KR20190060576A - Fluoro-polysilazane materials incorporating fluorine groups and methods for their preparation - Google Patents

Abstract

An embodiment of the present invention provides a water repellent fluorine polysilazane material. The fluorine polysilazane material can be represented by chemical formula 1. In the chemical formual 1, M_1 is a group in which a fluorine-based acrylic resin is substituted, M_2 is a group in which an acryl-based silane is substituted, and n is an integer of 1 to 10,000. According to an embodiment of the present invention, it is possible to provide a fluorine-based polysilazane material having improved printability and contact angle.

Description

FIELD OF THE INVENTION [0001] The present invention relates to fluorine-containing polysilazane materials,

The present invention relates to a water-repellent material, and more particularly, to a fluorine-based water-repellent material.

The demand for materials with new properties and innovative functions is rapidly increasing as technology is becoming more advanced and diversified throughout the industry such as electric / electronics, semiconductor, display, automobile, shipbuilding, bio, energy / environment.

As a solution to this demand, a water-repellent coating material of a high-performance water-repellent thin film or a molecular membrane is also being studied. There are various kinds of water-repellent materials such as acrylic resin, polyurethane resin, fluorine resin, silicone acrylic resin, silane system, siloxane system and silicate system.

Double silicone water repellent has excellent physical and chemical properties and processing characteristics, but water repellent and antifouling functions are rather weak. On the other hand, the fluorine-based material has a structure in which the hydrogen element substituted in the carbon-carbon main skeleton is substituted with fluorine and has excellent water repellency and anti-fouling characteristics, but it is difficult to process.

Therefore, research has been conducted on a composite water-repellent material combining the silicon-based material and the fluorine-based material, but the surface printability is still low, and research for improving it has been demanded.

Korean Patent Publication No. 10-2014-0082706

SUMMARY OF THE INVENTION The present invention provides a fluorine-based compound having improved water repellency.

It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory and are not intended to limit the invention to the precise form disclosed. There will be.

According to an aspect of the present invention, there is provided a water repellent fluoropolysilazane material.

The fluorine polysilazane material may be represented by the following chemical formula (1).

[Chemical Formula 1]

At this time, in the formula M 1 ₁ is characterized in that group which the fluorine-containing acrylic resin substituted.

In this case, M ₂ in the above formula (1) is a group in which acrylic silane is substituted.

Here, n in Formula 1 is an integer of 1 to 10,000.

Herein, M ₁ may have a structure represented by the following general formula (2).

(2)

The R 1 may include hydrogen, a straight chain hydrocarbon having 1 to 6 carbon atoms, or a branched hydrocarbon having 1 to 6 carbon atoms.

Here, a is an integer of 0 to 9.

Here, b is an integer of 1 to 3.

Herein, M ₂ may have a structure represented by the following formula (3).

(3)

The R 2 may include hydrogen, a straight chain hydrocarbon having 1 to 6 carbon atoms, or a branched hydrocarbon having 1 to 6 carbon atoms.

Herein, R3 is a hydrocarbon group having 1 to 3 carbon atoms.

Here, c is an integer of 1 to 9.

According to an aspect of the present invention, there is provided a method of manufacturing a fluoropolysilazane material.

The manufacturing method includes: preparing a mixed solution by mixing a fluorine-based acrylic resin and an acrylic silane in a solvent; adding perhydropolysilazane (PHPS) to the mixed solution and firstly stirring the mixed solution; And a second stirring step of adding a catalyst.

At this time, the solvent may include cyclohexanone, metheyl ethyl ketone (MEK), dimethyl sulfoxide (DMSO), or N-methyl pyrrolidone (NMP) .

At this time, in the mixed solution, the fluorine-based acrylic resin may have an amount of 20 wt% to 40 wt%.

At this time, the acrylic silane may have an amount of 0.01 wt% to 10 wt%.

At this time, the solid component may have 30% by weight to 40% by weight based on the total weight of the mixed solution.

At this time, the primary stirring step is performed at 25 ° C to 70 ° C for 0.5 hours to 2 hours.

At this time, the catalyst is a platinum (Pt) catalyst.

At this time, the secondary stirring step is characterized in that the step is carried out at 25 ° C to 70 ° C for 17 to 24 hours.

According to an aspect of the present invention, there is provided a method of manufacturing a fluoropolysilazane material thin film.

The thin film manufacturing method may include preparing the fluorine polysilazane material according to an embodiment of the present invention and curing the fluorine polysilazane material.

The curing may include an ammonia water immersion process, a steam curing process, a thermal curing process, an E-beam curing process or a pulse UV curing process.

