JPH11119017A - Production of color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a process for producing color filters having excellent heat resistance and chemical resistance, high sensitivity and a pattern profile by using a positive photosensitive coloring compsn. SOLUTION: This process for producing the color filters consists in applying the positive photosensitive coloring compsn. contg. (1) a resin insoluble in water and soluble in an aq. alkaline soln., (2) a compd. which generates an acid by irradiation with active rays or radiations, (3) a low-molecular acid decomposable dissolution prohibiting compd. of a mol.wt. of <=3000 which has a group decomposable by the acid and is increased in the solubility in an alkaline developer by the effect of the acid and (4) coloring agents on a transparent substrate and subjecting the coating to exposure, post-exposure heating and developing to form image patterns, then incorporating a crosslinking agent into the image patterns and successively subjecting the coating to full-surface exposure and heating.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive type photosensitive coloring composition containing a colorant, in particular, a color used for a liquid crystal display device or a solid-state imaging device using a positive type photosensitive coloring composition utilizing chemical amplification. The present invention relates to a method for manufacturing a filter.

[0002]

2. Description of the Related Art As a method for producing a color filter used for a liquid crystal display device or a solid-state imaging device, a dyeing method,
Printing, electrodeposition and pigment dispersion methods are known. Above all, the pigment dispersion method is a method of producing a color filter by a photolithography method using a colored radiation-sensitive composition in which a pigment is dispersed in various photosensitive compositions. This method
Since the pigments are used, they are stable to light and heat, and are patterned by the photolithography method. Therefore, they have sufficient positional accuracy and are suitable for producing a color filter for a large-screen, high-definition color display.

The photosensitive composition used in the pigment dispersion method is disclosed in JP-A-1-102469 and JP-A-1-15249.
9, JP-A-2-181704, JP-A-2-1994
03, JP-A-4-76062, JP-A-5-2734
No. 11, JP-A-6-184482, JP-A-7-140
As described in Japanese Patent No. 654, a negative photosensitive composition using a photopolymerizable monomer and a photopolymerization initiator in an alkali-soluble resin is generally proposed. Since these use radical polymerization, they are affected by polymerization inhibition by oxygen, or the light irradiated for exposure is blocked by the pigment, and the progress of polymerization of the system is insufficient. There was a problem with reproducibility.

Japanese Patent Application Laid-Open No. 9-61615 discloses a photosensitive composition of a chemical amplification system, which obtains an image by crosslinking an alkali-soluble resin with an acid catalyst generated from a photoacid generator. It is a negative photosensitive composition. It is known that when a pigment is added to such a chemically amplified negative photosensitive composition, the solubility of the system is reduced, and the difference in developability between exposed and unexposed areas is reduced. As a result, The development latitude becomes narrow and the developability deteriorates. In addition, the pattern profile is likely to be a reverse taper that cuts into the substrate side, which is not preferable as a color filter.

On the other hand, positive photosensitive coloring compositions are disclosed in JP-A-6-35182 and JP-A-6-194826.
JP-A-6-194827, JP-A-6-19483
No. 5, JP-A-6-230215, which uses a novolak resin and quinonediazide, and has problems such as coloring derived from these compounds.

Further, in a chemically amplified positive photosensitive composition, the so-called T-top in which the pattern profile protrudes on the surface side is apt to occur. This is thought to be caused by the acid generated in the exposed area due to the standing time until development after exposure, which is deactivated by the basic substance from the surroundings near the photoreceptor surface. Is not preferred. Furthermore, in the chemically amplified positive photosensitive composition, the image area obtained by development is kept as it is when coated, and is not subjected to any chemical treatment, so that heat resistance and chemical resistance are reduced. Inferior. JP-A-9-197121 describes a color filter using a positive photosensitive resin composition containing an acid-decomposable resin, a photoacid generator and a pigment. However, even with this method, the above problems are not sufficiently solved and are not practically satisfactory.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in order to improve the above-mentioned drawbacks of the prior art. The first object of the present invention is to include a crosslinking agent in an image area after development, and Accordingly, an object of the present invention is to provide a method for producing a color filter having excellent heat resistance and chemical resistance by crosslinking an image area. A second object is to provide a method of manufacturing a color filter having a high sensitivity, a forward taper, and an improved pattern profile, using a positive-type chemically amplified photosensitive coloring composition. The third object is that the development reproducibility of a wide latitude of development that does not require an oxygen barrier film is good,
It is another object of the present invention to provide a method for manufacturing a color filter which can provide a sharp image with little edge portion disturbance. A fourth object is to provide a method for producing a color filter having good dispersibility of a colorant and excellent transmittance.

[0008]

The above object has been attained by the following constitutions. (1) (1) a water-insoluble resin soluble in an aqueous alkali solution, (2) a compound capable of generating an acid upon irradiation with actinic rays or radiation, (3) having a group decomposable by an acid, and Molecular weight 3 whose solubility increases due to the action of acid
(4) a low-molecular acid-decomposable dissolution inhibiting compound having a molecular weight of 000 or less, and
A colorant, containing a positive-type photosensitive coloring composition, coated on a transparent substrate, exposed to light, heated after exposure, and developed to form an image pattern, then include a crosslinking agent in the image pattern, followed by overall exposure And heating the color filter. (2) The method for producing a color filter according to the above (1), wherein the positive photosensitive coloring composition further contains an organic basic compound. (3) (1) a resin having a group that decomposes under the action of an acid to increase solubility in an alkaline developer, (2) a compound that generates an acid upon irradiation with actinic rays or radiation, (3) an organic base Active compound, and (4) a colorant, a positive-type photosensitive coloring composition containing a, coated on a transparent substrate, exposed to light, heated after exposure, and developed to form an image pattern, the crosslinking agent in the image pattern A method for producing a color filter, comprising: adding, subsequently exposing, and heating. (4) The low-molecular-weight acid-decomposable dissolution-inhibiting compound having a molecular weight of 3000 or less, which has a group decomposable by an acid and whose solubility in an alkali developing solution is increased by the action of an acid. )). (5) The method for producing a color filter according to the above (3) or (4), comprising a resin which is insoluble in water and soluble in an aqueous alkali solution. (6) The method for producing a color filter according to (1) to (5), wherein the colorant is an organic pigment. (7) The average particle size of the organic pigment is 0.01 μm to 0.1 μm.
The method for producing a color filter according to the above (6), wherein the thickness is 2 μm.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. (1) Water-insoluble and alkali-soluble resin (alkali-soluble resin): Examples of the alkali-soluble resin used in the present invention include novolak resin, hydrogenated novolak resin, acetone-pyrogallol resin, o-polyhydroxystyrene, m Polyhydroxystyrene, p-polyhydroxystyrene, hydrogenated polyhydroxystyrene, halogen- or alkyl-substituted polyhydroxystyrene, hydroxystyrene-N-substituted maleimide copolymer, o / p- and m / p-hydroxystyrene copolymer A part of O- to the hydroxyl group of polyhydroxystyrene
Alkyl compounds (for example, 5 to 30 mol% of O-methyl compound, O- (1-methoxy) ethyl compound, O- (1-ethoxy) ethyl compound, O-2-tetrahydropyranyl compound, O- (t- Butoxycarbonyl) methylated product) or O-acylated product (for example, 5 to 30 mol% o-
Acetylated product, O- (t-butoxy) carbonylated product, etc.), styrene-maleic anhydride copolymer, styrene-
Examples include, but are not limited to, hydroxystyrene copolymers, α-methylstyrene-hydroxystyrene copolymers, carboxyl group-containing acrylic resins and derivatives thereof. Preferred alkali-soluble resins are o-polyhydroxystyrene, m-polyhydroxystyrene, p-polyhydroxystyrene and copolymers thereof, alkyl-substituted polyhydroxystyrene, partially O-alkylated polyhydroxystyrene, or O-polyhydroxystyrene.
-Acylated products, styrene-hydroxystyrene copolymers, α-methylstyrene-hydroxystyrene copolymers, and carboxyl group-containing (meth) acrylic resins.

In the present invention, two or more of these alkali-soluble resins may be used as a mixture. The amount of the alkali-soluble resin used is 10 to 80% by weight, preferably 20 to 70% by weight, based on the total solid content of the coloring composition. If the amount is less than this, the solubility of the entire system decreases,
The film property is unfavorably reduced, and if it is more than this, the pigment concentration is reduced and the image density is reduced.

