KR20150124828A - Thermally Curable Coating Compositions for plastic substrate - Google Patents

Abstract

The present invention relates to a thermally curable coating composition for coating a plastic substrate, and more specifically, to a thermally curable coating composition forming a transparent film with excellent weather resistance and high hardness without yellowing, by being thermally cured within a short time at a low temperature of 100-130°C through being applied on a plastic substrate. The thermally curable coating composition includes a) organic sol containing a sol-gel reactive triazine-based compound, b) inorganic sol including an inorganic precursor having a valency of three or four, and c) a plate-shaped or tube-shaped mineral as essential components.

Description

Technical Field [0001] The present invention relates to thermally curable coating compositions for plastic substrate coatings,

The present invention relates to a thermosetting coating composition for coating a plastic substrate, and more particularly to a thermosetting coating composition for coating a plastic substrate, which comprises a) an organic sol containing a triazine-based compound capable of sol-gel reaction, b) an inorganic sol containing an inorganic precursor having a valence of 3 or 4, And c) Since the plate or tube-like mineral is included as an essential component, it is thermally cured in a short time at a low temperature of 100 to 130 ° C. when coated on a plastic substrate, so that it has excellent weatherability without any yellowing, has a high hardness and forms a transparent film ≪ / RTI >

In general, coating is performed for the purpose of supplementing the surface characteristics of a material by applying a coating agent to the surface of the material to form a thin film. Such coatings are being made in a variety of industries, including ships, automotive exterior components, construction materials, paper, wood, furniture, soundproof walls, optical materials, and cosmetic containers. In recent years, studies have been actively conducted on curing-type coating agents that are processed on the surface of plastic substrates in the display field.

As an example of a conventional curable coating composition, Japanese Patent Application Laid-Open (kokai) No. 5-214044 discloses a composition comprising a polyfunctional monomer having three or more (meth) acryloyl groups, polyethylene glycol methacrylate, polyoxyethylene glycol acrylate, polyethylene glycol methacrylate , Polypropylene glycol methacrylate, and the like. Japanese Patent Application Laid-Open No. 214045 discloses a polyfunctional monomer having three or more (meth) acryloyl groups and at least one polyfunctional monomer selected from the group consisting of polyethylene glycol methacrylate, polyethylene glycol dimethacrylate, polyethylene trimethacrylate, polyoxyethylene glycol tetramethacrylate Discloses a coating composition comprising a monofunctional or bifunctional monomer such as acrylate.

In addition, conventional coating compositions have weak surface pencil hardness, and many efforts have been made to improve the hardness of the coating layer. As a representative example thereof, Japanese Patent No. 1815116 discloses a coating composition containing a powdery inorganic filler in order to increase the hardness of a multifunctional acrylate ester monomer component forming a resin. Japanese Patent No. 1416240 discloses a coating composition comprising a surface-treated inorganic filler composed of silica or alumina. However, these methods have the effect of slightly increasing the surface hardness of the coating film, but this alone does not sufficiently satisfy the surface hardness performance of the coating film recently required.

Therefore, the coating compositions known to date and the coating films using the coating compositions have a limit in that the durability and the like are less than the required specifications as compared with the high performance required for the miniaturization and high-definition trend such as display devices and mobile phone terminals.

On the other hand, the inventors of the present invention have conducted studies to develop an organic / inorganic hybrid coating composition having excellent corrosion resistance and abrasion resistance, including an epoxy resin substituted with a trialkoxysilylalkyl group, a triazine-based compound capable of sol-gel reaction and a crosslinkable silane compound A thermosetting coating composition has been developed. [Korean Patent No. 128927] The above-mentioned coating composition is applied to a metal substrate, and can not satisfy a thermosetting condition suitable for a plastic substrate. Further, since an epoxy resin is contained as a binder, there is a limit to obtaining a transparent coating film.

It is an object of the present invention to provide a thermosetting coating composition which can be applied to a plastic substrate.

Another object of the present invention is to provide a transparent coating film prepared by applying the above-mentioned thermosetting coating composition to a plastic substrate and thermally curing at a relatively low temperature within a short time.

Another object of the present invention is to provide a method for producing a coating film comprising a series of processes of applying and thermosetting the thermosetting coating composition on a plastic substrate.

In order to solve the above-mentioned problems, the present invention provides a process for preparing an organic sol comprising a) a triazine-based compound represented by the following general formula (1); b) an inorganic sol comprising an inorganic precursor represented by the following formula (2); And c) a thermosetting coating composition for coating a plastic substrate comprising plate or tube-like minerals.

