KR20190093115A - Colored photosensitive resin composition, color filter comprising black matrix and/or column spacer produced using the same, and image display device including color filter - Google Patents

Abstract

The present invention relates to a colored photosensitive resin composition in which the viscosity of each solvent is 20 mPa·s or less at 20°C, the vapor pressure of each solvent is 3.0 mmHg or less at 20°C, and all the solvents satisfy formula 1, ∑[(¦A_i-B_i¦)×M_i] < 1.5. In the formula 1, A_i is the viscosity (mPa·s) of each solvent at 20°C, B_i is the vapor pressure (mmHg) of each solvent at 20°C, and M_i is the weight ratio of each solvent in all the solvents. The colored photosensitive resin composition is excellent in leveling properties and can form a step to be designed, and surface defects or surface roughness of a formed black matrix, a column spacer or a black matrix-integrated column spacer can be effectively suppressed.

Description

Color photosensitive resin composition, an image display device including a color filter and a color filter comprising a black matrix and / or a column spacer manufactured using the same. COLORED PHOTOSENSITIVE RESIN COMPOSITION, COLOR FILTER COMPRISING BLACK MATRIX AND / OR COLUMN SPACER PRODUCED USING THE SAME, AND IMAGE DISPLAY DEVICE INCLUDING COLOR FILTER}

The present invention relates to a colored photosensitive resin composition, a black matrix manufactured by using the same, a column spacer or a black matrix integrated column spacer, a color filter including the same, and an image display device.

The display industry has undergone a radical change from cathode-ray tubes (CRTs) to flat panel displays represented by plasma display panels (PDPs), organic light-emitting diodes (OLEDs), liquid-crystal displays (LCDs), and the like. In particular, the LCD is a main product of the flat panel display market and is composed of a top plate with a color filter, a bottom plate with a thin film transistor (TFT), and a liquid crystal injected therebetween.

Color filters are a key component to express colors in LCDs, and have been adopted for a wide range of applications such as notebook PCs, monitors, and portable terminals, with the spread of flat panel displays. The color filter implements various colors on the screen through patterns of red (R), green (G), and blue (B) on the substrate, and between the red (R), green (G), and blue (B) patterns. A black matrix positioned at the to prevent light leakage between pixels, an overcoat (OC) to improve flatness by correcting the step difference between each pixel, and a column spacer to maintain a cell gap between the two substrates ( CS; column spacer).

Recently, a single material used in a display is required to simultaneously play various roles. A typical black matrix integrated column spacer requires not only the optical density (OD) required for the black matrix, but also excellent electrical insulation.

Korean Patent Laid-Open No. 2012-0033893 includes a binder resin, a polyfunctional monomer, a photopolymerization initiator or a photosensitizer, and a solvent, and a technique of adding black pigments such as aniline black, perylene black, and metal oxide as a coloring agent thereto. It is mentioned.

In addition, Korean Patent Publication No. 2013-0081019 further includes a copolymer having a specific polymerization unit in the photosensitive resin composition composed of an alkali-soluble resin, a polyfunctional monomer, a photopolymerization initiator and a solvent, and the copolymer is reactive to increase the degree of crosslinking. Mention is made to have functional groups to improve storage stability and chemical resistance in forming black matrix and black column spacers.

However, when the black matrix, the column spacer, or the black column spacer is formed using a conventional photosensitive resin composition, the leveling (flatness, degree of planarization) is somewhat insufficient, so that it is difficult to form a step to be desired and vacuum drying (VCD). ; vacuum dry) There are some problems with surface defects during the process.

Therefore, it is required to develop a colored photosensitive resin composition capable of easily forming a step to be excellent in leveling property and minimizing surface defects, thereby increasing the yield.

Republic of Korea Patent Publication No. 2013-0081019 (2013.07.16.) Republic of Korea Patent Publication No. 2012-0033893 (2012.04.09.)

An object of the present invention is to provide a colored photosensitive resin composition which is excellent in leveling property and capable of forming a desired step.

In addition, the present invention is to provide a black matrix, a column spacer or a black matrix integral column spacer, and a color filter and an image display apparatus including the same, which minimize surface defects or surface roughness.

This invention provides the coloring photosensitive resin composition in which the viscosity of each solvent is 2.0 mPa * s or less at 20 degreeC, the vapor pressure of each solvent is 3.0 mmHg or less at 20 degreeC, and the whole solvent satisfy | fills following formula (1).

[Equation 1]

∑ [(| A _i -B _i |) × M _i ] <1.5

In Formula 1,

A _i is the viscosity (mPa · s) of each solvent at 20 ° C.,

B _i is the vapor pressure (mmHg) of each solvent at 20 ℃,

M _i is the weight ratio of each solvent in the total solvent.

The present invention also provides a color filter comprising a black matrix, a column spacer, or a black matrix integrated column spacer containing the cured product of the above-mentioned colored photosensitive resin composition.

The present invention also provides an image display device including the above-described color filter.

As the coloring photosensitive resin composition according to the present invention has a low viscosity, it is possible to form a step to be designed with excellent leveling properties, and effectively suppresses surface defects or surface roughness of the formed black matrix, column spacer, or black matrix integrated column spacer. There is an advantage to this.

In addition, when the black matrix, the column spacer or the black matrix integrated column spacer is manufactured using the colored photosensitive resin composition according to the present invention, there is an advantage in that the acid resistance is increased.

In addition, a black matrix, a column spacer, or a black matrix integrated column spacer manufactured using the colored photosensitive resin composition according to the present invention has an advantage of minimizing surface defects and surface roughness, and the color filter and the image display apparatus including the same There is an advantage that the physical properties and performance is improved.

1 is a diagram illustrating a VCD surface stain evaluation image.

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

In the present invention, when a member is located "on" another member, this includes not only when one member is in contact with another member but also when another member exists between the two members.

In the present invention, when a part "includes" a certain component, this means that it may further include other components, without excluding the other components unless otherwise stated.

<Coloring Photosensitive Resin Composition>

An aspect of the present invention relates to a colored photosensitive resin composition in which the viscosity of each solvent is 2.0 mPa · s or less at 20 ° C., the vapor pressure of each solvent is 3.0 mmHg or less at 20 ° C., and the entire solvent satisfies the following formula (1). will be.

[Equation 1]

∑ [(| A _i -B _i |) × M _i ] <1.5

In Formula 1,

A _i is the viscosity (mPa · s) of each solvent at 20 ° C.,

B _i is the vapor pressure (mmHg) of each solvent at 20 ℃,

M _i is the weight ratio of each solvent in the total solvent.