At this time, the pulse ultraviolet curing is characterized by irradiating ultraviolet rays 100 to 1000 times under the condition of 1800 to 2200 V, 80 to 120, and 7.4 to 9.4 Hz.

According to one embodiment of the present invention, a fluorine-based polysilazane material having improved printability and contact angle can be provided.

According to one embodiment of the present invention, it is possible to provide a method for producing a fluorine-based polysilazane material having improved printability and contact angle.

According to one embodiment of the present invention, it is possible to provide a method for producing a fluorine-based polysilazane thin film having improved printability and contact angle.

It should be understood that the effects of the present invention are not limited to the above effects and include all effects that can be deduced from the detailed description of the present invention or the configuration of the invention described in the claims.

1 is a flow chart showing a method of manufacturing a fluoropolysilazane material according to an embodiment of the present invention.
2 is an infrared spectroscopic analysis graph of a fluoropolysilazane material according to an embodiment of the present invention.
3 is an H-NMR analysis graph of a fluorine polysilazane material according to an embodiment of the present invention.
4 is a Si-NMR analysis graph of a fluorine polysilazane material according to an embodiment of the present invention.
5 is a flowchart showing a method of manufacturing a fluorine polysilazane thin film according to an embodiment of the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described with reference to the accompanying drawings. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. In order to clearly illustrate the present invention, parts not related to the description are omitted, and similar parts are denoted by like reference characters throughout the specification.

Throughout the specification, when a part is referred to as being "connected" (connected, connected, coupled) with another part, it is not only the case where it is "directly connected" "Is included. Also, when an element is referred to as " comprising ", it means that it can include other elements, not excluding other elements unless specifically stated otherwise.

The terminology used herein is for the purpose of describing particular 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 "comprises" or "having" and the like refer to the presence of stated features, integers, steps, operations, elements, components, or combinations thereof, But do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, or combinations thereof.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

A water repellent fluoropolysilazane material according to an embodiment of the present invention will be described.

The fluorine polysilazane material may be represented by the following chemical formula (1).

[Chemical Formula 1]

At this time, in the formula M 1 ₁ is characterized in that group which the fluorine-containing acrylic resin substituted.

In this case, M ₂ in the above formula (1) is a group in which acrylic silane is substituted.

Here, n in Formula 1 is an integer of 1 to 10,000.

Herein, M ₁ may have a structure represented by the following general formula (2).

(2)

The R 1 may include hydrogen, a straight chain hydrocarbon having 1 to 6 carbon atoms, or a branched hydrocarbon having 1 to 6 carbon atoms.

Here, a is an integer of 0 to 9.

Here, b is an integer of 1 to 3.

Herein, M ₂ may have a structure represented by the following formula (3).

(3)

The R 2 may include hydrogen, a straight chain hydrocarbon having 1 to 6 carbon atoms, or a branched hydrocarbon having 1 to 6 carbon atoms.

Herein, R3 is a hydrocarbon group having 1 to 3 carbon atoms.

Here, c is an integer of 1 to 9.

In the carbon-fluorine bond, bond electrons of a fluorine atom are attracted close to the nucleus of a fluorine atom to form a short bond distance because the benthic polarization is small and the atomic radius is small. Due to the short bonding distance and the high electronegativity of fluorine, the carbon-fluorine bond energy has a larger energy than other bonds. This indicates that fluorine compounds having carbon-fluorine bonds exhibit high heat resistance, oxidation resistance and ultraviolet ray do. Moreover, it has low refractive index and low dielectric constant characteristics due to a small polarization ratio.

In addition, the polymer having a functional group whose terminal is CF _{3 has a} characteristic that a critical surface tension is lowered so that not only water but also hydrocarbons are extruded. However, due to such characteristics, there is a problem that the fluororesin having a carbon-fluorine bond has a low surface printability and adhesiveness when used as a coating agent.

To solve the above problem, a silane may be introduced into the fluorine-based polymer. The silane is a monomer to which four chemical groups are connected to the silicon element, and the four monomers may be the same or different. Since silane has both inorganic reactivity and organic reactivity, it can react with various substances and bind.

By using such a property, a fluoropolysilazane material having a high water repellency and an improved printing property by a silane group can be provided by introducing silane into the fluoropolymer.

Example

For example, according to one embodiment of the present invention, the following fluoropolysilazane materials can be provided.

The fluoropolysilazane material according to one embodiment of the present invention

When a fluoropolysilazane material according to an embodiment of the present invention is used, it is possible to provide a fluoropolysilazane material having water repellency and oil-repellency characteristics and improved printing properties and adhesiveness.

