WO2016126103A1

WO2016126103A1 - Composition for forming coating layer having self-healing characteristics, coating layer, and coating film

Info

Publication number: WO2016126103A1
Application number: PCT/KR2016/001187
Authority: WO
Inventors: 김영석; 이한나; 장영래
Original assignee: 주식회사 엘지화학
Priority date: 2015-02-03
Filing date: 2016-02-03
Publication date: 2016-08-11

Abstract

The present invention relates to: a composition for forming a coating layer having self-healing characteristics, containing a photoinitiator, an organic solvent, and a reversible covalent bond compound comprising a (thio)urea functional group comprising one or more sterically hindered (thio)urea bonds and a (meth)acrylate-based or vinyl-based functional group bound to the (thio)urea functional group; a coating film prepared from the composition; a coating film comprising the coating film; and an electric home appliance and a display device comprising the coating film.

Description

【Specification】

[Name of invention]

Composition for forming coating layer, coating layer and coating film having self-healing properties

Technical Field

Cross Citation with Related Application (s)

This application claims the benefit of priority based on Korean Patent Application No. 10-2015-0016887 dated February 3, 2015 and Korean Patent Application No. 10-2016-0013073 dated February 2, 2016. All content disclosed in the literature is included as part of this specification.

The present invention relates to a composition for forming a coating layer, a coating layer and a coating film having self-healing properties, and more particularly, is applied to exteriors of various home appliances or display devices, and has improved self-healing properties and improved mechanical properties. The present invention relates to a composition for forming a coating layer, a coating layer, and a coating film having a self-healing property enabling the provision of a laminated film. Background Art

In order to protect the product from damages caused by mechanical, physical and chemical influences from the outside, various coating layers or coating films are applied to the surfaces of electrical and electronic devices, electronic material parts, home appliances, automotive interior and exterior, and plastic molded parts such as mobile phones. have. However, scratches on the surface of the product coating or cracks on the outer layer deteriorate the appearance characteristics, the main performance, and the life of the product. Therefore, various studies are being conducted to maintain the product surface for a long time by protecting the product surface.

In particular, research and interest in coating materials having self-healing properties (SELF-HEALING) has recently increased rapidly. The self-healing property is a property in which damage such as scratches is gradually healed or reduced itself when damage occurs such as scratches on the coating layer as an external physical force or stimulus is applied to the coating layer. Refers to. Although the coating material exhibiting such self-healing properties and the mechanism of self-healing properties are variously known, the method of using a coating material exhibiting elasticity is most widely known. That is, using such a coating material, on the coating layer Even if physical damage such as a scratch is applied, due to the elasticity of the coating material itself, the damaged part may be gradually filled to exhibit the above-described self-healing properties.

However, in the case of the existing coating layer exhibiting such self-healing properties, since the elastic material is mainly included, mechanical properties of the coating layer, such as hardness, wear resistance, or coating film strength, are not easily separated. In particular, when applying a coating layer exhibiting self-healing properties to the appearance of various home appliances, such as kitchen appliances and washing machines, the mechanical properties of the coating layer is required to a high level, the conventional coating layer having a self-healing property is such a high mechanical properties In most cases they could not be satisfied. For this reason, when a strong external stimulus is applied to the existing coating layer, many times the coating layer itself is permanently damaged and even self-healing properties are lost.

Due to the problems of the prior art, there is a continuous demand for the development of a technology that enables the provision of a coating layer or a laminated film that exhibits improved mechanical properties with excellent self-healing properties.

Prior Art Documents

[Patent literature]

International Patent Publication WO2014-144539 (Published: 2014.09.18)

[Content of invention]

Problem to be solved

The present invention is to provide a composition for forming a coating layer having a self-healing property that can be applied to the exterior of various home appliances or display devices, such that it is possible to provide a laminated film exhibiting improved mechanical properties with excellent self-healing properties.

The present invention also provides a coating layer having a self-healing property formed using the composition for forming the coating layer, and a coating film including the same. [Measures of problem]

In the present specification, a reversible covalent bond containing a (thio) urea functional group including at least one sterically hindered (thio) urea bond and a (meth) acrylate-based or vinyl-based functional group bonded to the (thio) urea functional group. compound; Photoinitiators; And an organic solvent. A composition for forming a coating layer having self-healing properties is provided.