(2) Compound that generates an acid upon irradiation with actinic rays or radiation (photoacid generator): The photoacid generator used in the present invention is a compound that generates an acid upon irradiation with actinic rays or radiation. . As the photoacid generator used in the present invention, a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photodecolorant for dyes, a photochromic agent, or a microresist is used. Known light (400-2
00 nm ultraviolet light, far ultraviolet light, particularly preferably g-line,
h-rays, i-rays, KrF excimer laser light), ArF excimer laser light, electron beams, X-rays, compounds generating an acid by a molecular beam or an ion beam, and mixtures thereof can be appropriately selected and used.

Other compounds used in the present invention that generate an acid upon irradiation with actinic rays or radiation include, for example, SI Schlesinger, Photogr. Sci. Eng., 18, 3
87 (1974), TSBetal, Polymer, 21,423 (1980) and the like diazonium salts, U.S. Pat.Nos. 4,069,055 and 4,06
Ammonium salts described in 9,056, Re 27,992, Japanese Patent Application No. 3-140,140, etc., DC Necker et al., Macromolecules, 1
7,2468 (1984), CSWenetal, Teh, Proc.Conf.Rad.Curing
ASIA, p478 Tokyo, Oct (1988), U.S. Pat.No. 4,069,055
No. 4,069,056, etc.
vello etal, Macromorecules, 10 (6), 1307 (1977), Chem. &
Eng. News, Nov. 28, p31 (1988), European Patent No. 104,143, U.S. Patent Nos. 339,049 and 410,201, JP-A-2-150,848
No. 2, iodonium salts described in JP-A-2-296,514 and the like, J.
V. Crivello etal, Polymer J. 17, 73 (1985), JVCrivell
o et al. J. Org. Chem., 43, 3055 (1978), WRWatt et al.
J. Polymer Sci., Polymer Chem. Ed., 22, 1789 (1984), JV
Crivello etal, Polymer Bull., 14,279 (1985), JVCriv
ello etal, Macromorecules, 14 (5), 1141 (1981), JVCri
vello etal, J.PolymerSci., Polymer Chem.Ed., 17,2877
(1979), European Patent Nos. 370,693, 3,902,114 and 233,56
No. 7, 297,443, 297,442, U.S. Pat.No. 4,933,377
Nos. 161,811, 410,201, 339,049, 4,76
No. 0,013, 4,734,444, 2,833,827, Dokoku Patent No.
2,904,626, 3,604,580, 3,604,581, etc., sulfonium salts, JVCrivello etal, Macromorecule
s, 10 (6), 1307 (1977), JVCrivello etal, J. PolymerSc
Selenonium salts described in i., Polymer Chem.Ed., 17, 1047 (1979), etc., CSWen et al., Teh, Proc. Conf. Rad. Curing AS
Onium salts such as arsonium salts described in IA, p478 Tokyo, Oct (1988), U.S. Pat.No. 3,905,815, JP-B-46-4605
No., JP-A-48-36281, JP-A-55-32070, JP-A-60-2
39736, JP-A-61-169835, JP-A-61-169837, JP-A-62-58241, JP-A-62-212401, JP-A-63-70243
Nos., Organohalogen compounds described in JP-A-63-298339, K. Meier et al, J. Rad. Curing, 13 (4), 26 (1986), T.
P. Gill et al, Inorg.Chem., 19, 3007 (1980), D. Astruc, A
Chem. Res., 19 (12), 377 (1896), organometallic / organic halides described in JP-A-2-14145, etc., S. Hayase eta
l, J. Polymer Sci., 25, 753 (1987), E. Reichmanis et al., J.
Pholymer Sci., Polymer Chem. Ed., 23, 1 (1985), QQZhu
etal, J. Photochem., 36, 85, 39, 317 (1987), B. Amit etal, T
etrahedron Lett., (24) 2205 (1973), DHR Barton et al.
J. Chem Soc., 3571 (1965), PM Collins et al., J. Chem. So
C., Perkin I, 1695 (1975), M. Rudinstein et al, Tetrahedr
on Lett., (17), 1445 (1975), JWWalker etal J. Am. Chem.
Soc., 110, 7170 (1988), SCBusman et al., J. Imaging Tech
nol., 11 (4), 191 (1985), HMHoulihan et al, Macormolecu
les, 21, 2001 (1988), PM Collins et al., J. Chem. Soc., Che
m.Commun., 532 (1972), S.Hayaseetal, Macromolecules, 1
8,1799 (1985), E. Reichmanis et al., J. Electrochem. Soc.,
Solid State Sci.Technol., 130 (6), FMHoulihan etal,
Macromolcules, 21, 2001 (1988), European Patent 0290,750
Nos. 046,083, 156,535, 271,851, 0,38
No. 3,343, U.S. Pat.Nos. 3,901,710, 4,181,531, JP-A-60-198538, and photoacid generators having a 0-nitrobenzyl-type protecting group described in JP-A-53-133022, M. TUNOOKA
etal, Polymer Preprints Japan, 35 (8), G. Berner eta
l, J.Rad.Curing, 13 (4), WJMijs etal, Coating Techno
l., 55 (697), 45 (1983), Akzo, H. Adachi et al, Polymer Pr
eprints, Japan, 37 (3), European Patent Nos. 0199,672 and 84515
No. 199,672, No. 044,115, No. 0101,122, U.S. Pat. Compounds that generate sulfonic acid upon photodecomposition, such as iminosulfonate described in 140109 and the like, and disulfone compounds described in JP-A-61-166544 and the like can be mentioned.

A group generating an acid by the light;
Alternatively, a compound having a compound introduced into the main chain or side chain of a polymer, for example, MEWoodhouse et al., J. Am. Chem.
Soc., 104, 5586 (1982), SPPappas etal, J. Imaging Sc
i., 30 (5), 218 (1986), S. Kondoetal, Makromol.Chem., Rap
id Commun., 9,625 (1988), Y.Yamadaetal, Makromol.Che
m., 152, 153, 163 (1972), JVCrivello etal, J. PolymerS
ci., Polymer Chem. Ed., 17, 3845 (1979), U.S. Pat.
No. 9,137, Dokoku Patent No. 3914407, JP-A-63-26653, JP-A-55-164824, JP-A-62-69263, JP-A-63-146038
JP-A-63-163452, JP-A-62-153853, JP-A-63-163452
Compounds described in JP-A-146029 can be used.

Further, VNRPillai, Synthesis, (1), 1 (198
0), A. Abad etal, Tetrahedron Lett., (47) 4555 (1971),
Compounds that generate an acid by light described in DHR Barton et al., J. Chem. Soc., (C), 329 (1970), U.S. Pat. No. 3,779,778, and EP 126,712 can also be used.

Among the compounds capable of decomposing upon irradiation with actinic rays or radiation to generate an acid, those which are used particularly effectively are described below. (1) The following general formula (PAG) substituted with a trihalomethyl group
The oxazole derivative represented by 1) or the general formula (PA)
An S-triazine derivative represented by G2).

[0016]

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In the formula, R ²⁰¹ is a substituted or unsubstituted aryl group or alkenyl group, and R ²⁰² is a substituted or unsubstituted aryl group, alkenyl group, alkyl group, —C (Y) ₃
Show Y represents a chlorine atom or a bromine atom. Specific examples include the following compounds, but the present invention is not limited thereto.

[0018]

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[0019]

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[0020]

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(2) An iodonium salt represented by the following general formula (PAG3) or a sulfonium salt represented by the following general formula (PAG4).

[0022]

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In the formula, Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group. Here, preferred substituents include an alkyl group, a haloalkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a nitro group, a carboxyl group, an alkoxycarbonyl group, a hydroxy group,
And mercapto groups and halogen atoms.

R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ each independently represent a substituted or unsubstituted alkyl group or aryl group. Preferably, an aryl group having 6 to 14 carbon atoms, 1 to 8 carbon atoms
And substituted derivatives thereof. Preferred substituents are those having 1 to 8 carbon atoms for the aryl group.
And an alkyl group having 1 to 8 carbon atoms, a nitro group, a carboxyl group, a hydroxy group and a halogen atom. The alkyl group is an alkoxy group having 1 to 8 carbon atoms, a carboxyl group or an alkoxycarbonyl group. is there.

[0025] Z ^- represents a counter anion, for example BF ₄ ^{-,
_{AsF 6 -, PF 6 -,}} SbF 6 -, SiF 6 2-, ClO 4 -,
CF ₃ SO ₃ ^-, etc. perfluoroalkane sulfonate anion, pentafluorobenzenesulfonic acid anion, condensed polynuclear aromatic sulfonic acid anion such as naphthalene-1-sulfonic acid anion, anthraquinone sulfonic acid anion, a sulfonic acid group-containing dyes Examples include, but are not limited to:

Further, two of R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ and Ar ¹ and Ar ² may be bonded via a single bond or a substituent.

Specific examples include the following compounds, but are not limited thereto.

