KR20180106488A - Functional coating material for Anti-fingerprint using organic-inorganic hibrid and a method of manufacturing the same - Google Patents

Abstract

The present invention relates to an organic-inorganic hybrid anti-fingerprint coating agent and a method for preparing the same, and more specifically, to a coating agent having excellent anti-fingerprint properties when coated on substrate surfaces such as stainless steel, that prevent scratches from forming thereon; and to a method for preparing the same. According to the present invention, the method comprises the steps of: preparing an organic polymer resin; mixing a colloidal sol with a catalyst in the presence of a solvent to synthesize a modified polysilicate inorganic compound; mixing the organic polymer resin with the modified polysilicate inorganic compound to form an organic-inorganic hybrid material; and mixing the organic-inorganic hybrid material with a fluoro epoxide compound and aging the same at 50-70°C for 1-2 days to prepare a coating agent.

Description

TECHNICAL FIELD The present invention relates to an organic-inorganic hybrid coating composition and a method for manufacturing the same,

More particularly, the present invention relates to a coating agent having excellent performance and transparency so that scratches do not occur when coated on the surface of a substrate such as stainless steel, and a method for producing the coating agent .

In recent years, when touching a stainless steel surface of a refrigerator door or the like using a finger as well as a surface of a display device such as a touch screen panel, a television, a navigation device, an automation device (ATM), an electronic blackboard, a ticket dispenser, The surface of the finger is contaminated by moisture and oil, and fingerprints are frequently left on the finger.

Since the pollution by moisture and the generation of fingerprints due to oil pollution cause the visibility of the screen such as the touch screen to be greatly reduced, the pollutants and fingerprints are prevented from being generated firstly, and secondly, There is a growing demand for a coating that can be implemented by enhancing the transparency to easily and cleanly clean the generated contaminants and fingerprints.

In order to satisfy the requirements of the coating agent, a method of initially applying a silicone oil or a fluorine resin to a base material has been proposed. However, it takes a long time to dry the base material due to heat, And the hardness is low, so that there is a problem in that the temporal effect is not maintained over time.

Recently, a silicone resin such as silane or siloxane, a fluorine resin or a fluorine-based silane resin was used to improve the transparency and the photopolymerization was carried out by copolymerization in the form of a urethane (meth) acrylate oligomer. It was not enough to realize the Moon.

Therefore, there is a desperate need for the development of a coating agent excellent in transparency through removal of the existing coating agent system and organic / inorganic hybridization.

Korean Patent Laid-Open Publication No. 10-2017-0011696;

Disclosure of Invention Technical Problem [8] The present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide an organic-inorganic hybrid or greasy coating agent and a method for producing the hybrid inorganic or organic coating agent having excellent resistance to scratching when coated on the surface of a base material such as stainless steel .

According to an aspect of the present invention, there is provided a method of manufacturing a semiconductor device, comprising: preparing an organic polymer resin;

Synthesizing a modified polysilicate inorganic compound by mixing a colloidal sol and a catalyst in the presence of a solvent; Mixing the organic polymer resin and the modified polysilicate inorganic compound to form an organic hybrid material; And mixing the fluorinated epoxide compound with the organic-inorganic hybrid material, followed by aging at 50 to 70 ° C for 1 to 2 days to complete the coating agent. As a technical point.

Preferably, the fluoroepoxide compound in the step of completing the coating comprises a first step of heating the catalyst in a nitrogen atmosphere after the catalyst is introduced into the reaction vessel; A second step of removing oxygen from the reaction vessel, purging with nitrogen, and cooling the heated catalyst to room temperature; A third step of adding a solvent to the reaction vessel and heating the mixture to 120 to 150 ° C to form a mixed solvent in which the catalyst is melted and then purging with nitrogen to cool the heated mixed solvent to room temperature; And a fourth step of adding a fluoroepoxide to the cooled mixed solvent to synthesize a fluoroepoxide compound.

Preferably, the coating agent in the step of completing the coating agent is characterized by having a water contact angle in the range of 100 to 120 °.