The colored photosensitive resin composition of the present invention may further include a binder resin, a photopolymerizable compound, a photopolymerization initiator, a solvent or an additive, which are commonly used in the art.

solvent

The colored photosensitive resin composition which concerns on this invention is a viscosity of 20 mPa * s or less at 20 degreeC, the vapor pressure of each solvent is 3.0 mmHg or less at 20 degreeC, and the whole solvent contains the solvent which satisfy | fills following formula 1 do.

[Equation 1]

∑ [(| A _i -B _i |) × M _i ] <1.5

In Formula 1,

A _i is the viscosity (mPa · s) of each solvent at 20 ° C.,

B _i is the vapor pressure (mmHg) of each solvent at 20 ℃,

M _i is the weight ratio of each solvent in the total solvent.

Since the colored photosensitive resin composition according to the present invention includes a solvent satisfying the viscosity, vapor pressure, and Equation 1, it is possible to form a desired pattern step, high-speed coating is possible to shorten the production time, and also Surface defects, surface roughness, etc. that can occur during the VCD process can be suppressed to have an advantage of greatly increasing the productivity.

Specifically, the solvent according to the present invention satisfies the above-described viscosity, vapor pressure and the formula 1, but is compatible with the components that may be further included in the colored photosensitive resin composition, if not reacting in a conventional colored photosensitive resin composition The solvent to be used can be used without particular limitation. For example, the solvent may be various organic solvents such as ethers, acetates, aromatic hydrocarbons, ketones, alcohols or esters satisfying the above range.

In one embodiment of the present invention, the solvent is methyl-3-methoxy propionate (viscosity 1.1 mPa · s, vapor pressure 1.8 mmHg), propylene glycol methyl ether acetate (viscosity 1.3 mPa · s, vapor pressure 2.8 mmHg), Propylene glycol monoethyl ether acetate (viscosity 1.3 mPa · s, vapor pressure 2.8 mmHg), ethylene glycol monoethyl ether acetate (viscosity 1.3 mPa · s, vapor pressure 1.2 mmHg), methyl amyl ketone (viscosity 0.8 mPa · s, vapor pressure 2.1 mmHg) , Ethylene glycol monoethyl ether (viscosity 1.3 mPa · s, vapor pressure 1.2 mmHg), propylene glycol methyl ether propionate (viscosity 1.2 mPa · s, vapor pressure 0.9 mmHg), diethylene glycol dimethyl ether (viscosity 2.0 mPa · s, vapor pressure 3.0 mmHg), 2,6-dimethyl-4-heptanone (viscosity 0.9 mPa · s, vapor pressure 1.7 mmHg), pentyl propionate (viscosity 1.0 mPa · s, vapor pressure 1.5 mmHg), ethyl-3-ethoxy propio Nate (viscosity 1.3 mPas, vapor pressure 0.7 mmHg), 3-methoxybutyl acetate 0.7 mPa · s, vapor pressure 1.1 mmHg), dipropylene glycol dimethyl ether (viscosity 1.1 mPa · s, vapor pressure 0.6 mmHg), diethylene glycol ethylmethyl ether (viscosity 1.2 mPa · s, vapor pressure 0.7 mmHg), diethylene glycol iso At least one selected from the group consisting of propyl methyl ether (viscosity 1.3 mPa · s, vapor pressure 0.8 mmHg) and diethylene glycol diethyl ether (viscosity 1.4 mPa · s, vapor pressure 0.4 mmHg).

The said solvent may be used individually by 1 type, and may mix and use 2 or more types, if it satisfy | fills the said range. For example, when the solvent is included alone in the colored photosensitive resin composition, the solvent has a viscosity of 2.0 mPa · s or less at 20 ° C., a vapor pressure of 3.0 mmHg or less at 20 ° C., and the viscosity of the solvent. The value of vapor pressure | satisfies less than 1.5.

When the solvent is included as two kinds of the first solvent and the second solvent, the first solvent and the second solvent have a viscosity of 2.0 mPa · s or less at 20 ° C., and a vapor pressure of 3.0 mmHg or less at 20 ° C., | The sum of the viscosity of the 1st solvent-the vapor pressure of the 1st solvent | x ratio of the 1st solvent, and the viscosity of the 2nd solvent-the vapor pressure of the 2nd solvent | x 2nd solvent satisfies less than 1.5.

The solvent may have a viscosity of 20 mPa · s or less, preferably 1.8 mPa · s or less, and more preferably 0.8 mPa · s to 1.6 mPa · s at 20 ° C. In this case, since the viscosity of the solvent is low, the occurrence of coating stains and the like is suppressed even at high-speed coating in a large-sized line, so that mass production is easy, and the planarization characteristic is excellent, and thus, there is an advantage in that step formation can be designed. Specifically, as the viscosity of the resist becomes too low, it is possible to suppress the problem of increasing the solid content or increasing the discharge amount in order to form a sufficient coating film, and as the viscosity of the resist becomes too high, staining or flattening characteristics are poor at high speed coating. The problem that the desired step is not formed can be suppressed.

The solvent may be a vapor pressure of 20mmHg or less, preferably 2.9mmHg or less, more preferably 0.5mmHg to 2.8mmHg at 20 ℃. In this case, it is preferable to obtain a uniform coating film without defects on the pattern surface appearing in the VCD process when the vapor pressure of the solvent is within the above range, and to shorten the VCD process time to increase the mass production.

In still another embodiment of the present invention, the entire solvent may satisfy the following formula (2).

[Equation 2]

∑ [(| A _i -B _i |) × M _i ] <1.38

In Equation 2,

A _i , B _i , M _i are as defined in the formula (1).

Since the solvent according to the present invention satisfies Equation 1, preferably Equation 2 above, the coating uniformity is high even at high viscosity during high-speed coating in a large-scale production line, and stains and uncoating do not occur, and a rapid solvent by the VCD process. There is an advantage that the surface bonding due to volatilization or VCD process time does not increase, there is an advantage that can mass-produce a coating film having a uniform height difference to be made.

If the solvent according to the present invention satisfies the above range, it can be used irrespective of the boiling point has the advantage of minimizing the surface defects due to the strong volatilization of the solvent during the low viscosity VCD process.

In another embodiment of the present invention, the solvent may be included from 60 to 90 parts by weight, preferably 65 to 85 parts by weight based on 100 parts by weight of the total color photosensitive resin composition. When the solvent is included in the above range, it is easy to form a step to be designed because of excellent leveling property, and effectively suppresses surface defects or surface roughness of the coating film, that is, the black matrix and / or column spacer made of the colored photosensitive resin composition. Can be. In addition, the coloring photosensitive resin composition containing the solvent according to the present invention is preferred because it can satisfy processability and reliability, such as developability, solvent resistance and electrical properties, when forming the cured layer.

coloring agent

In still another embodiment of the present invention, the colored photosensitive resin composition of the present application may further include a colorant.