[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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The above onium salts represented by the general formulas (PAG3) and (PAG4) are known, for example, JWKnapczyk
etal, J. Am. Chem. Soc., 91, 145 (1969), ALMaycok eta
l, J. Org. Chem., 35, 2532, (1970), E. Goethas et al., Bul
l.Soc.Chem.Belg., 73,546, (1964), HM Leicester, JA
me.Chem.Soc., 51,3587 (1929), JVCrivello etal, J.Po
lym.Chem.Ed., 18,2677 (1980), U.S. Pat.
No. 4,247,473, JP-A-53-101,331 and the like.

(3) Disulfone derivatives represented by the following formula (PAG5) or iminosulfonate derivatives represented by the following formula (PAG6).

[0041]

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Where Ar^Three, Ar^FourAre each independently substituted
Or an unsubstituted aryl group. R ²⁰⁶Is replaced or
It represents an unsubstituted alkyl group or aryl group. A is a substitution
Or unsubstituted alkylene, alkenylene, arylene
Shows a substituent group. Specific examples include the compounds shown below.
However, the present invention is not limited to these.

[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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(4) An o-nitrobenzyl-type photoacid generator represented by the following general formula (PAG7).

[0049]

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Specific examples include the following compounds, but are not limited thereto.

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[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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In the present invention, the compound that generates an acid upon irradiation with actinic rays or radiation is preferably an onium salt, a disulfone, a 4-position DNQ sulfonic acid ester, a triazine compound, or an o-nitrobenzyl-type photoacid generator. .

The amount of the compound which decomposes upon irradiation with actinic rays or radiation to generate an acid is usually 0.01 to 40% by weight based on the total weight of the solid content of the photosensitive composition (excluding the coating solvent). %, Preferably 0.1 to 20% by weight. When the amount of the compound that decomposes upon irradiation with actinic rays or radiation to generate an acid is less than 0.01% by weight, the resolution is reduced,
Further, if the addition amount is more than 40% by weight, the film property is reduced,
Heat resistance is undesirably deteriorated.

(3) A low-molecular acid-decomposable dissolution-inhibiting compound having a molecular weight of 3,000 or less (a low-molecular dissolution-inhibiting compound) having a group that can be decomposed by an acid and having a solubility in an alkaline developer increased by the action of an acid: The low molecular weight dissolution inhibiting compound used in the present invention is a compound having (A) at least one group selected from tertiary alkyl ester groups and tertiary alkyl carbonate groups as an acid-decomposable group, or (B) A compound having at least one group selected from an acetal group and a silyl ether group is preferable, and in the present invention, it is preferable to select from these compounds.
In each compound, at least two acid-decomposable groups are present in the structure, and at the position where the distance between the acid-decomposable groups is the longest, at least one bond atom excluding the acid-decomposable group is attached.
0, preferably at least 11, more preferably at least 12 compounds, or at least three acid-decomposable groups, and at the position where the distance between the acid-decomposable groups is farthest, an acid-decomposable group At least 9 bonding atoms excluding
It is advantageous to use compounds via at least one, preferably at least 10, more preferably at least 11.

The low-molecular dissolution inhibiting compound suppresses the solubility of the alkali-soluble resin in alkali, and the acid generated upon exposure to light causes the acid-decomposable group to be deprotected, and conversely reduces the solubility of the resin in alkali. Has a promoting effect. JP-A-63-2
No. 7829 and JP-A-3-98059 disclose a dissolution inhibiting compound having a skeletal compound of naphthalene, biphenyl and diphenylcycloalkane, but have a low dissolution inhibiting property with respect to an alkali-soluble resin and are insufficient in terms of profile and resolution. It is.

In the present invention, a preferred low-molecular-weight dissolution inhibiting compound is a compound having at least three alkali-soluble groups in one molecule and having a molecular weight of 3,000 or less, in which 80% or more of the alkali-soluble groups are acid-decomposable. A compound protected by a group.

In the present invention, the preferred upper limit of the number of the bonding atoms is 50, more preferably 30. In the present invention, the low-molecular-weight dissolution inhibiting compound has three or more acid-decomposable groups.
Or more, preferably 4 or more, and even those having two acid-decomposable groups, when the acid-decomposable groups are separated from each other by a certain distance or more, the dissolution inhibitory property to the alkali-soluble resin is remarkable. improves.

The distance between the acid-decomposable groups in the present invention is indicated by the number of via-bond atoms excluding the acid-decomposable groups. For example, in the case of the following compounds (1) and (2), the distance between the acid-decomposable groups is 4 bonding atoms, and in the compound (3), the bonding atom is 12 bonding atoms.

[0063]

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Further, the low molecular weight dissolution inhibiting compound of the present invention
Both (A) and (B) may have a plurality of acid-decomposable groups on one benzene ring, but preferably from a skeleton having one acid-decomposable group on one benzene ring. It is a compound that is composed. Further, the low molecular weight dissolution inhibiting compound of the present invention has a molecular weight of 3,000 or less, preferably 500
~ 3,000, more preferably 1,000 ~ 2,500
It is. The molecular weight of the low molecular weight dissolution inhibiting compound of the present invention is preferably within the above range in terms of high resolution.

In a preferred embodiment of the present invention,
The acid-decomposable group in (A) is -COO-C (R⁰¹)
(R⁰²) (R⁰³), -O-CO-OC (R⁰¹)
(R⁰²) (R⁰³) Group. More preferably acid decomposition
The functional group is -R⁰-COO-C (R⁰¹) (R ⁰²) (R⁰³),
Or -Ar-O-CO-OC (R⁰¹) (R⁰²)
(R⁰³) When the compound is bonded to the compound
is there.

The acid-decomposable group in (B) is —O
-C (R⁰⁴) (R⁰⁵) -OR⁰⁶Or -O-Si (R
⁰⁷) (R⁰⁸) (R⁰⁹) Group. More preferably acid
The decomposable group is -Ar-OC (R⁰⁴) (R⁰⁵) -O-
R⁰⁶Or -Ar-O-Si (R ⁰⁷) (R⁰⁸) (R⁰⁹)
This is the case where the compound is bonded to the compound by the structure represented by the group.
R⁰¹, R⁰², R⁰³Are the same or different
Good, alkyl, cycloalkyl and alkenyl groups
Or an aryl group.

R⁰⁴, R⁰⁵, R⁰⁷, R⁰⁸And R⁰⁹Each
Hydrogen atom, alkyl
Group, cycloalkyl group, alkenyl group or aryl
A group represented by R⁰⁶Represents an alkyl group or an aryl group
You. Where R⁰⁷~ R⁰⁹At least two of them are hydrogen atoms or less
An outer group, and R⁰¹~ R⁰³, R⁰⁴~ R⁰⁵And R⁰⁷~
R ⁰⁹Two of which may combine to form a ring
No. R⁰Is a divalent or higher valent aliphatic which may have a substituent
Or an aromatic hydrocarbon group, and -Ar- is a monocyclic or
Or a divalent or higher valent aromatic optionally having a polycyclic substituent
Represents a group.

The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group and a t-butyl group. Preferred are those having 3 to 10 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclohexyl group and adamantyl group, and alkenyl groups having 2 to 2 carbon atoms such as vinyl group, propenyl group, allyl group and butenyl group. Preferably, the aryl group has 6 to 1 carbon atoms such as phenyl, xylyl, toluyl, cumenyl, naphthyl and anthracenyl.
Four are preferred.

The substituents include a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, and the above-mentioned alkyl groups, methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group. Alkoxy groups such as groups, n-butoxy group, isobutoxy group, sec-butoxy group, t-butoxy group, alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group, aralkyl groups such as benzyl group, phenethyl group and cumyl group, Aralkyloxy group, formyl group, acetyl group, butyryl group, benzoyl group, cyanyl group, acyl group such as valeryl group, acyloxy group such as butyryloxy group, the above alkenyl group, vinyloxy group, propenyloxy group, allyloxy group, butenyloxy group Alkenyloxy groups such as Serial aryl group, an aryloxy group such as phenoxy group, and an aryloxycarbonyl group such as benzoyloxy group.

Specific examples of the tertiary alkyl group of the tertiary alkyl ester group and tertiary alkyl carbonate group include t-butyl group, t-pentyl group, t-hexyl group,
Particularly preferred is a t-butyl group. Also, as the acetal group,

[0071]

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A group represented by the following formula:

[0073]

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The following groups can be mentioned. Further, as a silyl ether group,

[0075]

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The following groups may be mentioned.

