JP2003222997A - Photosensitive colored resin composition, method for producing the same and method for producing color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive colored resin composition excellent in uniformity of coating thickness and liquid saving property, having an enhanced transmittance and a broad development latitude and excellent in process admissibility and to provide a method for producing the same and a method for producing a color filter. <P>SOLUTION: In the photosensitive colored resin composition comprising (a) a colorant, (b) an alkali-soluble resin A, (c) a photosensitive polymerizable component, (d) a photopolymerization initiator and (e) a solvent, the alkali- soluble resin A is a copolymer consisting essentially of (i) at least one acid component monomer selected from maleic anhydride, acrylic acid, methacrylic acid and fumaric acid, (ii) an alkyl polyoxyethylene(meth)acrylate and (iii) benzyl(meth)acrylate. The method for producing a color filter uses the composition. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive colored resin composition suitable for producing a color filter used for a liquid crystal display device or a solid-state image pickup device, a method for producing the same, and a method for producing a color filter, particularly The present invention relates to a photosensitive colored resin composition having a wide development latitude and improved coating thickness uniformity and liquid saving, a method for producing the same, and a method for producing a color filter.

[0002]

2. Description of the Related Art A color filter is an essential component of a liquid crystal panel. Compared with a CRT as a display device, it is more compact and equal in performance, and is being replaced by a CRT as a television screen, a personal computer screen, and other display devices. However, liquid crystal display devices are expensive, and CR
In order to overcome the competition with T, it is essential to make it cheap.

In order to reduce the price of liquid crystal display devices, in addition to reducing the price of parts such as color filters and glass substrates,
It is required to improve the yield without producing defective products. In the case of a color filter, further reduction of the coating liquid amount of the photosensitive colored resin composition is indispensable. Further, improving the production yield of color filters can be one of the means for reducing the price. In order to improve the yield, it is necessary to manufacture more color filters in one treatment,
Specifically, it can be carried out by applying a photosensitive colored resin composition onto a larger substrate to produce a large color filter, and then cutting it into a desired size.
However, if the amount of the coating liquid is reduced as it is or coating is performed on a large substrate, coating unevenness occurs. Most of the coating unevenness is thickness unevenness, and in order to overcome this, it is necessary to improve the fluidity of the liquid and make it difficult for uneven coating to occur even with a small amount of liquid. The means for improving the fluidity of the coating liquid is generally to lower the viscosity of the coating liquid by lowering the molecular weight of the polymer or increasing the solubility in a solvent. However, simply lowering the viscosity is likely to cause thickness unevenness in the central portion and the peripheral portion of the coated substrate, which is a problem.

As described above, in order to reduce the amount of the coating liquid of the photosensitive colored resin composition and improve the yield, even when the amount of the coating liquid is small or when it is applied to a large substrate, the thickness is uniform and uniform. It is desired that it can be applied on a substrate.

Further, it is generally required that the photosensitive colored resin composition has a wide range of suitable development time in the development carried out after exposure, that is, has a wide development latitude and excellent process acceptability. However, as the area to be processed at one time becomes large as described above or the size of the display panel becomes large, the difference in the time of immersion in the developing solution at the leading and trailing ends of the substrate becomes large, resulting in a difference in the developing time.
For this reason, development unevenness expands and the size of the pattern varies. Therefore, a photosensitive colored resin composition having a wider development latitude is required.

The method of applying the photosensitive colored resin composition to the substrate is excellent in spin coating because it is possible to apply a thin film of 1 to 3 μm uniformly and with high accuracy, and it is widely and generally used for producing color filters. It is used. Further, in recent years, a rectangle having a slit (gap) with a width of several tens of microns disclosed in Patent Document 1 (JP-A-6-339656) and Patent Document 2 (JP-A-11-90295) at the tip thereof. The coating head having a length corresponding to the coating width of the substrate has a clearance (gap) with the substrate of several tens to several hundreds.
There is a slit coating method in which the coating liquid supplied from the slit is applied to the substrate at a predetermined discharge rate by holding the substrate at a micron and maintaining a constant relative speed between the substrate and the coating head. It is used as another application method. Compared to spin coating, this slit coating has less liquid loss, less scattering of coating liquid, less cleaning process, no re-mixing of scattered liquid components into the coating film, rotation start stop time Since it does not exist, it has advantages that the tact time can be shortened, coating on a large substrate is easy, and the like. Therefore, it is suitable for producing a color filter for a large-screen liquid crystal display device, and is expected as a coating method advantageous for reducing the amount of coating liquid.

However, in slit coating, there is a problem with the system itself in that it is difficult to keep the coating conditions of the coating liquid discharged from the slit outlet constant over the entire coating width. Therefore, coating unevenness easily occurs. In some cases, it was difficult to obtain a uniform coating film thickness in the width direction, and the coating film lacked uniformity.

Therefore, attempts have been made to improve the fluidity and viscoelastic properties of the coating solution in order to obtain a uniform and even coating film, and as described above, the molecular weight of the polymer is lowered and the solvent is used. Means such as selecting a polymer having excellent solubility in water and utilizing a fluorine-containing surfactant have been proposed, but they have not been sufficient to improve the above problems.

On the other hand, as a photosensitive resin composition for a color filter having an improved resin component, for example, Patent Document 3
(Patent No. 2665696), it is obtained by using a copolymer containing (meth) acrylic acid, (meth) acrylate having an ethylene oxide molecular chain, and a styrene derivative as a monomer component as a binder for dispersing pigments. It is described that the uniformity and transparency of the color filter can be improved. Further, Patent Document 4 (Japanese Patent Laid-Open No. H10 (1998) -109242
No. 204321), there is described an invention of a composition for a black matrix having improved light-shielding property, adhesiveness and resistivity, and a half ester of maleic anhydride in a copolymer of styrene and maleic anhydride. A copolymer in which the ester component is a polyethylene glycol monoacrylate is disclosed. Patent Document 5 (Japanese Patent Laid-Open No. 10-8
No. 7769), a resin composition containing an unsaturated group-containing resin obtained by reacting an epoxy (meth) acrylate with a polybasic acid anhydride is used to improve the developability of a color filter, pattern accuracy, and the like. The invention is disclosed, and polyethylene glycol mono (meth) acrylate is described as the unsaturated group-containing component.

Further, Japanese Patent Application Laid-Open No. 11-3231 (Patent Document 6)
43), Patent Document 7 (Japanese Patent Laid-Open No. 2000-22751).
3), Patent Document 8 (JP 2001-269564 A).
(Japanese Patent Laid-Open Publication) discloses the use of a fluorinated surfactant in order to improve the coating suitability of the color filter composition. However, with the above-mentioned improvement of the polymer used as the binder and the conventional technology using the fluorine-based surfactant, the above-mentioned coating liquid amount is reduced, the yield is improved, and the film thickness uniformity of the obtained coating liquid is further improved. It wasn't enough to let me do it. In particular, it was still insufficient for the slit coating method.

[0011]

[Patent Document 1] JP-A-6-339656

[Patent Document 2] Japanese Patent Laid-Open No. 11-90295

[Patent Document 3] Japanese Patent No. 2665696

[Patent Document 4] Japanese Patent Laid-Open No. 10-204321

[Patent Document 5] Japanese Patent Laid-Open No. 10-87769

[Patent Document 6] Japanese Patent Laid-Open No. 11-323143

[Patent Document 7] Japanese Patent Laid-Open No. 2000-227513

[Patent Document 8] Japanese Patent Laid-Open No. 2001-269564

[0012]

SUMMARY OF THE INVENTION An object of the present invention is to provide a photosensitive colored resin composition which is excellent in coating thickness uniformity and liquid saving, has improved transmittance, and has a wide development latitude and excellent process acceptability. Another object of the present invention is to provide a method for manufacturing the same and a method for manufacturing a color filter. In particular, in the present invention,
It is an object of the present invention to provide a photosensitive colored resin composition excellent in fluidity as a coating solution even in slit coating which can be easily coated on a large substrate, a method for producing the same, and a method for producing a color filter.

[0013]

According to the present invention, a photosensitive colored resin composition having the following constitution, a method for producing the same, and a method for producing a color filter are provided to achieve the above object.

Photosensitive colored resin composition containing (1) (a) colorant, (b) alkali-soluble resin A, (c) photosensitive polymerization component, (d) photopolymerization initiator, and (e) solvent Wherein the alkali-soluble resin A is at least (i) at least one acid component monomer selected from maleic anhydride, acrylic acid, methacrylic acid, and fumaric acid;
A photosensitive colored resin composition, which is a copolymer of i) an alkyl polyoxyethylene (meth) acrylate and (iii) benzyl (meth) acrylate.

(2) In the alkali-soluble resin A, the composition mass ratio of (i) acid component monomer, (ii) alkylpolyoxyethylene (meth) acrylate, and (iii) benzyl (meth) acrylate is 10 to 25 /. 5-
25 / 50-85 and polystyrene conversion mass average molecular weight (Mw) is 3,000-50,000, The photosensitive colored resin composition as described in (1) above.

