KR101911739B1 - Photocurable resin composition containing surface-modified Inorganic Particles - Google Patents

Abstract

The present invention relates to a photo-curable resin composition comprising a surface-modified inorganic particle, and more particularly to a photo-curable resin composition comprising a modified inorganic particle, a photoinitiator, a monomer and an oligomer, (Covalent bond) with the monomer or oligomer because the modified inorganic particles participate in the photo-curing reaction at the same time, and inorganic particles are not diffused and discharged from the cured film according to long-term use. (Acid resistance and alkali resistance) and scratch resistance due to the high thermal decomposition temperature of the cured film in a simple dispersion state and the excellent denseness of the film, and it has an excellent dispersibility in the light curing composition, It is possible to form a film, and there is an advantage that there is no variation in physical properties by the site of the light-cured film.

Description

[0001] The present invention relates to a photocurable resin composition containing surface-modified inorganic particles,

The present invention relates to a photo-curable resin composition comprising a surface-modified inorganic particle, and more particularly to a photo-curable resin composition comprising a modified inorganic particle, a photoinitiator, a monomer and an oligomer, Reactive group at the same time.

The photocuring reaction using the photocurable resin composition is used in various fields including a printed substrate, a color proof, a color filter, a solder resist, a photocurable ink, a protective coating film and an adhesive. In recent years, from the viewpoints of environmental pollution, energy saving, work stability, production cost, etc., photocuring having the greatest features of quick curing at room temperature and no solvent is attracting attention in various fields including these applications, Many researches and developments have been made.

   Among various uses of photocurable resins, photocurable films should have excellent physical properties such as chemical resistance (solvent resistance, acid resistance, alkali resistance), scratch resistance and heat resistance for application to protective coating films. The most commonly used method for improving such properties is to add a reinforcing agent to a photocurable resin to form a composite material. In particular, inorganic particles such as talc, mica, silica, zirconia, metal carbonate and the like are used as a reinforcing agent for improving the scratch resistance of the photocured film, It has been applied industrially by adding a small amount to a photocurable resin.

According to the prior art, in the case of a protective film made from a photo-curable resin composition containing inorganic particles such as talc, mica, silica, zirconia or metal carbonate, since the inorganic particles do not participate in the photo-curing reaction, There is a problem of deterioration. Further, after completion of curing, the inorganic particles diffuse out of the cured resin and are discharged to the outside as time elapses, resulting in deterioration of physical properties (scratch resistance, etc.) of the cured film (protective film).

Patent registration 10-1187712 Polyolefin resin composition excellent in scratch resistance for preventing surface damage Korea Patent Registration No. 10-0898046 Polypropylene resin composition having excellent scratch resistance Korea Patent Registration 10-0805633 Floor coverings with excellent abrasion resistance and scratch resistance Korean Patent Publication No. 10-2015-0058405 Process for producing a composition containing a heterophasic propylene copolymer and talc

R. Browing et al., Polymer Engineering & Science, 46 (5), 601-608 (2006)

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made keeping in mind the above problems occurring in the prior art, and an object of the present invention is to provide an improved photocurable resin composition which improves the efficiency of the photo-curing reaction and does not diffuse and discharge the inorganic particles from the photo- will be.

The present invention provides a photo-curable resin composition comprising a modified inorganic particle, a photoinitiator, a monomer, and an oligomer, wherein the modified inorganic particle has a sphere having a silicon atom, an amide group (-NH-CO-) To provide a resin composition.

The photocurable resin composition according to the present invention is characterized by containing modified inorganic particles having an amide group, a radical reactive group, silicon atoms and inorganic particles at the same time,

First, the amide group contained in the modified inorganic particles has a -NH- group capable of forming a hydrogen bond and a -CO- group having a polarity so that compatibility with various oligomers is improved, thereby improving the strength of the final photo-curable protective layer Can,

Secondly, since the modified inorganic particles directly participate in the photo-curing reaction due to the radical reactive groups contained in the modified inorganic particles, they are linked chemically (covalently) with monomers and oligomers in the photo-cured protective layer, (Acid resistance, alkali resistance, etc.) and scratch resistance because of the high thermal decomposition temperature of the cured film in a simple dispersion state and the excellent denseness of the film.

Thirdly, the amide group, the silicon atom and the radical reactive group contained in the modified inorganic particles serve as a surfactant between the inorganic particles and the photocurable organic compound, so that the dispersibility in the photocurable composition is good and a uniform cured film can be formed , There is an advantage that there is no variation in the physical properties by the position of the cured film,

Fourth, since the silicon atoms contained in the modified inorganic particles form SiO ₂ when exposed to high temperatures, they prevent the further combustion reaction from occurring. Therefore, it has an advantage of improving the flame retardancy and improving the heat resistance of the final cured film .

1 is a stress-strain curves of the photocurable protective film according to Example 1 of the present invention,
2 is a graph showing the hardness characteristics of the photocurable protective film according to Example 2 of the present invention.

 The present invention provides a photocurable resin composition comprising a modified inorganic particle, a photoinitiator, a monomer, and an oligomer, wherein the modified inorganic particle has a silicon atom, an amide group (-NH-CO-) Group at the same time.

Each component of the photocurable resin composition comprising the modified inorganic particles of the present invention will be described in detail as follows.

<Modified Inorganic Particles>

 In the photocurable resin composition of the present invention, the modified inorganic particle is a compound having at the same time an inorganic particle, a silicon atom, an amide group (-NH-CO-) and a radical reactive group, May be selected singly or in plural. Wherein the inorganic particles are selected from talc, mica, silica, zirconia, and metal carbonate. In addition, the radical reactive group means a carbon-carbon double bond shown in the general formula 1, a thiol group shown in the general formula 2, a disulfide group shown in the general formula 3, and a haloalkane group shown in the general formula 4 do.

