KR101673365B1

KR101673365B1 - Thermosensitive coating composition using silicone resin and making method thereof

Info

Publication number: KR101673365B1
Application number: KR1020150158739A
Authority: KR
Inventors: 천상훈
Original assignee: 삼화페인트공업주식회사
Priority date: 2015-11-12
Filing date: 2015-11-12
Publication date: 2016-11-22

Abstract

The present invention relates to a heat-sensitive coating composition using a silicone resin and a method for producing the same, and relates to a heat-sensitive coating composition using a silicone resin and a method for producing the same, which is excellent in heat resistance and color stability and has good surface coating properties and excellent in adhesion, storage stability, gloss and flexibility Sensitive coating composition and a process for producing the same. Accordingly, the present invention visually expresses that when the temperature-sensitive pigment is applied to the outer surface of the container, the painted color changes to an achromatic color when the cooking container reaches a predetermined temperature (70 ° C) It is possible to effectively provide a heat-sensitive coating composition and a method for producing the same, which can make the taste of the cooked food more abundant by timely introduction of the feed.

Description

TECHNICAL FIELD The present invention relates to a thermosensitive coating composition using a silicone resin,

The present invention relates to a heat-sensitive coating composition using a silicone resin and a method for producing the same, and more specifically, to a thermosensitive coating composition using silicone resin, which is excellent in heat resistance and color stability, has good surface coating film properties and excellent in adhesion, storage stability, gloss and flexibility Sensitive coating composition using a silicone resin and a process for producing the same.

It is possible to provide a function of changing the color according to the temperature at which heat is generated when the cooking vessel or the heating unit for heating and cooking is used, thereby preventing the image from being used when the temperature is increased.

In particular, when baking food or frying the food, it is impossible to visually confirm the temperature of the cookable container. Therefore, there is a disadvantage in that it is necessary to check whether the cooked food can be fed by putting a hunch or a certain amount of cooker.

In addition, the bottom surface of the container in contact with the flame to be cooked should be coated with a ceramic resin paint capable of withstanding heat of about 150 ° C or more, or a heat-resistant paint using silicone resin capable of withstanding heat , Most of the current kitchen appliances are applied.

As a conventional art 1, Patent No. 10-1269774 discloses a two-tone type thermochromic coating heating body which is not a coating composition but mainly a coating heating body, and the heat distortion composition is a specific heat- And a specific temperature thermal discoloration composition which is added so that heat discoloration occurs at a heating temperature (170 to 180 ° C, 200 ° C). This is because the actual temperature used during cooking (due to moisture and steam generated during cooking, (70 to 80 DEG C)).

As prior art 2, WO2012 / 085477 discloses a heat-stable coating having at least two colors of decorations having a continuous color tone, wherein the article of manufacture is characterized in that the heated article is cured There are disadvantages.

Ceramic paints generally have good hardness and scratch resistance, but they require 2 hours of aging time (at least 5 hours) as a two-part type paint, depending on the combination of the base and curing agent. After 2 to 3 days at room temperature The paint should be used within the serviceable time (48 hours) due to rapid physical property degradation (gloss disappearance, hardness decrease, paint viscosity increase, etc.). In addition, there is a disadvantage that the material must be applied by blasting with a sand or armor of # 80 ~ # 100 MESH for adhesion to the material.

In order to achieve the above object, the present invention provides a heat-resistant paint using a silicone polyester resin which is one-pack type and has a high heat resistance and resistance to food stains, and is free from pot life, Specific hardening accelerators and adhesion promoters are applied so that it can be dried at 230 ℃ or lower temperature, which is good in workability and productivity because it can be painted after simple sanding treatment and the color of temperature sensitive pigment is changed. ℃, the color changes to achromatic color and the color is restored after cooling the material to room temperature.

The present invention relates to a curable silicone composition comprising 65 to 75 parts by weight of a curable silicone polyester resin, 0.1 to 1.2 parts by weight of a wet dispersant, 0.3 to 3.0 parts by weight of a flow additive, and 3 to 15 parts by weight of a thermochromic pigment; 0.1 to 1.0 part by weight of a creping and wettability improving agent, and a second component containing a solvent. The present invention also relates to a one-pack coating material.

In another embodiment of the present invention, the solvent is 1 to 7 parts by weight of a propylene glycol monomethyl ether acetate solvent, 3 to 9 parts by weight of a ketone solvent and 5 to 35 parts by weight of an aromatic solvent .

Another embodiment of the present invention relates to the thermosensitive coating composition, wherein the aromatic solvent is one or two kinds selected from xylene and toluene, and the ketone solvent is cyclohexanone.

Another embodiment of the present invention relates to the heat-curing coating composition characterized in that the curable silicone polyester resin is represented by the following general formula (I).

The compound of formula (I)

(Wherein R < 1 > represents -C6H5,

X1 and X2 are represented by the following general formula (I-1)

In general formula (I-1)

H in the general formula (I-1) represents 10 to 200)

In another embodiment of the present invention, the thermochromic pigment comprises particles containing 40 wt% to 50 wt% of pigment, 40 wt% to 50 wt% of chromoionophore, and 1 wt% To 10% by weight of a thermosensitive coloring material, and the thermosensitive coloring material has a particle size of 1 to 10 탆.

Another embodiment of the present invention further includes a third component comprising 1 to 9 parts by weight of an aromatic solvent, 1 to 5 parts by weight of an adhesion-imparting resin, and 0.1 to 2 parts by weight of a curing accelerator. &Lt; / RTI >

Another embodiment of the present invention relates to the thermosensitive coating composition, wherein the curing accelerator comprises one or more of the compounds represented by the following formulas (a) to (c).

