KR20130128625A - Organic-inorganic hybrid waterborne polyurethane coating agent for interior parts ofautomobile and process thereof - Google Patents

Abstract

The present invention relates to an organic and inorganic hybrid water-dispersible polyurethane coating agent characterized by being manufactured by adding an inorganic compound when a water-soluble polyurethane is synthesized by reacting polyol with isocyanate, and a method for manufacturing the same, wherein flame retardancy and matt effect increase and stability and dispersivity of the coating agent due to enhancing physical cohesive force by an inorganic sorbent added when synthesizing polyurethane, and additionally, in particular, since the water-dispersible polyurethane coating agent does not contain volatile organic compounds (VOCs) so as to be environment-friendly such that the interior environment of an automobile is pleasant, and thereby, having an advantage of being suitable for a coating agent for automobil interior material.

Description

Organic-inorganic hybrid waterborne polyurethane coating agent for interior parts of automobile and process etc.

The present invention relates to a water-dispersed polyurethane coating agent for organic-inorganic hybrid vehicle interior materials and a method for producing the same, and more particularly, to an organic-inorganic hybrid water-dispersed polyurethane by adding an inorganic compound in the synthesis of an aqueous polyurethane by the reaction of a polyol and an isocyanate. By synthesizing the coating agent, it improves flame retardancy and matting effect, and improves stability and dispersion due to physical cohesion by the inorganic adsorbent added during polyurethane synthesis, and it is eco-friendly because it does not contain volatile organic compounds (VOCs). The present invention relates to a water-dispersed polyurethane coating agent for organic-inorganic hybrid vehicle interior materials and a method for producing the same, which is suitable for use in coating compositions.

The symptoms of new car syndrome that occur when you buy a car are headaches, respiratory diseases, dermatitis, chronic fatigue, and the biggest causes of these symptoms are raw materials, adhesives, foams, coatings, surface treatment agents, Plasticizers are due to volatile organic compounds (VOCs) generated from petroleum aromatics. Due to this problem, as reported in Non-Patent Documents 1 to 3, developed countries such as the United States, Japan, and Europe have been systematically managing hazardous substances since the 1980s, and the European REACH (New Chemical Substance Management System) implemented since 2005. In response, the development of eco-friendly materials and the improvement of manufacturing processes are required, and systematic management and response are required.

In addition, as reported in Patent Documents 4 and 5, VOCs are mainly emitted by various industrial and human activities as well as automobile interior materials. Extensive emissions of VOCs provide many causes for water pollution, soil pollution, and air pollution. Although it is directly harmful to the environment and health by itself, the most important issue with VOCs emissions is participating in photochemical reactions in the atmosphere, producing secondary pollutants such as photochemical oxides. Ozone in the troposphere, produced in the presence of sunlight and NOx and VOCs, is known to be toxic to humans, damage grains and cause acid rain. In addition, VOCs are destroying the ozone layer in the stratosphere and accelerating global warming. Therefore, there is a need for countermeasures, and related technologies are actively being developed.

In order to solve the above problems, development of an environmentally friendly coating treatment agent has recently been actively conducted, and as reported in Patent Documents 6 to 10, coating organicizers used in existing automobile interior materials currently use DMF. A solvent-based coating organicizing agent based on organic solvents, including non-VOCs, which does not contain VOCs due to problems such as fire hazard, environmental side effects and human hazards when applied to confined spaces. Although an organic agent is required, the present application range is very insufficient due to the characteristics of a product requiring high physical properties such as flex resistance and wear resistance.

In addition, as reported in Non-Patent Documents 11 to 13, the methods applied to the removal of VOCs using the inorganic agent contained in the coating additive in the form of inorganic materials are various treatment techniques such as catalytic oxidation, direct combustion, absorption, adsorption, condensation, biological treatment, etc. This is in the research and development stage. It is expected that VOCs reduction technology by adsorption using metal oxide is the most effective method that can be applied to the coating process of automobile interior materials by dual / inorganic mixing and considering dispersibility with organic agent. .

On the other hand, when looking at the contents of the patent application as a way to solve the above problems, the patent document 1 has a viscosity of 800 CPS, 20% urethane resin, silica and other additives (matte, dispersant, leveling agent, UV stabilizer, antifoaming agent) An aqueous surface treatment agent composed of 4% and 76% water is known, and in Patent Literature 2, a one-part aqueous metallic coating composition in which a coated aluminum paste is added to a water-soluble polyurethane dispersion is known. The present invention relates to a composition in which an inorganic compound is simply mixed with urethane.

The present invention is to exclude the existing solvent type coating composition, improve the physical properties, and develop an environmentally friendly treatment agent of the hybrid coating composition in accordance with the recent trend of increasing environmental regulations in many countries and unions, such as Europe, North America, etc. The present invention has been completed by developing an aqueous dispersion polyurethane coating agent for an organic-inorganic hybrid vehicle interior material that can be applied to automobile interior materials that can be free from odors, TVOCs removal, and other hazards such as worker's environment and environmental pollution.

