KR20150076652A - Photosensitive green resin composition, photosensitive material comprising the same, color filter manufactured by using the same and liquid crystal display device having the same - Google Patents

Abstract

Disclosed in the present specification are a photosensitive green resin composition, a photosensitive material manufactured using the same, a color filter, and a display device, which comprises: a) dye with solubility of 0.01-20% with respect to PGMEA at room temperature of 25°C; b) a binder resin; and c) a polymeric compound comprising an ethylene-type unsaturated bond.

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive green resin composition, a photosensitive material containing the same, a color filter manufactured using the same, and a liquid crystal display device including the same. BACKGROUND OF THE INVENTION [0001] THE SAME}

The present invention discloses a photosensitive green resin composition, a photosensitive material containing the same, a color filter manufactured using the same, and a liquid crystal display device including the same.

In recent years, LEDs or OLEDs have been widely used as light sources for liquid crystal displays (LCDs) instead of conventional CCFLs, and display products using LEDs or OLEDs that are not driven by liquid crystal are being produced. Generally, when an LED or OLED is used as a light source, red, green, and blue light are emitted, and therefore, a separate color filter is not required.

However, in most cases, color filters are used in order to improve the color purity of light emitted from an LED or OLED light source to achieve a high color reproduction ratio. Particularly, when a white light is produced by using an OLED light source, a color filter is necessarily required to distinguish colors.

At this time, it is necessary to optimize the spectrum of the OLED used as a light source and the spectrum of the color filter, thereby increasing the color purity and greatly improving the color reproduction rate.

In the case of a color filter using a conventional pigment type color photosensitive resin composition, the number of pigments having absorption and transmission spectra suited to a light source to be used is limited, and it is difficult to finely control absorption and transmission spectra.

Herein, a photosensitive green resin composition having a color coordinate system that can be used for a color filter of a liquid crystal display element and having improved luminance characteristics, and a photosensitive material, a color filter, and a liquid crystal display element using the photosensitive green resin composition are described.

An embodiment of the present disclosure includes a) a dye having a solubility in PGMEA of from 0.01 to 20% at room temperature (25 캜), b) a binder resin, and c) a polymeric compound comprising an ethylenically unsaturated bond, 0.240 to 0.320 and Gy: 0.550 to 0.650 when measured with a C light source of the CIE 1931 color coordinate system at 1 to 5 占 퐉. Here, the film thickness means the thickness of the film formed using the photosensitive green resin composition, and the film may be formed into a pattern as required. For example, when the photosensitive green resin composition is used as a material for a color filter, a film having a pattern can be formed using the photosensitive green resin composition.

Another embodiment of the present disclosure provides a photosensitive green resin composition wherein a) the dye absorbs light at 500 nm or less.

Another embodiment of the present disclosure provides a photosensitive green resin composition wherein a) the dye absorbs light at 380-500 nm.

Another embodiment of the present disclosure provides a photosensitive green resin composition wherein a) the dye absorbs at least 80% of light at 380-500 nm.

According to another embodiment of the present disclosure, the photosensitive green resin composition further comprises at least one of a green pigment and a yellow pigment.

Another embodiment of the present disclosure provides a photosensitive material formed using the photosensitive green resin composition.

Another embodiment of the present invention provides a color filter including the photosensitive material.

Another embodiment of the present invention provides a liquid crystal display element including the color filter.

The photosensitive green resin composition according to the present invention includes a dye having an excellent solubility in a specific solvent, so that other additives such as a dispersant or a binder may be additionally added in order to atomize the pigment through the existing chemical or physical method and maintain the atomized state It is possible to provide a photosensitive green resin composition having improved brightness. Therefore, the photosensitive green resin composition according to the present invention can achieve a green wavelength required for a color filter for a liquid crystal display device even at a thin film thickness, and the luminance characteristic can be improved. Specifically, by using the dye according to the present invention, when measured with a C light source of the CIE 1931 color coordinate system so as to be suitable for a liquid crystal display device even in a thin film thickness, the composition of Gx: 0.240 to 0.320, Gy: 0.550 to 0.650 Can be increased in the range of Gx: 0.270 to 0.290 and Gy: 0.550 to 0.570.

Figure 1 shows the absorption spectra of exemplary dyes used in accordance with the present disclosure.
Fig. 2 shows the spectra of the color patterns produced in Examples and Comparative Examples.
Fig. 3 shows a spectrum obtained by enlarging the green region in Fig.

