JP2000239558A - Photosensitive colored composition and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition capable of providing a photosensitive color composition having high sensitivity and a color film especially excellent in resistances, especially heat resistance and color purity by making the composition include a photocross-linkable resin, a dye and a sensitizer. SOLUTION: This composition comprises at least (A) a photocross-linkable resin containing at least one or more photocross-linkable imide group bond parts and at least one or more photocross-linkable amide group bond parts, (B) a dye, preferably an acid dye and (C) a sensitizer for sensitizing a photocross-linking reaction of imide group. In the component A, preferably the photocross-linkable imide is bonded to a main chain in a form of formula I [P is a polymer main chain; X is O or NH; n is an integer; Y is a group of formula II (R1 and R2 are each H, an alkyl, a substituted acryl or the like)]. For example, the amounts of the components are 100 pts.wt. of a resin dissolution solvent, 10-25 pts.wt. of the component A, 1.0-50 wt.% of the component B and 0.01-1 pt.wt. of the component C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is used for a photosensitive coloring composition for a high-quality color filter which can be developed with a solvent or an aqueous alkali solution after image exposure with ultraviolet rays, a solid-state imaging device, a liquid crystal display device and the like. Related to color filters.

[0002]

2. Description of the Related Art In recent years, liquid crystal display devices and the like have become thinner and larger, and color filters to be used have been required to be defect-free and thin. Transmission and high contrast are required. At the same time, cost reduction of color filters is strongly demanded, and it is necessary to improve the yield in the manufacturing process and to shorten the process. Color filters consist of two or more fine bands (stripe) of different hues arranged in parallel or intersecting on the surface of a transparent substrate such as glass, or those in which fine pixels are arranged in a fixed vertical and horizontal direction. Has become. The pixel size must be a fine shape of several tens to several hundreds of microns, and must be arranged in a predetermined order for each hue. For this reason, various methods have been conventionally proposed for producing color filters.

Since color filters are required to have smoothness and high dimensional accuracy, a method of forming an image using photolithography has been the mainstream conventionally. Also,
Because high transparency is required for color filters,
A coloring method using a dye, which is generally called a dyeing method, is performed. For example, a photosensitive substance to be dyed is applied on a substrate such as a crow, and then a pattern exposure of one filter color is performed, an unexposed portion is removed in a developing process, and a remaining pattern portion is removed by the filter color. Dye with dye. By repeating this operation sequentially for all filter colors, a color filter can be manufactured. However, when assembling a color liquid crystal display device, the IT
It is necessary to form a transparent conductive film such as O 2 and a liquid crystal alignment film. Since this step requires a very high temperature, the color filter is required to have high heat resistance. The required heat resistance depends on the driving method of the liquid crystal. For example, an active matrix type TFT (thin film transistor) type
Heat resistance of 1 hour at 230 ° C and 1 hour at 260 ° C is required for simple matrix STN (super twisted nematic) type.

[0004] The color filter obtained by the above-mentioned dyeing method is inferior in heat resistance (usually 200 ° C or lower) because the dye is not sufficiently dyed on the resin. At present, it is expected to find a way to improve this.

[0005] At present, a method of using a pigment having good heat resistance as a dye has become mainstream. Above all, a method using a coloring composition in which a pigment is dispersed in a photosensitive composition, which is called a pigment dispersion method, is widely used as a method for producing a color filter. That is, the photosensitive coloring composition of one filter color is coated on a transparent substrate such as glass, and is subjected to pattern exposure. The unexposed portion is developed and removed with a solvent or an aqueous alkaline solution to form a first color pattern. Subsequently, the same operation is sequentially repeated for all filter colors, whereby a color filter having excellent heat resistance can be manufactured. The photosensitive coloring composition is mainly a negative photosensitive coloring composition because of its physical properties as a color filter and the abundance of materials. Further, in developing, almost no solvent is used due to environmental problems. Development is the mainstream. Regarding the exposure, exposure with ultraviolet rays is usually performed.