(In the above formulas (a) to (c), R1 is -NH2 and R2 is -SO3H)

Another embodiment of the present invention relates to the thermosensitive coating composition, wherein the resin for adhesion-imparting comprises a compound represented by the following formula (d).

(D)

In the formula (d), R, R 1 are H and R 2 is -COOH)

Another embodiment of the present invention relates to a heat-sensitive coating composition characterized by having a temperature-sensitive property in a temperature range of 60 ° C to 100 ° C.

According to another embodiment of the present invention, there is provided a method for producing a thermosetting silicone resin composition, which comprises the step (1-1) of mixing and dispersing 0.1 to 1.2 parts by weight of a wet dispersant in 65 to 75 parts by weight of a curable silicone polyester resin and 0.3 to 3.0 parts by weight of a flowable additive, (2) a step 1-3 of mixing and dispersing the sensitizing pigment in an amount of 3 to 15 parts by weight; And a second step of mixing 0.1 to 1.0 part by weight of a creping and wettability enhancer, and further adding a solvent to the composition dispersed in the step 1-3, followed by stirring.

In another embodiment of the present invention, the additional mixed solvent is 1 to 7 parts by weight of a propylene glycol monomethyl ether acetate solvent, 3 to 9 parts by weight of a ketone solvent, and 5 to 35 parts by weight of an aromatic solvent. And a method for producing the same.

In another embodiment of the present invention, the aromatic solvent is one or two kinds selected from xylene and toluene, and the ketone solvent is cyclohexanone.

Another embodiment of the present invention relates to a process for producing a thermosensitive coating composition characterized in that the curable silicone polyester resin is represented by the following general formula (I).

The compound of formula (I)

(Wherein R < 1 > represents -C6H5,

X1 and X2 are represented by the following general formula (I-1)

In general formula (I-1)

H in the general formula (I-1) represents 10 to 200)

In another embodiment of the present invention, the thermochromic pigment is prepared by reacting 40 to 50% by weight of pigment and 40 to 50% by weight of chromoionophore and then encapsulating it in an amount of 1 to 10% by weight of polyethylene And a particle size of 1 to 10 mu m. The present invention also relates to a method for producing the thermosensitive coating composition.

In another embodiment of the present invention, the composition prepared in the second step is prepared by mixing and dispersing 1 to 9 parts by weight of an aromatic solvent, 1 to 5 parts by weight of a resin for attaching and 0.1 to 2 parts by weight of a curing accelerator, The present invention further relates to a method for producing a thermal coating composition,

Another embodiment of the present invention relates to a method for producing a thermosensitive coating composition, wherein the curing accelerator comprises one or more of the compounds represented by the following formulas (a) to (c).

(In the above formulas (a) to (c), R1 is -NH2 and R2 is -SO3H)

Another embodiment of the present invention relates to a method for producing a thermosensitive coating composition, wherein the resin for adhesion-imparting comprises a compound represented by the following formula (d).

(D)

In the formula (d), R, R 1 are H and R 2 is -COOH)

Another embodiment of the present invention relates to a method for producing a heat-sensitive coating composition, which has a temperature-sensitive property in a temperature range of 60 ° C to 100 ° C.

Accordingly, the present invention visually expresses that when the temperature-sensitive pigment is applied to the outer surface of the container, the painted color changes to an achromatic color when the cooking container reaches a predetermined temperature (70 ° C) It is possible to effectively provide a heat-sensitive coating composition and a method for producing the same, which can make the taste of the cooked food more abundant by timely introduction of the feed.

1 is a method for producing a heat-sensitive coating composition.

The present invention relates to a curable silicone composition comprising 65 to 75 parts by weight of a curable silicone polyester resin, 0.1 to 1.2 parts by weight of a wet dispersant, 0.3 to 3.0 parts by weight of a flow additive, and 3 to 15 parts by weight of a thermochromic pigment; 0.1 to 1.0 part by weight of a creping and wettability improving agent, and a second component containing a solvent.

The curable silicone polyester resin is preferably a thermosetting silicone polyester resin. When the amount of the curing silicone resin is less than 65 parts by mass, the gloss, adhesion and solvent resistance are insufficient. When the amount of the curing silicone resin exceeds 75 parts by mass, the cost of the curing agent and the curing accelerator increases, (Such as an increase in frequency of occurrence due to the environment of the tearing and cretering) due to the occurrence of the problem.

Here, preferred examples of the flowable additive are paraffin oil, mineral oil, and wax. Preferable examples of the flowable additive include a polyamide copolymer, a polyolefin copolymer, and an ethylene vinyl acetate wax system.

In addition, preferred examples of the wetting and dispersing agent are polydimethylsilane, polyester alkylol ammonium salt and polyalkyl acrylate ammonium salt. The wetting and dispersing agent is a high molecular weight urethane-based block copolymer solution having a pigment affinity, a modified polyether, and an alkyl alcohol alkyl ammonium salt.

An example of a preferred fluorocarbon of the crating and wettability improver is a fluorocarbon modified acrylic polymer.

The composition of the thermosensitive pigment is also important. The thermosensitive pigment is used in an amount of 3 to 15 parts by weight, preferably 3 to 10 parts by weight, and the ratio of the curable silicone polyester resin to the thermosensitive pigment is adjusted, have. This is because, if only a large amount of thermochromic pigment is retained, the remaining color is left in the temperature test.

