KR102130377B1 - Aqueous type surface treating agent excellent in anti-sunscreen property and method for producing the same - Google Patents

Abstract

The water-based surface treatment agent having excellent sunscreen resistance according to the present invention and a method for manufacturing the same are characterized by maximizing the sunscreen resistance and physical properties of the surface treatment agent by utilizing a water-dispersible polyurethane-acrylate resin and a polyethylene wax emulsion, The surface treatment agent according to the present invention is 100 parts by weight of a water-dispersible polyurethane-acrylate resin, 100 parts by weight of a matte resin, 10 parts by weight of a curing agent, 0.5 parts by weight of a leveling agent, 5 parts by weight of an antifoaming agent, 5 parts by weight of silica nano dispersion and polyethylene wax Contains 7 parts by weight of emulsion.

Description

Aqueous type surface treating agent excellent in anti-sunscreen property and method for producing the same}

The present invention relates to a water-based surface treatment agent and a manufacturing method that is excellent in sunscreen resistance and has excellent sunscreen resistance with reduced emission of harmful substances, and is environmentally friendly while utilizing water-dispersible polyurethane-acrylate resin and other additives. It relates to a surface treatment agent and a surface treatment agent manufacturing method having improved physical properties and sunscreen resistance.

In recent years, the global automotive industry is rapidly increasing consumer demand for eco-friendly, high-quality (high durability), and high-grade (high-sensitivity) materials. In terms of eco-friendliness and energy saving, consumers' interest in small and medium-sized light and hybrid cars is greatly increased. It is increasing. Automotive interior material protects occupants against accidents such as fire and rollover, and provides a pleasant indoor atmosphere to induce safe driving. It provides a high level of sensibility and aesthetic functions to enhance the car's dignity and value. Do it.

In addition, research on various materials has been actively conducted as consumer demand for environmentally friendly materials such as VOCs free as well as high durability, flame retardancy, and light resistance have recently increased. In particular, in the case of passenger cars, among formaldehyde and volatile organic compounds, most of the survey items such as benzene, toluene, and styrene were detected, and in some models, ethylbenzene (Ethyle Benzene) was 1.65 times higher than the recommended standard. Xylene was 1.31 times, and for large buses, 2 to 4 out of 6 items exceeded the recommended standards.

In addition, the government enacted the'new indoor car interior air quality recommendation standard (recommended standard)' in June 2007, and additionally, passenger cars newly manufactured and sold after July 1, 2010 must meet the recommended standards. It is expected to evaluate and announce compliance with the recommended standards after tests every two years.

However, until now, the domestic automobile industry has been making great efforts to solve TVOCs and odor problems, but it is in a very difficult situation at home and abroad because no proper measures have been prepared. Domestic automakers (since 2016) suggest a odor level of 2 or less and TVOCs guidelines of 2 ppm or less, but in the case of automotive interior parts (IP, Doortrim, synthetic leather, etc.), products with a level of 5 to 12 ppm are recommended. It is reality that you are using.

As a cause of such a problem, polyurethane resins used as a surface treatment agent resin for automobile interior materials include dimethylformamide (DMF), methylethylketone, toluene, acetone, and isopropyl alcohol. This is because the resin composition prepared by mixing with a highly volatile organic solvent such as alcohol) is used by coating and impregnating the fabric or sheet.

Organic solvents have the advantage of having excellent solvent properties for polyurethanes, but because they are organic chemicals, there are a lot of pollution during the manufacturing process of synthetic leather, which causes environmental pollution. Particularly, dimethylformamide (DMF) solidifies when it comes into contact with water, so the worker, after use, must wipe and remove the used machinery, chemicals, and supplies. In addition, it is necessary to install a device that easily penetrates the human body through the human respiratory system or the skin and recovers it from being released into the atmosphere as an environmentally harmful substance that causes liver disease, kidney cancer, and skin disease. In addition to this, the appearance of the product coated with dimethylformamide has the same color as spraying white powder, so a separate coloring process on the surface using a pigment is required, and the pigment also contains dimethylformamide. There is a problem that there is a lot of hassle and processing cost. Therefore, it is necessary to replace the main component of the coating agent used as a surface treatment agent in the manufacturing process of automotive interior materials with eco-friendly materials. In recent years, there has been a demand for a surface treatment agent capable of resolving the contamination of sunscreen, particularly an eco-friendly material and excellent stain resistance.