[Formula 1]

Wherein R ₁ , R ₂ , R ₃ , R ₄ and R ₅ , which may be the same or different, are hydrogen; A halogen atom; A hydroxy group; An alkoxy group of C1-C30; An alkyl group of C1-C30; A C1-C30 heteroalkyl group; A C1-C30 heteroalkoxy group; An aryl group of C6-C30; An arylalkyl group of C6-C30; An aryloxy group of C6-C30; A C2-C30 heteroaryl group; A C2-C30 heteroarylalkyl group; A C2-C30 heteroaryloxy group; A C5-C20 cycloalkyl group; A C2-C30 heterocycloalkyl group; An alkyl ester group of C1-C30; A C1-C30 heteroalkyl ester group; An aryl ester group of C2-C30; And a C2-C30 heteroaryl ester group. In particular, R ₁ and R ₂ may be connected to an inorganic particle by a covalent bond, a hydrogen bond or a van der Waals bond, or may be connected to a covalent bond with another adjacent silicon atom. X ₁ and X ₂ may be the same or different from each other; sulfur; An alkylene group of C1-C30; A C1-C30 heteroalkylene group; An oxyalkylene group of C1-C30; A thioalkylene group of C1-C30; An oxyheteroalkylene group of C1-C30; A C1-C30 thio heteroalkylene group; An arylene group of C6-C30; An oxyarylene group of C6-C30; A thioarylene group of C6-C30; An arylene alkylene group of C6-C30; A C2-C30 heteroarylene group; An oxyheteroarylene group of C2-C30; A thioheteroarylene group of C2-C30; A C2-C30 heteroarylene alkylene group; C5-C20 cycloalkylene group; An oxy cycloalkylene group of C5-C20; A thio cycloalkylene group of C5-C20; A C5-C20 cycloalkylene alkylene group; A C2-C30 heterocycloalkylene group; A C2-C30 oxyheterocycloalkylene group; A thioheterocycloalkylene group of C2-C30; A thioheterocycloalkylene alkylene group of C2-C30; An alkylene ester group of C1-C30; A C1-C30 heteroalkylene ester group; An arylene ester group of C6-C30; And a C2-C30 heteroarylene ester group. Also, a and b are selected from 0 or 1, and n means the number of silicon atom, amide group and radical reactive group introduced into the inorganic particle, and is selected from 1 to 5,000.

[Formula 2]

Here, R ₁ , R ₂ , X ₁ , X ₂ , a, b, and n are the same as defined in Formula 1.

[Formula 3]

Here, R ₁ , R ₂ , X ₁ , X ₂ , a, b, and n are the same as defined in Formula 1. R &lt; ₆ &gt; is hydrogen; A halogen atom; A hydroxy group; An alkoxy group of C1-C30; An alkyl group of C1-C30; A C1-C30 heteroalkyl group; A C1-C30 heteroalkoxy group; An aryl group of C6-C30; An arylalkyl group of C6-C30; An aryloxy group of C6-C30; A C2-C30 heteroaryl group; A C2-C30 heteroarylalkyl group; A C2-C30 heteroaryloxy group; A C5-C20 cycloalkyl group; A C2-C30 heterocycloalkyl group; An alkyl ester group of C1-C30; A C1-C30 heteroalkyl ester group; An aryl ester group of C2-C30; And a C2-C30 heteroaryl ester group.

[Formula 4]

Here, R ₁ , R ₂ , X ₁ , X ₂ , a, b, and n are the same as defined in Formula 1. Y ₁ , Y ₂ and Y ₃ may be the same or different and are selected from F, Cl, Br and I.

As mentioned above, R ₁ and R ₂ may be connected to an inorganic particle by a covalent bond, a hydrogen bond or a van der Waals bond, or may be connected to another adjacent silicon atom by a covalent bond. But the present invention is not limited thereto.

Formula 1

Formula 11

(2)

Formula 12

(3)

Formula 13

Formula 4

Formula 14

Formula 5

Formula 15

6

Formula 16

Formula 7

Formula 17

8

18

Formula 9

Formula 19

10

20

The above-mentioned general formulas 1 to 4 can be easily prepared by reacting a hydroxyl group (-OH) existing on the surface of an inorganic particle with a silane coupling agent as shown in Reaction Schemes 1 to 4 below. Examples of the inorganic particles of the present invention include talc, mica, silica, zirconia or metal carbonate. These surfaces include functional groups such as hydroxyl group (-OH), ketone group (C═O), carboxyl group (-COOH) . The modified inorganic particles represented by the general formulas (1) to (4) can be prepared by reacting the hydroxyl group and the silane coupling agent present in the inorganic particles. First, the reaction medium is adjusted to a ratio of alcohol (ethanol, methanol, etc.) to distilled water at 70:20 (v / v%). Acetic acid is added thereto to adjust the pH of the reaction medium to 5. The pH-controlled reaction medium is stirred for 30 minutes and then hydrolyzed by adding the silane coupling agent. When the inorganic particles are added after the hydrolysis reaction and then reacted with stirring for several hours, the hydroxyl group of the inorganic particles and the alkoxy group (or halogen group) of the silane coupling agent react with the inorganic particles -O-Si - bonds are formed. As a result, a modified inorganic particle in which silicon atoms, amide groups and radical reactive groups are simultaneously introduced into the inorganic particles is produced. After filtration or centrifugation, the compounds of the general formulas 1 to 4 can be obtained through a vacuum drying process. If the reaction is not smooth due to insufficient content of hydroxyl groups in the inorganic particles, oxygen plasma treatment and / or UV-O ₃ treatment may be applied to the inorganic particles, or the inorganic particles may be immersed in an acidic solution, There is no problem when used in the reaction. That is, a large number of hydroxyl groups can be formed on the inorganic particles by ultrasonic treatment in an oxygen plasma, UV-O ₃ and an acidic medium. As described above, the silane coupling agent used for implementing the present invention should have a functional group capable of reacting with a hydroxyl group in a molecule (generally, a halogen atom bonded to a silicon atom, an alkoxy group, a hydroxyl group, etc.) group and a radical reactive group (carbon-carbon double bond, thiol group, disulfide group or haloalkane group) at the same time.

Examples of the inorganic particles used for implementing the modified inorganic particles of the present invention include talc, mica, silica, zirconia, metal carbonate, It is suitable to use inorganic particles of various grades of 0.1 ~ 30μm. The talc is SiO _2, MgO and H ₂ O are components of these inorganic particles, as a hydrated magnesium silicate _{(Si 2 O 5) 2 Mg} 3 (OH) 2, Si 8 Mg 6 O 20 (OH) 4 or Mg ₁₂ Si ₁₆ O ₄₀ (OH) _8, and the like. Wherein among the inorganic particles of mica is formed of _{SiO 2, TiO 2, Al 2} O 3, Fe 2 O 3, MgO, Na 2 O, K 2 O, H 2 O, F KAl 2 (Al, Si) 4 O 10 by (OH, F) muscovite (muscovite) represented by ₂ and _{SiO 2, TiO 2, Al 2} O 3, Fe 2 O 3, FeO, BaO, MgO, Na 2 O, K 2 O, H 2 O, F Phlogopite, which is represented by KMg ₃ (Al, Si) ₄ O ₁₀ (OH, F) ₂ , can be mainly used. Among the inorganic particles, silica means SiO ₂ , which is silicon oxide, and zirconia means ZrO ₂ . Among the inorganic particles, the metal carbonate is at least one selected from the group consisting of Li ₂ CO _3, Na ₂ CO _{3 ,} K ₂ CO _{3 ,} Rb ₂ CO _{3 ,} Cs ₂ CO _{3 ,} Fr ₂ CO _{3 ,} BeCO _{3 ,} MgCO _{3 ,} CaCO _{3 ,} SrCO _{3 , 3,} there may be used RaCO _3, and _{FeCO 3, CuCO 3, ZnCO 3} , MnCO 3.

