WO2021137537A1 - Epoxy resin, epoxy paint composition containing same, coating film formed by epoxy paint composition, and substrate with coating film adhered thereto - Google Patents

Abstract

The present invention relates to an epoxy resin, an epoxy paint composition containing same, a coating film formed by said epoxy paint composition, and a substrate with said coating film adhered thereto. The epoxy resin according to the present invention can be used as a paint without adding a solvent and/or a thinner due to having a low viscosity, and the epoxy paint composition containing the epoxy resin can be used to produce a coating film with significantly improved drying speed and equal or better overall physical properties compared to conventional coating films.

Description

An epoxy resin, an epoxy paint composition comprising the same, a coating film formed by the epoxy paint composition, and a base material to which the coating film is attached

The present invention relates to an epoxy resin, an epoxy coating composition comprising the same, a coating film formed by the epoxy coating composition, and a substrate to which the coating film is attached.

Epoxy resins generally have high corrosion resistance and high chemical resistance, so they are the most widely used resins for ship paints, heavy-duty anticorrosive paints, and overall industries.

Generally, liquid BPA epoxy resin is produced through polycondensation reaction of epichlorohydrin with bisphenol A, and it is widely used. By adjusting the molar ratio of bisphenol A and ECH (Ephichloro Hydrine), it is suitable for the purpose of the product according to the molecular weight and epoxy equivalent. used

However, in the case of general epoxy resin, a large amount of volatile organic solvents such as xylene and alcohol are used when manufacturing marine paints and heavy anticorrosive paints with a viscosity of 13,000 cps at room temperature of 25 ℃, which causes air pollution and human body. lead to harmful consequences;

In addition, in the case of such a liquid epoxy resin, the coating film produced after the curing reaction with the epoxy curing agent is brittle because it is manufactured as a paint, causing cracks in the coating film due to external impact. cause major flaws in In order to solve this problem, it is necessary to use a product whose molecular weight and epoxy equivalent have been increased through an additional polymerization reaction of bisphenol A.

However, in this case, the liquid product is transferred to a semi-solid and solid phase due to the increase in viscosity due to the increase in molecular weight, so a larger amount of an organic solvent, which is a volatile organic compound, must be used. Moreover, polyamide or polyamide used as a curing agent for epoxy resin according to the increase in molecular weight Compatibility with phenalkamine and the like is problematic, and in this case, problems such as poor curing and poor adhesion of the coating film are caused.

In addition, the use of volatile organic solvents is regulated according to the recent regulations on the use of volatile organic compounds (VOCs), so there is an urgent need to research resins for paints that can solve this problem.

[Prior art literature]

[Patent Literature]

(Patent Document 1) Korean Patent No. 10-1264516

Accordingly, the technical problem to be solved by the present invention is to provide a low-viscosity epoxy resin capable of producing a solvent-free paint and an epoxy paint composition including the same.

In addition, it is to provide a coating film formed of the epoxy coating composition, and a substrate with a coating film comprising the coating film and the substrate.

One aspect of the present invention relates to an epoxy resin represented by the following Chemical Formula 1, and containing 50 mol% or more of a compound having n=0 in the following Chemical Formula 1.

[Formula 1]

In Formula 1, n is an integer of 0 to 4.

Another aspect of the present invention is It relates to an epoxy resin comprising a mixture of a compound represented by the following formula (1), and a compound having n=0, a compound having n=1, and a compound having n=2 in the following formula (1).

[Formula 1]

In Formula 1, n is an integer of 0 to 4.

Another aspect of the present invention relates to an epoxy paint composition comprising an epoxy resin represented by the following formula (1), wherein the epoxy resin comprises 50 mol% or more of a compound having n = 0 in the following formula (1).

[Formula 1]

In Formula 1, n is an integer of 0 to 4.

Another aspect of the present invention includes an epoxy resin represented by the following formula (1), wherein the epoxy resin includes a mixture of a compound in which n = 0, a compound in which n = 1, and a compound in which n = 2 in the following formula (1) It relates to a phosphorus epoxy paint composition.

[Formula 1]

In Formula 1, n is an integer of 0 to 4.

Another aspect of the present invention relates to a coating film formed of the epoxy coating composition.