[Chemical Formula 1]

R ¹ , R ² , and R ³ are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; Y ¹ , Y ² , and Y ³ are the same or different from each other; An alkylene group having 1 to 6 carbon atoms or a phenylene group, and n represents an integer of 1 to 6)

(2)

(Wherein M is at least one inorganic element selected from the group consisting of 3A, 4A and 4B in the periodic table; G is the same or different and is a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, A halogen atom, an alkoxy group having 1 to 6 carbon atoms, a phenyl group or a xylyl group, at least one of them represents an alkoxy group having 1 to 6 carbon atoms; a represents an oxidation number of an inorganic element or a substituted number of G,

In addition, the present invention is characterized in that a transparent coating film prepared by coating the above-mentioned thermosetting coating composition on the surface of a plastic substrate and then thermally curing at 100 to 130 캜 for 30 minutes to 90 minutes.

The present invention also provides a process for preparing an organic sol comprising the steps of: i) dissolving the triazine-based compound represented by Formula 1 in an alcohol having 1 to 10 carbon atoms to prepare an organic sol; Ii) dissolving the inorganic oxide precursor represented by Formula 2 in an organic solvent having 1 to 10 carbon atoms to prepare an inorganic sol; Iii) preparing a coating liquid by mixing 40 to 70% by weight of the organic sol, 20 to 50% by weight of the inorganic sol, and 0.1 to 10% by weight of a plate or tube-like mineral based on the solid content. And iv) coating the coating liquid on a plastic substrate and thermally curing the coating liquid at 100 to 130 캜 for 30 to 90 minutes to prepare a coating film; And a method of manufacturing a thermosetting coating film.

The coating composition of the present invention is thermally cured at 100 to 130 DEG C within 30 to 90 minutes, and thus is suitable for application to plastic substrates.

The coating film formed by thermosetting the coating composition of the present invention is excellent in transparency, has no discoloration such as yellowing, and has excellent surface hardness.

Accordingly, the coating composition of the present invention can be used as a surface coating agent for various plastic materials, and particularly, polycarbonate (PC), polyarylate (PAR), polyethersulfone (PES), polyimide (PI) , Polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polyether ether ketone (PEEK).

Fig. 1 shows FT-IR analysis results of haloisite surface-modified with a triazine compound.
2 is a TGA analysis result of the haloisite surface-modified with a triazine compound.

According to one aspect of the present invention, there is provided an organic electroluminescent device comprising: a) an organic sol comprising a triazine-based compound represented by the following formula (1); b) an inorganic sol comprising an inorganic precursor represented by the following formula (2); And c) a thermosetting coating composition for coating a plastic substrate comprising plate or tube-like minerals.

[Chemical Formula 1]

R ¹ , R ² , and R ³ are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; Y ¹ , Y ² , and Y ³ are the same or different from each other; An alkylene group having 1 to 6 carbon atoms or a phenylene group, and n represents an integer of 1 to 6)

(2)

(Wherein M is at least one inorganic element selected from the group consisting of 3A, 4A and 4B in the periodic table; G is the same or different and is a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, A halogen atom, an alkoxy group having 1 to 6 carbon atoms, a phenyl group or a xylyl group, at least one of them represents an alkoxy group having 1 to 6 carbon atoms; a represents an oxidation number of an inorganic element or a substituted number of G,

According to a preferred embodiment of the present invention, the coating composition of the present invention comprises, on a solids content basis, a) from 40 to 70% by weight of an organic sol; b) from 20 to 50% by weight of an inorganic sol; And c) from 0.1 to 10% by weight of the mineral. At this time, if the content of the organic sol is less than 40% by weight, adhesion with the plastic substrate and coating property may be deteriorated, and if it exceeds 70% by weight, abrasion resistance, hardness and the like may be reduced. When the content of the inorganic sol is less than 20% by weight, sufficient abrasion resistance and hardness can not be obtained. When the content of the inorganic sol is more than 50% by weight, the coating film is easily broken and adhesion with a plastic substrate may be deteriorated. If the content of the mineral is less than 0.1% by weight, physical properties such as required hardness can not be attained. If the content is more than 10% by weight, the dispersibility and transparency in the coating composition may be reduced.

Each component constituting the coating composition according to the present invention will be described in more detail as follows.

a) Organic Sol

The organic sol is prepared by dissolving the triazine-based compound represented by the formula (1) in an alcohol. Specifically, after adding a triazine-based compound to an alcohol having 1 to 10 carbon atoms, an acid solution is added to prepare a sol. The alcohol used for preparing the organic sol may be an alcohol having 1 to 10 carbon atoms such as methanol, ethanol, propanol, isopropanol, butanol, hexanol and the like. The acid solution is, for example, a solution diluted with an acid such as hydrochloric acid, nitric acid, or sulfuric acid, and a sol may be formed when the pH is about 1 to 2. The method for preparing such an organic sol and its concentration may be controlled by a conventional method.