As used herein, (thio) urea bond is meant to include both urea bonds and thiourea (thk) urea) bonds. In addition, (meth) acrylate is the meaning containing both an acrylate and a (meth) acrylate.

When the composition for forming a coating layer including the reversible covalent bond compound containing the (thio) urea functional group is used, the sterically hindered (thio) urea bond can be introduced into the crosslinked structure of the final coating layer. As such sterically hindered (thio) urea bonds are introduced into the crosslinked structure of the coating layer to be finally prepared, the bonds in the nitrogen moiety having sterically hindered properties among the sterically hindered (thio) urea bonds having relatively low bonding strength when an external force is applied to the coating layer. This breaks down preferentially and then recombines over time to restore the initial properties, or during the recovery process, the bond structure is rearranged as a whole to increase the bond strength. In addition, the stress can be absorbed by the reversible covalent bond can exhibit an improved layer resistance compared to other coating layers having the same surface hardness.

Accordingly, by using the composition for forming the coating layer, it is possible to provide a high hardness coating layer having self-healing properties and having high crack resistance, flex resistance and layer resistance.

In addition, the coating film provided from the composition for forming a coating layer having the self-healing property may be applied to a display device or the like by securing flexibility with high hardness to implement improved performance.

In addition, the coating film provided from the composition for forming a coating layer having the self-healing property may exhibit recovery characteristics in which the cut surface is bonded as the crosslinked structure is recombined when the cut surface is in close contact with the cut surface again.

The sterically hindered (thio) urea bond is a linear or branched alkyl group of 2 to 30 carbon atoms, a straight or branched chain alkenyl group of 2 to 30 carbon atoms, a cycloalkyl group of 4 to 30 carbon atoms, and 6 to 6 carbon atoms at least one nitrogen. A bulky functional group selected from the group consisting of 30 aryl groups, heteroalkyls, cycloheteroalkyls and heteroaryls can be substituted. The reversible covalent compound may include a compound of Formula 1 below.

[Formula 1]

In Chemical Formula 1,

L is an n-valent functional group derived from aliphatic, alicyclic or aromatic, n is an integer of 1 to 20 in the number of substituted L,

X is oxygen or sulfur,

Y is a direct bond, a straight or branched chain alkylene group having 1 to 30 carbon atoms, a straight or branched chain alkenylene group having 2 to 30 carbon atoms, a cycloalkylene group having 4 to 30 carbon atoms, an arylene group having 6 to 30 carbon atoms,

Z is a (meth) acrylate group or a vinyl group,

Rr straight or branched chain alkyl group of 2 to 30 carbon atoms, straight or branched chain alkenyl group of 2 to 30 carbon atoms, cycloalkyl group of 4 to 30 carbon atoms, aryl group of 6 to 30 carbon atoms, heteroalkyl, cycloheteroalkyl and hetero It is a bulky group selected from the group consisting of aryl.

In addition, in Formula 1, L may be a divalent to 10-valent functional group derived from linear or branched alkanes having 1 to 20 carbon atoms, cycloalkanes having 4 to 20 carbon atoms, or arenes having 6 to 20 carbon atoms. have.

On the other hand, a method for synthesizing a reversible covalent compound comprising a (thio) urea functional group containing at least one sterically hindered (thio) urea bond and a (meth) acrylate or vinyl functional group bonded to the (thio) urea functional group The present invention is not particularly limited, and for example, a reversible covalent compound having various physical properties may be synthesized by reacting (bulky alkylamino) alkyl (meth) acrylate with a polyvalent isocyanate compound [poly (NCO)] having various structures.

The polyhydric isocyanate compound may be an oligomer of a diisocyanate compound, a polymer of a diisocyanate compound, or a diisocyanate compound. Cyclic Multimers, Nucleated Methylene Diisocyanate Isocyanurate

(Hexamethylene diisocyanate isocyanurate), 1 member selected from the group consisting of an isophorone isocyanurate carbonate ⁰ isocyanurate (Isophorone diisocyanate isocyanurate), with toluene 2,6-diisocyanate isocyanurate, triisocyanate compounds and isomers thereof In addition, the above-mentioned binder can be formed using various trifunctional or more than trifunctional polyisocyanate compounds.

