WO2018199450A1 - Photo-curable composition for coating and coating film - Google Patents

Abstract

The present invention relates to a photo-curable composition for coating and a coating film, wherein the photo-curable composition for coating can form a coating film having high transparency and excellent flexibility, surface hardness, and adhesion. In addition, the coating film can be variously applied, due to excellent physical properties thereof, in several fields using a photo-curing system, such as a flexible display, a liquid crystal display, an OLED display, a molded product, an overlay, and a dental material.

Description

Photocurable coating composition and coating film

The present invention relates to a photocurable coating composition and a coating film, the photocurable coating composition may have a high transparency and at the same time can form a coating film excellent in flexibility, surface hardness and adhesion.

Recently, electronic device manufacturers are continuously trying to adopt a flexible display. When a flexible display is introduced to an electronic device, the display screen can be folded or unfolded, thereby greatly increasing the expandability of the screen. In order to commercialize such a flexible display, each layer, substrate material, and various electrode materials constituting the display, especially AMOLED, must have durability in repeated bending, and especially the outermost cover material has high surface hardness. And flexibility at the same time.

As described above, in order to have flexibility of the cover material, shrinkage control occurs during curing during the manufacturing process. Among the monomers known to date, spore orthocarbonate (SOC), Spiro orthoester (SOE), bicyclo orthoester (BOE), cyclic ether, cyclic acetal, cyclic allyl acetal, vinyl cyclo And propane (vinyl cyclopropane). Among these, the SOC compound which is easy to manufacture is attracting attention, and especially, it is developed for the use of the reinforcement composite material containing a dental material (refer Unexamined-Japanese-Patent No. 2001-0101854 and 2009-0087933).

On the other hand, the photopolymer which reacts by the mechanism which produces a polymerization difference according to the intensity of light is usually comprised from an acryl-type monomer, an epoxy-type monomer, an oligomer, an initiator, and a polymer binder. A film made of an acrylic monomer has a high applicability, but has a serious problem of shrinkage after curing by light or heat, and a film made of an epoxy monomer has a problem of low shrinkage but low reactivity. Therefore, in order to improve this, it is necessary to develop a novel photopolymerizable monomer having high reactivity during curing and high polymerization efficiency and low shrinkage rate.

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

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

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

The present invention is at least one spiro compound selected from the group consisting of Formula 1 to 5; And at least one siloxane compound selected from the group consisting of the following Chemical Formulas 6 to 8, a photocurable coating composition is provided.

In the above formula,

X is oxygen or -CHR ^1- ,

n is 2 or 3,

m is 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, alcohol substituted or unsubstituted with epoxy group, or C _1-10 alkoxy C _1- substituted or substituted with halogen or phenyl ₄ is alkyl,

R ¹⁴ are each independently substituted or unsubstituted C _1-5 alkoxy C _1-4 alkyl, C _4-8 epoxycycloalkyl substituted C _1-4 alkyl, (meth) acrylate C _1-4 alkyl or C _2-5 alkenyl.

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

The photocurable coating composition of the present invention may include a spiro compound and a siloxane compound to 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 a high transparency and excellent surface hardness, adhesion, flexibility, etc. can effectively prevent cracks or interfacial film removal due to shrinkage during curing, and thus flexible display, liquid crystal display device It can be applied to various fields using photocuring systems such as OLED displays, molded products, coatings, dental materials, and the like.

The photocurable coating composition of the present invention is at least one spiro compound selected from the group consisting of Formula 1 to 5; And at least one siloxane compound selected from the group consisting of:

[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 2 or 3,

m is 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, alcohol substituted or unsubstituted with epoxy group, or C _1-10 alkoxy C _1- substituted or substituted with halogen or phenyl ₄ is alkyl,

R ¹⁴ are each independently substituted or unsubstituted C _1-5 alkoxy C _1-4 alkyl, C _4-8 epoxycycloalkyl substituted C _1-4 alkyl, (meth) acrylate C _1-4 alkyl or C _2-5 alkenyl.