Patent Document 1: Korean Unexamined Patent Publication No. 2009-0121819 (Method for forming a uniform aqueous coating film on a TPO sheet for vehicle interior material and an aqueous surface treatment agent for the same) Patent Document 2: Korean Laid-Open Patent Publication No. 2008-0008524 (1-component aqueous metallic coating composition for automobile plastic interior material)

[Non-Patent Document 1] D. Z. Wang, Applied catalysis B: Environmental, 8 (3), 31-32 (1996). Non-Patent Document 2: K. W. You, Y. S. Ge, B. Hu, Z. W. Ning, S. T. Zhao, Y. N. Zhang, and P. Xie, Journal of Environmental Sciences, 19 (10), 1208-1213 (2007). Non Patent Literature 3: W. K. Jo, J. H. Lee, Environmental Engineering Research, 14 (3), 180-185 (2009). [Non-Patent Document 4] M. Zeinali, L. L. McConnell, C. J. Hapeman, A. Nguyen, W. F. Schmidt, C. J. Howard, Atmospheric Environment, 43 (21), 3407-3415 (2011). Non Patent Literature 5: B. K. Lee, and K. R. Jung, Journal of Korean Society for Atmospheric Environment, 16, 39-46 (2000). Non Patent Literature 6: N. V. Sastry, and R. R. Thakor, Journal of Coatings Technology and Research, 6 (1), 11-25 (2009). Non Patent Literature 7: M. L. Green, Journal of Coatings Technology, 73 (918), 55-62 (2001). [Non-Patent Document 8] F. A. Zhang, and C. L. Yu, Journal of Coatings Technology and Research, 4 (3), 289-294 (2007). [Non-Patent Document 9] T. Annable, R. A. Brown, J. C. Padget, and A. V. Den Elshout, Surface Coatings International Part B: Coatings Transactions, 81 (7), 321-329 (1998). [Non-Patent Document 10] M. R. Patel, J. V. Patel, D. Mishra, and V. K. Sinha, Journal of Polymers and the Environment, 15 (2), 97-105 (2007). [Non-Patent Document 11] B. Erdem, R. A. Hunsiker, G. W. Simmons, E. D. Sudol, V. L. Dimonie, and M. S. El-Aasser, Langmuir, 17 (9), 2664-2669 (2001). Non-Patent Document 12: W. J. Jo, and H. D. Chun, Journal of the Environmental Sciences (Korea), 14 (8), 785-792 (2005). [Non-Patent Document 13] S. Y. Yoon, J. H. Roh, B. K. Ryu, S. J. Par, and S. H. Lee, Korean Journal of Materials Research, 10 (5), 328-334 (2000).

The present invention for solving the problems described above in the background art by adding an inorganic compound in the synthesis of an aqueous polyurethane by the reaction of polyol and isocyanate to synthesize an organic-inorganic hybrid water-dispersible polyurethane coating, flame retardant and matt effect It provides a water-dispersed polyurethane coating agent for organic-inorganic hybrid vehicle interior materials and a method for producing the same, characterized in that the stability and dispersion properties due to the improvement of the physical cohesion by the inorganic adsorbent added during the synthesis of polyurethane and improved. It is a task.

In particular, the present invention is environmentally friendly because it does not contain volatile organic compounds (VOCs) in the water-dispersed polyurethane coating agent, so the interior environment in the car is comfortable even when coating in the car, the organic-inorganic hybrid characterized in that it is suitable for the use of the coating agent for automotive interior materials Another object of the present invention is to provide an aqueous polyurethane coating for automobile interior materials and a method of manufacturing the same.

The present invention for achieving the above object is 10 to 15% by weight polyol, 1.0 to 1.5% by weight ionic compound, 4 to 6% by weight isocyanate, 0.5 to 1.0% by weight neutralizer, 0.3 to 0.7% by weight chain extender, water A water-dispersed polyurethane coating agent for organic-inorganic hybrid vehicle interior materials, comprising a composition composed of 65.3 to 81.2 wt%, 0.5 to 4.0 wt% of an inorganic additive, 2 to 5 wt% of an emulsifier, and 0.5 to 1.5 wt% of a thickener. As a solution of

And the present invention by adding an ionic compound to the polyol step of stirring the temperature rise to 70 ~ 80 ℃ (P100) and

Isocyanate is added to proceed the reaction for 80 to 100 minutes to cool the resulting prepolymer to 50 ~ 55 ℃ (P200),

Adding a neutralizing agent to the cooled prepolymer to proceed with the neutralization reaction, and then adding water and stirring for 25 to 35 minutes to produce an aqueous dispersion prepolymer in an emulsified state (P300);

Adding a chain extender to the emulsified aqueous dispersion prepolymer, aging for 50 to 80 minutes to produce a polyurethane (P400),

Step of adding the emulsifier, thickener and inorganic additive to the aged water-dispersed polyurethane strongly disperse with a homogenizer (P500)

Another method of solving the problem is a method of manufacturing a water-dispersed polyurethane coating agent for an organic-inorganic hybrid vehicle interior, characterized in that it passes through.