Another aspect of the present invention relates to a substrate with a coating film including the coating film and the substrate.

The epoxy resin according to the present invention can be used as a paint without mixing of a solvent and/or a diluent based on a low viscosity, and the drying speed is significantly improved compared to the existing coating film in film forming using the epoxy paint composition containing the epoxy resin, , it is possible to manufacture a coating film having an equivalent or higher level of overall physical properties.

[Correction by Rule 91 25.02.2021]
Brief description of the drawing

[Correction by Rule 91 25.02.2021]
1 is a graph of the results of GPC analysis of the epoxy resin obtained in Example 1.

[Correction by Rule 91 25.02.2021]

[Correction by Rule 91 25.02.2021]
Hereinafter, various aspects and various embodiments of the present invention will be described in more detail.

The terms or words used in the present specification and claims should not be construed as being limited to their ordinary or dictionary meanings, and the inventor may properly define the concept of the term in order to best describe his invention. It should be interpreted as meaning and concept consistent with the technical idea of the present invention based on the principle that there is.

The terms used in the present invention are only used to describe specific embodiments, and are not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly dictates otherwise. In the present invention, terms such as 'comprise' or 'have' are intended to designate that the features, numbers, steps, operations, components, parts, or combinations thereof described in the specification exist, but one or more other features It should be understood that this does not preclude the existence or addition of numbers, steps, operations, components, parts, or combinations thereof.

Conventional epoxy resin paints have excellent physical properties such as adhesion, heat resistance, water resistance, chemical resistance, and mechanical strength, and are widely used as paints for ships, heavy-duty anticorrosives, and constructions. Bisphenol A type epoxy resin, which is a typical epoxy resin, must be designed using a solvent and/or diluent because of its high viscosity.

On the other hand, solvents and diluents used in the formulation of paints using bisphenol A-type epoxy resins intrinsically accompany VOC emission, but regulations related to volatile organic compounds (VOCs) are being strengthened in recent years. Paint companies are also concentrating on the development of solvent-free paints and high-solids (high solids) paints that do not use solvents from currently applied solvent paints to reduce VOCs, and are focusing on developing low-viscosity subjects or diluents with low VOC emissions. writing situation.

Accordingly, the present invention provides an epoxy paint composition comprising an epoxy resin in a low-viscosity form.

Specifically, one aspect of the present invention provides an epoxy resin comprising 50 mol% or more of a compound represented by the following formula (1), wherein n = 0 in the following formula (1).

[Formula 1]

In Formula 1, n is an integer of 0 to 4.

Another aspect of the present invention is It is represented by the following Chemical Formula 1, and provides an epoxy resin comprising a mixture of a compound having n=0, a compound having n=1, and a compound having n=2 in the following Chemical Formula 1.

[Formula 1]

In Formula 1, n is an integer of 0 to 4.

The catechol-type epoxy resin has a low-viscosity property, unlike the conventional high-viscosity bisphenol A-type epoxy resin, so that the amount of solvent and/or diluent is significantly reduced or not used, so a low-solvent-type or solvent-free coating composition with little VOC emission. can be manufactured. In addition, by including a catechol-type epoxy resin in which other functional groups, including an alkyl group, are not substituted in the benzene ring of the above formula, a coating film having physical properties equivalent to or higher than that of the conventional level can be implemented as a whole, and in particular, the drying rate can be improved. have.

According to one embodiment, the epoxy resin may include 50 mol% or more of the compound having n=0 in Formula 1 above. For example, the epoxy resin may include 55 mol% or more, 60 mol% or more, or 65 mol% or more of the compound having n=0 in Formula 1.

The epoxy paint composition including an epoxy resin that satisfies the condition of including 50 mol% or more of the compound of n=0 in Formula 1 has the advantage of being able to form a coating film without including any solvent or diluent.

According to another embodiment, the epoxy resin may include 90 mol% or more of the compound having n=0 to 1 in Formula 1 above. As can be seen in Examples to be described later, a coating film formed using an epoxy paint composition containing an epoxy resin that satisfies the mol % condition of the repeating unit satisfies the mol % condition in the measurement of mechanical strength such as impact resistance. It was confirmed that it has excellent mechanical strength compared to the epoxy resin not used.

