KR101142734B1 - Negative type resist composition for color filter, color filter using same, and liquid crystal display - Google Patents

Abstract

This invention aims at providing the negative type resist composition for color filters excellent in pigment dispersibility and alkali developability.

This invention is a negative type for color filters which has (A) pigment dispersant, (B) pigment, (C) alkali-soluble resin, (D) polyfunctional monomer, (E) photoinitiator, and (F) solvent. A resist composition, wherein (A) the pigment dispersant has a structural unit (1) represented by the following formula (1) and a structural unit (2) represented by the following formula (2), and the amino group which the structural unit (1) has The above-mentioned problem is solved by providing the negative type resist composition for color filters in which the acidic organophosphorus compound represented by this is a block copolymer which formed the salt.

<Formula 1>

<Formula 2>

<Formula 3>

Negative-type resist composition for color filters, pigment dispersant, pigment, alkali-soluble resin, polyfunctional monomer, photoinitiator, block copolymer, liquid crystal display device

Description

Negative resist composition for color filters, color filter and liquid crystal display using the same {NEGATIVE TYPE RESIST COMPOSITION FOR COLOR FILTER, COLOR FILTER USING SAME, AND LIQUID CRYSTAL DISPLAY}

The present invention relates to a negative type resist composition for color filters excellent in pigment dispersibility and alkali developability.

In recent years, with the development of personal computers, especially with the development of laptops, the demand for liquid crystal displays is increasing. In addition, in recent years, the diffusion rate of liquid crystal televisions for homes is also increasing, and the market for liquid crystal displays is gradually expanding. Moreover, the liquid crystal display which is spreading in recent years has the tendency of a big screen, and the tendency becomes strong especially for home liquid crystal television. In such a situation, the members constituting the liquid crystal display are required to manufacture high quality products at a lower cost with higher productivity. Particularly, color filters having a function of color display of the liquid crystal display have a high cost. Is rising. Here, as a manufacturing method of a general color filter, the coating film containing the photocurable resist composition which disperse | distributed the pigment of each color was formed on the board | substrate with which the light shielding part was formed in pattern form, and it exposed through the photomask of a desired pattern shape. By alkali development, the method of forming the colored layer of each color in a pattern form is used.

As a photocurable resist composition used for manufacture of such a color filter, in addition to the pigment of each color mentioned above normally, it has a pigment dispersant, alkali-soluble resin, a polyfunctional monomer, a photoinitiator, and a solvent added in order to disperse | distribute a pigment uniformly. Is used. As a pigment dispersant used for such a photocurable resist composition, when dispersibility of a pigment is inadequate when using it as the colored layer of a color filter, there exists a possibility that a color nonuniformity may arise in a colored layer, The thing which has the outstanding dispersibility is used. As the photocurable resist composition using the pigment dispersant having such excellent dispersibility, an AB block copolymer and / or BAB composed of an A block having a quaternary ammonium base in the side chain and a B block having no quaternary ammonium base as a pigment dispersant The composition for color filters using a block copolymer is disclosed (patent document 1 below).

Moreover, in recent years, the demand for high contrast of a liquid crystal display device is increasing, and in order to achieve such a request, refinement | miniaturization of a pigment is calculated | required. Therefore, the surface area of the pigment in the said photocurable resist composition increases, and the necessity to increase the addition amount of the pigment dispersant required for disperse | distributing a pigment uniformly has arisen.

However, as the pigment dispersant of the conventional type containing a quaternary ammonium base as disclosed in Patent Literature 1, the uniform dispersibility of the pigment can be ensured by increasing the addition amount thereof, but the alkali developability is lowered and alkali There have been problems such as lengthening of time required for development and a problem that an unexposed photocurable resist composition remains on the substrate, resulting in a decrease in productivity and quality.

[Patent Document 1] Japanese Patent Application Laid-Open No. 2002-31713

This invention is made | formed in view of the said problem, Comprising: It aims as a main objective to provide the negative type resist composition for color filters excellent in pigment dispersibility and alkali developability.

In order to solve the said subject, this invention provides (A) pigment dispersant, (B) pigment, (C) alkali-soluble resin, (D) polyfunctional monomer, (E) photoinitiator, (F) solvent It is a negative type resist composition for color filters which has a (A) pigment dispersing agent which has a structural unit (1) represented by following formula (1) and the structural unit 2 represented by following formula (2), and has the said structural unit (1) It provides a negative type resist composition for color filters, wherein the amino group is an acidic organophosphorus compound represented by the following formula (3) which is a block copolymer in which a salt is formed.

In formulas 1-3, R ¹ is a hydrogen atom or a methyl group, R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, A is an alkylene group having 1 to 8 carbon atoms,-[CH (R ⁶ A divalent group represented by) -CH (R ⁷ ) -O] _x -CH (R ⁶ ) -CH (R ⁷ )-or [(CH ₂ ) _y -O] _z- (CH ₂ ) _y- , R ⁴ is an alkyl group having 1 to 18 carbon atoms, a benzyl group, a phenyl group, a biphenyl group,-[CH (R ⁶ ) -CH (R ⁷ ) -O] _x -R ⁸ or-[(CH ₂ ) _y -O] _z- represents ^{R 8, R 5, R 5} ' are each independently a hydrogen atom, a hydroxyl group, a C 1 -C 18 alkyl group, a C2 to 18 alkenyl group, a benzyl group, a phenyl group, a biphenyl group of the - [CH (R ⁹⁾ Is _a monovalent group represented by -CH (R ¹⁰ ) -O] _a -R ¹¹ or-[(CH ₂ ) _b -O] _c -R ¹¹ or -OR ^{5 ''} ,

R ^{5 ''} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a benzyl group, a phenyl group, a biphenyl group,-[CH (R ⁹ ) -CH (R ¹⁰ ) -O] _a -R ¹¹ or- Is a monovalent group represented by [(CH ₂ ) _b -O] _c -R ¹¹ ,

R ⁶ , R ⁷ , R ⁹ and R ¹⁰ are each independently a hydrogen atom or a methyl group, R ⁸ and R ¹¹ are each independently a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, a benzyl group, a phenyl group, A biphenyl group, —CHO, —CH ₂ CHO, —CO—CH═CH ₂ , —CO—C (CH ₃ ) ═CH ₂ or —CH ₂ COOR ¹² is a monovalent group represented by R ¹² is a hydrogen atom or An alkyl group having 1 to 5 carbon atoms,

x and a are integers from 0 to 18, y and b are integers from 1 to 5, z and c are integers from 0 to 18, and m and n are each from 1 to 200;

According to the present invention, the pigment dispersant has a structural unit (1) represented by the formula (1) and a structural unit (2) represented by the formula (2), and the amino group of the structural unit (1) The acidic organophosphorus compound to be displayed is a block copolymer in which a salt is formed, thereby enhancing the adsorptivity of the structural unit (1) to the pigment to form a salt-forming site, and the structural unit (2) is compatible with the solvent. Since this is excellent, since the said pigment can be stabilized in the said solvent, it can be made excellent in the dispersibility and stability of the said pigment.

Furthermore, by having the acidic organophosphorus compound represented by the said Formula (3), the salt formation site formed by the amino group and the said acidic organophosphorus compound contained in the said structural unit (1) has high solubility with respect to the aqueous alkali solution at the time of alkali image development. Since it has, it can be made excellent in alkali developability. Therefore, when a color filter is manufactured using the negative type resist composition for color filters of this invention, alkali image development time can be shortened and it can be made excellent in productivity. Moreover, since it is excellent in alkali developability, the high quality color filter with few residues of the negative type resist composition for color filters in an unexposed part can be obtained.

In this invention, it is preferable that R <^5> and R <^5>' contained in the said acidic organophosphorus compound contain a polymeric group, and it is preferable that the said polymeric group is a vinyl group, a (meth) acryloyl group, or an allyl group. When the acidic organophosphorus compound contains a polymerizable group, the polymerizable groups and / or the polymerizable group and the present invention are exposed at the time of exposure when forming a colored layer using the negative type resist composition for color filters of the present invention. It is because alkali-soluble resin, polyfunctional monomer, etc. which are contained in the negative type resist composition for color filters can be superposed | polymerized easily, and it is possible for the said pigment dispersant to exist stably in the colored layer of a color filter. Therefore, when a liquid crystal display device is manufactured using such a color filter, the said pigment dispersant to a liquid crystal layer etc. can be prevented from bleeding out.

Moreover, before using for colored layer formation, by polymerizing the polymerizable groups which the said acidic organic phosphorus compound has, the negative type resist composition for color filters of an unexposed part can be made especially excellent in alkali developability.

In this invention, it is preferable that the average particle diameter of the said (B) pigment exists in the range of 10 nm-100 nm. It is because the high contrast and high quality liquid crystal display device can be produced by using the color filter using the negative type resist composition for color filters of this invention by having the particle diameter of the said pigment in the range of 10 nm-100 nm.

The present invention provides a color filter having a colored layer formed by using the negative resist composition for color filters.

According to this invention, since the colored layer is formed using the said negative type resist composition for color filters, since it is excellent in alkali developability, it can be set as the color filter excellent in productivity. Moreover, since it is excellent in alkali developability, it can be set as the high quality color filter with few residues of the negative type resist composition for color filters in an unexposed location.

 The present invention provides a liquid crystal display device having the color filter. According to the present invention, it is possible to obtain a liquid crystal display device having high quality and excellent productivity by using the color filter.