The colorant may include a colored organic pigment, and in some cases, a black organic / inorganic pigment may be mixed and used.

In another embodiment of the present invention, the colorant may further include one or more pigments selected from the group consisting of orange pigments, purple pigments and blue pigments.

In another embodiment of the present invention, the colorant may further include a black pigment.

The colorant may further include a green pigment and the like, and the black, orange, blue, green, and purple pigments may be used without limitation as long as they are pigments commonly used in the art. For example, a compound classified as a pigment in the color index may be used, and may further include a known dye.

The orange pigment is for example C.I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 43, 46, 48, 49, 61, 62, 64, 65, 67 , At least one selected from the group consisting of 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, and 79, and CI It is most preferable to use the pigment orange 64, 72 including.

The orange pigment may serve to improve optical density by reducing transmittance in the region of 400 to 550 nm.

The orange pigment may be included in an amount of 5 to 40 parts by weight, preferably 8 to 30 parts by weight, more preferably 10 to 20 parts by weight, based on 100 parts by weight of the total colorant solids, in which case the light absorption of the ultraviolet region is In other words, there is an advantage that a coating film having excellent pattern shape, step control and adhesion, and optical density can be obtained.

As said purple pigment, C.I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32 , 37, 39, 42, 44, 47, 49 and 50. Among these, C.I. Pigment violet 19, 23, 29, and C.I. It is more preferable to use pigment violet 23, 29.

The purple pigment may be included in 10 to 40 parts by weight, preferably 15 to 35 parts by weight, more preferably 20 to 35 parts by weight based on 100 parts by weight of the total colorant solids, but is not limited thereto. When the purple pigment is included in the above range, there is an advantage that a colored photosensitive resin composition having excellent light shielding properties can be obtained.

As said blue pigment, C.I. Pigment Blue 1, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36 , 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79. Among these, C.I. Pigment blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 60, and C.I. It is more preferable to use Pigment Blue 15: 6, 16, 60.

The blue pigment may be included in an amount of 10 to 40 parts by weight, preferably 15 to 40 parts by weight, and more preferably 20 to 40 parts by weight based on 100 parts by weight of the total colorant solids, but is not limited thereto. However, when the said range is satisfied, since the manufacture of the coloring photosensitive resin composition excellent in dispersibility and light-shielding properties is possible, it is preferable.

The green pigment is for example C.I. Pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58, 59 and the like. have. In terms of light shielding and color correction, C.I. It is preferable to use Pigment Green 7, 36, 54, 58, 59, more preferably in consideration of the electrical properties C.I. The use of pigment green 54 is mentioned.

In the case of combining pigments of different colors, the combination of colors is not particularly limited, but a combination of, for example, a blue pigment, a green pigment, an orange pigment, and a purple pigment may be used in view of light blocking properties, 950 nm transmittance, and reliability. It may be preferable because of excellent shielding properties.

Specifically, the colored photosensitive resin composition according to the present invention may further include a black pigment to adjust the optical properties. The black pigment may be an inorganic or organic pigment as a colorant, and more specifically, carbon black, atetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black, titanium black, ramtam black, perylene black And the like, and inorganic pigments and organic pigments may be used alone or in combination depending on the purpose.

Among these, carbon black is preferably used in terms of improving uniform light shielding and chemical resistance even at a small amount, and the carbon black is more than 0 and 20 parts by weight or less, preferably 100 parts by weight of the total colorant solids. It may be included in 4 to 20 parts by weight.

The black pigment may further include an organic black, in which case the organic black may be included in an amount of 3 to 25 parts by weight, more preferably 8 to 20 parts by weight, based on 100 parts by weight of the total colorant solids. When the organic black is included in the above range, there is an advantage in that a coating film having excellent optical density and excellent product reliability can be formed.

The colorant may be included in an amount of 20 to 55 parts by weight, preferably 23 to 50 parts by weight, based on 100 parts by weight of the total color photosensitive resin composition solids. When the said coloring agent is contained in the said range, while excellent shielding property (optical density, OD) can be obtained, there exists an advantage which is excellent in pattern formation property and reliability, and is preferable.

When the colored photosensitive resin composition according to the present invention is used as a black matrix, the coloring agent may serve to prevent light leakage of the black matrix by imparting light blocking properties, and the colored photosensitive resin composition according to the present invention may be used as a column spacer. If it is possible to maintain a constant elastic modulus, it can play a role to maintain the cell gap.

The black matrix and column spacer may be integral. In short, the coloring photosensitive resin composition which concerns on this invention can be used for manufacture of a black matrix integrated column spacer. The black matrix integrated spacer does not form the black matrix and the column spacer, respectively, but may serve as both the black matrix and the column spacer in one pattern, and the colored photosensitive resin composition according to the present invention may be used.

In another embodiment of the present invention, the colored photosensitive resin composition is an alkali-soluble resin; Photopolymerizable compounds; Photopolymerization initiator; And it may further include one or more selected from the group consisting of additives.

Alkali soluble resin

The colored photosensitive resin composition according to the present invention may include an alkali soluble resin.

The alkali-soluble resin has reactivity and alkali solubility due to the action of light or heat, and can act as a dispersion medium for solids including colorants and function as a binder resin.

Alkali-soluble resins according to the present invention are selected and used having an acid value of 50 to 200 (KOHmg / g). The acid value is a value measured as the amount of potassium hydroxide (mg) required to neutralize 1 g of the acrylic polymer and is involved in solubility. If the acid value of the alkali-soluble resin is less than the above range, it is difficult to secure a sufficient developing speed. On the contrary, if the acid value of the alkali-soluble resin exceeds the above range, adhesion to the substrate is reduced, so that short-circuit of the pattern is likely to occur, and the storage stability of the entire composition is lowered to increase the viscosity. The problem arises.

In addition, the alkali-soluble resin may consider the limitation of the molecular weight and the molecular weight distribution (Mw / Mn) in order to improve the surface hardness for use as a color filter. Preferably, the weight average molecular weight is 3,000 to 40,000, preferably 5,000 to 20,000, and the molecular weight distribution is 1.5 to 6.0, preferably 1.8 to 4.0 to directly polymerize or purchase and use. Alkali-soluble resins having a molecular weight and a molecular weight distribution in the above range have improved hardness, high residual film ratio, as well as solubility of non-exposed portions in the developing solution and can improve resolution.