According to one embodiment, the epoxy resin contains 50 to 90 mol% of the compound having n=0 in Formula 1, 5 to 40 mol% of the compound having n=1, and 1 to 11 mol% of the compound having n=2 or more may be doing For example, it may include 60 to 88 mol% of the compound having n=0, 8 to 30 mol% of the compound having n=1, and 3 to 10 mol% of the compound having n=2 or more. The epoxy paint composition including the epoxy resin satisfying the above conditions has the advantage of controlling the drying rate of the coating film as well as the improved drying rate described above. In addition, it was confirmed that it was possible to form a coating film having excellent adhesion and flexural adhesion, and at the same time improving overall physical properties such as solvent resistance, acid resistance, chemical resistance including basic resistance, and surface glossiness.

According to one embodiment, the viscosity of the epoxy resin may be 2000 cps or less at 25 °C, for example, 200 to 2000 cps or 200 to 1800 cps. When the above viscosity range is satisfied, workability is excellent, and good drying speed, adhesion, bending resistance, impact resistance, chemical resistance, and surface glossiness can be imparted to the paint containing the epoxy resin. In addition, in order to further improve the drying rate and surface glossiness of the paint containing the epoxy resin, the viscosity of the epoxy resin may be 200 to 1600 cps, 200 to 1000 cps, or 200 to 800 cps at 25°C. On the other hand, when the viscosity of the epoxy resin exceeds 2000 cps, it may be difficult to form a uniform coating film due to a decrease in applicability in a solvent-free coating material.

The epoxy equivalent of the epoxy resin may be 120 to 185 g / eq. For example, the equivalent weight of the epoxy resin may be 140 to 183 g / eq. When the epoxy equivalent of the epoxy resin satisfies the above range, there is an effect of lowering the viscosity of the resin.

Another aspect of the present invention provides an epoxy paint composition comprising an epoxy resin represented by the following formula (1), wherein the epoxy resin comprises 50 mol% or more of a compound having n = 0 in the following formula (1).

[Formula 1]

In Formula 1, n is an integer of 0 to 4.

Another aspect of the present invention includes an epoxy resin represented by the following formula (1), wherein the epoxy resin includes a mixture of a compound in which n = 0, a compound in which n = 1, and a compound in which n = 2 in the following formula (1) A phosphorus epoxy paint composition is provided.

[Formula 1]

In Formula 1, n is an integer of 0 to 4.

The epoxy resin may include 50 mol% or more of the compound having n=0 in Formula 1 above.

In Formula 1, n is an integer of 0 to 4.

The epoxy resin may include 90 mol% or more of the compound having n=0 to 1 in Formula 1 above.

The epoxy resin may include 50 to 90 mol% of a compound having n=0 in Formula 1, 5 to 40 mol% of a compound having n=1, and 1 to 11 mol% of a compound having n=2 or more, for example, For example, it may include 60 to 88 mol% of the compound having n=0, 8 to 30 mol% of the compound having n=1, and 3 to 10 mol% of the compound having n=2 or more.

The viscosity of the epoxy resin may be 2000 cps or less at 25 ° C. For example, 200 to 2000 cps, 200 to 1800 cps, 200 to 1600 cps 200 to 1000 cps, or 200 to 800 cps.

The epoxy equivalent of the epoxy resin may be 120 to 185 g / eq. For example, the epoxy equivalent of the epoxy resin may be 140 to 183 g / eq.

The description of the epoxy paint composition is the same as described above in the epoxy resin part, so it will be omitted.

According to one embodiment, the epoxy paint composition may include a main part and a curing agent part including the epoxy resin.

According to one embodiment, the main part may include 5 to 50 parts by weight of the epoxy resin and 50 to 95 parts by weight of the pigment based on 100 parts by weight of the main part.

According to another embodiment, the main part may include 15 to 30 parts by weight of the epoxy resin and 70 to 85 parts by weight of the pigment based on 100 parts by weight of the main part, for example, 20 to 30 parts by weight of the epoxy resin and the pigment. 70 to 80 parts by weight may be included.

The pigment may be an extender pigment or a color pigment, and the aforementioned pigments may be used alone or in combination of two or more.