The present invention has the effect of providing a negative type resist composition for color filters excellent in pigment dispersibility and alkali developability.

The present invention relates to a negative resist composition for a color filter, a color filter and a liquid crystal display device using the same. Hereinafter, the negative resist composition for color filters of this invention, a color filter, and a liquid crystal display device are demonstrated.

First, the negative resist composition for color filters of this invention is demonstrated.

Negative-type resist composition for color filters

The negative resist composition for color filters of the present invention (hereinafter may be simply referred to as a negative resist composition) includes (A) a pigment dispersant, (B) a pigment, (C) an alkali-soluble resin, and (D) It is characterized by including a polyfunctional monomer, (E) photoinitiator, and (F) solvent, The said (A) pigment dispersant has the following characteristics.

((A) Pigment Dispersant)

In the negative resist composition of the present invention, the pigment dispersant used as component (A) has a structural unit (1) represented by the following formula (1) and a structural unit (2) represented by the following formula (2), and the structural unit (1 ) Is a block copolymer (hereinafter sometimes referred to as a salt type block copolymer) in which an amino group and an acidic organophosphorus compound represented by the following formula (3) form a salt.

<Formula 1>

<Formula 2>

<Formula 3>

In formulas 1-3, R ¹ is a hydrogen atom or a methyl group, R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, A is an alkylene group having 1 to 8 carbon atoms,-[CH (R ⁶ ) -CH (R ⁷ ) -O] _x -CH (R ⁶ ) -CH (R ⁷ )-or [(CH ₂ ) _y -O] _Z- (CH ₂ ) _y- , a divalent group represented by ⁴ is an alkyl group having 1 to 18 carbon atoms, a benzyl group, a phenyl group, a biphenyl group,-[CH (R ⁶ ) -CH (R ⁷ ) -O] _x -R ⁸ or-[(CH ₂ ) _y -O] _z- represents ^{R 8, R 5, R 5} ' are each independently a hydrogen atom, a hydroxyl group, a C 1 -C 18 alkyl group, a C2 to 18 alkenyl group, a benzyl group, a phenyl group, a biphenyl group of the - [CH (R ⁹⁾ Is _a monovalent group represented by -CH (R ¹⁰ ) -O] _a -R ¹¹ or-[(CH ₂ ) _b -O] _c -R ¹¹ or -OR ^{5 ''} ,

R ^{5 ''} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a benzyl group, a phenyl group, a biphenyl group,-[CH (R ⁹ ) -CH (R ¹⁰ ) -O] _a -R ¹¹ or- Is a monovalent group represented by [(CH ₂ ) _b -O] _c -R ¹¹ ,

R ⁶ , R ⁷ , R ⁹ and R ¹⁰ are each independently a hydrogen atom or a methyl group, R ⁸ and R ¹¹ are each independently a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, a benzyl group, a phenyl group, A biphenyl group, —CHO, —CH ₂ CHO, —CO—CH═CH ₂ , —CO—C (CH ₃ ) ═CH ₂ or —CH ₂ COOR ¹² is a monovalent group represented by R ¹² is a hydrogen atom or An alkyl group having 1 to 5 carbon atoms,

x and a are integers from 0 to 18, y and b are integers from 1 to 5, z and c are integers from 0 to 18, and m and n are each from 1 to 200;

According to the present invention, the pigment dispersant has a structural unit (1) represented by the formula (1) and a structural unit (2) represented by the formula (2), and the amino group of the structural unit (1) The acidic organophosphorus compound to be displayed is a block copolymer in which a salt is formed, thereby enhancing the adsorptivity of the structural unit (1) to the pigment to form a salt-forming site, and the structural unit (2) is compatible with the solvent. By excellent in this, since the said pigment can be stabilized in the said solvent, it can be made excellent in the dispersibility and stability of the said pigment.

Furthermore, by having the acidic organophosphorus compound represented by the said Formula (3), the salt formation site formed by the amino group and the said acidic organophosphorus compound contained in the said structural unit (1) has high solubility with respect to the aqueous alkali solution at the time of alkali image development. Since it has, it can be made excellent in alkali developability. Therefore, when a color filter is manufactured using the negative type resist composition for color filters of this invention, alkali image development time can be shortened and it can be made excellent in productivity. Moreover, by being excellent in alkali developability, the high quality color filter with few residues of the negative type resist composition for color filters in an unexposed part can be obtained.

<Block copolymer>

The block copolymer in the pigment dispersant which consists of the said salt type block copolymer has a structural unit (1) represented by the said General formula (1), and a structural unit (2) represented by the said General formula (2).

In Formula 1, R ¹ represents a hydrogen atom or a methyl group, and R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Here, the C1-C8 alkyl group may be any of linear, branched or cyclic. As such an alkyl group, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, various pentyl groups, various hexyl groups, various octyl groups and cyclophene A methyl group, a cyclohexyl group, a cyclooctyl group, etc. are mentioned. Among these, methyl group and ethyl group are preferable.

In the present invention, R ² and R ³ may be the same as or different from each other.

A is an alkylene group having 1 to 8 carbon atoms,-[CH (R ⁶ ) -CH (R ⁷ ) -O] _x -CH (R ⁶ ) -CH (R ⁷ )-or [(CH ₂ ) _y -O] _z - (CH _{2) y} - is a divalent group represented by. Here, the alkylene group having 1 to 8 carbon atoms may be linear or branched, for example, methylene group, ethylene group, trimethylene group, propylene group, various butylene groups, various pentylene groups, various hexylene groups And various octylene groups.

R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group.

x is an integer of 0 to 18, preferably an integer of 0 to 4, more preferably an integer of 0 to 2, y is an integer of 1 to 5, preferably an integer of 1 to 4, more preferably 2 Or three. z is an integer of 0-4, Preferably it is an integer of 0-2. In this invention, if x, y, and z exist in the said range, the negative type resist composition for color filters of this invention will become excellent in the dispersibility of a pigment.

As said A, a C1-C8 alkylene group is preferable and a methylene group and ethylene group are more preferable. If carbon number exists in the range of 1-8, the dispersibility of a pigment can be maintained favorable.

In Formula 2, R ⁴ is an alkyl group having 1 to 18 carbon atoms, a benzyl group, a phenyl group, a biphenyl group,-[CH (R ⁶ ) -CH (R ⁷ ) -O] _x -R ⁸ or-[(CH ₂ ) _y -O] _z -R ⁸ . In addition, when R <^4> has an aromatic ring, you may have a suitable substituent on the said aromatic ring, for example, a C1-C4 linear, branched alkyl group, etc.

The alkyl group having 1 to 18 carbon atoms may be linear, branched or cyclic, and for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group , tert-butyl, various pentyl, various hexyl, various octyl, various decyl, various dodecyl, various tetradecyl, various hexadecyl, various octadecyl, cyclopentyl, cyclohexyl, cyclo Octyl group, cyclododecyl group, bornyl group, isobornyl group, dicyclopentanyl group, adamantyl group, lower alkyl group substituted adamantyl group and the like.

R ⁶ and R ⁷ are the same as described above, R ⁸ is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms which may have a substituent, benzyl group, phenyl group, biphenyl group, -CHO, -CH ₂ CHO, -CO- CH = CH ₂ , -CO-C (CH ₃ ) = CH ₂ or a monovalent group represented by -CH ₂ COOR ¹² , and R ¹² is a hydrogen atom or a linear, branched, cyclic alkyl group having 1 to 5 carbon atoms. .

R ⁸ may have a substituent, and examples of the substituent include a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms, halogen atoms such as F, Cl, and Br.

R ⁸ above The alkyl group having 1 to 18 carbon atoms is as shown in the above R ⁴ . In R ⁴ , x, y and z are as described above for A.

In this invention, it is preferable to use the thing which is excellent in the solubility with the solvent mentioned later as said R <^4> , Specifically, although it changes also depending on the structural unit etc. which comprise the said block copolymer, The said solvent is tetrahydrofuran , Toluene and the like, it is preferable to use a methyl group, ethyl group, benzyl group, etc., and when the solvent is lower polarity such as pentane, hexane, it is preferable to use a pentyl group, hexyl group, heptyl group and the like. .

Here, is a structural unit (2) including the R ⁴ have the availability of the solvent, the amino group and an acidic organic phosphorus compound to be described later of the structural units (1) forming the reason for setting, as the R ⁴ this It is because the dispersibility and stability of a pigment can be made especially excellent because the salt formation site to have high adsorption property with respect to a pigment.

In addition, the said R <^4> may be substituted by substituents, such as an alkoxy group, a hydroxyl group, a carboxyl group, an amino group, an epoxy group, a hydrogen bond forming group, in the range which does not prevent the dispersion performance of the said block copolymer, etc ..

As ratio m / n of the unit number m of the structural unit (1) used by this invention, and the unit number n of the structural unit (2), it is preferable to exist in the range of 0.01-1, and it is more preferable to exist in the range which is 0.05-0.5. Do. When ratio m / n exists in the said range, since the ratio of the salt formation site which the amino group which the said structural unit (1) has is formed becomes suitable, adsorption property with respect to the pigment mentioned later becomes favorable, and the said structural unit (2) Solubility with the said solvent does not become low, and dispersibility and stability of a pigment do not fall.

