KR20180031223A - Colored photosensitive resin composition, color filter and image display device produced using the same - Google Patents

Abstract

A colored photosensitive resin composition according to the present invention comprises: an alkali-soluble resin containing a repeating unit represented by chemical formula 1; and a photopolymerization initiator comprising at least one compound selected from the group consisting of a compound represented by chemical formula 2. The colored photosensitive resin composition of the present invention reduces display defects that may occur in manufacturing a color filter in a color-filter-on-array (COA) type, and can form contact holes having excellent alignment accuracy in the R, G, and B resin films.

Description

TECHNICAL FIELD [0001] The present invention relates to a colored photosensitive resin composition, and a color filter and an image display device using the same. BACKGROUND ART < RTI ID = 0.0 >

The present invention relates to a colored photosensitive resin composition, a color filter manufactured using the same, and an image display device.

Generally, in an image display apparatus, a color filter having a plurality of colored layers arranged to correspond to a plurality of pixels of an image display element is used to realize color image display.

Such a color filter is formed on the side of the counter substrate opposite to the TFT substrate, not on the substrate on which the thin film transistor (hereinafter referred to as TFT) on which the switching element is formed (hereinafter referred to as TFT substrate) is formed.

However, when the color filter is disposed on the side of the counter substrate, alignment with each pixel electrode on the TFT substrate is not simple and the aperture ratio is reduced. Further, since the distance between the color filter and the liquid crystal layer is relatively large, there arises a problem that the display quality due to the light incident from the oblique direction decreases. In order to solve such a problem, Japanese Patent Application Laid-Open No. 09-73078 discloses a technique of using a COA (Color Filter on Array) method of forming a color filter on a TFT substrate This problem is solved.

In the process of forming a color filter on the TFT substrate, a contact hole (conduction path) must be formed in the process. Therefore, development of a technique for controlling the contact hole is required.

In addition, when a color filter is formed on the TFT substrate, defective display due to instability of the pixel coating film may occur during the etching process and chemical processing, and development of a technique for improving the display defect is required.

Korean Patent No. 1,541,542 relates to a colored photosensitive resin composition and includes a binder resin having a specific weight average molecular weight for controlling an overlap step (Ra) of a colored layer formed of a colored photosensitive resin composition do.

However, in the case of the above-mentioned document, a solution to the problem of the residual phenomenon has been solved. However, a solution to the display defect has not been proposed, and a problem of the contact hole to be adjusted when forming the color filter on the TFT substrate I do not know at all.

Accordingly, development of a colored photosensitive resin composition capable of improving various display defects overall and controlling the size and shape of the contact hole has been demanded.

Korean Registered Patent No. 1,541,542 (2015.07.28)

The present invention relates to a colored photosensitive resin composition capable of improving defective display of a screen which may occur in the production of a color filter on a COA (Color Filter on Array) method, and forming a contact hole having excellent alignment accuracy in R, G, And to provide the above objects.

The present invention also provides a color filter and an image display device manufactured using the above-mentioned colored photosensitive resin composition.

To achieve the above object, the present invention provides a colored photosensitive resin composition comprising: an alkali-soluble resin containing a repeating unit represented by the following formula (1); And at least one compound selected from the group consisting of compounds represented by the following general formula (2):

[Chemical Formula 1]

(In the formula 1,

R ₁ and R ₂ are each independently a hydrogen atom or a methyl group,

R < ₃ > is a residue comprising a carboxylic acid derived by an acid anhydride)

(2)

(In the formula (2)

R ₄ to R ₁₃ are each independently hydrogen, halogen, C ₁ ~ C ₂₀ alkyl group, C of ₆ ~ C ₂₀ aryl group, C ₁ ~ C alkoxy group of _20, C ₇ ~ C ₄₀ arylalkyl group, C ₂ To C ₄₀ hydroxyalkoxyalkyl groups or C ₃ to C ₂₀ cycloalkyl groups).

Further, the present invention provides a color filter including a cured product of the above-mentioned colored photosensitive resin composition and an image display apparatus including the color filter.

In order to accomplish the above object, the colored photosensitive resin composition according to the present invention comprises an alkali-soluble resin containing a repeating unit having a specific structure and a photopolymerization initiator represented by a specific formula, so that when a color filter of COA (Color Filter on Array) Display defects that can occur are improved, and contact holes having excellent alignment accuracy can be formed on the R, G, and B resin films.

In addition, the color filter manufactured using the colored photosensitive resin composition of the present invention and the image display device including the color filter have the effect of improving the defective display of the screen.

1 is a process diagram for forming a color filter by a COA (Color Filter on Array) method using the colored photosensitive resin composition of the present invention.

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

When a member is referred to as being " on "another member in the present invention, this includes not only when a member is in contact with another member but also when another member exists between the two members.

In addition, when an element is referred to as being "comprising " in the present invention, it is understood that other elements may be included in the element, not the other element.

≪ Colored photosensitive resin composition &

One aspect of the present invention is a resin composition comprising an alkali-soluble resin containing a repeating unit represented by the following formula (1): And a photopolymerization initiator comprising at least one compound selected from the group consisting of compounds represented by the following general formula (2).

[Chemical Formula 1]

(In the formula 1,

R ₁ and R ₂ are each independently a hydrogen atom or a methyl group,

R < ₃ > is a residue comprising a carboxylic acid derived by an acid anhydride)

(2)

(In the formula (2)

R ₄ to R ₁₃ are each independently hydrogen, halogen, C ₁ ~ C ₂₀ alkyl group, C of ₆ ~ C ₂₀ aryl group, C ₁ ~ C alkoxy group of _20, C ₇ ~ C ₄₀ arylalkyl group, C ₂ To C ₄₀ hydroxyalkoxyalkyl groups or C ₃ to C ₂₀ cycloalkyl groups).

Alkali-soluble resin

The alkali-soluble resin according to the present invention is characterized by containing a repeating unit represented by the following formula (1).

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

[Chemical Formula 1]

(In the formula 1,

R ₁ and R ₂ are each independently a hydrogen atom or a methyl group,

R < ₃ > is a residue comprising a carboxylic acid derived by an acid anhydride.

The alkali-soluble resin of the present invention contains a repeating unit of the above formula (1), so that when a color pattern is formed with the colored photosensitive resin composition containing the alkali-soluble resin, the step of the pattern due to the colorant that can be contained in the colored photosensitive resin composition The smoothness can be remarkably improved and the color filter having an excellent transmittance can be manufactured.

The alkali-soluble resin containing the repeating unit represented by the formula (1) may have a glass transition temperature (Tg) of less than 0 ° C. In this case, the development speed of the colored photosensitive resin composition containing the repeating unit can be remarkably improved, Also, there is an effect that it is possible to suppress the problem of short circuit of the pattern due to the increase of the developing speed.

