KR101945486B1 - Methods of materials hydrophilization by nitrilopoly(methylenephosphonic acid)s or derivatives thereof containing siloxanes - Google Patents

Abstract

여기서, R₁, R₂, 및 R₃는 동일하거나 상이하며, 각각 독립적으로, 수소 또는 C1 내지 C3의 알킬기이고, A는 단일결합 또는 C1 내지 C5의 알킬렌이며, n은 2 내지 30의 범위이고;
[화학식 2]
BN[CH₂PO₃H₂]₂
여기서, B는 -CH₂PO₃H₂, 하기 화학식 3으로 나타내어지는 기, 또는 하기 화학식 4로 나타내어지는 기이고;
[화학식 3]

여기서, m은 2 내지 8의 정수이고;
[화학식 4]

여기서, a 및 b는 각각 동일하거나 상이하고, 2 내지 6의 정수임.Providing a substrate; Applying and chemically immobilizing a siloxane oligomer of formula 1 on the surface of the substrate to provide a siloxane modified surface; And applying and chemically immobilizing a phosphonic acid compound represented by the following formula (2) to the siloxane-modified surface:
[Chemical Formula 1]

Wherein R ₁ , R ₂ and R ₃ are the same or different and are each independently hydrogen or a C 1 to C 3 alkyl group, A is a single bond or a C 1 to C 5 alkylene, and n is a range of 2 to 30 ego;
(2)
BN [CH ₂ PO ₃ H ₂ ] ₂
Wherein B is -CH ₂ PO ₃ H ₂ , a group represented by the following formula (3), or a group represented by the following formula (4);
(3)

Wherein m is an integer from 2 to 8;
[Chemical Formula 4]

Here, a and b are the same or different and each is an integer of 2 to 6.

Description

TECHNICAL FIELD The present invention relates to a method for hydrophilization of a material by a siloxane containing poly (methylenephosphonic acid) or its derivative as a nitrile,

The present invention relates to the production of modified materials and to techniques capable of imparting hydrophilic surface properties to a variety of materials.

There is a hydrophilic treatment method of textile materials using a composition comprising a mixture of polyorganosiloxane and polydiorganosiloxane (German Patent No. 3932276 (composition and processing method for textile treatment) . The polyorganosiloxanes used in the process are hydrophilic but water-insoluble compounds. Other polyorganosiloxanes which serve as surfactants are added in order to increase the emulsifying ability in the treatment of textile materials. A disadvantage of this method is the instability of the emulsion, i.e. its cohesive ability, which is due to the physical properties of the applied polyorganosiloxane.

Other methods of imparting hydrophilicity to textile materials made from fibers having different physical properties are also known (see, for example, Russian Patent No. 2370583, in which an oxyalkylene organosiloxane block-copolymer is used to impart hydrophilicity to the textile material Way)]. This method uses an oxyalkylene organosiloxane in an amount of 1 to 5% by weight of the fiber material.

According to one embodiment, a method of imparting hydrophilicity to surfaces of various materials is provided.

According to another embodiment, an article having a hydrophilically modified surface is provided by the method.

According to one embodiment, a method of imparting hydrophilicity to a material surface comprises: providing a substrate; Applying a siloxane oligomer represented by the following formula (1) to the surface of the substrate and chemically fixing the siloxane oligomer to provide a siloxane modified surface; And applying and chemically immobilizing a phosphonic acid compound represented by the following formula (2) on the siloxane-modified surface:

[Chemical Formula 1]

Wherein R ₁ , R ₂ and R ₃ are the same or different and each independently hydrogen or a C 1 to C 3 alkyl group, A is a single bond or a C 1 to C 5 alkylene group, and n is a range of 2 to 30 ego;

(2)

BN [CH ₂ PO ₃ H ₂ ] ₂

Wherein B is -CH ₂ PO ₃ H ₂ , a group represented by the following formula (3), or a group represented by the following formula (4);

(3)

Wherein m is an integer from 2 to 8;

[Chemical Formula 4]

Here, a and b are the same or different and each is an integer of 2 to 6.

