KR102470542B1 - Photocurable coating composition and coating layer - Google Patents

Abstract

The present invention relates to a photocurable coating composition and a coating film, and the photocurable coating composition can form a coating film having high transparency and excellent flexibility, surface hardness and adhesion. In addition, due to the excellent physical properties of the coating film, it can be applied in various fields using photocuring systems such as flexible displays, liquid crystal displays, OLED displays, molded products, coatings, and dental materials.

Description

Photocurable coating composition and coating film {PHOTOCURABLE COATING COMPOSITION AND COATING LAYER}

The present invention relates to a photocurable coating composition and a coating film, and the photocurable coating composition can form a coating film having high transparency and excellent flexibility, surface hardness and adhesion.

Recently, electronic device manufacturers are continuously attempting to employ flexible displays. When a flexible display is introduced into an electronic device, the scalability of the screen can be greatly increased because the display screen can be folded or unfolded. In order to commercialize such a flexible display, each layer, substrate material, and various electrode materials constituting the display, especially AMOLED, must have durability against repeated bending. In particular, the cover material constituting the outermost layer has high surface hardness. and flexibility at the same time.

As described above, in order to have flexibility, it is necessary to control the shrinkage that occurs during curing, and among the known monomers, monomers with low volumetric shrinkage include spiro orthocarbonate (SOC) and spiro orthoester (SOE). ), bicyclo orthoester (BOE), cyclic ether, cyclic acetal, cyclic allyl acetal, and vinyl cyclopropane. Among them, SOC compounds that are easy to manufacture are attracting attention, and are being developed for use in reinforcing composite materials including dental materials (Refer to Korean Patent Publication Nos. 2001-0101854 and 2009-0087933).

On the other hand, a photopolymer that reacts with a mechanism in which a difference in polymerization occurs depending on the intensity of light is usually composed of an acrylic monomer or an epoxy monomer, an oligomer, an initiator, and a polymer binder. Films made of acrylic monomers have high applicability, but suffer from severe shrinkage after curing by light or heat, and films made of epoxy-based monomers have low shrinkage but low reactivity. Therefore, in order to improve this, it is necessary to develop a novel photopolymerizable monomer having excellent reactivity during curing, high polymerization efficiency, and low shrinkage rate.

Republic of Korea Patent Publication No. 2001-0101854 Republic of Korea Patent Publication No. 2009-0087933

Therefore, the present inventors have completed the present invention by developing a photocurable coating composition comprising a spiro structure compound and a siloxane structure compound capable of controlling curing shrinkage.

An object of the present invention is to provide a composition for photocuring coating having excellent flexibility, surface hardness and adhesion while having high transparency.

Another object of the present invention is to provide a coating film prepared from the photocurable coating composition.

The present invention relates to one or more spiro compounds selected from the group consisting of Formulas 1 to 5; and at least one siloxane compound selected from the group consisting of the following formulas 6 to 8:

In the above formula,

X is oxygen or -CHR ¹ -;

n is an integer of 2 or 3;

m is an integer of 1 or 2;

l is an integer from 1 to 20;

R ¹ to R ¹³ are each independently hydrogen, C _1-4 alkyl, C _2-5 alkenyl, C _1-4 alkyl substituted or unsubstituted acrylate, C _6-14 aryl, epoxy, Glycidyl, C _3-8 cycloalkyl, C _4-8 epoxycycloalkyl, epoxy group substituted or unsubstituted alcohol, or halogen atom or phenyl substituted or unsubstituted C _1-10 alkoxy C _1- an alkyl of ₄ ;

R ¹⁴ is C _1-5 alkoxy, C _1-4 alkyl with or without epoxy group, C _1-4 alkyl substituted with C _4-8 epoxycycloalkyl, (meth)acrylate C _1-4 of alkyl or C _2-5 of alkenyl.

In addition, the present invention provides a coating film prepared using the photocurable coating composition.

The photocurable coating composition of the present invention includes a spiro compound and a siloxane compound and can prepare a coating film having excellent surface hardness and flexibility through UV curing.

In addition, the coating film formed from the composition of the present invention has high transparency and excellent surface hardness, adhesion, flexibility, etc., and can effectively prevent cracks or interface detachment due to shrinkage during curing, so that flexible displays, liquid crystal displays, It can be applied in a variety of fields using photocuring systems such as OLED displays, molded products, coatings, and dental materials.

