TW200919087A - Negative type resist composition for color filter, color filter using same, and liquid crystal display - Google Patents

Abstract

The present invention is aimed mainly at providing a negative type resist composition for a color filter, which resist composition has excellent pigment dispersibility and alkaline developability. The above problem is solved according to the present invention by providing the negative type resist composition for the color filter comprising (A) a pigment dispersant, (B) a pigment, (C) an alkaline-soluble resin, (D) a polyfunctional monomer, (E) a photo initiator and (F) a solvent, wherein the pigment dispersant (A) is a block copolymer which includes constituent a unit (1) represented by the following general formula (I) and a constituent unit (2) represented by the following general formula (II), and in which a salt is formed between an amino group possessed by the constituent unit (1) and an acidic organic phosphorus compound represented by the following general formula (III).

Description

200919087 VI. Description of the Invention: [Technical Field to Which the Invention Is Ascribed] The present invention relates to a pigment-dispersible, negative-type photoresist composition. [Prior Art] Color filters with excellent alkali developability Near==Manpowered electric materials are developed, and the material side is turned off. The demand for liquid crystal displays is increasing. In addition, the popularity of the sputum is increasing. Moreover, the near-vehicle=crystal display market is showing a more ambiguous liquid crystal display with a much more sloppy mrr. In this case, the quality of the clothes, especially the color fishing with the function of making the liquid show dry and crying - ο A, ra 2 nights: display ^ (4) color is expected to be more HW ', In this way, as a method of manufacturing a general-purpose color light-receiving sheet, a substrate having a light-shielding portion formed in a pattern is used, and the shaft is divided into light-hard 2 light by the respective colors (four). A method in which a coating film composed of a product is subjected to exposure inspection through a photomask having a desired pattern shape to form a colored layer of each color into a pattern. (4) The photocurable silk composition is used in the production of the color (4), and the pigment dispersant is added to remove the pigment in a uniform manner, and the soluble resin is added. A polyfunctional monomer, a photoinitiator, and a solvent. The color of the photocurable photoresist composition is 97311527 200919087. The dispersant 4 is insufficient in the coloring layer of the color filter. The colored layer may have color unevenness. Excellent dispersibility. As a photocurable photoresist composition having such excellent dispersibility =: having a pigment dispersant, a dispersing agent is used, which has a structure of four powders and four elements. The composition of the segmented copolymer and/or the Β+Β block copolymer of the coloring material (Patent Document υ. /Coloring film ο Furthermore, the demand for high contrast of liquid crystal display devices in recent years is being It is possible to achieve such a requirement, and it is required to refine the pigment. Therefore, in the composition of the resistive photoresist, the surface area of the simple one is increased, and it is necessary to increase the amount of the pigment dispersant required for the uniform dispersion of the pigment. = However, as disclosed in the patent literature! Containing the four-level ammonium test, Knife-Temperant's can ensure the uniform dispersibility of the pigment by increasing the amount of addition. The time required for the long-term exposure of the unexposed photocurable photoresist composition on the board: and the problem of deterioration in quality occur. (4) Productivity [Patent Document 1] Japanese Patent Laid-Open No. Hei 2__31713 [Summary of the Invention] Solve the problem) ^ Listening is awkward The problem is formed by the person who is the main target. U-color excellent color light-emitting sheet is composed of a negative-type photoresist. 97115527 200919087 (Means for Solving the Problem) In order to solve the above problem, the color filter of the present invention is provided with a negative type. The photoresist composition includes: (A) a pigment dispersant, (B) a pigment, (C) an alkali-soluble resin, (D) a polyfunctional monomer, (E) a photoinitiator, and (F) a solvent. The color filter for a color filter is a negative resist composition, wherein the (A) pigment dispersant has the following structural formula (I) and the following general formula (II); The constituent unit (2) is a block copolymer of a salt of an acidic organic phosphorus compound represented by the following general formula (III), which is an amine group or a group of the above-mentioned structural unit (1). [Chemical 1] R1

Ο I A I (I) R2 ~ R3 [Chemical 2] R1

97131527 (II) 200919087 [Chemical 3] R5. R5-P-OH (III)

I o [In the formula (IMIII), R1 means a hydrogen atom or a methyl group; and 1^2 and R3 respectively mean a hydrogen atom or an alkyl group having 1 to 8 carbon atoms; a means a carbon number of 1 to 8; Alkyl, -[CH(R6)-CH(R7)-〇]x-CH(R6)-CH(R7)- or [(CH2)y-0]z-(CH2)y- 〇 a divalent group; R4 means an alkyl group having 1 to 18 carbon atoms, a benzyl group, a phenyl group, a pyridyl group, a biphenyl group, a pyridylphenyl group, or -[(CH2)y-〇]z-R8; R5, R5 means 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 pyridyl group, a biphenyl group, an acridine phenyl group, or a -CH. (R9)_CH(Rl〇)_〇]a_Rn or -[(1) valent group represented by CIWb-Ojc-R11 or -ο-r5" R5 means an alkyl group having 1 to 18 carbon atoms, carbon number 2~ Alkyl group of 18, alkenyl group, phenyl group, I) pyridyl group, biphenyl group, pyridylphenyl group, -[CIKWCIKIO-Oh-R11 or -[(CH2)b-0]c-Ru . R, R, R and R1() are each independently a hydrogen atom or a methyl group; and RS and R11 are each an independent hydrogen atom or an alkyl group, a benzyl group or a benzene having a carbon number of a substituent; Base, acridinyl, biphenyl, σ pyridine phenyl, —CH〇, —CH 2 CH 0 , —C0—CH=CH 2 , —C0—C(CH 3 )=CH 2 , or i valent group represented by —CHzCOOR 12 , R 12 Refers to a hydrogen atom or a carbon number of 5 carbon. X and a are integers of 〇18; 乂 and b are integers of 卜5; 2 and 〇 97131527 200919087 are integers of 0 to 18; ^ and η are integers of 1 to 200, respectively. According to the present invention, the pigment dispersant has the unit (1) which is not composed of the above general formula (I) and the unit (2) shown in the above general formula (II), and the constituent unit (1) The block copolymer of the amine group and the acidic organophosphorus compound represented by the above-mentioned general formula (III) enhances the adsorption of the above-mentioned constituent unit (1) to the above-mentioned constituent unit (1), and constitutes a unit (2) and The above-mentioned solvent is excellent in handle solubility, whereby the above-mentioned solvent can be obtained in the above-mentioned solvent, and thus the dispersibility and stability of the pigment can be excellent. Further, the salt formed by the amine group contained in the above-mentioned constituent unit (1) and the acidic organic dish compound by the acidic organic dish compound represented by the above formula (III) is used for the development of the acid. The water test solution used has ten solubility' and thus is excellent in developability. Therefore, when the if-color filter or the optical U-negative photoresist composition of the present invention is used, the development time can be shortened, and the productivity can be excellent. Further, since it is excellent in the developability of the test, it is possible to obtain a high-quality color calender having less residual composition of the negative-change photoresist composition for the color filter which is not exposed. In the present invention, R5 and R5 contained in the acidic organophosphorus compound preferably contain a polymerizable group, and the polymerizable group is preferably an ethylene group, a (meth) propyl group or an ally group. base. When the above-mentioned acidic organic squama compound contains a polymerizable group, when the photosensitive layer for a color filter of the present invention is used, when the exposure is performed for forming a coloring layer, the above polymerizable groups can be made to each other. And/or the above-mentioned polymerizable group, and the alkali-soluble resin and polyfunctional monomer contained in the negative disk resist group 97315527 200919087 of the present invention are easily polymerized in the I color; In the coloring layer of the light sheet, the above-mentioned pigment dispersing agent can be stably present. Therefore, when such a color light-passing sheet is used for the production of a liquid crystal display device, it is possible to prevent the above-mentioned pigment dispersant from penetrating into the liquid crystal layer or the like. Further, before the formation of the colored layer, by the polymerization of the (tetra)-compatible groups contained in the acidic organic filler, the color filter for the unexposed portion and the negative-filament composition for the optical sheet can be used. Alkali developability is particularly excellent. (In the invention, the average particle diameter of the above (8) pigment is preferably in the range of:: by setting the particle diameter of the above pigment to be within the range, by using the light filter using the color filter of the present invention The pure core piece formed by the resisting composition can be used for the high-contrast and high-quality liquid crystal display device. The available color-colored calendering sheet is formed by using the negative-type photoresist composition for the color filter described above. In the case of using the negative-type photoresist composition layer for the above-mentioned color light-receiving sheet, it is possible to provide excellent image properties, and it is possible to form an outer surface having excellent productivity. Exposure = color-sensitive film with high-quality color residue with less residue of the negative-type photoresist. No. The liquid crystal display device provided by Ming has the above-mentioned color filter. == Invention 'by using the above A color filter can form a liquid crystal display device of high quality and excellent productivity. 97131527 200919087 (Effect of the invention) Excellent color The present invention can provide a negative-type photoresist composition for a filter which provides both pigment dispersibility and alkali developability. Effect The present invention relates to a negative-type light for color filters, a composition, a color filter, and a liquid crystal display device using the same. Hereinafter, the present invention is directed to a negative-type photoresist. The composition, the color filter, and the liquid crystal display device are placed in the body. First, 'the color filter for the color filter of the present invention is used for the smear of the negative plastic photoresist composition. [Color filter for negative light (Resistance composition) The negative-type photoresist composition for color filters and optical sheets of the present invention (hereinafter referred to as "negative·photoresist composition") contains "(A) pigment dispersant, (B) pigment, ' (= alkali-soluble resin, (D) polyfunctional monomer, (phantom starter, and Q), a solvent, and the above-mentioned (A) pigment dispersant has the following properties. (Pigment dispersant) The material (t) type resist composition t is used as the component (4), and has the following structural formula (1): (1) 1 the following knife type ((1) (4) scale position (2), and the above composition The unit (1) 2 base = the general formula un) is an acidic organic compound = a segmental copolymer (hereinafter also referred to as "salt block copolymer"). 131527 12 (I)200919087 [Chemical 4]

