KR102246756B1 - Photocurable coating material compositions of vinyl-silicon compounds - Google Patents

Abstract

A photocurable coating composition of a vinyl-based silicone compound is provided. Specifically, silica particles substituted with an acrylate-based compound, polyorganosiloxane containing one or more vinyl groups in the molecule, polyfunctional acrylate monomers, photoinitiators, and a solvent. It is possible to provide a photocurable coating material composition of a vinyl-based silicone compound. Accordingly, the photocurable coating composition of the vinyl-based silicone compound of the present invention can improve the hardness of the photocurable coating composition applied thereto by controlling the degree of substitution of the acrylate-based compound substituted on the silica particles. In addition, physical properties such as printability of the coating material to which the coating material is applied according to the degree of substitution of the acrylate-based compound can be easily controlled depending on the material to which the coating material is applied, and thus can be applied as a coating material of various materials.

Description

Photocurable coating composition of vinyl silicone compound {PHOTOCURABLE COATING MATERIAL COMPOSITIONS OF VINYL-SILICON COMPOUNDS}

The present invention relates to a photocurable coating composition, and more particularly, to a photocurable coating composition of a vinyl-based silicone compound.

A coating material using silica is used in various fields as a hard coating material capable of reducing surface corrosion and improving mechanical strength of metal or plastic materials. Silica is a very stable material, has durability and high thermal insulation performance against various kinds of chemicals, and has a relatively high melting point (~1650℃), so it can be applied to materials requiring corrosion resistance at high temperatures. Such a coating material using silica is used for the application of a surface modification technology that can improve the surface hardness of the material to which it is applied, the scratch resistance of metal materials susceptible to daily life scratches, and the abrasion resistance of plastic materials. Various studies are being tried.

The conventional technique for surface modification of silica is a method of adding and using a light (ultraviolet (UV)) curable organic substance to inorganic silica, or methyltriethoxysilane (MTES), glycidyloxypropyltrimethoxysilane ( Glycidoxypropyl trimethoxysilane (GPTMS), phenyl trimethoxysilane (PTMS), or vinyltriethoxysilane (VTES). Compared to the method of adding the thermosetting organic substance that requires high temperature conditions for a long time, the method of adding the photocurable organic substance can be completely cured within a short time without the generation of condensate, thereby reducing manufacturing time and manufacturing cost. However, since it does not directly apply heat, there is an advantage that the coating composition can be applied to thermoplastic plastics or wood.

However, when a photocurable organic substance is added to silica, which is an inorganic substance, a phase separation phenomenon occurs due to opposite physical properties between the organic substance and the inorganic substance, and there is a disadvantage that the hardness of the coating film to which the photocurable organic substance is applied decreases. There is a need for further improvement.

An object to be solved by the present invention is to provide a photocurable coating composition capable of having excellent hardness by adding silica particles and a polyfunctional acrylate compound substituted with an acrylate-based compound to a vinyl-based silicone compound.

In order to achieve the above object, one aspect of the present invention is a silica particle substituted with an acrylate compound, a polyorganosiloxane containing at least one vinyl group in the molecule, a polyfunctional acrylate monomer, It is possible to provide a photocurable coating material composition of a vinyl-based silicone compound comprising a photoinitiator and a solvent.

The photocurable coating composition of the vinyl-based silicone compound of the present invention can improve the hardness of the photocurable coating composition to which the same is applied by controlling the degree of substitution of the acrylate-based compound substituted on the silica particles.

In addition, physical properties such as printability of the coating material to which the coating material is applied according to the degree of substitution of the acrylate-based compound can be easily controlled depending on the material to which the coating material is applied, and thus can be applied as a coating material of various materials.

1 is a chart comparing contact angles according to the content of silica particles in coating films of Example 4 and Comparative Example of the present invention.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings.

While the present invention allows various modifications and variations, specific embodiments thereof are illustrated and illustrated in the drawings, and will be described in detail below. However, it is not intended to limit the present invention to the particular form disclosed, but rather the present invention includes all modifications, equivalents, and substitutions consistent with the spirit of the present invention as defined by the claims.

The photocurable coating composition of the vinyl silicone compound of the present invention comprises component 1) silica particles substituted with an acrylate compound, component 2) polyorganosiloxane containing at least one vinyl group in the molecule. , Component 3) a multifunctional acrylate monomer, component 4) a photoinitiator, and component 5) a solvent.

