KR102221795B1 - Additive for Epoxy Paint Composition - Google Patents

Abstract

The present invention relates to an additive for an epoxy paint composition, and more particularly, an additive for an epoxy paint composition including styrenated phenol, epoxied soybean oil and castor oil, and using the same It relates to an epoxy coating composition having excellent workability.

Description

Additive for Epoxy Paint Composition {Additive for Epoxy Paint Composition}

The present invention relates to an additive for an epoxy paint composition, and specifically to an additive for an epoxy paint composition comprising styrenated phenol and a vegetable oil, and an epoxy paint composition comprising the same.

Epoxy resins have excellent performance in terms of mechanical properties, electrical properties, thermal properties, chemical resistance, adhesiveness, etc. of their cured products. As a general-purpose resin used in all fields of industry such as civil engineering, construction, etc., additives such as diluents, fillers, plasticizers, and denaturants are used in addition to hardeners depending on the purpose and use of use.

In addition, since epoxy resin has excellent physical properties such as hardening strength, hardening, sunlight resistance, and workability, and there is no fear of volatile substances or volume shrinkage during curing, a paint applied to concrete substrates by mixing a curing agent suitable for epoxy resin. It is also used as. Compared to other types of paints used for concrete protection, epoxy-curable paints have less shrinkage and high mechanical and chemical resistance, making them suitable as high-functional paints.

On the other hand, nonylphenol (Nonylphenol) is used as a curing agent or plasticizer in the field of epoxy curable paints due to its inherent physicochemical properties, and has been applied for a wide range of uses in various industrial fields. However, the nonylphenol is known to be a renal toxicity and endocrine hormone disruptor, and nonylphenols have a structure similar to the female hormone estrdiol, and according to reports that they cause disturbance of the aquatic ecosystem, the use of nonylphenols is prohibited in the industry or has gradually become increasingly used. It is limited.

May 26, 2016 Ministry of Environment Announcement No. 2016-446 Announcement on Designation of Toxic Substances, Restricted Substances and Prohibited Substances In the administrative notice regarding the expansion of restrictions on nonylphenols and mixtures containing 0.1% or more, specific As for the current nonylphenols (6 types), manufacturing, import, sale, storage, storage, transportation, and use are prohibited for household cleaning agents, ink, and paint, but the high possibility of being directly discharged to the water system is "industrial and commercial cleaning. ·Cleaning agent use" and "textile/leather processing use" were added as new restricted uses, and nonylphenols (8 types) that were not included in the domestic flow or restricted substance notice were additionally designated.

In order to develop a substitute for nonylphenol, which is an environmentally hazardous substance, research on substances having the same or similar physicochemical properties such as nonylphenol and the like with little adverse environmental impact is ongoing.

As a related art, in Korea Patent Registration 10-1397655 (published on January 22, 2014), styrenated phenol was used as a curing agent or plasticizer of an epoxy resin, and styrenated phenol has similar viscosity characteristics and It has a curing property, and in particular, since it has excellent curing properties for an epoxy resin, it was confirmed that styrenated phenol can be used as a curing agent or plasticizer for an epoxy curing paint.

Also, Korean Patent Registration 10-1638871 (Published: 04.03.2015) in the scan styrene Ney suited lactide produced by the addition of hydroxylamine to the nose, styrene phenol phenol added to promote curing additional conventional styrene Ney suited phenol water resistance and water eeun It was confirmed that while maintaining the plasticity property, it was possible to improve the appearance quality and storage stability of the product by preventing discoloration when mixed with a curing agent.

As described above, styrenated phenol has viscosity characteristics and curing characteristics similar to nonylphenol, so as the content of styrenated phenol in the paint composition increases, the hardness of the coating composition increases, while the pot life is shortened, resulting in workability. This deterioration problem may occur.