The photocurable coating composition of the present invention includes at least one spiro compound selected from the group consisting of Formulas 1 to 5; and at least one siloxane compound selected from the group consisting of Formulas 6 to 8 below:

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

In the above formula,

X is oxygen or -CHR ¹ -;

n is an integer of 2 or 3;

m is an integer of 1 or 2;

l is an integer from 1 to 20;

R ¹ to R ¹³ are each independently hydrogen, C _1-4 alkyl, C _2-5 alkenyl, C _1-4 alkyl substituted or unsubstituted acrylate, C _6-14 aryl, epoxy, Glycidyl, C _3-8 cycloalkyl, C _4-8 epoxycycloalkyl, epoxy group substituted or unsubstituted alcohol, or halogen atom or phenyl substituted or unsubstituted C _1-10 alkoxy C _1- an alkyl of ₄ ;

R ¹⁴ is C _1-5 alkoxy, C _1-4 alkyl with or without epoxy group, C _1-4 alkyl substituted with C _4-8 epoxycycloalkyl, (meth)acrylate C _1-4 of alkyl or C _2-5 of alkenyl.

spiro compound

The spiro compound is at least one selected from the group consisting of Chemical Formulas 1 to 5. At this time, X is oxygen or -CHR ¹ -, n is an integer of 2 or 3, m is an integer of 1 or 2, R ¹ to R ¹³ are each independently hydrogen, C _1-4 alkyl, C _{2 -5} alkenyl, C _1-4 alkyl substituted or unsubstituted acrylate, C _6-14 aryl, epoxy, glycidyl, C _3-8 cycloalkyl, C _4-8 epoxycycloalkyl , Epoxy group is substituted or unsubstituted alcohol, or halogen element or phenyl is substituted or unsubstituted C _1-10 alkoxy C _1-4 alkyl.

또는

일 수 있다. 보다 구체적으로, 상기 스파이로 화합물은 하기 화학식 9 내지 14로 이루어진 군으로부터 선택된 1종 이상일 수 있다:Specifically, the spiro compound has a structure of Formula 4 or 5, wherein X is oxygen, m is 1, and R ⁹ to R ¹³ are each independently hydrogen, methyl, phenyl, naphthyl, or epoxy , glycidyl, acrylate, methacrylate,

or

can be More specifically, the spiro compound may be one or more selected from the group consisting of Formulas 9 to 14 below:

일 수 있다. 구체적으로, 상기 스파이로 화합물은 하기 화학식 15 내지 18로 이루어진 군으로부터 선택된 1종 이상일 수 있다:In addition, the spiro compound has a structure of Formula 1, wherein X is oxygen or -CH ₂ -, n is 3, and R ² and R ³ are each independently hydrogen, methyl, propoxymethyl, phenylethoxymethyl or

can be Specifically, the spiro compound may be one or more selected from the group consisting of Formulas 15 to 18 below:

The spiro compound is prepared by a known method, for example, Chul-bae kim, et al., Applied Chemistry . 2001, 5, 248-251 can be synthesized by the method described. In addition, the spiro compound synthesized or prepared by a conventional method as described above can be confirmed by GC-MS, ¹ H-NMR and ¹³ C-NMR, and in particular, the central carbon characteristic of SOC compounds is It appears around 155 ppm in ¹³ C-NMR.

Siloxane compound

The siloxane compound is at least one selected from the group consisting of Chemical Formulas 6 to 8. At this time, l is an integer from 1 to 20, R ¹⁴ is C _1-5 alkoxy C _1-4 alkyl, C _4-8 epoxycycloalkyl substituted C _1-4 epoxy group is substituted or unsubstituted. Alkyl, (meth)acrylate C _1-4 alkyl or C _2-5 alkenyl.

Specifically, R ¹⁴ may be glycidyl ether propanyl, epoxycyclohexylethyl, methacrylate ethyl, or ethylene. More specifically, R ¹⁴ may be one selected from the group consisting of Formulas 19 to 22 below:

The siloxane compound may have a weight average molecular weight of 1,000 to 50,000.

Furthermore, whether the siloxane compound is synthesized can be confirmed through IR, ¹ H-NMR, and ²⁹ Si-NMR. Confirm the Si-OH content appearing around 3,000 to 3,400 cm ^-1 through IR analysis, Si-O appearing around 1,000 to 1,100 cm ^-1 and Si-O-Si peak observed at 1,100 to 1,200 cm ^-1 location can be checked. In addition, by using ¹ H-NMR, it was confirmed that all the alkoxy parts of the alkoxy monomers were -OH and condensed, and by observing T1, T2 and T3 structures such as Si-OH and Si-OCH ₃ through ²⁹ Si-NMR synthesis can be checked.

The photocurable coating composition may include a spiro compound and a siloxane compound in a weight ratio of 1:0.3 to 1:19 or 1:0.5 to 1:9.

The coating composition may further include additives such as an initiator, a solvent, a leveling agent, and the like, which may be included in conventional photocuring coating compositions. Specifically, 30 to 80% by weight of the solvent based on the total weight of the coating composition may be included. In addition, 1 to 10 parts by weight of an initiator and 0.05 to 5 parts by weight of a leveling agent may be included based on 100 parts by weight of the coating composition.

initiator

As the initiator, any one of commercially available initiators may be selected and used. Specifically, the initiator may be any one selected from the group consisting of a thermal initiator, a cationic initiator, a radical initiator, and a photoinitiator depending on the curing system, and in the case of a dual curing system, a mixture of thermal initiator and photoinitiator It is possible.