Component 1) of the present invention is a silica particle substituted with an acrylate compound.

The silica particles may be nano-sized monodisperse silica particles prepared through a sol-gel method and a macroemulsion method. The number of hydroxyl groups (-OH) on the surface of the silica particles may be controlled through the known silica manufacturing method. The nano-sized silica particles may have a known average particle diameter, for example, may have a size of about 5 nm to 300 nm, but are not limited thereto. The silica can be obtained and used from a commercial item.

The silica particles substituted with the acrylate-based compound may mean that the acrylate-based compound is substituted on the surface of the nano-sized silica particles. In other words, it may mean that the silica particles include a plurality of hydroxy groups (-OH) on the surface of the particles, and some of the plurality of hydroxy groups are substituted with the acrylate-based compound to be formed on the surface of the silica particles. .

The silica particles substituted with the acrylate-based compound may be obtained by combining silica particles into which a silane coupling agent is introduced with an acrylate-based compound. Accordingly, the silica particles substituted with the acrylate-based compound may be in a form in which an acrylate-based compound is bonded to a silane coupling agent surface-treated on the silica particles.

The silane coupling agent may have two or more different reactive groups in the molecule.

The silane coupling agent may include a silane coupling agent represented by Formula 1 or Formula 2 below.

In Formula 1,

R ₁ to R ₃ are each independently an alkoxy group having 1 to 20 carbon atoms,

R ₄ is each independently an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms,

R ₅ is a hydrogen atom, or an alkyl group or ester group having 1 to 20 carbon atoms.

In Chemical Formula 2,

A ₁ to A ₃ and A ₇ to A ₉ are each independently an alkoxy group having 1 to 20 carbon atoms,

A ₄ and A ₆ are each independently an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms,

A ₅ is a hydrogen atom, or an alkyl group or ester group having 1 to 20 carbon atoms.

The silane coupling agent may include an alkoxy group (-OR) and a primary amine group (-NH ₂ ) or a secondary amine group (-NH). For example, the silane coupling agent, 3-aminopropyltriethoxysilane (APTES), 3-aminopropyltrimethoxysilane (APTMS), and bis[3-(trie) It may be any one selected from among oxysilyl)propyl]amine (Bis[3-(triethoxysilyl)propyl]amine, TESPA).

When the silane coupling agent and the silica particles are blended, the hydroxy group (-OH) on the surface of the silica particles and the alkoxy group (-OR) of the silane coupling agent may react and bond. Accordingly, a hydroxyl group (-OH) group, which is a hydrophilic group on the surface of the silica particles, may be reduced, and a hydrophobic group or a specific functional group such as the acrylate compound may be provided through the silane coupling agent bonded to the surface of the silica particles. . When the silane coupling agent and the silica particles are blended, a solvent may be further included, and the solvent may be hydrolyzed by mixing with water, a mixture of water and alcohol, or various polar and non-polar solvents. For example, the solvent may be a 0.5% to 1% methanol or ethanol aqueous solution. A solution obtained by blending the silane coupling agent and the silica particles together with the solvent may be washed using a centrifuge and then dried.

As described above, the reaction mechanism between the silica particles and the silane coupling agent may be represented by Reaction Formula 1 below.

[Scheme 1]

In Scheme 1 above,

R ₁ to R ₃ are each independently an alkoxy group having 1 to 20 carbon atoms,

R ₄ is each independently an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms,

R ₅ is hydrogen or an alkyl group or ester group having 1 to 20 carbon atoms.

The acrylate-based compound may represent a compound containing an acrylate functional group, and the acrylate-based compound may be in an oligomer state and have a molecular weight of about 450 to 3,000.

The acrylate-based compound may include at least one selected from epoxy acrylate, urethane acrylate, polyester acrylate, and silicone acrylate, but preferably includes epoxy acrylate. The epoxy acrylate is not particularly limited as a known epoxy acrylate may be used, but, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, bisphenol A type propylene oxide addition reaction It may be a glycityl-end-ether and a fluorene-epoxy resin of the product, and the like.

The epoxy acrylate may include a compound represented by Formula 3 below.

In Chemical Formula 3,

R ₆ is a C 1 to C 20 alkyl group or a C 2 to C 20 alkenyl group,

R ₇ is an alkyl group having 1 to 20 carbon atoms, or an alkenyl group or ester group having 2 to 20 carbon atoms.