(3) The content of the colorant in the solid content of the photosensitive colored resin composition is 30 to 60% by mass, and the content of the alkali-soluble resin A is 10 to 50.
The photosensitive colored resin composition as described in (1) or (2) above, wherein the photosensitive colored resin composition is mass%. (4) The photosensitive colored resin composition further contains an alkali-soluble resin B1 which is a copolymer of (i) (meth) acrylic acid and (ii) benzyl methacrylate. ~ The photosensitive colored resin composition according to any one of (3) above. (5) The photosensitive colored resin composition further comprises an alkali-soluble resin B2 which is a copolymer of (i) (meth) acrylic acid, (ii) benzyl methacrylate, and (iii) hydroxyethyl (meth) acrylate. The photosensitive colored resin composition according to any one of (1) to (3) above, which further comprises: (6) In the solid content of the photosensitive colored resin composition,
The content of the colorant is 30 to 60% by mass, and the content of the alkali-soluble resin (sum of A, B1 and B2) is 10 to 50% by mass in total, (1) to
The photosensitive colored resin composition according to any one of (5) above.

(7) The photosensitive colored resin composition further contains a fluorine-containing organic compound having a fluorine content of 3 to 40% by mass, (1) to (6).
The photosensitive colored resin composition according to any one of 1. (8) The photosensitive colored resin composition as described in (7) above, wherein the fluorine-based organic compound is represented by the following formula (I). C ₈ F ₁₇ SO ₂ N (R ₁ ) CH ₂ CH ₂ O (CH ₂ CH ₂ O) _n R ₂ (I) In formula (I), R ₁ and R ₂ are each a hydrogen atom or a carbon number 1
Represents an alkyl group of 4 and n represents an integer of 2 to 30.

(9) Alkali-soluble resin B1 which is a copolymer of (meth) acrylic acid and benzyl methacrylate as a colorant or a copolymer of (meth) acrylic acid, benzyl methacrylate and hydroxyethyl (meth) acrylate Alkali-soluble resin B2 is mixed with the alkali-soluble resin B2 at a viscosity of 10,000 mPa · s or more, and then the alkali-soluble resin A is added to the kneaded dispersion.
Is added to perform a fine dispersion treatment at a viscosity of 1,000 mPa · s or less, and the method for producing a photosensitive colored resin composition according to (1) above. (10) A coating film is formed by slit coating the photosensitive colored resin composition according to any one of (1) to (8) above on a substrate directly or through another layer, and then prebaked. A method for producing a color filter in which pattern exposure and alkali development are sequentially performed.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION In order to achieve the above object of the present invention, the present invention provides a coating solution for a photosensitive colored resin composition by incorporating the alkali-soluble resin A into the photosensitive colored resin composition. By improving the properties as described above, and by further adding an alkali-soluble resin B1 or an alkali-soluble resin B2 to the composition, the dispersion stability of a colorant such as an organic pigment is improved. By adding a fluorine-containing organic compound having a fluorine content of 3 to 40% by mass to the photosensitive colored resin composition of the present invention, the properties of the composition as a coating liquid can be further improved.
In addition, after the composition containing the alkali-soluble resin B1 or the alkali-soluble resin B2 is kneaded and dispersed, the alkali-soluble resin A is added and finely dispersed to promote the dispersion of the colorant, thereby finally obtaining the composition. The dispersion stability of the colorant particles in the product also becomes high. The photosensitive colored resin composition of the present invention is suitable for the slit coating method, which is excellent in terms of liquid saving and coating on a large substrate,
Slit coating, which is prone to problems due to coating unevenness and coating film thickness uniformity, is favorably carried out, and a color filter with excellent characteristics can be obtained. Hereinafter, the compounding components used in the photosensitive colored resin composition of the present invention and the method of using the composition will be described.

The photosensitive colored resin composition of the present invention comprises (a)
It comprises a colorant, (b) alkali-soluble resin A, (c) photosensitive polymerization component, (d) photopolymerization initiator, and (e) solvent as essential components.

[I] Alkali-Soluble Resin The (b) alkali-soluble resin A used in the composition of the present invention is at least (i) maleic anhydride (MAA), acrylic acid (AA), methacrylic acid (MA), and It is a copolymer composed of at least one acid component monomer selected from fumaric acid (FA), (ii) alkylpolyoxyethylene (meth) acrylate, and (iii) benzyl (meth) acrylate.

In the alkali-soluble resin A,
(I) acid component monomer, (ii) alkyl polyoxyethylene (meth) acrylate (Acr (EO) _n : CH
₃ (OC ₂ H ₄ ) _n OCOC (CH ₃ ) = CHR), and (ii
The composition mass ratio of i) benzyl (meth) acrylate (BzMA) is preferably 10 to 25/5 to 25/50 to 8.
5, more preferably 15-20 / 5-20 / 60-80
Is. The polystyrene-equivalent weight average molecular weight (Mw) of the alkali-soluble resin A by GPC is preferably 3,000 to 50,000, more preferably 5,000.
It is 0 to 30,000.

If the compositional mass ratio of the (i) acid component monomer is less than the above range, the alkali solubility tends to decrease, and if it exceeds the above range, the solubility in a solvent tends to decrease. (Ii) alkylpolyoxyethylene (meth) acrylate _{(Acr (EO) n: CH} 3 (OC 2 H 4) n OCOC (C
If the compositional mass ratio of (H ₃ ) = CHR) is less than the above range, the spreading of the photosensitive coloring resin composition coating liquid onto the substrate becomes insufficient, and the present invention can be effectively achieved. Tends to disappear. On the other hand, if it exceeds the above range, the dispersibility of the colorant tends to decrease, which is not preferable. If the composition mass ratio of (iii) benzyl (meth) acrylate (BzMA) is less than the above range, the dispersion stability of the colorant and the solubility in the composition tend to be lowered, which is not preferable. On the other hand, if it exceeds the above range, the suitability for alkali development of the coating film is deteriorated, which is not preferable.

The above (ii) alkyl polyoxyethylene (meth) acrylate (Acr (EO) _n : CH ₃ (OC ₂
The repeating number n of polyoxyethylene (EO) _n of H ₄ ) _n OCOC (CH ₃ ) = CHR) is 2 to 15, preferably 2 to 10, and particularly preferably 4 to 10. If the number of repetitions n is less than the above range, a development residue tends to be generated after development with an alkali developing solution. This is a problem because coating unevenness is likely to occur and the uniformity of the coating film thickness and the liquid-saving property tend to decrease.

In the composition of the present invention, in addition to the above-mentioned alkali-soluble resin A as the alkali-soluble resin, an alkali-soluble resin B which is a copolymer of (i) (meth) acrylic acid and (ii) benzyl methacrylate.
1, or (i) (meth) acrylic acid, (ii) benzyl methacrylate, and (iii) a copolymer of hydroxyethyl (meth) acrylate, which is an alkali-soluble resin B2. In the present invention,
Alkali-soluble resin B1 and alkali-soluble resin B2
Has an effect on the dispersion stability of the colorant. When the kneading dispersion treatment is carried out prior to the fine dispersion treatment of the colorant in the production of the photosensitive colored resin composition of the present invention, the alkali-soluble resin B1 or the alkali-soluble resin B2 is used.
Can impart a strong shearing force to the colorant aggregate to promote its dispersion, and enhance the dispersion stability of the colorant in the composition finally obtained through the subsequent fine dispersion treatment. The content of the alkali-soluble resin B1 and the alkali-soluble resin B2 in the photosensitive colored resin composition is
It is preferably 50% by mass or less of the total amount of the alkali-soluble resin.

When the alkali-soluble resin A is used alone as the alkali-soluble resin, the resin content of the composition is preferably 10 to 50% by mass, more preferably 10 to 40% by mass based on the total solid content. When the alkali-soluble resin B1 or B2 is used in combination, the total resin content of the composition is preferably 10 to 50% by mass. If the content of the alkali-soluble resin in the composition of the present invention is too low, the alkali development tends to not proceed. On the other hand, if the amount is too large, the viscosity of the coating solution becomes high, the coating thickness uniformity is deteriorated, coating unevenness is likely to occur, and the development latitude is also likely to be lowered.

[II] Colorant As the colorant that can be used in the present invention, various conventionally known dyes and pigments can be used alone or in combination of two or more.

As the pigment that can be used in the present invention, various conventionally known inorganic pigments or organic pigments can be used. Further, the pigment, whether it is an inorganic pigment or an organic pigment, preferably has a high transmittance in consideration of having a high transmittance, but in consideration of handling property, an average particle diameter of 0.01 μm is preferable.
To 0.1 μm, more preferably 0.01 μm to 0.05
A μm pigment is used. 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,
Examples thereof include metal oxides such as titanium, magnesium, chromium, zinc and antimony, and complex oxides of the above metals.

