KR20220107861A - Temperature sensitive composition using water-based and oil-based binder resin and method for manufacturing the same - Google Patents

Abstract

The present invention relates to a temperature-sensitive paint composition using aqueous and oil-based binding resin and a manufacturing method thereof, and more specifically, to an epoxy-based temperature-sensitive paint composition and a manufacturing method thereof. The temperature-sensitive paint composition according to the present invention is manufactured by mixing a main agent and a curing agent. The main agent is composed of 99-99.8 wt% of solvent-free oil-based epoxy resin with a polar group and 0.2-1 wt% of an antifoaming agent. The curing agent is composed of 25-35 wt% of a water-soluble epoxy curing agent; 8-12 wt% of a coloring pigment; 4-7 wt% of a temperature-sensitive pigment; 30-45 wt% of fresh water; 12-19 wt% of a filler; and 1-5 wt% of an additive. Since an aqueous epoxy curing agent is combined with the solvent-free oil-based epoxy resin with the polar group, provided are an aqueous and oil-based binding eco-friendly coating agent and a manufacturing method thereof capable of taking advantage of aqueous and oil-based paints which do not emit environmental hormones, volatile organic compounds, formaldehyde, etc.

Description

TECHNICAL FIELD [0002] Temperature sensitive composition using water-based and oil-based binder resin and method for manufacturing the same

The present invention relates to a thermal coating composition and a method for manufacturing the same, and more particularly, to an epoxy-based thermal coating composition and a method for manufacturing the same.

Thermosensitive (Zion) pigments are pigments that change color depending on temperature. There are two types: reversible and non-reversible pigments that change color above a certain temperature and return to their original color when it drops below a certain temperature. By combining reversible thermal pigments, you can visually see the process of changing to various colors above a certain temperature.

The thermal pigment has a grade in which the color changes according to temperature from -20 to 70 ° C. In addition, various colors can be obtained by combining two or more types of thermal pigments or combining thermal pigments and general pigments.

Methods for forming a thermal coating film by mixing such a thermal pigment with a paint resin have been developed.

Korean Patent Registration No. 10-1673365 (Title of the invention: Thermal paint composition using silicone resin and manufacturing method thereof), Korean Patent Publication No. 10-2014-0024525 (Title of the invention: Paint composition that changes color by ultraviolet rays) Describes a thermal material that changes color according to temperature change using silicone resin and synthetic resin type (urethane, epoxy, acrylic resin), respectively.

However, the existing organic thermal coating film contains volatile compounds, and not only releases a large amount of environmental hormones, volatile organic compounds, formaldehyde, etc. Have. In particular, it is dangerous to use on a mask adjacent to the respiratory tract.

Accordingly, the demand for water-soluble thermal coatings continues, and in the publication of Korean Patent Registration No. 10-1911910 (title of invention: Method for manufacturing inorganic temperature-sensitive paint composition and thermal-sensitive inorganic ceramic paint using the same), a water-soluble inorganic resin is It is used to provide a thermosensitive material whose color changes according to the temperature change.

However, the water-soluble resin constituting the water-soluble thermal paint has a problem in that water resistance, mechanical, and chemical quality characteristics are inferior compared to the synthetic resin-based paint.

Republic of Korea Patent No. 10-1673365 Republic of Korea Patent Publication No. 10-2014-0024525 Republic of Korea Patent Registration No. 10-1911910

The problem to be solved in the present invention is water-based having excellent temperature sensitivity and color restoration at a specific temperature above and below, good spray workability, storage stability, wetting to non-woven fabrics, hiding power and adhesive strength To provide a thermal coating composition.

The problem to be solved in the present invention is water-based having excellent temperature sensitivity and color restoration at a specific temperature above and below, good spray workability, storage stability, wetting to non-woven fabrics, hiding power and adhesive strength To provide a method for producing a thermal coating composition.

The problem to be solved in the present invention is water-based having excellent temperature sensitivity and color restoration at a specific temperature above and below, good spray workability, storage stability, wetting to non-woven fabrics, hiding power and adhesive strength It is to provide a member for a respirator capable of warning of danger by forming a thermal coating film.

