KR102189124B1 - Composite epoxy coating composition - Google Patents

Abstract

The present invention relates to an organic-inorganic composite epoxy coating composition through which it provides a composition that can be used for a flooring material having weather resistance capable of outdoor painting.
The organic-inorganic composite epoxy coating composition according to the present invention comprises an organic-inorganic composite epoxy coating composition according to the present invention comprising 40 to 60 parts by weight of an organic-inorganic composite resin; 20 to 30 parts by weight of a hydrogenated bisphenol A type epoxy resin; 10 to 20 parts by weight of a bisphenol A epoxy resin; 5 to 10 parts by weight of a flame retardant; 2 to 5 parts by weight of a dodecylphenol plasticizer; 0.5 to 1 part by weight of an adhesion promoter; And 0.5 to 1 part by weight of an antifoaming agent; And a curing agent; and has the following effects.
First, since a coating composition for flooring with excellent chemical resistance, solvent resistance, water resistance, durability, abrasion resistance, and yellowing resistance is prepared, there is no skid mark on the floor material using the same, so that the cost of various repair and repainting can be reduced.
Second, if the organic-inorganic composite epoxy coating composition is used as a flooring material, the scope of application of the construction site is extended to the outdoors.
Third, it is used as a flooring material that satisfies the grade of non-combustible material, reducing the risk of fire.

Description

Organic-inorganic composite epoxy coating composition {Composite epoxy coating composition}

The present invention relates to an organic-inorganic composite epoxy coating composition.

In general, the epoxy coating composition used for flooring is excellent in high hardness, durability, abrasion resistance, and processability by reacting with polyamine or polyamide in bisphenol A type epoxy resin, and has great adhesion to the surface of the conductor, so that it has excellent mechanical and chemical properties. It is widely used as an epoxy flooring system.

In this regard, the prior art prepared to manufacture a solvent-free epoxy coating composition used in flooring construction ("Paint composition for solvent-free epoxy flooring and a floor construction method using the same) of No. 10-0873048) and a hybrid flooring coating composition for preparing There is a prior art (Registration Patent No. 10-1625410 "Hybrid flooring coating composition excellent in chemical resistance and scratch resistance").

However, the epoxy resin has a benzene ring due to its molecular structure, so the double bond of carbon in the benzene ring is easily broken by ultraviolet rays, and yellowing occurs easily as the molecular structure is deformed. Due to the modification of the molecular structure, the aging of the paint is accelerated, resulting in a problem of discoloration or deterioration of the physical properties of the epoxy, and thus the extremely limited problem of outdoor painting has not been solved.

As an improved prior art, formamidine-based and polyfunctional epoxy resins are used to improve the yellowing phenomenon and hardness, but the problem has not been solved continuously for a long time.

Accordingly, it is required to develop an epoxy flooring material that is more resistant to UV rays than existing epoxy paints and has excellent physical properties.

The organic-inorganic composite epoxy coating composition according to the present invention provides a composition that can be used for a flooring material having weather resistance capable of outdoor painting.

The organic-inorganic composite epoxy coating composition according to the present invention comprises 40 to 60 parts by weight of an organic-inorganic composite resin; 20 to 30 parts by weight of a hydrogenated bisphenol A type epoxy resin; 10 to 20 parts by weight of a bisphenol A epoxy resin; 5 to 10 parts by weight of a flame retardant; 2 to 5 parts by weight of a dodecylphenol plasticizer; 0.5 to 1 part by weight of an adhesion promoter; And 0.5 to 1 part by weight of an antifoaming agent; And a curing agent;

The organic-inorganic composite resin includes an organic resin and an inorganic resin, and the inorganic resin is obtained by partially hydrolyzing at least one of colloidal alumina or colloidal silica using a metal alkoxide so that the alkoxy group remains, or It is obtained by partial hydrolysis of an alkoxide, and the organic resin may be obtained by reacting an epoxy resin and an alkoxysilane by heating, or by adding a polyol to a reaction product of an epoxy resin and an alkoxysilane.

The hydrogenated bisphenol A type epoxy resin has an epoxy equivalent of 260 g/eq, the modified alicyclic amine curing agent has an active hydrogen equivalent of 100 to 120 g/eq, and the aliphatic amine curing agent has an activity of 55 to 65 g/eq It has a hydrogen equivalent weight, characterized in that the resin and the curing agent are blended so that the epoxy equivalent of the hydrogenated bisphenol A epoxy resin is the same as the sum of the active hydrogen equivalents of the modified alicyclic amine curing agent and the aliphatic amine curing agent. I can.