The number m of units of the structural unit (1) and the number n of units of the structural unit (2) in the block copolymer used in the present invention may each be an integer of 1 to 200, and are not particularly limited, but as m, 1 It is preferable to exist in the range of -20, and it is more preferable to exist in the range of 1-10. Moreover, as said n, it is preferable to exist in the range of 20-100.

Moreover, it is preferable that the weight average molecular weight Mw of the said block copolymer exists in the range of 500-20000, It is more preferable to exist in the range of 1000-15000, It is still more preferable to exist in the range of 3000-12000. By being in the said range, it becomes possible to disperse | distribute a pigment uniformly.

In addition, the said weight average molecular weight Mw is the value measured by GPC (gel permeation chromatography). Measurement was carried out using HLC-8120GPC manufactured by Tosoh Corporation, and the elution solvent was N-methylpyrrolidone added with 0.01 mol / liter of lithium bromide, and the polystyrene standard for calibration curve was Mw 377400, 210500, 96000. , 50400, 206500, 10850, 5460, 2930, 1300, 580 (above, Easi PS-2 series by Polymer Laboratories) and Mw 1090000 (manufactured by Tosoh Corporation) It was performed using TSK-GEL ALPHA-M × 2 (made by Tosoh Corporation).

 As a bonding order of the block copolymer used for this invention, what is necessary is just to have the structural unit (1) and the said structural unit (2), and to disperse | distribute the pigment mentioned later stably, although it does not specifically limit, The said structural unit It is preferable that (1) couple | bonded only at the end of the said block copolymer. That is, the structural unit (1) and the structural unit (2) may be combined in the order of the structural unit (1)-the structural unit (2), or the structural unit (1)-structural unit (2)-structural unit It may be combined in the order of (1), or may be combined in the order of structural unit (2) -structural unit (1) -structural unit (2), and structural unit (1) -structural unit (2) may be repeatedly Although it may be combined, in this invention, what combined together in order of structural unit (1)-structural unit (2) is especially preferable. This is because it is excellent in the adsorption property with respect to the pigment mentioned later, and can suppress aggregation of pigment dispersants using such a block copolymer effectively.

<Acidic organophosphorus compound>

The acidic organic phosphorus compound which forms a salt with the amino group which the structural unit (1) of the block copolymer which has the structural unit (1) represented by the said General formula (1) and the structural unit (2) represented by General formula (2) is It is a compound which has a structure represented by General formula (3). In the present invention, by using the acidic organophosphorus compound, it is possible to make the pigment dispersant excellent in dispersibility and stability of the pigment described later, and since the salt-forming site has high solubility in aqueous alkali solution during alkali development. It can be made excellent in alkali developability.

<Formula 3>

In the present invention, by using the acidic organophosphorus compound, it is possible to make the pigment dispersant excellent in dispersibility and stability of the pigment described later, and since the salt-forming site has high solubility in aqueous alkali solution during alkali development. It can be made excellent in alkali developability.

In Formula 3, R ⁵ and R ^{5 '} are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a benzyl group, a phenyl group, a biphenyl group,-[CH (R ⁹ ) -CH (R ¹⁰ ) -O] _a -R ¹¹ or-[(CH ₂ ) _b -O] _c -R ¹¹ or -OR ^{5 ''} . In addition, when R <^5> and R <^5>' has an aromatic ring, you may have a suitable substituent on the said aromatic ring, for example, a C1-C4 linear, branched alkyl group, etc.

The alkyl group having 1 to 18 carbon atoms is as shown in R ⁴ .

The alkenyl group having 1 to 18 carbon atoms may be any of linear, branched or cyclic. Examples of such alkenyl groups include vinyl groups, allyl groups, propenyl groups, various butenyl groups, various hexenyl groups, various octenyl groups, various desenyl groups, various dodecenyl groups, various tetradecenyl groups, and various hexadecenyl groups. A group, various octadecenyl groups, a cyclopentenyl group, a cyclohexenyl group, a cyclooctenyl group, etc. are mentioned.

R ^{5 ''} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a benzyl group, a phenyl group, a biphenyl group,-[CH (R ⁹ ) -CH (R ¹⁰ ) -O] _a -R ^11, or It is a monovalent group represented by-[(CH ₂ ) _b -O] _c -R ¹¹ . The alkyl group having 1 to 18 carbon atoms is as shown in R ⁴ , and the alkenyl group having 2 to 18 carbon atoms is as shown in R ⁵ and R ^{5 ′} . In addition, when R < ⁵ >> has an aromatic ring, you may have a suitable substituent on the said aromatic ring, for example, a C1-C4 linear, branched alkyl group, etc.

R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a methyl group. R ¹¹ is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms which may have a substituent, benzyl group, phenyl group, biphenyl group, -CHO, -CH ₂ CHO, -CO-CH = CH ₂ , -CO-C (CH ₃ ) = CH ₂ or a monovalent group represented by -CH ₂ COOR ¹² , and R ¹² is a hydrogen atom or a linear, branched, cyclic alkyl group having 1 to 5 carbon atoms.

As a substituent which can be contained in the monovalent group represented by said R <^11> , C1-C4 linear, branched or cyclic alkyl group, halogen atoms, such as F, Cl, Br, etc. are mentioned, for example.

The alkyl group having 1 to 18 carbon atoms in R ¹¹ is as described above for R ⁴ . R ¹² is a hydrogen atom or a straight, branched or cyclic alkyl group having 1 to 5 carbon atoms.

In said R <^5> , R <^5>' and R <^5>' , a is an integer of 0-18, b is an integer of 1-5, c is an integer of 0-18.

As the acidic organophosphorus compound represented by the formula (3), R ⁵ , R ^{5 ′} and R ^{5 ″} are methyl, isopropyl, n-butyl, 2-ethylhexyl, vinyl, allyl or-(CH (R ⁹ ) -CH (R ¹⁰ ) -O) _a -R ¹¹ or-((CH ₂ ) _b -O) _c -R ¹¹ , and R ¹¹ is -CO-CH = CH ₂ or -CO-C It is preferable that (CH ₃ ) = CH ₂ , and among them, having a polymerizable group, that is, a vinyl group, an allyl group, or-(CH (R ⁹ ) -CH (R ¹⁰ ) -O) _a -R ¹¹ or- ((CH ₂ ) _b -O) _c -R ¹¹ , and R ¹¹ is preferably -CO-CH = CH ₂ or -CO-C (CH ₃ ) = CH ₂ , in particular R ⁵ , R ^{5 ′} And R ^{5 ''} is preferably a (meth) acryloyl group such as vinyl group, allyl group, 2-methacryloyloxyethyl group, or 2-acryloyloxyethyl group.

R ⁵ , R ^{5 '} and R ^5'' in the acidic organophosphorus compound are methyl, isopropyl, n-butyl, 2-ethylhexyl, vinyl, allyl, or-(CH (R ⁹ )- CH (R ¹⁰ ) -O) _a -R ¹¹ or-((CH ₂ ) _b -O) _c -R ¹¹ , and R ¹¹ is -CO-CH = CH ₂ or -CO-C (CH ₃ ) = CH ₂ Im as can be the acid organophosphorus compound that is excellent in pigment dispersibility and alkali-developability. R ⁵ , R ^{5 ′} and R ^{5 ''} are a vinyl group, allyl group, or-(CH (R ⁹ ) -CH (R ¹⁰ ) -O) _a -R ¹¹ or-((CH ₂ ) _b -O) _c -R ¹¹ and R ¹¹ is -CO-CH = CH ₂ or -CO-C (CH ₃ ) = CH ₂ , such that the acidic organic phosphorus compound includes a polymerizable group. Therefore, at the time of exposure at the time of forming a colored layer using the negative type resist composition for color filters of this invention, it is contained in the said polymerizable groups and / or the said polymerizable group and the negative type resist composition for color filters of this invention. The alkali-soluble resin used, a polyfunctional monomer, etc. can be easily polymerized, and it becomes possible for the said pigment dispersant to exist stably in the colored layer of a color filter. Therefore, when manufacturing a liquid crystal display device using such a color filter, it can prevent that the said pigment dispersant bleeds out with a liquid crystal layer.

Moreover, since the said acidic organophosphorus compound contains a polymeric group, before using it for formation of a colored layer, the polymerizable groups which the said acidic organophosphorus compound have can be polymerized, and as a result, a pigment dispersing agent becomes high molecular weight, a colored layer In the case of development of formation, the negative type resist composition for color filters in unexposed part can be made especially excellent in alkali developability.

Here, the reason which can be made especially excellent in alkali developability by superposing | polymerizing the said polymerizable groups is inferred as follows.

That is, the added pigment dispersant does not contribute to the dispersibility improvement of the pigment which the whole mentions later, and a part of said pigment dispersant exists in the state liberated from the said pigment. In addition, since the said pigment dispersant generally reduces alkali developability, when there are many pigment dispersants in a free state, it will inhibit alkali image development at the time of image development of a colored layer.

On the other hand, the polymerizable groups are polymerized before being used for forming the colored layer to make high molecular weight, so that at the time of developing the colored layer, the pigment dispersant liberated in the negative type resist composition for color filters can be reduced. For this reason, the inhibition of alkali image development by the liberated pigment dispersant can be reduced, and the negative type resist composition for color filters in unexposed location can be made especially excellent in alkali developability.

Content of the said acidic organophosphorus compound in the (A) pigment dispersant used by this invention should just be what exhibits favorable pigment dispersion stability, and there is no restriction | limiting in particular, Generally, it is 0.05 with respect to the amino group contained in the said structural unit (1). About mol%-about 4.0 mol%, Preferably it exists in the range of 0.1 mol%-2.0 mol%, More preferably, it exists in the range of 0.2 mol%-1.0 mol%.

