KR20040027129A - Composition of liquid dispersion containing polyethylene wax with fine particle size for oil-based paint and preparation thereof - Google Patents

Abstract

PURPOSE: A liquid dispersion composition containing a particulate polyethylene wax for an oily paint and its preparation method are provided, to improve dispersion and storage stability, thereby enhancing slipping property, abrasion resistance and scratch resistance of an industrial oily paint. CONSTITUTION: The liquid dispersion composition comprises 1-30 wt% of a particulate polyethylene wax; 1-20 wt% of a solution of the copolymer having an organic functional group; 50-97 wt% of a solvent; and optionally 1-10 wt% of silica. Preferably the composition has an average particle size of 0.5-6 micrometers. Preferably the particulate polyethylene wax has a maximum particle size of 1-30 micrometers; the copolymer having an organic functional group is acryl copolymer, acryl modified urethane, a polyester modified urethane, or their mixtures; and the solvent is butyl cellosolve, toluene, xylene or their mixtures.

Description

Composition of liquid dispersion containing polyethylene wax with fine particle size for oil-based paint and preparation

The present invention relates to a liquid dispersion composition for an oil paint comprising a particulate polyethylene wax and a method for producing the same. More specifically, the present invention relates to a liquid dispersion composition prepared by mixing a high molecular weight copolymer solution having an organic functional group and particulate polyethylene wax as a medium, and to mixing silica as necessary, and to a method for preparing the same. By using the composition having excellent storage stability in various industrial oil paints, the slip surface, scratch resistance (scratch resistance, scratch resistance), abrasion resistance and matting power of the coating surface can be improved.

Since conventional dispersion composition products for oil-based paints have an average particle size of about 10 μm and a maximum particle size of 30 to 40 μm, it is difficult to disperse and re-agglomerate easily. (A phenomenon in which crater-shaped flaws occur on the surface), which is a cause of defects in the coating film, and agglomeration phenomenon and thixotropy (brokenness) between particles when the long-term storage increases, resulting in poor stability.

Once agglomerated particles are added to the paint and re-dispersed, it is difficult to disintegrate the agglomerates, so that the particles exist as granulated seeds on the paint surface and are insufficient to improve compatibility and surface properties with the application system.

Therefore, when the conventional dispersion composition having a large particle size, which is inferior in dispersibility and easily reaggregated, is applied to an oil paint, there is a problem in that slip properties, scratch resistance, and abrasion resistance, which are essential characteristics of the oil paint, are poor.

Accordingly, an object of the present invention is to provide a liquid dispersion composition for an oil paint, which has a fine particle size and excellent dispersibility and storage stability, thereby improving slip, wear resistance, and scratch resistance of an industrial oil paint.

Another object of the present invention is to provide a liquid dispersion composition for oil-based paint imparting matting power.

Still another object of the present invention is to provide a method for preparing a liquid dispersion composition for an oil paint, which is excellent in dispersibility and can improve slip resistance, wear resistance, scratch resistance, and / or matting power of an oil paint.

The liquid dispersion composition for oil paint according to the present invention for achieving the above object comprises 1 to 30% by weight of particulate polyethylene wax, 1 to 20% by weight of a copolymer solution having an organic functional group, and 50 to 97% by weight of a solvent. Preferably from 1 to 15% by weight polyethylene wax, 1 to 10% by weight of the copolymer solution having an organic functional group and 75 to 97% by weight of the solvent.

A characteristic of the present invention is to improve the slip resistance, abrasion resistance and scratch resistance of the oil paint, in order to achieve the object of the present invention in the present invention to stably disperse the particles of polyethylene wax in a solvent, specifically, polyethylene wax It is finely dispersed so as to have a maximum particle size of 1 to 30 µm, preferably 1 to 10 µm or less. If the maximum particle size is larger than 30 μm, the dispersion effect due to the fine particles cannot be expected. The longer the dispersion time, the finer the particles become, but the more the wax is dispersed, the higher the viscosity, the lower the fluidity and the more difficult the dispersion. It is difficult to produce polyethylene wax having a maximum particle size of less than 1 μm because of the risk of particle reaggregation.

