JPH04369653A - Coloring photosensitive resin composition - Google Patents

Abstract

PURPOSE:To prevent swelling, deformation and flowing out of an organic pigment from a pattern part by developer. CONSTITUTION:This coloring photosensitive resin composition contains a photosensitive resin such as photosensitive aromatic polyamide, a photo-polymerization initiater, a carboxylic acid compound and an acidic organic pigment. Since the carboxylic acid and the acidic organic compound are combined to use in the composition, when a coated film (coating film) of the composition is exposed and developed, the photoset pattern part does not swell or deform and the organic pigment does not flow out from the pattern part. Thus the coating film of the coloring photosensitive resin is formed composition on a substrate, and photoset in pattern shape by photoiradiation on the coating film, and finally unexposure part (uncured part) of the coated film with the developer is removed, thereby the coloring photosensitive resin composition is used for a production method of a colored pattern member such as a color filter for fine color resolution such as a color image pickup element, a color sensor, a color display.

Description

[Detailed description of the invention]

0001

[Field of Industrial Application] This invention generally relates to a colored photosensitive resin composition containing a photosensitive resin such as a photosensitive aromatic polyamide, a photopolymerization initiator, a carboxylic acid compound, and an acidic organic pigment. be. The colored photosensitive resin composition of the present invention is obtained by forming a coating film (film) of the composition on a base material,
By irradiating the coating film with light to photocure it in a pattern, and finally performing a development operation in which the unexposed portion (uncured portion) of the coating film is removed using a developer, color imaging elements,
It can be used in a method for manufacturing colored pattern members such as color filters for fine color separation of color sensors, color displays, etc.

0002

[Description of the Prior Art] Conventionally, as a method for producing colored pattern members such as color filters, (a) a dyed organic dye filter is produced using gelatin or the like on a transparent substrate such as glass, and the filter is attached with an adhesive. (b) The simplest method for manufacturing a multicolored surface-colored object such as a color filter is a printing method. (c) Japanese Patent Application Laid-Open No. 60-237403 (d) JP-A No. 62-212603 discloses a method of manufacturing a color filter using polyimide resin, which is known as a heat-resistant film-forming material with photosensitivity, and (d) a method of using transparent photosensitive polyamide. etc. are shown.

[0003] Conventionally known color filters using gelatin described above have a problem of poor heat resistance and fading during processing steps. Further, in the printing method described above, positioning during multicolor printing is difficult, and positional accuracy and dimensional accuracy are limited, making it impossible to manufacture highly accurate and fine color filters.

Furthermore, in the method described in JP-A No. 60-237403, since the photosensitive polyimide resin is used as a polyimide precursor, in order to convert it into a polyimide having good film properties, it is necessary to A high temperature treatment of 300° C. or higher is required, which poses problems such as deterioration of organic pigments due to heat. Furthermore, in the method described in JP-A-62-212603, although the heat resistance of the photosensitive polyamide resin composition was good, the sensitivity was not sufficient.

[0005] JP-A-2-12317 discloses a composition of a heat-resistant polyamide having a photosensitive group and a bisazide compound as a colored photosensitive composition that can solve the problems in the above-mentioned known techniques. , discloses a colored photosensitive polyamide composition in which an organic pigment is dispersed.

However, the above-mentioned known colored photosensitive polyamide compositions contain a considerable amount of pigment etc. for the purpose of selectively transmitting and blocking visible light. The "
The near-ultraviolet light necessary to cause photosensitivity does not reach the bottom of the film formed from the colored photosensitive composition (the surface of the substrate), and light There is a problem that peeling, blistering, deformation, etc. of the irradiated colored pattern part often occurs, and when trying to satisfy the color density etc. of a colored pattern (such as a color filter) consisting of a photocured layer of a colored photosensitive composition, pigment Even if attempts were made to increase the amount of such pigments, colored photosensitive compositions containing a high amount of such pigments had unsatisfactory photosensitivity of the film.

[0007] Furthermore, the above-mentioned known colored photosensitive polyamide compositions are used as a film formed by simply dispersing a pigment in a polymer solution and applying the resulting solution composition to a substrate. The pigment in the film is not sufficiently dispersed,
Paint films obtained from solutions with poor pigment dispersibility have poor flatness and smoothness, which not only deteriorates the uniformity of chromaticity of colored patterns (color filters, etc.), but also reduces the sensitivity and resolution of the film. etc. will be insufficient.