In the present invention, by adding an inorganic compound to synthesize an inorganic polyurethane in the synthesis of the aqueous polyurethane, the stability and dispersion degree of the coating agent due to the improvement of flame retardancy and matting effect and the increase of physical cohesion by the inorganic adsorbent added during the synthesis of polyurethane In addition to the improvement of properties, in particular, since the dispersion-free polyurethane coating does not contain volatile organic compounds (VOCs) and is environmentally friendly, the interior environment of the vehicle is comfortable even when coating in a vehicle, which is suitable for the use of the coating composition for automobile interiors.

1 is a graph showing a structure of a hybrid coating prepared according to the method of Example 1 using FT-IR.
Figure 2 is a graph showing the average particle size of the hybrid coating agent according to the application content of the inorganic additive Aeroxide P25 in the hybrid coating agent of Examples 1 to 4.
Figure 3 is a data graph showing the distribution of the particle size according to the content of the inorganic additive P25.
4 is a photograph showing the surface shape of the interior material to which Comparative Example 1 to which aeroxide P25 is not applied, and the inorganic additive aeroxide P25 is applied to the interior material after coating Example 4 to which 3% by weight of the inorganic additive aeroxide P25 is applied. .
5 is a graph showing that the Tg gradually increases as the amount of application of the inorganic additive aeroxide P25 increases.
6 is a graph showing the results of tensile strength and elongation according to the content of isocyanate.
7 is a graph showing the results of tensile strength and elongation according to the content of aeroxide P25, an inorganic additive.
8 is a graph showing the concentration of TVOCs according to the content of aeroxide P25, an inorganic additive.
9 is a graph showing the conversion rate of TVOCs with time of Example 4 applied with the inorganic additive aeroxide P25 3%.

The present invention for achieving the above effects will be described in detail with reference to the accompanying drawings only parts necessary for understanding the technical configuration of the present invention, it will be noted that the description of other parts will be omitted so as not to distract the subject matter of the present invention. shall.

Hereinafter, the components of the organic-inorganic hybrid vehicle interior water-dispersed polyurethane coating agent (hereinafter referred to as "hybrid coating agent") according to the present invention will be described in detail.

The hybrid coating agent according to the present invention is 10 to 15% by weight polyol, 1.0 to 1.5% by weight ionic compound, 4 to 6% by weight isocyanate, 0.5 to 1.0% by weight neutralizer, 0.3 to 0.7% by weight chain extender, 65.3 to 81.2 water It is characterized in that it is synthesized in a composition consisting of weight percent, inorganic additive 0.5 to 4% by weight, emulsifier 2 to 5% by weight, thickener 0.5 to 1.5% by weight.

In the present invention, the polyol reacts with isocyanate to improve the cohesion of the coating agent in the synthesis of polyurethane, and the amount of the polyol is preferably 10 to 15% by weight. If the addition amount of the polyol is less than 10% by weight, there is a problem that the cohesive strength of the coating agent is lowered, and if the addition amount of the polyol exceeds 15% by weight, unreacted polyol remains, which may cause a problem that the synthetic yield of the polyurethane is lowered. .

The polyol used in the present invention is one of polytetramethylene glycol (PTMG) or polycarbonate diol (polycarbonate diol, PCD), polypropylene glycol (PPG) or polycaprolactonediol (polycaprolactonediol, PCL) Or it is preferable to select and use more.

The ionic compound introduces a hydrophilic group to improve hydrolysis resistance when synthesizing a hybrid coating, and the amount of the ionic compound added is preferably 1.0 to 1.5% by weight. If the added amount of the ionic compound is less than 1.0 wt%, the emulsification and water dispersion stability may be lowered. If the amount of the ionic compound is more than 1.5 wt%, hydrolysis resistance may be lowered.

The ionic compound used in the present invention is preferably selected from one or more selected from dimethylol propionic acid (DMPA) or dimethylol butanoic acid (DMBA).

The isocyanate reacts with the polyol to synthesize polyurethane, and the amount of isocyanate added is preferably 4 to 6% by weight. When the amount of isocyanate added is outside the range defined above, unreacted polyols or isocyanates may remain in the reactants formed to deteriorate the physical properties of the hybrid coating agent.

Isocyanates used in the present invention are isophorone diisocyanate (IPDI), toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI) It is preferable to use one or more selected from naphthalene diisocyanate (NDI) or dicyclohexylmethane diisocyanate (H ₁₂ MDI).

And water acts to emulsify the prepolymer, the amount of water is preferably 65.3 ~ 82.2 weight%, but the amount of water is not necessarily limited to the above-mentioned range and may be appropriately adjusted as necessary.

In addition, the inorganic additives, which are a feature of the present invention, are added during the synthesis of polyurethane, thereby improving the stability and dispersion due to the increase in physical cohesion when applying the inorganic adsorbent, and in particular, increase the matt effect, and the amount of the inorganic additives added. It is preferable that it is 0.5 to 4.0 weight%. If the addition amount of the inorganic additive is less than 0.5% by weight, the above-described effects will be lowered. If the addition amount of the inorganic additive exceeds 4.0% by weight, the physical properties of the coating agent may be lowered.