The content of the repeating unit represented by the formula (1) may be in the range of 50 to 90 mol%, specifically 55 to 85 mol%, more specifically 60 to 75 mol% based on the total molar percentage of the alkali-soluble resin.

When the repeating unit represented by the above-mentioned formula (1) is contained within the above range, the alkali-soluble resin containing the same has a glass transition temperature of less than 0 ° C.

According to one embodiment of the present invention, the alkali-soluble resin of the present invention comprises the monomer (a1) containing the repeating unit represented by the formula (1) (A2) having a copolymerizable unsaturated double bond in addition to the monomer (a2).

The kind of the monomer (a2) having a copolymerizable unsaturated double bond is not particularly limited. Specific examples thereof include styrene, vinyltoluene,? -Methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethylether, m- Aromatic vinyl compounds such as ether, p-vinylbenzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether or p-vinyl benzyl glycidyl ether; N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm N-substituted maleimide-based compounds such as methylphenylmaleimide, Np-methylphenylmaleimide, No-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide or Np-methoxyphenylmaleimide; Propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, alkyl (meth) acrylates such as sec-butyl (meth) acrylate and t-butyl (meth) acrylate; (Meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylhexyl (meth) acrylate, 2-methylcyclohexyl Alicyclic (meth) acrylates such as mono (meth) acrylate, 2-dicyclopentanyloxyethyl (meth) acrylate or isobornyl (meth) acrylate; (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl Hydroxyethyl (meth) acrylates such as hydroxyethyl acrylamide; Aryl (meth) acrylates such as phenyl (meth) acrylate or benzyl (meth) acrylate; 3- (methacryloyloxymethyl) -2-trifluoromethyl oxetane, 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane and the like Unsaturated oxetane compounds. These monomers may be used alone or in combination of two or more.

The content of the monomer (a2) having a copolymerizable unsaturated double bond is not particularly limited and may be, for example, 10 to 50 mol% based on the total molar percentage of the monomers for polymerizing the alkali-soluble resin, May be 25 to 40 mol%. When the above range is satisfied, there is an advantage that the glass transition temperature of the resin is less than 0 占 폚 and the step can be minimized.

A method for producing an alkali-soluble resin according to still another embodiment of the present invention is as follows.

Conventionally, an alkali-soluble resin of a colored photosensitive resin composition is prepared by copolymerizing an ethylenically unsaturated monomer having a carboxyl group as an essential component in order to have solubility in an alkali developing solution used in a development processing step for forming a pattern. However, the alkali-soluble resin formed by such a production method has a problem that a resin having a carboxyl group in its main chain and having a glass transition temperature of less than 0 캜 is difficult to produce.

However, the alkali-soluble resin of the present invention can be prepared so that the carboxyl group is contained in the side chain other than the main chain in which the polymerization reaction is carried out. Thus, an alkali developable resin having a glass transition temperature of less than 0 ° C have.

Meanwhile, one embodiment of the method for producing an alkali-soluble resin includes the steps of: (S1) copolymerizing glycidyl (meth) acrylate (a1) and a monomer (a2) having an unsaturated double bond; (S2) reacting the prepared copolymer with an ethylenically unsaturated monomer having a carboxyl group; And (S3) reacting the reacted copolymer with an acid anhydride.

The step (S2) is a step for imparting photo-curability to the alkali-soluble resin of the present invention. In the step (S2), the kind of the ethylenically unsaturated monomer having a carboxyl group is not particularly limited as far as it functions For example, (meth) acrylic acid, ethyl acrylic acid and / or butyl acrylic acid, and specifically may be methacrylic acid.

The step (S3) is a step for imparting an appropriate acid value to the alkali-soluble resin of the present invention. More specifically, the step (S3) is a step of reacting a hydroxyl group derived from the glycidyl group of the alkali-soluble resin with an acid anhydride, To introduce a carboxyl group.

The kind of the acid anhydride used in the step (S3) is not particularly limited as long as it is within the range of its function. For example, phthalic anhydride, (2-dodecen-1-yl) succinic anhydride (2-Dodecen-1-yl) succinic anhydride, maleic anhydride, succinic anhydride, citraconic anhydride, glutaric anhydride, methylsuccinic anhydride Methylsuccinic anhydride, 3,3-Dimethylglutaric anhydride, Phenylsuccinic anhydride, Itaconic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, (3,4,5,6-Tetrahydrophthalic anhydride, trimellitic anhydride, and hexahydrophthalic anhydride). In particular, in view of cost and ease of reaction, maleic anhydride Maleic anhydride, A phthalic anhydride, a trimellitic anhydride, a succinic anhydride, a hexahydrophthalic anhydride and a carbamic anhydride may be used, and more specifically, trimellitic anhydride, succinic anhydride, hexahydrophthalic anhydride, Trimellitic anhydride, succinic anhydride, and hexahydrophthalic anhydride may be used.

The acid value of the alkali-soluble resin prepared according to the above-described production method of the present invention may be 30 to 150 mgKOH / g in order to ensure compatibility with the dye contained in the composition and storage stability of the composition. When the acid value of the alkali-soluble resin is less than 30 mgKOH / g, it may be difficult to secure a sufficient development rate of the colored photosensitive resin composition. When the acid value exceeds 150 mgKOH / g, the adhesion with the substrate is decreased, There arises a problem that compatibility with the dye occurs, so that the dye in the colored photosensitive resin composition is precipitated or the storage stability of the colored photosensitive resin composition is deteriorated and the viscosity may increase.

The content of the alkali-soluble resin containing the repeating unit represented by the formula (1) is, for example, from 1 to 80% by weight, more preferably from 5 to 75% by weight, based on the total weight of the solid content in the colored photosensitive resin composition, 10 to 70% by weight. When the alkali-soluble resin is contained within the above range, the solubility in the developing solution is sufficient, the formation of the pattern is easy, the reduction of the film of the pixel portion of the exposed portion is prevented, and the non-pixel portion can be expected to have a good dropout.

Photopolymerization initiator

The photopolymerization initiator according to the present invention is characterized by being at least one selected from the group consisting of compounds represented by the following general formula (2).

(2)

(In the formula (2)

R ₄ to R ₁₃ are each independently hydrogen, halogen, C ₁ ~ C ₂₀ alkyl group, C of ₆ ~ C ₂₀ aryl group, C ₁ ~ C alkoxy group of _20, C ₇ ~ C ₄₀ arylalkyl group, C ₂ To C ₄₀ hydroxyalkoxyalkyl groups or C ₃ to C ₂₀ cycloalkyl groups.)