The triazine-based compound represented by the above formula (1) used for the preparation of the organic sol is a compound disclosed in Korean Patent No. 1,228,927, which is specifically exemplified as follows:

2,2 ', 2 "- (1,3,5-triazine-2,4,6-triryl) tris (methylla turyl) tris (ethane- Ethoxysilyl) propyl carbamate);

2,2 ', 2 "- (1,3,5-triazine-2,4,6-triyl) tris (acanyl) tris (ethane- Lt; / RTI >propylcarbamate);

4,4 ', 4 "- (1,3,5-triazine-2,4,6-triryl) tris (acridine) tris (benzene- Lt; / RTI >propylcarbamate);

Tris (benzene-4,1-diyl) tris (3- (tri (4-methylphenyl) Ethoxysilyl) propyl carbamate), and the like can be used.

According to a more preferred embodiment, the organic sol may further comprise a silane-based compound represented by the following formula (3) together with a triazine-based compound.

(3)

(Wherein X ¹ , X ² , X ³ and X ⁴ are the same or different and each represents a hydrogen atom, a halogen, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ alkoxy group, a C ₂ -C ₆ alkenyl group, alkenyl -C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyloxy -C ₁ -C ₆ alkyl, -C ₁ -C ₆ alkyl acrylate, methacrylic -C ₁ -C ₆ alkyl group, acryloxy -C ₁ - C ₆ alkyl group, a methacryloxy -C ₁ -C ₆ alkyl group, or an epoxy -C ₁ -C ₆ alkyl group, X ^1, X ^2, X ^3, and X ⁴ is one or more of halogen or C ₁ -C ₆ Alkoxy group)

According to a more preferred embodiment, the silane-based compound represented by the formula (3) may be contained in the range of 0.5 to 1.5 molar ratio based on 1 mol of the triazine-based compound. The organic sol contains a triazine-based compound to form a coating film having a high transparency and a high hardness. In particular, a silane-based compound together with a triazine-based compound can form a coating film having higher hardness and flexibility .

The silane-based compound represented by the above-mentioned formula (3) used for the production of an organic sol may be specifically exemplified as follows:

But are not limited to, ethoxysilane, ethoxysilane, ethoxytrimethylsilane, diethoxydimethylsilane, methyltriethoxysilane, tetraethoxysilane, diethoxydimethoxysilane, ethoxytrimethoxysilane, chlorotriethoxysilane, trichloro 2- (acryloxy) ethyltrimethoxysilane, 2- (acryloxy) ethyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, At least one selected from ethyltrimethoxysilane, 2- (methacryloxy) ethyltrimethoxysilane, 3- (glycidoxy) propyltrimethoxysilane (GPTMS) and the like can be used.

b) Inorganic sol

Inorganic sol is prepared by dissolving an inorganic precursor in an organic solvent. Specifically, after adding an inorganic precursor to an organic solvent having 1 to 10 carbon atoms, an acid solution is added to prepare a sol. The organic solvent used for preparing the inorganic sol may include one species selected from ethyl acetoacetate, ethyl acetate, acetic acid, aqueous acetic acid solution, n-propanol, 1-butanol and the like. The acid solution is, for example, a solution diluted with an acid such as hydrochloric acid, nitric acid, or sulfuric acid, and a sol may be formed when the pH is about 1 to 2. The preparation method and concentration of the inorganic sol may be controlled by a conventional method.

The inorganic precursor used for preparing the inorganic sol may be represented by the following formula (2).

(2)

(Wherein M is at least one inorganic element selected from the group consisting of 3A, 4A and 4B in the periodic table; G is the same or different and is a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, A halogen atom, an alkoxy group having 1 to 6 carbon atoms, a phenyl group or a xylyl group, at least one of them represents an alkoxy group having 1 to 6 carbon atoms; a represents an oxidation number of an inorganic element or a substituted number of G,

Specific examples of the inorganic precursor represented by Formula 2 include aluminum methoxide, aluminum tetramethoxide, aluminum ethoxide, aluminum propoxide, aluminum butoxide, monoethoxysilane, methyltriethoxysilane, dimethyldiethoxy Silane, diphenyldiethoxysilane, triethoxysilane, tetramethoxysilane, tetraethoxysilane, titanium tetramethoxide, titanium tetraethoxide, titanium tetrapropoxide, titanium tetrabutoxide, zirconium tetramethoxide, At least one selected from the group consisting of zirconium tetramethoxide, zirconium tetraethoxide, zirconium tetrapropoxide, and zirconium tetrabutoxide can be used.

c) Minerals

Minerals use plate or tube minerals. This is because plate-like or tube-like minerals are effective for improving weatherability such as surface roughness of a transparent plastic substrate.