Inorganic additives used in the present invention may be based on titanium dioxide (TiO ₂ ), zeolite, mordenite or transition metal compounds (γ-Al ₂ O ₃ ). It is preferable to select one or more of transition metal oxides (Cu, Mn, Mo, Cr, Co, Ni, V, Fe).

In addition, neutralizing agents, chain extenders, emulsifiers, and thickeners, which are various additives used in the present invention, are compounds commonly used, and will be described in detail below.

The neutralizing agent serves to neutralize the prepolymer, and the amount of the neutralizing agent is preferably 0.5 to 1.0% by weight. If the amount of the neutralizing agent is less than 0.5% by weight, the water dispersion stability is lowered. If the amount of the neutralizing agent is more than 1.0% by weight, the storage stability of the mullion of the synthesized aqueous dispersion polymer may be deteriorated.

The neutralizing agent used in the present invention is preferably used by selecting one or more of triethylamine (TEA), trimethylamine (TMA) or sodium hydroxide (NaOH).

The chain extender serves to synthesize the water-dispersed polyurethane by chain-extending the prepolymer, and the amount of the chain extender is preferably 0.3 to 0.7% by weight. If the amount of the chain extender is less than 0.3% by weight, the effect of extending the chain is lowered, and coating adhesion is lowered. If the amount of the chain extender is more than 0.7% by weight, the emulsified state of the water-dispersed polyurethane is poor and the storage stability is deteriorated. There is.

Chain extender used in the present invention 1,4-butanediol (1,4-butanediol), 1,6-hexanediol (1,6-hexane diol), ethylene glycol (ethylene glycol), diethylene glycol (diethylene glycol ), Ethylene diamine, hydrazine or piperazine (piperazine) is preferably used to select one or more.

The emulsifier acts to emulsify the water dispersion polymer, and the amount of the emulsifier is preferably 2 to 5% by weight. When the amount of the emulsifier is less than 2% by weight, the water-dispersed polymer is not sufficiently emulsified and the stability is lowered. When the amount of the emulsifier is more than 5% by weight, the physical properties may be deteriorated due to deterioration in durability.

The emulsifier used in the present invention is a nonionic emulsifier polyoxyethylene decyl ether, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether or polyoxyethylene tridecyl It is preferable to use one or more selected from ethers (Polyoxyethylene Tridecyl Ether).

The thickener acts to enhance the viscosity of the water-dispersed polymer, the amount of the thickener is preferably 0.5 to 1.5% by weight. If the addition amount of the thickener is less than 0.5% by weight, there may be a problem in product stability due to the lowering of dispersion stability, and if the addition amount of the thickener is more than 1.5% by weight, the viscosity of the water-dispersed polymer increases, which may cause problems in the application process. have.

The thickener used in the present invention is ethylene oxide propylene oxide copolymer, poly (meth) acrylamide, hydroxyethyl cellulose, hydroxypropyl cellulose (hydroxypropyle cellulose) or modified polyurethane (modified polyurethane) it is preferable to use one or more selected.

Referring to the method of manufacturing a hybrid coating compound synthesized using the above components in detail as follows.

Hybrid coating agent according to the present invention by adding an ionic compound to the polyol and stirring the temperature rise to 70 ~ 80 ℃ (P100),

Isocyanate is added to proceed the reaction for 80 to 100 minutes to cool the resulting prepolymer to 50 ~ 55 ℃ (P200),

Adding a neutralizing agent to the cooled prepolymer to proceed with the neutralization reaction, and then adding water and stirring for 25 to 35 minutes to produce an aqueous dispersion prepolymer in an emulsified state (P300);

Adding a chain extender to the emulsified aqueous dispersion prepolymer, aging for 50 to 80 minutes to produce a polyurethane (P400),

The emulsifiers, thickeners and inorganic additives are added to the aged water-dispersed polyurethane, which is then strongly dispersed with a homogenizer (P500).

Since the compound used in each step of the manufacturing method has been described in detail when explaining the components of the hybrid coating agent, the description thereof will be omitted and the description will be mainly focused on the manufacturing method.

The P100 step is to add an ionic compound to the polyol in order to introduce a hydrophilic group, by adding the ionic compound to the polyol and stirred at a temperature of 70 ~ 80 ℃. In this step, the temperature rise temperature is preferably 70 ~ 80 ℃. If the elevated temperature is less than 70 ℃ physical properties such as durability due to the lowering of the reactivity is lowered, if it exceeds 80 ℃ it is difficult to control the reactivity and there is a risk of gelation phenomenon.

The P200 step is a step of synthesizing the prepolymer by adding isocyanate to the mixture by adding an ionic compound to the polyol, and stirring the reaction time, preferably 80 to 100 minutes. If the reaction time is less than 80 minutes, the prepolymer is not sufficiently synthesized. If the reaction time is more than 100 minutes, there may be a decrease in physical properties such as bending resistance of the applied product due to an increase in the molecular weight of the prepolymer due to overreaction. And it is preferable that the temperature which cools the produced prepolymer is less than 55 degreeC, and when a cooling temperature exceeds 55 degreeC, there exists a possibility that reaction may advance more.