The organic-inorganic composite epoxy coating composition according to the present invention may be formulated so that the weight ratio of the main material and the curing agent is 2.5:1 to 3.5:1.

The curing agent according to the present invention is SiO ₂ SOL-based reactive resin 45 to 65 parts by weight; 15 to 30 parts by weight of an aliphatic amine curing agent; 10 to 20 parts by weight of a modified alicyclic amine curing agent; And 1 to 3 parts by weight of a drying accelerator.

The organic-inorganic composite epoxy coating composition according to the present invention has the following effects.

First, since a coating composition for flooring with excellent chemical resistance, solvent resistance, water resistance, durability, abrasion resistance, and yellowing resistance is prepared, there is no skid mark on the floor material using the same, so that the cost of various repairs and repainting can be reduced.

Second, if the organic-inorganic composite epoxy coating composition is used as a flooring material, the scope of application of the construction site is extended to the outdoors.

Third, it is used as a flooring material that satisfies the grade of non-combustible material, reducing the risk of fire.

A preferred embodiment of the present invention will be described in more detail, but technical parts that are already well known will be omitted or compressed for conciseness of description.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.

1. Description of the organic-inorganic composite epoxy coating composition

The organic-inorganic composite epoxy coating composition according to the present invention includes a main material and a curing agent.

First, the subjects include organic-inorganic composite resins, hydrogenated bisphenol A type epoxy resins, bisphenol A type epoxy resins, dodecylphenol plasticizers, adhesion promoters, and antifoaming agents.

The curing agent includes a reactive resin, an aliphatic amine curing agent, a modified alicyclic amine curing agent, and a drying accelerator.

Organic-inorganic composite resin is excellent in abrasion resistance, high hardness, yellowing resistance (discoloration resistance), scratch resistance, and stain resistance.

In particular, the organic-inorganic composite resin uses EP175N4PTA manufactured by Hankook Firetech, and is preferably prepared in 40 to 60 parts by weight.

This is because if the organic-inorganic composite resin is provided in less than 40 parts by weight, relative hardness and abrasion resistance deteriorate, and if it exceeds 60 parts by weight, the hardness becomes too high, resulting in a problem that the intermediate adhesion is inferior during repainting.

The organic-inorganic composite resin preferably includes an organic resin and an inorganic resin, and the inorganic resin partially contains at least one of colloidal alumina or colloidal silica using metal alkoxide so that alkoxy groups remain. It is obtained by hydrolysis reaction or obtained by partial hydrolysis of a metal alkoxide, and the organic resin is obtained by reacting by raising the temperature of an epoxy resin and an alkoxysilane, or by adding a polyol to the reaction product of an epoxy resin and an alkoxysilane.

Bisphenol A type epoxy resin is a diglycidyl ether type epoxy resin produced by a condensation reaction of diphenylomethane and epichlorohydrin.

These bisphenol A-type resins are widely used, have excellent compatibility with other resins, and have excellent mechanical and chemical resistance, impact resistance, and adhesion.

In addition, hydrogenated bisphenol A type epoxy resin is a color-resistant epoxy resin produced by hydrogenation reaction under high temperature and high pressure to remove the benzene ring in the molecular structure. In other words, it is excellent in yellowing resistance (discoloration resistance) because there is no benzene ring having a double bond and no yellowing phenomenon occurs due to ultraviolet rays.

The bisphenol A type epoxy resin of the present invention uses an epoxy resin having an epoxy equivalent of 184 to 190 g/eq, and the hydrogenated bisphenol A type epoxy resin uses an epoxy resin having an epoxy equivalent of 260 to 290 g/eq.

Hydrogenated bisphenol A type epoxy resin is used in 20 to 30 parts by weight, and if it is less than 20 parts by weight, there is a problem that the yellowing resistance is deteriorated, and if it exceeds 30 parts by weight, drying is slow compared to the bisphenol A type epoxy liquid resin. There is a problem that is delayed.

The plasticizer should use 2 to 5 parts by weight of dodecyl phenol. At this time, if it is less than 2 parts by weight, the composition of the present invention may have poor impact resistance, and if it exceeds 5 parts by weight, the film hardness decreases, and there is a problem that the surface of the coating film rises after drying the coating film, resulting in a turbidity phenomenon in the coating film. to be.

The antifoaming agent is a polysiloxane-type antifoaming agent that is incompatible with an epoxy resin, and is preferably used through a combination of at least one or two or more of BYK-052, BYK-66N, EFKA-2022, and EFKA-2023, but is not limited thereto. It can be selected within the range of known antifoaming agents.

