KR102288310B1 - Method For Manufacturing Of Binder For Ceramic Resin - Google Patents

Abstract

The present invention relates to a method for manufacturing a ceramic resin binder for a fluoropolymer resin, and more particularly, to a method for manufacturing a ceramic resin binder for a fluoropolymer resin comprising: a first step of preparing a first mixture by mixing 3-glycidoxypropyltrimethoxysilane with distilled water containing hydrochloric acid or nitric acid, followed by stirring; a second step of preparing a second mixture by stirring after adding silica colloid to the first mixture obtained in the first step; and a third step of preparing a third mixture by stirring after adding a nonionic surfactant to the second mixture obtained in the second step.

Description

Manufacturing method of ceramic resin binder for fluoropolymer resin {Method For Manufacturing Of Binder For Ceramic Resin}

The present invention relates to a method for producing a ceramic resin binder for a fluoropolymer resin, and more particularly, by using 3-glycidoxypropyltrimethoxysilane, hydrochloric acid or nitric acid, silica colloid and a nonionic surfactant, toxic during production It relates to a method for producing a ceramic resin binder for a fluoropolymer resin that does not generate gas and can expect excellent adhesion and transparency.

The fluorine-based polymer resin is a thermoplastic and has fluidity in a temperature range of 300°C to 400°C, and forms a coating film after cooling. However, due to the nature of the carbon-bonded fluorine molecule, it does not bind well with materials such as aluminum, iron, stainless steel, and ceramics.

It is common to prepare and use such a polymer binder as an emulsion (same as dispersion including water-dispersed resin and surfactant) like fluororesin. In the process of manufacturing PES in emulsion form, strong alkali ammonia or sodium hydroxide The smell is very poisonous due to the use of PAI, and in particular, PAI has a problem that it is not suitable for the coating or paint industry that produces various colors because it shows a yellow or brown color at a high temperature.

Korean Patent Publication No. 2000-0046438

An object of the present invention is to provide a method of manufacturing a ceramic resin binder for a fluoropolymer resin that does not generate a toxic odor during the manufacturing process while imparting binding force to the fluorine-based polymer resin. do it with

Another object of the present invention is to provide a method for manufacturing a ceramic resin binder for a fluoropolymer resin that has excellent transparency and surface hardness as well as no yellowing phenomenon when forming a coating film using a fluoropolymer resin.

The method of manufacturing a ceramic resin binder for a fluoropolymer resin according to the present invention for solving the above problems is a mixture of 3-glycidoxypropyltrimethoxysilane (GPTMS) with distilled water containing hydrochloric acid or nitric acid and A first step of preparing a first mixture by stirring; a second step of preparing a second mixture by adding and stirring silica colloid to the first mixture obtained in the first step; and a third step of preparing a third mixture by adding and stirring a nonionic surfactant to the second mixture obtained in the second step.

In addition, in the method for producing a ceramic resin binder for a fluoropolymer resin according to the present invention, it is characterized in that it further comprises a fourth step of filtering the third mixture.

In addition, in the method for manufacturing a ceramic resin binder for a fluoropolymer resin according to the present invention, in the first step, 3-glycidoxypropyltrimethoxysilane (GPTMS) 35 to 55 based on the entire ceramic resin binder % by weight, hydrochloric acid or nitric acid 0.05 to 0.2% by weight, and distilled water 4 to 10% by weight mixed in a ratio, and stirred for 100 to 140 minutes while refluxing at 75 to 85 ℃, in the second step, the first mixture 20 ~ After cooling to 25 ° C., the silica colloid is mixed in a proportion of 30 to 45 wt % based on the total ceramic resin binder, and stirred at 20 to 25 ° C. for 100 to 140 minutes, and in the third step, the ceramic resin binder Based on the whole, the nonionic surfactant is mixed in a ratio of 1 to 10% by weight, stirred at a speed of 600 to 800 rpm in the range of 60 to 65 ° C. for 5 to 7 hours, and in the fourth step, filtration with a 380 to 400 mesh filter characterized in that

In addition, in the present invention, it is characterized in that it is a ceramic resin binder for a fluoropolymer resin manufactured by the method described above.