Examples of the photoinitiator include benzoin methyl ether, benzoin isopropyl ether, anisoin methyl ether, benzoin, and benzyl ketal. In addition, the cationic initiator is, for example, hexafluoroantimonate, diphenyl (4-phenylthio) phenylsulfonium hexafluorophosphate, (phenyl) [4- (2-methylpropyl) phenyl] -iodonium Hexafluorophosphate, (thiodi-4,1-phenylene)bis(diphenylsulfonium) dihexafluoroantimonate, triphenylsulfonium triflate or (thiodi-4,1-phenylene)bis( diphenylsulfonium) dihexafluorophosphate; and the like. Furthermore, the thermal initiator may be, for example, a peroxide system including benzoyl peroxide; azobisisobutyronitrile, amine type, etc. are mentioned.

menstruum

The solvent includes monohydric alcohols, polyhydric alcohols, alkyl ethers of polyhydric alcohols, alkyl ether acetates of polyhydric alcohols, ethers, cyclic ethers, alkanes, alkoxyalkanes, aromatic hydrocarbons, ketones, esters and Solvents selected from the group consisting of water may be used alone or in combination of two or more.

Examples of the monohydric alcohol include 1-butyl alcohol, 2-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, tert-amyl alcohol, Neopentyl alcohol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-3-pentanol, cyclopentanol, 1-hexanol, 2-hexanol, 3-hexanol, 2, 3-dimethyl-2-butanol, 3,3-dimethyl-1-butanol, 3,3-dimethyl-2-butanol, 2-diethyl-1-butanol, 2-methyl-1-pentanol, 2-methyl- 2-pentanol, 2-methyl-3-pentanol, 3-methyl-1-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, 4-methyl-3-pentanol, cyclohexanol, 2,6-dimethyl-4-heptanol, 3,5,5-trimethyl-1-hexanol, 1-nonanol , 1-decanol, methyl-n-octylcarbinol, ethylheptylcarbinol, hexylpropylcarbinol, amylbutylcarbinol, 2-undecanol, 3-undecanol, 4-undecanol, 5-undecanol, 3 and monohydric alcohols having 4 to 11 carbon atoms such as ,7-dimethyl-1-octanol.

The polyhydric alcohols, for example, ethylene glycol, propylene glycol, 4-hydroxy-4-methyl-2-pentanol, 2-ethyl-1,3-hexanediol, 1,3-butanediol, 1,2 -Propanediol, 1,3-propanediol, 1,2-heptanediol, etc., may be a dihydric alcohol having 4 to 8 carbon atoms.

Examples of the polyhydric alcohol alkyl ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol ethylmethyl ether, and propylene glycol monomethyl ether. ether, propylene glycol monoethyl ether, and the like.

Examples of the polyhydric alcohol alkyl ether acetates include ethylene glycol ethyl ether acetate, diethylene glycol ethyl ether acetate, propylene glycol ethyl ether acetate, and propylene glycol monomethyl ether acetate.

The ethers include, for example, diethyl ether, dipropyl ether, diisopropyl ether, butyl methyl ether, butyl ethyl ether, butyl propyl ether, dibutyl ether, diisobutyl ether, tert-butyl-methyl ether, tert-butylethyl ether, tert-butylpropyl ether, di-tert-butyl ether, dipentyl ether, diisoamyl ether, cyclopentylmethyl ether, cyclohexylmethyl ether, cyclopentylethyl ether, cyclohexylethyl ether, cyclopentyl Propyl ether, cyclopentyl-2-propyl ether, cyclohexyl propyl ether, cyclohexyl-2-propyl ether, cyclopentyl butyl ether, cyclopentyl-tert-butyl ether, cyclohexyl butyl ether, cyclohexyl-tert-butyl ether, etc. can

The cyclic ethers may be, for example, tetrahydrofuran or dioxane.

The alkanes may be, for example, decane, dodecane, and undecane.

The alkoxy alkanes may be dialkoxyalkanes, trialkoxyalkanes, or tetraalkoxyalkanes having 3 to 16 carbon atoms. The alkoxy alkanes include, for example, dimethoxymethane, diethoxymethane, dibutoxymethane, trimethoxymethane, triethoxymethane, tripropoxymethane, 1,1-dimethoxyethane, 1,2-dimethoxymethane. Toxyethane, 1,1-diethoxyethane, 1,2-diethoxyethane 1,2-dibutoxyethane, 1,1,1-trimethoxyethane, 1,1-diethoxypropane, 2,2-dimethane Toxypropane, 2,2-diethoxypropane, 1,1-diethoxyisobutane, 1,5-dimethoxypentane, 1,6-dimethoxyhexane, 1,1-dimethoxyoctane, 1-dimethoxydodecane , bis(2-ethoxyethyl) ether, bis(2-methoxyethyl) ether, and the like.

Examples of the aromatic hydrocarbons include benzene, toluene, xylene, and the like, and examples of the ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 4-hydroxy-4 -Methyl-2-pentanone, diacetone alcohol, etc. may be used.

The esters, for example, ethyl acetate, butyl acetate, 2-hydroxy ethyl propionate, 2-hydroxy-2-methyl methyl propionate, 2-hydroxy-2-methyl ethyl propionate, ethoxy ethyl acetate, hydroxy Ethyl hydroxyacetate, 2-hydroxy-3-methylmethylbutanoate, 3-methoxymethylpropionate, 3-methoxyethylpropionate, 3-ethoxyethylpropionate, 3-ethoxymethylpropionate, butyrolactone, caprolactone etc.