Furthermore, the film made of the above-mentioned known colored photosensitive polyamide composition is exposed through a pattern mask to photocure the pattern, and when sufficiently developed with a developer, the developer swells within the film and the pattern is formed. There was a problem that the film was deformed or the pigment in the film leaked out.

[0009]

[Problems to be Solved by the Present Invention] The purpose of the present invention is to improve the dispersibility of pigments, which is present in known colored photosensitive compositions used for forming colored patterns (particularly color filters, etc.). It is difficult to form a smooth film, or the sensitivity and resolution of the film are not sufficient.Furthermore, the photocured pattern is deformed by the swelling of the developer during development, and pigments are removed from the pattern. The purpose is to improve all at once various drawbacks such as the outflow of water.

0010

[Means for Solving the Problems] The present invention provides a colored photosensitive resin characterized by containing a photosensitive resin having a carbon-carbon unsaturated bond, a photopolymerization initiator, a carboxylic acid compound, and an acidic organic pigment. The present invention relates to a synthetic resin composition.

[0011] The colored photosensitive resin composition of the present invention can be applied to photosensitive resin compositions such as photosensitive (aromatic) polyamides and photosensitive (aromatic) polyimides having carbon-carbon double bonds (photosensitive groups). ■Photopolymerization initiators such as bisazide compounds, benzyl, benzoin ethers, and thioxanthone, ■Oxalic acid, glycolic acid, maleic acid,
A colored photosensitive resin composition or a solution composition thereof in which a "carboxylic acid compound" such as succinic acid, phthalic acid, lactic acid, etc. and (1) "acidic organic pigment" are uniformly blended, mixed or dispersed is suitable.

[0012] Examples of the photosensitive resin having a carbon-carbon unsaturated bond include (meth)acrylated epoxy resin, (meth)acrylated urethane resin,
Multifunctional acrylate resin such as (meth)acrylated polyester resin, photosensitive polyamide, photosensitive polyimide, photosensitive polysiloxane, photosensitive polyalkyl (meth)acrylate, photosensitive polyvinyl alcohol, or the like. Examples include photosensitive polymers having carbon-carbon unsaturated bonds such as derivatives of.

[0013] As the photosensitive resin, JP-A-2-1
A soluble photosensitive aromatic polyamide having a carbon-carbon unsaturated bond described in Japanese Patent No. 2317 and the like is suitable in terms of photosensitivity, heat resistance, and the like.

[0014] As the photosensitive aromatic polyamide,
For example, the following general formula (I)

40 to 100 mol% of the structural unit represented by the formula (wherein, Ar1 and Ar2 each represent an aromatic residue, and Ar2 represents an aromatic residue having a photosensitive group), and

00
15] The following general formula (II)

[Chemical formula 2] (However, Ar3 and Ar4 are Ar1 and Ar, respectively.
Indicates an aromatic residue other than 2. ) is shown as 0
Preferably, the heat-resistant aromatic polyamide has a proportion of ~60 mol%.

[0016] As the photosensitive aromatic polyamide,
20% by weight or more of a photosensitive aromatic polyamide consisting only of structural units represented by general formula (I), and general formula (II)
An aromatic polyamide consisting only of the structural units shown in 8
It may also be a mixture of aromatic polyamides mixed in a proportion of less than 0% by weight.

In the general formulas (I) and (II),
The aromatic residues represented by Ar1 and Ar3 are optimally aromatic residues of aromatic dicarboxylic acids, and examples of the aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, and 4,4'-dicarboxybiphenyl. , 4,4'-
Aromatic dicarboxylic acids such as dicarboxydiphenylmethane and 4,4'-dicarboxydiphenyl ether, or acid halides thereof can be mentioned. Among these aromatic dicarboxylic acid components, acid halides of the above-mentioned aromatic dicarboxylic acids, particularly aromatic dicarboxylic acid chlorides, are preferred.