Among the specific examples of the polyvalent isocyanate compound, the oligomer, polymer, cyclic multimer or isocyanurate of the diisocyanate compound may be formed from conventional aliphatic or aromatic diisocyanate compounds, and the like (For example, DN980S of Aekyung Chemical which is a trimer of HDI, etc.) can be obtained and used. More specific examples of such diisocyanate compounds include ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-nuclemethylene diisocyanate (HDI), 1,12-dodecane diisocyanate, cyclobutane-1,3 -diisocyanate, cyclohexane-1,3-diisocyanate, nucleic acid, nucleic acid-1,4-cyclohexane diisocyanate, 1-isocyanato -3,3,5-trimethyl-eu _{5-isocyanatomethyl} cyclohexane eu nucleic acid, 2,4-nucleohydroluene diisocyanate, 2,6-hexahydroluene diisocyanate, nucleohydro-1,3-phenylene diisocyanate, nucleohydro-1,4-phenylene diisocyanate, perhydro-2 , 4'-diphenylmethane diisocyanate, perhydro-4,4'-diphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 4,4'-stilbene diisocyanate Isocyanate, 3,3'-dimethyl-4,4'- Phenylene diisocyanate (TODI), toluene 2,4-diisocyanate, toluene 2,6- diisocyanate (TDI), diphenylmethane-2,4'- diisocyanate (MDI), 2,2'-di Phenylmethane diisocyanate (MDI), diphenylmethane-4,4'- diisocyanate (MDI), isophorone diisocyanate (IPDI), etc. are mentioned.

The composition for forming a coating layer having the self-healing property is at least one selected from the group consisting of (meth) acrylate monomers, vinyl monomers, and polyfunctional (meth) acrylate compounds. It may further comprise a compound.

The polyfunctional (meth) acrylate-based compound is tri / tetraacrylic polyfunctional urethane acrylate, 9-ethylene glycol diacrylate (9-EGDA), bisphenol A epoxy acrylate, polyether triacrylate, pentaerythri Pentaerythritol tri / tetraacrylate (PETA), dipentaerythritol hexa-acrylate (DPHA), trimethylolpropane triacrylate (TMPTA) and hexamethylene diacrylate; One or more compounds selected from the group consisting of HDD A).

In the composition for forming a coating layer having the self-healing property, the reversible covalent compound, (meth) acrylate monomers, vinyl monomers and polyfunctional

(Meth) total, based on the weight of the reversible covalent weight ratio of the compound is from about 5 weight ^_0/0 to about 99 weight ^_0/0, preferably about 20 to about 95 increased the one or more selected from the group consisting of acrylate-based compound compound It may be a%, or about 25 to about 95 weight ^_0/0, preferably about 50 to about 95% by weight. When the weight ratio of the reversible covalent compound is in the above-described range, the coating layer may exhibit sufficient self-healing properties.

The composition for forming a coating layer having the self-healing property may further include at least one polymer resin selected from the group consisting of polyurethane, urethane (meth) acrylate resin, and hydroxyalkyl (meth) acrylate resin.

The photoinitiator may include one or more compounds selected from the group consisting of acetophenone compounds, biimidazole compounds, triazine compounds, and oxime compounds.

The composition for forming a coating layer having the self-healing property may further include an inorganic filler.

The composition for forming a coating layer having the self-healing property may further include at least one additive selected from the group consisting of a surfactant, a leveling agent, and a dispersion stabilizer for dissolving or dispersing these components, in addition to the above-described components. The organic solvent may be used without any limitation as long as it is known in the art to be used in the coating composition. For example, ketone organic solvents, such as methyl isobutyl ketone, methyl ethyl ketone, and dimethyl ketone; Alcohol organic solvents such as isopropyl alcohol, isobutyl alcohol or normal butyl alcohol; Acetate organic solvents such as ethyl acetate or normal butyl acetate; A salusolve organic solvent such as ethyl cellusolve or butyl cellusolve may be used, but the organic solvent is not limited to the above-described example.

The composition for forming a coating layer having the self-healing property may further include an inorganic compound in which a (meth) acrylate-based functional group or a vinyl-based functional group is bonded through a (thio) urea functional group containing a sterically hindered urea bond. The inorganic compound may also be reversible covalent bond, and further comprising the inorganic compound, properties such as hardness, flexibility, layer resistance of the coating layer may be further improved.

The inorganic compound in which the (meth) acrylate-based functional group or vinyl-based functional group is bonded through a (thio) urea functional group containing a sterically hindered urea bond is

The (meth) acrylate-based functional group or vinyl-based functional group may include a silicone-based compound having a terminal bound through a (thio) urea functional group containing a sterically hindered urea bond.