R1

0==C I

0 1 A

c [化5]

R5' (II) [Chem. 6]

5 I R5—P_OH (III)

I o [In the formula (IMIII), R1 means a hydrogen atom or a fluorenyl group; R2 and R3 respectively mean an independent hydrogen atom or an alkyl group having 1 to 8 carbon atoms; and A means an alkylene group having 1 to 8 carbon atoms; -[CH(R6)-CH(R7)-〇]x-CH(R6)-CH(R> or [(CH2)y-0レ(CH2)y) as a 2-valent group; R4 means Alkyl, benzyl, phenyl, pyridyl, biphenyl, pyridyl, _[ch(r6kh(r7)_〇]x-r8 or -[(CH2)y-0] having 1 to 18 carbon atoms z-R8 ; R5, R5 · respectively, the company is a gentleman & corpse κ ~ refers to an independent hydrogen atom, hydroxyl group, carbon 97315527 13 200919087 number 18 alkyl, carbon number 2 ~ 18 alkenyl, node, Phenyl, pyridyl, biphenylyl, pyridylphenyl, or -[(Cf^b-OL-R11 or -〇-R5 represents a valent group. R refers to an alkyl group having 1 to 18 carbon atoms, carbon Number of 2 to 18 alkenyl, benzyl, phenyl, pyridyl, biphenyl, pyridylphenyl, _[CH(R9)_CH(RlQ)_〇]a_Rll or '-[(CfWb-OL-R11 R, R, R and R1() are each an independent hydrogen atom or a fluorenyl group; R8 and R11 f) are each independently a hydrogen atom or a carbon number which may have a substituent. Alkyl, benzyl, phenyl, pyridyl, hydrazine a group represented by a group of α, a pyridylphenyl, _CH〇, -CH2CH0, -C0-CH=CH2, -C0-C(CH3)=CH24-CH2C00R12, and R12 means a hydrogen atom or a carbon number of 丨~5. X and a are integers of 〇18; y and b are integers from 1 to 5; z and c are integers from 0 to 18; m and η are integers from 1 to 200, respectively. In the present invention, the pigment dispersant has the unit (1) which is not composed of the above formula (I), and the unit (2) represented by the above formula (1), and which is an amine of the above-mentioned constituent unit (1). The block copolymer of the base and the acidic organic lining compound represented by the above general formula (III) can enhance the adsorptivity of the above-mentioned constituent unit (1) to the above-mentioned constituents of the salt to form a salt, and constitute a unit ( 2) Since the compatibility with the solvent is excellent, the pigmentation in the solvent can be achieved, and thus the dispersibility and stability of the pigment can be excellent. Further, by having the above general formula (m) The acidic organic phosphorus compound shown is 97131527 14 200919087. The amine group contained in the above constituent unit (1) is not institutionalized with the above acidity. The salt-forming portion formed by the σ material has high solubility in the aqueous alkali solution used for alkali development, and thus can be excellent in alkali developability. Therefore, when a color negative U-type resist composition is used, The color filter can be used to shorten the alkali development time, and the productivity can be excellent. Further, since the alkali/center 11 is excellent, a high-quality color filter having a small amount of color filter u negative photoresist composition at an unexposed portion can be obtained. 〇 丧 丧 丧 丧 丧 丧 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料 颜料Shows the unit 〇. In the above general formula (I), R1 means a hydrogen atom or a methyl group; and r3 means an independent hydrogen atom or a carbon number of 8 carbon atoms, respectively. Among them, the burning base of carbon number 8 can be _ shape, minute (four), or ring towel. This secret group can be exemplified by G, for example, anthracenyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second T-based, tert-butyl, various pentyl groups, various hexyl groups, various octanes. Base, cyclopentyl, cyclohexyl, cyclooctyl and the like. Among these, methyl and ethyl are preferred. In the present invention, the above R2 and R3 may be the same or different from each other. A refers to an alkylene group having 1 to 8 carbon atoms, --[ch(R6)-ch(r7)-o]x-ch(r6)-CH(rV or [((5)y_0]z_(CH〇广所示The valence group of the above-mentioned carbon number 1 to § can be either linear or branched, for example, methylene, ethyl, trisyl, and propane 97,315,127 200919087 Group, various butyl groups, various pentyl groups, various kinds of hexyl groups, various kinds of octyl groups, etc. R6 and R7 respectively mean an independent hydrogen atom or a fluorenyl group. X means an integer of 0 to 18, preferably 0~ An integer of 4, more preferably an integer of 0 to 2; y means an integer of 1 to 5, preferably an integer of 1 to 4, more preferably 2 or 3. Preferably, z means an integer of 0 to 4, preferably 0~ In the present invention, when X, y, and z are within the above range, the negative-type photoresist composition for a color filter of the present invention is excellent in pigment dispersibility. The A is preferably a carbon number of 1. 〜8 alkylene, especially good methylene and ethyl. If the carbon number is in the range of 1 to 8, the pigment dispersibility can be well maintained. In the above general formula (II), R4 means carbon number 1. ～18 alkyl, benzyl, phenyl, pyridyl, biphenyl, pyridylphenyl, -[CH(R6)-CH(R7) -〇]x-R8 or -[(CH2)y-〇]z-R8. In addition, when R4 has an aromatic ring, it may have an appropriate substituent on the aromatic ring, for example, a carbon number of 1 to 4. a linear or branched alkyl group, etc. The alkyl group having 1 to 18 carbon atoms may be linear, branched or cyclic, and examples thereof include a mercapto group, an ethyl group, a n-propyl group, and a different group. Propyl, n-butyl, isobutyl, second butyl, tert-butyl, various pentyl groups, various hexyl groups, various octyl groups, various sulfhydryl groups, various twelve alkyl groups, various tetradecyl groups, various ten Hexavalent, various octadecyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, decyl, iso-methylene, dicyclopentyl, adamantyl, lower alkyl substituted adamantyl, etc. R6 and R7 are as described above; R8 is a hydrogen atom, or an alkyl group having a carbon number of 1 to 18 which may have a substituent, a phenyl group, a phenyl group, a pyridyl group, a biphenyl group, a pyr 97315527 16 200919087 TM'2Γ -0' 'CH2Cfl0' ~C0~CH=CH2' 'co'c(ch"^ ^ Implied 1 valent base; ruler refers to a straight bell, branch, or Cyclic alkyl group. The above R system may also have a substituent, and the substituent may, for example, be a straight, difficult, branched or cyclic alkyl group of a carbon number, or a tooth atom such as F or C, etc. The carbon number of the above R8 is 18 In the case of R4, x and y*z are as described in the above-mentioned eight. f In the present invention, as the above R4, it is preferable to use an excellent solubility with a solvent to be described later. The structure of the above-mentioned block copolymer is different, and it is preferable to use a T group, an ethyl group, a sulfhydryl group or the like in the case where the solvent is a tetrahydrogen or anthracene, and the above is a low polarity. In the case of 'the pentyl group, the hexyl group, and the gemene, the reason why the above R4 is set as described above is that the constituent unit (2) containing the above-mentioned oxime is soluble in the above solvent, and is composed of the above. The amine group of the unit (1) and the salt form formed by the acidic organic scale compound described later have a high adsorption property to the pigment, and thus the pigment is excellent in dispersibility and safety. Further, the above R4 may be a substituent which does not hinder the dispersibility of the above-mentioned block copolymer, and may also be substituted with a substituent such as an oxime, a silk, a mercapto group, an amine group, an epoxy group or a hydrogen bond. Replace it. The ratio m/η of the unit 、 of the constituent unit (1) used in the present invention and the unit number η of the constituent unit (2) is preferably set within the range of o.ou, and more preferably in the range of 0.05 to 31,527, 2009, 2009, 087, 0.05 to 0.5. When the ratio m/n is in the above range, the ratio of the salt-forming sites formed by the amine groups of the above-mentioned structural unit (1) is appropriate, so that the adsorptivity to the pigment described later is good, and the above-mentioned constituent unit (2) and the above solvent are preferable. _ Solubility does not decrease, and the dispersibility and enthalpy of the pigment are not reduced. - In the present invention, the number of units m of the constituent unit (1) and the unit number n of the constituent unit (2) may each be an integer of ^00, and 〇 is not particularly limited, and the above m is Good for 1 to 20 range, better for Bu 10 range. Further, the above η is preferably in the range of 2 〇 to 1 〇〇. Further, the weight average molecular weight Mw of the above block copolymer is preferably set in the range of 500 to 20,000, more preferably in the range of 1 Torr to 15 Torr, and particularly preferably in the range of 3,000 to 12,000. By setting it within the above range, the pigment can be uniformly dispersed. Further, the above weight average molecular weight Mw is a value measured by a GPC (Gel Penetration Chromatography Analyzer). For the measurement, HLC-8120GPC' elution solvent manufactured by Tosoh Co., Ltd. was used. The calibration curve of N-decylpyrrolidone was added using 〇.1 mol/liter bromine clock.