The alkali-soluble resin includes at least one member selected from the group consisting of polymers of carboxyl group-containing unsaturated monomers, copolymers with monomers having unsaturated bonds copolymerizable therewith, and combinations thereof.

In this case, the carboxyl group-containing unsaturated monomer may be unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, unsaturated tricarboxylic acid, or the like. Specifically, as unsaturated monocarboxylic acid, acrylic acid, methacrylic acid, crotonic acid, (alpha)-chloroacrylic acid, cinnamic acid etc. are mentioned, for example. As unsaturated dicarboxylic acid, a maleic acid, a fumaric acid, itaconic acid, a citraconic acid, a mesaconic acid, etc. are mentioned, for example. The unsaturated polyhydric carboxylic acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic anhydride and citraconic anhydride. In addition, the unsaturated polyhydric carboxylic acid may be mono (2-methacryloyloxyalkyl) ester thereof, for example, succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2-methacryloyloxyethyl ), Mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate, etc. are mentioned. The unsaturated polyhydric carboxylic acid may be mono (meth) acrylate of the sock end dicarboxy polymer, for example, ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate, and the like. . These carboxyl group-containing monomers can be used individually or in mixture of 2 or more types, respectively.

The monomers copolymerizable with the carboxyl group-containing unsaturated monomers include aromatic vinyl compounds, unsaturated carboxylic ester compounds, unsaturated carboxylic acid aminoalkyl ester compounds, unsaturated carboxylic acid glycidyl ester compounds, carboxylic acid vinyl ester compounds, and unsaturated monomers. In the group consisting of ether compounds, vinyl cyanide compounds, unsaturated imide compounds, aliphatic conjugated diene compounds, macromonomers having monoacryloyl groups or monomethacryloyl groups at the ends of the molecular chain, bulky monomers, and combinations thereof One selected is possible.

More specifically, the copolymerizable monomer may be styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p- Methoxy styrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl Aromatic vinyl compounds such as ether and indene; Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxy Ethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxy Hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl Relate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl Methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol meth Methacrylate, methoxy propylene glycol acrylate, methoxy propylene glycol methacrylate, methoxy dipropylene glycol acrylate, methoxy dipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadier Nyl acrylate, dicyclopentadiethyl methacrylate, adamantyl (meth) a Relate, norbornyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate, etc. Unsaturated carboxylic esters of; 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethyl Unsaturated carboxyl such as aminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate and 3-dimethylaminopropyl methacrylate Acid aminoalkyl ester compounds; Unsaturated carboxylic acid glycidyl ester compounds such as glycidyl acrylate and glycidyl methacrylate; Carboxylic acid vinyl ester compounds such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; Unsaturated ether compounds such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether; Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and vinylidene cyanide; Unsaturated amides such as acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethylacrylamide and N-2-hydroxyethyl methacrylamide; Unsaturated imide compounds such as maleimide, benzylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; And monoacryloyl or monomethacryloyl groups at the terminal of the polymer molecular chain of polystyrene, polymethylacrylate, polymethylmethacrylate, poly-n-butylacrylate, poly-n-butylmethacrylate, polysiloxane. Macromonomers having; Bulky monomers, such as a monomer having a norbornyl skeleton, a monomer having an adamantane skeleton, and a monomer having a rosin skeleton, can lower the dielectric constant.

The alkali-soluble resin may be included in 1 to 30 parts by weight, preferably 3 to 20 parts by weight, more preferably 5 to 10 parts by weight based on 100 parts by weight of the total color photosensitive resin composition.

When the alkali-soluble resin is included in the above range, the solubility in the developing solution is sufficient, so that pattern formation is easy, and the film reduction of the pixel portion of the exposed portion is prevented at the time of development, so that the dropping of the non-pixel portion is good, which is preferable.

If the alkali-soluble resin is included in less than the above range, the non-pixel portion may be somewhat missing, and when the alkali-soluble resin is included in more than the above range, the solubility in the developing solution is slightly lowered may be somewhat difficult to form a pattern.

Photopolymerizable  compound

The photopolymerizable compound contained in the coloring photosensitive resin composition of this invention is a compound which can superpose | polymerize by the action of light and the photoinitiator mentioned later, A monofunctional monomer, a bifunctional monomer, another polyfunctional monomer, etc. are mentioned.

The kind of the monofunctional monomer is not particularly limited, and for example, nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acryl The rate, N-vinylpyrrolidone, etc. are mentioned.

The kind of the said bifunctional monomer is not specifically limited, For example, 1, 6- hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and triethylene Glycol di (meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like.

The kind of the polyfunctional monomer is not particularly limited, and examples thereof include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylol propane tri (meth) acrylate, and propoxylated trimethylolpropane tree (meth). ) Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (Meth) acrylate, propoxylated dipentaerythritol hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are mentioned.

Commercially available examples of the photopolymerizable compound include, but are not limited to, DPHA of Nippon Gunpowder.

The photopolymerizable compound may be included in an amount of 1 to 30 parts by weight, preferably 1 to 20 parts by weight, and more preferably 2 to 10 parts by weight, based on the total weight of the coloring photosensitive resin composition. It is advantageous in terms of negative strength and smoothness.

When the photopolymerizable compound is included in the range below, the intensity of the pixel portion may be lowered slightly, and when the photopolymerizable compound is included in the above range, smoothness may be slightly lowered, so it is preferably included within the range. .

Photopolymerization Initiator

The coloring photosensitive resin composition which concerns on this invention can contain a photoinitiator.

The photoinitiator can use the photoinitiator generally used for a coloring photosensitive resin composition. For example, acetophenone series, benzophenone series, triazine series, thioxanthone series, oxime series, benzoin series, biimidazole series compounds and the like can be used.

Acetophenone compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-1- [4- (2-hydroxyethoxy) Phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl- Oligomers of 2-dimethylamino-1- (4-morpholinophenyl) butan-1-one and 2-hydroxy-2-methyl [4- (1-methylvinyl) phenyl] propan-1-one are possible. Among them, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one can be preferably used.

As the benzophenone compound, benzophenone, benzoyl benzoic acid, benzoyl benzoic acid methyl, 4-phenyl benzophenone, hydroxy benzophenone, acrylated benzophenone, 4,4'-bis (dimethyl amino) benzophenone, 4,4'-bis (Diethyl amino) benzophenone and the like are possible.