The substrate may be composed of an organic material, an inorganic material, or an organic-inorganic composite material, and may include a hydroxyl group, a carboxyl group, or a combination thereof.

The substrate may be subjected to a corona treatment such that the surface thereof includes a hydroxy group, a carboxyl group, or a combination thereof; UV treatment; Plasma treatment; It may be subjected to chemical treatment with hydrogen peroxide, hexafluoro isopropanol or an acid.

The siloxane oligomer represented by the above formula (1) may be selected from oligo (aminopropyl) ethoxysilane, oligo (aminopropyl) methoxysilane, oligo (aminoethyl) methoxysilane, oligo (aminoethyl) ethoxysilane, oligo (Aminobutyl) methoxysilane, oligo (aminopentyl) ethoxysilane, oligo (aminopentyl) methoxysilane, and combinations thereof.

The siloxane oligomer represented by Formula 1 may have an n value of 4 to 16.

The phosphonic acid compound represented by the general formula (2) may be at least one selected from the group consisting of nitrilotri (methylenephosphonic acid), ethylenebis (nitrilodimethylene) tetraphosphonic acid, hexamethylene diamine-N, N, N ' ), Diethylenetriamine pentaquis (methylphosphonic acid), and combinations thereof.

Applying and chemically fixing the siloxane oligomer to the substrate surface may include wetting the substrate surface with a solution comprising the siloxane oligomer, and drying and / or heating the siloxane oligomer.

The solution containing the siloxane oligomer may be prepared by dissolving the siloxane oligomer represented by the formula (1) in an alcohol of from C1 to C10 in an amount of 0.05 to 10% by weight.

Applying and chemically immobilizing the phosphonic acid compound to the siloxane-modified surface can include wetting, drying and heating the siloxane-modified surface with a solution comprising the phosphonic acid compound.

The solution containing the phosphonic acid compound may be prepared by dissolving the phosphonic acid compound represented by Formula 2 in water or C1 to C10 alcohol in an amount of 1 to 30 wt%.

According to another embodiment, an article having a hydrophilically modified surface comprises a substrate and a coating formed on the surface of the substrate, wherein the coating comprises a siloxane oligomer or polysiloxane derived therefrom, And a phosphonic acid compound represented by the following formula (2), wherein the siloxane oligomer or polysiloxane derived therefrom is chemically fixed to the surface of the substrate:

[Chemical Formula 1]

Wherein R ₁ , R ₂ and R ₃ are the same or different and each independently hydrogen or a C 1 to C 3 alkyl group, A is a single bond or a C 1 to C 5 alkylene group, and n is a range of 2 to 30 ego;

(2)

BN [CH ₂ PO ₃ H ₂ ] ₂

Wherein B is -CH ₂ PO ₃ H ₂ , a group represented by the following formula (3), or a group represented by the following formula (4);

(3)

Wherein m is an integer from 2 to 8;

[Chemical Formula 4]

Here, a and b are the same or different and each is an integer of 2 to 6.

The substrate may be composed of an organic material, an inorganic material, or an organic-inorganic composite material, and may include a hydroxyl group, a carboxyl group, or a combination thereof.

The substrate may comprise a polymer, leather, wood, metal, metal oxide or nitride, ceramic material, glass, or a combination thereof.

The siloxane oligomer represented by the above formula (1) may be selected from oligo (aminopropyl) ethoxysilane, oligo (aminopropyl) methoxysilane, oligo (aminoethyl) methoxysilane, oligo (aminoethyl) ethoxysilane, oligo (Aminobutyl) methoxysilane, oligo (aminopentyl) ethoxysilane, oligo (aminopentyl) methoxysilane, and combinations thereof.

The phosphonic acid compound represented by the general formula (2) may be at least one selected from the group consisting of nitrilotri (methylenephosphonic acid), ethylenebis (nitrilodimethylene) tetraphosphonic acid, hexamethylene diamine-N, N, N ' ), Diethylenetriamine pentaquis (methylphosphonic acid), and combinations thereof.

