KR102042801B1 - Solvent-free epoxy coating composition - Google Patents

Abstract

The present invention relates to a solvent-free epoxy coating composition, and provides a coating composition having little content of volatile solvents causing a decrease in working environment and air pollution, having good curability at low temperatures, and excellent coating appearance and overall physical properties after curing. .

Description

Solvent-free epoxy coating composition {SOLVENT-FREE EPOXY COATING COMPOSITION}

The present invention relates to a solvent-free epoxy floor coating composition excellent in low temperature curability.

Epoxy resins not only have excellent compressive strength, hardness and processability, but also do not generate volatiles or shrinkage in volume during curing, and have a large adhesion to the surface. Accordingly, it can be widely used in various applications in combination with suitable curing agents. In particular, the epoxy resin has excellent adhesion to the concrete body, less shrinkage than other types of paint to protect the concrete, as well as mechanical and chemical resistance is suitable for use in high-performance coating composition.

There are two types of epoxy flooring systems that are currently commercialized, which are thin film type (dry film thickness: about 300 µm) and double solvent coating, using solvent-based epoxy paint and solvent-free epoxy. There is a thick film type (dry coating thickness: 1,000 µm or more) that paints the solvent-based top coat after coating the paint.

In the case of the solvent type (thin film type) epoxy paint, there is a problem that it is harmful to environmental pollution and worker's health as a large amount of volatile solvent is used to obtain a good coating film such as roller workability and leveling. In addition, in order to form a coating film of at least 200 µm in order to have a solvent-type (thin film) epoxy coating function as a flooring material, a solvent-type coating material having a low solids content ratio should be coated at least twice. In general, one-time drying at room temperature is required for repainting after one painting, which leads to an increase in the working period and the man-hour of at least two days.

In contrast, the conventional thick film type epoxy flooring system is a type in which a solvent-free top coat is applied once after coating a solvent-free epoxy coating composition with a thick film (dry film thickness: 1,000 μm or more) using RAKE and TROWELL. . Such thick film epoxy flooring systems are environmentally friendly because they contain little volatile solvent. However, since the thickness of the coating film is thickly about 1.0-3.0 mm, when the coating at a low temperature of 5 ℃ or less, the curing speed is slow, the coating film appearance and physical properties are greatly reduced, there is a limit to use at low temperatures such as winter.

Patent Publication No. 10-2004-0074196 Patent Publication No. 10-2013-0024259

The present invention improves workability and environmental friendliness by using a solvent-free epoxy resin having a solid content of 96% or more, and at least one amine-based curing agent and a curing accelerator having excellent low temperature curing properties are mixed with the reactive diluent and non-reactive. By adjusting the mixing ratio of the diluent to a specific compounding ratio, to improve the workability during coating to a thickness of 1,000-3,000 ㎛ at a low temperature of 5-10 ℃, to provide a solvent-free epoxy flooring coating composition excellent in appearance and overall coating properties.

The present invention is 20-40% by weight of solvent-free epoxy resin, sieving pigment 45-65% by weight, reactive diluent 0.1-5% by weight, non-reactive diluent 2-10% by weight, color pigment 1-5% by weight and additives 1-8 A main portion containing 20% by weight and a curing agent portion containing 20-40% by weight of an aliphatic amine resin, 10-20% by weight of an aromatic amine resin, 10-30% by weight of a curing accelerator and 30-50% by weight of a non-reactive diluent, The mixing ratio (weight ratio) of the main part and the hardener part may be 70-80: 20-30 based on 100 parts by weight of the total composition of the main part and the hardener part.

The coating composition for a solvent-free epoxy flooring material of the present invention is excellent in low-temperature curing properties, and may exhibit excellent coating properties, appearance properties and good gloss after curing even when coated with a thick film at low temperatures.

In addition, the coating composition for a solvent-free epoxy flooring material of the present invention can increase the solids content of the coating to ensure excellent coating properties and beautiful appearance characteristics, to reduce the environmental pollution due to volatilization of the solvent and improve the workability, the Ministry of Environment regulation Since both the indoor air quality control law and the special air environment law of the standard agreement can be satisfied, it is possible to minimize the cost of using and managing conventional environmental equipment.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail. However, the present invention is not limited only to the following contents, and each component may be variously modified or optionally mixed as necessary. Therefore, it is to be understood that all changes, equivalents, and substitutes included in the spirit and scope of the present invention are included.