Preferably, the step of synthesizing the modified polysilicate inorganic compound further comprises a step of stabilizing the pH of the modified polysilicate inorganic compound.

Preferably, the colloidal sol in the step of synthesizing the modified polysilicate inorganic compound is characterized by being colloidal silica or colloidal alumina.

Preferably, the organic polymer resin in the step of preparing the organic polymer resin is at least one of an epoxy resin, an acrylic resin, a urethane resin, an acryl-urethane resin, and a polyvinyl alcohol resin.

On the other hand, an organic-inorganic hybrid or a greyish coating agent which is produced by the above-mentioned production method is also a technical point.

The organic-inorganic hybrid coating composition and the method for producing the same according to the present invention by the means for solving the above-mentioned problems have an effect of having good to smoothness since no scratch occurs when they are coated on the surface of a base material such as stainless steel.

1 is a process for synthesizing a fluoroepoxide compound according to a preferred embodiment of the present invention.

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

First, the organic polymer resin is prepared.

That is, an organic polymer resin is prepared in order to improve the adhesiveness and impart flexibility to the coating agent of the present invention. It is understood that the organic polymer resin is intended to improve the adhesion by imparting flexibility even when the coating agent is coated on angled portions such as a refrigerator or an elevator.

Here, at least one of epoxy resin, acrylic resin, urethane resin, acryl-urethane resin and polyvinyl alcohol resin can be selectively used as the organic polymer resin, but not limited to the above-mentioned kind, and various organic polymer resins It is possible to use.

Next, a step of synthesizing a modified polysilicate inorganic compound by mixing a colloidal sol and a catalyst in the presence of a solvent.

That is to say, 10 to 20 parts by weight of at least one colloidal sol selected from colloidal silica or colloidal alumina and 0.05 to 0.3 part by weight of a catalyst are mixed at 100 to 200 rpm for 30 to 60 minutes in the presence of 10 to 30 parts by weight of a solvent, It may be said that the polysilicate inorganic compound is formed.

First, the solvent is used for uniformly melting the colloidal sol and the catalyst. When the amount is less than 10 parts by weight, the meltability between the colloidal sol and the catalyst is not easily obtained. If the amount is more than 30 parts by weight, It is preferable that the solvent is added in the range of 10 to 30 parts by weight, since the superiority of the solvent is not shown.

For reference, at this stage, one or more solvents selected from (1) alcohols, (2) cellosolves, (3) ketones and (4) distilled water can be selectively used in this step. The alcohols may be selected from the group consisting of ethanol (EtOH), isopropyl alcohol (IPA), methanol (MeOH) and t-butyl alcohol (t-BA). Cellosolve can be selected from butyl cellosolve, (BC) and ethylcellosolve (EC). At least one ketone selected from the group consisting of methyl ethyl ketone (MEK) and acetone (ACT) can be selected.

The colloidal silica refers to colloidal silica or colloidal alumina. The colloidal silica or colloidal alumina improves the physical properties of the coating agent by improving the viscosity and hardness. When the amount is less than 10 parts by weight, improvement of the physical properties of the coating agent can not be expected. The mechanical strength of the undercoating agent may be improved. However, since the physical properties of the coating agent are also poor, the colloidal sol is preferably added in the range of 10 to 20 parts by weight.

The colloidal silica may be silicon-based colloidal silica, for example, SiO ₂ (Ludox silica HSA, Snow tex-O, Snow tex-N, Ludos silica SA).

Thirdly, the catalyst is used for the rapidity of the reaction. If the amount is less than 0.05 part by weight, the amount is insufficient for promoting the reaction. If the amount is more than 0.3 part by weight, the catalyst is not used. The catalyst is preferably added in the range of 0.05 to 0.3 parts by weight.

At this time, 1 to 10 parts by weight of a silane coupling agent may be added during the process of producing the modified polysilicate inorganic compound, and one or more kinds of the siloxane coupling agent may be selected from fluorosilane, alkoxysilane, alkylsilane and aminosilane, for example .