A method of manufacturing a fluoropolysilazane material according to an embodiment of the present invention will be described.

1 is a flow chart showing a method of manufacturing a fluoropolysilazane material according to an embodiment of the present invention.

Referring to FIG. 1, the method comprises: preparing a mixed solution by mixing a fluorine-based acrylic resin and an acrylic silane in a solvent (S100), adding perhydropolysilazane (PHPS) to the mixed solution, Step (S200), and a step (S300) of adding the catalyst to the mixed solution which has been firstly stirred and then performing the second stirring.

At this time, the solvent may include cyclohexanone, metheyl ethyl ketone (MEK), dimethyl sulfoxide (DMSO), or N-methyl pyrrolidone (NMP) .

At this time, the fluorine-based acrylic resin may have a structure represented by the following formula (4).

[Chemical Formula 4]

The R 1 may include hydrogen, a straight chain hydrocarbon having 1 to 6 carbon atoms, or a branched hydrocarbon having 1 to 6 carbon atoms.

Here, a is an integer of 0 to 9.

Here, b is an integer of 1 to 3.

At this time, the acrylic silane may have a structure represented by the following formula (3).

At this time, in the mixed solution, the fluorine-based acrylic resin may have an amount of 20 wt% to 40 wt%.

If the content of the fluorine-based acrylic resin is less than 20% by weight, the water repellency due to the fluorine functional group is decreased, and the water repellency and oil-repellency characteristics of the fluorine polysilazane material produced according to one embodiment of the present invention may be reduced.

When the content of the fluorine-based acrylic resin is more than 40% by weight, the printability and adhesiveness of the fluorine polysilazane material produced according to one embodiment of the present invention may be reduced due to excessive fluorine functional groups.

At this time, the acrylic silane may have a structure represented by the following general formula (5).

[Chemical Formula 5]

The R 2 may include hydrogen, a straight chain hydrocarbon having 1 to 6 carbon atoms, or a branched hydrocarbon having 1 to 6 carbon atoms.

Herein, R3 is a hydrocarbon group having 1 to 3 carbon atoms.

Here, c is an integer of 1 to 9.

At this time, the acrylic silane may have an amount of 0.01 wt% to 10 wt%.

If the content of the acrylic silane is less than 0.01% by weight, the effect of improving the contact force by the silane group is insignificant, so that the printability and adhesiveness of the fluoropolysilazane material produced according to one embodiment of the present invention can be reduced.

If the content of the acrylic silane is less than 10% by weight, the side reaction may be excessively generated due to the reactivity of the silane group, so that the yield of the fluorine polysilazane material produced according to one embodiment of the present invention may be lowered.

At this time, the solid component may have 30% by weight to 40% by weight based on the total weight of the mixed solution.

Here, the solid component means the fluorine-based acrylic resin or the acrylic silane.

If the content of the solid component is less than 30% by weight, the concentration of the reactant is low, so that the yield of the fluoropolysilazane material produced according to one embodiment of the present invention may be lowered.

At this time, when the content of the solid component exceeds 40% by weight, the occurrence of the side reaction is promoted by the high reactant concentration, so that the yield of the fluoropolysilazane material produced according to one embodiment of the present invention can be lowered.

At this time, the primary stirring step (S200) is performed at 25 ° C to 70 ° C for 0.5 hours to 2 hours.

At this time, the catalyst is a platinum (Pt) catalyst.

For example, the platinum-based catalyst may include Pt: B, Pt: C, Pt: Alloy, H ₂ PtCl _6, or PtCl ₄ .

At this time, the secondary stirring step (S300) is performed at 25 ° C to 70 ° C for 17 hours to 24 hours.

In the carbon-fluorine bond, bond electrons of a fluorine atom are attracted close to the nucleus of a fluorine atom to form a short bond distance because the benthic polarization is small and the atomic radius is small. Due to the short bonding distance and the high electronegativity of fluorine, the carbon-fluorine bond energy has a larger energy than other bonds. This indicates that fluorine compounds having carbon-fluorine bonds exhibit high heat resistance, oxidation resistance and ultraviolet ray do. Moreover, it has low refractive index and low dielectric constant characteristics due to a small polarization ratio.

In addition, the polymer having a functional group whose terminal is CF _{3 has a} characteristic that a critical surface tension is lowered so that not only water but also hydrocarbons are extruded. However, due to such characteristics, there is a problem that the fluororesin having a carbon-fluorine bond has a low surface printability and adhesiveness when used as a coating agent.