More specifically, the solvent may be monohydric alcohols, ethers, cyclic ethers, alkyl ethers of polyhydric alcohols, alkyl ether acetates of polyhydric alcohols, ketones or aromatic hydrocarbons, more specifically, having 9 to 11 carbon atoms. of monohydric alcohol; alkyl ethers of polyhydric alcohols having 4 to 10 carbon atoms; ketones having 2 to 6 carbon atoms; or aromatic hydrocarbons having 6 to 10 carbon atoms.

leveling agent

Commercial products of the leveling agent include BYK 371, BYK 377, BYK 353, BYK 356, BYK 359, BYK 361, BYK 067, and BYK 141 manufactured by BYK-Chemie, Tego Rad 2200, Tego Rad 2500, and Tego Glide manufactured by Tego Chemie. 410, Tego Glide 435 and Tego Glide 453, and TS 100 and OK 607 manufactured by Daeguusa.

coating film

The present invention provides a coating film obtained by coating and curing the photocurable coating composition as described above.

The coating is performed by spin coating, wet coating, spray coating, dip coating, roll coating, slow-die coating of the composition for photocuring coating of the present invention on a substrate such as an object to be coated, for example, a silicon wafer, glass substrate, plastic film, etc. It may be performed by coating by a method such as coating or bar coating.

Any method that can be conventionally used for photocuring may be used without particular limitation, and for example, it may be cured with a metal halide lamp, a high-pressure mercury lamp, a mercury short arc lamp, or an ultraviolet lamp.

The coating film has high transparency and excellent surface hardness, adhesion, flexibility, etc., so it can be applied in various fields using photocuring systems such as flexible displays, liquid crystal displays, OLED displays, molded products, coatings, and dental materials. can

Hereinafter, the present invention will be described in more detail by examples and experimental examples. However, the following examples and experimental examples are only for exemplifying the present invention, and the scope of the present invention is not limited only to these.

[ Example ]

synthesis example 1. Preparation of spiro compounds

In a reactor, 2-(2-oxiranyloxy)propane-1,3-diol (349 g) and dibutyltin oxide (655 g) ) was added and dissolved by adding 120 ml of toluene. After connecting a dean-stark trap to the reactor and creating a nitrogen atmosphere, the reactor was refluxed for 3 hours to remove water (47 g). Then, 4-chloromethyl-1,3-dioxolane-2-thione (400g) was added and stirred at room temperature for 4 hours. Thereafter, 1000 ml of toluene was added, washed with distilled water, and the solvent was removed under reduced pressure to obtain a compound of Chemical Formula 9 (Spyro).

synthesis example 2. Preparation of spiro compounds

2-(7-oxabicyclo[4.1.0]hepta-3-yl)propane-1,3-diol (2- Except for using (7-oxabicyclo[4.1.0]heptan-3-yl)propane-1,3-diol) (448 g), a spiro compound was prepared in the same manner as in Synthesis Example 1, Got the compound as a spy.

synthesis example 3. Preparation of spiro compounds

Except for using 2-methyl-1,3-propanediol (234 g) instead of 2-(2-oxiranyloxy)propane-1,3-diol (349 g) Then, a spiro compound of Formula 11 was obtained by preparing a spiro compound in the same manner as in Synthesis Example 1.

synthesis example 4. Preparation of spiro compounds

Except for using 2-phenylpropane-1,3-diol (396 g) instead of 2-(2-oxiranyloxy)propane-1,3-diol (349 g) Then, a spiro compound of Formula 12 was obtained by preparing a spiro compound in the same manner as in Synthesis Example 1.

synthesis example 5. Preparation of spiro compounds

Except for using 1,2,3-propanetriol (239 g) instead of 2-(2-oxiranyloxy)propane-1,3-diol (349 g), A spiro compound was prepared in the same manner as in Synthesis Example 1 to obtain an intermediate (2-methylene-1,4,6,10-tetraoxaspiro[4.5]decan-8-ol).

Thereafter, triethylamine (223 g) and toluene (2,000 ml) were added to the intermediate (328 g). Thereafter, the mixture was cooled to 5° C. in an argon atmosphere, and distilled methacryloyl chloride (209 g) and toluene (700 ml) were added dropwise thereto. Then, after stirring at room temperature for 18 hours, amine hydrochloride precipitate was removed by filtration. Then, the solvent was removed under reduced pressure to obtain the compound of formula 13 as spiro.

synthesis example 6. Preparation of spiro compounds

3,3-oxetane dimethanol (30.7 g) and dibutyltin oxide (65.5 g) were put in a reactor, and toluene (1,200 ml) was added to dissolve them. Thereafter, a Dean Stark trap was connected to the reactor, a nitrogen atmosphere was created, and water (4.7 g) was removed by refluxing for 3 hours. After adding 4-chloromethyl-1,3-dioxolane-2-thione (40 g), the mixture was stirred at room temperature for 4 hours. Potassium tert-butoxide (70 g) was added to the obtained product, and the mixture was stirred at room temperature for 6 hours. Thereafter, 1,000 ml of toluene was added, washed with distilled water, and the solvent was removed under reduced pressure to obtain a spiro compound of Chemical Formula 14.

synthesis example 7. Preparation of spiro compounds

1-propanol (233.5 g), epichlorohydrin (70.5 g), sodium hydroxide (24.8 g) and water (8.4 g) were put into a reactor, and the mixture was stirred at 400 rpm at high speed using a stirrer at 25 ° C. for 12 hours. . Then, the solvent was removed under reduced pressure to obtain a residue.

