KR20160112114A

KR20160112114A - Glass film Coating Agent

Info

Publication number: KR20160112114A
Application number: KR1020150037203A
Authority: KR
Inventors: 김진호
Original assignee: 김진호
Priority date: 2015-03-18
Filing date: 2015-03-18
Publication date: 2016-09-28
Also published as: KR101745951B1

Abstract

The present invention relates to a glass coating agent, specifically a glass coating agent by proper mixing of an organic polysilazane and a solvent, which comprises 5.5 to 7.5% by weight of organic polysilazane, butyl (butyl) (D-sol 150) in an amount of from 38 to 42 wt%, based on the total weight of the composition, from 6.5 to 8.5 wt% of the hydrodesulfurized light naphtha acetate, 44 to 48 wt% of hydrodesulfurized light naphtha (Solvent No. 2), and a mixture of N-Paraffin, %, Which is excellent in dryness of organic solvent at room temperature, can mask the odor of organic polysilazane, and has excellent hardness and long lasting after hardening. And has an excellent effect in glossiness as compared with a general coating agent.

Description

{Glass film Coating Agent}

The present invention relates to a glass-film coating agent, specifically, a glass-film coating agent having excellent gloss due to proper combination of an organic polysilazane and an organic solvent.

Various measures have been taken to prevent pollution on the surface of automobile customers' products that are expensive products. For example, the automobile body is easily contaminated with dust, combustion additives, exhaust gas, and the like. Therefore, the main body is coated with wax to form a wax coating, thereby preventing contamination of the main body.

Generally, the effect of the coating is to repel water on the surface of the body to form water droplets when it comes into contact with the surface of the body and roll down below the surface of the body, thereby preventing the contaminants in the water from sticking to the surface of the body and remaining And makes it difficult for the wax coating to adhere the contaminant component to the surface of the body, so that even if the contaminant component adheres to the surface, it can be easily washed with water.

The wax coating initially has an effect of improving water repellency and gloss. However, in order to sufficiently effect the waxing, it is necessary to perform a cleaning operation to manually clean the wax, and the effect is reduced by about three months. Further, when the wax components are eluted and adhered to the glass surface, there is a disadvantage that the driver's watch is bad.

Further, the effect of the water-repellent treatment by the conventional water-repellent wax can not be said to be successful, and even if sufficient water-repellent treatment is initially carried out, the effect does not last long and does not exhibit sufficient antifouling effect for a long time.

Such conventional hydrophobic coatings impart hydrophobicity only temporarily or in a short time, and therefore it is difficult to expect the hydrophobic effect to be maintained sufficiently long, and the water film on the hydrophobic coating surface is not formed uniformly, so that the transmission image or the reflection image is distorted And the practical application of the hydrophobic coating of the product leaves a problem.

In order to overcome the disadvantages of the wax coating and to be able to maintain the effect of the coating for a considerable period of time, polysilazane has been developed to make an interlayer insulating film of semiconductors, The glass coating was used as an automotive coating method.

However, since the glass coating layer has a relatively long curing time, it may take a long time to cure. Further, the glass coating layer has a relatively low hardness and thus has a problem of being easily broken. Furthermore, there is a problem that the coating side easily peels off from the coating surface after application.

SUMMARY OF THE INVENTION The present invention has been made in order to solve the above-mentioned problems, and it is an object of the present invention to provide a coating film for a glass coating which is semi-permanently maintained and can be easily removed.

The present invention also provides a glass coating agent capable of curing both at room temperature and at high temperature.

The present invention also provides a glass coating agent having excellent weatherability, non-flammability, durability and economical efficiency.

In order to accomplish the above object, the present invention provides a method for producing an organic polysilazane comprising 5.5 to 7.5% by weight of an organic polysilazane, 6.5 to 8.5% by weight of a butyl acetate organic solvent, a hydrodesulfurized light naphtha organic 44 to 48 wt% of a solvent, and 38 to 42 wt% of a mixture of N-Paraffin, Iso-Paraffin and Naphthenic organic solvent.

