KR20110045528A - A colored photo sensitive resin composition, color filter and liquid crystal display device having the same - Google Patents

Abstract

PURPOSE: A blue photosensitivity resin composition, a color filter and liquid crystal display including the same are provided to reduce an overlap step in a blue colorant layer and not to generate a display failure in a liquid crystal display device. CONSTITUTION: In a blue photosensitivity resin composition which is comprised of binder resin, photopolymerizable compound, photopolymerization initiator, coloring material, and solvent, the binder resin includes a unsaturated group containing first rinse and an unsaturated group containing second rinse.

Description

A blue photosensitive resin composition, a color filter and a liquid crystal display having the same {A COLORED PHOTO SENSITIVE RESIN COMPOSITION, COLOR FILTER AND LIQUID CRYSTAL DISPLAY DEVICE HAVING THE SAME}

The present invention relates to a blue photosensitive resin composition, a color filter, and a liquid crystal display device having the same.

In general, a color filter having a plurality of colored layers arranged to correspond to a plurality of pixels is used in a liquid crystal display device to realize color image display. This color filter is formed on an opposing substrate disposed opposite to the TFT substrate, not on the side of the substrate (hereinafter referred to as TFT substrate) on which a thin film transistor element (hereinafter referred to as TFT) on which a switching element is formed is formed.

However, when the color filter is disposed on the opposing substrate, alignment with each pixel electrode on the TFT substrate is not easy, and the aperture ratio is small. In addition, since the distance between the color filter and the liquid crystal layer is relatively far, a problem arises in that the display quality decreases due to light incident from the oblique direction. To solve this problem, Japanese Patent Laid-Open No. 09-73078 discloses a technique for forming a color filter on a TFT substrate.

As described above, when the color filter is formed on the TFT substrate, an overlap step problem occurring in the colored layer is solved by forming an overcoat layer on the colored layer. However, when forming a color filter on the TFT substrate, a contact hole must be formed in the process, so that the thermosetting type overcoat layer used in the prior art cannot be used.

As a result, when the overlap level of the colored layer is large or the flatness of the intra-pixel coating film is insufficient, the opening between the TFT and the color filter is narrowed. In this case, there is a problem that the overlap part is dark when the liquid crystal is driven. In particular, the overlap level and the flatness of the in-pixel coating film are the biggest problems in the blue photosensitive resin composition having the least pigment content among the colored photosensitive resin compositions. Accordingly, in the liquid crystal display device of large size and high color purity, the above-described overlap step and flatness of the intra-pixel coating film seriously cause display defects such as visibility, and therefore, a solution for this problem is required.

SUMMARY OF THE INVENTION The present invention has been made to overcome the above-mentioned conventional problems, and an object of the present invention is to provide a low overlap step in a blue colored layer even when an overcoat layer is not formed when a color filter is formed on a TFT substrate. It is an object of the present invention to provide a blue photosensitive resin composition which is excellent and does not cause display defects such as visibility in a liquid crystal display device of large size and high color purity.

Another object of the present invention is to provide a color filter of excellent quality in which display defects such as visibility do not occur in a liquid crystal display device of large size and high color purity.

Another object of the present invention is to provide a liquid crystal display device having the color filter.

In order to achieve the said objective, this invention is a blue photosensitive resin composition which consists of binder resin (A), a photopolymerizable compound (B), a photoinitiator (C), a coloring material (D), and a solvent (E), The said Binder resin (A) is made with the unsaturated group containing 1st resin (A-1) obtained by making the following (A-13) further react with the copolymer obtained by copolymerizing following (A-11) and (A-12) compounds. And an unsaturated group-containing second resin (A-2) obtained by further reacting the following (A-23) with a copolymer obtained by copolymerizing the following (A-21) and (A-22). It provides a photosensitive resin composition;

(A-11): aromatic vinyl compound,

(A-12): methacrylic acid,

(A-13): Compound which has an unsaturated bond and an epoxy group in 1 molecule,

(A-21): unsaturated carboxylic ester compound,

(A-22): unsaturated carboxylic acid compound,

(A-23): Compound which has an unsaturated bond and an epoxy group in 1 molecule.

It is preferable that 5-50 mass% of said unsaturated group containing 2nd resins (A-2) are contained with respect to binder resin (A) in a blue photosensitive resin composition based on solid content.

The coloring material (D) is C.I. Pigment Blue 15 (at least one selected from the group consisting of 15: 3, 15: 4 and 15: 6) is preferred.

The unsaturated carboxylic ester compound (A-21) of the unsaturated group-containing second resin (A-2) is benzyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and dish And at least one selected from the group consisting of clopentadiethyl (meth) acrylate and adamantyl (meth) acrylate.

The ratio of the structural unit derived from the said (A-11) in the said unsaturated group containing 1st resin (A-1) is the total mole number of the copolymer structural unit obtained by copolymerizing the said (A-21) and (A-22). It is preferable that it is 20 to 60 mol% with respect to.

In order to achieve the above another object, the present invention provides a color filter comprising a colored layer formed on a TFT substrate, wherein the colored layer comprises a blue colored layer formed using the blue photosensitive resin composition according to the present invention. It provides a color filter characterized in that.

In order to achieve the above another object, the present invention provides a liquid crystal display device comprising the color filter.

The blue photosensitive resin composition which concerns on this invention mentioned above has little overlap step | step, and is excellent in the flatness of a coating film in a pixel, and can suppress display defects, such as visibility, in which an overlap step part shows black. Therefore, the blue photosensitive resin composition which concerns on this invention can be used suitably for manufacture of the color filter and liquid crystal display device of excellent quality.

Hereinafter, the present invention will be described in detail so that those skilled in the art can easily carry out the present invention.

The blue photosensitive resin composition according to the present invention comprises a binder resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C), a coloring material (D) and a solvent (E), and optionally other It may further include an additive (F).

Binder Resin (A)

The binder resin (A) may include an unsaturated group-containing first resin (A-1) and an unsaturated group-containing second resin (A-2).

The unsaturated group-containing first resin (A-1) may be an unsaturated group-containing resin obtained by further reacting the following (A-13) with a copolymer obtained by copolymerizing the following (A-11) and (A-12) compounds. have.

(A-11): aromatic vinyl compound,

(A-12): methacrylic acid,

(A-13): Compound which has an unsaturated bond and an epoxy group in 1 molecule.

The aromatic vinyl compound (A-11) in the unsaturated group-containing first resin (A-1) is not limited as long as it is a commonly known aromatic vinyl compound.

Specific examples of (A-11) include styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl 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 ether, indene and the like. (A-11) illustrated above can be used individually or in combination of 2 types or more, respectively. Preferably, vinyltoluene is preferred among the compounds exemplified above because of its excellent copolymerization reactivity and solubility in a developing solution.

