KR20130120424A - Thermoset coating composition having self-healing capacity, coating film, and preparation method of coating film - Google Patents

Abstract

The present invention relates to the following: a thermoset coating composition which contains a polysiloxane resin, a silica particle in which the surface is processed with a (meth)acrylate based compound, and an organic solvent; a coating film; and a preparation method of the coating film. A coating material with excellent self-healing capacity and surface properties including high abrasion resistance, scratch resistance, staining resistance, and surface intensity is provided by the present invention.

Description

TECHNICAL FIELD [0001] The present invention relates to a thermosetting coating composition having self-healing ability, a coating film, and a method for producing the coating film. BACKGROUND ART < RTI ID = 0.0 >

The present invention relates to a thermosetting coating composition capable of self-healing, a coating film, and a process for producing a coating film, and more particularly, to a process for producing a coating film having a high transmittance, low haze property, excellent scratch resistance and self- Thermosetting coating compositions, coating films prepared from such coating compositions, and methods of making coating films using the coating compositions.

In order to protect the product from damage due to mechanical, physical and chemical influences from the outside, various coating layers or coating films are applied to the surfaces of electric and electronic devices such as cellular phones, electronic material parts, home appliances, automobile interior and exterior, have. However, scratches on the coated surface of the product and cracks due to external impacts deteriorate the appearance characteristics, major performance and life of the product, and various studies are being conducted to protect the surface of the product to maintain the quality of the product for a long period of time.

Particularly, coating materials having self-healing ability do not need additional coating or repair process even in the case of surface damage, and they are actively researched recently because they are very advantageous in maintaining appearance and performance of products. As a result of these studies, there has been disclosed an ultraviolet curable composition using an oligomer having self-healing ability and a composition containing inorganic particles or a fluorine compound added thereto in order to improve scratch resistance and stain resistance. However, The surface hardness and the self-healing ability can not be sufficiently obtained.

In addition, coating compositions comprising particles or capsules containing polymeric or polymeric active materials or treated on their surfaces have also been introduced. The coating layer produced from such compositions exhibits a certain degree of self-healing ability against cracking due to external impact, Mechanical properties such as scratch resistance or durability are not sufficient and compatibility between the respective components is low.

Accordingly, there is a demand for development of a coating material capable of having an improved self-healing ability while sufficiently securing surface characteristics such as scratch resistance and durability.

The present invention is to provide a thermosetting coating composition capable of providing a coating material having a high transmittance, a low haze characteristic, an excellent scratch resistance and a self-healing ability.

Further, the present invention is to provide a coating film having high transmittance, low haze property, excellent scratch resistance and self-healing ability.

The present invention further provides a method for producing the coating film.

The present invention relates to a resin composition comprising a polysiloxane-based resin; (Meth) acrylate-based compound is treated on its surface; And an organic solvent.

The present invention also provides a coating film comprising a cured product of the coating composition.

The present invention also relates to a resin composition comprising a polysiloxane-based resin; (Meth) acrylate-based compound is treated on its surface; And an organic solvent; And coating the mixture on a substrate and curing or drying the coating film.

Hereinafter, a thermosetting coating composition, a coating film, and a method for producing a coating film according to a specific embodiment of the present invention will be described in detail.

In the present specification, '(metha) acrylate' means that both (meth) acrylate and acrylate are included.

According to one embodiment of the invention, a polysiloxane-based resin; (Meth) acrylate-based compound is treated on its surface; And an organic solvent, may be provided.

Polysiloxane resins have low glass transition temperature and are excellent in flexibility and thermal stability. However, they have low mechanical properties such as durability and surface hardness, and because of their stickiness when used as a coating material, they have blocking resistance It is known to be bad.

Thus, the present inventors continued their research on a coating material having self-healing ability, and using the coating composition obtained by adding the silica particles treated on the surface of the (meth) acrylate compound to the polysiloxane resin, It is possible to provide a coating material capable of improving mechanical properties such as physical properties and surface hardness and having excellent self-healing ability.

Each of the silica and the (meth) acrylate-based compound is not highly compatible with the polysiloxane-based resin or the siloxane-based oligomer or the like, and when they are mixed with each other to produce a coating material, they are not well mixed to cause phase separation, And partially coalesce.