<Production of Salt Block Copolymers>

In this invention, as a manufacturing method of the salt type block copolymer used as the pigment dispersing agent of (A) component, it has the above-mentioned structural unit (1) and structural unit (2), and the amino group which structural unit (1) has, and the said chemical formula The acidic organophosphorus compound represented by 3 may be any method capable of producing a salt, and is not particularly limited. In the present invention, for example, the above-mentioned structural unit (1) and the structural unit (2) are polymerized using a known polymerization means, and then dissolved or dispersed in a solvent described later, and then the acidic organic phosphorus compound in the solvent. It can manufacture by adding and stirring.

As said polymerization means, what is necessary is just a means which can superpose | polymerize the said structural unit (1) and a structural unit (2) by a desired unit ratio, and can make it desired molecular weight, and is not specifically limited, The method generally used for superposition | polymerization of a compound which has a vinyl group. Can be adopted, and for example, anionic polymerization, living radical polymerization or the like can be used. In the present invention, inter alia, [J. Am. Chem. Soc. 105, 5706 (1983), it is preferable to use a method in which the polymerization proceeds in a living manner such as group transfer polymerization (GTP). According to this method, since it is easy to make molecular weight, molecular weight distribution, etc. into a desired range, characteristics, such as dispersibility and alkali developability, of the said pigment dispersant can be made uniform.

In the negative type resist composition for color filters of the present invention, as the pigment dispersant as the component (A), one type of the salt block copolymer may be used, or two or more types thereof may be used in combination, and the content of the pigment used is Although it selects suitably according to a kind, solid content concentration in the said negative resist composition, etc., with respect to 100 mass parts of (B) pigments mentioned later, it is normally in the range of 5 mass parts-200 mass parts, and is 10 mass parts-100 mass parts It is preferable to exist in it, and it is more preferable to exist in the range of 20 mass parts-80 mass parts. When content of a salt type block copolymer exists in the said range, a pigment can be disperse | distributed uniformly, and the coloring layer with sufficient hardness can be formed relatively without the compounding ratio of alkali-soluble resin and a polyfunctional monomer falling.

((B) Pigment)

In the negative type resist composition for color filters of the present invention, the pigment used as the component (B) may be one capable of desired color development when the color layer of the color filter is formed, and is not particularly limited, and various organic or inorganic colorants may be used alone. Or two or more kinds thereof can be mixed.

<Kind of pigment>

As said organic coloring agent, dye, an organic pigment, a natural pigment, etc. can be used, for example. As a specific example of an organic pigment, the compound classified by Pigment by the color index (C.I .; the Society of Dyers and Colorists) is mentioned.

As such a compound, it is C.I. Pigment Yellow 1, C.I. Pigment Yellow 3, C.I. Pigment Yellow 12, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 180, C.I. Yellow pigments such as pigment yellow 185; C.I. Pigment Red 1, C.I. Pigment Red 2, C.I. Pigment Red 3, C.I. Pigment Red 242, C.I. Pigment Red 254, C.I. Red pigments such as Pigment Red 177; C.I. Pigment Blue 15, C.I. Pigment Blue 15: 3, C.I. Pigment Blue 15: 4, C.I. Blue pigments such as Pigment Blue 15: 6; C.I. Violet pigments such as pigment violet 23; And Pigment Green 36, C.I. The color index (C.I.) numbers, such as green pigments, such as pigment green 58, are mentioned.

As the inorganic colorant, for example, an inorganic pigment, a sieving pigment, or the like can be used. Specific examples include titanium oxide, silica, barium sulfate, calcium carbonate, zinc oxide, lead sulfate, yellow lead, zinc sulfur, iron group (red iron oxide ( 3)), cadmium, ultramarine blue, bluish blue, chromium oxide, cobalt rust, umber, titanium black, synthetic iron black, carbon black and the like.

<Particle size of the pigment>

As an average particle diameter of the pigment used for this invention, what is necessary is just to be capable of color development, when it is set as the colored layer of a color filter, It does not specifically limit, Although it changes also depending on the kind of pigment used, it exists in the range of 10 nm-100 nm. It is preferable and it is more preferable to exist in the range of 10 nm-50 nm. When the average particle diameter of the said pigment is the said range, the liquid crystal display device manufactured using the negative type resist composition for color filters of this invention can be made into high contrast and high quality. In addition, in the case of the conventional pigment dispersant, a large amount of the pigment dispersant is required as the particle size of the pigment becomes smaller, and there is a possibility that problems such as deterioration of alkali developability and increase of residue may occur, but the negative type resist for a color filter of the present invention Since the pigment dispersant used for a composition is excellent in alkali developability, there is little possibility of causing such a problem. Therefore, as the average particle diameter of the said pigment is shown to the said range, it is possible to exhibit the characteristic which the negative type resist composition for color filters of this invention has, so that compared with the conventional.

In addition, the average particle diameter of the said pigment can be calculated | required by the method of directly measuring the magnitude | size of a primary particle from an electron micrograph. Specifically, the minor axis diameter and major axis diameter of each primary particle were measured, and the average was made into the particle diameter of the particle | grains. Next, with respect to 100 or more particles, the volume (weight) of each particle was calculated | required approximated to the rectangular parallelepiped of the particle size calculated | required, the volume average particle diameter was calculated | required, and it was made into the average particle diameter. On the other hand, the electron microscope can obtain the same result using either a transmission type (TEM) or a scanning type (SEM).

In the negative resist composition for color filters of this invention, content of the pigment used as (B) component should just be able to develop desired color, when it is set as the colored layer of a color filter, It does not specifically limit, According to the kind of pigment used Although different, it is preferable to exist in the range of 20 mass%-100 mass% with respect to solid content other than the said pigment in the negative type resist composition for color filters, and it is more preferable to exist in the range which is 30 mass%-80 mass%. When content of the said pigment is the said range, it can be set as the negative resist composition for color filters which can form the colored layer which can develop desired color, and can disperse | distribute uniformly in the said negative resist composition for color filters.

In addition, the said solid content is all other than the solvent mentioned above, and also contains the polyfunctional monomer etc. which are melt | dissolved in the solvent.

((C) Alkali Soluble Resin)

In the negative type resist composition for color filters of the present invention, as the alkali-soluble resin used as the component (C), those generally used for the negative type resist can be used, and those having a solubility in the aqueous alkali solution may be used, and are not particularly limited. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) Acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n- In octyl (meth) acrylate, n-decyl (meth) acrylate, benzyl (meth) acrylate, styrene, (gamma) -methylstyrene, N-vinyl-2-pyrrolidone, glycidyl (meth) acrylate, etc. 1 kind selected 1 selected from a dimer of (meth) acrylic acid and acrylic acid (for example, Toagosei Chemical Co., Ltd. M-5600), itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid, and anhydrides thereof. The copolymer containing species or more can also be illustrated. Moreover, although the polymer etc. which added the ethylenically unsaturated compound which has glycidyl group or a hydroxyl group to the said copolymer can be illustrated, it is not limited to these.

Among them, by adding an ethylenically unsaturated compound having a glycidyl group or a hydroxyl group to the copolymer, the polymer having an ethylenically unsaturated bond, etc. can be polymerized with the polyfunctional monomer described later at the time of exposure, and the colored layer is more. It is especially preferable at the point which becomes stable.

In the negative type resist composition for color filters of the present invention, the alkali-soluble resin used as the component (C) may be used alone or in combination of two or more types, and as the content thereof, the negative type resist for color filters may be used. With respect to 100 mass parts of pigments contained in a composition, it is normally in the range of 10 mass parts-1000 mass parts, Preferably it exists in the range of 20 mass parts-500 mass parts. If the content of the alkali-soluble resin is too small, sufficient alkali developability may not be obtained. If the content of the alkali-soluble resin is too large, the proportion of the pigment may be relatively low, and a sufficient coloring concentration may not be obtained.

((D) polyfunctional monomer)

In the negative type resist composition for color filters of the present invention, the polyfunctional monomer used as the component (D) may be polymerizable by a photoinitiator described later, and is not particularly limited. Usually, two or more ethylenically unsaturated double bonds are used. The compound which has is used, and it is especially preferable that it is a polyfunctional (meth) acrylate which has 2 or more of acryloyl group or methacryloyl group.

As such a polyfunctional (meth) acrylate, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, long chain aliphatic di (meth) acrylate Neopentyl glycol di (meth) acrylate, hydroxypivalate neopentyl glycoldi (meth) acrylate, stearic acid-modified pentaerythritoldi (meth) acrylate, propylene glycol di (meth) acrylate, glycerol di ( (Meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, dicyclopentanyldi ( Meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene di (meth) acrylate, triglycerol di (meth) acrylate, neopentyl Col modified trimethylolpropanedi (meth) acrylate, allylated cyclohexyldi (meth) acrylate, methoxylated cyclohexyldi (meth) acrylate, acrylated isocyanurate, bis (acryloxy neopentyl glycol) adipate , Bisphenol A di (meth) acrylate, tetrabromobisphenol A di (meth) acrylate, bisphenol S di (meth) acrylate, butanedioldi (meth) acrylate, di (meth) acrylate, phosphate ( And bifunctional (meth) acrylates such as meth) acrylate and zinc di (meth) acrylate.