The inorganic compound in which the (meth) acrylate-based functional group or vinyl-based functional group is bonded through a (thio) urea functional group containing a sterically hindered urea bond may include a compound of Formula 2 below.

[Formula ² ]

In Chemical Formula 2, X is oxygen or sulfur,

L and Y are each a direct bond, a straight or branched chain alkylene group having 1 to 30 carbon atoms, a straight or branched chain alkenylene group having 2 to 30 carbon atoms, a cycloalkylene group having 4 to 30 carbon atoms, and an aryl having 6 to 30 carbon atoms. It's Rengi,

Z is a (meth) acrylate group or a vinyl group,

^ Is a straight or branched chain alkyl group of 2 to 30 carbon atoms, a straight or branched chain alkenyl group of 2 to 30 carbon atoms, a cycloalkyl group of 4 to 30 carbon atoms, an aryl group of 6 to 30 carbon atoms, heteroalkyl, cycloheteroalkyl, and A bulky group selected from the group consisting of heteroaryl,

R ₂ is hydrogen, a straight or branched chain alkyl group having 1 to 10 carbon atoms, or a straight or branched chain alkoxy group having 1 to 10 carbon atoms,

p is an integer of 1-4, p + q is 4.

The compound of Formula 2 may be obtained by, for example, reacting a bulky alkylamino) alkyl (meth) acrylate with an alkoxy silane compound having an isocyanate function, but the present invention is not limited thereto. It is also possible for the compound of formula (2) to react with the surface of the silica material to modify the silica material.

On the other hand, in the present specification, a coating film including a cured product of the composition for forming a coating layer having the self-healing property is provided.

The specific manufacturing method of the coating film is not particularly limited, and for example, the coating film may be prepared by applying a composition for forming a coating layer having the self-healing property onto a substrate and then photocuring the same.

In the step of applying the composition for forming the coating layer having the self-healing property on the resin substrate layer, for example, using a conventional coating method such as Meyer bar coating method, applicator coating method, roll coating method without any particular limitation A composition can be apply | coated on a resin base material layer. Then, ^at a temperature of about 20 to about 80 ^° C, it may be dried for about 1 to about 30 minutes to remove substantially all of the organic solvent included in the composition.

In the subsequent UV curing step, UV (e.g., UV light having a wavelength of about 200 to 400 nm) is applied at a light amount of about 50 to about 2,000 mJ / cm ² . By irradiating, the composition for forming a coating layer having the self-healing property may be UV cured, and thus, a coating layer having the self-healing property according to another embodiment may be formed.

In addition, in the present specification, a coating film comprising a polymer resin in which a (meth) acrylate-based or vinyl-based backbone forms a crosslink via a (thio) urea functional group containing at least one sterically hindered (thio) urea bond Is provided.

The polymer resin may further include a polyurethane, urethane (meth) acrylate resin, and hydroxyalkyl (meth) acrylate resin.

The coating film may further include an inorganic filler dispersed in the polymer resin.

The coating film may further include an inorganic compound in which the (meth) acrylate-based functional group or the vinyl-based functional group dispersed in the polymer resin is bonded through a (thio) urea functional group containing a hindered urea bond.

In the present specification, a polymer resin substrate; And a coating layer formed on one surface of the polymer resin substrate and including the coating film described above.

In addition, in the present specification, a home appliance to which the coating film is attached may be provided.

In addition, in the present specification, a display device in which the coating film is attached to the exterior may be provided.

The coating film may be applied to the exterior of various household appliances or decorative molded products, such as a washing machine or a washing machine, or may be applied to the exterior of a display device, and may be applied to an exterior material for screen protection of a mobile phone display device (for example, a back cover). Or it can be preferably applied to the field of appearance molding of various products, thereby exhibiting excellent self-healing properties to restore itself even if damages such as scratches are caused by external stimuli, and exhibit excellent mechanical properties to display the various home appliances and displays. It can serve to properly protect the exterior of the device or molded article.

【Effects of the Invention】

According to the present invention, such as various home appliances or display elements A coating layer forming composition having a self-healing property, a coating film prepared from the composition, a coating film including the coating film, which is applied to an exterior and has a self-healing property, which enables to provide a coating film exhibiting improved mechanical properties with excellent self-healing properties. Home appliances and display devices including the coating film may be provided.

