WO2017078193A1 - Radiation curable coating composition, and coating film - Google Patents

Abstract

The present invention relates to a radiation curable coating composition, and a coating film. The radiation curable coating composition can form a coating film having excellent flexibility, hardness, adhesion, and heat resistance, and the coating film can be applied to various fields such as those of liquid crystal display devices, OLED displays, molded products, coated products and dental materials.

Description

Photocurable coating composition and coating film

The present invention relates to a photocurable coating composition and a coating film, the photocurable coating composition can form a coating film excellent in flexibility, hardness, adhesion and heat resistance.

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. In particular, the outermost cover material has high hardness and It must be flexible at the same time.

On the other hand, monomers, which generally maintain relatively long van der waals distances, are bound by short covalent bonds during the polymerization of polymers, resulting in volume shrinkage due to the difference in distance between monomers before and after polymerization. Conversely, if the monomers have covalent bonds broken under the same reaction conditions, the distance between the monomers will be far from shrinkage will occur, in this case it can offset the volume reduction by the polymerization reaction. Since the breakage of the covalent bonds should not be to cut the backbone of the polymer itself, the reaction of breaking the bond occurs mainly at the bonds having a ring structure in the monomer. Because of this, the break of the covalent bond is mainly in the form of a ring-opening reaction. Therefore, these monomers have a carbon-carbon double bond which mainly undergoes radical or cationic polymerization and a ring structure that is fragile under these reaction conditions.

Monomers known to meet low shrinkage properties include spiro orthocarbonate (SOC), spiro orthoester (SOE), bicyclo orthoester (BOE), and cyclic ether ( cyclic ether, cyclic acetal, cyclic allyl acetal, vinyl cyclopropane and the like. Among them, SOC compounds having the greatest shrinkage preventing effect during polymer polymerization have been attracting attention, and have been developed for the use of reinforcing composite materials including dental materials.

Korean Patent Laid-Open Publication No. 2009-0087933 discloses minimizing residual stress by adding a compound containing SOC and spiro orthosilicate groups to control shrinkage. The minimization of the residual stress is suppressed by shrinkage of the entire adhesive by ring opening by spiro compound participation in the crosslinking reaction of the component having adhesive crosslinkability. This method exhibits a shrinkage-preventing effect upon curing without degrading other physical properties and reliability compared to the method of alleviating curing shrinkage and residual stress depending on the content of the thermoplastic resin.

In addition, Korean Patent Laid-Open Publication No. 2001-0021700 discloses a polyglycidyl compound based on spiro bisindane, a method for preparing the compound, and its use for producing a casting compound or an adhesive. This publication discloses a mixture of spiro bisindane as a polyfunctional and weather resistant epoxy compound that can be used as a curing agent in place of a tri-glycidyl isocyanurate (TGIC) curing agent in a polyester powder coating composition. A novel polyglycidyl compound having a base is disclosed.

Furthermore, Korean Patent Laid-Open Publication No. 2001-0101854 relates to a photopolymerizable composition comprising a vinyl ether and a photoinitiator, wherein the composition may include an epoxide, a polyol, and an SOC. The composition includes a photoinitiator with specific properties and is useful as a dental material, such as adhesives and composites.

In addition, Korean Patent Publication No. 2009-0069012 discloses a novel photopolymerizable monomer having at least one unsaturated double bond and an epoxy group at the same time, and a curable photopolymerizable composition containing the photopolymerizable monomer and an initiator. The monomer having an unsaturated double bond is easily polymerized by light or heat and exhibits high sensitivity to light.

The photopolymer which reacts by the mechanism which produces a polymerization difference according to the light intensity generally consists of an acryl-type monomer, an epoxy monomer, an initiator, and a polymer binder. The acrylic film has a high applicability, but has a serious problem of shrinkage after curing by light or heat, and the epoxy film has a problem of low shrinkage but low reactivity. Accordingly, in order to improve this, there is a need for a novel photopolymerization monomer having a high reactivity during curing and a low shrinkage rate and a curable photopolymerization composition containing the photopolymerization monomer.