In addition, precautions when using a curing agent include workability at the time of curing according to working conditions and uses such as viscosity at work temperature, pot life, heat generation, toxicity, physical, mechanical, electrical, and chemical properties and required curing temperature, curing It is very important to select and mix the curing agent by careful consideration in time.

Therefore, the present inventors tried to develop a novel epoxy paint composition additive by controlling the selection and blending of the curing agent, and as an additive for an epoxy paint composition, not only has excellent workability, but also has excellent performance and competitiveness in terms of price, Eco-friendly additives for epoxy coating compositions and epoxy coating compositions containing the same have been invented.

Domestic registration patent 10-1397655 (Publication date: 2014.01.22.) Domestic registration patent 10-1638871 (Publication date: 2015.04.03.)

In order to solve the above problems, the present researchers aim to provide an additive for an epoxy coating composition having excellent workability and performance, and an epoxy coating composition including the same.

In order to solve the above problems, the present invention comprises 50 to 80% by weight of styrenated phenol represented by the following formula (1) and 20 to 50% of oil components including epoxizied soybean oil and castor oil. It provides an additive for an epoxy coating composition comprising the.

[Formula 1]

(In Formula 1, n is 1, 2, or 3)

In an embodiment of the present invention, the additive for the epoxy paint composition is 50 to 80% by weight of styrenated phenol, and the vegetable oil is 5 to 40% by weight of epoxizied soybean oil and castor oil 5 It is characterized in that it contains ~ 40% by weight. In the styrenated phenol, the content of mono-styrenated phenol (n=1) may be 80 to 95% by weight of the total styrenated phenol.

In addition, the additive for the epoxy coating composition may additionally include hydroxyl amine, and the content of the hydroxyl amine may be 0.1 to 2.0% by weight based on the total weight of the additive for the epoxy coating composition, and the hydroxyl amine is mono Methylhydroxylamine, dimethylhydroxylamine, monoethylhydroxylamine, diethylhydroxylamine, monopropylhydroxylamine, dipropylhydroxylamine, monobutylhydroxylamine, dibutylhydroxylamine, isopropylhydro It may be one or more selected from the group consisting of hydroxylamine and diisopropylhydroxylamine.

In addition, in another embodiment of the present invention, 50 to 80% by weight of styrenated phenol represented by the following formula (1) and the main part including an epoxy resin, and epoxizied soybean oil and castor oil It provides an epoxy coating composition comprising an additive for an epoxy coating composition, characterized in that it comprises 20 to 50% by weight of the oil component containing).

[Formula 1]

(In Formula 1, n is 1, 2, or 3)

In an embodiment of the present invention, the additive for the epoxy paint composition is 50 to 80% by weight of styrenated phenol, and the vegetable oil is 5 to 40% by weight of epoxizied soybean oil and castor oil 5 It may contain ~ 40% by weight. In the coating composition, the styrenated phenol may be characterized in that it contains 80 to 95% by weight of mono-styrenated phenol (n=1).

In addition, the additive for the epoxy coating composition may additionally include hydroxyl amine, and the content of the hydroxyl amine may be 0.1 to 2.0% by weight based on the total weight of the additive for the epoxy coating composition, and the additive for the epoxy coating composition May be 5 to 10% by weight based on the total weight of the epoxy coating composition.

The additive for a paint composition according to the present invention exhibits a long pot life and is excellent in workability after mixing, as well as an equivalent degree of hardness compared to nonylphenol.

In addition, the additives for paint compositions according to the present invention obtained the same level of physical properties as nonylphenol in chemical resistance, adhesion strength, and yellowing resistance. In addition, it has excellent anti-foaming properties and can obtain a beautiful appearance, showing excellent performance for solvent-free epoxy flooring paints.

1 is a photograph after storing the epoxy coating composition (Example 1) and the epoxy coating composition (Comparative Example 2) containing nonylphenol according to the present invention at 60° C. for 7 days.
FIG. 2 is a photograph of a specimen treated with an epoxy coating composition (Example 1) and nonylphenol-containing epoxy coating composition (Comparative Example 2) according to the present invention and exposed outdoors for 7 days. It is represented by ΔY and ΔE values with a color difference meter.