[Reaction Scheme 1]

[Reaction Scheme 2]

[Reaction Scheme 3]

[Reaction Scheme 4]

The content of the modified inorganic particles may be 0.03 to 55 wt%, preferably 0.3 to 30 wt%, based on the total amount of the photocurable resin composition of the present invention. If the content of the modified inorganic particles is less than 0.03% by weight, the amount of the modified inorganic particles is too small and the effect of the additive (reinforcing agent) is insignificant. If the content is more than 55% by weight, the capability of forming a photo-

As mentioned above, the modified inorganic particle means a compound having at the same time an inorganic particle, a silicon atom, an amide group and a radical reactive group. The inorganic particles serve to improve physical properties such as scratch resistance of the protective film formed by final photo-curing. The silicon atoms contained in the modified inorganic particles form SiO ₂ when exposed to a high temperature, thereby preventing further combustion reaction, thereby improving the flame retardancy and heat resistance of the final cured film. The amide group (-NH-CO-) group contained in the modified inorganic particles has NH- and polar CO- group capable of forming a hydrogen bond, thus improving compatibility with various oligomers. In the case of urethane acrylate in the oligomer, it has good compatibility with the amide group (NH-CO-) because it has a NH-CO-O- group in the molecule, And it has excellent compatibility with amide group due to increase of intermolecular attraction due to dipole-dipole interaction with epoxy group, and OH group in epoxy acrylate has excellent compatibility with amide group and hydrogen bond. have. In addition, the radical reactive group contained in the modified inorganic particles participates in the polymerization (curing) reaction when radical polymerization is caused by light, so that all the monomer, oligomer and inorganic particles are connected by chemical bonds, (Protective film) to prevent the film from diffusing from the film. The silicon atom, the amide group and the radical reactive group serve as a surfactant for preventing agglomeration between the inorganic particles and the inorganic particles, so that the dispersibility in the photo-curable composition is improved. The mechanism by which these radical reactive groups participate in the photo-curing reaction is as follows.

   The following reaction formula 5 corresponds to the case where the radical reactive group is a carbon-carbon double bond. Since the growing polymer radical attacks a carbon-carbon double bond to form a new radical, the inorganic particles are chemically bonded (covalently bonded) .

[Reaction Scheme 5]

When a polymer is prepared by radical polymerization, the growth radical reacts with other materials in the reaction system to form a dead polymer, and the addition of the monomer to the newly formed radical is initiated, ). Thiol, disulfide, and haloalkane groups are examples of such a chain transfer reaction. Since the S-H bond of the thiol group and the S-S bond of the disulfide group are weak, they are easily decomposed by the growing polymer radical or the initiator radical to form a new radical (-S.) While forming a dead polymer. The new radical (-S ·) formed reacts with the surrounding monomers or oligomers to continue the polymerization reaction. In addition, a chain transfer reaction occurs well in the case of a haloalkane, since a new radical generated by a chain transfer reaction is resonantly stabilized by a non-covalent electron pair (3 pairs of unpaired electron pairs per halogen atom) contained in a halogen atom to be. The new radicals thus formed react with the surrounding monomers or oligomers to continue the polymerization reaction.

   The reaction scheme 6 corresponds to the case where the radical reactive group is a thiol group, and the growing polymer radical reacts with the thiol (SH) group to stop the growth and form a new radical (-S.), As the polymerization proceeds with the surrounding monomer or oligomer, the inorganic particles are chemically (covalently) linked to the monomer and / or oligomer.

[Reaction Scheme 6]

Reaction Scheme 7 corresponds to the case where the radical reactive group is a disulfide group, and the growing polymer radical reacts with SS- to stop the growth and form a new radical (-S.), As the polymerization proceeds with the oligomer, the inorganic particles are chemically bonded (covalently bonded) with the monomer and / or oligomer.

[Reaction Scheme 7]

The following Reaction Scheme 8 corresponds to the case where the radical reactive group is a haloalkane group, and the growing polymer radical reacts with the haloalkane group to stop the growth and to form a new radical, which causes polymerization reaction with the surrounding monomer or oligomer The inorganic particles are chemically bonded (covalently bonded) with the monomer and / or the oligomer.

[Reaction Scheme 8]

As described above, the radical reactive groups contained in the modified inorganic particles participate in the photo-curing reaction so that the monomer, the oligomer, and the inorganic particles are all connected by the chemical bond. As a result, the inorganic particles are diffused from the cured film (protective film) It plays a role of preventing. In addition, when the modified inorganic particles according to the present invention are used, the dispersion in the photo-curable composition is much easier than when the unmodified pure inorganic particles are used, so that a cured film free from agglomerates of inorganic particles can be realized. Since there is no agglomerate of the inorganic particles in this way, it has an advantage of being excellent in film uniformity as well as having excellent transmittance.

<Optical Initiator >

In the photocurable resin composition of the present invention, the photoinitiator may be a radical polymerization type benzophenone based compound, an acetophenone based compound, a benzoin ether based compound, a thioxanthone based compound, a triazine based compound, a nonimidazole based compound, It should be understood that the present invention is well known to those skilled in the art so that it can be purchased commercially and used singly or in combination. Examples include 1-hydroxy-cyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2- 1-propanone, methylbenzoylformate, oxy-phenyl-acetic acid 2- [2-oxo-2phenyl-acetoxy-ethoxy] phenylamino] -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2 Bis (2,4,6-trimethylbenzoyl) phosphine oxide, phenyl bis (2,4,6-trimethylbenzoyl) phosphine oxide, bis (eta 5-2,4-cyclopentadien -1-yl), bis [2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl] titanium, iodonium, (4-methylphenyl) [4- (2-methylpropyl) phenyl] -hexafluorophosphate -), but are not limited thereto.

   The content of the photoinitiator may be 0.1 to 10 wt%, preferably 0.1 to 5 wt%, based on the total amount of the photocurable resin composition of the present invention. When the content of the photoinitiator is less than 0.1% by weight, the amount of radicals generated is small and the photo-curable resin composition can not be effectively reacted. When the content exceeds 10% by weight, initiator fragments are present in the final photo- As shown in FIG.