On the other hand, the silica particles treated with the (meth) acrylate compound on the surface may have a high compatibility with the polysiloxane, and thus, in the thermosetting coating composition of the embodiment, the components are phase- Can be minimized.

In addition, the thermosetting coating composition of this embodiment can make the crosslinked structure of the coating material to be produced more densified by the (meth) acrylate-based compound including the silica particles treated on the surface, thereby improving the abrasion resistance and the film strength And it is possible to prevent the phenomenon that the coating material is permanently damaged due to a large external stimulus or impact and the free healing ability is lost.

The (meth) acrylate compound bonded to the surface of the silica particles may include a urethane (meth) acrylate resin or a hydroxyalkyl (meth) acrylate modified with a polylactone compound.

Preferably, the silica particles treated with the (meth) acrylate compound on the surface may include silica particles treated with a hydroxyalkyl (meth) acrylate modified with a polylactone compound, May include silica particles having a polylactone-modified hydroxyalkyl (meth) acrylate bonded to its surface via a urethane bond.

The polylactone-based compound may be a compound derived from a cyclic ester having 3 to 10 carbon atoms, preferably a compound derived from a cyclic ester having 4 to 8 carbon atoms, more preferably 6 carbon atoms. Accordingly, the hydroxyalkyl (meth) acrylate modified with the polylactone-based compound may be a compound in which a polylactone-based compound is bonded to the end of a hydroxyalkyl (meth) acrylate.

The polylactone-based modified acrylate may comprise a compound of formula (7).

(7)

In Formula 2, R ₃ is hydrogen or methyl, b is an integer from 2 to 9, p is an integer from 1 to 5, q is an integer of 1 to 10. Preferably, b is an integer of 4 to 8, more preferably 5 or 6.

Specific examples of the polycaprolactone-based modified acrylate include Placcel FA (acrylate) or Placcel FM (methacrylate) products manufactured by Daicel.

Specifically, the silica particles having hydroxyalkyl (meth) acrylate modified with a polylactone-based compound through the urethane bond bonded to the surface thereof may include a compound represented by the following formula (8).

[Chemical Formula 8]

In Formula 8, R ₃ is hydrogen or methyl, R ₄ is an aliphatic, a cycloaliphatic or aromatic divalent organic functional group, p is an integer from 1 to 5, q is an integer from 1 to 10, a is at least 1 B is an integer of 2 to 9, and 'Silica' means a silica particle.

As described later, R ₄ may be an aliphatic, alicyclic or aromatic divalent organic functional group derived from a diisocyanate compound, and specific examples of such a diisocyanate compound are as follows.

The (a) may be the number of the hydroxyalkyl (meth) acrylate modified with the polylactone compound bonded to the surface of the silica particles through the urethane bond, and may be an integer of 1 to 30, for example. Preferably, b is an integer of 4 to 8, more preferably 5 or 6.

On the other hand, the silica particles may have an average particle diameter of 10 to 100 nm. If the size of the silica particles is too small, it can not sufficiently serve as a physical support. If the silica particles are too large, the optical properties of the coating composition or the resultant product may be deteriorated.

R ₄ may be derived from a diisocyanate compound (NCO-R ₄ -NCO) containing two isocyanates. Specific examples of such diisocyanate compounds include hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate , Xylene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, and the like.

On the other hand, a polysiloxane-based resin such as polydimethylsiloxane which is commonly used contains a part of silica, but a reactor having a short length such as dimethylvinyl is adhered thereto, which does not affect the restoring force of the material itself. On the other hand, the silica particles having hydroxyalkyl (meth) acrylate modified with a polylactone-based compound via the urethane bond bonded to the surface improve the resilience of the polysiloxane-based resin by elasticity and exhibit excellent self-healing ability And the mechanical properties such as scratch resistance and surface hardness can be compensated.

On the other hand, the polysiloxane-based resin that can be used in the thermosetting coating composition of one embodiment of the present invention can be used without limitation as long as it is a commonly used polysiloxane-based resin. The polysiloxane-based resin is meant to include not only a polysiloxane-based resin in a polymerized or copolymerized state, but also a siloxane-based oligomer capable of synthesizing a polysiloxane-based polymer resin.

Specifically, the polysiloxane-based resin may specifically include a repeating unit represented by the following formula (1).