By substituting the acrylate-based compound on the surface of the silica particle into which the silane coupling agent is introduced, the surface of the silica particle may be modified. This may be that the acrylate-based compound is bonded to and substituted with an amine group (a primary amine group or a secondary amine group) of the silane coupling agent on the surface of the silica. That is, due to the substitution of the acrylate-based compound, the number of hydroxy groups on the surface of the silica particles into which the silane coupling agent is introduced may be adjusted. In addition, a vinyl group may be imparted to the surface of the silica particles by a _{vinyl group (-CH=CH 2) at the end of the acrylate compound.}

As described above, a reaction mechanism between the silica particles whose surface has been modified with the silane coupling agent and the acrylate-based compound may be represented by Scheme 2 below.

[Scheme 2]

In Scheme 2 above,

R ₁ to R ₃ are each independently an alkoxy group having 1 to 20 carbon atoms,

R ₄ is each independently an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms,

R ₅ is hydrogen or an alkyl group or ester group having 1 to 20 carbon atoms,

R ₆ is a C 1 to C 20 alkyl group or a C 2 to C 20 alkenyl group,

R ₇ is an alkyl group having 1 to 20 carbon atoms, or an alkenyl group or ester group having 2 to 20 carbon atoms.

The silica particles substituted with the acrylate group generated through the reaction as in Scheme 2 may be represented by Formula 4 below.

In Chemical Formula 4,

R ₄ is each independently an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms,

R ₅ is hydrogen or an alkyl group or ester group having 1 to 20 carbon atoms,

R ₆ is a C 1 to C 20 alkyl group or a C 2 to C 20 alkenyl group,

R ₇ is an alkyl group having 1 to 20 carbon atoms, or an alkenyl group or ester group having 2 to 20 carbon atoms.

As described above, the surface of the silica particles substituted with the acrylate-based compound of the present invention may be made of a hydroxy group (having hydrophilicity) and an acrylate-based compound. Accordingly, the photocurable coating composition containing silica particles substituted with the acrylate-based compound by the vinyl group (having hydrophobicity) at the end of the acrylate-based compound can improve the hardness of the cured coating film. That is, the photocurable coating composition of the present invention may have an effect of controlling the hydrophobicity and hydrophilicity of the coating film to which the coating material is applied by appropriately controlling the content of the acrylate-based compound substituted on the surface of the silica particles. Thus, by adjusting the degree of substitution of the acrylate compound, it can be configured to suit the material using physical properties such as hardness and printability of the cured coating film. It can be applied as a coating material of various materials such as, and surface treatment of metal.

The degree of substitution of the acrylate-based compound on the surface of the silica particles may be 60% to 92%. This may correspond to a degree in which the hydroxyl group (-OH) on the surface of the silica particles is reduced by substitution of the silane coupling agent and the acrylate compound. When the degree of substitution of the acrylate-based compound substituted on the surface of the silica particles is less than 60%, the hydrophilicity is maintained by the hydroxyl groups present on the surface of the silica particles, so that the hardness of the coating film obtained by curing the photocurable coating composition may decrease. have. In addition, when the degree of substitution of the acrylate-based compound substituted on the surface of the silica particles is 92% or more, due to the large amount of vinyl groups at the ends of the acrylate-based compound substituted on the silica particles, the printability of the coating material to which it is applied This can be significantly reduced, the range of the material to which the photocurable coating composition can be applied can be reduced.

When the silica particles into which the silane coupling agent is introduced and the acrylate compound are polymerized, a silica dispersion solvent into which the silane coupling agent is introduced may be added. The silica dispersion solvent into which the silane coupling agent is introduced may be a known solvent, and is not particularly limited. For example, alcohols such as methanol, ethanol, isobutanol, and 3-methyl-3-methoxybutanol, Ketones such as methyl isobutyl ketone (MIBK), methyl ethyl ketone (MEK), and cyclohexanone, diethyl ether, isopropyl ether, tetrahydrofuran (THF), dioxane, ethylene glycol dimethyl ether, diethylene glycol di Ethers such as ethyl ether, ethyl acetate, n-butyl acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol toluene, xylene, acetonitrile, dimethylformamide (DMF), dimethylacetamide , Or, it may be dimethyl sulfoxide (DMSO) or the like. The solvent may be, for example, 1 to 1000 parts by mass based on 100 parts by mass of the acrylate compound. If the amount of the solvent is small, the reaction rate may be high, but since the viscosity of the solution to be polymerized can be increased, it may be added within an appropriate range.