The coating composition for a solventless epoxy flooring material according to the present invention comprises a main portion comprising a solventless epoxy resin and a curing agent portion containing an amine-based curing agent, wherein the main portion and the curing agent portion have a specific ratio (eg, 70-80: 20). -30 weight ratio). Hereinafter, the composition of the low-temperature curing type solventless epoxy flooring coating composition will be described in detail.

<Topic>

In the solventless epoxy flooring coating composition according to the present invention, the main portion includes a solventless epoxy resin, a sieving pigment, a reactive diluent, a nonreactive diluent, a color pigment and an additive.

Solvent free  Epoxy resin

The solvent-free epoxy resin included in the main part of the present invention combines with the amine-based curing agent contained in the curing agent portion to form a coating film, imparts gloss, and serves to secure basic physical properties of the coating film.

As the epoxy resin, a conventional non-solvent type epoxy resin known in the art may be used without limitation, and for example, an epoxy resin having a solid content of at least 96% having little content of a volatile solvent may be used. Non-limiting examples of solvent-free epoxy resins that can be used may be bisphenol-A diglycidyl ether (DGEBA), bisphenol-F, or a mixture thereof. This bisphenol-A diglycidyl ether is a diglycidyl ether of bisphenol A produced by reacting diphenyl called bisphenol-A with epichlorohydrin.

According to one embodiment of the invention, the solvent-free epoxy resin has an epoxy equivalent weight (EEW) of 180-200 g / eq, in another example 182-192 g / eq, the viscosity is 11,000-14,000 cps (25 ℃), Bisphenol-A diglycidyl ether with a solids content of at least 96%.

In the present invention, the content of the solventless epoxy resin is not particularly limited, and may be, for example, 20 to 40% by weight based on the total weight (100% by weight) of the main part. When the content of the solvent-free epoxy resin is less than 20% by weight, the appearance of the coating film is poor, and the coating film properties such as chemical properties are deteriorated.When the content of the solventless epoxy resin exceeds 40% by weight, the pot life is shortened, and the mechanical properties such as workability and coating hardness are reduced. Can be degraded.

Sieving pigment

The extender pigment included in the main part of the present invention serves to fill pores in the coating film, to compensate for hardness and chemical properties, and to adjust gloss. In particular, since the solvent-free epoxy composition of the present invention is applied to flooring applications, it is required to select a pigment having excellent abrasion resistance and hardness in consideration of the abrasion of the coating film, which greatly affects the storage properties and workability of the paint.

The extender pigments may be used without limitation conventional customary pigments known in the art, for example, silica, barite (natural barium sulfate), Blancpix (synthetic barium sulfate), talc, calcium carbonate, calcium carbonate and the like. The above-mentioned components may be used alone or in combination of two or more thereof.

In the present invention, the content of the extender pigment is not particularly limited and may be, for example, 45 to 65% by weight based on the total weight of the main part. If the content of the extender pigment is less than 45% by weight, the mechanical properties of the coating film is lowered, and when the content of the extender pigment exceeds 65% by weight, the physical properties of the coating film and poor workability is caused.

diluent

Diluents included in the subject matter of the present invention overcome the limitations of pigment application due to the high viscosity of solvent-free epoxy resins and serve to control the self-leveling (1,000-3,000 μm) operation to have a viscosity that is possible.

The diluent may be classified into a reactive diluent that participates in the reaction with the curing agent and a non-reactive diluent that does not participate in the reaction but remains in the coating film and affects physical properties. In the present invention, a reactive diluent and a non-reactive diluent are mixed, and the use ratio thereof is adjusted to a specific range.

In the present invention, as the reactive diluent, conventional diluents known in the art having an epoxide group can be used without limitation. For example, monoepoxides such as cresyl glycidyl ether and alkyl glycidyl ether, glycidyl ester, phenyl glycidyl ether, 2-ethylhexyl glycidyl ether and parabutyl butylphenyl glycidyl Diepoxides such as versatic acid such as ether, neopentyl diglycidyl ether, 1,4-butane diglycidyl ether, cyclohexanedimethanol diglycidyl ether, and resorcinol diglycidyl ether have. The above-mentioned components may be used alone or in combination of two or more thereof.