The spiro compound is at least one selected from the group consisting of Chemical Formulas 1 to 5. Wherein X is oxygen or —CHR ¹ —, n is 2 or 3, m is 1 or 2, and R ¹ to R ¹³ are each independently hydrogen, alkyl of C _1-4 , C _2-5 al Kenyl, acrylate substituted or unsubstituted with C _1-4 alkyl, C _6-14 aryl, epoxy, glycidyl, C _3-8 cycloalkyl, C _4-8 epoxycycloalkyl, epoxy group substituted Or unsubstituted alcohol or alkyl of C _1-10 alkoxy C _1-4 unsubstituted or substituted with halogen or phenyl.

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 the structure of Formula 4 or 5, X is oxygen, m is 1, and R ⁹ to R ¹³ are each independently hydrogen, methyl, phenyl, naphthyl, epoxy Glycidyl, acrylate, methacrylate,

or

Can be. More specifically, the spiro compound may be at least one selected from the group consisting of Formulas 9 to 14:

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 the structure of Formula 1, X is oxygen or -CH _2- , n is 3, and R ² and R ³ are each independently hydrogen, methyl, propoxymethyl, Phenylepoxymethyl or

Can be. Specifically, the spiro compound may be at least one selected from the group consisting of Formulas 15 to 18:

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

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

Specifically, R ¹⁴ may be each independently glycidyl etherpropyl, epoxycyclohexylethyl, methacrylate ethyl or ethenyl. More specifically, each R ¹⁴ may be independently one selected from the group consisting of Formulas 19 to 22:

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

In addition, the siloxane compound can be confirmed whether the synthesis through IR, ¹ H-NMR, ²⁹ Si-NMR. The IR analysis confirmed the Si-OH content in the vicinity of 3,000 to 3,400 cm ^-1 , and the Si-O in the vicinity of 1,000 to 1,100 cm ^-1 and the Si-O-Si peak observed at 1,100 to 1,200 cm ^-1 . You can check the location. In addition, it was confirmed that all of the alkoxy moieties of the alkoxy monomers were condensed by hydroxy (-OH) using ¹ H-NMR, and T1, T2 and T3 such as Si-OH, Si-OCH ₃ and the like through ²⁹ Si-NMR. By observing the structure it can be confirmed whether or not synthesis.

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 by weight.

The coating composition may further include additives such as an initiator, a solvent, a leveling agent, and the like, which may typically be included in the photocurable coating composition. Specifically, the coating composition may further include one or more additives selected from the group consisting of an initiator, a solvent and a leveling agent.

It may include 30 to 80% by weight of the solvent based on the total weight of the coating composition. In addition, based on 100 parts by weight of the coating composition may include 1 to 10 parts by weight of the initiator and 0.05 to 5 parts by weight of the leveling agent.

The initiator may be used by selecting any one of commercially available initiators. Specifically, the initiator may use any one selected from the group consisting of a thermal initiator, a cationic initiator, a radical initiator and a photoinitiator according to the curing system, and in the case of a dual curing system, the mixed use of the thermal initiator and the photoinitiator may be used. It is possible.

Examples of the photoinitiator include benzoin methyl ether, benzoin isopropyl ether, anisoin methyl ether, benzoin, benzyl ketal, and the like. In addition, the cation 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. Further, the thermal initiator may include, for example, a peroxide system including benzoyl peroxide; Azobisisobutyronitrile, an amine system, etc. are mentioned.

The solvents include 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 the like. Solvents selected from the group consisting of water may be used alone or in combination of two or more thereof.

Examples of the monohydric alcohols 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 Monohydric alcohols having 4 to 11 carbon atoms such as, 7-dimethyl-1-octanol and the like.

Examples of the polyhydric alcohols include 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, and the like, and may be a divalent alcohol having 4 to 8 carbon atoms.

The alkyl ethers of the polyhydric alcohols are, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol ethylmethyl ether, propylene glycol monomethyl Ether, propylene glycol monoethyl ether, and the like.

The alkyl ether acetates of the polyhydric alcohols may be, for example, ethylene glycol ethyl ether acetate, diethylene glycol ethyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol monomethyl ether acetate, or the like.

The ethers may be, 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, cyclohexylpropyl ether, cyclohexyl-2-propyl ether, cyclopentyl butyl ether, cyclopentyl-tert-butyl ether, cyclohexyl butyl ether, cyclohexyl-tert-butyl ether, etc. Can be.