In the present invention, as a method of using the above-mentioned ceramic resin binder as a binder for forming a coating film of a fluoropolymer resin, 58 to 62 parts by weight of a fluorine-based polymer resin and 38 to 42 parts by weight of a ceramic resin binder are mixed to form a coating film of a fluoropolymer resin. It is characterized in that it is a method used as a binder.

According to the manufacturing method of the ceramic resin binder for fluoropolymer resin of the present invention, a resin having a highly developed two-dimensional chain structure is formed through a ceramic sol-gel reaction, and then silica colloid is bound as heat-resistant nanoparticles. This has the advantage that no toxic gas is generated.

In addition, when the ceramic resin binder obtained by the manufacturing method of the present invention and the fluoropolymer resin are mixed, adhesion to the substrate is improved and a coating film having excellent transparency can be formed.

Moreover, when the ceramic resin binder obtained by the manufacturing method of the present invention is mixed with the fluoropolymer resin, the formed coating film is transparent and yellowing does not occur, and excellent surface strength and surface lubricity can be expected.

1 is a flowchart for explaining a method of manufacturing a ceramic resin binder for a fluoropolymer resin according to the present invention.

In the present application, terms such as “comprises”, “have” or “have” are intended to designate the existence of features, numbers, steps, components, parts, or combinations thereof described in the specification, and one or more other It is to be understood that this does not preclude the possibility of the presence or addition of features or numbers, steps, operations, components, parts, or combinations thereof.

In addition, unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs. Terms such as those defined in a commonly used dictionary should be interpreted as having a meaning consistent with the meaning in the context of the related art, and should not be interpreted in an ideal or excessively formal meaning unless explicitly defined in the present application. does not

Hereinafter, a method for manufacturing a ceramic resin binder for a fluoropolymer resin according to the present invention will be described.

1 is a flowchart for explaining a method of manufacturing a ceramic resin binder for a fluoropolymer resin according to the present invention. Referring to FIG. 1 , a method for manufacturing a ceramic resin binder used as a binder for forming a coating film of a fluoropolymer resin is distilled water containing hydrochloric acid or nitric acid in 3-glycidoxypropyltrimethoxysilane (GPTMS). The first step of preparing a first mixture by mixing and stirring, the second step of preparing a second mixture by adding and stirring silica colloid to the first mixture obtained in the first step, the second step obtained in the second step A third step of preparing a third mixture by adding and stirring a nonionic surfactant to the second mixture, and a fourth step of filtering the third mixture.

Specifically, in the first step, based on the total ceramic resin binder, 35 to 55 wt% of 3-glycidoxypropyltrimethoxysilane (GPTMS), 0.05 to 0.2 wt% of hydrochloric acid or nitric acid, and distilled water 4 It is a step of mixing at a ratio of ~10% by weight, and stirring for 100~140 minutes while refluxing at 75~120℃.

At this time, when GPTMS is less than 35% by weight, the surface hardness of the coating film formed by the fluoropolymer resin is lowered, and when it exceeds 55% by weight, yellowing occurs, so GPTMS is preferably included in the above range.

If hydrochloric acid or nitric acid is less than 0.05 wt%, the polymerization degree of GPTMS is low and the reaction is insufficient. Conversely, if it exceeds 0.2 wt%, the reaction rate is too fast and homogeneous reaction is difficult. Therefore, hydrochloric acid or nitric acid is preferably included in the above range.

In addition, if the distilled water is less than 4% by weight, the hydrolysis is very slow and the overall manufacturing time is prolonged. Conversely, if the distilled water exceeds 10% by weight, the two-dimensional chain structure is reduced due to too much increase in the three-dimensional crosslinking, resulting in a gel state. Since the fluidity deteriorates due to change, it is preferable that distilled water is included in the above range.