<Monomer>

In the photocurable resin composition of the present invention, the monomer may be monofunctional, bifunctional or polyfunctional, and may be an aromatic vinyl compound, an unsaturated carboxylic acid ester, an unsaturated carboxylic acid aminoalkyl ester, an unsaturated carboxylic acid glycidyl And may be selected from the group consisting of esters, carboxylic acid vinyl esters, unsaturated ethers, unsaturated amides, aliphatic conjugated dienes, unsaturated oxetanecarboxylate compounds, and fluorine-substituted compounds. Specific examples include tetrahydrofurfuryl (meth) acrylate, perlyl (meth) acrylate, benzyl 2-propyl (meth) acrylate, ethylene glycol phenyl ether (meth) acrylate, 2-hydroxy- Acrylates such as methyl (meth) acrylate, propyl (meth) acrylate, benzyl (meth) acrylate, phenyl methacrylate, Styrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p- methoxystyrene, o-vinylbenzyl methyl ether, Benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n- Acrylate, n-propyl methacrylate propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec- butyl methacrylate Acrylate, methacryloxypropyleneglycol methacrylate, methacryloxypropyleneglycol methacrylate, methacryloxypropyleneglycol methacrylate, isobornyl acrylate, isobornyl acrylate, isobornyl acrylate, isobornyl acrylate, Aminopropyl methacrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl methacrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropylacrylate, 2- Aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropylacrylate, 3-amyl Acrylate, 3-methyl-3-acryloxymethyloxetane, 3-methyl-3-methylaminopropyl methacrylate, glycidyl acrylate, glycidyl methacrylate, Ethyl-3-acryloxymethyloxetane, 3-ethyl-3-methacryloxymethyloxetane, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, acrylonitrile Methacrylonitrile, N-2-hydroxyethylacrylamide, N-2-hydroxyethylmethacrylamide, N-2-hydroxyethylmethacrylamide, , Maleimide, N-phenylmaleimide, N-cyclohexylmaleimide, 1,3-butadiene, isoprene, chloroprene, 2,2,3,3,4,4,5,5,6,6,7,7 (Dodecafluoroheptyl (meth) acrylate, 3,3,4,4,5,5,6,6,7,8,8,8-dodecafluoro-7- Octyl (meth) acrylate, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12, 12-heneicosafluorododecyl (meth) acrylate, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,12 , 12,12-Eicosa fluoro-11- (trifluoromethyl) dodecyl (meth) acrylate, 3,4,4,5,5,6,6,7,7,8,8,9,9 , 10,10,10-heptadecafluorodecyl (meth) acrylate, 2,2,3,3,4,4,4-heptafluorobutyl (meth) acrylate, 4,4,5,5,5- Hexadecafluoro-2-hydroxy-10- (trifluoromethyl) undecyl (meth) acrylate, 6,6,7,7,8,8,9,9,10,11,11,11- 3,3,4,4,5,5,6,6,7,7,8,8,9,10,10,10-hexadecafluoro-9- (trifluoromethyl) decyl (meth) acrylate (Meth) acrylate, 2,2,3,4,4,4-hexafluorobutyl (meth) acrylate, 1,1,1,3,3,3-hexafluoroisopropyl (meth) , 5,5,6,7,7,7-octafluoro-2-hydroxy-6- (trifluoromethyl) heptyl methacrylate, 2,2,3,3,4,4,5,5 - octafluor Pentyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) , 3-butafluoropropyl (meth) acrylate, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-2-hydroxy-6- (Meth) acrylate, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl (meth) acrylate, 2,2,2 (Meth) acrylate, 1,1,1-trifluoro-2- (trifluoromethyl) -2-hydroxy-4-methyl- (Meth) acrylate, 4,4,5,6-trichloro-2- (trifluoromethyl) -2'-hydroxypropyl] (Meth) acrylate, 1H, 1H, 2H, 2 H (2H, m, 2H) - perfluorodecyl (meth) acrylate, 4,4,5,5,6,6,7,7,8,8,9,9,9-tridecafluoro-2-hydroxynonyl Acrylate), and the like. On the other hand, a monoacryloyl group or monoacryloyl group at the end of the polymer molecular chain of polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly- And the like are also included in the scope of the present monomers. In addition, poly (ethylene glycol) diacrylate, trimethylolpropane triacrylate, di (trimethylolpropane) tetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate and the like, such as polyfunctional 1,6-hexanediol diacrylate, tripropylene glycol diacrylate, 3,4,5,6 functional monomers are also included in this category of monomers.

   The content of the monomer may be 5 to 70 wt%, preferably 10 to 50 wt%, based on the total amount of the photocurable resin composition of the present invention. When the content of the monomer is less than 5% by weight, it is difficult to dissolve the oligomer, initiator, etc. constituting the photocurable resin composition, so that the homogeneous photo-crosslinking reaction can not proceed. When the monomer content is more than 70% by weight, Sufficient durability can not be ensured.

<Oligomer>

   In the photocurable resin composition of the present invention, the oligomer may be monofunctional, bifunctional or polyfunctional and may be an epoxy acrylate, a urethane acrylate, a polyester acrylate, a urethane-based modified epoxy acrylate, a polyether acrylate, , Silicone acrylates, melamine acrylates, acrylic acrylates, polythiol acrylate derivatives, and polythiocyanate acetal acrylates, and the like can be commercially available and used for those having ordinary skill in the art , And they may be used alone or in combination of two or more. Examples of such oligomers include, but are not limited to, those of Cytec's EBECRYL 230, EBECRYL 242, EBECRYL 264, EBECRYL 265, EBECRYL 270, EBECRYL 284, EBECRYL 1290, EBECRYL 4833, EBECRYL 4858, EBECRYL 4883, EBECRYL 5129, EBECRYL 8210, EBECRYL 8296, EBECRYL 8301-R , EBECRYL 8309, EBECRYL 8311, EBECRYL 8402, EBECRYL 8405, EBECRYL 8411, EBECRYL 8412, EBECRYL 8414, EBECRYL 8465, EBECRYL 8501, EBECRYL 8701, EBECRYL 8702, EBECRYL 8800, EBECRYL, EBECRYL 8800-20R, EBECRYL 8804, EBECRYL 8807, EBECRYL 8808, EBECRYL 220, EBECRYL 4827, EBECRYL 4849, EBECRYL 80, EBECRYL 81, EBECRYL 450, EBECRYL 657, EBECRYL 809, EBECRYL 810, EBECRYL 812, EBECRYL 830, EBECRYL 838, EBECRYL 870, EBECRYL 885, EBECRYL 888, EBECRYL 889 , EBECRYL 891, EBECRYL 893, EBECRYL 600, EBECRYL 605, EBECRYL 608, EBECRYL 3200, EBECRYL 3201, EBECRYL 3300, EBECRYL 3415, EBECRYL 3500, EBECRYL 3600, EBECRYL 3700, EBECRYL 3701, EBECRYL 3702, EBECRYL 3703, EBECRYL 3708, 3720, and the like.