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

The alkanes may be, for example, decane, dodecane, undecane, or the like.

The alkoxy alkanes may be dialkoxyalkanes, trialkoxyalkanes or tetraalkoxyalkanes having 3 to 16 carbon atoms. The alkoxy alkanes are, for example, dimethoxymethane, diethoxymethane, dibutoxymethane, trimethoxymethane, triethoxymethane, tripropoxymethane, 1,1-dimethoxyethane and 1,2-dimethane. Methoxyethane, 1,1-diethoxyethane, 1,2-diethoxyethane 1,2-dibutoxyethane, 1,1,1-trimethoxyethane, 1,1-diethoxypropane, 2,2-dimeth Oxypropane, 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 and xylene, and the ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and 4-hydroxy-4. -Methyl-2-pentanone, diacetone alcohol, and the like.

Examples of the esters include ethyl acetate (ethyl acetate), butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate and ethoxy Ethyl acetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, butyl Lactone, caprolactone and the like.

Specifically, the solvent may be at least one selected from the group consisting of monohydric alcohols, ethers, cyclic ethers, alkyl ethers of polyhydric alcohols, alkyl ether acetates of polyhydric alcohols, ketones, aromatic hydrocarbons and esters. have. More specifically, the solvent includes monohydric alcohols having 9 to 11 carbon atoms, alkyl ethers of polyhydric alcohols having 4 to 10 carbon atoms, ketones having 2 to 6 carbon atoms, aromatic hydrocarbons having 6 to 10 carbon atoms, and esters having 3 to 7 carbon atoms. It may be one or more selected from the group consisting of.

Commercially available leveling agents include BYK-Chemie's BYK 371, BYK 377, BYK 353, BYK 356, BYK 359, BYK 361, BYK 067 and BYK 141, Tego Chemie's Tego Rad 2200, Tego Rad 2500, Tego Glide 410, Tego Glide 435 and Tego Glide 453, and TS 100 and OK 607 available from Daeguusa.

The present invention provides a coating film prepared using the photocurable coating composition as described above. Specifically, the coating film may be prepared by coating and curing the photocurable coating composition.

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

The curing method can be used without any particular limitation as long as it can be used for photocuring, for example, can be cured with a metal halide lamp, a high pressure mercury lamp, a mercury short arc lamp, an ultraviolet lamp.

The coating film has high transparency and excellent surface hardness, adhesiveness, and flexibility, so that the coating film can be used in various applications such as flexible displays, liquid crystal displays, OLED displays, molded products, coatings, dental materials, and the like. Can be.

Hereinafter, the present invention will be described in more detail with reference to Examples and Experimental Examples. However, the following Examples and Experimental Examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto.

Synthesis Example 1 Preparation of Spyro Compound

In the reactor 2- (2-oxiranyloxy) propane-1,3-diol (349 g) and dibutylthylt oxide (655 g) ) Was added and 120 ml of toluene was added to dissolve. A dean-stark trap was connected to the reactor, a nitrogen atmosphere was formed, and refluxed for 3 hours to remove water (47 g). Then 4-chloromethyl-1,3-dioxolane-2-thione (4-chloromethyl-1,3-dioxolane-2-thione) (400 g) was added and stirred at room temperature for 4 hours. Thereafter, 1000 ml of toluene was added thereto, washed with distilled water, and the solvent was removed under reduced pressure to obtain a spiro compound of Formula 9.

Synthesis Example 2 Preparation of Spyro Compound

2- (7-oxabicyclo [4.1.0] hepta-3-yl) propane-1,3-diol (2- instead of 2- (2-oxyranyloxy) propane-1,3-diol (349 g) Except for using (7-oxabicyclo [4.1.0] heptan-3-yl) propane-1,3-diol) (448 g), to prepare a spiro compound in the same manner as in Synthesis Example 1 The compound was obtained by spy.

Synthesis Example 3 Preparation of Spyro Compound

Except for using 2-methyl-1,3-propanediol (234 g) instead of 2- (2-oxyranyloxy) propane-1,3-diol (349 g) Then, a spiro compound was prepared in the same manner as in Synthesis example 1 to obtain a spiro compound of the formula (11).