To solve the above problem, a silane may be introduced into the fluorine-based polymer. The silane is a monomer to which four chemical groups are connected to the silicon element, and the four monomers may be the same or different. Since silane has both inorganic reactivity and organic reactivity, it can react with various substances and bind.

By using such a property, a fluoropolysilazane material having a high water repellency and an improved printing property by a silane group can be provided by introducing silane into the fluoropolymer.

Manufacturing example

A fluoropolysilazane material was prepared according to one embodiment of the present invention.

<Reaction Scheme 1>

Referring to Reaction Scheme 1, first, 29.9 wt% of 15PFOMA and 5.2 wt% of TMSPA were dissolved in cyclohexane to prepare a mixed solution.

Next, perhydropolysilazane (PHPS) was added to the mixed solution, and primary stirring was performed at 70 ° C for 1 hour.

Then, 50 ㎕ of a platinum catalyst was added to the primary stirring solution, followed by secondary stirring at 70 캜 for 24 hours to prepare P (PH-g-PFO / TM).

2 is an infrared spectroscopic analysis graph of a fluoropolysilazane material according to an embodiment of the present invention.

Referring to FIG. 2, the P (PH-g-PFO / TM) prepared by carrying out the second stirring step (S300) of the IR of the pre- IRd, we can see that the wavelength of the Si-H bonds present before the reaction was reduced. This means that the hydrosilylation reaction occurs through the catalyst in the second stirring step (S300), and the hydrogen bonded to the silicon (Si) is replaced with another functional group.

3 is an H-NMR analysis graph of a fluorine polysilazane material according to an embodiment of the present invention.

Referring to FIG. 3, it can be seen that a peak corresponding to Si-CH2 exists in the H-NMR spectrum of the material prepared by the method for producing a fluorine polysilazane material according to an embodiment of the present invention. It can be seen that the P (PH-g-PFO / TM) was produced by the hydrolysis reaction by the peak not present in the reactant.

4 is a Si-NMR analysis graph of a fluorine polysilazane material according to an embodiment of the present invention.

Referring to FIG. 4, it can be seen that the peak of Si-NMR was -35 ppm in the pre-reaction product PHPS, but it was shifted to -43 ppm in the post-reaction P (PH-g-PFO / TM) according to an embodiment of the present invention . This means that the Si-H bond existing in the PHPS is replaced with the Si-C bond by the fluoropolysilazane material manufacturing method according to an embodiment of the present invention.

When the fluoropolysilazane material manufacturing method according to an embodiment of the present invention is used, it is possible to provide a fluoropolysilazane material having water repellency and oil-repellency characteristics and improved printability and adhesiveness.

A method for producing a fluorine polysilazane thin film according to an embodiment of the present invention will be described.

5 is a flowchart showing a method of manufacturing a fluorine polysilazane thin film according to an embodiment of the present invention.

Referring to FIG. 5, the thin film manufacturing method includes a step (S400) of applying the fluorine polysilazane material according to an embodiment of the present invention (S400) and a step (S500) of hardening the fluorine polysilazane material can do.

At this time, the base material may include glass, plastic, metal, stone, wood, concrete, or a polymer material.

The curing may include an ammonia water immersion process, a steam curing process, a thermal curing process, an E-beam curing process or a pulse UV curing process.

At this time, the pulse ultraviolet curing is characterized by irradiating ultraviolet rays 100 to 10000 times under the condition of 1800 to 2200 V, 80 to 120, and 7.4 to 9.4 Hz.

The contact angle according to the number of times of pulsed ultraviolet irradiation Sample Contact Angle (H ₂ O) After prebake (150 ° C, 1 min) 105 ° 2000 V, 100,, 8.4 Hz, 100 times 106 ° 2000 V, 100,, 8.4 Hz, 200 times 101 ° 2000 V, 100,, 8.4 Hz, 300 times 100 ° 2000 V, 100,, 8.4 Hz, 400 times 100 ° 2000 V, 100,, 8.4 Hz, 500 times 100 ° 2000 V, 100,, 8.4 Hz, 600 times 99 ° 2000 V, 100,, 8.4 Hz, 700 times 93 ° 2000 V, 100,, 8.4 Hz, 800 times 96 ° 2000 V, 100,, 8.4 Hz, 900 times 94 ° 2000 V, 100,, 8.4 Hz, 1000 times 91 ° 2000 V, 100,, 8.4 Hz, 2000 times 87 ° 2000 V, 100,, 8.4 Hz, 3000 times 76 ° 2000 V, 100 μs, 8.4 Hz, 4000 times 65 °

Referring to Table 2, when the pulse ultraviolet ray is irradiated more than 1000 times, it can be seen that the contact angle of the fluoropolysilazane material produced according to one embodiment of the present invention drastically decreases below 90 °.