The coating may exhibit a band of P = O bonds, P-OH bonds, Si-O-Si bonds, Si-O-C bonds and Si-C bonds in an infrared spectroscopy.

The article may have, at its surface, a water contact angle of 15 ° or less.

The article may be a built-in or external component of household electrical appliances, a glass for preventing visual blurring caused by moisture, or a glass for automobiles.

Figure 1 schematically illustrates the chemical structure of a coating of a material surface formed according to one embodiment.

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

In one embodiment, a method of imparting hydrophilicity to a material surface comprises: providing a substrate; Applying and chemically immobilizing a siloxane oligomer of formula 1 on the surface of the substrate to provide a siloxane modified surface; And applying and chemically immobilizing a phosphonic acid compound represented by the following formula (2) on the siloxane-modified surface:

[Chemical Formula 1]

Wherein R ₁ , R ₂ , R ₃ , A and n are as defined above.

(2)

BN [CH ₂ PO ₃ H ₂ ] ₂

Where B is as defined above.

The substrate may include a hydroxy group, a carboxyl group, or a combination thereof on the surface. The substrate may be made of an organic material, an inorganic material, or an organic-inorganic composite material. Specifically, the base material is polyester, polyethylene, polypropylene, polycarbonate, polyvinyl chloride and various polymers, wood, leather, glass, _{metal, SiO 2, TiO 2, SnO} 2, ZnO 2, Fe 2 O 3, Al ₂ O ₃ , anodic aluminum oxide (AAO), or the like, or a ceramic substrate. The shape of the substrate is not particularly limited, and may specifically be a fiber, a film, a plate, a sphere, a cube, a rectangular parallelepiped, or a polyhedron or a profile product of an irregular shape. The substrate may be surface treated to include a hydroxy group, a carboxyl group, or a combination thereof on the surface. As a non-limiting example, the surface treatment may include chemical treatment using corona treatment, plasma treatment, ultraviolet radiation treatment, hydrogen peroxide, hexafluoropropane, acid, and the like.

The method comprises forming an organosiloxane coating having poly (methylenephosphonic acid) or a derivative thereof as a nitrile on the surface of various materials by molecular assembling to impart hydrophilicity to the material. As a first step in molecular assembly, the method comprises applying and fixing the siloxane oligomer of Formula 1 to the surface of the substrate to provide a siloxane modified surface. As a second step of molecular assembly, the method includes applying nitrile poly (methylenephosphonic acid) or a derivative thereof represented by Formula 2 to the siloxane-modified surface and chemically fixing the same.

Specific examples of the siloxane oligomer represented by Formula 1 include oligos (aminopropyl) ethoxysilane, oligo (aminopropyl) methoxysilane, oligo (aminoethyl) methoxysilane, oligo- (aminoethyl) ethoxysilane, oligo Aminobutyl) ethoxysilane, oligo (aminobutyl) methoxysilane, oligo (aminopentyl) ethoxysilane, and oligo (aminopentyl) methoxysilane. For example, the siloxane oligomer may be oligo (aminopropyl) ethoxysilane represented by the following formula (3)

(3)

Specific examples of the phosphonic acid compound represented by Formula 2 include nitrile compounds such as nitrilotri (methylenephosphonic acid), ethylenebis (nitrilodimethylene) tetraphosphonic acid, hexamethylenediamine-N, N, N ' N, N ', N'-tetrakis (methylphosphonic acid), diethylenetriaminepentakis (methylphosphonic acid) and its derivatives For example, the phosphonic acid compound may be nitrilotri (methylenephosphonic acid) represented by the following formula (5).

