KR101310791B1 - Two component type epoxy resin composition - Google Patents

Abstract

PURPOSE: A two-component epoxy resin composition is provided to have no problem of stimulating smells due to volatile materials, to be able to be coated with a roller, to be able to form a good appearance coating, and to be able to secure enough time required to do the coating task. CONSTITUTION: A two-component epoxy resin composition comprises a base component and a curing component. The base component includes 80-90 weight% of epoxy resin, 1-10 weight% of low viscosity reactive diluent epoxy resin, 1-10 weight% of non-reactive diluent, and 1-10 weight% of color pigment, but does not include the extender pigment. The curing component includes 20-30 weight% of cycloaliphatic amine, 30-40 weight% of aliphatic amine, 20-30 weight% of benzylalcohol and 1-10 weight% of a hardening accelerator. The epoxy resin is bisphenol A diglycidyl ether which is formed by a reaction of bisphenol A and epichlorohydrin.

Description

Two Component Type Epoxy Resin Composition

The present invention relates to a two-component epoxy resin composition, and more particularly, to a two-component epoxy resin composition that is a solvent-free type that does not use an organic solvent and does not contain a extender pigment.

An epoxy resin refers to a dendritic substance having two or more epoxy groups in a molecule. The epoxy resin is cured by a thermosetting reaction between its epoxy group and the curing agent to form various finishes such as flooring, walling and the like. The thermosetting epoxy resin is widely used as a coating material because of its excellent mechanical properties such as bending strength and hardness, no generation of volatile materials and no shrinkage in volume during curing, and a large adhesive strength in terms of materials when curing.

The two-component epoxy resin composition is used by mixing before coating the main component comprising the epoxy resin and the curing agent component comprising the curing agent. The two-component epoxy resin composition has been used in the form of a solvent-type epoxy resin composition in which the main component and the hardener component contain an organic solvent in order to efficiently paint, but the solvent-type epoxy resin composition has been used in an environment due to volatilization of the solvent. Destruction, pollution of production facilities, harmful to the human body, etc. have emerged as a problem in recent years, a solvent-free epoxy resin composition has been developed.

Patent Publication No. 10-2004-0074196 (published Aug. 23, 2004) discloses a low temperature curable two-component solvent-free epoxy floor coating composition. The composition shown consists of a main component of an epoxy resin, a sieving pigment, a reactive diluent, an unreactive diluent, an additive, and a curing agent component comprising an amine-based curing agent and a curing accelerator.

In addition to the above patents, Patent Registration No. 10-0630439 (registered on September 25, 2006), Patent Registration No. 10-0848812 (registered on July 22, 2008), Patent Registration No. 10-1173837 (2012. 08. 08. Registration), Patent Publication No. 10-2011-0135617 (published Dec. 19, 2011), Patent Publication No. 10-2012-0032769 (published Apr. 06, 2012), Patent Registration No. 10-1046212 (2011. 06. 28. registration), Patent Registration No. 10-1115011 (2012. 02. 03. registration), etc. also disclosed the epoxy resin composition of a solvent-free type.

As described above, the conventionally proposed solvent-free type epoxy resin composition contains a extender pigment, and thus, paint cannot be painted by roller coating, which makes it difficult to beautifully decorate the exterior of the building's floor, walls, and the like. In order to solve this problem, it is necessary to finish the coating with a solvent-type epoxy resin composition after such a painting work. However, when the solvent-type epoxy resin composition is used, the above-mentioned problems are manifested and the meaning of using a solvent-free epoxy resin composition is faded. Done.

On the other hand, if it does not contain the extender pigment, the epoxy resin should be included in the main component in a content of 70% by weight or more, preferably 80% by weight or more. In such a case, the pot life is shortened so that there is no time for painting work. There is also a problem that the workability worsens.

Accordingly, the present invention has been made to solve the above problems. Therefore, an object of the present invention is a solvent-free type that does not use an organic solvent, so that roller coating is possible without problems such as irritating odor due to volatile substances, so that a beautiful appearance can be formed, which is required for painting. It is to provide a two-component epoxy resin composition having a sufficient pot life and having excellent workability.

In addition, an object of the present invention is to provide a two-component epoxy resin composition that can minimize the dust caused by the wear of the flooring and wall material formed by the epoxy resin composition because it does not contain a extender pigment.

The two-component epoxy resin composition according to the present invention for achieving the above object is 80 to 90% by weight epoxy resin, 1 to 10% by weight low viscosity reactive diluent epoxy resin, 1 to 10% by weight non-reactive diluent, and color pigment 1 Includes ~ 10% by weight of the main ingredient, but not including the extender pigment 20-30% by weight of alicyclic amine, 30-40% by weight of aliphatic amine, 20-30% by weight of benzyl alcohol and 1-10% by weight of curing accelerator It consists of a hardening | curing agent component.