Using the composition for forming the coating layer may provide a high hardness coating layer having self-healing properties and having high crack resistance, bending resistance, and impact resistance. In addition, the coating film provided from the composition for forming a coating layer having the self-healing property may secure flexibility with high hardness to be applied to a flexible display device and the like to achieve improved performance.

[Specific contents to carry out invention]

The invention is explained in more detail in the following examples. However, the following examples are merely to illustrate the invention, but the content of the present invention is not limited by the following examples.

Preparation Example Preparation of Reversible Covalently Bonded Compound Preparation Example 1

25 g of methyl ethyl ketone and 59.23 g of Duranate E402-90T (Asahi asei) which are urethane isocyanates were mixed and stirred to make a homogeneous state. At the same time as stirring the homogeneous solution, a tert-butylaminoethyl methacrylate (TBAEMA) 21. 69 g was added dropwise. After the addition was completed, the mixture was further stirred at room temperature for 1 day, and it was confirmed that the isocyanate peak (wavenumber-2270 cm) disappeared on IR spectroscopy. Preparation Example 1

Methyl ethyl ketone and brought to 25g hex diisocyanate / isophorone diisocyanate the isocyanate Duranate MHG-80B (Asahi Kasei) 4 8. homogeneous state with stirring after the heunhap ⁴ 5g. While stirring the homogeneous solution, one drop of TBAEMA 36.24g Added. After the addition was completed, the mixture was further stirred for 1 day at room temperature, and it was confirmed that the isocyanate peak (wavenumber-2270 cm ^-1 ) disappeared on IR spectroscopy. Preparation Example 3

While stirring 57.18 g of KBE-9007 (3-isocyanatopropyltriethoxysilane, Shin-Etsu), 42.82 g of TBAEMA was added dropwise. After further stirring at room temperature for 1 day, it was confirmed that the isocyanate peak (wavenumber-2270 cm ^" disappeared on IR spectroscopy. 1.48 g of the preparation solution was added to 98.52 g of silica particle dispersion IP A-ST (Nissan Chemical) to obtain 3 The mixture was stirred for 1 day.

25 g of methyl ethyl ketone, 64.79 g of Duranate E402-90T (Asa i Kasei) and 16.67 g of hydroxyethylmethacrylate (HEMA), which were urethane-based isocyanates, were mixed and stirred to obtain a homogeneous state. After adding 0.02 g of dibutyltin dilaurate solution (methyl ethylene ketone solvent, 1 wt%) to the homogeneous solution, the mixture was further stirred at room temperature for 1 day, and the isocyanate peak (wavenumber ˜2270 cm ^“ ) disappeared on IR spectroscopy. Comparative Production Example 2

25 g of methyl ethyl ketone, 59.65 g of Duranate MHG-80B (Asahi Kasei), which is an allophanate nucleated methylene diisocyanate / isophorone diisocyanate isocyanate, and 27.26 g of HEMA were mixed and stirred to make a homogeneous state. To the homogeneous solution, 0.03 g of dibutyltin dilaurate solution (methyl ethtone ketone solvent, 1 weight ⁰ /.) Was added, followed by further stirring at room temperature for 1 day, and an isocyanate peak (wavenumber -2270 cm ᅳ ^) on IR spectroscopy. It was confirmed that extinction Comparative Comparative Example 3

KBE-9007 (3-isocyanatopropyltriethoxysilane, Shin-Etsu) 63.62g and HEMA 33.47 g was stirred and then stirred. The solution was the dibutyltin dilaurate solution was stirred for one more at room temperature after the addition of 0.03g (tone ketone solvent, 1 part by weight ^{_0/0-methyl),} an isocyanate peak (wavenumber -2270 cm ^{^"1)} 7 on IR spectroscopy } 1.48 g of the solution was added to 98.52 g of silica particle dispersion IP A-ST (Nissan Chemical) and stirred for 3 days.