Mw377400, 210500, 96000, 50400, 206500, 10850, 5460, . 2930, 1300, 580 (all of which are Easi PS-2 series manufactured by Polymer Laboratories) and Mwl090000 (made by Tosoh), measuring column system It was implemented using TSK-GEL ALPHA-Mx2 (Tosoh). The bonding sequence of the block copolymer used in the present invention is the same as that of the above-mentioned constituent unit (2), and the above-mentioned constituent unit (2), and the remaining pigments can be settled in a stable manner. A particular limitation 'preferably belongs to the above-mentioned conformation (1) only to the above-mentioned block copolymer-end. In other words, the constituent unit (1) and the constituent unit (2) may be sequentially bonded according to the constituent unit (1)-constituting unit, or may be bonded in accordance with the constituent unit (η_casting w (1)). Early) - constituent units convert..., constitute early position (2) - constituent unit (1) - configuration point 单位 unit (2) sequential bond ' can also be a constituent unit (1) _ constituent unit (2) heavy bond, this The date of the day, (4) is the key binding according to the unit (1). The reason for this is that the adsorptivity to the post-feed is excellent and: = pigment dispersion with such a block copolymer: <acidic organic phosphorus compound> The constituent unit is a unit (1), and the compound of the formula (1) is a group of the acidic organic constituents of the salt (1). The compound bovine compound having the structure shown by the amine has the following general formula (in the present invention, The use of the above-mentioned acidic dispersant _ the dispersibility of the pigment described later and the secret material 5 can make the pigment excellent for use in the development of the _ water surface, and (4) excellent developability of the site. "The liquid has (four) solution, _ will be Test [Chemical 7] 97131527 19 (III) 200919087 R5'

5 I R5—Ρ—ΟΗ ο In the present invention, by using the above-mentioned acidic organic phosphorus compound, the pigment dispersant can be made different from that of Anken, and the salt formation site is verified by the development of the salt. The aqueous solution has high solubility and thus is excellent in developability. Ο ϋ

In the above general formula (111), R5 and R5· respectively represent an independent hydrogen atom, a meridine, a filament having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a nodal group, a stupid group, a bite group, and a combination. Phenyl, pyridylphenyl, —[ch(r9) is r1Q)U-_bP R" or traitor. Further, when R5 has an aromatic ring, the aromatic ring may be substituted with a substituent such as a carbon number, a branched alkyl group or the like. The alkyl group having 1 to 18 carbon atoms is represented by the above R4. The alkenyl group having 1 to 18 carbon atoms may be linear, branched or cyclic. Examples of such a dilute group include an ethylene group, a dipropyl group, a propyl group, and various butenyl groups. Hexyl group, various octenyl groups, various decyl groups, various twelve-thick bases, four carbon counties, various sixteen bases, each needle ^ cyclopentane, cyclohexenyl, cyclooctyl group, etc. . Field group, the above R5 means a carbon group of carbon number 18, an alkenyl group having a carbon number of 2 to 18, a benzyl group, a phenyl group, a butyl group, a phenyl group, a phenyl group, and a [CIKiO-CKR10). -〇]a~Ru or a 1-valent group represented by [(CH2)b 〇]c_Ru. The carbon number of the above-mentioned carbon number is 97115227 20 200919087. The above-mentioned carbon number is as shown by the above-mentioned V and r5, and the § R has an aromatic ring, and the aromatic ring may have an appropriate The substituent is, for example, a linear or branched garden base having a carbon number of four. R9 and R1 above. They refer to independent hydrogen atoms or methyl groups, respectively. R11 means a nitrogen atom or an alkyl group having 1 to 18 carbon atoms which may have a substituent, a benzyl group, a phenyl group, a ° group, a biphenyl group, a phenyl group, a -CH0, a -CH2CH0 group, -C0-CH=Cfi2, -C0-C(CH3)=CH2 or the i-valent group represented by -CIKOOR12; γ means a hydrogen atom Ο or a linear, branched or cyclic alkane having a carbon number of 1 to 5. base. Examples of the substituent which may be contained in the above-mentioned R-valent monovalent group include a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms, or a halogen atom such as F, Cl or Br. Wait. In the above R11, the alkyl group having 1 to 18 carbon atoms is as shown in the above R4. Rlz means a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 5 carbon atoms. In the cases of R5, R5 and R5", a is an integer of 1818, an integer of b is 5, and an integer of c 00 18 . In the acidic organophosphorus compound represented by the above general formula (III), R5, R5. and R are a sulfhydryl group, an isopropyl group, a n-butyl group, a 2-ethylhexyl group, a vinyl group, an allyl group, or -(CH(R9)-CfKOoX-R11 or -((CH2)b-0)C-Rii, and Ru is preferably -C0-CH=CH2 or -C0-C(CH3)=CH2, of which preferably Having a polymeric base, that is, vinyl, allyl or -(CHOO-CiKiO-COa-R11 or -((CH2)b-0X-R11, R11 is preferably -C〇-CH=CH2 or -C0-C(CH3)=CH2 'Specially good R5, R5' and R5" are vinyl, allyl, 2-97131527 21 200919087 f-based acryloxyethyl, 2-propanyloxy (M) propylene-based base. Because of the acidic organic hybrid R5, R5 and r5" are methyl, isopropyl, n-butyl, 2-ethylhexyl, vinyl, #propyl, Or -(_9)-_1())-〇)3-1^ or _((CH2)b_〇)c_Rll, and ru system • -c〇-CH_—CH2 or ic(ch〇=CH2 ' The acid organic scaly compound is excellent in both pigment dispersibility and developability, since r5, R5 and R5" are set to n-vinyl, allyl, or -(CHOO-CiKOoVR" or -((αί2ν〇)πAnd R11 is set to .ch=ch2 or -CO-C(CH3)=CH2', so the acidic organophosphorus compound contains a polymerizable group. Therefore, when the (four) photoresist composition for the color filter of the present invention is used, The alkali-soluble resin and polyfunctionality contained in the polymerizable group and/or the polymerizable group and the negative-type photoresist composition for a color calendering sheet of the present invention at the time of exposure to form the coloring layer. The monomer or the like can be easily polymerized so that the pigment dispersant can be stably present in the coloring layer of the G color filter. Therefore, when such a color filter is used to manufacture a liquid crystal display device, it can be prevented. The pigment dispersant is permeated into the liquid crystal layer or the like. Further, since the acidic organophosphorus compound contains a polymerizable group, the polymerizable group contained in the acidic organic compound can be used before the coloring layer is opened. By polymerizing each other, as a result, the pigment dispersant can be highly polymerized, and therefore, in the development of the colored layer, the color filter of the unexposed color filter can be particularly excellent in alkali developability of the negative resist composition. 22 200919087 The reason why the polymerizable property is polymerized by the above-mentioned polymerizable group is particularly excellent in the testability is as follows. That is, not all of the added pigment dispersants contribute to the improvement of the dispersibility of the pigment described later. This is a dispersion of the above-mentioned parts, the above-mentioned parts are free, first and exist, and 'because the pigment dispersant generally has a problem of reducing the developability', and when the free (four) pigment is difficult to disperse, the development of the colored layer is formed. When 'will hinder alkali development. On the other hand, by polymerizing the above-mentioned polymerizable groups before use in the formation of the colored layer, the polymer is polymerized, and the in-situ colored layer can be shaped into a heart color; the optical sheet is free from the negative resist composition. The pigment dispersant can reduce the testability caused by the free pigment dispersant by the Hn-like Hn. It is particularly excellent in the developability of the negative-type resist composition of the color calender sheet which is not exposed.