   The content of the oligomer may be 15 to 85 wt%, preferably 20 to 60 wt%, based on the total amount of the photocurable resin composition of the present invention. If the content of the oligomer is less than 15% by weight, the crosslinking density is low and it is difficult to exhibit sufficient physical properties. If the amount of the oligomer is more than 85% by weight, the viscosity is high and the workability is decreased or the content of the modified inorganic particles is decreased, There may be a problem.

In the photocurable resin composition of the present invention, at least one member selected from the group consisting of a solvent, a silane coupling agent, a polymer compound, a filler, a defoaming agent, a thickening agent, an antioxidant and a heat resistance improver, in addition to the modified inorganic particles, photoinitiator, Lt; / RTI &gt; material.

<Solvent>

In the photocurable resin composition of the present invention, since the monomer is often in a liquid state at room temperature, the use of an additional solvent is not necessary, When the components constituting the composition are not easily dissolved in the monomer or when the monomer exhibits a solid phase at room temperature, it may further comprise a solvent as an additive. The solvent may include water, ethanol, methanol, tetrahydrofuran, acetone, methyl ethyl ketone, ethyl ether, dimethyl ether, dichloromethane, tetrachloromethane, chloroform, benzene, toluene, xylene, But is not limited thereto.

< Silane coupling agent >

The modified inorganic particles can be prepared by the reaction of the inorganic particles with the silane coupling agent, and the conventional silane coupling agent can be added as other additives. That is, a silane coupling agent may be added to improve adhesion between the final cured film obtained from the photocurable resin composition of the present invention and various substrates, and a functional group capable of reacting with a hydroxyl group in the molecule (generally, A carbon-carbon double bond, a thiol group, a disulfide group, or a haloalkane group] at the same time as the above-mentioned compound (a compound having a halogen atom, an alkoxy group, a hydroxy group, etc.) Can be used. The silane coupling agent added to the photo-curable composition reacts with the hydroxyl group present on the substrate and the alkoxy group (or halogen atom, hydroxyl group) of the silane coupling agent to introduce a silane coupling agent onto the substrate surface. When the photo curing proceeds, the radical reactive groups constituting the silane coupling agent participate in the photo-curing reaction, so that the substrate and the final cured film are chemically bonded (covalently bonded) so that the adhesion between the substrate and the cured film is greatly improved. Typical example, vinyltrimethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropyl methyldimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl methyldiethoxysilane, 3-methacryloxypropyl triethoxysilane, 3-acryloxypropyl trimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, and the like, but are not limited thereto.

&Lt; Polymer compound &

In order to compensate the physical properties of the final cured film obtained from the photocurable resin composition of the present invention, a polymer compound may be further included. The polymer compound used in this case includes, but is not limited to, an epoxy resin, an acrylic resin, a melamine resin, a phenol resin, a polyester, a polyurethane, a polyamide and the like.

< Filler >

In order to increase the mechanical strength of the final cured film obtained from the photocurable resin composition of the present invention, a filler may be included, and carbon black, alumina, silicate and the like may be used, but the present invention is not limited thereto.

<Defoamer>

In order to remove the bubbles contained in the photocurable resin composition of the present invention, a defoaming agent may be included. Examples of the defoaming agent include a mineral oil defoamer, a silicone defoamer, a polymer defoamer, and the like.

< Incrementer >

In order to control the viscosity of the photocurable resin composition of the present invention, an increasing agent may be included, and potassium carbomer, potassium chloride, modified cellulose, polyethylene glycol, and the like may be used. Do not.

<Antioxidant>

Antioxidants may be included to improve the oxidation resistance of the final cured film obtained from the photocurable resin composition of the present invention, and bisphenol, polyphenol, thiobisphenol, 2,6-di-t-butyl-4-methylphenol, 2,6-di Hindered phenols, aromatic amines (p-phenylenediamine, diphenylamine), hydroxylamine (bis-tallow amine, methyl-bis-tallow amine), benzofuranones such as -tert-butyl-p-cresol, (2,4-di-tert-butylpyridine), thiodipropionic acid, tris (2,4-di-tert-butylphenyl) phosphate, thiourea, tri- (nonylphenyl) phosphite, sulfinic acid, sulfonic acid, sulfur trioxide, -butylphenyl) -phosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylnediaphosphonite, areoxalylbis (benzylidene) hydrazide, N, 4-hydroxy hydrocinnamoylhydrazine), 2,2'-oxamidobis-ethyl (3,5-di-tert-butyl-4-hydroxyhydrocinnamate), N, N '- (disalicylidene) peroxide decomposer such as hylenediaminetetra-acetic acid, and the like may be used, but the present invention is not limited thereto.

<Heat resistance Enhancer >

(Si-O-Si) -based compounds may be included in order to further improve the heat resistance of the final cured film obtained from the photocurable resin composition of the present invention, and trans- cyclohexane diol isobutyl POSS (polyhedral oligomeric silsesquioxane) propane diol isobutyl POSS, octa (3-hydroxy-3-methylbutyldimethylsiloxy) POSS, aminopropyl isobutyl POSS, aminoethyl aminopropyl isobutyl POSS, epoxy cyclohexyl isobutyl POSS, epoxy cyclohexyl POSS, glycidyl ethyl POSS, triglycidyl cyclohexyl POSS, trifluoropropyl isobutyl POSS, Such as acrylonitrile butyrate POSS, acrylo isobutyl POSS, methacryl isobutyl POSS, methacrylate isobutyl POSS, methacrylate isooctyl POSS, methacryl phenyl POSS, dodecaphenyl POSS, phenyl isobutyl POSS, octatrimethylsiloxy POSS, norbornenylethyl ethyl POSS, allyl isobutyl POSS, Oxalic acid, siloxane-based polymers, and ladder-like polysilsesquioxanes. But is not limited thereto.

   The photocurable resin composition containing modified inorganic particles according to the present invention may contain various kinds of metals such as a protective coating layer for various metal, non-metal, wood and plastic surfaces, a protective coating layer for strengthening glass, a passivation layer for thin film transistor, Application to various fields such as encapsulation layer of organic light emitting diode, color filter and black matrix of liquid crystal display, transparent electrode for electronic device, gas barrier layer of flexible substrate for flexible electronic device But is not limited thereto.