Also, the present invention provides a glass-film coating agent wherein the organic polysilazane has a unit represented by the following formula (1) as a repeating unit.

[Chemical Formula 1]

The present invention also provides a glass coating agent characterized in that the substituent R in the above formula (1) has H or CH ₃ .

Also, the present invention provides a glass coating agent characterized by having a hydrodesulfurized light naphtha organic solvent having an Aromatic component and an Aliphatic component ratio of 1: 0.7 to 1: 1.5 by weight.

The present invention also provides a glass coating agent characterized in that the composition ratio of the organic solvent mixture of N-Paraffin, Iso-Paraffin and Naphthenic is 1: 1: 1.2 to 2.2.

The glass coating agent of the present invention is characterized by excellent water repellency, easy removal of external contaminants, and excellent glossiness.

In addition, the coating of the glass coating according to the present invention has an advantage of durability because it enables natural drying and curing by moisture hardening without using a catalyst at room temperature.

Hereinafter, the present invention will be described in more detail with respect to embodiments of the present invention. However, the present invention should not be construed as limited to the embodiments described below, but may be embodied in various other forms. The following examples are provided so that those skilled in the art can fully understand the scope of the present invention, rather than being provided so as to enable the present invention to be fully completed.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Furthermore, all terms including technical and scientific terms have the same meaning as will be understood by those skilled in the art having ordinary skill in the art, unless otherwise specified. These terms, such as those defined in conventional dictionaries, shall be construed to have meanings consistent with their meanings in the context of the related art and the description of the present invention, and are to be interpreted as being ideally or externally grossly intuitive It will not be interpreted.

As used herein, the terms "substantially", "substantially", and the like are used herein to refer to a value in or near the numerical value when presenting manufacturing and material tolerances inherent in the meanings mentioned, Absolute numbers are used to prevent unauthorized exploitation by unauthorized intruders of the mentioned disclosure.

Glass coating agent

(1) 5.5 to 7.5% by weight of organic polysilazane (2) organic solvent: 1) butyl acetate 6.5 to 8.5% by weight 2) desulfurized treated light naphtha hydrodesulfurized light naphtha organic solvent 44-48 wt% 3) 38-42 wt% mixture of N-Paraffin, Iso-Paraffin and Naphthenic organic solvent.

When the amount of the organopolysilazane exceeds the upper limit of the composition ratio in the composition ratio, cracking or bleed out may occur. When the amount of the organopolysilazane is less than the lower limit of composition ratio, And failures of improved cross-linking can occur. First, components of the glass coating agent will be described in detail below.

(1) Organic polysilazane

Silazanes include monomers, oligomers, cyclic and linear polymers with 1-4 Si-N repeat units in the compound. In particular, polysilazane refers to oligomers, cyclic, polycyclic and straight chain polymers or resinous polymers having at least five Si-N repeat units in the compound.

Polysilazanes can be largely divided into inorganic polysilazanes and organic polysilazanes.

In the present invention, organic polysilazanes are used, and dihalosilane (preferably dichlorosilane) and R ₁ R ₂ SiX ₂ [R ₁ and R ₂ represent a hydrogen atom or an alkyl group (preferably a methyl group)] . Provided that R ₁ and R ₂ do not simultaneously represent a hydrogen atom.

The organopolysilazane used in the present invention is characterized in that three units are repeatedly constituted as shown in Chemical Formula 1 below.

Wherein R is composed of a H or CH _3.

On the other hand, the inorganic polysilazane has a unit of the following formula (2), which is characterized by having only a Si-H bond as a repeating unit.

The organopolysilazane, which is a constituent component of the present invention, is characterized in that the amount of the silicon-hydrogen bond is reduced compared to the inorganic polysilazane. As the amount of silicon-hydrogen bond is reduced, the viscosity of the polysilazane increases relative to the viscosity.