Under these circumstances, the present inventors have developed a photocurable coating composition comprising a compound having an spiro structure and an epoxy structure that can control shrinkage rate, and the photocurable coating composition is formed not only in a liquid crystal display device and an OLED display but also in a molding process. It can be used in various fields such as products, coatings and dental materials.

It is an object of the present invention to provide a composition for photocurable coating that can form a coating layer having excellent flexibility, hardness, adhesion and heat resistance.

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

The present invention is a spiro compound represented by the formula (1); And it provides a photocurable coating composition comprising at least one siloxane compound selected from the group consisting of:

In the above formula,

R ₁ is hydrogen, C _1-6 alkyl, C _1-6 alkoxy, C _2-8 alkylene, C _3-8 cycloalkyl, C _6-14 aryl, C _6-14 aryl-C _1-6 alkyl, C _6-14 aryl-, and _{(CH 2) m -OC (O} ) R 3, - di-C _{1 -6} alkyl, C _5-8 cycloalkenyl, C _2-6 alkyl, or epoxy

M is an integer of 1 to 9,

Wherein R ₃ is hydrogen, C _1-6 alkyl or C _6-14 aryl,

R ₂ is C _1-6 alkyl, C _1-6 alkylamine, C _6-14 aryl, halogen element, C _3-8 cycloalkyl, C _2-6 alkenyl, thiol, phosphate, isocyanate, epoxy or C _{1- 6 is} acrylic

n is an integer from 1 to 20,

R ₁ and R ₃ are unsubstituted or C _1-6 alkyl, C _1-6 alkoxy, C _2-8 alkylene, C _5-8 cycloalkyl, C _6-14 aryl, C _3-8 cycloalkenyl At least one substituent selected from the group consisting of C _1-6 amine and C _1-6 acryl,

R ₂ is unsubstituted or C _1-6 alkyl, C _2-8 alkylene, C _5-8 cycloalkyl, C _6-14 aryl, C _3-8 cycloalkenyl, C _1-6 amine, glycy At least one substituent selected from the group consisting of dialkyl, C _3-8 epoxycycloalkyl and C _1-6 acryl.

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 hardness, flexibility, heat resistance, and shrinkage through ultraviolet curing.

In addition, the coating film formed from the composition of the present invention has a high transparency and at the same time excellent in surface hardness, adhesion, flexibility, heat resistance, and the like can effectively prevent cracks or interfacial film removal due to shrinkage during curing, flexible display, liquid crystal display device It can be applied in 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 a spiro compound represented by the formula (1); And at least one siloxane compound selected from the group consisting of:

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

In the above formula,

R ₁ is hydrogen, C _1-6 alkyl, C _1-6 alkoxy, C _2-8 alkylene, C _3-8 cycloalkyl, C _6-14 aryl, C _6-14 aryl-C _1-6 alkyl, C _6-14 aryl-, and _{(CH 2) m -OC (O} ) R 3, - di-C _{1 -6} alkyl, C _5-8 cycloalkenyl, C _2-6 alkyl, or epoxy

M is an integer of 1 to 9,

R ₃ is hydrogen, C _1-6 alkyl or C _6-14 aryl,

R ₂ is C _1-6 alkyl, C _1-6 alkylamine, C _6-14 aryl, halogen element, C _3-8 cycloalkyl, C _2-6 alkenyl, thiol, phosphate, isocyanate, epoxy or C _{1- 6 is} acrylic

n is an integer from 1 to 20,

R ₁ and R ₃ are unsubstituted or C _1-6 alkyl, C _1-6 alkoxy, C _2-8 alkylene, C _5-8 cycloalkyl, C _6-14 aryl, C _3-8 cycloalkenyl At least one substituent selected from the group consisting of C _1-6 amine and C _1-6 acryl,

R ₂ is unsubstituted or C _1-6 alkyl, C _2-8 alkylene, C _5-8 cycloalkyl, C _6-14 aryl, C _3-8 cycloalkenyl, C _1-6 amine, glycy At least one substituent selected from the group consisting of dialkyl, C _3-8 epoxycycloalkyl and C _1-6 acryl.