 Hereinafter, the photocurable resin composition containing the modified inorganic particles of the present invention will be described in detail with reference to Examples. However, the present invention is not limited to the following Examples.

Example 1

First, 1.6 g of phenyl bis (2,4,6-trimethylbenzoyl) phosphine oxide as a photoinitiator was added to 20.3 g of? -Methylstyrene as a monomer, and the mixture was stirred for 1 hour to dissolve the mixture. Tripropylene glycol diacrylate Respectively. Subsequently, 3.5 g of the modified inorganic particles (modified talc) of the following structural formula 1 was added and dispersed by stirring for 2 hours. Then, 88.2 g of bifunctional aromatic urethane acrylate (EBECRYL 210) as an oligomer was added to prepare Photo- Respectively. The prepared photocurable composition was coated on top of the glass substrate by spin coating (2000 rpm, 30 seconds), and then placed in an exposure apparatus of a nitrogen atmosphere to irradiate light (365 nm) Was prepared. Also, a photocurable composition 1-2 was prepared using the structural formula 2 instead of the structural formula 1, and a photocurable protective layer containing the structural formula 2 was prepared in the same manner as described above. On the other hand, a photocurable composition 1-3 containing pure talc was prepared separately instead of the modified talc (structural formula 1), coated on a glass substrate by a spin coating method, and photocured to prepare a protective film. The prepared three kinds of protective films were desorbed from the glass substrate and then added to 50 mL of tetrahydrofuran solvent to swell the protective film. After ultrasonic treatment for 1 hour, the films were allowed to stand for 24 hours. After 24 hours, the swollen protective layer was vacuum dried and mass was measured to calculate the mass change before and after swelling. As a result, when the photo-curable composition 1-1 was used, the mass loss of the photo-curable composition 1-2 was 0.05% and the mass decrease of the photo-curable composition 1-2 was 0.27%. appear. The modified inorganic particles according to the present invention participate in the photo-curing reaction and are chemically bonded (covalently bonded) with the monomer, oligomer, etc. in the photo-curing protective layer, so that the modified inorganic particles are not diffused from the protective film and discharged to the outside under the swelling condition by the solvent Could know. Comparing the photocurable compositions 1-1 and 1-2, the mass loss was smaller than that in the case of not having an amide group (-NH-CO- group) (structural formula 1) (structural formula 2) It was found that the amide group and the aromatic urethane acrylate were more strongly bonded by hydrogen bonding.

   The stress-strain characteristics of the protective film prepared under the above three conditions were analyzed using a universal testing machine, and the results are shown in FIG. As can be seen from FIG. 1, the protective film produced from the structural formula 1 exhibited the greatest strain and stress, and the least when the unmodified talc (photocurable composition 1-3) was used. In the case of using the structural formula 2, that is, in the case of not including the amide group, the stress-strain characteristic was superior to that of the unmodified talc, but the characteristic was lower than that of the structural formula 1. From this, it was confirmed that the presence of the amide group formed stronger bonds by the hydrogen bonding and the dipole interaction with the -NH-CO-O- group contained in the oligomer, so that it was not torn easily.

[Structural formula 1]

Includes both silicon, amide groups and photoreactive groups

[Structural formula 2]

Containing amide groups, i.e., only silicon and photoreactive groups

Example  2

0.5 g of 2-benzyl-2- (dimethylamino) -1- [4- (4-morphonyl) phenyl] -1-butanone as a photoinitiator was added to 7.4 g of 2-hydroxy-3-phenoxypropyl acrylate as a monomer And the mixture was stirred for 1 hour to dissolve. Then, 4.2 g of pentaerithritol triacrylate was added as a second monomer. Then, 5.7 g of modified inorganic particles (modified mica) of the following structural formula 3 were added and dispersed by stirring. Then, 26.4 g of bifunctional aliphatic urethane acrylate (EBECRYL 270) was added as an oligomer. In addition, 1.3 g of a silane coupling agent (3-mercaptopropylmethylsilane) was added as another additive in order to improve adhesion to the glass substrate to prepare a photo-curing composition 2-1. The prepared photocurable composition was coated on the top of the glass substrate by spin coating (2000 rpm, 30 seconds), and the resultant was placed in an exposure apparatus of a nitrogen atmosphere, and light (320 nm) Was prepared. In addition, a photocurable composition 2-2 was prepared by using the structural formula 4 instead of the structural formula 3, and a photocurable protective layer containing the structural formula 4 was prepared in the same manner as described above. On the other hand, a photocurable composition 2-3 was prepared by adding pure mica (inorganic particles) in place of the modified mica (structural formula 3), coated on a glass substrate by a spin coating method, and photocured to prepare a protective film. The protective film / glass substrate thus prepared was added to 60 mL of tetrahydrofuran solvent to swell the protective film. After ultrasonic treatment for 1 hour, the film was allowed to stand for 24 hours. After 24 hours, the swollen protective layer was vacuum dried and mass was measured to calculate the mass change before and after swelling. As a result, the mass loss of the photocurable composition 2-1 was 0.09%, the mass loss of the photocurable composition 2-2 was 0.33%, but the mass loss of the photocurable composition 2-3 was 8.45% Respectively. From this, the modified inorganic particles (modified mica) of the present invention participates in the photo-curing reaction and is chemically bonded (covalently bonded) with the monomer, oligomer or the like in the photocurable protective film, so that it diffuses from the protective film in the swelling condition by the solvent, And it was found that it was not discharged. Comparing the photocurable compositions 2-1 and 2-2, the mass loss was smaller than that in the case of not having the amide group (-NH-CO- group) (formula 3) (formula 4) It was found that the amide bond and the aliphatic urethane acrylate are more strongly bonded by the hydrogen bond.

   From this, the modified inorganic particles of the present invention participate in the photo-curing reaction and are chemically bonded (covalently bonded) with monomers, oligomers and the like in the cured film, so that they are diffused from the cured film under the swelling condition by the solvent, Could know. In addition, microscopic observation was performed to evaluate the dispersibility of the inorganic particles present in the cured film. As a result, aggregation of inorganic particles was not observed in the case of the photocurable composition 2-1 as shown in Fig. 1 (a) In the case of the photocuring composition 2-2, aggregation of inorganic particles was observed as shown in Fig. 1 (b). From these results, it was found that the modified inorganic oxide oxide sheet had excellent dispersibility in the photo-curable composition, and after the photo-curing, cohesion did not occur because it was covalently bonded to the monomer, oligomer and the like.