In order to solve the above problems, the present invention

A main agent consisting of 99 to 99.8 wt% of a solvent-free oil-based epoxy resin imparted with a polar group and 0.2 to 1 wt% of an antifoaming agent, 25 to 35 wt% of a water-soluble epoxy curing agent, 8 to 12 wt% of a coloring pigment, 4 to 7 wt% of a thermal pigment, fresh water There is provided a composition for a thermally sensitive material, characterized in that a curing agent consisting of 30 to 45% by weight, 12 to 19% by weight of a filler, and 1 to 5% by weight of an additive is mixed.

The present invention in one aspect,

Preparing a main agent consisting of 99 to 99.8 wt% of a solvent-free oil-based epoxy resin imparted with a polar group and 0.2 to 1 wt% of an antifoaming agent;

A curing agent consisting of 25 to 35% by weight of a water-soluble epoxy curing agent, 8 to 12% by weight of a color pigment, 4 to 7% by weight of a thermal pigment, 30 to 45% by weight of fresh water, 12 to 19% by weight of a filler, and 1 to 5% by weight of an additive manufacturing steps, and

Mixing the prepared subject and curing agent

It provides a method for producing a thermal coating composition comprising a.

In another aspect, the present invention

A main agent consisting of 99 to 99.8 wt% of a solvent-free oil-based epoxy resin imparted with a polar group and 0.2 to 1 wt% of an antifoaming agent, 25 to 35 wt% of a water-soluble epoxy curing agent, 8 to 12 wt% of a coloring pigment, 4 to 7 wt% of a thermal pigment, fresh water 30 to 45% by weight, 12 to 19% by weight of filler, and 1 to 5% by weight of additives A thermal pigment mixed with a thermosensitive pigment is coated with a composition of a water-based and oil-based combination thermally-dried thermal coating film containing It provides a member for breathing apparatus.

In the practice of the present invention, the respirator member may be a mask.

Hereinafter, the composition according to the present invention will be described for each component.

The composition of the thermosensitive material according to the present invention comprises a main agent comprising 99 to 99.8 wt% of a solvent-free oil-based epoxy resin imparted with a polar group and 0.2 to 1 wt% of an antifoaming agent, 25 to 35 wt% of a water-soluble epoxy curing agent, and 8 to 12 wt% of a color pigment %, 4 to 7% by weight of a thermal pigment, 30 to 45% by weight of fresh water, 12 to 19% by weight of a filler, and 1 to 5% by weight of an additive.

In the present invention, the mixture of the main agent and the curing agent may be made in an equivalence ratio, preferably in an equivalence ratio of 1:1.

First, the composition of the water-based and oil-based eco-friendly coating agent according to the present invention is an epoxy resin using a solvent-free oil-based epoxy resin to which a polar group is imparted and a water-soluble epoxy curing agent that can be cured at room temperature with the solvent-free oil-based epoxy resin and has excellent mixing properties, the temperature-sensitive It is added that by adding a pigment, the composition is characterized by imparting a color change function at a specific temperature.

As a result, the composition of the water-based and oil-based eco-friendly thermosensitive material can easily detect the color change according to the temperature change, thereby ensuring safety in daily life, and drying of the eco-friendly thermosensitive material with excellent quality characteristics. Including the effect of obtaining a coating film.

(A) Subject component

The main component according to the present invention is characterized in that it consists of 99 to 99.8% by weight of a solvent-free oil-based epoxy resin imparted with a polar group and 0.2 to 1% by weight of an antifoaming agent.

In the present invention, the polar group of the solvent-free oil-based epoxy resin to which the polar group is imparted may be a hydroxyl group or an alkoxy group, and the alkoxy group may be a methoxy or ethoxy group.

In the practice of the present invention, the solvent-free oil-based epoxy resin having the polar group It may be a reaction product of a bisphenol-based epoxy resin and an isocyanate silane.