According to one embodiment of the present invention, the reactive diluent has an epoxy equivalent weight (EEW) of 4,000-4,500 g / eq, and in another example 4,100-4,250 g / eq.

The content of the reactive diluent is not particularly limited, and may be, for example, 0.1 to 5% by weight based on the total weight of the main part. If the content of the reactive diluent is less than 0.1% by weight, the workability is poor and the appearance properties of the coating film is lowered. When the content of the reactive diluent is more than 5% by weight, curing is delayed and the hardness of the coating film is lowered.

Non-reactive diluents used in combination with the above-mentioned reactive diluents can employ without limitation conventional customary non-reactive diluents known in the art. For example, dodecyl phenol, styrene phenol, benzyl alcohol or a mixture of two or more thereof.

In the present invention, the content of the non-reactive diluent is not particularly limited, and may be, for example, 2 to 10% by weight based on the total weight of the main part. When the content of the non-reactive diluent is less than 2% by weight, the workability is poor and the appearance property of the coating is lowered, and when it is more than 10% by weight, the mechanical properties of the coating are lowered.

Color Pigment

The color pigments included in the main part of the present invention are included for the purpose of expressing a desired color (colour) in the paint by mixing with an epoxy resin.

The pigment may be used without limitation organic pigments, inorganic pigments, metallic pigments, aluminum paste (Al-paste), pearl, etc. commonly used in the art, these may be used alone or in combination of two or more. . For example, one or a mixture of two or more selected from the group consisting of titanium dioxide, bismuth vanadate, cyanine green, carbon black, iron oxide, iron oxide, navy blue, and cyanine blue can be used.

In the present invention, the content of the color pigment may be 1 to 5% by weight based on the total weight of the main portion. When the content of the color pigment is out of the above range, the color representation of the coating film to which the floor coating composition of the present invention may be applied.

additive

The subject matter constituting the solvent-free epoxy flooring coating composition of the present invention may include conventional additives known in the art, without departing from the inherent properties of the composition.

Non-limiting examples of additives that can be used include dispersants, antifoams, defoamers, leveling agents, weathering additives, desiccants, appearance control agents, sedimentation agents, coupling agents or mixtures of two or more thereof. For example, two or more additives selected from the group consisting of antisettling agents, dispersants, antifoaming agents, defoamers and leveling agents may be used. In the present invention, the content of the additive may be appropriately adjusted within the content range known in the art, for example, may be 1 to 8% by weight based on the total weight of the subject portion.

The anti-settling agent serves to prevent the sedimentation of the materials to form a uniform film, a conventional known in the art can be used without limitation. One example is a clay type anti-settling agent. The content of the anti-settling agent is not particularly limited, and may be, for example, 0.1 to 0.7% by weight. If the content of the anti-settling agent is less than 0.1% by weight level of the coating film is very good, but the storage of the paint is poor, if the content exceeds 0.7% by weight of the coating material is excellent storage stability but may be poor leveling of the coating film.

In the case of epoxy flooring, a defoaming agent and a defoamer may be mixed so that the bubble in a coating film may rise to a surface quickly with bubble removal of the coating film surface. If bubbles inside do not rise and remain in the coating film, poor adhesion to the substrate and / or physical properties may be deteriorated, and even if bubbles inside the film, the flowability of the coating film becomes poor when the coating film is hardened to some extent. As a result, bubble marks may remain on the surface of the coating film. In addition, when various color pigments are used, fluidity is different for each pigment, color separation may occur, and the color before and after curing may be different, or the appearance may be poor due to different colors for each painted part. When the main part contains at least one additive such as the above-described dispersant, antifoaming agent, defoamer, leveling agent, it is possible to improve the occurrence of coating defects such as defoaming defects, crettering and color separation.

The dispersant serves to disperse each material constituting the composition and to prevent re-agglomeration through distance maintenance so as to express uniform physical properties of the coating film. As the dispersant, conventional ones known in the art may be used, and examples thereof include a high molecular weight block copolymer type dispersant.

Antifoaming agent is a mixture of lipophilic and polysiloxane and serves to enhance the appearance of the coating film by suppressing bubbles generated during coating, and conventional antifoaming agents known in the art can be used without limitation. As an example, a polysiloxane type antifoaming agent can be used.