Moreover, as trifunctional or more than trifunctional (meth) acrylate, For example, trimethylol propane tri (meth) acrylate, trimethylol ethane tri (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol tree ( Meth) acrylate, pentaerythritol tetra (meth) acrylate, alkyl modified pentaerythritol tri (meth) acrylate, succinic anhydride modified pentaerythritol tetra (meth) acrylate, triphosphate tri (meth) acrylate, tris ( Acryloxyethyl) isocyanurate, tris (methacryloxyethyl) isocyanurate, dipentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetraacrylate, alkyl modified dipentaerythritol tetra (meth) Acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl modified dipene Taerythritol penta (meth) acrylate, succinic anhydride modified dipentaerythritol penta (meth) acrylate, urethane tri (meth) acrylate, ester tri (meth) acrylate, urethane hexa (meth) acrylate, ester hexa (Meth) acrylate etc. are mentioned.

These polyfunctional (meth) acrylates may be used individually by 1 type, and may be used in combination of 2 or more type. In addition, when the photoresist (high sensitivity) which is excellent in the negative resist composition for color filters of this invention is required, it is preferable to have three (trifunctional) or more double bonds which a polyfunctional monomer can superpose | polymerize, for example, Pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are used preferably.

Although the content of the said polyfunctional monomer used as (D) component in the negative type resist composition for color filters of this invention does not have a restriction | limiting in particular, Usually, it is 5 mass parts-with respect to 100 mass parts of alkali-soluble resin of (C) component. It is about 500 mass parts, Preferably it exists in the range of 20 mass parts-300 mass parts. When content of a polyfunctional monomer is less than the said range, photocuring may not fully advance, an exposure part may elute, and when content of a polyfunctional monomer is more than the said range, alkali developability may fall.

((E) photoinitiator)

There is no restriction | limiting in particular as a photoinitiator used as (E) component in the negative type resist composition for color filters of this invention, It can select suitably from various photoinitiators conventionally known, and can use. For example, aromatic ketones such as benzophenone, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-ethylanthraquinone, phenanthrene, and benzo Benzoin ethers, such as phosphorus methyl ether, benzoin ethyl ether, and benzoin phenyl ether, benzoin, such as methyl benzoin and ethyl benzoin, 2- (o-chlorophenyl) -4,5-phenylimidazole 2 Dimer, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4,5-triarylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (m-methylphenyl) imidazole dimer, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2-trichloromethyl-5-styryl-1,3,4- Oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-methoxystyryl) -1,3 Halomethyl jade such as 4-oxadiazole Diazole Compound, 2,4-bis (trichloromethyl) -6-p-methoxystyryl-S-triazine, 2,4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl -1,3-butadienyl) -S-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-S-triazine, 2- (naphtho-1-yl)- 4,6-bis-trichloromethyl-S-triazine, 2- (4-ethoxy-naphtho-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- (4 Halomethyl-S-triazine-based compounds such as -butoxy-naphtho-1-yl) -4,6-bis-trichloromethyl-S-triazine and 2,2-dimethoxy-1,2-diphenyl Ethan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 1,2-benzyl-2-dimethylamino-1- (4-mor Polynophenyl) -butanone-1,1-hydroxy-cyclohexyl-phenylketone, benzyl, benzoylbenzoic acid, methyl benzoylbenzoate, 4-benzoyl-4'-methyldiphenylsulfide, benzyl methyl ketal, dimethylaminobenzo Ate, p-dimethylaminobenzoisoamyl, 2-n-butoxyethyl-4- Dimethylaminobenzoate, 2-chlorothioxanthone, 2,4-diethyl thioxanthone, 2,4-dimethyl thioxanthone, isopropyl thioxanthone, ethanone, 1- [9-ethyl-6- ( 2-Methylbenzoyl) -9H-carbazol-3-yl] -1- (o-acetyloxime), 4-benzoyl-methyldiphenylsulfide, 1-hydroxy-cyclohexyl-phenylketone, 2-benzyl- 2- (dimethylamino) -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, α-dimethoxy-α-phenylacetophenone, phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide, 2-methyl-1- [4 -(Methylthio) phenyl] -2- (4-morpholinyl) -1-propanone etc. are mentioned. These photoinitiators may be used individually by 1 type, and may be used in combination of 2 or more type.

In the negative type resist composition for color filters of this invention, content of the photoinitiator used as (E) component is about 0.01 mass part-about 100 mass parts normally with respect to 100 mass parts of polyfunctional monomers of (D) component, Preferably Is in the range of 5 parts by mass to 60 parts by mass. If the content is less than the above range, the polymerization reaction cannot be sufficiently caused. Therefore, the hardness of the colored layer may not be sufficient. On the other hand, if the content is more than the above range, the pigment in the solid content of the negative type resist composition for color filters, etc. The content of is relatively small, and sufficient coloring concentration may not be obtained.

((F) solvent)

In the negative type resist composition for color filters of the present invention, the solvent used as the component (F) may be an organic solvent that does not react with each component in the resist composition, but may dissolve or disperse them, and is not particularly limited. . Specifically, Alcohol type, such as methyl alcohol, ethyl alcohol, N-propyl alcohol, isopropyl alcohol; Ether alcohols such as methoxy alcohol, ethoxy alcohol, methoxy ethoxy ethanol and ethoxy ethoxy ethanol; Ester systems such as ethyl acetate, butyl acetate, 3-methoxybutyl acetate, methyl methoxypropionate, ethyl ethoxypropionate and ethyl lactate; Ketones such as acetone, methyl isobutyl ketone and cyclohexanone; Ether alcohol acetates such as methoxy ethyl acetate, methoxy propyl acetate, methoxy butyl acetate, ethoxy ethyl acetate, ethyl cellosolve acetate, methoxy ethoxy ethyl acetate and ethoxy ethoxy ethyl acetate; Ethers such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and tetrahydrofuran; Aprotic amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; lactones such as γ-butyrolactone; Unsaturated hydrocarbons such as benzene, toluene, xylene and naphthalene; Organic solvents, such as saturated hydrocarbon type, such as n-heptane, n-hexane, and n-octane, are mentioned.

Among these, ether alcohol acetates such as methoxy ethyl acetate, ethoxy ethyl acetate, ethyl cellosolve acetate, methoxy ethoxy ethyl acetate and ethoxy ethoxy ethyl acetate; Ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and propylene glycol diethyl ether; Ester type | system | groups, such as 3-methoxy butyl acetate, methyl methoxy propionate, ethyl ethoxy propionate, ethyl lactate, etc. can be used preferably.

Especially, as a solvent used for this invention, MBA (3-methoxybutyl acetate), PGMEA (propylene glycol monomethyl ether acetate), DMDG (diethylene glycol dimethyl ether), diethylene glycol methyl ethyl ether, PGME (propylene) Glycol monomethyl ether) or a mixture thereof is preferable in view of solubility and coating suitability of the pigment dispersant.

Content of the solvent which is (F) component in the negative type resist composition for color filters of this invention should just be what can melt | dissolve or disperse | distribute each structure of the said negative type resist composition uniformly, and is not specifically limited. In this invention, it is preferable that the component except the solvent in the said negative resist composition exists in the range of 5 mass%-40 mass%, and it is more preferable to exist in the range of 10 mass%-30 mass%. By being in the said range, it can be set as the viscosity suitable for application | coating.

(Optional additive component)

In the negative resist composition for color filters of the present invention, various additives such as a polymerization terminator, a chain transfer agent, a leveling agent, a plasticizer, a surfactant, an antifoaming agent, and a silane, if necessary, within the range in which the object of the present invention is not impaired. Coupling agents, ultraviolet absorbers, adhesion promoters, and the like.

Among these, as the surfactant that can be used, for example, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol Dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine modified polyurethanes, and the like. In addition, fluorine-based surfactants can also be used.

Moreover, as a plasticizer, dibutyl phthalate, dioctyl phthalate, tricresyl, etc. are mentioned, for example. As a defoaming agent and a leveling agent, a silicone type, a fluorine type, an acryl type compound, etc. are mentioned, for example.

(Production of Negative Resist Composition for Color Filter)

As a manufacturing method of the negative type resist composition for color filters of this invention, the above-mentioned (A) pigment dispersant, (B) pigment, (C) alkali-soluble resin, (D) polyfunctional monomer, (E) photoinitiator And various additive components to be used if desired, as long as the method can dissolve or disperse uniformly in the solvent (F), and is not particularly limited, and can be produced by mixing using a known mixing means.

As a manufacturing method of the said negative resist composition, for example, (1) adding a pigment dispersant and a pigment in a solvent, and disperse | distributing using a dispersing agent to produce a pigment dispersion, to this alkali-soluble resin and a polyfunctional monomer And a photoinitiator, a method of adding and mixing various additives used if desired, and (2) simultaneously adding the above-described pigment dispersant, pigment, alkali-soluble resin, polyfunctional monomer, photoinitiator, and various additives used if desired in a solvent. And (3) adding and mixing the above-mentioned pigment dispersant, alkali-soluble resin, polyfunctional monomer, photoinitiator, and various additives used if desired, in a solvent, and then adding and mixing pigments therein. Can be mentioned.

Among these methods, the method of (1) is preferable in that the aggregation of pigments can be effectively prevented and uniformly dispersed. In this case, as content of the solvent in a pigment dispersion liquid, the inside of the range of 60 mass%-90 mass% is preferable from a viewpoint of the dispersibility of the said pigment, stability of pigment dispersion time, chromaticity of the color filter obtained, etc.