EXAMPLES Production of Coating Layer Forming Composition Having Self-Healing Properties and Preparation of Coating Film Having Self-Healing Properties Example 1

The composition of Preparation Example 1 83.55g, trimethylol propane triacrylate 6.96g, male photosensitive polymerization initiator Esacure KIP 100 F (Lamberti) diluting liquid (methyl ethyl ketone solvent, 10 parts by weight ^_0/0) 3.48g, 5.69g of methyl ethyl ketone , surfactants Tego Glide 432 (Evonik) was prepared in a diluent (solvent of methyl ethyl ketone, 10 parts by weight ^_0/0), the combined common 0.32g photocurable coating composition. The composition was coated on a polyethylene terephthalate film (Toray, 250μηι) with Meyer bar # 70, dried in a convection oven at 60 ^° C. for 2 minutes, and then irradiated with UV light at 500mJ / cm ² under a nitrogen atmosphere to have a self-healing coating layer. Was completed. Example 2

A film having a self-healing coating layer was completed in the same manner as in Example 1 except that the composition of Preparation Example 1 was replaced with the composition of Preparation Example 2. Example 3

Kayarad DPCA 60 (Nippon Kayaku) 16.58g , 22.10g Preparation Example 2, the composition of, the composition of Preparation Example 3 53.43g, male photosensitive polymerization initiator Esacure KIP 100 F (Lamberti) dilution liquid (methyl ethyl ketone solvent, 10 parts by weight ^_0/0 ) was prepared in 2.49g, 5.25g of methyl ethyl ketone, surfactant Tego Glide 432 (Evonik) dilution fluid (common in the combined solvent of methyl ethyl ketone, 10 parts by weight ^_0/0) 0.1 ⁵ g photocurable coating composition. Convection of the composition by applying Meyer bar # 70 on polyethylene terephthalate film (Toray, 250μπι) After drying for 2 minutes at 60 ^° C. in an oven under UV atmosphere 500mJ / cm ² irradiated with ultraviolet light to complete the film having a self-healing coating layer. Example 4

2 mL of the coating composition of Example 1 was placed in an aluminum dish (about 43 mm in diameter) and then dried in a convection oven at 60 ^° C. for 30 minutes. Thereafter, 500 mJ / cm ² ultraviolet rays were irradiated with black light as a light source to complete a self-healing film. Comparative Example 1

A film having a urethane-based coating layer was completed in the same manner as in Example 1 except that the composition of Preparation Example 1 was replaced with the composition of Comparative Preparation Example 1. Comparative Example 2

A film having a urethane-based coating layer was completed in the same manner as in Example 1 except that the composition of Preparation Example 2 was replaced with the composition of Comparative Preparation Example 2. Comparative Example 3

A film having a urethane-based coating layer was completed in the same manner as in Example 1 except for replacing the composition of Preparation Example 2 with the composition of Comparative Preparation Example 2 and the composition of Preparation Example 3 with the composition of Comparative Preparation Example 3, respectively. Comparative Example 4

A film having a urethane-based coating layer was completed in the same manner as in Example 4 except that the composition of Example 1 was replaced with the composition of Comparative Example 1.

[Test Example: Formation of coating layer and coating film, physical properties evaluation I

The physical properties of the coating layers obtained in Examples and Comparative Examples were measured and evaluated in the following manners and are shown in Tables 1 and 2, respectively. 1. Initial pencil hardness: The pencil hardness of the coating layer was measured in accordance with JIS K5400 at 500g load. The maximum pencil hardness that can be seen immediately after the evaluation was taken.

2. Surface Scratch Restoration Characteristics: The maximum pencil hardness and maximum temperature condition at which scratches can be recovered when left for 1 hour after the pencil hardness evaluation are indicated. Regardless of temperature, if the surface scratch did not recover, it is marked with X.

3. Flex resistance: The steel rod having a specific diameter in cross section was wound with the coating surface facing outward to obtain the minimum diameter value at which the coating layer was not broken.

4. Transmittance and haze: Transmittance and haze are measured by using a spectrophotometer (COH-400, Nippon Denshoku), and OK when the transmittance is> 90% and haze <1.5%. It was.

5. Layer resistance: After fixing the specimen in a zig of 76mm inner diameter, drop the 21.7g sphere weight at 10cm intervals at different heights to increase the maximum height without cracks and other defects. Notation. 6. Cutting of bonded surface: After cutting the specimen, the cut surface was fixed and taped and stored at 60 ^° C for 3 hours to compare the bonded surface and the tensile properties (elastic modulus, elongation at break, tensile strength) before and after recovery.