Wherein the solvent is 1 to 7 parts by weight of a propylene glycol monomethyl ether acetate solvent, 3 to 9 parts by weight of a ketone solvent and 5 to 35 parts by weight of an aromatic solvent.

Here, when methanol, acetone, ethanol or the like is used as a solvent, since the solvent penetrates into the pigment, the color becomes turbid or becomes thin and it is difficult to display the original color.

Preferred aromatic solvents are one or two selected from xylene and toluene, and the preferred ketone solvent is cyclohexanone.

The compound of formula (I)

(Wherein R < 1 > represents -C6H5,

X1 and X2 are represented by the following general formula (I-1)

In general formula (I-1)

Wherein h in the general formula (I-1) represents 10 to 200)

The compound represented by the general formula (I) is excellent in heat resistance, processability, dryness and chemical resistance, and has an advantage that the drying time is not long.

The above general formula (I) can be obtained by the following process.

->

(Wherein R < 1 > represents -C6H5,

X1 and X2 are represented by the following general formula (I-1)

In general formula (I-1)

H in the general formula (I-1) represents 10 to 200)

The thermosensitive pigment comprises particles containing 40 wt% to 50 wt% of pigment, 40 wt% to 50 wt% of chromoionophore, and 1 wt% to 10 wt% of coating layer covering the surface of the particles Wherein the thermosensitive pigment has a particle size of 1 to 10 mu m. More preferably, the particle size is 3 to 7 mu m, and most preferably 5 to 6 mu m.

The thermochromic pigments have the characteristic of changing color due to structural changes under specific conditions, but they are very sensitive to the external environment, so they are microencapsulated to protect the foreign matter for a long time. Sand mill, bead mill, etc., the encapsulation is destroyed due to high shear force and can not exhibit this function. Therefore, it is necessary to use a roll mill or a high-speed agitation so that the particle size is less than 10 μm.

And a third component containing 1 to 9 parts by weight of an aromatic solvent, 1 to 5 parts by weight of a resin for imparting adhesion, and 0.1 to 2 parts by weight of a curing accelerator.

Wherein the curing accelerator comprises one or more of the compounds represented by the following formulas (a) to (c). This is an aromatic compound in which an amine group and a sulfone group are introduced, and serves to accelerate the curing of the resin composition. These compounds can be used in a mixing ratio of 20 to 70% by weight of isopropyl alcohol, ethyl alcohol, and 30 to 80% by weight of a solvent of methyl alcohol. Here, isopropyl alcohol is most preferable.

(In the above formulas (a) to (c), R1 is -NH2 and R2 is -SO3H)

Wherein the adhesion-imparting resin comprises a phosphoric acid ester compound represented by the following formula (d).

(D)

In the formula (d), R, R 1 are H and R 2 is -COOH)

The compound represented by the formula (d) is used after being diluted with 50 to 80% by weight of a xylene or butyl cellosolve solution, but more preferably diluted with xylene from the viewpoint of viscosity control.

Figure 1 shows a flow chart for producing the coating composition of the present invention. Hereinafter, the production method will be specifically described.

(1-1) step of mixing and dispersing 0.1 to 1.2 parts by weight of a wet dispersant in 65 to 75 parts by weight of a curable silicone polyester resin, and 0.3 to 3.0 parts by weight of a flowable additive are further mixed and dispersed with stirring, 3 to 15 parts by weight of a water-soluble polymer; And a second step of mixing 0.1 to 1.0 part by weight of a creping and wettability enhancer, and further adding a solvent to the composition dispersed in the step 1-3, followed by stirring.

The mixed solvent further comprises 1 to 7 parts by weight of a propylene glycol monomethyl ether acetate solvent, 3 to 9 parts by weight of a ketone solvent and 5 to 35 parts by weight of an aromatic solvent.

As a third step, 1 to 10 parts by weight of an aromatic solvent is mixed and diluted with 1-5 parts by weight of a resin for attaching and 0.1 to 2.0 parts by weight of a curing accelerator, and the mixture is further mixed and dispersed uniformly in the first and second steps. To a process for producing a thermosensitive coating composition.

Wherein the aromatic solvent is one or two kinds selected from xylene and toluene, and the ketone solvent is cyclohexanone.

Wherein the curable silicone polyester resin is represented by the following general formula (I).

The compound of formula (I)

(Wherein R < 1 > represents -C6H5,

X1 and X2 are represented by the following general formula (I-1)

In general formula (I-1)

H in the general formula (I-1) represents 10 to 200)

The thermosensitive pigment may be prepared by reacting 40 to 50% by weight of pigment and 40 to 50% by weight of chromoionophore and then encapsulating the mixture into 1 to 10% by weight of polyethylene. 10 占 퐉. The present invention also relates to a method for producing the thermosensitive coating composition.

Wherein the curing accelerator comprises at least one compound selected from compounds represented by the following formulas (a) to (c).

(In the above formulas (a) to (c), R1 is -NH2 and R2 is -SO3H)

(D)

In the formula (d), R, R 1 are H and R 2 is -COOH)

And has a temperature-sensitive property in a temperature range of 60 ° C to 100 ° C. It can also be dried at 230 ° C within 1 hour, preferably at 200 ° C within 30 minutes.

In order to maximize the effect according to the color of the temperature, pastel white heat-resistant paint is applied as the paste composition for the base, heat-resistant paint is applied as the middle layer paint, and the gloss and the visual effect are maximized, There is an effect that a transparent heat-resistant paint of pearl system can be obtained as a TOP.