As the viscosity increases, an organic solvent, which is a diluting solvent, is required for use as a coating agent on automobile bodies and the like. In order to be able to apply as thin as possible, the viscosity of the glass coating agent is important and the weight percentage of the added solvent should be controlled. The appropriate concentration is convenient because it allows the thickness of the coating to be thinner and does not need to be cured at high temperature and can have a relatively short curing time even at room temperature.

(2) Organic solvents

The organic solvent may be a petroleum solvent aromatic or alicyclic solvent, an ether, a halogenated hydrocarbon or a terpene mixture or a mixture of these solvents.

The diluting solvent used in the coating solution of the present invention may be any other diluting solvent capable of dissolving the polysilazane having Si-H bonds. In view of storage stability, the diluting solvent is preferably a solvent in which the ability to dissolve the organic polysilazane can be maintained, and the solvent used for a long time preferably does not emit gas, for example, silane, hydrogen, .

The diluting solvent used in the coating solution of the present invention may be selected from petroleum solvents, for example, mineral spirits, paraffin solvents, aromatic solvents, alicyclic solvents, ethers and halogenated hydrocarbons.

Examples of the solvent or solvent component include paraffinic solvent or solvent components such as octane and 2,2,3-trimethylpentane with a carbon number of 8, nonane with a carbon number of 9 and 2,2,5-trimethylhexane with a carbon number of 10 Decane and n-undecane of carbon number 11, aromatic solvents or solvent components such as xylene of 8 carbon atoms, cumene of 9 carbon atoms and mesitylene, naphthalene, tetrahydronaphthalene, butylbenzene, p-cymene, diethyl For example, methylcyclohexane having 7 carbon atoms, ethylcyclohexane having 8 carbon atoms, p-menthane having a carbon number of 10, alpha -cyclopentane having a carbon number of 10, and alicyclic solvents or solvent components such as benzene and tetramethylbenzene having a carbon number of 10 and pentylbenzene having a carbon number of 11, For example, dichloromethane, dichloroethane, dichloromethane, dichloromethane, tetrahydrofuran and the like, ethers such as dimethyl ether, diethyl ether, dibutyl ether, polyglycol ether, tetrahydrofuran and the like and halogenated hydrocarbons such as dichloromethane, Or a fluorinated hydrocarbon such as chloroform, may include aromatic compounds, such as bromide or iodide, and chlorinated hydrocarbons as chlorobenzene.

It has also been found useful to use a terpene mixture such as, for example, Depanol as a solvent. However, the above-mentioned solvents are merely exemplified as examples, and the solvents or solvent components are not particularly limited by these examples. In addition, the above solvent or solvent component may be used alone or as a mixture thereof.

In the present invention, a mixture of butyl acetate, hydrodesulfurized light naphtha and N-Paraffin, Iso-Paraffin and Naphthenic was used as an organic solvent. This will be described in detail below.

1) Butyl acetate Organic solvent

Butyl acetate is one of the most commonly used organic solvents and is a colorless, flammable liquid. The functional group is an ester. It is difficult to dissolve in water, which is a general characteristic of esters, but it easily dissolves in organic solvents.

It is a solvent which is strong in volatility and has the best dissolving power and is used for securing dilution stability. However, since it is odorous and can not be used in large quantities, it is mixed with other organic solvents.

2) hydrodesulfurized light naphtha organic solvent

The naphtha organic solvent is a product in which an aromatic component and an aliphatic component coexist at a proper ratio and the ratio of the aromatic component and the aliphatic component is 1: 0.7 to 1: 1.5. It is suitable for applications such as adhesives and mold release agents requiring low-temperature evaporation and proper solubility, and is also generally used for paint thinner.

It is also used for masking the toxic smell of organic polysilazane and for adjusting the dryness, especially for increasing the drying speed at low temperature.

3) Mixture of N-Paraffin, Iso-Paraffin and Naphthenic Organic solvents

The mixture organic solvent has excellent stability because it has almost no unsaturated compounds and impurities, and contains naphthene component, so that it has better dissolving power than nomal and iso-paraffin solvents. It is appropriate that the composition ratio of the organic solvent mixture of N-Paraffin, Iso-Paraffin and Naphthenic is 1: 1: 1.2 to 2.2.

