KR20100009996A - A red color photosensitive resin composition, color filter and liquid crystal display device having the same - Google Patents

Abstract

PURPOSE: A red color photosensitive resin composition is provided to be used for forming a color filter on a TFT substrate, and to obtain a color filter with excellent thermal stability, chemical stability and brightness when forming an electrical contact hole of a pixel electrode and TFT. CONSTITUTION: A red color photosensitive resin composition comprises a binder resin(A), a coloring material(B), a photopolymerizable compound(C), a photopolymerization initiator(D) and solvent (E). The binder resin(A) is a copolymer containing a compound containing a compound represented by chemical formula 1. The coloring material(B) comprises C.I. pigment red 242. In chemical formula 1, R1 and R2 are independently aliphatic, aromatic hydrocarbon that contains or does not contain C1-12 hetero atom.

Description

Red photosensitive resin composition, color filter and liquid crystal display device having the same {A RED COLOR PHOTOSENSITIVE RESIN COMPOSITION, COLOR FILTER AND LIQUID CRYSTAL DISPLAY DEVICE HAVING THE SAME}

The present invention provides a red photosensitive resin composition, a color filter, and the like, which are used to form a colored layer including a pixel and / or a black matrix of a color liquid crystal display on a driving substrate of a thin film transistor (TFT) type color liquid crystal display. It relates to a liquid crystal display device provided.

In a color liquid crystal display device using a thin film transistor (TFT) substrate, a color filter substrate for displaying a color image is conventionally manufactured separately from a driving substrate on which a thin film transistor (TFT) is disposed, and the color filter substrate is described above. It was manufactured by bonding to a driving substrate. However, in this system, since the positional accuracy at the time of joining is low, the width | variety of a black matrix must be enlarged and it is difficult to raise an aperture ratio (namely, the ratio of the opening which permeate | transmits light).

On the other hand, with respect to the above method, a colored layer is formed directly on the surface of the driving substrate on which the thin film transistor (TFT) is arranged or on a protective film such as a silicon nitride film, and the substrate on which the colored layer is formed is sputtered by ITO (Indium). A method of bonding to a substrate on which a tin oxide electrode or an indium zinc oxide (IZO) is formed has been developed. In this method, since a colored layer including a pixel or a black matrix is formed directly on the driving substrate, the bonding process between the color filter substrate and the driving substrate is unnecessary, and the aperture ratio can be greatly improved as compared with the former method. It is possible to obtain a bright and high precision display device.

In addition, in the colored layer formed by such a method, contact holes are formed by dry etching in order to conduct the common electrode disposed on the colored layer and the driving substrate terminal under the colored layer. This is required, and a conductive path such as a rectangular through hole or U-shaped concave of about 1 to 30 µm in length, preferably 5 to 20 µm or less is formed. At this time, in the red photosensitive resin composition used to form a colored layer on a driving substrate of a thin film transistor (TFT) type color liquid crystal display device, thermal and chemical stability of the pixel coating film is poor, so that the pixel coating film is peeled off or the inside of the pixel coating film is poor. Erosion phenomenon occurs or there is a problem that the brightness is lowered.

An object of the present invention, when forming a pixel (colored layer) with a red photosensitive resin composition, a red photosensitive resin composition, a color filter formed on a TFT substrate having excellent thermal stability and chemical stability, and a liquid crystal having the same It is to provide a display device.

The present invention for achieving the above object is a red photosensitive resin composition for a color filter layer formed on a TFT substrate, a binder resin (A), a coloring material (B), a photopolymerizable compound (C), a photopolymerization initiator (D) And a solvent (E), The said binder resin (A) is a copolymer obtained by the copolymerization reaction containing the following A1, The said coloring material (B) is CI It provides a red photosensitive resin composition comprising Pigment Red 242.

A1: a compound represented by the following formula (1),

<Formula 1>

Wherein n is 0 or 1, R 1 and R 2 are each independently hydrogen or an aliphatic or aromatic hydrocarbon containing or without a hetero atom having 1 to 12 carbon atoms, and R 3, R 4, R 5, and R 6 are Are each independently hydrogen, an aliphatic or aromatic hydrocarbon containing or without a hetero atom having 1 to 30 carbon atoms, and two of R 3, R 4, R 5, and R 6 are selected to be linked or unbranched.)

In addition, the compound represented by Formula 1 provides a red photosensitive resin composition, characterized in that at least one selected from the compounds represented by the following formula.

Further, the binder resin (A) is a copolymer obtained by copolymerization reaction including A1 and A2 and A3 below, or an unsaturated group-containing resin obtained by further reacting A4 below. to provide.

A2: a compound having an unsaturated bond copolymerizable with A1 and A3,

A3: unsaturated carboxylic acid,

A4: The compound which has an unsaturated bond and an epoxy group in 1 molecule.

The ratio of the constituents derived from each of A1 to A3 is based on the total moles of the copolymer constituents,

Structural units derived from A 1: 2 to 30 mole%,

Structural units derived from A 2: 2 to 95 mole%,

Structural units derived from A 3: 2 to 70 mole%,

It provides a red photosensitive resin composition characterized by reacting A4 with 5 to 80 mol% with respect to the component derived from A3 at the time of reacting A4 further.

The binder resin (A) may be a copolymer obtained by copolymerizing A1 with A2 and A4, or an unsaturated group-containing resin obtained by further reacting A5 below with the following A3. It provides a red photosensitive resin composition characterized by the above-mentioned.

A2: a compound having an unsaturated bond copolymerizable with A1 and A4,

A3: unsaturated carboxylic acid,

A4: the compound which has an unsaturated bond and an epoxy group in 1 molecule,

A5: polybasic acid anhydride.

The present invention further provides a color filter comprising a color layer formed by exposing and developing a red photosensitive resin composition in a predetermined pattern, wherein the red photosensitive resin composition is the color photosensitive resin composition described above. To provide.

The present invention also provides a liquid crystal display device having the above-described color filter.

The red photosensitive resin composition according to the present invention is used to form a color filter on a TFT substrate, thereby providing excellent thermal stability and chemical stability when forming a contact hole between a pixel electrode and an active element (TFT), A color filter having good luminance can be provided. Accordingly, it is possible to provide a high-quality liquid crystal display device while maintaining the high opening ratio characteristic, which is an advantage of the color filter on array (COA) type liquid crystal display device.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings such that those skilled in the art may easily implement the present invention.

The red photosensitive resin composition of embodiment which concerns on this invention is a red photosensitive resin composition for color filter layers formed on a TFT substrate, and is binder resin (A), a coloring material (B), a photopolymerizable compound (C), and a photoinitiator ( D) and a solvent (E), The said binder resin (A) is a copolymer obtained by the copolymerization reaction containing the following A1, The said coloring material (B) is CI Pigment red 242. Moreover, it is preferable that the other additive (F) is melt | dissolved or disperse | distributed in the solvent (E) arbitrarily.