Specifically, the R ₁ is methyl, ethyl, butyl, propyl, methylene, ethylene, n-flofilene, propene, butene, pentene, hexene, heptene, octene, 1,2- and 1,3-cyclopentenyl, 1,2-, 1,3- and 1,4-hexenyl, 1,2-, 1,3- and 1,4-heptenyl, 1,2-, 1,3-, 1,4- and 1 , 5-octenyl, 1,2-norbornyl, phenyl, tolyl, naphthyl, 6-oxabicyclo [3.1.0] hex-2-yl, 6-oxabicyclo [3.1.0] hex-3- 1, (6-oxabicyclo [3.1.0] hex-2-yl) methyl, (6-oxabicyclo [3.1.0] hex-3-yl) methyl, (6-oxabicyclo [3.1.0 ] Hex-2-yl) methoxy, (6-oxabicyclo [3.1.0] hex-3-yl) methoxy, 7-oxabicyclo [4.1.0] hept-2-yl, 7-oxabicycle Ro [4.1.0] hept-3-yl, (7-oxabicyclo [4.1.0] hept-2-yl) methyl, (7-oxabicyclo [4.1.0] hept-3-yl) methyl, (7-oxabicyclo [4.1.0] hept-2-yl) methoxy, (7-oxabicyclo [4.1.0] hept-3-yl) methoxy, phenyl-1,2-dimethyl, 1- Phenyl-2-dimethylpropyl and 2,3-epoxy It is any one selected from the group consisting of c. More specifically, R ₁ is unsubstituted or C _1-4 alkyl, C _1-4 alkoxy, C _2-4 alkylene, C _5-8 cycloalkyl, C _6-12 aryl and C _5-8 cycloal At least one substituent selected from the group consisting of kenyl.

Specifically, R ₂ is C _1-5 alkyl, phenyl, fluorine, thiol, phosphate, isocyanate, C _3-8 epoxycycloalkyl-C _1-6 alkyl, glycidyloxy-C _1-6 alkyl, (meth) It may be any one selected from the group consisting of acryloyl group, (meth) acryloyloxy group and vinyl group.

More specifically, the spiro compound represented by Chemical Formula 1 may be a compound represented by Chemical Formula 5 or 6 below, and R ₂ in Chemical Formulas 2 to 4 may be represented by Chemical Formula 7 or 8.

Spy to the compound of Formula 1 is a known method, 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 of Formula 1, obtained as described above or prepared by a conventional method, may be synthesized through GC-MS, ¹ H-NMR, and ¹³ C-NMR, and in particular, a central carbon characterizing SOC compounds Appears near 155 ppm in ¹³ C-NMR.

The weight average molecular weight of the siloxane compound may be 1,000 to 50,000.

Further, the siloxane compound may be (3-chloropropyl) trimethoxysilane, (3-bromopropyl) trimethoxysilane, (3-iodopropyl) trimethoxysilane, (3-aminopropyl) trimethoxy Silane, (3-mercaptopropyl) trimethoxysilane, trimethoxy [3- (methylamino) propyl] silane, trimethoxy (7-octen-1-yl) silane, [2- (3,4- Epoxycyclohexyl) ethyl] trimethoxysilane, [3- (2-aminoethylamino) propyl] trimethoxysilane, N1- (3-trimethoxysilylpropyl) diethylenetriamine, 3- (trimethoxy Silyl) propyl methacrylic acid, 3- (trimethoxysilyl) propyl methacrylic acid, (3-glycidyloxypropyl) trimethoxysilane, 3- (trimethoxysilyl) propyl acrylic acid, N- [3- (Trimethoxysilyl) propyl] aniline, (3-chloropropyl) triethoxysilane, (3-aminopropyl) triethoxysilane, (3-mercaptopropyl) triethoxysilane and (3-glycidyl Oxypropyl) triethoxy seal , (N, N-dimethylaminopropyl) trimethoxysilane, trimethoxy (3,3,3-trifluoropropyl) silane, trimethoxy (2-phenylethyl) silane, vinyltrimethoxysilane, 1- [3- (trimethoxysilyl) propyl] urea, trimethoxy [2- (7-oxabicyclo [4,1,0] hept-3-yl) ethyl] silane, n-propyltriethoxy Silane, 3- (triethoxysilyl) propionitrile, triethoxy (isobutyl) silane, triethoxypentylsilane, hexyltriethoxysilane, triethoxy (octyl) silane, 3-thiopropyltrie At least one selected from the group consisting of oxysilane, N-octadecyltriethoxysilane, cyclopentyltriethoxysilane and (triethoxysilyl) cyclohexane is known as a starting material, for example, Korean Patent Application It can be synthesized by the method described in 2012-0017133.