Examples of triazine compounds include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine and 2- (3 ', 4' '-dimeth Methoxy styryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-methoxy naphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(p-methoxy phenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tril) -4,6-bis (trichloromethyl) -s-triazine, 2 -Biphenyl-4,6-bis (trichloromethyl) -s-triazine, bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho 1-yl) -4,6 -Bis (trichloro methyl) -s-triazine, 2- (4-methoxy naphtho 1-yl) -4,6-bis (trichloro methyl) -s-triazine, 2,4-trichloro methyl (Piperonyl) -6-triazine, 2,4-trichloro methyl (4'-methoxy styryl) -6-triazine and the like.

Examples of the thioxanthone compound include 2-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichloro thioxanthone, 1-chloro-4-propoxy thioxanthone, and the like.

Examples of the oxime compound include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one and the like, and commercially available products such as OXE-01 and OXE-02 from Ciba.

As the benzoin compound, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal and the like can be used.

Biimidazole type compounds include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5' '-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl ) -4,4 ', 5,5' '-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5 ''-tetra (alkoxyphenyl) biimi Dazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5' '-tetra (trialkoxyphenyl) biimidazole, phenyl group at 4,4', 5,5 '' position The imidazole compound etc. which are substituted by the carboalkoxy group are possible.

The photopolymerization initiator may be used in an amount of 0.01 to 10 parts by weight, preferably 0.01 to 5 parts by weight within 100 parts by weight of the colored photosensitive resin composition. This content range takes into account the photopolymerization rate of the photopolymerizable compound and the physical properties of the final obtained coating film, and if it is less than the above range, the overall polymerization time may be low due to the low polymerization rate. Since the physical property of a coating film may fall rather, it uses suitably within the said range.

In addition, a photopolymerization initiation aid may be used together with the photopolymerization initiator. When the photopolymerization initiation aid is used together with the photopolymerization initiator, the photosensitive resin composition is more sensitive, and thus productivity is preferable. As the photopolymerization initiation aid, one or more compounds selected from the group consisting of amines and carboxylic acid compounds may be preferably used.

Such photopolymerization initiation adjuvant is preferably used in the range of usually 10 mol or less, preferably 0.01 to 5 mol per mol of the photopolymerization initiator. When using a photopolymerization start adjuvant within the said range, it can anticipate the effect of productivity improvement by raising polymerization efficiency.

additive

The colored photosensitive resin composition according to the present invention may further include additives such as a dispersant, an adhesion promoter, and a leveling agent to enhance the coating property or adhesion.

For example, the coloring photosensitive resin composition according to the present invention may further include a dispersant so that the optical and physical quality of the color filter to be produced is excellent. The dispersant is not particularly limited as long as it is commonly used in the art, and examples thereof include polyacrylic dispersants, polyester dispersants, polyethyleneimine dispersants, polyurethane dispersants, and the like, and are commercially available SOLSPERSE 5000/20000 /. 24000 (manufactured by Lubrisol) can be used.

The adhesion promoter may include a silane coupling agent having a reactive substituent selected from the group consisting of carboxyl groups, methacryloyl groups, isocyanate groups, epoxy groups, and combinations thereof, which may be added to increase adhesion to the substrate. It is not limited. For example, the silane coupling agent is trimethoxysilyl benzoic acid, γ-methacryl oxypropyl trimethoxy silane, vinyltriacetoxysilane, vinyl trimethoxysilane, γ-isocyanate propyl triethoxysilane, γ-glycidoxy If propyl trimethoxysilane, (beta)-(3, 4- epoxycyclohexyl) ethyltrimethoxysilane, etc. are mentioned, these can be used individually and in combination of 2 or more types.

When the colored photosensitive resin composition according to the present invention includes the leveling agent, there is an advantage that the coating property can be improved. For example, the leveling agent is BM-1000, BM-1100 (BM Chemie Co., Ltd.), Proride FC-135 / FC-170C / FC-430 (Sumitomo 3M Co., Ltd.), SH-28PA / -190 / SZ-6032 (Dore Siri Fluorine leveling agents such as F-475 and F554 of DIC Corporation, but are not limited thereto.

In addition, the coloring photosensitive resin composition according to the present invention may further include additives such as antioxidants, ultraviolet absorbers, and anti-agglomerating agents in a range that does not impair the effects of the present invention, and the additives also do not impair the effects of the present invention. It can be used by those skilled in the art as appropriate without departing from the scope. For example, the additive may be used in an amount of 0.05 to 10 parts by weight, specifically 0.1 to 10 parts by weight, more specifically 0.1 to 5 parts by weight, based on 100 parts by weight of the total color photosensitive resin composition, but is not limited thereto.

<Color filter>

Another aspect of the present invention relates to a black matrix of a color filter comprising the cured product of the above-mentioned colored photosensitive resin composition.

Another aspect of the present invention relates to a column spacer of a color filter comprising a cured product of the above-mentioned colored photosensitive resin composition.

Another aspect of the present invention relates to a black matrix-integrated column spacer of a color filter comprising a cured product of the above-mentioned colored photosensitive resin composition.

Moreover, another aspect of this invention is related with the color filter which contains the hardened | cured material of the coloring photosensitive resin composition mentioned above as a black matrix, a column spacer, or a black matrix integrated column spacer.

Specifically, the color filter may include a black matrix manufactured using the above-mentioned colored photosensitive resin composition.

In addition, the color filter may include a column spacer manufactured using the above-described colored photosensitive resin composition.

In addition, the color filter may include a black matrix integrated column spacer manufactured by using the above-mentioned colored photosensitive resin composition.

Specifically, the black matrix, the column spacer, the black matrix integrated column spacer may be a layer including a cured product of the colored photosensitive resin composition of the present invention, and the coated photosensitive resin composition may be coated and exposed, developed, and heated in a predetermined pattern. It may be a layer formed by curing, and a method of manufacturing a color filter including the black matrix, the column spacer, or the black matrix integrated column spacer may be formed by performing a method commonly known in the art.

The black matrix, the column spacer and the black matrix integrated column spacer have a viscosity of 2.0 mPa · s or less at 20 ° C., a vapor pressure of 3.0 mmHg or less at 20 ° C., and a solvent that satisfies Equation 1 below. Since it is manufactured by using the optical effect for the basic light-shielding performance is not only excellent, but also excellent in elastic modulus and reliability, excellent leveling properties, there is an advantage that the formation of the step is excellent and the surface defects or surface roughness is minimized.

<Image display device>

Further, another aspect of the present invention relates to an image display apparatus including the color filter described above.

The color filter of the present invention can be applied to various image display devices such as electroluminescent display devices, plasma display devices, field emission display devices, as well as ordinary liquid crystal display devices.

The image display device according to the present invention has a viscosity of 2.0 mPa · s or less at 20 ° C., a vapor pressure of 3.0 mmHg or less at 20 ° C., and a solvent that satisfies Equation 1 below; Since the color filter is included, there is an advantage not only in excellent processability but also in reliability.