Specifically, at least one selected from the group consisting of montmorillonite (MMT), Halloysite, bentonite and hectorite may be used.

According to a more preferred embodiment, the present invention is a method for surface-treating a plate or tube-like mineral described above with a triazine-based compound represented by the formula (1) The minerals modified with the triazine compound are excellent in compatibility with the coating composition and dispersibility, so that a more uniform coating film can be formed and a larger amount of minerals can be added, thereby improving the hardness of the coating film on the plastic substrate The effect can be expected more. A method for surface modification of a mineral can be specifically described by adding a mineral and a triazine-based compound to a conventional organic solvent, followed by heating and refluxing. As the organic solvent, aromatic hydrocarbons such as toluene and tetrahydrofuran may be used. The reaction temperature may be in the range of about 80 to 150 DEG C as the reflux temperature of the solvent.

According to another aspect of the present invention, there is provided a coating film prepared by thermally curing a coating composition on a surface of a plastic substrate.

According to an even more preferred embodiment, the thermosetting can be carried out at 100-130 < 0 > C for 30 minutes to 90 minutes.

According to a more preferred embodiment, the plastic substrate is made of polycarbonate (PC), polyarylate (PAR), polyethersulfone (PES), polyimide (PI), polyethylene terephthalate (PET), polyethylene naphthalate ), And polyether ether ketone (PEEK).

According to another aspect of the present invention, there is provided a process for preparing an organic sol comprising the steps of: i) dissolving the triazine-based compound represented by Formula 1 in an alcohol having 1 to 10 carbon atoms to prepare an organic sol; Ii) dissolving the inorganic precursor represented by Formula 2 in an organic solvent to prepare an inorganic sol; Iii) preparing a coating solution by mixing 40 to 70% by weight of the organic sol, 20 to 50% by weight of the inorganic sol, and 0.1 to 10% by weight of a plate or tube-like mineral based on the solid content. And iv) coating the coating liquid on a plastic substrate and thermally curing the coating liquid at 100 to 130 캜 for 30 to 90 minutes to prepare a coating film; And a method of manufacturing a thermosetting coating film.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited by the following examples.

[Preparation Example] Preparation of Composition Component of Coating Composition

Production Example 1. Preparation of an organic sol

To the isopropanol (16.3 mL, 0.213 mol) was added the triazine-based compound and the silane-based compound shown in the following Table 1, and then 0.1 M nitric acid (2.5 mL) was added and stirred for 1 hour to prepare an organic sol.

Organic sol division Triazine compound Silane compound Kinds Usage (mol) Kinds Usage (mol) Production Example 1-1 Triazine-1 0.14 - - Production Example 1-2 Triazine-2 0.14 - - Production Example 1-3 Triazine-1 0.07 GPTMS 0.07 Production Example 1-4 Triazine-1 0.07 AOETMS 0.07 Production Example 1-5 Triazine-1 0.07 AETMS 0.07 Production Example 1-6 Triazine-1 0.07 VDMS 0.07 Preparation Example 1-7 Triazine-2 0.07 GPTMS 0.07 Production Example 1-8 Triazine-2 0.07 AOETMS 0.07 Production Example 1-9 Triazine-2 0.07 AETMS 0.07 Production Example 1-10 Triazine-2 0.07 VDMS 0.07 Triazine compound :
Triazine-1: 2,2 ', 2 "- (1,3,5-triazine-2,4,6-triyl) tris
(Ethane-2,1-diyl) tris (3- (triethoxysilyl) propyl carbamate)
Triazine-2: 4,4 ', 4 "- (1,3,5-triazine-2,4,6-triyl) tris
(Benzene-4,1-diyl) tris (3- (triethoxysilyl) propyl carbamate)
Silane compound :
GPTMS: 3- (glycidoxy) propyl trimethoxysilane
AOETMS: 2- (acryloxy) ethyltrimethoxysilane
AETMS: 2- (acrylate) ethyltrimethoxysilane
VDMS: vinyl dimethyldimethoxysilane

Production Example 2. Preparation of inorganic sol

Ethyl acetoacetate (8 mL, 0.063 mol) was charged with the inorganic precursor shown in Table 2 below, and then 0.1 M nitric acid (1.3 mL) was added slowly. The mixture was ultrasonically vibrated for 1 hour and further stirred for 30 minutes to prepare an inorganic sol.