(Assessment Methods)

* Appearance of coating film: It grasps the state of surface, swelling, discoloration degree in naked eyes

* Adhesion 1: The dried film is scratched with a knife at an interval of 1 mm at a distance of 1 mm to make 100 chambers. Adhesion is made to the area with 3M transparent tape and then peeled off to reveal the degree of the chamber. (The film should be fallen within 5%)

* Adhesion 2: The dried film is scratched with a knife at a distance of 2mm with a knife to make 100 squares. Adhesion is made to the area with 3M transparent tape and then peeled off to reveal the degree of the chamber. (The film should be fallen within 5%)

* Gloss: The gloss of the film was measured using a 60 ⁰ gloss meter on a dry test piece. The higher the value, the higher the gloss

Flexibility: For coated specimens, make sure that the coated side is facing upwards on the top of the ream (diameter 1/2 inch) to make the bendability test equipment, and peel off and peel off the specimens folded 180 degrees downward.

* Storage stability: The prepared solution was put into a 0.5L TIN can, and the upper part was sealed so that it did not come into contact with air, then left at room temperature (20 ° C) for 1 month and then the top was opened to lump the liquid, Grasp the back

* Solvent resistance: In order to determine the hardness of the coating, XYLENE, an aromatic solvent, was wetted with gauze on the dried film, and the surface of the film was reciprocated 50 times with a load of about 500g.

* Temperature Sensitivity: The coated specimen or material is kept in the oven to maintain the temperature for 30 minutes and visually confirmed that it changes from the color before the experiment to the achromatic color.

* Color stability: The specimens or objects that were subjected to the temperature sensitivity test were taken out and cooled for 30 minutes at room temperature. Then, the color was restored from the achromatic color to the original color, and the temperature sensitivity test (30 minutes) Cycles 3 Cycles

(Example)

The following Examples are one way of implementing the present invention, and the claims of the present invention are not limited thereto. The component ratio used here is the mass part.

(Example 1) An intermediate layer paste composition Raw material Amount of blending Process 1 Methylphenyl silicone resin
(Trade name: 806A, DOW CORNING) 57.0 Wet dispersive additive
(Trade name: DISPERBYK-164, BYK) 1.0 Flowable additive
(Trade name: HPA-405, Kunsan Chemical Industry Co., Ltd.) 4.0 Heat-sensitive pigment
(Trade name: THERMOCHROMIC PIGMEMT, KELLY CHEMICAL) 20.0 Step 2 Cracking prevention and wettability improving additive
(Trade name: AFKONA 3700, AFKONA) 0.5 Propylene glycol monomethyl ether acetate solvent
(Trade name: DOWANOL PMA, DOW CHEMICAL) 3.0 Ketone solvent
(Product name: CYCLOHEXANONE, Capro Korea) 4.0 Aromatic solvent 1
(Trade name: XYLENE, NCC) 7.4 Aromatic solvent 2
(Trade name: TOLUENE, NCC) 3.1

(Step 1)

The silicone resin was mixed with a wetting and dispersing agent. The mixture was stirred at 400 RPM for 15 minutes. The fluidity additive was then added. The mixture was uniformly stirred and dispersed at 750 RPM for 25 minutes. The sensitizing pigment was added thereto and stirred at 1,650 rpm for 10 minutes.

(Step 2)

Craying prevention and wettability-improving dispersion additive, propylene glycol monomethyl ether acetate solvent, ketone solvent and aromatic solvent were added to the dispersion of step 1 in this order and uniformly stirred at 400 RPM for 15 minutes to prepare a coating. The aluminum material was heated and dried at 200 캜 for 20 minutes by air spray coating to form a dry film of 30 탆.

(Example 2) An intermediate layer paste composition Raw material Amount of blending Process 1 Silicone polyester resin
(Trade name: KPE-796-59, Samhwa Paint) 57.0 Wet dispersant
(Trade name: DISPERBYK-164, BYK) 1.0 Flowable additive
(Trade name: HPA-405, Kunsan Chemical Industry Co., Ltd.) 4.0 Heat-sensitive pigment
(Trade name: THERMOCHROMIC PIGMEMT, KELLY CHEMICAL) 20.0 Step 2 Cracking prevention and wettability improving additive
(Trade name: AFKONA 3700, AFKONA) 0.5 Propylene glycol monomethyl ether acetate solvent
(Trade name: DOWANOL PMA, DOW CHEMICAL) 3.0 Ketone solvent
(Product name: CYCLOHEXANONE, Capro Korea) 4.0 Aromatic solvent 1
(Trade name: XYLENE, NCC) 7.4 Aromatic solvent 2
(Trade name: TOLUENE, NCC) 3.1

(Step 1)

The silicone resin was mixed with a wetting and dispersing agent. The mixture was stirred at 400 RPM for 15 minutes. The fluidity additive was then added. The mixture was uniformly dispersed at 7500 rpm for 25 minutes. The sensitizing pigment was added thereto and stirred at 1,650 rpm for 10 minutes.