Preferred low molecular weight dissolution inhibiting compounds are described in JP-A-1-289946, JP-A-1-289947, JP-A-2-2560, JP-A-3-128959, JP-A-3-158855, and JP-A-3-158855. 179353, JP-A-3-191351, JP-A-3-200251, JP-A-3-200252, JP-A-3-200253,
JP-A-3-200254, JP-A-3-200255
JP-A-3-259149, JP-A-3-27995
8, JP-A-3-279959, JP-A-4-1650
No., JP-A-4-1651, JP-A-4-11260,
JP-A-4-12356, JP-A-4-12357, JP-A-3-33229, JP-A-3-230790, JP-A-3-320438, JP-A-4-25157, JP-A-4 -52732, Japanese Patent Application No. 4-103215, Japanese Patent Application No. 4-104542, Japanese Patent Application No. 4-107885,
A group in which part or all of the phenolic OH group of the polyhydroxy compound described in the specification of Japanese Patent Application Nos. 4-107889 and 4-152195 is -R ^0-
Linked by COO-A ⁰ or B ⁰ groups include protected compound.

More preferably, JP-A-1-289946.
JP-A-3-128959, JP-A-3-15885
5, JP-A-3-179353, JP-A-3-2002
No. 51, JP-A-3-200252, JP-A-3-200
255, JP-A-3-259149, JP-A-3-27
9958, JP-A-4-1650, JP-A-4-112
No. 60, JP-A-4-12356, JP-A-4-1235
7, Japanese Patent Application No. 4-25157, Japanese Patent Application No. 4-10321
No. 5, Japanese Patent Application No. 4-104542, Japanese Patent Application No. 4-1078
No. 85, Japanese Patent Application Nos. 4-107889 and 4-15219
No. 5 using the polyhydroxy compound described in the specification.

More specifically, general formulas [I] to [XV]
The compound represented by I] is mentioned.

[0080]

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[0081]

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[0082]

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[0083]

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Here, R ¹⁰¹ , R ¹⁰² , R ¹⁰⁸ ,
R ¹³⁰ : which may be the same or different, a hydrogen atom, -R
^{0 -COO-C (R 01)} (R 02) (R 03) or -CO-
^{O-C (R 01) (} R 0 2) (R 03), where, R ^0, R ^01,
The definitions of R ⁰² and R ⁰³ are the same as described above.

R ¹⁰⁰ : —CO—, —COO—, —NHC
ONH-, -NHCOO-, -O-, -S-, -SO
-, -SO _2- , -SO _3- , or

[0086]

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[0087] Here, G = 2 to 6, provided that at least one alkyl group of R ^0.99, R ¹⁵¹ when the ^{G = 2, R 150, R} 151: may be the same or different, a hydrogen atom, an alkyl Group, alkoxy group, -OH, -COOH,
-CN, halogen atom, -R ¹⁵² -COOR ^{15 3} or ^{-R 154 -OH, R 152, R} 154: an alkylene group, R ^153: a hydrogen atom, an alkyl group, an aryl group or an aralkyl group,, R ^99, R ¹⁰³ ~ R ¹⁰⁷ , R ¹⁰⁹ , R ^{111
~R 118, R 121 ~R 123,} R 128 ~R 129, R 131 ~
R ¹³⁴ , R ^{138 to} R ¹⁴¹ and R ¹⁴³ may be the same or different and represent a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, an aryloxy group, an aralkyl group, an aralkyloxy group; A halogen atom, a nitro group, a carboxyl group, a cyano group, or -N ( ^R155 ) ( ^R156 ) ( ^R155 , ^R156 : H, an alkyl group, or an aryl group) ^R110 : a single bond, an alkylene group, or

[0088]

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R ¹⁵⁷ and R ¹⁵⁹ may be the same or different, and represent a single bond, an alkylene group, —O—, —S—, —CO
— Or a carboxyl group, R ¹⁵⁸ : a hydrogen atom, an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, a nitro group, a hydroxyl group, a cyano group, or a carboxyl group, provided that the hydroxyl group is an acid-decomposable group (for example, t-butoxycarbonylmethyl group, tetrahydropyranyl group, 1-ethoxy-1-ethyl group,
(1-t-butoxy-1-ethyl group).

R ¹¹⁹ and R ¹²⁰ may be the same or different and are each a methylene group, a lower alkyl-substituted methylene group, a halomethylene group, or a haloalkyl group, provided that the lower alkyl group means an alkyl group having 1 to 4 carbon atoms. R ^{124 to} R ¹²⁷ may be the same or different and may be a hydrogen atom or an alkyl group; R ^{135 to} R ¹³⁷ may be the same or different and a hydrogen atom;
An alkyl group, an alkoxy group, an acyl group, or an acyloxy group, R ¹⁴² : a hydrogen atom, —R ⁰ —COO—C (R ⁰¹ )
( ^R02 ) ( ^R03 ) or -CO-OC ( ^R01 ) ( ^R02 )
(R ⁰³ ), or

[0091]

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R ¹⁴⁴ and R ¹⁴⁵ may be the same or different and represent a hydrogen atom, a lower alkyl group, a lower haloalkyl group,
Or an aryl group, R ^{146 to} R ¹⁴⁹ : may be the same or different, and may be hydrogen, hydroxyl, halogen, nitro, cyano, carbonyl, alkyl, alkoxy, alkoxycarbonyl, aralkyl, aralkyloxy A group, an acyl group, an acyloxy group, an alkenyl group, an alkenyloxy group, an aryl group, an aryloxy group, or an aryloxycarbonyl group, provided that the four substituents having the same symbols do not have to be the same group. : —CO— or —SO ₂ —, Z, B: single bond or —O—, A: methylene group, lower alkyl-substituted methylene group, halomethylene group, or haloalkyl group; E: single bond or oxymethylene group , A to z, a1 to y1: when plural, the groups in () may be the same or different; a to q, s, t, v, g1 to i1, k1 m1, o1, q1, s1, u1: 0 or an integer of 1 to 5, r, u, w, x, y, z, a1~f1, p1, r1, t1, v1~x1: 0 or 1
An integer of 4, j1, n1, z1, a2, b2, c2, d2: an integer of 0 or 1 to 3, at least one of z1, a2, c2, d2 is 1 or more, y1: an integer of 3 to 8, (a + b), (e + f + g), (k + l + m), (q + r + s), (w
+ x + y), (c1 + d1), (g1 + h1 + i1 + j1), (o1 + p1), (s1 + t1) ≧ 2,
(j1 + n1) ≦ 3, (r + u), (w + z), (x + a1), (y + b1), (c1 + e1), (d1
+ f1), (p1 + r1), (t1 + v1), (x1 + w1) ≦ 4, provided that the general formula [V]
In the case of (w + z), (x + a1) ≦ 5, (a + c), (b + d), (e + h), (f + i),
(g + j), (k + n), (l + o), (m + p), (q + t), (s + v), (g1 + k1), (h1 + l
1), (i1 + m1), (o1 + q1), (s1 + u1) ≦ 5.

[0093]

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[0094]

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[0095]

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[0096]

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Specific examples of preferred compound skeletons are shown below.

[0098]

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[0099]

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[0100]

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[0101]

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[0102]

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[0103]

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[0104]

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[0105]

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[0106]

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[0107]

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[0108]

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[0109]

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[0110]

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[0111]

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[0112]

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[0113]

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[0114]

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[0115]

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[0116]

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R in the compounds (1) to (63) is a hydrogen atom or

In the case of the compound of the type (A), -CH _{2-
COO-C (CH 3) 2} C 6 H 5, -CH 2 -COO-C
A group selected from (CH ₃ ) ₃ and —COO—C (CH ₃ ) ₃ ;

[0119]

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This is a group selected from the following. However, at least two, or three depending on the structure, are groups other than hydrogen atoms, and each substituent R may not be the same group.

The amount of the low molecular weight dissolution inhibiting compound used in the present invention is 3 to 30% by weight, preferably 5 to 25% by weight, based on the total solid content (excluding the solvent) of the photosensitive coloring composition. % Range. When the amount of the low molecular weight dissolution inhibiting compound used in the present invention is less than 3% by weight, the solubility of the whole system is reduced or the film property is reduced. Image density is undesirably reduced.

(4) Organic basic compound: When the acid generated in the photosensitive layer is deactivated in the vicinity of the surface by a basic substance in the environment, it tends to form a so-called T-top-shaped shouldered pattern. In the present invention, it is preferable to use an organic basic compound in the photosensitive composition. The use of a photosensitive composition containing an organic basic compound prevents the diffusion of acids, reduces the action of basic substances in the environment,
This prevents the top shape. Further, this organic basic compound improves the dispersibility of the pigment, and acts to prevent aggregation by adsorbing to the pigment, thereby improving the stability over time of the photosensitive composition containing the same, and reducing aggregation of the pigment. Therefore, a color filter having higher transmittance and better panel characteristics can be manufactured. Preferred organic basic compounds that can be used in the present invention include nitrogen-containing basic compounds. Preferred chemical environments include the structures of the following formulas (A) to (E).