[0006] As described above, since the pigment dispersion method uses a photosensitive composition in which a pigment is dispersed in advance, ultraviolet rays are absorbed by the pigment, and the exposure sensitivity generally decreases significantly.
Therefore, there is a problem in productivity because the exposure time becomes long. Further, in the negative photosensitive composition, since a radical polymerization reaction is mainly used, inhibition of the reaction by oxygen in the air also causes a decrease in sensitivity. In this regard, after applying the photosensitive composition, measures have been taken to expose the image after providing an oxygen barrier film such as polyvinyl alcohol thereon, but since the number of steps is increased, the problem of productivity remains. Therefore, a highly sensitive material that does not require an oxygen barrier film has been strongly desired (Japanese Patent Laid-Open No. 1-152449).

[0007] Further, the color purity is an important factor in the performance of the color filter. In the pigment type described above, a large amount of a photoinitiator is usually blended in order to secure exposure sensitivity. As a result, there is a problem that it is difficult to obtain the performance of the manufactured color filter, particularly high color purity, due to the effect of heat discoloration or the like such as residue. Therefore, in recent years, methods using dyes have been reexamined (see Japanese Patent Application Laid-Open No. 5-333207).
. This is a color filter obtained by coloring a thermosetting resin with a dye formed with an alkyl ammonium ion. However, since a photoinitiator is used for pattern formation, there are problems in heat resistance and color purity. Therefore, development of a photosensitive coloring composition and a color filter using a dye without using a photoinitiator is desired.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a high-sensitivity photosensitive coloring composition which solves the above problems and a color filter which is excellent in various resistances, especially in heat resistance and color purity. That is, in the present invention, a photocrosslinkable site capable of forming a pattern without using a photoinitiator is contained in a resin, and in order to further impart heat resistance, an amide bond is used as a dyeing site in the resin. It is a photocrosslinkable composition provided with sites. Provided are a photosensitive coloring composition and a color filter which are excellent in heat resistance and light resistance, characterized by using an acidic dye as a dye.

[0009]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and the invention of claim 1 has at least one imide group capable of photocrosslinking and at least one amide bonding site. Photocrosslinkable resin (A), dye (B), and a sensitizer (C) that sensitizes the photocrosslinking reaction of the imide group.
Is a photosensitive coloring composition characterized by containing at least

According to a second aspect of the present invention, the photocrosslinkable imide group according to the first aspect is

[0011]

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(In the formula (1), P represents a polymer main chain;
Represents O or NH, n represents an integer, Y can be represented by the formula (2),

[0013]

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R ₁ and R ₂ each independently represent H or an alkyl group, a substituted acryl group, —COOH, or a halogen atom. 2. The photosensitive coloring composition according to claim 1, wherein the photosensitive coloring composition is bonded to a main chain in the form of

A third aspect of the present invention is the photosensitive coloring composition according to the first aspect, wherein the dye according to the first aspect is an acid dye.

According to a fourth aspect of the present invention, on a transparent substrate,
A color filter comprising a pixel formed by using the photosensitive coloring composition according to claim 1 or 2.

[0017]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The configuration and effects of the present invention will be described in detail below. The photocrosslinkable resin having an imide group or an amide group used in the present invention can be obtained, for example, by copolymerization of a polymerizable monomer having a functional group or a binding site.
Polymerizable monomers having an imide group include dicarboxylic anhydrides having an unsaturated bond in the ring (eg, 1,2-dimethyl anhydride maleic acid, cis-aconic acid anhydride, etc.) and diamines or alcohol amines. (E.g., ethylenediamine, hexamethylenediamine, hydroxylamine, monoethanolamine, etc.) by heating an alcohol having an imide structure or an amine having an imide structure;
It can be synthesized by reacting with (meth) acrylic acid chloride (hereinafter, (meth) includes both compounds with and without meta). Alternatively, it can also be synthesized by an esterification reaction between an alcohol having an imide structure and (meth) acrylic acid.

In the above-mentioned reaction between the dicarboxylic anhydride and the diamine or the alcoholamine, the molar ratio of the charge is not particularly limited, but it is preferable to use the diamine or the alcoholamine in an amount of about 0.5 to 3.0 mol per 1.0 mol of the dicarboxylic anhydride. preferable. The reaction temperature is preferably from 90 to 110 ° C. After completion of the reaction, the reaction solution is washed with water, reduced pressure distillation, reduced pressure thin film distillation, recrystallization, etc. to remove unreacted raw materials and purify to obtain an amine having an imide structure or an alcohol having an imide structure. it can.