In the P300 step, water is added to the cooled prepolymer to prepare an aqueous dispersion prepolymer in an emulsified state. When the stirring time is less than the range defined above, the water and the prepolymer are not sufficiently mixed so that the stability of the prepolymer is not sufficient. There is a risk of deterioration.

The P400 step is a step of producing a polyurethane by injecting a chain extender into the water-disperse prepolymer, when the aging time is less than the range defined above, the physical properties of the polyurethane changes due to changes in molecular weight, etc. If it exceeds the range defined above, there is a fear that the efficiency due to the increase in the total reaction time is reduced.

The P500 step is to prepare a hybrid coating agent by dispersing the emulsifier, thickener and inorganic additive in the matured water-dispersed polyurethane with a homogenizer, and inputting an emulsifier and a thickener for securing stability and viscosity control of the hybrid coating agent. In particular, the step of adding an inorganic additive to improve the stability and dispersion of the polyurethane due to the increase in physical cohesion when applying the inorganic adsorbent, in particular to increase the matt effect.

In addition, an inert organic solvent such as methyl ethyl ketone, dimethylformamide or N-methylpyrrolidone, which does not react with isocyanate during the reaction is added during or after the reaction to adjust the viscosity.

Therefore, by removing the organic solvent by distillation under reduced pressure at a pressure of 20 ~ 150mmHg to remove the organic solvent used for viscosity control in the synthesis of the water dispersion polymer in the above step, the hybrid coating agent according to the present invention volatile organic compounds (VOCs) Since it is environmentally friendly because it does not contain it, it is suitable for the use of the coating composition for automobile interiors, since the interior environment of the vehicle is comfortable even when coating in the vehicle. In the case where the reduced pressure is less than 20mmHg, not only the organic solvent contained in the water-dispersed polyurethane coating agent but also water may be distilled under reduced pressure to change the overall physical properties and solid content. There is a concern that the organic solvent contained may not be sufficiently removed.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, these examples are only presented to understand the content of the present invention and should not be construed that the scope of the present invention is necessarily limited to these examples.

1. Preparation of Hybrid Coatings

(Example 1)

In a 1 L four-necked flask, 5% by weight of polyol PTMG (Mw = 2000, Aldrich), 5% by weight of polyol PCD (Mw = 2000, Asahi Kase), dimethylol propionic acid (DMPA, Pestorp Co.) was added 1.0% by weight, and the temperature was raised to 75 ℃ and stirred. After stirring, 4 wt% of isophorone diisocyanate (IPDI, Asahi Kase Co., Ltd.) was added thereto, followed by reaction for 90 minutes. After the reaction was cooled to 50 ° C., triethylamine (triethyl amine, TEA, Junsei Chemical Co., Ltd.) 0.5 wt% was added to the neutralization reaction, and 81.2 wt% water was added thereto, followed by stirring for 30 minutes. 0.3 wt% of 1,4-butanediol (1,4-butanediol, Aldrich), a chain extender, was added thereto, and aged for 60 minutes. 2% by weight of a nonionic emulsifier (KoremulDE-7, thickener), 0.5% by weight of a thickener (RM-825, Hohm & Haas), and an inorganic additive, aeroxide with a particle size of 20 to 40 nm 0.5 wt% of TiO ₂ P25 (Evonik) was added and strongly dispersed with a homogenizer to synthesize a hybrid coating. Then, methyl ethyl ketone was added to adjust the viscosity during the reaction, and the methyl ethyl ketone was 20 to 150 mmHg. Distillation under reduced pressure to remove methyl ethyl ketone contained in the hybrid coating agent.

(Example 2)

In a 1 L four-necked flask, 5% by weight of polyol PTMG (Mw = 2000, Aldrich), 5% by weight of polyol PCD (Mw = 2000, Asahi Kase), dimethylol propionic acid (DMPA, Pestorp Co.) was added 1.0% by weight, and the temperature was raised to 75 ℃ and stirred. After stirring, 4 wt% of isophorone diisocyanate (IPDI, Asahi Kase Co., Ltd.) was added thereto, followed by reaction for 90 minutes. After the reaction was cooled to 50 ° C., triethylamine (triethyl amine, TEA, Junsei Chemical Co., Ltd.) 0.5 wt% was added to the neutralization reaction, and 80.7 wt% water was added thereto, followed by stirring for 30 minutes. 0.3 wt% of 1,4-butanediol (1,4-butanediol, Aldrich), a chain extender, was added thereto, and aged for 60 minutes. 2% by weight of a nonionic emulsifier (KoremulDE-7, thickener), 0.5% by weight of a thickener (RM-825, Hohm & Haas), and an inorganic additive, aeroxide with a particle size of 20 to 40 nm 1 wt% of TiO ₂ P25 (Evonik) was added and strongly dispersed with a homogenizer to synthesize a hybrid coating. Then, methyl ethyl ketone was added to adjust the viscosity during the reaction, and the methyl ethyl ketone was 20 to 150 mmHg. Distillation under reduced pressure to remove methyl ethyl ketone contained in the hybrid coating agent.