There are various products with different distillation ranges for each type, and it is possible to select appropriate products for each use, and there are almost no harmful substances such as aromatic components and sulfur, which are carcinogenic substances, and they are easy to work with low odor products.

The odor is comparatively mild and the solvent is a high-boiling solvent. Solubility is somewhat poor, but it is used because it has no reactivity and has a delayed drying speed. In the process of coating the glass, the drying is too fast, the smear is lost and the gloss is partially lost, so it is necessary to select a solvent with a low odor and a low odor.

Example One

The organopolysilazane is a Kion HTA-1500 product from AZ Electronic Materials, consisting of a mixture of silane substituents dimethly, methyl-hydrogens or silazane nitrogen substituted with triethoxysilane 6.5 wt% based on the total weight, 7.5 wt% butyl acetate organic solvent manufactured by SK Chemical, 46 wt% hydrodesulfurized light naphtha organic solvent, solvent 2 manufactured by Samsung Chemical Industry Co., 40% by weight of a mixture of D-sol 150, N-Paraffin, Iso-Paraffin and Naphthenic organic solvents prepared in the literature.

Solvent No. 2 having the largest weight ratio among the above components was first charged into a magnetic stirrer, and then D-sol 150, butyl acetate and HTA-1500 were sequentially added thereto in order and thoroughly stirred for about 30 minutes. .

Since the HTA-1500 has a strong odor, the HTA-1500 product should be put into the final batch in order to minimize the odor during operation.

Example 2

Organic polysilazane of Kion HTA-1500 manufactured by AZ Electronic Materials Co., which is 7.5% by weight based on the total weight, 6.5% by weight of butyl acetate organic solvent manufactured by SK Chemical, 2) 44% by weight of hydrodesulfurized light naphtha organic solvent, and 42% by weight of a mixture of N-Paraffin, Iso-Paraffin and Naphthenic organic solvent D-sol 150 manufactured by Ishihara Chemical Co., Other conditions are the same as those in the first embodiment.

Comparative Example One

Organic polysilazane of Kion HTA-1500 manufactured by AZ Electronic Materials Co., which is 10% by weight based on the total weight, 7.5% by weight of butyl acetate organic solvent manufactured by SK Chemical, 2) 42.5% by weight of a hydrodesulfurized light naphtha organic solvent, and 40% by weight of a mixture of N-Paraffin, Iso-Paraffin and Naphthenic organic solvent D-sol 150 manufactured by Ishihara Chemical Co., Other conditions are the same as those in the first embodiment.

Comparative Example 2

Organic polysilazane, a product of Kion HTA-1500 manufactured by AZ Electronic Materials Co., was 3.0% by weight based on the total weight, 7.5% by weight of a butyl acetate organic solvent manufactured by SK Chemicals, and 2) 49.5% by weight of a hydrodesulfurized light naphtha organic solvent, and 40% by weight of a mixture of N-Paraffin, Iso-Paraffin and Naphthenic organic solvent D-sol 150 manufactured by Ishihara Chemical Co., Other conditions are the same as those in the first embodiment.

Coating with coating liquid

Approximately 5 g of a liquid-state glass coating agent was applied on a 70 mm long, 150 mm thick 0.7 T SUS 303 stainless steel specimen. 5 Bar Coater.

In each of the above tests, each sample was coated on the SUS 303 stainless steel specimen of the same type as the same Bar Coater in a room at 25 ° C. The prepared coating samples were then cured at about < RTI ID = 0.0 > 25 C < / RTI > for 5 days to complete the specimens.

After coating, if left at room temperature for a certain time, it reacts with H ₂ O or O _{2 in} the air to form a pure and hard SiO ₂ thin film.

Evaluation of Coating Agent

With respect to the glass coating agent of the present invention, after coating on the surface of an automobile and after 2 days at room temperature, the quality of the coating agent was commissioned to the Korea Testing and Research Institute, and the following results were obtained.