Hereinafter, the present invention will be described in detail with reference to Examples. However, the embodiments according to the present disclosure may be modified in various other forms, and the scope of the present specification is not to be interpreted as being limited to the embodiments described below. The embodiments of the present specification are provided to more fully describe the present specification to those skilled in the art. In addition, "%" and "part" which show content below are a basis of weight unless there is particular notice.

Synthesis Example : Synthesis of Alkali-Soluble Resin (B)

277 g of methoxybutyl acetate was added to a 1-liter separate flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen inlet tube, and then heated to 80 ° C, followed by 3,4-epoxytricyclo [5.2. 1.0 A mixture of ^2,6 ] decane-9-ylacrylate and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8-ylacrylate [50:50 (molar ratio)] Compound, R ^a = H,] 301 g, methacrylic acid 49 g, and a mixed solution of 23 g of azobisdimethylvaleronitrile dissolved in 350 g of methoxybutyl acetate were added dropwise over 5 hours, and 3 The copolymer solution [solid content (NV) 35.0 weight%] was obtained by time aging. The dry value of the obtained copolymer was 69.8 KOH mg / g, the weight average molecular weight (Mw) was 9,500, and the dispersion degree (Mw / Mn) was 1.9.

[Formula 1]

Example  And Comparative example : Preparation of Colored Photosensitive Resin Composition

A colored photosensitive resin composition was prepared according to the composition of Table 1 below. In this case, the physical and chemical properties of the solvent are shown in Table 2 below.

coloring agent B M PI D1 D2 solvent A-1 A-2 A-3 A-4 A-5 S-1 S-2 S-3 S-4 S-5 S-6 S-7 S-8 Example 1 1.0 2.8 - 2.4 1.4 5.5 2.9 0.6 3.1 0.3 80 - - - - - - - Example 2 1.0 2.8 - 2.4 1.4 5.5 2.9 0.6 3.1 0.3 - 80 - - - - - - Example 3 1.0 2.8 - 2.4 1.4 5.5 2.9 0.6 3.1 0.3 - - 80 - - - - - Example 4 1.0 2.8 - 2.4 1.4 5.5 2.9 0.6 3.1 0.3 - - - 80 - - - - Example 5 1.0 - 2.8 2.4 1.4 5.5 2.9 0.6 3.1 0.3 - - 80 - - - - - Example 6 1.0 - 3.0 2.4 1.2 5.4 2.9 0.6 3.2 0.3 - - - 80 - - - - Comparative Example 1 1.0 2.8 - 2.4 1.4 5.5 2.9 0.6 3.1 0.3 - - - - 80 - - - Comparative Example 2 1.0 2.8 - 2.4 1.4 5.5 2.9 0.6 3.1 0.3 - - - - - 80 - - Comparative Example 3 1.0 2.8 - 2.4 1.4 5.5 2.9 0.6 3.1 0.3 - - - - - - 80 - Comparative Example 4 1.0 2.8 - 2.4 1.4 5.5 2.9 0.6 3.1 0.3 - - - - - - - 80 A-1: Or64, CI Pigment Orange 64
A-2: B15: 6, CI Pigment Blue 15: 6
A-3: B16, CI Pigment Blue 16
A-4: V29, CI Pigment Violet 29
A-5: CB, carbon black
B: alkali-soluble resin according to the synthesis example
M: photopolymerizable compound, DPHA (manufactured by Nippon Kayaku Co., Ltd., Japan)
PI: photoinitiator, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -ethanone-1- (O-acetyloxime) (Irgacure OXE-02: BASF Corporation Produce)
D1: Additive, SOLSPERSE 20000 (manufactured by Lubrisol, Japan)
D2: Additive, F554 (manufactured by DIC Japan)
Solvent (S-1): Propylene glycol methyl ether acetate (PGMEA) / diethylene glycol ethyl methyl ether (MEDG) = 90:10
Solvent (S-2): ethylene glycol monoethyl ether acetate (EGA)
Solvent (S-3): Propylene glycol methyl ether acetate (PGMEA) / diethylene glycol ethyl methyl ether (MEDG) = 85: 20
Solvent (S-4): Propylene glycol methyl ether acetate (PGMEA) / 3-methoxybutyl acetate (3-MBA) = 85: 20
Solvent (S-5): propylene glycol methyl ether acetate (PGMEA)
Solvent (S-6): Propylene glycol methyl ether acetate (PGMEA) / 1,2-propylene glycol monomethyl ether (PGME) = 90:10
Solvent (S-7): Propylene glycol methyl ether acetate (PGMEA) / Propylene glycol monomethyl ether (PGME) / 1,2-propylene glycol diacetate (PGDA) = 80: 10: 10
Solvent (S-8): Propylene glycol methyl ether acetate (PGMEA) / 1, 2-propylene glycol diacetate (PGDA) = 93: 7

No. Kinds Viscosity
(mPas) Vapor pressure
(mmHg) | Δ (viscosity-steam pressure) | One Propylene Glycol Methyl Ether Acetate (PGMEA) 1.3 2.8 1.5 2 Ethylene Glycol Monoethyl Ether Acetate (EGA) 1.3 1.2 0.1 3 3-methoxybutyl acetate (3-BMA) 0.7 1.1 0.4 4 Diethylene glycol ethyl methyl ether (MEDG) 1.2 0.7 0.5 5 1,2-propylene glycol diacetate (PGDA) 2.9 0.2 2.6 6 Propylene Glycol Monomethyl Ether (PGME) 1.9 8.7 6.8

Experimental Example

(1) Preparation of colored substrate

A 5 cm x 5 cm glass substrate (Corning) was washed with a neutral detergent and water and dried. Each of the colored photosensitive resin compositions prepared in Examples and Comparative Examples was spin-coated on the glass substrate to have a final film thickness of 3.0 μm, prebaked at 100 ° C., and dried for 90 seconds to remove a solvent. Then, the pattern was formed by exposing at an exposure dose of 35 mJ / cm ² and the non-exposed portion was removed using an aqueous alkali solution. Subsequently, after baking for 30 minutes at 230 ℃ to produce a colored substrate.

(2) viscosity measurement

The viscosity of the solvent and the coloring photosensitive resin composition which concerns on an Example and a comparative example was measured using the Brookfield viscometer (Brookfield Viscometer DV-I +, the Brookfield company make) at 25 degreeC.

(3) Optical property measurement (optical density, UV-vis)

The cured film of the colored substrate prepared through the above experimental example was measured by using an optical density meter (361T, X-rite) to measure the transmittance at 550nm, to obtain the optical density of 1㎛ thickness are shown in Table 3 below.

