KR20140026922A - Visible light-blocking composition, hardened product thereof, and device including the hardened product - Google Patents

Abstract

The present invention relates to a visible light-blocking composition, a hardened product thereof, and a device including the same. The visible light-blocking composition of the present invention reduces visible light transmittance when exposed to ultraviolet rays and maintains reduced visible light transmittance after ultraviolet rays are blocked.

Description

TECHNICAL FIELD [0001] The present invention relates to a visible light shielding composition, a cured product thereof, and a device comprising the same. BACKGROUND OF THE INVENTION [0001]

The present invention relates to a visible light shielding composition that reacts with ultraviolet rays, a cured product thereof, and an apparatus including the same.

Recently, the demand for an organic light-emitting diode (OLED) display having low power and high efficiency has been greatly increased. Generally, an OLED display includes an OLED, a TFT layer, and a base substrate including an electrode and an organic layer.

In order to prevent an electrode pattern or a circuit wiring used for driving from being visually recognized by a user, an OLED display is generally provided with a blocking film for black patterning under the base substrate of a polymer or a glass material. At this time, a protective film may be used between the pattern-visible blocking film and the base substrate.

However, since a protective film having separate functions and a film for blocking the pattern are attached, respectively, the manufacturing process of the display is complicated and the thickness of the display is increased.

SUMMARY OF THE INVENTION The technical problem of the present invention has been devised in this respect, and an object of the present invention is to provide a visible light blocking composition, a cured product thereof, and a display device which can simplify the OLED display manufacturing process and reduce the thickness thereof.

In order to achieve the above object, the present invention provides a visible light shielding composition having reduced transmittance to visible light when exposed to ultraviolet light.

The visible light shielding composition according to the present invention is characterized in that the transmittance to visible light is reduced when exposed to ultraviolet light.

The visible light shielding composition according to the present invention has a transmittance of visible light of 30% or more before being exposed to ultraviolet rays and a transmittance of visible light of 3% or less when exposed to ultraviolet light.

The visible light shielding composition according to the present invention is characterized in that, after exposure to ultraviolet rays, the transmittance to visible light is maintained at 3% or less even when ultraviolet rays are blocked.

The visible light shielding composition according to the present invention is characterized by comprising a photochromic dye and a solvent blocking agent. The content of the original blocking agent may be 50 to 400 parts by weight based on 100 parts by weight of the photochromic dye.

When the composition is exposed to ultraviolet light, at least one of the ring structures of the photochromic dye is opened, and the ring-opened portion of the photochromic dye can be blocked from being restored to the ring structure by the original blocker.

The composition may be characterized in that when exposed to ultraviolet light, at least a portion of the raw blocker is cleaved into cation radicals and radicals, and the hydrogen ion concentration may be increased.

The photochromic dye may include at least one selected from the group consisting of spirooxazine-based compounds, spiropyran-based compounds and chromene-based compounds.

The photochromic dye may include a compound represented by the following formula (1).

≪ Formula 1 >

In Formula 1, X represents C or N,

R ₁ to R ₉ each independently represent a hydrogen atom, a cyano group, a nitro group, a halogen group, an amino group, a carboxyl group, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, An aryl group having 6 to 30 carbon atoms or a heterocyclic group having 4 to 30 carbon atoms,

R ₆ and R _7, or R ₇ and R _8, or R ₈ and R _{9 may} each independently represent a fused ring,

The fused rings represented by R ₆ and R ₇ , R ₇ and R _8, or R ₈ and R ₉ are each independently a cyano group, a nitro group, a halogen group, a hydroxyl group, an alkyl group having 1 to 30 carbon atoms, , An aryl group having 6 to 30 carbon atoms, or a heterocyclic group having 4 to 30 carbon atoms, which is unsubstituted or substituted with at least one substituent selected from the group consisting of a halogen atom, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, Or a heterocyclic group having 4 to 30 carbon atoms,

The hydrogen atoms of the substituents represented by R ₁ to R ₉ each independently represent an amino group, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms And a heterocyclic group having 4 to 30 carbon atoms.

The chromene-based compound may include a compound represented by the following general formula (2) or (3).

