KR101471506B1 - Fast drying and curing type polyurethane coating composition - Google Patents

Abstract

The present invention relates to a quick-drying curable coating composition, which comprises various modified polyols obtained by modifying (modifying) a vegetable oil as an essential material, and is environmentally friendly, It is possible to minimize the production of industrial wastes during manufacturing and recycle due to the decomposition of the production residue. Also, since vegetable oil is used as the main raw material, there is no problem of volatile organic compounds or residual heavy metals, It has excellent resistance to salt and weathering, abrasion resistance, water resistance, impact resistance, adhesion strength, flexibility and hardness.

Description

[0001] FAST DRYING AND CURING TYPE POLYURETHANE COATING COMPOSITION [0002]

The present invention relates to a quick drying curing type polyurethane coating composition, and more particularly, to an environmentally friendly, non-solvent fast drying curing type polyurethane coating composition containing various modified polyols obtained by modifying (modifying) The use of polyol modified with natural vegetable oil as a main component minimizes the production of industrial waste at the time of production and enables recycling due to decomposition of the production residue. Also, since vegetable oil is used as the main raw material, It is harmless to the human body because there is no problem of compound or residual heavy metal, and is excellent in salt resistance, weather resistance, abrasion resistance, water resistance, impact resistance, adhesion strength, flexibility and hardness.

In general, a paint (coating material) is defined as a material which is applied to the surface of an object to protect an object or improve a beauty by forming a cured coating layer, that is, a coating film, and includes an opaque coloring pigment, A paint for forming a cured coating film, a varnish which does not contain a pigment but is cured by evaporation of the solvent and oxidation or polymerization of the resin to form a clear transparent coating film, or a transparent or translucent lacquer which is quickly dried by evaporation of the solvent . ≪ / RTI >

Usually, the paint is composed of a resin binder as a coating film forming component, a vehicle composed of an additive and a solvent, and optionally a pigment.

Resin binders are the main ingredients that determine the physical properties of paints. They determine the drying mechanism of the paints and determine the properties of the paints. Petroleum chemical compounds are used, but natural resins and oils are also used.

The solvent is used for controlling the viscosity for imparting appropriate fluidity for facilitating the coating operation of the coating, which affects the coating state and affects the properties or performance of the coating film although it is volatilized.

The auxiliary agent is variously added such as a defoaming agent, a drying agent, an antioxidant, a dispersant, an anti-settling agent, an ultraviolet absorber, a stabilizer, an antistatic agent, and an antifouling agent as a small amount of a component added for the purpose of improving or improving the physical properties of the paint.

The pigment not only imparts its own color but also is a component that mainly determines the effect of the pigment on the substrate including hiding power, glossiness, light fastness, etc., and is selected according to various purposes and conditions.

The paint has a beautifying function that gives various colors and gloss to the substrate to make the substrate beautiful and gives a predetermined special function such as anticorrosive property by coating film, electric insulation, bruxism, anticorrosive property, heat resistance and antifouling property It is also said.

Here, since most of conventional paints use compounds derived from petrochemicals as main raw materials, they have a problem of promoting depletion of resources from a macroscopic point of view. In addition, from a microscopic point of view, In addition, since the generated waste is non-degradable or deteriorated, it is difficult to treat the waste, thereby causing environmental pollution. In addition, since the raw material itself is chemically toxic or is an environmental hormone, (VOCs: Volatile (VOCs): volatile organic compounds (VOCs), volatile organic compounds (VOCs), and the like) Organic compounds such as lead, chromium, and cadmium. There is a serious problem that it is harmful to the human body due to high possibility of causing sick house syndrome, chemical hypersensitivity, heavy metal poisoning, cancer and the like because the carcinogenic substances such as heavy metals are continuously leaked.

Due to these problems, the legal regulations on volatile organic compounds and environmental hormones have been greatly strengthened in developed countries in recent years, and the necessity of development of environmentally friendly paints is strongly emerged.

Therefore, as a conventional method for alleviating or solving such a problem, in view of the fact that about 70% of the paint currently in circulation uses a volatile organic solvent, which is a cause of fire, poisoning and environmental pollution, as a diluent, Efforts have been made to increase the water content to replace the organic compound with water or to increase the ratio of solid components in the coating to increase the solubility of the solvent and to develop powder coatings and solvent- However, since such a method can not be a fundamental solution for solving the problem, development of an environmentally friendly paint using a natural plant compound or its derivative has been attempted. However, most of the problems are that the performance of the coating film is less than the required level, It is too expensive in terms of enemy, so it is not economical. Is not widely spread due to problems.

On the other hand, as we broaden our horizons and look at the aspects of the biochemical industry, the biochemical industry can significantly reduce its dependence on fossil fuels and significantly reduce its greenhouse gas emissions. Therefore, the global attention is focused on the biomass, and the added value per unit biomass Bio-chemical products are about five times more likely to show high growth potential in the future. While the global chemical market is growing at a rate of 3 to 6% per year, platform compounds that refer to C2 compounds such as ethanol, general-purpose biochemicals such as lactic acid and glycerol that can be prepared using the above-mentioned C2 compounds, The market of biochemical products such as bio-plastics such as polyamides and polyurethanes, and bio-functional chemicals as functional compounds that can be used in the production of foods and cosmetics has been growing 40 to 50% annually so far, By 2025, it is expected to show a growth of 8 ~ 10%. However, the domestic biochemical industry accounts for only 2% of the domestic chemical industry. Therefore, it is urgent to raise international competitiveness in the field.

Typical examples of conventional paints using vegetable resins as main raw materials include the following.

Korean Patent Registration No. 0989091 (registered on October 14, 2010) proposes an antimicrobial paint composition comprising a natural vegetable resin and zeolite as a main component, but it is not a solvent-free paint but a water-soluble paint, and the above- It is not.

In addition, Korean Patent Registration No. 0428589 (registered on Apr. 12, 2004) discloses a method for producing a vegetable polymer by adding ethanol to palm oil or coconut oil to produce a fatty acid alcohol by hydrogenation, and then reacting the starch to produce a vegetable polymer. The present invention also discloses a method for producing an environmentally friendly functional paint comprising a vegetable resin in the form of a milky white emulsion obtained by mixing an organic solvent, It is not about paint.

Korean Patent Registration No. 0380218 (registered on April 2, 2003) proposes a natural paint improved workability and coating property produced by mixing vegetable oil and lecithin in a mixture of tung oil, flax oil, rosin ester and citrusuterephrine oil However, the above-mentioned coating material is not related to the crosslinking polymerization type coating material.

Meanwhile, Korean Patent Laid-Open No. 10-2008-0103052 discloses a biodegradable polyhydroxybutyrate or a copolymer thereof, a degradable polyol polyester comprising at least one vegetable oil, an isocyanate and a foaming agent A one-pack type foamed polyurethane which is decomposable by using a polyolefin.

Also, USP 4,324,880, USP 5,352,763, USP 5,665,831, WO 2002/06368 A and the like discloses a process for producing a polyurethane by reacting an isocyanate with an esterification reaction using hydroxybutyrate as a main raw material, However, these are not related to polyurethane paints using vegetable oils.

Accordingly, the inventors of the present invention have extensively conducted tests to formulate a variety of polyols by modifying vegetable oils and then formulating them into two-part polyurethane coatings in order to thoroughly examine the above-mentioned matters and solve the above problems. As a result, And has been developed to develop a fast drying curing type polyurethane coating composition which is excellent in flame retardancy, weather resistance, abrasion resistance, water resistance, impact resistance, adhesion strength, flexibility and hardness and is economical.

Accordingly, a first object of the present invention is to provide an environmentally friendly polyurethane coating composition comprising various modified polyols obtained by modifying (modified) vegetable oils as main raw materials.

A second object of the present invention is to provide a solvent-resistant, quick-setting curable polyurethane coating composition.

A third object of the present invention is to provide a polyurethane coating composition capable of minimizing the production of industrial waste at the time of production and capable of being recycled by decomposition of the production residue.

A fourth object of the present invention is to provide a polyurethane coating composition that is harmless to the human body since there is no problem of volatile organic compounds, environmental hormones, and residual heavy metals after painting as well as painting process.

A fifth object of the present invention is to provide a polyurethane coating composition excellent in physical properties of a coating film such as salt resistance, weather resistance, abrasion resistance, water resistance, impact resistance, adhesion strength, flexibility and hardness.

A sixth object of the present invention is to provide an environmentally friendly polyurethane coating composition which can be supplied at a price competitive advantage.

(A) 18 to 34% by weight, preferably 20 to 32% by weight of a petroleum-based polyether polyol, and 30 to 50% by weight of a polyether polyol (MDI) A first liquid as an isocyanate prepolymer comprising 55 to 75% by weight, preferably 60 to 72% by weight of diisocyanate and 7 to 11% by weight, and preferably 8 to 10% by weight of HDI (hexamethylene diisocyanate); (B) 30 to 70% by weight, preferably 40 to 62% by weight of modified polyol derived from vegetable oil, 8 to 25% by weight of aromatic secondary amine, 10 to 30% by weight of tetrafunctional tertiary amine polyol, And 8 to 15% by weight of a polyol as a main component, wherein the first liquid is contained in an amount such that the NCO content is 20 to 23% by weight, wherein the first liquid is a liquid-type quick drying curable polyurethane coating composition / RTI >

In the present invention, the first liquid is preferably composed of 20 to 32% by weight of a petroleum-based polyether polyol, 60 to 72% by weight of MDI (methylene diphenyl diisocyanate) and 8 to 10% by weight of HDI (hexamethylene diisocyanate) .

In the present invention, it is preferable that the first liquid has an NCO content of 20 to 23% by weight, a viscosity of 970 to 1400 cps (85 to 98 KU) and a specific gravity of 1.13 to 1.15.

In the present invention, the petroleum-derived polyether polyol in the first liquid may have an OH equivalent of 800 to 1200, a hydroxyl value of 48 to 62 mgKOH / g, and a viscosity of 200 to 420 cps.
In the present invention, the MDI in the first liquid may be a polymerizable MDI having an NCO content of 30 to 32% by weight.

delete

In the present invention, the MDI in the first liquid may be a monomodal MDI having an NCO content of 33.58% by weight.

In the present invention, the HDI in the first liquid may be a low viscosity HDI trimer having an NCO content of 24.98 wt% and a viscosity of 400 to 1400 cps (65 to 95 KU).

According to the present invention, it is preferable that the first liquid and the second liquid are designed to be mixed in a 1: 1 equivalent volume ratio.

According to the present invention, the modified polyol derived from the vegetable oil in the second liquid comprises a methoxypolyol of the following formula (1), a hydroxylpolyol of the following formula (2), a hydroxyl fatty acid methyl ester of the following formula (3) And an introduced polyol.

[Chemical Formula 1]

(2)

(3)

Wherein R ₁ is the same as each other H or OH, and, if R ₁ is OH and R ₂ is also OH R ₃ is H, when R ₃ is OH R ₂ is an OH and R ₁ is H.

[Chemical Formula 4]

또는

이다.
Wherein R is

or

to be.

Here, the modified polyol derived from vegetable oil in the second liquid preferably has an OH equivalent of 200 to 400, a hydroxyl value of 180 to 260 mgKOH / g, and a viscosity of 600 to 4,700 cps.

According to the present invention, the modified polyol derived from the vegetable oil in the second liquid comprises 5 to 29% by weight of the methoxypolyol of the formula (1), 1 to 10% by weight of the hydroxylpolyol of the formula (2) And 70 to 90% by weight of a fatty acid methyl ester.

According to the present invention, the modified polyol derived from the vegetable oil in the second solution may be a mixture of 10 to 30% by weight of the hydroxylpolyol of the formula 2 and 70 to 90% by weight of the hydroxyl fatty acid methyl ester of the formula 3 .

According to the present invention, the modified polyol derived from the vegetable oil in the second liquid may be a mixture of 10 to 30% by weight of the methoxypolyol of Formula 1 and 70 to 90% by weight of the hydroxyl fatty acid methyl ester of Formula 3.

According to the present invention, the modified polyol derived from the vegetable oil in the second solution may contain 8 to 27% by weight of the methoxypolyol of the formula 1, 1 to 5% by weight of the hydroxylpolyol of the formula 2, 50 to 81% by weight of a fatty acid methyl ester and 10 to 30% by weight of an acrylate ester-introduced polyol of the formula (4).

In the present invention, it is preferable that the above tetrafunctional tertiary amine polyol is a tetrahydroxypolyol quaternary amine.

It is particularly preferable that the above-mentioned aromatic secondary amine has an OH or amine equivalent of 155, and the above-mentioned tetrafunctional tertiary amine polyol is OH or amine equivalent of the tetrahydroxypolyol quaternary amine of 73.1.

Further, the above-mentioned other additives may be dispersants, defoaming agents, dehumidifiers, pigments, stabilizers.

Here, the dispersant may be an ammonium salt, the defoaming agent may be a silicone oil, the dehumidifying agent may be an aluminum silicate molecular sieve, and the stabilizer may be triethylo-sulpho mate.

It is also possible to include dibutyltin dilaurate as a urethane curing catalyst.