(Step 2)

(Example 3) An intermediate layer paste composition Raw material Amount of blending Process 1 Silicone polyester resin
(Trade name: KPE-796-59, Samhwa Paint) 57.0 Wet dispersant
(Trade name: DISPERBYK-164, BYK) 1.0 Flowable additive
(Trade name: HPA-405, Kunsan Chemical Industry Co., Ltd.) 4.0 Heat-sensitive pigment
(Trade name: THERMOCHROMIC PIGMEMT, KELLY CHEMICAL) 20.0 Step 2 Cracking prevention and wettability improving additive
(Trade name: AFKONA 3700, AFKONA) 0.5 Propylene glycol monomethyl ether acetate solvent
(Trade name: DOWANOL PMA, DOW CHEMICAL) 3.0 Ketone solvent
(Product name: CYCLOHEXANONE, Capro Korea) 4.0 Aromatic solvent 1
(Trade name: XYLENE, NCC) 4.7 Aromatic solvent 2
(Trade name: TOLUENE, NCC) 4.4 Step 3 Aromatic solvent 1
(Trade name: XYLENE, NCC) 0.7 Hardening accelerator
(Trade name: NACURE XC-128, KING INDUSTRIES) 0.7

(Step 1)

The silicone resin was mixed with a wetting and dispersing agent. The mixture was stirred at 400 RPM for 25 minutes. The fluidity additive was then added. The mixture was uniformly dispersed at 750 RPM for 25 minutes. The sensitizing pigment was added thereto and stirred at 1,650 rpm for 10 minutes.

(Step 2)

Craying prevention and wettability-improving dispersion additive, propylene glycol monomethyl ether acetate solvent, ketone solvent and aromatic solvent were added to the dispersion of step 1 in this order and uniformly stirred at 400 RPM for 15 minutes to prepare a coating.

(Step 3)

A curing accelerator was added to the aromatic solvent to make it uniform at 400 RPM. The mixture was added to the mixture of Process 1 and Process 2 and uniformly stirred at 400 RPM for 15 minutes to prepare a paint.

The aluminum material was heated and dried at 200 캜 for 20 minutes by air spray coating to form a dry film of 30 탆.

(Example 4) An intermediate layer paste composition Raw material Amount of blending
(Parts by weight) Process 1 Silicone polyester resin
(Trade name: KPE-796-59, Samhwa Paint) 57.0 Wet dispersant
(Trade name: DISPERBYK-164, BYK) 1.0 Flowable additive
(Trade name: HPA-405, Kunsan Chemical Industry Co., Ltd.) 4.0 Heat-sensitive pigment
(Trade name: THERMOCHROMIC PIGMEMT, KELLY CHEMICAL) 20.0 Step 2 Cracking prevention and wettability improving additive
(Trade name: AFKONA 3700, AFKONA) 0.5 Propylene glycol monomethyl ether acetate solvent
(Trade name: DOWANOL PMA, DOW CHEMICAL) 3.0 Ketone solvent
(Product name: CYCLOHEXANONE, Capro Korea) 4.0 Aromatic solvent 1
(Trade name: XYLENE, NCC) 1.9 Aromatic solvent 2
(Trade name: TOLUENE, NCC) 1.6 Step 3 Aromatic solvent 1
(Trade name: XYLENE, NCC) 3.5 Resin for adhesion
(Trade name: ADDBOND LTW, DEGUSSA) 2.8 Curing accelerator (trade name: NACURE XC-128, KING INDUSTRIES) 0.7

(Step 1)

The silicone resin was mixed with a wetting and dispersing agent. The mixture was stirred at 400 RPM for 15 minutes. The fluidity additive was added thereto. The mixture was uniformly dispersed at 750 RPM for 25 minutes. The sensitizing pigment was added thereto and stirred at 1,650 rpm for 10 minutes.

(Step 2)

(Step 3)

A resin for imparting adhesion to the aromatic solvent and a curing accelerator were added and uniformed to 400 RPM. The mixture was mixed with the mixture of Step 1 and Step 2, and uniformly stirred at 400 RPM for 15 minutes to prepare a coating. (Here, the resin used as the adhesion-imparting resin was diluted with 60 wt% of xylene)

(Example 5) Paste composition for intermediate layer Raw material Amount of blending Process 1 Silicone polyester resin
(Trade name: KPE-796-59, Samhwa Paint) 57.0 Wet dispersant
(Trade name: DISPERBYK-164, BYK) 1.0 Flowable additive
(Trade name: HPA-405, Kunsan Chemical Industry Co., Ltd.) 4.0 Heat-sensitive pigment
(Trade name: THERMOCHROMIC PIGMEMT, KELLY CHEMICAL) 20.0 Step 2 Cracking prevention and wettability improving additive
(Trade name: AFKONA 3700, AFKONA) 0.5 Propylene glycol monomethyl ether acetate solvent
(Trade name: DOWANOL PMA, DOW CHEMICAL) 3.0 Ketone solvent
(Product name: CYCLOHEXANONE, Capro Korea) 4.0 Aromatic solvent 1
(Trade name: XYLENE, NCC) 1.9 Aromatic solvent 2
(Trade name: TOLUENE, NCC) 1.6 Step 3 Aromatic solvent 1
(Trade name: XYLENE, NCC) 3.5 Resin for adhesion
(Trade name: LUBRIZOL 2063, LUBRIZOL CORPORATION) 2.8 Hardening accelerator
(Trade name: NACURE XC-128, KING INDUSTRIES) 0.7

(Step 1)

The silicone resin was mixed with a wetting and dispersing agent. The mixture was stirred at 400 RPM for 15 minutes. The fluidity additive was added thereto. The mixture was uniformly stirred and dispersed at 750 RPM for 25 minutes. The sensitizing pigment was added thereto and stirred at 1,650 rpm.

(Step 2)

(Step 3)

A resin for imparting adhesion to an aromatic solvent and a curing accelerator were added and uniformed at 400 RPM and then mixed with the mixture of Step 1 and Step 2 and uniformly stirred at 400 RPM for 15 minutes to prepare a paint. (Here, the resin used as the adhesion-imparting resin was diluted with 60% by weight of butyl cellosolve)

Table 6 shows the results of the solvent resistance test for determining adhesion and hardenability after drying for 20 minutes at 200 ° C in an aluminum material having a purity of 955 or more according to Examples 1 to 5.