(Example 3)

In a 1 L four-necked flask, 5% by weight of polyol PTMG (Mw = 2000, Aldrich), 5% by weight of polyol PCD (Mw = 2000, Asahi Kase), dimethylol propionic acid (DMPA, Pestorp Co.) was added 1.0% by weight, and the temperature was raised to 75 ℃ and stirred. After stirring, 4 wt% of isophorone diisocyanate (IPDI, Asahi Kase Co., Ltd.) was added thereto, followed by reaction for 90 minutes. After the reaction was cooled to 50 ° C., triethylamine (triethyl amine, TEA, Junsei Chemical Co., Ltd.) was added 0.5% by weight of the reaction to neutralize, followed by 79.7% by weight of water, followed by stirring for 30 minutes. 0.3 wt% of 1,4-butanediol (1,4-butanediol, Aldrich), a chain extender, was added thereto, and aged for 60 minutes. 2% by weight of a nonionic emulsifier (KoremulDE-7, thickener), 0.5% by weight of a thickener (RM-825, Hohm & Haas), and an inorganic additive, aeroxide with a particle size of 20 to 40 nm 2 wt% of TiO ₂ P25 (Evonik) was added and strongly dispersed with a homogenizer to synthesize a hybrid coating. Then, methyl ethyl ketone was added to adjust the viscosity during the reaction, and the methyl ethyl ketone was 20 to 150 mmHg. Distillation under reduced pressure to remove methyl ethyl ketone contained in the hybrid coating agent.

(Example 4)

7.5 wt% of polyol PTMG (Mw = 2000, Aldrich), 7.5 wt% of polyol PCD (Mw = 2000, Asahi Kase), dimethylol propionic acid (DMPA, Pestorp Co.) 1.5% by weight, and then heated to 80 ℃ stirred. After stirring, 6 wt% of isophorone diisocyanate (IPDI, Asahi Kase) was added thereto, and the reaction was allowed to proceed for 90 minutes. After the reaction was cooled to 55 ° C., triethylamine (triethyl amine, TEA, Junsei Chemical Co., Ltd.) was added 1.0 wt% to neutralize the reaction, and then 66.3 wt% of water was added thereto, followed by stirring for 30 minutes. 0.7 wt% of 1,4-butanediol (1,4-butanediol, Aldrich), a chain extender, was added thereto, and aged for 60 minutes. 5% by weight of nonionic emulsifier (KoremulDE-7, thickener), 1.5% by weight of thickener (RM-825, Hohm & Haas), and aeroxide with particle size of 20-40 nm in water-dispersed polyurethane aged for 60 minutes 3 wt% of TiO ₂ P25 (Evonik) was added and strongly dispersed with a homogenizer to synthesize a hybrid coating. Then, methyl ethyl ketone was added to adjust the viscosity during the reaction, and the methyl ethyl ketone was 20 to 150 mmHg. Distillation under reduced pressure to remove methyl ethyl ketone contained in the hybrid coating agent.

(Example 5)

7.5 wt% of polyol PTMG (Mw = 2000, Aldrich), 7.5 wt% of polyol PCD (Mw = 2000, Asahi Kase), dimethylol propionic acid (DMPA, Pestorp Co.) 1.5% by weight, and then heated to 80 ℃ stirred. After stirring, 6 wt% of isophorone diisocyanate (IPDI, Asahi Kase) was added thereto, and the reaction was allowed to proceed for 90 minutes. After the reaction was cooled to 55 ° C., triethylamine (triethyl amine, TEA, Junsei Chemical Co., Ltd.) was added 1.0 wt% to neutralize the reaction, and then 65.3 wt% of water was added thereto, followed by stirring for 30 minutes. 0.7 wt% of 1,4-butanediol (1,4-butanediol, Aldrich), a chain extender, was added thereto, and aged for 60 minutes. 5% by weight of nonionic emulsifier (KoremulDE-7, thickener), 1.5% by weight of thickener (RM-825, Hohm & Haas), and aeroxide with particle size of 20-40 nm in water-dispersed polyurethane aged for 60 minutes 4 wt% of TiO ₂ P25 (Evonik) was added and strongly dispersed with a homogenizer to synthesize a hybrid coating. Then, methyl ethyl ketone was added to adjust the viscosity during the reaction. Distillation under reduced pressure to remove methyl ethyl ketone contained in the hybrid coating agent.

(Comparative Example 1)

Synthesis of the hybrid coating in the same manner as in Example 1, followed by distillation under reduced pressure at a pressure of 20 ~ 150mmHg to remove volatile organic compounds (VOCs) contained in the hybrid coating, unlike inorganic additives, unlike Examples 1 to 4 Did.