Each of R ₁₀ to R ₁₇ independently represents a hydrogen atom, a cyano group, a nitro group, a halogen group, an amino group, a carboxyl group, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, An alkoxy group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a heterocyclic group having 4 to 30 carbon atoms.

(2)

(3)

In each of formulas (2) and (3), the hydrogen of the substituent represented by R ₁₀ to R ₁₇ is independently selected from an amino group, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, An aryl group having 6 to 30 carbon atoms, or a heterocyclic group having 4 to 30 carbon atoms.

The original blocking agent may include a photoacid generator (PAG). The original blocking agent may include at least one selected from the group consisting of an iodonium compound, a sulfonium compound, and a sulfonate compound.

The visible light shielding composition may further comprise a polymer.

The content of the photochromic dye may be 1 to 30 parts by weight based on 100 parts by weight of the polymer.

The content of the raw material blocking agent may be 0.5 to 30 parts by weight based on 100 parts by weight of the polymer.

The visible light shielding composition may be thermosetting.

The visible light shielding composition, the cured product thereof, and the display device including the visible light shielding composition according to the present invention are advantageous in that the thickness of the display device can be reduced and the manufacturing process can be simplified.

1 is a cross-sectional view of a photochromic film according to an embodiment of the present invention.
2 is a cross-sectional view of a photochromic film according to another embodiment of the present invention.
3 is a cross-sectional view conceptually showing a structure of an AMOLED display device according to an embodiment of the present invention.
4 is a cross-sectional view conceptually showing a structure of an AMOLED display device according to an embodiment of the present invention.

The visible light shielding composition according to the present invention is characterized in that the transmittance of visible light is reduced when exposed to ultraviolet rays.

That is, when the transmittance of visible light to the composition before exposure to ultraviolet ray is T1 and the transmittance of visible light to the composition exposed to ultraviolet light is T2, the composition according to the present invention has a characteristic of T1 > T2. The "transmittance" is defined as an arithmetic mean value of the transmittance of each wavelength obtained by measuring with a transmittance measuring instrument such as a Cary-4000 instrument (trade name, Agilent Technologies, USA) The transmittance per wavelength is measured in a wavelength range of 400 nm to 700 nm as a visible light wavelength band.

The composition may have a transmittance of 30% or more with respect to visible light before being exposed to ultraviolet light. At this time, the transmittance of the composition with respect to visible light before being exposed to ultraviolet rays may be 100% or less. Hereinafter, a state before the composition is exposed to ultraviolet rays is referred to as a "light projecting state ".

When the composition in the light-transmitting state is exposed to ultraviolet rays, the transmittance of visible light to the composition decreases, and the transmittance thereof may be 3% or less. The transmittance of visible light after the composition is exposed to ultraviolet rays may be 0% or more. Hereinafter, the state in which the composition is exposed to ultraviolet light and the transmittance of visible light is reduced compared to the light transmission state is referred to as "light shielding state ". That is, the composition in the light-transmitting state can be in the light-shielding state when exposed to ultraviolet rays.

After the composition is put into the light shielding state, the light shielding state is maintained even when the ultraviolet light is blocked. That is, even when the light source for providing ultraviolet rays is removed, the transmittance of the composition to visible light can be kept at 3% or less.

In the present invention, the wavelength band of ultraviolet light may be from 100 nm to 380 nm, and the wavelength band of visible light may be from 380 nm to 780 nm.

In one embodiment of the invention, the composition may comprise a photochromic dye and a confinement blocker. When the composition is exposed to ultraviolet rays, the transmittance of visible light is decreased, and the composition becomes a light shielding state. In the present invention, even if ultraviolet rays are blocked by using the raw shielding agent, the composition is not turned from the light shielding state to the light projecting state. That is, even if ultraviolet rays are blocked, the composition once converted to the light shielding state maintains the light shielding state.

Hereinafter, the photochromic dye and the original blocker will be described in more detail.

The photochromic dye comprises at least one ring structure. Hereinafter, the original structure of the photochromic dye at this time is referred to as "first structure ". When ultraviolet light is irradiated to the composition in the projected state, at least one ring structure of the photochromic dye is opened. Hereinafter, the structure in which ultraviolet rays are irradiated to change the photochromic dye differently from the first structure will be referred to as "second structure ". For example, the second structure may have a ring-shaped portion of the ring structure. When the ultraviolet rays are blocked, the ring-opened portion of the photochromic dye is again converted into the original ring structure, and the composition is again in a light-projecting state. That is, the photochromic dye having the second structure is restored to the first structure, which is the original structure.