On the other hand, when the reflux temperature is less than 75 ℃, the two-dimensional polymerization takes too much time. Conversely, if it exceeds 120 ℃, the hydrolysis reaction is not smooth and there is a risk of explosion during production due to the high vapor pressure, so the reflux temperature is 75 ~ 120 It should be carried out at °C. In addition, if the stirring time is less than 100 minutes, the polymerization reaction does not sufficiently occur, and conversely, if it exceeds 140 minutes, it is meaningless because the polymerization has already been completed, so the stirring time is preferably performed in the range of 100 to 140 minutes.

In the second step, after the first mixture is cooled to 20-25 ° C., it is mixed in a proportion of 30 to 45 wt % of silica colloid based on the total ceramic resin binder, and 100 in the range of 20 to 25 ° C. It is a step of stirring for ~140 minutes.

At this time, if the silica colloid is less than 30% by weight, there is a possibility that it may cause yellowing by lowering heat resistance, and if it exceeds 45% by weight, the transparency of the coating film formed by the fluoropolymer resin may decrease, so Silica colloid) is preferably included in the above range.

On the other hand, silica colloid should be added after cooling the first mixture to a range of 20 to 25°C. To prevent this, it is preferable to add silica colloid after cooling to a range of 20 to 25°C.

And if the stirring time is out of the range of 100 to 140 minutes, the polymerization is insufficient or meaningless stirring is performed, so the stirring conditions are preferably performed in the above range.

In the third step, a nonionic surfactant is mixed in a ratio of 1 to 10 wt% based on the entire ceramic resin binder, and stirred at a speed of 600 to 800 rpm in a range of 40 to 80° C. for 2 to 7 hours.

At this time, if the nonionic surfactant is less than 1% by weight, the emulsifying rate is very slow, and on the contrary, if it exceeds 10% by weight, the bonding strength with the substrate during coating may decrease, so the nonionic surfactant is included in the above range. it is preferable

Here, the nonionic surfactant is preferably a secondary alcohol ethoxylate, which is an alkoxysilane (OR) that is not hydrolyzed when an alkoxysilane having silicon (Si) as a central metal forms a two-dimensional polymerization. , O is an oxygen atom, R is an alkyl group) and alcohol ethoxylate are mixed well with each other and the emulsifying effect is high.

On the other hand, after adding the nonionic surfactant, it is preferable to stir for 2 to 7 hours at a speed of 600 to 800 rpm in the range of 40 to 80 ° C. At less than 40 ° C, the two-dimensional silane polymer cannot be sufficiently emulsified, so that the It causes phase separation, and, conversely, if it exceeds 80°C, the chemical structure begins to change and the emulsification effect decreases, so it is better to stir in the range of 40 to 80°C. In addition, if the stirring time is less than 2 hours, sufficient emulsification does not occur and phase separation of the material occurs. In particular, if the stirring speed is less than 600 rpm, the emulsification speed is too slow, and on the contrary, if it exceeds 800 rpm, bubbles are generated to inhibit emulsification.

The final fourth step is a step of filtering the composition obtained through the first to third steps with a 200-400 mesh filter, which is a nano-particle, which causes agglomeration by itself when stored for a long time. It is preferable to perform filtration, but if it is less than 200 mesh, large particles such as agglomerate are not filtered, and if it exceeds 400 mesh, the emulsified binder does not come out well, so it is preferable to filter with a 200 to 400 mesh filter.

The ceramic resin binder obtained through the above manufacturing process is a coating material in which the fluoropolymer resin is dispersed, more specifically, as a solid content, PTFE (Polytetrafluoroethylene) 55-65 wt% and solvent (please indicate an appropriate solvent) 35-45 wt% is incorporated into the mixed coating material, and serves as a binder so that the fluoropolymer resin can be well bonded to the substrate.

Here, the fluoropolymer resin and the ceramic resin binder are preferably mixed in a ratio of 58 to 62 parts by weight: 38 to 42 parts by weight. because it cannot be expected.