In the reaction of an amine having an imide structure or an alcohol having an imide structure with (meth) acrylic acid chloride, the charged molar ratio is not particularly limited.
It is preferable to use about 2.0 to 3.0 moles of (meth) acrylic acid chloride per 1.0 mole of an amine having an imide structure or an alcohol having an imide structure.

The reaction temperature is not particularly limited, but is preferably about -20 to 100 ° C. because polymerization occurs at a high temperature. At this time, as a polymerization inhibitor, hydroquinone, hydroquinone monomethyl ether, t-butylhydroquinone, t-butylcatechol, benzoquinone, phenothiazine and the like may be added in an amount of about 0.01 to 5% by weight based on the weight of the reaction solution.

The reaction solvent is not particularly limited as long as it does not react with an amine having an imide structure, an alcohol having an imide structure, or (meth) acrylic acid chloride. For example, dimethylacetamide, tetrahydrofuran, ethyl acetate, toluene, xylene , Acetone, diethyl ether and the like can be used.

In the above reaction, it is preferable to use a hydrochloric acid scavenger in order to make the reaction proceed smoothly.
The kind of the hydrochloric acid scavenger is not particularly limited, and for example, triethylamine, pyridine, dimethylaniline and the like can be used. The charged molar ratio of the hydrochloric acid scavenger is not particularly limited,
1.0 to 10 per 1.0 mol of (meth) acrylic acid chloride
It is preferable to use about mol.

After completion of the reaction, the reaction solution is subjected to filtration, washing with water, reduced pressure distillation, reduced pressure thin film distillation, recrystallization and the like to remove unreacted starting materials, solvent and hydrochloride, and to purify the compound of formula (1). Can be obtained.

Alcohol having imide structure and (meth)
In the esterification reaction of acrylic acid, the charged molar ratio is not particularly limited, but alcohol having an imide structure 1.
It is preferable to use (meth) acrylic acid in an amount of about 1.0 to 5 mol per 0 mol.

As the catalyst, a general esterification catalyst (for example, sulfuric acid, paratoluenesulfonic acid, tetraisopropoxytitanium, etc.) can be used. The use amount of the catalyst is not particularly limited, but it is preferable to add about 0.01 to 10% by weight based on the weight of the reaction solution. In order to prevent polymerization from occurring during the reaction, a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, t-butylhydroquinone, t-butylcatechol, benzoquinone, phenothiazine, etc. is added in an amount of about 0.01 to 5% by weight based on the weight of the reaction solution. It is preferred to add.

The reaction temperature is not particularly limited. However, the reaction does not proceed at a low temperature, and the reaction solution tends to gel at a high temperature. Therefore, the reaction temperature is preferably about -4.0 to 90 ° C. After completion of the reaction, the reaction solution is washed with water, distilled under reduced pressure, thin-film distillation under reduced pressure, recrystallized, or the like to remove the unreacted raw materials and purify the compound to obtain the compound of the formula (1).

The polymerizable monomer having an amide bond has a function of improving heat resistance together with the polymerizable monomer having an imide group described above. As the polymerizable monomer having an amide bond used in the present invention, for example, N- (meth) acryloxysuccinimide, N- (meth) allylacrylamide, N-(-3 aminopropyl) (meth) acrylamide hydrochloride , N-benzyl (meth) acrylamide, N- (iso-butoxymethyl) (meth) acrylamide, N- (tert-butyl) (meth) acrylamide,
N-cyclohexyl (meth) acrylamide, N, N-diallyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-
Diphenyl (meth) acrylate, N-dodecyl (meth)
Acryamide, N-ethyl (meth) acrylamide, N- (2
-Hydroxypropyl) (meth) acrylamide, N-methoxy (meth) acrylamide, N-methyl-N-vinylacetamide, N- (n-octadecyl) (meth) acrylamide, N-tert-octyl (meth) acrylamide, N -
Mono (meth) acrylic compounds such as (phthalimidomethyl) (meth) acrylamide and N-isopropyl (meth) acrylamide are exemplified. In addition, it is possible to use without being limited to this.