In order to solve the above problems, Korean Patent Publication No. 10-2017-0119141 discloses a technique for manufacturing interior materials for vehicles using water-dispersed polyurethane, but the use of organic solvents due to adhesives or the like is not used at all when manufacturing interior materials. There is a problem that VOC emission cannot be minimized because it cannot be excluded.

In addition, the water-dispersible polyurethane resin has unstable distribution in water, molecular size, dispersion conditions, etc., and physical properties such as hardening of the polyurethane resin coated by heat generated by mechanical friction, etc., is unstable, and anti-sunscreen. There is a problem that sex is not excellent.

An object of the present invention is to provide an aqueous surface treatment agent having excellent sunscreen resistance and a method for manufacturing the same, which is environmentally friendly and maximizes sunscreen resistance by utilizing a water-dispersible polyurethane-acrylic resin.

In addition, the object of the present invention is to provide a water-based surface treatment agent having excellent sunscreen resistance that can maximize physical properties such as bending friction resistance, light fastness, abrasion resistance, and contamination, and a method for manufacturing the same.

The water-based surface treatment agent having excellent sunscreen resistance according to the present invention for achieving the above object is 100 parts by weight of a water-dispersible polyurethane-acrylate resin, 100 parts by weight of a matte resin, 10 parts by weight of a curing agent, 0.5 parts by weight of a leveling agent, and an antifoaming agent Characterized in that it comprises 5 parts by weight, 5 parts by weight of silica nano dispersion and 7 parts by weight of polyethylene wax emulsion.

And the water-dispersible polyurethane-acrylate resin is polycarbonate diol, polypropylene glycol (PPG), dipropylene glycol (Dipropylene glycol, DPG), isophorone diisocyanate (Isophorone diisocyanate, IPDI), dimethylol propionic acid ( Prepolymer prepared by mixing Dimethylol propionic acid (DMPA), methyl methacrylate (MMA), butyl acrylate (BA), 2-hydroxyethyl acrylate (2-hydroxyethyl acrylate, 2- HEA), ethyl acrylate (Ethyl acrylate, EA), sodium persulfate (Sodium persulfate, SPS) and is characterized in that it is prepared by containing an acrylic resin syrup containing an emulsifier.

In addition, the matte resin comprises a water-dispersible polyurethane resin and porous silica having a particle size of 2-3 um, the curing agent is hexamethylene diisocyanate (HDI), and the leveling agent is polydimethyl siloxane, The antifoaming agent is characterized by being a polyether siloxane copolymer.

On the other hand, the method of manufacturing a water-based surface treatment agent having excellent sunscreen resistance according to the present invention is polycarbonate diol, polypropylene glycol (PPG), dipropylene glycol (Dipropylene glycol, DPG), isophorone diisocyanate (Isophorone diisocyanate, IPDI), a prepolymer preparation step of preparing a prepolymer by mixing dimethylol propionic acid (DMPA), an acrylic end prepolymer preparation step of adding an acrylate monomer and a neutralizing agent to the prepolymer to prepare an acrylic end prepolymer, the acrylic end Water dispersion polyurethane-acrylate resin production step of adding an acrylic resin syrup to the prepolymer to prepare a water-dispersible polyurethane-acrylate resin, and 100 parts by weight of matte resin and 10 parts by weight of a curing agent in the water-dispersible polyurethane-acrylate resin , 0.5 parts by weight of the leveling agent, 5 parts by weight of the antifoaming agent, 5 parts by weight of the silica nano dispersion, and 7 parts by weight of the polyethylene wax emulsion are characterized by including a surface treatment agent preparation step of preparing a surface treatment agent.

