KR20130142568A - Pollution proof and light stability surface coating materials and manufacturing method thereof - Google Patents

Abstract

The present invention relates to a surface coating material with pollution resistance and light stability and a manufacturing method thereof, wherein the surface coating material prevents pollution by being easily coated on the surface of natural leather, synthetic leather, and artificial leather used for furniture which requires flexibility and bending, bags, and shoes, easily removes pollutants, has beautiful patterns of natural leather and artificial leather, touch feeling of napping, and noncombustible and biodegradable properties using nanoadditives for adhesion improvement, prevention of static electricity, and blocking of ultraviolet rays. [Reference numerals] (101) Produce basic polymer solution;(103) Produce first additive (curing agent, surface energy-adjusting agent, reaction promoter);(105) Add CNT nano-dispersed composites;(107) High speed stirring;(109) Produce second additive (posay, dispersant, antioxidant, suspending agent);(111) High speed stirring and dispersion

Description

Surface coating agent having pollution resistance and light resistance and its manufacturing method {Pollution proof and light stability surface coating materials and manufacturing method

The present invention relates to a surface coating agent and a method for manufacturing the same, in particular to prevent the surface contamination by various contaminants and easily remove the target contaminants, surface having excellent stain resistance and light resistance excellent in visible light transmittance and UV blocking light functionality It relates to a coating agent and a method for producing the same.

In general, the stain-resistant surface coating agent achieves the desired purpose by introducing other inorganic additives into the fluororesin or silicone resin to lower the surface energy of the coating film to suppress the adsorption of foreign matter or dust.

Conventional methods for such a stain-resistant surface coating agent is a film-forming coating composition (Japanese Patent No. 10-0185679) excellent in stain resistance of Kansai Paint, a stain-resistant steel sheet resin coating solution having excellent stain resistance of POSCO, and a steel sheet using the same. Manufacturing method (Republic of Korea Patent No. 10-0627473), LG Chem's coating and coating composition having a low reflection resistance and its manufacturing method (Korea Patent No. 10-0522832) and Korea Paint Ink Co. It is disclosed in a resin composition (Korean Patent No. 10-0240600).

The patent of Korea Paint Ink Co., Ltd. discloses a technique for easily cleaning a contaminated surface by adding 10 μm beads to a hard coating film of a thermosetting resin. Thus, a silicone polyol resin and melamine / Platinum catalyst to introduce hard segment and soft segment into the polymer coating layer, and also micro- and organic-inorganic bead introduced pollution and decontamination performance Excellent non-combustible biodegradable patent has been registered (Republic of Korea Patent Registration 10-1136462) and published (Republic of Korea Patent Publication No. 10-2011-0104357) by Songjeong Chemical Co., Ltd. co-applicant of the present invention.

As described above, in the case of substrates such as natural leather, artificial leather, synthetic leather, interior film, biodegradable nonwoven fabric, etc. used for furniture, bags, shoes, etc. In addition to the removal function, UV blocking, high light transmittance, scratch resistance, environmental resistance, durability, antistatic and brushing (fuzz) touch, flexibility, room temperature flexibility and permanent adhesion is required.

Therefore, with the development of the industry, the required physical properties are strengthened and the thickness of the coating is thinning (1 μm to 5 μm). Therefore, the development of the surface coating agent having the various required properties as the additive of the micro size (the size of 10 μm) is urgently needed. It is necessary.

Republic of Korea Patent Publication No. 10-0185679 (Dec. 28, 1998) Republic of Korea Patent Publication No. 10-0627473 (September 15, 2006) Republic of Korea Patent Publication No. 10-0522832 (October 12, 2005) Republic of Korea Patent Publication No. 10-0240600 (October 28, 1999) Republic of Korea Patent Publication No. 10-1136462 (2012. 04. 06) Republic of Korea Patent Publication No. 10-2011-0104357 (2011. 09. 22)

Therefore, an object of the present invention for solving the problems of the prior art as described above is a natural leather, synthetic leather, artificial leather, interior film, biodegradable used in furniture, bags, shoes, interior that require flexibility, flame retardancy and flexibility Biodegradability is expressed by easy surface coating on non-woven fabrics, and also has gloss control, flame retardancy, high light transmittance, scratch resistance, environmental resistance, durability, antistatic and brushing touch, and decontamination. The present invention provides a surface coating agent having contamination and light resistance and a method of manufacturing the same.