The epoxy resin is a bisphenol A diglycidyl ether produced by the reaction of bisphenol A and epichlorohydrin, having an equivalent weight of 185 to 192 g / eq and a viscosity of 11500 to 13500 cps (25 ° C). The low viscosity reactive diluent epoxy resin is a glycidyl ester of versatic acid 10. The aliphatic amine is a polyetheramine having an oxypropylene structure in its molecular structure, and has a weight average molecular weight of 230 and an amine value of 240 to 240. 270 mgKOH / g, specific gravity 0.95 and viscosity 9.5 cps, the cycloaliphatic amine is an alicyclic diamine formed by the reaction of isophorondiamine and bisphenol A epoxy resin, the amine is 260 ~ 285 mgKOH / g, viscosity 350 600 cps and specific gravity 1.03.

The non-reactive diluent is preferably 2,2,4-trimethylpentanediol diisobutyrate.

The curing accelerator is preferably 2,4,6-tris ((methylamino) methyl) phenol.

The composition may further comprise 0.1 to 1% by weight of the silicone-based antifoaming agent, 0.1 to 1% by weight of the silicone-based leveling agent and 0.1 to 1% by weight of the polymeric dispersant.

Since the two-component epoxy resin composition of the present invention does not contain a solvent, there is no problem such as environmental damage, pollution of production equipment, or harmful effects to human body due to volatilization of the solvent. It is possible to form a beautiful appearance of the flooring material, the wall material and the like thereby formed, it is possible to minimize the dust generated when such flooring material, the wall material and the like. In addition, the two-component epoxy resin composition of the present invention has a high content of the epoxy resin in the main component, while ensuring sufficient pot life for painting work, it has excellent workability.

Hereinafter, the present invention will be described in detail.

The two-component epoxy resin composition of the present invention consists of a main component and a curing agent component.

The main components include 80 to 90% by weight epoxy resin, 1 to 10% by weight low viscosity reactive diluent epoxy resin, 1 to 10% by weight non-reactive diluent, and 1 to 10% by weight color pigment, but do not include extender pigments.

Epoxy resin used in the present invention is a bisphenol A diglycidyl ether produced by the reaction of bisphenol A and epichlorohydrin, and has a structure as shown in the following formula (1).

Formula 1

(Here, n is 0 or 1, on average is 0.11 to 0.15, so it has the following properties.)

The epoxy resin used has an equivalent of 185 to 192 g / eq, a viscosity of 11500 to 13500 cps (25 ° C), and is included in the range of 80 to 90% by weight in the main component. When too few epoxy resins are included in the main component, the epoxy resin composition of the present invention does not include the extender pigment, and thus, other components must be included correspondingly, which makes it difficult to meet the physical properties required for the epoxy resin composition. On the other hand, too much content of the epoxy resin is not good because the pot life is shortened and workability is worse. Therefore, the above range is appropriate. Epoxy resin used in the present invention is present in the liquid phase at room temperature (25 ℃). Typically, many epoxy resins are used, but specific epoxy resins as described above must be used to satisfy the physical properties required by the composition of the present invention.

The low viscosity reactive diluent epoxy resin used in the present invention is a glycidyl ester of versatic acid 10. Versatic acid 10 is a highly branched 10 carbonic acid carboxylic acid, as shown in Formula 2 below.

(2)

Where R 1 and R 2 are alkyl groups and the total number of carbons is 10

The glycidyl ester of the versatic acid 10 has a reactivity to participate in the curing reaction with the curing agent while serving to give flexibility by lowering the high viscosity of the epoxy resin in the main component. This ingredient is included in the range of 1 to 10% by weight in the main ingredient, if too small, the effect to be achieved by it is insignificant, and if it is contained in too much amount, the content of other ingredients should be less. If you do so, you will not be able to obtain a balanced property.

As the non-reactive diluent used in the present invention, a plasticizer generally used may be used. For example, DOP (Dioctylphthalate), DBP (Dibutylphthalate), etc. may be used as the phthalate-based plasticizer, but since these substances are regulated as environmentally harmful substances, it is preferable not to use them. Preference is given to using 4-trimethylpentanediol diisobutyrate. These non-reactive diluents serve to lower the viscosity and impart flexibility to the coating film without any participation in the curing reaction with the curing agent. This ingredient is included in the range of 1 to 10% by weight in the main ingredient, if too small, the effect to be achieved by it is insignificant, and if it is contained in too much amount, the content of other ingredients should be less. If you do so, you will not be able to obtain a balanced property.

The color pigments used in the present invention are for producing color. Inorganic pigments generally used for producing colors such as titanium dioxide, cyanine green, cyanine blue, carbon black, and the like may be used in the present invention. Color pigments are contained in the main components in an amount of 1 to 10% by weight. If they are contained too little, the effect of color development is insignificant, and in too many cases, the content of other components should be reduced, so that overall balanced properties can be obtained. There will be no.