In the unsaturated resin-containing first resin (A-1) of the binder resin (A), the copolymer of (A-11) and (A-12) includes (A-11) and (A-12), A-11) and compounds having a polymerizable unsaturated bond with (A-12) can be copolymerized together.

Specific examples of the compound having an unsaturated bond polymerizable with the above (A-11) and (A-12) include 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-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxy Propyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxy Roxybutyl meta Relate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate, 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, methoxy Sidiethylene glycol methacrylate, methoxy triethylene glycol acrylate, methoxy triethylene glycol methacrylate, methoxy propylene glycol acrylate, methoxy propylene glycol methacrylate, methoxy dipropylene glycol acrylate, methoxy dipropylene glycol Methacrylate, isobornyl acrylate, isobornyl methacrylate, Pentadienyl acrylate, dicyclopentadiethyl methacrylate, adamantyl acrylate, adamantyl methacrylate, norbornyl acrylate, norbornyl methacrylate, 2-hydroxy-3-phenoxypropyl Unsaturated carboxylic acid esters such as acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, and glycerol monomethacrylate; 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2- Unsaturated carboxylates such as dimethylaminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate and 3-dimethylaminopropyl methacrylate Acid aminoalkyl esters; Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; Unsaturated ethers 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; Maleimide, benzylmaleimide, N-phenylmaleimide. Unsaturated imides such as 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. The macromonomer which has, etc. are mentioned.

Compounds having an unsaturated bond that can be polymerized with the above (A-11) and (A-12) may be used alone or in combination of two or more thereof, and among them, two containing a hydrophilic group for improving adhesion and developability. -Hydroxyethyl (meth) acrylate can be preferably used.

Specific examples of (A-13) further reacted with the copolymer obtained by copolymerizing the above (A-11) and (A-12) include glycidyl (meth) acrylate and 3,4-epoxycyclohexyl (meth). ) Acrylate, 3, 4- epoxycyclohexyl methyl (meth) acrylate, methylglycidyl (meth) acrylate, etc. are mentioned. Among these, glycidyl (meth) acrylate is preferably used. These can be used individually or in combination of 2 types or more, respectively.

As used herein, (meth) acrylate means acrylate and / or methacrylate.

Unsaturated group obtained by further reacting (A-13) with the copolymer obtained by copolymerizing the unsaturated group-containing first resin (A-1) according to the present invention (A-11) and (A-12) as described above. When containing resin containing, the ratio of the structural unit derived from (A-11) in the copolymer obtained by copolymerizing the said (A-11) and (A-12) is the total number of moles of the structural unit which comprises the said copolymer. It is preferable to exist in the range of 20-60 mol% with respect to a mole fraction with respect to it, More preferably, it exists in the range of 30-50 mol%. In this case, the copolymer may further include other compounds in addition to the above (A-11) and (A-12) as described above may be copolymerized.

When said (A-11) satisfy | fills the said range, the binder resin (A) containing the said unsaturated group containing 1st resin (A-1) shows the outstanding characteristic with little overlap step.

It is preferable to make 5 to 80 mol% of said (A-13) react with respect to the mole number of the structural unit derived from (A-12) of the said copolymer, Especially 10-80 mol% is good. If the composition ratio of (A-13) is within the above range, sufficient photocurability and thermosetting are obtained, and the sensitivity and pencil hardness are compatible, and further, it is preferable because it is excellent in developability.

An example of the manufacturing method of the unsaturated group containing 1st resin (A-1) obtained by making said (A-13) further react with the copolymer obtained by copolymerizing the said (A-11) and (A-12) is as follows. .

To the flask equipped with the stirrer, the thermometer, the reflux cooling tube, the dropping lot and the nitrogen introduction tube, 0.5 to 20 times the solvent was introduced on a mass basis with respect to the total amount of the above (A-11) and (A-12), and the atmosphere in the flask was introduced. Is replaced by nitrogen in air. Then, after heating a solvent to 40-140 degreeC, it is 0 on a mass basis with respect to the predetermined amount of said (A-11) and (A-12), and the total amount of said (A-11)-(A-13). 0.1 to 8 times the amount of the solvent and the polymerization initiator to which 0.1-10 mol% of the polymerization initiator was added based on the total number of moles of the above-mentioned (A-11) and (A-12) were added dropwise from 0.1 to 8 from the dropping lot. It is dripped at the said flask over time, and it stirred further at 40-140 degreeC for 1 to 10 hours.

In the above process, part or all of the polymerization initiator may be put in the flask, or part or all of the above (A-11) and (A-12) may be put in the flask.

In addition, as a solvent used in the said process, the solvent used at the time of a normal radical polymerization reaction can be used, As a specific example of the said solvent, tetrahydrofuran, dioxane, ethylene glycol dimethylethyl, diethylene glycol dimethylethyl, acetone , Methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, propylene glycol monomethyl ethyl acetate, 3-methoxybutyl acetate, methanol, ethanol, propanol, n-butanol, ethylene glycol monomethyl Ether, propylene glycol monomethyl ether, toluene, xylene, ethylbenzene, chloroform, dimethyl sulfoxide and the like. These solvents can be used individually or in combination of 2 or more types, respectively.

In addition, the polymerization initiator used for the said process can add the polymerization initiator normally used, and is not specifically limited. Specific examples of the polymerization initiator include diisopropylbenzenehydroperoxide, di-t-butylperoxide, benzoyl peroxide, t-butylperoxyisopropylcarbonate, t-amylperoxy-2-ethylhexanoate, organic peroxides such as t-butylperoxy-2-ethylhexanoate; 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylbareronitrile), dimethyl 2,2'-azobis (2-methylpropionate) Nitrogen compounds; Etc. can be mentioned. These may be used alone or in combination of two or more thereof.

In addition, in said process, in order to control molecular weight and molecular weight distribution, mercapto type chain transfer agents, such as n-dodecyl mercapto, mercapto acetic acid, and mercapto acetate, alpha-methylstyrene dimer, etc. are used as a chain transfer agent, for example. It may be. The usage-amount of the said (alpha) -methylstyrene dimer and a mercapto compound is 0.005-5 mass% with respect to the total amount of (A-11)-(A-13) on a mass basis. In addition, the said polymerization conditions can also adjust an input method and reaction temperature suitably in consideration of the amount of heat generation by a manufacturing facility, superposition | polymerization, etc ..

By doing it above, the copolymer obtained by copolymerizing the said (A-11) and (A-12) is manufactured.

