KR102480868B1 - Heat-resistant coating composition improved crack resistance and method for manufacturing coated body using the same - Google Patents

Abstract

A heat-resistant coating composition with improved crack resistance and a method for manufacturing a coating using the same are disclosed. The heat-resistant coating composition with improved crack resistance includes 30 to 40 parts by weight of a polysiloxane resin; 10 to 20 parts by weight of a pigment; and 45 to 50 parts by weight of a solvent.

Description

Heat-resistant coating composition with improved crack resistance and method for producing a coating using the same

The present disclosure relates to a heat-resistant coating composition having improved crack resistance and a method for manufacturing a coating body using the same.

Recently, the need for a resin having various physical properties, such as high hardness and high heat resistance, has been highlighted compared to conventional organic resins. In this regard, Korean Patent Registration No. 10-0432211 discloses a technique for a coating composition for coating the surface of an article requiring heat resistance (eg, an electric device, an automobile lamp, etc.).

Conventionally, polymer composite paints prepared by adding inorganic fillers to organic binders have been prepared, but recently, organic-inorganic hybrid paints having excellent stability, heat resistance, and compatibility with paints have been developed. Polysiloxane is used as a binder in the manufacture of such an organic-inorganic hybrid paint, and the polysiloxane serves to improve adhesion between different constituents in the paint, paint performance, and heat resistance. However, since the conventional pure polysiloxane has poor shrinkage resistance and crack resistance at high temperatures, cracks occur in the coating film when the painted surface is cured at a high temperature of 200 ° C. or higher, and the original binder function is not properly performed. existed. Therefore, there is a demand for the development of a new heat-resistant coating composition that improves the conventional problems.

The technical idea of the present disclosure is to solve the above problems, and an object thereof is to provide a technique for preparing a paint composition having excellent heat resistance and improved shrink resistance and crack resistance.

The problem to be solved by the present invention is not limited to the above problem, and other technical problems not mentioned will be clearly understood by those skilled in the art from the description below.

In order to achieve this object, as an embodiment of the present invention, a heat-resistant coating composition having improved crack resistance includes 30 to 40 parts by weight of a polysiloxane resin; 10 to 20 parts by weight of a pigment; and 45 to 50 parts by weight of a solvent, wherein the polysiloxane resin is prepared by reacting different types of organic silanes, and the organic silanes are methyltrimethoxysilane, phenyltrimethoxysilane and 3-(meth) contains acryloxypropyltrimethoxysilane, and the polysiloxane resin comprises 20 to 25 parts by weight of the methyltrimethoxysilane, 10 to 20 parts by weight of the phenyltrimethoxysilane, and the 3-(meth)acryloxypropyltrimethine It is prepared by reacting 5 to 10 parts by weight of toxysilane and 30 to 65 parts by weight of an organic solvent, and the organic solvent is xylene, butyl acetate, butyl cellosolve, ethyl alcohol, isopropyl alcohol, butyl alcohol, methyl ethyl ketone, methyl It is provided with at least one selected from the group consisting of isobutyl ketone and propylene glycol monomethyl ether acetate.

In addition, the heat-resistant coating composition may further include 4 to 10 parts by weight of additives.

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As another embodiment of the present invention to achieve this object, a method for manufacturing a coated body using a heat-resistant coating composition includes a coating step of applying the above-described heat-resistant coating composition to an object to be coated; and a curing step of curing the coating layer formed in the coating step.

The solutions to the problems described above are merely illustrative and should not be construed as limiting the present invention. In addition to the exemplary embodiments described above, there may be additional embodiments described in the drawings and detailed description.

As described above, according to various embodiments of the present invention, since the coating composition is prepared using polysiloxane resins prepared by reacting different types of organic silanes, the content of inorganic substances contained in the heat-resistant coating composition is increased, so that heat resistance and flame retardancy are improved. It has an excellent effect.

In addition, according to various embodiments of the present invention, when preparing a polysiloxane resin, a certain amount of phenyltrimethoxysilane is added to methyltrimethoxysilane and reacted together to synthesize a polysiloxane resin, or methyltrimethoxysilane is mixed with phenyltrimethoxysilane. By synthesizing a polysiloxane resin by adding a certain amount of silane and 3-(meth)acryloxypropyltrimethoxysilane and reacting, flame retardancy, curing property, adhesion, hardness, solvent resistance and stain resistance are maintained while maintaining a high inorganic content of the heat-resistant coating composition. , shrinkage resistance, smoothness, etc.

The effects of the present invention are not limited to the effects mentioned above, and other effects not mentioned will be clearly understood by those skilled in the art from the description of the claims.

1 is a flow chart showing a method for manufacturing a coating body according to an embodiment of the present invention.

A preferred embodiment of the present invention will be described in more detail with reference to the accompanying drawings, but the already well-known technical parts will be omitted or compressed for conciseness of description.

It should be noted that references herein to “one” or “an” embodiment of the invention are not necessarily to the same embodiment, they mean at least one.

In the following examples, expressions in the singular number include plural expressions unless the context clearly indicates otherwise.

In the following embodiments, terms such as include or have mean that features or elements described in the specification exist, and do not preclude the possibility that one or more other features or elements may be added.

In the following embodiments, when a part such as a film, region, component, etc. is said to be on or on another part, not only when it is directly above the other part, but also when another film, region, component, etc. is interposed therebetween. Including if there is

When an embodiment is otherwise implementable, a specific process sequence may be performed differently from the described sequence. For example, two processes described in succession may be performed substantially simultaneously, or may be performed in an order reverse to the order described. That is, each step of the method described herein may be suitably performed in any order unless otherwise stated in the specification or clearly contradicted by context.