In addition, the siloxane compound can be confirmed whether the synthesis through IR, ¹ H-NMR, ²⁹ Si-NMR. IR analysis confirmed the Si-OH content in the vicinity of 3000 to 3400 cm ^-1 , and the Si-O in the vicinity of 1000 to 1100 cm ^-1 and the Si-O-Si peak observed at 1100 to 1200 cm ^-1 . Check the location. In addition, it was confirmed that all of the alkoxy moieties of the alkoxy monomers were condensed by using ¹ H-NMR, and T1, T2 and T3 structures such as Si-OH and Si-OCH ₃ were observed through ²⁹ Si-NMR. Check for synthesis.

In addition, 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 in a weight ratio of 1: 0.5 to 1: 9.

In addition, the coating composition may additionally include additives such as an initiator, a solvent, a labeling agent, and the like, which may be included in the photocurable coating composition. The initiator may be included in 1 to 10% by weight based on the total weight of the composition, the solvent may be included in 30 to 80% by weight based on the total weight of the composition. In addition, the additive may be included in 0.1 to 5% by weight based on the total weight of the labeling agent.

As the initiator, any one of commercially available initiators may be selected and used. Specifically, any one selected from the group consisting of a thermal initiator, a cationic initiator and a photoinitiator may be used according to the curing system, and in the case of a dual curing system, a mixture of the thermal initiator and the photoinitiator may be used. More specifically, the photoinitiator may be used benzoin methyl ether, benzoin isopropyl ether, anisoin methyl ether, benzoin, benzyl ketal and the like. Moreover, the said cation initiator is hexafluoro antimonate, diphenyl (4-phenylthio) phenylsulfonium hexafluoro phosphate, (phenyl) [4- (2-methylpropyl) phenyl]-iodonium hexafluoro phosphate, (Thiodi-4,1-phenylene) bis (diphenylsulfonium) dihexafluoroantimonate or (thiodi-4,1-phenylene) bis (diphenylsulfonium) dihexafluorophosphate can be used Can be. Furthermore, the thermal initiator may be a peroxide-based compound including benzoyl peroxide; It may be any one or more selected from the group consisting of azobisisobutyronitrile and amines, but is not limited thereto. What is supplied commercially can be used as said initiator, It does not restrict | limit in particular.

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

Specifically, the monohydric alcohols are, for example, 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-pentane Ol, 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 Monohydric alcohols having 4 to 11 carbon atoms such as 3,7-dimethyl-1-octanol and the like There. In addition, the said polyhydric alcohol is ethylene glycol, propylene glycol, 4-hydroxy-4-methyl- 2-pentanol, 2-ethyl- 1, 3- hexanediol, 1, 3- butanediol, 1, for example. , 2-propanediol, 1,3-propanediol, 1,2-heptanediol, and the like, and may be a divalent alcohol having 4 to 8 carbon atoms. Examples of the alkyl ethers of the polyhydric alcohols 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, 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, and the like, and the alkoxyalkanes may be dialkoxyalkanes, trialkoxyalkanes or tetraalkoxyalkanes having 3 to 16 carbon atoms. Examples of the alkoxy alkanes include dimethoxymethane, diethoxymethane, dibutoxymethane, trimethoxymethane, triethoxymethane, tripropoxymethane, 1,1-dimethoxyethane, 1,2-dimethoxyethane, 1,1-diethoxyethane, 1,2-diethoxyethane 1,2-dibutoxyethane, 1,1,1-trimethoxyethane, 1,1-diethoxypropane, 2,2-dimethoxypropane, 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. The esters are, for example, ethyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, and hydroxide. Ethyl oxyacetate, 2-hydroxy-3-methyl butyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, butyrolactone, caprolactone And the like.