As the organic pigment, CI Pigment Yellow 1
1, 24, 31, 53, 83, 93, 99, 108, 109, 110, 138, 13
9, 147, 150, 151, 154, 155, 167, 180, 185, 199,;
CIPigment Orange 36, 38, 43, 71; CIPigment Red
81, 105, 122, 149, 150, 155, 171, 175, 176, 177,20
9, 220, 224, 242, 254, 255, 264, 270; CI Pigment V
iolet 19, 23, 32, 39; CIPigment Blue 1, 2, 15, 1
5: 1, 15: 3, 15: 6, 16, 22, 60, 66; CIPigment Green
7, 36, 37; CIPigment Brown 25, 28; CIPigment Bla
ck 1, 7; carbon black and the like.

In the present invention, pigments having a basic N atom in the structural formula can be preferably used. The pigments having these basic N atoms exhibit good dispersibility in the composition of the present invention. Although the cause has not been fully clarified, it is presumed that the good affinity between the photosensitive polymerization component and the pigment has an effect.

The pigments that can be preferably used in the present invention include the following.
It is not limited to these.

CI Pigment Yellow 11, 24, 108, 109, 1
10, 138, 139, 150, 151, 154, 167, 180, 185, CIPig
ment Orange 36, 71, CIPigment Red 122, 150, 171,
175, 177, 209, 224, 242, 254, 255, 264, CIPigment
Violet 19, 23, 32, CIPigment Blue 15: 1, 15: 3, 1
5: 6, 16, 22, 60, 66, CIPigment Black 1

These organic pigments are used alone or in various combinations for increasing the color purity. A specific example is shown below.
As the red pigment, anthraquinone pigment, perylene pigment, diketopyrrolopyrrole pigment alone or at least one of them mixed with a disazo yellow pigment, an isoindoline yellow pigment, a quinophthalone yellow pigment or a perylene red pigment. Are used. For example, as the anthraquinone pigment, C.I. I. Pigment Red 17
7, perylene pigments include C.I. I. Pigment Red 155, C.I. I. Pigment Red 224 and diketopyrrolopyrrole pigment include C.I. I. Pigment Red 254, and C.I. I. Pigment Yellow 83 or C.I. I. Pigment Yellow 13
Mixing with 9 was good. The mass ratio of the red pigment to the yellow pigment was 100: 5 to 100: 50. 1
If it is less than 00:04, the light transmittance from 400 nm to 500 nm cannot be suppressed and the color purity cannot be increased.
If the wavelength is 100: 51 or more, the dominant wavelength is shorter than N and N
The deviation from the TSC target hue became large. Especially 10
The optimum range was from 0:10 to 100: 30. In the case of a combination of red pigments, the chromaticity is adjusted.

As the green pigment, a halogenated phthalocyanine type pigment alone or a mixture with a disazo type yellow pigment, a quinophthalone type yellow pigment, an azomethine type yellow pigment or an isoindoline type yellow pigment may be used. I. Pigment Green 7, 36, 37 and C.I. I. Pigment Yellow 83, C.I. I. Pigment Yellow 138, C.I.
I. Pigment Yellow 139, C.I. I. Pigment Yellow 150, C.I. I. Pigment Yellow 180 or C.I. I. Pigment Yellow 185 was mixed well. The mass ratio of the green pigment and the yellow pigment is 100: 5 to 1
00: 150 was good. 40 below 100: 5
The light transmittance from 0 nm to 450 nm could not be suppressed and the color purity could not be increased. On the other hand, when it exceeds 100: 150, the dominant wavelength becomes longer and the deviation from the NTSC target hue becomes large. More preferable mass ratio is 10
It is in the range of 0:30 to 100: 120.

As the blue pigment, a phthalocyanine pigment alone or a mixture with a dioxazine purple pigment is used. I. Pigment Blue 15: 6 and C.I.
I. Pigment Violet 23 was mixed well. The mass ratio of blue pigment to purple pigment is 1 from 100: 0.
It is preferably 00:30, more preferably 100: 10 or less.

Further, by using a powdered processed pigment in which the above pigment is finely dispersed in an acrylic resin, a maleic acid resin, a vinyl chloride-vinyl acetate copolymer, an ethyl cellulose resin, etc., a pigment having good dispersibility and dispersion stability. A photosensitive resin containing can be obtained.

As the pigment for the black matrix, carbon, titanium carbon, iron oxide, titanium oxide alone or in mixture are used, and the case of carbon and titanium carbon is good. The mass ratio is from 100: 0 to 10
The range of 0:60 was good. When it was 100: 61 or more, the dispersion stability tended to decrease.

The method of treating the pigment will be described below. Generally, these pigments are supplied after being dried by various methods after synthesis. Usually, it is dried from an aqueous medium and supplied as a powder body, 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 primary particles are aggregated.

It is not easy to disperse the pigment forming such aggregates into fine particles. Therefore, it is preferable to treat the pigment with various resins in advance. Examples of these resins include the above-mentioned alkali-soluble resins. As the treatment method, there are a flushing treatment and a kneading method using a kneader, an extruder, a ball mill, a two or three roll mill, or the like. Of these, the flushing process and the kneading method using a two- or three-roll mill are suitable for atomization.

The flushing treatment is usually 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 a resin. . According to this method, since the pigment is not dried, aggregation of the pigment can be prevented and dispersion becomes easy. In a two- or three-roll mill, by mixing a pigment and a resin or a solution of a resin and then kneading the pigment and the resin while applying a high shear (shearing force), the pigment surface is coated with the resin. , A method of treating a pigment. The pigment particles aggregated in this process are dispersed from lower-order aggregates to primary particles.

In the present invention, a processed pigment previously treated with an acrylic resin, a vinyl chloride-vinyl acetate resin, a maleic acid resin, an ethyl cellulose resin, a nitrocellulose resin or the like can also be conveniently used. In the present invention, as a form of the processed pigment treated with the above various resins, a powder in which the resin and the pigment are uniformly dispersed,
A paste form, a pellet form, and a paste form are preferable. In addition, a gelled nonuniform mass of resin is not preferable. The colored dispersion thus obtained is mixed with a photosensitive component and provided as a photosensitive colored resin composition.

In the present invention, when the colorant is a dye, it is uniformly dissolved in the composition to obtain a photosensitive colored resin composition. The dye that can be used as the colorant that constitutes the photosensitive colored resin composition of the present invention is not particularly limited, and conventionally known dyes for color filters can be used. For example, JP-A-64-90403 and JP-A-64-91.
102, JP 1-94301, JP 6
-11614, Japanese Patent No. 2592207, US Pat. No. 4,808,501, US Pat. No. 5,66.
7,920, US Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-3.
5183, JP-A-6-51115, JP-A-6-194828, JP-A-8-21159, JP-A-4-249549, and JP-A-10-12.
No. 3316, No. 11-302283, No. 7-286107, No. 2001-4823.
JP-A-8-15522, JP-A-8-29
771, JP-A-8-146215, JP-A-11-343437, JP-A-8-62416, JP-A-2002-14220, and JP-A-2002.
14221 gazette, Unexamined-Japanese-Patent No. 2002-14222 gazette,
JP-A-2002-14223, JP-A-8-3022
24, JP-A-8-73758, and JP-A-8-
The dyes disclosed in JP-A-179120 and JP-A-8-151531 can be used. The chemical structure, pyrazole azo, anilino azo, triphenylmethane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, Dyes of xanthene type, phthalocyanine type, penzopyran type, indigo type and the like can be used.

In the case of a resist system which undergoes water or alkali development, an acidic dye and / or its derivative may be preferably used from the viewpoint of completely removing the binder and / or dye by development. In addition, direct dyes, basic dyes, mordant dyes, acidic mordant dyes, azoic dyes, disperse dyes, oil-soluble dyes, food dyes, and / or derivatives thereof can also be used effectively.

The acidic dye is not particularly limited as long as it has an acidic group such as sulfonic acid or carboxylic acid.
Considering all of the required performance such as solubility in organic solvents and developers, salt formation with basic compounds, absorbance, interaction with other components in the composition, light resistance, heat resistance, etc. To be selected. Specific examples of the acid dye will be given below, but the acid dye is not limited thereto. For example, acid a
lizarin violet N; acid bla
ck 1, 2, 24, 48; acid blue 1,
7, 9, 15, 18, 23, 25, 27, 29, 40,
45, 62, 70, 74, 80, 83, 86, 87, 9
0, 92, 103, 112, 113, 120, 129,
138, 147, 158, 171, 182, 192, 2
43, 324: 1; acid chrome viol.
et K; acid Fuchsin; acid gr
een 1, 3, 5, 9, 16, 25, 27, 50; a
cid orange 6, 7, 8, 10, 12, 5
0, 51, 52, 56, 63, 74, 95; acid
red 1, 4, 8, 14, 17, 18, 26, 27,
29, 31, 34, 35, 37, 42, 44, 50, 5
1, 52, 57, 66, 73, 80, 87, 88, 9
1, 92, 94, 97, 103, 111, 114, 12
9, 133, 134, 138, 143, 145, 15
0, 151, 158, 176, 183, 198, 21
1, 215, 216, 217, 249, 252, 25
7, 260, 266, 274; acid violet
6B, 7, 9, 17, 19; acid yellow
1, 3, 7, 9, 11, 17, 23, 25, 29, 3
4, 36, 42, 54, 72, 73, 76, 79, 9
8, 99, 111, 112, 114, 116, 184,
243; Food Yellow 3; and derivatives of these dyes.