The adhesion promoter is an epoxy functional silane type and is preferably provided in an amount of 0.5 to 1 parts by weight, and if it is less than 0.5 parts by weight, the interlayer adhesion strength decreases during repainting, and if it exceeds 1 part by weight, the problem of poor impact resistance occurs. Because it does.

The flame retardant is a transparent phosphorus-based liquid flame retardant (DISFLAMOLL DPK (chempia)) is preferably provided in 5 to 10 parts by weight, because if it is less than 5 parts by weight, the flame retardancy decreases, and if it exceeds 10 parts by weight, the hardness decreases. to be.

Next, a curing agent for optimizing the physical properties of the organic-inorganic composite epoxy coating composition of the present invention by mixing with the above-described subject will be described.

The curing agent suitable for the organic-inorganic composite resin is SiO ₂ SOL-based reactive resin and is preferably provided in an amount of 45 to 65 parts by weight. This is because if the reactive resin is less than 45 parts by weight, drying delay and hardness decrease, and if it exceeds 65 parts by weight, the hardness becomes too high, resulting in a problem that the interlayer adhesion decreases during repainting.

Suitable curing agents for the epoxy resin include aliphatic amines, aromatic amines, amides, anhydrides, polymercaptans, polysulfides, and the like, and specifically modified type curing agents.

Here, the modified type curing agent is aliphatic amine base, EDA (Ethylene Diamine), DETA (Diethylen Triamine), TETA (Triethylene Tetramine), TEPA (Tetraethylene Pentamine), and alicyclic amine base (Aliphtic Ring Amine Base) It refers to a curing agent that has improved effects such as improvement of workability, reduction of toxicity, control of pot life, and adhesion by denaturing MDA (Methylene Dianiline) and IPDA (Isophorone Diamine).

The modified alicyclic amine-based curing agent may be KH-812, KH-815, KH-816, KH-818B, KH-819, etc., and is preferably provided in an amount of 10 to 20 parts by weight.

This is because if the modified alicyclic amine-based curing agent is less than 10 parts by weight, yellowing resistance and initial hardness may be deteriorated, and if it exceeds 20 parts by weight, the pot life may be shortened, resulting in a problem in workability.

In addition, the modified alicyclic amine-based curing agent in the curing agent is preferably provided to have an active hydrogen equivalent of 100 to 120 g/eq.

The aliphatic amine-based curing agent D-230 (HUNTSMAN) (Polyoxypropylenediamine), Kukdo Chemical KH-500, KH-240, KH-505, KH-602, etc. may be used, and it is preferably provided in 15 to 30 parts by weight.

This is because if the aliphatic amine-based curing agent is less than 20 parts by weight, a problem of lowering the hardness after drying may occur, and if it exceeds 30 parts by weight, the drying time is delayed.

In addition, the aliphatic amine-based curing agent in the curing agent is preferably provided to have an active hydrogen equivalent of 55 to 65 g/eq.

For the drying accelerator, it is preferable to use an aliphatic type drying accelerator that does not have a phenol group for yellowing resistance. In other words, when using 2,4,6-Tris(dimethylaminomethyl)phenol, DPM-30, K-54, etc., which have both phenol and tertiary amine groups to promote the reaction between epoxy and amine, yellowing occurs. It is preferable to use aliphatic type triethanolamine (ACCELERATOR 399 (HUNTSMAN)) that does not have a group.

Here, the drying accelerator is provided in an amount of 1 to 5 parts by weight. This is because if the drying accelerator is less than 1 part by weight, initial drying and lowering of the initial hardness occur, and if it exceeds 5 parts by weight, the hardness may decrease over time.

That is, the organic-inorganic composite epoxy coating composition having excellent weather resistance (yellowing resistance) and hardness of the present invention is mixed so that the ratio of the epoxy equivalent of the main agent and the active hydrogen equivalent of the curing agent is 1:1. Specifically, hydrogenated bisphenol A epoxy resin having an epoxy equivalent of 260 to 290 g/eq to improve hardness, durability and chemical resistance, flame retardancy, and weather resistance than the existing epoxy coating film is modified with an active hydrogen equivalent of 100 to 120 g/eq. In a blending ratio in which the content of the composition in the main material and the curing agent is adjusted so that the sum of the active hydrogen equivalents of the curing agent including the alicyclic amine curing agent and the aliphatic amine curing agent having an active hydrogen equivalent of 55 to 65 g/eq and the epoxy resin equivalent are the same. It is preferred to be blended. The blending ratio described above is a weight ratio, and the ratio of the main material to the hardener may be about 3 to 1.

