KR20140147054A - Curable composition, cured film manufactured by using the curable composition and display device having the same - Google Patents

Abstract

The present invention relates to a curable composition, a cured film manufactured by using the same, and a display device including the same. The curable composition is produced by using a monomer mixture including one or more compounds represented by Chemical Formula 1 and one or more compounds represented by Chemical Formula 2. According to the present invention, the amount of gas emission from the cured film manufactured by using an organic and inorganic compound as a binder resin can be reduced.

Description

Technical Field [0001] The present invention relates to a curable composition, a cured film made therefrom, and a display device including the same. BACKGROUND OF THE INVENTION [0002]

TECHNICAL FIELD The present invention relates to a curable composition, a cured film produced thereby, and a display device including the same.

Liquid crystal displays (LCDs) using backlight units (BLU) of liquid crystal displays (LCDs) and light emitting diodes (LEDs), which occupy the largest portion in the display market in recent years, Is getting bigger. In general, organic light emitting devices (OLEDs) can be manufactured not only in thin films but also in improved color characteristics, and the response speed is significantly faster than that of a liquid crystal display (LCD) using liquid crystal driving. It has the advantage of being suitable.

In the small mobile market, active matrix organic light emitting diodes (AMOLED) and commercial matrix organic light emitting diodes (OLED) have already been commercialized. Various methods and technologies have been tried for large TVs. Among them, the white organic light emitting diode (WOLED) is a technique that can be more easily applied to a large display product using an organic light emitting diode (OLED), and a separate color filter layer is required in order to implement color for each pixel .

On the other hand, the organic light emitting diode (OLED) is easily deteriorated by a minute amount of an organic matter component or moisture, and the lifetime may be shortened. For this reason, if there are many materials that emit out-gassing among the materials used for forming the color filter, it may have a bad influence on the function of the OLED element.

Patent Publication No. 2001-0018075

The present invention is intended to provide a curable composition, a cured film made therefrom, and a display device including the same.

The present invention provides a curable composition comprising a binder resin prepared by using a monomer mixture comprising at least one compound represented by the following formula (1) and at least one compound represented by the following formula (2).

[Chemical Formula 1]

(2)

In the above Formulas 1 and 2,

R1 and Y1 are each independently a hydroxyl group, a linear or branched alkoxy or halogen group,

R2 and Y2 are each independently H, an aryl group having 6 to 12 carbon atoms or an alkyl group having 1 to 10 carbon atoms,

R3 and Y3 each independently represent an alkylene group having 1 to 10 carbon atoms,

R4, R5, R6, Y4, Y5 and Y6 are each independently H or an alkyl group having 1 to 10 carbon atoms,

l and o are each independently an integer of 2 to 4,

m, n, p and q are each independently an integer of 0 to 2,

l + m + n = 4, o + p + q = 2 to 4.

The present disclosure provides a cured film made from the curable composition.

The present specification provides a display device including the cured film.

The present specification has the effect of reducing the amount of gas discharged from a cured film produced by using an organic-inorganic compound as a binder resin.

Hereinafter, the present invention will be described in detail.

The present disclosure provides a curable composition comprising a binder resin made from an organic-inorganic compound.

The present disclosure provides a curable composition comprising a binder resin made of at least one silane compound and at least one titanium compound.

The present invention provides a curable composition comprising at least one compound represented by the following formula (1) and at least one compound represented by the following formula (2).

[Chemical Formula 1]

(2)

In the above Formulas 1 and 2,

R1 and Y1 are each independently a hydroxyl group, a linear or branched alkoxy or halogen group,

R2 and Y2 are each independently H, an aryl group having 6 to 12 carbon atoms or an alkyl group having 1 to 10 carbon atoms,

R3 and Y3 each independently represent an alkylene group having 1 to 10 carbon atoms,

R4, R5, R6, Y4, Y5 and Y6 are each independently H or an alkyl group having 1 to 10 carbon atoms,

l and o are each independently an integer of 2 to 4,

m, n, p and q are each independently an integer of 0 to 2,

l + m + n = 4, o + p + q = 2 to 4.

In the present specification, R1 and Y1 each independently may be a hydroxy group or a linear or branched alkoxy.