The quick-setting curable coating composition according to the present invention is characterized in that it contains various modified polyols obtained by modifying (modifying) a vegetable oil as a main raw material and is essentially solvent-free and minimizes the production of industrial waste at the time of manufacture Of course, since it can be recycled due to decomposition of the production residue, it has high environmental friendliness and is not harmful to the human body because there is no problem of volatile organic compound, environmental hormone and residual heavy metal after painting as well as painting process, And excellent physical properties such as abrasion resistance, water resistance, impact resistance, adhesion strength, flexibility, hardness and the like, and has sufficient price competitiveness, and the production method according to the present invention can effectively provide the above quick drying curable coating composition There is a number.

Figs. 1A to 1C are ¹³ C-NMR, ¹ H-NMR and FT-IR graphs of epoxidized soybean oil, respectively.
2A to 2C are ¹³ C-NMR, ¹ H-NMR and FT-IR graphs of methoxypolyol, respectively.
FIGS. 3A to 3C are ¹³ C-NMR, ¹ H-NMR and FT-IR graphs of the hydroxyl polyol, respectively.
4A to 4C are ¹³ C-NMR, ¹ H-NMR and FT-IR graphs of the epoxidized fatty acid methyl ester, respectively.
5A to 5C are ¹³ C-NMR, ¹ H-NMR and FT-IR graphs of the hydroxyl fatty acid methyl ester, respectively.
6A to 6C are ¹³ C-NMR, ¹ H-NMR and FT-IR graphs of 3 - ((2-hydroxyethoxy) carbonyl) acrylic acid.
7A to 7C are ¹³ C-NMR, ¹ H-NMR and FT-IR graphs of 3 - ((2,3-dihydroxypropoxy) carbonyl) acrylic acid.
8A to 8C are ¹³ C-NMR, ¹ H-NMR and FT-IR graphs of ester polyols, respectively.
FIGS. 9A to 9C are ¹³ C-NMR, ¹ H-NMR and FT-IR graphs of different ester polyols, respectively.
10A to 10G are external photographs of a coating film (coating film) coated with the coating composition according to the present invention.
11A to 11G are photographs of the surface of the coated film formed from the coating composition according to the present invention, respectively.
12A to 12G are photographs showing the results of the flexibility test of a coating film formed from the coating composition according to the present invention.
13A to 13G are photographs showing the results of the impact resistance test of the coating film formed from the coating composition according to the present invention.
14A to 14G are photographs showing the results of the abrasion resistance test of the coating film formed from the coating composition according to the present invention, respectively.
15A to 15H are photographs showing the chemical resistance test results of the coating film formed from the coating composition according to the present invention, respectively.
16A to 16F are external photographs of coatings of other specimens coated with the coating composition according to the present invention.
Figs. 17A to 17F are photographs showing the results of the flexibility tests of other coating films formed from the coating composition according to the present invention.
18A to 18F are photographs showing the results of the impact resistance test of other coating films formed from the coating composition according to the present invention.
19A to 19F are photographs showing the results of the abrasion resistance test of other coating films formed from the coating composition according to the present invention.
20A to 20D are photographs showing the results of chemical resistance test of other coating films formed from the coating composition according to the present invention.
Figs. 21A and 21B are photographs of external appearance of another test piece coated with the coating composition according to the present invention, respectively.

The present invention relates to a quick-setting curing type non-solvent type polyol, in which a polyol, which is one of the main ingredients in polyurethane paint, is replaced with a modified polyol (not petroleum-based) The present invention relates to a urethane coating composition, and the coating composition according to the present invention has excellent coating properties such as salt resistance, weather resistance, abrasion resistance, water resistance, impact resistance, adhesion strength, flexibility and hardness.

Generally, the polyurethane is an elastomer having a urethane group (-NH-COO-), a flexible foam, a curing property and a curing property by a chemical reaction between the OH group of the polyol resin and the NCO group of the isocyanate curing agent Refers to polymeric materials such as rigid foam, plastic, paint, adhesive, and fiber synthetic leather. The weight ratio of urethane groups contained in the polyurethane is usually only about several percent, and most of them have various polymer properties Of the molecular chain.

Typically, the polyurethane reaction refers to a series of chemical reactions that produce urethane bonds, urea bonds, allophanate bonds, and Biuret bonds, and in general, chain extender is used as the main raw material. A polyol as a polymerizable glycol which determines the elasticity and flexibility of a coating film which forms a soft segment and a polyisocyanate which forms a hard segment as a curing agent are used.

On the other hand, polyurethane paints have excellent tensile strength, chemical resistance and abrasion resistance, and have excellent water resistance, weatherability and high hardness, as well as flexibility, and are widely used as architectural, industrial, .

The above-mentioned polyurethane coating composition is a one-shot one-shot method in which a polyol, a chain extending agent and a polyisocyanate as a curing agent are reacted at once, a first liquid comprising an isocyanate prepolymer obtained by reacting an excess of polyisocyanate with a polyol, A two-pack type prepolymer method in which a polyol for chain extension and a second solution for chain extender made of amine are allowed to react. Particularly, when there is a considerable difference in reaction rate between polyol and isocyanate, a two- This is mainly used.

Hereinafter, the present invention will be described in detail.

A quick drying curable, solventless polyurethane coating composition according to the present invention comprises (A) from 18 to 34% by weight, preferably from 20 to 32% by weight of petroleum polyether polyol, from 55 to 75% by weight of MDI (methylene diphenyl diisocyanate) A first liquid as an isocyanate prepolymer comprising 60 to 72% by weight, preferably 7 to 11% by weight, and preferably 8 to 10% by weight of HDI (hexamethylene diisocyanate); (B) 30 to 70% by weight, preferably 40 to 62% by weight of modified polyol derived from vegetable oil, 8 to 25% by weight of aromatic secondary amine, 10 to 30% by weight of tetrafunctional tertiary amine polyol, And 8 to 15% by weight of a polyol as a main component. The first liquid is contained in an amount such that the NCO content is 20 to 23% by weight.

In the present invention, the first liquid, which is an isocyanate prepolymer part, is a very important factor that determines the hardness, flexibility, adhesion, curability, reaction stability, chemical resistance and the like of the coating film. The choice of isocyanate type and NCO content is therefore particularly important.

Monomeric isocyanate as a main raw material is highly volatile and not only harmful to human body but also has a too high degree of crosslinking so that it is difficult to design a 1: 1 volume ratio for application of the first liquid and the second liquid to the isothermal mixture immediately before the application Therefore, in the present invention, therefore, in order to impart flexibility by reacting urethane with a petroleum-based polyol which will be described later even in the case of the monomeric (ie, monomeric) isocyanate as well as the polymeric (ie, polymeric) The first liquid is designed with an NCO content of 20 to 23% by weight.

 In the present invention, monomelic MDI having an NCO content of 33.58% by weight and polymerizable MDI having an NCO content of 30 to 32% by weight can be preferably used as the monomeric isocyanate and polymerizable isocyanate as an HDI, oligomeric HDI, preferably a low viscosity HDI trimer having an NCO content of 24.98% by weight and a viscosity of 400 to 1400 cps (about 65 to 95 KU) is used.

Here, in order to improve the reaction rate, leveling property, adhesion, etc., it is preferable to add low viscosity HDI as HDI as described above.

If the content of MDI is less than 55% by weight, the target NCO content may be lowered, and the NCO content may be lowered. As a result, the MDI content tends to be higher, The NCO content may be exceeded, and the reactivity with the polyol may become excessively high, which is also undesirable.

If the content of HDI is less than 7% by weight, the effect of the above-mentioned reason may be insufficient. On the other hand, when the content of HDI exceeds 11% by weight, the reactivity with polyol may be excessively decreased. I can not.

Next, the petroleum-based polyether polyol used in the first liquid in the coating composition of the present invention is preferably a petroleum-based polyether polyol having a high viscosity in the case of converting the polyurethane paint according to the present invention into an environmentally friendly solvent- So as to lower the viscosity of the resin component having a polyol group.

In the present invention, a petroleum-based polyether polyol is used as the polyol in the first liquid, but the use of the petroleum-based polyester polyol is not completely excluded.

Specific examples of the petroleum-based polyester polyols usable in the present invention include polyethylene glycol, polypropylene glycol, polyoxypropylene triol, polytetramethylene glycol, and mixed ether polyols. Preferably, the petroleum- The use of polypropylene glycol having an OH equivalent of about 800 to 1,200, a hydroxyl value of 48 to 62 mg KOH / g, and a viscosity of about 200 to 420 cps is used as the reaction stability and rate of the prepolymer, And in view of workability due to a decrease in viscosity, but polyoxypropylene triols can be preferably used depending on the case.

When the content of the petroleum-based polyether polyol is less than 18% by weight, the viscosity lowering effect may be insufficient. Conversely, when the content of the petroleum-based polyether polyol is more than 34% by weight, the final coating material becomes sensitive to moisture and moisture. There is a high possibility that a coating film having an inferior leveling property is generated, which is undesirable.

The essential reason for using the petroleum-based polyether polyol without using the modified polyol derived from the vegetable oil described later in the first liquid is that the modified polyol derived from the vegetable oil is too high in viscosity to be added to both the first solution and the second solution It is difficult to use it as a coating material when applied. Therefore, in the present invention, a petroleum-based polyol is used as the first liquid, which is an isocyanate prepolymer, and a second liquid as a chain- Use a polyol.

In the present invention, the MDI and the petroleum-based polyether polyol are first heated to 70 to 90 ° C, specifically to 80 ° C, for about 1.5 to 2.5 hours, Is reacted for 2 hours and then the NCO weight percentage is measured. When the target value reaches 20 to 23 wt%, the mixture is immediately cooled to about 55 to 65 DEG C, specifically about 60 DEG C, and the HDI is mixed and stirred to obtain a first liquid as an isocyanate prepolymer , And the viscosity of the first liquid is in the range of 970 to 1400 cps (85 to 98 KU). If it exceeds this range, the viscosity of the coating composition due to the mixing of the first liquid and the second liquid becomes excessively high, .

Next, the second liquid which is the polyol part in the quick drying curable polyurethane coating composition according to the present invention will be described.

The second liquid as the polyol part functioning as a chain extender is a polymeric polyol having the largest amount of use that gives softness by forming a soft segment portion, a cross-linking agent for improving the cross-linking density of the polyol and isocyanate, A desizing agent for preventing the generation of carbon dioxide gas due to reaction with moisture, a pigment for realizing color, a dispersing agent for effectively preventing the pigment from dispersing to prevent sedimentation prevention and preventing color separation, And a defoaming agent for removing air bubbles generated in the air, and the respective components will be described later.

The main constituent of the second liquid as the polyol part is a modified polyol derived from vegetable oil and a cross-linking agent. When only the modified polyol derived from vegetable oil is used alone without a cross-linking agent, the molecular weight is large, and flexibility and impact resistance can be improved. However, The use of a crosslinking agent for improving such chemical properties is essential, and the crosslinking agent that can be used is an amine and / or a polyol. However, the quick-setting curing type polyurethane coating material of the present invention There are certain limitations to use in the compositions.

More specifically, the present inventors have found that the use of a primary amine having relatively high reactivity can not control the reaction rate with isocyanate, and the gelation time is less than about 5 seconds, so that the spray is sprayed from the spray gun, To form a coating film in an embossed form, and a sufficient wetting time can not be obtained in the material to be coated, resulting in deterioration of adhesion.

In addition, when a relatively monomolecular polyether-based or polyester-based polyol, which is a petroleum-based polyol, is used, not only the water content is high but also the moisture in the air is absorbed well and the urethane foam is formed after the spray coating, The more likely it will be.

Therefore, the present invention effectively solves this problem by using a modified polyol derived from vegetable oil in the second solution, and it should be noted that the modified polyol derived from vegetable oil is more preferable than the petroleum-based polyol in view of reactivity to MDI It is possible to obtain an ideal coating film having a good leveling property by reacting with the MDI prepolymer, which is a first solution, and the modified polyol derived from the vegetable oil generally has a higher reactivity with the polymeric MDI than the monofunctional MDI Is more stable and less sensitive to moisture. However, it is a matter of course that the above-mentioned monomeric MDI can also be used in the present invention.

It has been found that the modified polyol derived from vegetable oil in the coating composition according to the present invention can form an ideal coating film when used in combination with a specific crosslinking agent and the quick drying curing type polyurethane coating composition using the modified polyol derived from vegetable oil according to the present invention It can be designed as a completely solvent-free coating with a gel time ranging from 40 to 90 seconds, in particular from 40 to 60 seconds. The coating is designed to enable 1: 1 isometric mixing of the first and second solutions It can be carried out using various known painting equipment.

In addition, the coating composition according to the present invention can control the curing rate using a catalyst, and can obtain an excellent coating film surface state. Particularly, by designing the NCO content of the isocyanate prepolymer to be about 22 wt% A coating composition excellent in abrasion resistance, hardness, flexibility, and chemical resistance can be produced.

As the vegetable oil as a raw material of the modified polyol derived from vegetable oil in the second liquid, there may be mentioned castor oil, rapeseed oil, linseed oil, soybean oil, cottonseed oil, palm oil, palm kernel oil and jatropha oil can be used. However, soybean oil and flaxseed oil may be preferable in terms of economy and ease of commercial purchase.

In general, vegetable oils include triglycerides in which glycerin and various three fatty acids are formed by esterification bonds. Depending on the type of vegetable oil, various kinds of fatty acids are included. Therefore, The production method of the polyol is changed according to the amount of the polyol. In the case of an oil having no hydroxyl group in the fatty acid, the epoxidation and the ring opening reaction or the transesterification ) To introduce a hydroxyl group to produce a polyol.