Among them, as the above-mentioned acid dye, aci
d black 24; acid blue 23, 2
5, 29, 62, 80, 86, 87, 92, 138, 1
58, 182, 243, 324: 1; acid ora
nge 8, 51, 56, 63, 74; acid r
ed 1, 4, 8, 34, 37, 42, 52, 57, 8
0, 97, 114, 143, 145, 151, 183,
217; acid violet 7; acid ye
low 17, 25, 29, 34, 42, 72, 7
6, 99, 111, 112, 114, 116, 184,
243; dyes such as acidgreen 25 and derivatives of these dyes are preferred. Other than the above, azo, xanthene, and phthalocyanine acid dyes are also preferable, and C.I. I. Solvent Blue 44, 3
8; C.I. I. Solvent orange 45; R
Acid dyes such as hodamine B and Rhodamine 110, and derivatives of these dyes are also preferably used.

As the derivative of the acidic dye, an inorganic salt of an acidic dye having an acidic group such as sulfonic acid or carboxylic acid, a salt of an acidic dye and a nitrogen-containing compound, a sulfonamide of the acidic dye, etc. can be used. It is not particularly limited as long as it can be dissolved as a solution, but it is necessary to have solubility in an organic solvent or a developing solution, absorbance, interaction with other components in the curable composition, light resistance, heat resistance and the like. It is selected in consideration of all the performances.

The content of the colorant in the total solid content of the photosensitive colored resin composition of the present invention is not particularly limited, but is preferably 30 to 60% by mass. If the amount of the colorant is too small, it tends to be impossible to obtain an appropriate chromaticity as a color filter. On the other hand, if the amount is too large, the photo-curing does not proceed sufficiently and the strength of the film decreases, and the development latitude in the alkali development tends to become narrow.

In the present invention, conventionally known pigment dispersants and surfactants can be added for the purpose of improving the dispersibility of the pigment. Although many kinds of compounds are used as these dispersants, for example, a phthalocyanine derivative (commercial item EFKA-745 (manufactured by Efka)), Solsperse 5000 (manufactured by Zeneca); organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) ), (Meth) acrylic acid-based (co) polymer polyflow No. 75, No. 90, No. 9
5 (manufactured by Kyoeisha Oil and Fat Chemical Co., Ltd.) and W001 (manufactured by Yusho); cationic surfactants; polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxy Nonionic surfactants such as ethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester; W00
4, W005, W017 (manufactured by Yusho) and the like; anionic surfactants; EFKA-46, EFKA-47, EFKA-
47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 4
Polymer dispersants such as 50 (above Morishita Sangyo), Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (manufactured by San Nopco); Solspers 3000, 5000, 9000, 12
000, 13240, 13940, 17000, 240
00, 26000, 28000, etc. Solsperse dispersant (manufactured by Zeneca Corporation); ADEKA Pluronic L3
1, F38, L42, L44, L61, L64, F6
8, L72, P95, F77, P84, F87, P9
4, L101, P103, F108, L121, P-1
23 (manufactured by Asahi Denka Co., Ltd.) and ISONET S-20 (manufactured by Sanyo Kasei).

[III] Photosensitive Polymerization Component Next, the photosensitive polymerization component used in the photosensitive colored resin composition of the present invention will be described. As the above-mentioned photosensitive polymerization component, a compound having at least one addition-polymerizable ethylene group and having an ethylenically unsaturated group having a boiling point of 100 ° C. or higher under normal pressure is preferable, and among them, a tetra-functional or higher functional group is used. Acrylate compounds are more preferred.

Examples of the compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C. or higher at normal pressure include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxy. Monofunctional acrylates and methacrylates such as ethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, penta Erythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) Ether, tri (acryloyloxyethyl) isocyanurate, polyfunctional alcohols such as glycerin and trimethylolethane added with ethylene oxide and propylene oxide and then (meth) acrylated, pentaerythritol or dipentaerythritol poly ( (Meth) acrylated,
Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 50-6034,
Urethane acrylates as described in JP-A-51-37193, JP-A-48-64183
No. 4, Japanese Patent Publication No. 49-43191, Japanese Patent Publication No. 52-3049
Polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates, which are reaction products of epoxy resin and (meth) acrylic acid, described in JP-A No. 0 can be mentioned. Furthermore, the Journal of Japan Adhesion Association, Vol. The materials introduced as photocurable monomers and oligomers on page 20, No. 7, pages 300 to 308 can also be used.

Further, a compound obtained by adding ethylene oxide or propylene oxide to the above-mentioned polyfunctional alcohol and then converting it into (meth) acrylate is disclosed in JP-A-10-6.
It is described in JP-A-2986 as general formulas (1) and (2) together with specific examples thereof, and these can also be used as a photosensitive polymerization component.

Of these, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and acryloyl groups thereof having a structure with an ethylene glycol or propylene glycol residue interposed therebetween are preferable. These oligomer types are also used. These photosensitive polymerization components may be used alone or in combination of two or more. The amount of these photosensitive polymerization components used is preferably 20 to 200% by mass, more preferably 50 to 120% by mass, based on 100 total solids of the photosensitive colored resin composition. If the amount of the photosensitive polymerizing component used is too small or too large, the curing will be insufficient, which is not preferable.

[IV] Photopolymerization Initiator As the photopolymerization initiator, active halogen compounds such as halomethyloxadiazole and halomethyl-s-triazine,
Examples thereof include 3-aryl-substituted coumarin compounds and at least one kind of lophine dimer.

Among the active halogen compounds such as halomethyloxadiazole and halomethyl-s-triazine, the halomethyloxadiazole compound is described in JP-B-57-6.
2-halomethyl-5-vinyl-1,3,4-oxadiazole compounds represented by the following general formula IV described in JP-A No. 096 are cited.

[0055]

[Chemical 1]

In the general formula IV: W represents a substituted or unsubstituted aryl group, and X represents a hydrogen atom, an alkyl group or an aryl group. Y represents a fluorine atom, a chlorine atom or a bromine atom. n represents an integer of 1 to 3. Specific compounds of the general formula IV include 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4- Oxadiazole, 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4-oxadiazole and the like can be mentioned.

Examples of the halomethyl-s-triazine compounds include vinyl-halomethyl-s-triazine compounds represented by the following general formula V described in JP-B-59-1281 and JP-A-53-133428. 2- (naphth-1-yl) -4,6-represented by the following general formula VI
Bis-halomethyl-s-triazine compound and 4- (p-aminophenyl) -2,6 represented by the following general formula VII
-Di-halomethyl-s-triazine compounds.

[0058]

[Chemical 2]

In the general formula V: Q represents Br or Cl.
P is, -CQ ₃ (Q is as defined above), - NH _2, -
Represents NHR, -N (R) ₂ , or -OR (wherein R represents a phenyl or alkyl group). n represents an integer of 0 to 3. W represents an aromatic group which may be substituted, a heterocyclic group which may be substituted, or a monovalent group represented by the following general formula VA.

[0060]

[Chemical 3]

In the general formula VA, Z is —O— or —S—, and R has the same meaning as above.

[0062]

[Chemical 4]

In the general formula VI: X represents Br or Cl. m and n are integers of 0-3. R'represents a group represented by the following general formula VIA.

[0064]

[Chemical 5]

(In the above general formula VIA, R ₁ represents a hydrogen atom or ORc (R c represents an alkyl, cycloalkyl, alkenyl or aryl group), and R ₂ represents Cl, Br, alkyl, alkenyl, aryl or alkoxy group. )

[0066]

[Chemical 6]

In the general formula VII: R ₁ and R ₂ are the same or different and each represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, or a group represented by the following general formula VIIA or VIIB. R ₃ and R ₄ are the same or different,
It represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. X and Y are the same or different and each represents Cl or Br. m and n are the same or different and represent 0, 1 or 2.

[0068]

[Chemical 7]

In the general formulas VIIA and VIIB, R ₅ , R ₆ and R ₇
Represents an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group. Examples of the substituent in the substituted alkyl group and the substituted aryl group include an aryl group such as a phenyl group, a halogen atom, an alkoxy group, a carboalkoxy group, a carboaryloxy group, an acyl group, a nitro group, a dialkylamino group and a sulfonyl derivative. Is mentioned.

In the general formula VII, R ₁ and R ₂ may form a heterocyclic ring composed of a non-metal atom together with the nitrogen atom bonded to them, in which case the heterocyclic ring is shown below. There are things.