In addition, it is possible to produce a liquid dispersion with fine and uniform particle distribution and improved dispersibility and storage stability by optimum mixing and dispersing conditions, and when the liquid dispersion composition is applied to an oil paint, particulate polyethylene waxes By being uniformly distributed in the coating film, it is possible to improve the surface properties of the coating film, such as slip resistance, wear resistance and scratch resistance of the oil paint. By finely dispersing the liquid dispersion composition including polyethylene wax according to the present invention, a composition having an average particle size of 0.5 to 6 μm can be prepared. The average particle size may be adjusted by dispersion blending and dispersion conditions.

Polyethylene wax used in the present invention is a copolymer of ethylene and polar monomer obtained by decomposing natural gas or naphtha, and is a powdery synthetic wax imparted with a polar group by various chemical modifications such as oxidative decomposition. Various types of polyethylene waxes having various particle sizes and characteristics are used according to the polymerization method and processing process, but in the present invention, fine polyethylene waxes are selected such that the maximum particle size is preferably dispersed to 10 μm or less. As polyethylene wax meeting the above conditions, for example, the PRINTWAX series of DEUREX (DEUREX Wachs-Chemie GmbH, Germany), the PINNACLE series of LUBRIZOL (USA), and the MPP of MICRO POWDERS (Micro Powders, Inc., USA) Series and CRODA products are available. The content of polyethylene wax in the liquid dispersion of the present invention is 1 to 30% by weight, preferably 1 to 15% by weight. If the polyethylene wax is more than 30% by weight, the dispersibility is lowered due to the deterioration of the fluidity due to the excessive content (using a flow type disperser) .When the amount of the polyethylene wax is less than 1% by weight, the dispersion time becomes too long. Must be added.

The copolymer solution having an organic functional group used in the present invention is a high molecular weight copolymer solution having a dispersion affinity group, and serves to improve the dispersibility of the composition. The organic functional group is a hydroxyl group, a carboxyl group or an amine group here. Specifically, the copolymer solution may be an acrylic copolymer, an acrylic modified urethane, a polyester modified urethane, or a mixture thereof. For example, DISPERBYK-108, DISPERBYK-116, manufactured by BYK (BYK-Chemie GmbH & Co., Germany), DISPERBYK-140, DISPERBYK-160, DISPERBYK-161, DISPERBYK-168, DISPERBYK-170, DISPERBYK-171, DISPERBYK-174, ANTITERRA-U, ANTITERRA-U80, ANTITERRA-204, AVECIA (AVECIA Pigments & Additives, UK) SOLSPERSE-31845, SOLSPERSE-32500, SOLSPERSE-34750, SOLSPERSE-24000SC, SOLSPERSE-24000GR, EFKA-4046, EFKA-4047, EFKA-4050, EFKA-4055, EFKA-4080, EFKA-4400 from EFKA Corporation (Netherlands) Can be used. The content of the copolymer solution having an organic functional group in the liquid dispersion of the present invention is 1 to 20% by weight, preferably 1 to 10% by weight. When applied to paints, dispersions are generally added in consideration of solid content. Therefore, when the content of the copolymer solution is large, the concentration of polyethylene wax is relatively low, so that it is difficult to obtain the desired surface properties. The effect is reduced.

The solvent used in the present invention should be compatible with the high molecular weight copolymer solution having a dispersion affinity group, and can control the drying rate if necessary, such as butyl cellosolve, toluene, xylene Volatile organic solvents may be used alone or in combination. According to an embodiment of the present invention, when using a butyl cellosolve having a high intrinsic viscosity can be prepared a liquid dispersion of excellent physical properties. The solvent occupies most of the composition of the liquid dispersion of the present invention, and the rest is the solvent except for the content of the copolymer solution having polyethylene wax and an organic functional group.