According to the present invention, the modified polyol derived from the vegetable oil in the second liquid comprises a methoxypolyol of the following formula (1), a hydroxylpolyol of the following formula (2), a hydroxyl fatty acid methyl ester of the following formula (3) And an introduced polyol, and the mixing ratio thereof is mixed at a mixing ratio to find an optimum polyol property by controlling the hydroxyl value and the viscosity.

[Chemical Formula 1]

(2)

(3)

Wherein R ₁ is the same as each other H or OH, and, if R ₁ is OH and R ₂ is also OH R ₃ is H, when R ₃ is OH R ₂ is an OH and R ₁ is H.

[Chemical Formula 4]

또는

이다.
Wherein R is

or

to be.

The methoxypolyol of Formula 1 is prepared by the following Reaction Scheme 1 and epoxidation reaction of the conjugated double bond position of the vegetable oil of Formula 5 below to obtain an epoxidized oil of Formula 6, To obtain a methoxypolyol of the above formula (1).

[Chemical Formula 5]

[Chemical Formula 6]

[Reaction Scheme 1]

                    ↓ catalyst

             Methanol ↓ acid catalyst

In the above Scheme 1, epoxidation is carried out in the presence of H ₂ O ₂ and peracetic acid (CH ₃ COOOH) catalysts at the double bonds of a vegetable oil, usually composed of C ₁₆ -C ₁₈ fatty acid hydrocarbons, Followed by the addition reaction of methanol in the presence of an acid catalyst such as maleic acid, citric acid, sulfuric acid, or acetic acid, and adding a hydroxyl group to obtain a methoxypolyol represented by the above formula (1).

The hydroxylpolyol of formula (2) is prepared from the epoxidized oil of formula (6) by the following reaction formula (2).

[Reaction Scheme 2]

Hydrolysis acid catalyst

In the above reaction formula 2, hydroxyl group is obtained by hydrolyzing an epoxy group by adding water to the epoxidized oil in the presence of an acid catalyst as described above to add a hydroxyl group.

The hydroxyl fatty acid methyl ester of the above formula (3) is obtained by obtaining an epoxidized fatty acid methyl ester of the following formula (7) from the epoxidized oil of the above formula (6) in the above reaction formula 1 according to the following reaction formula 3, To obtain a hydroxyl fatty acid methyl ester of the above formula (3).

(7)

[Reaction Scheme 3]

Methanol ↓ Alkali catalyst

Hydrolysis acid catalyst

In the above Scheme 3, the epoxidized oil in Scheme 1 is converted into methyl ester from triglyceride by methylation with methanol in the presence of an alkali catalyst such as NaOH or KOH to obtain an epoxy fatty acid methyl ester, , Hydroxyl group is added by adding water to hydrolyze the epoxy group to obtain a hydroxyl fatty acid methyl ester.

The acrylate-introduced polyol of formula (4) is obtained by the following reaction formula (5) showing the reaction between the reaction product of maleic acid and polyhydric alcohol obtained by the following reaction formula 4 with the epoxidized fatty acid methyl ester in the above reaction formula (3).

In the following Reaction Scheme 4, 3 - ((2-hydroxyphenyl) -1,3-thiadiazol-2-ylmethyl] -1,3-thiadiazol-2-ylmethyl ester having the following structural formula (11) is obtained by reacting maleic anhydride of the following formula (8) with ethylene glycol of the following formula Ethoxy) carbonyl) acrylic acid or 3 - ((2,3-dihydroxypropoxy) carbonyl) acrylic acid of formula (12).

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

[Reaction Scheme 4]

The acrylate-introduced polyol of formula (4) can be prepared by reacting the epoxidized fatty acid methyl ester of formula (7) with the compound of formula (11) or the compound of formula (12) .

[Reaction Scheme 5]

↓ acid catalyst

또는

이다.
Wherein R is

or

to be.

In the present invention, the content of the modified polyol derived from vegetable oil in the second liquid is 30 to 70% by weight, preferably 40 to 62% by weight.

More specifically, in the present invention, the mixture of the modified polyol derived from vegetable oil in the second solution contains 5 to 29% by weight of the methoxypolyol of the above formula (1), 1 to 10% by weight of the hydroxylpolyol of the above formula And 70 to 90% by weight of the hydroxyl fatty acid methyl ester of Formula 3, specifically 10 to 25% by weight of the methoxypolyol of Formula 1, 1 to 5% by weight of the hydroxylpolyol of Formula 2, And 70 to 89% by weight of a hydroxyl fatty acid methyl ester of the formula (3), and more preferably 5 to 10% by weight of a methoxypolyol of the formula (1) and 5 to 10% by weight of a hydroxylpolyol of the formula (2) And 80 to 90% by weight of a hydroxyl fatty acid methyl ester of the formula (3).

According to the present invention, the mixture of the modified polyol derived from the vegetable oil in the second liquid is a mixture of 10 to 30% by weight of the hydroxylpolyol of the formula (2) and 70 to 90% by weight of the hydroxyl fatty acid methyl ester of the formula And may specifically be a mixture of 20 to 30% by weight of the hydroxylpolyol of the formula (2) and 70 to 80% by weight of the hydroxyl fatty acid methyl ester of the formula (3). In particular, the hydroxylpolyol 10 to 20% by weight of the hydroxy fatty acid methyl ester of Formula 3 and 80 to 90% by weight of the hydroxy fatty acid methyl ester of Formula 3.

According to the present invention, the mixture of the modified polyol derived from the vegetable oil in the second liquid may be a mixture of 10 to 30% by weight of the methoxypolyol of the formula (1) and 70 to 90% by weight of the hydroxyl fatty acid methyl ester of the formula Specifically, it may be a mixture of 20 to 30% by weight of the methoxypolyol of the formula (1) and 70 to 80% by weight of the hydroxyl fatty acid methyl ester of the formula (3). In particular, the methoxypolyol To 20% by weight of the hydroxy fatty acid methyl ester of Formula 3 and 80 to 90% by weight of the hydroxy fatty acid methyl ester of Formula 3.

According to the present invention, the mixture of the modified polyol derived from vegetable oil in the second liquid may contain 8 to 27% by weight of the methoxypolyol of Formula 1, 1 to 5% by weight of the hydroxylpolyol of Formula 2, A mixture of 50 to 81% by weight of a hydroxyl fatty acid methyl ester and 10 to 30% by weight of an acrylate ester-introduced polyol of the formula (4), specifically about 17% by weight of the methoxypolyol of the formula A mixture of about 2% by weight of a hydroxyl polyol, about 71% by weight of a hydroxyl fatty acid methyl ester of Formula 3 and 10% by weight of an acrylate ester-introduced polyol of Formula 4 or about 15% by weight of a methoxy polyol of Formula 1, About 2% by weight of the hydroxyl polyol of Formula 2, about 63% by weight of the hydroxyl fatty acid methyl ester of Formula 3, Or about 20% by weight of a terpolyene-containing polyol, or about 13% by weight of a methoxypolyol of Formula 1, about 2% by weight of a hydroxylpolyol of Formula 2, about 55% by weight of a hydroxyl fatty acid methyl ester of Formula 3, The acrylate-introduced polyol of Formula 4 may be a mixture of 30 wt% of the acrylate-introduced polyol of Formula 4,

또는

임은 앞서 언급한 바와 같다.

or

As mentioned above.

The mixture of modified polyols derived from vegetable oil in the second liquid has OH equivalent of 200 to 400, hydroxyl value of 180 to 260 mg KOH / g, viscosity of 600 to 4700 cps, preferably 600 to 1800 cps , And if the viscosity is too large, there is a possibility that mixing with the above-mentioned first liquid may cause a problem, which is not preferable.

If the hydroxyl group equivalent of the modified polyol derived from vegetable oil is less than 200, the content of the crosslinking agent having a small molecular weight is decreased to adjust the reactivity ratio to 1: 1 with the isocyanate moiety, and the properties such as chemical resistance, chemical resistance and abrasion resistance are deteriorated The amount of the modified polyol derived from the vegetable oil is decreased and the sufficient flexibility and impact resistance can not be ensured. Therefore, it is likewise undesirable.

In the present invention, the content of the modified polyol derived from vegetable oil in the second liquid is 30 to 70% by weight, preferably 40 to 62% by weight, and if it is less than 30% by weight, There is a possibility that the desired coating film characteristics may not be obtained and also the security of environment friendliness may be insufficient. Conversely, if it exceeds 70% by weight, it may be difficult to formulate into the coating material due to viscosity increase, Which is also undesirable.

On the other hand, as the crosslinking agent for improving the crosslinking density of the polyol and the isocyanate in the present invention, there can be used a tetrafunctional polyol such as an aromatic primary amine and an aromatic secondary amine, a tetrafunctional polyol tertiary amine, a tetrahydroxylpolyol, Of the polyols and polyamines, aromatic polyamines having a high reactivity and tetrafunctional polyols having no amine groups are not preferred because of the problems such as the ununiform reaction or the generation of bubbles during the reaction. In the case of using a tetrafunctional polyol tertiary amine having an autocatalytic crosslinking agent structure in which a chaamine is present, especially a tertiary amine of a tetrahydroxylpolyol and an aromatic secondary amine having a somewhat slower reactivity, modified polyol derived from vegetable oil and tact In the reaction with an isocyanate prepolymer as a first liquid, Since creating a coating it is particularly preferred in the present invention.

In the present invention, it is particularly preferable that the above-mentioned aromatic secondary amine has an OH or amine equivalent of 155, and the tetrafunctional tertiary amine polyol as the tetrahydroxypolyol quaternary amine has OH or an amine equivalent of 73.1 can do.

The types and characteristics of the crosslinking agent are shown in Table 1 below.

Cross-linking  Types and characteristics Types of crosslinking agents Reactivity
(Isocyanate) Reaction catalyst problem Usability Aromatic primary amine 5 Unnecessary Too fast reactivity X Aromatic secondary amine 4 Unnecessary - O Tetrafunctional tertiary amine polyol 3 Unnecessary - O Tetrafunctional polyol 2 need Reactivity with Moisture by Catalyst X Trifunctional petroleum polyol One need Catalyzed
Reactivity with moisture X

In the present invention, the aromatic secondary amine is contained in an amount of 8 to 25% by weight, and when it is less than 8% by weight, there is a high possibility of bubbling into the coating film due to too fast reaction, The reaction is excessively delayed, so that a uniform coating film may not be formed, which is also undesirable.

In the present invention, the tetrafunctional tertiary amine polyol is contained in an amount of 10 to 30% by weight, and if it is less than 10% by weight, the reaction becomes uneven and the properties of the coating film become uneven, If the content is more than 30% by weight, the reaction may be delayed excessively to cause bubbling in the coating film, and it is also undesirable because it may cause problems due to the flow after the coating operation.

On the other hand, the second liquid contains a dispersant, defoaming agent, deodorant, pigment or stabilizer in a total amount of 8 to 15% by weight as other additives, wherein the dispersant is selected from the group consisting of alkylol ammonium salts, polysiloxane, Aluminum silicate molecular sieves, and the stabilizers described above are triethylo-sulpho-mates, all of which are well known in the art and, in addition to these, various ones well known in the art may be used as appropriate.

Here, the dehumidifying agent is added to prevent isocyanate from reacting with moisture to form carbon dioxide gas, and the pigment is added in order to realize a desired predetermined hue. The dispersing agent is dispersed in the pigment to prevent precipitation and stability The antifoaming agent is added in order to remove air bubbles generated during the coating process or during the coating operation, and triethyl ososoformate as a stabilizer reacts with water molecules contained in the air or paint separately from the above-mentioned dehumidifying agent Is added for the purpose of contributing to the stabilization of the coating composition by decomposition with formyl ethyl ether and alcohol.

Therefore, when these additives are appropriately mixed and controlled, the composition can be effectively formulated such that the volume ratio of the first liquid as the isocyanate prepolymer portion having an NCO content of about 22.5% and the second liquid as the polyol portion is 1: 1.

The amount of the other additives is 3 to 6% by weight, 0.3 to 0.8% by weight of a dispersant, 0.3 to 0.7% by weight of an antifoaming agent, 4.0 to 7.0% by weight of a molecular sieve as a dehumidifying agent, and 0.4 to 4.0% May be contained in an amount of 1 to 20% by weight.

Meanwhile, the present invention may further include 0.3 to 0.5 wt% of dibutyltin dilaurate (DBDTL) as a urethane curing catalyst. In the second solution, the aromatic secondary amine content is decreased and the tetrafunctional If the content of the polyol tertiary amine crosslinking agent is accompanied by an increase in the content of the polyol tertiary amine crosslinking agent, it is necessary to control the curing rate by adding it.

The use of DBTDL has the advantage of accelerating the reactivity and reducing the tack free time. However, the wetting time for the material is insufficient, which further deteriorates the adhesion.

In the present invention, if the coating composition of the present invention is an elastic urethane flooring agent, 5 to 20% by weight of an alkylene oxide polyol which is conventionally used may be further contained, if necessary for lowering the viscosity of the second liquid.

In the quick drying curable polyurethane coating composition according to the present invention, the ratio of the specific gravity conversion equivalent weight of the first liquid as the isocyanate prepolymer portion to the specific gravity conversion equivalent weight of the second liquid as the polyol portion is 1.01 to 1.03, When the two liquids are mixed in a volume ratio of 1: 1, the equivalence of the first liquid portion is larger by 0.01 to 0.02.