In one embodiment of the present invention, the isocyanate silane is not limited, but 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, 3-isocyanatopropylmethyldiethoxysilane, tris[3-(trimethoxysilyl)propyl]isocyanurate, tris[3-(triethoxysilyl)propyl]isocyanurate, isocyanurate methyltrimethoxysilane, isocyanate methyltriethoxysilane.

In a preferred embodiment of the present invention, an epoxy resin and an isocyanate silane were added in an OH equivalent ratio of 1:1 (weight ratio) and stirred, then a reaction catalyst was added and maintained and reacted at 75 to 85° C. for 5 hours to 6 hours.

A specific method for producing the solvent-free epoxy resin to which the polar group is imparted is 78 to 89 parts by weight of a bisphenol F type epoxy resin having an equivalent weight of 160 to 180 g/eq in a 5 L flask equipped with a thermometer, a condenser, a stirrer, and a temperature rising device, and an isocyanate silane (weight Average molecular weight of about 225) After adding 10 to 21 parts by weight, the temperature was raised to 50° C. while slowly stirring and maintained for 30 minutes, 0.01 parts by weight of the reaction catalyst was added dropwise, the temperature was raised to 80° C., and the reaction was maintained for 5 to 6 hours. After the final NCO is 0.01 parts by weight or less to stop the reaction and cooled to 50 ° C. or less to prepare a solvent-free epoxy resin with an epoxy equivalent of 165 to 185 g/eq of a polar group.

As the reaction catalyst, DBTDL (Di-N-BUTYLTIN DILAURATE) is preferable, but in addition, bismuth (BISMUTH) may be used alone or in combination.

The solvent-free epoxy resin prepared above has a weight average molecular weight of 410 to 1,700, an epoxy-equivalent weight of 165 to 185, a solid content of 96 to 99.99 parts by weight, a viscosity (25 ℃) 700 to 2,000 cps, a specific gravity (25 ℃) 1.1 to 1.2 g / mL is preferred.

When the weight average molecular weight of the solvent-free epoxy resin exceeds 1,700, the viscosity of the resin becomes excessively high, and the miscibility with the water-soluble epoxy curing agent decreases, which may cause curing failure. If the weight average molecular weight is less than 410, mechanical and chemical properties decrease problems may arise.

The solvent-free oil-based epoxy resin to which the above-described polar group is given can improve water resistance, hardness, stain resistance, adhesion and mechanical and chemical properties by excluding or minimizing the use of surfactants in the coating agent, in particular, to the resin. By giving polarity to increase miscibility with water, it has excellent compatibility with water-based epoxy curing agents and has the advantage that the curing reaction proceeds smoothly, and the content is preferably 99 to 99.8 parts by weight based on 100 parts by weight of the total main component do. The content is not particularly limited, but may be limited depending on the amount of antifoaming agent used.

The antifoaming agent serves to remove air bubbles generated during the preparation of the main component and suppress or remove air bubbles during application after mixing the curing agent. It may be preferable in terms of preventing the generation inhibitory effect or the antifoaming agent from floating on the surface of the coating film to prevent poor interlayer adhesion between the coating films and wrinkles on the surface of the coating film. As an example of the defoaming agent, one or more of TECH-405W, TECH-371W (above China Tech Polymer), BYK-066N, BYK-A555, BYK-354 (above Germany BYK company) may be used.

(B) curing agent component

The curing agent of the water-based and oil-based combination eco-friendly thermal material according to the present invention is 25 to 35% by weight of a water-soluble epoxy curing agent, 8 to 12% by weight of a color pigment, 4 to 7% by weight of a thermal pigment, 30 to 45% by weight of fresh water, 12 to 12% by weight of filler 19% by weight, and 1 to 5% by weight of additives.

The water-soluble epoxy curing agent can be cured at room temperature with a solvent-free oil-based epoxy resin to which the polar group of the main component is imparted, and is not particularly limited as long as it is a curing agent with excellent compatibility, but preferably has excellent low-temperature curing properties in winter, long pot life, particularly room temperature reactivity It may be preferable to select and use a water-soluble epoxy curing agent having a solid content of 45 to 55, a viscosity of 400 to 1,000 cps, and an equivalent Wt/H of 220 to 260. An amine-based curing agent may be used in the water-soluble epoxy curing agent, and for example, at least one selected from the group consisting of polyamines, modified polyamines, and polyetheramines is preferable.