And the acrylic resin syrup is methyl methacrylate (Methyl methacrylate, MMA), butyl acrylate (Butyl acrylate, BA), 2-hydroxyethyl acrylate (2-hydroxyethyl acrylate, 2-HEA), ethyl acrylate (Ethyl acrylate, EA), sodium persulfate (SPS), and emulsifiers.

According to the present invention as described above, the water-based surface treatment agent having excellent sunscreen resistance according to the present invention and a method of manufacturing the same are mixed with a water-dispersible polyurethane-acrylate resin prepared to maximize sunscreen resistance at an appropriate mixing ratio. By manufacturing the surface treatment agent, there is an advantage that the sunscreen resistance can be maximized.

In addition, since the polyethylene wax emulsion is added at a blending ratio that can maximize sunscreen resistance and physical properties, there is an advantage that the sunscreen resistance and physical properties of the surface treatment agent can be maximized.

1 to 3 is a test report of the fabric coated with a water-based surface treatment agent excellent in sunscreen resistance prepared according to the present invention.

Hereinafter, the technical spirit of the present invention will be described in more detail with reference to the accompanying drawings.

The accompanying drawings are only examples shown in order to describe the technical spirit of the present invention in more detail, so the technical spirit of the present invention is not limited to the form of the accompanying drawings.

The water-based surface treatment agent having excellent sunscreen resistance according to the present invention is 100 parts by weight of a water-dispersible polyurethane-acrylate resin, 100 parts by weight of a matte resin, 10 parts by weight of a curing agent, 0.5 parts by weight of a leveling agent, 5 parts by weight of silica nano dispersion, and It is prepared by including 7 parts by weight of a polyethylene wax emulsion.

At this time, the water-dispersible polyurethane-acrylate resin is prepared by adding an acrylic resin syrup to the prepolymer. The prepolymer is a mixture of polycarbonate diol, polypropylene glycol (PPG), dipropylene glycol (DPG), isophorone diisocyanate (IPDI), and dimethylol propionic acid (DMPA). Manufactured, acrylic resin syrup is methyl methacrylate (MMA), butyl acrylate (Butyl acrylate, BA), 2-hydroxyethyl acrylate (2-hydroxyethyl acrylate, 2-HEA), ethyl acrylate ( Ethyl acrylate (EA), sodium persulfate (SPS) and emulsifier are mixed.

In addition, the prepolymer is preferably prepared by reacting polycarbonate diol, polypropylene glycol, dipropylene glycol, isophorone diisocyanate and dimethylol propionic acid at a temperature of 70°C to 80°C for at least 3 hours. At this time, the reaction time is preferably reacted until the NCO peak through FT-IR analysis no longer decreases. The prepolymer prepared as described above has a molecular weight of 1000 to 2000 Mw.

In addition, an acrylate monomer and a neutralizing agent are added to the prepolymer reacted as described above. This is for preparing a prepolymer having an acrylic end, first adding an acrylate monomer at room temperature, then reacting the copolymer until the NCO peak through FT-IR analysis is no longer present, and then adding a neutralizing agent. Proceeds. At this time, the neutralizing agent to be added is triethylamine (Triethyl amine, TEA), the amount added is added to the number of moles of dimethylol propionic acid used previously, the acrylate monomer used is 2-hydroxyethyl acrylate (2-hydroxyethyl acrylate, 2-HEA).

An acrylic resin syrup is added to a prepolymer having an acrylic end as described above to prepare a water-dispersible polyurethane-acrylate resin. Acrylic resin syrup is methyl methacrylate (MMA), butyl acrylate (Butyl acrylate, BA), 2-hydroxyethyl acrylate (2-hydroxyethyl acrylate, 2-HEA), ethyl acrylate (Ethyl acrylate, EA), sodium persulfate (SPS), and emulsifiers. At this time, it is preferable to drop the acrylic syrup into a prepolymer having an acrylic end at constant speed for 2 hours and react at a temperature of 70 to 80°C.