In the production of the pigment dispersion in the method (1), as a disperser for dispersing the pigment, a roll mill such as a biaxial roll or a triaxial roll, a ball mill such as a ball mill or a vibrating ball mill, a paint shaker, a continuous disk type Bead mills, such as a bead mill and a continuous annular bead mill, etc. are mentioned. As preferable dispersion conditions of the bead mill, the bead diameter used is preferably in the range of 0.03 mm to 2 mm, more preferably in the range of 0.1 mm to 1 mm. Moreover, it is preferable to filter with a membrane filter of about 5.0 micrometers-about 0.2 micrometers after dispersion | distribution. Thereby, the pigment dispersion liquid excellent in the dispersibility of a pigment is obtained.

In addition, when the acidic organophosphorus compound contained in the pigment dispersant used for this invention has a polymeric group, after the said pigment dispersant and a photoinitiator are added to a solvent, for example, the pigment dispersant, a pigment, and a photoinitiator are added to a solvent. After dispersing or dissolving, light irradiation may be performed to polymerize the pigment dispersants. Thus, by disperse | distributing a pigment dispersing agent, the dispersion stability of a pigment can be improved in the negative type resist composition for color filters of this invention.

Next, the color filter of this invention is demonstrated.

[Color filter]

The color filter of this invention has a colored layer formed using the negative type resist composition for color filters of this invention mentioned above. It is characterized by the above-mentioned.

The color filter of this invention is demonstrated, referring drawings. 1 is a schematic cross-sectional view showing an example of the color filter of the present invention. According to FIG. 1, the color filter 10 of the present invention has a transparent substrate 1, a light shielding portion 2, and a colored layer 3.

Since the color filter of this invention is excellent in alkali developability by forming a colored layer using the negative type resist composition for color filters of this invention mentioned above, it has high productivity. Moreover, since it is excellent in alkali developability, it is a high quality with few residues of the negative type resist composition for color filters in an unexposed location.

(Color layer)

The colored layer used for the color filter of this invention should just be formed using the negative type resist composition for color filters of this invention mentioned above, Although it does not specifically limit, Usually, it is formed in the opening part of the light shielding part on the transparent substrate mentioned later According to the kind of pigment contained in the said negative resist composition for color filters, it is comprised by the coloring pattern of three or more colors.

In addition, the arrangement of the colored layer is not particularly limited, and can be, for example, a general arrangement such as a stripe type, a mosaic type, a triangle type, or a four pixel arrangement type. In addition, the width, area, etc. of a colored layer can be set arbitrarily.

Although the thickness of the said colored layer is suitably controlled by adjusting solid content concentration, a viscosity, etc. of a coating method, the negative type resist composition for color filters, it is preferable to exist in the range of 1 micrometer-5 micrometers normally.

The colored layer can be formed, for example, by the following method.

First, the negative resist composition for color filters of the present invention described above is applied onto a transparent substrate to be described later using a coating means such as spray coating method, dip coating method, bar coating method, call coating method or spin coating method. To form a wet coating film.

Subsequently, after drying the said wet coating film using a hotplate, oven, etc., it exposes to this through the mask of a predetermined pattern, photo-polymerizes alkali-soluble resin, a polyfunctional monomer, etc., and is negative type for a color filter. It is set as the coating film of a resist composition. As a light source used for exposure, ultraviolet rays, such as a low pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, an electron beam, etc. are mentioned, for example. The exposure amount is appropriately adjusted according to the thickness of the light source and the coating film to be used.

Moreover, in order to accelerate | stimulate a polymerization reaction after exposure, you may heat-process. Heating conditions are suitably selected according to the compounding ratio of each component in the negative type resist composition for color filters to be used, the thickness of a coating film, etc.

Next, it develops using a developing solution, and melt | dissolves and removes an unexposed part, and a coating film is formed in a desired pattern. As a developing solution, the solution which melt | dissolved alkali in water or a water-soluble solvent is used normally. An appropriate amount of surfactant or the like may be added to this alkaline solution. In addition, the developing method can adopt a general method.

After the development treatment, washing of the developer and drying of the cured coating film of the negative resist composition are usually performed, and a colored layer is formed. In addition, in order to fully harden a coating film after image development processing, you may heat-process. There is no restriction | limiting in particular as heating conditions, According to the use of a coating film, it selects suitably.

(Shading part)

The light shielding part in the color filter of this invention is formed in pattern shape on the transparent substrate mentioned later, and can be made to be the same as what is used as a light shielding part in a general color filter.

The pattern shape of the light shielding portion is not particularly limited, and examples thereof include shapes such as a stripe shape and a matrix shape. As this light-shielding part, what disperse | distributed or melt | dissolved black pigment in binder resin, metal thin films, such as chromium and chromium oxide, etc. are mentioned, for example. The metal thin film may be formed by stacking two layers of CrO _x films (x is an arbitrary number) and Cr films, and further reduces the reflectance of the CrO _x films (x is an arbitrary number), and CrN _y films (y is any ) And a Cr film may be stacked in three layers.

When the said light-shielding part disperse | distributes or melt | dissolves a black coloring agent in binder resin, as a formation method of this light-shielding part, what is necessary is just a method which can pattern a light-shielding part, It does not specifically limit, For example, using the photosensitive resin composition for light-shielding parts Photolithography, printing, inkjet, and the like.

In this case, when the printing method or the inkjet method is used as the method for forming the light shielding portion, as the binder resin, for example, polymethyl methacrylate resin, polyacrylate resin, polycarbonate resin, polyvinyl alcohol resin, polyvinyl film Lollidon resin, hydroxyethyl cellulose resin, carboxymethyl cellulose resin, polyvinyl chloride resin, melamine resin, phenol resin, alkyd resin, epoxy resin, polyurethane resin, polyester resin, maleic acid resin, polyamide resin, etc. Can be mentioned.

In addition, in the above case, when the photolithography method is used as the method for forming the light shielding portion, the binder resin may be, for example, a photosensitive resin having a reactive vinyl group such as acrylate, methacrylate, polyvinyl cinnamate or cyclized rubber. Resin is used. In this case, a photoinitiator may be added to the photosensitive resin composition for light-shielding parts containing a black coloring agent and photosensitive resin, Furthermore, a sensitizer, an applicability | paintability improving agent, a developing improving agent, a crosslinking agent, a polymerization inhibitor, a plasticizer, a flame retardant, etc. can be added as needed. May be added. In this invention, as said photosensitive resin composition for light shielding parts, the said negative type resist composition for color filters which has black pigments, such as carbon black and titanium black, can also be used as a pigment.

On the other hand, when the light shielding portion is a metal thin film, the method of forming the light shielding portion may be any method capable of patterning the light shielding portion, and is not particularly limited. Examples thereof include a photolithography method, a deposition method using a mask, a printing method, and the like. have.

As a film thickness of a light shielding part, in the case of a metal thin film, it sets to about 0.2 micrometer-about 0.4 micrometer, and when it disperses or dissolves a black colorant in binder resin, it sets to about 0.5 micrometer-2 micrometers.

(Transparent board)

As a transparent substrate in the color filter of this invention, what is necessary is just a base material transparent with respect to visible light, It does not specifically limit, The transparent substrate used for a general color filter can be used. Specific examples include transparent rigid materials having no flexibility, such as quartz glass, alkali free glass, and synthetic quartz plates, or transparent flexible materials having flexibility, such as transparent resin films and optical resin plates.

Although the thickness of the said transparent substrate is not specifically limited, According to the use of the color filter of this invention, the thing of about 100 micrometers-about 1 mm can be used, for example. The color filter of the present invention may be, for example, an overcoat layer, a transparent electrode layer, an alignment film, a columnar spacer, or the like formed on top of the transparent substrate, the light shielding portion, and the colored layer.

Next, the liquid crystal display device of the present invention will be described.

[Liquid crystal display device]

The liquid crystal display device of this invention has the color filter of this invention mentioned above, It is characterized by the above-mentioned. Such a liquid crystal display of the present invention will be described with reference to the drawings. 2 is a schematic view showing an example of the liquid crystal display of the present invention. As illustrated in FIG. 2, the liquid crystal display device 40 of the present invention includes a counter substrate 20 having a color filter 10, a TFT array substrate, and the like, the color filter 10, and the counter substrate 20. ) And the liquid crystal layer 30 formed therebetween.

In addition, the liquid crystal display device of this invention is not limited to the structure shown by this FIG. 2, In general, it can be set as a structure known as a liquid crystal display device using a color filter.

There is no restriction | limiting in particular as a drive system of the liquid crystal display device of this invention, The drive system generally used for a liquid crystal display device can be employ | adopted. As such a drive system, a TN system, an IPS system, an OCB system, an MVA system, etc. are mentioned, for example. In the present invention, any of these methods can be preferably used.

Moreover, as an opposing board | substrate, it can select suitably and can use according to the drive system etc. of the liquid crystal display device of this invention.

As the liquid crystal constituting the liquid crystal layer, various liquid crystals having different dielectric anisotropies and mixtures thereof can be used depending on the driving method of the liquid crystal display device of the present invention and the like.

As a formation method of a liquid crystal layer, the method generally used as a manufacturing method of a liquid crystal cell can be used, For example, a vacuum injection system, a liquid crystal dropping system, etc. are mentioned.