The invention has the following formula (A)_dispersed wealth, and the compound has _the compound 2 quantity is T before the energy of the Lin liang liang, and the rest is... (4) (4) the amine soil contained in the above constituent unit (1), Use 0.05 mol% ~ 4. 〇 耳 % %, preferably 〇 1 mol % ~ 2 〇 Mo "in the range, better 〇. 2 莫% ~ 1 〇 Mo Er · inside. <Production of a Salt-Type Block Copolymer> In the present invention, a method for producing a salt-type block polymer used as a pigment dispersant of the component (A) is produced as long as it can produce the above-mentioned constituent unit (1) And the constituent unit (2), and the amine group of the constituent unit (1), and the general formula (III) described in the above 97315527 23 200919087, the other method is not particularly: the method of forming the salt by the organophosphorus compound The position (1) and the constituent units. In the present invention, the above-mentioned constituents are simply dispersed or dispersed in a solvent to be described later, and then polymerized by a known polymerization means, and then the compound is dissolved, and the x-producer adds the acidic organic dish to the solvent. Escape component (1) and component (2) Ο i) There are no special restrictions, and the molecular weight can be used. The method generally used can be used. For example, if there is a compound of the compound of the county, the anion polymerization is carried out. Active free radicals, special. In the present invention, a method of performing living polymerization using a group transfer polymerization (GTP) as disclosed in "JAm. Chemsoc" 105, 57〇6 (1983) is preferred: a branch, a molecular weight, a good amount The distribution or the like is set to be in the range of jin and fen, and the properties such as dispersibility and developability of the pigment dispersant can be made uniform. In the color light-receiving sheet of the present invention, the pigments of the component (4) may be used in combination with the pigments of the component (4), and the above-mentioned salt-type block yarns may be used alone or in combination of two or more. The amount can be appropriately selected according to the kind of the pigment to be used and the solid content concentration (4) in the negative-type photoresist composition, and is usually set to 5 parts by mass, and 〇 = part by weight, preferably with respect to 100 parts by mass of the pigment (8) described later. 10 parts by mass, within the range of parts by mass, especially good for 2 〇 罝 〜 〜 80 parts by weight _. If the content of the salt-type block copolymer is in the above-mentioned range, the shot is uniformly dispersed, and the formation can be sufficiently formed without lowering the blending ratio of the alkali-soluble resin and the polyfunctional monomer in the 97115527 24 200919087 The color layer of hardness. ((β) Pigment) In the negative-type photoresist composition for a color filter of the present invention, a pigment used as a (ruthenium) component can be emitted when a coloring layer of a color filter is formed. The coloring is not particularly limited, and various organic or inorganic coloring agents may be used singly or in combination of two or more. &lt;Type of Pigment&gt; For the above organic colorant, for example, a dye, an organic pigment, a natural pigment or the like can be used. Specific examples of the organic pigment include, for example, a pigment index (c. I.; The