Specifically, R ₄ to R ₁₃ are each independently selected from the group consisting of hydrogen, bromo, chloro, iodo, methyl, ethyl, n-propyl, i- A naphthyl group, an naphthyl group, a biphenyl group, a terphenyl group, an anthryl group, an indenyl group, a phenanthryl group, a methoxy group, an ethoxy group, a n-propyl group, a n-propyl group, a n-propyl group, an i-propyl group, Butyl group, a hydroxy i-butyl group, a hydroxy n-pentyl group, a hydroxy i-pentyl group, a hydroxy n-hexyl group, a hydroxy i-hexyl group, a hydroxymethoxymethyl group, a hydroxymethoxyethyl group, A propyl group, a propyl group, a hydroxymethoxybutyl group, a hydroxyethoxymethyl group, a hydroxyethoxyethyl group, a hydroxyethoxypropyl group, a hydroxyethoxybutyl group, a hydroxyethoxypentyl group or a A hydroxyethoxyhexyl group, and more specifically, R _{4 is} hydrogen, a methyl group, an ethyl group, a propyl group, or a butyl group; R ₅ is a methyl group, an ethyl group, or a propyl group; R ₆ is a methyl group, an ethyl group, a propyl group, or a butyl group; R ₇ to R ₁₃ may be hydrogen.

The colored photosensitive resin composition of the present invention has an effect of improving the sensitivity and the degree of curing by being selected from the group consisting of the compounds represented by the general formula (2).

Further, the photopolymerization initiator of the present invention can be used together with the alkali-soluble resin of the present invention to form contact holes having excellent alignment accuracy in R, G, and B resin films in an image display device of a COA (Color Filter on Array) structure In forming the electrical path between the resin film, that is, the pixel electrode and the active element (TFT), R and G in the IZO (Indium Zinc Oxide) deposition used as a pixel electrode and the contact hole formation by the dry etching method, , The pattern stability of the resin film B can be ensured and the pixel defects due to R, G, and B disconnection for securing a high aperture ratio can be improved.

The alkyl group means a straight or branched chain hydrocarbon chain radical consisting solely of carbon and hydrogen atoms and having no unsaturation and bonded to the remainder of the molecule by a single bond. Specifically, the alkyl group may be a straight or branched alkyl group having 1 to 20 carbon atoms, more specifically a straight or branched alkyl group having 1 to 10 carbon atoms, more specifically, a straight or branched alkyl group having 1 to 6 carbon atoms Chain or branched alkyl group. Examples of such unsubstituted alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, And the like. The at least one hydrogen atom contained in the alkyl group may be substituted with at least one substituent selected from the group consisting of a halogen atom, a hydroxyl group, a thiol group (-SH), a nitro group, a cyano group, a substituted or unsubstituted amino group, an amidino group, a hydrazine group, a phosphoric acid group, a hetero group of C ₁ to C ₂₀ alkyl group, C ₁ to halogenated alkyl group of C _20, C ₁ to C ₂₀ alkenyl groups, C ₁ to C ₂₀ alkynyl group, C ₁ to C ₂₀ of the, C ₆ to an aryl group of C _20, which may be substituted with a heteroaryl group of C ₆ to C ₂₀ arylalkyl group, C ₆ to C ₂₀ heteroaryl group, or C ₆ to C ₂₀ of the.

The aryl group means an aromatic monocyclic or multicyclic hydrocarbon ring system consisting only of hydrogen and carbon, wherein the ring system may be partially or fully saturated. At least one hydrogen atom in the aryl group may be substituted with the same substituent as in the case of the alkyl group. The aryl group may be an organic radical derived from an aromatic hydrocarbon by one hydrogen elimination and may comprise a single or fused ring system comprising from 4 to 7, in particular 5 or 6, ring atoms in each ring, Or a form in which the aryl is linked by a single bond. The aryl group may include 6 to 20 carbon atoms, and may specifically include 6 to 18 carbon atoms.

The alkoxy group may be an oxygen-containing straight-chain or branched alkoxy group each having an alkyl moiety of 1 to 20 carbon atoms. Specifically, it may be an alkoxy group having 1 to 10 carbon atoms, more specifically, an alkoxy group having 1 to 4 carbon atoms. The alkoxy group includes, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a t-butoxy group. The alkoxy group may be further substituted with one or more halogen atoms such as fluoro, chloro or bromo to provide a haloalkoxy group. Examples thereof include a fluoromethoxy group, a chloromethoxy group, a trifluoromethoxy group, a trifluoroethoxy group, a fluoroethoxy group, and a fluoropropoxy group. At least one hydrogen atom of the alkoxy group may be substituted with the same substituent as the alkyl group.

The arylalkyl group means that at least one hydrogen atom of the alkyl group is substituted with the aryl group. The arylalkyl group may have 7 to 40 carbon atoms, specifically 7 to 28 carbon atoms, and more specifically, 7 to 24 carbon atoms.

The hydroxyalkyl group means an OH-alkyl group in which a hydroxy group is bonded to the alkyl group defined above, and the hydroxyalkoxyalkyl group means a hydroxyalkyl-O-alkyl in which the hydroxyalkyl group and the alkyl group are connected by oxygen. The hydroxyalkyl group may have 1 to 20 carbon atoms, specifically 1 to 10 carbon atoms, more specifically 1 to 6 carbon atoms. The hydroxyalkoxyalkyl group may have from 2 to 40 carbon atoms, specifically from 2 to 20 carbon atoms, and more specifically from 2 to 9 carbon atoms.

The cycloalkyl group may include not only a single ring system but also a plurality of cyclic hydrocarbons, and at least one hydrogen atom in the cycloalkyl group may be substituted with the same substituent as the alkyl group. The cycloalkyl group may have 3 to 20 carbon atoms, specifically 3 to 10 carbon atoms, more specifically 3 to 8 carbon atoms.

The content of the photopolymerization initiator is preferably from 0.1 to 40% by weight, more preferably from 0.5 to 35% by weight, more preferably from 1 to 30% by weight based on the total weight of the solid content of the alkali-soluble resin and the photopolymerizable compound in the colored photosensitive resin composition % ≪ / RTI > by weight. When the photopolymerization initiator is contained within the above range, the colored photosensitive resin composition containing the photopolymerization initiator is highly sensitized and the exposure time is shortened. Thus, productivity is improved and high resolution can be maintained, and the strength of the pixel portion and the smoothness There is an advantage to be lost.

The colored photosensitive resin composition according to one embodiment of the present invention may further include a conventional photopolymerization initiator capable of polymerizing a photopolymerizable compound which may be further included in the present invention in addition to the photopolymerization initiator described above, And may further include an initiator.