2. Measurement and Structure Analysis Method of Hybrid Coating

Structural analysis of the hybrid coating agent prepared according to Examples 1 to 4 and Comparative Example 1 according to the present invention was used by the BOMEM MB-104 spectrometer and Q of TA instruments to measure the glass transition temperature (Tg) according to various conditions -100 was used. The glass transition temperature was measured under nitrogen atmosphere at -90 ° C to 150 ° C at 10 / min. In order to measure the mechanical properties of the synthesized hybrid coating, a universal test machine of Houns-field's H5K5 model was used. Field analysis scanning electron microscope (FEESEM) of JEOL's JSM-6701F model was used to analyze the particle and surface properties of the prepared hybrid coatings, and Beckman's LS-13320 (Laser diffraction particle size analyzer) was used to measure the particle size. The average particle size was measured by application. For the TVOC measurement, the experiment was carried out by the method of automobile VOC standard MS 300-55, and RAE3000 of RAE system was applied. After cutting the inner sheet test specimen to which the hybrid coating agent was applied to 4 × 9 cm and inserting it into a tedlar bag over time, the TVOC was measured after 65 and 2 hours.

3. Evaluation of Hybrid Coatings

1) structural analysis

The structure of the hybrid coating prepared according to the method of Example 1 was analyzed using FT-IR and the results are shown in FIG. (A) is the FT-IR of WC-6, and the characteristic peak by NH of urethane group in 3300 ~ 3400cm ^-1 was confirmed, the characteristic peak of carbonyl group in urethane around 1740cm ^-1 , and the NCO group was around 2250cm-1. It was confirmed that the reaction was terminated by confirming that no peak of. (C) is a graph of 3% application of aeroxide P25 to FT-IR of WC-9. It was confirmed that the characteristic peak of the aeroxide P25 of 500 ~ 800cm ^-1 appeared while maintaining the overall characteristic peak of the urethane coating agent, it was confirmed that the organic-inorganic hybrid coating agent was synthesized.

2) particle size analysis

The average particle size of the hybrid coating agent according to the application content of the inorganic additive aeroxide P25 in the hybrid coating agent of Examples 1 to 4 is shown in FIG. 2. When the inorganic additive aeroxide P25 was applied, it was confirmed that the particle size of the hybrid coating agent increased by about 10 nm, and that the average particle size did not show a large change as the content increased. The average particle size of the inorganic additive, aeroxide P25, is 20 ~ 25nm, and the application of emulsifier and homogenizer does not show any significant change in particle size during the application process. As a result, the dispersion of the hybrid coating agent is excellent. It was found that the stability is excellent. Figure 3 is a data showing the distribution of the particle size according to the content of the inorganic additive P25 It was confirmed that the particle distribution increases by 10 ~ 15nm with the application and content of aeroxide P25 increased but the trend of the overall distribution of the aeroxide P25 After the application, it was confirmed that the emulsion stability of the hybrid coating agent was excellent. For reference, (A) Comparative Example 1, (B) Example 3, and (C) Example 5 in FIG. 3.

3) Surface Characterization

After coating the environmentally friendly hybrid coating on the vehicle interior material, the surface characteristics were analyzed using a field emission scanning electron microscope (FESEM). 4 shows the surface shape of the interior material to which Comparative Example 1 to which the inorganic additive aeroxide P25 is not applied, and the right photo shows the surface after coating Example 4 to which the inorganic additive aeroxide P25 was applied to 3% by weight. It shows the shape. In the case of Comparative Example 1, as shown in the photograph, the transparent surface can be confirmed, and in the case of the right photograph to which Example 4 is applied, it can be seen that the particles of the acroxide P25, which is an inorganic additive, are uniformly distributed. In addition, the size of the particles shown in the coating film coated with Example 4 was confirmed to be the same as the analysis results of the particle size of about 40 ~ 50nm.

4) Thermal Characterization

5 shows the results of DSC according to the content of aeroxide P25, an inorganic additive. It can be seen that the Tg gradually increases as the content of aeroxide P25, an inorganic additive, increases, which results in a decrease in the flexibility of the molecular structure due to the physical cohesion of the hybrid coating molecule chain as the content of aeroxide P25 increases. . For reference, (A) in FIG. 5 is Comparative Example 1, (B) is Example 3, and (C) is Example 5.

5) Physical characterization

6 and 7 show the results of tensile strength and elongation according to the content of isocyanate and the content of aeroxide P25, which is an inorganic additive, respectively. As the R ratio and the content of aeroxide P25 were increased, the tensile strength increased and the elongation decreased. Increasing the R ratio increases the tensile strength due to the increase in the crosslink density due to the increase of the hard segment in the molecular structure, thereby reducing the fluidity of the molecular structure and thus reducing the elongation. In the case of tensile strength, the increase was significantly reduced when the R ratio was 1.5 or more. It was confirmed that the tensile strength increased with increasing application amount of the inorganic additive aeroxide P25.

6) TVOCs Analysis

Figure 8 shows the concentration of TVOCs according to the content of the inorganic additive aeroxide P25. TVOCs results were measured after 7 days of fabrication of the sheet specimens. As the application amount of aeroxide P25, an inorganic additive, increased, the concentration of TVOCs gradually decreased. This is believed to be due to the reduced function of TVOCs removal due to the saturated state of adsorption. Figure 9 shows the TVOCs conversion with time of Example 4 applied aeroxide P25 3%. After about 7 days, the conversion rate of TVOCs was about 30%. If the time increased more than that, the decrease of TVOCs was not smooth. The decrease of TVOCs was determined by photolysis. TiO ₂ is a photocatalyst. When light energy is irradiated, electron exciting occurs, and as a result, a potential difference between valence band and conduction band is generated, thereby oxidizing and reducing VOCs adsorbed on the sheet surface. It is expected to degrade through.