Example 1 Example 2 Example 3 Example 4 Example 5 Adhesion 1 70/100 50/100 70/100 100/100 100/100 Solvent resistance Material Exposure Material Exposure Material Exposure Good Good Zhejiang Province Good Good Good Good 65% Viscosity increase

According to the above Table 6, it was found that the adhesive strength 1 was excellent in Examples 4 and 5, and the solvent resistance was also excellent in Examples 4 and 5. It was found that the storage stability was excellent in Examples 1 to 4.

In a further embodiment, the compounding ratio was adjusted based on Example 4. In addition, pastel color (white or beige) was applied as a base paste, a thermosensitive pigment was applied as a middle layer, and a pearl clear paint was applied for aesthetic effect and durability.

It is preferable that the dry coating film of the base layer is 15 to 20 μm, the dry coating film of the intermediate layer is 10 to 20 μm, and the dried coating film of the top layer forms 5 to 10 μm as a continuous spray coating of the organic on-film (WET ON WET) Do. However, the present invention is not limited thereto. Hereinafter, examples will be described in detail.

(Example 5-1) Paste composition for base Raw material Amount of blending Process 1 Silicone polyester resin
(Trade name: KPE-796-59, Samhwa Paint) 40.0 Wet dispersant
(Trade name: DISPERBYK-164, BYK) 1.0 Anti-settling agent 1
(Trade name: CAB-O-SIL M5, CABOT) 0.8 Anti-settling agent 2
(Trade name: BENTONE 38, ELEMENT SPECIALTIES) 0.5 Propylene glycol monomethyl ether acetate solvent
(Trade name: DOWANOL PMA, DOW CHEMICAL) 2.0 Ketone solvent
(Product name: CYCLOHEXANONE, Capro Korea) 2.0 Aromatic solvent 1
(Trade name: XYLENE, NCC) 2.0 Colored pigment
(Trade name: TIONA 595, MILLENNIUM CHEMICALS) 29.0 Step 2 Silicone polyester resin
(Trade name: KPE-796-59, Samhwa Paint) 15.0 Cracking prevention and wettability improving additive
(Trade name: AFKONA 3700, AFKONA) 0.5 Leveling additive
(Trade name: BYKETOL OK, BYK) 1.0 Ketone solvent
(Product name: METHYL ISO BUTYL KETONE, Kumho P & N Biochemistry) 2.0 Aromatic solvent 1
(Trade name: XYLENE, NCC) 2.2 Aromatic solvent 2
(Trade name: TOLUENE, NCC) 2.0

(Step 1)

A resin, a wetting and dispersing agent and an anti-settling agent were mixed in this order and stirred at 400 rpm for 15 minutes. Thereafter, a propylene glycol monomethyl ether acetate solvent, a ketone solvent, an aromatic solvent and a colored pigment were added and stirred uniformly at 750 rpm for 25 minutes , And DYNO MILL were used to soften the composition to a particle size of 10 mu m or less.

(Step 2)

After the step 2 of the step 2, the silicone polyester resin, the anti-creasing agent and the wettability improving additive, the leveling additive, and the aromatic solvent were added to the soft cargoes of the step 1 in the order of stirring at a stirring speed of 750 rpm, Followed by stirring to prepare beige PASTE.

(Example 5-2) Paste composition for base Raw material Amount of blending Process 1 White PASTE for BASE
(Trade name: Hion 2600, Samhwa Paint) 90.4 Aromatic solvent 1
(Trade name: XYLENE, NCC) 3.8 Resin for adhesion
(Trade name: ADDBOND LTW, DEGUSSA) 3.0 Hardening accelerator
(Trade name: NACURE XC-128, KING INDUSTRIES) 0.8 Yellow pigments for coloring
(Trade name: Hion 2600, Samhwa Paint) 2.0

(Step 1)

The resin for adhesion to the aromatic solvent and the curing accelerator were added thereto, and the mixture was uniformly mixed at 400 RPM. Then, the mixture was put into a white paste for base, stirred uniformly at 400 RPM for 15 minutes, The paint was uniformly prepared for a minute.

(Example 5-3) Top paste composition Raw material Amount of blending Process 1 Silicone polyester resin
(Trade name: KPE-796-59, Samhwa Paint) 75.0 Flowable additive
(Trade name: HPA-405, Kunsan Chemical Industry Co., Ltd.) 5.0 Step 2 Cracking prevention and wettability improving additive
(Trade name: AFKONA 3700, AFKONA) 0.5 Leveling additive
(Trade name: BYKETOL OK, BYK) 1.0 Surface slip additive
(Trade name: BYK 3550, BYK) 0.2 Ketone solvent (trade name: CYCLOHEXANONE, Capro Korea) 4.5 Propylene glycol monomethyl ether acetate solvent
(Trade name: DOWANOL PMA, DOW CHEMICAL) 3.0 Aromatic solvent 2
(Trade name: TOLUENE, NCC) 2.6 Pearl pigment 1
(Trade name: IRIODIN 100 SILVER PEARL, MERCK) 0.3 Pearl pigment 2
(Trade name: IRIODIN 153 FLASH PEARL, MERCK) 0.3 Step 3 Aromatic solvent 1
(Trade name: XYLENE, NCC) 3.8 Adhesion-imparting resin (trade name: ADDBOND LTW, DEGUSSA) 3.0 Hardening accelerator
(Trade name: NACURE XC-128, KING INDUSTRIES) 0.8

(Step 1)

The fluidity additive was added to the silicone polyester resin and stirred and dispersed uniformly at 750 RPM for 25 minutes.