Hereinafter, preferred examples are presented to help the understanding of the present invention. However, the following examples are only provided for easier understanding of the present invention, and the content of the present invention is not limited thereto.

Preparation Example 1

Fill a 1L Erlenmeyer flask with 517 g of 3-glycidoxypropyltrimethoxysilane (GPTMS), slowly drop 45 g of distilled water containing 1.2 g of hydrochloric acid (43.8 g of distilled water + 1.2 g of hydrochloric acid), seal it, and reflux at 78-80 ° C. A first mixture was prepared by stirring for 2 hours.

Then, after cooling the first mixture to 20 ~ 22 ℃, 388 g of silica colloid (containing 30% by weight of solid content) was put, sealed, and further stirred at 20 ~ 22 ℃ for 2 hours to prepare a second mixture.

Next, 50 g of secondary alcohol ethoxylate, a nonionic surfactant, was added to the second mixture, sealed, and stirred for 6 hours while refluxing at a speed of 780 rpm at 60 to 65 ° C. A mixed solution was prepared. Finally, the third mixed solution was passed through a 400 mesh filter to obtain a ceramic resin binder.

Preparation 2

Except that 368 g of 3-glycidoxypropyltrimethoxysilane (GPTMS) was used, the rest were prepared under the same conditions as in Preparation Example 1.

Preparation 3

Except that 417g of 3-glycidoxypropyltrimethoxysilane (GPTMS) was used, the rest were prepared under the same conditions as in Preparation Example 1.

Preparation 4

The rest was prepared under the same conditions as in Preparation Example 1 except that 322 g of silica colloid (containing 30% by weight of solid content) was used.

Preparation 5

The rest was prepared under the same conditions as in Preparation Example 1, except that 436 g of silica colloid (containing 30% by weight of solid content) was used.

Preparation 6

The remainder was prepared under the same conditions as in Preparation Example 1, except that 89 g of Secondary Alcohol Ethoxylate was used.

Preparation 7

The remainder was prepared under the same conditions as in Preparation Example 1, except that 16 g of Secondary Alcohol Ethoxylate was used.

Preparation 8

Except that 312 g of 3-glycidoxypropyltrimethoxysilane (GPTMS) was used, the rest were prepared under the same conditions as in Preparation Example 1.

Preparation 9

Except that 592 g of 3-glycidoxypropyltrimethoxysilane (GPTMS) was used, the rest were prepared under the same conditions as in Preparation Example 1.

Preparation 10

The rest was prepared under the same conditions as in Preparation Example 1, except that 278 g of silica colloid (containing 30% by weight of solid content) was used.

Preparation 11

Except for using 469 g of colloidal silica (containing 30% by weight of solid content), the rest were prepared under the same conditions as in Preparation Example 1.

Preparation 12

The remainder was prepared under the same conditions as in Preparation Example 1, except that 115 g of Secondary Alcohol Ethoxylate was used.

Preparation 13

The remainder was prepared under the same conditions as in Preparation Example 1, except that 8 g of Secondary Alcohol Ethoxylate was used.

Preparation 14

Except that the 400 mesh filter did not pass, the rest were prepared under the same conditions as in Preparation Example 1.

GPTMS Hydrochloric acid Distilled water silica
colloid secondary alcohol ethoxylate percolation Preparation Example 1 517g 1.2g 43.8g 388g 50g ○ Preparation 2 368g 1.2g 43.8g 388g 50g ○ Preparation 3 417g 1.2g 43.8g 388g 50g ○ Preparation 4 517g 1.2g 43.8g 322g 50g ○ Preparation 5 517g 1.2g 43.8g 436g 50g ○ Preparation 6 517g 1.2g 43.8g 388g 89g ○ Preparation 7 517g 1.2g 43.8g 388g 16g ○ Preparation 8 312g 1.2g 43.8g 388g 50g ○ Preparation 9 592g 1.2g 43.8g 388g 50g ○ Preparation 10 517g 1.2g 43.8g 278g 50g ○ Preparation 11 517g 1.2g 43.8g 469g 50g ○ Preparation 12 517g 1.2g 43.8g 388g 115g ○ Preparation 13 517g 1.2g 43.8g 388g 8g ○ Preparation 14 517g 1.2g 43.8g 388g 50g ×