The photocurable resin may contain a carboxyl group in order to impart alkali developability. As a method containing a carboxyl group, for example, a functional group,
Alternatively, it can be obtained by a copolymerization method using a polymerizable monomer having a binding site. Specific examples of the polymerizable monomer include a monomer having a carboxyl group such as (meth) acrylic acid. In addition, it is possible to use without being limited to this.

The photocrosslinkable resin having an imide group or an amide group used in the present invention can be obtained, for example, by copolymerizing a polymerizable monomer having a functional group or a binding site. The type of the copolymerization method may be any of solution polymerization, suspension polymerization, emulsion polymerization, bulk polymerization and the like. Further, when copolymerized, the chemical structural form of the copolymer is not particularly limited, and may be any of a random copolymer, a block copolymer, a graft copolymer and the like.

The molecular weight of the resin (A) is not particularly limited. However, in using the photosensitive coloring composition of the present invention, it is necessary to apply the resin on a substrate as a uniform film. Usually, the weight average molecular weight in terms of polystyrene is preferably about 5,000 to 500,000. However, it is also possible to select a weight average molecular weight in terms of polystyrene outside the above range according to the thickness of the film to be formed, the coating method, and the purpose of use.

The copolymerization ratio of the imide group-containing polymerizable monomer in the resin (A) is usually 30 to 98% by weight, preferably 70 to 98% by weight.
~ 98% by weight. In this case, if the copolymerization ratio of the photocrosslinkable imide group-containing polymerizable monomer is less than 30% by weight, good sensitivity tends not to be obtained.

In the present invention, a pigment can be used,
The color tone is not particularly limited, and is appropriately selected according to the use of the color filter, and may be an organic pigment, an inorganic pigment, or an inorganic salt called an extender. Organic pigments include, for example, Color Index (CI; The Society)
of Dyers and Colorists, Inc.), specifically those having the following color index (CI) numbers. CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Y 14, CI Pigment Yellow 17, CI Pigment Yellow 20, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 55, CI Pigment Yellow 83, CI Pigment Yellow 93, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 139, CI Pigment Yellow 150,
CI Pigment Yellow 153, CI Pigment Yellow
154, CI Pigment Yellow 155, CI Pigment Yellow 166, CI Pigment Yellow 168, CI Pigment Orange 36, CI Pigment Orange 43, CI Pigment Orange 51, CI Pigment Orange 71; CI Pigment Red 9, CI Pigment Red 97, CI Pigment Red 122, CI Pigment Red 123, CI Pigment Red 149, CI Pigment Red 176, CI
Pigment Red 177, CI Pigment Red 180, C.I.
I. Pigment Red 215, CI Pigment Red 254
,; CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 29, CI
Pigment Blue 15, CI Pigment Blue 15: 3, C.I.
I. Pigment Blue 15: 6, CI Pigment Green 7
, CI Pigment Green 36, CI Pigment Brown 23, CI Pigment Brown 25, CI Pigment Black 1, Pigment Black 7.

Specific examples of the inorganic pigment include titanium oxide, barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron oxide (III)),
Cadmium red, ultramarine, navy blue, chromium oxide green, cobalt green, amber, titanium black, synthetic iron black, carbon black and the like can be mentioned. The pigments may be used alone or as a plurality.

In the present invention, a dispersant and a dispersing aid may be used. Such dispersants include, for example, cationic, anionic, nonionic, amphoteric, silicone,
A surfactant such as a fluorine-based surfactant can be used. As the surfactant, specifically, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether,
Polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether; polyoxyethylene alkyl phenyl ethers such as polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether; polyethylene glycol such as polyethylene glycol dilaurate and polyethylene glycol distearate Diesters; sorbitan fatty acid esters;
Fatty acid-modified polyesters; tertiary amine-modified polyurethanes; and the like, and more specifically, trade names such as KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Yushi Kagaku Kogyo), F-Top (Tochem) Products), Megafac (Dainippon Ink and Chemicals), Florard (Sumitomo 3M), Asahi Guard, Surflon (Asahi Glass) and the like. These surfactants can be used alone or in combination of two or more. The surfactant is used in an amount of usually 50 parts by weight or less, preferably 0 to 40 parts by weight, based on 100 parts by weight of the pigment.