In addition, another object of the present invention can be easily coated on a variety of substrates that require easy removal of surface contaminants, and can easily remove contaminants such as ball-point pens, magic, etc., simply by removing the mop. It provides excellent surface contamination removal property and nanocomposites with UV and thermal barrier function to provide surface coating agent having pollution resistance and light resistance that can realize beautiful patterns such as natural and artificial leather with excellent visible light transmission. It is.

In addition, another object of the present invention is to improve the environmental resistance and durability of nano composite materials (shoes, bags, etc.) as well as adhesion and coating properties on the brushed surface of natural leather by thinning the surface coating agent, as well as repeat The present invention provides a surface coating agent having a stain resistance and light resistance that can exhibit excellent performance in movement and surface flexibility, and a method of manufacturing the same.

In addition, another object of the present invention is biodegradation by microorganisms under a certain condition more easily and faster time is not harmful to the human body and to prevent dust adsorption by antistatic function, to remove the environmentally friendly surface pollution with its own non-flammable And it provides a surface coating agent having a fouling resistance and light resistance having a non-flammable and a method of manufacturing the same.

Surface coating agent having a fouling resistance and light resistance according to the present invention for achieving the above objects, 100 parts by weight of a basic polymer solution of at least one polymer resin and 20 to 80 wt% of a silicone polyol, silicone polymer, silicone curing agent It is characterized by containing 5 to 30 parts of curing agent, 1 to 5 parts of reactive additive, 1 to 10 parts of reaction accelerator, 1 to 5 parts of nano colloidal silica, and 0.1 to 3 parts of CNT nano dispersion solution. .

In addition, the surface coating agent having a fouling resistance and light resistance according to the present invention for achieving the above object, the base polymer consisting of 20-50 wt% of the polymer resin composition containing urethane and urea and 20-80wt% of the solvent in the polymer 5 parts by weight to 30 parts by weight of a curing agent, 1 to 5 parts of reactive additives, 1 to 10 parts of reaction accelerators, and 1 to 5 parts of one or more nano-dispersed solutions in nanosilicate, nanosilver, nano TiO 2 and MWCNT It is characterized by the removal of surface contamination and nonflammability.

At this time, the surface coating agent having a stain resistance and light resistance according to the present invention, by using the nano-additives (MWCNT) MWCNT, DISPER BYK-2001, PMA, Soisperse # 5000, EA, PEDOT to prepare a dispersion solution, adding It features.

In addition, the surface coating agent having a fouling resistance and light resistance according to the present invention, the nano additive is characterized in that at least one selected from antioxidants, antifoaming agent, dispersant and anti-settling agent.

Method for producing a surface coating agent having a stain resistance and light resistance according to the present invention for achieving the above object, 3 to 70wt% of silicone polyol, silicone polymer, silicone curing agent composition; 5 to 30 parts by weight of a silicone curing agent based on 100 parts by weight of a basic polymer solution containing 20 to 80 wt% of two or more solvents selected from a silicone solvent, toluene, xylene, PMA, EA, and MEK; 1-10 parts of platinum-based catalyst, 1-5 parts of modified dimethylsiloxane and hydroxy silicone-modified polyacrylate, and high-speed stirring at room temperature for 60 minutes, followed by nanosilica, nano silver, nano TiO2, MWCNT, dispersant and 0.1 to 10 parts of two or more selected from the anti-settling agent is added and characterized in that the second stirring for 60 minutes.