In addition, it is preferable that the step of synthesizing the modified polysilicate inorganic compound further includes a step of stabilizing the pH of the modified polysilicate inorganic compound. This is to prevent troubles of the coating agent, and 10% AMP95 which is an amine-based pH stabilizer can be used.

Next, the organic polymer resin and the modified polysilicate inorganic compound are mixed to form an organic hybrid material.

That is to say, 10 to 20 parts by weight of the organic polymer resin completed in the preceding step and 60 to 70 parts by weight of the modified polysilicate inorganic compound are mixed to carry out organic / inorganic hybridization.

When the organic polymer resin is added in an amount of less than 10 parts by weight, adhesion is poor, and even if the organic polymer resin is coated on angled portions of the substrate, flexibility is poor. When the organic polymer resin is added in an amount exceeding 20 parts by weight, physical properties of the coating agent may deteriorate. To 20 parts by weight.

When the modified polysilicate inorganic compound is added in an amount of less than 60 parts by weight, the hardness of the coating agent is insufficient and the physical properties of the coating agent are not good and the product properties are hardly recognized. When the amount is more than 70 parts by weight, adhesion with stainless steel or the like is low, Therefore, the modified polysilicate inorganic compound is preferably added in an amount of 60 to 70 parts by weight.

Finally, the fluorine epoxide compound is mixed with the organic / inorganic hybrid material and then aged at 50 to 70 ° C for 1 to 2 days to complete the coating agent.

Prior to this step, that is, before the fluorine epoxide compound is mixed with the organic hybrid material, a mixed solvent of ethanol (EtOH) and distilled water (D) at a weight ratio of 6: 4 at 20 to 35 ° C is added at a rate of 100 to 200 rpm For 30 to 60 minutes to dilute the organic hybrid material. Through such a diluting step, the effect of improving the liquid stability of the coating agent can be exhibited.

It is important to mix the fluorinated epoxide compound with the organic hybrid material and aged at 50 to 70 ° C for 1 to 2 days. When aged at less than 50 ° C or less than 1 day, it is difficult to obtain a coating material having desired physical properties. Or aging in a condition exceeding 2 days may cause denaturation in the physical properties of the coating, it is preferable to aged for 1 to 2 days at a temperature of 50 to 70 캜.

1 is a process for synthesizing a fluoroepoxide compound according to a preferred embodiment of the present invention. As shown in FIG. 1, the fluoroepoxide compound can be produced through the first step (S10), the second step (S20), the third step (S30) and the fourth step (S40) as follows.

(S10) In the first step, the catalyst is put in a reaction vessel, and then the catalyst is heated in a nitrogen atmosphere.

That is, the first step is a step of putting 0.05 to 0.1 part by weight into a reaction vessel (for example, a round-bottomed three-necked flask), heating the reaction vessel to a nitrogen atmosphere using a reflex apparatus at 100 to 120 ° C .

If the catalyst is added in an amount of less than 0.05 part by weight in the first step, the amount of the added catalyst is insufficient so that the reaction with the fluoroepoxide can not proceed smoothly. If the amount of the catalyst exceeds 0.1 part by weight, , And the catalyst is added preferably in the range of 0.05 to 0.1 part by weight, and most preferably 0.07 part by weight.

Subsequently, when the interior of the reaction vessel is heated to a temperature of less than 100 ° C. or more than 120 ° C., the reaction between the catalyst and the fluoroepoxide can not be performed. Therefore, in the first step, It is preferable to perform heating.

For reference, as a catalyst, one of the Group 1 elements such as hydrogen fluoride (HF), potassium fluoride (KF), and cesium fluoride (CsF) using hydrogen (H), potassium (K) And it is not limited to these catalysts. In some cases, a metal phosphate catalyst, a hydrochloric acid metal catalyst, and a phosphoric acid-hydrochloric acid complex catalyst may also be used.

(S20) In the second step, oxygen in the reaction vessel is removed, and nitrogen purging is performed to cool the heated catalyst to room temperature.