The extender pigment fills the pores in the coating film, complements hardness and chemical properties, and controls gloss.

As the extender, conventional extender pigments known in the art may be used without limitation, and examples thereof include silica, barite (natural barium sulfate), blancfix (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.

The color pigment is included for the purpose of expressing a desired color (colored) in the paint by mixing with the epoxy resin.

As the color pigment, organic pigments, inorganic pigments, metallic pigments, aluminum-pastes, pearls, etc. commonly used in the art may be used without limitation, and 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 sulfur, navy blue, and cyanine blue may be used.

The curing agent may include a curing agent and a curing accelerator. As long as it is a curing agent used in a subject including an epoxy resin, it may include a conventional curing agent known in the art without being particularly limited. For example, it may include an amine-based curing agent or a polyamide-based curing agent. According to one embodiment, the curing agent part may include an amine-based curing agent.

As the amine-based curing agent, a conventional resin for an amine-based curing agent known in the art may be used without limitation. For example, there is an aliphatic amine base, an aromatic amine base, or a mixture thereof.

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 part. 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 part, and the content of the aromatic amine resin may be 10 to 20% by weight based on the total weight of the curing agent part. can be If the content of the amine-based curing agent is less than the above range, the appearance of the coating film after curing may be poor, and a problem of lowering the hardness may occur. If the content of the amine-based curing agent is less than the above range, workability is deteriorated and drying time is delayed. can occur

The curing accelerator 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 the curing accelerator that can be used may be at least one selected from the group consisting of tridimethylamino methylphenol, triphenyl phosphite, and amino ethylpiperazine.

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 part. If 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 deteriorate, and the appearance of the coating film may deteriorate.

The epoxy paint composition may include conventional additives known in the art within a range that does not impair the inherent properties of the composition as additives.

Non-limiting examples of additives that can be used include a dispersant, an antifoaming agent, a defoaming agent, a leveling agent, a weathering additive, a desiccant, an appearance control agent, an anti-settling agent, a coupling agent, or a mixture of two or more thereof. For example, two or more additives selected from the group consisting of an anti-settling agent, a dispersing agent, an antifoaming agent, a defoaming agent, and a leveling agent may be mixed. In the present invention, the content of the additive may be appropriately adjusted within a content range known in the art, and for example, may be 1 to 8% by weight based on the total weight of the main part.

The anti-settling agent serves to prevent sedimentation of materials to form a coating film with a uniform property, and conventional ones known in the art may be used without limitation. For example, there is a clay-type anti-settling agent and the like. The content of the anti-settling agent is not particularly limited, and may be, for example, 0.1 to 0.7 wt%. When the content of the anti-settling agent is less than 0.1 wt %, the leveling of the coating film is very good, but the storability of the paint is poor, and when it exceeds 0.7 wt %, the storage stability of the paint is excellent, but the leveling of the coating film may be poor.

An antifoaming agent and a defoaming agent can be mixed together to remove air bubbles from the surface of the coating film and allow the bubbles in the coating film to rise to the surface quickly. If the bubbles inside do not rise and remain in the coating film, poor adhesion to the material and/or deterioration of physical properties may result. Even if the bubbles inside rise, the flowability of the coating film decreases when the coating film is cured 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, color separation occurs due to different fluidity for each pigment, so that the color before and after curing is different, or the appearance is poor because the color is different for each painted part. When the main part includes one or more additives such as the above-described dispersing agent, defoaming agent, defoaming agent, and leveling agent, it is possible to improve the occurrence of coating film defects such as defoaming defects, cratering, and color separation.

The dispersant serves to disperse each material constituting the composition and prevent re-agglomeration by maintaining a distance to express uniform physical properties of the coating film. As the dispersant, a conventional dispersant known in the art may be used, for example, a high molecular weight block copolymer type dispersant.

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

The defoaming agent serves to prevent and remove bubbles during coating and improve the manufacturing process. For example, a non-silicone-based polymer-type defoaming agent may be used.

The leveling agent is to improve the appearance characteristics of the coating film while enhancing adhesion in the composition by leveling the composition so that the composition is coated evenly and smoothly. As the leveling agent, a conventional leveling agent known in the art may be used without limitation, and for example, an acrylic-based, silicone-based, polyester-based, or amine-based leveling agent may be used.