[0123]

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Further preferred compounds are nitrogen-containing basic compounds having two or more nitrogen atoms having different chemical environments in one molecule, and particularly preferred is a ring structure containing a substituted or unsubstituted amino group and a nitrogen atom. Or a compound having an alkylamino group. Preferred specific examples include substituted or unsubstituted guanidine, substituted or unsubstituted aminopyridine, substituted or unsubstituted aminoalkylpyridine, substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted indazol,
Substituted or unsubstituted pyrazole, substituted or unsubstituted pyrazine, substituted or unsubstituted pyrimidine, substituted or unsubstituted purine, substituted or unsubstituted imidazoline, substituted or unsubstituted pyrazoline, substituted or unsubstituted piperazine, substituted Or, unsubstituted aminomorpholine, substituted or unsubstituted aminoalkylmorpholine and the like can be mentioned. Preferred substituents are an amino group,
An aminoalkyl group, an alkylamino group, an aminoaryl group, an arylamino group, an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, an aryloxy group, a nitro group, a hydroxyl group, and a cyano group. As particularly preferred compounds, guanidine, 1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, 2-
Aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine, 2- (aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-amino -4-methylpyridine, 2-amino-5
-Methylpyridine, 2-amino-6-methylpyridine,
3-aminoethylpyridine, 4-aminoethylpyridine, 3-aminopyrrolidine, piperazine, N- (2-aminoethyl) piperazine, N- (2-aminoethyl) piperidine, 4-amino-2,2,6,6 -Tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine, 1- (2-aminoethyl) pyrrolidine, pyrazole, 3-amino-5-methylpyrazole, 5-amino-3-methyl-1-p- Tolylpyrazole, pyrazine, 2- (aminomethyl) -5-methylpyrazine, pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline,
Examples include, but are not limited to, N-aminomorpholine and N- (2-aminoethyl) morpholine.

These nitrogen-containing basic compounds are used alone or in combination of two or more. The amount of the nitrogen-containing basic compound used is the solid content (excluding the solvent) of the photosensitive coloring composition.
Usually, 0.01 to 30% by weight, preferably 0.1% by weight.
01 to 20% by weight. If the amount is less than 0.01% by weight, the effect of the present invention cannot be obtained.

(5) Colorant: As the colorant used in the present invention, various conventionally known dyes, inorganic pigments or organic pigments can be used. As the dye, disperse dyes, oil-soluble dyes, direct dyes, acid dyes and the like described in the Color Index can be used. Suitable dyes include oily dyes and basic dyes. Specifically, Oil Yellow # 101, Oil Yellow # 103, Oil Pink # 312, Oil Green BG, Oil Blue BOS,
Oil Blue # 603, Oil Black BY, Oil Black BS, Oil Black T-505 (all manufactured by Orient Chemical Industries, Ltd.), Crystal Violet (C
I42555), methyl violet (CI4253)
5), rhodamine B (CI45170B), malachite green (CI42000), methylene blue (CI5
2015).

The inorganic pigment is a metal compound represented by a metal oxide, a metal complex salt or the like, and specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony or the like. Metal oxides,
And composite oxides of the above metals. In the present invention, it is desirable to use various organic pigments.

As the organic pigment, CI Pigment Yellow 11, 24, 31, 53, 83, 93, 99, 10
8, 109, 110, 138, 139, 150,
151, 154, 167, 185, 191, 193, 194 CIPigment Orange 36, 38, 43, 66, 67, 68, 71 CIPigment Red 105, 122, 149, 150, 155, 171, 1
75, 176, 177, 209 224, 254, 255, 260 CIPigment Violet 19, 23, 32, 39 CIPigment Blue 1, 2, 15: 1, 15: 2, 15: 3, 15: 6, 1
6, 22, 60, 66 CIPigment Green 7, 36, 37 CIPigment Brown 25, 28 CIPigment Black 1, 20, 31, 32 and the like.

Examples of preferable pigments include, but are not limited to, the following.

[0130]

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[0131]

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[0132]

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[0133]

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[0134]

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[0135]

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After the synthesis, these pigments are supplied after drying by various methods. Usually, it is dried from an aqueous medium and supplied as a powder, but since water requires a large latent heat of vaporization to dry, a large amount of heat energy is applied to dry it into a powder. Therefore, the pigment usually forms an aggregate (secondary particle) in which the primary particles are aggregated.

It is not easy to disperse the pigment forming such an aggregate in fine particles. Therefore, it is preferable that the pigment is previously treated with various resins. Examples of the treatment method include a flushing treatment and a kneading method using a kneader, an extruder, a ball mill, a two or three roll mill, or the like. Among them, a flushing treatment and a kneading method using a two- or three-roll mill are suitable for forming fine particles.

The flushing treatment is generally a method in which an aqueous dispersion of a pigment and a resin solution dissolved in a solvent immiscible with water are mixed, the pigment is extracted from an aqueous medium into an organic medium, and the pigment is treated with the resin. . According to this method, since the pigment does not undergo drying, aggregation of the pigment can be prevented and dispersion becomes easy. In kneading with two or three roll mills, a pigment and a resin or a solution of a resin are mixed, and then the pigment and the resin are kneaded while applying a high shear (shearing force) to coat the pigment surface with the resin. And a method of treating a pigment.

In the present invention, the resin, acrylic resin, vinyl chloride-
Processed pigments treated with a vinyl acetate resin, a maleic acid resin, an ethylcellulose resin, a nitrocellulose resin or the like can also be conveniently used. The resin used in the present invention,
The form of the processed pigment treated with the above-mentioned various resins is preferably a powder, paste, pellet, or paste in which the resin and the pigment are uniformly dispersed. In addition, a non-uniform lump having a gelled resin is not preferable.

These organic pigments are used alone or in various combinations in order to increase color purity. Specific examples are shown below.
As the red pigment, an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment alone, or a mixture of at least one of them with a disazo yellow pigment or an isoindoline yellow pigment is used. Further, a mixture of an anthraquinone-based pigment and a perylene-based pigment or a diketopyrrolopyrrole-based pigment, or a mixture of the above-mentioned yellow pigment is used. For example, as anthraquinone pigments, C.I. I. Pigment Red 177 and perylene pigments include C.I. I. Pigment Red 155 is a diketopyrrolopyrrole-based pigment such as C.I. I. Pigment Red 254, and C.I. I. Pigment yellow 83, C.I. I. Pigment Yellow 13
9, C.I. I. Pigment Yellow 150, C.I. I. Pigment Yellow 185, C.I. I. Pigment Yellow 1
10, C.I. I. Pigment Yellow 109 was good. The weight ratio of the red pigment to the yellow pigment is 100:
From 5 to 100: 100 was good. When the ratio is 100: 4 or less, the light transmittance from 400 nm to 500 nm cannot be suppressed, and the color purity cannot be increased. Also 100:
At 51 or more, the main wavelength was shorter than the short wavelength, and the deviation from the NTSC target hue was large. Especially from 100: 10 1
The range of 00:60 was optimal.

As a green pigment, a halogenated phthalocyanine pigment alone or a mixture with a disazo yellow pigment or an isoindoline yellow pigment is used. I.
Pigment Green 7, 36, 37 and C.I. I. Pigment Yellow 83 or C.I. I. Pigment Yellow 13
9, C.I. I. Pigment Yellow 150, C.I. I. Pigment Yellow 185, C.I. I. Pigment Yellow 1
10, C.I. I. Pigment Yellow 109 was good. The weight ratio of green pigment to yellow pigment is 100: 5
100: 40 was better. When the ratio is 100: 4 or less, the light transmittance from 400 nm to 450 nm cannot be suppressed, and the color purity cannot be increased. 100: 41
Above, the main wavelength became longer and the deviation from the NTSC target hue increased. Especially from 100: 5 to 100:
A range of 20 was optimal. Thus, the yellow pigment is used in combination with the red and green pigments. If the dispersibility of the yellow pigment is poor, a sufficiently transparent color filter cannot be obtained.

As the blue pigment, a phthalocyanine pigment alone or a mixture with a dioxazine purple pigment is used. I. Pigment Blue 15: 3 or C.I. I. Pigment Blue 15: 6 and C.I. I. Pigment Violet 23 was good. The weight ratio of the blue pigment to the violet pigment was preferably from 100: 5 to 100: 50. 400 to 420 for 100: 4 or less
The light transmittance of nm could not be suppressed, and the color purity could not be increased. At 100: 51 or more, the dominant wavelength became longer and the deviation from the NTSC target hue increased. In particular, the range of 100: 5 to 100: 20 was optimal.