Inorganic sol division Inorganic precursor Kinds Usage (mol) Production Example 2-1 Aluminum tetrabutoxide 0.025 Production example 2-2 Triethoxysilane 0.025 Production Example 2-3 Titanium tetrapropoxide 0.025 Production example 2-4 Zirconium tetrapropoxide 0.025

PREPARATION EXAMPLE 3. Preparation of haloacids modified with triazine

4,4 ', 4 "- (1,3,5-triazine-2,4,6-triryl) tris (acridine) tris (benzene-4,1-diyl) tris (1.4 g, 1.35 mmol) and toluene (20 mL) were mixed and thoroughly stirred to be dissolved. Then, 3 g (10.2 mmol) of haloisite was added and the mixture was refluxed at 110 ° C for 24 hours. The precipitate obtained was washed three times with methanol and then lyophilized for 24 hours. To confirm the surface modification of the halo-site, FT- IR and TGA were measured.

According to the FT-IR measurement results shown in Fig. 1, an NH stretching vibration peak was observed at 3000 cm ^-1 , and an NH bending vibration peak was observed at around 1550 cm ^-1 . Then, a carbonyl (C = O) peak was observed at 1760 cm ^-1 and a triazine peak was observed near 1600 to 1500 cm ^-1 . Also, the C = O, CN absorption peaks included in the urethane bond were observed at 1400 cm ^-1 . According to the FT-IR measurement results, it can be confirmed that the surface of the haloisite was modified with a triazine-based compound.

According to the results of the TGA analysis of FIG. 2, when the results obtained by pyrolysis at 500 ° C. of the haloisite before and after the modification were compared, it was confirmed that about 3.5% of the organic material was contained in the surface of the haloisite after the modification have.

[Example] Preparation of Coating Coating Film

The coating composition was prepared by mixing and stirring the organic sol prepared in Preparation Example 1, the inorganic sol prepared in Preparation Example 2, and the modified halosite prepared in Preparation Example 3 (or unmodified haloisite) .

The surface of the substrate was coated by dip coating a polycarbonate (PC) substrate on the coating composition (dip coating method). The thickness of the coating film was adjusted to 20 to 30 μm. The coated substrate was thermally cured at 130 DEG C for 1 hour to form a coating film.

With respect to the coated coating films prepared as described above, permeability and abrasion resistance of the coated surfaces were confirmed by the following test methods.

1) Transmittance

The transmittance of light at a wavelength of 450 nm was measured using a UV-vis spectrophotometer (Shimadzu UV-2550). The transmittance of each of the coated polycarbonate (PC) substrates was expressed in% when the transmittance of the uncoated polycarbonate (PC) substrate was taken as 100.

2) Yellowing degree

Each coated polycarbonate (PC) group was irradiated with UV to check the degree of color change of the coating film. The color difference before and after UV irradiation after 300 hours was measured and expressed as? YI value.

3) Abrasion resistance

The pencil hardness test was carried out in accordance with ASTM D3363 to confirm the abrasion resistance of the coating film.

The pencil hardness test was carried out as follows. The upper side was level with the table so that the pencil fixing part did not touch the table. A uniform load was placed on the upper part of the pencil fixing part, and the prepared test piece was set on the sample part, and the handle was adjusted so that the pencil was contacted by the breaking load. With reference to the drawing of the test piece, the pencil lead specified in KS G 2603 (pencil) at an angle of about 45 degrees was slowly moved while pressing the drawing with a load of about 1 kgf (9.8 N). The shim was attached to the sample surface and the operation was performed until the tip was pushed. After the hardness test was completed, the fixing part was placed on the upper side, the weight was removed, and the test piece was taken out. 7H, 6H, 5H, 4H, 3H, 2H, H, HB, F, B, 2B, 3B, 4B, 5B, 6B, 7B and 8B were used as KS G 2603 (pencil)

Examples 1 to 10 and Comparative Examples 1 and 2: Physical properties of the coating film according to the composition of the organic sol

As shown in Table 3 below, the organic sol, the inorganic sol and the unmodified haloisite were mixed and stirred at a composition ratio based on the weight of the solid content to prepare a coating composition. By the dip coating method, a polycarbonate (PC) substrate surface To a thickness of 20 탆. The results of measurement of physical properties of each coating film thus prepared are shown in Table 3 below.