Throughout this specification, the term "about" used before a numerical value is used at or close to that numerical value, when manufacturing and material tolerances inherent in the stated meaning are given, and is used as accurate or Absolute numbers are used to prevent exploitation by unscrupulous infringers of the stated disclosure.

<Description of heat-resistant paint composition>

A heat-resistant coating composition according to an embodiment of the present invention may include a polysiloxane resin, a pigment, and a solvent. In one embodiment, the polysiloxane resin may be prepared by reacting different types of organic silanes. For example, a polysiloxane resin may be obtained through hydrolysis and condensation reactions using a catalyst and water under a certain temperature by adding an organic solvent to different types of organosilane.

Here, organic silane is methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane Toxysilane, i-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane , n-octyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-chloro Propyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3-aminopropyltri Methoxysilane, 3-aminopropyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-hydroxypropyltrie Toxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatepropyltrimethoxy Silane, 3-isocyanatepropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-ureidopropyltrimethine Toxysilane, 3-ureidopropyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldie Toxysilane, di-i-propyldimethoxysilane, di-i-propyldiethoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-pentyldimethoxysilane, di- n-pentyldiethoxysilane, di-n-hexyldimethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyldiethoxysilane, di-n-octyldimethoxysilane, di-n-octyldiethoxy Silane, di-n-cyclohexyldimethoxysilane, di-n-cyclohexyldiethoxysilane, It may be provided with at least one selected from the group consisting of diphenyldimethoxysilane and diphenyldiethoxysilane.

Polysiloxane resin according to an embodiment may be prepared through hydrolysis and condensation reactions. That is, the polysiloxane resin may be obtained by adding an organic solvent, a catalyst, and water to various kinds of organosilanes under a constant temperature condition, followed by hydrolysis and condensation.

In one embodiment, a polysiloxane resin may be synthesized by adding an organic solvent and a catalyst to a mixture of two or more organic silanes, and stirring for about 1 hour to 24 hours at a temperature of room temperature (eg, 25 ° C.) to 150 ° C. there is. In addition, distillation and removal of hydrolysis by-products or condensation by-products may be performed during stirring. Also, when preparing the polysiloxane resin, the reaction temperature and stirring time may be appropriately changed according to experimental conditions.

The polysiloxane resin according to an embodiment may be prepared by reacting 20 to 25 parts by weight of methyltrimethoxysilane and 20 to 25 parts by weight of phenyltrimethoxysilane. As a specific example, the content of methyltrimethoxysilane may be about 20 parts by weight, about 21 parts by weight, about 22 parts by weight, about 23 parts by weight, about 24 parts by weight, or about 25 parts by weight. In addition, the content of methyltrimethoxysilane may be in a range of one or more of the above values and less than or equal to one of the above values.

For example, the content range of methyltrimethoxysilane is about 20 parts by weight to about 22 parts by weight, about 21 parts by weight to about 23 parts by weight, about 22 parts by weight to about 24 parts by weight, about 23 parts by weight to about 25 parts by weight It may be provided in the range of parts by weight or about 20 parts by weight to about 25 parts by weight. Methyltrimethoxysilane according to an embodiment can maintain the physical properties and flame retardancy of a coating film at an excellent level within the above range.

If the amount of methyltrimethoxysilane is less than 20 parts by weight, the content of inorganic substances in the polysiloxane resin is reduced, and as a result, the content of inorganic substances contained in the heat-resistant coating composition is reduced, thereby reducing heat resistance and flame retardancy. When the content of inorganic substances in the paint composition is too high, cracks may occur in the coating film or physical properties of the coating film may be deteriorated. Therefore, it is preferable that the amount of methyltrimethoxysilane used during the synthesis of the polysiloxane resin is applied within the above range.

In one embodiment, when synthesizing the polysiloxane resin, the content of phenyltrimethoxysilane may be applied in an amount of 15 to 25 parts by weight. As specific examples, the content of phenyltrimethoxysilane is about 15 parts by weight, about 17 parts by weight, about 19 parts by weight, about 20 parts by weight, about 21 parts by weight, about 22 parts by weight, about 23 parts by weight, about 24 parts by weight part or about 25 parts by weight. Further, the amount of phenyltrimethoxysilane may range from one or more of the above numerical values to less than one of the above numerical values.

For example, the content range of phenyltrimethoxysilane is about 15 parts by weight to about 22 parts by weight, about 21 parts by weight to about 23 parts by weight, about 22 parts by weight to about 24 parts by weight, about 23 parts by weight to about 25 parts by weight It may be provided in the range of parts by weight or about 20 parts by weight to about 25 parts by weight. Phenyltrimethoxysilane according to an embodiment can prevent cracks in the coating film and maintain stability of the coating film within the above range.

If the amount of phenyltrimethoxysilane is less than 15 parts by weight, cracks may occur while the coating film shrinks during curing at a high temperature of 200 ° C. The content of phenyltrimethoxysilane is preferably applied within the aforementioned range.

In the preparation of the polysiloxane resin according to an embodiment, the usable organic solvents include xylene, butyl acetate, butyl cellosolve, ethyl alcohol, isopropyl alcohol, butyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, and propylene glycol mono At least one selected from the group consisting of methyl ether acetate may be applied. The organic solvent content is 30 to 65 parts by weight (eg, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, 55 parts by weight, 56 parts by weight, 57 parts by weight, 58 parts by weight, 59 parts by weight, 60 parts by weight, 61 parts by weight, 62 parts by weight, 63 parts by weight, 64 parts by weight or 65 parts by weight).

As a specific example, the content of the organic solvent added during production of the polysiloxane resin may be about 30 parts by weight, about 40 parts by weight, about 50 parts by weight, about 55 parts by weight, about 60 parts by weight, or about 65 parts by weight. In addition, the content of the organic solvent may be in the range of one or more of the above numerical values and one or less of the above numerical values. For example, the content range of the organic solvent may be provided in the range of about 30 parts by weight to about 60 parts by weight or about 62 parts by weight to about 65 parts by weight.