A method of blending the acrylate-based compound to the silica particles into which the silane coupling agent is introduced may use a known blending method, for example, a solution blending method, a melt blending method, or an emulsion. It may be a blending method (emulsion blending) or the like, but is not limited thereto.

The solution blending is a solvent in which the acrylate-based compound is dissolved by dissolving the acrylate-based compound in a solvent in which the silane coupling agent is introduced and the acrylate-based compound can be well dispersed. In a method of uniformly mixing the silica particles into which the silane coupling agent is introduced, and then removing the solvent, a method of uniformly blending the silica particles into which the silane coupling agent is introduced as an inorganic particle and an acrylate compound as an organic material Can be

The melt blending method is a method of putting silica particles into the acrylate-based compound into which the silane coupling agent is introduced and blending through mechanical mixing, and is most commonly used, but the silica particles into which the silane coupling agent is introduced. It may be difficult to uniformly mix the silica into which the silane coupling agent is introduced due to the cohesive force between particles.

The emulsion blending method is a method of precipitating after adding silica particles into which the silane coupling agent is introduced to the acrylate compound emulsion, and adding an emulsion inhibitor, and is an organic material such as the solution blending method. There may be a disadvantage in that the acrylate-based compound and the silica particles into which the silane coupling agent, which is an inorganic particle, is introduced may aggregate with each other.

Component 2) of the present invention is a polyorganosiloxane containing at least one vinyl group in the molecule.

The polyorganosiloxane may be a mixture containing the compound of Formula 5 below.

In Chemical Formula 5,

R ₈ to R ₁₂ are each independently an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms,

R ₁₃ to R ₁₅ are vinyl groups,

m is an integer of 3 to 10.

In the specification of the present invention, the "alkyl group" in the above formula is not particularly limited, but, for example, an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 16 carbon atoms, an alkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 8 carbon atoms Or, it may mean an alkyl group having 1 to 4 carbon atoms. For example, the alkyl group may be an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, or an octyl group.

In the specification of the present invention, the "alkenyl group" in the above formula is not particularly limited, but, for example, an alkenyl group having 2 to 20 carbon atoms, an alkenyl group having 2 to 16 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, and 2 It may mean an alkenyl group of to 8 or an alkenyl group of 2 to 4 carbon atoms. For example, the alkenyl group may be an allyl group, propenyl group, isopropenyl group, butenyl group, hexenyl group, cyclohexenyl group, octenyl, or decenyl group.

In the specification of the present invention, the "alkoxy group" in the above formula is not particularly limited, but, for example, an alkoxy group having 1 to 20 carbon atoms, an alkoxy group having 1 to 16 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, 1 It may mean an alkoxy group of to 8 or an alkoxy group of 1 to 4 carbon atoms. For example, the alkoxy group may be a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, or a tert-butoxy group.

The "alkyl group", "alkenyl group", and "alkoxy group" may each independently be linear, branched, or cyclic.

As described above, the polyorganosiloxane contains at least one vinyl group in its molecule, which is by radical reaction with the silica particles substituted with the acrylate-based compound and the polyfunctional acrylate monomer to be described later, Hardness can be improved. The viscosity of the polyorganosiloxane may be generally known in the range of 100 mPa·S to 100,000 mPa·S at 25°C, and preferably 500 mPa·S to 10,000 mPa·S, but is not limited thereto. By appropriately setting the viscosity of the polyorganosiloxane within the above range, the physical properties of the coating film obtained by curing the photocurable coating composition may be improved.

The method for preparing a polyorganosiloxane containing at least one vinyl group in the molecule may be performed by a generally known method, and may further include a catalyst for accelerating the reaction when preparing the polyorganosiloxane. As the catalyst, a known catalyst may be used, and it is not particularly limited, but, for example, tetramethylammonium hydroxide, an acid, or an alkali catalyst may be used.

Component 3) of the present invention is a polyfunctional acrylate monomer.