The present invention prepared an eco-friendly hybrid coating applied inorganic adsorbent (aeroxide P25) as in the above embodiment and analyzed the characteristics according to the change in the content of isocyanate and the applied content of the inorganic adsorbent, the particle size analysis result of the content of aeroxide P25 There was no significant change rate with the increase. This is expected to be a result of the application process of the emulsifier and homogenizer in the preparation of the hybrid coating, and it was confirmed that the dispersion of the hybrid coating applied with aeroxide P25 was considered in consideration of the particle distribution results. As a result of surface characteristic analysis, the coating of aeroxide P25 was uniformly distributed and coated on the interior sheet surface, and the particle size was 40 ~ 50nm. In addition, the glass transition temperature (Tg) and tensile strength increased as the content of isocyanate increased (R ratio increased). This is considered to be a phenomenon in which the crosslinking density increases due to the increase of hard segments in the molecular structure as the content of isocyanate increases. Increasing the glass transition temperature (Tg) and tensile strength with increasing application amount of the inorganic additive aeroxide P25 is believed to decrease the flexibility of the molecular structure due to the physical cohesion of the hybrid coating molecule chain. In addition, the results of TVOCs analysis according to the content of aeroxide P25, an inorganic additive, showed that the concentration of TVOCs gradually decreased as the applied content increased. This is believed to be due to the reduced function of TVOCs removal due to the saturated state of adsorption.

As described above, the present invention has proved its superiority through the above embodiments, but the present invention is not necessarily limited only to the above embodiments, and various modifications may be made without departing from the technical spirit of the present invention. Substitutions, modifications and variations are possible.

Claims (7)

10 to 15 weight percent polyol, 1.0 to 1.5 weight percent ionic compound, 4 to 6 weight percent isocyanate, 0.5 to 1.0 weight percent neutralizing agent, 0.3 to 0.7 weight percent chain extender, 65.3 to 81.2 weight percent water, 0.5 to inorganic additives A water-dispersed polyurethane coating agent for an organic-inorganic hybrid vehicle interior, characterized in that the composition is composed of 4.0 wt%, emulsifier 2-5 wt%, thickener 0.5-1.5 wt%.
The method of claim 1,
The polyol is characterized in that one or more selected from polytetramethylene glycol (PTMG), polycarbonate diol (PCD), polypropylene glycol (PPG), or polycaprolactonediol (PCL) Dispersed polyurethane coating for organic and inorganic hybrid automotive interiors.
The method of claim 1,
The ionic compound is an aqueous inorganic polyurethane coating for organic-inorganic hybrid vehicle interior, characterized in that one or more selected from dimethylol propionic acid (DMPA) or dimethylol butanoic acid (DMBA).
The method of claim 1,
The chain extender 1,4-butanediol (1,4-butanediol), 1,6-hexanediol (1,6-hexane diol), ethylene glycol (ethylene glycol), diethylene glycol (diethylene glycol), ethylene diamine A water-dispersed polyurethane coating agent for organic-inorganic hybrid vehicle interiors, characterized in that one or more selected from (ethylene diamine), hydrazine, or piperazine.
The method of claim 1,
The inorganic additive is a transition metal oxide (Cu, Mn, Mo, Cr, Co) supported on a titanium dioxide (TiO ₂ ), zeolite (zeolite), mordenite or transition metal compound (γ-Al ₂ O ₃ ) as a carrier. , Ni, V, Fe) water-dispersible polyurethane coating agent for organic-inorganic hybrid vehicle interior material, characterized in that at least one selected.
Adding an ionic compound to the polyol and stirring the temperature at 70 to 80 ° C. (P100);
Isocyanate is added to proceed the reaction for 80 to 100 minutes to cool the resulting prepolymer to 50 ~ 55 ℃ (P200),
Adding a neutralizing agent to the cooled prepolymer to proceed with the neutralization reaction, and then adding water and stirring for 25 to 35 minutes to produce an aqueous dispersion prepolymer in an emulsified state (P300);
Adding a chain extender to the emulsified aqueous dispersion prepolymer, aging for 50 to 80 minutes to produce a polyurethane (P400),
Adding emulsifiers, thickeners, and inorganic additives to the aged water-dispersed polyurethane to disperse strongly with a homogenizer (P500),
Method for producing a water-dispersed polyurethane coating for organic-inorganic hybrid vehicle interior, characterized in that through.
The method according to claim 6,
Method for producing a water-dispersed polyurethane coating for organic-inorganic hybrid vehicle interior material, characterized in that to remove the organic solvent used for viscosity control when the synthesis of the water-dispersed polymer by distillation under reduced pressure at a pressure of 20 ~ 150mmHg.

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