In the Society of Dyers and C〇l〇urists, a compound classified as Pigment. Such a compound may, for example, be C. L pigment xanthine, c. 丨·pigment yellow 3, c. I. Pigment yellow 12, CI pigment yellow 138, C. 丨. Pigment yellow 139, c. 丨. 'Materials 150, c. 丨. Pigment Yellow 180, CI Pigment Yellow 185 and other yellow pigments; 〇.1. Pigment Red 1^.1. Pigment Red 2, (:.1 Pigment Red 3, (:.1. Red pigments such as Pigment Red 242, CI Pigment Red 254, CI Pigment Red 177; CI·Pigment Blue 15, CI Pigment Blue 15 : 3, c. ί, Pigment Blue 15 : 4, c. Worker. Pigment Blue 15 : 6 Others such as blue pigments; purple pigments such as CI Pigment Violet 23; and pigments such as Pigment Green 36, C.I. Pigment Green 58 and other pigments (CI) numbers. Further, inorganic colorants For example, inorganic pigments, extender pigments, etc. can be used, and the formula 97321527 25 200919087 is as follows: titanium oxide, cerium oxide, barium sulfate, calcium carbonate, zinc oxide, lead sulfate, yellow lead, zinc yellow, iron oxide red (red iron oxide) (111)), cadmium red, ultramarine blue, dark blue, chrome oxide green, cobalt green, amber, titanium black, synthetic iron black, carbon black, etc. • &lt;pigment particle size&gt; * The average particle diameter of the pigment used in the invention is as long as it is used as a coloring layer of a color filter, and the desired color can be emitted. The rest is not particularly limited, depending on the type of pigment used. The difference is preferably in the range of 10 nm to 100 nm, more preferably in the range of i 〇 nm to 5 〇 nm. By setting the average particle diameter of the pigment within the above range, the color filter of the present invention can be used negatively. The liquid crystal display device prepared by the type of photoresist composition has high contrast and high quality. In addition, if it belongs to a conventional pigment dispersant, a large amount of pigment dispersant is required depending on the miniaturization of the pigment particle size, and there is a fear of alkali. The problem that the developability is lowered and the residue is increased, but the pigment dispersant used in the negative-type light t) resistive composition of the color light-receiving sheet of the present invention is excellent in alkali developability, and thus such a problem occurs. Therefore, the average particle diameter of the pigment is such that the smaller the size is, the smaller the conventional particle size is, the more the characteristics of the negative-type photoresist composition for a color filter of the present invention are exhibited. The average particle size It can be obtained by directly measuring the size of the secondary particle from the electron micrograph. Specifically, the diameter of each of the secondary particles and the diameter of the secondary particle are measured, and the average value is taken as the particle diameter of the particle. For 1 〇 (H solid or larger particles, the individual particles of 97113527 26 200919087 are approximated by the 彳 ( (4) reading (4) row, and the volume T:=rr::=r (4) In the light μ negative type silk group secret ▲ the pigment content of the user's use is based on the premise that the desired color is emitted when the colored layer of the color material is formed, and the rest is not particularly limited. There are also differences in the types of negative-type photoresists for color filters: solid parts other than the pigment, preferably (4) f. (10) mass% better than 30 mass, please be within the mass. By setting the content of the pigment to the above-mentioned range, a negative-type photoresist composition for a color light-emitting sheet capable of emitting a coloring layer of a desired color can be formed, and a negative-type photoresist for the above-mentioned color light-emitting sheet can be formed. The composition can be uniformly dispersed. Further, the above solid content means the remainder other than the above solvent, and also includes a polyfunctional monomer dissolved in a solvent. ((C) alkali-soluble resin) In the negative-type photoresist composition for color filters of the present invention, as the alkali-soluble resin used as the component (c), a compound generally used for a negative-type photoresist can be used. There is no particular limitation on the solubility of the aqueous alkali solution, and the remainder is not particularly limited, and examples thereof include decyl acrylate (meth) acrylate, propyl acrylate, and fluorenyl acrylate. Isopropyl acrylate, n-butyl (meth)acrylate, dibutyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, (mercapto)acrylic acid N-amyl ester, (methyl) 97131527 27 200919087 n-hexyl acrylate, (meth)acrylic acid - 2-ethylhexyl vinegar, (methyl) endo-octyl octyl ester, (mercapto) decyl decyl acrylate, (fluorenyl) One or more selected from the group consisting of benzyl acrylate, stupid ethyl amide &amp; r-mercaptostyrene, N-vinyl-2·-pyrrolidone, and glycidyl (meth) acrylate, and Mercapto) acrylic acid, propylene 2 = - dimer (eg East Asian Synthetic Chemicals Co., Ltd. M) -5600), a copolymer of one or more selected from the group consisting of itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetate, and the like. In addition, the above-mentioned oxime copolymer towel may be exemplified by a polymer containing a ring or a heteropolyunsaturated compound, and is not limited to the above. When an adult contains a glycidyl group or a reduced ethylenically unsaturated compound, the (tetra) residue and the bond (tetra) compound can be polymerized with a polyfunctional monomer described later when exposed, and (10) the colored layer is more stable. In the negative-type photoresist composition for color filters of the present invention, the soluble resin used as the component (C) may be used alone or in combination of two or more. And the content (10) parts by mass of the negative-type photoresist composition for the color-based calendering sheet is usually in the range of 10 parts by mass to round parts by mass, preferably 20 parts by mass to 5% by weight. Too little, there is no _ / ^ part of the _. New soluble resin to check the content of the soluble content of the readability of the case of the 'reverse' when the failure to obtain sufficient reduction of the reduction, lead (10) polyfunctional monomer ^ The situation occurred. 97131527 28 200919087 In the negative-type photoresist composition for a color filter, the polyfunctional monomer used as the component (9) is not particularly limited until it can be polymerized by a photoinitiator to be described later. A compound having two or more ethylenically unsaturated double bonds, particularly a polyfunctional (meth) acrylate having two or more propylene-based or fluorenyl fluorenyl groups is preferred. The acrylate may, for example, be ethylene glycol bis(indenyl) acrylate, diethylene glycol bis(indenyl) acrylate, hexanediol bis(indenyl) oxime acrylate, long-chain aliphatic bis (A) Acrylate, neopentyl glycol bis(indenyl) acrylate, hydroxytrimercaptoacetic acid neopentyl glycol di(mercapto) acrylate, stearic acid modified pentaerythritol di(meth) acrylate, propylene glycol II (Meth) acrylate, glycerol di(meth) acrylate, triethylene glycol di(meth) acrylate, tetraethylene glycol di(meth) acrylate, tetramethylene glycol di(methyl) Acrylate, butanediol di(indenyl)acrylic acid , bis(indenyl)acrylic acid bis-amyl ester, polyethylene glycol di(meth)acrylate, polypropylene di(methyl) ° acrylate, triglycerin di(meth)acrylate, neopentyl glycol Dimethylol propyl (meth)acrylate, allylated cyclohexyl di(meth)acrylate, methoxycyclohexyl (meth)acrylate, acrylated isocyanate, double (Propylene methoxy neopentyl glycol) adipate, bisphenol A di(methyl) propylene vinegar, Si Mo Shuang A (di) (meth) acrylate, bisphenol s bis (meth) propylene Dimethicone, butanediol di(indenyl) acrylate, bis(meth) acrylate, di(meth) acrylate, di(meth) acrylate, etc. Further, a trifunctional or higher polyfunctional (meth) acrylate may, for example, be trimethylolpropyl tri(meth)acrylate or trishydroxypropyltriethyl acrylate. Ester, tris(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol Alcohol tetra (meth) acrylate, alkyl modified pentaerythritol tris(meth) acrylate, succinic anhydride modified pentaerythritol tetra (meth) acrylate, • tris (meth) acrylate, propylene (propylene)醯 oxiranyl ethyl) tripoly isocyanate, stilbene (mercaptopropyl methoxyethyl) dimeric isocyanate, dipentaerythritol tetradecyl (meth) acrylate, di(trimethylol) tetraacrylate Propyl ester, alkyl modified dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (indenyl) acrylate, alkyl modified dipentaerythritol penta (meth) acrylate Succinic anhydride modified dipentaerythritol penta(indenyl) acrylate, ethyl urethane tri(meth) acrylate, ester tris(mercapto) acrylate, amino decanoic acid hexa(indenyl) acrylate , ester hexa(meth) acrylate, and the like. Ij These polyfunctional (fluorenyl) acrylates may be used alone or in combination of two or more. Further, when the negative-type photoresist composition for a color filter of the present invention is required to have excellent photocurability (high sensitivity), the polyfunctional monomer preferably has three (trifunctional) or more. As the compound of the double bond of the polymerization, for example, dipentaerythritol penta(indenyl)acrylic acid, dipentaerythritol hexakisyl acrylate or the like can be suitably used. In the negative-type resist composition for a color light-emitting sheet of the present invention, the content of the polyfunctional monomer used as the component (8) is not limited, and is 100 parts by mass of the soluble resin of the component (6) 97131527 30 200919087. It is usually used in an amount of from 5 parts by mass to about 500 parts by mass, preferably from 20 parts by mass to 300 parts by mass. When the content of the polyfunctional monomer is less than the above range, photohardening cannot be sufficiently performed, and there is a case where the exposed portion is eluted. Conversely, if the content of the polyfunctional monomer is more than the above range, there is a fear that it is inspected. The possibility of reduced developability. - (E) Photoinitiator The photoinitiator used as the (E) component in the negative-type photoresist composition for color filters of the present invention is not particularly limited and can be known from the prior art. The various photoinitiators are suitably selected for use. For example: diphenyl ketone, Michler's ketone, 4, 4'-bisdiethylaminodiphenyl ketone, 4-decyloxy-4'-diguanidinodiphenyl ketone, 2-ethyl hydrazine Aromatic ketones such as fluorene and phenanthrene; benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether; benzoin such as methyl benzoin and ethyl benzoin; 2-( 〇-chlorophenyl)-4,5-phenyl-flavored α-somer, 2-(indolyl-chlorophenyl)-4,5-di(m-methoxyphenyl)-flavored β-somer, 2-(〇-fluorophenylindenyl)-4,5-diphenylimidazole dimer, 2-(anthracene-methoxyphenyl)-4,5-diphenylimidazole dimer, 2, 4 , 5-triaryl imidazole dimer, 2-(indolyl-chlorophenyl)-4,5-di(m-decylphenyl)imidazole dimer, 2-benzyl-2-dimethylamino- 1-(4-Phenylphenyl)-butanone, 2-trichloromethyl-5-styryl-1, 3, 4-. oxadiazole, 2-trichloromethyl-5-(pair Cyanostyryl-1,3,4-oxadiazole, • 2-trichloroindolyl-5-(p-methoxystyryl)-1,3,4-oxadiazole, etc. Oxadiazole compound; 2,4-bis(trichloroindenyl)-6-p-nonyloxystyryl-S-three tillage, 2,4-bis(trichloroindenyl)-6-(1- p-D-aminophenyl-1,3-97131527 31 200919087 Butyl-alkenyl)-S-III. Well, 2-trichloromethyl_4-amino_6_p-methoxystyryl-S-three tillage, 2-(naphthalen-1-yl)_4,6_bis-trichloromethyl_s _ trimorphine, 2_(4_ethoxy-naphthalen-1-yl)-4,6-bis-trichloromethyl_s_trimorphine, 2-(4-butoxy-naphthalen-1-yl)-4 , 6-bis-tris-methylmethyl_s-three-till, etc. Halomethyl _s_三讲系化,2'2-dimethoxy-1,2-diphenylethane_; -ketone, 2-methyl'-l_[4-(methylthio)phenyl]-2-carbolinepropan-1-one, 1,2-benzyl-2-di-family-1- U-味琳基phenyl)-^^--cyclohexyl-benzophenone, benzyl, benzhydrylbenzoic acid, methyl benzylidenebenzoate, 4-benzylidene-4-yl Phenyl sulfide, benzyl methyl ketal, hydrazinium dimethylaminobenzoate to isoamyl monomethylaminobenzoate, 2-n-butoxyethyl 4-dimethylaminobenzoate, 2 -Chloro 9-oxopurine, 2,4-diethyl 9-oxothioxanthene, 2,4-dimethyl 9-oxopurine, isopropyl 9-oxosulfonate, ethyl ketone, anthracene _[9_Ethyl-6-(2-methylbenzhydryl)_9H_carbazole_3_yl-ethyl hydrazine), 4_ benzoyl hydrazino-decyldiphenyl thiol, Hexyl-benzene酉同,二节基ϋ _2_(dimethylamino)-bu [4-(4-carbolinyl)phenyl]-1-butanone, 2-(dimethylamino)-2-[(4 -nonylphenyl)indenyl]porphyrinyl)phenyl-butanone, α-dimethoxy-α-phenylacetophenone, phenylbis(2,4,6-trimethylbenzhydrazide Phosphine oxide, 2-methylmethylthio)phenyl]_2_(4-carbolyl)-1-propanone, etc. These photoinitiators can be used alone or in combination. In the negative-type photoresist composition for a color filter of the present invention, the photoinitiator content used as the (Ε) component is a polyfunctional monomer of the component (D), 9713,327, 32, 2009, 19,087, 100, Berry. The portion is usually used in an amount of from about 0.01 parts by mass to about 100 parts by mass, preferably in a range of from 5 parts by mass to 6 parts by mass. If the content is less than the above range, the polymerization reaction is carried out by a method. Therefore, the hardness of the coloring layer may be insufficient. In the above range, the content of the pigment in the solid portion of the negative-type photoresist composition for the color light-receiving sheet is relatively small, and sufficient coloring cannot be obtained. The situation ((F) solvent) 0 In the negative-type photoresist composition for a color filter of the invention, the solvent used as the component (F) is an organic compound which does not react with each component in the photoresist composition, and which can be dissolved or dispersed. The solvent is raised beforehand, and the rest is not particularly limited. Specific examples thereof include alcohols such as decyl alcohol, ethanol, N-propanol, and isopropanol, methoxy alcohol, ethoxylated alcohol, and decyloxyethoxyethanol. An ether alcohol such as ethoxyethoxyethanol; an ester of ethyl acetate, butyl acetate, decyl acetate 3-methoxybutyl oxalate, ethyl ethoxy propionate, ethyl lactate, etc. Department; two ketone systems such as isobutyl ketone and cyclohexanone; methoxyethyl acetate, methyl propyl acetate, butyl butyl acetate, ethoxyethyl acetate, ethyl aceta Acetyl acetate, ethoxyethoxyethyl acetate, ethoxyethoxyethyl acetate, etc.; diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl hydrazine, four An ether such as hydrogen 'furan; an aprotic amide such as N,N-dimercaptoamine, N,N-dimercaptoacetamide or N-methylpyrrolidone; and r-butyrolactone g is an unsaturated hydrocarbon system such as benzene, diphenylbenzene or naphthalene; an organic solvent such as a saturated hydrocarbon such as n-heptane, n-hexane or n-octyl. 97131527 33 200919087 Among these, for example, methoxyethyl acetate, ethoxyethyl acetate, ethyl cyproterone acetate, methoxyethoxyethyl acetate, ethoxy ethoxy acetate Ether ether acetate such as ethyl ester; ether system such as ethylene glycol diterpene ether, diethylene glycol dimethyl ether, propylene glycol diethyl ether; acetate 3-oxime butyl acrylate, oxime oxalate vinegar Ethyl ethoxypropionate, S-lactide, etc. In particular, the solvent used in the present invention is preferably, for example, MBA (-3-methoxybutyl (acetate), PGMEA (propylene glycol) from the viewpoints of solubility of the pigment dispersant, coating suitability, and the like.曱 ether acetate), DMDG (diethylene glycol dimethyl ether), diethylene glycol decyl ether, PGME (propylene glycol monomethyl ether), or a mixture thereof. Negative light for color filters of the present invention In the composition of the resist, the solvent content of the component (F) is not particularly limited until the constituent components of the negative resist composition are uniformly dissolved or dispersed. In the present invention, The remaining component of the negative resist composition excluding the solvent is preferably in the range of 5 〇 mass% to 40 mass%, more preferably 10 mass% to 30 mass%, and is set within the above range. A viscosity suitable for coating is formed. (Optional addition component) The negative-type photoresist composition for a color filter of the present invention may contain various additives as needed within the range not impairing the purpose of the present invention. For example: polymerization terminator, chain transfer agent, leveling agent, plastic , a surfactant, an antifoaming agent, a decane coupling agent, a UV absorber, a adhesion promoter, etc. Among the surfactants which can be used, for example, polyoxyethylene month 97311527 34 200919087 cassia ether, polyoxygen Vinyl stearyl ether, polyoxyethylene ether ether, polyoxyethylene octyl ether, polyoxyethylene sulfhydryl fine, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitol An anhydride fatty acid ester, a fatty acid modified polyester, a tertiary amine modified polyamine phthalic acid vinegar, etc. Other fluorine-based surfactants may be used. Further, the plasticizer may be, for example, bismuth citrate Examples of the defoaming agent and the leveling agent may be, for example, a shirt, a fluorine-based or an acrylic-based compound, etc. ❶ (negative light for color filters) Modulation of Resistive Composition) The method for preparing a negative-type photoresist composition for a color filter of the present invention belongs to the above (A) pigment dispersant, (B) pigment, alkali-soluble resin, (D) Functional monomer, (phantom starter, and various added ingredients as needed) evenly The method of dissolving or dispersing in the solvent of (F) is not particularly limited, and it can be prepared by mixing by a well-known mixing means. The preparation method of the negative-type photoresist composition is as follows: (1) in a solvent In the above, G is added with the above pigment dispersant and pigment, and dispersed by a dispersing machine to obtain a pigment dispersion liquid, and then an alkali-soluble resin, a polyfunctional monomer, a photoinitiator, and a desired one are added thereto. a method of mixing various components used and mixing; (2) simultaneously introducing the above-mentioned pigment dispersant, pigment, alkali-soluble resin, polyfunctional monomer, photoinitiator, and various kinds as needed in a solvent a method of adding a component and mixing; and (3) adding a pigment dispersant, an alkali-soluble resin, a polyfunctional monomer, a photoinitiator, and optionally various components as needed in a solvent, and performing 97131527 35 200919087 A method of adding a pigment and mixing it after mixing. The method of the above (1) is a preferred method from the viewpoint of effectively preventing the pigment from agglomerating and being uniformly dispersed. In this case, the solvent content in the pigment dispersion liquid is preferably set at 60% by mass, based on the dispersibility of the pigment, the stability over time of the pigment dispersion, and the color of the color filter (10). Within 90% by mass.