To the residue was added ε-caprolactone (23.3 g) and BF ₃ O(CH ₂ CH ₃ ) ₂ (132 mL, 6 mol% aqueous solution) under CCl ₄ (75 g). Then, 2-(propoxymethyl)oxirane (93.5 g) was added under CCl ₄ (75 g) and stirred at 0 °C for 1 hour. The mixture was allowed to stand for 6 hours after the addition of (CH ₃ CH ₂ ) ₃ N (150 mL, 6 mol% aqueous solution) at 0-5 °C. Thereafter, the organic layer was separated to obtain a spyro compound of Chemical Formula 15.

synthesis example 8. Preparation of spiro compounds

Synthesis, except that 1H,1H,2H,2H-perfluorodecan-1-ol (1H,1H,2H,2H-perfluorodecan-1-ol) (233.5 g) was used instead of 1-propanol (233.5 g). A spiro compound of Formula 16 was obtained by preparing a spiro compound in the same manner as in Example 6.

synthesis example 9. Preparation of spiro compounds

A spiro compound of Formula 17 was obtained by preparing a spiro compound in the same manner as in Synthesis Example 6, except that 2-phenylethanol (233.5 g) was used instead of 1-propanol (233.5 g).

synthesis example 10. Siloxane synthesis of compounds

(3-glycidyloxypropyl)trimethoxy silane ((3-glycidyloxypropyl)trimethoxy silae) (236.3 g) was dissolved in 82.74 ml of toluene, water (16.2 g) and acetic acid (0.54 g) were added and the mixture was stirred at room temperature. The mixture was hydrolyzed by stirring for 3 hours. After adding (3-glycidyloxypropyl)trimethoxysilane (45 g) and 150 ml of methanol to the hydrolyzate, sodium bicarbonate (3.34 g) was added and refluxed for 8 hours. Thereafter, the reactants were distilled under reduced pressure to obtain a siloxane compound represented by Chemical Formula 6 in which R ¹⁴ is Chemical Formula 19.

synthesis example 11. Siloxane synthesis of compounds

2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (246.3 g) was dissolved in tetrahydrofuran (THF) (250.4 g), and water (18.0 g) and sodium bicarbonate (3.01 g) were added and stirred at room temperature for 12 hours. Thereafter, the reactants were distilled under reduced pressure to obtain a siloxane compound represented by Chemical Formula 6 in which R ¹⁴ is Chemical Formula 20.

synthesis example 12. Siloxane synthesis of compounds

Vinyltrimethoxysilane (204.5 g) was dissolved in 32.79 ml of toluene and 32.79 ml of isopropanol, water (72 g) and sodium bicarbonate (12.1 g) were added, and the mixture was stirred at room temperature for 12 hours. Thereafter, the reactants were distilled under reduced pressure to obtain a siloxane compound represented by Chemical Formula 6 in which R ¹⁴ is Chemical Formula 22.

Experimental example One.

The weight average molecular weight and molecular formula of the spiro compounds prepared in Synthesis Examples 1 to 9 and the siloxane compounds prepared in Synthesis Examples 10 to 12 were determined using GC-MS spectroscopy (manufacturer: Waters), and nuclear magnetic resonance spectroscopy (NMR) ) (Manufacturer: Varian) and FT-IR (manufacturer: PerkinElmer) were used to obtain ¹ H-NMR and ¹³ C-NMR spectra of the Spiro compounds of Synthesis Examples 1 to 9. In addition, ¹ H-NMR and ²⁹ Si-NMR spectra of the siloxane compounds of Synthesis Examples 10 to 12 were obtained.

Example One. photocuring Preparation of composition for coating

4% by weight of the spiro compound (compound of Formula 9) prepared in Synthesis Example 1, 36% by weight of the siloxane compound prepared in Synthesis Example 10, and 30% by weight of propylene glycol monomethyl ether as a diluent, methyl 10% by weight of ethyl ketone, 10% by weight of ethyl acetate and 10% by weight of toluene were mixed and stirred at room temperature for 30 minutes to obtain a mixture. Subsequently, 3 parts by weight of triphenylsulfonium triflate as an initiator was added to 100 parts by weight of the mixture, and the mixture was stirred for 20 minutes. Thereafter, 0.1 part by weight of BYK 377 (BYK Chemie, Germany) was added as a leveling agent based on 100 parts by weight of the mixture, and stirred and mixed for 10 minutes to prepare a photocuring coating composition.

Example 2.