In one embodiment, when the polysiloxane resin is synthesized using xylene as an organic solvent added during production of the polysiloxane resin, it is easy to reduce the moisture content of the resin and adjust the resistance value, thereby facilitating the electrostatic painting of the paint. In addition, when xylene and butyl cellosolve are mixed and used at a constant weight ratio (eg, 1:1, 2:1, or 3:1) as an organic solvent, coating properties, compatibility, and stability of the coating film are improved. can be further improved.

On the other hand, the polysiloxane resin according to another embodiment reacts 20 to 25 parts by weight of methyltrimethoxysilane, 10 to 20 parts by weight of phenyltrimethoxysilane and 5 to 10 parts by weight of 3-(meth)acryloxypropyltrimethoxysilane It can be manufactured by

In another embodiment, when the amount of methyltrimethoxysilane is less than 20 parts by weight, the inorganic content in the polysiloxane resin is reduced, and as a result, the heat resistance and flame retardancy may be reduced due to the decrease in the inorganic content contained in the heat-resistant paint composition, and in excess of 25 parts by weight If the content of inorganic substances in the heat-resistant coating composition is too high, cracks may occur in the coating film or physical properties of the coating film may be deteriorated.

In another embodiment, when synthesizing the polysiloxane resin, the content of phenyltrimethoxysilane may be applied in an amount of 10 to 20 parts by weight. As specific examples, the content of phenyltrimethoxysilane is about 10 parts by weight, about 11 parts by weight, about 12 parts by weight, about 13 parts by weight, about 14 parts by weight, about 15 parts by weight, about 16 parts by weight, about 17 parts by weight part, about 18 parts by weight, about 19 parts by weight or about 20 parts by weight. Further, the amount of phenyltrimethoxysilane may range from one or more of the above numerical values to less than one of the above numerical values.

For example, the content range of phenyltrimethoxysilane is about 10 parts by weight to about 13 parts by weight, about 11 parts by weight to about 14 parts by weight, about 12 parts by weight to about 15 parts by weight, about 13 parts by weight to about 15 parts by weight About 14 parts by weight to about 17 parts by weight, about 15 parts by weight to about 18 parts by weight, about 16 parts by weight to about 19 parts by weight, about 17 parts by weight to about 20 parts by weight or about 10 parts by weight to about 20 parts by weight It may be provided in the range of parts by weight. Phenyltrimethoxysilane according to another embodiment may prevent cracks in the coating film and maintain stability of the coating film within the above range. If the amount of phenyltrimethoxysilane is less than 10 parts by weight, there is a risk of cracking while the coating film shrinks during curing at a high temperature of 200 ° C. or higher, and if the amount of phenyltrimethoxysilane exceeds 20 parts by weight, 3-(meth)acryloxypropyltri It is preferable that the content of phenyltrimethoxysilane is applied within the above-mentioned range because the compatibility with methoxysilane may be lowered and the physical properties of the coating film may be adversely affected.

When the polysiloxane resin according to another embodiment is prepared by adding 3-(meth)acryloxypropyltrimethoxysilane together with methyltrimethoxysilane and phenyltrimethoxysilane to make the polysiloxane resin, other components included in the heat-resistant paint composition Compatibility with the field is better, and the crosslinking density and curability during curing of the heat-resistant paint composition can be further improved.

As a specific example, the content of 3-(meth)acryloxypropyltrimethoxysilane may be about 5 parts by weight, about 6 parts by weight, about 7 parts by weight, about 8 parts by weight, about 9 parts by weight or about 10 parts by weight. can In addition, the content of 3-(meth)acryloxypropyltrimethoxysilane may be in a range of one or more of the above numerical values and one or less of the above numerical values.

For example, the content range of 3-(meth)acryloxypropyltrimethoxysilane is about 5 parts by weight to about 7 parts by weight, about 6 parts by weight to about 8 parts by weight, about 7 parts by weight to about 9 parts by weight, It may be provided in the range of about 8 parts by weight to about 10 parts by weight or about 5 parts by weight to about 10 parts by weight. 3-(meth)acryloxypropyltrimethoxysilane according to an embodiment can be easily cured within the above range and maintain excellent coating film properties. If 3-(meth)acryloxypropyltrimethoxysilane is less than 5 parts by weight, the effect of improving physical properties is insignificant, and if it exceeds 10 parts by weight, the hardness of the coating film decreases and yellowing may occur. - When (meth)acryloxypropyltrimethoxysilane is added, it is preferably applied in an amount of 5 to 10 parts by weight. In addition, since the type and content of the organic solvent that can be used in the preparation of the polysiloxane resin according to another embodiment are the same as those described above, overlapping descriptions will be omitted.

In preparing the polysiloxane resin according to an embodiment, at least one of acetic acid, formic acid, hydrochloric acid, nitric acid, phosphoric acid, ammonia water, and sodium hydroxide may be used as an acidic or basic catalyst. For example, when synthesizing a polysiloxane resin, an 8w/w% formic acid aqueous solution may be used as a catalyst composed of water and an acid.

In addition, in one embodiment, the content of the catalyst for hydrolysis and condensation of organosilane may be applied in an amount of 7 to 10 parts by weight (eg, 7 parts by weight, 8 parts by weight, 9 parts by weight or 10 parts by weight). . And, the content of the catalyst may be in the range of one or more of the above values and one or less of the above values. For example, the content range of the catalyst for hydrolysis and condensation of organic silane may be provided in the range of about 7 parts by weight to about 9 parts by weight or about 8 parts by weight to about 10 parts by weight. Of course, the content range of the catalyst is not limited to the above-described range, and may be flexibly changed according to the amount of organic silane introduced during synthesis of the polysiloxane resin. In addition, the concentration of the catalyst for hydrolysis and condensation of organosilane may be applied in a wide range.