Advantages and features of the present invention, and a method of achieving them will become apparent with reference to the following embodiments. However, the present invention is not limited to the embodiments disclosed below, but will be implemented in a variety of different forms, only to completely inform the scope of the invention to those of ordinary skill in the same technical field as the present invention. It is provided, and the invention is only defined by the matters set forth in the claims. The same reference numerals refer to the same elements throughout the specification.

Hereinafter, the present invention will be described in detail.

According to an aspect of the present invention, 50 to 80% by weight of styrenated phenol represented by the following formula (1), preferably 55 to 75% by weight, and epoxied soybean oil (Epoxizied soybean oil) and castor oil (Castor oil) are included. There is provided an additive for an epoxy coating composition comprising 20 to 50% by weight, preferably 25 to 45% by weight of the oil component.

[Formula 1]

(In Formula 1, n has a value of one of an integer of 1 to 3)

The styrenated phenol is a non-toxic substance and has an advantage of excellent environmental friendliness, and has a weight average molecular weight, hydroxy value (OH value), viscosity, color value, and moisture content that are almost similar to nonylphenol. In particular, styrenated phenol has a special advantage of excellent workability due to improved plasticity when mixed with an epoxy resin because the viscosity is maintained lower than that of nonylphenol. Therefore, the styrenated phenol represented by Chemical Formula 1 is useful as a substitute for nonylphenol and has excellent environmental friendliness as a non-toxic material.

In the present invention, when naming the styrenated phenol represented by Formula 1, the compound having n=1 is abbreviated as'MSP', the compound having n=2 is abbreviated as'DSP', and the compound having n=3 Should be abbreviated as'TSP'.

The styrenated phenol represented by Formula 1 is prepared by an alkylation reaction under conditions of heating phenol and styrene at a temperature of 100°C to 150°C under an acid catalyst. Specifically, when 1 to 1.5 moles of styrene are reacted with 1 mole of phenol, a compound containing all of mono-styrenated (MSP), di-styrenated (DSP), and tri-styrenated (TSP) is produced.

The weight ratio of mono-styrenated, di-styrenated, and tri-styrenated is determined by the reaction molar ratio of phenol and styrene used as reactants. The styrenated phenol suitable for the present invention is preferably adjusted so that the content of MSP is 80 to 95% by weight, preferably 80 to 90% by weight.

The higher the content of mono-styrenated, the lower the viscosity, so when mixed with an epoxy resin, plasticity is imparted to improve workability.Therefore, the content of MSP is preferably 80% by weight or more. Value) is 260 to 270, and it is maintained similarly to the existing nonylphenol (240 to 250) to promote the curing reaction, so the content of mono styrenated is preferably 95% by weight or less.

At this time, the additive for the epoxy coating composition is styrenated phenol 50 to 80% by weight, vegetable oils containing 5 to 40% by weight of epoxizied soybean oil and 5 to 40% by weight of castor oil. It is desirable. More preferably, 55 to 75% by weight of styrenated phenol, and the vegetable oil includes 10 to 35% by weight of epoxizied soybean oil and 5 to 30% by weight of castor oil.

In addition, the additive for the epoxy coating composition according to the present invention may additionally include hydroxyl amine, and when the hydroxyl amine is added, it provides an effect of preventing discoloration of the epoxy coating composition.

At this time, the content of the hydroxyl amine is preferably 0.1 to 2.0% by weight based on the total weight of the additive for the epoxy coating composition. If the content of the hydroxylamine is less than 0.1% by weight, it may be difficult to obtain the required discoloration prevention property, and if it exceeds 2.0% by weight, the hydroxylamine not bound to the styrenated phenol remains, resulting in reaction efficiency and storage stability. It can be degraded.