The content of the epoxy curing agent may be preferably 25 to 35 parts by weight based on 100 parts by weight of the total curing agent component. If it is out of the above range, the curing of the epoxy resin contained in the main component does not proceed normally, so that the coating agent is mechanically and chemically Physical properties may be deteriorated, and problems such as delayed drying may occur.

The color pigment is used to impart the color of the thermosensitive material, and the content thereof is preferably 8 to 12 parts by weight based on 100 parts by weight of the total curing agent component. When the content of the coloring pigment is less than 10 parts by weight, the hiding power is reduced, and when it is more than 12 parts by weight, the effect of improving the hiding power is inferior compared to the amount used. Examples of the color pigment include TiO2, iron oxide red, cobalt blue, cyanine blue, carbon black, iron oxide black, oxide green, and the like, and one or more of them may be used.

The thermal pigment serves to impart temperature sensitivity and color restoration properties to the dry coating film above and below a specific temperature, and the content thereof is preferably 4 to 7 parts by weight based on 100 parts by weight of the total curing agent component. When the content of the thermal pigment is less than 3 parts by weight based on 100 parts by weight of the total curing agent component, the degree of color change is poor, and when it exceeds 7 parts by weight, the increase in the effect of temperature sensitivity and color restoration compared to the amount used is insufficient.

The thermal pigment may have a solid content of 98 to 100%, an average particle size of 1 to 5 microns, a color temperature range of 36.8 to 37.2° C., and preferably a moisture content of 0.4% or less.

The water serves to adjust the viscosity of the thermosensitive material, and the content thereof is preferably 30 to 45 parts by weight based on 100 parts by weight of the total curing agent component. If the content of water is less than 30 parts by weight based on 100 parts by weight of the total curing agent component, the viscosity becomes too high when mixing the coating agent, making it difficult to mix, and if it exceeds 45 parts by weight, the reactivity with the solvent-free oil-based epoxy resin and the viscosity of the coating agent are too low and stored Heavy precipitation may occur.

The filler is for improving workability by increasing the volume of the eco-friendly thermal material, and the content thereof is preferably 12 to 19 parts by weight based on 100 parts by weight of the total curing agent component.

When the content of the filler is less than 12 parts by weight, the volume shape effect is reduced, and when it is more than 19 parts by weight, the overall physical properties are not significantly affected, but the amount of the coloring pigment, water, etc. can be limited due to the increase in the amount of the filler used. As an example of the filler, one or more of talc, silica, barium sulfate, mica, mica, and the like may be used.

The additive may be preferably 1 to 5 parts by weight based on 100 parts by weight of the total components of the curing agent. More specifically, it may be preferable to include 7 to 15 parts by weight of an antifoaming agent, 10 to 15 parts by weight of a dispersant, and 70 to 80 parts by weight of a thickener based on 100 parts by weight of the total additive content.

The antifoaming agent serves to remove bubbles generated during manufacturing of the curing agent, and to suppress or remove bubbles when applied after mixing with the main agent, and the content thereof is 7 to 15 parts by weight based on 100 parts by weight of the total additive content. Effects or antifoaming agents may be preferable in terms of preventing the phenomenon of poor adhesion between the layers of the coating film by bleeding on the surface of the coating film.

Examples of the defoaming agent include BYK-024, BYK-015, BYK-1711 (above BYK, Germany), Tech-405W, Tech-371W (above China Tech Polymer), Foamstar ED 2522, Foamstar ST 2150AC (above BASF Germany) G), one or more of them can be used.