A heat-resistant paint composition according to an embodiment may include a polysiloxane resin, a pigment, a solvent, an additive, and silica. In one embodiment, the polysiloxane resin may be provided in 30 to 40 parts by weight. Specifically, the content of the polysiloxane resin is about 30 parts by weight, about 31 parts by weight, about 32 parts by weight, about 33 parts by weight, about 34 parts by weight, about 35 parts by weight, about 36 parts by weight, about 37 parts by weight, about 38 parts by weight. It may be provided in parts by weight, about 39 parts by weight or about 40 parts by weight. In addition, the content range of the polysiloxane resin may be a range of one or more of the above numerical values and one or less of the above numerical values.

For example, the content range of the polysiloxane resin is about 30 parts by weight to about 33 parts by weight, about 31 parts by weight to about 34 parts by weight, about 32 parts by weight to about 35 parts by weight, about 33 parts by weight to about 37 parts by weight, It may be provided in the range of about 34 parts by weight to about 38 parts by weight, about 35 parts by weight to about 39 parts by weight, about 36 parts by weight to about 40 parts by weight, or about 30 parts by weight to about 40 parts by weight. The polysiloxane resin according to an embodiment may maintain excellent heat resistance and flame retardancy within the above range.

If the content of the polysiloxane resin is less than 30 parts by weight, the content of inorganic materials in the entire heat-resistant coating composition decreases, resulting in a decrease in heat resistance and flame retardancy, and overall physical properties of the coating film may be reduced. Since there is a concern that adhesion to and deterioration, the content of the polysiloxane resin is preferably applied within the above-mentioned range.

In one embodiment, the amount of pigment may be applied in an amount of 10 to 20 parts by weight. Specifically, the content of the pigment is about 10 parts by weight, about 11 parts by weight, about 12 parts by weight, about 13 parts by weight, about 14 parts by weight, about 15 parts by weight, about 16 parts by weight, about 17 parts by weight, about 18 parts by weight part, about 19 parts by weight or about 20 parts by weight. Further, the content of the pigment may range from one or more of the above numerical values to less than one of the above numerical values.

For example, the content of the pigment ranges from about 10 parts by weight to about 15 parts by weight, from about 12 parts by weight to about 17 parts by weight, from about 15 parts by weight to about 20 parts by weight, or from about 10 parts by weight to about 20 parts by weight. can be provided. The pigment according to one embodiment can maintain the physical properties of the coating film at an excellent level within the above range. If the pigment is less than 10 parts by weight, it may be difficult to realize the color of the paint due to a decrease in hiding power, and if it exceeds 20 parts by weight, aggregation of pigment particles occurs due to an increase in the content of the pigment, lowering dispersibility and increasing viscosity As a result, painting workability may deteriorate.

The heat-resistant coating composition according to an embodiment includes 45 to 50 parts by weight of a solvent (eg, 45 parts by weight, 46 parts by weight, 47 parts by weight, 48 parts by weight, 49 parts by weight, 50 parts by weight) for coatability and painting workability. ) may be included. Here, the solvent may be applied as ethyl alcohol, isopropyl alcohol, butyl alcohol, butyl cellosolve, xylene, methyl ethyl ketone, methyl isobutyl ketone, or propylene glycol monomethyl ether acetate, but is not limited to the above-described examples and is known in the art. Other types of solvents may also be used. In addition, the content of the solvent may be appropriately adjusted in consideration of the content of other components added to the heat-resistant coating composition. In addition, when xylene and butyl cellosolve are mixed and used at a constant weight ratio (eg, 1:1, 2:1, or 3:1) as a solvent when preparing the paint composition, electrostatic painting of the paint is easy, and the paint film Coatability, compatibility, stability, etc. of can be further improved.

In addition, the heat-resistant coating composition according to an embodiment includes 4 to 10 parts by weight of additives (eg, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, or 10 parts by weight) may further include. In one embodiment, as an additive, at least one may be selected from the group consisting of a general dispersing agent, an antifoaming agent, a leveling agent, and a viscosity stabilizer, and two or more additives may be mixed in an appropriate amount to exhibit optimal coating film performance. .

<Description of the manufacturing method of the coating body using the heat-resistant paint composition>

A method for manufacturing a coating body according to an embodiment of the present invention will be described according to the flow chart shown in FIG. 1, but will be described in order for convenience. In the present specification, the coating body refers to an interior or exterior material in which a coating layer is formed by coating and curing a heat-resistant coating composition on the surface of an object to be coated. For example, the coating body may be applied as an automobile interior material or a subway interior material in which a coating layer of a heat-resistant paint composition is formed on the surface. However, articles that can be coated with the heat-resistant coating composition are not limited to the above-described examples, and can be applied to other types of articles such as building interior materials or exterior materials requiring heat resistance and flame retardancy.

1. Coating step <S101>

In this step, a coating layer may be formed on the surface of the object to be coated by applying the above-described heat-resistant coating composition to the object to be coated. In this step, a coating layer may be formed on the surface of the object to be coated with a coating film thickness of 15 to 100 μm. As a specific example, the thickness of the coating film coated on the surface of the object to be coated is about 15 μm, about 16 μm, about 17 μm, about 18 μm, about 19 μm, about 20 μm, about 21 μm, about 22 μm, about 23 μm, About 24 μm, about 25 μm, about 26 μm, about 27 μm, about 28 μm, about 29 μm, about 30 μm, about 40 μm, about 50 μm, about 60 μm, about 70 μm, about 80 μm, about 90 μm or about 100 μm. In addition, the thickness of the coating film may be applied within a range of one or more of the above values and less than one of the above values. For example, the range of the thickness of the coating film coated on the object to be coated is about 15 μm to about 16 μm, about 16 μm to about 17 μm, about 17 μm to about 18 μm, about 18 μm to about 19 μm, about 19 μm to about 20 μm or about 15 μm to about 100 μm. Of course, the coating film thickness is not limited to the above example and may be changed as needed.