On the other hand, it is preferable that the main component further contains 0.1-1 weight% of a silicone type antifoamer, 0.1-1 weight% of a silicone type leveling agent, and 0.1-1 weight% of a polymeric type dispersing agent. Antifoaming agents, leveling agents, and dispersants in the subject ingredients are commonly used, and thus detailed descriptions thereof will be omitted.

On the other hand, the curing agent component includes 20 to 30% by weight of alicyclic amine, 30 to 40% by weight of aliphatic amine, 20 to 30% by weight of benzyl alcohol and 1 to 10% by weight of curing accelerator.

The aliphatic amine is a polyetheramine having an oxypropylene structure in its molecular structure, and preferably has a weight average molecular weight of 230, an amine value of 240 to 270 mgKOH / g, a specific gravity of 0.95, and a viscosity of 9.5 cps. For example, the aliphatic amine may have a structure as shown in Formula 3 below.

(3)

(Where x is approximately 2.5)

The alicyclic amine is an aliphatic diamine formed by the reaction of isophorondiamine and bisphenol A epoxy resin, and preferably has an amine value of 260 to 285 mgKOH / g, a viscosity of 350 to 600 cps, and a specific gravity of 1.03. Here, the bisphenol A epoxy resin is formed by the reaction of bisphenol A and epichlorohydrin, and may be the same as that used for the main component, and in the following Chemical Formula 1, n may be 0.

Formula 1

The cycloaliphatic amines used are those having an amine group at the end of the sock, formed by reacting and bonding two epoxy groups formed at the ends of the bisphenol A epoxy resin with one amine group of two isophorone diamines.

When the cycloaliphatic amine and the aliphatic amine are included in the curing agent component in the ratio of the above-mentioned composition, their properties are formed in harmony to provide appropriate physical properties to the composition of the present invention, and particularly, it is possible to obtain suitable pot life. Alicyclic amines and aliphatic amines are included in the curing agent component in the range of 20 to 30% by weight and 30 to 40% by weight, respectively, if they are contained too little or too much, the balanced physical properties required by the present invention cannot be obtained. It is therefore preferred to be included in the above range.

Benzyl alcohol used in the present invention serves to lower the viscosity in the hardener component and also to impart coating workability to the composition of the present invention by acting as a non-reactive diluent when the main component and the hardener component are mixed. Benzyl alcohol is included in the curing agent component in the range of 20 to 30% by weight. If it is included too little, the effect to be achieved by it, that is, the effect of improving the paintability becomes weak, and in many cases the paintability is improved. It becomes difficult to obtain the required physical properties.

As the curing accelerator used in the present invention, it is also possible to use a general curing accelerator used for the curing agent component of the two-component epoxy resin composition, but preferably 2,4,6-tris ((methylamino) methyl) phenol is used. do. When 2,4,6-tris ((methylamino) methyl) phenol is used as a curing accelerator, it is advantageous to control pot life and to obtain desired mechanical properties. The curing accelerator is used in the amount of 1 to 10% by weight in the curing agent component. If the amount is used too small, the effect of the curing accelerator is insignificant. If the curing accelerator is used too much, the curing time is progressed too fast to satisfactorily control the pot life. In addition, the content of other components, that is, benzyl alcohol, is reduced, which makes it difficult to satisfy the desired physical properties.

Hereinafter, the present invention will be described in detail through examples.

Example

Example  One

85% by weight of bisphenol A diglycidyl ether as epoxy resin, 5% by weight of glycidyl ester of versatic acid 10, 4% by weight of 2,2,4-trimethylpentanediol diisobutyrate as non-reactive diluent, silicone antifoam 0.3 28% by weight of a cycloaliphatic diamine formed by reacting a main component consisting of 5% by weight of a titanium-based leveling agent, 0.3% by weight of a silicone-based leveling agent, 0.4% by weight of a polymeric pigment, and isophoronediamine and a bisphenol A epoxy resin, 38% by weight of aliphatic diamine represented by the formula (3), 27% by weight of benzyl alcohol, and 7% by weight of 2,4,6-tris ((methylamino) methyl) phenol as a curing accelerator were mixed and painted to prepare a flooring material. . At this time, the blending ratio of the main component and the curing agent component is equivalent to the epoxy group of the epoxy resin component included in the main component and the glycidyl ester of the versatic acid 10, which is a reactive diluent, and the alicyclic diamine, aliphatic diamine and The equivalent of the amine group which the hardening accelerator has was set to be the same ratio.