As described above, by coating the surface coating agent according to the present invention on various substrates, the results of UV protection, antistatic, biodegradability, scratch, surface wear, decontamination, bending test, flame retardant test, furniture, bags, shoes, interior It exhibits the physical properties required by various substrates for use, and is very effective in removing antifouling properties and surface contaminants such as artificial leather, synthetic leather, and natural leather, which are materials used for furniture, bags, interiors, shoes, and the like.

1 is a manufacturing process showing the manufacturing method of the surface coating agent according to the present invention,
2 is a graph showing the visible light transmittance of the surface coating agent according to the present invention,
3a is an electron micrograph of a surface coating using a conventional microsize additive,
Figure 3b is an electron micrograph of the surface coating agent using a nanosize additive according to the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a detailed description of preferred embodiments of the present invention will be given with reference to the accompanying drawings. It should be noted that the same configurations of the drawings denote the same reference numerals as possible whenever possible. Specific details are set forth in the following description, which is provided to provide a more thorough understanding of the present invention. In the following description of the present invention, detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.

1 is a manufacturing process diagram showing a manufacturing method of the surface coating agent according to the present invention, with reference to Figure 1 will be described in detail the manufacturing method of the surface coating agent according to the present invention.

As shown in Figure 1, in order to prepare a surface coating agent according to the present invention, first, 3 to 70wt% of at least one polymer resin selected from silicon polyol (silicon polyol), silicone polymer, silicone curing agent in the polymer molecule; A basic polymer solution having a ratio of 20 to 80 wt% of at least two solvents selected from a silicone solvent, toluene, xylene, EA, MEK, and PMA is prepared (step 101).

Next, based on 100 parts by weight of the basic polymer solution 1 to 5 parts by weight of silicone curing agent to prevent contaminants and act as a curing agent, colloidal silica of 20nm size for surface energy control (Colloid silica, Cas No.7631-86 -9) 1 to 5 parts by weight, a reaction catalyst for controlling the reaction by giving a maximum crosslinking density to mix 1 to 5 parts by weight of the platinum-based catalyst (step 103).

Meanwhile, 0.1 to 5 parts by weight of the UV-blocking CNT nanocomposite may be added to the mixture based on 100 parts by weight of the polymer solution (step 105). Subsequently, in step 107, the primary additive and the CNT nano dispersion complexes of steps 103 and 105 were stirred at about 1,800 RPM at high speed, and then, in step 109, the UV-blocking CNT nanocomposites 0.5 to 100 parts by weight of the basic polymer solution. Addition of 2 parts by weight, 0.1-5 parts by weight of antioxidant and surface gloss regulator, and 0.1-0.5 parts by weight of anti-settling agent may be used to supplement the physical properties (step 109). Subsequently, in step 111, the high speed stirring resultant and the secondary additives of steps 107 and 109 are rapidly stirred and dispersed at 500 to 3,000 RPM (step 111).

In the above, the main reason for using at least one polymer resin selected from silicon polyol, silicone polymer, silicone curing agent as the main polymer in the surface coating agent according to the present invention is the decontamination function, flame retardancy, biodegradability, flexibility, etc. Although the weight ratio between the compositions is not particularly limited, the reason for using 3 to 70wt% of the total basic polymer solution is that it is necessary to control the viscosity for the ease of coating process (coating amount), This is to maintain an appropriate ratio of.

In addition, the solvent is used to control the viscosity for the ease of the coating process and to obtain a stable solution of the polymer, the reason for the content of 20 to 80wt% of the total basic polymer solution, and the equipment conditions and coating amount during coating This is because if the viscosity is too high, the coating is impossible, and if it is less than that, the coating amount of the solid content is small and it is difficult to achieve the object of the present invention.

In the above, the reason for using the silicone curing agent as a curing agent is to maximize the crosslinking density to prevent the fundamental penetration of contaminants, and the tactile aspects that are basically required in various substrates of furniture, bags, shoes, interior applications, which is the end use of the present invention To get the naturalness in. Here, the reason why the amount of the silicone curing agent added is 1 to 5 parts by weight based on 100 parts by weight of the basic polymer solution is less than this, and the effect of the present invention is not sufficiently obtained, and when it is more than that, the degree of the effect does not increase any more. Because it does not.