[Structural Formula 3]

Includes both silicon, amide groups and photoreactive groups

[Structural Formula 4]

Containing amide groups, i.e., only silicon and photoreactive groups

The hardness characteristics of the protective film prepared under the above three conditions were measured using a Shore A hardness meter, and the results are shown in FIG. The amount of inorganic particles was varied from 0 to 20 wt% relative to the photocurable resin, and a photocurable protective film was prepared and used for hardness measurement. As can be seen from FIG. 2, the protective film prepared from the structural formula 3 (the photo-curable composition 2-1 containing modified mica) had the best hardness characteristics, and the use of the unmodified mica (photo-curable composition 2-3) Respectively. In the case of using the structural formula 4, that is, in the case of not containing an amide group, the hardness characteristic was superior to that of the unmodified mica (photocurable composition 2-3), but the characteristic was lower than that of the structural formula 3. From this, it was found that the presence of the amide group formed stronger bonds by the hydrogen bonding and the dipole interaction with the -NH-CO-O- group contained in the urethane acrylate oligomer, and thus the hardness characteristics were better. Also, it was confirmed that the hardness characteristics were increased with the increase of the inorganic particle content.

Example  3

As a monomer, 3.1 g of 1-hydroxy-cyclohexyl-phenyl-ketone as a photoinitiator was added to 20.3 g of methacrylonitrile, followed by stirring for 1 hour to dissolve the monomer. 19.3 g of pentaerithritol tetraacrylate was added as a second monomer . Subsequently, 10.6 g of the modified inorganic particles (modified silica) of the following structural formula 5 was added and dispersed by stirring for 5 hours. Then, 59.1 g of bifunctional epoxy acrylate (EBECRYL 3500) was added as an oligomer. Further, in order to remove bubbles, 0.4 g of a silicone-based defoaming agent was added as another additive to prepare a photo-curing composition 3-1. The prepared photocurable composition was coated on top of the glass substrate by spin coating (1500 rpm, 30 seconds), and then placed in an exposure apparatus of a nitrogen atmosphere to irradiate light (254 nm) Was prepared. Also, a photocurable composition 3-2 was prepared by using the structural formula 6 instead of the structural formula 5, and a photocurable protective layer containing the structural formula 6 was prepared in the same manner as described above. On the other hand, a photocurable composition 3-3 was prepared by adding pure silica (inorganic particles) in place of the above-mentioned modified silica (structural formula 5), separately coated on a glass substrate by a spin coating method, and photocured to prepare a protective film. The stress-strain characteristics of the photocurable protective films prepared from the above three compositions were analyzed using a universal testing machine. The destructive stress of the protective layer by the photo-curable composition 3-1 was 2.4 MPa, and the deformation of the protective layer was 93%. The protective layer of the photo-curable composition 3-2 showed 1.7 MPa and 75% The protective film of Composition 3-3 showed 0.9 MPa and 61%. From this, it was found that when the radical reactive group and the amide group were present at the same time, the breaking strength was much larger, and the OH group contained in the amide group and the epoxy oligomer included in the structural formula 5 formed a strong bond by hydrogen bonding and dipole interaction, .

[Structural Formula 5]

Includes both silicon, amide groups and photoreactive groups

[Structural Formula 6]

Containing amide groups, i.e., only silicon and photoreactive groups

Example  4

0.9 g of 2-benzyl-2- (dimethylamino) -1- [4- (4-morpholinyl) phenyl] -1-butene as a photoinitiator was added to 10.4 g of 2-aminopropyl methacrylate as a monomer, And 4.1 g of ditrimethylolpropane tetraacrylate as a second monomer was added thereto. Subsequently, 7.1 g of the modified inorganic particles (modified calcium carbonate) of the following structural formula 7 was added and dispersed by stirring for 3 hours. Then, 40.7 g of trifunctional polyester acrylate (EBECRYL 884) was added as an oligomer. Further, in order to enhance the denseness of the cured film, 3.2 g of melamine resin was added as another additive, and 0.7 g of a silane coupling agent (p-styryltriethoxysilane) was added as another additive to improve adhesion to the glass substrate, -1. The prepared photocurable composition was coated on the top of the glass substrate by spin coating (1500 rpm, 30 seconds), and the resultant was placed in an exposure apparatus of a nitrogen atmosphere, and light (324 nm) Was prepared. Also, a photocurable composition 4-2 was prepared by using the structural formula 8 instead of the structural formula 7, and a photocurable protective layer containing the structural formula 8 was prepared in the same manner as described above. Meanwhile, a photocurable composition 4-3 prepared by adding pure calcium carbonate (inorganic particles) in place of the modified calcium carbonate (structural formula 7) was separately prepared, coated on a glass substrate by a spin coating method, and photocured to prepare a protective film Respectively. The stress-strain characteristics of the photocurable protective films prepared from the above three compositions were analyzed using a universal testing machine. The destructive stress of the protective layer by the photo-curable composition 4-1 was 2.5 MPa, and the deformation of the protective layer by the photo-curable composition 4-1 was 92%. The protective layer by the photo-curing composition 4-2 was 1.9 MPa and 77% The protective film of the composition 4 - 3 showed 0.8 MPa and 63%. From this, it was found that when the radical reactive group and the amide group were present at the same time, the breaking strength was much larger, which formed stronger bonds by the dipole interaction of the amide group included in the structural formula 7 and the CO-O- It was confirmed that it was not torn easily.

[Structural Formula 7]

Includes both silicon, amide groups and photoreactive groups

[Structural formula 8]

Containing amide groups, i.e., only silicon and photoreactive groups

Example  5

A photocurable protective film was prepared under the same conditions except that the structural formulas 3 and 4 of Example 2 were changed to the following structural formulas 9 and 10, respectively, and the stress-strain characteristics were measured using a universal testing machine. Respectively. The destructive stress of the photocurable protective film including the structural formula 9 was 2.7 MPa, and the strain at this time was 94%. In the protective film containing the structural formula 10, 1.8 MPa and 76% were exhibited, and unmodified zirconia was included The protective film showed 0.9 MPa and 61%. From this, it was found that when the radical reactive group and the amide group were present at the same time, the fracture strength was much larger, which was due to the fact that the amide group contained in the structural formula 9 and the NH-CO-O- group (urethane group) It is confirmed that the stronger bond is formed by the action and the tear is not easily touched.