The dye used in the present invention is not particularly limited in color tone, and is appropriately selected according to the use of the color filter. In addition, the dye may be an acidic dye, a basic dye, a reactive dye, or an oil-soluble dye. Good, preferably acid dyes are used. For example, as the red dye, Suminol Milling Scarlet G (Sumitomo Chemical), Cibacron Scarlet G-P (Ciba Keigi), Cibacron Pronto Scarlet (Ciba Keigi), Suminol Fast Red (Sumitomo Chemical), Suminol Supra Red 4BL (Sumitomo Chemical), Aminil Red E-
3BL (Sumitomo Chemical), Azide Scarred 901 (Sumitomo Chemical)
, Suminol Milling Scarred FG (Sumitomo Chemical), Suminol Milling Orange SG (Sumitomo Chemical), Suminol Fast Orange PO (Sumitomo Chemical), Maxillon Red GRL (Ciba Geigy), Eriocin Scarred RE (Ciba Geigy), Mikawan Brilliant Red 8BS (Mitsubishi Chemical), Acid Light Scarred GL130% (Mitsubishi Chemical), Kayanol Milling Red RS125 (Nippon Kayaku) And Kayanol Milling Red 3BW (Nippon Kayaku). In addition, it is possible to use without being limited to this.

Green dyes include Suminol Milling Brilliant Green 5G (Sumitomo Chemical), Acid.
Brilliant Milling Green G (Sumitomo Chemical), Acid Brilliant Milling Green B (Sumitomo Chemical), Mycation Olive Green 3GS (Ciba Geigy), Kayanol Milling Green 5GW (Japanization) Drug), sooliidazole green / P-GG (Hoechst), paper fast green / 5G (Bayer), and the like. In addition, it is possible to use without being limited to this.

As blue dyes, Sumilite Supra
Turquoise Blue G (Sumitomo Chemical), Cibacron Blue 3G-A (Ciba Geigy), Kayathione Turquoise PA (Nippon Kayaku), Kayathione Turquoise P-NGF (Nippon Kayaku), Sumika Blue E-FBL (Sumitomo Chemical), Sumicaron Brilliant Blue S-BL (Sumitomo Chemical), Suminol Leveling Sky Blue R Extra
Conch (Sumitomo Chemical), Kayanol Milling Blue GW
(Nippon Kayaku) and the like. In addition, it is possible to use without being limited to this. Further, the above-mentioned pigments and dyes may be mixed and used.

Further, various additives such as an antioxidant and a light stabilizer can also be used.

As the sensitizer (C) for sensitizing the photocrosslinking reaction of the imide group used in the present invention, a triplet sensitizer that absorbs light in a range of 300 nm or more is preferably used. Such sensitizers include thioxane, thioxanthone derivatives,
For example, 2-chlorothioxatone, 2-isopropylthioxanthone, dimethylthioxanthone, methylthioxanthone-1-ethylcarboxylate and the like, 5-nitroacenaphthene and the like can be mentioned. In addition, it is possible to use without being limited to this.

When the photosensitive coloring composition of the present invention is applied, the composition may be diluted with an appropriate solvent, if necessary. In such a case, the composition is dried after being applied on a substrate. The solvent that can be used for the adjustment is not particularly limited as long as the base material to be coated is not affected by dissolution, swelling, whitening, erosion, and the like, and most common organic solvents can be used. Specifically, cyclohexanone, isophorone, cellosolve acetate, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, xylene, ethylbenzene, ethyl cellosolve, butyl cellosolve, methyl-
Examples thereof include n-amyl ketone, propylene glycol monomethyl ether, isoamyl acetate, and ethyl lactate, and these can be used alone or in combination of two or more. Note that the present invention is not limited to these.

In the photosensitive coloring composition of the present invention, the amount of each component is 100 parts by weight of the solvent for dissolving the resin, 10 to 10 parts of the photocrosslinkable resin.
25 parts by weight, 1.0 to 5.0 parts by weight of a dye, and 0.01 to 1 part by weight of a sensitizer.

Examples of the transparent substrate used for forming a color filter include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamide imide, and polyimide. These transparent substrates may be subjected to an appropriate pretreatment such as a chemical treatment with a silane coupling agent or the like, a plasma treatment, an ion plating, a sputtering, a gas phase reaction method, or a vacuum deposition, if desired.