At this time, the content of the photopolymerization initiator is preferably 0.1 to 40% by weight, more preferably 0.5 to 35% by weight, more preferably 1 to 30% by weight, based on the solid content in the colored photosensitive resin composition with respect to the content of the alkali- 30% by weight. When the content of the photopolymerization initiator is within the above range, the sensitivity of the colored photosensitive resin composition containing the photopolymerization initiator is improved and the productivity of the color filter including the photopolymerization initiator improves.

The colored photosensitive resin composition according to still another embodiment of the present invention may further include at least one selected from the group consisting of a photopolymerizable compound, a colorant, a solvent and an additive.

Photopolymerizable compound

The colored photosensitive resin composition according to one embodiment of the present invention may further comprise a photopolymerizable compound.

The photopolymerizable compound is a compound capable of polymerizing under the action of the photopolymerization initiator, and examples thereof include monofunctional monomers, bifunctional monomers, and other polyfunctional monomers.

The type of the monofunctional monomer is not particularly limited, and examples thereof include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate N-vinylpyrrolidone, and the like.

The type of the bifunctional monomer is not particularly limited and examples thereof include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) Glycol di (meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol A, and 3-methylpentanediol di (meth) acrylate.

The type of the polyfunctional monomer is not particularly limited and includes, for example, trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipenta (Meth) acrylate, erythritol hexa (meth) acrylate, propoxylated dipentaerythritol hexa (meth) acrylate, dipentaerythritol hexa (metha) acrylate and the like.

The photopolymerizable compound may be contained in the colored photosensitive resin composition in an amount of 5 to 45% by weight, specifically 6 to 44% by weight, more specifically 7 to 43% by weight, based on the total weight of the solid components. When the photopolymerizable compound is contained within the above range, the strength and smoothness of the pixel portion including the photopolymerizable compound are improved.

coloring agent

The colored photosensitive resin composition according to one embodiment of the present invention may further comprise a colorant comprising at least one pigment or at least one dye.

Pigment

The pigment may be an organic pigment or an inorganic pigment generally used in the art. The above-mentioned pigments can be used in various kinds of pigments used in printing ink, ink jet ink and the like. Specific examples thereof include water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, And an anthanthrone pigment, an anthanthrone pigment, a pravanthrone pigment, a pyranthrone pigment, an anthanthrone pigment, an anthanthrone pigment, an anthanthrone pigment, an anthanthrone pigment, an anthanthrone pigment, a pyranthrone pigment, pyranthrone pigments, diketopyrrolopyrrole pigments, and the like. Examples of the inorganic pigments include metallic compounds such as metal oxides and metal complex salts. Specific examples of the inorganic pigments include oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony and carbon black Or composite metal oxides. Particularly, the organic pigments and inorganic pigments may be specifically classified into pigments in the Society of Dyers and Colourists, and more specifically, those having a color index (CI) number And pigments. However, it is not necessarily limited to these pigments. These pigments may be used alone or in combination of two or more kinds.

C.I. Pigment Yellow 13, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180 And 185;

C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, and 71;

C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 208, 215, 216, 224, 242, 254, 255 and 264;

C.I. Pigment Violet 14, 19, 23, 29, 32, 33, 36, 37 and 38;

C.I. Pigment Blue 15 (15: 3, 15: 4, 15: 6, etc.), 21, 28, 60, 64 and 76;

C.I. Pigment Green 7, 10, 15, 25, 36, 47, 59, 62 and 63;

C.I. Pigment Brown 28;

C. I. Pigment Black 1 and 7; Etc

The above-mentioned pigments may be organic pigments or inorganic pigments generally used in the art. These pigments may be used alone or in combination of two or more.

The exemplified C.I. Among the pigment pigments, specifically, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 185, C.I. Pigment Orange 38, C.I. Pigment Red 122, C.I. Pigment Red 166, C.I. Pigment Red 177, C.I. Pigment Red 208, C.I. Pigment Red 242, C.I. Pigment Red 254, C.I. Pigment Red 255, C.I. Pigment Violet 23, C.I. Pigment Blue 15: 3, Pigment Blue 15: 6, C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment selected from Pigment Green 58 may be used.

It is preferable to use a pigment dispersion in which the particle diameter of the pigment is uniformly dispersed. An example of a method for uniformly dispersing the particle diameter of the pigment includes a method of dispersing the pigment by adding a pigment dispersant. According to this method, a pigment dispersion in which the pigment is uniformly dispersed in a solution can be obtained.

Specific examples of the pigment dispersant include cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, polyester surfactants, and polyamine surfactants. These surfactants may be used singly or in combination of two or more thereof .

Pigment dispersant

The pigment dispersant is added for maintenance of deagglomeration and stability of the pigment, and any of those generally used in the art can be used without limitation. (Hereinafter referred to as an acrylic dispersant) containing BMA (butyl methacrylate) or DMAEMA (N, N-dimethylaminoethyl methacrylate). At this time, it is preferable to apply the acrylic dispersant prepared by a living control method as disclosed in Korean Patent Laid-Open Publication No. 2004-0014311. DISCLOSURE OF INVENTION It is an object of the present invention to provide an acrylic dispersant, 2000, DISPER BYK-2001, DISPER BYK-2070, and DISPER BYK-2150.

The acrylic dispersants exemplified above may be used alone or in combination of two or more.

As the pigment dispersant, other resin type pigment dispersants other than the acrylic dispersant may be used. The other resin type pigment dispersing agent may be a known resin type pigment dispersing agent, especially a polycarboxylic acid ester such as polyurethane, polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) Amine salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long chain polyaminoamide phosphate salts, esters of hydroxyl group-containing polycarboxylic acids and their modified products, or free ) Oil-based dispersants such as amides formed by reaction of a polyester having a carboxyl group with poly (lower alkyleneimine) or salts thereof; Soluble resin or water-soluble polymer compound such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylate ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol or polyvinylpyrrolidone; Polyester; Modified polyacrylates; Adducts of ethylene oxide / propylene oxide, and phosphate esters. DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK-160, BYK (trade name) 164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; EFKA-4060, EFKA-4060, EFKA-4055, EFKA-4055, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA- 4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800; SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10 from Lubirzol; Hinoact T-6000, Hinoact T-7000, Hinoact T-8000; available from Kawaken Fine Chemicals; AJISPUR PB-821, Ajisper PB-822, Ajisper PB-823 manufactured by Ajinomoto; FLORENE DOPA-17HF, fluorene DOPA-15BHF, fluorene DOPA-33, and fluorene DOPA-44 are trade names of Kyoeisha Chemical Co., In addition to the above acrylic dispersant, other resin type pigment dispersants may be used alone or in combination of two or more, and may be used in combination with an acrylic dispersant.