In addition, the platinum-based curing catalyst as a reaction accelerator is used to control the degree and rate of crosslinking between one or more polymers selected from the group consisting of silicone polyols, silicone polymers, silicone curing agents, and the like. 1 to 5 parts by weight is based on the stability of the solution in relation to the coating process and the efficiency of the curing conditions.

In addition, the UV-blocking CNT nanocomposite is used to prevent surface discoloration and durability by ultraviolet rays, and uses a nanosize of 100 to 200 nm smaller than the micro size (for example, Hanwha's multiwall CNT nanocomposite) The reason for this is that not only the low price but also the pigment size at a coating thickness of 5 μm or less should be used at 1 μm or less. In addition, since the surface area of the nano-size is proportional to the square of the size, it exhibits a sufficient effect as a smaller amount, there is an advantage that it is easy to control the physical properties in the overall formulation (use) by using a small amount. In particular, nanocomposites must be used for thin film coating thicknesses of 1 μm or less used for brushing fleece of natural and artificial leather.

The reason for using the nanocomposite in the range of 0.5 to 2 parts by weight based on 100 parts by weight of the polymer solution is that the effect is less than 0.1 parts by weight or less, and more than 3 parts by weight can not be expected further effects and economical. Meanwhile, silica used as an antioxidant and a surface gloss regulator may also be used in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the basic polymer solution.

The silica and silicon-based additives used for controlling the surface energy are used to minimize the surface energy of the surface of the coating film through reaction with silicon, and the content thereof is 1 to 5 parts by weight based on 100 parts by weight of the polymer solution. If less, it is difficult to obtain the effect of the present invention sufficiently, and if it is more than that, the effect of the present invention does not increase any more, it acts as an impurity and lowers the strength of the coating film, thereby obtaining rationality of manufacturing cost.

In the above, the reason for using two or more of the silicone solvent, EA, MEK, n-Hexane, toluene, xylene for viscosity and solids control is to consider the characteristics of the polymer solubility parameter (Solubility parameter) and the general formulation to form a coating film ( This is because the use of cosolvent as a method of optimizing the drying rate and film formation process and coating process (viscosity, solution discharge rate) is excellent in overall physical properties and production / processability.

In addition, an antioxidant, an antifoamer, a sedimentation inhibitor etc. in this invention can use a normal thing.

Hereinafter, the present invention will be described in more detail with reference to Examples. The following examples are intended to illustrate the invention through practice, not to limit the invention to these.

First, since the CNT nanocomposite has a large specific surface area, the CNT nanocomposite is dispersed in the composition shown in Table 1 using an ultrasonic disperser rather than a ball mill or other stirrer and added to the basic polymer solution as necessary.

CNT nanocomposites do not pulverize by ultrasonic wave because dozens or hundreds of molecules are aggregated in a powder state, or when the aggregated CNT nanocomposites do not nanodisperse in molecular state, they absorb visible light and appear black. In addition, the nano-dispersed CNT solution becomes unstable and turns black even when reagglomeration occurs.

Therefore, CNT aggregation is disrupted by ultrasonic waves (that is, crushed by CNT molecules), and then PEDOT having excellent affinity with CNT molecules is introduced to attach CNT molecules to a conductive polymer chain to prevent aggregation between CNT molecules. Prepare a stable CNT dispersion solution (Master batch).

As such, the CNT nano dispersion is easily determined by the presence or absence of visible light absorption, but in the present invention, the evaluation of the CNT nano dispersion is performed by coating and drying the CNT dispersion solution on a PET film to measure surface resistance, transmittance, and electron microscope (SEM) measurement. The dispersion state of CNTs was evaluated by performing. At this time, through the durability of the anti-static / shielding film, the transmittance was improved to produce a film conforming to the LCD and IT component materials. In addition, the SWCNT composite resin coating liquid was coated on a PET base film with a thickness of 1 μm to prepare a transparent electrode having a final transmittance of 85% and a sheet resistance of 100Ω / sq.