Subsequently, the atmosphere in the flask was replaced with nitrogen from air, and the reaction catalyst of (A-13), carboxyl group and epoxy group, of 5 to 80 mole% (A-13) in molar fraction with respect to the constituent derived from (A-12), for example. For example, trisdimethylaminomethylphenol is 0.01 to 5% by mass relative to the total amount of (A-11) to (A-13) and as a polymerization inhibitor, for example, hydroquinone (A-11) to (A-13 The copolymer and (A-13) can be reacted by adding 0.001 to 5% by mass in a flask on a mass basis and reacting at 60 to 130 ° C for 1 to 10 hours, based on the total amount of. Similarly, the input method and the reaction temperature may be appropriately adjusted in consideration of the amount of heat generated by the production equipment, polymerization, and the like.

Thereby, the unsaturated group containing 1st resin (A-1) obtained by making the said (A-13) react with the copolymer obtained by copolymerizing the said (A-11) and (A-12) further is manufactured.

The unsaturated group-containing second resin (A-2) is added to reduce the film reduction or color change during development, and is added to the copolymer obtained by copolymerizing the following compounds (A-21) and (A-22). It may be an unsaturated group-containing resin obtained by further reacting (A-23).

(A-21): unsaturated carboxylic ester compound,

(A-22): unsaturated carboxylic acid compound,

(A-23): Compound which has an unsaturated bond and an epoxy group in 1 molecule.

Specific examples of the unsaturated carboxylic acid ester compound (A-21) include 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-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxy Propyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4- Hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate Acrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacryl Latex, methoxy triethylene glycol acrylate, methoxy triethylene glycol methacrylate, methoxy propylene glycol acrylate, methoxy propylene glycol methacrylate, methoxy dipropylene glycol acrylate, methoxy dipropylene glycol methacrylate, iso Borylacrylate, isobornyl methacrylate, dicyclopentadienyl Relate, dicyclopentadiethyl methacrylate, adamantyl acrylate, adamantyl methacrylate, norbornyl acrylate, norbornyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate, etc. are mentioned.

Especially, said (A-21) is benzyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentadiethyl (meth) acrylate, and adamantyl (meth) In the case of including at least one selected from acrylates, it is preferable because there is little film reduction or color change during development to obtain a better blue photosensitive resin composition.

The unsaturated carboxylic acid compound (A-22) is not particularly limited as long as it is a compound having a carboxyl group and an unsaturated bond, and may be used alone or in combination of two or more thereof. Specific examples of the above (A-22) include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; Dicarboxylic acids such as fumaric acid, mesaconic acid and itaconic acid; And anhydrides of the dicarboxylic acids; and mono (meth) acrylates of polymers having carboxyl groups and hydroxyl groups at both ends thereof, such as? -carboxypolycaprolactone mono (meth) acrylate. Acrylic acid and methacrylic acid among the compounds are preferred because of their excellent copolymerization reactivity and solubility in a developing solution.

In the unsaturated resin-containing second resin (A-2) of the binder resin (A), the copolymer of (A-21) and (A-22) may be used in addition to the (A-21) and (A-22). A-21) and a compound having a polymerizable unsaturated bond with (A-22) can be copolymerized together. Specific examples of the compound having an unsaturated bond polymerizable with the above (A-21) and (A-22) include 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethyl Aminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate Unsaturated carboxylic acid aminoalkyl esters such as acrylate, 3-dimethylaminopropyl acrylate and 3-dimethylaminopropyl methacrylate; Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; Unsaturated ethers 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; Maleimide, benzylmaleimide, N-phenylmaleimide. Unsaturated imides such as 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. The macromonomer which has, etc. are mentioned.

Specific examples of the compound (A-23) having an unsaturated bond and an epoxy group in one molecule further reacted with the copolymer obtained by copolymerizing the above-mentioned (A-21) and (A-22) are glycidyl (meth) acrylates. And 3,4-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, methylglycidyl (meth) acrylate, and the like. Among these, glycidyl (meth) acrylate is preferably used. These can be used individually or in combination of 2 types or more, respectively.

Unsaturated group obtained by further reacting (A-23) with the copolymer obtained by copolymerizing the unsaturated group-containing second resin (A-2) according to the present invention to (A-21) and (A-22) as described above. When containing resin, the ratio of the structural unit derived from (A-21) in the copolymer obtained by copolymerizing the said (A-21) and (A-22) is the total mole number of the structural unit which comprises said copolymer. It is preferable to exist in the range of 20-60 mol% with respect to a mole fraction with respect to it, More preferably, it exists in the range of 30-50 mol%. In this case, the copolymer may further include other compounds in addition to the above (A-21) and (A-22) as described above may be copolymerized.

When said (A-21) satisfy | fills the said range, the binder resin (A) containing the said unsaturated group containing 2nd resin (A-1) shows the outstanding characteristic with little film | membrane reduction or color change at the time of image development.

It is preferable to make 5 to 80 mol% of said (A-23) react with respect to the mole number of the structural unit derived from (A-22) of the said copolymer, Especially 10-80 mol% is good. When the composition ratio of the above (A-23) is within the above range, sufficient photocurability and thermosetting properties are obtained, and the sensitivity and pencil hardness are compatible, and further, the developability is preferable.

The method for producing an unsaturated group-containing second resin (A-2) obtained by further reacting (A-23) with a copolymer obtained by copolymerizing the above (A-21) and (A-22) contains an unsaturated group as described above. Since it is similar to the manufacturing method of the 1st resin (A-1), referring to this, an unsaturated group containing 2nd resin (A-2) can be manufactured easily.

According to this invention, it is preferable that the said unsaturated group containing 2nd resin (A-2) is contained 5-50 mass% with respect to binder resin (A) in a blue photosensitive resin composition based on solid content. When the content of the unsaturated group-containing second resin is included in the above range, it may exhibit excellent characteristics with less film reduction or color change during development.

It is preferable that the weight average molecular weight of polystyrene conversion of the said binder resin (A) exists in the range of 5,000-20,000, and it is more preferable to exist in the range of 6,000-20,000. When the weight average molecular weight of the binder resin (A) satisfies the above range, film reduction is unlikely to occur at the time of development, and the non-pixel portion has good omission property, and in particular, it is preferable because it reduces the overlap step.

It is preferable that it is 1.5-4.0, and, as for the molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the said binder resin (A), it is more preferable that it is 1.8-3.5. If the molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] is 1.5 to 4.0, it is preferable because of its excellent acidity.

It is preferable that the said binder resin (A) has an acid value of 20-200 (KOHmg / g). When the acid value of the binder resin (A) is in the above range, the solubility in the developing solution is improved, so that the non-exposed part is easily dissolved and the sensitivity is increased, and as a result, the pattern of the exposed part remains during development, resulting in a film remaining ratio. It is desirable to improve. The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the acrylic polymer, and can usually be obtained by titration using an aqueous potassium hydroxide solution.