Wherein n is an integer from 1 to 2 and m is 0, m is an integer from 1 to 2, n is 0,

and l may be an integer of 2 to 4.

In the present specification, o may be four.

In the present specification, the compound represented by the formula (1) may be represented by the following formula (3) or (4).

(3)

[Chemical Formula 4]

R1, R2, R3, R4, R5, R6, l, m and n are as defined in the formula (1).

In the present specification, the compound represented by the formula (1) may be represented by the following formula (5) or (6).

[Chemical Formula 5]

[Chemical Formula 6]

In the general formulas (5) and (6), R2, R3, R4, R5, R6, l, m and n are as defined in formula (1), and R is a linear or branched alkyl group having 1 to 10 carbon atoms.

In the present specification, the compound represented by the formula (1) may be represented by the following formula (7).

(7)

In the above formula (7), R3, R4, R5 and R6 are as defined in the formula (1), and R is a linear or branched alkyl group having 1 to 10 carbon atoms.

In the present specification, the compound represented by the formula (1) may be represented by the following formula (8) or (9).

[Chemical Formula 8]

[Chemical Formula 9]

R 2, R 3, R 4, R 5, R 6, l and n in the general formulas (8) and (9)

In the present specification, the compound represented by the formula (1) may be represented by the following formula (10) or (11).

[Chemical formula 10]

(11)

In the general formulas (10) and (11), R 3 and R 4 are as defined in the formula (1), R is an alkyl group having 1 to 10 carbon atoms, and R 7 is an aryl group having 6 to 12 carbon atoms.

In the present specification, the compound represented by the formula (1) may be represented by the following formula (12) or (13).

[Chemical Formula 12]

[Chemical Formula 13]

In the above formula (12), R 3 and R 4 are as defined in formula (1).

In the present specification, the compound represented by Formula 2 may be represented by Formula 14 below.

[Chemical Formula 14]

Y1, Y2, o and p are as defined in the formula (2).

In the present specification, the compound represented by the formula (2) may be represented by the following formula (15).

[Chemical Formula 15]

Y2, o and p are as defined in the formula (2), and R is a linear or branched alkyl group having 1 to 10 carbon atoms.

In the present specification, the compound represented by the formula (2) may be represented by the following formula (16).

[Chemical Formula 16]

In Formula 16, R is a linear or branched alkyl group having 1 to 10 carbon atoms.

In the present specification, the compound represented by the formula (2) may be represented by the following formula (17).

[Chemical Formula 17]

According to one embodiment of the present invention, the molar ratio of the at least one compound represented by the formula (1) to the at least one compound represented by the formula (2) in the binder resin may be 5: 1 to 1: 5.

According to one embodiment of the present invention, the molar ratio of titanium (Ti) to silicon (Si) in the binder resin may be 5: 1 to 1: 5.

According to one embodiment of the present invention, the weight average molecular weight of the binder resin may be 1000 or more and 10,000 or less.

According to one embodiment of the present invention, the acid value of the binder resin may be 0 KOH mg / g or more and 100 KOH mg / g or less.

According to one embodiment of the present invention, the content of the binder resin may be 2 wt% or more and 50 wt% or less based on the total weight of the curable composition. In this case, there is an effect that the amount of gas discharged from the cured film manufactured using the same is reduced.

In the present specification, it may further include at least one of a polyfunctional monomer having an ethylenically unsaturated double bond, a thermal polymerization initiator, a surfactant, a curing accelerator, a plasticizer, an adhesion promoter, a filler, a coupling agent, a dispersant and a solvent.

The multifunctional monomer having an ethylenically unsaturated double bond may be selected from the group consisting of trimethylol ethane triacrylate, trimethylol propane triacrylate, neopentyl glycol (meth) acrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, di Pentaerythritol pentaacrylate, and the like. Other multifunctional monomers that can be used include epoxy acrylates of bisphenol A derivatives, novolac-epoxy acrylates, and urethane-based polyfunctional acrylates such as U-324A, U15HA, or U -4HA and the like can be used. The multifunctional monomers having an ethylenically unsaturated double bond may be used singly or in combination of two or more.