Another aspect of the present invention relates to a coating film formed of the epoxy coating composition, and a substrate with a coating film comprising the coating film and the substrate formed of the epoxy coating composition. The coating film is formed using the above-described epoxy coating composition, and the substrate with the coating film is a laminate including the coating film and an object (substrate) to be coated.

The thickness of the coating film may vary depending on the use of the coating film, but is not particularly limited, and may be, for example, 50 to 500 μm, or 100 to 300 μm.

Hereinafter, the present invention will be described in more detail through examples. These examples are only for illustrating the present invention in more detail, and it will be apparent to those of ordinary skill in the art to which the present invention pertains that the scope of the present invention is not limited by these examples.

Example 1. Preparation of epoxy resin

In a four-neck flask equipped with a stirrer, condenser, and thermometer, 500 g (4.541 mol) of catechol and 3571 g (38.601 mol) of epichlorohydrin were put, and the temperature was raised to 65 ° C., and then 48 g (0.599 mol) of 50% caustic soda. ) was uniformly dripped for 30 minutes and then reacted for 3 hours. After cooling the temperature to 62 °C, 613 g (7.666 mol) of 50% caustic soda was uniformly added dropwise for 2 hours and 30 minutes, and water was removed under a vacuum degree of 130 to 170 torr. Thereafter, in order to remove unreacted epichlorohydrin, degassing was performed at a temperature of 150° C. less than 10 torr.

In order to remove the generated NaCl salt, 1513 g of MIBK and 1215 g of water were added and washed with water. At this time, the epoxy equivalent was 143 g/eq chlorine content was 1940 ppm.

For further ring closure reaction, 6.6 g of caustic soda and 9.9 g of water were added and reacted at 85° C. for 1 hour and 30 minutes.

After completion of the reaction, 832 g of water was added, stirred for 30 minutes, and then left standing to proceed with water separation. Water washing was repeated three times, and the pH of the water layer was measured during the last washing, and neutralized with phosphoric acid to a level of 5.0 to 7.5, followed by water separation.

To remove the solvent, degassing was performed at a temperature of 150 ° C. less than 10 torr, and the epoxy equivalent of the final resin was 142 g/eq, 226 ppm chlorine, 85% yield, and 220 cps viscosity.

[Formula 1]

[Correction by Rule 91 25.02.2021]
At this time, the resin is represented by Chemical Formula 1, and it was confirmed through GPC analysis provided in FIG. 1 that 87 mol% of the compound with n=0, 9 mol% of the compound with n=1, and 4 mol% of the compound with n=2 or more.

[Correction by Rule 91 25.02.2021]
[delete]

GPC analysis result (Retention Time)

36.648 min: n=0 compound, 34.608 min: by-product, 33.417 min: n=1 compound, 31.692 min: n=2 or more compounds

Example 2. Preparation of Epoxy Resin

2435 g (26.340 mol) of epichlorohydrin, 25 g (0.318 mol) of initial 50% caustic soda, and 58 g (0.727 mol) of caustic soda were divided into two portions and uniformly dripped, reacted for 4 hours, and then added 50% caustic 218 g (2.725 mol) of soda and 428 g (5.359 mol) of soda were divided into two portions and uniformly dripped for 40 minutes and 75 minutes, respectively, and then the reaction was carried out in the same manner as in Example 1, except that the reaction was carried out for 1 hour. The final resin had an epoxy equivalent of 166 g/eq, a chlorine content of 184 ppm, and a viscosity of 787 cps. At this time, the resin is represented by Formula 1, and contains 76 mol% of a compound of n=0, 15 mol% of a compound of n=1, and 9 mol% of a compound of n=2 or more.

Example 3. Preparation of Epoxy Resin

1932 g (20.890 mol) of epichlorohydrin, 25 g (0.318 mol) and 58 g (0.727 mol) of 50% caustic soda in the initial stage were divided into two portions and uniformly dripped, reacted for 2 hours each, and then added 50% Caustic soda 182 g (2.275 mol) and 465 g (5.812 mol) were divided into two portions and uniformly dripped for 60 minutes and 180 minutes, respectively, and the reaction was carried out in the same manner as in Example 1, except that the reaction was carried out for 1 hour. . The final resin had an epoxy equivalent of 181 g/eq, a chlorine content of 560 ppm, and a viscosity of 1640 cps. In this case, the resin is represented by Formula 1, and contains 58 mol% of a compound having n=0, 32 mol% of a compound having n=1, and 10 mol% of a compound having n=2 or more.