(A1): a compound represented by the following formula (1),

<Formula 1>

Wherein n is 0 or 1, R 1 and R 2 are each independently hydrogen or an aliphatic or aromatic hydrocarbon containing or without a hetero atom having 1 to 12 carbon atoms, and R 3, R 4, R 5, and R 6 are Are each independently hydrogen, an aliphatic or aromatic hydrocarbon containing or without a hetero atom having 1 to 30 carbon atoms, and two of R 3, R 4, R 5, and R 6 are selected to be linked or unbranched.)

Binder Resin (A)

The binder resin (A) usually has reactivity and alkali solubility due to the action of light or heat, and acts as a dispersion medium of the coloring material.

The binder resin (A) contained in the red photosensitive resin composition of this invention is an unsaturated group containing resin containing the structural unit which can be obtained by superposition | polymerization (this is also a concept including copolymerization) of the said Formula (1). That is, the compound of Formula 1 is polymerized alone or together with other compounds to form the binder resin.

Preferably, the binder resin of the embodiment according to the present invention comprises a compound (A2) having an unsaturated bond copolymerizable with compound (A1), A1 and A3 of Formula 1, and an unsaturated carboxylic acid compound (A3). It is preferable that it is a copolymer obtained by a copolymerization reaction, and also it is preferable that it is unsaturated group containing resin obtained by making the said obtained copolymer react with the compound (A4) which has an unsaturated bond and an epoxy group in 1 molecule further.

In addition, the binder resin (A) of another embodiment according to the present invention copolymerizes the compound of formula (A1), the compound (A2) having an unsaturated bond and the compound (A4) having an unsaturated bond and an epoxy group in one molecule After reacting the obtained copolymer or unsaturated carboxylic acid compound (A3), the red photosensitive resin which is unsaturated group containing resin obtained by making a polybasic acid anhydride (A5) further react is also included in this invention.

In one embodiment of the present invention, as an example of the compound (A1) of the general formula (1), a more specific structural formula is as follows, at least any one of these may be selected and included.

The present invention is not limited to the structure of the above formula, and all derivatives or all derivatives of the compound of Formula 1 including the norbornene skeleton are included in the present invention. These can be used individually or in combination of 2 types or more, respectively. Preferably, 2-norbornene has few residual monomers and is excellent in heat resistance.

In addition, the (meth) acrylate recorded in this specification means an acrylate and / or a methacrylate.

In embodiment of this invention, if the compound (A2) which has said unsaturated bond is a compound which has a unsaturated double bond which can superpose | polymerize, it will not restrict | limit, As a specific example, methyl (meth) acrylate and ethyl (meth) acryl Unsubstituted or substituted alkyl ester compounds of unsaturated carboxylic acids such as acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, aminoethyl (meth) acrylate, cyclopentyl (meth) acrylate, Cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl (meth) acrylate, menthyl (meth) acrylate, cyclopentenyl (meth) acrylate, cyclo Hexenyl (meth) acrylate, cycloheptenyl (meth) acrylate, cyclooctenyl (meth) acrylate, mentadienyl (meth) acrylate, isobo Unsaturated car including alicyclic substituents such as renyl (meth) acrylate, pinanyl (meth) acrylate, adamantyl (meth) acrylate, norbornyl (meth) acrylate, and pineneyl (meth) acrylate Substituents having aromatic rings, such as monosaturated carboxylic acid ester compounds of glycols, such as an acid ester compound and oligoethylene glycol monoalkyl (meth) acrylate, benzyl (meth) acrylate, and phenoxy (meth) acrylate, Carboxylic acid vinyl esters, such as unsaturated carboxylic acid ester compound, styrene, aromatic vinyl compounds, such as (alpha) -methylstyrene and vinyltoluene, vinyl acetate, and a vinyl propionate, (meth) acrylonitrile, and (alpha)-chloro acrylonitrile Maleimide compounds, such as vinyl cyanide compounds, N-cyclohexyl maleimide, and N-phenyl maleimide, etc. are mentioned. These can be used individually or in combination of 2 types or more, respectively.

In embodiment of this invention, as said unsaturated carboxylic acid (A3), if it is a carboxylic acid compound which has a unsaturated double bond which can superpose | polymerize, it will not restrict | limit, Acrylic acid, methacrylic acid, etc. are mentioned as a specific example. Acrylic acid and methacrylic acid can be used individually or in combination of 2 types or more, respectively. In addition to these acrylic acid and methacrylic acid, one or more other acids may be used. As another acid, it is also possible to specifically use together the carboxylic acid chosen from 1 type or more of other unsaturated carboxylic acids, such as crotonic acid, itaconic acid, maleic acid, and fumaric acid. Moreover, you may use together the monomer containing a hydroxyl group and a carboxyl group in the same molecule, such as (alpha)-(hydroxymethyl) acrylic acid.

In one embodiment of the present invention, in the copolymer obtained by copolymerizing (A1) to (A3) used in the present invention (even when monomers other than A1 to A3 are further included and copolymerized, they are included in the present invention). And the ratio of the constituents derived from each of (A1) to (A3) are preferably in the following ranges in mole fraction with respect to the total moles of the constituents constituting the copolymer.

Structural unit derived from (A1): 2 to 30 mol%,

Structural unit derived from (A2): 2 to 95 mol%,

Structural units derived from (A3): 2 to 70 mol%

That is, the copolymer obtained by the copolymerization reaction containing the compound (A1) of the general formula (1), the compound having an unsaturated bond (A2) and the unsaturated carboxylic acid compound (A3) is a compound of the general formula (1) Monomers, monomers having unsaturated bonds and unsaturated carboxylic acid monomers are not limited but are preferably included in the range of 2 to 30 mol%, 2 to 95 mol%, and 2 to 70 mol%, respectively.

In particular, it is more preferable that the ratio of said structural component is the following ranges.

Structural unit derived from (A1): 3 to 30 mol%,

Structural unit derived from (A2): 10 to 70 mol%,

Structural units derived from (A3): 5-65 mol%

If said composition ratio is in the said range, since the balance of developability, solubility, and heat resistance is favorable, a preferable copolymer can be obtained.

In embodiment of this invention, when obtaining by copolymerizing (A1)-(A3) as an example of the manufacturing method of the said copolymer, it can manufacture by copolymerizing by the following methods.

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 amount of the solvent (E) was introduced together on a mass basis with respect to the total amount of (A1) and (A1) to (A3). The atmosphere in the flask is replaced with nitrogen in air. Then, after heating up the solvent (E) at 40-140 degreeC, 0-20 times the solvent (E) by mass basis with respect to the predetermined amount of (A2)-(A3) and the total amount of (A2)-(A3). ) And a solution obtained by adding 0.1 to 10 mol% of a polymerization initiator such as azobisisobutyronitrile or terbutyryl peroxy 2-ethylhexyl carbonate to the total number of moles of (A1), (A2) to (A3) ( Stirring at room temperature or under heating) is added dropwise to the flask over 0.1 to 8 hours from the dropping lot, and further stirred at 40 to 140 ° C for 1 to 10 hours.