More specifically, the solvent may be monohydric alcohols, ethers, cyclic ethers, alkyl ethers of polyhydric alcohols, alkyl ether acetates of polyhydric alcohols or hydrocarbons having 4 to 14 carbon atoms, and more specifically, 9 carbon atoms. Monohydric alcohol of 11 to 11; Or an alkyl ether having an alkyl chain having 4 to 10 carbon atoms.

The labeling agent BYK-Chemie manufactured BYK 371, 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, TS 100 and OK 607 available from Daeguusa.

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

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

Furthermore, the method for curing may be used without particular limitation as long as it can be used for photocuring. For example, the curing method may be a metal halide lamp, a high pressure mercury lamp, a mercury short arc lamp, or the like.

The coating film has excellent surface hardness, adhesiveness, flexibility, heat resistance, and the like, and thus may be used in various applications using a photocuring system such as a flexible display, a liquid crystal display, an OLED display, a molded product, a coating, a dental material, and the like.

Synthesis Example  1. Synthesis of Spyro Compounds

1,2-phenylenedimethanol (26 mmol) and dibutyltin oxide (6.55 g, 26 mmol) were added to the reactor, and toluene (120 mL) was added thereto to dissolve it. A Dean-Stark trap was connected to the reactor, a nitrogen atmosphere was formed, and refluxed for 3 hours to remove water (26 mmol). 4-chloromethyl-1,3-dioxolane-2-thione (4-chloromethyl-1,3-dioxolane-2-thione) (4 g, 26.3 mmol) was added and stirred at room temperature for 4 hours. Potassium tert-butoxide (7.03 g, 52.6 mmol) was added to the obtained product, and the mixture was stirred at room temperature for 3 days. 100 ml of toluene was added thereto, washed five times with distilled water, dried over saturated aqueous NaCl solution and MgSO ₄ , and then the solvent was removed under reduced pressure to obtain a spiro compound of Chemical Formula 5 (see Scheme 1 below).

Scheme 1

Synthesis Example  2. Synthesis of Spyro Compounds

2,3-oxiranediyldimethanol (72 g, 0.5 mol) was used instead of 1,2-phenylenedimethanol, except that 2,3-oxiranediyldimethanol (72 g, 0.5 mol) was used. To give a compound (see Scheme 2 below).

Scheme 2

Synthesis Example  3. Siloxane  Synthesis of Compound

2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (100 g, 0.406 mol) was dissolved in tetrahydrofuran (THF; Tetrahydrofuran) (30 g) 22 g of water and 0.20 g of potassium carbonate were added and stirred at room temperature for 24 hours. Water (20 g) was added from the reaction mixture using a separatory funnel to separate an organic layer, and THF was distilled under reduced pressure from the organic layer to obtain 80 g of a siloxane compound represented by Formula 4 below.

[Formula 4]

In Formula 4, R ₂ is

to be.

Synthesis Example  4. Siloxane  Synthesis of Compound

(3-glycidyloxypropyl) trimethoxysilane (70.1 g, 0.3 mol) was dissolved in 70 ml of toluene, water (16.2 g, 0.9 mol) and acetic acid (0.54 g, 0.09 mol) was added and stirred at room temperature for 3 hours to hydrolyze. To the hydrolyzate was added (3-glycidyloxypropyl) trimethoxysilane (45 g, 0.3 mol) and 150 ml of methanol, followed by barium hydroxide monohydrate (4.92 g, 0.03 mol) was added and refluxed for 4 hours. After the reaction was distilled under reduced pressure to obtain a siloxane compound of the formula (4).

[Formula 4]

In Formula 4, R ₂ is

to be.

Example  One.

20 mass% of spiro compound prepared in Synthesis Example 1, 20 mass% of siloxane compound prepared in Synthesis Example 3, and 60 mass% of propylene glycol monomethyl ether were mixed and stirred at room temperature for 30 minutes. Obtained. Triphenylsulfonium triflate was then added as an photocuring initiator in an amount of 3% by mass of the mixture and stirred for 20 minutes. Thereafter, BYK 377 (BYK Chemie, Germany) was added as a leveling improving additive in an amount of 0.1% by mass 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 siloxane compound of Synthesis Example 4 was used instead of the siloxane compound of Synthesis Example 3.