In addition, the formed cured film was evaluated for optical properties using UV-vis (UV-2550; Shimadzu). At this time, the evaluation criteria are as follows, and the results are shown in Table 3 below.

<Optical Characteristic Evaluation Criteria 1: Within 700 to 750 nm Wavelength>

○: Excellent, 10% or less light transmittance

△: insufficient, more than 10% light transmittance and less than 12% light transmittance

×: worsened, exceeding 12% light transmission

<Optical Characteristic Criteria 2: Within 950 nm wavelength range>

○: excellent, 15% or more light transmission

△: insufficient, 13% light transmittance or more

×: worse, less than 13% light transmission

(4) Degree of Planarization (DOP) measurement

Each coated photosensitive resin composition prepared in Examples and Comparative Examples was spin-coated to a final film thickness of 3.0 (± 0.2) μm on a substrate (5 cm × 5 cm glass substrate) on which a pattern was formed, and linearly baked at 100 ° C. After drying for 90 seconds, the solvent was removed to form a precured film. Thereafter, the entire surface is exposed at an exposure dose of 35 mJ / cm ² to form a front surface pattern, and development is carried out using an aqueous alkali solution. Subsequently, after firing at 230 ° C. for 130 minutes, a front colored substrate was prepared. After measuring the thickness of the part with and without the pattern on the lower surface of the front colored substrate through the film thickness meter (DEKTAK6M, Veeco), the flatness (DOP) was measured using the pattern thickness of the lower substrate measured in advance. The measurement is shown in Table 3 below.

<DOP Evaluation Criteria>

The substrate prepared in advance so that the lower pattern thickness was 1.17 μm was coated so that the thickness of the flattening part without the lower pattern was 3.20 μm, and the flatness was measured using Equation 3 below.

[Equation 3]

DOP (%) = {(ⓐ-ⓓ) / ⓐ} × 100, 0 ≤ ⓓ ≤ 1.5 μm, ⓓ ≤ ⓐ ≤ ⓑ

In Equation 3,

Ⓐ is the thickness of the lower pattern, ⓓ is the value of ⓐ + ⓒ-ⓑ, ⓑ is the thickness of the portion without the pattern formed in the flatness formed by the colored photosensitive composition, and ⓒ is the flatness by the colored photosensitive composition. The thickness of the portion of the formed film except for the highest point of the lower pattern.

◎ very good, 30% or more but less than 60%

○: Excellent, 15% or more but less than 30%, 60% or more and less than 75%

△: insufficient, 10% or more but less than 15%, 75% or more and less than 85%

×: worse, less than 10%, 85% or more

(5) VCD surface stain evaluation

Each of the colored photosensitive resin compositions prepared according to Examples and Comparative Examples was spin coated to have a final film thickness of 3.0 (± 0.2) μm, followed by vacuum drying (VCD) to 65 Pa, and then to 65 Pa. The time was measured, and then the coating surface was checked with an optical microscope to measure the surface defects and the Tact time according to the VCD decompression, and are shown in Table 3. 1 is an example of classifying a VCD surface stain evaluation image according to the following evaluation criteria.

<VCD Evaluation Criteria>

◎ very good, less than 5 surface stains

○: Excellent, less than 10 or more surface stains

(Triangle | delta): Deficiency, less than 20 or more surface stains

×: Deterioration, 20 or more surface stains

 (6) reliability measurement

The color substrate prepared in (2) was cut to 3 × 3 cm, immersed in NMP solution, and then heated at 100 ° C. for 60 minutes. Thereafter, only the NMP solution was extracted, and the absorbance of the NMP solvent was measured using a UV-vis spectrometer. The results are shown in Table 3 below. At this time, evaluation criteria are as follows.

<Reliability Evaluation Criteria>

○: excellent, absorbance 0.5 or less

△: insufficient, absorbance more than 0.5 and less than 0.8

×: deterioration, absorbance 0.8 or more

(7) Evaluation of elastic recovery rate

(1) The thickness and width of the pattern were measured in a reference state using SNU (SIS-2000, SNU Co., Ltd.) of the substrate prepared according to the production of the colored substrate. Subsequently, the hardness tester (Nano-indenter HM500, Fisher) was pressed at a speed of 2 mN / sec to the point where the pattern was deformed by 1 μm using a planar indenter, and had a holding time for 5 seconds at the point where the 1 μm was deformed. Thereafter, the thickness and the width of the pattern were measured using SNU, and the elastic recovery rate was measured by changing the thickness of the pattern before and after. Specific evaluation criteria are as follows, and the evaluation results are shown in Table 3 below.

<Evaluation criteria for elastic recovery rate>

◎: very good, more than 98%

○: excellent, 96% or more and less than 98%

△: lack, 96% or more and less than 94%

×: worse, less than 94%

Resist Viscosity Value of expression 1 Optical Density (O.D./㎛) Optical Characteristics (700 ~ 750nm) Optical characteristics (950 nm) DOP VCD Stain VCD Tact
(Blank: 15sec) responsibility Elastic recovery Example 1 3.70 1.40 1.68 ○ ○ ◎ ○ 23 sec ◎ ◎ Example 2 3.68 0.12 1.68 ○ ○ ◎ ◎ 32 sec ◎ ◎ Example 3 3.65 1.30 1.67 ○ ○ ◎ ◎ 29 sec ◎ ◎ Example 4 3.61 1.28 1.68 ○ ○ ◎ ◎ 27 sec ◎ ◎ Example 5 3.71 1.30 1.65 ○ ○ ◎ ◎ 28 sec ◎ ◎ Example 6 3.65 1.28 1.61 ○ ○ ◎ ◎ 27 sec ◎ ◎ Comparative Example 1 3.62 1.50 1.64 ○ ○ △ △ 20 sec ◎ ◎ Comparative Example 2 3.67 2.03 1.60 △ ○ X X 18 sec ◎ ○ Comparative Example 3 4.13 2.14 1.67 ○ ○ X ○ 24 sec ◎ ○ Comparative Example 4 4.01 1.64 1.67 ○ ○ △ ○ 22 sec ◎ ○

In Table 3, when the value of Equation 1 is satisfied, the flatness of the coating film is excellent, and the step difference to design is advantageous. have.