In addition, a part or whole quantity of a polymerization initiator may be put in a flask at the said process, and a part or whole quantity of (A1), (A2)-(A3) may be put in a flask. Moreover, in order to control molecular weight and molecular weight distribution, (alpha) -methylstyrene dimer and a mercapto compound can also be used as a chain transfer agent. The usage-amount of (alpha) -methylstyrene dimer and a mercapto compound is 0.005 to 5% on a mass basis with respect to the total amount of (A1) and (A2)-(A3). 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 ..

The binder resin (A) contained in the red photosensitive resin composition of one embodiment of the present invention further reacts a compound (A4) having an unsaturated bond and an epoxy group in one molecule to a copolymer obtained by copolymerizing (A1) to (A3). Can be obtained. By adding (A4) to the copolymer, light / thermosetting property can be imparted to the binder resin.

In one Embodiment of this invention, as a specific example of the compound (A4) which has an unsaturated bond and an epoxy group in 1 molecule, glycidyl (meth) acrylate, 3, 4- epoxycyclohexyl (meth) acrylate, 3, 4-epoxycyclohexylmethyl (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.

The compound having the unsaturated bond and the epoxy group is preferably reacted with 5 to 80 mol%, particularly preferably 10 to 80 mol%, based on the number of moles of unsaturated carboxylic acid compound (A3) contained in the copolymer. If the composition ratio of (A4) is in the said range, since sufficient photocurability and thermosetting are obtained, a sensitivity and pencil hardness are compatible, and since it is excellent in reliability, it is preferable.

In embodiment of this invention, binder resin (A) can be manufactured by making said copolymer and (A4) react by the following methods, for example.

5 to 80 mole% of (A4) and carboxyl groups in molar fraction with respect to the structural unit derived from (A3) of the copolymer obtained by substituting the atmosphere in a flask with nitrogen for air, and copolymerizing said (A1)-(A3). As the reaction catalyst of the epoxy group, for example, trisdimethylaminomethylphenol is 0.01 to 5% by mass relative to the total amount of (A1) to (A4) and as a polymerization inhibitor, for example, hydroquinone (A1) to (A4). The copolymer and (A4) can be reacted by adding 0.001 to 5% in a flask on a mass basis with respect to the total amount of) and reacting at 60 to 130 ° C for 1 to 10 hours. In addition, similarly to the polymerization conditions, the charging method and the reaction temperature may be appropriately adjusted in consideration of the amount of heat generated by the production equipment, the polymerization and the like.

In one embodiment of the present invention, the binder resin (A) preferably has a weight average molecular weight in terms of polystyrene thereof in the range of 3,000 to 100,000, and more preferably in the range of 5,000 to 50,000. When the weight average molecular weight of binder resin (A) exists in the range of 3,000-100,000, film | membrane decrease hardly arises at the time of image development, and since the missing property of a non-pixel part at the time of image development tends to be favorable, it is preferable.

The acid value of the binder resin (A) is preferably in the range of 30 to 150 mgKOH / g based on solid content. If the acid value is less than 30 mgKOH / g, there is a possibility that the developability to the alkaline water is lowered, leaving a residue on the substrate, and if the acid value exceeds 150 mgKOH / g, the possibility of desorption of the pattern is increased.

It is preferable that it is 1.5-6.0, 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 1.8-4.0. Molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] is preferable because it is excellent in developability when it is 1.5-6.0.

In another embodiment of the present invention, the compound (A1) of the formula (1) may be the same as that described in one embodiment of the present invention.

In another embodiment of this invention, the compound (A2) which has said unsaturated bond can use the same thing as what was described in one Embodiment of this invention.

In another embodiment of this invention, the compound (A4) which has an unsaturated bond and an epoxy group in the said 1 molecule can use the thing similar to what was described in one Embodiment of this invention.

In another embodiment of the present invention, monomers other than the copolymers ((A1), (A2) and (A4) obtained by copolymerizing (A1), (A2) and (A4) used in the present invention are further included. In the case of copolymerization, the proportion of the constituents derived from each of (A1), (A2) and (A4) is in the molar fraction with respect to the total moles of the copolymer constituents in the following ranges. It is desirable to have.

Structural unit derived from (A1): 2 to 30 mol%,

Structural unit derived from (A2): 2 to 95 mol%,

Structural unit derived from (A4): 2 to 85 mol%,

That is, the copolymer obtained by the copolymerization reaction containing the compound (A1) of the said General formula (1), the compound (A2) which has an unsaturated bond, and the compound (A4) which has an unsaturated bond and an epoxy group in 1 molecule, with respect to the total number of moles of a component In addition, the monomer of Formula 1, a monomer having an unsaturated bond and a monomer having an unsaturated bond and an epoxy group in one molecule are not limited, but are included in the range of 2 to 30 mol%, 2 to 95 mol%, 2 to 85 mol%, respectively. desirable.

In particular, it is more preferable that the ratio of said structural component is the following ranges.

Structural unit derived from (A1): 5-30 mol%,

Structural unit derived from (A2): 5 to 80 mol%,

Structural units derived from (A4): 5-75 mol%

If said composition ratio is in the said range, since the balance of developability, solubility, and heat resistance is favorable, a preferable copolymer can be obtained.

In another embodiment of the present invention, as an example of the method for producing the copolymer, the copolymer can be produced by copolymerizing in the following manner when it is obtained by copolymerizing (A1), (A2) and (A4).

0.5-20 times of solvent (E) by mass relative to the total amount of (A1) and (A1), (A2) to (A4) in a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping lot and a nitrogen introduction tube. Are introduced together and the atmosphere in the flask is replaced with nitrogen in air. Then, after heating up the solvent (E) at 40-140 degreeC, 0-20 times the solvent (E) by mass basis with respect to the predetermined amount of (A2)-(A4) and the total amount of (A2)-(A4). ) And a solution obtained by adding 0.1 to 10 mol% of a polymerization initiator such as azobisisobutyronitrile or terbutyryl peroxy 2-ethylhexyl carbonate to the total number of moles of (A1), (A2) to (A4) ( Stirring at room temperature or under heating) is added dropwise to the flask over 0.1 to 8 hours from the dropping lot, and further stirred at 40 to 140 ° C for 1 to 10 hours.