[Chemical Formula 5]

N [CH ₂ PO ₃ H ₂ ] ₃

In the first stage of the molecular assembly, a siloxane oligomer such as (aminopropyl) ethoxysilane or the like represented by the above formula (1) is applied on the surface of the material and chemically fixed to obtain a siloxane-modified surface Scheme 1):

[Reaction Scheme 1]

Application and fixation of the siloxane oligomer can be achieved by dissolving the siloxane oligomer in an appropriate solvent (e.g., an alcohol having from 1 to 10 carbon atoms) to prepare a siloxane oligomer solution, wetting (e.g., impregnating) This can be carried out by drying and / or heat treatment in air. Since the siloxane oligomer represented by the general formula (1) has an appropriate solubility, the material surface can be uniformly modified (coated). Chemically fixing the siloxane oligomer of formula (1) to the substrate may be accomplished by exposure to air and / or heating.

The siloxane oligomer having the desired n value can be prepared by reacting a trialkoxysilane compound containing an appropriate amount of an aminoalkyl group in the presence of an appropriate amount of water.

The concentration of the siloxane oligomer solution is not particularly limited, but may be in the range of about 0.05 to 10% by weight , specifically about 0.1 to 1% by weight. Exposure to air or temperature at the time of heating is not particularly limited, and may be room temperature or 20 degrees Celsius or more, specifically, 30 degrees Celsius to 150 degrees Celsius. The time for exposure to air or heating is not particularly limited, and may be suitably selected, for example, from 5 minutes to 24 hours.

As shown in Reaction Scheme 1, the siloxane oligomer of Chemical Formula 1 is fixed on the surface of the substrate by covalent bond by condensation reaction with a functional group such as a hydroxyl group present on the surface of the substrate, and the siloxane oligomer of Chemical Formula 1 A micro-nano coating containing the polysiloxane derived therefrom is formed.

The weight of the siloxane coating formed on the substrate surface after soaking, drying and / or heat treatment can be estimated from the weight increase of the substrate. This weight gain can be expressed as a percentage of the initial weight of the material. After one time of impregnation, drying and heat treatment, if the weight gain of the material does not reach the desired value, the impregnation, drying and heat treatment are repeated several times until the required value is reached.

In the second stage of molecular assembly, a nitrile poly (methylenephosphonic acid) represented by the general formula (2) is used. Specifically, the siloxane-modified surface can be wetted with a solution of nitrile (methylenephosphonic acid), and then dried and heat-treated in air. For example, when nitrilotri (methylenephosphonic acid) is used as the phosphonic acid compound represented by the general formula (2), the alkylamino group of the amino group-containing organosiloxane grafted onto the substrate surface during the condensation reaction with the nitrile compound (methylenephosphonic acid) condensation. Thereby, a hydrophilic group can be formed on the surface of the substrate by reacting with the amino group of the siloxane oligomer or polysiloxane in which poly (methylenephosphonic acid) is chemically immobilized on the surface of the substrate with nitrile (refer to Scheme 2)

[Reaction Scheme 2]

The concentration of the solution of poly (methylenephosphonic acid) as the nitrile is not particularly limited and may be appropriately selected. For example, the concentration of the phosphonic acid solution may be about 1 to 30 wt%, but is not limited thereto. The temperature at the time of drying or heating is not particularly limited, and may be in the range of 20 ° C or more, specifically 30 ° C to 150 ° C. The time for drying or heating is not particularly limited, and can be suitably selected, for example, from 5 minutes to 24 hours.

By the above-described molecular assembly, a modified coating layer having a brush geometry as shown in Fig. 1 can be formed on the surface of the substrate.

The hydrophilic (water soluble) group present in the coating can impart hydrophilicity to the surface of the substrate.

In the first stage of molecular assembly, a mechanism for forming a hydrophilic organosiloxane coating on the silicate glass surface is to form a silanol group on the surface of the silicate glass and a siloxane oligomer represented by the formula (1) Based on the reaction of a hydrophilic alkoxysilyl group (e.g., an ethoxysilyl group) of a hydroxyalkyl (methoxymethyl) aminopropyl) ethoxysilane (I-III)

[Reaction Scheme 3]

In Scheme 3 above, ethanol is separated and can be removed during the heat treatment of the material.