The multifunctional acrylate monomer may be used to improve the hardness of the photocurable coating composition of the present invention, and may be used as a reactive diluent to reduce the viscosity of the photocurable coating composition. The polyfunctional acrylate monomer may participate in polymerization by itself when irradiated with light. The polyfunctional acrylate monomer refers to a monomer containing two or more acrylate functional groups, for example, the polyfunctional acrylate monomer is pentaerythritol triacrylate (PETA), dipentaerythritol hexaacrylic Rate (DPHA), dipentaerythritol pentaacrylate (DPPA), and trimethylolpropane triacrylate (TMPTA).

Component 4) of the present invention is a photoinitiator.

The photoinitiator may mean a material that is added to the photocurable coating composition of the present invention and absorbs energy from a light source (preferably ultraviolet) to initiate a polymerization reaction. The photoinitiator may be initiated by a free radical polymerization method and a cationic polymerization method according to a curing method, and the photoinitiator in the present invention may preferably be a photoinitiator for free radical polymerization. The mixing ratio of the photoinitiator may be variously applied depending on the embodiment, but may be, for example, 1 part by weight to 10 parts by weight. When the photoinitiator is excited by receiving energy from a light source, the polyorganosiloxane of the photocurable coating composition, the polyfunctional acrylate monomer, and silica particles modified with the acrylate-based compound within a very short time by the excited initiator Instantaneous polymerization reaction occurs and can be cured. The photoinitiator may be a known photoinitiator, and it is not particularly limited, for example, acetophenones, benzoin, benzophenones, ketones, anthraquinones, thioxanthones, azo compounds, peroxides, 2 Any one selected from ,3-dialkyldione compounds, disulfide compounds, thioram compounds, fluoroamine compounds, and oxime esters can be used.

Component 5) of the present invention is a solvent.

The solvent may be a solvent used in a known photocurable coating material composition, so it is not particularly limited, but, for example, alcohol, toluene, xylene, methyl ethyl ketone, isopropanol, methyl isobutyl ketone, diethylene glycol monoethyl ether acetate , Diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol mono-, or di-ethyl ether. The solvent may be 50 to 100 parts by weight based on 100 parts by weight of the photocurable coating composition. When the content of the solvent is less than 50 parts by weight, the reaction rate may decrease due to the non-uniform reaction of the mixture in the photocurable coating composition, and when the content of the solvent is more than 100 parts by weight, the photocurable coating composition The viscosity of the photocurable coating material may be lowered, and thus practicality as a photocurable coating material composition may decrease.

Thus, based on 100 parts by weight of the photocurable coating composition, 1 to 20 parts by weight of silica modified with the acrylate-based compound, 1 to 10 parts by weight of a polyorganosiloxane containing at least one vinyl group in the molecule, It may be composed of 70 to 90 parts by weight of the multifunctional acrylate monomer, 1 to 10 parts by weight of the photoinitiator, and 50 to 100 parts by weight of the solvent. The photocurable coating composition is composed of the above mixing ratio, so that the cured coating film has an appropriate viscosity, can maintain adhesion, and can impart excellent hardness and scratch resistance.

In addition to the above components 1) to 4) of the present invention, according to an embodiment, one or more additives mainly used in the photocurable coating composition such as a thermosetting agent and a pigment may be further included.

The thermosetting agent or the additive such as the pigment may be used as an additive of a known photocurable coating material composition, and is not particularly limited.

The thermosetting agent may be, for example, triphenyl phosphine, tri(nitrobenzyl)phosphate, nitrobenzyl cyclohexyl carbamate, or di(methoxybenzyl)hexamexylene dicarbamate.

The pigment is, for example, selected from the group of organic pigments such as carbon black, quinacridone, naphthol red, cyanine blue, cyanine green, or Chinese character yellow, or inorganic pigments such as barium sulfate, titanium oxide, and complex metal oxides. One or more combinations can be used.

A coating film may be formed by applying the photocurable coating composition of the present invention including the above components on a material requiring coating and curing by irradiating light. The curing conditions of the photocurable coating composition are not particularly limited, but for example, ^{ultraviolet rays of 1000 mJ/cm 2} to 1300 mJ/cm ² may be irradiated for about 10 seconds to 30 seconds.

The thickness of the coating film on which the photocurable coating composition is cured may be 1 μm to 10 μm, and specifically, in order for the coating layer to maintain stable adhesion for a long time without cracking, the thickness of the coating layer may be 1 μm to 5 μm. However, it is not limited thereto.