The coating method performed in this step is not limited to any specific method as long as it is a method of forming a coating layer by coating a paint on a substrate, which is an object to be coated, and is not limited to a specific method, such as bar coating, slit coating, dip coating, roll coating, spin coating, spray coating, and dip coating. A person skilled in the art can arbitrarily select and apply known coating methods such as a paper method, an impregnation method, and a gravure coating method.

2. Curing step <S102>

In this step, the coating layer formed in step S101 may be cured. In one embodiment, heat treatment may be performed on the coating layer. As a specific example, in this step, the coating layer may be thermally cured at a temperature of 50 to 250° C. for 10 to 60 minutes. The heat treatment temperature and time in this step may be adjusted within an appropriate range so that the coating layer can be sufficiently cured.

Hereinafter, the present invention will be described in more detail through specific examples and experimental examples. Since the following examples and experimental examples are only examples for helping understanding of the present invention, the scope of the present invention is not limited or limited thereto.

1. Synthesis of polysiloxane resin

The contents of methyltrimethoxysilane, phenyltrimethoxysilane, and 3-(meth)acryloxypropyltrimethoxysilane described in Table 1 in a 4-necked glass flask reactor equipped with a reflux condenser, nitrogen inlet, stirrer and heating device (Unit: g), 47 g of organic solvent (the organic solvent is mixed by setting the weight ratio of xylene and butyl cellosolve to 2: 1) and 8 g of 8 w / w% formic acid aqueous solution are added, and After stirring for 2 hours at ° C. and stirring at 110 ° C. for 1 hour, unreacted materials, reaction by-products and moisture were removed through a Dean Star Trap, and filtered through a 1 μm bag filter to obtain a polysiloxane resin.

ingredient Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 ¹ methyltrimethoxysilane 24 22 20 25 18 27 ² Phenyltrimethoxysilane 10 13 16 20 22 8 ³ 3-(meth)acryloxypropyltrimethoxysilane 10 8 6 5 3 12
main)
1: Methyltrimethoxysilane (OFS-6060 from DOW)
2: Phenyltrimethoxysilane (OFS-6124 from DOW)
3: 3-(meth)acryloxypropyltrimethoxysilane (CG-0174 from QUFU)

2. Preparation of heat-resistant coating composition using the polysiloxane resin of Example 1

The mixture was mixed in the composition shown in Table 2 below, but each polysiloxane resin, pigment, solvent and additives (dispersant, antifoaming agent) were mixed in the amount (unit: g) shown in Table 2 below in a 1L container, and stirred for 1 hour. After that, the heat-resistant coating composition was completed.

ingredient manufacturing example
One manufacturing example
2 manufacturing example
3 Comparative Preparation Example 1 Comparative Preparation Example 2 ¹ polysiloxane resin 30 35 40 25 45 ² pigment 20 15 10 25 5 ³ solvent 46 46 46 46 46 ⁴ Dispersant 2 2 2 2 2 ⁵ defoamer 2 2 2 2 2
main)
1: polysiloxane resin (Example 1)
2: Pigment (Tiona RCl 575 from Cristal)
3: Solvent (mixing GS Caltex's Xylene and Yeochun NCC's Butyl cellosolve at a weight ratio of 2:1)
4: Dispersing agent (Disperbyk 182 from BYK)
5: Defoamer (BYK's BYK-054)

3. Preparation of heat-resistant coating composition using the polysiloxane resin of Example 2

The mixture was mixed in the composition shown in Table 3 below, but each polysiloxane resin, pigment, solvent and additives (dispersant, antifoaming agent) were mixed in the amount (unit: g) shown in Table 3 below in a 1L container, and stirred for 1 hour. After that, the heat-resistant coating composition was completed.

ingredient manufacturing example
4 manufacturing example
5 manufacturing example
6 Comparative Preparation Example 3 Comparative Preparation Example 4 ¹ polysiloxane resin 30 35 40 25 45 ² pigment 20 15 10 25 5 ³ solvent 46 46 46 46 46 ⁴ Dispersant 2 2 2 2 2 ⁵ defoamer 2 2 2 2 2
main)
1: polysiloxane resin (Example 2)
2: Pigment (Tiona RCl 575 from Cristal)
3: Solvent (mixing GS Caltex's Xylene and Yeochun NCC's Butyl cellosolve at a weight ratio of 2:1)
4: Dispersing agent (Disperbyk 182 from BYK)
5: Defoamer (BYK's BYK-054)

4. Preparation of heat-resistant coating composition using the polysiloxane resin of Example 3

The mixture was mixed in the composition shown in Table 4 below, but each polysiloxane resin, pigment, solvent and additives (dispersant, antifoaming agent) were mixed in the amount (unit: g) shown in Table 4 below in a 1L container, and stirred for 1 hour. After that, the heat-resistant coating composition was completed.

ingredient manufacturing example
7 manufacturing example
8 manufacturing example
9 Comparative Preparation Example 5 Comparative Preparation Example 6 ¹ polysiloxane resin 30 35 40 25 45 ² pigment 20 15 10 25 5 ³ solvent 46 46 46 46 46 ⁴ Dispersant 2 2 2 2 2 ⁵ defoamer 2 2 2 2 2
main)
1: polysiloxane resin (Example 3)
2: Pigment (Tiona RCl 575 from Cristal)
3: Solvent (mixing GS Caltex's Xylene and Yeochun NCC's Butyl cellosolve at a weight ratio of 2:1)
4: Dispersing agent (Disperbyk 182 from BYK)
5: Defoamer (BYK's BYK-054)