Hereinafter, the present invention will be described in more detail.

The photosensitive green resin composition according to one embodiment of the present invention is a composition comprising a) a dye having a solubility in PGMEA of from 0.01 to 20% at 25 ° C at room temperature, b) a binder resin, and c) a polymerizable compound comprising an ethylenically unsaturated bond 0.240 to 0.320, Gy: 0.550 to 0.650, more preferably Gx: 0.270 to 0.290, and Gy: 0.550 to 0.570 when measured with a C light source of the CIE 1931 color coordinate system at a film thickness of 1 to 5 占 퐉. .

Another embodiment of the present disclosure provides a photosensitive green resin composition wherein a) the dye absorbs light at 500 nm or less.

Another embodiment of the present disclosure provides a photosensitive green resin composition wherein a) the dye absorbs light at 380-500 nm.

Another embodiment of the present disclosure provides a photosensitive green resin composition wherein a) the dye absorbs at least 80% of light at 380-500 nm.

As the dye (a), the dye absorbs light of 500 nm or less and has a maximum absorption wavelength in the range of 380 to 500 nm. Particularly, it is preferable to use a dye which transmits at least 80% of light of 500 nm or more as the dye (a). For example, the a) dyes include GPX-115. The dyes selected from GPX-116, GPX-117, GPX-119, GPX-128 and GPX-159 may be used alone, Together with at least one of GPX-116, GPX-117, GPX-119, GPX-128 and GPX-159. Dyes other than GPX-116, GPX-117, GPX-119, GPX-128 and GPX-159, or a mixture thereof may be used.

The a) dye may be contained in an amount of 0.01 to 20% by weight in the whole photosensitive green resin composition. Even in the case where such a small amount is included, a desired color coordinate can be obtained. Therefore, even in the case of a thin film thickness, the green wavelength of the color filter required in the liquid crystal display element can be realized.

Particularly, in the case of a color filter using a pigment type photosensitive resin composition containing only conventional pigments, the number of pigments having absorption and transmission spectra suitable for a light source to be used is limited, and it is difficult to finely control absorption and transmission spectra. Also, in the case of pigment, particle scattering and transmission light are reduced due to particle behavior, thereby lowering the contrast ratio and brightness. On the other hand, in the case of dyes, the scattering of light and the reduction of transmitted light can be reduced due to the molecular behavior, which can increase the contrast ratio and brightness. A hybrid type photosensitive composition of a dye type or a salt / pigment containing a dye and a pigment can be expected to have a higher contrast ratio and higher luminance than a photosensitive resin composition containing no dye.

In one embodiment of the present invention, the photosensitive green resin composition contains only the a) dye as a coloring material. For example, the photosensitive green resin composition is GPX-115. And may include a dye type coloring material composed solely of GPX-116, GPX-117, GPX-119, GPX-128 or GPX-159.

In one embodiment of the present invention, the photosensitive green resin composition comprises one or more additional coloring agents in addition to the dye (a). For example, the photosensitive green resin composition is prepared by mixing the above-mentioned GPX-115. At least one of GPX-116, GPX-117, GPX-119, GPX-128 and GPX-159 and one or more additional colorants selected from the group consisting of pigments and dyes.

Specifically, in one embodiment, the photosensitive green resin composition comprises the GPX-115. A dye comprising at least one of GPX-116, GPX-117, GPX-119, GPX-128 and GPX-159; And a coloring material of a mixed type of dyes not containing GPX-116, GPX-117, GPX-119, GPX-128 or GPX-159.

In another embodiment, the photosensitive green resin composition comprises the GPX-115. Pigment type, including dyes and pigments including GPX-116, GPX-117, GPX-119, GPX-128 and GPX-159.

In another embodiment, the photosensitive green resin composition comprises the GPX-115. GPX-115, GPX-117, GPX-119, GPX-128 and GPX-159. Including pigment and dye, which do not contain GPX-116, GPX-117, GPX-119, GPX-128 or GPX-159.

In the case of the color filter using the photosensitive green resin composition according to one embodiment of the present invention, absorption and transmission spectra suitable for a light source to be applied can be obtained by using various dyes and pigments, and a high color reproducibility, a high brightness and a high contrast ratio Can be achieved.

In the present specification, a pigment means a powdery coloring material that is insoluble in water and an organic solvent.