Example

The ceramic resin binder prepared according to Preparation Example 1-14 was mixed with the coating material in the same ratio as in Table 2. At this time, the coating material is in a dispersed state of a fluoropolymer resin, and consists of 55 to 63 wt% of PTFE (Polytetrafluoroethylene) as a solid content, 35 to 40 wt% of water as a solvent, and 1 to 10 wt% of trimethylnonyl ether ethoxylated.

The coating material and the resin binder mixture according to each Example and Comparative Example was dip-coated on a stainless substrate, and then heat-treated at 400° C. for 20 minutes to form a coating film.

ceramic resin binder coating material Example 1 40 parts by weight (Preparation Example 1) 60 parts by weight Example 2 40 parts by weight (Preparation Example 2) 60 parts by weight Example 3 40 parts by weight (Preparation Example 3) 60 parts by weight Example 4 40 parts by weight (Preparation Example 4) 60 parts by weight Example 5 40 parts by weight (Preparation Example 5) 60 parts by weight Example 6 40 parts by weight (Preparation Example 6) 60 parts by weight Example 7 40 parts by weight (Preparation Example 7) 60 parts by weight Comparative Example 1 40 parts by weight (Preparation Example 8) 60 parts by weight Comparative Example 2 40 parts by weight (Preparation Example 9) 60 parts by weight Comparative Example 3 40 parts by weight (Preparation Example 10) 60 parts by weight Comparative Example 4 40 parts by weight (Preparation Example 11) 60 parts by weight Comparative Example 5 40 parts by weight (Preparation Example 12) 60 parts by weight Comparative Example 6 40 parts by weight (Preparation Example 13) 60 parts by weight Comparative Example 7 40 parts by weight (Preparation Example 14) 60 parts by weight

Experimental example

The adhesion, transparency, surface condition, yellowing occurrence, surface lubricity and surface hardness of the coating films formed according to Examples and Comparative Examples were measured, and the results are shown in Table 3.

Adhesiveness was evaluated by whether the coating layer was peeled off when a 10×10 grid was scraped with a knife at intervals of 1 mm (cross-cut) and a vinyl tape was attached thereon and then peeled off.

Transparency was measured using a UV-VIS spectrometer to measure the light transmittance in the visible region, and if there was a difference in transmittance of about 5% compared to the glass substrate, it was marked as transparent.

In addition, yellowing was measured using a spectrophotometer, and the higher the b value, the more severe the yellowing.

Surface lubricity was evaluated to the extent that the surface was wetted with ethanol and rubbed with rubber under a load of 1 kg, and after 1000 round trips, oily magic was applied to the surface and easily wiped with a tissue.

Surface hardness was measured by pencil hardness (KS M ISO 15184:2013 evaluation method).

adherence Transparency surface cracks yellowing surface lubricity surface hardness Example 1 no peeling Transparency does not exist does not exist very good 7H Example 2 no peeling Transparency does not exist does not exist very good 6H Example 3 no peeling Transparency does not exist does not exist very good 6H Example 4 no peeling Transparency does not exist does not exist very good 7H Example 5 no peeling Transparency does not exist does not exist very good 7H Example 6 no peeling Transparency does not exist does not exist very good 7H Example 7 no peeling Transparency does not exist does not exist very good 7H Comparative Example 1 some peeling Transparency does not exist does not exist Great 4H Comparative Example 2 no peeling Transparency has exist has exist very bad 5H Comparative Example 3 no peeling Transparency does not exist has exist Great 7H Comparative Example 4 no peeling Haze does not exist does not exist bad 7H Comparative Example 5 some peeling Transparency has exist does not exist bad 7H Comparative Example 6 some peeling Transparency does not exist does not exist bad 7H Comparative Example 7 no peeling Transparency does not exist does not exist Great 7H