[Chemical Formula 1]

In Formula 1, R ₁ and R ₂ may be the same or different, and each independently may be hydrogen, an alkyl having 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms.

The polysiloxane-based resin may have a viscosity of 1,000 Mpa · s to 10,000 Mpa · s at 23 ° C. If the viscosity of the polysiloxane-based resin is too low, it is difficult to control the thickness of the coating layer. If the viscosity is too high, wetting may not be performed well and the coating layer may be difficult to be flattened.

Specifically, the polysiloxane-based resin may be, for example, a polymer or copolymer obtained by subjecting a polymerizable functional group-introduced siloxane oligomer to a predetermined polymerization reaction, or a siloxane oligomer (subject) into which a polymerizable functional group has been introduced and a crosslinking agent Lt; / RTI >

Specific examples of the polymerizable functional group include a halogen group, a hydroxyl group, a glycidoxy group, an amine group, a vinyl group, an epoxy group, a methacrylate group, an amino group, a mercapto group, a cyano group, a nitro group or an imide group, The siloxane oligomer may be substituted with one or more of such polymerizable functional groups, and may be substituted at the terminal of the oligomer.

The vinyl functional group such as a dialkylvinyl polymerizable functional group substituted with the siloxane oligomer may be crosslinked with a specific functional group included in the crosslinking agent such as silicone hydride (Si-H) Followed by reaction to form a polysiloxane-based resin.

An example of the siloxane oligomer into which the polymerizable functional group is introduced is a compound represented by the following formula (2).

(2)

In Formula 2, n is an integer of 1 to 10.

The siloxane oligomer to which the polymerizable functional group is introduced may further comprise a compound represented by the following general formula (3) or (4).

(3)

[Formula 4]

Commercially available examples of the siloxane oligomer include SYLGARD 184A of Dow Corning Corp. or KR-271 or KR281 of Shin-Etsu.

On the other hand, as the crosslinking agent which reacts with the siloxane oligomer to which the polymerizable functional group is introduced, a polysiloxane-based resin can be formed by a cross-linking reaction with a siloxane oligomer.

Specific examples of such crosslinking agents include polysiloxane-based compounds or organosilane compounds substituted with reactive functional groups; Or a polysiloxane-based compound or an organic silane compound containing a silicon hydride (SiH) functional group.

Examples of the reactive functional group to be substituted with such a crosslinking agent include hydroxy, alkenyl having 2 to 10 carbon atoms, alkoxy having 1 to 20 carbon atoms, alkylamido having 1 to 20 carbon atoms, benzamido having 6 to 20 carbon atoms, Alkenyloxy, aryloxy having 6 to 20 carbon atoms, halogen, and the like, and these functional groups may be substituted with one or more of the above polysiloxane-based compounds or organosilane compounds.

One example of the polysiloxane-based compound containing a silicon hydride (SiH) functional group used as the crosslinking agent is a polymer containing a repeating unit represented by the following formula (5).

[Chemical Formula 5]

In Formula 5, n and m may each be an integer of 1 to 10.

The crosslinking agent may include cyclotetrasiloxane such as a compound represented by the following formula (6).

 [Chemical Formula 6]

Useful examples of the crosslinking agent include SYLGARD 184B of Dow Corning Inc. or ES-100T of Shin-Etsu.

When the siloxane oligomer into which the polymerizable functional group is introduced reacts with the crosslinking agent to form a polysiloxane resin, the silicone oligomer into which the polymerizable functional group is introduced and the crosslinking agent are used in a ratio of 3: 1 to 30: 1, preferably 5: 1 to 20: : 1. ≪ / RTI > In order to thoroughly mix the silicone oligomer with the crosslinking agent, the two materials should be slowly mixed to prevent the injection of unnecessary air bubbles. If the air bubbles do not disappear even after slowly stirring for 10 minutes to 1 hour, a defoaming process must be carried out.

Specific examples of such a catalyst include platinum (Pt), ruthenium (Ru), iridium (Ir), rhodium (Rh), rhodium Palladium (Pd) tin (Sn), or organic compounds thereof. The catalyst may be used in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the silicone oligomer.