In the present specification, a dye means a coloring material which is dissolved in water and an organic solvent and is dispersed as a single molecule to be colored with a molecule such as a fiber.

The colorant in this specification means a pigment, a dye or a mixture of a pigment and a dye.

According to one embodiment of the present invention, the photosensitive green resin composition is GPX-115. At least one of GPX-116, GPX-117, GPX-119, GPX-128, and GPX-159 and a mixture of the coloring materials.

In one embodiment of the present invention, the photosensitive green resin composition comprises at least one of a green pigment and a yellow pigment.

In one embodiment of the present invention, the photosensitive green resin composition comprises a green pigment and a yellow pigment.

Examples of the green pigment include C.I. Pigment 7, 36, 37, 58 and the like, and is characterized in that 90% or more of 430 to 600 nm light is transmitted, and G7, G36, G58 and the like can be used. Especially, in the case of G58, it is effective to increase the luminance of the color filter using the green photosensitive green resin composition, and the structure is as follows.

The green pigment may be contained in an amount of 0.01 to 20% by weight in the total photosensitive green resin composition.

CI Pigment 11, 24, 31, 53, 83, 93, 99, 108, 109, 110, 138, 139, 147, 150, 151, 154, 155, 167, 180, 185, 199, , Absorbs light of 500 nm or less, and has a maximum absorption wavelength in the range of 380 to 500 nm. And transmits at least 80% of light having a wavelength of 500 nm or more. Especially, in the case of Y138, it is effective to increase the luminance of the color filter using the green photosensitive green resin composition, and the structure is as follows.

The yellow pigment may be contained in an amount of 0.01 to 20% by weight in the whole photosensitive green resin composition.

In the photosensitive green resin composition according to the present specification, as the binder resin, those generally used in the art such as an alkali-soluble binder resin can be used. Concretely, an acrylic binder resin containing a carboxyl group as alkali solubility can be used, and those having an acid value of 30 to 300 KOH mg / g and a weight average molecular weight of 1,000 to 200,000 can be used.

When the acid value is less than 30 KOH mg / g, the development is not performed well and a clear pattern can not be obtained. Also, when the acid value exceeds 300 KOH mg / g, the washing property is excessively improved and the pattern may be deteriorated.

When the weight average molecular weight of the alkali-soluble binder resin is less than 1,000, heat resistance and chemical resistance deteriorate. When the weight average molecular weight exceeds 200,000, the solubility of the alkali soluble binder resin in the developer becomes low and the viscosity of the solution becomes excessively high. It is not desirable.

The content of the binder resin is preferably 1 to 30% by weight based on the total weight of the photosensitive green resin composition, but is not limited thereto.

In the photosensitive green resin composition according to the present specification, examples of the polymerizable compound containing an ethylenically unsaturated bond include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethylene glycol di (meth) . Polyethylene glycol di (meth) acrylate, and the like, but is not limited thereto.

The content of the polymerizable compound containing an ethylenically unsaturated bond is preferably 1 to 30% by weight based on the total weight of the photosensitive green resin composition, but is not limited thereto.

The photosensitive green resin composition according to the present invention may further comprise d) a photoinitiator or e) a solvent.

In the photosensitive green resin composition according to the present specification, examples of the photoinitiator include 2,4-trichloromethyl- (4'-methoxyphenyl) -6-triazine, 2,4-trichloromethyl- 6-triazine, 1-hydroxycyclohexyl phenyl ketone, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy) propyl ketone, benzophenone, 2,4,6-trimethylaminobenzophenone, and the like, but the present invention is not limited thereto.

The content of the photoinitiator is preferably 0.1 to 5% by weight based on the total weight of the photosensitive green resin composition, but is not limited thereto.

In the photosensitive green resin composition according to the present invention, the solvent may be at least one selected from methyl ethyl ketone, propylene glycol diethyl ether, propylene glycol methyl ether acetate, 3-methoxybutyl acetate, dipropylene glycol monomethyl ether, Compounds may be used, but are not limited thereto.

The content of the solvent is preferably 45 to 95% by weight based on the total weight of the photosensitive green resin composition, but is not limited thereto.

The photosensitive green resin composition according to the present invention may further contain at least one selected from the group consisting of a curing accelerator, a thermal polymerization inhibitor, a surfactant, a photosensitizer, a plasticizer, an adhesion promoter, a filler, can do.