In the present invention, the method of producing the second liquid described above is a method in which an organic and / or inorganic pigment and a dispersant, a dehumidifying agent and a defoaming agent are uniformly added to a part of the aromatic secondary amine and / or the modified polyol derived from vegetable oil as a cross- And dispersed at room temperature for about 30 to 50 minutes, particularly about 40 minutes, using a dispersing machine until the dispersed particle size becomes 10 탆 or less, preferably 1 to 8 탆, and then the remaining balance of the vegetable oil- A polyol and a tetrafunctional polyol tertiary amine as a crosslinking agent, a defoaming agent, a stabilizer and the like are uniformly mixed and defoamed using a vacuum deaerator to obtain a second solution as a polyol portion.

The most important consideration in selecting a coating method of a natural polyol-based solvent-free paint is that it is not necessary to use a solvent. Conventional general solvent-free paints use a solvent having a high boiling point or a viscosity In general, plasticizers are used in order to lower the viscosity of the coating, and even if the coating is designed as a completely solvent-free coating, the solvent must be used inevitably for smooth coating

Since the two-part type non-solvent-based quick-drying curing type polyurethane coating composition as in the present invention is cured within a few seconds to several minutes when the first liquid and the second liquid are mixed, it is impossible to coat with a general airless spray coating apparatus, A mixture of Reactor XP-2 from Graco (USA) and a Reactor E-10 from a simple testing machine is used as a preferred example. Etc. may be used. In order to use such a device, the viscosity of the first liquid and the second liquid should be kept between 50 and 100 KU, and the viscosity of the first liquid and the second liquid should be similar to each other, and the mixing volume ratio should be set to be 1: . On the other hand, the surface treatment on the surface of the object is also important.

Hereinafter, the present invention will be described in detail by way of Examples, Comparative Examples and Test Examples, but this is not intended to limit the present invention, but merely to illustrate the present invention.

Example  One: Epoxidation Soybean oil  Produce

A thermometer, a reflux condenser and a stirrer were attached to a 2 L three-necked flask, and 800 g of soybean oil (iodine 132) was added thereto. The mixture was heated to 70 ° C while stirring slowly. 110 g (4.78 mol) of 80% For 1 hour. A mixed solution of 634 g (16.3 mol) of 35% hydrogen peroxide and 47.2 g of 85% phosphoric acid was slowly added to the flask over 1 to 5 hours, and the reaction temperature was maintained at 70 ° C. The total reaction time was 10 hours. After completion of the reaction, the organic layer was separated from the separatory funnel, washed with distilled water until the pH became neutral, dried under reduced pressure in a rotary evaporator, and filtered.

The synthesized epoxidized oil was confirmed by ¹³ C-NMR, ¹ H-NMR and FT-IR.

The results are shown in Figs. 1A to 1C.

Example  2: Methoxy Of polyol  Produce

A thermometer, a reflux condenser and a stirrer were attached to a 2 L three-necked flask, and 800 g of the epoxidized soybean oil synthesized in Example 1 was introduced. The mixture was heated to 50 캜 while stirring slowly. Then, 800 g of methanol and 15.36 g of maleic acid as a catalyst were added thereto. Lt; / RTI > to add a hydroxyl group. After the reaction was completed, 32 g of NaHCO ₃ was added to neutralize and further reaction was carried out for 30 minutes. After filtration to remove salt due to neutralization, it was dried under reduced pressure in a rotary evaporator to remove excess methanol.

The synthesized methoxypolyols were confirmed by ¹³ C-NMR, ¹ H-NMR and FT-IR.

The results are shown in Figs. 2A to 2C.

Example  3: Hydroxyl Of polyol  Produce

A thermometer, a reflux condenser and a stirrer were attached to a 2 L three-necked flask, and 800 g of the epoxidized soybean oil of Example 1 was added. The mixture was heated to 50 캜 while stirring slowly. Then, 800 g of water and 15.36 g of maleic acid as a catalyst were added thereto. . After the reaction was completed, 32 g of NaHCO ₃ was added to neutralize and further reaction was carried out for 30 minutes. After filtration to remove salt due to neutralization, it was dried under reduced pressure in a rotary evaporator to remove excess water.

The synthesized hydroxylpolyol was confirmed by ¹³ C-NMR, ¹ H-NMR and FT-IR.

The results are shown in Figs. 3A to 3C.

Example  4: Epoxidation  fatty acid methyl  Preparation of esters

The epoxidized soybean oil of Example 1 was methylated to convert the triglyceride type into the methyl ester type, thereby preparing an intermediate for the synthesis of the modified polyol.

A thermometer, a reflux condenser and a stirrer were attached to a 2 L three-necked flask, and 800 g of epoxidized soybean oil was added thereto. The mixture was heated to 80 ° C while stirring slowly, and then a mixed solution of methanol and 160 g of NaOH as an alkali catalyst was added thereto. . After the reaction was completed, the lower layer was removed from the separating funnel to remove glycerin, and the reaction was carried out twice in the same manner. After the reaction was completed, the reaction mixture was washed with water to remove the soap. And dried under reduced pressure in a rotary evaporator to remove moisture.

The synthesized epoxidized fatty acid methyl ester was confirmed by ¹³ C-NMR, ¹ H-NMR and FT-IR.

The results are shown in Figs. 4A to 4C.

Example  5: Hydroxyl  fatty acid methyl  Preparation of esters

A thermometer, a reflux condenser and a stirrer were attached to a 2 L three-necked flask, 800 g of the epoxidized fatty acid methyl ester obtained in Example 4 was introduced and heated to 90 ° C while stirring slowly. Then, 800 g of water and 60 g of maleic acid as a catalyst were added thereto, The reaction was anomaly. To neutralize, 120 g of NaHCO ₃ was added and further reacted for 30 minutes. After completion of the reaction, the resulting salt was filtered off and dried under reduced pressure in a rotary evaporator to remove moisture.

The synthesized hydroxyl fatty acid methyl ester was confirmed by ¹³ C-NMR, ¹ H-NMR and FT-IR.

The results are shown in Figs. 5A to 5C.

Example  6: 3 - ((2- Hydroxyethoxy ) Carbonyl) acrylic acid

100 g (1 eq) of maleic anhydride was placed in a 500 ml beaker, and 63.3 g (1 eq) of ethylene glycol was added thereto, and then the temperature was gradually increased to 60 ° C. When the maleic anhydride started to melt, the temperature rose. When the maleic anhydride dissolved, the temperature rose to about 90 ° C. The reaction was terminated when the temperature had dropped to 60 ° C again. If the temperature rises above 100 ° C, impurities may be generated.

The resulting compound was confirmed by ¹ H-NMR, ¹³ C-NMR and FT-IR.

The results are shown in Figs. 6A to 6C.

Example  7: 3 - ((2,3- Dihydroxypropoxy ) Carbonyl) acrylic acid

100g (1eq) of maleic anhydride was placed in a 500ml beaker, 93.9g (1eq) of glycerol was added, and then the temperature was gradually raised to 60 ° C. When the maleic anhydride started to melt, the temperature rose. When the maleic anhydride dissolved, the temperature rose to about 90 ° C. The reaction was terminated when the temperature had dropped to 60 ° C again. If the temperature rises above 100 ° C, impurities may be generated.

The resulting compound was confirmed by ¹ H-NMR, ¹³ C-NMR and FT-IR.

The results are shown in Figs. 7A to 7C.

Example  8: ester Of polyol  Produce

Into a 2 L three-necked round flask, 500 ml of THF was added, and 261 g of the 3 - ((2-hydroxyethoxy) carbonyl) acrylic acid obtained in Example 6 was added thereto and dissolved. 180 g of the epoxidized fatty acid methyl ester obtained in Example 4 9.8 g of maleic acid as an acid catalyst was added and the temperature was raised to 75 캜. After reacting for 4 hours, the reaction was allowed to cool slowly. The reaction was extracted with methylene chloride and water to remove unreacted 3 - ((2-hydroxyethoxy) carbonyl) acrylic acid and THF. At this time, the unreacted 3 - ((2-hydroxyethoxy) carbonyl) acrylic acid was completely removed by extraction with water twice. The methylene chloride was completely removed by filtration under reduced pressure to obtain a light brown liquid ester polyol (344 g, yield: 97%).

The synthesized ester polyol was confirmed by ¹ H-NMR, ¹³ C-NMR and FT-IR.

The results are shown in Figs. 8A to 8C.

Example  9: ester Of polyol  Produce

500 ml of THF was added to a 2 L three-neck round flask, and 320 g of the 3 - ((2,3-dihydroxypropoxy) carbonyl) acrylic acid obtained in Example 7 was added to dissolve the epoxy resin. 180 g of fatty acid methyl ester and 9.8 g of acidic acid maleic acid were placed and the temperature was raised to 75 캜. After reacting for 4 hours, the reaction was allowed to cool slowly. To remove unreacted 3 - ((2,3-dihydroxypropoxy) carbonyl) acrylic acid and THF, the reactants were extracted with methylene chloride and water. At this time, the unreacted 3 - ((2,3-dihydroxypropoxy) carbonyl) acrylic acid was completely removed by extraction with water twice. After filtration under reduced pressure, methylene chloride was completely removed to obtain a light brown liquid ester polyol (340 g, yield: 96%).

The synthesized ester polyol was confirmed by ¹ H-NMR, ¹³ C-NMR and FT-IR.

The results are shown in Figs. 9A to 9C.

Example  10 ~ 21: Modification from vegetable oils Polyol  Preparation of mixtures

The modified polyol mixture derived from the vegetable oil used as the main component of the second solution which is the polyol portion is used as the methoxypolyol of Example 2, the hydroxylpolyol of Example 3, the hydroxyl fatty acid methyl ester of Example 5, the ester polyol of Example 8 , And the ester polyol of Example 9, and the unit is expressed in weight%.

Vegetable oil-derived modification Polyol  Preparation of mixtures Example 2 Example 3 Example 5 Example 8 Example 9 Total (% by weight) Example 10 19 3 78 - - 100 Example 11 - 20 80 - - 100 Example 12 20 - 80 - - 100 Example 13 8 7 85 - - 100 Example 14 15 - 85 - - 100 Example 15 - 20 80 - - 100 Example 16 17 2 71 10 - 100 Example 17 15 2 63 20 - 100 Example 18 13 2 55 30 - 100 Example 19 17 2 71 - 10 100 Example 20 15 2 63 - 20 100 Example 21 13 2 55 - 30 100

Test Example  1: Modification from vegetable oils Polyol  And physical and chemical characterization of mixtures

The physicochemical properties of the modified polyol derived from vegetable oils of Examples 2, 3, 5, 8, and 9 and the modified polyol derived from vegetable oils of Examples 10 to 21 were analyzed. The results are shown in Table 3 below. .

^{Density: 25 ℃ (g / cm 3} ) - ISO 2811

Viscosity: 25 占 폚 (mPa 占 퐏) - (ISO 2555 RVDVII + spindle 21-12 rpm)

Acid value: mg KOH / g - ISO 660

OH: mg KOH / g - ISO 4326

Oxirane Oxygen:% - AOCS Official Method Cd 9-57

Moisture content: ppm - ISO 4317

Vegetable oil-derived modification Polyol  And its chemical and physical properties Density 20 (g / cm ³ ) Viscosity
(cP) Acid value (x10 ³ )
(mgKOH / g) OH
(mgKOH / g) Oxy lane oxygen (%) Moisture content
(ppm) Nonvolatile matter
(%) Example 2 1.01218 4605 0.589 199.8 1.68 754 97.3 Example 3 1.04130 1800 0 250.1 0.5 942 98.2 Example 5 1.00488 1510 37.9 184.0 0.42 1396 95.0 Example 8 1.236 30720 138.7 202.7 0.0163 2001 97.3 Example 9 1.238 34140 127.5 376.7 0.0183 1564 92.9 Example 10 0.96697 1700 0 214.0 0.05 1838 95.4 Example 11 0.97183 1020 0 225.0 0.02 2216 97.3 Example 12 0.98101 627 4.7 219.7 0.20 1935 96.5 Example 13 0.99812 2485 5.0 221.8 0.99 1394 94.7 Example 14 1.00969 895 15.3 232.2 0.85 1354 95.0 Example 15 0.99479 1125 4.1 220.3 0.58 1576 95.0 Example 16 1.090 770 5.1 184.8 0.0181 1811 94.8 Example 17 1.122 820 13.7 194.1 0.0371 1859 95.0 Example 18 1.140 830 17.5 189.5 0.0197 1904 97.2 Example 19 1.088 760 3.9 185.0 0.0396 1129 96.4 Example 20 1.126 820 14.4 198.34 0.0524 1647 93.7 Example 21 1.142 910 16.5 202.90 0.0299 1934 95.5

Examples 22 to 24 and Comparative Examples 1 and 2: Preparation of first liquid of isocyanate prepolymer

An isocyanate prepolymer was prepared with compositional components and composition ratios as shown in Table 4 below.

The composition and composition ratio of the isocyanate prepolymer The first sum Example 22 Example 23 Example 24 Comparative Example 1 Comparative Example 2 Monomelic MDI 62.50 - - - - Polymerizable MDI - 61.40 68.00 72.00 68.00 Low Viscosity HDI Trimer 10.00 10.00 9.00 10.00 10.00 Petroleum-based polyether polyol (PP2000D) 27.50 28.60 23.00 - - The polyol mixture of Example 10 - - - 18.00 - The polyol mixture of Example 11 - - - - 22.00 Sum 100.00 100.00 100.00 100.00 100.00 Viscosity 85KU 95KU 88KU Very high Very high density 1.134 1.134 1.148 - - NCO wt% 22.14% 20.13% 22.53% 22.12% 20.00%

Specific details of the composition components of the above-mentioned isocyanate prepolymer are shown in Tables 5 and 6 below.