Meanwhile, the matte resin is a resin in which porous silica having a particle size of 2-3 um is dispersed in a water-dispersible polyurethane resin, a curing agent is hexamethylene diisocyanate (HDI), a leveling agent is polydimethyl siloxane, and an antifoaming agent is polyether. Siloxane copolymers are used. At this time, as the antifoaming agent, EVONIK's TEGO Airex 902W product is used, and a defoaming agent may be used together with the antifoaming agent. When adding a defoaming agent, it is preferable to add only 1 to 5 parts by weight based on 100 parts by weight of the water-dispersible polyurethane-acrylate resin. When a defoaming agent is used, it takes less than an hour to completely defoam bubbles in the treatment liquid.

In addition, the silica nano-dispersed liquid is added to improve the scratch resistance of the surface treatment liquid according to the present invention, and it is preferable to use BYK's NANOBYK-3620 product.

In addition, the polyethylene wax emulsion is added to maximize the sunscreen resistance of the surface treatment agent according to the present invention, and the related contents will be described in detail in Experimental Example 1 below.

Accordingly, since the water-dispersible polyurethane is prepared as described above, not only can an eco-friendly surface treatment agent be prepared, but also the water-dispersible polyurethane-acrylate resin and polyethylene wax emulsion prepared to maximize sunscreen resistance are properly proportioned. Since it is added to the furnace surface treatment agent, it is possible to maximize the sunscreen resistance of the surface treatment agent.

On the other hand, the surface treatment agent according to the present invention is preferably applied to automobile seats or the like that require excellent sunscreen resistance.

The method for preparing a water-based surface treatment agent having excellent sunscreen resistance according to the present invention includes a prepolymer production step, an acrylic terminal prepolymer production step, a water-dispersible polyurethane-acrylate resin production step, and a surface treatment agent production step.

First, a prepolymer preparation step is performed. The prepolymer preparation step is polycarbonate diol, polypropylene glycol (PPG), dipropylene glycol (DPG), isophorone diisocyanate (IPDI), dimethylol This step is to prepare a prepolymer by mixing propionic acid (Dimethylol propionic acid, DMPA). At this time, as described above, the prepolymer is prepared by reacting polycarbonate diol, polypropylene glycol, dipropylene glycol, isophorone diisocyanate, and dimethylol propionic acid at a temperature of 70°C to 80°C for at least 3 hours, FT-IR It is preferably prepared by reacting until the NCO peak through the analysis no longer decreases. The prepolymer prepared in this way has a molecular weight of 1000 to 2000 Mw.

Thereafter, an acrylic terminal prepolymer preparation step is performed. The acrylic terminal prepolymer manufacturing step is a step of preparing an acrylic terminal prepolymer by adding an acrylate monomer and a neutralizing agent to the prepolymer. The step of preparing the acrylic end prepolymer proceeds first by adding the acrylate monomer at room temperature, and then reacting the prepolymer until the NCO peak through FT-IR analysis is no longer present and adding the neutralizing agent. At this time, the neutralizing agent to be added is triethylamine (Triethyl amine, TEA), the amount added is added to the number of moles of dimethylol propionic acid used previously, the acrylate monomer used is 2-hydroxyethyl acrylate (2-HEA ).

Next, a water dispersion-acrylate resin manufacturing step is performed. The water dispersion-acrylate resin manufacturing step is a step of preparing a water-dispersible polyurethane-acrylate resin by adding an acrylic resin syrup to an acrylic terminal prepolymer. At this time, the acrylic resin syrup is methyl methacrylate (Methyl methacrylate, MMA), butyl acrylate (Butyl acrylate, BA), 2-hydroxyethyl acrylate (2-hydroxyethyl acrylate, 2-HEA), ethyl acrylate (Ethyl It is preferred that acrylate, EA), sodium persulfate (SPS) and emulsifier are mixed. The water-dispersible polyurethane-acrylate resin is preferably prepared by continuously dropping acrylic syrup into an acrylic terminal prepolymer for 2 hours and reacting at a temperature of 70 to 80°C.