Examples of the curing accelerator include 2-mercaptobenzoimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2,5-dimercaptan-1,3,4-thiadiazole, 2- (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis Trimethylolpropane tris (2-mercaptoacetate), trimethylolpropane tris (2-mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate), trimethylolethane tris (3-mercaptopropionate), and the like, and may include those generally known in the art.

Examples of the thermal polymerization inhibitor include p-anisole, hydroquinone, pyrocatechol, t-butyl catechol, N-nitrosophenylhydroxyamine ammonium salt, N-nitrosophenylhydroxy Amine aluminum salt, and phenothiazine, but it is not limited thereto and may include those commonly known in the art.

The above-mentioned surfactants, photosensitizers, plasticizers, adhesion promoters, fillers, and the like can be used as well as any compounds that can be included in conventional photosensitive green resin compositions.

The content of the additive is preferably 0.01 to 5% by weight based on the total weight of the photosensitive green resin composition, but is not limited thereto.

Meanwhile, the photosensitive green resin composition according to the present invention is used for a roll coater, a curtain coater, a spin coater, a slot die coater, various printing, Substrate or the like. It is also possible to apply it onto a support such as a film and then transfer it to another support or coat it on a first support, transfer it to a blanket or the like, and transfer it to a second support again.

The present invention also provides a color filter manufactured using the photosensitive green resin composition.

The preparation of the color filter can be carried out by methods known in the art, except using the photosensitive green resin composition according to the present invention.

Specifically, a metal film such as Cr or a black resin film is coated on the transparent substrate and then patterned by a photolithography method or the like to form a black matrix as a boundary other than the pixel region where the color filter is formed.

Green, and blue color filters may be formed by injecting and curing the photosensitive green resin composition according to the present invention having a red, green, and blue color by an ink jet method on a pixel region defined as a transparent opening between the partition walls .

The present invention also provides a liquid crystal display element including the color filter. The display element may use a CCFL, an LED, or an OLED as a light source.

The manufacturing method of a liquid crystal display element according to this specification can use the art in the art, except that the photosensitive green resin composition of the present invention is used.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are intended to illustrate the invention and are not intended to limit the scope of the invention.

< Example >

A photosensitive green resin composition was prepared using the components shown in Table 1 below.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 G58 (g) 3.774 3.650 3.660 3.372 3.593 3.672 3.06 Y138 (g) 0.50 0.485 0.621 0.574 0.997 1.071 2.04 GPX-115 (g) 0.826 - - - - - - GPX-116 (g) - 0.965 - - - - - GPX-117 (g) - - 0.819 - - - - GPX-119 (g) - - - 1.154 - - - GPX-128 (g) - - - - 0.51 - - GPX-159 (g) - - - - - 0.357 - Binder resin (g) 17.84109 17.84109 17.84109 17.84109 17.84109 17.84109 17.84109 Photoinitiator (g) 1.19 1.19 1.19 1.19 1.19 1.19 1.19 Additive (g) 0.00391 0.00391 0.00391 0.00391 0.00391 0.00391 0.00391 The photopolymerizable compound (g) 5.865 5.865 5.865 5.865 5.865 5.865 5.865 Solvent (g) 70 70 70 70 70 70 70 Total content (g) 100 100 100 100 100 100 100 Binder resin: Copolymer of benzyl methacrylate and methacrylic acid (molar ratio 70:30, acid value 113 KOH mg / g, weight average molecular weight 20,000 as measured by GPC, molecular weight distribution (PDI) 2.0, solids content 25% , Solvent PGMEA)
Photoinitiator: I-369 (BASF)
Photopolymerizable compound: DPHA (Japanese explosive)
Additive: DIC F-475
Solvent: PGMEA (Propylene Glycol Mnomethyl Ether Acetate)

The photosensitive resin composition prepared in Example 1 was spin-coated on glass and pre-baked at 100 ° C for 100 seconds to form a film. The distance between the substrate on which the film was formed and the photo mask was set to 300 mu m, and an exposure amount of 40 mJ / cm &lt; ² &gt;

The exposed substrate was developed in a developing solution (KOH, 0.05%) for 60 seconds and post baked at 230 캜 for 20 minutes to obtain a color pattern. The color coordinates and brightness of the formed pattern were measured using an MCPD-2000 spectrometer.

In Examples 2 to 6 and Comparative Example 1, a color pattern was obtained in the same manner as in Example 1.

The color coordinates and the luminance of the color patterns formed using the compositions prepared in Examples 1 to 6 and Comparative Example 1 were measured, and the results are shown in Table 2 below.