Polyol Types of polyols ingredient OH equivalent Polyol PP2000D Petroleum-based polyether polyol 1000 Example 10 Modified polyol derived from vegetable oil 303.24 Example 11 Modified polyol derived from vegetable oil 273.66

Polyisocyanate Kinds ingredient NCO
weight% Reactivity with polyol Polyisocyanate Polymerizable MDI MDI 31 Very fast Monomelic MDI MDI 33.58 speed Low Viscosity HDI Trimer HDI 24.98 lateness

In preparing the first solution, the target NCO content was designed to be in the range of 20 to 23 wt%. First, the MDI and polyol were reacted at 80 to 90 ° C for 2 hours, and then the NCO weight percentage was measured. And HDI, preferably a low viscosity HDI trimer as mentioned above, was mixed and stirred.

The above-mentioned HDI was added for the purpose of improving the reaction rate, leveling property, adhesion and the like, and the addition amount thereof was about 10 wt%, and the viscosity was 73 KU.

Comparative Example 1 and Comparative Example 2 using the polymerized MDI having a reactivity higher than that of the monomeric MDI and the modified polyol mixture derived from vegetable oil, which were Examples 10 and 11, were evaluated to be difficult to use as a coating because of too high viscosity.

Example 22, which is an isocyanate prepolymer using monomelic MDI and PP2000D as a petroleum-based polyether polyol, and Example 23 and Example 24, which is an isocyanate prepolymer using PP2000D, a polymeric MDI and a petroleum-based polyether polyol, And the viscosity was less than 100 KU, which was evaluated to be suitable for use as the first liquid of the polyurethane coating composition.

Example  25 and 26 Comparative Example  3 to 6: Polyol  Preparation of second solution

A second liquid as the polyol portion was prepared with compositional components and composition ratios as shown in Table 7 below.

Polyol  And the composition ratio Second sum Example 25 Example 26 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Petroleum-based polyether polyol (PP-2000D) - - 15.00 - - 15.00 The polyol mixture of Example 10 15.00 - - 15.00 - - The polyol mixture of Example 11 - 15.00 - - 15.00 - Pigment (CR-828) 6.00 6.00 6.00 6.00 6.00 6.00 Dispersant 0.50 0.50 0.50 0.50 0.50 0.50 Defoamer 0.50 0.50 0.50 0.50 0.50 0.50 Desiccant 7.00 7.00 7.00 7.00 7.00 7.00 Petroleum-based polyether polyol (PP-2000D) - - 41.00 - - 46.00 The polyol mixture of Example 10 31.00 - - 41.00 - - The polyol mixture of Example 11 - 31.00 - - 41.00 - Aromatic primary amine - - - - - 25.00 Aromatic secondary amine 20.00 20.00 - - - - Tetrahydroxypolyol tertiary amine 20.00 20.00 - - - - Tetrahydroxypolyol - - - 30.00 30.00 - Petroleum-based polyether polyol (GP-400) - - 30.00 - - - Sum (wt%) 100.00 100.00 100.00 100.00 100.00 100.00

The second solution, which is the polyol part, is the most expensive and flexible polymer polyol, and the cross-linking agent and polyurethane reaction for improving the cross-linking density of the high-molecular polyol and isocyanate react with moisture to form carbon dioxide gas, A pigment for realizing color, a dispersing agent for dispersing the pigment to give stability to sedimentation and preventing color separation, and a defoaming agent for removing air bubbles generated during the coating or during the operation The ingredients are formulated to blend together.

Specific details of the polyol, the chain extender (crosslinking agent) and the additive of the second liquid are shown in Table 8, Table 9 and Table 10, respectively.

Chain extender Kinds OH or amine equivalent Chain extenders (crosslinking agents)



Aromatic primary amine 89.1 Aromatic secondary amine 155.0 Tetrahydroxypolyol tertiary amine 73.1 Tetrahydroxypolyol 70.1 Petroleum-based polyether polyol (GP-400) 140.3

Polyol Kinds ingredient OH equivalent Polyol






PP2000D Petroleum-based polyether 1000 GP3000 Petroleum-based polyether 1000 Example 10 Modified polyol derived from vegetable oil 303.24 Example 11 Modified polyol derived from vegetable oil 273.66 Example 12 Modified polyol derived from vegetable oil 255.31 Example 13 Modified polyol derived from vegetable oil 222.77 Example 14 Modified polyol derived from vegetable oil 198.77 Example 15 Modified polyol derived from vegetable oil 224.09

additive Kinds ingredient Pigment





CR-828 TiO ₂ MA-100 Carbon black PANAX Blue 2500 Organic pigment PANAX Green 3500 Organic pigment N Red F5RK Organic pigment Ideal Yellow Y42G Inorganic pigments Panax I.O. Red 3000 Inorganic pigments Dispersant BYK 180 Ammonium salt Defoamer BYK 1790 silicon Desiccant Molecular Sieve Al-silicate

In Examples 25 and 26 and Comparative Examples 3 to 6, polyol and polyamine were used as the cross-linking agent for the polyol portion as the second liquid, and the polyol was composed of two polyols having a functional group of four and one polyol having three functional groups , One polyamine with two functional groups and one with different reactivity and one secondary amine were used. Six main polyols derived from natural vegetable oils and two polyols derived from petroleum were used as main polyols.

The preparation of the second solution, which is a polyol part, is carried out by first uniformly mixing a part of the main polyol, a pigment, a dispersant, a dehumidifying agent and a defoaming agent, and using a dispersing machine until the dispersion particle size becomes 10 μm or less, preferably 1 to 8 μm And then the remaining main polyol, the cross-linking agent and the defoaming agent were uniformly mixed and defoamed by using a vacuum deaerator.

Example  27 and 28 Comparative Example  7 to 10: 2-pack type  Polyurethane paint

The first liquid of the isocyanate prepolymer of each of Examples 22 and 23 and the second liquid of the polyol portion of Examples 25 and 26 and Comparative Examples 3 to 6 were mixed in a two- The mixture was sprayed with an equal volume of mixture using a mixed impact spray apparatus (USA, Graco Reactor XP-2), and then the gelation time and the surface state of the coating film were evaluated.

The gelation time of the final coating composition, the surface condition of the coating film, and the NCO content of the first liquid are shown in Table 11 below.

Two-component polyurethane paint Two-component polyurethane paint Example 27 Example 28 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 The isocyanate prepolymer (first liquid) Example 23 Example 23 Example 22 Example 23 Example 23 Example 22 The polyol portion (second liquid) Example 25 Example 26 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 The NCO weight% of the first liquid 20.13% 20.13% 21.14% 20.13% 20.13% 21.14% Gel time 38s 40s 30s 25s 25s 30s Surface condition Very good Very good Bubble generation Bubble slightly Bubble slightly Heterogeneous reaction

Comparative Example 7 in which the first liquid of the isocyanate prepolymer using the monomeric MDI (Example 22) and the second liquid of the petroleum-based polyol (Comparative Example 3) were mixed using Table 11 above; (Example 23) using a polymerizable MDI and a second liquid (Comparative Examples 4 and 5) using a modified polyol mixture derived from a natural vegetable oil (Examples 10 and 11) and a tetrafunctional polyol without an amine group Comparative Example 8 and Comparative Example 9 used; In the case of Comparative Example 10 in which the isocyanate prepolymer first liquid (Example 22) using monomelic MDI and the second liquid (Comparative Example 6) comprising a petroleum-based polyol and an aromatic primary amine crosslinking agent having a high reactivity were mixed , The reaction was not uniform or air bubbles were generated during the reaction. The generation of air bubbles during the reaction of the first liquid and the second liquid is mainly caused by moisture in the air or moisture contained in the polyol. However, the dehumidifying agent added to suppress the bubbles effectively suppresses the reaction between water and isocyanate It turned out that there is no number.

On the other hand, a first liquid (Example 23) as a prepolymer using a polymerizable MDI, a second type amine crosslinking agent having a structure in which quaternary functional groups and tertiary amines are present simultaneously, a second amine crosslinking agent having a somewhat slower reactivity, In the case of Example 27 and Example 28 where the second liquid comprising the derived modified polyol (Examples 25 and 26) were mixed, a complete coating film was formed without bubbling during the reaction.

Example  29 to 33: Polyol  Preparation of second solution

A second liquid as a polyol portion was prepared with compositional components and composition ratios as shown in Table 12 below.

Polyol  And the composition ratio Second sum Example 29 Example 30 Example 31 Example 32 Example 33 Aromatic secondary amine 10.00 15.00 15.00 15.00 15.00 Pigment 6.00 3.00 3.00 3.00 3.00 Dispersant 0.50 0.30 0.30 0.30 0.30 Defoamer 0.50 0.30 0.30 0.30 0.30 Desiccant 7.00 5.00 5.00 5.00 5.00 Example 10 49.50 - - - - Example 12 - 54.60 - - 31.00 Example 13 57.60 - - Example 14 - - - - 60.60 Example 15 - - - 57.60 - Tetrahydroxypolyol tertiary amine 26.00 21.00 18.00 18.00 15.00 DBTDLl - 0.50 0.50 0.50 0.50 BYK-1790 0.50 0.30 0.30 0.30 0.30 Sum 100.00 100.00 100.00 100.00 100.00

In Examples 29 to 33, the first liquid of Example 24 in which the content of NCO was increased to further improve the degree of crosslinking, the liquid of Example 29 in which the content of the crosslinking agent was increased, the content of the crosslinking agent was lowered, , The OH content was dispersed in each of the colors using Examples 12, 13, 14 and 15 in comparison with those of Examples 10 and 11 to prepare a paint.

As can be seen from the following Table 13 to be described later, the curing time becomes longer as the content of the aromatic secondary amine crosslinking agent is decreased and the content of the polyol crosslinking agent is increased in Example 29. Therefore, in Examples 30 to 33, the urethane curing catalyst DBTDL (Dibutyltin dilaurate) was used in small amounts to control the curing time.

Example  34 to 38: 2-pack type  Polyurethane paint

The first liquid of the isocyanate prepolymer of Example 24 and the second liquid of the polyol portion of Examples 29 to 33 were mixed in a two-component mixed impingement spray apparatus (USA, Graco Reactor XP -2), and then the gelling time and the surface state of the coating film were evaluated.

The gelation time of the final coating composition, the surface condition of the coating film, and the NCO content of the first liquid are shown in Table 13 below.

Two-component polyurethane paint Two-component polyurethane paint Example 34 Example 35 Example 36 Example 37 Example 38 The isocyanate prepolymer (first liquid) Example 24 Example 24 Example 24 Example 24 Example 24 The polyol portion (second liquid) Example 29 Example 30 Example 31 Example 32 Example 33 The NCO weight% of the first liquid 22.50% 22.50% 22.50% 22.50% 22.50% Gel time 1m18s 25s 25s 25s 25s Tack free time 10m 2m 2m 2m 2m Surface condition Good Very good Very good Very good Very good

As can be seen from the results of Table 13, all of the coating films of Examples 34 to 38 showed good results, and in the case of Examples 35 to 38 using DBTDL as a polyurethane curing accelerator, 34, the gelling time was reduced to about 1/3, and the tack-free drying time was reduced to about 1/5.

Test Example  2: Quick drying hardening type  Basic Properties of Polyurethane Coating Composition

The basic properties of the quick drying curable polyurethane coating compositions containing the modified polyols derived from vegetable oils of Examples 27 and 28 and Examples 34 to 38 were measured by the method of Test Example 1 and the results are shown in the following Table 14 Respectively.

The main physical properties of Examples 23 and 24 for the first liquid are also shown in Table 15 below.

Quick drying hardening type  Basic Properties of Polyurethane Coating Composition Paint (1 + 2 liquid) Example 27 Example 28 Example 34 Example 35 Example 36 Example 37 Example 38 The first sum Example 23 Example 23 Example 24 Example 24 Example 24 Example 24 Example 24 Second sum Example 25 Example 26 Example 29 Example 30 Example 31 Example 32 Example 33 The second liquid polyol Example 10 Example 11 Example 10 Example 12 Example 13 Example 15 Example 14 Viscosity 105KU 102KU 110KU 91KU 112KU 94KU 101KU importance 1.063 1.065 1.054 1.028 1.029 1.028 1.027 Gel time 38s 40s 1m18s 25s 25s 25s 25s Touch dry time 5m 3m 10m 2m 2m 2m 2m Surface condition Very good Very good Good Very good Very good Very good Very good

Basic properties of the first liquid division Example 23 Example 24 Major components Polymerizable MDI prepolymer Polymerizable MDI prepolymer NCO wt% 20.13% 22.53% Viscosity 95.0KU 88.3KU importance 1.134 1.148

Test Example  3: Preparation of specimen

A test piece using a quick drying curing type polyurethane coating composition containing the modified polyols derived from the vegetable oil of Examples 27 and 28 and Examples 34 to 38 was prepared by the following method.