Examples of the photochromic dye include spirooxazine-based compounds, spiropyran-based compounds, and chromene-based compounds. These may be used alone or in combination.

The photochromic dye may be combined so that the composition absorbs the entire visible light region. Alternatively, a combination of photochromic dyes that absorb only a part of the wavelength band of the visible light region is possible if necessary. For example, photochromic dyes of the blue series and the green series, photochromic dyes of the blue series and the red series, photochromic dyes of the red series and green series can be combined, and photochromic dyes of the blue series, green series and red series Dyes may be combined.

Specifically, the photochromic dye may include a compound represented by the following formula (1).

≪ Formula 1 >

In Formula 1, X represents C or N,

R ₁ to R ₉ each independently represent a hydrogen atom, a cyano group, a nitro group, a halogen group, an amino group, a carboxyl group, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, An aryl group having 6 to 30 carbon atoms or a heterocyclic group having 4 to 30 carbon atoms,

R ₆ and R _7, or R ₇ and R _8, or R ₈ and R _{9 may} each independently represent a fused ring,

The fused rings represented by R ₆ and R ₇ , R ₇ and R _8, or R ₈ and R ₉ are each independently a cyano group, a nitro group, a halogen group, a hydroxyl group, an alkyl group having 1 to 30 carbon atoms, , An aryl group having 6 to 30 carbon atoms, or a heterocyclic group having 4 to 30 carbon atoms, which is unsubstituted or substituted with at least one substituent selected from the group consisting of a halogen atom, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, Or a heterocyclic group having 4 to 30 carbon atoms.

The hydrogen atoms of the substituents represented by R ₁ to R ₉ are each independently selected from the group consisting of an amino group, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, An aryl group and a heterocyclic group having 4 to 30 carbon atoms.

Specific examples of the compound represented by the formula (1) include 1,3,3-trimethyl spiro (indoline-2,3'-naphtho (2,1-b) 3-trimethylspiro (indoline-2,3'-naphtho (2,1-b) (1,4) oxazine), 6 '- (indolin- (Indolin-2-yl) -3,3-dimethyl-1-propylspiro (indoline- 2,3'-naphtho (2,1-b) (1,4) oxazine), 6 '- (indolin-1-yl) , 3'-naphtho (2,1-b) (1.4) oxazine) (6 '- (indolin-1-yl) -1-isobutyl-3,3-dimethylspiro (indoline-2,3'-naphtho 2,1-b) (1,4) oxazine), 1,3,3-trimethyl-5 '- (piperidin- 1 -yl) spiro (indolin- 1-b) (1,4) oxazine) (1,3,3-trimethyl-5 '- (piperidin-1-yl) spiro (indoline-2,3'-naphtho , 4) oxazine)).

The chromene-based compound may include a compound represented by the following general formula (2) or (3).

(2)

(3)

In each of formulas (2) and (3), R ₁₀ to R ₁₇ are each independently selected from the group consisting of hydrogen, cyano group, nitro group, halogen group, amino group, carboxyl group, alkyl group having 1 to 30 carbon atoms, cycloalkyl group having 3 to 30 carbon atoms, An alkoxy group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a heterocyclic group having 4 to 30 carbon atoms.

In each of formulas (2) and (3), the hydrogen of the substituent represented by R ₁₀ to R ₁₇ is independently selected from the group consisting of an amino group, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, An aryl group having 6 to 30 carbon atoms, and a heterocyclic group having 4 to 30 carbon atoms, which may be substituted or unsubstituted.

Specific examples of the compound represented by the formula (2) include 4- (4- (6-morpholino-3-phenyl-3H-benzo - (6-morpholino-3-phenyl-3H-benzo (f) chromen-3-yl) phenyl) morpholine).