The dispersant serves to improve the dispersibility of the colored pigment, and the content thereof is preferably 10 to 15 parts by weight based on 100 parts by weight of the total additive component. If the content is less than 10 parts by weight of the additive component, the dispersibility of the colored pigment may deteriorate and a dichroic phenomenon may occur. If the content exceeds 15 parts by weight, the color pigment bleeding may occur due to the overdispersion effect. As an example of the dispersant, one or more of Disperbyk-187, Disperbyk-190, Disperbyk-199 (above BYK, Germany), FDA-111 (Tech Polymer, China), Dixpex CX 4320 (BASF, Germany) It can be selected and used, and is not necessarily limited thereto.

The thickener serves to prevent precipitation of the pigment, and the content thereof is preferably 70 to 80 parts by weight based on 100 parts by weight of the total additive component. If the content is less than 70 parts by weight of the additive component, the effect of preventing the precipitation of the pigment is insignificant. As an example of the thickener, one or more of OPTIBENT 940, OPTIBENT 987, OPTIBENT NT10 (above BYK, Germany), RM 2020, and RM 825 (above, DOW, Germany) can be selected and used. not to put

Hereinafter, a manufacturing method according to the present invention will be described.

A method for producing a water-based and oil-based combination eco-friendly thermal material according to the present invention; a first step of preparing the main ingredient by sequentially adding the main ingredient and then stirring at high speed at room temperature for 30 minutes using a high-speed stirrer; a second step of preparing a curing agent component by sequentially adding the curing agent component of the composition of the ceramic coating agent, followed by high-speed stirring at room temperature for 100 minutes using a high-speed stirrer; and a third step of mixing the main component and the curing agent component in a 1:1 equivalent ratio, followed by high-speed stirring for 3 to 4 minutes with a high-speed stirrer.

The water-based and oil-based combination eco-friendly thermal material comprising the (A) main component and the (B) curing agent component is airless spray, air spray, roller or brush, etc. at room temperature by adjusting the viscosity without dilution or using water. It can be prepared as a coating agent in a form that can be painted, and in this case, (A) the main component and (B) the curing agent component can be used by adjusting the mixing ratio so that the equivalent ratio is 1:1.

By combining a water-based epoxy curing agent with a solvent-free oil-based epoxy resin imparted with a polar group according to the present invention, an eco-friendly coating agent combining water and oil that takes only the advantages of water-based and oil-based paints without emission of environmental hormones, volatile organic compounds, formaldehyde, etc. and a method for manufacturing the same this was provided

The thermal coating film formed by the coating agent of the present invention overcomes the disadvantages of the non-environmental nature of oil-based paints and the deterioration of the quality characteristics of water-based paints, and is environmentally friendly and has excellent quality characteristics of the coating film.

In addition, the thermal coating film formed by the coating agent of the present invention enables temperature identification because it can change to a desired color at a specific temperature by adding a thermal pigment to the water-based and oil-based eco-friendly coating agent, thereby reducing the risk of temperature change. can be presented visually.

1 is a method for preparing a water-based and oil-based combination eco-friendly thermal material composition according to the present invention.
2 is a photograph for showing the color change at a specific temperature (37.5° C.) or higher after printing the water-based and oil-based eco-friendly thermal material according to the present invention on a mask.

Hereinafter, the present invention will be described in detail through examples. It should be noted that the following examples are not intended to limit the present invention, but to illustrate the present invention.

Hereinafter, as shown in FIGS. 1 and 2 , the following examples were tested in order to confirm the effect of the water-based and oil-based eco-friendly thermosensitive material according to the present invention as an example.

First, according to the composition of the main component as shown in Table 1, the antifoaming agent, dispersing and wetting agent are added to the solvent-free oil-based epoxy resin presented above, and then using a high-speed stirrer at room temperature for 30 minutes at RPM 1200 or higher. Thus, the subject component was prepared.