A photocurable coating composition was prepared in the same manner as in Example 1, except that the Spiro compound of Synthesis Example 2 (the compound of Formula 10) was used instead of the Spiro compound of Synthesis Example 1.

Example 3.

A photocurable coating composition was prepared in the same manner as in Example 1, except that the Spiro compound of Synthesis Example 6 (the compound of Formula 10) was used instead of the Spiro compound of Synthesis Example 1.

Example 4.

4% by weight of the spiro compound (compound of Formula 12) prepared in Synthesis Example 4, 36% by weight of the siloxane compound (compound of Formula 20) prepared in Synthesis Example 11 and 30% by weight of propylene glycol monomethyl ether as a diluent, methyl 10% by weight of ethyl ketone, 10% by weight of ethyl acetate and 10% by weight of toluene were mixed and stirred at room temperature for 30 minutes to obtain a mixture. 3 parts by weight of triphenylsulfonium triflate as a photocuring initiator was added to 100 parts by weight of the mixture and stirred for 20 minutes. Thereafter, 0.1 part by weight of BYK 377 (BYK Chemie, Germany) was added to 100 parts by weight of the mixture and stirred and mixed for 10 minutes to prepare a photocuring coating composition.

Example 5.

A photocurable coating composition was prepared in the same manner as in Example 4, except that the Spiro compound of Synthesis Example 5 (the compound of Formula 13) was used instead of the Spiro compound of Synthesis Example 4.

Example 6.

A photocurable coating composition was prepared in the same manner as in Example 4, except that the Spiro compound of Synthesis Example 8 (the compound of Formula 16) was used instead of the Spiro compound of Synthesis Example 4.

Example 7.

A photocurable coating composition was prepared in the same manner as in Example 4, except that the Spiro compound of Synthesis Example 9 (the compound of Formula 17) was used instead of the Spiro compound of Synthesis Example 4.

Example 8.

4% by weight of the spiro compound (compound of Formula 11) prepared in Synthesis Example 3, 36% by weight of the siloxane compound (compound of Formula 22) prepared in Synthesis Example 12, and 30% by weight of propylene glycol monomethyl ether as a diluent, methyl 10% by weight of ethyl ketone, 10% by weight of ethyl acetate and 10% by weight of toluene were mixed and stirred at room temperature for 30 minutes to obtain a mixture. 3 parts by weight of Irgacure 184 (Ciba, Germany) as a photocuring initiator was added to 100 parts by weight of the mixture, followed by stirring for 20 minutes. Thereafter, 0.1 part by weight of BYK 377 (BYK Chemie, Germany) was added to 100 parts by weight of the mixture and stirred and mixed for 10 minutes to prepare a photocuring coating composition.

Example 9.

A photocurable coating composition was prepared in the same manner as in Example 8, except that the Spiro compound of Synthesis Example 4 (the compound of Formula 12) was used instead of the Spiro compound of Synthesis Example 3.

Example 10.

12 wt% of the spiro compound (compound of Formula 13) prepared in Synthesis Example 5, 28 wt% of the siloxane compound (compound of Formula 22) prepared in Synthesis Example 12, and 30 wt% of propylene glycol monomethyl ether as a diluent, methyl 10% by weight of ethyl ketone, 10% by weight of ethyl acetate and 10% by weight of toluene were mixed and stirred at room temperature for 30 minutes to obtain a mixture. 3 parts by weight of Irgacure 184 (Ciba, Germany) as a photocuring initiator was added to 100 parts by weight of the mixture, followed by stirring for 20 minutes. Thereafter, 0.1 part by weight of BYK 377 (BYK Chemie, Germany) was added to 100 parts by weight of the mixture and stirred and mixed for 10 minutes to prepare a photocuring coating composition.

Example 11.

12 wt% of the spiro compound (compound of Formula 15) prepared in Synthesis Example 7, 28 wt% of the siloxane compound (compound of Formula 19) prepared in Synthesis Example 10, and 30 wt% of propylene glycol monomethyl ether as a diluent, methyl 10% by weight of ethyl ketone, 10% by weight of ethyl acetate and 10% by weight of toluene were mixed and stirred at room temperature for 30 minutes to obtain a mixture. Then, 3 parts by weight of triphenylsulfonium triflate as an initiator was added to 100 parts by weight of the mixture, and the mixture was stirred for 20 minutes. Thereafter, 0.1 part by weight of BYK 377 (BYK Chemie, Germany) was added to 100 parts by weight of the mixture and stirred and mixed for 10 minutes to prepare a photocuring coating composition.

Example 12.

A photocurable coating composition was prepared in the same manner as in Example 11, except that the Spiro compound of Synthesis Example 6 (the compound of Formula 14) was used instead of the Spiro compound of Synthesis Example 7.

Example 13.

A photocurable coating composition was prepared in the same manner as in Example 11, except that the Spiro compound of Synthesis Example 8 (the compound of Formula 16) was used instead of the Spiro compound of Synthesis Example 7.

Example 14.