In addition, in order to manufacture an antistatic / electromagnetic shielding protective film, MWCNT (Multi Wall Carbon Nano Tube) is ultrasonically pulverized and PEDOT (Poly Ethylene Dioctyl Thiopene) is used as a binder to prepare a nano dispersion solution. The nano-dispersed composite resin coating solution and PSA tape were prepared by adding to the pressure-sensitive adhesive. The prepared specimens were examined by electron microscopy (SEM), thermal properties, adhesive force, change with time, and physical properties of the composite resin solution.

First, 30 parts by weight of a silicone polymer (Dow corning 5600; 100% solids) was added to a four-necked flask, 30 parts by weight of a silicone solvent and 40 parts by weight of toluene were sequentially added, followed by low speed stirring at 30 ° C. for 60 minutes to give a solution of 30% of a solid content. Was prepared.

Separately from solution A, 70 parts by weight of toluene was added to a four-necked flask, and 20 parts by weight of a silicone hardening agent (Dow corning t-2; solid content 100%) was slowly added while stirring at low speed, followed by stirring at room temperature for 60 minutes to prepare solution B solution. Prepared.

Thereafter, 100 parts by weight of A solution and 10 parts by weight of B solution were added to the medium speed stirrer mixing tank, and stirred at low temperature for 30 minutes at 30 ° C. to prepare a C solution having a solid content of 30%.

After that, 6 parts by weight of a reactive additive (hydroxy silicone-modified polyacrylate) BYK-SILCLEAN 3700 (trademark, product name) was added and stirred at medium speed for 30 minutes, after which the antifoaming agent BYK-066N (trademark, product name) ) 0.2 parts by weight and 0.5 parts by weight of an antioxidant Irganox 1135 (trade name, product name) were added thereto, followed by a high speed stirring for 30 minutes.

Thereafter, 0.1-5 parts by weight of colloidal silica (Cas No.7631-86-9) and 1.5 parts by weight of nano-dispersed CNT solution were added in rapid stirring, followed by 60 minutes of high-speed stirring, and then 3 parts by weight of the reaction catalyst was added at medium speed. It stirred for 20 minutes and obtained the coating agent of this invention. The stirring speed in the above was 500-3000 RPM.

Thereafter, the surface coating agent according to the present invention was coated with 5g / SQM using a gravure coater on a flame retardant dry polyurethane (Pu) synthetic leather, and then dried and cured at 175 ° C. for 1 minute.

The surface coating agent according to the present invention was confirmed to be completely cleaned by performing a cleaning with a general mop after graffiti with a ballpoint pen, magic on the substrate coated. In addition, it was confirmed that there is no abnormality up to 100,000 times by room temperature bending test of the motive material, it was confirmed that there is no coating crack phenomenon which is a problem of the conventional UV-curable paint.

In addition, to investigate the antistatic and optical properties, MWCNT (multi-wall carbon nanotube) was ultrasonically ground, and a nano dispersion solution (Master batch) was prepared using PEDOT (polyethylene dioctyl thiopene) as a binder. The nano-dispersion composite resin coating solution was prepared by adding 1.5 parts by weight of the nano-dispersion solution to the prepared base polymer solution, and coating the nano-dispersion composite resin coating solution on a PET film with a thickness of 1 μm and measured with a spectrophotometer (Spectropotometer, U-3501). It was.

As a result of the measurement, as shown in FIG. 1, UV blocking 95% or more and visible light transmittance of 80% or more were obtained. 1 is a graph showing the visible light transmittance of the surface coating agent according to the present invention.