Cold rolled steel (CRS) with a thickness of 2 ~ 3mm was finished with short blast to rust and other foreign substances to a grade of Sa 2 _1/2 or higher of ISO 8501-1. However, it is hard to use 2 ~ 3mm CRS (Cold rolled steel) to undergo the flexing test for the test items. The surface is polished with CRS (cold rolled steel) with a thickness of 1mm or less and rust and foreign matter .

On the other hand, in the chemical resistance and abrasion resistance test items, it is coated on a plate having an acrylic plate or a releasing paper which can easily peel a film and a substrate because it should be tested in the form of a film.

The painting was carried out in a special spray chamber equipped with a paint dust suction and filter facility at room temperature. The two-component warm-air mixed impact airless sprayer was used to carefully mix each of the first and second liquids prepared beforehand in a Reactor XP-2 coating apparatus of Graco (USA). The coating liquid was continuously circulated, And then connected to a two-component mixed impingement spray gun and heated hose.

The coating was applied once to a thickness of about 130 탆 and a total coating thickness of 800 탆 to prepare a test piece.

Test Example  4: Appearance Evaluation of Coating Film

The appearance of the coating film of the test piece coated with the quick drying curing type polyurethane coating composition containing the modified polyols derived from the vegetable oil of Examples 27 and 28 and Examples 34 to 38 was visually observed. The results are shown in Figs. 10A to 10G .

For reference, the coating compositions of Examples 27, 28 and 34 to 38 are sky blue, gray, ivory, blue, green, yellow green and iron colors, respectively.

The coating films of the test pieces coated with the coating compositions of Examples 27, 28 and 34 to 38 exhibited excellent gloss and smooth surface activity as a whole except for the case of Example 34. [

Test Example  5: Evaluation of coating film surface

The appearance of the test piece coated with the fast drying curing type polyurethane coating composition containing the modified polyols derived from the vegetable oil of Examples 27 and 28 and Examples 34 to 38 was observed on the surface of the coated film using a digital camera, Are shown in Figs. 11A to 11G.

The coating films of the test pieces coated with the coating compositions of Examples 27, 28 and 34 to 38 were excellent in gloss as a whole and had no bubble marks or pinholes on their surfaces.

No blister phenomenon was instantaneously observed due to the reaction of isocyanate with moisture in the air as in the case of the polyurethane paint using the petroleum-based polyol as the second liquid at all, and the film forming reaction was stable.

However, when the reaction rate was lowered in order to improve the leveling of the surface of the coating film, it was confirmed that the surface state of the coating film of the coating composition of Example 34 was lowered.

Test Example  6: Coating Attachment  evaluation

The adhesion of the coating film formed from the quick drying curable polyurethane coating composition containing the modified polyols derived from the vegetable oil of Examples 27 and 28 and Examples 34 to 38 was evaluated according to ASTM D4541.

As the adhesion test device, Pioitest AT adhesion tester of Delfelsko was used, and Araldite 2011 of the liquid epoxy adhesive Huntsman was used. In the test method, the surface of the coated film of the test piece is polished with a sandpaper to remove foreign substances on the surface, then the above-mentioned adhesive is applied, a dolly is adhered thereon to cure the dolly, And the force exerted when it was pulled out was measured.

The evaluation results are shown in Table 16 below.

Attachment  evaluation Example 27 Example 28 Example 34 Example 35 Example 36 Example 37 Example 38 The second liquid polyol Example 10 Example 11 Example 10 Example 12 Example 13 Example 14 Example 15 Adhesion (psi)
1143 1089 1621 661 796 895 530 1589 1296 2073 868 797 497 535

Examples 27 and 28, which used the first liquid of Example 23 with an NCO content of 20.13 wt.%, Exhibited an adherence of 1000 psi or greater and had a first NCO content of 22.53 wt% with an NCO content of about 2 wt% The adhesiveness was improved by 500 psi or more in Example 34, but in Examples 35 to 38 in which the same Example 24 was used as the first solution, the adhesive force was reduced by 30 to 50%.

In order to minimize the reaction with moisture in the air, the catalyst was used to increase the reactivity to improve the surface state of the coating film. However, since the gelation time was shortened, the wetting time to the substrate was insufficient, .

Therefore, it has been found that an optimal coating film can be obtained by sufficiently considering the wetting time for the substrate and the reaction rate for improving the surface condition of the coating film.

Test Example  7: Flexibility of coating film ( Flexibility ) evaluation

The flexibility of the coating film formed from the quick drying curable polyurethane coating composition containing the modified polyols derived from the vegetable oil of Examples 27 and 28 and Examples 34 to 38 was measured according to ASTM D622.

The coating film was completely cured and dried, and then resistance to cracking and peeling was evaluated by bending using a conical mandrel or a cylindrical mandrel. All of the coating films by the coating composition of the above example were evaluated for bending flexibility The test showed sufficient flexibility not to show any defects such as cracks and dropouts after bending.

The results are shown in Figs. 12A to 12G.

Test Example  8: Evaluation of Impact Resistance of Coating Film

The impact resistance of the coating film formed of the quick drying curable polyurethane coating composition containing the modified polyols derived from the vegetable oil of Examples 27 and 28 and Examples 34 to 38 was measured according to ASTM D2794.

In the test method, a weight of 1 kg was dropped from a height of 50 cm, and cracks or peeling at the impacted portion were observed and evaluated.

The coating films formed by Examples 27 and 28 and Examples 34 to 37 had sufficient flexibility and flexibility, so that there was no breakage, detachment or cracking of the coating film, but in Example 38, a slight crack was observed on the lower end portion .

This is because the equivalence of the modified polyol derived from vegetable oil used in Example 38 is lower than that of the other modified polyol derived from vegetable oil, the equivalent of 198.77 is the lowest, and the molecular weight is relatively small, (See Tables 14 and 9 above).

The results are shown in Figs. 13A to 13G.

Test Example  9: Evaluation of abrasion resistance of coating film

The abrasion resistance of the coating films formed from the quick drying curable polyurethane coating compositions containing the modified polyols derived from the vegetable oil of Examples 27 and 28 and Examples 34 to 38 was measured according to ASTM D4060.

The Taber Abrasion Tester from Yasuda was used for the abrasion resistance test, and Calibrase CS-10 and CS-17 from Taber were used as the abrasive. In this experiment, CS-17 was used for the experiment under severe conditions. Weights were weighed 500g on each side, and the test specimens were cut into 11cm lengthwise and 11cm lengthwise. Then, grooves were drilled in the center to remove the foreign substances. After the test, the weight was measured and the difference was evaluated as abrasion resistance.

The results are shown in Table 17 and shown in Figs. 14A to 14G.

Abrasion resistance test result Example 27 Example 28 Example 34 Example 35 Example 36 Example 37 Example 38 The polyol type of the second solution Example 10 Example 11 Example 10 Example 12 Example 13 Example 15 Example 14 Abrasion resistance (mg) 90.0 52.8 39.7 39.9 47.7 48.3 46.0

As can be seen from the results of Table 16 above, the abrasion resistance performance was improved by increasing the hardness of the coating film as the NCO content increased. Particularly, in the case of Examples 34 and 35, the result is 40 mg or less, which indicates that the abrasion resistance is remarkably excellent.

Test Example  10: Evaluation of hardness of coating film

The hardness of the coating film formed of the quick drying curable polyurethane coating composition containing the modified polyols derived from the vegetable oil of Examples 27 and 28 and Examples 34 to 38 was measured according to ASTM D2240.

The hardness of the coating film was measured by a Durometer hardness tester D type manufactured by Telock, Inc. The results are shown in Table 18 below.

Hardness measurement result Example 27 Example 28 Example 34 Example 35 Example 36 Example 37 Example 38 The polyol type of the second solution Example 10 Example 11 Example 10 Example 12 Example 13 Example 15 Example 14 Durometer hardness 72D 73D 75D 74D 78D 77D 74D

The hardness of the coating film was all above 70 D, and it was found that the lower the molecular weight of the polyol in the second liquid used, and the higher the NCO content, the greater the hardness.

Test Example 11: Evaluation of Chemical Resistance (Chemical Resistance) of Coating Film

The chemical resistance of the coating films formed from the quick drying curable polyurethane coating compositions containing the modified polyols derived from the vegetable oil of Examples 27 and 28 and Examples 34 to 38 was measured according to ASTM D543.

The chemical resistance evaluation is to measure the resistance to chemical solvents. It is obtained by cutting the fully cured dried film specimen, washing, drying, measuring the weight, immersing it in the chemical to be tested for a certain period of time Removed, cleaned, and completely dried. The chemical resistance was evaluated by measuring the change in weight and hardness of the specimen.

The test results are shown in Table 19 below and shown in Figs. 15A to 15H.

Chemical resistance (chemical resistance) evaluation Chemical resistance Example 27 Example 28 Example 34 Example 35 Example 36 Example 37 Example 38 10% H ₂ SO ₄
(30 days passed) Weight change + 2.546% + 2.532% + 1.578% + 1.624% + 1.439% + 1.398% + 1.624% Change in hardness -2D -4D -3D -4D -3D -4D -4D 30% NaOH
(30 days passed) Weight change -0.160% -0.111% -0.089% -0.107% -0.131% -0.101% -0.080% Change in hardness 0D + 1D 0D + 1D 0D + 1D + 1D 30% NaCl
(30 days passed) Weight change + 0.091% + 0.172% + 0.065% + 0.102% + 0.128% + 0.099% + 0.069% Change in hardness 0D 0D 0D 0D 0D 0D 0D Diesel oil
(30 days passed) Weight change + 1.456% + 1.589% + 1.389% + 1.230% + 1.650% + 1.781% + 1.391% Change in hardness 0D -4D -2D -1D -2D -2D -2D

As can be seen from the above Table 19, the general characteristics of the polyurethane coating film are that the change rate in the sulfuric acid solution of the coating film of Example 27 is increased to 2.546% and the hardness is decreased .

However, in the case of Examples 34 to 38 in which the NCO content was increased to increase the degree of crosslinking, it was confirmed that the rate of change was all increased within the range of 1% by weight to 2% by weight. On the other hand, there was almost no change in the alkaline solution and the aqueous salt solution. In the diesel oil experiment, the weight was increased, but the hardness of the coating film was not significantly changed.

From the results described above and the test results, it has been found that the quick drying curable polyurethane coating composition according to the present invention has excellent alkali resistance and flame retardancy, and thus shows particularly high suitability for a coastal facility and the like.

The results of the tests of Test Examples 6 to 11 are summarized in Table 20 below.

Coating evaluation result Example 27 Example 28 Example 34 Example 35 Example 36 Example 37 Example 38 The type of polyol in the second liquid Example 10 Example 11 Example 10 Example 12 Example 13 Example 15 Example 14 Gel time 38s 40s 1m18s 25s 25s 25s 25s Touch dry time 4m 4m 10m 2m 2m 2m 2m Vegetable polyol content 23% 23% 24.75% 27.3% 28.8% 28.8% 30.3% Adhesion to steel 1143 psi 1089 psi 1621 psi 661 psi 796 psi 530 psi 859 psi 1589 psi 1296 psi 2073 psi 868 psi 797 psi 535 psi 497 psi flexibility OK OK OK OK OK OK OK Impact resistance OK OK OK OK OK OK Crack slightly Abrasion resistance 90.0 mg 52.8 mg 39.7 mg 39.9 mg 47.7 mg 48.3 mg 46.0 mg Durometer hardness 72D 73D 75D 74D 78D 77D 74D Chemical resistance 10% H ₂ SO ₄
(30 days passed) Weight change + 2.546% + 2.532% + 1.578% + 1.624% + 1.439% + 1.398% + 1.624% Change in hardness -2D -4D -3D -4D -3D -4D -4D 30% NaOH
(30 days passed) Weight change -0.160% -0.111% -0.089% -0.107% -0.131% -0.101% -0.080% Change in hardness 0D + 1D 0D + 1D 0D + 1D + 1D 30% NaCl
(30 days passed) Weight change + 0.091% + 0.172% + 0.065% + 0.102% + 0.128% + 0.099% + 0.069% Change in hardness 0D 0D 0D 0D 0D 0D 0D Diesel oil
(30 days passed) Weight change + 1.456% + 1.589% + 1.389% + 1.230% + 1.650% + 1.781% + 1.391% Change in hardness 0D -4D -2D -1D -2D -2D -2D

From the results shown in the above Table 20, it can be seen that, in the quick drying curable polyurethane coating composition, the modified polyol derived from the vegetable oil in the second liquid is much less reactive to water than the petroleum-based polyether polyol in view of reactivity with MDI, It was found that the modified polyol derived from the vegetable oil was more stable to react with the polymeric MDI than the monomeric MDI and was less sensitive to moisture, and the modified polyol derived from the vegetable oil derived modified polyol Has been found to be capable of forming an ideal coating film when used in combination with a specific crosslinking agent, specifically an aromatic secondary amine, with a tetrafunctional polyol tertiary amine, especially a tetrahydroxypolyol tertiary amine, Quick-drying curable poly The retanning paint composition can be designed as a 100% non-solvent paint using a specific coating equipment. Particularly, when the gelation time is within the range of 40 to 60 seconds and the NCO content of the first solution, the isocyanate prepolymer, is in the range of 22 to 23% by weight It is possible to obtain a coating composition which is more excellent in adhesion, abrasion resistance, hardness, flexibility and chemical resistance.