The mechanism by which the hydrophilic organosiloxane coating is formed in the second stage of molecular assembly is based on the interaction of the grafted aminoalkyl group-containing coating with nitrile lactide (methylenephosphonic acid), from which the siloxane-modified surface A chemical bond of an aminoalkyl group and a hydrophilic nitrile (methylenephosphonic acid) group is generated on the surface of the siloxane coating.

Mechanism for forming a hydrophilic organosiloxane coating on the surface of the polyester film in the first stage of the molecular assembly includes a hydrophilic ethoxysilyl group of a siloxane oligomer of formula (1) (for example, oligo (aminopropyl) ethoxysilane (I-III) (-COOH) and a hydroxy group (-OH) present on the surface of the polyester film (see Reaction Scheme 4). In the reaction, ethanol is released and removed by heat treatment.

 [Reaction Scheme 4]

In the second stage of molecular assembly, the mechanism of formation of the hydrophilic organosiloxane coating is such that at the organosiloxane coating surface the amino group of the siloxane oligomer of Formula 1 or the polysiloxane derived therefrom and the phosphonic acid compound of Formula 2 (e.g., (See Scheme 2), thereby forming a bond of a hydrophilic nitrile lactide (methylenephosphonic acid) group on the surface of the siloxane-modified substrate.

An article having a hydrophilically modified surface provided according to another embodiment comprises a substrate and a coating formed on the surface of the substrate, wherein the coating comprises a siloxane oligomer or polysiloxane derived therefrom and represented by formula Wherein the siloxane oligomer or polysiloxane is chemically immobilized on the surface of the substrate: < RTI ID = 0.0 >

[Chemical Formula 1]

Wherein R ₁ , R ₂ , R ₃ , A and n are as defined above.

(2)

BN [CH ₂ PO ₃ H ₂ ] ₂

Where B is as defined above.

In the above article, the content of the siloxane oligomer represented by the formula (1), the phosphonic acid compound represented by the following formula (2), and the reaction product formed therebetween are as described above.

Here, the term "chemical fixation" means that a chemical bond is formed by a bond (e.g., ionic bond, covalent bond, etc.) formed by an interaction between the compounds.

The coating may exhibit a vibration band for P = O bond, P-OH bond, Si-O-Si bond, Si-OC bond, and Si-C bond on its infrared spectroscopic spectrum. Specifically, the infrared spectroscopic spectrum of the coating contained in the substrate has P = O bonds in the range of 2700 to 2600 cm ^-1 , P-OH bonds in the range of 1040 to 1180 cm ^-1 , and a P-O bond in the range of 1080 to 1020 cm ^-1 in the Si-O-Si bond, 880-810 ㎝ ^-1 range Si-OC bond, 1260 and 800 ㎝ ^- from ¹ it may include a vibration band for the Si-C bond. From this, it can be confirmed that the above-mentioned organic siloxane coating was formed on the substrate surface.

The article has a hydrophilically modified surface including a coating formed on the substrate, and the water contact angle of the coated surface can be 15 or less. Such a low water contact angle can be effective in preventing dew condensation and the like on the article surface. Therefore, the article can find its usefulness in various fields where it is necessary to prevent such condensation. The article may be, for example, an interior or exterior part material of various household appliances such as a refrigerator, an air conditioner, a humidifier, an anti-fogging glass by moisture, It may be glass for automobiles.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are for illustrative purposes and are not intended to limit the present invention.

Example  One

A siloxane oligomer (I) solution (0.1% and 1%) of the following formula is impregnated with silicate glass, dried in air, and heat treated at 140 ° C to fix the siloxane oligomer to the glass surface:

(I)

(I)

The silicate glass with the siloxane modified surface is impregnated with an aqueous solution of 10% nitrilotri (methylenephosphonic acid), dried in air and heat treated at 140 ° C. The increase in hydrophilicity of the silicate glass was confirmed by the water contact angle value, and the results are summarized in Table 1. The water contact angle is measured on a drop tensiometer (Tracker, IT Concept, France) by dropping water droplets on the support surface and after 2 minutes (static condi- tion).