division Coating composition (% by weight) Transmittance
(%) Yellowing degree
(ΔYI) Pencil hardness
(H) Organic sol Inorganic sol Mineral Example 1 Production Example 1-1
(67) Production example 2-4
(32) Halo site
(One) 90 0.7 4 Example 2 Production Example 1-2
(66) Production example 2-4
(31) Halo site
(3) 89 0.6 5 Example 3 Production Example 1-3
(65) Production example 2-4
(30) Halo site
(5) 87 0.6 5 Example 4 Production Example 1-4
(66) Production example 2-4
(33) Halo site
(One) 88 0.9 4 Example 5 Production Example 1-5
(64) Production example 2-4
(33) Halo site
(3) 87 0.7 5 Example 6 Production Example 1-6
(62) Production example 2-4
(33) Halo site
(5) 86 0.7 5 Example 7 Preparation Example 1-7
(66) Production example 2-4
(33) Halo site
(One) 89 0.8 5 Example 8 Production Example 1-8
(64) Production example 2-4
(33) Halo site
(3) 87 0.6 5 Example 9 Production Example 1-9
(62) Production example 2-4
(33) Halo site
(5) 87 0.5 5 Example 10 Production Example 1-10
(62) Production example 2-4
(33) Halo site
(5) 88 0.6 5 Comparative Example 1 Production Example 1-1
(77) Production example 2-4
(33) - 93 0.9 4 Comparative Example 2 Production Example 1-1
(95) - Halo site
(5) 86 0.7 4

According to the above Table 3, it was confirmed that Examples 1 to 10, in which the organic sol, inorganic sol, and mineral were contained in a predetermined composition ratio, were excellent in the translucency, yellowing degree and pencil hardness. The coatings of Examples 1 and 2 prepared using the organic sols (Production Examples 1-1 and 1-2) containing the triazine-based compound alone exhibited somewhat poor physical properties in terms of hardness, but were applied to a plastic substrate coating film It was never a problem to do. Further, it can be seen that the coatings of Examples 3 to 10 prepared using the organic sol containing both the triazine-based compound and the silane-based compound are more flexible and have higher hardness and thus have an improved effect of improving the physical properties.

On the other hand, it can be confirmed that the coating film of Comparative Example 1 containing no minerals has a low hardness and an insufficient improvement in yellowing resistance, and a coating film of Comparative Example 2 containing no inorganic sol has a decreased hardness.

Examples 11 to 20: Physical properties of a coating film containing a modified mineral

As shown in Table 4, the organic sol, the inorganic sol, and the modified halosite (Production Example 3) were mixed and stirred at a composition ratio based on the weight of solid content to prepare a coating composition. The dip coating method was used to prepare polycarbonate PC) substrate surface with a thickness of 20 탆. The physical properties of each coating film thus prepared were measured and the results are shown in Table 4 below.

division Coating composition (% by weight) Transmittance
(%) Yellowing degree
(ΔYI) Pencil hardness
(H) Organic sol Inorganic sol Mineral Example 11 Production Example 1-1
(67) Production example 2-4
(32) Production Example 3
(One) 95 0.5 5 Example 12 Production Example 1-2
(66) Production example 2-4
(31) Production Example 3
(3) 93 0.3 6 Example 13 Production Example 1-3
(65) Production example 2-4
(30) Production Example 3
(5) 92 0.2 6 Example 14 Production Example 1-4
(66) Production example 2-4
(33) Production Example 3
(One) 93 0.4 6 Example 15 Production Example 1-5
(64) Production example 2-4
(33) Production Example 3
(3) 92 0.3 6 Example 16 Production Example 1-6
(62) Production example 2-4
(33) Production Example 3
(5) 92 0.3 6 Example 17 Preparation Example 1-7
(66) Production example 2-4
(33) Production Example 3
(One) 94 0.4 6 Example 18 Production Example 1-8
(64) Production example 2-4
(33) Production Example 3
(3) 93 0.2 6 Example 19 Production Example 1-9
(62) Production example 2-4
(33) Production Example 3
(5) 91 0.1 6 Example 20 Production Example 1-10
(62) Production example 2-4
(33) Production Example 3
(5) 92 0.3 6

Table 4 shows the physical properties of a coating film containing halosite surface-modified with a triazine-based compound as a mineral. It can be confirmed that the improved effects can be obtained in terms of physical properties such as hardness, transparency and sulfur denaturation as compared with the results of Table 3 above. Thus, it can be confirmed that the coating composition of the present invention contains a mineral as an essential component, and more preferably includes a mineral surface-modified with a triazine-based compound represented by the general formula (1).