Specifically, the coating composition of Example 34 was obtained by using the modified polyol mixture derived from the vegetable oil of Example 10, having a gelation time of 1 minute 18 seconds, an adhesion force of 1600 psi or more, a hardness of 75 D, excellent flexibility and impact resistance It has been confirmed that it has superior abrasion resistance and chemical resistance in addition to Gy.

In addition, the coating compositions of Examples 35 to 38, which exhibit a very excellent coating film surface state, can be obtained by sufficiently retarding the curing rate by controlling the curing rate using a catalyst to sufficiently wet the substrate surface, It was found possible to form.

Example  39 to 44: Polyol  Preparation of second solution

A second liquid as a polyol portion was prepared with compositional components and composition ratios as shown in Table 21 below.

To accurately determine the reactivity between the polyol of the second liquid and the isocyanate of the first liquid, the modified polyol mixture derived from the vegetable oil, the crosslinking agent and the additive were all used in the same amount. However, it was easily distinguished by the color of the coating film obtained by using pigments of different colors for classification.

On the other hand, the use of DBTDL, which is the most effective catalyst for the urethane reaction, is excluded because DBTDL is advantageous in that it can shorten the touch-drying time by a quick reaction, but conversely, This is because there is a disadvantage in that the adhesiveness is further lowered.

The second solution was designed so that the reaction volume equivalents of the first solution and the isocyanate were the same.

As shown in the following Table 21, the equivalents of the respective raw materials with respect to the hydroxyl groups were determined and then divided by the amount per 100 g of the coating material to obtain the hydroxyl group equivalent in 100 g of the coating material. The equivalence of the hydroxyl groups was determined and expressed as the relative weight equivalent.

Polyol  And the composition ratio Second sum equivalent weight importance Example 39 Example 40 Example 41 Example 42 Example 43 Example 44 Secondary amine 155.0 1.08 20.00 20.00 20.00 20.00 20.00 20.00 Pigment 0.0 4.00 6.00 6.00 6.00 6.00 6.00 6.00 Dispersant 0.0 1.07 0.30 0.30 0.30 0.30 0.30 0.30 Defoamer 0.0 0.85 0.30 0.30 0.30 0.30 0.30 0.30 Desiccant 0.0 1.10 5.00 5.00 5.00 5.00 5.00 5.00 Example 16 330.9 0.97 42.10 - - - - - Example 17 350.3 0.97 - 42.10 - - - - Example 18 369.6 0.97 42.10 - - - Example 19 325.0 0.97 - - - 42.10 - - Example 20 334.5 0.97 - - - - 42.10 - Example 21 344.0 0.97 - - - - - 42.10 Tertiary amine 73.1 22.00 22.00 22.00 22.00 22.00 22.00 22.00 Defoamer 0.0 0.30 0.30 0.30 0.30 0.30 0.30 0.30 stabilizator 0.0 4.00 4.00 4.00 4.00 4.00 4.00 4.00 Sum 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 Equivalent of second solution - - 0.5655 0.5597 0.5545 0.6102 0.6069 0.5545 Specific gravity of second solution - - 1.075 1.075 1.075 1.075 1.075 1.075 Equivalent weight equivalent - - 0.6082 0.6019 0.5962 0.6082 0.6019 0.6038 Viscosity of the second liquid - - 95KU 101KU 107KU 98KU 103KU 109KU

In Table 21, the secondary amine and the tertiary amine are aromatic secondary amine and tetrahydroxypolyol tertiary amine, respectively. The stabilizer reacts with water molecules contained in the air or paint in addition to zeolite, and is reacted with formyl ethyl ester and ethanol Triethyl orthoformate, and the remainder is as described above.

Meanwhile, details of the polyols of Examples 16 to 21 used for the production of the second liquid are shown in Table 22 below.

Vegetable oil-derived modification Polyol Polyol Molecular Weight Average molecular weight OH number Number of COOH OH equivalent

) Formula 4
(R =

) 526 526 1.9 1.3 276.8 Formula 4
(R =

) 565.57 566 3.8 1.3 148.9 Example 16 900 ~ 920 910 3.0 0.05 303.3 Example 17 840 to 860 850 2.9 0.2 293.1 Example 18 840 to 860 850 2.9 0.2 293.1 Example 19 900 ~ 920 910 3.0 0.05 303.3 Example 20 850-870 860 3.0 0.2 286.7 Example 21 850-870 860 3.1 0.2 277.4

In Table 22, the acrylate-introduced polyol of Formula 4 is not only highly viscous at room temperature but also solidified at low temperature storage, so that it is mixed with other modified polyol derived from vegetable oil to obtain a low viscosity polyol of Examples 16 to 21 The polyol mixtures described above are sufficiently usable at room temperature and have a suitable molecular weight. This was calculated by calculating the hydroxyl group equivalent.

On the other hand, as the first solution, the equivalent weight-equivalent equivalent of the isocyanate prepolymer of Example 24 is shown in Table 23 below.

Isocyanate Prepolymer The first sum Example 24 NCO content (wt.%) 22.50% Paint equivalent 186.6 Paint specific gravity 1.146 Equivalent weight equivalent 0.6138 Viscosity 88.3KU

Examples 45 to 50: Two-pack type polyurethane paint

The first liquid of the isocyanate prepolymer of Example 24 and the second liquid of the polyol portion of Examples 39 to 44 were mixed in a two-component mixed impingement spray apparatus (Graco Reactor XP -2), and then the gelling time and the surface state of the coating film were evaluated.

The ratio of the equivalent weight conversion equivalent (see Table 23) of the isocyanate prepolymer as the first solution to the specific gravity conversion equivalent weight (see Table 21) of the polyol portion as the second solution was found to be 1.01 to 1.03, Is 1: 1 equivalent, the equivalence of the isocyanate moiety is more than 0.01 to 0.02.

Two-component polyurethane paint Two-component polyurethane paint Example 45 Example 46 Example 47 Example 48 Example 49 Example 50 The prepolymer (first liquid) Example 24 Example 24 Example 24 Example 24 Example 24 Example 24 The polyol (second liquid) Example 39 Example 40 Example 41 Example 42 Example 43 Example 44 The NCO weight% of the first liquid 22.50% 22.50% 22.50% 22.50% 22.50% 22.50% NCO / OH (vol) 1.01 1.02 1.03 1.01 1.01 1.02 Gel time 58s 58s 58s 58s 58s 58s Touch dry time 2m16s 2m16s 2m16s 2m16s 2m16s 2m16s

Test Example 12: Preparation and Appearance Evaluation of Test Specimens

The test pieces using the two-part fast drying curable polyurethane paint compositions containing the modified polyols derived from the vegetable oil of Examples 45 to 50 were prepared in the same manner and under the same conditions as those in Test Example 3 using pigments having different colors, As a result of visual observation of the outer appearance of the coating film as in Test Example 4, the gloss was uniform throughout and pinholes and the like were not observed.

The results are shown in Figs. 16A to 16F.

There was no problem of incompatibility between the modified polyol mixture derived from vegetable oil and pigments, dispersants and other additives, and it showed stable dispersibility against inorganic pigment or organic pigment. The dispersing machine used for dispersing the modified polyol derived from vegetable oil and the pigment was dispersed for 1 hour at 1000 rpm using a ring mill of Amstec (domestic), and the pigment particles after dispersing for 1 hour were less than 10 탆 . When the pigment particle size is more than 10 탆, when the various pigments are mixed and dispersed, the color may be uneven or a phenomenon of dichroism may appear. Also, since the specific gravity of the pigment may cause precipitation during storage of the paint for a long period of time, In order to disperse finely, compatibility of dispersant, resin and pigment is important.

Test Example  13: Coating Attachment  evaluation

The adhesion of the coating film formed from the quick drying curable polyurethane coating composition containing the modified polyols derived from the vegetable oil of Examples 45 to 50 was evaluated in accordance with ASTM D4541 as in Test Example 6 and the evaluation results are shown in the following Table 25 .

Attachment  evaluation Example 45 Example 46 Example 47 Example 48 Example 49 Example 50 The second liquid polyol Example 16 Example 18 Example 19 Example 21 Example 17 Example 20 Adhesion to steel (psi) 1855 883 1968 853 1570 1674

Sufficient gelling time was given to give sufficient wetting time to the substrate. Examples 45, 47, 49, and 50, which were the coating compositions of Examples 16, 17, 19 and 20, respectively, of the polyol mixture in the second liquid had a standard value of 1500 psi or more, 46 and Example 48, it was confirmed that the adhesive strength was lowered to 1000 psi or less, which was lower than the reference value having a sufficient adhesion strength of the film, although the wetting time to the substrate was sufficient but the film was broken at 883 and 853 psi.

Test Example  14: Flexibility of coating film Flexibility ) evaluation

The flexibility of the coating film formed from the quick drying curable polyurethane coating composition containing the modified polyols derived from the vegetable oil of Examples 45 to 50 was evaluated by Mandrel bend tester of Gardner in accordance with ASTM D622.

The results are shown in Figs. 17A to 17F.

Except for Example 46 and Example 48, all of them showed sufficient flexibility in a 180 占 bending flexural test, and no cracks or dropping of the coating film after flexing were observed. In the case of Examples 46 and 48, it was found that there was a close relationship with the cause of the above-mentioned decrease in the adhesion force. This is because the modified polyol derived from the vegetable oil did not sufficiently cross-link the polyol to form a sufficient three-dimensional network after curing .

Test Example  15: Evaluation of Impact Resistance of Coating Film

The impact resistance of the coating films formed from the quick drying curable polyurethane coating compositions containing the modified polyols derived from the vegetable oil of Examples 45 to 50 was evaluated in accordance with ASTM D2794 as in Test Example 8.

In all of the examples, there was no breakage or dropout of the coating film or occurrence of cracks, which was the same even in the coating films of Examples 46 and 48 which were judged to lack flexibility.

The results are shown in Figs. 18A to 18F.

Test Example  16: Evaluation of abrasion resistance of coating

The abrasion resistance of the coating films formed from the quick drying curable polyurethane coating compositions containing the modified polyols derived from the vegetable oil of Examples 45 to 50 was tested according to ASTM D4060 in the same manner and under the same conditions as in Test Example 9.

The results are shown in Table 26 below and shown in Figs. 19A to 19F.

Abrasion resistance test result Example 45 Example 46 Example 47 Example 48 Example 49 Example 50 The polyol type of the second solution Example 16 Example 18 Example 19 Example 21 Example 17 Example 20 Abrasion resistance (mg) 15.9 14.9 14.2 8.6 10.8 15.2

As can be seen from the results of Table 26, the abrasion resistance showed excellent results regardless of the kind of the modified polyol derived from vegetable oil. Here, the difference of about 5 mg can be caused by the error. Therefore, These minute differences were not considered to have any different meaning.

Test Example  17: Evaluation of Hardness of Coating Film

The hardness of the coating film formed from the quick drying curable polyurethane coating composition containing the modified polyols derived from the vegetable oil of Examples 45 to 50 was measured according to ASTM D2240 in the same manner and under the same conditions as in Test Example 10.

The results are shown in Table 27 below.

Hardness measurement result Example 45 Example 46 Example 47 Example 48 Example 49 Example 50 The polyol type of the second solution Example 16 Example 18 Example 19 Example 21 Example 17 Example 20 Durometer hardness 73D 72D 73D 75D 77D 72D

All of the coating film hardnesses were 70D or more, which was excellent regardless of the kind of the polyol in the second liquid used.

Test Example  18: Evaluation of Chemical Resistance (Chemical Resistance) of Coating Film

The chemical resistance of the coating films formed from the quick drying curable polyurethane coating compositions containing the modified polyols derived from the vegetable oil of Examples 45 to 50 was tested according to ASTM D543 in the same manner and under the same conditions as in Test Example 11.

The test results are shown in Table 28 below and shown in Figs. 20A to 20D.

Chemical resistance (chemical resistance) evaluation Chemical resistance Example 45 Example 46 Example 47 Example 48 Example 49 Example 50 10% H ₂ SO ₄
(30 days passed) Initial weight (g) 3.6054 3.8841 4.1702 2.3053 3.3756 2.8911 Weight after experiment (g) 3.6480 3.9392 4.2171 2.3535 3.4412 2.9385 Weight change rate (%) 1.18 1.42 1.12 2.09 1.94 1.64 Change in hardness -2D -3D -2D -4D -3D -3D 30% NaOH
(30 days passed) Initial weight (g) 3.4877 3.9104 3.9968 2.2778 3.0014 3.0552 Weight after experiment (g) 3.4941 3.9191 4.0042 2.2791 3.0049 3.0587 Weight change rate (%) 0.18 0.22 0.19 0.06 0.12 0.11 Change in hardness 0D 0D 0D 0D 0D 0D 30% NaCl
(30 days passed) Initial weight (g) 3.4362 3.8559 3.8747 2.3837 3.1764 3.5945 Weight after experiment (g) 3.4519 3.8785 3.9001 2.3955 3.1860 3.6065 Weight change rate (%) 0.46 0.59 0.66 0.50 0.62 0.63 Change in hardness 0D 0D 0D 0D 0D 0D Diesel oil
(30 days passed) Initial weight (g) 3.6541 3.9186 3.8747 2.3837 3.0572 2.9021 Weight after experiment (g) 3.6700 3.9253 3.8842 2.3851 3.0741 2.9133 Weight change rate (%) 0.44 0.17 0.25 0.06 0.55 0.39 Change in hardness -4D -2D -2D -2D -3D -2D

As can be seen from the above Table 28, the weight change and hardness change of the polyurethane coating film did not appear in the remaining chemicals except the acidic solution. However, the rate of change in the acid resistance test was about 1 ~ 2%, but it was evaluated as having a relatively excellent acid resistance as less than 5% as a whole.