Example  2

The silicate glass was treated in the same manner as in Example 1 except that a silicone oligomer (II) solution (0.1% and 1%) of the following formula was used:

(II)

(II)

The increase in hydrophilicity of the silicate glass was confirmed by the water contact angle value, and the results are summarized in Table 1.

Example  3

The silicate glass was treated in the same manner as in Example 1 except that a silicone oligomer (III) solution (0.1% and 1%) of the following formula was used:

(III)

(III)

The increase in hydrophilicity of the silicate glass was confirmed by the water contact angle value, and the results are summarized in Table 1.

Example  4

The substrate was treated in the same manner as in Example 1, except that a polyester film was used as the substrate. The increase in hydrophilicity of the polyester film was confirmed by the water contact angle value, and the results are summarized in Table 1.

Example  5

The substrate was treated in the same manner as in Example 1 except that a polyester film was used as the substrate and a silicone oligomer (II) solution (0.1% and 1%) of the following formula was used:

(II)

(II)

The increase in hydrophilicity of the polyester film was confirmed by the water contact angle value, and the results are summarized in Table 1.

Example  6

The substrate was treated in the same manner as in Example 1 except that a polyester film was used as the substrate and a silicone oligomer (III) solution (0.1% and 1%) of the following formula was used:

(III)

(III)

The increase in hydrophilicity of the polyester film was confirmed by the water contact angle value, and the results are summarized in Table 1.

From the analysis of the results of the material surface treatment described in Examples 1 to 6, it can be seen that high hydrophilicity can be imparted to various materials by the above-described method of imparting hydrophilicity to the material surface. The contact angle of the material surface can be reduced by about 3.6 to about 15.3 times by using 0.1 to 1 wt% of oligo (aminopropyl) ethoxysiloxane (I to III).

From this, it can be seen that the above-described method of imparting hydrophilicity to the material surface can increase the hydrophilicity of various material surfaces such as silicate glass, polyester film and the like by about 3.6 to about 15.3 times. The hydrophilicity of organosiloxane coatings with hydrophilic nitrile (methylenephosphonic acid) groups exceeds the similar compounds and requires a minimal amount of initial material because they form them by molecular assembly at the surface of the material.

Claims (18)

As a method for imparting hydrophilicity to the material surface,
Providing a substrate; Applying and chemically immobilizing a siloxane oligomer of formula 1 on the surface of the substrate to provide a siloxane modified surface; And applying and chemically fixing a phosphonic acid compound represented by the following formula (2) to the siloxane-modified surface:
[Chemical Formula 1]

Wherein R ₁ , R ₂ and R ₃ are the same or different and each independently hydrogen or a C 1 to C 3 alkyl group, A is a single bond or a C 1 to C 5 alkylene group, and n is a range of 2 to 30 ego;
(2)
BN [CH ₂ PO ₃ H ₂ ] ₂
Wherein B is -CH ₂ PO ₃ H ₂ , a group represented by the following formula (3), or a group represented by the following formula (4);
(3)

Wherein m is an integer from 2 to 8;
[Chemical Formula 4]