In one embodiment, the hydroxylamine is monomethylhydroxylamine, dimethylhydroxylamine, monoethylhydroxylamine, diethylhydroxylamine, monopropylhydroxylamine, dipropylhydroxylamine, monobutylhydro It may be one or more selected from the group consisting of hydroxylamine, dibutylhydroxylamine, isopropylhydroxylamine, and diisopropylhydroxylamine.

According to another aspect of the present invention, there is provided an epoxy coating composition comprising the additive for the epoxy coating composition.

The additive for the epoxy coating composition according to the present invention is used as a non-reactive diluent for the epoxy resin main part, and not only improves the plasticity and fluidity of the epoxy resin main part, but also increases the pot life to improve the workability of the epoxy coating composition. do.

At this time, the additive for the epoxy paint composition may be 5 to 10% by weight based on the total weight of the epoxy paint composition, and if the content of the additive for the epoxy paint composition is less than 5% by weight, plasticity is imparted and diluted to the epoxy paint composition. The effect may be weak and workability and impact resistance may be lowered, and if it exceeds 10% by weight, the strength and hardness of the epoxy resin characteristics may be lowered.

Hereinafter, specific embodiments of the present invention are presented. However, the examples described below are only for illustrating or explaining the present invention in detail, and the present invention is not limited thereto.

material

As for the styrenated phenol, styrenated phenol consisting of 82.7% MSP (n = 1), 16.4% DSP (n = 2) and 0.5% TSP (n = 3) and others was purchased from SANKO and used.

In addition, nonylphenol was purchased and used from Sigma-Aldrich, epoxidized soybean oil from Chemfine International, and castor oil from CASTOR GIRNAR INDUSTRIES.

Example And Comparative example

An epoxy coating composition including an epoxy resin and an additive for a coating composition was prepared according to the ratio in Table 1, and its physical properties were measured by the method of the following Experimental Examples, and are shown in Table 1.

The epoxy coating composition was prepared by mixing and stirring the main part and the curing agent part at a weight ratio of 6:1. The main part is a non-reactive epoxy liquid resin modified with bisphenol A type epoxy, a non-reactive diluent, plasticizer and paint additive, and antifoaming agent are added, and the curing agent part is a mixture of a modified alicyclic amine resin, an aliphatic amine resin, a drying accelerator, and a paint additive. . The product name (Epideck 3000) of Jogwang Paint was used as the main part of the paint, and 20 parts by weight of the modified alicyclic amine resin (100% solid content, AHEW: 100-120 g/eq, Kukdo Chemical, KH-816) as the hardener part , Aliphatic amine resin (100% solid content, AHEW: 55-65 g/eq, HUNTSMAN product, D-230) 58 parts by weight, drying accelerator (AIR PRODUCTS, ANCAMINE K-54) 8 parts by weight, non-reactive diluent (Benzyl Alcohol) 2 parts by weight and 12 parts by weight of the additives prepared in Examples and Comparative Examples (solid content 100%, NH Chemicals, SPESCAST 631) as a paint additive were mixed and used as a curing agent.

Experimental example 1: viscosity

Mix the paint well, put about 2/3 of it in the test cup, and leave it for about 1 hour to remove air bubbles. After fixing the sample at 25°C, measure the viscosity using a paddle-type stomer viscometer (KU viscometer) with a rotating shaft.

Experimental Example 2: Specific gravity

After mixing the paint well, let it stand for about 1 hour, remove air bubbles, fix the sample at 25℃, fill the 100CC specific gravity cup with the paint, and measure the specific gravity.

Experimental Example 3: Color change

After preparing the curing agent part, store it in an oven at 60° C. for 7 days and check for discoloration.

Experimental Example 4: Hardness of coating film

A coating composition is coated 3mm on a steel panel with a thickness of 3mm or more, and the hardness is measured using Shore D Type the next day and after 7 days have elapsed.