In addition, a part or whole quantity of a polymerization initiator may be put in a flask at the said process, and a part or whole quantity of (A1), (A2), and (A4) may be put in a flask. Moreover, in order to control molecular weight and molecular weight distribution, (alpha) -methylstyrene dimer and a mercapto compound can also be used as a chain transfer agent. The usage-amount of (alpha) -methylstyrene dimer and a mercapto compound is 0.005 to 5% by mass with respect to the total amount of (A1), (A2), and (A4). 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 ..

The binder resin (A) contained in the red photosensitive resin composition of another embodiment of the present invention reacts the unsaturated carboxylic acid compound (A3) with a copolymer obtained by copolymerizing (A1), (A2) and (A4). And a copolymer (A-1) containing an unsaturated group or hydroxyl group of a side chain produced by the reaction [a hydroxyl group produced by reaction of a carboxyl group and an epoxy group or a hydroxyl group contained in the component (A1) from the beginning]] You can get it.

In another embodiment of this invention, the said unsaturated carboxylic acid compound (A3) can use the thing similar to what was described in one Embodiment of this invention.

The unsaturated carboxylic acid compound (A3) preferably reacts (A3) with 10 to 100 mol% of the number of moles of the compound (A4) having an unsaturated bond and an epoxy group in one molecule contained in the copolymer, particularly 15 to 100 It is preferable that mol% is preferable, and 30-100 mol% is especially preferable.

In another embodiment of this invention, a copolymer (A-1) can be manufactured by making it react by the following methods, for example.

10 to 100 mole percent (A3) in molar fraction of the structural unit derived from (A4) of the copolymer obtained by substituting the atmosphere in the flask with nitrogen for air and copolymerizing the above (A1), (A2) and (A4). As the reaction catalyst of the carboxyl group and the epoxy group, for example, trisdimethylaminomethylphenol is 0.01 to 5% by mass based on the total amount of (A1) to (A4) and as a polymerization inhibitor, for example hydroquinone (A1 To 0.001 to 5% by mass in a flask and reacted at 60 to 150 ° C for 1 to 10 hours, more preferably at 80 to 130 ° C for 1 to 10 hours, to the total amount of (A4). A-1) can be obtained. In addition, similarly to the polymerization conditions, the charging method and the reaction temperature may be appropriately adjusted in consideration of the amount of heat generated by the production equipment, the polymerization and the like. The binder resin (A) of this invention can be obtained by making the hydroxyl group of (A-1) obtained above react with the polybasic acid anhydride compound which is (A5) component.

The polybasic acid anhydride compound (A5) is not particularly limited, and specific examples thereof include coharic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and hexahydro. Phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, etc. are mentioned. Tetrahydrophthalic anhydride and coharic anhydride are preferable above, and these 1 type, or 2 or more types may be used together.

The polybasic acid anhydride compound (A5) is preferably reacted 5 to 100 mol% with respect to the number of moles of unsaturated carboxylic acid compound (A3) contained in the copolymer, particularly preferably 20 to 80 mol%.

In another embodiment of this invention, binder resin (A) can be manufactured by making said copolymer and (A5) react by the following methods, for example.

After making the unsaturated carboxylic acid compound (A3) react with the reactor of (A4) contained in the copolymer (A-1) obtained by the above, ie, a side chain, it can obtain by adding an appropriate amount (A5) component as it is. The total reaction temperature is 50 to 150 ° C., preferably, heated to 80 to 130 ° C. for reaction. There is no need to add a catalyst in particular.

In another embodiment of the present invention, the binder resin (A) preferably has a weight average molecular weight in terms of polystyrene thereof in the range of 3,000 to 100,000, and more preferably in the range of 5,000 to 50,000. When the weight average molecular weight of binder resin (A) exists in the range of 3,000-100,000, film | membrane decrease hardly arises at the time of image development, and since the missing property of a non-pixel part at the time of image development tends to be favorable, it is preferable.

The acid value of the binder resin (A) is preferably in the range of 30 to 150 mgKOH / g based on solid content. If the acid value is less than 30 mgKOH / g, there is a possibility that the developability to the alkaline water is lowered, leaving a residue on the substrate, and if the acid value exceeds 150 mgKOH / g, the possibility of desorption of the pattern is increased.

It is preferable that it is 1.5-6.0, and, as for the molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of binder resin (A), it is more preferable that it is 1.8-4.0. The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] is preferably 1.5 to 6.0 because it is excellent in developability.

Content of the said binder resin (A) is a mass fraction with respect to solid content in a red photosensitive resin composition, and is 5-85 mass% normally, Preferably it is the range of 10-70 mass%. If the content of the binder resin (A) is 5 to 85% by mass based on the above criteria, the solubility in the developing solution is sufficient, and development residues are less likely to occur on the substrate of the non-pixel portion. Since it is hard to produce and the missing property of a non-pixel part tends to be favorable, it is preferable.

Coloring material (B)

Pigments used for red pixels in the coloring material (B) are C.I. Pigment red 242, and optionally C.I. Pigment Red 242 may include other pigments. Hereinafter, the expression "other pigments" is referred to as C.I. Pigment Red 242 indicates a different pigment.

In addition, in order to manufacture a color filter composed of each pixel pattern of red (R), green (G), and blue (B), as a usable pigment, specifically, in the color index (Published by The society of Dyers and Colourists) The compound classified by the pigment is mentioned, More specifically, Although the pigment of the following color index (CI) numbers is mentioned, It is not necessarily limited to these.

C.I. Pigment Yellow 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, 215, 216, 224, 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 and 58,

Pigment Brown 28,

C.I pigment black 1 and 7, etc.

The said coloring material (B) can be used individually or in combination of 2 or more types, respectively. The coloring material (B) is 3 to 60 mass%, preferably 5 to 55 mass% in terms of mass fraction with respect to the solid content in the red photosensitive resin composition. If the thickness is in the range of 3 to 60 mass%, the color density of the pixel is sufficient even when a thin film is formed, and since the omission property of the non-pixel portion during development does not decrease, it is preferable because residue tends not to occur.

In addition, the pigment C.I. The content of Pigment Red 242 is 30 mass% or more, preferably 50 mass% or more, based on the total amount of the pigment. Color distribution and luminance are good in the above range.

Photopolymerization  Compound (C)

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

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

Specific examples of the bifunctional monomer 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, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, and pentaerythritol Tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaeryte Lithol hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are mentioned.

Of these, bifunctional or higher polyfunctional monomers are preferably used. Especially preferably, it is a polyfunctional monomer more than 5-functional.

The photopolymerizable compound (C) is used in the range of 5 to 50% by mass, preferably 7 to 45% by mass, with respect to the solids content in the red photosensitive resin composition. If the photopolymerizable compound (C) is in the range of 5 to 50% by mass on the basis of the above standard, the strength and smoothness of the pixel portion tend to be good, so it is preferable.