On the other hand, when the pulsed ultraviolet ray is irradiated less than 100 times, the fluoropolysilazane material according to an embodiment of the present invention may not be completely cured.

The characteristics of the fluorine polysilazane thin film according to an embodiment of the present invention were analyzed.

PHPS thin film and physical properties of fluoropolysilazane thin film according to one embodiment of the present invention Example After curing Transmittance
(Haze) Surface condition CA (Water) PHPS 27 ° 92.0% (0.1%) good P (PH-g-PFO / TM) 105 ° 92.5% (0.4%) good

Referring to Table 3, the contact angle of the fluorine polysilazane material P (PH-g-PFO / TM) thin film prepared according to one embodiment of the present invention is increased by about 80 °. In addition, it shows a high transmittance of 92.5% and a good surface condition. This means that when the fluoropolysilazane thin film is produced according to an embodiment of the present invention, the contact angle is improved due to the high water repellency and oil repellency, and the printing property is improved, thereby making it possible to produce a thin film having a smooth surface.

When the fluoropolysilazane material thin film manufacturing method according to an embodiment of the present invention is used, it is possible to provide a fluoropolysilazane material thin film having water repellency and oil-repellency characteristics and improved printability and adhesiveness.

It will be understood by those skilled in the art that the foregoing description of the present invention is for illustrative purposes only and that those of ordinary skill in the art can readily understand that various changes and modifications may be made without departing from the spirit or essential characteristics of the present invention. will be. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. For example, each component described as a single entity may be distributed and implemented, and components described as being distributed may also be implemented in a combined form.

The scope of the present invention is defined by the appended claims, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be construed as being included within the scope of the present invention.

Claims (12)

A water repellent fluoropolysilazane material represented by the following formula (1).
[Chemical Formula 1]

Wherein M ₁ is a group substituted with a fluorine-based acrylic resin, M ₂ is a group substituted with an acrylic silane, and n is an integer of 1 to 10000. The method according to claim 1,
Wherein M ₁ has a structure represented by the following formula (2)
(2)

Wherein R 1 may be hydrogen, a straight chain hydrocarbon having 1 to 6 carbon atoms or a branched hydrocarbon having 1 to 6 carbon atoms, a is an integer of 0 to 9, and b is an integer of 1 to 3. Polysilazane material. The method according to claim 1,
The M &lt; ₂ &gt; has a structure represented by the following formula (3)
(3)

R 2 may be hydrogen, a straight chain hydrocarbon having 1 to 6 carbon atoms or a branched hydrocarbon having 1 to 6 carbon atoms, R 3 is a hydrocarbon group having 1 to 3 carbon atoms, and c is an integer of 1 to 9 Fluorinated polysilazane material. Mixing a fluorine-based acrylic resin and an acrylic silane in a solvent to prepare a mixed solution;
Adding ferric hydrogen polysilazane (PHPS) to the mixed solution and stirring the mixture; And
And adding the catalyst to the mixed solution which has been firstly stirred, followed by secondary stirring. 5. The method of claim 4,
Characterized in that the solvent comprises cyclohexanone, metheyl ethyl ketone (MEK), dimethyl sulfoxide (DMSO) or N-methyl pyrrolidone (NMP) Method for producing fluorine polysilazane material. 5. The method of claim 4,
In the mixed solution, the fluorinated acrylic resin has an amount of 20 to 40 wt%, the acrylic silane has an amount of 0.01 to 10 wt%, and the solid component has a content of 30 wt% To 40% by weight of the fluoropolysilazane material. 5. The method of claim 4,
Wherein the primary stirring step is performed at 25 ° C to 70 ° C for 0.5 hour to 2 hours. 5. The method of claim 4,
Wherein the catalyst is a platinum (Pt) -based catalyst. 5. The method of claim 4,
Wherein the second stirring step is carried out at 25 ° C to 70 ° C for 17 to 24 hours. Applying the fluoropolysilazane material of claim 1 to a base material; And
And curing the fluorine polysilazane material to form a fluorine polysilazane thin film. 11. The method of claim 10,
Wherein the curing step comprises an ammonia water immersion method, steam curing, thermal curing, E-beam curing or pulse UV curing. 12. The method of claim 11,
Wherein the pulsed ultraviolet curing is performed by irradiating ultraviolet rays at 100 to 1000 times under the condition of 1800 to 2200 V, 80 to 120, and 7.4 to 9.4 Hz.

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