The coating composition may contain 1 to 30 parts by weight, preferably 3 to 20 parts by weight, of the (meth) acrylate compound-treated silica particles per 100 parts by weight of the siloxane oligomer.

In addition, the coating composition of one embodiment may comprise an organic solvent. The organic solvent may be any organic solvent which can be used in the coating composition without any limitations as long as it is known in the art. Specific examples thereof include methyl isobutyl ketone, methyl ethyl ketone, dimethyl ketone ketone-based organic solvents such as dimethyl ketone; An alcohol organic solvent such as isopropyl alcohol, isobutyl alcohol or normal butyl alcohol; An acetate organic solvent such as ethyl acetate or normal butyl acetate; And cellosolve organic solvents such as ethyl cellusolve or butyl cellusolve.

The organic solvent can be appropriately used depending on the characteristics of the coating material. For example, the coating composition may include 10 to 1,000 parts by weight of an organic solvent per 100 parts by weight of the siloxane oligomer.

Meanwhile, the thermosetting coating composition according to an embodiment of the present invention may further include a thermosetting monomer, a thermosetting accelerator, or other additives according to properties or uses of the coating film finally prepared.

On the other hand, according to another embodiment of the invention, there can be provided a coating film comprising a cured product of the coating composition.

As described above, the polysiloxane-based resin obtained by adding the silica particles treated with the (meth) acrylate compound to the surface of the polysiloxane-based resin can have excellent self-healing ability along with high scratch resistance and surface hardness.

In particular, the silica particles treated with the (meth) acrylate-based compound on the surface may have high compatibility with the polysiloxane, so that in the thermosetting coating composition of the embodiment, the respective components are phase- The phenomenon of aggregation can be minimized.

The silica particles treated with the (meth) acrylate compound on the surface can react with the polysiloxane resin to form a more dense crosslinked structure, and thus the final coated film can secure an improved abrasion resistance and film strength , It is possible to prevent the phenomenon that the coating material is permanently damaged due to a large external stimulus or impact and the free healing ability is lost.

Specifically, the coating film may include a polysiloxane-based resin; And the (meth) acrylate-based compound may include silica particles treated on the surface, and the surface-treated silica particles are dispersed by the polycarboxylic acid-modified acrylate through the (meth) acrylate- Can be chemically bonded to the resin.

The polysiloxane-based resin may be formed by cross-linking a siloxane-based oligomer, for example, a compound containing a repeating unit of formula (1) and a cross-linking agent in the presence of a catalyst. The details of the crosslinking agent and the catalyst are as described above. The coating film may contain a small amount of a crosslinking agent, a catalyst, or an organic solvent.

The specific contents of the polysiloxane resin, the silica particles treated on the surface of the (meth) acrylate compound, and the organic solvent are as described above.

In the coating film, the polysiloxane-based resin; And the silica particles treated with the (meth) acrylate compound on the surface may be crosslinked. As described above, when the composition is cured or dried, a network crosslinked structure having silica particles as crosslinking points can be formed. The crosslinking structure can be formed by the chemical bonding of the double bond of the (meth) acrylate compound bonded to the surface of the silica particle with the polysiloxane-based resin, so that the mechanical properties such as abrasion resistance, scratch resistance and surface hardness are complemented And it is possible to improve the resilience by the elasticity of the polysiloxane-based resin and to exhibit excellent self-healing ability.

As described above, the (meth) acrylate compound bonded to the surface of the silica particles may include a hydroxyalkyl (meth) acrylate modified with a urethane (meth) acrylate resin or a polylactone compound.

Preferably, the silica particles treated with the (meth) acrylate compound on the surface may include silica particles treated with a hydroxyalkyl (meth) acrylate modified with a polylactone compound, May include silica particles having a polylactone-modified hydroxyalkyl (meth) acrylate bonded to its surface via a urethane bond.

The polylactone-based compound may be a compound derived from a cyclic ester having 3 to 10 carbon atoms, preferably a compound derived from a cyclic ester having 4 to 8 carbon atoms, more preferably 6 carbon atoms.

Accordingly, the hydroxyalkyl (meth) acrylate modified with the polylactone-based compound may be a compound in which a polylactone-based compound is bonded to the end of a hydroxyalkyl (meth) acrylate.