Content of the said binder resin (A) is 5-85 mass% in mass fraction with respect to solid content in a blue photosensitive resin composition, Preferably it is the range of 10-70 mass%. When the content of the binder resin (A) is 5 to 85% by mass based on the above criteria, the solubility in the developer is sufficient, and development residues are less likely to occur on the substrate of the non-pixel portion, and the film of the pixel portion of the exposed portion is reduced during development. Is difficult to occur, and the omission of the non-pixel portion is good, which is preferable.

Solid content in a blue photosensitive composition in this invention means the sum total of the component which removed the solvent.

Photopolymerizable Compound (B)

The said photopolymerizable compound (B) 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.

Specific examples of the monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate and N-vinylpyrroly Money, etc.

Specific examples of the bifunctional monomers include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, Bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, etc. are mentioned.

Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Dipentaerythritol hexa (meth) acrylate and the like.

In the photopolymerizable compound (B) exemplified above, a bifunctional or higher polyfunctional monomer can be preferably used. The above-mentioned photopolymerizable compound (B) can be used individually or in combination of 2 types or more, respectively.

The photopolymerizable compound (B) is usually used in a mass fraction of 5 to 50% by mass, preferably 7 to 45% by mass, with respect to the solids in the blue photosensitive resin composition. Since the intensity | strength and smoothness of a pixel part become it favorable that the said photopolymerizable compound (B) is 5-50 mass% on the said reference | standard, it is preferable.

Photoinitiator (C)

Although the said photoinitiator (C) is not restrict | limited, 1 or more types of compounds chosen from the group which consists of a triazine type compound, an acetophenone type compound, a biimidazole type compound, and an oxime compound can be used. The blue photosensitive resin composition containing said photoinitiator (C) is highly sensitive, and the film | membrane formed using this composition becomes favorable the intensity | strength and surface smoothness of the pixel part.

As said triazine type compound, it is 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1, 3, 5- triazine, 2, 4-bis (trichloromethyl)-, for example. 6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4- Bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2 -Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-tri Azine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloro Methyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like.

As said acetophenone type compound, for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 2-hydroxy-1- [4- (2 -Hydroxyethoxy) phenyl] -2-methylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1- On, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane And oligomers of -1-ones.

Moreover, as said acetophenone type compound, the compound represented by following formula (1) is mentioned, for example.

<Formula 1>

In Formula 1, R1 to R4 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a phenyl group which may be substituted by an alkyl group having 1 to 12 carbon atoms, a benzyl group or 1 carbon atom which may be substituted by an alkyl group having 1 to 12 carbon atoms. The naphthyl group which may be substituted by the alkyl group of -12 is shown.

Specific examples of the compound represented by Formula 1 include 2-methyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-ethyl-2-amino (4-morpholinophenyl) ethane- 1-one, 2-propyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-butyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-methyl- 2-amino (4-morpholinophenyl) propane-1-one, 2-methyl-2-amino (4-morpholinophenyl) butan-1-one, 2-ethyl-2-amino (4-morpholin Nophenyl) propane-1-one, 2-ethyl-2-amino (4-morpholinophenyl) butan-1-one, 2-methyl-2-methylamino (4-morpholinophenyl) propane-1- On, 2-methyl-2-dimethylamino (4-morpholinophenyl) propan-1-one, 2-methyl-2-diethylamino (4-morpholinophenyl) propan-1-one, etc. may be mentioned. have.

As said biimidazole compound, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- tetraphenyl biimidazole, 2,2'-bis (2,3-, for example) Dichlorophenyl) -4,4 ', 5,5'-tetra phenylbiimidazole, 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, and a phenyl group at the 4,4', 5,5 'position is carbo The imidazole compound substituted with the alkoxy group etc. are mentioned. Among them, 2,2'bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole is preferably used.

Examples of the oxime compound include compounds represented by the following formulas (2), (3) and (4).

<Formula 2>

<Formula 3>

<Formula 4>

Moreover, as long as it does not impair the effect of this invention, the other photoinitiator etc. which are normally used in this field can also be used together. As another photoinitiator, a benzoin compound, a benzophenone type compound, a thioxanthone type compound, an anthracene type compound etc. are mentioned, for example. These can be used individually or in combination of 2 or more types, respectively.

As said benzoin type compound, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. are mentioned, for example.

As said benzophenone type compound, for example, benzophenone, methyl 0- benzoyl benzoate, 4-phenyl benzophenone, 4-benzoyl-4'- methyl diphenyl sulfide, 3, 3 ', 4, 4'- tetra ( tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, etc. are mentioned.

As said thioxanthone type compound, 2-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro-4- propoxy thioxanthone, etc. are mentioned, for example. Can be mentioned.

Examples of the anthracene-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and the like. Can be mentioned.

Other 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, phenylclioxylic acid Methyl, a titanocene compound, etc. are mentioned as another photoinitiator.

You may use combining the photoinitiator (C-1) with the said photoinitiator (C). When photopolymerization start adjuvant (C-1) is used together with the said photoinitiator (C), since the blue photosensitive resin composition containing these becomes more sensitive and the productivity at the time of forming a color filter using this composition is preferable, it is preferable.

An amine compound and a carboxylic acid compound are used suitably as said photoinitiator starting adjuvant (C-1).

Specific examples of the amine compound in the photopolymerization initiation assistant (C-1) include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-dimethyl. Isoamyl aminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoic acid, 2-dimethylaminoethyl benzoic acid, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (common name: Michler's ketone) And aromatic amine compounds such as 4,4'-bis (diethylamino) benzophenone. Among them, an aromatic amine compound is preferably used as the amine compound.

Specific examples of the carboxylic acid compound in the photopolymerization initiation assistant (C-1) include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenyl And aromatic heteroacetic acids such as thioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine and naphthoxyacetic acid.

The amount of the photopolymerization initiator (C) used is 0.1 to 40% by mass, preferably 1 to 30% by mass, based on the total amount of the binder resin (A) and the photopolymerizable compound (B). The amount of the photopolymerization initiation assistant (C-1) to be used is 0.1 to 50% by mass, preferably 1 to 40% by mass, based on the total amount of the binder resin (A) and the photopolymerizable compound (B).

When the usage-amount of the said photoinitiator (C) exists in said range on the said reference | standard, since a blue photosensitive resin composition becomes high sensitivity, the intensity | strength of the pixel part formed using this composition and the smoothness in the surface of this pixel part become favorable. desirable. Moreover, when the usage-amount of the said photoinitiator (C-1) exists in said range on the said reference | standard, since the sensitivity of a blue photosensitive resin composition becomes higher and the productivity of the color filter formed using this composition improves, it is preferable. .