2. Description of coating properties of organic-inorganic composite epoxy coating composition

For each coating film formed by preparing an organic-inorganic composite epoxy coating composition having excellent weather resistance and hardness according to the present invention in various examples, its physical properties were measured through various experimental methods as follows, which are obvious to those skilled in the art. The following experimental methods were used for the purpose of defining properties by means.

The examples described below are tested by preparing the components constituting the organic-inorganic composite epoxy coating composition of the present invention with excellent weather resistance and hardness at various mixing ratios, solving the problem of the coating film caused by the existing epoxy paint, and new high hardness, flame retardancy, and weather resistance. This is to verify the blending ratio that can provide.

Hereinafter, the present invention will be described in more detail through examples. However, these examples are only intended to aid understanding of the present invention, and the scope of the present invention is not limited to these examples in any sense.

(1) Outdoor exposure test: Using an applicator, apply each organic-inorganic composite epoxy coating composition to a 5mm-thick glass plate of 15cm in width and 30cm in length with a dry film thickness of 50µm, and then dried at room temperature for 3 days and exposed to UV rays outdoors. After 7, 14, 21, 30, 40, 50, and 60 days after exposure to, the △Y value (a value representing the difference in the degree of yellowing changed based on the initial degree of yellowing) was determined by ASTME313. Measured.

(2) Chemical resistance

Using an applicator, each organic-inorganic composite epoxy coating composition was applied to a 5mm-thick glass plate with a width of 15cm and a length of 30cm with a dry film thickness of 50㎛ and dried at 20°C for 5 days. A solution of 30% sulfuric acid, 20% hydrochloric acid, 30% nitric acid, 30% phosphoric acid, and 30% NaOH was applied to the dried coating film, and the appearance of the specimen was observed after 48 hours and evaluated based on the criteria.

Evaluation criteria, O: No abnormality in the coating film, X: Discoloration and defects such as parts, peeling, blisters, etc.

(3) Pencil hardness: ASTM D 3363

(4) Abrasion resistance (CS-17, 1,000g, 1,000 times): ASTM D 4060

(5) Pollution resistance-Yuseong Magic: LH specification 45510

After contaminating the organic/inorganic composite epoxy coating composition with oil-based magic, wipe it off with alcohol to check if contamination remains.

(6) Flame retardancy: measured according to EN45545

Formulations constituting Examples 1 to 3 and Comparative Examples of the organic-inorganic composite epoxy coating composition according to the present invention are shown in Table 1 below.

Example 1 Example 2 Example 3 Comparative example Subject part Organic-inorganic composite resin 55 55 55 - KST-1701 25 35 - - YD-128 10 - 35 78 DPK 6 6 6 - Dodecylphenol 3 3 3 15 Adhesion enhancer 0.5 0.5 0.5 - Antifoam 0.5 0.5 0.5 One Benzyl alcohol - - - 6 Hardener part SiO ₂ SOL-based reactive resin 60 60 60 - Aliphatic amine
(Jeffamine D-230) 25 25 25 47 Modified alicyclic amine
(KH-818B) 12 12 12 36 Drying accelerator
(A-399) 3 3 3 - Dodecylphenol - - - 17 -Organic/inorganic composite resin: EP175N4PTA (Firetech Korea)
-Hydrogenated bisphenol A type epoxy resin: KST-1701 (Kukdo Chemical)
-Bisphenol A type epoxy resin: YD-128 (Kukdo Chemical)
Flame retardant (liquid phosphorus flame retardant): DISFLAMOLL DPK (chempia)
Plasticizer (phenolic): Dodecyl phenol (SI Group)
Epoxy functional silanes: silquest A-187 (Momentive)
Defoamer (polysiloxane type): BYK-066N (BYK)
SiO ₂ SOL-based reactive resin: EP175N4PTB (Firetech Korea)
Modified alicyclic amine resin: KH-818B (Kukdo Chemical)
Aliphatic amine resin: D-230 (HUNTSMAN)
Drying accelerator: Triethanolamine (ACCELERATOR 399 (HUNTSMAN))

Examples of each of the organic-inorganic composite epoxy compositions prepared by mixing the subject and curing agent of Examples 1 to 3 and Comparative Examples prepared in the formulation form as shown in Table 1 so that the ratio of the epoxy equivalent to the active hydrogen equivalent is 1:1. A predetermined coating film was formed for each, and the physical properties of each coating film were measured by various experimental methods described above, and the results are shown in Table 2 below.