5. Preparation of heat-resistant coating composition using the polysiloxane resin of Example 4

The mixture was mixed in the composition shown in Table 5 below, but each polysiloxane resin, pigment, solvent and additives (dispersant, antifoaming agent) were mixed in the amount (unit: g) shown in Table 5 below in a 1L container, and stirred for 1 hour. After that, the heat-resistant coating composition was completed.

ingredient manufacturing example
10 manufacturing example
11 manufacturing example
12 Comparative Preparation Example 7 Comparative Preparation Example 8 ¹ polysiloxane resin 30 35 40 25 45 ² pigment 20 15 10 25 5 ³ solvent 46 46 46 46 46 ⁴ Dispersant 2 2 2 2 2 ⁵ defoamer 2 2 2 2 2
main)
1: polysiloxane resin (Example 4)
2: Pigment (Tiona RCl 575 from Cristal)
3: Solvent (mixing GS Caltex's Xylene and Yeochun NCC's Butyl cellosolve at a weight ratio of 2:1)
4: Dispersing agent (Disperbyk 182 from BYK)
5: Defoamer (BYK's BYK-054)

6. Preparation of heat-resistant coating composition using the polysiloxane resin of Comparative Example 1

The composition shown in Table 6 below was mixed, but each polysiloxane resin, pigment, solvent, and additives (dispersant, antifoaming agent) were mixed in the amount (unit: g) shown in Table 6 below in a 1L container, and stirred for 1 hour. After that, the heat-resistant coating composition was completed.

ingredient Comparative Preparation Example 9 Comparative Preparation Example 10 Comparative Preparation Example 11 ¹ polysiloxane resin 30 35 40 ² pigment 20 15 10 ³ solvent 46 46 46 ⁴ Dispersant 2 2 2 ⁵ defoamer 2 2 2
main)
1: polysiloxane resin (Comparative Example 1)
2: Pigment (Tiona RCl 575 from Cristal)
3: Solvent (mixing GS Caltex's Xylene and Yeochun NCC's Butyl cellosolve at a weight ratio of 2:1)
4: Dispersing agent (Disperbyk 182 from BYK)
5: Defoamer (BYK's BYK-054)

7. Preparation of heat-resistant coating composition using the polysiloxane resin of Comparative Example 2

The composition as shown in Table 7 below is mixed, but each polysiloxane resin, pigment, solvent and additives (dispersant, antifoaming agent) are mixed in the amount (unit: g) shown in Table 7 below in a 1L container, and stirred for 1 hour. After that, the heat-resistant coating composition was completed.

ingredient Comparative Preparation Example 12 Comparative Preparation Example 13 Comparative Preparation Example 14 ¹ polysiloxane resin 30 35 40 ² pigment 20 15 10 ³ solvent 46 46 46 ⁴ Dispersant 2 2 2 ⁵ defoamer 2 2 2
main)
1: polysiloxane resin (Comparative Example 2)
2: Pigment (Tiona RCl 575 from Cristal)
3: Solvent (mixing GS Caltex's Xylene and Yeochun NCC's Butyl cellosolve at a weight ratio of 2:1)
4: Dispersing agent (Disperbyk 182 from BYK)
5: Defoamer (BYK's BYK-054)

8. Fabrication of test specimens

Each heat-resistant coating composition was applied to a steel plate having a size of 7 cm X 15 cm using an electrostatic spray device so that the thickness of the coating film was 100 μm. After that, the coating layer was cured at 230° C. for 10 minutes to prepare test specimens.

9. Test and evaluation methods

For the test specimen prepared as described above, the curability, adhesion, hardness, solvent resistance, stain resistance, shrinkage resistance, flame retardancy and smoothness of the coating film were evaluated through the method described below, and the results are shown in Table 8.

Experiment environment conditions

The experimental environment, that is, the place where the experiment is conducted, is a place with a temperature of 20 ± 2 ℃ and humidity of 65 ± 5% (hereinafter referred to as 'room temperature'), no direct sunlight, and very little gas, steam, dust, and ventilation. In principle, those left unattended for more than 72 hours after painting were used in the experiment.

Hardenability evaluation

The coating film of the cured test specimen was scratched with a fingernail to check whether nail scratches occurred. When nail scratches occurred, curability was evaluated as poor, and when nail scratches did not occur, it was evaluated as good.

Adhesion evaluation

A cross cutting test method was performed on the coating film of the cured test specimen, and at this time, glass tape was used. That is, the film or layer formed on the specimen is cut into 100 checkered slices with a size of 1 mm * 1 mm, glass tape is attached to the slices, and the number of slices attached to the substrate without falling off is measured and attached. gender was evaluated.

hardness evaluation

Hardness was evaluated by applying a 45° inclination and a 1Kg load using a Mitsubishi pencil to evaluate the abnormality of the coating film when moving 2cm. In the case of 5 evaluations, if the maximum pencil hardness value when there is no scratch in all 5 times is 3H or more (ie, 3H or harder than 3H), the hardness is evaluated as good, and if it is less than 3H (ie, softer than 3H) Hardness was evaluated as poor.

Solvent resistance evaluation

After applying methyl ethyl ketone to the gauze and rubbing the gauze by applying a certain force to the specimen on which the coating film was formed, the number of times of rubbing was measured until the coating film was peeled off to reveal the base material.