Comparative example  One

In the same manner as in Example 1, the main component and the hardener component were mixed and coated to prepare a flooring material. At this time, the main component is 85% by weight of bisphenol A diglycidyl ether as an epoxy resin, 5% by weight of 2-ethylhexyl glycidyl ether as a reactive diluent, and dioctylphthalate as a non-reactive diluent. phthalate) 4% by weight, silicone antifoam 0.3% by weight, silicone leveling agent 0.3% by weight, polymer type dispersant 0.4% by weight, and titanium dioxide 5% by weight as color pigment, and isophoronediamine as alicyclic modified amine as hardener component. 66 wt% of the added type of alicyclic modified amine (isophrondiamine adduct), 27 wt% of benzyl alcohol and 7 wt% of 2,4,6-tris ((methylamino) methyl) phenol as a curing accelerator.

Comparative example  2

In the same manner as in Example 1, the main component and the hardener component were mixed and coated to prepare a flooring material. At this time, the main component is 40% by weight of bisphenol A diglycidyl ether as an epoxy resin, 10% by weight of benzyl alcohol as a non-reactive diluent, 45% by weight of calcium carbonate as a sieving pigment, 3% by weight of titanium dioxide as a color pigment and other additives 2 It is composed of weight percent, 20% by weight of meta-xylene diamine as aliphatic modified amine as a hardener component, 75% by weight of polyetheramine and 2,4,6-tris ((methylamino) methyl as a curing accelerator. 5% by weight of phenol.

Test result

1) Whether roller painting is possible

The compositions of Example 1 and Comparative Example 1 were capable of roller coating, and as a result, it was possible to form a floor covering 0.7 mm thick. The composition of Example 1 and Comparative Example 1 was excellent in the smoothness and hiding power as the roller coating is possible, the appearance of the flooring formed was very beautiful. On the other hand, the composition of Comparative Example 2 was impossible to coat the roller, it was possible to form a flooring thickness of 3 mm using a conventional coating method. Comparative Example 2 The composition was not good smoothness and hiding power was poor appearance of the flooring formed.

2) housework time

The pot life of the composition of Comparative Example 1 was about 15 to 20 minutes when operating at room temperature (25 ° C.), the pot life of the composition of Example 1 was about 25 to 30 minutes, and the pot life of the composition of Comparative Example 2 was It took about 30-40 minutes. Example composition of the present invention compared to the composition of Comparative Example 1 was confirmed that the pot life of about 10 minutes is extended to ensure sufficient time to work.

3) Mechanical Properties

The coating hardness (shore 'D' type, ASTM D2240 method) was about 80 for Comparative Example 1, about 75 to 80 for Comparative Example 2, and about 78 to 84 for Example 1.

According to the above test results, the composition according to the present invention improved workability by significantly increasing pot life compared to Comparative Example 1 product while maintaining mechanical properties such as hardness, and also improved roller coating compared to Comparative Example 2 product. By making it possible, it was confirmed that a thin coating film can be formed and a beautiful appearance can be formed.

Claims (4)

Subject matter and alicyclic containing 80-90 wt% epoxy resin, low viscosity reactive diluent 1-10 wt% epoxy resin, 1-10 wt% non-reactive diluent, and 1-10 wt% color pigment, but no extender pigment It consists of a curing agent component comprising 20 to 30% by weight of the group amine, 30 to 40% by weight of the aliphatic amine, 20 to 30% by weight of benzyl alcohol and 1 to 10% by weight of the curing accelerator,
The epoxy resin is a bisphenol A diglycidyl ether produced by the reaction of bisphenol A and epichlorohydrin, having an equivalent weight of 185 to 192 g / eq and a viscosity of 11500 to 13500 cps (25 ° C). The low viscosity reactive diluent epoxy resin is a glycidyl ester of versatic acid 10. The aliphatic amine is a polyetheramine having an oxypropylene structure in its molecular structure, and has a weight average molecular weight of 230 and an amine value of 240 to 240. 270 mgKOH / g, specific gravity 0.95 and viscosity 9.5 cps, the cycloaliphatic amine is an alicyclic diamine formed by the reaction of isophorondiamine and bisphenol A epoxy resin, the amine is 260 ~ 285 mgKOH / g, viscosity 350 A two-component epoxy resin composition, characterized in that it has a ~ 600 cps and specific gravity 1.03. The method of claim 1,
The non-reactive diluent is 2,2,4-trimethylpentanediol diisobutyrate, two-component epoxy resin composition. The method according to claim 1 or 2,
The curing accelerator is a two-component epoxy resin composition, characterized in that 2,4,6-tris ((methylamino) methyl) phenol. The method of claim 3,
The composition is a two-component epoxy resin composition, characterized in that further comprises 0.1 to 1% by weight of the silicone-based antifoaming agent, 0.1 to 1% by weight of the silicone-based leveling agent and 0.1 to 1% by weight of the polymeric dispersant.