Coloring material (D)

The coloring material (D) was selected from C.I. Pigment blue 15 (at least one selected from the group consisting of 15: 3, 15: 4 and 15: 6).

The coloring material (D) is the C.I. Pigment Blue 15 (at least one selected from the group consisting of 15: 3, 15: 4 and 15: 6) may be used in combination with other pigments commonly used in the art without departing from the object of the present invention. Can be. At this time, C.I. Pigment Blue 15 (at least one selected from the group consisting of 15: 3, 15: 4 and 15: 6) and other pigments are preferably mixed in a mass ratio of 40:60 to 100: 0, in particular 60:40 to It is more preferable to mix in mass ratio of 100: 0. When the content of C.I. Pigment Blue 15 (at least one selected from the group consisting of 15: 3, 15: 4, and 15: 6) is included in the above range, high contrast and brightness can be obtained.

C.I. Pigments other than Pigment Blue 15 (at least one selected from the group consisting of 15: 3, 15: 4 and 15: 6) include C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Green 7 or C.I. Pigment Green 36 etc. can be mentioned 1 or more types, Preferably Pigment Yellow 139 and C.I. It is more preferable to use at least one selected from Pigment Yellow 150 in terms of improving the characteristics of brightness and contrast.

Content of said coloring material (D) is 3-60 mass% normally with respect to solid content in a blue photosensitive resin composition, Preferably it is the range of 5-55 mass%. If the content of the coloring material (D) is in the range of 3 to 60% by mass based on the above criteria, even if a thin film is formed, the color density of the pixel is sufficient, and residues are generated because the omission of the non-pixel portion during development is not reduced. It is preferable because it is difficult.

The coloring material (D) contains a pigment dispersant to perform a dispersion treatment, thereby obtaining a pigment dispersion in a state in which the pigment used as the coloring material (D) is uniformly dispersed in a solution.

As the pigment dispersant, for example, cationic, anionic, nonionic, amphoteric, polyester-based and polyamine-based, polyacrylic-based surfactants and the like can be mentioned, and these may be used alone or in combination of two or more thereof. Can be used.

When using the said pigment dispersant, the usage-amount is preferably 1 mass part or less per 1 mass part of coloring materials, More preferably, it is 0.05 mass part-0.5 mass part. When the usage-amount of the said pigment dispersant exists in the said range, since the pigment of a uniform dispersion state is obtained, it is preferable.

Solvent (E)

The solvent (E) is not particularly limited and various organic solvents used in the art can be used.

Specific examples of the solvent (E) 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, and diethylene glycol di. Diethylene glycol dialkyl ethers such as ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate, and ethyl cellosolve acetate, and propylene glycol monomethyl Alkylene glycol alkyl ether acetates such as ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; methyl Ketones such as methyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone, ethanol, propanol, butanol, hexanol, cyclohexanol, alcohols such as ethylene glycol, glycerin, ethyl 3-ethoxypropionate, Ester, such as 3-methoxy propionate, cyclic ester, such as (gamma) -butyrolactone, etc. are mentioned.

In view of the applicability and drying properties in the above solvent, preferably an organic solvent having a boiling point of 100 to 200 ℃ can be used, more preferably alkylene glycol alkyl ether acetates, ketones, ethyl 3-ethoxypropionate And esters such as methyl 3-methoxypropionate can be used, and more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate and 3-methoxypropionic acid The one selected from methyl etc. can be used.

The said solvent (E) can be used individually or in mixture of 2 or more types, respectively.

Content of the said solvent (E) is 60-90 mass% normally with a mass fraction with respect to the whole blue photosensitive resin composition containing it, Preferably it is 70-85 mass%. When the content of the solvent (E) is in the range of 60 to 90% by mass based on the above criteria, it is applied with a coating device such as a roll coater, spin coater, slit and spin coater, slit coater (sometimes referred to as die coater), inkjet, or the like. Since applicability | paintability becomes favorable at the time, it is preferable.

Additive (F)

The additive (F) is optionally added to the blue photosensitive resin composition of the present invention as needed, and specific examples thereof include fillers, other polymer compounds, pigment dispersants, adhesion promoters, antioxidants, ultraviolet absorbers, anti-agglomerating agents, and the like. have.

Specific examples of the filler include glass, silica, alumina and the like.

Specific examples of the other high molecular compounds include curable resins such as epoxy resins and maleimide resins, polyvinyl alcohols, polyacrylic acids, polyethylene glycol monoalkyl ethers, thermoplastic resins such as polyfluoroalkyl acrylates, polyesters, and polyurethanes. Can be mentioned.

Commercially available surfactants can be used as the pigment dispersant, and examples thereof include surfactants such as silicones, fluorines, esters, cations, anions, nonionics, and amphoterics. These can be used individually or in combination of 2 types or more, respectively. Specific examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine modified polyurethanes, Polyethylene imine and the like, and in addition, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by Tochem Products) MEGAFAC (manufactured by Dainippon Ink & Chemicals Co., Ltd.), Florard (manufactured by Sumitomo 3M Inc.), Asahi guard, Suflon (manufactured by Asahi Glass Co., Ltd.) , SOLSPERSE (manufactured by Genka Corp.), EFKA (manufactured by EFKA Chemicals), PB 821 (manufactured by Ajinomoto Co., Ltd.), and the like.

As the adhesion promoter, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2 -(3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyl Trimethoxysilane etc. are mentioned.

Specific examples of the antioxidant include 2,2'-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butyl-4-methylphenol, and the like.

Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzothiazole, alkoxybenzophenone and the like. Specific examples of the aggregation inhibitor include sodium polyacrylate and the like.

 Specific examples of the aggregation inhibitor include sodium polyacrylate and the like.

The blue photosensitive resin composition which concerns on this invention which has said composition can be manufactured by the following method, for example.

The coloring material (D) is previously mixed with the solvent (E) and dispersed using a bead mill or the like until the average particle diameter of the coloring material (D) is about 0.2 µm or less. At this time, a pigment dispersant is used as needed, and some or all of binder resin (A) may be mix | blended. The remainder of binder resin (A), the photopolymerizable compound (B), the photoinitiator (C), the other components used as needed, and the additional solvent as needed in the obtained dispersion liquid (henceforth a mill base). Is further added to a predetermined concentration to obtain a desired blue photosensitive resin composition.

The present invention provides a color filter comprising a colored layer formed on a TFT substrate, wherein the colored layer comprises a blue colored layer formed using the blue photosensitive resin composition according to the present invention.

Hereinafter, an example of a method of manufacturing a color filter by a COA method using a colored photosensitive resin composition will be described. In the following description, the blue colored layer (or the blue pixel pattern) is formed using the blue photosensitive resin composition according to the present invention, and the other colored layer is a colored photosensitive resin composition generally known in the art. And the present invention is not limited thereto.