Gx Gy Y Example 1 0.282 0.565 62.9 Example 2 0.285 63.2 Example 3 0.278 62.7 Example 4 0.281 62.6 Example 5 0.277 62.2 Example 6 0.284 63.5 Comparative Example 1 0.280 62.1

As shown in Table 2, it can be seen that the luminance is improved as compared with Comparative Example 1. [ Specifically, in the related art, when the same Gx or Gy is converted into a value, the luminance value Y is interpreted as a significant increase when the value is larger than 0.1.

The absorption spectra of the dyes used in Examples 1 to 6 are shown in Fig.

2 and 3 show the absorption spectra of the color patterns prepared using the compositions prepared in Examples 1 to 6 and Comparative Example 1.

As compared with the comparative example using only the pigment as shown in FIG. 2 and FIG. 3, the brightness was increased in Examples 1 to 6 as compared with the comparative example. This is because the permeability increased. According to FIG. 2, it can be seen that the transmittance of light is widened in the embodiment, and the luminance is increased as compared with the comparative example.

Claims (20)

a) a dye having a solubility in PGMEA of from 0.01 to 20% at room temperature (25 캜), b) a binder resin, and c) a polymerizable compound comprising an ethylenically unsaturated bond, 0.240 to 0.320 and Gy: 0.550 to 0.650, as measured by a C light source of the 1931 color coordinate system. 2. The photosensitive green resin composition according to claim 1, wherein the photosensitive green resin composition has a Gx of 0.270 to 0.290 and a Gy of 0.550 to 0.570 when measured with a C light source of a CIE 1931 color coordinate system when a thickness of 1 to 5 탆 is formed. The photosensitive green resin composition according to claim 1, wherein the dye absorbs light of 500 nm or less. The photosensitive green resin composition according to claim 1, wherein the dye absorbs light of 380 to 500 nm. The photosensitive green resin composition according to claim 1, wherein the dye absorbs light of 380 to 500 nm at 80% or more. [2] The composition of claim 1, wherein the a) dye is GPX-115. At least one selected from the group consisting of GPX-116, GPX-117, GPX-119, GPX-128 and GPX-159. The photosensitive green resin composition according to claim 1, wherein the photosensitive resin composition further comprises one or more additional colorants in addition to the dye (a). The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition is GPX-115. At least one selected from GPX-116, GPX-117, GPX-119, GPX-128 and GPX-159; And at least one of dyes and pigments other than those selected from GPX-116, GPX-117, GPX-119, GPX-128 and GPX-159. The photosensitive green resin composition according to claim 1, further comprising at least one of a green pigment and a yellow pigment. The photosensitive green resin composition according to claim 1, further comprising a green pigment and a yellow pigment. The photosensitive resin composition according to claim 10, wherein the photosensitive resin composition is GPX-115. And at least one selected from GPX-116, GPX-117, GPX-119, GPX-128 and GPX-159, G58, and Y138. The photosensitive green resin composition according to claim 1, further comprising d) a photoinitiator and e) a solvent. The photosensitive green resin composition according to claim 1, wherein the b) binder resin comprises an acrylic binder resin containing a carboxyl group. The photosensitive green resin composition according to claim 1, wherein the b) binder resin has an acid value of 30 to 300 KOH mg / g and a weight average molecular weight of 1,000 to 200,000. [12] The method of claim 12, wherein the content of the binder resin is 1 to 30% by weight based on the total weight of the photosensitive green resin composition, and the content of the polymerizable compound containing the ethylenically unsaturated bond c) %, The content of the d) photoinitiator is 0.1 to 5 wt%, and the content of the solvent is 45 to 95 wt%. The photosensitive green resin composition according to claim 1, wherein the photosensitive green resin composition further comprises at least one member selected from the group consisting of a curing accelerator, a thermal polymerization inhibitor, a surfactant, a photosensitizer, a plasticizer, an adhesion promoter, a filler, Sensitive green resin composition. A photosensitive material formed using the photosensitive green resin composition according to any one of claims 1 to 16. The photosensitive material according to claim 17, wherein Gx: 0.240 to 0.320 and Gy: 0.550 to 0.650 when measured with a C light source in the CIE 1931 color coordinate system at a film thickness of 1 to 5 탆. A color filter comprising the photosensitive material of claim 17. A liquid crystal display element comprising the color filter of claim 19.

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