Further, by using a powdery pigment obtained by finely dispersing the above pigment in an acrylic resin, a maleic acid resin, a vinyl chloride-vinyl acetate copolymer, an ethyl cellulose resin or the like, a pigment having good dispersibility and dispersion stability can be obtained. Containing photosensitive resin was obtained.

The concentration of the pigment of each color in the total solid content of the photosensitive coloring composition is 5% by weight to 70% by weight. 5
If the content is less than 70% by weight, the color density does not appear and the color filter is not suitable. If the content exceeds 70% by weight, problems such as a decrease in sensitivity and a deterioration in film properties are caused. Preferably 20% by weight
To 60% by weight. In the color filter produced by the pigment dispersion method, if the particle size of the pigment is large,
The display contrast ratio is remarkably deteriorated due to a decrease in transmittance and a depolarizing effect. Further, the photosensitive coloring composition in which the pigment is dispersed causes aggregation with the passage of time, and the transmittance and the contrast ratio are lower than those at the initial stage. In addition, a problem arises in applicability and the like. In recent years, color filters have been required to have higher definition, and higher transmittance and higher contrast have been desired. It is necessary that the pigment particle size be equal to or less than the wavelength of visible light in order to satisfy transparency and contrast. In the present invention, the average particle size is 0.01 to 0.1.
It is preferably 2 μm.

(6) Decomposed by the action of acid,
Resin having group that increases solubility in image solution: the present invention
Depending on the acid used in the photosensitive coloring composition in
Groups that decompose and increase solubility in alkaline developers
As the resin having, the main chain or side chain of the resin, or
Is a tree having an acid-decomposable group in both the main chain and the side chain.
It is fat. Among them, those with acid-decomposable groups on the side chain
Fat is more preferred. Preferred groups that can be decomposed by acid
Is -COOA⁰, -OB⁰And these are
The group to be contained is -R⁰-COOA⁰Or -A_r-O
-B⁰The group shown by these is mentioned. Where A⁰Is -C
(R⁰¹) (R⁰²) (R⁰³), -Si (R⁰¹) (R⁰²)
(R ⁰³) Or -C (R⁰⁴) (R⁰⁵) -OR⁰⁶Base
Show. B⁰Is -A⁰Or -CO-OA⁰Indicates a group
(R⁰, R⁰¹~ R⁰⁶, And Ar are as defined below).

The acid-decomposable group is preferably a silyl ether group, a cumyl ester group, an acetal group, a tetrahydropyranyl ether group, a tetrahydropyranyl ester group, an enol ether group, an enol ester group,
And a tertiary alkyl ester group and a tertiary alkyl carbonate group. More preferred are a tertiary alkyl ester group, a tertiary alkyl carbonate group, a cumyl ester group, an acetal group, and a tetrahydropyranyl ether group.

Next, these acid-decomposable groups form side chains.
When the base resin is bonded with --OH in the side chain,
Or -COOH, preferably -R⁰-COOH or
-A _rIt is an alkali-soluble resin having an -OH group. An example
For example, the alkali-soluble resin described above can be mentioned.
You.

The alkali dissolution rate of these alkali-soluble resins was measured (at 23 ° C.) using 0.261N tetramethylammonium hydroxide (TMAH).
A / sec or more is preferable. Particularly preferably 330A
/ Sec or more (A is angstroms). From such a viewpoint, a particularly preferred alkali-soluble resin is
o-, m-, p-poly (hydroxystyrene) and copolymers thereof, hydrogenated poly (hydroxystyrene), halogen- or alkyl-substituted poly (hydroxystyrene), part of poly (hydroxystyrene), O-alkyl And styrene-hydroxystyrene copolymers, α-methylstyrene-hydroxystyrene copolymers and hydrogenated novolak resins.

The resin having an acid-decomposable group used in the present invention is disclosed in EP 254853, JP-A No. 2-25.
No. 850, No. 3-223860, No. 4-251259
As disclosed in US Pat. No. 6,086,098, an alkali-soluble resin is reacted with a precursor of an acid-decomposable group, or an alkali-soluble resin monomer having an acid-decomposable group bonded thereto is copolymerized with various monomers. Can be obtained.

Specific examples of the resin having a group capable of being decomposed by an acid used in the present invention are shown below, but the present invention is not limited thereto.

[0151]

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[0152]

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[0153]

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[0154]

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The content of acid-decomposable groups is determined by the number of acid-decomposable groups in the resin (B) and the number of alkali-soluble groups not protected by acid-decomposable groups (S). B /
It is represented by (B + S). The content is preferably 0.01 to
0.5, more preferably 0.05 to 0.40, and still more preferably 0.05 to 0.30. B / (B + S)>
A value of 0.5 is not preferred because it causes film shrinkage after PEB, poor adhesion to the substrate and scum. On the other hand, B / (B + S) <
A value of 0.01 is not preferable because standing waves may be remarkably left on the pattern side wall. The weight-average molecular weight of the resin containing an acid-decomposable group is 3000 to 200,00
0 is preferable, and 8000 to 70,000 is more preferable.
It is. In this range, the film thickness of the unexposed portion hardly occurs, and the solubility of the exposed portion is good. The content of the resin containing an acid-decomposable group in the composition is preferably 10 to 90% by weight, more preferably 20 to 90% by weight in terms of solid content.
７０70% by weight.

(7) Other components usable in the present invention:
The photosensitive coloring composition of the present invention may further contain, if necessary, a plasticizer, a surfactant, a photosensitizer, a compound having two or more phenolic OH groups that promote solubility in a developer, and the like. be able to.

The compound having two or more phenolic OH groups which can be used in the present invention is preferably a phenol compound having a molecular weight of 1,000 or less. Further, it is necessary to have at least two phenolic hydroxyl groups in the molecule. If the number exceeds 10, the effect of improving the development latitude is lost. When the ratio of the phenolic hydroxyl group to the aromatic ring is less than 0.5, the film thickness dependency is large, and the development latitude tends to be narrow. If this ratio exceeds 1.4, the stability of the composition deteriorates, and it becomes difficult to obtain high resolution and good film thickness dependency, which is not preferable.

The preferred addition amount of this phenol compound is 2 to 50% by weight, more preferably 5 to 30% by weight, based on the alkali-soluble resin. An addition amount exceeding 50% by weight is not preferable because new development defects such as development residue deterioration and pattern deformation during development occur.

Such a phenol compound having a molecular weight of 1,000 or less can be prepared by those skilled in the art by referring to the methods described in, for example, JP-A-4-122938, JP-A-2-28531, US Pat. No. 4,916,210, and EP 219294. It can be easily synthesized at Specific examples of the phenol compound are shown below, but the compounds that can be used in the present invention are not limited to these.

Resorcin, phloroglucin, 2, 3, 4
-Trihydroxybenzophenone, 2,3,4,4'-
Tetrahydroxybenzophenone, 2,3,4,3 ',
4 ', 5'-hexahydroxybenzophenone, acetone-pyrogallol condensation resin, fluoroglucoside,
4,2 ', 4'-biphenyltetrol, 4,4'-thiobis (1,3-dihydroxy) benzene, 2,2',
4,4'-tetrahydroxydiphenyl ether, 2,
2 ', 4,4'-tetrahydroxydiphenylsulfoxide, 2,2', 4,4'-tetrahydroxydiphenylsulfone, tris (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) Cyclohexane, 4,4- (α-methylbenzylidene) bisphenol, α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene,
α, α ', α "-tris (4-hydroxyphenyl)-
1-ethyl-4-isopropylbenzene, 1,2,2-
Tris (hydroxyphenyl) propane, 1,1,2-
Tris (3,5-dimethyl-4-hydroxyphenyl)
Propane, 2,2,5,5-tetrakis (4-hydroxyphenyl) hexane, 1,2-tetrakis (4-hydroxyphenyl) ethane, 1,1,3-tris (hydroxyphenyl) butane, para [α, α , Α ', α'-tetrakis (4-hydroxyphenyl)]-xylene.