Photopolymerization Initiator (D)

Although the photoinitiator (D) contained in the red photosensitive resin composition of this invention is not restrict | limited, It is 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. The red photosensitive resin composition containing said photoinitiator (D) is highly sensitive, and the film | membrane formed using this composition becomes favorable the intensity | strength and surface smoothness of the pixel part.

When the photopolymerization initiation aid (D-1) is used in combination with the photopolymerization initiator (D), the red photosensitive resin composition containing these is more sensitive, so that the productivity when forming the color filter using the composition is improved. Do.

As a triazine type compound, it is 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1, 3, 5- triazine, 2, 4-bis (trichloromethyl) -6, for example. -(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-triazine , 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl ) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like.

As an 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-morpholinopropan-1-one , 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane- 1-one oligomer etc. are mentioned. As an acetophenone type compound, the compound represented by following formula (2) is mentioned, for example.

<Formula 2>

In Formula 2, 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 which may be substituted by an alkyl group having 1 to 12 carbon atoms, or The naphthyl group which may be substituted by the C1-C12 alkyl group is shown.

Specific examples of the compound represented by Formula 2 include 2-methyl-2-amino (4-morpholinophenyl) ethan-1-one and 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 a biimidazole compound, it is 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- tetraphenyl biimidazole, 2,2'-bis (2,3-dichloro, for example. Phenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimidazole , 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, phenyl group in 4,4', 5,5 'position And imidazole compounds substituted with groups. 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 the following general formulas (3), (4) and (5).

<Formula 3>

<Formula 4>

<Formula 5>

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

As a 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) -Butyl peroxycarbonyl) benzophenone, 2,4, 6-trimethyl benzophenone, etc. are mentioned.

As a 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.

As an anthracene type compound, 9,10- dimethoxy anthracene, 2-ethyl-9,10- dimethoxy anthracene, 9,10- diethoxy anthracene, 2-ethyl-9, 10- diethoxy anthracene, etc. are mentioned, for example. Can be.

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.

In addition, you may use combining a photoinitiator (D-1) with a photoinitiator (D).

As the photopolymerization initiation assistant (D-1), an amine compound and a carboxylic acid compound are preferably used.

Specific examples of the amine compound in the photopolymerization initiation aid include aliphatic amine compounds such as triethanolamine, methyl diethanolamine, and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoic acid, and 4- Dimethylaminobenzoic acid 2-ethylhexyl, benzoic acid 2-dimethylaminoethyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (common name: Michler's ketone), 4,4'-di ( Aromatic amine compounds, such as N, N'- dimethylamino)-benzophenone and 4,4'-bis (diethylamino) benzophenone, are mentioned. As an amine compound, an aromatic amine compound is used preferably.

Specific examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenyl And aromatic heteroacetic acids such as thioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

The amount of the photopolymerization initiator (D) used is a mass fraction with respect to the total amount of the (A) binder resin and the (B) photopolymerizable compound, based on the solid content, usually 0.1 to 40% by mass, preferably 1 to 30% by mass, and photopolymerization. The usage-amount of a starting adjuvant (D-1) is 0.1-50 mass% normally on the said reference | standard, Preferably it is 1-40 mass%.

When the usage-amount of a photoinitiator (D) exists in the said range, since the red photosensitive resin composition becomes highly sensitive and the intensity | strength of the pixel part formed using this composition and the smoothness in the surface of this pixel part tend to become favorable, it is preferable. . Moreover, when the usage-amount of a photoinitiator auxiliary (D-1) exists in the said range, since the sensitivity of a red photosensitive resin composition becomes higher and the productivity of the color filter formed using this composition tends to improve, it is preferable.

Solvent (E)

The solvent (E) contained in the red photosensitive resin composition of this invention is not specifically limited, Various organic solvents used in the field of a red photosensitive resin composition can be used.

Specific examples thereof 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, and diethylene. Propylene glycols such as diethylene glycol dialkyl ethers such as glycol dipropyl ether and diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, and propylene glycol monomethyl ether Alkylene glycol alkyl ether acetates such as dialkyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxy butyl acetate and methoxy pentyl acetate, benzene, tol Aromatic hydrocarbons such as ruene, xylene, mesitylene, ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, Alcohols such as glycerin, esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, and cyclic esters such as γ-butyrolactone.

Among the solvents described above, organic solvents having a boiling point of 100 to 200 ° C in the solvent are preferably used in terms of coating properties and drying properties, and more preferably alkylene glycol alkyl ether acetates, ketones and 3-ethoxy. Esters such as ethyl propionate and methyl 3-methoxypropionate; and more preferably propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, and 3-ether. Ethyl oxypropionate, methyl 3-methoxypropionate, and the like.

These solvents (E) can be used individually or in mixture of 2 or more types, respectively.

Content of the solvent (E) in the red photosensitive resin composition of this invention is 60-90 mass% normally with a mass fraction with respect to the whole red 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. It is preferable because the coating property tends to be good at the time.

Additive (F)

In the red photosensitive resin composition of this invention, it is also possible to add additives (F), such as a filler, another high molecular compound, a hardening | curing agent, a pigment dispersing agent, an adhesion promoter, antioxidant, a ultraviolet absorber, and an anticoagulant, as needed.

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

Specific examples of other high molecular compounds include curable resins such as epoxy resins and maleimide resins, thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ethers, polyfluoroalkyl acrylates, polyesters, polyurethanes, and the like. have.

A hardening | curing agent is used in order to raise a deep part hardening and mechanical strength, As a hardening | curing agent, an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, an oxetane compound, etc. are mentioned.

Examples of the epoxy compound in the curing agent include bisphenol A epoxy resins, hydrogenated bisphenol A epoxy resins, bisphenol F epoxy resins, hydrogenated bisphenol F epoxy resins, noblock type epoxy resins and other aromatic epoxy resins and alicyclic compounds. Epoxy resins, glycidyl ester resins, glycidylamine resins, or brominated derivatives of these epoxy resins, aliphatic, alicyclic or aromatic epoxy compounds other than epoxy resins and their brominated derivatives, butadiene (co) polymer epoxides, Isoprene (co) polymer epoxide, glycidyl (meth) acrylate (co) polymer, triglycidyl isocyanurate and the like.

As said oxetane compound in the said hardening | curing agent, carbonate bis oxetane, xylene bis oxetane, adipate bis oxetane, a terephthalate bis oxetane, a cyclohexane dicarboxylic acid bis oxetane, etc. are mentioned, for example. .

The curing agent may include a curing aid compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound with the curing agent. As a hardening auxiliary compound, polyhydric carboxylic acid, polyhydric carboxylic anhydride, an acid generator, etc. are mentioned, for example.

As the carboxylic anhydrides, those commercially available as epoxy resin curing agents can be used. As this epoxy resin hardening | curing agent, a brand name (Adekahadona EH-700) (made by Adeka Industrial Co., Ltd.), a brand name (Rikaditdo HH) (made by Nippon Ewha Co., Ltd.), a brand name (MH-700) ( New Nippon Ewha Co., Ltd.) etc. are mentioned. The said hardening | curing agent can be used individually or in mixture of 2 or more types.