Defoamer is used to prevent and remove the generation of bubbles during painting, and improve the manufacturing process, for example, a non-silicone polymer type defoamer may be used.

The leveling agent is for leveling the composition so that it is coated smoothly and smoothly, thereby improving the appearance properties of the coating film while promoting adhesion in the composition. As the leveling agent, conventional ones known in the art may be used without limitation, and examples thereof include acrylic, silicone, polyester, and amine leveling agents.

<Hardener part>

In the solventless epoxy flooring coating composition according to the present invention, the curing agent portion comprises an amine curing agent, a curing accelerator and a non-reactive diluent.

Amine  Hardener

The amine-based curing agent included in the curing agent of the present invention forms a coating film by combining with the solvent-free epoxy resin included in the main portion, and serves to secure the basic physical properties of the coating film.

As the amine-based curing agent may be used without limitation a conventional amine-based curing agent known in the art. Examples include aliphatic amine bases, aromatic amine bases, or mixtures thereof.

According to one embodiment of the invention, the aliphatic amine resin has an amine value of 400-500 mgKOH / g, a viscosity of 100-1,000 cps (25 ℃), the aromatic amine resin has an amine value of 350-400 mgKOH / g, viscosity May be 500-2,000 cps (25 ° C.). Here, the use ratio of the aliphatic amine resin and the aromatic amine resin may be, for example, 1-3: 1 by weight, and in another example, 1-2.5: 1 by weight.

The content of the amine-based curing agent is not particularly limited, and may be, for example, 30 to 60% by weight based on the total weight of the curing agent portion. For example, the content of the aliphatic amine resin may be 20 to 40% by weight based on the total weight of the curing agent portion, the content of the aromatic amine resin is 10 to 20% by weight based on the total weight of the curing agent portion. Can be. If the content of the amine-based curing agent is smaller than the above-mentioned range, the appearance of the coating film after curing is poor, the hardness may occur, if the above-mentioned range workability is lowered and the drying time is a problem May occur.

Curing accelerator

The curing accelerator included in the curing agent of the present invention is a material that promotes the reaction between the epoxy resin and the amine-based curing agent, and any conventional material known in the art may be used without limitation.

Non-limiting examples of curing accelerators that can be used may be one or more selected from the group consisting of tridimethylamino methylphenol, triphenyl phosphite and amino ethyl piperazine.

The content of the curing accelerator is not particularly limited, and may be, for example, 10 to 30% by weight based on the total weight of the curing agent. When the content of the curing accelerator is out of the range, physical properties such as chemical resistance and water resistance of the coating film may be lowered, and the appearance of the coating film may be poor.

According to one embodiment of the present invention, the amine-based curing agent and the curing accelerator may be 50-95: 5-50 weight ratio based on 100 parts by weight of the total total of these. Outside the above range, the chemical resistance, water resistance, etc. are lowered, and the appearance of the coating film is poor.

Non-reactive  diluent

In addition to the curing agents and curing accelerators described above, the curing agent portion of the present invention includes conventional non-reactive diluents known in the art.

The non-reactive diluent may be the same as or different from the non-reactive diluent component of the above-mentioned main part, and for example, dodecylphenol, styrene phenol, benzyl alcohol, or a mixture of two or more thereof.

In the present invention, the content of the non-reactive diluent is not particularly limited, and may be, for example, a residual amount that satisfies 100% by weight of the curing agent part, and in another example, may be 30 to 50% by weight based on the total weight of the curing agent part. have. When the content of the non-reactive diluent is less than 30% by weight, the workability is poor and the appearance property of the coating is lowered. When the content of the non-reactive diluent is higher than 50% by weight, the mechanical properties of the coating are reduced.

The mixing ratio (weight ratio) of the aromatic amine resin and the non-reactive diluent in the curing agent part may be 1: 1.5-5. When the mixing ratio of the aromatic amine resin and the non-reactive diluent is less than 1: 1.5, the workability is poor, and the appearance property of the coating film is lowered. When the mixing ratio is more than 1: 5, the mechanical properties of the coating film are lowered.