Another feature of the present invention is to impart a matting effect to the oil paint, in order to achieve this object is provided a liquid dispersion composition for oil paint further comprises a matting agent, preferably silica. As such silica, for example, SYLOID 244, 161, ED30, ED50, ED52, C906, C907 from GRACE Davison (WR Grace & Co., USA), ACEMATT OK412, OK500, TS100, from DEGUSSA (USA) AEROSIL TT600, TT200 and LANCO MATT 2000 from LUBRIZOL (USA) can be used. The amount of silica added to the liquid dispersion of the present invention is 1 to 10% by weight, and when the silica is more than 10% by weight, metal marking (metal marking: a metal component where friction occurs when friction occurs with the metal on the surface of the coating film. This black color may occur. If the amount is less than 1% by weight, no matting effect can be expected. In addition, an organic matting agent such as polypropylene wax may be used as the matting agent.

Liquid dispersion composition for oil-based paints of the present invention is a high molecular weight copolymer solution having an organic functional group and a portion of the solvent to agitate at low speed to increase the dispersion efficiency and dispersion efficiency, after preparing a mixed solution, fine particulate polyethylene in the mixed solution After adding the wax and stirring the mixture, it is added to a disperser to prepare a dispersion. Then, the remaining solvent is added to the dispersion as a filling step, and finally prepared by stirring at a low speed. In this case, to give a matting effect for a special purpose, silica is added to the dispersion.

More specifically, the method for preparing a liquid dispersion composition for an oil paint according to the present invention may include (a) 1 to 20% by weight of a high molecular weight copolymer solution having an organic functional group, based on 100% by weight of the liquid dispersion composition. 1 to 10% by weight and 50 to 97% by weight of the solvent, preferably 75 to 97% by weight in a container and stirred at 500 to 2,000 rpm for 1 to 10 minutes at room temperature with a mixing stirrer;

(b) 1 to 30% by weight, preferably 1 to 15% by weight, of fine particulate polyethylenwax, preferably 1 to 15% by weight, based on 100% by weight of the liquid dispersion composition while stirring the mixture of step (a). Stirring at 1,000 to 2,000 rpm for 30 minutes;

(c) dispersing the mixture of step (b) at 2,000 to 4,000 rpm for 1 to 5 hours by adding it to a mixed dispersion machine using a dispersion medium; And

(d) separating the dispersion of step (c) from the mixed disperser and adding 5 to 20% by weight of the solvent, followed by stirring at 1,000 to 2,000 rpm for 5 to 30 minutes.

Method for producing a liquid dispersion composition of the present invention for imparting a matting effect to the oil paint is based on (1) silica step 1 to 10 while stirring the dispersion separated from the mixed dispersion after step (c) Stirring at 500 to 3,000 rpm after addition of weight percent; And dispersing the mixture at 2,000 to 4,000 rpm for 1 minute to 1 hour by adding the mixture to a mixed disperser using a dispersion medium.

The liquid dispersion composition of the present invention may be dispersed in the substrate by a mixed dispersion method using a medium such as glass beads or zirconium beads or a dispersion method by high pressure. In particular, when the dispersion is applied by a high pressure method by applying an ultra-high pressure (1,000 to 3,500 kgf / cm 2) to the dispersion and dispersing the dispersion into two streams, it collides with each other in a recombination part or by pushing it through a fine gap to disperse the dispersion. It is possible to prevent wear of metal powder and beads, which have been a problem in the dispersion system, and to shorten the process time.

Hereinafter, the present invention will be described in detail through examples. However, the following examples are only to specifically illustrate the present invention, and the scope of the present invention is not limited to these examples.