1A to 1H are schematic diagrams illustrating a process of forming a color filter using a color photosensitive resin composition in a color filter on array (COA) method.

First, as shown in FIG. 1A, each pixel pattern 2 of red (R), green (G), and blue (B) is directly formed on the TFT substrate 1 on which a SiNx (protective layer) film is formed using a colored photosensitive resin composition. ) Is formed on the SiNx coating film at a constant thickness.

For example, the red pixel pattern is completed by coating, exposing, developing and curing the red photosensitive resin composition on the red pixel. Next, the green pixel pattern is completed by coating, exposing, developing and curing the green photosensitive resin composition on the green pixel. At this time, since the green pixel pattern overlaps the red pixel pattern by a predetermined width, an overlap step occurs. Finally, the blue pixel pattern is completed by coating, exposing, developing and curing the blue photosensitive resin composition on the blue pixel. In this case, the blue pixel pattern overlaps the green pixel pattern and the red pixel pattern by a predetermined width, thereby causing an overlap step.

On the other hand, although not shown, the black matrix for preventing color mixing may be formed of a resin or a metal separately from the formation of the colored photosensitive resin composition.

Next, as shown in FIG. 1B, as a process for forming an electrical contact hole between the TFT element 3 and the electrode (IZO layer), the positive photosensitive resin film 5 is patterned using a mask to remove the nitride film. do.

Thereafter, as illustrated in FIG. 1C, a contact hole is formed by dry etching (dry etching) the insulating film 4 disposed on the lower surface (electrically conductive path) of the positive photosensitive resin film 5.

Then, as shown in Fig. 1D, the positive photosensitive resin film 5 remaining on each pixel pattern 2 is removed using a stripper developer.

After removal of the positive photosensitive resin film 5, as shown in FIG. 1E, an IZO layer 6 to be used as a common electrode with the TFT element 3 is deposited on the entire upper surface.

Next, as shown in FIG. 1F, a positive photosensitive resin film 7 is formed on the common electrode (IZO layer) 6 to form the common electrode (IZO layer) 6, and the positive photosensitive resin film ( Pattern 7).

When the patterning of the positive photosensitive resin film 7 is completed, as shown in FIG. 1G, the common electrode (IZO layer) 6 of the exposed portion (the portion where the Izo layer is exposed) of the positive photosensitive resin film 7 is wetted. All are removed by etching (wet etching).

Then, as shown in FIG. 1H, the remaining positive photosensitive resin film 7 on the IZO layer 6 is removed with a stripper developer to complete a COA color filter.

In the manufacturing process of the color filter described above, in the case of the blue colored layer of the colored layer is formed using the blue photosensitive resin composition according to the present invention, the colored layer of another color using a colored photosensitive resin composition generally used in the art Will be formed.

In this case, as described above, if the green pixel pattern is formed after the red pixel pattern is formed in the process of manufacturing the color filter, a step occurs at an overlapping portion thereof. Similarly, when the blue pixel pattern is formed after the green pixel pattern is formed, a step occurs at an overlapping portion thereof. However, when the blue photosensitive resin composition according to the present invention is used to form the blue pixel pattern, the overlap step may be minimized.

In particular, FIG. 2 is a photograph showing an overlap step formed by application of the coloring photosensitive resin composition, and as shown in FIG. 2, the boundary between the red pixel pattern and the blue pixel pattern overlaps each other. It can be seen that an overlap step of a certain height is formed. Of course, as described above, the larger the overlap step, the darker this part appears. However, when the blue photosensitive resin composition according to the present invention is used, the level difference of the portion overlapping with the green pixel pattern is controlled to a value smaller than 0.6 mu m, so that such a dark phenomenon does not occur in the liquid crystal display according to the present invention.

The present invention provides a liquid crystal display device having the color filter.

The liquid crystal display device includes all configurations known in the art, except that the color filter according to the present invention is provided. That is, all of the liquid crystal display devices to which the color filter of the present invention can be applied are included in the present invention. For example, the liquid crystal display device has a transmissive type liquid crystal layer in which a counter electrode substrate including a thin film transistor (TFT element), a pixel electrode, and an alignment layer faces each other at predetermined intervals, and a liquid crystal material is injected into the gap portion. And a liquid crystal display device. The liquid crystal display device can also be applied to a reflective liquid crystal display device in which a reflective layer is provided between the substrate and the colored layer of the color filter. Of course, the present invention includes a liquid crystal display including a backlight.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is by no means limited to these embodiments. The scope of the invention is indicated in the appended claims, and further includes all modifications within the meaning and range equivalent to those of the claims. In addition, "%" and "part" which show content below are mass references | standards unless there is particular notice.

Binder resin

Synthesis Example 1 Unsaturated group-containing first resin (A-1a)

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube was prepared, and as the monomer dropping lot, 47.2 g (0.2 mol) of benzylmaleimide, 25.8 g (0.3 mol) of methacrylic acid, vinyltoluene 59.0 g (0.5 mole), 4 g of t-butylperoxy-2-ethylhexanoate and 40 g of propylene glycol monomethyl ether acetate (PGMEA) were added thereto, followed by stirring and mixing, and n-dodecanethiol as a chain transfer agent dropping tank. 6g and PGMEA24g were added, and the thing mixed with stirring was prepared. Thereafter, 395 g of PGMEA was introduced into the flask, and the atmosphere in the flask was changed to nitrogen from air, and then the temperature of the flask was raised to 90 ° C. while stirring. Subsequently, dropping of the monomer and the chain transfer agent was started from the dropping lot. The dropwise addition was carried out for 2 hours while maintaining 90 ° C, and after 1 hour, the temperature was raised to 110 ° C and maintained for 5 hours, and then a gas introduction tube was introduced to provide oxygen / nitrogen = 5/95 (v / v) mixed gas. Bubbling of was started.

Subsequently, 14.2 g (0.1 mol) of glycidyl methacrylate, 0.4 g of 2,2'-methylenebis (4-methyl-6-t-butylphenol) and 0.8 g of triethylamine were added to the flask at 110 ° C. The reaction was continued for 8 hours to obtain a resin (A-1a) having a solid acid value of 85 mgKOH / g. The weight average molecular weight of polystyrene conversion measured by GPC was 13,000, and molecular weight distribution (Mw / Mn) was 2.2.

In this case, the weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured by using an HLC-8120GPC (manufactured by Tosoh Corporation) apparatus, and the column was used by serially connecting TSK-GELG4000HXL and TSK-GELG2000HXL. Tetrahydrofuran at 40 ° C, mobile phase solvent, flow rate 1.0 ml / min, injection volume 50 µl, and detector RI were used, the measurement sample concentration was 0.6 mass% (solvent = tetrahydrofuran), and the calibration standard was TSK STANDARD. POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation) was used.