Here, a and b are the same or different and each is an integer of 2 to 6. The method according to claim 1,
Wherein the substrate is made of an organic material, an inorganic material, or an organic composite material, and the surface of the substrate contains a hydroxyl group, a carboxyl group, or a combination thereof. 3. The method of claim 2,
The substrate may be subjected to a corona treatment such that the surface thereof includes a hydroxy group, a carboxyl group, or a combination thereof; UV treatment; Plasma treatment; Wherein the solution is subjected to chemical treatment with hydrogen peroxide, hexafluoro isopropanol or an acid. The method according to claim 1,
The siloxane oligomer represented by the above formula (1) may be selected from oligo (aminopropyl) ethoxysilane, oligo (aminopropyl) methoxysilane, oligo (aminoethyl) methoxysilane, oligo (aminoethyl) ethoxysilane, oligo Methoxy silane, oligo (aminobutyl) methoxy silane, oligo (aminopentyl) ethoxy silane, oligo (aminopentyl) methoxy silane, and combinations thereof. The method according to claim 1,
Wherein the siloxane oligomer represented by Formula 1 has an n value of 4 to 16. The method according to claim 1,
The phosphonic acid compound represented by the general formula (2) may be at least one selected from the group consisting of nitrilotri (methylenephosphonic acid), ethylenebis (nitrilodimethylene) tetraphosphonic acid, hexamethylene diamine-N, N, N ' ), Diethylenetriamine pentaquis (methylphosphonic acid), and combinations thereof. The method according to claim 1,
Applying and chemically fixing the siloxane oligomer to the substrate surface comprises wetting the substrate surface with a solution comprising the siloxane oligomer and drying, heating, or drying and heating the siloxane oligomer. 8. The method of claim 7,
Wherein the solution containing the siloxane oligomer is prepared by dissolving the siloxane oligomer represented by the formula (1) in an alcohol of from C1 to C10 in an amount of from 0.05 to 10% by weight. The method according to claim 1,
Applying and chemically immobilizing said phosphonic acid compound to said siloxane-modified surface comprises wetting said siloxane-modified surface with a solution comprising said phosphonic acid compound, drying and heating said siloxane-modified surface. 10. The method of claim 9,
Wherein the solution containing the phosphonic acid compound is prepared by dissolving the phosphonic acid compound represented by Formula 2 in water or C1 to C10 alcohol in an amount of 1 to 30 wt%. An article having a hydrophilically modified surface, the article comprising a substrate and a coating formed on the surface of the substrate, wherein the coating comprises a siloxane oligomer or polysiloxane derived therefrom having the formula: Wherein the siloxane oligomer or polysiloxane derived therefrom is chemically fixed to the surface of the substrate:
[Chemical Formula 1]

Here, the R _1, R _2, and R ₃ are, the same or different, each independently, an alkyl group of hydrogen or C1 to C3, A is an alkylene group of a single bond or a C1 to C5, n is 2 to 30 Range;
(2)
BN [CH ₂ PO ₃ H ₂ ] ₂
Wherein B is -CH ₂ PO ₃ H ₂ , a group represented by the following formula (3), or a group represented by the following formula (4);
(3)

Wherein m is an integer from 2 to 8;
[Chemical Formula 4]

Here, a and b are the same or different and each is an integer of 2 to 6. 12. The method of claim 11,
Wherein the substrate is made of an organic material, an inorganic material, or an organic-inorganic composite material, and the surface of the substrate contains a hydroxyl group, a carboxyl group, or a combination thereof. 13. The method of claim 12,
The substrate includes a polymer, leather, wood, metal, metal oxide or nitride, ceramic material, glass, or combinations thereof. 12. The method of claim 11,
The siloxane oligomer represented by the above formula (1) may be selected from oligo (aminopropyl) ethoxysilane, oligo (aminopropyl) methoxysilane, oligo (aminoethyl) methoxysilane, oligo (aminoethyl) ethoxysilane, oligo An oligosiloxane, an ethoxysilane, an oligo (aminobutyl) methoxysilane, an oligo (aminopentyl) ethoxysilane, an oligo (aminopentyl) methoxysilane, and combinations thereof. 12. The method of claim 11,
The phosphonic acid compound represented by the general formula (2) may be at least one selected from the group consisting of nitrilotri (methylenephosphonic acid), ethylenebis (nitrilodimethylene) tetraphosphonic acid, hexamethylene diamine-N, N, N ' ), Diethylenetriamine pentaquis (methylphosphonic acid), and combinations thereof. 12. The method of claim 11,
Wherein the coating exhibits a band of P = O bonds, P-OH bonds, Si-O-Si bonds, Si-OC bonds and Si-C bonds in an infrared spectroscopy spectrum. 12. The method of claim 11,
Said article having, at its surface, a water contact angle of 15 ° or less. 12. The method of claim 11,
Interior or exterior parts of household appliances, glass for preventing visual blur due to moisture, or glass for automobiles.

Images