In the vacuum injection method, for example, a liquid crystal cell is prepared in advance using a color filter and a counter substrate, the liquid crystal is heated to be an isotropic liquid, and the liquid crystal cell is injected into the liquid crystal cell in the form of an isotropic liquid using a capillary effect, A liquid crystal layer can be formed by sealing with an adhesive agent. Thereafter, the liquid crystal cell can be aligned by slow cooling to room temperature.

In the liquid crystal dropping method, for example, a sealing compound is applied to the periphery of the color filter, the color filter is heated to a temperature at which the liquid crystal becomes isotropic, and the liquid crystal is dropped into the isotropic liquid state using a dispenser or the like, The liquid crystal layer can be formed by superimposing a color filter and a counter substrate under reduced pressure and adhering them through a sealing agent. Thereafter, the liquid crystal cell can be aligned by slow cooling to room temperature.

Next, although an Example demonstrates this invention still in detail, this invention is not limited at all by these examples.

1. Preparation of Block Copolymer A

In a 500 ml round-bottom four-necked flask equipped with a cooling tube, an addition rotor, an inlet for nitrogen, a mechanical stirrer, and a digital thermometer, 250 parts by weight of tetrahydrofuran (THF) and 5.81 parts by weight of dimethylketenemethyltrimethylsilylacetal as an initiator It added through the addition rotor, and performed nitrogen substitution sufficiently. 0.5 part by weight of a 1 M acetonitrile solution of tetrabutylammonium m-chlorobenzoate as a catalyst was injected using a syringe, and 100 parts by weight of methyl methacrylate of the first monomer was added dropwise over 60 minutes using an addition rotor. The temperature was kept below 40 ° C. by cooling the reaction flask in an ice bath. After 1 hour, 33.3 parts by weight of dimethylaminoethyl methacrylate as the second monomer was added dropwise over 20 minutes. After reacting for 1 hour, 1 part by weight of methanol was added to stop the reaction. The obtained block copolymer THF solution was reprecipitated in hexane, and refine | purified by filtration and vacuum drying, and the block copolymer A was obtained. Thus obtained block copolymer A was identified by GPC (gel permeation chromatography) under conditions of N-methylpyrrolidone, 0.01 M lithium bromide addition / polystyrene standard, and methyl methacrylate (MMA) and methacryl. The structural ratio MMA / DMAEMA of dimethylaminoethyl acid (DMAEMA) was 3/1, and the weight average molecular weight M _w : 4500, the average molecular weight M _n : 5330, and the polydispersity: 1.18.

2. Preparation of Block Copolymer B

2.32 parts by weight of dimethylketenmethyltrimethylsilyl acetal, 0.2 part by weight of a 1 M acetonitrile solution of tetrabutylammonium m-chlorobenzoate, 120 parts by weight of methyl methacrylate, 13.3 parts by weight of dimethylaminoethyl methacrylate, and 0.5 parts by weight of methanol A block copolymer B was obtained by the same method as the block copolymer A except for the above. The block copolymer B thus obtained was confirmed by the same method as the above block copolymer A, and the composition ratio MMA / DMAEMA of MMA and DMAEMA was 9/1, the weight average molecular weight M _w : 9940 and the average molecular weight M _n : 11800, polydispersity: 1.19.

3. Preparation of Salt Block Copolymer Solution

In a 100 ml round bottom flask, 5.0 parts by weight of block copolymer A was dissolved in 24.68 parts by weight of propylene glycol monomethyl ether acetate (PGMEA), and a methacryloxyethyl acid phosphate (hosmer M: Uni Chemical Co., Ltd.) as a salt-forming component. 1.17 parts by weight (equal molar amount with the DMAEMA unit of the block copolymer) was added, followed by stirring at a reaction temperature of 25 ° C. for 6 hours to obtain a salt type block copolymer solution A in which a phosphate having a solid content of 20% by mass was formed.

In the same manner, as shown in Table 1 below, salt block copolymer solutions B to G having a phosphate having a solid content of 20% by mass were formed by changing the block copolymer, the salt forming component, and the reaction temperature to form a quaternary ammonium salt. Salt type block copolymer solution H-K and the block copolymer solution L which did not form salt were obtained.

In addition, the said salt formation component was added so that it might be equimolar with the DMAEMA unit of a block copolymer.

4. Preparation of Pigment Dispersion

Next, 12 parts by weight of the prepared salt type block copolymer solution (block copolymer solutions A to L), 15 parts by weight of PGMEA, 3 parts by weight of a diketopyrrolopyrrole pigment (a) (PR254: average primary particle diameter: 30 nm), 0.3 60 parts by weight of mm zirconia beads were placed in a mayonnaise bottle, shaken for 1 hour with a paint shaker (manufactured by Asada Iron Works) as preliminary disintegration, and then 30 parts by weight of the dispersion and 60 parts by weight of zirconia beads having a particle diameter of 0.1 mm were placed in a mayonnaise bottle. It disperse | distributed for 3 hours with the paint shaker as this disintegration, and pigment dispersion liquids A-L were obtained.

Example 1

31 parts by weight of a binder component (9 parts by weight of an acrylic copolymer (54% active ingredient) as an alkali-soluble resin) and dipentaerythritol hexa which is a light or thermally polymerizable monomer as a polyfunctional monomer, in 46 parts by weight of the pigment dispersion A obtained above. 5 parts by weight of acrylate, and 2 parts by weight of 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one as a photoinitiator, and 15 parts by weight of propylene glycol monomethyl ether acetate) And 22 parts by weight of propylene glycol monomethyl ether acetate as a solvent were added, mixed until uniform, and further filtered through a pressure filtration device having a mesh size of 0.2 µm to obtain a negative type resist composition A for color filters.

[Examples 2 to 7, Comparative Examples 1 to 5]

In the same manner as in Example 1, except that the pigment dispersions B to L were used instead of the pigment dispersion A, the negative resist compositions B to L for color filters were obtained.

[evaluation]

The pigment dispersion stability and alkali developability were evaluated about the negative type resist composition for color filters obtained by the Example and the comparative example. The results are shown in Table 2 below.

(Pigment dispersion stability evaluation)

As an evaluation of the pigment dispersion stability of the negative type resist composition for color filters prepared in Examples and Comparative Examples, the pigment dispersion liquid used for the production of the negative type resist composition for color filters was allowed to stand at 40 ° C. for 1 week, before and after standing. The particle diameter of the said pigment dispersion liquid was measured. The microtrack particle size distribution meter by Nikkiso Corporation was used for the measurement of a particle size.

(Alkali developability evaluation)

After applying the negative type resist composition for color filters obtained by each example to the glass substrate (NH Technoglass Co., Ltd. product, "NA35") of thickness 0.7mm and 10 mm using a spin coater, And drying at 80 ° C. for 3 minutes using a hot plate to form a red colored layer having a thickness of 3.0 μm. 60 mJ / cm <2> of ultraviolet-rays were irradiated to this colored layer using the super-pressure mercury lamp through the photomask. Then, the glass plate in which the said colored layer was formed was shower-developed using 0.05 mass% potassium hydroxide aqueous solution as alkaline developing solution, and the time until the colored layer melt | dissolved completely and the glass surface of the location which formed the said colored layer appears is shown. It measured as developing time.

In Table 2, as apparent from the contrast between Examples 1 to 7 and Comparative Examples 1 to 4, in Examples 1 to 7, it was confirmed that the alkali development time was greatly shortened and the alkali developability was excellent. In addition, it was confirmed that the pigment dispersion liquid used in the preparation of the negative type resist composition for color filters of Examples 1 to 7 exhibited excellent dispersion stability because no particle increase of pigment particles occurred.

In addition, the comparative example 5 using the block copolymer solution L which did not form a salt was gelatinized after 1 week standing in the said pigment dispersion stability evaluation. Moreover, the particle size of the particle | grains in a pigment dispersion liquid was large, the filtration by the pressure filtration apparatus of mesh size 0.2 micrometer was not possible, and the negative type resist composition for color filters could not be manufactured.

Example 8

2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) (V-70: Wako Pure Chemical Industries, Ltd.) as an initiator with respect to 30 weight part of pigment dispersion A obtained above in a 50 ml screw tube. 0.025 parts by weight of the prepared product) was reacted at 50 ° C for 10 hours while sonicating, thereby obtaining a complexed pigment dispersion M obtained by polymerizing double bond sites contained in methacryloxyethyl phosphate as a salt-forming component.

Subsequently, the negative type resist composition M for color filters was obtained like Example 1 except having used complexed pigment dispersion M instead of pigment dispersion A.

[evaluation]

The pigment dispersion stability and alkali developability were evaluated about the negative resist composition M for color filters obtained by Example 8. The results are shown in Table 2 above.

1 is a schematic diagram showing an example of a color filter of the present invention.

2 is a schematic view showing an example of a liquid crystal display of the present invention.