And the surface treatment agent manufacturing step is water dispersion polyurethane-acrylate resin 100 parts by weight of matte resin, 10 parts by weight of curing agent, 0.5 parts by weight of leveling agent, 5 parts by weight of antifoaming agent, 5 parts by weight of silica nano dispersion and 7 parts by weight of polyethylene wax emulsion This is a step of adding a surface treatment agent. At this time, as the antifoaming agent, EVONIK's TEGO Airex 902W product is used, and a defoaming agent may be used together with the antifoaming agent. When adding a defoaming agent, it is preferable to add only 1 to 5 parts by weight based on 100 parts by weight of the water-dispersible polyurethane-acrylate resin. When a defoaming agent is used, it takes less than an hour to completely defoam bubbles in the treatment liquid.

In addition, the silica nano-dispersed liquid is added to improve the scratch resistance of the surface treatment liquid according to the present invention, and it is preferable to use BYK's NANOBYK-3620 product.

In addition, the prepolymer is prepared by mixing 7.8 parts by weight of polycarbonate diol, 7.8 parts by weight of polypropylene glycol, 0.5 parts by weight of dipropylene glycol, 5.1 parts by weight of isophorone diisocyanate, and 0.8 parts by weight of dimethylol propionic acid with respect to 100 parts by weight of prepolymer. It is preferred.

In addition, the acrylic resin syrup is based on 100 parts by weight of acrylic resin syrup, 7.1 parts by weight of methyl methacrylate, 5.7 parts by weight of butyl acrylate, 3.4 parts by weight of 2-hydroxyethyl acrylate, 55.5 parts by weight of ethyl acrylate, and sodium persulfate. It is preferable that 0.3 parts by weight and 4.4 parts by weight of emulsifier are mixed.

<Experimental Example 1>

In this Experimental Example 1, the flexural resistance, light fastness, abrasion resistance, stain resistance, and sunscreen resistance of the fabric coated with a surface treatment agent having a different addition amount of the polyethylene wax emulsion were tested.

Water-dispersible polyurethane-acrylate resin 100 parts by weight, matte resin 100 parts by weight, curing agent 10 parts by weight, leveling agent 0.5 parts by weight, antifoaming agent 5 parts by weight, silica nano dispersion 5 parts by weight, polyethylene wax emulsion 0-7 parts by weight ( After preparing Examples 1 to 5), the prepared surface treatment agent was coated on a synthetic leather fabric made of PVC material using a bar coater #7 to a thickness of 10 to 20 um and dried at 130°C for 5 minutes. . Finally, it was prepared by coating the surface treatment agent twice.

Table 1 shows the evaluation methods and evaluation results according to each property.

For the evaluation of sunscreen resistance, the method MS321-16:2018 was used, and as a requirement, there should be no discoloration, fading, swelling, cracking, exposure to adherent, etc. on the coating film, and the test conditions were acrylic (50mm ㅧ50mmㅧ3 mm), and after putting two pieces of white cotton fabric of the same size on top, 0.25g of'Coppertone Waterbabies SPF 45' sunscreen was applied by hand to the front. At this time, the entire area of the back cotton fabric was divided into 9 equal parts so that the sunscreen could be applied evenly, and then evenly distributed. Place the part of the white cotton fabric coated with sunscreen on the test piece, and put a 500 g load weight on the acrylic plate to close it. After standing for 1 hour in a constant temperature bath at (80ㅁ2)℃, it was taken out and the white cotton cloth, acrylic plate, and 500g weight were removed. After leaving it at room temperature for about 10 to 15 minutes, it was washed with a neutral detergent and dried, and then the experiment was conducted by evaluating the surface of the coating film according to the requirements as described above.