12 wt% of the spiro compound (compound of Formula 15) prepared in Synthesis Example 7, 28 wt% of the siloxane compound (compound of Formula 20) prepared in Synthesis Example 11, and 30 wt% of propylene glycol monomethyl ether as a diluent, methyl 10% by weight of ethyl ketone, 10% by weight of ethyl acetate and 10% by weight of toluene were mixed and stirred at room temperature for 30 minutes to obtain a mixture. 3 parts by weight of triphenylsulfonium triflate as a photocuring initiator was added to 100 parts by weight of the mixture and stirred for 20 minutes. Thereafter, 0.1 part by weight of BYK 377 (BYK Chemie, Germany) was added to 100 parts by weight of the mixture and stirred and mixed for 10 minutes to prepare a photocuring coating composition.

Example 15.

A photocurable coating composition was prepared in the same manner as in Example 14, except that the Spiro compound of Synthesis Example 2 (the compound of Formula 10) was used instead of the Spiro compound of Synthesis Example 7.

Example 16.

12 wt% of the spiro compound (compound of Formula 11) prepared in Synthesis Example 3, 28 wt% of the siloxane compound (compound of Formula 22) prepared in Synthesis Example 12, and 30 wt% of propylene glycol monomethyl ether as a diluent, methyl 10% by weight of ethyl ketone, 10% by weight of ethyl acetate and 10% by weight of toluene were mixed and stirred at room temperature for 30 minutes to obtain a mixture. 3 parts by weight of Irgacure 184 (Ciba, Germany) as a photocuring initiator was added to 100 parts by weight of the mixture, followed by stirring for 20 minutes. Thereafter, 0.1 part by weight of BYK 377 (BYK Chemie, Germany) was added to 100 parts by weight of the mixture and stirred and mixed for 10 minutes to prepare a photocuring coating composition.

Example 17.

A photocurable coating composition was prepared in the same manner as in Example 16, except that the Spiro compound of Synthesis Example 4 (the compound of Formula 12) was used instead of the Spiro compound of Synthesis Example 3.

Example 18.

A photocurable coating composition was prepared in the same manner as in Example 16, except that the Spiro compound of Synthesis Example 5 was used instead of the Spiro compound of Synthesis Example 3.

Example 19.

A photocurable coating composition was prepared in the same manner as in Example 11, except that a compound having the structure of Chemical Formula 18 (obtained from Chemtik) was used as the spiro compound.

Example 20.

A photocurable coating composition was prepared in the same manner as in Example 19, except that the siloxane compound of Synthesis Example 11 was used as the siloxane compound.

comparative example One.

40% by weight of the spiro compound of Synthesis Example 3 and 30% by weight of propylene glycol monomethyl ether, 10% by weight of methyl ethyl ketone, 10% by weight of ethyl acetate, and 10% by weight of toluene as a diluent were mixed and stirred at room temperature for 30 minutes. A mixture was obtained. Thereafter, 3 parts by weight of Irgacure 184 (Ciba, Germany) was added as an initiator to 100 parts by weight of the mixture, followed by stirring for 20 minutes. A coating composition was prepared by adding 0.1 part by weight of BYK 377 (BYK Chemie, Germany) as a leveling agent to 100 parts by weight of the mixture and stirring and mixing for 10 minutes.

comparative example 2.

A coating composition was prepared in the same manner as in Comparative Example 1, except that the Spiro compound of Synthesis Example 5 was used instead of the Spiro compound of Synthesis Example 3.

comparative example 3.

A mixture of 40% by weight of the siloxane compound of Synthesis Example 12 and 30% by weight of propylene glycol monomethyl ether, 10% by weight of methyl ethyl ketone, 10% by weight of ethyl acetate and 10% by weight of toluene as a diluent and stirred at room temperature for 30 minutes was obtained. Then, Irgacure 184 (ciba, Germany) by weight was added as an initiator to 100 parts by weight of the mixture and stirred for 20 minutes. A coating composition was prepared by adding 0.1 part by weight of BYK 377 (BYK Chemie, Germany) as a leveling agent to 100 parts by weight of the mixture and stirring and mixing for 10 minutes.

comparative example 4.

A photocurable coating composition was prepared in the same manner as in Example 17, except that UP118 from ENTIS was used instead of the siloxane compound.

comparative example 5.

A photocurable coating composition was prepared in the same manner as in Example 18, except that U15HA from Kyoeisha Chemical was used instead of the siloxane compound.

comparative example 6.

A photocurable coating composition was prepared in the same manner as in Example 15, except that DGEBA (diglycidyl ether of bisphenol-A, manufacturer: Kukdo Chemical, product name: YD128) was used instead of the siloxane compound.

comparative example 7.

A photocurable coating composition was prepared in the same manner as in Example 14, except that DGEBA (diglycidyl ether of bisphenol-A, manufacturer: Kukdo Chemical, product name: YD128) was used instead of the spiro compound.

Experimental example 2. on the coating film Evaluation of physical properties for

2-1: of coating film Produce

Polyethylene terephthalate (250 μm in thickness) was used as a base material for the coating. After washing the surface of the substrate with isopropyl alcohol, the compositions of Examples 1 to 20 and Comparative Examples 1 to 7 were spin coated. At this time, the temperature was maintained at 25 °C and humidity at 50%.