Synthesis Example 2 Unsaturated Group-Containing First Resin (A-1b)

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube was prepared, and as the monomer dropping lot, 70.4 g (0.4 mole) of benzyl methacrylate, 34.4 (0.4 mole) of methacrylic acid, vinyltoluene 23.6 g (0.2 mol), 4 g of t-butylperoxy-2-ethylhexanoate and 40 g of propylene glycol monomethyl ether acetate (PEGMA) were added to the mixture, followed by stirring and mixing. As a chain transfer agent dropping tank, n-dodecane 6 g of thiols and 24 g of PGMEA were added thereto, and a mixture of stirring was prepared. Thereafter, 395 g of PGMEA was introduced into the flask, the atmosphere in the flask was changed to nitrogen from air, and the temperature of the flask was raised to 90 ° C. while stirring. Subsequently, dropping of the monomer and the chain transfer agent was started from the dropping lot. The dropwise addition was performed for 2 hours while maintaining 90 ° C, and after 1 hour, the temperature was raised to 110 ° C and maintained for 3 hours. Bubbling of was started.

Subsequently, 14.2 g (0.1 mol) of glycidyl methacrylate, 0.4 g of 2,2'-methylenebis (4-methyl-6-t-butylphenol) and 0.8 g of triethylamine were added to the flask at 110 ° C. The reaction was continued for 8 hours to obtain a resin (A-1b) having a solid acid value of 99 mgKOH / g. The weight average molecular weight of polystyrene conversion measured by GPC was 14,000, and molecular weight distribution (Mw / Mn) was 2.6. At this time, the weight average molecular weight and molecular weight distribution were measured by the same method as in Synthesis Example 1.

Synthesis Example 3 Unsaturated Group-Containing First Resin (A-1c)

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube was prepared, and as a monomer dropping lot, 47.2 g (0.40 mol) of vinyltoluene, 37.4 g (0.2 mol) of benzylmaleimide, and 28.8 g of acrylic acid were prepared. (0.4 mol), 4 g of t-butylperoxy-2-ethylhexanoate and 40 g of propylene glycol monomethyl ether acetate (PGMEA) were added thereto, followed by stirring and mixing. As a chain transfer agent dropping tank, 6 g of n-dodecanethiol was added. PGMEA 24g was added and the thing mixed with stirring was prepared. Thereafter, 395 g of PGMEA was introduced into the flask, and the atmosphere in the flask was changed to nitrogen from air, and then the temperature of the flask was raised to 90 ° C. while stirring. Subsequently, dropping of the monomer and the chain transfer agent was started from the dropping lot. The dropwise addition was carried out for 2 hours while maintaining 90 ° C, and after 1 hour, the temperature was raised to 110 ° C and maintained for 3 hours, and then a gas introduction tube was introduced to provide oxygen / nitrogen = 5/95 (v / v) mixed gas. Bubbling of was started. Subsequently, 14.2 g (0.1 mol) of glycidyl methacrylate, 0.4 g of 2,2'-methylenebis (4-methyl-6-t-butylphenol) and 0.8 g of triethylamine were added to the flask at 110 ° C. The reaction was continued for 8 hours to obtain Resin A-4 having a solid acid value of 71 mgKOH / g. The weight average molecular weight of polystyrene conversion measured by GPC was 22,000, and molecular weight distribution (Mw / Mn) was 2.3. At this time, the weight average molecular weight and molecular weight distribution were measured by the same method as in Synthesis Example 1.

Synthesis Example 4 Unsaturated Group-Containing Second Resin (A-2a)

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube was prepared, and as the monomer dropping lot, 37.4 g (0.2 mol) of benzyl maleimide, 21.6 g (0.3 mol) of acrylic acid, and benzyl methacrylate were prepared. 88 g (0.5 mole), 4 g of t-butylperoxy-2-ethylhexanoate and 40 g of propylene glycol monomethyl ether acetate were added thereto, followed by stirring and mixing. As a chain transfer agent dropping tank, 6 g of n-dodecanethiol and PGMEA were added. 24g was prepared and the thing which stirred and mixed was prepared. Thereafter, 395 g of PGMEA was introduced into the flask, and the atmosphere in the flask was changed to nitrogen from air, and then the temperature of the flask was raised to 90 ° C. while stirring. Subsequently, dropping of the monomer and the chain transfer agent was started from the dropping lot. The dropwise addition was carried out for 2 hours while maintaining 90 ° C, and after 1 hour, the temperature was raised to 110 ° C and maintained for 3 hours, and then a gas introduction tube was introduced to mix oxygen / nitrogen = 5/95 (v / v). The bubbling of the gas was started.

Subsequently, 14.2 g (0.1 mol) of glycidyl methacrylate, 0.4 g of 2,2'-methylenebis (4-methyl-6-t-butylphenol) and 0.8 g of triethylamine were added to the flask at 110 ° C. The reaction was continued for 8 hours to obtain Resin A-3 having a solid acid value of 73 mgKOH / g. The weight average molecular weight of polystyrene conversion measured by GPC was 17,300, and molecular weight distribution (Mw / Mn) was 2.3. At this time, the weight average molecular weight and molecular weight distribution were measured by the same method as in Synthesis Example 1.

Examples 1-5, Comparative Examples 1 and 2

Among the components shown in Table 1 below, a portion of the solvent (E) is previously mixed with a coloring material (D) and other additives (F), sufficiently dispersed using a bead mill, and the bead mill is separated, and the solvent (E) The remaining amount and the remaining components were further added and mixed to obtain a blue photosensitive resin composition.

Example (mass part) Comparative example (mass part) One 2 3 4 5 One 2 Binder Resin (A) A-1a 5.00 0 0 0 7.00 5.00 0 A-1b 0 5.00 0 4.00 0 0 0 A-1c 0 0 5.00 0 0 0 0 A-2a 2.50 2.50 2.50 3.50 0.50 0 7.50 Photopolymerizable Compound (B) 8.47 8.47 8.47 8.47 8.47 8.47 8.47 Photoinitiator (C) (C-1) 1.42 1.42 1.42 1.42 1.42 1.42 1.42 (C-2) 0.85 0.85 0.85 0.85 0.85 0.85 0.85 Coloring material
(D) (D-1) 2.39 2.39 2.39 2.39 2.39 2.39 2.39 (D-2) 0.60 0.60 0.60 0.60 0.60 0.60 0.60 Solvent (E) 77.02 77.02 77.02 77.02 77.02 77.02 77.02 Additive (F) (F-1) 1.65 1.65 1.65 1.65 1.65 1.65 1.65 (F-2) 0.10 0.10 0.10 0.10 0.10 0.10 0.10

Each component used in Table 1 is as follows.