(Step 2)

A leveling additive, a surface slip additive, a ketone solvent, a propylene glycol monomethyl ether acetate solvent, and an aromatic solvent were added in this order to the dispersion of the step 1, uniformly dispersed at 400 RPM for 15 minutes, Based pigment was uniformly dispersed at 400 RPM for 15 minutes.

(Step 3)

A resin for imparting adhesion to the aromatic solvent and a curing accelerator were added and uniformed to 400 RPM. The mixture was mixed with the mixture of Step 1 and Step 2, and uniformly stirred at 400 RPM for 15 minutes to prepare a coating.

(Example 6) Heat sensitive coating composition for intermediate layer Raw material Amount of blending Process 1 Silicone polyester resin
(Trade name: KPE-796-59, Samhwa Paint) 57.0 Wet dispersant
(Trade name: DISPERBYK-164, BYK) 1.0 Flowable additive
(Trade name: HPA-405, Kunsan Chemical Industry Co., Ltd.) 4.0 Heat-sensitive pigment
(Trade name: THERMOCHROMIC PIGMEMT, KELLY CHEMICAL) 20.0 Step 2 Cracking prevention and wettability improving additive
(Trade name: AFKONA 3700, AFKONA) 0.5 Propylene glycol monomethyl ether acetate solvent
(Trade name: DOWANOL PMA, DOW CHEMICAL) 2.5 Ketone solvent
(Product name: CYCLOHEXANONE, Capro Korea) 3.5 Aromatic solvent 1
(Trade name: XYLENE, NCC) 2.3 Aromatic solvent 2
(Trade name: TOLUENE, NCC) 1.6 Step 3 Aromatic solvent 1
(Trade name: XYLENE, NCC) 3.8 Resin for adhesion
(Trade name: ADDBOND LTW, DEGUSSA) 3.0 Hardening accelerator
(Trade name: NACURE XC-128, KING INDUSTRIES) 0.8

(Step 1)

The silicone resin was mixed with a wetting and dispersing agent and stirred at 400 RPM for 15 minutes. The fluidity additive was then added. The mixture was uniformly dispersed at 750 RPM for 25 minutes. The sensitizing pigment was added thereto and stirred at 1,650 rpm.

(Step 2)

(Step 3)

A resin for adhering to aromatic solvent 1 and a curing accelerator were added and uniformed at 400 RPM. The mixture was mixed with the mixture of Process 1 and Process 2, and uniformly stirred at 400 RPM for 15 minutes to prepare a paint.

Three layers (base layer paste composition of Example 5-2 and base layer paste composition of Example 5-3 were used as a top layer) were coated with an aluminum spray coating by air spray, Min to form a total dry film of 40 mu m.

(Example 7) A heat-sensitive coating composition for an intermediate layer Raw material Amount of blending Process 1 Silicone polyester resin
(Trade name: KPE-796-59, Samhwa Paint) 70.5 Wet dispersant
(Trade name: DISPERBYK-164, BYK) 0.3 Flowable additive
(Trade name: HPA-405, Kunsan Chemical Industry Co., Ltd.) 1.0 Heat-sensitive pigment
(Trade name: THERMOCHROMIC PIGMEMT, KELLY CHEMICAL) 5.0 Step 2 Cracking prevention and wettability improving additive
(Trade name: AFKONA 3700, AFKONA) 0.5 Propylene glycol monomethyl ether acetate solvent
(Trade name: DOWANOL PMA, DOW CHEMICAL) 3.0 Ketone solvent
(Product name: CYCLOHEXANONE, Capro Korea) 4.8 Aromatic solvent 1
(Trade name: XYLENE, NCC) 3.3 Aromatic solvent 2
(Trade name: TOLUENE, NCC) 4.0 Step 3 Aromatic solvent 1
(Trade name: XYLENE, NCC) 3.8 Resin for adhesion
(Trade name: ADDBOND LTW, DEGUSSA) 3.0 Hardening accelerator
(Trade name: NACURE XC-128, KING INDUSTRIES) 0.8

(Step 1)

(Step 2)

(Step 3)

A three-layer (base layer paste composition of Example 5-2 was used as a base layer, and a paste composition for a top layer of Example 5-3 was used as a top layer) was coated on an aluminum material by air spray coating in a WET ON WET manner, And dried by heating for 17 minutes to form a total dry film of 40 mu m.

(Example 8) A heat-sensitive coating composition for an intermediate layer Raw material Amount of blending Process 1 Example 5-2) White for BASE (Samhwa Paint) 77.0 Example 6) Thermosensitive paint for MID (Samhwa paint) 23.0

(Step 1)

The paint was prepared by uniformly stirring the thermosensitive paint for MID for the base produced at 750 RPM for 25 minutes while stirring.

A three-layer (base layer paste composition of Example 5-2 was used as the base layer, and the top layer composition of Example 5-3 was used as the top layer) was coated on the aluminum material by air spray coating in a WET ON WET manner, Min to form a total dry film of 40 mu m.

In Examples 6, 7 and 8, the paste compositions for the top, bottom and bottom layers were the same as those of Examples 5-3, 5-2 and 7, 8, respectively. Using the example 5-1 instead of the example 5-2, the results of coating on the aluminum material below were similar.

The results of the experiment on the aluminum material according to the above examples are as follows.

In Example 6, the thermosensitive property was weak, and in Example 8, the thermosensitive property was found to be white. Therefore, in Example 7, it was good in temperature sensitivity and color stability.