The color filter of the present invention is applied onto the transparent substrate described above by an application method such as spray coating, spinner coating, roll coating, screen coating, etc.
It is made. These film thicknesses can be adjusted by appropriate coating methods such as spin coating, casting coating, and roll coating.
Preferably 0.2 to 5.0 μm, particularly preferably 0.2 to 3.0 μm
μm. For the purpose of obtaining appropriate fluidity in these coaters, the photosensitive coloring composition of the present invention contains, in addition to the above-mentioned solvents, extenders such as barium sulfate, calcium carbonate, and silica, and an antifoaming agent. A small amount of a silicon-based or fluorine-based surfactant may be added. The applied photosensitive coloring composition is dried in a hot air oven or a hot plate at 60 ° C. to 80 ° C. for 10 minutes to 30 minutes. If the temperature at this time is too high or the drying time is too long, partial polymerization or cross-linking occurs, the solubility of the unexposed portion in the developing solution is reduced, and a so-called "burn-in" is caused, which is a development defect. .

The dried coating film is usually exposed to ultraviolet light through a photomask having a color filter pattern.
An ultra-high pressure mercury lamp is generally used as a light source. However, since ultraviolet light transmitted through a photomask is usually light of 300 nm or more, the i-line (365 nm
), H-rays (405 nm) and g-rays (436 nm) are used for polymerization or crosslinking reactions. Therefore, the sensitivity of the photosensitive coloring composition for a color filter to the above three bright line spectra is important.

After exposure, the unexposed portion of the coating film is dissolved and removed with a developing solution, leaving a pattern of the exposed portion. Although this step is generally called development, the photosensitive coloring composition of the present invention can be developed with a solvent or an aqueous alkaline solution, particularly due to the solubility of the photocrosslinkable resin (A) used. However, as described above, alkali development is mainly used due to environmental problems. As the alkali developer, an aqueous solution of an inorganic alkali such as sodium carbonate or sodium hydroxide, or an aqueous solution of an organic alkali such as dimethylbenzylamine, triethanolamine, or tetramethylammonium hydroxide can be used. After the development, if necessary, further irradiation with ultraviolet rays or heating is performed to further advance the reaction, whereby the various resistances as a color filter can be improved.

[0046]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Comparative Examples and Examples, but the present invention is not limited thereto.

Example 1 Synthesis Example 1,3-dimethyl maleic anhydride (1.0 mol) was placed in a three-necked flask.
l) and 500 ml of toluene.
Stirred at 0 ° C. 1-aminohexanol (1.0 m
ol) was dropped by a dropping funnel over about 1 hour. After the completion of the dropwise addition, the mixture was stirred for 30 minutes. After completion of the reaction, the reaction solution was distilled off under reduced pressure. A yellow oil was obtained (90% yield).

N- (6-hydroxyhexyl) -dimethylmaleimide (1.0 mol) and triethylamine (2.0 mol) were dissolved in 400 ml of diethyl ether and stirred in an ice-water bath.
Methacrylic acid chloride (1.0 mol) is added dropwise to the solution. After completion of the reaction, triethylamine hydrochloride is separated by filtration. The ether solution is washed several times with a slightly acidified water in a separating funnel, further washed with water, dried over sodium sulphate and subsequently concentrated under vacuum. As a result, a yellow oil was obtained (yield: 45%).

[0049]

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60 parts by weight of compound A synthesized according to the synthesis example, N-hexyl-dimethylmaleimide acrylic ester
10 parts by weight, 30 parts by weight of methacrylic acid, in dimethylformamide, using azobisisobutyronitrile as a catalyst, N ₂
The reaction was carried out in an air stream, the mixture was precipitated in water, filtered and dried to obtain the desired photocrosslinkable resin (1). The molecular weight was 500,000.

[0051]

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A photocrosslinkable resin (A) containing at least one photocrosslinkable imide group and at least one amide bond site
25 parts by weight of the obtained photocrosslinkable resin (1)
(B) is 5.0 parts by weight of Suminol Milling Brilliant Green 5G, 0.01 parts by weight of 2-isopropylthioxanthone is used as a sensitizer (C) to enable light absorption in the range of 300 nm or more, and these are toluene. It was dissolved in 100 parts by weight of a solvent and stirred to obtain a photosensitive colored composition. This photosensitive coloring composition is spin-coated on a glass substrate (1500r
pm) to a thickness of about 1.0 μm.