Experiment item Example 1 Example 2 Example 3 Comparative example Yellowing resistance
Experiment
(Outdoor exposure) △Y value Day 7 0.50 0.48 0.82 11.90 Day 14 0.55 0.51 1.21 12.83 Day 21 0.59 0.55 1.40 17.51 Day 30 0.61 0.59 1.72 19.55 Day 40 0.72 0.68 2.15 31.63 Day 50 0.79 0.73 2.84 - Day 60 0.83 0.78 3.11 - Chemical resistance 30% sulfuric acid O X O X Hydrochloric acid 20% O O O X 30% nitric acid O X O X 30% phosphoric acid O O O X NaOH 30% O O O O Pencil hardness (scratch resistance) 3H 2H 3H H Wear resistance 0.028g 0.051g 0.026g 0.087g Flame retardant Great Great usually none Pollution resistance-Yuseong magic Removed Removed Removed Not removed

As shown in Table 2, in the case of the organic-inorganic composite epoxy coating composition (Example 1) according to the present invention, by increasing the crosslinking density by using an organic-inorganic composite resin and a SiO ₂ SOL-based reactive resin, fouling resistance and scratch resistance (Pencil hardness), chemical resistance, and abrasion resistance could be improved, and using a hydrogenated BPA epoxy resin, a liquid flame retardant and an aliphatic, modified alicyclic amine, it has flame retardancy and excellent yellowing resistance, and Example 1 is the organic-inorganic composite epoxy nonflammable of the present invention. It was found to be most appropriate among the blending ratios of the floor coating composition.

In other words, as can be seen from the experimental results in Table 2, not only excellent physical properties such as chemical resistance, solvent resistance, abrasion resistance, scratch resistance, etc., which are the characteristics of the prior art, but also flame retardancy and yellowing resistance are excellent. ) It can be seen that the organic-inorganic composite epoxy coating composition that can be used as a flooring material for general buildings without restrictions even in outdoor and indoor UV-exposed spaces where exposure is a concern, is prepared as in Example 1, thereby satisfying the optimum required physical properties. .

As described above, the specific description of the present invention has been made by examples, but since the above-described embodiments have been only described with reference to preferred examples of the present invention, it is understood that the present invention is limited to the above embodiments. It is not, and the scope of the present invention should be understood as the claims and equivalent concepts to be described later.

Claims (5)

40 to 60 parts by weight of organic-inorganic composite resin; 20 to 30 parts by weight of a hydrogenated bisphenol A type epoxy resin; 10 to 20 parts by weight of a bisphenol A epoxy resin; 5 to 10 parts by weight of a flame retardant; 2 to 5 parts by weight of a dodecylphenol plasticizer; 0.5 to 1 part by weight of an adhesion promoter; And 0.5 to 1 part by weight of an antifoaming agent; And a curing agent;
Including,
The curing agent
45 to 65 parts by weight of a SiO ₂ SOL-based reactive resin; 15 to 30 parts by weight of an aliphatic amine curing agent; 10 to 20 parts by weight of a modified alicyclic amine curing agent; And 1 to 3 parts by weight of an aliphatic amine-based drying accelerator; characterized in that it comprises
Organic-inorganic composite epoxy coating composition.
The method of claim 1,
The organic-inorganic composite resin
Contains organic and inorganic resins,
The inorganic resin is
Obtained by partial hydrolysis reaction of at least one of colloidal alumina or colloidal silica using metal alkoxide so that alkoxy groups remain, or obtained by partial hydrolysis of metal alkoxide,
The organic resin,
Characterized in that it is obtained by reacting an epoxy resin and an alkoxysilane by raising the temperature, or by adding a polyol to a reaction product of an epoxy resin and an alkoxysilane.
Organic-inorganic composite epoxy coating composition. The method of claim 1,
The hydrogenated bisphenol A type epoxy resin has an epoxy equivalent of 260 g/eq,
The modified alicyclic amine-based curing agent has an active hydrogen equivalent of 100 to 120 g/eq,
The aliphatic amine-based curing agent has an active hydrogen equivalent of 55 to 65 g/eq,
It characterized in that the epoxy equivalent of the hydrogenated bisphenol A type epoxy resin is blended in a blending ratio of the main agent and the curing agent determined to be equal to the sum of the active hydrogen equivalents of the modified alicyclic amine curing agent and the aliphatic amine curing agent
Organic-inorganic composite epoxy coating composition.
The method of claim 1,
Characterized in that the weight ratio of the main body and the curing agent is 2.5:1 to 3.5:1
Organic-inorganic composite epoxy coating composition.
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