Comparative Example 1. Preparation of epoxy resin

The reaction was carried out in the same manner as in Example 1, except that 2.5 g (0.5 wt%) of benzyl trimethyl ammonium chloride (BTMAC) was added instead of 48 g (0.599 mol) of 50% caustic soda. The final resin had an epoxy equivalent of 193 g/eq, a chlorine content of 177 ppm, and a viscosity of 2403 cps. In this case, the resin is represented by Formula 1, and contains 47 mol% of a compound of n=0, 42 mol% of a compound of n=1, and 11 mol% of a compound of n=2 or more.

Comparative Example 2. Preparation of epoxy resin

1132 g of isopropyl alcohol and 300 g of water were added and the reaction was performed in the same manner as in Example 1 above. The epoxy equivalent of the final resin was 279 g/eq, chlorine content 122 ppm, and viscosity 11270 cps. At this time, the resin is represented by Formula 1, and contains 14 mol% of a compound of n=0, 33 mol% of a compound of n=1, and 53 mol% of a compound of n=2 or more.

Comparative Example 3. Bisphenol-A type epoxy resin (EEW 188 g/eq) commercial product (using solvent)

Commercially available bisphenol A epoxy KE-8128 (manufactured by Kolon Industries, EEW 188 g/eq) was completely dissolved in 112.5 g of xylene 50 g and MIBK 22.5 g at 60° C. to prepare a bisphenol-A epoxy solution having a solid content of 60%.

Comparative Example 4. Bisphenol-A type epoxy (EEW 188 g/eq) commercial product (without solvent)

112.5 g of commercial bisphenol A epoxy KE-8128 (manufactured by Kolon Industries, EEW 188 g/eq) was used without adding a solvent, and 100% solid content bisphenol-A type epoxy resin was used.

Below are the epoxy equivalent and chlorine content analysis methods of the Examples and Comparative Examples.

Epoxy Equivalent Analysis Method

An appropriate amount of the sample was collected in a static Erlenmeyer flask and completely dissolved by adding 10 ml of 1,4-dioxane. After dissolution, exactly 25 ml of 0.2 N HCl (dioxane) was added.

Close the lid and drop one or two drops of dioxane on the boundary with the flask, and then react at room temperature for 30 minutes. After the reaction, the flask and stopper were washed with about 10 ml 2-methoxyethanol and included in the flask.

3 drops of cresol red indicator were added, and titration was performed with a 0.1 NaOH (methanol) solution at the point where the color changed from pink to yellow and became purple as the endpoint. At the same time, a blank test was performed.

*Calculation method

Equivalent (g/eq) = 10,000 x W/(B-A) x F

B: 0.1 N NaOH (methanol) consumption during blank titration (ml)

A: 0.1 N NaOH (methanol) consumption (ml) for sample titration

F: 0.1 N NaOH (methanol) Factor

W: Sample amount (g)

Analysis of hydrolyzable chlorine (Hy-Cl)

A sample was collected in a 200 ml Erlenmeyer flask and calibrated to 0.1 mg. After dissolving by adding 25 ml of 1,4-dioxane, 25 ml of a 0.1 N KOH (methanol) solution was added, and a glass cooling tube was attached, followed by reaction in a water bath at 70° C. for 30 minutes. After cooling to room temperature, the glass cooling tube was washed with 5-10 ml of methanol and added to the flask. The solution in the Erlenmeyer flask was transferred to a 200 ml beaker, the Erlenmeyer flask was washed 2-3 times with 80% acetone again, and the washing solution was added to the beaker, and the total amount was 100 ml. 3 ml of acetic acid was added and titrated with _{0.01 N AgNO 3 aqueous solution.} Measurements were performed at two points simultaneously, and if the difference between the measurements was within 0.003%, the average value was recorded to the third decimal place. At the same time, a blank test was conducted.