On the other hand, as a result of observing the specimens prepared by an electron microscope (SEM), as shown in Figure 3a as a result of applying a surface coating agent using a conventional micro-size additive to a polyurethane sheet, a dry coating film of 10μm thickness It was observed that surface irregularities of 1 μm or more in size, but as shown in FIG. 3b, surface irregularities caused by nano pigments were not observed in nano-sized pigment and 100 nm CNT nanocomposite coating. Therefore, it is proved that in the 1-3μm thin film coating, the nanodispersion should be used once again in the surface shape as well as the advantages of the various properties of the nanodispersion. 3A is an electron micrograph of a surface coating agent using a conventional microsize additive, and FIG. 3B is an electron micrograph of a surface coating agent using a nanosize additive according to the present invention.

As described above, the surface coating agent having a fouling resistance and light resistance according to the present invention and a method of manufacturing the same are used in chairs, etc., which are provided in various public places to prevent them from becoming dirty, and the contamination of heavy pollutants such as ballpoint pens or magic can be washed with a simple mop. It is effective, so it can be used for a long time and can be effectively used for various substrates that can keep clean in appearance.

In addition, the surface coating agent having a fouling resistance and light resistance according to the present invention has a completely non-flammable effect of the coating itself is made of silicone can exhibit flame retardancy when applied to the interior, marine, aircraft, vehicle substrates.

In addition, the surface coating agent having a fouling resistance and light resistance according to the present invention is suitable for household goods such as various furniture, interiors, bags, etc., which easily burns dirt, and can be used for a wide variety of substrates such as shoes and book covers.

While the present invention has been described in connection with what is presently considered to be the most practical and preferred embodiment, it is to be understood that the invention is not limited to the disclosed embodiments, but is capable of various modifications within the scope of the invention. Therefore, the scope of the present invention should not be limited by the described embodiments, but should be determined by the scope of the appended claims and equivalents thereof.

Claims (5)

5 to 30 parts of a curing agent, 1 to 5 parts of a reactive additive, and 1 to 10 parts of a reaction additive based on 100 parts by weight of a basic polymer solution composed of at least one polymer resin and a solvent of 20 to 80 wt% among silicone polyols, silicone polymers, and silicone curing agents. And 1 to 5 parts of nano colloidal silica (Colloid silica), 0.1 to 3 parts of CNT nanodispersion solution, the surface coating agent having a stain resistance and light resistance.
5 to 30 parts of a curing agent, 1 to 5 parts of reactive additives, and 1 to 10 parts of a reaction polymer in 100 parts by weight of a basic polymer solution composed of 20 to 50 wt% of a polymer resin composition containing urethane and urea and 20 to 80 wt% of a solvent. And Surface coating agent having the surface contamination removal and non-flammability, characterized in that containing 1 to 5 parts of one or more nano-dispersed solution in nanosilicate, nanosilver, nano TiO 2, MWCNT.
According to claim 1 and 2, MWCNT, DISPER BYK-2001, PMA, Soisperse # 5000, EA, PEDOT using the nano-additives (MWCNT) to prepare a dispersion solution to remove the surface contamination characterized in that And surface coatings having incombustibility.
The surface coating agent of claim 3, wherein the nano additive is at least one selected from an antioxidant, an antifoaming agent, a dispersing agent, and an antisettling agent.
As a method for producing a coating for removing surface contamination of any one of claims 1 and 2,
3 to 70 wt% of a silicone polyol, a silicone polymer, and a silicone curing agent composition;
5 to 30 parts by weight of a silicone curing agent based on 100 parts by weight of a basic polymer solution containing 20 to 80 wt% of two or more solvents selected from a silicone solvent, toluene, xylene, PMA, EA, and MEK; 1-10 parts of platinum-based catalyst, 1-5 parts of modified dimethylsiloxane and hydroxy silicone-modified polyacrylate, and high-speed stirring at room temperature for 60 minutes, followed by nanosilica, nano silver, nano TiO2, MWCNT, dispersant and 0.1 to 10 parts of two or more selected from the anti-settling agent is added to the surface coating having a surface non-flammable and non-flammable, characterized in that the second stirring for 60 minutes.

Images