Test result Test Items Example 1 Example 2 Comparative Example 1 Comparative Example 2 Test Methods Pencil hardness 8H 8H 8H 5H KS D 6711: 1992 Heat resistance test
[(500 ± 20) ° C, 1 hour] clear clear offshoot clear KS M 5000: 2009 Heat resistance test
[(700 ± 20) ° C, 1 hour] clear clear offshoot clear KS M 5000: 2009 Heat resistance test
[(1000 ± 20) ° C, 1 hour] offshoot offshoot offshoot offshoot KS M 5000: 2009 Stain resistance
[Meteor magic (black)]
clear
clear
clear
clear Determine whether the specimen is contaminated after the contamination source has been left for 24 hours. Gloss (60 °) 19% 19% 21% 15% KS MISO 2813: 2007

The hardness of the coating is determined by pencil hardness measurement. One of the methods for measuring the hardness is to measure the hardness with a sharp object. 8H, 7H, 6H, 5H, 4H, 3H, 2H, F, HB, B, 2B, 3B, 4B, 5B, 6B, 7B, 8B and 9B as hardness units use.

In conclusion, the larger the number before H, the better the ability to protect the film surface from various scratch hazards.

As shown in Table 1, after the curing process of the coating agent, the glass membranes of Examples 1 and 2 of the present invention exhibit 8H hardness values. Comparative Example 1 showed no abnormality in the pencil hardness test even when the organic polysilazane was added in an excess amount of 10% by weight in Example 1, but in Comparative Example 2, the organic polysilazane content was 3.0% It can be seen that the pencil hardness is lowered to 5H.

The heat resistance test shall be made by confirming whether there is any abnormality when heating to a specific temperature for 1 hour. Anomalies include swelling, cracking, and falling. As can be seen from the above Table 1, in Examples 1 and 2 and Comparative Example 2, no abnormal symptoms can be found up to 700 ° C, but cracking can be observed at 1000 ° C. On the other hand, in Comparative Example 1, abnormal symptoms that are cracked even at 500 DEG C occur.

The contamination test does not have a separate standard technique measurement method. The test plate is contaminated with the contamination source, which is the method provided by the test applicant, and left for 24 hours. After removing the contamination source with a remover (ethyl alcohol), the contamination of the test piece is determined. As a result of measuring the pollution source using a magic pan (black), it can be seen that all of the examples and comparative examples are easily removed without any abnormality.

The standard gloss measurement is determined by measuring the degree of light reflection at a 60 ° angle after coating. The general coating showed 3% glossiness under the same conditions, but the coating with the glass coating showed 19% glossiness in Examples 1 and 2, indicating that the gloss of the glass coating was excellent. On the other hand, in Comparative Example 1, the content of the organic polysilazane was high, which was 21% higher than those of Examples 1 and 2. In Comparative Example 2, the content of the organic polysilazane was low, so that the 15% Can be seen.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the inventions. It will be clear to those who have knowledge of.

Claims

5.5 to 7.5% by weight of organic polysilazane;
6.5 to 8.5 wt% butyl acetate organic solvent;
44 to 48% by weight of hydrodesulfurized light naphtha organic solvent,
A mixture of N-Paraffin, Iso-Paraffin and Naphthenic, and 38 to 42% by weight of an organic solvent.

The method according to claim 1,
Characterized in that the organic polysilazane has units of the following formula (I) as repeating units Glass coating agent.
[Chemical Formula 1]

3. The method of claim 2,
Wherein the substituent R of Formula 1 has H or CH ₃ .

The method according to claim 1,
Wherein the hydrodesulfurized light naphtha organic solvent has an Aromatic component and an Aliphatic component ratio of 1: 0.7 to 1: 1.5 by weight.

The method according to claim 1,
Wherein the composition ratio of the organic solvent mixture of N-Paraffin, Iso-Paraffin and Naphthenic is 1: 1: 1.2 to 2.2.