That is, after the heating is completed in the first step, the stability of the reaction can be induced by cooling the nitrogen purging to a normal temperature while purging the nitrogen with 2 ~ # times in a vacuum state.

(S30) In the third step, a solvent is added to a reaction vessel, and the mixture is heated to 120 to 150 DEG C to form a mixed solvent in which the catalyst is dissolved in a solvent, followed by purging with nitrogen, and cooling the heated mixed solvent to room temperature.

In other words, the third step is a step for melting the solid catalyst. When the solvent is added to the reaction vessel and heated to less than 120 ° C, the temperature is low enough to uniformly melt the catalyst in the solvent. The catalyst is not pumped due to the high temperature due to the melting of the catalyst due to the high temperature. In the third step, the catalyst is heated at a temperature of 120 to 150 ° C It is preferable to heat it to a temperature range.

Propylene glycol monomethyl ether acetate (PMA), Dimethylformamide (DMF), Triglycol (TG), Acetylacetone, Ethylacetoacetate, Isopropanol (IPA), Butyl cabitol (BC), Propylene glycol monomethyl ether May be selectively used. However, the solvent may be any solvent that can melt the catalyst, but is not necessarily limited thereto.

(S40) In the fourth step, a fluoroepoxide is added to the cooled mixed solvent to synthesize a fluoroepoxide compound.

The fourth step is a step of characterizing the present invention. In the third step, 2 to 8 parts by weight (more preferably, 5.78 g (17 equivalents)) of a fluoroepoxide is added into the reaction vessel cooled by nitrogen purging After the reaction is completed by heating at 70 to 140 ° C with stirring, the liquid is cooled to room temperature to obtain a liquid fluorine epoxide compound which has been synthesized.

The reason for adding the fluoroepoxide in the range of 2 to 8 parts by weight is to adjust the molecular weight of the fluoroepoxide compound to 2,000 to 5,000 g / mole. When the amount of the fluoroepoxide compound is less than 2 parts by weight, the fluorine epoxide compound And if it exceeds 8 parts by weight, the molecular weight of the ultimately obtained fluorine epoxide compound is exceeded, so that it can be appropriately controlled.

Additionally, the fluoroepoxide used in the fourth step can be used in place of hexafluoropropylene oxide.

Here, the process of obtaining the fluoroepoxide compound will be described with reference to FIG.

의

가 반복적인 단위를 가지는 것을 특징으로 하는바(M은 주기율표 1족 원소 중에서 선택된 1종이고, R₁은 C1-C2의 플루오르알킬기이다.), 촉매(예컨대, CsF)가 가지고 있던 1개의 전자가 플루오르 에폭사이드를 공격하면서 개환(고리 열림)되는 반응이 발생하는데, 이는 촉매의 전자가 에폭시 링을 순차적으로 깨면서 최종적으로 플루오르 에폭사이드화합물이 단분자 형태에서 고분자 형태로 늘어나게 되는 것을 말한다.That is, the fluoroepoxide compound is a ring-

of

(Wherein M is one selected from Group 1 elements of the periodic table and R ₁ is a fluoroalkyl group of C ₁ -C ₂ ), a single electron possessed by a catalyst (for example, CsF) has a repeating unit (Ring opening) occurs while attacking the fluoroepoxide, which means that the electrons of the catalyst sequentially break the epoxy ring and ultimately the fluoroepoxide compound is stretched into a polymer form in the form of a single molecule.

If the content of the fluoroepoxide compound is in the range of 2,000 to 5,000 g / mole, it can be met when the fluoroepoxide compound meets the substrate such as metal or stainless steel, since it is coated with the fluororesin for coating and then wiped off. , And in the fourth step, a chain opening reaction is performed to satisfy the molecular weight in the range of 2,000 to 5,000 g / mole.