Synthesis Example 4 Preparation of Spyro Compound

Except for using 2-phenylpropane-1,3-diol (396 g) instead of 2- (2-oxyranyloxy) propane-1,3-diol (349 g) Then, a spiro compound was prepared in the same manner as in Synthesis example 1 to obtain a spiro compound of the formula (12).

Synthesis Example 5 Preparation of Spyro Compound

Except for using 1,2,3-propanetriol (239 g) instead of 2- (2-oxyranyloxy) 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).

Triethylamine (223 g) and toluene (2,000 mL) were then added to the intermediate (328 g). After cooling to 5 ° C. in argon atmosphere, distilled methacryloyl chloride (209 g) and toluene (700 mL) were added dropwise. After stirring for 18 hours at room temperature and filtered to remove the amine hydrochloride precipitate (amine hydrochloride precipitate). Thereafter, the solvent was removed under reduced pressure to obtain a spiro compound of Formula 13.

Synthesis Example 6 Preparation of Spyro Compound

3,3-oxetane dimethanol (30.7 g) and dibutyltin oxide (65.5 g) were added to the reactor, and toluene (1,200 mL) was added to dissolve it. Thereafter, a Deanstock trap was connected to the reactor, a nitrogen atmosphere was formed, and refluxed for 3 hours to remove water (4.7 g). Then 4-chloromethyl-1,3-dioxolane-2-thione (40 g) was added and stirred at room temperature for 4 hours. Potassium tert-butoxide (70 g) was added to the obtained product, followed by stirring at room temperature for 6 hours. Thereafter, 1,000 ml of toluene was added thereto, washed with distilled water, and then the solvent was removed under reduced pressure to obtain a spiro compound of Formula 14.

Synthesis Example 7 Preparation of Spyro Compound

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

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 addition of (CH ₃ CH ₂ ) ₃ N (150 mL, 6 mol% aqueous solution) while maintaining 0 to 5 ° C. Thereafter, the organic layer was separated to obtain a spiro compound of Formula 15.

Synthesis Example 8 Preparation of Spyro Compound

Synthesis, except that 1H, 1H, 2H, 2H-pulfluoroodecan-1ol (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 producing a spiro compound in the same manner as in Example 6.

Synthesis Example 9 Preparation of Spyro Compound

Except for using 2-phenylethanol (233.5 g) instead of 1-propanol (233.5 g) to prepare a spiro compound in the same manner as in Synthesis Example 6 to obtain a spiro compound of the formula (17).

Synthesis Example 10 Synthesis of Siloxane Compound

(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 at room temperature It stirred for 3 hours and hydrolyzed. To the hydrolyzate was added (3-glycidyloxypropyl) trimethoxysilane (45 g) and 150 ml of methanol, followed by addition of sodium bicarbonate (3.34 g) and refluxed for 8 hours. Thereafter, the reaction product was distilled under reduced pressure to obtain a siloxane compound represented by Chemical Formula 6, in which R ¹⁴ was Formula 19.

Synthesis Example 11. Synthesis of Siloxane Compound

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 reaction product was distilled under reduced pressure to obtain a siloxane compound represented by Chemical Formula 6, in which R ¹⁴ was Formula 20.

Synthesis Example 12 Synthesis of Siloxane Compound

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 stirred at room temperature for 12 hours. Thereafter, the reaction product was distilled under reduced pressure to obtain a siloxane compound represented by Chemical Formula 6, in which R ¹⁴ was Chemical Formula 22.

Experimental Example 1.

The weight average molecular weight and molecular formula of the spiro compound prepared in Synthesis Examples 1 to 9 and the siloxane compound prepared in Synthesis Examples 10 to 12 were determined using a GC-MS spectrometer (Waters), and the nuclear magnetic resonance spectrum (NMR ) (manufacturer: Varian) and FT-IR (Manufacturer: PerkinElmer) for use in the synthesis examples 1 to 9 of the spy to obtain the ¹ H-NMR and ¹³ C-NMR spectrum of the compound. Furthermore, ¹ H-NMR and ²⁹ Si-NMR spectra of the siloxane compounds of Synthesis Examples 10 to 12 were obtained.