In the method of the above (1), in the preparation of the pigment dispersion liquid, the pigment dispersion treatment is carried out. (4) Dispersing machine, for example, a grain crusher such as a Wei machine or a three-roll mill; a ball mill such as a ball mill or a vibratory ball mill; and a paint agitator ; continuous disc type bead mill, continuous ring bead mill and other bead mill materials. The preferred dispersion conditions of the bead mill are preferably in the range of 1 and more preferably in the range of 〇_1_~1_. Moreover, after dispersion, it is best to use 5. 〇心 G. 2, the left and right film processor to filter. Thereby, a pigment dispersion liquid excellent in pigment dispersibility can be obtained. Further, when the acidic organic scaly compound contained in the pigment dispersant used in the present invention has a polymerizable group, for example, the above-mentioned pigment dispersant may be added to the light, or the pigment may be classified. After the pigment and the light are dissolved in the solvent, light irradiation is performed to polymerize the pigment dispersant. By polymerizing the pigment dispersants with each other, the pigment dispersion stability in the negative-type photoresist composition for the present color filter is improved. Next, the color filter of the present invention will be described. 97131527 36 200919087 [Color grading sheet] The color filter of the present invention is characterized by having a coloring layer formed using the negative-type photoresist composition for the color filter of the present invention. The color filter of the present invention will be described with reference to the drawings. Fig. 1 is a schematic cross-sectional view showing an example of a 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 coloring layer 3. The color filter of the present invention has high alkalinity by using the negative-type photoresist composition for a color filter of the present invention to form a coloring layer, and has excellent alkali developability. Further, by forming excellent alkali developability, it is possible to obtain a high-quality product having a small amount of negative photoresist composition for color filters which are not exposed. (Colored layer) The coloring layer used in the color filter of the present invention is not particularly limited as long as it is formed by using the negative-type photoresist composition for the color filter of the present invention. The opening 邛 formed in the light-shielding portion formed on the transparent substrate to be described later is composed of three or more color patterns in accordance with the type of the pigment contained in the negative-type photoresist composition for the color filter. Further, the arrangement of the colored layer is not particularly limited, and may be, for example, a general arrangement such as a belt type, a mosaic type, a triangular type, or a 4-pixel arrangement type. Further, the width, area, and the like of the colored layer can be arbitrarily set. The thickness of the colored layer can be appropriately controlled according to the thinning method, the adjustment of the solid concentration, the viscosity, and the like of the composition of the negative-type photoresist 971352727 200919087 of the color filter, and is usually preferably set at 1 // Within the zm range. The colored layer can be formed by the following method. First, the negative color resist composition of the color filter of the present invention described above is used. The coating method is applied to a transparent substrate to be described later by a coating means such as a spray coating method, a dip coating method, a bar coating method, a roll coating method or a spin coating method to form a wet coating film. (Secondly, after drying the wet coating film using a hot plate, an oven, etc., and then exposing it to the mask of the predetermined method, the alkali-soluble and the polyfunctional monomer are subjected to photopolymerization. The reaction is carried out as a coating film of a silky light-emitting (four) 光^ photoresist composition. The light source used for the exposure towel may be, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp or the like; or an electron beam p-exposure system may be used. The light source to be used, the thickness of the coating film, and the like are appropriately adjusted. Further, in order to promote the polymerization reaction after exposure, heat treatment may be performed, and the heating conditions may be in accordance with the color of the color light (4) type used: It is appropriately selected by blending (4), coating rotation degree, etc. Next, development treatment is carried out using a developing solution, and a coating film is formed by removing the film from the desired pattern by the field. The knife is each in water or a water-soluble solution. Β(10) ((10) The solvent for dissolving the armor. In the test solution, the active agent, etc. are also used. In addition, the development method can be carried out by using the _4 boundary development treatment, and then performing the cleaning and drying of the coating film. And forming a color layer. The outer = resistive composition hardens the coating film sufficiently, and can be heated, and after 1~ treatment, 'for _27 ..., the heating conditions are not particularly limited by the limit of 200919087, and can be appropriately selected in accordance with the use of the coating film. The light-shielding portion of the color filter of the present invention is formed into a pattern on a transparent substrate to be described later, and can be used as a light-shielding portion as in a general color filter. The pattern shape of the light-shielding portion is not particularly limited. The limitation may be, for example, a strip shape or a matrix shape, etc. The light shielding portion may be, for example, a black pigment dispersed or dissolved in a binder resin; or a metal thin film such as chromium or chromium oxide. The metal film may be Cr ( ^(x is an arbitrary number) and a two-layer laminate of Cr臈, and may be a three-layered layer of a Cr film which is obtained by further reducing the reflectance (10), any number of (4) films, and any number of Cr films. ^ shading # belongs to dispersing or dissolving the black colorant (4) knot =,: the method of forming the shading portion is a method that can be used, and the rest is not particularly limited.