* 0.5 parts by weight of a water-soluble degassing agent was added as an additive in all Examples and Comparative Examples

As can be seen from the results in Table 3, when 40 parts by weight of the binder prepared according to 1 to 7, which is a preferred embodiment of the present invention, and 60 parts by weight of the coating material were mixed, there was no surface cracking and yellowing, adhesion, surface hardness, etc. It can be seen that this is very good.

On the other hand, in Comparative Example 1, in which the amount of 3-glycidoxypropyltrimethoxysilane (GPTMS) was insufficient, transparency was excellent, but some peeling occurred and the surface hardness was only 4H.

In Comparative Example 2 in which 3-glycidoxypropyltrimethoxysilane (GPTMS) was used in excess, surface cracks and yellowing occurred, and it was confirmed that the surface lubricity was also very bad.

In addition, as can be seen in Comparative Examples 3 and 4, when a small amount or an excessive amount of silica colloid is added, it can be confirmed that transparency, yellowing phenomenon, or surface lubricity is deteriorated.

In the results according to the amount of the second alcohol ethoxylate added (Comparative Examples 5 and 6), it can be seen that when the content is not in the preferred range, some peeling of the coating film, surface cracks, or surface lubricity is lowered.

On the other hand, as can be seen in Comparative Example 7, even if each material is mixed and reacted in the same ratio as in Preparation Example 1, when not filtered, the surface lubricity is relatively higher than in Examples 1 to 7 due to aggregation of particles. turned out not to be good.

So far, the present invention has been looked at with respect to preferred embodiments thereof. Those of ordinary skill in the art to which the present invention pertains will understand that the present invention can be implemented in modified forms without departing from the essential characteristics of the present invention. Therefore, the disclosed embodiments are to be considered in an illustrative rather than a restrictive sense. The scope of the present invention is indicated in the claims rather than the above description, and the scope equivalent thereto should be construed as being included in the present invention.

Claims (5)

A first step of preparing a first mixture by mixing and stirring 3-glycidoxypropyltrimethoxysilane (GPTMS) with distilled water containing hydrochloric acid;
a second step of preparing a second mixture by adding and stirring silica colloid to the first mixture obtained in the first step;
a third step of preparing a third mixture by adding and stirring a second alcohol ethoxylate to the second mixture obtained in the second step; and
A fourth step of filtering the third mixture,
In the first step, based on the total ceramic resin binder, 35 to 55 wt% of 3-glycidoxypropyltrimethoxysilane (GPTMS), 0.05 to 0.2 wt% of hydrochloric acid, and 4 to 10 wt% of distilled water Mix in a ratio, and stir for 100-140 minutes while refluxing at 75-85°C,
In the second step, after the first mixture is cooled to 20-25 ° C., it is mixed in a proportion of 30 to 45 wt % of silica colloid based on the total ceramic resin binder, and in the range of 20 to 25 ° C. for 100 to 140 minutes. agitate,
In the third step, the second alcohol ethoxylate is mixed in a ratio of 1 to 10% by weight based on the entire ceramic resin binder, and stirred at a speed of 600 to 800 rpm in a range of 60 to 65° C. for 5 to 7 hours,
In the fourth step, the method for producing a ceramic resin binder for fluoropolymer resin, characterized in that the filtering with a 380 ~ 400 mesh filter.
delete delete A ceramic resin binder for a fluoropolymer resin manufactured by the method of claim 1 .
A method of using the ceramic resin binder of claim 4 as a binder for forming a coating film of a fluoropolymer resin,
58 to 62 parts by weight of a fluorine-based polymer resin and 38 to 42 parts by weight of the ceramic resin binder are mixed and used as a binder for forming a coating film of a fluoropolymer resin.

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