Example  3.

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

Example  4.

A photocurable coating composition was manufactured in the same manner as in Example 1, except that 2 mass% of spiro compounds of Synthesis Example 1 and 38 mass% of siloxane compounds of Synthesis Example 3 were used.

Example  5.

A photocurable coating composition was prepared in the same manner as in Example 1, except that 28 mass% of the spiro compound of Synthesis Example 1 and 12 mass% of the siloxane compound of Synthesis Example 3 were used.

Comparative example  One.

The spiro compound of Synthesis Example 1 was mixed with 40% by mass of compound and 60% by mass of propylene glycol monomethyl ether and stirred at room temperature for 30 minutes to obtain a mixture. The photocuring initiator triphenylsulfonium triflate was then added in a content of 3% by mass of the mixture and stirred for 20 minutes. As a leveling improving additive, BYK 377 (BYK Chemie, Germany) was added in an amount of 0.1% by mass 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 siloxane compound of Synthesis Example 4 was used instead of the spiro compound of Synthesis Example 1.

Comparative example  3.

A coating composition was prepared in the same manner as in Comparative Example 1, except that DGEBA (Diglycidyl ether of bisphenol-A) was used instead of the spiro compound of Synthesis Example 1.

Comparative example  4.

A coating composition was prepared in the same manner as in Example 1, except that 36 mass% of spiro compounds of Synthesis Example 1 and 4 mass% of siloxane compounds of Synthesis Example 3 were used.

Test Example  1. Shrinkage control On the coating film  For evaluation

Test Example  1-1: Of coating film  Produce

Polyethylene terephthalate (thickness 0.5 mm) was used as the base of the coating. The surface of the substrate was washed with isopropyl alcohol and then the compositions of Examples 1-5 and Comparative Examples 1-5 were spin coated. 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 1000 mJ / cm ² .

Test Example  1-2: Evaluation Method

The coating films prepared from the compositions of Examples 1 to 5 and Comparative Examples 1 to 5 were evaluated for the following items. The size of the test specimen is 100 mm x 100 mm.

1) Surface hardness: measured by ASTM D3502 (pencil hardness tester).

2) Shrinkage: The degree of occurrence of warpage of the coating appearance was confirmed after standing for 24 hours at room temperature after coating.

Very good when absolute value of coating film deflection is less than 0 mm ~ 1 mm

Excellent when the absolute value of the warpage of the coating film is less than 1 mm to 3 mm

Normal when the absolute value of the warpage of the coating film is less than 3 mm to 5 mm

Insufficient when absolute value of warpage of coating film is 5mm or more

3) Flexibility: After 12 hours of coating, the coated surface was bent in a 40 pie cylinder for 5 seconds to determine the presence of cracks.

4) Adhesiveness: It was evaluated by ASTM D3359.

The evaluation results are shown in Table 1 below.

	Example 1	Example 2	Example 3	Example 4	Example 5	Comparative Example 1	Comparative Example 2	Comparative Example 3	Comparative Example 4
Surface hardness	4H	4H	3H	4H	3H	H	4H	H	4H
contractility	◎	◎	◎	○	◎	◎	X	○	△
flexibility	radish	radish	radish	radish	radish	radish	U	radish	U
Adhesiveness	5B	5B	5B	5B	5B	5B	4B	5B	4B

In Table 1, ◎ is very good, ○ is excellent, △ is usually, X means poor.

As shown in Table 1, in the case of the coating film of the photocurable coating composition comprising the spiro compound and the siloxane compound of the present invention, it was confirmed that the surface hardness, shrinkage, adhesion and the like is excellent. In particular, the coating film of the present invention was confirmed that it is suitable as a film for display because the shrinkage and excellent flexibility.