The coated substrate was dried at 60° C. for 3 minutes using a dryer, and a UV lamp was irradiated with a light intensity of 1,000 mJ/cm 2 to prepare a coating film.

2-2: Evaluation method

Coating films prepared from the compositions of Examples 1 to 20 and Comparative Examples 1 to 7 were evaluated for the following items. The test specimen was cut into 100 mm × 100 mm (width × length) and used, and the evaluation results are shown in Tables 1 and 2 below.

1) Surface hardness: measured according to ASTM D 3502 (pencil hardness tester).

2) Flexibility: After 12 hours of coating, the coated surface was bent in a 20 pie cylinder for 5 seconds, and then the presence or absence of cracks was determined.

3) Adhesion: evaluated according to ASTM D 3359.

4) Transparency: Transmittance was measured with a hazemeter (NDH7000, manufactured by NIPPON DENSHOKU).

surface hardness flexibility adhesion transparency Example 1 6H radish 5B 90.5 Example 2 5H radish 5B 91.1 Example 3 7H radish 5B 91.5 Example 4 6H radish 5B 90.6 Example 5 6H radish 5B 90.8 Example 6 7H radish 3B 91.2 Example 7 7H radish 5B 90.9 Example 8 6H radish 5B 91.1 Example 9 6H radish 5B 91.0 Example 10 5H radish 5B 90.5 Example 11 4H radish 5B 91.0 Example 12 6H radish 5B 90.9 Example 13 6H radish 2B 91.0 Example 14 5H radish 5B 90.7 Example 15 6H radish 5B 90.8 Example 16 5H radish 5B 91.2 Example 17 6H radish 5B 91.0 Example 18 5H radish 5B 90.8 Example 19 7H radish 5B 91.4 Example 20 7H radish 5B 91.0

surface hardness flexibility adhesion transparency Comparative Example 1 B radish 5B 90.7 Comparative Example 2 H radish 5B 91.1 Comparative Example 3 7H you 2B 91.2 Comparative Example 4 H you 5B 90.6 Comparative Example 5 3H you 5B 90.8 Comparative Example 6 HB radish 5B 91.1 Comparative Example 7 4H you 4B 91.2

As shown in Tables 1 and 2, it was confirmed that the coating film prepared from the photocurable coating composition containing the spiro compound and the siloxane compound of the present invention had excellent surface hardness and adhesion. In particular, the coating film prepared from the composition of the examples has high transparency and excellent surface hardness, adhesion, flexibility, etc., and can effectively prevent cracks or interface detachment due to shrinkage during curing, so that flexible displays, liquid crystal displays, It can be applied in a variety of fields using photocuring systems such as OLED displays, molded products, coatings, and dental materials.

On the other hand, the coating films prepared from the photocurable coating compositions of Comparative Examples 1 to 7 had a surface hardness of B or less, or lacked flexibility due to a lot of shrinkage after coating, so they were not suitable as films for flexible displays.

Claims (8)

A spiro compound represented by Formula 1 below; And one or more siloxane compounds selected from the group consisting of Formulas 6 to 8 below,
The weight ratio of the spiro compound and the siloxane compound is 1: 2.33 to 1: 9, photocurable coating composition:
[Formula 1]

[Formula 6]

[Formula 7]

[Formula 8]

In the above formula,
X is oxygen or -CH ₂ -;
n is 3;
R ² and R ³ are each independently hydrogen, methyl, propoxymethyl, phenylethoxymethyl or

ego,
R ¹⁴ is C _1-5 alkoxy, C _1-4 alkyl with or without epoxy group, C _1-4 alkyl substituted with C _4-8 epoxycycloalkyl, (meth)acrylate C _1-4 of alkyl or C _2-5 of alkenyl.
At least one spiro compound selected from the group consisting of Formulas 4 and 5; And one or more siloxane compounds selected from the group consisting of Formulas 6 to 8 below,
The weight ratio of the spiro compound and the siloxane compound is 1: 2.33 to 1: 9, photocurable coating composition:
[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

In the above formula,
X is oxygen;
m is 1;
R ⁹ to R ¹³ are each independently hydrogen, methyl, phenyl, naphthyl, epoxy, glycidyl, acrylate, methacrylate,

or

ego,
R ¹⁴ is C _1-5 alkoxy, C _1-4 alkyl with or without epoxy group, C _1-4 alkyl substituted with C _4-8 epoxycycloalkyl, (meth)acrylate C _1-4 of alkyl or C _2-5 of alkenyl.
According to claim 2,
The spiro compound is at least one selected from the group consisting of Formulas 9 to 14, a composition for photocuring coating:
[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

delete According to claim 1,
The spiro compound is at least one selected from the group consisting of Formulas 15 to 18, a composition for photocuring coating:
[Formula 15]

[Formula 16]

[Formula 17]

[Formula 18]

According to claim 1 or 2,
Wherein R ¹⁴ is glycidyl ether propanyl, epoxycyclohexylethyl, ethylene or

Phosphorus, a composition for photocuring coating.
delete A coating film prepared using the photocurable coating composition of any one of claims 1 or 2.