의 형태를 가지게 되는데, 이때 O에 (-)전자가 남게 되며, 이러한 O의 (-)전자가 다시 플루오르 에폭사이드의 O-CF 사슬을 끊음에 따라,

형태로 사슬이 늘어나게 된다. 이처럼 사슬이 연쇄적으로 늘어나게 되면서 2,000~5,000g/mole 범위의 분자량을 만족하게 된다.This ring-opening reaction, as illustrated in Figure 1, when the (-) electrons present in the catalyst break the O-CF chain of the fluoroepoxide,

(-) electrons remain in O, and as the (-) electrons of O break again the O-CF chain of fluorine epoxide,

The chain will increase in shape. As the chain grows in a chain, it meets molecular weights ranging from 2,000 to 5,000 g / mole.

When the molecular weight of the fluoroepoxide compound is less than 2,000 g / mole or more than 5,000 g / mole, the fluoroepoxide compound tends to separate from the substrate such as metal or stainless steel due to friction, Range.

In the fourth step, in order to increase the hardness of the fluoroepoxide compound, a metal additive may be further added. For example, an aluminum chloride compound or the like may be optionally used.

In addition, in order to control the hardness of the coating material, it is preferable to use an aliphatic polyamine series such as ethylene diamine, triethylene tetramine, tetraethylene pentamine, acrylonitrile-modified amine, amidoamine, Dicyandiamide, amino resin, isocyanate, At least one of melamine may be selectively used.

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

denaturalization Polysilicate  Preparation of inorganic compounds

The modified polysilicate inorganic compound can be produced under the conditions of Example 1, Example 2, Example 3 and Example 4 of Table 1 as follows.

Example 1 Example 2 Example 3 Example 4 Stirring time (30 to 60 minutes)
Stirring speed (100 to 200 rpm)
Agitation temperature (20-50 < 0 > C) Colloidal silica 15 15 15 15 EtOH 14 14 IPA 14 14 D 5 5 5 5 BC Hydrates (hydrochloric acid) 0.1 0.1 An acid metal catalyst (metal chloride acid) 0.2 0.2 Stirring time (30 to 60 minutes)
Stirring speed (100 to 200 rpm)
Agitation temperature (20-50 < 0 > C) Fluorine silane 2 5 2 5 Stirring time (20-30 minutes)
Stirring speed (100 to 200 rpm)
Agitation temperature (20-50 < 0 > C) Methyltrimethoxysilane 20 20 20 20 Stirring time (30 to 60 minutes)
Stirring speed (100 to 200 rpm)
Agitation temperature (20-50 < 0 > C) 3-glucidoxytrimethylsilane 10 10 10 10 Stirring time (60-120 minutes)
Stirring speed (100 to 200 rpm)
Agitation temperature (20-50 < 0 > C) Acetylacetone 0.2 0.2 0.5 0.5 Unit: parts by weight

The liquid stability, graininess and cross-cut of the modified polysilicate inorganic compound prepared according to the above-described Examples 1, 2, 3 and 4 are shown in Table 2 below.

Example 1 Example 2 Example 3 Example 4 Liquid stability (℃) ◎ ◎ ◎ ◎ (98 ° C, 1 hour) ○ ○ ○ ○ crosscut ◎ ◎ ◎ ◎ ?: Very good,?: Good,?: Poor, X: poor

Manufacture of coatings

Using the modified polysilicate inorganic compound prepared through the above-described Example 4, the coating agent can be produced under the conditions of Example 5, Example 6, Example 7 and Example 8 shown in Table 3 below.

Example 5 Example 6 Example 7 Example 8 Stirring time (30 to 60 minutes)
Stirring speed (100 to 200 rpm)
Agitation temperature (20-35 < 0 > C) Example 4 40 40 40 40 EtOH / D (6: 4) 51 51 51 51 Stirring time (30 to 60 minutes)
Stirring speed (100 to 200 rpm)
Agitation temperature (20-35 < 0 > C) 10% AMP95 0.1 0.2 0.3 0.5 Stirring time (30 to 60 minutes)
Stirring speed (100 to 200 rpm)
Agitation temperature (20-35 < 0 > C) Amino resin (30%) 20 20 20 Stirring time (60-120 minutes)
Stirring speed (100 to 200 rpm)
Stirring temperature (60 DEG C) fluorine
Epoxide compound 12 12 12 Aging at 60 ° C for 1 day Unit: parts by weight

The liquid stability, appearance, breakability, cross-cut, alkali resistance, salt water spray test and water contact angle of the modified polysilicate inorganic compound prepared according to the above-described Example 5, Example 6, Example 7 and Example 8 were as shown in the following Table 4 shows the results.