Fouling resistance evaluation

The stain resistance evaluation was evaluated by contaminating the surface of the coating film formed on the test specimen with oil-based magic and 30 seconds later, applying a certain force to remove the magic mark with a tissue, and then visually determining the surface state of the coating film. That is, stain resistance was evaluated as poor if traces of magic marks remained on the surface of the coating film, and as good if traces did not remain.

Shrinkage resistance (crack resistance) evaluation

Each heat-resistant coating composition was applied to a steel plate with a size of 7cm X 15cm using electrostatic spray equipment to a thickness of 100㎛, and immediately after curing the coating layer at 230℃ for 10 minutes, visually inspected for cracks in the coating layer. When cracks did not occur, the shrinkage resistance was evaluated as good, and when cracks occurred, the shrinkage resistance was evaluated as poor.

Flammability evaluation

The mass reduction rate is less than 30% when measured by the nonflammability test method (KS F ISO 1182), and the gas hazard when measured by the gas hazard test method (KS F 2271) If the stopping time) was 11 minutes or more, the flame retardancy was evaluated as excellent, and if all of the above conditions were not satisfied, the flame retardancy was evaluated as poor.

smoothness evaluation

Evaluate the degree to which the presence of surface waviness is felt when touching the painted surface of the cured specimen with a hand. If the surface waviness can be clearly felt by touch, the surface smoothness is poor. It was evaluated as good.

division curability adhesiveness Hardness solvent resistance stain resistance shrinkage resistance flame retardant smoothness Preparation Example 1 Good 95/100 Good Episode 45 Good Good Great Good Preparation Example 2 Good 95/100 Good Episode 46 Good Good Great Good Preparation Example 3 Good 95/100 Good Episode 46 Good Good Great Good Production Example 4 Good 95/100 Good Episode 46 Good Good Great Good Preparation Example 5 Good 95/100 Good Episode 47 Good Good Great Good Preparation Example 6 Good 95/100 Good Episode 57 Good Good Great Good Preparation Example 7 Good 98/100 Good Episode 48 Good Good Great Good Preparation Example 8 Good 99/100 Good Episode 49 Good Good Great Good Preparation Example 9 Good 98/100 Good Episode 49 Good Good Great Good Preparation Example 10 Good 99/100 Good 50 times Good Good Great Good Preparation Example 11 Good 99/100 Good 50 times Good Good Great Good Preparation Example 12 Good 100/100 Good 50 times Good Good Great Good Comparative Manufacturing Example 1 Good Measurement impossible due to cracks Measurement impossible due to cracks Measurement impossible due to cracks error error Great Good Comparative Manufacturing Example 2 Good 100/100 error 40 times Good Good Great Good Comparative Preparation Example 3 Good Measurement impossible due to cracks Measurement impossible due to cracks Measurement impossible due to cracks error error Great Good Comparative Preparation Example 4 Good 100/100 error Episode 42 Good Good Great Good Comparative Manufacturing Example 5 Good Measurement impossible due to cracks Measurement impossible due to cracks Measurement impossible due to cracks error error Great Good Comparative Preparation Example 6 Good 100/100 error Episode 43 Good Good Great Good Comparative Preparation Example 7 Good Measurement impossible due to cracks Measurement impossible due to cracks Measurement impossible due to cracks error error Great Good Comparative Preparation Example 8 Good 100/100 error Episode 38 error Good Great Good Comparative Preparation Example 9 Good 95/100 error Episode 48 Good Good Great Good Comparative Preparation Example 10 Good 95/100 error Episode 48 Good Good Great Good Comparative Preparation Example 11 Good 94/100 error Episode 49 Good Good Great Good Comparative Preparation Example 12 Good 90/100 Good Episode 42 error error Great Good Comparative Preparation Example 13 Good 90/100 Good Episode 42 error error Great Good Comparative Preparation Example 14 Good 95/100 Good Episode 43 error error Great Good

As shown in Table 8, Preparation Examples 1 to 12 of the present invention confirmed that the surface properties of the coating film, such as curability, adhesion, hardness, solvent resistance, stain resistance, shrinkage resistance, flame retardancy and smoothness, were generally excellent. can In addition, through the experimental results of Comparative Preparation Examples 1 to 8, it was confirmed that when the content of each component included in the coating composition exceeds or is less than the input amount range for each component, the surface properties of the coating film are relatively deteriorated compared to the Preparation Examples. can In addition, looking at the results of Comparative Preparation Examples 9 to 14, even if the content of the polysiloxane resin is set to be the same as the Preparation Examples, when the content of each organic silane added during the preparation of the polysiloxane resin is out of a specific range, the physical properties of the coating film are deteriorated. it can be seen that

10. Additional fabrication of test specimens and measurement of inorganic content

The polysiloxane resins of Examples 1 to 4 were applied to a steel plate having a size of 7 cm X 15 cm using an electrostatic spray device so that the thickness of the coating film was 100 μm. After that, the coating layer was cured at 230° C. for 10 minutes to prepare test specimens. The prepared specimen was put into a thermogravimetric analysis and the inorganic content was measured at a high temperature of 750 ° C or higher. The measured inorganic content results are listed in Table 9.

division Example 1 Example 2 Example 3 Example 4 mineral content 73% by weight 71% by weight 71% by weight 70% by weight

As can be seen from the measurement results of Table 9, since the inorganic content of the polysiloxane resins of Examples 1 to 4 remaining at a high temperature of 750 ° C. or higher is 70% by weight or more, it can be seen that a high proportion of inorganic substances is contained in the polysiloxane resin. .