Specific examples of the compound represented by the formula (3) include, but are not limited to, methyl 9- (dimethylamino) -2-phenyl-2- (4- (piperidin- 5-carboxylate, ethyl 9- (dimethylamino) -2-phenyl-2- (4- (piperidin- Benzyl (h) chromene-5-carboxylate (ethyl 9- (dimethylamino) -2,2-bis (4- ( piperidin-1-yl) phenyl) -2H-benzo (h) chromene-5-carboxylate.

As described above, the original blocking agent serves to prevent the ultraviolet ray from being restored to the first structure, which is the original structure, after the photochromic dye has already been opened. As a result, the composition can be kept in a light shielding state without being roughened from the light shielding state to the light shielding state by the raw blocker.

The original blocking agent may include a photoacid generator (PAG).

The photoacid generator may include an onium salt, a halogenated organic compound, a bis (sulfonyl) diazomethane compound, a sulfon compound, a sulfonate compound, an organic acid ester compound, an organic acid amide compound, an organic acid imide compound, May be used alone or in combination.

Examples of the onium salt include a diazonium salt, an ammonium salt, an iodonium compound, a sulfonium salt, a phosphonium salt, an arsonium salt, and an oxonium salt, which may be used alone or in combination.

Specific examples of the iodonium compound include di- (t-butylphenyl) iodonium triflate, diphenyliodonium tetrakis (pentafluorophenyl) borate, diphenyliodonium hexafluorophosphate, diphenyliodo (Octyloxy) phenyl] phenyliodonium hexafluoroantimonate, 4-methylphenyl [4- (octyloxy) phenyl] phenyl iodonium hexafluoroantimonate, (2-methylpropyl) phenyl] iodonium hexafluorophosphate (IRGACURE® 250, BASF, Germany).

Specific examples of the sulfonium salts include cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethane sulfonate, dicyclohexyl (2-oxocyclohexyl) sulfonium trifluoromethane sulfonate, 2-oxocyclohexyl 2-norbornyl) sulfonium trifluoromethanesulfonate, 2-cyclohexylsulfonylcyclohexanone, dimethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoromethane Sulfonate, diphenyl iodonium trifluoromethanesulfonate, N-hydroxysuccinimidyl trifluoromethanesulfonate, phenyl paratoluene sulfonate, tris [4- (4-acetylphenyl) sulfanylphenyl] sulfonium (IRGACURE 占 PAG 290, trade name, BASF, Germany), IRGACURE 占 270 and the like.

Specific examples of the halogenated organic compound include halogen-containing oxadiazole compounds, halogen-containing triazine compounds, halogen-containing acetophenone compounds, halogen-containing benzophenone compounds, halogen-containing sulfoxide compounds, halogen- Examples of the halogen-containing heterocyclic compound include halogen-containing oxazole-based compounds, halogen-containing triazole-based compounds, halogen-containing 2-pyrone compounds, other halogen-containing heterocyclic compounds, halogen-containing aliphatic hydrocarbon compounds, halogen-containing aromatic hydrocarbon compounds, . Specifically, there can be mentioned tris (2,3-dibromopropyl) phosphate, tris (2,3-dibromopropyl) phosphate, tris (2,3-dibromo-3- chloropropyl) Butane, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -S-triazine, hexachlorobenzene, hexabromobenzene, hexabromocyclo Tetrachlorobisphenol A, tetrabromobisphenol A, bis (chloroethyl) ether of tetrachlorobisphenol A, tetrachlorobisphenol S, tetrachlorobisphenol S, tetrachlorobisphenol S, tetrachlorobisphenol A, Bromobisphenol S, bis (2,3-dichloropropyl) ether of tetrachlorobisphenol A, bis (2,3-dibromopropyl) ether of tetrabromobisphenol A, bis (chloroethyl) ether of tetrachlorobisphenol S, Ether, bis (bromoethyl) ether of tetrabromobisphenol S, (2,3-dichloropropyl) ether of bisphenol S, bis (2,3-dibromopropyl) ether of bisphenol S, tris (2,3-dibromopropyl) isocyanurate, 2,2- Bis (4- (2-hydroxyethoxy) -3,5-dibromophenyl) propane, dichlorodiphenyltrichloro 2,4-dichlorophenyl ether, 2,4-dichlorophenyl ether, 3'-methoxy-4'-nitrophenyl ether, 2,4-dichlorophenoxy (4-chlorophenyl) ethanol, 1,1-bis (4-chlorophenyl) -2,2,2-trichloro Ethanol, 2,4,4 ', 5-tetrachlorodiphenylsulfide, 2,4,4'5-tetrachlorodiphenylsulfone and the like, which may be used alone or in combination.