The thermal polymerization initiator may be an azo-based compound such as Wako Pure Chemical Industris. V-60, V-65, V-59, V-70, and V-40, which are azonitrile compounds, Azoester type V-601; VA-086, VA-085, VA-080, Vam-110, Vam-111, VF-096; V-50, VA-044, VA-046B, Aam-027, VA-060, VA-057, VA-061; And VPS-0501, VPS-1001, VPE-0201, VPE-0401, VPE-0601 and VPTG-0301 which are macroadjugging initiators may be further used.

The surfactant may be a silicone surfactant or a fluorine surfactant. Specifically, the silicone surfactant is BYK-077, BYK-085, BYK-300, BYK-301, BYK-302, BYK-306, BYK-307, BYK-310, BYK- , BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-335, BYK-341v344, BYK-345v346, BYK-348, BYK-354, BYK-355, BYK-370, BYK-371, BYK-370, BYK-380 and BYK-390 may be used. Examples of the fluorine surfactant include DIC (Dai Nippon Ink & Chemicals) F-177, F-410, F-411, F-450, F-493, F-494, F-443, F-444, F- F-474, F-477, F-478, F-479, F-480SF, F-482, F-483, F- MCF-350SF, TF-1025SF, TF-1117SF, TF-1026SF, TF-1128, TF-1127, TF-1129, TF- 1126, TF- 1441 or TF-1442 may be used, but the present invention is not limited thereto.

Examples of the curing accelerator include F-475 (Dai Nippon Ink & Chemicals), 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2- mercaptobenzoxazole, (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate), pentaerythritol (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), trimethylolpropane tris (2-mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate), trimethylolethane Tris (2-mercaptoacetate), and trimethylolethane tris (3-mercaptopropionate).

The coupling agent may be 3-methacryloxypropyltrimethoxysilane, and the dispersing agent may be a polyester dispersing agent or the like, but is not limited thereto.

The solvent is selected from the group consisting of propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, cyclohexanone, 2-heptanone, 3- 3-methoxypropionate, ethyl-3-methoxypropionate, methyl-3-ethoxypropionate, ethyl-3-ethoxypropionate Butyl acetate, butyl acetate, butyl acetate, amyl perate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, ethyl pyruvate, , Ethyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, Diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, 2-ethoxypropanol, 2-methoxypropanol, 3-methoxybutanol, cyclohexanone, cyclopentanone, 3-methoxy But are not limited to, butyl acetate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, methyl cellosolve acetate, butyl acetate, ethyl acetate, propyl acetate or dipropylene glycol monomethyl ether, It is not.

As the polyfunctional monomer having an ethylenically unsaturated double bond, a thermal polymerization initiator, a surfactant, a curing accelerator, a plasticizer, an adhesion promoter, a filler, a coupling agent, a dispersant or a solvent, those generally known in the art can be used.

According to one embodiment of the present disclosure, the curable composition may comprise a surfactant and a solvent.

According to one embodiment of the present invention, the content of the surfactant may be 0.01 wt% or more and 10 wt% or less based on the total weight of the curable composition.

According to one embodiment of the present invention, the content of the solvent may be 40 wt% or more and 90 wt% or less based on the total weight of the curable composition.

The present disclosure provides a cured film made from the curable composition.

The curable composition according to the present invention may be applied to a substrate such as a metal, a paper, a glass plastic substrate or the like through a roll coater, a curtain coater, a spin coater, a slot die coater, Lt; / RTI > support.

The curable composition according to one embodiment of the present invention may be applied onto a support such as a film and then transferred onto another support to prepare a cured film. It is also possible to apply the curable composition to a first support, transfer it to a blanket or the like, and transfer it to a second support again, and the application method is not particularly limited.

At this time, the curable composition may be a photo-curing composition or a thermosetting composition. The curable composition according to the present invention is preferably a thermosetting composition.

According to one embodiment of the present invention, in order to produce the cured film, the curable composition is pre-baked at 80 ° C or more and 100 ° C or less for 1 minute to 2 minutes, Min to 60 minutes to post-baked.

In some cases, an infrared lamp or the like may be used to obtain the same effect, and the present invention is not limited thereto.