TABLE 1

(Recoverable

Pencil hardness and

Temperature)

Transmittance OK OK OK OK OK OK Haze OK OK OK OK OK OK Flex resistance (Φ) 2 4 10 2 6 12 Layer resistance 90 90 70 90 80 50

(cm)

TABLE 2

Referring to Tables 1 and 2, the coating layer or the coating film formed using the composition for forming a coating layer of the present invention exhibited excellent surface hardness, flex resistance, and layer resistance along with scratch recovery characteristics or cut surface recovery characteristics. Comparing Comparative Example 2 and Comparative Example 3, each having the same pencil hardness as Examples 2 and 3, respectively, the coating films of Examples 2 and 3 exhibited surface scratch recovery properties, whereas Comparative Examples 2 and 3 exhibited such restorations. There was no property and the flex resistance and impact resistance were inferior to Examples 2 and 3. In addition, Comparative Example 1 had a scratch recovery property, Comparative Example 4 prepared in the form of a single-filled film using the same coating composition does not show the same cutting surface recovery characteristics as Example 4 of the present invention, the steric hindrance in the bonding mechanism of the cutting surface It can be seen that (thio) urea binding plays an important role. In addition, Example 1 has a somewhat low scratch hardness at room temperature instead of a somewhat low pencil hardness, Examples 2 and 3 exhibit a high pencil hardness while the scratch recovery temperature is higher than room temperature to use the coating composition of the present invention It seems that the use and physical properties can be controlled.

On the other hand, in Example 4, the elastic modulus increased as the cut surface was recovered after cutting, which is considered to be due to the rearrangement of the crosslinked structure as a whole.

Claims

【Patent Claims】

【Claim 1】

A reversible covalent compound containing a (thio)urea functional group containing at least one sterically hindered (thio)urea bond and a (meth)acrylate-based or vinyl-based functional group bonded to the (thio)urea functional group; photoinitiator; and an organic solvent. A composition for forming a coating layer having self-restoring properties.

[Claim 2]

According to clause 1,

The sterically hindered (thio)urea bond is a straight-chain or branched alkyl group with 2 to 30 carbon atoms, a straight-chain or branched alkenyl group with 2 to 30 carbon atoms, a cycloalkyl group with 4 to 30 carbon atoms, and 6 to 6 carbon atoms to at least one nitrogen. A composition for forming a coating layer having self-restoring properties, wherein a bulky functional group selected from the group consisting of an aryl group, heteroalkyl, cycloheteroalkyl, and heteroaryl is substituted.

【Claim 3】

According to clause 1,

The reversible covalent compound is a composition for forming a coating layer having self-restoring properties, comprising a compound of the following formula (1):

[Formula 1]

In Formula 1,

L is an n-valent functional group derived from aliphatic, alicyclic or aromatic, and n is the number of substituted L and is an integer of 1 to 20,

X is oxygen or sulfur,

Y is a direct bond, a straight or branched alkylene group having 1 to 30 carbon atoms _: A straight or branched alkenylene group with 2 to 30 carbon atoms, a cycloalkylene group with 4 to 30 carbon atoms, and an arylene group with 6 to 30 carbon atoms,

Z is a (meth)acrylate group or a vinyl group,

^ is a straight-chain or branched alkyl group with 2 to 30 carbon atoms, a straight-chain or branched alkenyl group with 2 to 30 carbon atoms, a cycloalkyl group with 4 to 30 carbon atoms, an aryl group with 6 to 30 carbon atoms, heteroalkyl, cycloheteroalkyl, and It is a bulky functional group selected from the group consisting of heteroaryl.

【Claim 4】

In clause 3,

The L is a divalent to ten-valent functional group derived from a straight-chain or branched alkane with 1 to 20 carbon atoms, a cycloalkane with 4 to 20 carbon atoms, or an arene with 6 to 20 carbon atoms,

A composition for forming a coating layer having self-restoring properties.

[Claim 5]

In clause 11,

A composition for forming a coating layer having self-restoring properties, further comprising at least one compound selected from the group consisting of (meth)acrylate-based monomers, vinyl-based monomers, and multifunctional (meth)acrylate-based compounds.

【Claim 6】

In clause 5,

The multifunctional (meth)acrylate-based compounds include polyfunctional urethane acrylate, 9-ethylene glycol diacrylate (9-EGDA), bisphenol A epoxy acrylate, polyether triacrylate, and pentaerythrylate. pentaerythritol tri/tetraacrylate (PETA), dipentaerythritol hexa-acrylate (DPHA), trimethylolpropane triacrylate (TMPTA), and hexamethylene diacrylate; To HDD A) One or more species selected from the group consisting of

A composition for forming a coating layer having self-restoring properties.