Light-based resin composition 峨 微 ( (4) ° = Partial sensation In the above case, when using the K-jet method or the like. In the case of the method, the sticking tree wax can be, for example, 13, the ink method is formed as a light-shielding portion, the polycarbonate resin, the mercapto-acrylic acid methyl vinegar resin, the polypropylene ketone resin, the ethyl cellulose tree t-polyethylene glycol Correction, polyethylene base ratio bite resin, melamine tree wax, diced methyl cellulose resin, polyvinyl chloride resin, polyester resin, sterol oxime resin, epoxy resin, Further, in the case of the polyamine, in the above case, Chuan 1 butyl diacid resin, polyamine resin, and the like. 97131527 光学The use of optical lithography as the formation of the sunshade 39 200919087

In the case of the binder resin, for example, a photosensitive resin having a reactive vinyl group such as an acrylate type, a methacrylate type, a polyvinyl cinnamate type, or a cyclized rubber type can be used. In this case, a photopolymerization initiator may be added to the photosensitive resin composition for a light-shielding portion containing a black coloring agent and a photosensitive resin, and a sensitizer or a coating improver may be added as necessary. , development improver, crosslinking agent, polymerization terminator, plasticizer, flame retardant, and the like. In the present invention, the photosensitive resin composition for a light-shielding portion may be a negative-type photoresist composition for a color filter having a black pigment such as carbon black or black pigment as a pigment. On the other hand, when the light-shielding portion is a metal thin film, the method for forming the light-shielding portion is a method for patterning the light-shielding portion, and the rest is not particularly limited. For example, an optical lithography method or a mask is used. A vapor deposition method, a printing method, and the like. The film thickness of the light-shielding portion is set to about 44 mm in the case of the metal thin film. When the black colorant is dispersed or dissolved in the binder resin, it is set to about 55_~2_. (Transparent Substrate) The transparent substrate in the color filter or the optical sheet of the present invention is not particularly limited as long as the visible light is a transparent substrate, and a transparent substrate for a general color filter can be used. Specific examples thereof include a transparent rigid material such as quartz glass, a non-glass, a synthetic quartz plate, or a flexible transparent material such as a transparent resin film or an optical resin plate. Further, in the color light-receiving sheet of the present invention, in addition to the transparent substrate, the light-shielding portion, and the colored layer, for example, a protective layer, a transparent electrode layer, or even an alignment film, a columnar spacer, or the like can be formed. Next, a liquid crystal display device of the present invention will be described. [Liquid crystal display device] The liquid crystal display device of the present invention is characterized by having the above-described color filter of the present invention. The liquid crystal display device of the present invention will be described with reference to the drawings. Fig. Γ is a schematic view of an example of the present invention. As shown in FIG. 2, the liquid crystal display device 4 of the present invention has a color filter ι, an opposite substrate 20 having a TFT array substrate, and the like, and the color filter 10 and the counter substrate 20 described above. The liquid crystal layer is between 3 〇. Further, the liquid crystal display device of the present invention is not limited to the known structure of the liquid crystal display device in which the color light-receiving sheet can be used as shown in Fig. 2 . The driving method of the present invention liquid crystal display device is not particularly limited, and the _ mode used in the general liquid crystal display device can be employed. Such a method, a receiving method, a (10) mode, a current mode, etc. can be used as appropriate. Further, the counter substrate can be appropriately selected and used in accordance with the driving method of the liquid crystal display device of the present invention. Further, the liquid (4) constituting the liquid crystal layer may be mixed with the driving method of the liquid crystal display device of the present invention, etc., (4) dielectric anisotropy, and the mixture of 97131527 200919087. As a method of forming the liquid crystal layer, a method generally used as a method for producing a liquid crystal cell, for example, a vacuum injection method, a liquid crystal dropping method, or the like can be employed. In the vacuum injection method, for example, a liquid crystal cell is prepared in advance using a color filter and a counter substrate, an isotropic liquid is formed by heating the liquid crystal, and the liquid crystal is injected into the isotropic liquid state by capillary action. In the liquid crystal cell, blocking is performed by using a binder to form a liquid crystal layer. Then, by cooling the liquid crystal cell to a normal temperature, the sealed liquid crystal can be aligned. Further, in the liquid crystal dropping method, for example, a sealant is applied to the periphery of the color filter, and the color filter is heated to a temperature at which the liquid crystal is in an isotropic phase, and the liquid crystal isotropically used by a dispenser or the like. After dropping in a liquid state, the color filter and the counter substrate are overlapped under reduced pressure, and bonding is performed by a sealant to form a liquid crystal layer. Then, by gradually cooling the liquid crystal cell to a normal temperature, the sealed liquid crystal can be aligned. [Embodiment] Next, the present invention will be described in more detail with reference to the embodiments, but the present invention is not limited by the examples. 1. Production of Block Copolymer A - 500 ml round bottom four separable flask equipped with a cooling tube, an addition funnel, a nitrogen gas inlet, a mechanical stirrer, and a digital thermometer The funnel was added with 250 parts by weight of tetrahydrofuran (THF) and 5.81 parts by weight of the starting agent of dimethylketomethyltridecylfluorenylacetaldehyde, and fully 97131527 42 200919087 200919087

Execution of chaos. 0.5 parts by weight of a HI-acetonitrile solution of a tetrabutyl-bonded benzoic acid vinegar of a catalyst was injected using a syringe, and the addition of a funnel was used to treat (10) parts by weight of the dimethyl group of the first working body for 6 minutes. Drop in. The reaction flask was cooled using an ice bath and the temperature was kept below the paper. After 1 hour, 33.3 parts by weight of methyl enedetate dimethylaminoethyl vinegar of the second monomer was added dropwise over 20 minutes. After the reaction for 1 hour, methanol was added in an amount of part by weight to stop the reaction. The obtained block copolymer THF solution was reprecipitated in hexane, and it was difficult to perform dry reduction and vacuum drying to obtain the copolymer A. The block copolymer A obtained in accordance with the above was confirmed by Gpc (gel permeation chromatography) according to the conditions of adding N-methylpyrrolidone and 〇·〇1M bromine clock/polystyrene standards. RESULTS: The composition ratio of methacrylic acid methacrylate (MMA) and decyl methacrylate DMAEMA was MMA/DMAEMA 3/1, weight average molecular weight Mw: 45 〇〇, average molecular weight Mn: 533 〇, more Dispersity: 1.18.

2. The production of block copolymer B is set to be: dimethyl δ with methyltridecyl decyl acetaldehyde 2.32 weight damage tetrabutyl sulphur chloroformic acid , the methacrylic hydrazine hydrazine S 曰 120 parts by weight, dimethylaminoethyl methacrylate ΐ 3. 3 里 f f knife methanol 0. 5 parts by weight, the rest are in accordance with the above block copolymer _ get block copolymer B. The oxime &amp; copolymer obtained according to this was confirmed in the same manner as the above-mentioned filament group copolymer A. [Results MMA rujAn. Λ &amp; DMAEMA composition ratio MMA/DMAEMA system 97315527 43 200919087 9/1, weight average Molecular weight Mw: 9940, average molecular weight Μη: 11800, polydispersity: 1.19. 3. Addition of a salt-type block copolymer solution In a 100 ml round bottom flask, the block copolymer A (5.0 parts by weight) was dissolved in 24.68 parts by weight of propylene glycol monoterpene ether acetate (PGMEA), and then added. a mercapto acryloxyethyl acid phosphate (Phosmer M: manufactured by Yuni-Chemical Co., Ltd.) belonging to a salt-forming component: 1.17 parts by weight (the DMAEMA unit of the copolymer with the ester group p is an equimolar amount), The reaction was carried out for 6 hours under the reaction temperature of 25 t to obtain a salt type block copolymer solution A in which a solid content of 20% by mass of phosphate was formed. Similarly, as shown in the following Table 1, the block copolymer, the salt-forming component, and the reaction temperature were changed to obtain a salt-type block copolymer solution B to G in which a solid content of 20% by mass of phosphate was formed, and four stages were formed. The salt-type block copolymer solution of the ammonium salt is Η~K, and the block copolymer solution L which does not form a salt. Further, the salt-forming component is added in such a manner that the DMAEMA unit of the block copolymer is equal to the molar amount. 97131527 44 200919087 [Table 1] Block copolymerization solution block copolymerization salt formation component amount (parts by weight) Reaction temperature 嵌段 Block copolymer salt formation component solvent (PGMEA) Salt type block copolymer solution A block copolymerization Complex A Methacryloxyethyl phosphate 5.0 1.17 24. 68 25 Salt block copolymer solution B Block copolymer A Dimercaptopropenyloxyethyl acid phosphate 5.0 1.47 25.88 25 Salt Type block copolymer solution C block copolymer A monobutyl acid phosphate 5.0 0. 86 23.44 40 salt type block copolymer solution D block copolymer A dibutyl acid phosphate 5.0 1.17 24. 68 40 salt type block copolymer solution E block copolymer A vinyl phosphonate 5.0 0. 58 22.32 40 salt type block copolymer solution F block copolymer A phenyl phosphonate 5.0 0.79 23.16 40 salt block copolymerization Complex solution G block copolymer B methacryloxyethyl acid phosphate 5.0 0. 53 22.12 25 salt type block copolymer solution 嵌段 block copolymer A benzyl chloride 5.0 0.72 22.89 80 salt type Copolymer solution I Block copolymer A 浠 propyl chloride 5.0 0.44 21.76 80 Salt block copolymer solution J Block copolymer A allylic bromide 5.0 0.69 22.76 25 Salt block copolymer solution Κ Block copolymer A 4 -Chloromethylstyrene 5.0 0.86 23.44 80 Salt type block copolymer solution L Block copolymer A - 5.0 0 20 - 4. Preparation of pigment dispersion Next, the prepared salt type block copolymer solution (embedded) 12 parts by weight of the segment copolymer solution A to L), PGMEA (15 parts by weight), and ruthenium ratio of 51. Specific pigments (a) (PR254: average primary particle size 30 nm) 3 parts by weight, and 0. 3mm 97131527 45 200919087 Oxidized pellets 6 0 weight ^, , .^ ” ' into the mayonnaise bottle The 1mm zirconia ball is used for the first time of the pulverization of the pulverized zirconium ball. 60 reset the farm into the US, milk / bottle, the same, the official crushing is carried out using a paint blender for 3 hours to divide the leaf knife to obtain the pigment dispersions A to L. [Example 1] (10) (4) Dispersion A (46 parts by weight) towel, 31 parts by weight of a binder component added [alkali-soluble resin-based acrylic copolymer (active component 54/09 aliquots, polyfunctional single-system light or thermal polymerizable monomer) 5 parts by weight of dipentaerythritol hexaacrylate; and 2 parts by weight of a photoinitiator 2-methyl-i[4-(methylthio)phenyl]-2- morpholinopropan-1-one, and 15 parts by weight of propylene glycol monomethyl ether acetate], and 22 parts by weight of propylene glycol monomethyl ether acetate of the solvent, and mixed until all After homogenization, filtration was carried out using a pressure filter device having a mesh size of 2. 2# m to obtain a negative-type photoresist composition GA ° for color filters [Examples 2 to 7, Comparative Examples 1 to 5] The pigment dispersion liquid A was changed to the negative-type photoresist composition B to L for the color filter as in Example 1 except that the pigment dispersion liquids β to l were used instead. [Evaluation] For the examples and comparative examples The obtained color filter was subjected to evaluation of pigment dispersion ampereness and developability using a negative-type photoresist composition. The results of the implementation were 97115227 46 200919087 &lt;The following is shown in Table 2. (Pigment Dispersion Stability Evaluation)