According to one embodiment of the invention, the solvent-free epoxy floor coating composition is a solvent-free epoxy resin 20-40% by weight, sieving pigment 45-65% by weight, reactive diluent 0.1-5% by weight, non-reactive diluent 2-10 20-40% by weight of main part and aliphatic amine resin, 10-20% by weight of aromatic amine resin, 10-30% by weight of curing accelerator, containing 1% by weight, 1-5% by weight of color pigment and 1-8% by weight of additive. A curing agent portion containing 30-50% by weight of a non-reactive diluent, wherein the mixing ratio (weight ratio) of the main portion and the curing agent portion based on 100 parts by weight of the total composition of the main portion and the curing agent portion is 70-80: 20-30. When the mixing ratio of the main portion and the curing agent portion is outside the above-described range, solvent resistance, hardness, etc. may be lowered, and the appearance of the coating film may be poor.

In the present invention, a non-reactive diluent is included in the main part together with a reactive diluent, and at the same time, a non-reactive diluent is included as a component of the curing agent part. As a result, the content of the non-reactive diluent is increased compared to the conventional epoxy floor coating, and the workability is improved because of the plasticity of the non-reactive diluent. In particular, when a phenolic plasticizer is used, excellent physical properties can be exhibited at low temperature curing performance.

According to one embodiment of the invention, the content of the non-reactive diluent may be 5-25% by weight based on the total weight of the total composition of the main portion and the curing agent portion.

In addition, the solvent-free epoxy floor coating composition may have a viscosity of 900-1,200 cps (25 ℃), the solid content of 93-98% by weight.

The solvent-free epoxy floor coating composition of the present invention may be prepared according to conventional methods known in the art, and may be prepared by, for example, constituting the main portion and the hardener portion of the above-described composition, and then mixing them in a specific ratio. .

For example, a solvent-free epoxy resin, a reactive diluent, a non-reactive diluent, and an additive (for example, a dispersant, an antifoaming agent, an antisettling agent, a defoamer, a leveling agent, etc.) may be added and stirred to prepare a reaction solution. In the first step, the second step of preparing the main part by adding and stirring the extender pigment and color pigment to the reaction solution, the third step of preparing a curing agent by adding and stirring the amine-based curing agent, curing accelerator and non-reactive diluent An agent for preparing a solvent-free epoxy flooring coating composition by adding a mixing ratio (weight ratio) of the main part and the hardener part to 70-80: 20-30 based on 100 parts by weight of the total composition of the main part and the hardener part. It can be configured to include four steps.

For example, in the second step, the sieving pigment is slowly added and stirred to the reaction solution until the reaction solution reaches a specific particle size (for example, 40-50 μm) or less using a high speed dissolver. After dispersing, the main part may be prepared by slowly adding and stirring the color additive to which the color pigment is added.

As described above, the solvent-free epoxy floor coating composition of the present invention is hard to use solvents harmful to humans and the environment, the construction is safe, it is possible to finish a thick film with a dry film thickness of 1,000-3,000 ㎛ in one coat, 5 Even after hardening at the temperature of -10 degreeC, a coating film external appearance and physical property are favorable. Therefore, the solvent-free epoxy floor coating composition of the present invention can be applied to the use of the flooring, but is not particularly limited thereto, and can be applied to various process steps and uses.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following examples are only for the understanding of the present invention, and the scope of the present invention is not limited to the examples in any sense.

[ EXAMPLE  And Comparative example ]

Epoxy resins, reactive diluents, non-reactive diluents, color pigments, additives and extender pigments were added to the contents shown in Table 1 to proceed with Bead Mill dispersion to uniformly prepare the main parts of Examples 1-2 and Comparative Examples 1-7. . The aliphatic amine resin, the aromatic amine resin, the curing accelerator, and the non-reactive diluent of the contents shown in Table 1 were added thereto, followed by mixing with low speed stirring to uniformly prepare the curing agent parts of Examples 1-2 and Comparative Examples 1-7. Detailed specifications of the components used in Examples and Comparative Examples are shown in Table 2 below.

 [ Experimental Example Property Evaluation of Coating Film

Physical properties of the coating compositions of Examples 1-2 and Comparative Examples 1-7 were measured as follows, and the results are shown in Tables 3 and 4.

<Measurement of Properties>

1. Hardness

SHORE-D hardness: The coating film coated at 2,000 μm was measured using a SHORE-D hardness tester.