The amount of the pigment dispersant to be used may be 5 to 60 parts by weight, specifically 10 to 55 parts by weight, more specifically 15 to 50 parts by weight, based on the total weight of the solid content of the pigment used. If the content of the pigment dispersant exceeds the above range, the viscosity may be increased. If the content of the pigment dispersant is less than the above range, it may be difficult to atomize the pigment or gelation may occur after dispersion.

dyes

The dye can be used without limitation as long as it has solubility in an organic solvent. Specifically, dyes having solubility in an organic solvent and securing reliability such as solubility in an alkali developing solution, solvent resistance, and stability with time can be used.

Examples of the dye include acid dyes having an acidic group such as a sulfonic acid and a carboxylic acid, salts of an acidic dye and a nitrogen-containing compound, sulfonamides of an acidic dye and derivatives thereof, and azo, xanthate, phthalocyanine Based acid dyes and derivatives thereof.

The dye may be a compound classified as a dye in the color index (published by The Society of Dyers and Colourists), or a known dye described in a dyeing note (coloring yarn).

Specific examples of the dye include C.I. As solvent dyes,

C.I. Yellow dyes such as Solvent Yellow 4, 14, 15, 16, 21, 23, 24, 38, 56, 62, 63, 68, 79, 82, 93, 94, 98, 99, 151, 162, 163;

C.I. Red dyes such as Solvent Red 8, 45, 49, 89, 111, 122, 125, 130, 132, 146, 179;

C.I. Orange dyes such as solvent orange 2, 7, 11, 15, 26, 41, 45, 56, 62;

C.I. Blue dyes such as Solvent Blue 5, 35, 36, 37, 44, 59, 67 and 70;

C.I. Violet dyes such as solvent violet 8, 9, 13, 14, 36, 37, 47, 49;

C.I. Green dyes such as Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35 and the like.

C.I. Among the solvent dyes, specifically C.I. Solvent Yellow 14, 16, 21, 56, 151, 79, 93; C.I. Solvent Red 8, 49, 89, 111, 122, 132, 146, 179; C.I. Solvent Orange 41, 45, 62; C.I. Solvent Blue 35, 36, 44, 45, 70; C.I. Solvent violet 13 can be used, more specifically C.I. Solvent Yellow 21, 79; C.I. Solvent Red 8, 122, 132; C.I. Can be used.

Also, C.I. As an acid dye

CI Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112 , 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184 Yellow dyes such as 1,1,1,2,2,2,2,2,2,23,28, 240,242, 243,251 and the like, such as, for example, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, ;

CI Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88 , 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217 , 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349 Red dyes such as 382, 383, 394, 401, 412, 417, 418, 422, 426;

Orange dyes such as C.I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;

CI Acid Blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, , 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, , 335, 340 and the like;

Violet dyes such as C.I. Acid Violet 6B, 7, 9, 17, 19, 66 and the like;

Green dyes such as C.I. acid green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106,

Among the above acid dyes, C.I. Acid Yellow 42 having excellent solubility with respect to an organic solvent; C.I. Acid Red 92; C. I. Acid Blue 80, 90; C.I. Acid Violet 66; C.I. Acid Green 27 may be used.

As a C.I. direct dye,

CI Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129 , Yellow dyes such as 136, 138, and 141;

CI Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211 , 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;

Orange dyes such as C.I. Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;

CI Direct Blue 38, 44, 57, 70, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113 , 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189 , 190, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248 , 250, 251, 252, 256, 257, 259, 260, 268, 274, 275 and 293;

Violet dyes such as C.I. Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;

Green dyes such as C.I. Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79,

Also, C.I. As a modantoic dye

Yellow dyes such as C.I. Modatto Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

CI Modal Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, Red dyes such as 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;

CI Modanato Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, dyes;

CI Modanito Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 43, 44, 48, 49, 53, 61, 74, 77, 83, and 84;

Violet colored dyes such as C.I. Modanth violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;

Green dyes such as C.I. Modatto Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43,

These dyes may be used alone or in combination of two or more.

The content of the colorant may be 5 to 60 parts by weight, specifically 7 to 50 parts by weight, more specifically 10 to 45 parts by weight, based on the total weight of the solid content in the colored photosensitive resin composition. When the content of the coloring agent is within the above range, even when a thin film is formed using the colored photosensitive resin composition, the color density of the pixel is sufficient, and the occurrence of the residue can be suppressed There is an advantage.

solvent

The colored photosensitive resin composition according to one embodiment of the present invention may further comprise a solvent.

The solvent used in the conventional colored photosensitive resin composition is not particularly limited so long as it is effective in dissolving the other components contained in the colored photosensitive resin composition. Specific examples thereof include ethers, aromatic hydrocarbons, ketones, alcohols, Esters, amides and the like.

Specific examples of the solvent include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, Diethylene glycol dialkyl ethers such as diethylene glycol dipropyl ether and diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, Alkylene glycol alkyl ether acetates such as propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene , Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin, Ethyl and 3-methoxypropionate; cyclic esters such as? -Butyrolactone; and the like.

The solvent may be an organic solvent having a boiling point of 100 ° C to 200 ° C in terms of coatability and dryness, and more specifically propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, Ethyl lactate, butylacetate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like.

The solvents exemplified above may be used alone or in admixture of two or more. The solvent may be used in an amount of 60 to 90% by weight, specifically 65 to 88% by weight, more preferably 70 to 90% by weight, based on the total weight of the colored photosensitive resin composition of the present invention. 85% by weight. When the solvent is contained within the above range, an effect of improving the applicability can be expected when the solvent is applied by a coating apparatus such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater) have. When the content of the solvent is less than the above range, the coating property may be somewhat lowered, and the process may be somewhat difficult. When the content is above the range, the performance of the color filter formed of the red photosensitive resin composition may be somewhat deteriorated May occur.

additive

The colored photosensitive resin composition according to one embodiment of the present invention may further contain an additive, if necessary.

The additive may be at least one selected from a dispersant, a wetting agent, a silane coupling agent and an anti-aggregation agent.

As the dispersing agent, a commercially available surfactant may be used. Examples of the surfactant include a silicone surfactant, a fluorinated surfactant, a silicon surfactant having a fluorine atom, and a mixture thereof. Examples of the silicone surfactant include a surfactant having a siloxane bond. As commercially available products, Toray Silicon DC3PA, Toray Silicon SH7PA, Toray Silicon DC11PA, Toray Silicon SH21PA, Toray Silicon SH28PA, Toray Silicon 29SHPA, Toray Silicon SH30PA, Polyether Modified Silicon Oil SH8400 (Toray Silicone Co., Ltd.), KP321, KP322 (Manufactured by Shin-Etsu Silicones), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 and TSF4460 have. Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain. Concretely, it is possible to use a propylene glycol (trade name) FC430, a prolineate FC431 (manufactured by Sumitomo 3M Ltd.), Megapack (trade name) F142D, Megapack F171, Megapack F172, Megafac F173, Megafac F177, (Trade name) EF301, Eftop EF303, Eftop EF351, and Eftop EF352 (manufactured by Shin-Aitaku Kasei Co., Ltd.), Megapack F183, Megapack R30 1000, BM-1100 (product name) S381, Surfron S382, Surfron SC101, Surfron SC105 (manufactured by Asahi Glass Co., Ltd.), E5844 (manufactured by Daikin Fine Chemical Co., Ltd.) Manufactured by BMChemie). Examples of the silicone surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain. Specific examples thereof include Megapac (trade name) R08, Megapack BL20, Megapack F475, Megapack F477, Megapack F443 (manufactured by Dainippon Ink and Chemicals, Incorporated).