Example 6 Example 7 Example 8 Surface coat state Good Good Good Adhesion 2 100/100 100/100 100/100 Storage stability Good Good Good Gloss (60 ℃) 91G 102G 98G Flexibility (1/2 inch) Good Good Good Sensitivity (60 ℃) and color stability No temperature sensitivity No temperature sensitivity No temperature sensitivity Sensitivity (70 ℃)
And color stability Sensitivity: Weak color presence
Color stability: Good Sensitivity: Good (achromatic)
Color stability: Good Sensitivity: Present in white
Color stability: Good Temperature Sensitivity (80 ℃)
And color stability Sensitivity: Weak color presence
Color stability: Good Sensitivity: Good (achromatic)
Color stability: Good Sensitivity: Present in white
Color stability: Good Sensitivity (90 ℃) and color stability Sensitivity: Weak color presence
Color stability: Good Sensitivity: Good (achromatic)
Color stability: Good Sensitivity: Present in white
Color stability: Good

Claims

A first component containing 65 to 75 parts by weight of a curable silicone polyester resin, 0.1 to 1.2 parts by weight of a wet dispersant, 0.3 to 3.0 parts by weight of a flow additive, and 3 to 15 parts by weight of a thermochromic pigment;
0.1 to 1.0 part by weight of a creping and wettability improving agent, and a second component containing a solvent;
A heat-sensitive coating composition comprising:
Wherein the curable silicone polyester resin is represented by the following general formula (I).
The compound of formula (I)

(Provided that where R1 is a -C ₆ H _5,
X1 and X2 are represented by the following general formula (I-1)
In general formula (I-1)

H in the general formula (I-1) represents 10 to 200)

The method according to claim 1,
Wherein the solvent is 1 to 7 parts by weight of a propylene glycol monomethyl ether acetate solvent, 3 to 9 parts by weight of a ketone solvent and 5 to 35 parts by weight of an aromatic solvent.

3. The method of claim 2,
Wherein the aromatic solvent is one or two kinds selected from xylene and toluene, and the ketone solvent is cyclohexanone.

delete

The method according to claim 1,
The thermosensitive pigment comprises particles containing 40 wt% to 50 wt% of pigment, 40 wt% to 50 wt% of chromoionophore, and 1 wt% to 10 wt% of coating layer covering the surface of the particles Wherein the thermosensitive pigment has a particle size of 1 to 10 mu m.

The method according to claim 1,
In addition, a third component containing 1 to 10 parts by weight of an aromatic solvent, 1 to 5 parts by weight of a resin for imparting adhesion, and 0.1 to 2 parts by weight of a curing accelerator;
Wherein the thermosensitive coating composition is a thermosensitive coloring composition.

The method according to claim 6,
Wherein the curing accelerator comprises one or more of the compounds represented by the following formulas (a) to (c).

(In the formula (a) to (c), R1 is a -NH _2, R2 denotes a -SO ₃ H)

The method according to claim 6,
Wherein the adhesion-imparting resin comprises a compound represented by the following formula (d).
(D)

In the formula (d), R, R 1 are H and R 2 is -COOH)

8. The method according to any one of claims 1 to 7,
Wherein the heat-sensitive coating composition has a temperature-sensitive property in a temperature range of 60 ° C to 100 ° C.

(1-1) step of mixing and dispersing 0.1 to 1.2 parts by weight of a wet dispersant in 65 to 75 parts by weight of a curable silicone polyester resin, and 0.3 to 3.0 parts by weight of a flowable additive are further mixed and dispersed with stirring, 3 to 15 parts by weight of a water-soluble polymer;
And a second step of mixing 0.1 to 1.0 part by weight of a creping and wettability enhancer, and further adding a solvent to the composition dispersed in the step 1-3, and stirring the composition,
Wherein the curable silicone polyester resin is represented by the following general formula (I).
The compound of formula (I)

H in the general formula (I-1) represents 10 to 200)

11. The method of claim 10,
Wherein the additional mixed solvent is 1 to 7 parts by weight of a propylene glycol monomethyl ether acetate solvent, 3 to 9 parts by weight of a ketone solvent and 5 to 35 parts by weight of an aromatic solvent.

12. The method of claim 11,
Wherein the aromatic solvent is one or two kinds selected from xylene and toluene, and the ketone solvent is cyclohexanone.

delete

11. The method of claim 10,
The thermosensitive pigment may be prepared by reacting 40 to 50% by weight of pigment and 40 to 50% by weight of chromoionophore and then encapsulating the mixture into 1 to 10% by weight of polyethylene. Wherein the heat-sensitive coating composition is a thermosensitive coating composition.

11. The method of claim 10,
A third step of mixing and dispersing 1 to 10 parts by weight of an aromatic solvent, 1 to 5 parts by weight of an adhesion-imparting resin, and 0.1 to 2 parts by weight of a curing accelerator in the composition prepared in the second step;
Wherein the heat-sensitive coating composition further comprises a thermosetting resin.

16. The method of claim 15,
Wherein the curing accelerator comprises one or more of the compounds represented by the following formulas (a) to (c).

(In the formula (a) to (c), R1 is a -NH _2, R2 denotes a -SO ₃ H)

16. The method of claim 15,
Wherein the adhesion-imparting resin comprises a compound represented by the following formula (d).
(D)

In the formula (d), R, R 1 are H and R 2 is -COOH)

The method according to any one of claims 10 to 12, 14 to 17,
Wherein the thermosensitive coating composition has a temperature-sensitive characteristic in a temperature range of 60 ° C to 100 ° C.