<Brief description of symbols for the main parts of the drawings>

One … Transparent substrate

2 … Shading part

3…. Colored layer

10... Color filter

20... Opposing substrate

30. Liquid crystal layer

40…. Liquid crystal display

Claims (16)

It is a negative type resist composition for color filters which has (A) a pigment dispersant, (B) pigment, (C) alkali-soluble resin, (D) polyfunctional monomer, (E) photoinitiator, and (F) solvent, The (A) pigment dispersant has a structural unit (1) represented by the following general formula (1) and a structural unit (2) represented by the following general formula (2), and an amino group which the structural unit (1) has and an acid represented by the following general formula (3) An organic phosphorus compound is a block copolymer in which a salt was formed, The negative type resist composition for color filters. <Formula 1>

<Formula 2>

<Formula 3>

In Formulas 1-3, R <^1> is a hydrogen atom or a methyl group, R <^2> and R <^3> is respectively independently a hydrogen atom or a C1-C8 alkyl group, A is a C1-C8 alkylene group, R <^4> is C1-C8 18 alkyl groups, benzyl groups, phenyl groups Or-[(CH ₂ ) _y -O] _z -R ⁸ , and R ⁵ and R ^{5 '} each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, and a benzyl group , A phenyl group, a biphenyl group, represented by-[CH (R ⁹ ) -CH (R ¹⁰ ) -O] _a -R ¹¹ or-[(CH ₂ ) _b -O] _c -R ¹¹ or -OR ^{5 ''} Monovalent, R ^{5 ''} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a benzyl group, a phenyl group, a biphenyl group,-[CH (R ⁹ ) -CH (R ¹⁰ ) -O] _a -R ¹¹ or- Is a monovalent group represented by [(CH ₂ ) _b -O] _c -R ¹¹ , R ⁹ and R ¹⁰ are each independently a hydrogen atom or a methyl group, R ⁸ and R ¹¹ are each independently a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, a benzyl group, a phenyl group, a biphenyl group, -CHO, Is a monovalent group represented by -CH ₂ CHO, -CO-CH = CH ₂ , -CO-C (CH ₃ ) = CH ₂ or -CH ₂ COOR ¹² , and R ¹² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms ego, a is an integer from 0 to 18, y and b are integers from 1 to 5, z and c are integers from 0 to 18, and m and n each represent an integer from 1 to 200.] The negative type resist composition for color filters according to claim 1, wherein R ⁵ and R ^{5 '} in the acidic organic phosphorus compound have a polymerizable group. The negative type resist composition for color filters according to claim 2, wherein the polymerizable group is a vinyl group, a (meth) acryloyl group or an allyl group. The negative resist composition for color filters according to any one of claims 1 to 3, wherein the average particle diameter of the pigment (B) is in the range of 10 nm to 100 nm. It has a colored layer formed using the negative type resist composition for color filters in any one of Claims 1-3, The color filter characterized by the above-mentioned. It has the color filter of Claim 5, The liquid crystal display device characterized by the above-mentioned. It has a colored layer formed using the negative type resist composition for color filters of Claim 4, The color filter characterized by the above-mentioned. It has the color filter of Claim 7, The liquid crystal display device characterized by the above-mentioned. (A) It is a pigment dispersion liquid which has a pigment dispersant, (B) pigment, and (F) solvent, The structural unit represented by the structural unit (1) represented by following General formula (1), and the following general formula (2) The pigment dispersion liquid for color filters which has (2), The amino group which the said structural unit (1) has, and the acidic organic phosphorus compound represented by following formula (3) is a block copolymer in which the salt formed. <Formula 1>

<Formula 2>

<Formula 3>

In Formulas 1-3, R <^1> is a hydrogen atom or a methyl group, R <^2> and R <^3> is respectively independently a hydrogen atom or a C1-C8 alkyl group, A is a C1-C8 alkylene group, R <^4> is C1-C8 18 alkyl groups, benzyl groups, phenyl groups Or-[(CH ₂ ) _y -O] _z -R ⁸ , and R ⁵ and R ^{5 '} each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, and a benzyl group , A phenyl group, a biphenyl group, represented by-[CH (R ⁹ ) -CH (R ¹⁰ ) -O] _a -R ¹¹ or-[(CH ₂ ) _b -O] _c -R ¹¹ or -OR ^{5 ''} Monovalent, R ^{5 ''} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a benzyl group, a phenyl group, a biphenyl group,-[CH (R ⁹ ) -CH (R ¹⁰ ) -O] _a -R ¹¹ or- Is a monovalent group represented by [(CH ₂ ) _b -O] _c -R ¹¹ , R ⁹ and R ¹⁰ are each independently a hydrogen atom or a methyl group, R ⁸ and R ¹¹ are each independently a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, a benzyl group, a phenyl group, a biphenyl group, -CHO, Is a monovalent group represented by -CH ₂ CHO, -CO-CH = CH ₂ , -CO-C (CH ₃ ) = CH ₂ or -CH ₂ COOR ¹² , and R ¹² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms ego, a is an integer from 0 to 18, y and b are integers from 1 to 5, z and c are integers from 0 to 18, and m and n each represent an integer from 1 to 200.] 10. The pigment dispersion liquid for color filters according to claim 9, wherein R ⁵ and R ^{5 '} in the acidic organophosphorus compound have a polymerizable group. The pigment dispersion liquid for color filters according to claim 10, wherein the polymerizable group is a vinyl group, a (meth) acryloyl group or an allyl group. The pigment dispersion liquid for color filters as described in any one of Claims 9-11 whose average particle diameter of the said (B) pigment exists in the range of 10 nm-100 nm. (A) As a pigment dispersant, it has the structural unit (1) represented by following formula (1) and the structural unit (2) represented by following formula (2), The amino group which the structural unit (1) has is represented by the acid represented by following formula (3) Preparing a block copolymer in which an organic phosphorus compound has formed a salt, The manufacturing method of the pigment dispersion liquid for color filters which has the process of adding the said (A) pigment dispersing agent and (B) pigment in (F) solvent and disperse | distributing a pigment. <Formula 1>

<Formula 2>

<Formula 3>

In Formulas 1-3, R <^1> is a hydrogen atom or a methyl group, R <^2> and R <^3> is respectively independently a hydrogen atom or a C1-C8 alkyl group, A is a C1-C8 alkylene group, R <^4> is C1-C8 18 alkyl groups, benzyl groups, phenyl groups Or-[(CH ₂ ) _y -O] _z -R ⁸ , and R ⁵ and R ^{5 '} each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, and a benzyl group , A phenyl group, a biphenyl group, represented by-[CH (R ⁹ ) -CH (R ¹⁰ ) -O] _a -R ¹¹ or-[(CH ₂ ) _b -O] _c -R ¹¹ or -OR ^{5 ''} Monovalent R ^{5 ''} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a benzyl group, a phenyl group, a biphenyl group,-[CH (R ⁹ ) -CH (R ¹⁰ ) -O] _a -R ¹¹ or- Is a monovalent group represented by [(CH ₂ ) _b -O] _c -R ¹¹ , R ⁹ and R ¹⁰ are each independently a hydrogen atom or a methyl group, R ⁸ and R ¹¹ are each independently a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, a benzyl group, a phenyl group, a biphenyl group, -CHO, Is a monovalent group represented by -CH ₂ CHO, -CO-CH = CH ₂ , -CO-C (CH ₃ ) = CH ₂ or -CH ₂ COOR ¹² , and R ¹² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms ego, a is an integer from 0 to 18, y and b are integers from 1 to 5, z and c are integers from 0 to 18, and m and n each represent an integer from 1 to 200.] (A) As a pigment dispersant, it has the structural unit (1) represented by following formula (1) and the structural unit (2) represented by following formula (2), The amino group which the structural unit (1) has is represented by the acid represented by following formula (3) Preparing a block copolymer in which an organic phosphorus compound has formed a salt, (F) adding the said (A) pigment dispersing agent and (B) pigment in a solvent, and disperse | distributing a pigment, The manufacturing method of the negative resist composition for color filters which has a process of adding and mixing (C) alkali-soluble resin, (D) polyfunctional monomer, and (E) photoinitiator to the pigment dispersion liquid obtained at the said process. <Formula 1>

<Formula 2>

<Formula 3>

In Formulas 1-3, R <^1> is a hydrogen atom or a methyl group, R <^2> and R <^3> is respectively independently a hydrogen atom or a C1-C8 alkyl group, A is a C1-C8 alkylene group, R <^4> is C1-C8 18 alkyl groups, benzyl groups, phenyl groups Or-[(CH ₂ ) _y -O] _z -R ⁸ , and R ⁵ and R ^{5 '} each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, and a benzyl group , A phenyl group, a biphenyl group, represented by-[CH (R ⁹ ) -CH (R ¹⁰ ) -O] _a -R ¹¹ or-[(CH ₂ ) _b -O] _c -R ¹¹ or -OR ^{5 ''} Monovalent, R ^{5 ''} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a benzyl group, a phenyl group, a biphenyl group,-[CH (R ⁹ ) -CH (R ¹⁰ ) -O] _a -R ¹¹ or- Is a monovalent group represented by [(CH ₂ ) _b -O] _c -R ¹¹ , R ⁹ and R ¹⁰ are each independently a hydrogen atom or a methyl group, R ⁸ and R ¹¹ are each independently a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, a benzyl group, a phenyl group, a biphenyl group, -CHO, Is a monovalent group represented by -CH ₂ CHO, -CO-CH = CH ₂ , -CO-C (CH ₃ ) = CH ₂ or -CH ₂ COOR ¹² , and R ¹² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms ego, a is an integer from 0 to 18, y and b are integers from 1 to 5, z and c are integers from 0 to 18, and m and n each represent an integer from 1 to 200.] It has a colored layer formed using the negative type resist composition for color filters obtained by the manufacturing method of Claim 14, The color filter characterized by the above-mentioned. It has the color filter of Claim 15, The liquid crystal display device characterized by the above-mentioned.

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