Specific examples of sulfonates include sulfonic acid esters of quinone diazide derivatives such as 1,2-benzoquinone diazide-4-sulfonic acid ester and 1,2-naphthoquinone diazide-4-sulfonic acid ester; Diazide-4-sulfonic acid chloride, 1,2-naphthoquinone-2-diazide-4-sulfonic acid chloride, 1,2-naphthoquinone-diazide- Sulfonic acid chloride of a quinone diazide derivative such as a sulfonic acid chloride, 1,2-naphthoquinone-1-diazide-6-sulfonic acid chloride or 1,2-benzoquinone-1-diazide- ; Oxime sulfonates such as IRGACURE PAG 103 (trade name, BASF, Germany), IRGACURE PAG 121, IRGACURE PAG 203, IRGACURE CGI 1380, IRGACURE CGI 1907 and IRGACURE CGI 725.

Examples of the bis (sulfonyl) diazomethane-based compounds include α, α'-bis (sulfonyl) diazomethane having an unsubstituted, symmetrically or asymmetrically substituted alkyl group, alkenyl group, aromatic group, or heterocyclic group For example. These may be used alone or in combination.

Specific examples of the sulfone compound include a sulfone compound and a disulfone compound having an unsubstituted, symmetrical or asymmetrically substituted alkyl group, an alkenyl group, an aralkyl group, an aromatic group, or a heterocyclic group. These may be used alone or in combination.

Specific examples of the organic acid ester include a carboxylic acid ester, a sulfonic acid ester, and a phosphoric acid ester. Examples of the organic acid amide include a carboxylic acid amide, a sulfonic acid amide, and a phosphoric acid amide. , Carboxylic acid imides, sulfonic acid imides, and phosphoric acid imides. These may be used alone or in combination.

The content of the original blocking agent according to the present invention may be 50 to 400 parts by weight based on 100 parts by weight of the photochromic dye. Preferably, the content of the raw material blocking agent is 100 parts by weight to 200 parts by weight based on 100 parts by weight of the photochromic dye.

For example, when the content of the photo-discoloring dye is less than 50 parts by weight with respect to 100 parts by weight of the photochromic dye, the composition may be turned into a light-transmitting state when ultraviolet light is blocked. If the content of the raw blocker is more than 400 parts by weight based on 100 parts by weight of the photochromic dye, the effect of blocking the photochromic dye may be excellent, but the hydrogen ion concentration may be excessively increased, have.

When the composition is exposed to ultraviolet light, the composition can be blocked from being turned from a light shielding state to a light transmitting state by cation radicals and / or radicals decomposed from the raw shielding agent.

Alternatively, when the composition is exposed to ultraviolet light, the concentration of hydrogen ions ([H ⁺ ]) of the composition is increased by the above-mentioned blocking agent, thereby preventing the composition from being restored from the light shielding state to the light transmitting state. The composition has a pH of from about 5.5 to about 7.0 before being exposed to ultraviolet light, but the pH of the composition decreases from about 1.5 to about 3.0 after exposure to ultraviolet light. Hydrogen ion exponent (pH) is not that reduced the pH value ([H ^+]) is because it is synonymous with that increase, the hydrogen ion concentration ([H ^+]) of the composition after exposure to ultraviolet radiation is being exposed to ultraviolet It can be said that it is increased compared with the previous hydrogen ion concentration. For example, when IRGACURE (R) 250 (trade name, BASF, Germany) is used as the antifouling agent, the pH of the composition before UV irradiation is about 6 and the pH of the composition after UV irradiation is about 2 , The hydrogen ion concentration ([H ⁺ ]) increases after the irradiation compared to before the ultraviolet irradiation.

The visible light shielding composition according to the present invention may further comprise a polymer.

As the polymer, an acrylic polymer, a silicone polymer, an epoxy polymer or a urethane polymer may be used. These may be used alone or in combination of two or more.

In addition, the visible light shielding composition according to the present invention may further comprise a crosslinking agent together with the polymer. With the crosslinking agent, the polymer can be crosslinked to form a polymer resin.