Commercially available surfactants can be used as the pigment dispersant, and examples thereof include surfactants such as silicone, fluorine, ester, cationic, anionic, nonionic and amphoteric. These can be used individually or in combination of 2 types or more, respectively. As said surfactant, For example, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyethylene glycol diester, sorbitan fatty ester, fatty acid modified polyester, tertiary amine modified polyurethane , Polyethylenimine, etc., trade names include 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 (made by Genka Corporation), EFKA (made by EFKA Chemicals), PB 821 (made by Ajinomoto Co., Ltd.), etc. are mentioned.

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, 3-isocyanate propyl trimethoxysilane, 3-isocyanate propyl triethoxysilane, etc. are mentioned.

These adhesion promoters can be used individually or in combination of 2 or more types, respectively. It is 0.01-10 mass% normally with respect to solid content of a red photosensitive resin composition, Preferably it contains 0.05-2 mass%.

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.

The red photosensitive resin composition of this invention can be manufactured by the following method, for example. The coloring material (B) 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 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. A binder resin (A), a polymeric compound (C), a photoinitiator (D), the other components used as needed, and the additional solvent as needed are prescribed | regulated to the obtained dispersion liquid (henceforth a mill base). It further adds so that it may become the density | concentration of, and obtains the target red photosensitive resin composition.

As an example, it can apply | coat on a base material as follows, and perform a photocuring and image development to form a pattern, and can be used as a black matrix or a colored pixel (colored image).

First, the composition is applied onto a substrate (not limited, usually glass or silicon wafer) or a layer containing the solids of the red photosensitive resin composition formed first and preliminarily dried to remove volatile components such as solvents to obtain a smooth coating film. . The thickness of the coating film at this time is about 1-3 micrometers normally. In order to obtain the desired pattern to the coating film obtained in this way, an ultraviolet-ray is irradiated to a specific area | region through a mask. At this time, it is preferable to use apparatuses, such as a mask aligner and a stepper, so that a parallel light beam may be irradiated uniformly to the whole exposure part, and a mask and a board | substrate will be correctly aligned. In addition, a desired pattern can be produced by contacting the aqueous coating solution after completion of curing with an aqueous alkali solution to dissolve and develop the non-exposed areas. After image development, after-drying for about 10 to 60 minutes can be performed at 150-230 degreeC as needed.

The developing solution used for image development after patterned exposure is the aqueous solution containing an alkaline compound and surfactant normally.

The alkaline compound may be either an inorganic or organic alkaline compound.

Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate, hydrogen carbonate Sodium, potassium hydrogen carbonate, sodium borate, potassium borate, ammonia and the like.

In addition, specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, mono Isopropylamine, diisopropylamine, ethanolamine, etc. are mentioned. These inorganic and organic alkaline compounds can be used individually or in combination of 2 or more types, respectively.

Preferable concentration of the alkaline compound in the alkaline developer is in the range of 0.01 to 10% by mass, more preferably 0.03 to 5% by mass.

Surfactant in alkaline developing solution can use all of a nonionic surfactant, anionic surfactant, or a cationic surfactant.

Specific examples of non-ionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkyl aryl ethers, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, and poly Oxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine and the like.

Specific examples of the anionic surfactant include higher alcohol sulfate ester salts such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfate salts such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, Alkyl aryl sulfonates, such as sodium dodecyl naphthalene sulfonate, etc. are mentioned.

Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryl trimethylammonium chloride, and quaternary ammonium salts.

These surfactant can be used individually or in combination of 2 or more types, respectively.

The concentration of the surfactant in the alkaline developer is usually 0.01 to 10% by mass, preferably 0.05 to 8% by mass, more preferably 0.1 to 5% by mass.

Hereinafter, the pattern formation method and color filter of the colored layer using the red photosensitive resin composition concerning this invention are demonstrated below using FIGS. 1A-1H.

As shown in Fig. 1A, each pixel pattern 2 of red (R), green (G), and blue (B) is directly placed on the TFT element 3 using the colored photosensitive resin composition. It is formed to a certain thickness. In the figure, reference numeral 4 denotes a nitride film (SiNx).

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. Finally, the blue pixel pattern is completed by coating, exposing, developing and curing the blue photosensitive resin composition on the blue pixel.

Meanwhile, 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 coloring photosensitive resin composition, and may also be formed through the lamination of the coloring photosensitive resin composition.

In addition, after this process, the colored photosensitive resin composition in the region corresponding to the source / drain electrodes is removed by a conventional photolithography process so that the source / drain electrodes of the TFT elements are exposed.

In FIG. 1A, a predetermined portion of the colored photosensitive resin composition corresponding to the source / drain electrodes of the TFT element is shown in an etched state. However, the nitride film 4 is not yet etched.

As shown in FIG. 1B, in the process of 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.

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

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

As shown in Fig. 1E, an IZO layer 6, which will be used as a common electrode with the TFT element 3, is deposited on the entire upper surface.

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.

As shown in FIG. 1G, all of 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 removed by wet etching (wet etching).

As shown in FIG. 1H, the COA method color filter is completed by removing the remaining positive photosensitive resin film 7 on the IZO layer 6 with a stripper developer.

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

The liquid crystal display device of the present invention includes all the configurations known in the art, except that the color filter 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, a transmissive liquid crystal display device in which a counter electrode substrate including a thin film transistor (TFT element), a pixel electrode, and an alignment layer is faced at predetermined intervals, and a liquid crystal material is injected into the gap to form a liquid crystal layer. Can be. Moreover, the present invention can also be applied to a reflective liquid crystal display device. Of course, the present invention includes a liquid crystal display including a backlight.

< Example >

Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited by an Example. In addition, "%" and "part" which show content in a following example and a comparative example are a mass reference | standard unless there is particular notice.

<Synthesis of Resin A-1>

90 g of propylene glycol monomethyl ether acetate, 90 g of propylene glycol monomethyl ether, and 11.0 g of 2-norbornene were mixed and introduced into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen introduction tube. After making the atmosphere into nitrogen in the air, the temperature was raised to 80 ° C., and then a tert part was added to a mixture containing benzyl methacrylate 70.5 g (0.40 mole), methacrylic acid 45.0 g (0.50 mole), and 136 g of propylene glycol monomethyl ether acetate. The solution to which 3.2 g of tyrperoxy 2-ethylhexyl carbonate was added was dripped at the flask over 2 hours from the dropping lot, and stirring was continued at 100 degreeC for 5 hours. Subsequently, the atmosphere in the flask was changed from nitrogen to air, and 30 g of glycidyl methacrylate [0.2 mol, (40 mol% of the carboxyl groups of methacrylic acid used in this reaction)], 0.9 g of trisdimethylaminomethylphenol, and hydroquinone 0.145 g was poured into the flask, and the reaction was continued at 110 ° C. for 6 hours to obtain a resin A-1 having a solid acid value of 100 mgKOH / g. The weight average molecular weight of polystyrene conversion measured by GPC was 31,000, and molecular weight distribution (Mw / Mn) was 2.3.