[Claim 7]

According to clause 5,

The weight ratio of the reversible covalent compound to the total weight of the reversible covalent compound and one or more compounds selected from the group consisting of (meth)acrylate-based monomers, vinyl monomers, and multifunctional (meth)acrylate-based compounds is 5. A composition for forming a coating layer having self-restoring properties, ranging from % to 95% by weight.

[Claim 8]

In paragraph 11,

A composition for forming a coating layer having self-restoring properties, further comprising at least one polymer resin selected from the group consisting of polyurethane, urethane (meth)acrylate resin, and hydroxyalkyl (meth)acrylate resin.

【Claim 9】

According to clause 1,

The photoinitiator is a composition for forming a coating layer having self-restoring properties, including one or more compounds selected from the group consisting of acetophenone-based compounds, biimidazole-based compounds, triazine-based compounds, and oxime-based compounds.

【Claim 10】

According to clause 1,

A composition for forming a coating layer having self-restoring properties, further comprising an inorganic filler.

【Claim 1 1】

In paragraph 1 A composition for forming a coating layer having self-restoring properties, further comprising an inorganic compound in which a (meth)acrylate-based functional group or a vinyl-based functional group is bonded through a (thio)urea functional group containing a sterically hindered urea bond.

[Claim 12]

According to clause 11,

The inorganic compound in which the (meth)acrylate-based functional group or vinyl-based functional group is bonded through a (thio)urea functional group containing a sterically hindered urea bond is

A composition for forming a coating layer having self-restoring properties, comprising a silicone-based compound in which a (meth)acrylate-based functional group or a vinyl-based functional group is bonded to an end via a (thio)urea functional group containing a sterically hindered urea bond.

【Claim 13】

According to clause 11,

The inorganic compound in which the (meth)acrylate-based functional group or vinyl-based functional group is bonded via a (thio)urea functional group containing a sterically hindered urea bond includes a compound of the following formula (2), for forming a coating layer having self-restoring properties: Composition:

[Formula ² ]

In Formula 2,

X is oxygen or sulfur,

L and Y are each a direct bond, a straight-chain or branched alkylene group with 1 to 30 carbon atoms, a straight-chain or branched alkenylene group with 2 to 30 carbon atoms, a cycloalkylene group with 4 to 30 carbon atoms, and an aryl group with 6 to 30 carbon atoms. It's Rengi,

Z is a (meth)acrylate group or a vinyl group,

¾ is a straight or branched alkyl group having 2 to 30 carbon atoms, and 2 to 30 carbon atoms. It is a bulky functional group selected from the group consisting of straight-chain or branched alkenyl group of 30, cycloalkyl group of 4 to 30 carbon atoms, aryl group of 6 to 30 carbon atoms, heteroalkyl, cycloheteroalkyl and heteroaryl,

R ₂ is hydrogen, a straight-chain or branched alkyl group having 1 to 10 carbon atoms, or a straight-chain or branched alkoxy group having 1 to 10 carbon atoms,

p is an integer from 1 to 4, and p+q is 4.

[Claim 14]

A coating film comprising a cured product of the coating composition of any one of claims 1 to 13.

【Claim 15】

A coating film comprising a polymer resin in which a (meth)acrylate-based or vinyl-based main chain forms a crosslink via a (thio)urea functional group containing one or more sterically hindered (thio)urea bonds.

【Claim 16】

According to clause 15,

The polymer resin further includes polyurethane, urethane (meth)acrylate resin, and hydroxyalkyl (meth)acrylate resin. A coating film.

[Claim 17]

According to clause 15,

A coating film further comprising an inorganic filler dispersed in the polymer resin.

【Claim 18】

In clause 15,

A coating film dispersed in the polymer resin, further comprising an inorganic compound in which a (meth)acrylate-based functional group or a vinyl-based functional group is bonded through a (thio)urea functional group containing a sterically hindered urea bond.

[Claim 19]

polymer resin base; and

A coating film formed on one surface of the polymer resin substrate and comprising a coating layer comprising the coating film of claim 14 or 15.

[Claim 20]

Home appliances to which the coating film of claim 14 or 15 is attached. [Claim 21]

A display device having the coating film of claim 14 or 15 attached to its exterior.