Examples of the crosslinking agent include isocyanate compounds, epoxy compounds, silane compounds, melamine compounds, urea compounds, dialdehydes, methylol polymers, propyleneimine compounds, metal chelate compounds, metal alkoxides and metal salts . These may be used individually or in combination of two or more.

In the visible light blocking composition according to the present invention, the content of the photochromic dye may be 1 to 30 parts by weight based on 100 parts by weight of the polymer, and the content of the raw blocker may be 0.5 to 30 parts by weight based on 100 parts by weight of the polymer .

For example, when the content of the photochromic dye is less than 1 part by weight or less than 0.5 parts by weight based on 100 parts by weight of the polymer, the photochromic dye can be blocked, The transmittance according to the color change may be increased. If the content of any one of the photochromic dye and the original blocking agent is more than 30 parts by weight based on 100 parts by weight of the polymer, the effect of blocking the original coat is excellent and the transmittance of the composition after UV irradiation is lowered, The properties (coating property, uniformity) of the visible light shielding composition may be lowered. That is, it is possible to obtain a good original coat blocking effect without deteriorating other physical properties within the content range of the photochromic dye and the original blocking agent.

The visible light shielding composition according to the present invention may include a solvent for dissolving the dye and the original blocker. Examples of the solvent include ethyl acetate (EA), styrene monomer, methylene chloride, toluene, Tetrahydrofuran (THF) and the like can be used. These may be used alone or in combination of two or more.

The present invention provides a cured product obtained by curing the above-mentioned visible light shielding composition, wherein the cured product is a thermosetting product. The cured product has adhesiveness. The cured product may have a thickness of 5 탆 to 100 탆. For example, the composition may be coated on a base substrate and then cured to form a cured product having a thickness of 5 to 100 탆. Preferably, the thickness of the cured product is from 10 [mu] m to 30 [mu] m.

Hereinafter, specific examples of the light-shielding composition according to the present invention and evaluation of their properties will be described.

Example 1

0.15 g of a photo-discoloring dye as an isocyanate compound, 0.3 g of a photo-acid generator iodonium-based compound as a raw blocker, and 4 g of ethyl acetate (EA) as a solvent And 2 g of a styrene monomer were prepared, and the resulting composition was coated and thermally cured to prepare a cured product having a thickness of 25 탆.

The transmittance of the cured product in the light transmitting state was 82%, the transmittance in the light shielding state after irradiation with ultraviolet light of 13.4 J / cm 2 was 0.1% or less, and the transmittance was maintained at 0.1% or less even after one month. At this time, the transmittance was measured using a Cary-4000 instrument (trade name, Agilent Technologies, USA).

[Example 2]

The same procedure as in Example 1 was carried out except that an epoxy polymer was used as a polymer. The transmittance in the light transmitting state before the ultraviolet ray irradiation was 73%, the transmittance in the light shielding state after the ultraviolet ray irradiation was 0.07% or less, and the transmittance was maintained at 0.07% or less even after one month.

[Example 3]

The same procedure as in Example 1 was carried out except that a chromene-based compound was used as a photochromic dye. The transmittance in the light transmitting state before the ultraviolet ray irradiation was 64%, the transmittance in the light shielding state after the ultraviolet ray irradiation was 0.14% or less, and the transmittance was maintained at 0.14% or less even after one month.

Example 4

The same procedure as in Example 1 was carried out except that a photoacid generator sulfonium salt-based compound was used as a solvent blocking agent. The transmittance in the light transmitting state before ultraviolet ray irradiation was 82%, the transmittance in the light shielding state after ultraviolet ray irradiation was 0.04% or less, and the transmittance was maintained at 0.04% or less even after one month.

[Example 5]

The same as in Example 1 except that the dose of ultraviolet light was changed to 150 mJ / cm 2. The transmittance in the light transmitting state before the ultraviolet ray irradiation was 82%, the transmittance in the light shielding state after the ultraviolet ray irradiation was 2.8%, and the transmittance was maintained at 2.8% even after one month.