11. Additional fabrication of test specimens and evaluation of physical properties

The mixture was mixed in the composition as shown in Table 10 below, but each polysiloxane resin, pigment, solvent and additives (dispersant, antifoaming agent) were mixed in the amount (unit: g) shown in Table 10 below in a 1L container, and stirred for 1 hour. After that, the heat-resistant coating composition was completed. Thereafter, the heat-resistant coating composition was applied to a steel sheet having a size of 7 cm X 15 cm using electrostatic spray equipment, and the coating was applied so that the thickness of the coating film was 100 μm. After that, the coating layer was cured at 230° C. for 10 minutes to prepare test specimens. For the prepared test specimen, the curability, adhesion, hardness, solvent resistance, stain resistance, shrinkage resistance, flame retardancy and smoothness of the coating film were evaluated in the same way as the above evaluation method, and the results are shown in Table 11.

ingredient Comparative Preparation Example 15 Comparative Preparation Example 16 ¹ polysiloxane resin 40 40 ² pigment 10 10 ³ solvent 46
(Using butyl cellosolve alone) 46
(The weight ratio of xylene and butyl cellosolve is 4:1) ⁴ Dispersant 2 2 ⁵ defoamer 2 2
main)
1: polysiloxane resin (Example 4)
2: Pigment (Tiona RCl 575 from Cristal)
3: Solvent (Xylene from GS Caltex, Butyl cellosolve from Yeochun NCC)
4: Dispersing agent (Disperbyk 182 from BYK)
5: Defoamer (BYK's BYK-054)

division curability adhesiveness Hardness solvent resistance stain resistance shrinkage resistance flame retardant smoothness Comparative Preparation Example 15 evaluation
not allowed evaluation
not allowed evaluation
not allowed evaluation
not allowed evaluation
not possible evaluation
not possible not rated not rated Comparative Preparation Example 16 Good 94/100 Good Episode 45 Good Good Great error

As shown in Table 11, in Comparative Preparation Example 15 in which butyl cellosolve was used alone in the solvent, it was difficult to adjust the resistance value of the paint to a level suitable for electrostatic painting, and an operation error occurred in the electrostatic spray equipment, resulting in the painting itself. was not made, so a coating film could not be formed. In addition, in Comparative Preparation Example 16 in which xylene and butyl cellosolve were blended at a weight ratio of 4:1, it was confirmed that the coating film smoothness was reduced due to the excessive addition of xylene.

As described above, according to various embodiments of the present invention, since the coating composition is prepared using polysiloxane resins prepared by reacting different types of organic silanes, the content of inorganic substances contained in the heat-resistant coating composition is increased, thereby improving heat resistance and flame retardancy. It has an excellent effect.

In addition, according to various embodiments of the present invention, when preparing a polysiloxane resin, a certain amount of phenyltrimethoxysilane is added to methyltrimethoxysilane and reacted together to synthesize a polysiloxane resin, or methyltrimethoxysilane is mixed with phenyltrimethoxysilane. By adding a certain amount of oxysilane and 3-(meth)acryloxypropyltrimethoxysilane to react to synthesize a polysiloxane resin, the stability and compatibility of the paint is increased while the inorganic content of the heat-resistant paint composition is maintained high, and the heat resistance properties are further improved. It can be improved, and has excellent properties of coating films such as curability, adhesion, hardness, solvent resistance, and stain resistance. Moreover, the heat-resistant coating composition according to various embodiments of the present invention has excellent shrinkage resistance and crack resistance even without a separate polymer resin, so that cracks do not occur on the surface of the coating film when cured at a high temperature of 200 ° C or higher.

In addition, according to various embodiments of the present invention, since the content of inorganic substances is relatively high compared to the content of organic substances, the amount of carbonization during combustion is small and the amount of harmful gases is reduced, resulting in excellent flame retardancy. Therefore, it is possible to manufacture a coated body having a beautiful appearance and excellent flame retardancy by coating a heat-resistant coating composition on an article requiring heat resistance.

In addition, the coating composition according to various embodiments of the present invention satisfies important physical properties such as shrinkage resistance, crack resistance, hardness, and coating property as a high-temperature bake-type heat-resistant coating agent, while reducing the content of organic matter in the paint and improving stability and compatibility. It is possible to further improve the heat resistance property by increasing the , and it is possible to secure excellent levels of chemical resistance and contamination resistance.

As described above, the detailed description of the present invention has been made by way of examples, but since the above-described embodiments have only been described with preferred examples of the present invention, it should not be understood that the present invention is limited only to the above embodiments. No, the scope of the present invention should be understood as the following claims and their equivalent concepts.

Claims (7)

30 to 40 parts by weight of polysiloxane resin;
10 to 20 parts by weight of a pigment; and
Contains 45 to 50 parts by weight of a solvent;
The polysiloxane resin is prepared by reacting different kinds of organic silanes,
The organosilane includes methyltrimethoxysilane, phenyltrimethoxysilane and 3-(meth)acryloxypropyltrimethoxysilane,
The polysiloxane resin includes 20 to 25 parts by weight of the methyltrimethoxysilane, 10 to 20 parts by weight of the phenyltrimethoxysilane, 5 to 10 parts by weight of the 3-(meth)acryloxypropyltrimethoxysilane, and 30 parts by weight of an organic solvent. It is prepared by reacting ~ 65 parts by weight,
The organic solvent is provided with at least one selected from the group consisting of xylene, butyl acetate, butyl cellosolve, ethyl alcohol, isopropyl alcohol, butyl alcohol, methyl ethyl ketone, methyl isobutyl ketone and propylene glycol monomethyl ether acetate characterized by
A heat-resistant coating composition having improved crack resistance. According to claim 1,
The heat-resistant coating composition
4 to 10 parts by weight of additives; characterized in that it further comprises
A heat-resistant coating composition having improved crack resistance. delete delete delete delete A coating step of applying the heat-resistant coating composition according to any one of claims 1 to 2 to an object to be coated; and
Characterized in that it comprises a; curing step of curing the coating layer formed in the coating step
A method for producing a coated body using a heat-resistant coating composition.

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