<Synthesis of Resin A-2>

90 g of propylene glycol monomethyl ether acetate, 90 g of propylene glycol monomethyl ether, and 11.0 g of 2-norbornene were mixed and introduced into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen introduction tube. After the atmosphere was nitrogen in the air, the temperature was raised to 80 ° C., and then terbutyrruff was added to a mixture containing 47.2 g (0.40 mol) of vinyltoluene, 45.0 g (0.50 mol) of methacrylic acid, and 136 g of propylene glycol monomethyl ether acetate. The solution to which 3.2 g of hydroxy 2-ethylhexyl carbonate was added was dripped at the flask over 2 hours from the dropping lot, and stirring was continued at 100 degreeC for 5 hours. Subsequently, the atmosphere in the flask was changed from nitrogen to air, 22.5 g of glycidyl methacrylate [0.15 mol, (50 mol% of the carboxyl groups of methacrylic acid used in this reaction)], 0.9 g of trisdimethylaminomethylphenol, and 0.145 g of hydroquinone was thrown in the flask, reaction was continued at 110 degreeC for 6 hours, and resin A-2 whose solid acid value was 123.7 mgKOH / g was obtained. The weight average molecular weight of polystyrene conversion measured by GPC was 20,000, and molecular weight distribution (Mw / Mn) was 2.3.

<Synthesis of Resin A-3>

90 g of propylene glycol monomethyl ether acetate, 90 g of propylene glycol monomethyl ether, and 22.1 g of 2-norbornene were introduced into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube, and the flask was introduced. After raising the atmosphere to nitrogen in the air, the temperature was raised to 80 ° C., and then to a mixture containing 70.5 g (0.40 mol) of benzyl methacrylate, 24 g (0.40 mol) of glycidyl methacrylate and 136 g of propylene glycol monomethyl ether acetate. The solution to which 3.2 g of terbutyryroxy 2-ethylhexyl carbonates was added was dripped at the flask over 2 hours from the dropping lot, and stirring was continued at 100 degreeC for 5 hours. Subsequently, the atmosphere in the flask was changed from nitrogen to air, 25.8 g (0.30 mol) of methacrylic acid, 0.9 g of trisdimethylaminomethylphenol, and 0.145 g of hydroquinone were charged into the flask, and the reaction was continued at 120 ° C. The reaction was stopped when 0.8 mgKOH / g was reached, to obtain Copolymer C-1. Subsequently, 99.7 g (0.6 mol) of tetrahydrophthalic anhydride was added and reacted at 115 degreeC for 2 hours, and solid content acid value was 77 mgKOH / g. Phosphorus resin A-3 was obtained. The weight average molecular weight of polystyrene conversion measured by GPC was 19,500, and molecular weight distribution (Mw / Mn) was 2.3.

<Synthesis of Resin A-4>

182 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen introduction tube. The atmosphere in the flask was changed from nitrogen to air, and then heated to 100 ° C., and then benzyl methacrylate 70.5. azobisisobuty in a mixture comprising g (0.40 mole), 43.0 g (0.50 mole) methacrylic acid, 44.5 g (0.10 mole) 2-hydroxypropyldehydroabietic acid acrylate and 136 g propylene glycol monomethyl ether acetate The solution to which 3.6 g of ronitrile was added was dripped at the flask over 2 hours from the dropping lot, and stirring was continued at 100 degreeC for 5 hours. Then, the atmosphere in the flask was changed from nitrogen to air, and 30 g of glycidyl methacrylate [0.2 mol, (50 mol% based on the carboxyl group of methacrylic acid used in this reaction)], 0.9 g of trisdimethylaminomethylphenol, and hydroquinone 0.145 g was poured into the flask, and the reaction was continued at 110 ° C. for 6 hours to obtain a resin A-4 having a solid acid value of 94 mgKOH / g. The weight average molecular weight of polystyrene conversion measured by GPC was 30,000, and molecular weight distribution (Mw / Mn) was 2.1.

<Synthesis of Resin A-5>

182 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube, and the atmosphere in the flask was changed from nitrogen to air, and the temperature was raised to 100 ° C., followed by benzyl methacrylate 105.7. azobisisobuty in a mixture comprising g (0.60 moles), 25.3 g (0.30 moles) methacrylic acid, 44.5 g (0.10 moles) of 2-hydroxypropyldehydroabietic acid acrylate, and 136 g of propylene glycol monomethyl ether acetate The solution to which 3.6 g of ronitrile was added was dripped at the flask over 2 hours from the dripped lot, and stirring was further continued at 100 degreeC for 5 hours, and the resin A-5 whose solid acid value was 120 mgKOH / g was obtained. The weight average molecular weight of polystyrene conversion measured by GPC was 24,000, and molecular weight distribution (Mw / Mn) was 2.1.

About the measurement of the weight average molecular weight (Mw) and number average molecular weight (Mn) of the said binder polymer, it carried out on condition of the following using GPC method.

Equipment: HLC-8120GPC (manufactured by Tosoh Corporation)

Column: TSK-GELG4000HXL + TSK-GELG2000HXL (Serial Connection)

Column temperature: 40 ℃

Mobile phase solvent: tetrahydrofuran

Flow rate: 1.0 ml / min

Injection volume: 50µl

Detector: RI

Measurement sample concentration: 0.6 mass% (solvent = tetrahydrofuran)

Calibration standard: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation)

The ratio of the weight average molecular weight and number average molecular weight obtained above was made into molecular weight distribution (Mw / Mn).

< Example  1>

In each component of the following Table 1, it mixes so that the total amount of the pigment which is a coloring material (B), and the pigment dispersant which is an additive (F) may be 20 mass% with respect to the mixture of a pigment, a pigment dispersant, and a propylene glycol monomethyl ether acetate. After the pigment was sufficiently dispersed using the bead mill, the bead mill was separated, and the remaining components including the remaining amount of propylene glycol monomethyl ether acetate were further added and mixed to obtain a red photosensitive resin composition.

