of methyl group. The method of claim 1, wherein component C is dibutyltin dilaurate, Tetrabutyltin, Stenous bis (2-ethylhexoate), Steno Stanusous oleate, Dibutyltin diacetate, Dibutyltin bis (2-ethylhexoate), Zinc octoate, Zinc naphthene Zinc naphthenate, cobalt octoate, cobalt naphthenate, titanium ethoxide, tetrabutyl titanate and tetra (tert-butyl) ortho titanate (tetra (tert-butyl) orthotitanate).