The solvent of the photosensitive coloring composition applied on the glass substrate was dried at 80 ° C. for 10 minutes using a hot plate or the like. The dried coating is exposed to UV light through a photomask
(100 mJ / cm ² ). An ultra-high pressure mercury lamp was used as a light source. After exposure, development was performed using dimethylbenzylamine.
An image with a width of 2 μm appeared, and the transparency was good.

In the heat resistance test, the photosensitive coloring composition was spin-coated on a glass substrate to form a coating film having a thickness of 1.0 μm and placed in an oven at 230 ° C. for 1 hour to transmit a light transmittance of 546 nm. (%). As a result, the light transmittance before the test was 80%, and the light transmittance after the test was 78%.

<Examples 2 to 6> Photocrosslinkable resin of Example 1
N- (2-hydroxypropyl) of the copolymer composition of (A)
Instead of methacrylamide, N, N dimethyl methacrylamide (photocrosslinkable resin 2), N- (n-octadecyl) methacrylamide (photocrosslinkable resin 3), N-isopropyl methacrylamide (photocrosslinkable resin 4), A photocrosslinkable resin was synthesized using N, N-diallyl methacrylamide (photocrosslinkable resin 5) and N-(-3 aminopropyl) methacrylamide hydrochloride (photocrosslinkable resin 6). Except for the above, the same operation as in Example 1 was performed. Table 1 shows the results of the heat resistance test.

[0056]

[Table 1]

<Examples 7 to 10> The photocrosslinkable resin of Example 1
N- (6-hydroxyhexyl) of the copolymer composition of (A)
Instead of dimethylmaleimide, N- (2-hydroxyethyl) dimethylmaleimide (photocrosslinkable resin 7), N- (3
-Hydroxypropyl) dimethylmaleimide (photocrosslinkable resin 8), N- (4-hydroxybutyl) dimethylmaleimide (photocrosslinkable resin 9), N- (5-hydroxypentyl) dimethylmaleimide (photocrosslinkable resin) Using 10), a photocrosslinkable resin was synthesized. Except for the above, the same operation as in Example 1 was performed. Table 2 shows the results of the sensitivity evaluation. Table 3 shows the results of the heat resistance test.

[0058]

[Table 2]

[0059]

[Table 3]

<Comparative Examples 1-2> Photocrosslinkable resin of Example 1
N- (2-hydroxypropyl) of the copolymer composition of (A)
A photocrosslinkable resin was synthesized using ethyl acrylate (photocrosslinkable resin 11) and hydroxyethyl methyl acrylate (photocrosslinkable resin 12) instead of methacrylamide. Except for the above, the same operation as in Example 1 was performed. Table 4 shows the results of the heat resistance test.

[0061]

[Table 4]

[Evaluation] As is clear from Table 4, the photocrosslinkable resin not containing at least one amide bond site (Comparative Example 1) is inferior in heat resistance and shows a remarkable decrease in transmittance after heating. Was done.

On the other hand, in the photocrosslinkable resin containing at least one amide bond site (Examples 1 and 2), it was confirmed that the heat resistance was improved and the transmittance change by heating was small. .

[0064]

As described above, the photosensitive coloring composition according to the present invention is excellent in various resistances, especially in heat resistance and color purity. Therefore, it can be expected to be used for manufacturing color filters.

Claims (4)

[Claims] 1. A photocrosslinkable resin (A) containing at least one photocrosslinkable imide group and at least one amide bond site.
And a dye (B) and a sensitizer (C) for sensitizing the photocrosslinking reaction of the imide group. 2. The photocrosslinkable imide group according to claim 1, wherein (In the formula (1), P represents a polymer main chain, and X represents O or NH
, N represents an integer, Y is represented by the formula (2), and R ₁ and R ₂ each independently represent H or an alkyl group, a substituted acryl group, —COOH, or a halogen atom. )
The photosensitive coloring composition according to claim 1, wherein the photosensitive coloring composition is bonded to the main chain in the form of: 3. The photosensitive coloring composition according to claim 1, wherein the dye according to claim 1 is an acid dye. 4. A color filter, wherein pixels are formed on a transparent substrate using the photosensitive coloring composition according to claim 1 or 2.