Examples 21 to 28 and Comparative Examples 3 to 4: Physical properties of the coating film according to the composition of the inorganic sol

As shown in Table 5 below, an organic sol, an inorganic sol, and halosite (or a modified halosite of Production Example 3) were mixed and stirred to prepare a coating composition at a composition ratio based on the weight of solid content, To a polycarbonate (PC) substrate surface with a thickness of 20 탆. The physical properties of each coating film thus prepared were measured and the results are shown in Table 5 below.

division Coating composition (% by weight) Transmittance
(%) Yellowing degree
(ΔYI) Pencil hardness
(H) Organic sol Inorganic sol Mineral Example 21 Production Example 1-1
(64) Production Example 2-1
(33) Halo site
(3) 88 0.8 5 Example 22 Production Example 1-1
(64) Production example 2-2
(33) Halo site
(3) 85 0.7 5 Example 23 Production Example 1-1
(64) Production Example 2-3
(33) Halo site
(3) 86 0.7 5 Example 24 Production Example 1-1
(64) Production example 2-4
(33) Halo site
(3) 87 0.7 5 Example 25 Production Example 1-1
(64) Production Example 2-1
(33) Production Example 3
(3) 94 0.3 6 Example 26 Production Example 1-1
(64) Production example 2-2
(33) Production Example 3
(3) 93 0.3 6 Example 27 Production Example 1-1
(64) Production Example 2-3
(33) Production Example 3
(3) 92 0.4 6 Example 28 Production Example 1-1
(64) Production example 2-4
(33) Production Example 3
(3) 95 0.2 6 Comparative Example 3 Production Example 1-1
(82) Production example 2-4
(15) Halo site
(3) 89 0.9 3 Comparative Example 4 Production Example 1-1
(27) Production example 2-4
(70) Halo site
(3) 80 0.8 5

According to the results shown in Table 5, it can be seen that the differences in physical properties do not appear much depending on the composition of the inorganic sol. However, it can be confirmed that Examples 25 to 28 including the haloitanium mineral modified as compared with Examples 21 to 24 containing the haloiticide minerals can obtain further improved effects in terms of transparency, sulfur denaturation and hardness.

In Comparative Examples 3 and 4, Comparative Example 3 is a coating film containing a small amount of inorganic sol. Comparative Example 4 is a coating film containing an inorganic sol in an excessive amount. It is possible to confirm that the physical properties such as physical properties can be poor.

Claims (16)

a) an organic sol comprising a triazine-based compound represented by the following formula (1);
b) an inorganic sol comprising an inorganic precursor represented by the following formula (2); And
c) a thermally curable coating composition for coating a plastic substrate, characterized by comprising a plate or tube-like mineral.
[Chemical Formula 1]

R ¹ , R ² , and R ³ are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; Y ¹ , Y ² , and Y ³ are the same or different from each other; An alkylene group having 1 to 6 carbon atoms or a phenylene group, and n represents an integer of 1 to 6)
(2)

(Wherein M is at least one inorganic element selected from the group consisting of 3A, 4A and 4B in the periodic table; G is the same or different and is a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, A halogen atom, an alkoxy group having 1 to 6 carbon atoms, a phenyl group or a xylyl group, at least one of them represents an alkoxy group having 1 to 6 carbon atoms; a represents an oxidation number of an inorganic element or a substituted number of G,
The method according to claim 1,
A) from 40 to 70% by weight of an organic sol; b) from 20 to 50% by weight of an inorganic sol; And c) 0.1 to 10% by weight of the mineral.
The method according to claim 1,
The thermosetting coating composition for plastic substrate coating according to claim 1, wherein the a) organic sol further comprises a silane compound represented by the following formula (3).
(3)