Further, the photosensitive coloring composition of the present invention is added by adding a spectral sensitizer as described below and sensitizing the photoacid generator to be used in the region of longer wavelength than far ultraviolet, which has no absorption. Can be made sensitive to the i or g line.
Examples of suitable spectral sensitizers include benzophenone, p, p'-tetramethyldiaminobenzophenone,
p, p'-tetraethylethylaminobenzophenone,
2-chlorothioxanthone, anthrone, 9-ethoxyanthracene, anthracene, pyrene, perylene, phenothiazine, benzyl, acridine orange, benzoflavin, setoflavin-T, 9,10-diphenylanthracene, 9-fluorenone, acetophenone, phenanthrene, 2-nitro Fluorene, 5-nitroacenaphthene, benzoquinone, 2-chloro-4-nitroaniline, N-acetyl-p-nitroaniline, p-nitroaniline, N-acetyl-4-nitro-1-naphthylamine, picramide, anthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone 1,2-benzanthraquinone, 3-methyl-1,3-diaza-
1,9-benzanthrone, dibenzalacetone, 1,
2-naphthoquinone, 3,3′-carbonyl-bis (5,
7-dimethoxycarbonylcoumarin) and coronene, but are not limited thereto. Further, these spectral sensitizers can also be used as a light absorbing agent for far ultraviolet light of a light source. In this case, the light absorbing agent exerts the effect of improving the standing wave by reducing the reflected light from the substrate and reducing the influence of multiple reflection in the photosensitive coloring composition film.

The photosensitive coloring composition of the present invention is dissolved in a solvent in which each of the above components is dissolved, and coated on a support. As the solvent used herein, ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, γ-
Butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, methyl lactate, ethyl lactate, Methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N-
Dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, tetrahydrofuran and the like are preferable, and these solvents are used alone or in combination.

A surfactant may be added to the above solvent. Specifically, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether,
Polyoxyethylene alkyl allyl ethers such as polyoxyethylene nonylphenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, Sorbitan fatty acid esters such as sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate Surfactants such as polyoxyethylene sorbitan fatty acid esters such as acrylates and the like, F-top EF301, E 303, EF352 (manufactured by Shin Akita Kasei Co., Ltd.), Megafac F171, F173 (manufactured by Dainippon Ink Co., Ltd.), Flora - de FC430, FC43
1 (manufactured by Sumitomo 3M Limited), Asahi Guard AG71
0, Surflon S-382, SC101, SC102,
Fluorinated surfactants such as SC103, SC104, SC105 and SC106 (manufactured by Asahi Glass Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), and acrylic or methacrylic (co) polymerized polyflow No. 75, no. 95 (manufactured by Kyoeisha Yushi Kagaku Kogyo KK) and the like. The amount of these surfactants is usually 2 parts by weight or less, preferably 1 part by weight or less, per 100 parts by weight of the solids in the composition of the present invention. These surfactants may be added alone or in some combination.

Examples of the developer of the photosensitive coloring composition of the present invention include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, and n-propylamine. Primary amines such as diethylamine, di-n-
Secondary amines such as butylamine, triethylamine, tertiary amines such as methyldiethylamine, dimethylethanolamine, alcoholamines such as triethanolamine, tetramethylammonium hydroxide, quaternary ammonium salts such as tetraethylammonium hydroxide, An alkaline aqueous solution of a cyclic amine such as pyrrole or pyriidine can be used.

To produce a color filter according to the present invention, the photosensitive coloring composition of the present invention is coated on a transparent substrate, exposed, heated and developed after exposure to form an image pattern, and then crosslinked to the image pattern. The agent is contained by means such as application of the solution, and then the entire surface is exposed and heated. Here, as the transparent substrate, for example, soda glass used for a liquid crystal display device, Pyrex glass, quartz glass, and those in which a transparent conductive film is attached thereto, or a photoelectric conversion element substrate used for a solid-state imaging device, For example, a silicon substrate or the like can be used. These substrates are generally formed with black stripes for isolating each pixel. The composition of the present invention is applied to a substrate by a coating method such as spin coating, casting coating, or roll coating to form a radiation-sensitive composition layer, exposed through a predetermined mask pattern, and developed with a developer. By doing so, a colored pattern is formed. The radiation used in this case is particularly g
Ultraviolet rays such as line and i-line are preferably used.

Exposure may be performed by using the following light source and through an image mask by, for example, contact exposure, proxy (proximity) exposure, or a direct drawing method using a laser. After the exposure, heating is performed by close contact heating using a hot plate, heating by an oven, a heating method by infrared irradiation, or the like. Further, the photosensitive coloring composition remaining in the image area can be decomposed and stabilized by exposing the entire surface and / or heating after development, and it is more preferable to perform the entire exposure while heating. The heating temperature is 120
C. or higher, preferably 150 ° C. or higher. The exposure amount is not particularly limited as long as it is equal to or more than the exposure amount when forming an image. Exposure light sources include ultra-high pressure mercury lamp, high pressure mercury lamp, low pressure mercury lamp, Deep
UV mercury lamp, xenon lamp, metal halide lamp, excimer laser lamp, etc., exposure wavelength 150 to 40
0 nm is mentioned.

(8) Crosslinking agent: Various known crosslinking agents can be used in the present invention. Also,
The crosslinking agent of the present invention includes a compound capable of curing the composition used in the present invention by crosslinking or polymerization reaction under an acid catalyst or in combination with heating. One of the typical crosslinking agents that can be used in the present invention is a compound having a methylol group or a substituted methylol group as a formaldehyde precursor, and examples thereof include those having a structure represented by the following general formula. _{(R 10 O-CH 3)} n -A- (CH 3 -OR 11) m in the above formula, A: a group represented by the formula B or B-Y-B, B: a substituted or unsubstituted single nuclear or fused polynuclear aromatic hydrocarbon or oxygen, means a sulfur and / or nitrogen-containing heterocyclic compounds, Y: an alkylene single bond, or C ₁ -C _4, substituted alkylene, arylene, substituted arylene, arylalkylene , - - or -O, S -, - SO ₂ -, - CO-,
It means a -COO-, -OCOO-, -CONH- bond and a substituted or unsubstituted alkylene group having such a bond, and Y may be a polymer such as a phenol resin. R ₁₀ and R _11: identical to each other or separate H,, C ₁ ~C ₄
Alkyl, cycloalkyl, substituted or unsubstituted aryl, alkaryl, arylalkyl, or acyl group, wherein n is 1 to 3, and m is 0 to 3.

Specific examples of such compounds include various aminoplasts or phenoplasts, that is, urea-
Formaldehyde, melamine-formaldehyde, benzoguanamine-formaldehyde, glycoluril-
There are formaldehyde resins and their monomers or oligomers. Many of these are commercially available from manufacturers for uses such as vehicles for paints. For example, Cymel® manufactured by American Cyanamid
300, 301, 303, 350, 370, 380, 1
116, 1130, 1123, 1125, 1170, etc.
Or Nikarac (registered trademark) MW manufactured by Sanwa Chemical Co., Ltd.
30, MW30M, MW30HM, MX45, BX40
00, VESTANAT T1890, VESTANA
A series such as TB1358 can be cited as a typical example. These may be used alone or in combination of two or more.

Another specific example is a methylolated or alkoxymethylated phenol derivative which can be a formaldehyde precursor. These may be used as a monomer or may be used as a resin such as a resole resin or a benzyl ether resin.
Further, as another system of the acid crosslinkable compound, a compound having a silanol group, for example, JP-A-2-154266,
Compounds as disclosed in JP-A-2-173647 can also be used.

Further, an alkyl-modified compound of melamine, benzoguanamine, glycoluril or a compound obtained by reacting urea with formaldehyde, an epoxy compound, a resole compound, an isocyanate compound and the like can also be used.

Specifically, Cymel (registered trademark) 300, 301, 303, 350, 73 manufactured by Mitsui Cyanamid Co., Ltd.
6, 738, 370, 771, 325, 327, 70
3,701,266,267,285,232,23
5, 238, 1141, 272, 254, 202, 11
56 and 1158 are examples of a compound obtained by reacting melamine with formaldehyde or an alkyl-modified product thereof. Cymel® 1123, 1125, 1128
This is an example of a compound obtained by reacting benzoguanamine with formaldehyde or an alkyl-modified product thereof. Cymel (registered trademark) 1170, 1171, 1174, 1172 is an example of a compound obtained by allowing formaldehyde to act on glycoluril or an alkyl-modified product thereof. Examples of a compound obtained by reacting urea with formaldehyde or an alkyl-modified product thereof include UFR (registered trademark) 6 of Mitsui Cyanamid Co., Ltd.
5,300.

Examples of epoxy compounds include novolak epoxy resins (VDPN-638, 701, manufactured by Toto Kasei Co., Ltd.).
702, 703, 704, etc.), amine epoxy resin (YH-434, manufactured by Toto Kasei), bisphenol A epoxy resin, sorbitol (poly) glycidyl ether,
(Poly) glycerol (poly) glycidyl ether, pentaerythritol (poly) glycidyl ether, triglycidyl trishydroxyethyl isocyanurate,
Allyl glycidyl ether, ethylhexyl glycidyl ether, phenyl glycidyl ether, phenol glycidyl ether, lauryl alcohol glycidyl ether, glycidyl adipic ether, glycidyl phthalate, dibromophenyl glycidyl ether,
Dibromoneopentyl glycol diglycidyl ether, glycidyl phthalimide, (poly) ethylene glycol glycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerin polyglycidyl ether, trimethylolpropane polyglycidyl ether, butyl glycidyl ether, and the like. be able to.