Test Example  19: Reliability Evaluation (I)

A quick-setting curing type polyurethane coating composition containing the modified polyol derived from vegetable oil of Example 45 was evaluated for its suitability as an inner coating agent for tap water pipes by the Korea Research Institute of Chemical Fusion Test. The results are shown in Table 29 below.

Reliability evaluation results and Reference value Test Items Test result Reference value Test Specification One Bond strength 15.5N / mm ² (2248psi) 1500 psi or more ASTM D 4541 2 flexibility 10mm, no abnormality 100mm, no more ASTM D 522 3 Impact 19.6 N.m (2 kg.m) 0.46 kg.m or more ASTM D 2794 4 Abrasion resistance 2 mg 100 mg or less ASTM D 4060 5 10% H ₂ SO ₄ (30 days) 0.4% Dimensional change rate, 5% or less ASTM D 543 1.3% Weight change rate, less than 5% 6 30% NaOH (30 days) 0.2% Dimensional change rate, 5% or less ASTM D 543 0.4% Weight change rate, less than 5% 7 30% NaCl (30 days) 0.2% Dimensional change rate, 5% or less ASTM D 543 0.6% Weight change rate, less than 5% 8 Diesel (30 days) 0.4% Dimensional change rate, 5% or less ASTM D 543 1.2% Weight change rate, less than 5% 9 Water absorption rate 0.3% 3% or less ASTM D 570 10 Hardness 86D 65D or more ASTM D 2240 11 Drinking Water Quality Test Suitable Must meet national standards KSD 8502 12 Cathodic peeling test Average peel distance: 4.4 mm 12mm or less ASTM G8 Maximum separation distance: 4.6mm 13 Nonvolatile matter A part: 99.0% over 90 KS M ISO 3251 B part: 99.1%

The reference values in Table 29 are based on AWWA C222 Polyurethane coatings for the interior and exterior steel water pipes and fittings, USA standards, and the drinking water quality test method is based on KS D 8502 liquid epoxy resin paint and coating method, will be.

Test Example  20: Reliability evaluation II )

Whether or not the fast drying curing type polyurethane coating composition containing the modified polyol derived from vegetable oil of Example 45 is suitable as a coating material for a heavy crude oil tank is determined by the presence or absence of lifting of the blister or the coating film with time, The results are shown in Table 30 below.

Reliability evaluation results and Reference value time Early 10 days 30 days 40 days 50 days 60 ° C / 60 days 60 ° C / 90 days 60 ° C / 150 days Polish 84 86 86 86 86 86 85 86 Hardness (D) 79 78 78 78 76 76 75 77 Surface blister - none none none none none none none

After a certain period of time, the pieces of crude oil were taken out of the crude oil, cleaned with a soft cloth, and left at room temperature for 1 hour. No blisters or film peeling on the surface were found, and there was little change in gloss and hardness. Since there was no change in the film state after 80 days, the test conditions were changed to change to the immersion test at 60 ° C. Also, after 30 days and 90 days at 60 ° C, no shine nor hardness decreased, and thus resistance to crude oil was excellent Proved.

Example  51: Isocyanate Prepolymer  Preparation of the first liquid

The curing agent used in general waterproofing agent or flooring agent is generally an adduct having an NCO content of about 4 to 10% by weight, which is obtained by reacting TDI (toluene diisocyanate) with a polyol. However, in order to improve the hardness, When the content is increased to about 20% by weight, the unreacted glass TDI component results in a very harmful effect to the human body during the painting operation.

Therefore, in this embodiment, an isocyanate prepolymer was designed using MDI having a higher vapor pressure than TDI, and a first liquid, which is an isocyanate prepolymer using polymeric MDI and monomelic MDI as a curing agent, .

The composition and composition ratio of the first liquid of the isocyanate prepolymer The first sum      Example 24 Example 51 Polymerizable MDI 68.00 - Monomelic MDI - 60.30 Low Viscosity HDI Trimer 9.00 9.00 PP2000D 23.00 30.70 Sum 100.00 100.00 Viscosity 88KU 84.6KU density 1.148 1.143 NCO content (wt.%) 22.53% 22.50%

Example  52 and Example  53: Polyol  Preparation of Partial Second Liquid

The pigment was first dispersed using a secondary amine crosslinking agent, and then the polyols of Examples 10 and 16 were respectively added and stirred to prepare a second solution as a polyol portion with the composition components and composition ratios shown in Table 32 below. Respectively.

Polyol  The composition and composition ratio of the second liquid as a part Second sum Example 52 Example 53 Aromatic secondary amine 22.00 15.00 Inorganic pigments 5.50 5.00 Organic pigment 0.50 1.00 Dispersant 0.30 0.30 Defoamer 0.30 0.30 Desiccant 5.00 5.00 Dispersed for 40 minutes The polyol mixture of Example 10 43.60 - The polyol mixture of Example 16 - 40.60 Alkylene oxide polyol - 10.00 Tetrahydroxypolyol tertiary amine 22.00 22.00 Defoamer 0.30 0.30 stabilizator 0.50 0.50 Sum 100.00 100.00 Viscosity 95.1KU 113.2KU Granularity 5 μm or less 5 μm or less Color separation none none importance 1.061 1.065

In Example 52, the amount of the aromatic secondary amine was increased and dispersed in order to smoothly disperse the inorganic and organic pigments. In Example 53, the alkylene oxide polyol (GP-3000, KPX) was added in an amount of 10 wt% for the purpose of viscosity reduction.

Since the alkylene oxide polyol has low reactivity with the isocyanate curing agent and may cause coating failure due to swelling of the coating film due to moisture in the air, it is preferably used in an amount of 10 wt% or less.

Example  54-56: 2-pack type  Polyurethane paint

A first liquid containing the above-mentioned second liquid of Example 52, a first liquid containing the monomeric MDI of Example 51, and a first liquid containing the polymerizable MDI of Example 24 were mixed and coated using the above-described coating apparatus These were Examples 54 and 55, respectively.

Further, the second liquid of Example 53 and the first liquid containing the monomelic MDI of Example 51 were mixed and similarly coated using the above-described coating apparatus to prepare Example 56.

The reactivity and reaction stability of the coating compositions of Examples 54 to 56 are shown in Table 33 below.

Reactivity and reaction stability Example 54
(Example 51 using the first liquid) Gel time 70 seconds Reaction stability Homogeneous reaction without clogging.
Flexible without bending during forced bending. Example 55
(Example 24 using the first liquid) Gel time 55 seconds Reaction stability Homogeneous reaction without clogging.
Breaking during forced flexion. Example 56
(Example 51 using the first liquid) Gel time 77 seconds Reaction stability Homogeneous reaction without clogging.
Flexible without bending during forced bending.

From the results of Table 33, it can be seen that when the prepolymer of Example 24 containing polymeric MDI is used as the floor coating composition, the hardness of the coating film is increased and the coating film is broken at the time of forced bending, (Examples 54 and 55), the first liquid of the isocyanate prepolymer of Example 24 containing the polymerizable MDI was found to be excellent in flexibility in Examples Was found to be faster than the first liquid of the isocyanate prepolymer of < RTI ID = 0.0 > 51. ≪ / RTI >

On the other hand, it has been found that the surface state of the coating film is superior as the use amount of the alkylene oxide polyol which can be added by taking ease of the coating operation is reduced.

21A and 21B show the coating films of Examples 54 and 56 described above.

From the foregoing, the two-part, solvent-free, quick drying curable polyurethane coating composition according to the present invention can be used for waterproof and anti-corrosive coatings for waterproofing and waterproofing of interior and exterior surfaces of water pipes, It has excellent quality characteristics as a waterproof and anti-corrosive coating material inside a tunnel, and also has excellent quality characteristics as a concrete waterproofing floor coating material such as a roof or an underground parking lot of an apartment, a concrete water treatment facility or a watering facility, .

Claims (20)

(A) a first liquid as an isocyanate prepolymer comprising 18 to 34% by weight of a petroleum-based polyether polyol, 55 to 75% by weight of MDI (methylene diphenyldiisocyanate) and 7 to 11% by weight of HDI (hexamethylene diisocyanate)
(B) 30 to 70% by weight of a modified polyol derived from a vegetable oil, 8 to 25% by weight of an aromatic secondary amine, 10 to 30% by weight of a tetrafunctional tertiary amine polyol, and 8 to 15% Solution:
The non-solvent which is contained in an amount such that the above-mentioned first liquid has an NCO content of 20 to 23 wt%
Fast drying curing type polyurethane coating composition. The method of claim 1, wherein the first liquid is a quick-drying material comprising 20 to 32% by weight of a petroleum-based polyether polyol, 60 to 72% by weight of MDI (methylene diphenyl diisocyanate) and 8 to 10% by weight of HDI (hexamethylene diisocyanate) Curable polyurethane coating composition. The fast drying curing-type polyurethane coating composition according to claim 1 or 2, wherein the first liquid has an NCO content of 20 to 23% by weight, a viscosity of 970 to 1400 cps (85 to 98 KU), and a specific gravity of 1.13 to 1.15. The quick-setting curable polyurethane paint of claim 1 or 2, wherein the petroleum-based polyether polyol in the first liquid has an OH equivalent of 800 to 1200, a hydroxyl value of 48 to 62 mg KOH / g, and a viscosity of 200 to 420 cps Composition. The composition of claim 1 or 2, wherein the MDI in the first liquid is a polymerizable MDI having an NCO content of 30 to 32% by weight. The composition of claim 1 or 2, wherein the MDI in the first liquid is a monomeric MDI having an NCO content of 33 to 34% by weight. The quick drying curable polyurethane paint according to claim 1 or 2, wherein the HDI in the first liquid is a low viscosity HDI trimer having an NCO content of 22 to 25% by weight and a viscosity of 400 to 1400 cps (65 to 95 KU) Composition. The quick drying curable polyurethane coating composition according to claim 1 or 2, wherein the modified polyol derived from vegetable oil in the second liquid is contained in an amount of 40 to 62% by weight. The quick drying curable polyurethane coating composition according to claim 1 or 2, wherein the first liquid and the second liquid are mixed in a 1: 1 equivalent volume ratio. The method according to claim 1 or 2, wherein the modified polyol derived from the vegetable oil in the second liquid is selected from the group consisting of a methoxypolyol of the following formula (1), a hydroxylpolyol of the following formula (2), a hydroxyl fatty acid methyl ester of the following formula And an acrylate ester-introduced polyol of the following formula (4): < EMI ID = 2.0 >
[Chemical Formula 1]

(2)

(3)

Wherein R ₁ is the same as each other H or OH, and, if R ₁ is OH and R ₂ is also OH R ₃ is H, when R ₃ is OH R ₂ is an OH and R ₁ is H.
[Chemical Formula 4]

Wherein R is

or

to be. The quick-setting curable polyurethane coating composition according to claim 10, wherein the modified polyol derived from vegetable oil in the second liquid has an OH equivalent of 200 to 400, a hydroxyl value of 180 to 260 mg KOH / g and a viscosity of 600 to 4700 cps. The method according to claim 10, wherein the modified polyol derived from vegetable oil in the second solution contains 5 to 29% by weight of a methoxypolyol of the formula (1), 1 to 10% by weight of a hydroxylpolyol of the formula (2) And 70 to 90% by weight of a hydroxy fatty acid methyl ester. 11. The method of claim 10, wherein the modified polyol derived from the vegetable oil in the second liquid is a mixture of 10 to 30% by weight of the hydroxylpolyol of the formula (2) and 70 to 90% by weight of the hydroxyl fatty acid methyl ester of the formula Curable polyurethane coating composition. The composition of claim 10, wherein the modified polyol derived from the vegetable oil in the second liquid is a mixture of 10 to 30% by weight of the methoxypolyol of the formula (1) and 70 to 90% by weight of the hydroxyl fatty acid methyl ester of the formula Curable polyurethane coating composition. [10] The method according to claim 10, wherein the modified polyol derived from vegetable oil in the second solution comprises 8 to 27% by weight of the methoxypolyol of the formula 1, 1 to 5% by weight of the hydroxylpolyol of the formula 2, 50 to 81% by weight of a hydroxyl fatty acid methyl ester, and 10 to 30% by weight of an acrylate ester-introduced polyol of the formula (4). The quick drying curable polyurethane coating composition according to claim 1 or 2, wherein the tetrafunctional tertiary amine polyol is a tetrahydroxypolyol quaternary amine. The composition of claim 16, wherein the aromatic secondary amine has an OH or amine equivalent of 155 and the tetrafunctional tertiary amine polyol is OH or amine equivalent of tetrahydroxypolyol quaternary amine of 73.1. Coating composition. The quick drying curing type polyurethane coating composition according to claim 1 or 2, wherein the other additives are a dispersing agent, an antifoaming agent, a dehumidifying agent, a pigment, and a stabilizer. 19. The composition of claim 18, wherein the dispersant is an ammonium salt, the defoaming agent is a silicone oil, the dehumidifying agent is an aluminum silicate molecular sieve, and the stabilizer is triethyloisocyanate. The quick drying curable polyurethane coating composition according to claim 1 or 2, wherein dibutyltin dilaurate is contained as a urethane curing catalyst.

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