Binder Resin (A-1a), (A-1b), (A-1c) and (A-2a): See Synthesis Examples 1-4

Photopolymerizable compound (B): dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)

Photoinitiator (C-1): 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (Irgacure 369; manufactured by Ciba Specialty Chemical)

Photoinitiator (C-2): 4,4'-bis (diethylamino) benzophenone (EAB-F; manufactured by Hodogaya Kagaku Co., Ltd.)

Coloring material (D-1): C.I. Pigment Blue 15: 6

Coloring material (D-2): C.I. Pigment Violet 23

Solvent (E): propylene glycol monomethyl ether acetate

Additive (F-1): Pigment Dispersant (Acrylic)

Additive (F-2): 3-methacryloxypropyl trimethoxysilane

Experimental Example

The developing process was omitted by exposing the blue photosensitive resin composition prepared in the above Examples and Comparative Examples to an exposure amount (365 nm) of 75 mJ / cm 2 on a 2M square inch BM (Black Matrix) glass substrate (manufactured by Corning, E2K). It was spin-coated so that the film thickness after baking at time might be set to 3.3 micrometers, and then preliminarily dried at 100 degreeC in the clean oven for 3 minutes. After cooling, the distance between the substrate coated with the blue photosensitive resin composition and the quartz glass photomask (having a pattern of changing the transmittance stepwise in the range of 1 to 100% and a line / space pattern from 1 μm to 50 μm) was 100. It was set as a micrometer, and it irradiated with the exposure amount (365 nm) of 75 mJ / cm <2> in air | atmosphere using the ultrahigh pressure mercury lamp (brand name USH-250D) by Ushio Denki Corporation. Thereafter, the coating film was immersed in a water-based developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 26 ° C. for a predetermined time, and then dried at 230 ° C. for 30 minutes after washing with water. Overlap step and pattern flatness were measured and the results are shown in Table 2 below.

For reference, in the COA color filter, the overlap step and the pattern flatness substantially occur between the R, G, and B pixel patterns, but here, the overlap step was indirectly formed on the BM glass substrate for the convenience of the experiment.

(1) Overlap step evaluation

Specimens formed with a blue colored layer on a 2 inch square inch BM (Black Matrix) glass substrate in the same manner as shown in Figure 3, wherein the specimens were each stepped using a Veeco Dektek 6M Stylus Profiler After the measurement, the overlap step was calculated by Equation 1. In FIG. 3, reference numeral 13 denotes a glass substrate, 12 denotes a BM, and 11 denotes a blue colored layer.

&Quot; (1) &quot;

Ra * (μm) = a (height from glass substrate to colored layer on BM layer) -b (height of BM)

It evaluated as follows using the overlap step value Ra * (micrometer) obtained in this way.

○: Ra * (μm) less than 0.6um, X: Ra * (μm) 0.6um or more

(2) pattern flatness evaluation

The blue colored layer formed on the 2 inch square inch BM (Black Matrix) glass substrate in the same manner as shown in Figure 3, wherein the specimen using the Veeco Dektek 6M Stylus Profiler pattern flatness Measured. As shown in FIG. 4, the measurement results may be classified into A and B types according to the shape thereof. When the measurement result is A Type (the upper and lower profile of the profile is flat): Good flatness (○) and B Type (upper And the profile of the lower film is not flat): evaluated as a flatness (X).

Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Overlap step ○ ○ ○ ○ ○ ○ X Pattern flatness ○ ○ ○ ○ ○ X ○

As can be seen in Table 2, the blue photosensitive resin composition of the embodiment, in which the binder includes the unsaturated group-containing first resin (A-1) and the unsaturated group-containing second resin (A-2) according to the present invention, has an overlap step. And it can be seen that the pattern flatness is excellent, so that it is possible to obtain a color filter of excellent quality without the aperture ratio, visibility, and poor display.

1A to 1H are schematic views illustrating a process of forming a color filter using a color photosensitive resin composition in a color filter on array (COA) method.

2 is a photograph for showing an overlap step formed by application of the colored photosensitive resin composition.

FIG. 3 is a view schematically illustrating a test piece coated with a blue photosensitive resin composition on a BM organic substrate.

<Description of Major Symbols in Drawing>

One; TFT substrate 2; Pixel pattern

3; TFT element 4; Nitride Film (SiNx)

5; Positive photosensitive resin film 6; IZO layer

7; Positive photosensitive resin film 11; Pixel Pattern (Color Layer)

12; Black matrix (BM) 13; Glass substrate

Claims (7)

In the blue photosensitive resin composition which consists of binder resin (A), a photopolymerizable compound (B), a photoinitiator (C), a coloring material (D), and a solvent (E), The binder resin (A) is an unsaturated group-containing first resin (A-1) obtained by further reacting the following (A-13) with a copolymer obtained by copolymerizing the following (A-11) and (A-12) compounds. And an unsaturated group-containing second resin (A-2) obtained by further reacting the following (A-23) with a copolymer obtained by copolymerizing the following (A-21) and (A-22). Blue photosensitive resin composition; (A-11): aromatic vinyl compound, (A-12): methacrylic acid, (A-13): Compound which has an unsaturated bond and an epoxy group in 1 molecule, (A-21): unsaturated carboxylic ester compound, (A-22): unsaturated carboxylic acid compound (A-23): Compound which has an unsaturated bond and an epoxy group in 1 molecule. The blue photosensitive resin composition according to claim 1, wherein the unsaturated group-containing second resin (A-2) is contained in an amount of 5 to 50 mass% based on the binder resin (A) in the blue photosensitive resin composition based on solid content. The unsaturated carboxylic acid ester compound (A-21) of the said unsaturated group containing 2nd resin (A-2) is a benzyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth). ) Acrylic, dicyclopentadiethyl (meth) acrylate and adamantyl (meth) acrylate at least one selected from the group consisting of blue photosensitive resin composition. The method according to claim 1, wherein the coloring material (D) is C.I. Pigment blue 15 (at least one selected from the group consisting of 15: 3, 15: 4 and 15: 6). The copolymer of Claim 1 in which the ratio of the structural unit derived from said (A-11) in the said unsaturated group containing 1st resin (A-1) is copolymerized with said (A-21) and (A-22). It is 20-60 mol% with respect to the total number of moles of a structural unit, The blue photosensitive resin composition characterized by the above-mentioned. A color filter comprising a colored layer formed on a TFT substrate, wherein the colored layer comprises a blue colored layer formed by using the blue photosensitive resin composition of any one of claims 1 to 5. A liquid crystal display device comprising the color filter according to claim 6.

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