The evaluation of the pigment dispersion stability of the negative-type photoresist composition for a color filter prepared according to the examples and the comparative examples is used in the modulation of the above-mentioned color filter using a negative-type photoresist composition. The pigment dispersion liquid was allowed to stand at 4 (TC - for 1 week), and the particle diameter of the above pigment dispersion liquid was measured before and after standing. The particle size was measured by using "Microtrac particle size distribution". The evaluation of the alkali developability is carried out according to the negative color resist composition of the color filter obtained in each example, and the thickness of 0. 7 mm l〇mmxi〇min glass substrate (manufactured by Banbao Technology Glass Co., Ltd.) And the "NA35") was coated with a spin coater, and then dried using a hot plate at 8 ° C for 3 minutes to form a red colored layer having a thickness of 3. Oym. The ultra-depressurized mercury lamp was used to perform 6 〇mJ/cm2 ultraviolet ray irradiation. Then, the above-mentioned glass plate on which the color layer was formed was sprayed and developed using a 0.50% potassium hydroxide aqueous solution as a test solution. Making the above "_ π king cold solution" will form the above colored layer When the glass surface appears: Immediately, it is regarded as the development time and measured. 97131527 47 200919087 [Table 2] Pigment Dispersion Pigment Dispersion Stability Evaluation Particle Size before Stability Test (nm) Particle Size after Stability Test (nm) (Second) Example 1 Pigment Dispersion A 42 42 35 Example 2 Pigment Dispersion B 43 42 35 Example 3 Pigment Dispersion C 42 42 45 Example 4 Pigment Dispersion D 42 42 40 Example 5 Pigment Dispersion E 41 41 35 Example 6 Pigment Dispersion F 44 44 45 Example 7 Pigment Dispersion G 53 53 40 Example 8 Composite Pigment Dispersion Μ 54 54 25 Comparative Example 1 Pigment Dispersion Η 48 66 110 Comparative Example 2 Pigment Dispersion Liquid I 41 45 120 Comparative Example 3 Pigment Dispersion J 42 56 110 Comparative Example 4 Pigment Dispersion Κ 42 46 Undevelopable Comparative Example 5 Pigment Dispersion L 300 Gelation - Table 2, Comparison with Examples 1 to 7 In the comparison of Examples 1 to 4, it was found that Examples 1 to 7 were greatly shortened in alkali development time, and it was confirmed that the alkali developability was excellent. Further, the negative-type photoresist compositions for color filters of Examples 1 to 7 were used. The pigment dispersion used in the preparation, In the case where the increase of the pigment particles did not occur at all, it was confirmed that the dispersion stability was excellent. ' Further, Comparative Example 5 using the block copolymerized solution L formed without salt, &quot; In the above evaluation of the dispersion stability of the pigment, Gelation occurs after standing for 1 week. Moreover, the particle size of the particles in the pigment dispersion is large, and the size of the mesh is 0. 2 // m 97131527 48 200919087 The pressure filter device cannot be filtered and cannot be colored. The filter uses a negative photoresist composition. [Example 8] In a 50 ml screw tube, 2,2'-azobis(4-decyloxy-2, 4) as a starter was added to the above-obtained pigment dispersion A (30 parts by weight). - dimethyl valeronitrile (V-70: manufactured by Wako Pure Chemical Industries, Ltd.), 0. 025 parts by weight, and subjected to ultrasonic treatment, and reacted at 50 ° C for 10 hours to obtain a genus f, which is a salt-forming component. In the mercapto acryloxyethyl acid phosphate, the composite pigment dispersion liquid in which the double bond sites are polymerized with each other. Next, a negative-type photoresist composition for a color filter was obtained in the same manner as in Example 1 except that the pigment dispersion liquid A was replaced and the composite pigment dispersion liquid was used instead. [Evaluation] For the color filter obtained in accordance with Example 8, the composition of the negative resist was used. I) The evaluation of the pigment dispersion stability and the developability was carried out. The results of the implementation are shown in Table 2 above. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing an example of a color filter of the present invention. * Fig. 2 is a schematic view showing an example of a liquid crystal display device of the present invention. • [Main component symbol description] 1 Transparent substrate 2 Light-shielding part 97131527 49 200919087 3 Colored layer 10 Color filter 20 Counter substrate 30 Liquid crystal layer 40 Liquid crystal display device

97131527 50

Claims (1)

200919087 VII. Patent application scope: 1. A negative-type photoresist composition for color filters, including: (A) pigment dispersant, (B) pigment, (C) alkali-soluble resin, (D) polyfunctional The (A) pigment dispersant has a constituent unit (1) represented by the following general formula (I), and the following, in the case of a monomer, (E) photoinitiator, and (F) solvent. a constituent unit (2) represented by the above formula (II), and a block copolymer obtained by forming an amine group of the above-mentioned structural unit (1) and a salt of an acidic organic phosphorus compound represented by the following general formula (III); [1] R1 • ch2 c- o=c Iο I A I R2 (I) [Chemical 2] R1( Ir I 0=? o (II) [Chemical 3] 97131527 51 200919087 R5, R5-P-OH (HI) ΰ [In the formulae (I) to (I II), R1 means a hydrogen atom or a fluorenyl group; and R2 and R3 respectively mean independent A hydrogen atom or a carbon group having a carbon number of 1 to 8; A means a stretching group having a carbon number of 1 to 8, -[CH(R6)-CH(R7)-O]x-CH(R6)-CH〇〇- Or a divalent group represented by [(CH2)y-〇]z-(CH2)y; R4 means an alkyl group having 1 to 18 carbon atoms, a benzyl group, a phenyl group, a fluorenyl group, a biphenyl group , pyridine phenyl, _[CH(R6)-CH(R7)-〇]x-R8 or -[(CH2)y-〇]z-R8; R5, R5 are respectively independent hydrogen atoms, hydroxyl groups, carbon a calendyl group of 1 to 18, an alkenyl group having 2 to 18 carbon atoms, a benzyl group, a phenyl group, an acridinyl group, a biphenyl group, a fluorenylphenyl group, -[CiKlO-CHaO-Oh-R11 or -[(CH2) B_0]c - R11 or a monovalent group represented by -0-R5; R means a carbon group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a benzyl group, a phenyl group, a pyridyl group, and a biphenyl group. a group, a pyridylphenyl group, or an O-[(a valence group represented by CHdb-OkR11; R, R, R, and β respectively represent an independent hydrogen atom or a methyl group; r8 and rii each refer to an independent hydrogen atom, Or an alkyl group having a carbon number of a substituent, a benzyl group, a phenyl group, or a π ratio Iridinyl, biphenyl, σ pyridine phenyl, _CH 〇, -CHzCHO, -C0-CH=CH2, -C0-C(CH3)=CH2 or -CH2C00R12 1 • Known, R12 is hydrogen An atom or an alkyl group having a carbon number of 55; X and a are integers of 〇18; y&amp;b is an integer of 卜5; an integer of 〇8; "! and η are respectively referred to as Integer]. 97131527 52 200919087 2. As claimed in the patent scope i item #, a negative-type photoresist composition for a ruthenium filter', wherein the above-mentioned acidic organic dance is beautiful. R5 and R5 in the compound are aggregated. (3) 2 full-time (4) 2 slave color "photon negative photoresist composition" wherein the above-mentioned polymerizable base vinyl, (fluorenyl) propyl group, or propyl propyl group 4: as claimed in the scope of (1) A negative-thickness resist composition for a color filter according to any one of the preceding claims, wherein the (8) pigment has an average particle diameter in the range of 1〇11111 to 1〇〇11111. 5. A color filter having A coloring layer formed by a negative-type photoresist composition for a color filter according to any one of claims 4 to 4. 6 A liquid crystal display device having a application Please select the color filter of item 5 of the patent. 97131527 53