According to one embodiment of the present disclosure, the cured film made of the curable composition may be for display.

The curable composition of the present invention can be used for a transparent protective film of a touch panel made of glass or a film. Specifically, the cured film may be used as a protective layer of a touch sensor.

In addition, it can be used as a transparent or colored layer thin film material used for manufacturing a thin film transistor liquid crystal display device color filter, general curable paint, ink, adhesive, printing plate, thermal curing agent for printed wiring board and the like.

The present specification has the effect of reducing the amount of gas discharged from a cured film produced by using an organic-inorganic compound as a binder resin.

The present invention provides a protective film comprising the cured film. Specifically, the protective film may be a transparent protective film.

According to one embodiment of the present disclosure, the cured film may have a visible light transmittance of 85% or more. More specifically, the transmittance may be 90% or 95% or more.

The present application discloses a method of manufacturing a semiconductor device, comprising: applying the curable composition on a substrate; And a step of curing the applied curable composition.

According to one embodiment of the present disclosure, the applied curable composition can be cured by heat.

The present specification provides a display device including the cured film.

The display device may include a plasma display panel (PDP), a touch panel, a light emitting diode (LED), an organic light emitting diode (OLED), a liquid crystal display (LCD) , A thin film transistor liquid crystal display (TFT-LCD), and a cathode ray tube (CRT).

The present specification provides a color filter comprising the cured film.

The color filter may further include a black mattress, a color pattern, and a common electrode. The color pattern may include, but is not limited to, a red pattern, a green pattern, and a blue pattern (RGB pattern).

According to one embodiment of the present disclosure, the color filter may include the cured film as the overcoat layer or the planarization layer provided on the black mattress, the color pattern, and the common electrode.

According to one embodiment of the present invention, the planarization degree of the cured film formed on the color filter is preferably 50% or more.

The test conditions for the planarization degree were a line-and-space pattern formed on a glass substrate such that the line width and the space pattern were 50 μm and 1.5 μm and the line and line spacing was 50 μm. On the substrate, the cured film composition obtained in the present invention was subjected to a pre-baked process at 100 캜 for 200 seconds so as to have a thickness of 5 탆 to volatilize the solvent. Thereafter, the cured film was further left in an oven at 230 ° C for 30 minutes to conduct a thermosetting reaction. The unevenness of the surface of the cured film was measured, the value obtained by dividing the value by 1.5 was subtracted from 1, and then multiplied by 100 to calculate the degree of planarization.

For example, assuming that the depth of the unevenness of the cured film is 0.5 占 퐉, the degree of planarization of the cured film is (1-0.5 / 1.5) 占 100 = 67%.

According to one embodiment of the present invention, it is preferable that the chemical resistance of the cured film formed on the color filter is within 10% based on the change in thickness under the condition of immersing in N-methylpyrrolidone at 70 캜 for 10 minutes.

The present specification will be described in more detail with reference to the following Synthesis Examples, Examples and Comparative Examples. However, the following synthesis examples, examples, and comparative examples are for illustrative purposes only, and the present invention is not limited thereto.

[Example 1]

19.94% by weight of a copolymer of methacryloxypropyltrimethoxysilane, titanium isopropoxide and diphenylsilane diol as a binder resin in a molar ratio of 1: 1: 3, based on the total weight of the curable composition, 80% by weight of propylene glycol monomethyl ether acetate was mixed with 0.06% by weight of F-475 (DaiNippon Ink & Chemicals) as a solvent, and the mixture was stirred for 5 hours to prepare a composition.

[Example 2]

The resin binder of Example 1 was added to the curable composition in a molar ratio of methacryloxypropyltrimethoxysilane, titanium isopropoxide and diphenylsilanediol of 0.5: 1.5: 3 as a low-temperature curable resin binder 19.94% by weight of the formed copolymer, and the other components were the same as in Example 1 to prepare a curable composition.

[Comparative Example 1]

(Meth) acrylate, N-phenylmaleimide, styrene and (meth) acrylic acid in a molar ratio of 50: 10: 10: 30 as a binder resin with respect to the total weight of the curable composition = 7,500, AV 125) 19.94% by weight, and the other components were the same as Example 1 to prepare a curable composition.