[0071]

[Chemical 8]

As a concrete example of the general formula V, 2,4-
Bis (trichloromethyl) -6-p-methoxystyryl-s-triazine, 2,4-bis (trichloromethyl)
-6- (1-p-dimethylaminophenyl-1,3-butadienyl) -s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine and the like can be mentioned.

As a concrete example of the general formula VI, 2-
(Naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-methoxy-naphth-1)
-Yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-ethoxy-naphth-1-yl)-
4,6-bis-trichloromethyl-s-triazine, 2
-(4-butoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2
-Methoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- [4-
(2-Ethoxyethyl) -naphth-1-yl] -4,6
-Bis-trichloromethyl-s-triazine, 2- [4
-(2-butoxyethyl) -naphth-1-yl] -4,
6-bis-trichloromethyl-s-triazine, 2-
(2-Methoxy-naphth-1-yl) -4,6-bis-
Trichloromethyl-s-triazine, 2- (6-methoxy-5-methyl-naphth-2-yl) -4,6-bis-
Trichloromethyl-s-triazine, 2- (6-methoxy-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (5-methoxy-naphtho-
1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- ( 6-ethoxy-naphth-2-yl) -4,6
-Bis-trichloromethyl-s-triazine, 2-
(4,5-Dimethoxy-naphth-1-yl) -4,6-
Examples thereof include bis-trichloromethyl-s-triazine.

Specific examples of the general formula VII include 4- [p-
N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-methyl-p-N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-Di (trichloromethyl) -s-triazine, 4- [p-N, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o -Methyl-
p-N, N-di (chloroethyl) aminophenyl]-
2,6-di (trichloromethyl) -s-triazine, 4
-(P-N-chloroethylaminophenyl) -2,6-
Di (trichloromethyl) -s-triazine, 4- (p-
N-ethoxycarbonylmethylaminophenyl) -2,
6-di (trichloromethyl) -s-triazine, 4-
[P-N, N-di (phenyl) aminophenyl] -2,
6-di (trichloromethyl) -s-triazine, 4-
(P-N-chloroethylcarbonylaminophenyl)-
2,6-di (trichloromethyl) -s-triazine, 4
-[P-N- (p-methoxyphenyl) carbonylaminophenyl] 2,6-di (trichloromethyl) -s-triazine, 4- [m-N, N-di (ethoxycarbonylmethyl) aminophenyl] -2 , 6-di (trichloromethyl) -s-triazine, 4- [m-bromo-pN,
N-di (ethoxycarbonylmethyl) aminophenyl]
-2,6-di (trichloromethyl) -s-triazine,
4- [m-chloro-p-N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-fluoro-p-
N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-p
-N, N-di (ethoxycarbonylmethyl) aminophenyl-2,6-di (trichloromethyl) -s-triazine, 4- [o-fluoro-p-N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-p
-N, N-di (chloroethyl) aminophenyl] -2,
6-di (trichloromethyl) -s-triazine, 4-
[O-chloro-p-N, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-fluoro-p-N, N-di (chloroethyl) Aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-pN,
N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-chloro-p-N, N-di (chloroethyl) aminophenyl] -2,6-di (Trichloromethyl) -s-triazine, 4- [m-fluoro-p-N, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo -P-N-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-chloro-p-N-ethoxycarbonylmethylaminophenyl) -2,6-di ( Trichloromethyl) -s-triazine, 4- (m-fluoro-p-N-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4 (O-Bromo-p-N-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-chloro-p-N-ethoxycarbonylmethylaminophenyl) -2, 6-di (trichloromethyl) -s-triazine, 4- (o-fluoro-p-N-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo -P-N-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-chloro-p-N
-Chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-fluoro-p
-N-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-p-N-chloroethylaminophenyl) -2,6-di (trichloromethyl)- s-triazine, 4- (o-chloro-p-N-chloroethylaminophenyl) -2,6
-Di (trichloromethyl) -s-triazine, 4- (o
-Fluoro-p-N-chloroethylaminophenyl)-
2,6-di (trichloromethyl) -s-triazine and the like can be mentioned.

The following sensitizers can be used in combination with these initiators. Specific examples thereof include benzoin, benzoin methyl ether, benzoin, 9-fluorenone,
2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-anthrone, 2-bromo-9-anthrone, 2-ethyl-9-anthrone, 9,10-anthraquinone, 2-ethyl-9,10-. Anthraquinone, 2-
t-Butyl-9,10-anthraquinone, 2,6-dichloro-9,10-anthraquinone, xanthone, 2-methylxanthone, 2-methoxyxanthone, 2-methoxyxanthone, thioxanthone, benzyl, dibenzalacetone, p- (Dimethylamino) phenyl styryl ketone, p- (dimethylamino) phenyl-p-methylstyryl ketone, benzophenone, p- (dimethylamino) benzophenone (or Michler's ketone), p-
(Diethylamino) benzophenone, benzoanthrone and the like and benzothiazole compounds described in JP-B-51-48516.

The 3-aryl-substituted coumarin compound is, for example, a compound represented by the following general formula VIII.

[0077]

[Chemical 9]

R₈Is hydrogen atom, alkyl having 1 to 8 carbon atoms
Group, an aryl group having 6 to 10 carbon atoms (preferably hydrogen atom)
Child, methyl group, ethyl group, propyl group, butyl group),
R₉Is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and 6 carbon atoms
10 aryl groups, groups represented by the following general formula VIIIA
(Preferably methyl group, ethyl group, propyl group, butyl
A group represented by the general formula VIIIA, particularly preferably the general formula
Group represented by VIIIA). R_Ten, R₁₁Each is water
Elementary atoms, alkyl groups having 1 to 8 carbon atoms (for example, methyl group,
Ethyl group, propyl group, butyl group, octyl group), carbon
A haloalkyl group having a number of 1 to 8 (eg, chloromethyl group, fluorine
(Loromethyl group, trifluoromethyl group, etc.), carbon number 1 to
8 alkoxy groups (eg methoxy, ethoxy, bromo,
Toxy group), optionally substituted aryl having 6 to 10 carbon atoms
Group (eg phenyl group), amino group, -N (R₁₆) (R
₁₇) And a halogen atom (for example, Cl, Br, F).
Preferably hydrogen atom, methyl group, ethyl group, methoxy
Group, phenyl group, -N (R₁₆) (R₁₇), Cl. R
₁₂Is an optionally substituted aryl group having 6 to 16 carbon atoms.
(Eg phenyl, naphthyl, tolyl, cumyl
Group). As a substituent, an amino group, -N (R ₁₆) (R
₁₇), An alkyl group having 1 to 8 carbon atoms (for example, a methyl group, an ether group).
Cyl group, propyl group, butyl group, octyl group), carbon number
1-8 haloalkyl groups (eg chloromethyl group, fluoro)
(Methyl group, trifluoromethyl group, etc.), carbon number 1-8
Alkoxy groups (eg methoxy, ethoxy, buto
Xoxy group), hydroxy group, cyano group, halogen atom (eg
For example, Cl, Br, F) may be mentioned. R₁₃, R₁₄,
R₁₆, R₁₇Are the same or different and are
Child, an alkyl group having 1 to 8 carbon atoms (eg, methyl group, ethyl group)
Group, propyl group, butyl group, octyl group). R
₁₃And R₁₄And R₁₆And R₁₇Are bonded to each other and the nitrogen atom and
A heterocyclic ring (eg piperidine ring, piperazine ring, mol
Folin ring, pyrazole ring, diazole ring, triazole
Ring, benzotriazole ring, etc.) may be formed. R₁₅
Is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms (for example, methyl group).
Group, ethyl group, propyl group, butyl group, octyl group
Group), an alkoxy group having 1 to 8 carbon atoms (eg, methoxy)
Group, ethoxy group, butoxy group), optionally substituted carbon
Number 6 to 10 aryl group (for example, phenyl group), amino
Group, N (R₁₆) (R₁₇), A halogen atom (eg Cl, B
r, F). Zb is = O, = S or = C
(R₁₈) (R₁₉) Represents. Preferably = O, = S, = C
(CN)₂And particularly preferably = 0. R₁₈, R
₁₉Are the same or different, and are a cyano group, -COOR₂₀,
-COR_{twenty one}Represents R₂₀, R_{twenty one}Each has 1 to 8 carbon atoms
Alkyl groups (eg methyl, ethyl, propyl
Group, butyl group, octyl group), C 1-8 haloal
Kill groups (eg chloromethyl, fluoromethyl, tri
Fluoromethyl group, etc.), 6 to 1 carbon atoms which may be substituted
Represents an aryl group of 0 (for example, a phenyl group).

Particularly preferred 3-aryl substituted coumarin compounds are the {(s-triazin-2-yl) amino} -3-arylcoumarin compounds of the general formula IX.

[0080]

[Chemical 10]

The lophine dimer means a 2,4,5-triphenylimidazolyl dimer consisting of two lophine residues, and its basic structure is shown below.