[Structural Formula 9]

Includes both silicon, amide groups and photoreactive groups

[Structural Formula 10]

Containing amide groups, i.e., only silicon and photoreactive groups

Claims (7)

Wherein the modified inorganic particle is at least one selected from the general formulas 2 to 4 having at least the inorganic particles, the silicon atom, the amide group and the radical reactive group at the same time, wherein the modified inorganic particles are selected from the group consisting of modified inorganic particles, photoinitiators, monomers and oligomers .
[Formula 2]

Here, R1 and R2 are the same or different and represent hydrogen; A halogen atom; A hydroxy group; An alkoxy group having 1 to 30 carbon atoms; An alkyl group having 1 to 30 carbon atoms; A heteroalkyl group having 1 to 30 carbon atoms; A heteroalkoxy group having 1 to 30 carbon atoms; An aryl group having 6 to 30 carbon atoms; An arylalkyl group having 6 to 30 carbon atoms; An aryloxy group having 6 to 30 carbon atoms; A heteroaryl group having 2 to 30 carbon atoms; A heteroarylalkyl group having from 2 to 30 carbon atoms; A heteroaryloxy group having from 2 to 30 carbon atoms; A cycloalkyl group having 5 to 30 carbon atoms; A heterocycloalkyl group having from 2 to 30 carbon atoms; An alkyl ester group having 1 to 30 carbon atoms; A heteroalkyl ester group having 1 to 30 carbon atoms; An aryl ester group having 2 to 30 carbon atoms; And a heteroaryl ester group having 2 to 30 carbon atoms. Here, R1 and R2 may be connected to an inorganic particle by a covalent bond, a hydrogen bond or a van der Waals bond, or may be connected to a covalent bond with another adjacent silicon atom. X1 and X2 may be the same or different and are selected from the group consisting of oxygen; sulfur; An alkylene group having 1 to 30 carbon atoms; A heteroalkylene group having 1 to 30 carbon atoms; An oxyalkylene group having 1 to 30 carbon atoms; A thioalkylene group having 1 to 30 carbon atoms; An oxyheteroalkylene group having 1 to 30 carbon atoms; A thio heteroalkylene group having 1 to 30 carbon atoms; An arylene group having 6 to 30 carbon atoms; An oxyarylene group having 6 to 30 carbon atoms; A thioarylene group having 6 to 30 carbon atoms; An arylene alkylene group having 6 to 30 carbon atoms; A heteroarylene group having 2 to 30 carbon atoms; An oxyheteroarylene group having 2 to 30 carbon atoms; A thioheteroarylene group having 2 to 30 carbon atoms; A heteroarylene alkylene group having 2 to 30 carbon atoms; A cycloalkylene group having 5 to 30 carbon atoms; An oxy cycloalkylene group having 5 to 30 carbon atoms; A thio cycloalkylene group having 5 to 30 carbon atoms; A cycloalkylene alkylene group having 5 to 30 carbon atoms; A heterocycloalkylene group having from 2 to 30 carbon atoms; An oxyheterocycloalkylene group having 2 to 30 carbon atoms; A thio heterocycloalkylene group having 2 to 30 carbon atoms; A thio heterocycloalkylene alkylene group having 2 to 30 carbon atoms; An alkylene ester group having 1 to 30 carbon atoms; A heteroalkylene ester group having 1 to 30 carbon atoms; An arylene ester group having 6 to 30 carbon atoms; And a heteroarylene ester group having 2 to 30 carbon atoms. Also, a and b are selected from 0 or 1, and n means the number of silicon atom, amide group and radical reactive group introduced into the inorganic particle, and is selected from 1 to 5,000.
[Formula 3]

Here, R1, R2, X1, X2, a, b and n are the same as defined in the general formula 2. R6 is hydrogen; A halogen atom; A hydroxy group; An alkoxy group having 1 to 30 carbon atoms; An alkyl group having 1 to 30 carbon atoms; A heteroalkyl group having 1 to 30 carbon atoms; A heteroalkoxy group having 1 to 30 carbon atoms; An aryl group having 6 to 30 carbon atoms; An arylalkyl group having 6 to 30 carbon atoms; An aryloxy group having 6 to 30 carbon atoms; A heteroaryl group having 2 to 30 carbon atoms; A heteroarylalkyl group having from 2 to 30 carbon atoms; A heteroaryloxy group having from 2 to 30 carbon atoms; A cycloalkyl group having 5 to 30 carbon atoms; A heterocycloalkyl group having from 2 to 30 carbon atoms; An alkyl ester group having 1 to 30 carbon atoms; A heteroalkyl ester group having 1 to 30 carbon atoms; An aryl ester group having 2 to 30 carbon atoms; And a heteroaryl ester group having 2 to 30 carbon atoms.
[Formula 4]

Here, R1, R2, X1, X2, a, b and n are the same as defined in the general formula 2. Y1, Y2 and Y3 may be the same or different and are selected from F, Cl, Br and I.
The method according to claim 1,
Wherein the inorganic particle is at least one selected from the group consisting of talc, mica, silica, zirconia, and metal carbonate.
The method according to claim 1,
The photoinitiator may be selected from the group consisting of 1-hydroxy-cyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2- 1-propanone, methylbenzoylformate, oxy-phenyl-acetic acid 2- [2-oxo-2phenyl-acetoxy-ethoxy] phenylamino] -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2 Bis (2,4,6-trimethylbenzoyl) phosphine oxide, phenyl bis (2,4,6-trimethylbenzoyl) phosphine oxide, bis (eta 5-2,4-cyclopentadien 1-yl), bis [2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl] titanium, iodonium, (4-methylphenyl) &Lt; / RTI &gt; or more.
The method according to claim 1,
The monomer is one to six functional and is an aromatic vinyl compound, an unsaturated carboxylic acid ester, an unsaturated carboxylic acid aminoalkyl ester, an unsaturated carboxylic acid glycidyl ester, a carboxylic acid vinyl ester, an unsaturated ether , Unsaturated amides, aliphatic conjugated dienes, unsaturated oxetanecarboxylate compounds, fluorine-substituted monomers, and macromolecular monomers.
The method according to claim 1,
The oligomer is 1 to 6 functional and is selected from the group consisting of epoxy acrylate, urethane acrylate, polyester acrylate, urethane based modified epoxy acrylate, polyether acrylate, acrylic acrylate, silicone acrylate, melamine acrylate, polythiol acrylate Derivatives, and polythiol acetal-based acrylates. &Lt; Desc / Clms Page number 13 &gt; The method according to claim 1,
Wherein the photocurable composition further comprises an additive, wherein the additive is at least one selected from the group consisting of a solvent, a silane coupling agent, a polymer compound, a filler, a defoaming agent, an additive, an antioxidant and a heat resistance improver.
A photocurable film produced by the composition of any one of claims 1 to 6.

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