2. Low temperature amine blushing

The coating composition was coated on the concrete plate, and after 7 days, the amine blushing of the coating film was measured using a polisher.

3. Appearance

The coating composition was coated on a glass plate and visually observed for defoaming, creting and leveling defects.

4. polished

The coating composition was coated on a glass plate, and cured for 10 days at low temperature (5 ° C.) to observe a change in glossiness (60 °) of the coating film.

5. Workability

Recoat was used for the night light to coat the coating composition, and the ease of operation, leveling, antifoaming and the like were observed.

6. Gel-Time

After containing 80% by volume of each coating composition in the tin can, the stick test was performed at a constant temperature and a constant humidity, and the time for which the stick did not move was measured.

7. Smoothness

After painting horizontally using Sag Meter, the smoothness of the paint was measured.

◎: Very good, ○: Excellent, △: Normal, X: Poor

As shown in Table 3 and Table 4, the solvent-free epoxy coating composition according to the present invention is a specific ratio of the main portion and the curing agent portion, the mixing ratio of aliphatic amine and aromatic amine, the mixing ratio of reactive diluent and non-reactive diluent As satisfactory, excellent effects were achieved in all properties evaluation items, and it was confirmed that the quality of the solvent-free epoxy paint at low temperature could be optimized. On the other hand, the mixing ratio of the main portion and the curing agent portion is outside the scope of the present application (Comparative Example 1-2), the mixing ratio of the aliphatic amine and the aromatic amine is outside the scope of the present application, or the mixing ratio of the reactive diluent and the non-reactive diluent is the scope of the present application In case of deviation (Comparative Example 3-7), one or more of the evaluation items showed poor effects.

Claims (10)

20-40 wt% solvent-free epoxy resin, sieving pigment 45-65 wt%, reactive diluent 0.1-5 wt%, non-reactive diluent 2-10 wt%, color pigment 1-5 wt% and additives 1-8 wt% Containing the subject matter and
A curing agent portion containing 20-40% by weight of an aliphatic amine resin, 10-20% by weight of an aromatic amine resin, 10-30% by weight of a curing accelerator, and 30-50% by weight of a non-reactive diluent,
In the curing agent portion, the mixing ratio (weight ratio) of the aromatic amine resin and the non-reactive diluent is 1: 1.5-5,
A solvent-free epoxy coating composition having a mixing ratio (weight ratio) of the main part and the curing agent part based on 100 parts by weight of the total composition in which the main part and the curing agent part are mixed. delete The solvent-free epoxy coating composition according to claim 1, wherein the content of the non-reactive diluent is 5-25% by weight based on the total weight of the total composition of the main part and the curing agent part. The solvent-free epoxy coating composition according to claim 1, wherein the solvent-free epoxy resin has an epoxy equivalent weight (EEW) of 180-200 g / eq, a viscosity of 11,000-14,000 cps (25 ° C), and a solid content of 96% or more. The solvent-free epoxy coating composition according to claim 1, wherein the non-reactive diluent is at least one selected from the group consisting of dodecylphenol, styrenephenol and benzyl alcohol. The method of claim 1, wherein the aliphatic amine resin has an amine value of 400-500 mgKOH / g, a viscosity of 100-1,000 cps (25 ℃), the aromatic amine resin has an amine value of 350-400 mgKOH / g, the viscosity is 500- A solventless epoxy coating composition which is 2,000 cps (25 ° C.). The solvent-free epoxy coating composition according to claim 1, wherein the aliphatic amine resin and the aromatic amine resin have a ratio of 1-3: 1 by weight. The solvent-free epoxy coating composition according to claim 1, wherein the curing accelerator is at least one member selected from the group consisting of tridimethylamino methylphenol, triphenyl phosphite and amino ethyl piperazine. The solvent-free epoxy coating composition according to claim 1, wherein the additive is at least one selected from the group consisting of a dispersant, an antifoaming agent, a defoamer, a leveling agent, a weathering additive, a drying agent, an appearance control agent, an antisettling agent, and a coupling agent. The solvent-free epoxy coating composition according to claim 1, wherein the composition is capable of bottoming at a film thickness of 1.0-3.0 mm at a low temperature of 5-10 ° C.