Example 5 Example 6 Example 7 Example 8 Liquid stability (60 ° C) ◎ ◎ ◎ ◎ Exterior △ ○ ◎ ○ (98 ° C, 1 hour) ○ ○ ◎ ○ cross cut (100 * 100) ◎ ◎ ◎ ◎ Alkali resistance (5% Na ₂ CO ₃ ) ○ ○ ◎ ◎ Salt spray test (72hr) ○ ◎ ◎ ◎ My fingerprint (water contact angle) 100 110 115 115 ?: Very good,?: Good,?: Poor, X: poor

As shown in Table 4, although most of the results were good, it was confirmed that the best physical properties were obtained in Example 7.

Particularly in the case of a water contact angle, it is measured by using a water contact angle with respect to the surface of a coating agent, and it can be found that only when the water contact angle is in the range of 100 to 120 (most preferably, 115) I could.

For reference, the external appearance is the measurement of embossing, staining, and rainbow phenomenon when coated on the surface of stainless steel. The cross cut is to test the adhesion and to check whether the coating falls or not when the coating is applied. If it is attached to 100 pieces of 1mm width and 1mm length piece with 3M tape and there is no adhesion when it is removed The phenomenon of rising and falling occurs, and it is judged whether adhesion is good depending on how many of the 100 pieces are raised and raised.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention may be embodied otherwise without departing from the spirit and scope of the invention.

Therefore, the embodiments disclosed in the present invention are not intended to limit the technical spirit of the present invention, but to illustrate them, and the scope of the technical idea of the present invention is not limited by these embodiments.

The scope of protection of the present invention should be construed according to the claims, and all technical ideas within the scope of the claims should be construed as being included in the scope of the present invention.

Claims (7)

Preparing an organic polymer resin;
Synthesizing a modified polysilicate inorganic compound by mixing a colloidal sol and a catalyst in the presence of a solvent;
Mixing the organic polymer resin and the modified polysilicate inorganic compound to form an organic hybrid material; And
Mixing the fluorinated epoxide compound with the organic or inorganic hybrid material, and aging the mixture at 50 to 70 ° C for 1 to 2 days to complete the coating agent. The method according to claim 1,
The fluoroepoxide compound in the step of completing the coating agent may contain,
A first step of introducing a catalyst into a reaction vessel and then heating the catalyst under a nitrogen atmosphere;
A second step of removing oxygen from the reaction vessel, purging with nitrogen, and cooling the heated catalyst to room temperature;
A third step of adding a solvent to the reaction vessel and heating the mixture to 120 to 150 ° C to form a mixed solvent in which the catalyst is melted and then purging with nitrogen to cool the heated mixed solvent to room temperature; And
And a fourth step of adding a fluoroepoxide to the cooled mixed solvent to synthesize a fluoroepoxide compound. The method according to claim 1,
The coating agent in the step of completing the coating agent,
Wherein the water contact angle is in the range of 100 to 120 DEG. The method according to claim 1,
After the step of synthesizing the modified polysilicate inorganic compound,
And stabilizing the pH of the modified polysilicate inorganic compound. ≪ RTI ID = 0.0 > 11. < / RTI > The method according to claim 1,
The colloidal sol in the step of synthesizing the modified polysilicate inorganic compound,
Characterized in that the colloidal silica or the colloidal alumina is phosphorus. The method according to claim 1,
In the step of preparing the organic polymer resin,
An organic resin, an epoxy resin, an acrylic resin, a urethane resin, an acryl-urethane resin and a polyvinyl alcohol resin, and a method for producing the same. 7. An organic-inorganic hybrid or greyish coating agent which is produced by the production method according to any one of claims 1 to 6.

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