Experimental Example 5: Chemical resistance

Paint the paint composition 3mm on the release fingerboard (after complete drying), and immerse the coated release fingerboard in each 5% sulfuric acid, hydrochloric acid, nitric acid, acetic acid, NaOH solution, and conduct semi-deposition tests on the 1st and 7th days. Observe the change in gloss and the presence of other coating defects.

Experimental Example 6: Solvent Resistance

Paint the paint composition 3mm on the release fingerboard (after complete drying), and conduct semi-deposition tests on the 1st and 7th days to observe color, gloss change, and other defects in the coating film.

Experimental Example 7: Water resistance

Paint the paint composition 3mm on the release fingerboard (after complete drying), and conduct semi-deposition tests on the 1st and 7th days to observe color, gloss change, and other defects in the coating film.

Experimental Example 8: Wear resistance

Paint 1mm of the paint composition on the balmlight (after complete drying) and test using a TABER ABRASION tester.

NO. Using the ABRASION WHEEL of CS-10 and applying a load of 1000g, test 1000 rotations to measure the loss of the coating film.

Experimental Example 9: Impact resistance

After coating 3mm of the paint composition on the release paper plate (after complete drying), use it as a DuPont type impact tester, but after applying the impact of each drop height and weight of the weight, observe whether the coating film is damaged or cracked.

Experimental Example 10: Migratory resistance

After coating 3mm using a sawtooth on a balmlight, and after complete drying, observe the surface of the coating film to check for migration resistance.

Experimental Example 11: Workability

3mm coating is applied to the balmlight using a sawtooth, and the mixability and mixed viscosity of the main and hardener parts, ease of work, gloss, leveling, defoaming, gloss, and other appearances of the coating film are observed.

Experimental Example 12: Resistance to yellowing

A coating composition of 3 mm is coated on a steel panel having a thickness of 3 mm or more, and the yellowing property is visually observed by exposure to the outside (5 days).

Experimental Example 13: Pot life

After filling the tin can with about 75% (volume%) of paint, measure the elapsed time and temperature until the paint's temperature rises to its maximum in the state of insulation with a styrofoam box.

Experimental Example 14: Adhesion

After coating 3mm of paint on a concrete plate (provided by Korea Testing and Research Institute) (after complete drying), conduct 3 times with an adhesion tester (elcometer, Model 108) to check numerical measurement and adhesion to concrete.

[Table 1]

(NP: nonylphenol, S: styrenated phenol, E: epoxidized soybean oil, C: castor oil)

Looking at the results of the comparative physical property test of the paint additives in Table 1, Example 1 shows that when compared to the coating composition (Comparative Example 2) to which nonylphenol was added, the other physical properties were comparable and the pot life was a little longer. Was found to be excellent in

When the amount of styrenated phenol was 50% or more, it was confirmed that the same degree of hardness compared to nonylphenol was observed, and the ratio of styrenated phenol, epoxidized soybean oil, and castor oil was added to 1/1/1 to adjust the scope of the present application. It was confirmed that the hardness of the coating composition deviated was considerably lower than that of Comparative Example 2 in which only nonylphenol was added, and the physical properties of the coating composition were lowered. In addition, it was confirmed that the additive according to the present invention was superior to Comparative Example 3 in which only styrenated phenol was used in hardness and pot life.

Examples 1 and 2 are additives of paint compositions, although they show almost the same physical properties, but the unit cost of epoxidized soybean oil is lower than that of castor oil. It was found that the additive for a paint composition (Example 1) added at a ratio of 6/3/1 was the most useful as a material replacing the existing nonylphenol as an additive for a paint composition.

In Table 2 below, the viscosity and specific gravity of the coating composition to which the additives of Example 1 and Comparative Example 2 are added were measured at 25° C. and the results are shown.

The viscosity of the curing agent was expressed as time (seconds) using Ford cup (F#4, 25°C, KSM5000-2123).