Examples of the wetting agent include glycerin, diethylene glycol, ethylene glycol, and the like, and may include at least one selected from the group.

Examples of the silane coupling agent include aminopropyltriethoxysilane,? -Mercaptopropyltrimethoxysilane and? -Methacryloxypropyltrimethoxysilane, and commercially available products include SH6062, SZ6030 (Toray-Dow (Manufactured by Corning Silicon co., Ltd.), KBE903 and KBM803 (manufactured by Shin-Etsu silicone co., Ltd.).

The anti-aggregation agent includes, for example, sodium polyacrylate.

<Color filter>

Another aspect of the present invention relates to a color filter manufactured using the above-mentioned colored photosensitive resin composition.

The color filter includes a substrate and a pattern layer formed on the substrate.

The substrate may be the substrate of the color filter itself, or may be a portion where a color filter is placed on a display device or the like, and is not particularly limited. The substrate may be glass, silicon (Si), silicon oxide (SiOx), or a polymer substrate, and the polymer substrate may be polyethersulfone (PES) or polycarbonate (PC).

The pattern layer may be a layer including the colored photosensitive resin composition of the present invention, and may be a layer formed by applying the colored photosensitive resin composition and exposing, developing, and thermosetting the colored photosensitive resin composition in a predetermined pattern. The pattern layer may be formed by performing a method commonly known in the art.

The color filter including the substrate and the pattern layer as described above may further include a partition wall formed between each pattern, and may further include a black matrix, but is not limited thereto.

Further, the color filter may further include a protective film formed on the pattern layer of the color filter.

<Image Display Device>

Further, another aspect of the present invention relates to an image display apparatus including the color filter described above. At this time, the image display apparatus may be an image display apparatus of a COA structure in which a color filter is formed on a substrate on which a thin film transistor element (TFT) is formed. When the colored photosensitive resin composition of the present invention is included, a contact hole having an excellent alignment accuracy can be formed in the R, G, and B resin films of the image display apparatus of the COA structure. The resin film, that is, In forming the electrical path of the element (TFT), it is necessary to secure the pattern stability of the R, G, and B resin films in the contact hole formation by the dry etching method and the IZO deposition to be used as the pixel electrode, , There is an advantage that the defective pixel due to the B disconnection can be improved.

The color filter of the present invention is applicable not only to a general liquid crystal display device but also to various image display devices such as an electroluminescence display device, a plasma display device, and a field emission display device.

Hereinafter, the present invention will be described in detail by way of examples to illustrate the present invention. However, the embodiments according to the present disclosure can be modified in various other forms, and the scope of the present specification is not construed as being limited to the above-described embodiments. Embodiments of the present disclosure are provided to more fully describe the present disclosure to those of ordinary skill in the art. In the following, "%" and "part" representing the content are by weight unless otherwise specified.

Synthesis Example: An alkali-soluble resin (A-1)

A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube was prepared. The flask was charged with 100 g of propylene glycol monomethyl ether acetate (PGMEA), 100 g of propylene glycol monomethyl ether (PGME), 8.2 g of azobisisobutyronitrile (AIBN), 73.6 g of 2-ethylhexyl acrylate, g, 78.1 g of glycidyl methacrylate and 6.1 g of n-dodecanethiol were charged and replaced with nitrogen. Thereafter, the temperature of the reaction solution was raised to 80 캜 with stirring, and the reaction was carried out for 4 hours. The temperature of the reaction solution was lowered to room temperature, and the atmosphere of the flask was replaced with air with nitrogen. Then, 0.2 g of triethylamine, 0.1 g of 4-methoxyphenol and 39.6 g of acrylic acid were added and reacted at 100 ° C for 6 hours. Thereafter, the temperature of the reaction solution was lowered to room temperature, 6.0 g of succinic anhydride was added, and the reaction was carried out at 80 DEG C for 6 hours to synthesize an alkali-soluble resin of the following formula (3).

(3)

(3)

R ₁ is a methyl group,

And R ₂ to R ₃ are hydrogen.

The acid value of the synthesized alkali-soluble resin was 32.8 mgKOH / g.

The weight average molecular weight (Mw) of the synthesized alkali-soluble resin was 6,230 as measured by GPC and the glass transition temperature measured by differential scanning calorimetry was -21.0 ° C.

Production Example: Preparation of Pigment Dispersion Composition (D)

C.I. 30 parts by weight of Pigment Blue 15: 6, 4.0 parts by weight of BYK-2001 (BYK) as a pigment dispersant, and 66 parts by weight of propylene glycol monomethyl ether acetate as a solvent were mixed and the pigment was sufficiently dispersed using a bead mill.

Examples 1 to 6 and Comparative Examples 1 to 4: Preparation of colored photosensitive resin composition

Example 1.

15.869% by weight of the alkali-soluble resin (A-1) of the above Synthesis Example, 4.015% by weight of dipentaerythritol hexaacrylate (KAYARAD DPHA, Nippon Kayaku) as a photopolymerizable compound (B) (E-1) as a solvent, 57.646% by weight of propylene glycol monomethyl ether acetate (E-2), and 0.964% by weight of the pigment dispersion composition (D) And 0.006% by weight of a polyether-modified silicone oil (SH8400, Toray Silicone Co., Ltd.) as an additive were mixed to prepare a colored photosensitive resin composition.

Examples 2-6.

A colored photosensitive resin composition was prepared in the same manner as in Example 1 with the ingredients and contents shown in Table 1 below.

Comparative Examples 1 to 4.

A colored photosensitive resin composition was prepared in the same manner as in Example 1 with the ingredients and contents shown in Table 1 below.