<Example 1>

3 g of DISPERBYK-160 and 70 g of toluene were added to a stainless steel special use stainless (SUS) container, followed by stirring at room temperature at 1,000 rpm for 5 minutes using a mixing stirrer (manufacturer: Hwasung Chemical Co., Ltd.). While stirring the mixture, 8 g of powdery polyethylene wax having a maximum particle size of 30 to 35 μm was added thereto, followed by stirring at 3,000 rpm for 20 minutes. After the stirring was completed, the contents were added to a mixed disperser (type: Eiger Mill, manufacturer: Hwasung) using a dispersion medium (type: yttria stabilized beads, size: 0.8 to 1.0 mm), and dispersed at 2,000 rpm for 3 hours. After the dispersion was completed, the dispersion was separated from the disperser, 20 g of toluene was added thereto, stirred at 3,000 rpm for 10 minutes, and filtered to prepare a resultant liquid dispersion composition.

Average particle size and viscosity of the prepared composition were as follows. In this example and the following examples, the average particle size was measured by a particle analyzer (PSA: Particle Size Analyzer, Brookhaven Instruments Corp., 90 Plus), and the final viscosity was Brookfield Viscometer (Model name: RVDV-) at 25 ° C. 1, manufacturer: Brookfield).

Average particle size (after 3 hours dispersion): 3.0 μm

Final viscosity (25 ℃): 350 cps

<Example 2>

A powdery polyethylene wax having a maximum particle size of 20 to 25 μm was used in the same manner as in Example 1, and the average particle size and viscosity of the prepared composition were as follows.

Average particle size (after 3 hours dispersion): 2.5 μm

Final viscosity (25 ℃): 300 cps

<Example 3>

A powdery polyethylene wax having a maximum particle size of 10 to 15 μm was used in the same manner as in Example 1, and the average particle size and viscosity of the prepared composition were as follows.

Average particle size (after 3 hours dispersion): 2.5 μm

Final viscosity (25 ℃): 310 cps

<Example 4>

The average particle size and viscosity of the composition prepared by adding silica to the composition prepared in Example 3 were as follows.

Average particle size (after 3 hours dispersion): 5 μm

Final viscosity (25 ℃): 260 cps

Example 5

Butyl cellosolve was used instead of toluene as a solvent, and the average particle size and viscosity of the prepared composition were as follows.

Average particle size (after 3 hours dispersion): 1.0 μm

Final viscosity (25 ℃): 280 cps

<Example 6>

In order to analyze the effect of the high molecular weight block copolymer having an organic functional group on the physical properties of the composition, it was carried out in the same manner as in Example 1, but instead of the DISPERBYK-160 containing only an amine group in the formula, DISPERBYK-170 containing only group) was used, and the average particle size and viscosity of the prepared composition were as follows.

Average particle size (after 3 hours dispersion): 3 μm

Final viscosity (25 ℃): 200 cps

<Example 7>

2.5 g of DISPERBYK-160 and 70 g of toluene were added to a SUS container, and then stirred at low speed for 5 minutes at room temperature at 1,000 rpm using a mixing stirrer. While stirring the mixture, 6 g of powdery polyethylene wax having a maximum particle size of 30 to 35 μm was added thereto, followed by stirring at 3,000 rpm for 30 minutes. After the stirring was completed, the mixture was added to a mixed disperser using a dispersion medium and dispersed at 2,000 rpm for 3 hours. After the dispersion was completed, the dispersion was separated from the disperser, 20 g of toluene was added, stirred for about 10 minutes at 3,000 rpm, and then filtered to prepare a resultant liquid dispersion composition. Average particle size and viscosity of the prepared composition were as follows.

Average particle size (after 3 hours dispersion): 3.0 μm

Final viscosity (25 ℃): 310 cps

<Example 8>

A powdery polyethylene wax having a maximum particle size of 20 to 25 μm was used in the same manner as in Example 7, and the average particle size and viscosity of the prepared composition were as follows.