[Table 2]

Looking at the results of Table 2, it can be seen that when Example 1 of the present invention is used, the viscosity and specific gravity are comparable to those of Comparative Example 2 using nonylphenol.

Various experiments were conducted to confirm the substitution of nonylphenol as an existing additive of the present invention, and the results are shown in Table 3.

[Table 3]

Looking at the comparative physical property test results of the additives for the coating composition in Table 3, it was possible to obtain the same results as nonylphenol in all of the coating hardness, solvent resistance, and water resistance.

In addition, the coating composition according to Example 1 has a slightly longer pot life than the composition to which the conventional additive (nonylphenol) was added (Comparative Example 2), so it is excellent in workability, and it is also excellent in defoaming properties, so that a better appearance can be obtained.

In addition, in terms of chemical resistance, adhesion strength, and yellowing resistance, the coating composition according to Example 1 obtained comparable physical property results compared to the composition of Comparative Example 1.

Therefore, it was confirmed that the additive according to the present invention can be used in place of the existing nonylphenol.

One embodiment of the present invention described above should not be construed as limiting the technical spirit of the present invention. The protection scope of the present invention is limited only by the matters described in the claims, and those of ordinary skill in the technical field of the present invention can improve and change the technical idea of the present invention in various forms. Therefore, such improvements and changes will fall within the scope of the present invention as long as it is apparent to those of ordinary skill in the art.

Claims (10)

In the additive for an epoxy paint composition for increasing the pot life of the epoxy paint,
Epoxy paint comprising 50 to 80% by weight of styrenated phenol represented by the following formula (1) and 20 to 50% by weight of an oil component including epoxizied soybean oil and castor oil Additives for the composition.
[Formula 1]

(In Formula 1, n is 1, 2, or 3) The method of claim 1,
The additive for the epoxy coating composition is characterized in that it comprises 50 to 80% by weight of styrenated phenol, 5 to 40% by weight of epoxied soybean oil and 5 to 40% by weight of castor oil. An additive for an epoxy coating composition. The method of claim 1,
The styrenated phenol is an additive for an epoxy coating composition, characterized in that the content of mono-styrenated phenol (n=1) is 80 to 95% by weight of the total styrenated phenol. The method of claim 1,
The additive for the epoxy coating composition additionally includes a hydroxyl amine, and the content of the hydroxyl amine is 0.1 to 2.0% by weight based on the total weight of the additive for the epoxy coating composition. The method of claim 4,
The hydroxyl amine is monomethylhydroxylamine, dimethylhydroxylamine, monoethylhydroxylamine, diethylhydroxylamine, monopropylhydroxylamine, dipropylhydroxylamine, monobutylhydroxylamine, dibutylhydro Additive for epoxy coating composition, characterized in that at least one selected from the group consisting of hydroxylamine, isopropylhydroxylamine and diisopropylhydroxylamine. In the epoxy coating composition for increasing the pot life of the epoxy coating,
The main part including an epoxy resin and 50 to 80% by weight of styrenated phenol represented by the following formula (1), and 20 to 50% by weight of an oil component including epoxizied soybean oil and castor oil Epoxy coating composition comprising an additive for an epoxy coating composition, characterized in that it comprises.
[Formula 1]

(In Formula 1, n is 1, 2, or 3) The method of claim 6,
The additive for the epoxy coating composition is characterized in that it comprises 50 to 80% by weight of styrenated phenol, 5 to 40% by weight of epoxied soybean oil and 5 to 40% by weight of castor oil. Epoxy coating composition. The method of claim 6,
The styrenated phenol is an epoxy coating composition comprising 80 to 95% by weight of mono-styrenated phenol (n=1). The method of claim 6,
The epoxy coating composition is an epoxy coating composition, characterized in that it further comprises a hydroxyl amine. The method of claim 6,
The additive for the epoxy coating composition is an epoxy coating composition, characterized in that 5 to 10% by weight based on the total weight of the epoxy coating composition.

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