division Example comparative example note One 2 3 4 5 One 2

main
My
castle
minute Give polarity
Solvent-free epoxy resin 99.7 99.7 99.7 99.7 99.7 - - Equivalent 170 g/eq, solids 99.9 parts by weight (self-synthesis) water-soluble epoxy resin - - - - - 99.7 - KEM-128R (Kukdo Chemical) Solvent-free epoxy resin - - - - - - 99.7 YD-128 (Kukdo Chemical) antifoam 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Tech-405W
BYK-066N (Comparative Example 2) Total (g) 100 100 100 100 100 100 100
kyung
fury
My
castle
minute modified polyamines 30.0 30.0 30.0 25.0 35.0 30.0 30.0 Anquamin 287 dispersant 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Disperbyk-190 color pigment 10.0 10.0 10.0 10.0 10.0 10.0 10.0 TiO2:8/iron oxide:2 thermal pigment 3 6 8 6 6 6 6 Pigment BLUE37 filler 15 15 15 15 15 15 15 Silica #325 antifoam 0.3 0.3 0.3 0.3 0.3 0.3 0.3 TECH-405W water 39 36 33 41 31 36 36 Distilled water thickener 2.3 2.3 2.3 2.3 2.3 2.3 2.3 RM-2020 Total (g) 100 100 100 100 100 100 100

Then, as the curing agent component, a dispersant, a color pigment, a thermal pigment, fresh water (water), a filler, an antifoaming agent, and a thickener are added to the modified polyamine-type curing agent, and then, using a high-speed stirrer, the curing agent is stirred at high speed at room temperature of at least 2000 RPM for 100 minutes. ingredients were prepared. At this time, the temperature was maintained below 60 °C.

Then, after preparing the main component and the curing agent component, based on the composition ratio in Table 1, eco-friendly thermally sensitive materials according to Examples 1 to 5 and Comparative Examples 1 to 2 including the main component and the curing agent component were obtained. .

In order to examine the physical properties of the eco-friendly thermal material formed from the composition containing the main component and the curing agent component of Examples 1 to 5 and Comparative Examples 1 to 2, the main component and the curing agent component were mixed in a weight ratio of 0.26:1 (implementation). Examples 1, 2, 3), a weight ratio of 0.22:1 (Example 4), a weight ratio of 0.30:1 (Example 5), and a weight ratio of 0.24:1 (Comparative Examples 1 and 2) were mixed.

At this time, the equivalence ratio of the main component and the curing agent component was adjusted to be 1:1, and for the ease of airless spraying, 0 to 10 parts by weight of fresh water as a diluent was mixed to dilute the temperature sensitive material, and then In order to evaluate the coating film performance, test specimens as shown in Table 2 were prepared.

Test Items Dimensions of test piece (unit: mm) Count film exterior 70x150x1.2 3 storage stability 500g One water resistance test 70x150x1.2 3 Flexibility test 70x150x0.5 3 adhesion test 70x150x1.2 3 Miscibility (subject + hardener) 300g One Reactivity (dryness) 70x150x1.2 3 Temperature sensitivity (37.5℃) and color restoration 50x50x0.5 (dry film) 3 Temperature sensitivity (60.0℃) and color restoration 50x50x0.5 (dry film) 3

In order to evaluate the coating performance using the eco-friendly thermal material prepared in this way, first, a cold-rolled steel sheet (KS D 3512) having a thickness of 1.2T is surface-treated using sandpaper (#400), and then the relative humidity is 85% or less, Each of the thermally-sensitive materials prepared above at a temperature of 15 to 30°C was coated with an airless sprayer to a dry coating film thickness of about 100㎛, dried at room temperature for 7 days, and then the coating film properties were tested. Specimens are produced using only dry coatings)

① Appearance of the film

The surface state of the coating film, swelling, wrinkles, and the like of the specimen prepared above were observed with the naked eye.

② Storage stability

Put the prepared thermal material into a 0.5L plastic container, seal the upper part so that it does not come into contact with air, and then open the upper part after preventing it in an oven at 60℃ for 7 days. was understood.

③ Water resistance test

The specimen prepared above was immersed in distilled water at 60° C. for 7 days. At this time, take it out every 24 hours and check for any abnormalities on the surface of the coating film (blooding, brittleness, swelling, cracks, peeling, etc.) immersion was observed).