Claims (7)

1. A spiro compound represented by Formula 1; And at least one siloxane compound selected from the group consisting of the following Chemical Formulas 2 to 4:

   [Formula 1]

   

   [Formula 2]

   

   [Formula 3]

   

   [Formula 4]

   

   In the above formula,

   R ₁ is hydrogen, C _1-6 alkyl, C _1-6 alkoxy, C _2-8 alkylene, C _3-8 cycloalkyl, C _6-14 aryl, C _6-14 aryl-C _1-6 alkyl, C _6-14 aryl-, and _{(CH 2) m -OC (O} ) R 3, - di-C _{1 -6} alkyl, C _5-8 cycloalkenyl, C _2-6 alkyl, or epoxy

   M is an integer of 1 to 9,

   R ₃ is hydrogen, C _1-6 alkyl or C _6-14 aryl,

   R ₂ is C _1-6 alkyl, C _1-6 alkylamine, C _6-14 aryl, halogen element, C _3-8 cycloalkyl, C _2-6 alkenyl, thiol, phosphate, isocyanate, epoxy or C _{1- 6 is} acrylic

   n is an integer from 1 to 20,

   R ₁ and R ₃ are unsubstituted or C _1-6 alkyl, C _1-6 alkoxy, C _2-8 alkylene, C _5-8 cycloalkyl, C _6-14 aryl, C _3-8 cycloalkenyl At least one substituent selected from the group consisting of C _1-6 amine and C _1-6 acryl,

   R ₂ is unsubstituted or C _1-6 alkyl, C _2-8 alkylene, C _5-8 cycloalkyl, C _6-14 aryl, C _3-8 cycloalkenyl, C _1-6 amine, glycy At least one substituent selected from the group consisting of dialkyl, C _3-8 epoxycycloalkyl and C _1-6 acryl.
2. The method of claim 1,

   Wherein R ₁ is hydrogen, methyl, ethyl, butyl, propyl, methylene, ethylene, n-flofilene, propene, butene, pentene, hexene, heptene, octene, 1,2- and 1,3-cyclopentenyl, 1 , 2-, 1,3- and 1,4-hexenyl, 1,2-, 1,3- and 1,4-heptenyl, 1,2-, 1,3-, 1,4- and 1, 5-octenyl, 1,2-norbornyl, phenyl, tolyl, naphthyl, 6-oxabicyclo [3.1.0] hex-2-yl, 6-oxabicyclo [3.1.0] hex-3-yl , (6-oxabicyclo [3.1.0] hex-2-yl) methyl, (6-oxabicyclo [3.1.0] hex-3-yl) methyl, (6-oxabicyclo [3.1.0] Hex-2-yl) methoxy, (6-oxabicyclo [3.1.0] hex-3-yl) methoxy, 7-oxabicyclo [4.1.0] hept-2-yl, 7-oxabicyclo [4.1.0] hept-3-yl, (7-oxabicyclo [4.1.0] hept-2-yl) methyl, (7-oxabicyclo [4.1.0] hept-3-yl) methyl, ( 7-oxabicyclo [4.1.0] hept-2-yl) methoxy, (7-oxabicyclo [4.1.0] hept-3-yl) methoxy, phenyl-1,2-dimethyl, 1-phenyl -2-dimethylpropyl and 2,3-epoxy part Any one selected from the group consisting of, a photocurable coating composition for
3. The method of claim 2,

   R ₁ is unsubstituted or is a group consisting of C _1-4 alkyl, C _1-4 alkoxy, C _2-4 alkylene, C _5-8 cycloalkyl, C _6-12 aryl and C _5-8 cycloalkenyl Having at least one substituent selected from, a photocurable coating composition.
4. The method of claim 1,

   R ₂ is C _1-5 alkyl, phenyl, fluorine, thiol, phosphate, isocyanate, C _3-8 epoxycycloalkyl-C _1-6 alkyl, glycidyloxy-C _1-6 alkyl, (meth) acrylo Diary, (meth) acryloyloxy group and any one selected from the group consisting of a vinyl group, a photocurable coating composition.
5. The method of claim 1,

   The weight average molecular weight of the siloxane compound is 1,000 to 50,000, the photocurable coating composition.
6. The method of claim 1,

   The spiro compound and the siloxane compound is contained in a weight ratio of 1: 0.3 to 1: 19, the photocurable coating composition.
7. A coating film prepared using the composition for photocurable coating of any one of claims 1 to 6.