^- unit Experiment Assessment Methods Example 1 Example 2 Example 3 Example 4 Example 5 Polyethylene wax emulsion addition amount phr 0 One 3 5 7 - 1.Bending friction resistance ppm 1,000↑ 1,000↑ 1,000↑ 1,000↑ 1,000↑ MS 321-08 2.Light fastness time 4 4 4 4 4 MS 321-08 3.Abrasion resistance class 3 3 4 4 4 MS 321-08 4. Pollution class 3 3 4 4 4 MS 321-08 5.Sun cream resistance class

Bad

Bad

Bad

usually

Good

MS321-16:2018

As shown in Table 1, it can be seen that adding a polyethylene wax emulsion to the surface treatment agent by 7 parts by weight is excellent in abrasion resistance, stain resistance, and sunscreen resistance.

1 to 3 is a test report of the fabric coated with a water-based surface treatment agent excellent in sunscreen resistance prepared according to the present invention. 1 to 3 show the results of testing the sunscreen resistance of the fabric coated with a water-based surface treatment agent having excellent sunscreen resistance prepared according to the present invention by testing the FITI test institute, and as a result, abnormality according to the requirements It was confirmed that there is no. That is, it was found that there was no abnormality such as discoloration, fading, swelling, cracking, and adhesion of the coating film.

The present invention is not limited to the above-described embodiments, and of course, the scope of application is various, and various modifications can be implemented without departing from the gist of the present invention as claimed in the claims.

Claims (5)

100 parts by weight of a water-dispersible polyurethane-acrylate resin;
100 parts by weight of matte resin;
10 parts by weight of curing agent;
Leveling agent 0.5 parts by weight;
5 parts by weight of an antifoaming agent;
Silica nano dispersion 5 parts by weight; And
Polyethylene wax emulsion 7 parts by weight; includes,
The water-dispersible polyurethane-acrylate resin,
Prepolymer prepared by mixing polycarbonate diol, polypropylene glycol (PPG), dipropylene glycol (DPG), isophorone diisocyanate (IPDI), and dimethylol propionic acid (DMPA),
Contains acrylic resin syrup including methyl methacrylate (MMA), butyl acrylate (BA), 2-hydroxyethyl acrylate (2-HEA), ethyl acrylate (EA), sodium persulfate (SPS) and emulsifier Manufactured by
The matte resin comprises a water-dispersible polyurethane resin and porous silica having a particle size of 2-3 um, the curing agent is hexamethylene diisocyanate (HDI), the leveling agent is polydimethyl siloxane, and the antifoaming agent is polyether A water-based surface treatment agent having excellent sunscreen resistance, characterized in that it is a siloxane copolymer.
delete delete A prepolymer preparation step of preparing a prepolymer by mixing polycarbonate diol, polypropylene glycol (PPG), dipropylene glycol (DPG), isophorone diisocyanate (IPDI), and dimethylol propionic acid (DMPA);
An acrylic terminal prepolymer preparation step of preparing an acrylic terminal prepolymer by adding an acrylate monomer and a neutralizing agent to the prepolymer;
An aqueous polyurethane-acrylate resin production step of adding an acrylic resin syrup to the acrylic terminal prepolymer to prepare a water-dispersible polyurethane-acrylate resin; And
The surface treatment agent was added to the water-dispersible polyurethane-acrylate resin by adding 100 parts by weight of matte resin, 10 parts by weight of curing agent, 0.5 parts by weight of leveling agent, 5 parts by weight of antifoaming agent, 5 parts by weight of silica nano dispersion, and 7 parts by weight of polyethylene wax emulsion. The manufacturing method of the surface treatment agent having excellent sunscreen resistance, characterized in that it comprises a;
The method of claim 4,
The acrylic resin syrup
It is characterized by being prepared by including methyl methacrylate (MMA), butyl acrylate (BA), 2-hydroxyethyl acrylate (2-HEA), ethyl acrylate (EA), sodium persulfate (SPS) and emulsifier. A method for manufacturing a water-based surface treatment agent having excellent sunscreen resistance.

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