④ Flexibility test

Peeling, peeling, etc. were identified with respect to the specimen prepared above, the side painted on the top of the Mundre rod (1/2 inch in diameter), which is a flexibility testing device, was turned upward, and then folded 180 degrees downward.

⑤ Adhesion test

The specimens prepared above were scraped with a knife to cross each other 11 at an interval of 2 mm to make 100 cells, and then peeled off after bonding to the area with 3M transparent tape to determine the number of cells in which the coating film did not fall.

⑥ Mixability test

After mixing the main component and the curing agent component prepared above at the specified mixing ratio, the degree of miscibility was expressed as a number from 1 to 10 at the minimum after visual observation.

⑦ Reactivity test (dry)

After mixing the main component and curing agent component prepared above at the specified mixing ratio, forming a coating film with a wet film thickness of 76 μm with a film applicator, after 24 hours have elapsed, the degree of drying was observed.

⑧ Temperature sensitivity and color restoration

In the case of temperature sensitivity, it was found that the specimen prepared above was left in an oven to maintain temperature and maintained for 30 minutes, and then changed from the color before the experiment to pink. It was found that the original color (blue) was restored from pink. The temperature sensitivity test for each temperature (30 minutes) => room temperature cooling (30 minutes) was performed as 1 cycle, and 5 cycles were performed.

Table 3 shows the results of evaluation of the physical properties of the specimens by the tests of ① to ⑧.

Evaluation items Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 3 film exterior Good Good Good Good Good Good poor drying storage stability nothing strange nothing strange nothing strange nothing strange nothing strange nothing strange layer separation water resistance test 10 10 10 8 10 7 (buried) not measurable Flexibility test 10 10 10 10 10 10 not measurable adhesion test 100/100 100/100 100/100 95/100 99/100 92/100 not measurable Mixability (Subject + Hardener) 9.5 9.5 9.5 9.5 9.5 10 3 Reactivity (dryness) 10 10 10 8 10 10 poor drying Temperature sensitivity (37.5℃) /

color restoration Weak color change /
Good Good color change /
Good Good color change /
Good Good color change /
Good Good color change /
Good Good color change /
Good not measurable Temperature sensitivity (60.0℃) /

color restoration Weak color change /
Good Good color change /
Good Good color change /
Good Good color change /
Good Good color change /
Good Good color change /
Good not measurable

As summarized in Table 3, it can be confirmed that the use of the self-synthesized solvent-free oil-based epoxy resin having a polar group contributes to the improvement of the physical properties of water resistance and adhesion, which are disadvantages of the water-soluble epoxy resin (Comparative Example 1), and the temperature reduction It can be seen that the performance of restoring the original color back to the original color when the temperature is lowered after the color change at a specific temperature or higher by the use of the pigment is good.

In addition, in the case of a known oil-based solvent-free epoxy resin (Comparative Example 2), it can be seen that the coating film formation itself is impossible due to very poor miscibility with the water-soluble epoxy curing agent.

In the case of the coating film appearance and storage stability test, as shown in the evaluation results of Examples 1, 2, 3, 4, 5 and Comparative Example 1, all were good.

In the case of the temperature sensitivity and color restoration test, in the case of Example 1, the color restoration property was good, but the degree of color change was somewhat poor due to the low content of the thermal pigment, and in Examples 2, 3, 5 and Comparative Example 1, the temperature sensitivity and color It was confirmed that the degree of change was good.

In the case of the water resistance test, as shown in the evaluation results of Examples 1, 2, 3, 4, and 5, a self-synthesized polar group-containing oil-based solvent-free epoxy resin that solves the problem of poor water resistance, which is a disadvantage of the water-soluble epoxy binder itself, is used. It can be seen that Example 1 is greatly improved.

In the case of the miscibility test, although the miscibility is slightly lower than that of Comparative Example 1 using Examples 1, 2, 3, 4, and 5-valent water-soluble epoxy resin and water-soluble epoxy curing agent using self-synthesized oil-based solvent-free epoxy resin (at room temperature after mixing) It can be seen that a slight layer separation phenomenon is observed when left alone) and reactivity (dryness) during coating is normally achieved in the same manner as in Comparative Example 1.