Category (% by weight) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 alkali
Availability
Suzy A-1 15.869 6.853 6.715 15.319 7.660 7.723 - - 6.715 - A-2 - 7.935 - - 6.625 - 13.707 - 6.853 6.714 A-3 - - 7.935 - - 6.429 - 13.429 - 7.935 Photopolymerizable compound B 4.015 4.015 4.015 3.844 3.844 3.844 4.015 4.015 4.015 4.015 Light curing
Initiator C-1 0.964 0.964 0.964 0.922 0.922 0.922 - - - 0.964 C-2 - - - 0.384 0.384 0.384 0.964 0.964 0.964 - Pigment dispersion composition D 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 solvent E-1 17 17 17 17 17 17 17 17 17 17 E-2 57.646 58.727 58.865 58.025 59.059 59.192 59.808 60.086 59.947 58.866 additive F 0.006 0.006 0.006 0.006 0.006 0.006 0.006 0.006 0.006 0.006

C-2: 2-메틸-2-모르폴리노-1-(4-메틸티오페닐)프로판-1-온(바스프사 제조)
D: 제조예의 안료분산조성물
E-1: 3-에톡시프로피온산에틸
E-2: 프로필렌글리콜모노메틸에테르아세테이트
F: 폴리에테르 변성 실리콘 오일 SH8400(토레이실리콘(주) 제조)A-1: Alkali-soluble resin
A-2: A copolymer having a molar ratio of glycidyl methacrylate: 2-hydroxy-3- (vinyloxycarbonyloxy) propyl methacrylate to octane-3-yl acrylate units of 45:10:45 Coalescence (average molecular weight 12,600)
A-3: copolymer (average molecular weight: 18,000) having a molar ratio of methacrylic acid: benzyl methacrylate unit of 42:
B: dipentaerythritol hexaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.)
C-1:

C-2: 2-Methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one (BASF)
D: Pigment dispersion composition of Preparation Example
E-1: Ethyl 3-ethoxypropionate
E-2: Propylene glycol monomethyl ether acetate
F: polyether-modified silicone oil SH8400 (Toray Silicone Co., Ltd.)

Color Filter Manufacturing Example

The colored photosensitive resin compositions of Examples 1 to 6 and Comparative Examples 1 to 4 were coated on a 5 × 5 glass substrate (Corning Co.) by spin coating, then placed on a heating plate and maintained at 100 ° C. for 3 minutes to obtain 3.0 Mu] m thick. Then, a test photomask having a pattern for changing the transmittance in the range of 1 to 100% to a step-like pattern and a line / space pattern of 1 to 50 μm was placed on the thin film, and the distance from the test photomask was set to 100 μm And irradiated with ultraviolet rays. At this time, the ultraviolet light source was irradiated at 100 mJ / cm 2 using 1 kw high pressure mercury containing g, h and i lines, and no special optical filter was used. The thin film irradiated with ultraviolet rays was immersed in a KOH aqueous solution of pH 10.5 for 2 minutes to develop. The glass plate coated with the thin film was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 200 ° C for 30 minutes. The pattern shape (film) thickness of the color filter thus obtained was 3 m.

Experimental Example 1: Development speed, sensitivity, pattern stability, taper line width test

1) Development speed: Development (Spray Developer HPMJ method) The time taken for the first non-visible part to dissolve in the developer was measured, and the results are shown in Table 2 below.

2) Sensitivity: The minimum exposure amount necessary to form a thin film without peeling of the pattern after development was measured, and the results are shown in Table 2 below.

3) Pattern stability: The degree of error (degree of pattern peeling, defect in straightness, etc.) of the post-exposure pattern of the pattern mask at a low exposure dose (20 to 100 mJ) was measured. The criteria for pattern stability were evaluated as follows, and the results are shown in Table 2 below. At this time, an error on the pattern was confirmed by the above-mentioned optical microscope (ECLIPSE LV100POL Model, manufactured by Nikon Corporation) of the three-dimensional surface type.

○: No error in pattern

×: Error in pattern 3 or more

4) Tapered line width: The patterned mask was exposed in a pattern of 100 mu m, and the resulting cured film was observed with a scanning electron microscope (S-4600, Hitachi, Ltd.) to measure the line width of the pattern. 2.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Development speed (sec) 17 22 20 18 19 20 19 17 20 22 Sensitivity (mJ / cm ² ) 14 14 14 16 16 16 22 20 20 18 Pattern stability ○ ○ ○ ○ ○ ○ × × × × Taper line width (탆) 103 103 102 102 102 102 105 103 103 104

The results are shown in Table 2. The results are shown in Table 2. In the case where both the alkali-soluble resin and the photopolymerization initiator of the present invention are included (Examples 1 to 6) and the alkali-soluble resin and the photopolymerization initiator of the present invention are not all included (Comparative Examples 1 to 2 , Pattern stability and taper line width were improved, and it was confirmed that development speed, sensitivity and pattern stability were improved in the case where the photopolymerization initiator of the present invention was not included (Comparative Example 3), and the alkali of the present invention It was confirmed that the development speed, sensitivity, pattern stability and taper line width were improved in the case of not including the soluble resin (Comparative Example 4).

Experimental Example  2: Hardness, Solvent resistance , Experiment to confirm the change in brightness before and after heat resistance and heat resistance

1) Pencil hardness: The pencil hardness test was carried out according to JIS K5600-5-4, and the results are shown in Table 3 below.

2) Solvent resistance: The color change (DELTA E * ab) was measured by immersing the n-methyl-2-pyrrolidone (NMP) solvent at 23 DEG C constantly for 30 minutes. At this time, the CIE color coordinate values before and after the solvent resistance evaluation were measured using a microscopic spectrophotometer (Model No. OSP-SP2000, Olympus), and the degree of color change was determined through the following equation (1) And the results are shown in Table 3 below.

[Equation 1]

△ E * ab = [(△ L *) 2 + (△ a *) 2 + (△ b *) 2] 1/2

∘: ΔE * ab <1

?: 1?? E * ab? 3

×: ΔEab> 3

3) Change in luminance (ΔY) before and after heat resistance and heat resistance: The color filter prepared in the production example of the present invention was heated in a heating oven at 230 ° C. for 2 hours, And the change in brightness before and after the heat resistance evaluation was confirmed with a microscopic spectrophotometer (Model No. OSP-SP2000, Olympus) to determine whether the luminance was deteriorated due to thermal yellowing. The heat resistance evaluation standard is the same as the above-mentioned content formulation, and the brightness change criterion is as described below. The experimental results are shown in Table 3 below.

?: -0.04?? Y? 0.00

×: -0.04 <ΔY

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Pencil hardness 6H 6H 6H 6H 6H 6H 4H 4H 5H 4H NMP content ○ ○ ○ ○ ○ ○ × × × × Heat resistance ○ ○ ○ ○ ○ ○ × × × × Y
(Change in luminance) ○ ○ ○ ○ ○ ○ × × × ×

In the case where all of the alkali-soluble resin and the photopolymerization initiator of the present invention (Examples 1 to 6) were not included in both of the alkali-soluble resin and the photopolymerization initiator of the present invention (Comparative Examples 1 to 2 ), The hardness, the solvent resistance, the heat resistance and the change in brightness were all improved as compared with the case of not containing the photopolymerization initiator of the present invention (Comparative Example 3) and the case of not containing the alkali soluble resin of the present invention (Comparative Example 4) Respectively.