Claims (14)

The viscosity of each solvent is 2.0 mPa * s or less at 20 degreeC,
Vapor pressure of each solvent is 3.0 mmHg or less at 20 ℃,
All the solvents satisfy the following formula 1,
Colored photosensitive resin composition for black matrices, column spacers or black matrix integral column spacers having a light transmittance of 10% or less within a wavelength range of 700 to 750 nm according to the following optical property measurement, and having a light transmittance of 15% or more at a wavelength of 950 nm:
[Equation 1]
∑ [(| A _i -B _i |) × M _i ] <1.5
In Formula 1,
A _i is the viscosity (mPa · s) of each solvent at 20 ° C.,
B _i is the vapor pressure (mmHg) of each solvent at 20 ℃,
M _i is the weight ratio of each solvent in the total solvent.
<Optical characteristic measurement>
The colored photosensitive resin composition is spin-coated on a glass substrate so that the final film thickness may be 3.0 micrometers, it is prebaked at 100 degreeC, it is dried for 90 second, and a solvent is removed. Then, the pattern is exposed by exposure with an exposure dose of 35 mJ / cm ² and the non-exposed part is removed using an aqueous alkali solution. Subsequently, post-firing was carried out at 230 ° C. for 30 minutes to produce a colored substrate. Optical properties of the cured film of the prepared colored substrate were evaluated using UV-vis. The method of claim 1,
The solvent is methyl-3-methoxy propionate (viscosity 1.1 mPa · s, vapor pressure 1.8 mmHg), propylene glycol methyl ether acetate (viscosity 1.3 mPa · s, vapor pressure 2.8 mmHg), propylene glycol monoethyl ether acetate (viscosity 1.3) mPas, vapor pressure 2.8 mmHg), ethylene glycol monoethyl ether acetate (viscosity 1.3 mPas, vapor pressure 1.2 mmHg), methyl amyl ketone (viscosity 0.8 mPa.s, vapor pressure 2.1 mmHg), ethylene glycol monoethyl ether (viscosity 1.3) mPas, vapor pressure 1.2mmHg), propylene glycol methyl ether propionate (viscosity 1.2mPas, vapor pressure 0.9mmHg), diethylene glycol dimethyl ether (viscosity 2.0mPas, vapor pressure 3.0mmHg), 2,6-dimethyl 4-heptanone (viscosity 0.9 mPa · s, vapor pressure 1.7 mmHg), pentyl propionate (viscosity 1.0 mPa · s, vapor pressure 1.5 mmHg), ethyl-3-ethoxy propionate (viscosity 1.3 mPa · s, vapor pressure 0.7 mmHg), 3-methoxybutyl acetate (viscosity 0.7 mPas, vapor pressure 1.1 mmHg), dipro Lene glycol dimethyl ether (viscosity 1.1 mPa · s, vapor pressure 0.6 mmHg), diethylene glycol ethylmethyl ether (viscosity 1.2 mPa · s, vapor pressure 0.7 mmHg), diethylene glycol isopropyl methyl ether (viscosity 1.3 mPa · s, vapor pressure 0.8 mmHg) and diethylene glycol diethyl ether (viscosity 1.4 mPa · s, vapor pressure 0.4 mmHg) containing at least one selected from the group consisting of a colored photosensitive resin composition for black matrix, column spacer or black matrix integral column spacer. The method of claim 1,
Colored photosensitive resin composition for a black matrix, a column spacer, or a black matrix integrated column spacer in which the said whole solvent satisfy | fills following Formula 2:
[Equation 2]
∑ [(| A _i -B _i |) × M _i ] <1.38
In Equation 2,
A _i , B _i , M _i are as defined in the formula (1). The method of claim 1,
A colored photosensitive resin composition for black matrix, column spacer or black matrix integral column spacer, wherein the flatness according to the following flatness (DOP) measurement is 30% or more and less than 60%:
<DOP measurement>
On the glass substrate in which the pattern is formed, spin-coating a coloring photosensitive resin composition so that a final film thickness may be set to 3.0 +/- 0.2 micrometer, it is prebaked at 100 degreeC, it is dried for 90 second, a solvent is removed, and a precured film is formed. Thereafter, the entire surface is exposed at an exposure dose of 35 mJ / cm ² to form a front surface pattern, and development is carried out using an aqueous alkali solution. Subsequently, after firing at 230 ° C. for 130 minutes, a front colored substrate was produced. After measuring the thickness of the portion with and without the pattern on the lower surface of the prepared front color substrate through a film thickness meter, the flatness (DOP) is measured using the pattern thickness of the lower substrate previously measured.
Flatness Evaluation Criteria
The substrate prepared in advance so that the lower pattern thickness is 1.17 μm is coated so that the thickness of the flattening part without the lower pattern is 3.20 μm, and the flatness is measured using Equation 3 below.
[Equation 3]
DOP (%) = {(ⓐ-ⓓ) / ⓐ} × 100, 0 ≤ ⓓ ≤ 1.5 μm, ⓓ ≤ ⓐ ≤ ⓑ
In Equation 3,
Ⓐ is the thickness of the lower pattern, ⓓ is the value of ⓐ + ⓒ-ⓑ, ⓑ is the thickness of the portion without the pattern formed in the flatness formed by the colored photosensitive composition, and ⓒ is the flatness by the colored photosensitive composition. The thickness of the portion of the formed film except for the highest point of the lower pattern. The method of claim 1,
The coloring photosensitive resin composition for the black matrix, column spacer, or black-matrix integral column spacer which further contains a coloring agent. The method of claim 5,
The colorant is a colored photosensitive resin composition for a black matrix, a column spacer or a black matrix integrated column spacer that comprises at least one pigment selected from the group consisting of orange pigments, purple pigments and blue pigments. The method of claim 6,
The coloring agent further comprises a black pigment, a colored photosensitive resin composition for a black matrix, a column spacer or a black matrix integrated column spacer. The method of claim 1,
The solvent is contained in 60 to 90 parts by weight based on 100 parts by weight of the total of the colored photosensitive resin composition colored photosensitive resin composition for black matrix, column spacer or black matrix integrated column spacer. The method of claim 1,
Alkali-soluble resins; Photopolymerizable compounds; Photopolymerization initiator; And at least one selected from the group consisting of additives. The colored photosensitive resin composition for black matrix, column spacer, or black matrix integrated column spacer. The black matrix of the color filter containing the hardened | cured material of the coloring photosensitive resin composition of any one of Claims 1-9. The column spacer of the color filter containing the hardened | cured material of the coloring photosensitive resin composition of any one of Claims 1-9. The black matrix integrated column spacer of the color filter containing the hardened | cured material of the coloring photosensitive resin composition of any one of Claims 1-9. The color filter which contains the hardened | cured material of the coloring photosensitive resin composition of any one of Claims 1-9 as a black matrix, a column spacer, or a black matrix integrated column spacer. An image display device comprising the color filter according to claim 13.

Images