Specifically, the silica particles having hydroxyalkyl (meth) acrylate modified with a polylactone-based compound through the urethane bond bonded to the surface thereof may include the compound of the above formula (8).

The coating film may be in the form of a layer formed on a certain substrate and may be in the form of a film processed into a form that can be adhered or bonded to an application product.

On the other hand, according to another embodiment of the invention, a polysiloxane-based resin; (Meth) acrylate-based compound is treated on its surface; And an organic solvent; And applying the mixture to a substrate and curing or drying the coating film.

The specific contents of the polysiloxane resin, the silica particles treated on the surface of the (meth) acrylate compound, and the organic solvent are as described above. These mixing steps can uniformly mix the components using an apparatus or method known to be commonly used for mixing organic compounds at room temperature.

In the step of applying the mixture, methods and apparatuses commonly used for coating the coating composition can be used without any limitations. For example, a spray method, a roll coating method, or a meyer bar coating method can be used.

The step of drying or curing the applied mixture on the substrate can be carried out at room temperature for about 1 hour to 60 hours or for about 24 hours. Also, the step of drying or curing the mixture applied on the substrate may be carried out at a temperature of 30 ° C to 150 ° C for 30 minutes to 10 hours. In the drying or curing step, drying or curing may be performed using an oven.

There are no particular restrictions on the substrate used. For example, PET or TAC (triacetate cellulose) may be used.

Meanwhile, the method for producing the coating film may further include the step of preparing silica particles having a surface treated with a (meth) acrylate compound.

As described above, the (meth) acrylate compound bonded to the surface of the silica particles may include a urethane (meth) acrylate resin or a hydroxyalkyl (meth) acrylate modified with a polylactone compound .

Preferably, the silica particles treated with the (meth) acrylate compound on the surface may include silica particles treated with a hydroxyalkyl (meth) acrylate modified with a polylactone compound, May include silica particles having a polylactone-modified hydroxyalkyl (meth) acrylate bonded to its surface via a urethane bond.

The polylactone-based compound may be a compound derived from a cyclic ester having 3 to 10 carbon atoms, preferably a compound derived from a cyclic ester having 4 to 8 carbon atoms, more preferably 6 carbon atoms.

Accordingly, the hydroxyalkyl (meth) acrylate modified with the polylactone-based compound may be a compound in which a polylactone-based compound is bonded to the end of a hydroxyalkyl (meth) acrylate.

Accordingly, the step of preparing the silica particles treated with the (meth) acrylate compound on the surface may include the steps of: reacting silica particles with a diisocyanate compound; And reacting the reaction product between the silica particles and the diisocyanate compound with a hydroxyalkyl (meth) acrylate modified with a urethane (meth) acrylate resin or a polylactone compound.

The specific content of the hydroxyalkyl (meth) acrylate modified with the urethane (meth) acrylate resin or the polylactone compound includes the above-mentioned contents with respect to the coating composition of one embodiment.

The silica particles may have an average particle diameter of 5 to 100 nm and may be dispersed in an organic solvent.

As the diisocyanate compound, an organic compound containing two isocyanate groups can be used without limitation, and specific examples thereof include hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, xylene di Isocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, and the like.

The step of reacting the silica particles with the diisocyanate compound may be performed at about 20 ° C to 80 ° C for about 24 hours, and the reaction is preferably carried out in the presence of a metal catalyst. Examples of the catalyst that can be used here include metals such as platinum (Pt), ruthenium (Ru), iridium (Ir), rhodium (Rh), palladium (Pd), tin , And a more specific example is DBTDL (Dibutyl Tin Dilaurate).

The silica particles and the diisocyanate compound may be mixed and reacted in an organic solvent. Examples of the organic solvent that can be used at this time are as described above.

The step of reacting the reaction product between the silica particles and the diisocyanate compound with a hydroxyalkyl (meth) acrylate modified with a urethane (meth) acrylate resin or a polylactone-based compound is carried out at a temperature of from 20 ° C. to 100 ° C. for 30 minutes to For 10 hours, and is preferably carried out in the presence of such a metal catalyst. Examples of the catalyst that may be used herein include metals such as platinum (Pt), ruthenium (Ru), iridium (Ir), rhodium (Rh), and palladium (Pd) tin (Sn) A more specific example is DBTDL (Dibutyl Tin Dilaurate).