Experimental Example  3: Contact hole  Size / shape, Stripper liquid , IZO Ethene fluid  Immunity experiment

Negative PRs (Photoresist) of Examples 1 to 6 and Comparative Examples 1 to 4 were coated on an R / G / B pattern coating film and then placed on a heating plate and kept at 90 DEG C for 1 minute to form a thin film. Then, a test photomask having a pattern for changing the transmittance in the range of 1 to 100% to a step-like pattern and a line / space pattern of 1 to 50 μm was placed on the thin film, and the distance from the test photomask was set to 100 μm And irradiated with ultraviolet rays. At this time, the ultraviolet light source was irradiated at 100 mJ / cm 2 using 1 kw high pressure mercury containing g, h and i lines, and no special optical filter was used. The thin film irradiated with ultraviolet rays is further placed on a heating plate and held at a temperature of 110 ° C for 1 minute to cure the thin film again. The thin film irradiated with ultraviolet rays was immersed in a 2.38% aqueous solution of TMAH for 30 seconds to develop. The glass plate coated with the thin film was washed with distilled water, blown with nitrogen gas, dried, and heated in a heating oven at 130 캜 for 2 minutes. The thickness of the negative PR pattern (film) thus obtained was 3 탆. The deposition conditions of the IZO thin film are preferably 500 to 2000 angstroms, more preferably 500 to 1000 angstroms, using a sputter. The examination criteria for each experiment are as follows, and the results are shown in Table 4 below.

1) Size of contact hole: Diameter of contact hole after exposure of a 40 탆 pattern of Contact Hole Mask

2) Form of contact hole: The degree of implementation of mask pattern of 40 mu m on the image after exposure of 40 mu m square pattern of contact hole mask on SEM (S-4300, manufactured by Hitachi, Ltd.)

In this case, the degree of implementation indicates the degree of the contact hole diameter after exposure corresponding to the diameter of the contact hole mask in%, and the closer to 100%

3) Stripper solution, IZO etant solution Resistance: Stripper solution (PRS-2000, Dongwoo Fine-Chem) to IZO etchant solution (MA-S03 / MASZ02, Dongwha FineChem) was the same as Spray Developer . The IZO etching conditions were as follows: the substrate was immersed in water at 35 ° C for 2 minutes and then washed with water to confirm the stability of the coating film by the IZO etchant. The condition of the stripper solution was evaluated at a temperature of 70 to 80 ° C for 4 minutes Respectively. The evaluation of the stripper solution also confirmed the stability of the coating film. Specifically, the resistance to the stripper solution and the IZO etching solution was evaluated as a pattern error after exposure of a pattern pattern of 100 mu m in a pattern mask, and the error of the pattern was confirmed through the optical microscope of the three-dimensional surface type, And the results are shown in Table 4 below.

○: 1 to 3 pattern errors

&Lt; / RTI &gt; &lt; RTI ID = 0.0 &gt; x: &lt;

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Contact hole size (μm) 36 36.8 36 36.8 36.4 36 32.4 33.6 33.2 33.6 Contact hole type (%) 90 92 90 92 91 90 81 84 83 84 Stripper liquid resistance ○ ○ ○ ○ ○ ○ × × × × IZO etching solution resistance ○ ○ ○ ○ ○ ○ × × × ×

In the case where all of the alkali-soluble resin and the photopolymerization initiator of the present invention (Examples 1 to 6) were not included in all of the alkali-soluble resin and the photopolymerization initiator of the present invention (Comparative Examples 1 to 2 ) And the photoresist composition of the present invention (Comparative Example 3), it was confirmed that the contact hole size, shape, stripper solution resistance and IZO etching solution resistance were both improved, and the alkali soluble resin of the present invention (Comparative Example 4), it was confirmed that the contact hole type, the stripper liquid resistance and the IZO etching solution resistance were improved.

Experiment 4: Outgas measurement experiment

The color filters prepared in the above Preparation Example were pyrolyzed at 230 ° C for 30 minutes through Py-GC / FID to analyze the collected compounds. The evaluation criteria are as follows.

The value of Comparative Example 1 was expressed as a percentage based on 100%, and the lower the value, the better. The results are shown in Table 5 below.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Out Gas (%) 60 50 60 70 60 70 100 90 90 80

When the alkali-soluble resin and the photopolymerization initiator of the present invention were all included (Examples 1 to 6) in the case of not containing both the alkali-soluble resin and the photopolymerization initiator of the present invention (Comparative Examples 1 to 2 ), It was confirmed that the outgas phenomenon was improved as compared with the case of not containing the photopolymerization initiator of the present invention (Comparative Example 3) and the case of not containing the alkali soluble resin of the present invention (Comparative Example 4).

1: TFT substrate
2: Pixel pattern
3: TFT element
4: nitride film (SiNx)

Claims (8)

An alkali-soluble resin containing a repeating unit represented by the following formula (1); And a photopolymerization initiator comprising at least one compound selected from the group consisting of compounds represented by the following general formula (2):
[Chemical Formula 1]

(In the formula 1,
R ₁ and R ₂ are each independently a hydrogen atom or a methyl group,
R &lt; ₃ &gt; is a residue comprising a carboxylic acid derived by an acid anhydride)
(2)

(In the formula (2)
R ₄ to R ₁₃ are each independently hydrogen, halogen, C ₁ ~ C ₂₀ alkyl group, C of ₆ ~ C ₂₀ aryl group, C ₁ ~ C alkoxy group of _20, C ₇ ~ C ₄₀ arylalkyl group, C ₂ To C ₄₀ hydroxyalkoxyalkyl groups or C ₃ to C ₂₀ cycloalkyl groups). The method according to claim 1,
Wherein the content of the repeating unit represented by the formula (1) is 50 to 90 mol% based on the total molar percentage of the alkali-soluble resin. The method according to claim 1,
Wherein the content of the photopolymerization initiator is 0.1 to 40% by weight based on the total weight of the solid content in the colored photosensitive resin composition. The method according to claim 1,
Wherein the colored photosensitive resin composition further comprises at least one selected from the group consisting of a photopolymerizable compound, a colorant, a solvent and an additive. A color filter comprising a cured product of the colored photosensitive resin composition according to any one of claims 1 to 4. 6. The method of claim 5,
Wherein a match degree between a diameter of the contact hole included in the color filter and a diameter of the contact hole mask used for contact hole exposure is 90% or more. An image display device comprising the color filter of claim 5. 8. The method of claim 7,
Wherein the image display apparatus is applied with a color filter on a color filter on array (COA) system.

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