Among them, particularly preferred compounds include compounds having a —N (CH ₂ OR) ₂ group in the molecule (wherein R represents a hydrogen atom or an alkyl group). Specifically, a compound obtained by reacting formaldehyde with urea or melamine or an alkyl-modified compound thereof is preferable. As a resol compound, for example, PR manufactured by Gunei Chemical Co., Ltd.
-3000s, PP-3000A, RP-2978, S
P-1974, SP-1975, SP-1976, SP
-1977, RP-3993 and the like are preferred.

A method for including a crosslinking agent in an image pattern is as follows.
There is no particular limitation, and for example, a method of applying a crosslinking agent solution to the image pattern, a method of immersing the image pattern in the crosslinking agent solution, or the like can be employed. Here, the solvent is not particularly limited as long as it can dissolve the cross-linking agent.
A solvent having a relatively high boiling point is preferable, and a solvent having a relatively low boiling point is preferable when the above immersion method is employed.

[0175]

(Preparation of pigment dispersion)

Pigment Dispersion R EFKA-452 (Pigment Dispersant manufactured by EFKA) 2 parts CIPigment Red 177 20 parts Propylene glycol monomethyl ether acetate 80 parts Agitated with a disper to obtain a uniform dispersion.
Using a 5 mm zirconia bead, the particles were dispersed with a Dynomill (manufactured by Shinmaru Enterprises) and the particle size was measured using a centrifugal transmission type particle size distribution analyzer CAPA-700 (manufactured by Horiba, Ltd.). The average particle size was 0.08 μm. Met. Similarly, yellow, green, and blue pigment dispersions having the following compositions were prepared. Pigment Dispersion Y Disperseid-170 (Pigment Dispersant manufactured by Big Chemie) 2.5 parts CIPigment Yellow 139 20 parts Propylene glycol monomethyl ether acetate 50 parts Cyclohexanone 29.5 parts Similarly, average particle size is 0.07 μm Pigment dispersion liquid G Disperseid-170 (Pig Dispersant) 3 parts CI Pigment Green 36 20 parts Propylene glycol monomethyl ether acetate 50 parts Cyclohexanone 27 parts Pigment average particle size 0.10 μm Pigment dispersion B Disperseid-170 (Bic Chemie Inc.) Pigment dispersant) 3 parts CIPigment Blue 15: 6 17 parts Propylene glycol monomethyl ether acetate 50 parts Cyclohexanone 30 parts Average particle size of pigment 0.06 μm

Examples 1 to 10 Photosensitive coloring compositions were prepared using the above pigment dispersions and the compounds of the present invention described in Table 1 below. The solvent used was propylene glycol monomethyl ether acetate. The solid content concentration is 20 wt% in each case. This composition was applied to a substrate for a color filter and dried at 100 ° C. for 2 minutes. Next, exposure was performed with a deep UV lamp through a patterned mask. After exposure, the film was heated at 110 ° C. for 60 seconds, immersed in a 2 wt% aqueous solution of tetramethylammonium hydroxide, and developed. Subsequently, 5 of the crosslinking agents described in Table 1 below was used.
A wt% methanol solution was applied, dried, and then exposed entirely with a deep UV lamp. Next, heating was performed at 150 ° C. for 5 minutes. After heating, the entire substrate was washed with methanol.

[0177]

[Table 1]

The following cross-linking agents of the methylolmelamine type were used. G-1: Cymel 301 (manufactured by American Cyanamid) G-2: Nikarac MW-30 (manufactured by Sanwa Chemical) G-3: Nikarac MW-30M (manufactured by Sanwa Chemical)

Comparative Examples 1 to 10 The same procedure as in Examples 1 to 10 was carried out except that a photosensitive coloring composition for comparison was prepared using the pigment dispersion and the compounds shown in Table 2 below, and no crosslinking agent was applied. A sample was prepared.

[0180]

[Table 2]

[Evaluation] The samples of Examples 1 to 10 were evaluated as shown in Table 3 below. The results are shown in Table-3.

[0182]

[Table 3]

The samples of Comparative Examples 1 to 10 were evaluated as shown in Table 4 below. The results are shown in Table-4.

[0184]

[Table 4]

[Evaluation Method and Criteria] Heat resistance ○ When the line width change after heating at 220 ° C. for 30 minutes is less than ± 2% Δ2 to less than 10% × ± 10% or more Chemical resistance Post bake 220 ° C. 30 After minute treatment ○ The change in film thickness after immersion in γ-butyrolactone for 1 hour at 25 ° C. is less than ± 2% △ 2 to less than 10% × 10% or more Pattern profile ○ The taper angle of the line (sidewall angle with respect to the substrate) is 60
Degree or less △ The taper angle of the line is 90-60 degrees x the reverse taper when the taper angle of the line is 90 degrees or more. Transmittance: In the obtained image, red: 580 nm, when the transmittance is 10% or less,
場合 (good) when the transmittance at 0 nm is 80% or more 8
The case of less than 0% was evaluated as x (defective). Green, blue: maximum transmittance of green and blue ± 10 nm at ± 50 nm
% Or less, the case where the maximum transmittance was above 80% was evaluated as ○ (good), and the case where the maximum transmittance was less than 80% was evaluated as × (bad). The compounds used in the above Examples and Comparative Examples are as follows.

[0186]

Embedded image

[0187]

Embedded image

[0188]

Embedded image

[0189]

Embedded image

[0190]

Embedded image

The weight average molecular weight of each of the resins (E-1) to (E-5) is (E-1): 28000 (E-2): 23000 (E-3): 22000 (E-4) : 30000 (E-5): 24000.

Example 11 The R, G, and B photosensitive coloring compositions of Examples 4, 6, and 7 were sequentially coated, exposed, developed, and patterned in the same manner as in Example 1, followed by crosslinking. G-2, G-
2. Apply 5 wt% methanol solution of G-1 and dry it.
The whole surface was exposed with a deep UV lamp. Next, heating was performed at 150 ° C. for 5 minutes. After heating, the entire substrate was washed with methanol to produce a color filter. A color filter with high transmittance was obtained.

[0193]

According to the present invention, a color filter having excellent heat resistance and chemical resistance can be manufactured. Further, the positive photosensitive coloring composition of the present invention can produce a color filter having high sensitivity and excellent pattern profile. In addition, a color filter having good dispersibility of the colorant and excellent transmittance can be obtained. Furthermore, it is possible to manufacture a color filter which does not require an oxygen barrier film, has a wide development latitude, has good development reproducibility, and gives a sharp image with little edge portion disturbance.

Claims (7)

[Claims] (1) a resin which is insoluble in water and is soluble in an aqueous alkali solution, (2) a compound which generates an acid upon irradiation with actinic rays or radiation, and (3) an alkali developing solution having a group which can be decomposed by an acid. A low-molecular-weight acid-decomposable dissolution-inhibiting compound having a molecular weight of 3,000 or less whose solubility in a compound increases by the action of an acid, and
(4) a coloring agent, containing a positive photosensitive coloring composition containing a coating on a transparent substrate, exposure, heating after exposure, forming an image pattern by developing, then including a crosslinking agent in the image pattern, followed by A method for producing a color filter, wherein the entire surface is exposed and heated. 2. The method for producing a color filter according to claim 1, wherein the positive photosensitive coloring composition further contains an organic basic compound. (3) a resin having a group which is decomposed by the action of an acid to increase solubility in an alkaline developer, (2) a compound which generates an acid upon irradiation with actinic rays or radiation,
(3) An organic basic compound, and (4) a colorant, containing a positive photosensitive coloring composition, coated on a transparent substrate, exposed, heated after exposure, developed to form an image pattern, then the image A method for producing a color filter, comprising: adding a cross-linking agent to a pattern; and subsequently exposing and heating the entire surface. 4. A compound having a molecular weight of 30 which has a group decomposable by an acid and whose solubility in an alkaline developer is increased by the action of an acid.
4. The method for producing a color filter according to claim 3, comprising a low molecular weight acid-decomposable dissolution inhibiting compound of not more than 00. 5. The method for producing a color filter according to claim 3, further comprising a resin which is insoluble in water and soluble in an aqueous alkali solution. 6. The method for producing a color filter according to claim 1, wherein the colorant is an organic pigment. 7. The organic pigment has an average particle size of 0.01 μm.
7. The method for producing a color filter according to claim 6, wherein the thickness is from 0.2 to 0.2 [mu] m.