Average particle size (after 3 hours dispersion): 2.5 μm

Final viscosity (25 ℃): 300 cps

Example 9

A powdery polyethylene wax having a maximum particle size of 10 to 15 μm was used in the same manner as in Example 7, and the average particle size and viscosity of the prepared composition were as follows.

Average particle size (after 3 hours dispersion): 2.5 μm

Final viscosity (25 ℃): 320 cps

<Example 10>

The average particle size and viscosity of the composition prepared by adding silica to the composition prepared in Example 7 were as follows.

Average particle size (after 3 hours dispersion): 6 μm

Final viscosity (25 ℃): 280 cps

<Example 11>

In the same manner as in Example 7, except for using DISPERBYK-170 containing an acid group in the formula instead of DISPERBYK-160 containing an amine group, the average particle size and viscosity of the prepared composition were as follows.

Average particle size (after 3 hours dispersion): 3 μm

Final viscosity (25 ℃): 220 cps

<Example 12>

Butyl cellosolve was used instead of toluene as a solvent, and the average particle size and viscosity of the prepared composition were as follows.

Average particle size (after 3 hours dispersion): 900 nm

Final viscosity (25 ℃): 300 cps

Example 13: Physical Property Comparison Test

Each liquid dispersion composition prepared in the above Example was tested for physical properties by the test method specified as follows, and the results are shown in Table 1.

1. Particle Distribution Analysis

The particle size and distribution were measured by adding a predetermined amount of diluted sample to the particle analyzer, and classified according to the average particle size as follows.

◎: excellent, average particle size 1 탆 or less

(Circle): good, average particle size 2-3 micrometers

(Triangle | delta): Usually, average particle size 3 micrometers or more

2. Dispersibility Comparison Test

After 1 hour in the dispersion process, a small amount of samples were taken, and the particle size was measured by a particle analyzer, and classified according to the particle size as follows.

(Double-circle): Excellent, 3 micrometers or less after 1 hour dispersion

○: good, 5 μm or less after dispersion for 1 hour

(Triangle | delta): Usually, 10 micrometers or less after dispersion | distribution for 1 hour

X: 10 micrometers or more after failure and dispersion | distribution for 1 hour

3. Storage stability comparison test

The sample was placed in a glass test tube with a diameter of 20 cm and a height of 2.5 cm, and left for 15 days at a low temperature of 5 ° C. and then the degree of layer separation was measured.

◎: excellent, layer separation 0-0.1 mm

○: good, layer separation 0.1 to 0.2 mm

(Triangle | delta): Usually, layer separation 0.2-0.3 mm

Particle distribution Dispersibility Storage stability Example 1 ○ × △ Example 2 ○ △ ○ Example 3 ○ ◎ ○ Example 4 △ △ △ Example 5 ◎ ◎ ◎ Example 6 ○ × △ Example 7 ○ × △ Example 8 ○ △ ○ Example 9 ○ ◎ ○ Example 10 △ △ ○ Example 11 ○ × △ Example 12 ◎ ◎ ◎

According to Table 1, the smaller the maximum particle size of the polyethylene wax used, the better the dispersibility, and especially in the case of using a solvent having a high intrinsic viscosity such as butyl cellosolve, the particle distribution, dispersibility, and storage stability were excellent. According to the average particle size of the composition after a certain dispersion time there was no significant difference in dispersibility. Although the type of high molecular weight block copolymers having organic functional groups did not significantly affect the dispersibility and storage stability, the final viscosity of the composition was higher than that of the copolymer having only an acid group when the copolymer having only an amine group was used. There was a tendency to appear.

<Example 14>

In this embodiment, the oil paint was prepared using the liquid dispersion composition prepared in the above embodiment.

First, a two-component acrylic urethane-type transparent paint is prepared by mixing an acrylic polyol and an isocyanate curing agent, and the wax weight of the liquid dispersion composition and the conventional dispersion of the present invention prepared in the above-described examples are 3% by weight, respectively. It was added so as to prepare an oily transparent paint.