[0082]

[Chemical 11]

Specific examples thereof include 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer and 2
-(O-Fluorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-methoxyphenyl) -4,
5-diphenylimidazolyl dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (2 , 4-Dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2
Examples include-(p-methylmercaptophenyl) -4,5-diphenylimidazolyl dimer.

In the present invention, other known initiators can be used in addition to the above initiators. For example, vicinal polyketolualdonyl compounds disclosed in US Pat. No. 2,367,660, US Pat.
Α-carbonyl compounds disclosed in US Pat. Nos. 7,661 and 2,367,670, US Pat.
Acyloin ethers disclosed in US Pat. No. 4,828,828, .alpha.-hydrocarbon substituted aromatic acyloin compounds disclosed in US Pat. No. 2,722,512, US Pat. No. 3,046. , 127 and 2,9
No. 51,758, a polynuclear quinone compound, and a combination of triallyl imidazole dimer / p-aminophenyl ketone disclosed in US Pat. No. 3,549,367, JP-B-51-48516. Examples thereof include benzothiazole-based compounds / trihalomethyl-s-triazine-based compounds disclosed in the publication. In addition, Asahi Denka Co., Ltd. Adekaoptomer SP-150, 151, 170, 171, N-1717, N1
414 etc. can also be used as a polymerization initiator.

The amount of the initiator used is 0.1 to 10.0% by mass, preferably 0.1% by mass based on the total solids of the photosensitive colored resin composition.
It is 5 to 5.0 mass%. If the amount of the initiator used is less than 0.1% by mass, the polymerization is difficult to proceed, and 10.0% by mass is also used.
If it exceeds, the film strength becomes weak.

[V] Solvent The solvent used when preparing the photosensitive colored resin composition of the present invention includes esters such as ethyl acetate and acetic acid.
n-Butyl, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate , Methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc.
-Oxypropionic acid alkyl esters; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, 2
-Ethyl oxypropionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2- Methyl oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate,
Ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate,
Methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like; ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate,
Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, etc .; Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc .;
Aromatic hydrocarbons, such as toluene and xylesi, are mentioned.

Of these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimeter ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl Carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether acetate and the like are preferably used.

These solvents may be used alone or in combination of two or more kinds.

[VI] Fluorine-based organic compound The photosensitive colored resin composition of the present invention has a fluorine content of 3 to 40% by mass, preferably 5 to 30% by mass, more preferably 7 to 25% by mass. It is desirable to contain certain fluorine-based organic compounds. When the fluorine content of the fluorine-containing organic compound is low, a sufficient effect cannot be obtained in coating thickness uniformity and liquid-saving property. On the contrary, when the content is too large, the solubility in the composition is insufficient. Become. Incorporation of a fluorine-based organic compound in the present invention makes it possible to improve the liquid properties of the coating liquid and improve the uniformity of the coating thickness and the liquid saving property. In particular, the wettability to the substrate is improved, and a coating film having a uniform film thickness without unevenness in thickness can be obtained even with a small amount of liquid.

Examples of such a fluorine-based organic compound include Megafac F171, F172 and F17.
3, Same F177, Same F141, Same F142, Same F14
3, the same F144, the same R30, the same F437 (above, manufactured by Dainippon Ink and Chemicals, Inc.), Florard FC430, the same FC4
31, FC171 (above, manufactured by Sumitomo 3M Limited), Surflon S-382, SC-101, SC
-103, SC-104, SC-105, SC1
068, SC-381, SC-383, S39
3, the same KH-40 (above, Asahi Glass Co., Ltd. make) etc. are mentioned. Among them, MegaFac F177, MegaFac F143, MegaFac R30 and the like are preferable.

Among the above-mentioned fluorine-based organic compounds, compounds having a structure represented by the following formula (I) are particularly preferable. C ₈ F
₁₇ SO ₂ N (R ₁ ) CH ₂ CH ₂ O (CH ₂ CH ₂ O) _n R ₂
(I) In formula (I), R ₁ and R ₂ each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 2 to 30. In formula (I), preferably R ₁ is a methyl group,
It is an ethyl group or an iso-propyl group, and R ₂ is a hydrogen atom. The preferable range of n is 10 to 25, and the particularly preferable range is 10 to 20.

By adding a fluorine-containing organic compound represented by the above formula (I) to the composition of the present invention, the liquid characteristics of the composition are further improved. That is, the fluidity of the coating liquid is improved, the adhesion of the liquid in the spin coater nozzles, pipes, and containers used in the coating process is improved, and the residue remaining as stains can be almost eliminated. The amount of cleaning liquid and the working time required for cleaning when switching liquids can be reduced, and process suitability is improved. It is considered that the above-mentioned fluorine-based organic compound acts as a nonionic surfactant in the photosensitive combined colored resin composition of the present invention. Further, the fluidity of the coating liquid is improved, the interfacial tension between the substrate and the coating liquid is lowered, and the wettability to the substrate is improved. Can be obtained. In particular, when the coating film becomes thin, good results are obtained for coating unevenness and thickness unevenness, and also for slit coating in which liquid breakage easily occurs on the coated surface.

In the present invention, the addition amount of the fluorine-based compound represented by the formula (I) is preferably 0.001 to 2.0 mass% with respect to the total coating solution, and more preferably 0.
055 to 1.0% by mass, most preferably 0.003 to
It is 0.5% by mass.

Examples of the fluorine-based compound represented by the above formula (I) include Megafac F-141 (n = 5) and F-142 (n = 1) manufactured by Dainippon Ink and Chemicals, Inc.
0), F-143 (n = 15), F-144 (n = 2)
0) can be mentioned.

[VII] Other Components In the photosensitive colored resin composition of the present invention, various additives such as a filler, a polymer compound other than the above alkali-soluble resin, and a surfactant other than the above may be added, if necessary. Adhesion promoters, antioxidants, ultraviolet absorbers, anti-agglomeration agents and the like can be added.

Specific examples of these additives include fillers such as glass and alumina; itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, acidic celluloses. Derivatives, polymers with hydroxyl groups to which acid anhydrides have been added, alcohol-soluble nylons, alkali-soluble resins such as phenoxy resins formed from bisphenol A and epichlorohydrin; nonionic, catechin, anionic surface active agents Agents, specifically phthalocyanine derivatives (commercially available EFKA
-745 (manufactured by Morishita Sangyo); organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid-based (co) polymer Polyflow No. 75, No. 90, No. 9
5 (manufactured by Kyoeisha Oil and Fat Chemical Co., Ltd.) and W001 (manufactured by Yusho); cationic surfactants; polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxy Ethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (BASF Corporation Pluronic L1
0, L31, L61, L62, 10R5, 17R2, 2
5R2, Tetronic 304, 701, 704, 90
Nonionic surfactants such as 1,904,150R1; W
Anionic surfactants such as 004, W005, W017 (manufactured by Yusho); EFKA-46, EFKA-47, EFK.
A-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (above Morishita Sangyo), Disperse Aid 6,
Polymer dispersants such as Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (manufactured by San Nopco); Solspers 3000, 5000, 9000, 1
2000, 13240, 13940, 17000, 24
000, 26000, 28000 and other Solsperse dispersants (manufactured by Zeneca Corporation); ADEKA Pluronic L
31, F38, L42, L44, L61, L64, F6
8, L72, P95, F77, P84, F87, P9
4, L101, P103, F108, L121, P-1
23 (manufactured by Asahi Denka) and ISONET S-20 (manufactured by Sanyo Kasei);

Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy)
Silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl)
-3-Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxy Adhesion promoters such as silane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-) 6-
Antioxidants such as t-butylphenol) and 2,6-di-t-butylphenol; UV rays such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenone Absorption agents; and anti-aggregation agents such as sodium polyacrylate.

Further, in order to promote the alkali solubility of the unirradiated area and further improve the developability of the composition of the present invention, the composition of the present invention may be added with an organic carboxylic acid, preferably a molecular weight of 1,000 or less. The low molecular weight organic carboxylic acid can be added. Specifically, for example, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid and other aliphatic monocarboxylic acids; oxalic acid, malonic acid, succinic acid, glutaric acid. Acids, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid and other aliphatic dicarboxylic acids; tri Aliphatic tricarboxylic acids such as carballylic acid, aconitic acid and camphoronic acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesin Aromatic polycarboxylic acids such as acids, melophanoic acid and pyromellitic acid; phenylacetic acid, Doroatoropa acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, other carboxylic acids such as umbellic acid.

In addition to the above, it is preferable to add a thermal polymerization inhibitor to the photosensitive colored resin composition of the present invention, for example, hydroquinone, p-methoxyphenol, di-t-butyl-p-. Cresol, pyrogallol,
t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,
2'-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole and the like are useful.

[VII] Method for Producing and Using Composition of the Present Invention The photosensitive colored resin composition of the present invention comprises a colorant, an alkali-soluble resin, a photosensitive polymerization component, a photopolymerization initiator and, if necessary, further. It can be prepared by mixing other additives to be used with a solvent and mixing and dispersing using various mixers and dispersers. The mixing and dispersing step preferably comprises kneading and dispersing and subsequent fine dispersing treatment, but the kneading and dispersing can be omitted.