TABLE 1

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Binder Resin (A) Part 4.57 (A-1) Part 4.57 (A-2) Part 4.57 (A-3) Part 4.57 (A-4) Part 4.57 (A-5) Part 4.57 (A-1) Coloring material (B-1) Part 3.99 Part 3.99 Part 3.99 Part 3.99 Part 3.99 - Coloring material (B-2) Part 3.26 Part 3.26 Part 3.26 Part 3.26 Part 3.26 Part 1.45 Coloring material (B-3) - - - - - Part 5.80 Photopolymerizable Compound (C) Part 4.06 Part 4.06 Part 4.06 Part 4.06 Part 4.06 Part 4.06 Photoinitiator (D-1) 0.60part 0.60part 0.60part 0.60part 0.60part 0.60part Photoinitiator (D-2) 0.30part 0.30part 0.30part 0.30part 0.30part 0.30part Photoinitiator (D-3) 0.37part 0.37part 0.37part 0.37part 0.37part 0.37part Solvent (E) Part 82.51 Part 82.51 Part 82.51 Part 82.51 Part 82.51 Part 82.51 Additive (F) 0.34part 0.34part 0.34part 0.34part 0.34part 0.34part

[Detailed Composition of Components Used in Tables 1 and 2]

 (A) Binder Resin: A-1 to A-5 Synthesized in Preparation Example

(B) coloring material

(B-1): C.I. pigment red 242

(B-2): C.I. pigment yellow 177

(B-3): C.I. pigment yellow 254

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

(D) photopolymerization initiator

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

(D-2): 4,4'-di (N, N'-dimethylamino)-benzophenone (EAB-F; Hodogaya Kagaku Co., Ltd. product)

(D-3): ethanone-1- [9-ethyl-6- (2-methyl-4tetrahydropyranyloxybenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (Irgacure OXE02; manufactured by Ciba Specialty Chemical)

(E) Solvent: Propylene glycol monomethyl ether acetate

(F) Additive: Pigment Dispersant (Polyester)

A glass substrate of 2 square inches (# 1737, manufactured by Corning) was washed sequentially with a neutral detergent, water, and alcohol, and then dried. On the glass substrate, the red photosensitive resin composition (Table 1) was exposed to an exposure dose (365 nm) of 100 mJ / cm 2, and spin-coated so that the film thickness after post-firing when the developing step was omitted was 3.2 μm, Subsequently, it was pre-dried at 100 degreeC for 3 minutes in the clean oven. After cooling, the gap between the substrate coated with the red photosensitive resin composition and a 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 made into 100 micrometers, and it irradiated with the exposure amount (365 nm) of 100 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 at 26 ° C. for a predetermined time in an aqueous developer containing 0.12% of a nonionic surfactant and 0.06% of potassium hydroxide, and then dried at 220 ° C. for 30 minutes after washing with water.

TABLE 2

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Color coordinate transmittance (measured value) * 1 Excellent (18.8) Excellent (18.8) Excellent (18.8) Poor (18.4) Poor (18.3) Poor (18.4) Etch resistance * 2 ○ ○ ○ X X ○

* 1: The transmittance | permeability (luminance value) in x and y equivalent target on a color coordinate was evaluated using the microscopic spectrometer OSP-SP2000.

* 2: The etching resistance is visually evaluated for the degree of swelling of the film at 100 ° C./5 minutes under strip etching solution (trade name: PRS-2000, manufactured by Dongwoo Finechem Co., Ltd.). It was.

○: No swelling, X: Swelling.

Table 2 shows the photosensitive resin compositions of Examples 1, 2, and 3 containing the unsaturated group-containing binder resin of the present invention through color coordinate transmittance of high brightness color characteristics and stable thermal stability. It was found that no color filter was obtained. It does not contain the binder resin of the present invention or C.I. The red photosensitive resin compositions of Comparative Examples 1, 2, and 3 that do not contain Pigment Red 242 have low luminance and thermal stability, or swelling occurs in the etching solution, and thus a high quality color filter cannot be obtained.

1A to 1H are schematic views showing a pattern forming method using a red photosensitive resin composition according to the present invention.

-Description of the main symbols in the 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

Claims (8)

In the red photosensitive resin composition for color filter layers formed on a TFT substrate, it contains binder resin (A), a coloring material (B), a photopolymerizable compound (C), a photoinitiator (D), and a solvent (E), The said Binder resin (A) is a copolymer obtained by the copolymerization reaction containing following A1, The said coloring material (B) is CI Red photosensitive resin composition containing pigment red 242. A1: the compound represented by the following formula (1) <Formula 1>

(In Formula 1, n is 0 or 1, and R 1 and R 2 are each independently an aliphatic or aromatic hydrocarbon containing or not including a hydrogen, a hetero atom having 1 to 12 carbon atoms, and R 3, R 4, R 5, and R 6. Are each independently an aliphatic or aromatic hydrocarbon containing or not containing hydrogen, a hetero atom having 1 to 30 carbon atoms, and are selected from R3, R4, R5, and R6 in a linked or unlinked branch form. ) The method of claim 1, The compound represented by Formula 1 is a red photosensitive resin composition, characterized in that at least one selected from the compounds represented by the following formula.

The method of claim 1, Said binder resin (A) is a copolymer obtained by the copolymerization reaction containing said A1 and following A2, or A3, or unsaturated group containing resin obtained by making the following A4 react further, The red photosensitive resin composition characterized by the above-mentioned. A2: a compound having an unsaturated bond copolymerizable with A1 and A3, A3: unsaturated carboxylic acid, A4: The compound which has an unsaturated bond and an epoxy group in 1 molecule. The method of claim 3, The ratio of the constituents derived from each of A1 to A3 is relative to the total moles of the copolymer constituents, Structural units derived from A 1: 2 to 30 mole%, Structural units derived from A 2: 2 to 95 mole%, Structural units derived from A 3: 2 to 70 mole%, The red photosensitive resin composition which is a range, and reacts A4 with 5 to 80 mol% with respect to the component derived from A3 at the time of reaction of A4 further. The method of claim 1, The binder resin (A) is a copolymer obtained by copolymerizing A1 with the following A2 or A4, or an unsaturated group-containing resin obtained by further reacting the following A5 after the following A3 is reacted. Red photosensitive resin composition. A2: a compound having an unsaturated bond copolymerizable with A1 and A4, A3: unsaturated carboxylic acid, A4: the compound which has an unsaturated bond and an epoxy group in 1 molecule, A5: polybasic acid anhydride The method of claim 5, The ratio of the constituents derived from each of the above (A1), (A2) and (A4) to the total moles of the copolymer constituents, Structural unit derived from (A1): 2 to 30 mol%, Structural unit derived from (A2): 2 to 95 mol%, Structural unit derived from (A4): 2 to 85 mol%, And (A3) is 10 to 100 mol% of the constituents derived from (A4), and 5 to 100 mol% of (A5) to the hydroxyl group of the material obtained after the reaction. Resin composition. In the color filter manufactured by apply | coating a red photosensitive resin composition to a board | substrate, exposing and developing, The said red photosensitive resin composition is a red photosensitive resin composition of any one of Claims 1-6, The color filter characterized by the above-mentioned. A liquid crystal display device comprising the color filter of claim 7.

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