[Example]

<Example 1: Silica particles substituted with acrylate compounds>

3-aminopropyltrimethoxysilane, a silane coupling agent, was hydrolyzed by stirring in an aqueous ethanol solution, and then Aerosil 200 manufactured by Evonik Degussa (specific surface area: 200 m ² /g, The surface of the silica particles was modified by adding and stirring silica having an average primary size: 12 nm, 2.5 particles -OH/nm2). The surface-modified silica was washed using a centrifuge and then dried. After the silica into which the dried silane coupling agent is introduced is uniformly dispersed in tetrahydrofuran (THF), a solvent for dispersion, glycidyl methacrylate, one of the epoxy acrylates, is used as an acrylate compound. , GMA) was added and stirred. The stirred solution was washed using a centrifuge and then dried to obtain silica particles substituted with an acrylate compound. When the silane coupling agent is added, the content of the silane coupling agent is adjusted so that the degree of substitution is 60%, 75%, and 92%, respectively, and the degree of substitution of the acrylate by reacting acrylate thereto (acrylate group/hydroxyl group ( It was prepared by dividing so that OH)) was 60%, 75%, and 92%, respectively.

The reaction mechanism of Example 1 may be represented by Reaction Scheme 3 below.

[Scheme 3]

As the surface of the silica particles is substituted with an acrylate-based compound as described above, the surface of the silica particles may contain a vinyl group at the terminal of the acrylate-based compound.

<Example 2: Polyorganosiloxane containing one or more vinyl groups in the molecule>

_{1,3,5-trimethyl-1,3,5,-trivinylcyclotrisiloxane (D 3} ^{Me, Vi} ), 1,3-divinyl to prepare polyorganosiloxane containing one or more vinyl groups in the molecule Hexamethyldisiloxane (VMS) and a catalyst (tetramethylammonium hydroxide) were added and polymerized to obtain a polyorganosiloxane containing a vinyl group and a methyl group.

<Example 3: Photocurable coating composition containing silica particles substituted with an acrylate-based compound>

Based on the polyorganosiloxane prepared in Example 2, a polyfunctional acrylate monomer, a photoinitiator, a solvent, and silica particles with different degrees of substitution of the acrylate compound of Example 1 were respectively blended to obtain the present invention. A photocurable coating composition was prepared. As the polyfunctional acrylate monomer, dipentaerythritol hexaacrylate (DPHA) was used.

<Example 4: Preparation of a coating film obtained by curing a photocurable coating composition>

A photocurable coating composition containing silica particles having different degrees of substitution of the acrylate-based compound of Example 3 was applied to each PET film with a predetermined thickness using a wire bar. The solvent of the photocurable coating composition was dried for 1 minute in a dryer at 80°C. Thereafter, ultraviolet light was irradiated using a UV irradiation device equipped with a high-pressure mercury lamp to obtain a coating film on which the respective photocurable coating composition was cured.

<Comparative Example 1: Photocurable coating composition not containing silica particles substituted with acrylate compounds>

For comparison, as a control, except that the silica particles substituted with acrylate were not added, a coating material composition was prepared in the same manner as in Example 4, and the coating material of Comparative Example 1 was prepared in the same manner as in Example 4 above. A coating film obtained by curing the composition was prepared.

<Example 5: Analysis of physical properties of the coating film>

1) Surface hardness measurement

Table 1 shows the measurement of the surface hardness of the coating films of Example 4 and Comparative Example 1 by inserting a pencil for measuring pencil hardness into a pencil hardness measuring machine at an angle of 45° and pushing by applying a constant load (750 g).

Type of coating film
Pencil hardness
Does not contain silica particles
2H
Silica particles with a degree of substitution of 60%
3H
Silica particles with a degree of substitution of 75%
3H
Silica particles with a degree of substitution of 92%
3H

Referring to Table 1, the surface hardness of the coating films cured with the photocurable coating composition including silica particles substituted with the acrylate compound of the present invention is 3H, and the photocurable coating material without the silica particles substituted with the acrylate compound. It can be seen that the surface hardness is improved compared to 2H, which is the surface hardness of Comparative Example 1 which is the composition.

2) Surface scratch depth measurement

Table 2 shows that the surface of the coating films of Example 4 and Comparative Example was scratched with a pointed iron rod and then the scratch depth was measured.