Example 1. Preparation of the composition for photocurable coating

4 wt% of the spiro compound prepared in Synthesis Example 1 (compound of formula 9), 36 wt% of the siloxane compound prepared in Synthesis Example 10, and 30 wt% of propylene glycol monomethyl ether as a diluent solvent (solvent). %, Methyl ethyl ketone 10% by weight, ethyl acetate 10% by weight and toluene 10% by weight were mixed and stirred at room temperature for 30 minutes to obtain a mixture. Subsequently, 3 parts by weight of triphenylsulfonium triflate was added as an initiator to 100 parts by weight of the mixture, followed by stirring for 20 minutes. Thereafter, 0.1 parts 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 photocurable coating composition.

Example 2.

A photocurable coating composition was prepared in the same manner as in Example 1, except that the spiro compound (Compound 10) of Synthesis Example 2 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 (Compound 14) of Synthesis Example 6 was used instead of the spiro compound of Synthesis Example 1.

Example 4.

4% by weight of the spiro compound (Compound 12) prepared in Synthesis Example 4, 36% by weight of the siloxane compound prepared in Synthesis Example 11, 30% by weight of propylene glycol monomethyl ether as a diluent, 10% by weight of methyl 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. To 100 parts by weight of the mixture was added 3 parts by weight of triphenylsulfonium triflate as a photocuring initiator and stirred for 20 minutes. Thereafter, 0.1 parts by weight of BYK 377 (BYK Chemie, Germany) was added as a leveling agent to 100 parts by weight of the mixture, and stirred and mixed for 10 minutes to prepare a photocurable coating composition.

Example 5.

A photocurable coating composition was prepared in the same manner as in Example 4, except that the spiro compound (Compound Formula 13) of Synthesis Example 5 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 (Compound 16) of Synthesis Example 8 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 (Compound 17) of Synthesis Example 9 was used instead of the spiro compound of Synthesis Example 4.

Example 8.

4 wt% of the spiro compound (compound of formula 11) prepared in Synthesis Example 3, 36 wt% of the siloxane compound prepared in Synthesis Example 12, 30 wt% of propylene glycol monomethyl ether as a diluent, 10 wt% of methyl 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. To 100 parts by weight of the mixture was added 3 parts by weight of Irgacure 184 (ciba, Germany) as a photocuring initiator and stirred for 20 minutes. Thereafter, 0.1 parts by weight of BYK 377 (BYK Chemie, Germany) was added as a leveling agent to 100 parts by weight of the mixture, and stirred and mixed for 10 minutes to prepare a photocurable coating composition.

Example 9.

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

Example 10.

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

Example 11.

12% by weight of a spiro compound prepared in Synthesis Example 7 (compound of Formula 15), 28% by weight of siloxane compound prepared in Synthesis Example 10, 30% by weight of propylene glycol monomethyl ether as a diluent, 10% by weight of methyl 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 stirred for 20 minutes. Thereafter, 0.1 parts by weight of BYK 377 (BYK Chemie, Germany) was added as a leveling agent to 100 parts by weight of the mixture, and stirred and mixed for 10 minutes to prepare a photocurable coating composition.

Example 12.

A photocurable coating composition was prepared in the same manner as in Example 11, except that the spiro compound (Compound 14) of Synthesis Example 6 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 (Compound Formula 16) of Synthesis Example 8 was used instead of the spiro compound of Synthesis Example 7.

Example 14.

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

Example 15.

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

Example 16.

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

Example 17.

A photocurable coating composition was prepared in the same manner as in Example 16, except that the spiro compound (Compound 12) of Synthesis Example 4 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 (Compound Formula 13) 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 the compound having the structure of Chemical Formula 18 (obtained from Chemtik) was used instead of the spiro compound of Synthesis Example 7.

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 instead of the siloxane compound of Synthesis Example 10.

Comparative Example 1.