Reacting the resultant reaction product of the silica particles and the diisocyanate compound with a hydroxyalkyl (meth) acrylate modified with a urethane (meth) acrylate resin or a polylactone compound to obtain a compound of the following formula have.

 [Chemical Formula 8]

In Formula 8, R ₃ is hydrogen or methyl, R ₄ is an aliphatic, a cycloaliphatic or aromatic divalent organic functional group, p is an integer from 1 to 5, q is an integer from 1 to 10, a is at least 1 B is an integer of 2 to 9, and silica means silica particles. More specific details are as described above.

The polysiloxane-based resin; (Meth) acrylate-based compound is treated on its surface; In the step of applying the mixture between the organic solvent and the organic solvent, and curing or drying the mixture, the silica particles treated with the polysiloxane-based resin and the (meth) acrylate-based compound may react. Thus, a network crosslinked structure having the silica particles as crosslinking points can be formed. That is, the coating film obtained by the above-mentioned production method may include a cross-link between the polysiloxane-based resin and the silica particles treated on the surface of the (meth) acrylate-based compound.

According to the present invention, there is provided a coating composition capable of providing a coating material with excellent self-healing ability together with excellent surface properties such as high abrasion resistance and surface hardness, a coating film using the coating composition and a process for producing the coating film.

The invention will be described in more detail in the following examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.

< Example  >

Example 1 . Preparation of silica particles surface-treated with polycaprolactone- modified acrylate

(1) Introduction of cyanate (NCO) groups onto the silica surface

4 g of toluene diisocyanate (TDI) was diluted with 16 g of methyl ethyl ketone, and then methyl ethyl ketone-silica sol (MEK-ST, Nissan Chemical Co., Ltd., average particle size of silica particles = 22 nm, silica content 30% ) And 0.05 g of tin catalyst (DBTDL, dibutyl tin dilaurate) was added thereto, followed by stirring at 50 ° C for 24 hours.

(2) Introduction of polycaprolactone-modified acrylate

10 g of polycaprolactone-modified hydroxyacrylate (Placcel FA-5) was diluted with 20 g of methyl ethyl ketone, and the mixture was stirred at 60 ° C for 5 hours. The progress of the reaction was confirmed by FT-IR.

Example 2 . Preparation of Coating Composition and Coating Film

20 parts by weight of the surface-treated silica dispersion obtained in Example 1 was mixed and uniformly dispersed in 100 parts by weight of Sylgard 184 (used as a base and a curing agent in a ratio of 10: 1) of Dow Corning to prepare a coating composition.

The obtained coating composition was coated on PET using Meyer bar No. 75 and then cured at 150 ° C for 3 hours to form a coating film having self-healing ability.

< Comparative Example >

A coating film was prepared in the same manner as in Example 2, except that the surface-treated silica obtained in Example 1 was not used and the nanosilica dispersion MEK-ST was used.

< Experimental Example : Evaluation of physical properties of coating film>

The physical properties of the coating film obtained through the above Examples and Comparative Examples were evaluated as follows.

1. Optical properties: Measurement of light transmittance and haze using a haze meter

2. Self-healing ability: Visually observes the degree of scratch recovery after rubbing with a copper brush

3. Scratch: Scratch by reciprocating with 150 g of steel wool. Observe haze value difference with haze meter.

The measurement results of the above experimental examples are shown in Table 1 below.

Results of Experimental Example Example Comparative Example Permeability (%) / Haze (%) 93.1% / 1.1% 92.8% / 5.0% Self-healing (Dongsol) Good Bad Scratch (△ haze) 0.5 2.1

It was confirmed that the coating film of the above example has self-healing ability and has good scratch resistance. On the contrary, the coating film of the comparative example has not self-healing ability, and when the steel wool is applied under the same condition as the above-mentioned embodiment, many scratches occur and the haze value is increased.

In addition, the coating films of Examples have relatively high transmittance and low haze characteristics, and have excellent optical properties, while the coating films of Comparative Examples have low transmittance and high haze characteristics.