After extracting a certain amount of the oil-based transparent paint prepared by each application and using an applicator at the same time to prepare a coating film having the same coating thickness, the prepared specimen with the surface properties such as slip properties, scratch resistance, wear resistance Measured.

The test method was carried out as a coin test commonly used in the art, and in the case of slip property, the coin was put on the coating film at a constant slope and the coin slipped down, and the abrasion resistance and the scratch resistance were the same on the coating film with the coin. When scratched with force, the degree of scratches was measured, and the results are shown in Table 2.

Comparative Example 1 (Primary Dispersion) Comparative Example 2 (Primary Dispersion) Example 14 (invention) Input amount (% by weight) 3 3 3 Main dispersion Carnauba Wax Polyethylene wax Polyethylene wax Average particle size 10 μm 10 μm 3 μm Slip ○ ◎ ◎ Scratch resistance △ △ ○ Wear resistance △ △ ○ NOTE: Excellent, ○: Good, △: Normal

As shown in Table 2, the coating film coated with the oil paint prepared using the pigment dispersion composition containing the particulate polyethylene wax of the present invention is scratch-resistant and abrasion resistant compared to the coating film coated with a conventional dispersion. In particular, the slip property was excellent.

Liquid dispersion composition of the present invention is a particle size of the polyethylene wax and finely dispersed particle size to maximize the floating capacity of the wax after forming the coating film and to be present as an even thin film on the surface properties essential for industrial oil paint It not only gives sufficient slip resistance, abrasion resistance and scratch resistance of the phosphor coating film but also has excellent dispersion stability. Moreover, the matting effect of an oil-based paint can be provided by adding silica as needed.

Claims (8)

Particle polyethylene wax 1 to 30% by weight, a liquid dispersion composition for an oil paint comprising 1 to 20% by weight of a copolymer solution having an organic functional group and 50 to 97% by weight of a solvent. The liquid dispersion composition for oil paint according to claim 1, wherein the composition has an average particle size of 0.5 to 6 µm. The liquid dispersion composition for oil paint according to claim 1, wherein the maximum particle size of the particulate polyethylene wax is 1 to 30 µm. The liquid dispersion composition for oil paint according to claim 1, wherein the copolymer solution having an organic functional group is an acrylic copolymer, an acrylic modified urethane, a polyester modified urethane or a mixture thereof. The liquid dispersion composition for oil paint according to claim 1, wherein the solvent is butyl cellosolve, toluene, xylene or a mixture thereof. The liquid dispersion composition of claim 1, further comprising 1 to 10% by weight of silica. (a) 1 to 20% by weight of a high molecular weight copolymer solution and a solvent 50 to 97% by weight based on 100% by weight of the liquid dispersion composition in a container were put into a container for 1 to 10 minutes, and 500 to Stirring at 2,000 rpm; (b) adding 1 to 30% by weight of powdery polyethylene wax based on 100% by weight of the liquid dispersion composition while stirring the mixture of step (a) and then stirring at 1,000 to 2,000 rpm for 10 to 30 minutes; (c) adding the mixture of step (b) to a mixed disperser using a dispersion medium and dispersing at 2,000 to 4,000 rpm for 1 to 5 hours; And (d) separating the dispersion of step (c) from the mixed disperser and adding 5 to 20% by weight of the solvent, followed by stirring at 1,000 to 2,000 rpm for 5 to 30 minutes. Manufacturing method. The method of claim 7, wherein the step (c) is followed by adding 1 to 10% by weight of silica based on 100% by weight of the liquid dispersion composition while stirring the dispersion separated from the mixed disperser, followed by stirring at 500 to 3,000 rpm. ; And The method of preparing a liquid dispersion composition for an oil paint, further comprising the step of dispersing the mixture at 2,000 to 4,000 rpm for 1 minute to 1 hour by adding the mixture to a mixed dispersion machine using a dispersion medium.