Type of coating film
Scratch depth (angstrom)
Does not contain silica particles
463
Silica particles with a degree of substitution of 60%
394
Silica particles with a degree of substitution of 75%
384
Silica particles with a degree of substitution of 92%
365

Referring to Table 2, the surface scratch depth of the coating films cured with the photocurable coating composition including silica particles substituted with the acrylate-based compound of the present invention gradually increases as the degree of substitution of the acrylate substituted with the silica particles increases. It can be seen that it represents a low value. On the other hand, the surface scratch depth of Comparative Example 1, which is a photocurable coating composition without containing silica particles substituted with acrylate, is 463 (angstrom), which is a relatively high value. Accordingly, it can be seen that the surface scratch of the photocurable coating composition comprising the same can be reduced depending on the degree of substitution of the acrylate-based compound substituted on the silica particles of the present invention, thereby improving the scratch resistance of the material to which it is applied. have.

3) Contact angle measurement

1 is a chart comparing the contact angle according to the content (wt%) of silica particles in the coating films of Example 4 and Comparative Example 1 of the present invention.

Referring to FIG. 1, the contact angle of the coating film of Comparative Example 1 in which the photocurable coating composition containing no silica particles substituted with the acrylate compound is cured is about 80.46°, whereas the acrylate compound of the present invention is It can be seen that the contact angle of the coating films on which the photocurable coating composition including the substituted silica particles is cured shows a contact angle of 68.5° to 76.5° depending on the content of the acrylate-based compound-substituted silica particles. This may mean that the acrylate group at the end of the acrylate-based compound substituted on the silica particles exhibits hydrophobicity, and thus the contact angle is changed.

As described above, the photocurable coating composition of the vinyl-based silicone compound of the present invention can improve hardness and scratch resistance by controlling the degree of substitution of the acrylate-based compound and replacing it with silica particles. In addition, the content of the vinyl group at the end of the acrylate group on the surface of the silica particles can be adjusted according to the degree of substitution of the surface of the silica particles of the acrylate compound. It can have the effect of being able to easily control (printability).

On the other hand, the embodiments of the present invention disclosed in the specification and drawings are merely presented specific examples to aid understanding, and are not intended to limit the scope of the present invention. In addition to the embodiments disclosed herein, it is apparent to those of ordinary skill in the art that other modified examples based on the technical idea of the present invention may be implemented.

Claims (7)

Silica particles substituted with an acrylate compound;
Polyorganosiloxane containing one or more vinyl groups in the molecule;
Polyfunctional acrylate monomers;
Photoinitiators; And
Containing a solvent,
Silica particles substituted with the acrylate-based compound,
The silica particles into which the silane coupling agent is introduced are bonded to the acrylate-based compound,
The silane coupling agent includes an alkoxy group and an amine group,
3-aminopropyltriethoxysilane (APTES), 3-aminopropyltrimethoxysilane (APTMS), and bis[3-(triethoxysilyl)propyl]amine (Bis[3 -(triethoxysilyl)propyl]amine, TESPA) photocurable coating composition of a vinyl-based silicone compound, characterized in that at least one selected from. The method of claim 1,
A photocurable coating composition of a vinyl-based silicone compound, characterized in that the degree of substitution of the acrylate-based compound on the surface of the silica particles is 60% to 92%. delete delete In paragraph 1,
The acrylate-based compound is a photocurable coating material composition of a vinyl-based silicone compound, characterized in that it contains an epoxy acrylate. In paragraph 1,
The polyfunctional acrylate monomer includes two or more acrylate groups,
At least any selected from the group consisting of pentaerythritol triacrylate (PETA), dipentaerythritol hexaacrylate (DPHA), dipentaerythritol pentaacrylate (DPPA), and trimethylolpropane triacrylate (TMPTA) A photocurable coating composition of a vinyl-based silicone compound, characterized in that one. In paragraph 1,
Based on 100 parts by weight of the photocurable coating composition, 1 to 20 parts by weight of silica modified with the acrylate-based compound, 1 to 10 parts by weight of polyorganosiloxane containing at least one vinyl group in the molecule, the multi-tube A photocurable coating composition of a vinyl-based silicone compound, comprising 70 to 90 parts by weight of a functional acrylate monomer, 1 to 10 parts by weight of the photoinitiator, and 50 to 100 parts by weight of the solvent.

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