*Calculation method

Chlorine content (%) = {[(V-B) x 0.01 x 35.5 x F] / (1,000 x W)} x 100

V: 0.01 N AgNO ₃ consumption during sample titration (ml)

B: 0.01 N AgNO ₃ consumption (ml) during blank titration

F: 0.01N AgNO ₃ Factor

W: Sample amount (g)

Experimental Example 1. Evaluation of paint performance

film formation

Liquid paints were prepared using the resins of Examples and Comparative Examples, and a coating film was formed.

144 g (27.54%) of the resin prepared according to the above Examples and Comparative Examples was put into a circular plastic container, and 2 g (0.38 g) of a wetting agent and 5 g (0.96%) of Soya lecithin were added. While adding and stirring, 10 g (1.91%) of bentone was added little by little. Then, TiO ₂ , talc (Talc), iron oxide black (iron oxide black) 80 g (15.29%), 280 g (53.54%), 2 g (0.38%) was added, respectively, after 15 minutes at a speed of 1000 rpm stirred.

1.5 cups of glass beads were added to the stirred mixture based on a paper cup. It was dispersed using a shaker, and the particle size was measured every 20 minutes. When the particle size became 40 μm or less, the dispersion was terminated. The glass beads were filtered to complete the preparation of the subject matter.

By mixing LITE 2002 (AHEW = 104 g/eq), a phenalkamine-type curing agent, and the above-prepared main agent at an equivalent ratio of epoxy and active hydrogen of 1:1, the glass and iron samples were applied to a thickness of 75 μm and 120 μm, respectively. After coating, it was completely dried at room temperature to form a coating film.

The paint performance evaluation method is described below.

(1) Drying rate: ASTM D5895

It was judged by looking at the shape recorded on the painted surface over time using an automatic drying speed measuring device.

(2) Adhesion: ASTM D4541 (Dolly test)

After attaching the dolly to the surface of the coating film, the force required for the dolly to fall was measured using a portable adhesion test device.

(3) Flexural adhesion (flex resistance): ASTM E643 (Erichen Cupping test)

When a gradual deformation by press-fitting (pressing in) was applied to the coating film, the crack generation resistance and peeling resistance from the metal substrate were evaluated.

(4) Impact resistance: ASTM D2794

Using a Dupont-type impact tester, it was dropped to a height of 45 cm with a weight of 1 kg and evaluated as good if the coating film was not peeled off, and bad if the coating film was peeled off.

(5) Solvent resistance and acid/base resistance

After dropping xylene, 5% sulfuric acid aqueous solution, and 5% caustic soda on each coating film and leaving it at room temperature for 72 hours, the degree of damage to the coating film was visually determined.

(6) surface glossiness

The 30° mirror glossiness of the paint film was measured with a reflectometer.

The physical properties of the coating film prepared as described above by the above method were measured as follows, and the results are shown in Table 1 below, and specific values of the physical properties are shown in Table 2 below.

		Example 1	Example 2	Example 3	Comparative Example 1	Comparative Example 2	Comparative Example 3	Comparative Example 4
drying speed		◎	◎	○	△	film formation impossible	X	film formation impossible
adhesion		◎	◎	◎	△		△
Flexibility		○	○	○	X		△
impact resistance		○	○	○	X		△
chemical resistance	solvent resistance	◎	○	○	△		△
	acid/base	○	○	○	X		△
surface gloss		◎	◎	○	△		△

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

	Example 1	Example 2	Example 3	Comparative Example 1	Comparative Example 2	Comparative Example 3	Comparative Example 4
Drying speed (min)	173	207	235	291	film formation impossible	359	film formation impossible
Adhesion (MPa)	7.5	7.6	7.3	5.6		5.3
Flexibility (mm)	6.9	6.7	6.7	5.8		6.3
surface gloss	30.9	31.1	28.9	20.5		19.8

As shown in Tables 1 and 2, in Comparative Examples 2 and 4, it was confirmed that a coating film was not formed due to high viscosity without a solvent or diluent. In the case of the epoxy resin of Comparative Example 1, a coating film was formed without mixing of a solvent, but compared to the coating film of Comparative Example 3 in which a solvent was mixed, overall physical properties such as bending resistance, impact resistance, acid/base resistance, etc. were poor except for the drying speed.