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 were mixed and stirred at room temperature for 30 minutes. A mixture was obtained. Then 3 parts by weight of Irgacure 184 (ciba, Germany) as an initiator was added to 100 parts by weight of the mixture and stirred for 20 minutes. 0.1 parts by weight of BYK 377 (BYK Chemie, Germany) was added as a leveling agent to 100 parts by weight of the mixture, and stirred and mixed for 10 minutes to prepare a coating composition.

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.

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

Comparative Example 4.

A photocurable coating composition was prepared in the same manner as in Example 17, except that ENTIS Corporation UP118 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 a spiro compound.

Experimental Example 2. Evaluation of Physical Properties of Coating Film

2-1: Preparation of Coating Film

Polyethylene terephthalate (thickness 250 μm) was used as the base of the coating. The surface of the substrate was washed with isopropyl alcohol, followed by spin coating the compositions of Examples 1-20 and Comparative Examples 1-7. At this time, the temperature was maintained at 25 ℃, humidity 50%.

The coated substrate was dried at 60 ° C. for 3 minutes using a dryer, and the coating film was prepared by irradiating the light amount of the ultraviolet lamp with 1,000 mJ / cm 2.

2-2: Evaluation Method

The 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 x 100 mm (width x length), and the evaluation results are shown in Tables 1 and 2 below.

1) Surface hardness: measured by 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 to determine the presence of cracks.

3) Adhesiveness: evaluated according to ASTM D 3359.

4) Transparency: The transmittance (%) was measured by Hazemeter (NDH7000, 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 U 2B 91.2 Comparative Example 4 H U 5B 90.6 Comparative Example 5 3H U 5B 90.8 Comparative Example 6 HB radish 5B 91.1 Comparative Example 7 4H U 4B 91.2

As shown in Tables 1 and 2, it was confirmed that the coating film prepared from the photocurable coating composition comprising the spiro compound and the siloxane compound of the present invention is excellent in surface hardness, adhesion. In particular, the coating film prepared from the composition of the embodiment has a high transparency and at the same time excellent in surface hardness, adhesion, flexibility, etc. can effectively prevent cracks or interfacial film removal due to shrinkage during curing, such as a flexible display, a liquid crystal display, Various applications include photocuring systems such as OLED displays, molded articles, coatings, dental materials, and the like.

On the other hand, the coating film prepared from the composition for the photocurable coating of Comparative Examples 1 to 7 has a surface hardness of B or less, or a lot of shrinkage after coating is insufficient flexibility, it was not suitable as a flexible display film.

Claims (8)

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, a photocurable coating composition: [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 2 or 3, m is 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, alcohol substituted or unsubstituted with epoxy group, or C _1-10 alkoxy C _1- substituted or substituted with halogen or phenyl ₄ is alkyl, R ¹⁴ are each independently substituted or unsubstituted C _1-5 alkoxy C _1-4 alkyl, C _4-8 epoxycycloalkyl substituted C _1-4 alkyl, (meth) acrylate C _1-4 alkyl or C _2-5 alkenyl. The method of claim 1, The spiro compound has the structure of Formula 4 or 5, X is oxygen, M is 1, R ⁹ to R ¹³ are each independently hydrogen, methyl, phenyl, naphthyl, epoxy, glycidyl, acrylate, methacrylate,

or

Phosphorus, photocurable coating composition. The method of claim 2, The spiro compound is at least one selected from the group consisting of Formulas 9 to 14, a photocurable coating composition. [Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

The method of claim 1, The spiro compound has the structure of Formula 1, X is oxygen or -CH _2- , N is 3, R ² and R ³ are each independently hydrogen, methyl, propoxymethyl, phenylepoxymethyl or

Phosphorus, photocurable coating composition. The method of claim 4, wherein The spiro compound is at least one selected from the group consisting of Formulas 15 to 18, a photocurable coating composition. [Formula 15]

[Formula 16]

[Formula 17]

[Formula 18]

The method of claim 1, R ¹⁴ is each independently glycidyl etherpropyl, epoxycyclohexylethyl, methacrylate ethyl or ethenyl, a photocurable coating composition. The method of claim 1, The spiro compound and the siloxane compound is contained in a weight ratio of 1: 0.3 to 19, the photocurable coating composition. A coating film prepared using the composition for photocurable coating of any one of claims 1 to 7.