Referring to the results of the evaluation of the characteristics of the compositions according to Examples 1 to 5, it can be seen that the cured product of the composition according to the present invention contains the photo-discoloring dye together with the photosensitizing dye,

Meanwhile, the present invention provides a display device including the cured product. The display device may be an OLED, an LCD, or the like.

Hereinafter, a photochromic film using the composition according to the present invention and a display device using the same will be described with reference to the accompanying drawings. The range of the display device according to the present invention is not particularly limited, but an active matrix organic light-emitting diode (AMOLED) display device will be described as an example.

1 is a cross-sectional view of a photochromic film according to an embodiment of the present invention.

Referring to Fig. 1, the photochromic film 1 includes release films 1a and 1b and a photochromic layer 1c. The photochromic layer 1c includes a cured product of the composition according to the present invention described above. The photochromic layer 1c has a light-transmitting state.

2 is a cross-sectional view of a photochromic film according to another embodiment of the present invention.

Referring to Fig. 2, the photochromic film 2 includes a release film 2a, a base film 2b and a photochromic layer 2c. The photochromic layer 2c includes the cured product of the composition according to the present invention described above. The photochromic layer 2c has a light-transmitting state.

3 is a cross-sectional view conceptually showing a structure of an AMOLED display device according to an embodiment of the present invention.

Referring to FIG. 3, the AMOLED display device includes a light emitting element layer 10, a TFT layer 20, a base substrate 30, and a photochromic layer 40.

The light emitting device layer 10 includes an organic layer interposed between two electrodes facing each other. The organic layer may include a light emitting layer.

The TFT layer 20 is disposed between the base substrate 30 and the light emitting element layer 10 and includes an electrode pattern or circuit wiring used for driving the light emitting element of the light emitting element layer 10, .

The base substrate 30 may be a transparent substrate. The base substrate 30 may be a polymer substrate or a glass substrate. The polymer substrate may include a polyimide-based compound.

The photochromic layer 40 of FIG. 3 is such that the photochromic film 1 shown in FIG. 1 is attached to the base substrate 30 after the release films 1a and 1b on both sides are removed. Various kinds of deposits can be attached to the lower portion of the photochromic layer 40 as shown in FIG. 3, if necessary.

The photochromic layer 40 may be attached to the base substrate 30 in a light-transmitting state. Thereafter, when ultraviolet light is irradiated, the photochromic layer 40 is converted into a light shielding state.

In the manufacturing process of the AMOLED display device, the inspection process and / or the alignment process is performed through the base substrate 30 in the light-transmitting state. For this, the photochromic layer 40 is in a light-transmitting state during the inspection or alignment process.

However, after the inspection or alignment process is completed, the photochromic layer 40 is changed to a light shielding state by irradiating ultraviolet light to prevent the user from visually recognizing electrodes, wiring lines, pixel patterns, etc. existing in the AMOLED display device .

4 is a cross-sectional view conceptually showing a structure of an AMOLED display device according to an embodiment of the present invention.

The photochromic layer 50 shown in FIG. 4 can be formed by attaching the photochromic film 2 shown in FIG. 2 to the base substrate 30 after the release film 2a on one side is removed. Accordingly, one surface of the photochromic layer 50 is attached to the base substrate 30, and a base film 2b is attached to the other surface. As the base film 2b, a light transmitting film such as a PET film is generally used, and the surface of the base substrate 30 can be protected.

The photochromic layer 50 may be attached to the base substrate 30 in a light-transmitting state. Thereafter, when ultraviolet light is irradiated, the photochromic layer 50 is converted into a light shielding state.

As described above, the cured product according to the present invention has a photochromic property as well as a tackiness. This means that the light shielding state can be maintained by imparting photochromism to the adhesive layer used in the conventional display device and using the original blocking agent together. As a result, when the adhesive layer used for attaching the conventional protective film is replaced with the cured product according to the present invention, the process of the display device can be simplified and the thickness can be reduced.