[Experimental Example 1]

Visible light transmittance measurement

Each of the curable composition solutions prepared in Examples 1 and 2 and Comparative Example 1 was spin-coated on glass and then pre-baked at about 90 ° C for 100 seconds. At this time, spin coating conditions were adjusted so that the thickness of each formed film was 2 mm. Then, the film was post-heat treated at 230 ° C. for 30 minutes, and then the transmittance was measured at a wavelength of 380 nm to 780 nm using an ultraviolet visible spectrophotometer (UV / Vis).

[Experimental Example 2]

Out-gassing measurement

Each of the curable composition solutions prepared in Examples 1 and 2 and Comparative Example 1 was spin-coated on glass and then pre-baked at about 90 ° C for 100 seconds. At this time, spin coating conditions were adjusted so that the thickness of each formed film was 2 mm. Then, the film was post-heated at 230 ° C for 30 minutes to form a film, and cut into 0.5 cm × 5 cm. Then, the obtained five substrates were used.

The prepared sample was subjected to a cold trap (purge & trap) method at a temperature of -40 DEG C after the gas component was heated at 230 DEG C for 20 minutes and then the trapped component Was quantitatively and qualitatively analyzed with a gas chromatograph-mass spectrometer (GC-MS) using toluene as a reference material.

Claims (13)

A curable composition comprising a binder resin prepared by using a monomer mixture comprising at least one compound represented by the following formula (1) and at least one compound represented by the following formula (2)
[Chemical Formula 1]

(2)

In the above Formulas 1 and 2,
R1 and Y1 are each independently a hydroxyl group, a linear or branched alkoxy or halogen group,
R2 and Y2 are each independently H, an aryl group having 6 to 12 carbon atoms or an alkyl group having 1 to 10 carbon atoms,
R3 and Y3 each independently represent an alkylene group having 1 to 10 carbon atoms,
R4, R5, R6, Y4, Y5 and Y6 are each independently H or an alkyl group having 1 to 10 carbon atoms,
l and o are each independently an integer of 2 to 4,
m, n, p and q are each independently an integer of 0 to 2,
l + m + n = 4, o + p + q = 2 to 4. The curable composition of claim 1, wherein R1 and Y1 are each independently a hydroxy group or a linear or branched alkoxy. The curable composition according to claim 1, wherein the compound represented by Formula 1 is represented by Formula 3 or 4:
(3)

[Chemical Formula 4]

R1, R2, R3, R4, R5, R6, l, m and n are as defined in the formula (1). The curable composition according to claim 1, wherein the compound represented by Formula 1 is represented by Formula 5 or 6:
[Chemical Formula 5]

[Chemical Formula 6]

In the general formulas (5) and (6), R2, R3, R4, R5, R6, l, m and n are as defined in formula (1), and R is a linear or branched alkyl group having 1 to 10 carbon atoms. The curable composition according to claim 1, wherein the compound represented by Formula 2 is represented by Formula 14:
[Chemical Formula 14]

Y1, Y2, o and p are as defined in the formula (2). The curable composition according to claim 1, wherein the compound represented by Formula 2 is represented by Formula 15:
[Chemical Formula 15]

Y2, o and p are as defined in the formula (2), and R is a linear or branched alkyl group having 1 to 10 carbon atoms. The thermosetting resin composition according to claim 1, which further comprises at least one of a polyfunctional monomer having an ethylenically unsaturated double bond, a thermal polymerization initiator, a surfactant, a curing accelerator, a plasticizer, an adhesion promoter, a filler, a coupling agent, Composition. The curable composition of claim 1, wherein the molar ratio of titanium (Ti) to silicon (Si) in the binder resin is from 5: 1 to 1: 5. A cured film made from the curable composition of any one of claims 1 to 8. The cured film according to claim 9, wherein the cured film has a visible light transmittance of 85% or more. Applying the curable composition of any one of claims 1 to 8 on a substrate; And curing the applied curable composition. 12. The method of claim 11, wherein the applied curable composition is cured by heat. A display device comprising the cured film of claim 9.