As a preferred method for producing the composition of the present invention, an alkali-soluble resin B1 which is a copolymer of (meth) acrylic acid and benzyl methacrylate as a colorant is used.
Or (meth) acrylic acid, benzyl methacrylate,
And the viscosity of the alkali-soluble resin B2, which is a copolymer of hydroxyethyl (meth) acrylate, after kneading and dispersing is 10,000 mPa · s or more, preferably 10
Kneading and dispersion treatment is performed so that the viscosity becomes relatively high of 50,000 mPa · s or more, and then the alkali-soluble resin A is added, and the viscosity after the fine dispersion treatment is 1,000 mPa · s or less, preferably 100 mPa · s. The following is a fine dispersion treatment so that the viscosity becomes relatively low.

In the kneading / dispersing step, the surface of the particles of the raw material colorant is promoted to be wetted with the constituent components mainly composed of the resin component of the vehicle, and the colorant particles and the vehicle are removed from the solid / gas interface between the colorant particles and the air. Convert to solid / solution interface of solution.
In the fine dispersion step, the colorant particles are dispersed to a fine state close to the primary particles by mixing and stirring with a medium for dispersing fine particles of glass or ceramic. Therefore, in the kneading / dispersing step, it is necessary to convert the interface formed by the surface of the colorant particles into a solution from air, and thus a strong shearing force and compression force are required, and a kneading machine suitable for it and a material to be kneaded are preferably highly viscous. On the other hand, in the fine dispersion process, it is necessary to uniformly and stably distribute the particles to a fine state,
It is desirable that the disperser that does not require impact and shear forces on the agglomerated colorant particles and that the relatively low object to be dispersed have a relatively low viscosity.

Using the photosensitive colored resin composition of the present invention,
For example, in the kneading / dispersing step for producing a color filter, first, a colorant such as an organic pigment or carbon black and a dispersant or a surface treating agent, the resin B1 or B of the present invention are used.
Knead with 2 (part or all of resin A when neither resin B1 nor B2 is used) and a solvent. The machine used for kneading is a two-roll machine, a three-roll machine, a ball mill, a tron mill, a disper, a kneader, a co-kneader, a homogenizer, a blender, a single-screw extruder or a twin-screw extruder, which disperses while giving a strong shearing force. Then, the solvent and the resin A of the present invention (the balance used in the kneading step) are added, and a vertical or horizontal sand grinder, a pin mill, a slit mill, an ultrasonic disperser, or the like is used.
Disperse with beads made of glass, zirconia, etc. having a particle size of 1 mm. Incidentally, this kneading step can be omitted.
In that case, beads are dispersed with the pigment, the dispersant or the surface treatment agent, the resin B1 or B2 of the present invention (a part or all of the resin A when neither is used) and the solvent. In this case, it is preferable to add the remaining resin A in the kneading step during the dispersion. For details on kneading and dispersion, see "Paint Flow and Pigment Dispe" by TC Patton.
rsion "(published by John Wiley and Sons in 1964).

The photosensitive colored resin composition of the present invention is applied to the substrate directly or through another layer by a coating method such as spin coating, slit coating, cast coating, roll coating, etc. to give a radiation sensitive composition. By forming a layer, exposing through a predetermined mask pattern, curing only the coating film portion irradiated with light, and developing with a developer, each color (3 colors or 4 colors) is developed.
A color filter can be manufactured by forming a patterned film composed of (color) pixels. Ultraviolet rays such as g rays and i rays are preferably used as the radiation used at this time. Then, an alkali development treatment is performed to elute the light-unirradiated portion into the alkaline aqueous solution by the above exposure, and only the light-cured portion remains. As a developer,
Any material can be used as long as it dissolves the photosensitive layer in the non-irradiated area and does not dissolve the light-irradiated area.
Then, after the excess developer is removed by washing and dried, heat treatment (post-baking) is performed at a temperature of 50 ° C to 240 ° C. In this way, the cured film can be manufactured by sequentially repeating the above steps for each color. This gives a color filter.

As the substrate, for example, non-alkali glass, soda glass, Pyrex (registered trademark) glass, quartz glass used for liquid crystal display elements, those obtained by attaching a transparent conductive film to these, or solid-state image pickup elements are used. A photoelectric conversion element substrate such as a silicon substrate can be used. Furthermore, plastic substrates are also possible. On these substrates, black stripes that normally isolate each pixel are formed.

The raw materials for the plastic substrate are (1) amorphous polyolefin, (2) polyether sulfone, from the viewpoint of optical properties, heat resistance, mechanical strength, etc.
(3) polyglutarimide, (4) polycarbonate,
(5) polyethylene terephthalate, (6) polyethylene naphthalate, (7) norbornene polymer, (8)
Examples thereof include polyimide containing bisanilinefluorene as a diamine component, and (9) polyester composed of bisphenolfluorene and dibasic acid. Among these, (2) polyether sulfone, (4) polycarbonate, (5)
Polyethylene terephthalate and (7) norbornene polymer are preferred. The above raw materials are particularly preferred for LCD applications. The properties required of plastic substrates are low thermal expansion (prevention of deterioration of display accuracy due to curing treatment when making color filters), gas barrier property (ensuring liquid crystal stability), optical properties such as light transmittance and optical isotropy. There are characteristics and surface smoothness. Regarding thermal expansion, the coefficient of thermal expansion is 1
It is preferably ^0-4 or less. Further, the plastic substrate preferably has a gas barrier layer and / or a solvent resistant layer on the surface thereof.

The photosensitive colored resin composition layer of the present invention coated on the substrate is dried (prebaked) by hot plate,
It can be performed in an oven or the like at a temperature of 50 ° C. to 140 ° C. for 10 to 300 seconds.

The coating thickness (after drying) of the photosensitive colored resin composition of the present invention is generally 0.3 to 5.0 μm, preferably 0.5 to 3.5 μm, and most preferably 1.0 to 2 .5
μm.

As the developing solution, any composition can be used as long as it dissolves the photosensitive colored resin composition of the present invention but does not dissolve the radiation-irradiated portion. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used. Examples of the organic solvent include the above-mentioned solvents used when preparing the composition of the present invention. The developing temperature is usually 20 ° C. to 30 ° C., and the developing time is 20 to 90 seconds.

Examples of the alkali include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, Tetraethylammonium hydroxide, choline,
Pyrrole, piperidine, 1,8-diazabicyclo-
The concentration of the alkaline compound such as [5,4,0] -7-undecene is 0.001 to 10% by mass, preferably 0.0
An alkaline aqueous solution which is dissolved so as to be 1 to 1% by mass is used. When a developer made of such an alkaline aqueous solution is used, it is generally washed (rinsed) with water after the development.

Post-baking is heating after development to complete curing, and is usually about 200 ° C to 220 ° C.
Heating (hard baking). This post-baking treatment is performed in a continuous system or a batch system by using a heating means such as a hot plate, a convection oven (a hot-air circulation dryer), or a high-frequency heater so that the coating film after development is under the above conditions. be able to.

The application of the photosensitive colored resin composition of the present invention has been mainly described mainly for use in color filters, but it goes without saying that it can also be applied to a black matrix provided between pixels of color filters. The black matrix is carbon black in the composition of the present invention,
A composition containing a black colorant such as titanium black may be exposed to light, subjected to alkali development, and then post-baked to accelerate curing of the film to form a film. In addition to the color filter body (coloring layer) and the black matrix, various components for a color filter can be applied to a spacer, a protective layer, a contact hole forming layer, and the like. Further, the colored resin composition of the present invention can be used as a potting sealant for COB (chip on board) and a sealant for LCD, in addition to the above-mentioned various components for color filters.

[0113]

The present invention will be described in more detail with reference to the following examples, but the present invention is not construed as being limited to the following examples.

[0114] Preparation of photosensitive colored resin composition -C. I. Pigment Red 254 27 parts by mass -C. I. Pigment Yellow 139 4 parts by mass -Resin B1 or B2 shown in Table 1 below (Example 1 and Comparative Example 1 is resin A only) propylene glycol monomethyl Ether acetate solution (solid content 50%)                                                             22 parts by mass 2 parts by weight of dispersant (BY-K company BY-161)   The above components are kneaded and dispersed with a three-roll mill, and then -Propylene glycol monomethyl resin A shown in Table 1 below Ether acetate solution (solid content 50%) 22 parts by mass ・ Propylene glycol monomethyl ether acetate (solvent) 200 parts by mass Was added and finely dispersed for 24 hours in a sand mill.