1: photochromic film 1a: release film
1b: release film 1c: photochromic layer
2: photochromic film 2a: release film
2b: Base film 2c: Photochromic layer
10: light emitting element layer 20: TFT layer
30: base substrate 40: photochromic layer
50: photochromic layer

Claims (22)

Wherein the transmittance to visible light decreases when exposed to ultraviolet light.
The method of claim 1,
Wherein the visible light shielding composition has a transmittance to visible light of 30% or more before being exposed to ultraviolet light.
The method of claim 1,
And when exposed to ultraviolet rays, has a transmittance of 3% or less with respect to visible light.
The method of claim 3,
Wherein the visible light shielding composition is maintained at a transmittance of 3% or less with respect to visible light even when ultraviolet light is blocked after exposure to ultraviolet light.
The method of claim 1,
A visible light blocking composition comprising a photochromic dye and a sunscreen.
6. The method of claim 5,
Wherein the content of the original blocking agent is 50 to 400 parts by weight based on 100 parts by weight of the photochromic dye.
6. The method of claim 5,
When exposed to ultraviolet light, at least one of the ring structures of the photochromic dye is ring-
Wherein the ring-opened portion of the photochromic dye is blocked from being restored to the ring structure by the original blocking agent.
6. The method of claim 5,
Wherein upon exposure to ultraviolet light, at least a portion of the original blocking agent is cleaved to cation radicals and radicals.
6. The method of claim 5,
Wherein the hydrogen ion concentration is increased when exposed to ultraviolet rays.
6. The method of claim 5,
The photochromic dye is a visible light blocking composition, characterized in that it comprises at least one selected from the group consisting of a spirooxazine-based compound, a spiropyran-based compound and a chromium-based compound.
11. The method of claim 10,
Wherein the photochromic dye comprises a compound represented by the following formula (1);
≪ Formula 1 >

In Formula 1, X represents C or N,
R ₁ to R ₉ each independently represent a hydrogen atom, a cyano group, a nitro group, a halogen group, an amino group, a carboxyl group, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, An aryl group having 6 to 30 carbon atoms or a heterocyclic group having 4 to 30 carbon atoms,
R ₆ and R _7, or R ₇ and R _8, or R ₈ and R _{9 may} each independently represent a fused ring,
The fused rings represented by R ₆ and R ₇ , R ₇ and R _8, or R ₈ and R ₉ are each independently a cyano group, a nitro group, a halogen group, a hydroxyl group, an alkyl group having 1 to 30 carbon atoms, , An alkoxy group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, and a heterocyclic group having 4 to 30 carbon atoms, and having 6 to 30 carbon atoms, which is unsubstituted or substituted with at least one substituent selected from the group consisting of Or a heterocyclic group having 4 to 30 carbon atoms,
The hydrogen atoms of the substituents represented by R ₁ to R ₉ each independently represent an amino group, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms And a heterocyclic group having 4 to 30 carbon atoms.
11. The method of claim 10,
Wherein the chromene-based compound comprises a compound represented by the following general formula (2) or (3);
(2)

(3)

In each of formulas (2) and (3), R ₁₀ to R ₁₇ are each independently selected from the group consisting of hydrogen, cyano group, nitro group, halogen group, amino group, carboxyl group, alkyl group having 1 to 30 carbon atoms, cycloalkyl group having 3 to 30 carbon atoms, An alkoxy group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a heterocyclic group having 4 to 30 carbon atoms,
The hydrogen atoms of the substituents represented by R ₁₀ to R ₁₇ are each independently an amino group, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms And a heterocyclic group having 4 to 30 carbon atoms.
6. The method of claim 5,
The sunscreen agent is a visible light blocking composition, characterized in that it comprises a photoacid generator (PAG).
6. The method of claim 5,
The sunscreen agent comprises at least one selected from the group consisting of an iodonium compound, a sulfonium compound, and a sulfonate compound.
6. The method of claim 5,
Wherein the composition further comprises a polymer.
16. The method of claim 15,
Wherein the content of the photochromic dye is 1 to 30 parts by weight based on 100 parts by weight of the polymer.
16. The method of claim 15,
Wherein the content of the raw material blocking agent is 0.5 to 30 parts by weight based on 100 parts by weight of the polymer.
6. The method of claim 5,
Wherein the composition has a thermosetting property.
Hardened | cured material which hardened the visible light blocking composition of any one of Claims 1-18.
20. The method of claim 19,
Wherein the cured product is a thermoset.
20. The method of claim 19,
And has a thickness of 5 占 퐉 to 100 占 퐉.
A display device comprising the cured product of claim 19.

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