In the case of the flexibility test, as shown in the evaluation results of Examples 1, 2, 3, 4, 5 and Comparative Example 1, it can be seen that all of them are good.

In the case of the adhesion test, as shown in the evaluation results of Examples 1, 2, 3, 4, 5 and Comparative Examples 1 and 2, when applying a self-synthesized solvent-free epoxy resin, a comparative example using a water-based resin regardless of the curing agent content It can be seen that it is better than 1.

In the case of Comparative Example 2, the mixing property of the oil-based solvent-free epoxy resin and the water-soluble epoxy curing agent was very poor, and thus the formation of the coating film itself was impossible, making it impossible to test the overall physical properties.

As described above, the composition of the water-based and oil-based eco-friendly thermosensitive material according to the present invention and its manufacturing method have been described through examples, and the superiority of its physical properties has been confirmed. It is not limited, and various substitutions, modifications, and changes are possible without departing from the technical spirit of the present invention.

Claims (9)

A main agent consisting of 99 to 99.8 wt% of a solvent-free oil-based epoxy resin imparted with a polar group and 0.2 to 1 wt% of an antifoaming agent;
A curing agent consisting of 25 to 35% by weight of a water-soluble epoxy curing agent, 8 to 12% by weight of a color pigment, 4 to 7% by weight of a thermal pigment, 30 to 45% by weight of water, 12 to 19% by weight of a filler, and 1 to 5% by weight of an additive A thermal material composition, characterized in that it is mixed. According to claim 1,
The polar group of the solvent-free oil-based epoxy resin to which the polar group is imparted is a hydroxyl group or an alkoxy group. 3. The method of claim 1 or 2,
The temperature-sensitive paint composition, characterized in that the solvent-free oil-based epoxy resin to which the polar group is imparted is a reaction product of an epoxy resin and an epoxy silane. 4. The method of claim 3,
The epoxy silane is 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, 3-isocyanatopropylmethyldiethoxysilane, tris Among [3-(trimethoxysilyl)propyl]isocyanurate, tris[3-(triethoxysilyl)propyl]isocyanurate, isocyanatomethyltrimethoxysilane, isocyanate methyltriethoxysilane One or more thermal coating compositions are selected. 3. The method of claim 1 or 2,
The solvent-free epoxy resin to which a polar group is imparted has a weight average molecular weight of 410 to 1,700, an epoxy-equivalent weight of 165 to 185, and a viscosity (25° C.) of 700 to 2,000 cps. 3. The method of claim 1 or 2,
The water-soluble epoxy curing agent is a thermal coating composition, characterized in that the amine curing agent. 3. The method of claim 1 or 2,
The temperature-sensitive paint composition, characterized in that the temperature-sensitive temperature of the thermal pigment is 36.8 to 37.2 ℃. Preparing a main agent consisting of 99 to 99.8 wt% of a solvent-free oil-based epoxy resin imparted with a polar group and 0.2 to 1 wt% of an antifoaming agent;
A curing agent consisting of 25 to 35% by weight of a water-soluble epoxy curing agent, 8 to 12% by weight of a color pigment, 4 to 7% by weight of a thermal pigment, 30 to 45% by weight of fresh water, 12 to 19% by weight of a filler, and 1 to 5% by weight of an additive manufacturing steps, and
Mixing the prepared subject and curing agent
A method for producing a thermal coating composition comprising a. A main agent consisting of 99 to 99.8 wt% of a solvent-free oil-based epoxy resin imparted with a polar group and 0.2 to 1 wt% of an antifoaming agent, and
A curing agent consisting of 25 to 35% by weight of a water-soluble epoxy curing agent, 8 to 12% by weight of a color pigment, 4 to 7% by weight of a thermal pigment, 30 to 45% by weight of fresh water, 12 to 19% by weight of a filler, and 1 to 5% by weight of an additive A respiratory member comprising a temperature-sensitive coating film that is naturally dried by applying a composition of a mixed thermal material.

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