(Wherein X ¹ , X ² , X ³ and X ⁴ are the same or different and each represents a hydrogen atom, a halogen, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ alkoxy group, a C ₂ -C ₆ alkenyl group, alkenyl -C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyloxy -C ₁ -C ₆ alkyl, -C ₁ -C ₆ alkyl acrylate, methacrylic -C ₁ -C ₆ alkyl group, acryloxy -C ₁ - C ₆ alkyl group, a methacryloxy -C ₁ -C ₆ alkyl group, or an epoxy -C ₁ -C ₆ alkyl group, X ^1, X ^2, X ^3, and X ⁴ is one or more of halogen or C ₁ -C ₆ Alkoxy group)
The method of claim 3,
Wherein the silane-based compound is contained in the range of 0.5 to 1.5 molar ratio based on 1 mol of the triazine-based compound.
The method according to claim 1,
The inorganic sol may be selected from the group consisting of aluminum methoxide, aluminum tetramethoxide, aluminum ethoxide, aluminum propoxide, aluminum butoxide, monoethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, diphenyldiethoxysilane, Tetramethoxysilane, tetraethoxysilane, titanium tetramethoxide, titanium tetraethoxide, titanium tetrapropoxide, titanium tetrabutoxide, zirconium tetramethoxide, zirconium tetramethoxide, zirconium tetraethoxide, Wherein the thermosetting coating composition comprises an inorganic precursor selected from the group consisting of zirconium tetrabutoxide, zirconium tetrapropoxide, and zirconium tetrabutoxide.
The method according to claim 1,
Wherein the c) minerals are at least one platy or tubular minerals selected from the group consisting of montmorillonite (MMT), Halloysite, bentonite and hectorite. Thermosetting coating composition.
The method according to claim 1,
Wherein the c) mineral is surface-treated and modified by the triazine-based compound represented by the formula (1).
A transparent coating film prepared by coating the composition of any one of claims 1 to 7 on the surface of a plastic substrate and then thermally curing at 100 to 130 캜 for 30 to 90 minutes.
The method of claim 8,
The plastic substrate may be made of a material selected from the group consisting of polycarbonate (PC), polyarylate (PAR), polyethersulfone (PES), polyimide (PI), polyethylene terephthalate (PET), polyethylene naphthalate PEEK). ≪ / RTI >
(I) dissolving a triazine-based compound represented by the following formula (1) in an alcohol having 1 to 10 carbon atoms to prepare an organic sol;
Ii) dissolving the inorganic precursor represented by the following formula 2 in an organic solvent having 1 to 10 carbon atoms to prepare an inorganic sol;
Iii) preparing a coating solution by mixing 40 to 70% by weight of the organic sol, 20 to 50% by weight of the inorganic sol, and 0.1 to 10% by weight of a plate or tube-like mineral based on the solid content. And
Iv) coating the coating solution on a plastic substrate and thermally curing the coating solution at 100 to 130 ° C for 30 to 90 minutes to prepare a coating film;
≪ / RTI > wherein the thermosetting coating comprises a thermosetting coating.
[Chemical Formula 1]

R ¹ , R ² , and R ³ are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; Y ¹ , Y ² , and Y ³ are the same or different from each other; An alkylene group having 1 to 6 carbon atoms or a phenylene group, and n represents an integer of 1 to 6)
(2)

(Wherein M is at least one inorganic element selected from the group consisting of 3A, 4A and 4B in the periodic table; G is the same or different and is a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, A halogen atom, an alkoxy group having 1 to 6 carbon atoms, a phenyl group or a xylyl group, at least one of them represents an alkoxy group having 1 to 6 carbon atoms; a represents an oxidation number of an inorganic element or a substituted number of G,
The method of claim 10,
Wherein the organic sol in the process (i) further comprises a silane compound represented by the following formula (3).
(3)

(Wherein X ¹ , X ² , X ³ and X ⁴ are the same or different and each represents a hydrogen atom, a halogen, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ alkoxy group, a C ₂ -C ₆ alkenyl group, alkenyl -C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyloxy -C ₁ -C ₆ alkyl, -C ₁ -C ₆ alkyl acrylate, methacrylic -C ₁ -C ₆ alkyl group, acryloxy -C ₁ - C ₆ alkyl group, a methacryloxy -C ₁ -C ₆ alkyl group, or an epoxy -C ₁ -C ₆ alkyl group, X ^1, X ^2, X ^3, and X ⁴ is one or more of halogen or C ₁ -C ₆ Alkoxy group)
The method of claim 10,
Wherein the silane-based compound is contained in an amount of 0.5 to 1.5 molar ratio based on 1 mol of the triazine-based compound.
The method of claim 10,
The inorganic sol in the process (ii) may be at least one selected from the group consisting of aluminum methoxide, aluminum tetramethoxide, aluminum ethoxide, aluminum propoxide, aluminum butoxide, monoethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, Titanium ethoxide, titanium propoxide, titanium butoxide, zirconium methoxide, zirconium tetramethoxide, zirconium tetraethoxide, zirconium tetraethoxide, zirconium tetraethoxide, Wherein the inorganic precursor comprises an inorganic precursor selected from the group consisting of ethoxide, zirconium propoxide, and zirconium butoxide.
The method of claim 10,
The mineral in the step iii) is at least one plate-shaped or tube-shaped mineral selected from the group consisting of montmorillonite (MMT), Halloysite, bentonite and hectorite A method for producing a thermosetting coating film.
The method of claim 10,
Wherein the mineral in the step iii) is a mineral modified by surface treatment with the triazine-based compound represented by the formula (1).
The method of claim 10,
The plastic substrate in the process (iv) may be a polycarbonate (PC), a polyarylate (PAR), a polyether sulfone (PES), a polyimide (PI), a polyethylene terephthalate (PET), a polyethylene naphthalate Polyether ether ketone (PEEK). ≪ RTI ID = 0.0 > 11. < / RTI >

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