On the other hand, it was confirmed that the epoxy resins of Examples 1 to 3 can form a coating film without solvent mixing and can be used as a solvent-free paint, and overall physical properties such as adhesion, bending resistance, impact resistance, chemical resistance, and surface gloss are compared. It was superior to the coating film using the solvent-type bisphenol-A type epoxy resin as well as the resin of Example 1, and it was confirmed that the drying rate was also greatly shortened.

Therefore, the epoxy resin according to the present invention can be used as a paint without mixing a solvent and/or a diluent based on a low viscosity, and the drying rate is significantly higher than that of the existing coating film in film forming using the epoxy paint composition containing the epoxy resin. It is improved, and it is possible to manufacture a coating film having an equivalent or higher level of overall physical properties.

The above-described Examples and Comparative Examples are examples for explaining the present invention, but the present invention is not limited thereto. Those of ordinary skill in the art to which the present invention pertains will be able to practice the present invention with various modifications therefrom, so the technical protection scope of the present invention should be defined by the appended claims.

Claims (15)

1. Represented by the following formula (1),

   An epoxy resin comprising 50 mol% or more of a compound having n = 0 in the following formula (1)

   [Formula 1]

   

   In Formula 1, n is an integer of 0 to 4.
2. Represented by the following formula (1),

   An epoxy resin comprising a mixture of a compound in which n = 0, a compound in which n = 1, and a compound in which n = 2 in the following formula (1):

   [Formula 1]

   

   In Formula 1, n is an integer of 0 to 4.
3. 3. The method of claim 2,

   The epoxy resin is an epoxy resin comprising 50 mol% or more of the compound of n = 0 in Formula 1 above.
4. 3. The method of claim 1 or 2,

   The epoxy resin is an epoxy resin comprising 90 mol% or more of the compound of n = 0 to 1 in Formula 1 above.
5. 3. The method of claim 1 or 2,

   The epoxy resin is 50 to 90 mol% of the compound of n = 0 in Formula 1,

   5 to 40 mol% of a compound with n=1 and

   An epoxy resin comprising 1 to 11 mol% of a compound of n = 2 or more.
6. 3. The method of claim 1 or 2,

   The viscosity of the epoxy resin is 2000 cps or less at 25 ℃, the epoxy equivalent of the epoxy resin of 120 to 185 g / eq.
7. Including an epoxy resin represented by the following formula (1),

   The epoxy resin is an epoxy paint composition comprising 50 mol% or more of a compound having n = 0 in the following formula (1):

   [Formula 1]

   

   In Formula 1, n is an integer of 0 to 4.
8. Including an epoxy resin represented by the following formula (1),

   The epoxy resin is an epoxy paint composition comprising a mixture of a compound in which n = 0, a compound in which n = 1, and a compound in which n = 2 in the following formula (1):

   [Formula 1]

   

   In Formula 1, n is an integer of 0 to 4.
9. 9. The method of claim 8,

   The epoxy resin is an epoxy paint composition comprising 50 mol% or more of the compound of n = 0 in Formula 1 above.
10. 9. The method of claim 7 or 8,

    The epoxy resin is an epoxy paint composition comprising 90 mol% or more of the compound having n = 0 to 1 in Formula 1 above.
11. 9. The method of claim 7 or 8,

    The epoxy resin is 50 to 90 mol% of the compound of n = 0 in Formula 1,

    5 to 40 mol% of a compound with n=1 and

    An epoxy paint composition comprising 1 to 11 mol% of a compound of n=2 or more.
12. 9. The method of claim 7 or 8,

    The viscosity of the epoxy resin is 2000 at 25 ° C. cps or less and an epoxy equivalent of 120 to 185 g/eq.
13. 9. The method of claim 7 or 8,

    The epoxy paint composition includes a main part and a curing agent part containing the epoxy resin,

    The main part is an epoxy paint composition comprising 5 to 50 parts by weight of the epoxy resin and 50 to 95 parts by weight of the pigment based on 100 parts by weight of the main part.
14. A coating film formed of the epoxy paint composition according to claim 7 or 8.
15. A substrate with a coating film comprising the coating film according to claim 14 and the substrate.

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