Claims (18)

Polysiloxane-based resin;
Silica particles having a (meth) acrylate compound treated on a surface thereof; And
Wherein the thermosetting coating composition comprises an organic solvent.
The method of claim 1,
Silica particles in which the (meth) acrylate-based compound is treated on the surface,
The polylactone modified acrylate comprises a silica particle bonded to the surface via a urethane bond, the thermosetting coating composition.
3. The method of claim 2,
Wherein the polylactone-based modified acrylate comprises a compound of formula (7): &lt; EMI ID =
(7)

B is an integer of 2 to 9, p is an integer of 1 to 5, and q is an integer of 1 to 10, and R &lt; ₃ &gt;
The method of claim 1,
Wherein the silica particles have a particle size of 5 to 100 nm.
3. The method of claim 2,
Wherein the silica particles wherein the polylactone-based modified acrylate is bonded to the surface via a urethane bond comprise a compound represented by the following formula (8):
[Chemical Formula 8]

In Formula 8,
R &lt; ₃ &gt; is hydrogen or methyl,
R ₄ is an aliphatic, alicyclic or aromatic divalent organic functional group,
p is an integer of 1 to 5, q is an integer of 1 to 10,
a is an integer of 1 or more,
b is an integer of 2 to 9,
silica means silica particles.
The method of claim 1,
Wherein the polysiloxane-based resin comprises a repeating unit represented by the following formula (1): &lt; EMI ID =
[Chemical Formula 1]

In the above formula (1), R ₁ and R ₂ may be the same or different and are each independently hydrogen, an alkyl having 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms.
The method of claim 1,
Wherein the polysiloxane-based resin has a viscosity of from 1,000 Mpa 占 퐏 to 10,000 Mpa 占 퐏 at 23 占 폚.
The method of claim 1,
The above-mentioned polysiloxane-
A polymer of a siloxane oligomer to which a polymerizable functional group is introduced; Or a reaction product of a siloxane oligomer to which a polymerizable functional group is introduced and a crosslinking agent.
9. The method of claim 8,
Wherein the polymerizable functional group is at least one selected from the group consisting of a halogen group, a hydroxyl group, a glycidoxy group, an amine group, a vinyl group, an epoxy group, a methacrylate group, an amino group, a mercapto group, a cyano group, Composition.
9. The method of claim 8,
The cross-
Hydroxy, an alkenyl group having 2 to 10 carbon atoms, alkoxy having 1 to 20 carbon atoms, alkyl amido having 1 to 20 carbon atoms, benzamido having 6 to 20 carbon atoms, alkenyloxy having 2 to 20 carbon atoms, and having 6 to 20 carbon atoms Polysiloxane-based or organic siliceous compounds substituted with one or more reactive functional groups selected from the group consisting of aryl oxy and halogen; or
A polysiloxane-based compound comprising a silicon hydride (SiH) functionality.
The method of claim 1,
A coating composition comprising 1 to 50 parts by weight of the silica particles, the (meth) acrylate compound is treated on the surface with respect to 100 parts by weight of the polysiloxane resin.
The method of claim 1,
The organic solvent may be selected from the group consisting of methyl isobutyl ketone, methyl ethyl ketone, dimethyl ketone, isopropyl alcohol, isobutyl alcohol, a coating composition comprising at least one selected from the group consisting of normal butyl alcohol, ethyl acetate, normal butyl acetate, ethyl cellusolve and butyl cellusolve. .
A coating film comprising a cured product of the coating composition of claim 1.
The method of claim 13,
Polysiloxane-based resin; And a coating film in which silica particles having a (meth) acrylate compound treated on a surface thereof are crosslinked.
Polysiloxane-based resin; Silica particles having a (meth) acrylate compound treated on a surface thereof; And an organic solvent; And
Applying the mixture to a substrate, and curing or drying the coating.
16. The method of claim 15,
And polymerizing or curing the siloxane oligomer to which the polymerizable functional group has been introduced to prepare the polysiloxane-based resin.
16. The method of claim 15,
The (meth) acrylate-based compound further comprises the step of producing silica particles treated on the surface, a method for producing a coating film.
18. The method of claim 17,
The step of preparing the silica particles, the (meth) acrylate compound is treated on the surface,
Reacting the silica particles with a diisocyanate compound; And
Reacting the reaction product between the silica particles and the diisocyanate compound with a hydroxyalkyl (meth) acrylate modified with a urethane (meth) acrylate resin or a polylactone compound.