Next, the following components were added and mixed with stirring to prepare a photosensitive colored resin composition (resist liquid). 20 parts by mass of dipentaerythritol penta, hexaacrylate 4- [o-bromo-pN, N-di (ethoxycarbonyl) aminophenyl] 2,6-di (trichloromethyl) -S-triazine (photopolymerization initiation Agent) 1 part by mass, surfactant BASF's Tetronic 150R1 0.5 parts by mass, fluorine compound DIC's Megafac F-143 0.01 parts by mass, propylene glycol monomethyl ether acetate (solvent) 150 parts by mass. Table 1 shows the viscosity of each dispersion liquid after kneading and dispersion in the process.

Examples 1 to 11 and Comparative Examples 1 to 5 The compositions obtained above were evaluated for coating thickness uniformity, liquid usage, coating unevenness, development latitude, and transmittance by the following methods. .

(1) <Spin coating> Uniformity of coating thickness: 5
Onto a glass substrate of 50 mm × 650 mm, 30 g of the resist solution prepared above was dropped in the center and spin-coated at 600 rpm. The thickness from the central portion of the coated substrate to the portion 300 mm inside from the edge in the diagonal direction was measured. The unevenness of the coating thickness is expressed by the following formula and expressed in%. Thickness unevenness = (thickness of central portion−thickness of 30 mm inside edge portion)
/ Center thickness (2) <Spin coating> Amount of coating liquid used: 550 mm x 65
The resist solution 20 prepared above on a 0 mm glass substrate
When 40 g was dropped in the center and spin-coated at 800 rpm, the minimum liquid amount at which a part of the outermost edge was not applied was measured.

(3) <Slit coating> Coating unevenness: Using a slit coating apparatus equipped with a slit head having a slit gap of 50 μm and a coating effective width of 20 mm, slits were formed so that the coating thickness after drying was 2 μm. A rectangular glass substrate having a width of 230 mm, a length of 300 mm, and a thickness of 0.7 mm was prepared by adjusting the gap between the substrates and applying the coating solution of the photosensitive colored resin composition of each Example or Comparative Example at a coating speed of 50 mm / sec. The coating was applied on the top to obtain a coating surface having a coating width of 21 mm and a length of 260 mm. After application, prebaking was performed at 90 ° C. for 60 seconds on a hot plate, and then the number of stripe-shaped unevenness on the application surface was visually calculated. ○ 1 with no streaky unevenness on the coated surface
.About.5 pieces were evaluated as .DELTA., And 6 or more m pieces were evaluated as x.

(4) Development latitude: The resist solution prepared above was spin-coated on a glass substrate (Corning 1737) so that the film thickness after drying was 1.5 μm, and prebaked at 90 ° C. for 60 seconds using an oven. 20 μm later
200 mj / cm ² exposure (illuminance: 20 mW / cm ² ) was performed with a mask having a line width of, and development was performed at 30 ° C. with a 10% diluted solution of an alkaline developer CD (manufactured by Fuji Film Arch Co., Ltd.). The development time was 10 to 100 seconds in steps of 10 seconds. The number of development seconds in which the line width remained stable was expressed as the development latitude. (5) Transmittance: Chromaticity values of the substrates spin-coated with the above-prepared resist solution were measured using MCPD-2000 manufactured by Otsuka Electronics Co., Ltd., and compared with Y values when the X value was 0.640. did. The larger the Y value, the larger the transmittance. The above results are shown in Tables 1 and 2.

[0120]

[Table 1]

[0121]

[Table 2]

Explanation of symbols in the table Acr (EO) _n : CH ₃ (OC ₂ H ₄ ) _n OCOC (CH ₃ ) = CHR BzMA: benzyl methacrylate St: styrene AA: acrylic acid MAA: methacrylate HEMA: hydroxyethyl Methacrylate Further, the molecular weights in the table are polystyrene-equivalent weight average molecular weights by GPC.

The photosensitive colored resin composition of the present invention is uniform in coating thickness by spin coating, liquid saving (amount of liquid used), uneven coating resistance by slit coating, and further, in terms of transmittance and development latitude. Was also excellent. Particularly, good characteristics are exhibited even in slit coating, which has conventionally been problematic in terms of coating unevenness and coating film thickness uniformity. Further, the photosensitive colored resin composition of the present invention may contain a colorant, a photosensitive polymerization component, a photopolymerization initiator, a solvent and a specific terpolymer as an alkali-soluble resin as constituent components, Further, better physical properties can be obtained by further containing a specific other copolymer and / or a fluorine-based organic compound as the alkali-soluble resin.

[0124]

EFFECT OF THE INVENTION The photosensitive colored resin composition of the present invention is excellent in coatability even at high pigment concentration and high solid content concentration, has a wide development latitude, is excellent in process acceptability, and is also improved in transmittance. it can. In addition, the entire surface of the substrate can be coated with a small amount of coating liquid. Therefore, from the composition of the present invention, a color filter used in a liquid crystal display device or a solid-state image pickup device can be produced with less process difficulty, high quality and low cost.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G02B 5/20 101 G02B 5/20 101 5/22 5/22 G03F 7/004 501 G03F 7/004 501 504 504 505 505 F Term (Reference) 2H025 AB13 AC01 AD01 BC13 BC42 CA00 CB13 CB14 CB41 CB43 CB45 CB55 CC04 CC12 CC20 FA17 2H048 BA02 BA11 BA45 BA48 BB02 BB14 BB15 BB15 PA02 P11A02 B11 PA02 P11A02 CA01 CA22 PA04 A02 CA01 CA22 A04 B02 CA01 A23 CA05 A02 CA01 A23 CA05 A11 CA01 A23 CA05 A02 QA07 RA03 SA00 SA78 UA01 VA01 WA01 WA02 4J026 AA42 AA45 AC09 AC23 BA26 BA27 BA28 DA02 DB02 DB36 GA07

Claims (10)

[Claims] 1. A photosensitive colored resin composition containing (a) a colorant, (b) an alkali-soluble resin A, (c) a photosensitive polymerization component, (d) a photopolymerization initiator, and (e) a solvent. The alkali-soluble resin A is at least (i) at least one acid component monomer selected from maleic anhydride, acrylic acid, methacrylic acid, and fumaric acid, (ii) an alkylpolyoxyethylene (meth) acrylate, and (iii) ) A photosensitive colored resin composition, which is a copolymer composed of benzyl (meth) acrylate. 2. The alkali-soluble resin A,
The composition mass ratio of (i) acid component monomer, (ii) alkyl polyoxyethylene (meth) acrylate, and (iii) benzyl (meth) acrylate is 10 to 25/5 to 25.
/ 50-85, and polystyrene conversion mass average molecular weight (Mw) is 3,000-50,000, The photosensitive colored resin composition of Claim 1 characterized by the above-mentioned. 3. The solid content of the photosensitive colored resin composition, the content of the colorant is 30 to 60 mass%, the content of the alkali-soluble resin A is 10 to 50 mass%. The photosensitive colored resin composition according to claim 1 or 2. 4. An alkali-soluble resin B1 in which the photosensitive colored resin composition is a copolymer of (i) (meth) acrylic acid and (ii) benzyl methacrylate.
The photosensitive colored resin composition according to any one of claims 1 to 3, further comprising: 5. An alkali-soluble resin in which the photosensitive colored resin composition is a copolymer composed of (i) (meth) acrylic acid, (ii) benzyl methacrylate, and (iii) hydroxyethyl (meth) acrylate. B2 is contained, The photosensitive colored resin composition in any one of the Claims 1-3 characterized by the above-mentioned. 6. The content of the colorant in the solid content of the photosensitive colored resin composition is 30 to 60% by mass, and the content of the alkali-soluble resin (sum of A, B1 and B2).
Is 10 to 50 mass% in total, The photosensitive colored resin composition according to any one of claims 1 to 5, wherein 7. The photosensitive colored resin composition further contains a fluorine-containing organic compound having a fluorine content of 3 to 40% by mass, according to any one of claims 1 to 6. The photosensitive colored resin composition of. 8. The photosensitive colored resin composition according to claim 7, wherein the fluorine-based organic compound is represented by the following formula (I). C ₈ F ₁₇ SO ₂ N (R ₁ ) CH ₂ CH ₂ O (CH ₂ CH ₂ O) _n R ₂ (I) In formula (I), R ₁ and R ₂ are each a hydrogen atom or a carbon number 1
Represents an alkyl group of 4 and n represents an integer of 2 to 30. 9. The colorant is an alkali-soluble resin B1 which is a copolymer of (meth) acrylic acid and benzyl methacrylate or a copolymer of (meth) acrylic acid, benzyl methacrylate and hydroxyethyl (meth) acrylate. It is characterized in that it is kneaded and dispersed with a certain alkali-soluble resin B2 at a viscosity of 10,000 mPa · s or more, then the above-mentioned alkali-soluble resin A is added to the kneaded dispersion, and finely dispersed at a viscosity of 1,000 mPa · s or less. The method for producing the photosensitive colored resin composition according to claim 1. 10. A coating film is formed by slit coating the photosensitive colored resin composition according to claim 1 on a substrate directly or through another layer, and then prebaked. A method for producing a color filter in which pattern exposure and alkali development are sequentially performed.