Furthermore, in the general formula (I), Ar2
The aromatic residue having a photosensitive group represented by "aromatic diamine having a photosensitive group such as an organic group having a photosensitive carbon-carbon unsaturated bond (ethylene group, acetylene group, methacryloyl group, etc.)" ” aromatic residues are optimal.

Examples of such aromatic diamines include 3,5-diaminobenzoic acid ethyl methacrylate, 2,4-diaminobenzoic acid ethyl methacrylate, 3,5-diaminobenzoic acid diglycidyl methacrylate, Benzoic acid esters such as 2,4-diaminobenzoic acid diglycidyl methacrylate ester, 3,5-diaminobenzoic acid cinnamic acid ester, 2,4-diaminobenzoic acid cinnamic acid ester, 3,5-diaminobenzyl methacrylate, Benzyl methacrylates such as 2,4-diaminobenzyl methacrylate, 4-methacrylamido-3,4'-diaminodiphenyl ether, 2-methacrylamido-3,4'-diaminodiphenyl ether, 4-cinnamamide-3,4'-diaminodiphenyl ether , 3,4'-dimethacrylamide-
Diphenyl ethers such as 3',4-diaminodiphenyl ether, 3,4'-dicinnamamide-3',4-diaminodiphenyl ether, 4-methyl-2'-(2-methacryloyloxyethoxycarbonyl)-3,4'-diaminodiphenyl ether , and 4,4'-diaminochalcone, 3,3'-diaminochalcone, 3,4
'-diaminochalcone, 3',4-diaminochalcone,
4'-Methyl-3',4-diaminochalcone, 4'-methoxy-3',4-diaminochalcone, 3'-methyl-
Examples include chalcones such as 3,5-diaminochalcone.

Further, in the general formula (II), the aromatic residue represented by Ar4 is an aromatic residue based on "aromatic diamine having no photosensitive group." Examples of the above-mentioned aromatic diamines having no photosensitive group include (
i) Aromatic diamines having one benzene ring such as 3,5-diaminobenzoic acid, paraphenylenediamine, metaphenylenediamine, 2,4-diaminotoluene, (
ii) 4,4'-diaminodiphenyl ether, 4,4
Aromatic diamines having two benzene rings such as '-diaminodiphenylmethane, o-tolidine, o-toluidine sulfone, 4,4'-diaminobenzophenone, 4'-N,N-dimethylamino-3,5-diaminobenzophenone , (iii) 1,4-bis(4-aminophenoxy)benzene, 2,2-bis(4-aminophenoxyphenyl)propane, and 9,9-bis(4-aminophenyl)-10-anthrone, 1 , 5-diaminoanthraquinone, 1,4-diaminoanthraquinone, 1-dimethylamino-4-(3,5-diaminobenzophenone)-
Examples include aromatic diamines having three or more benzene rings such as naphthalene.

The photosensitive aromatic polyamide is made of, for example, the acid component of the aromatic dicarboxylic acids described above, the aromatic diamine having the aforementioned photosensitive group, and the aromatic diamine not having the aforementioned photosensitive group. It is produced by carrying out a polymerization reaction in an organic polar solvent at a reaction temperature of 80° C. or less for 1 to 20 hours using approximately equimolar amounts of the aromatic diamine component.

[0022] In the photosensitive aromatic polyamide,
The presence of the structural unit represented by general formula (II) has the effect of improving the thermal properties of polyamide, but if it is too large, the concentration of photosensitive groups in the polymer chain becomes low and the photosensitivity decreases. It is preferable to adjust the ratio appropriately so that it falls within the above range.

[0023] Furthermore, the photosensitive aromatic polyamide is
The concentration of the aromatic polyamide is 0.5 g/100 ml; N
-Methyl-2-pyrrolidone and 30
The logarithmic viscosity measured at a temperature of 0.1 to 3.5, especially 0
．． It is preferably about 2 to 2.5.

Examples of the photosensitive aromatic polyamides include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, hexamethylenephosphoramide, diglyme, triglyme, and tetraglyme. It is soluble in organic polar solvents such as glyme and γ-butyrolactone, and is preferably used after being uniformly dissolved in the organic solvent at a concentration of about 1 to 40% by weight.

The above-mentioned photosensitive aromatic polyamide is produced by adding a reactive organic compound such as methacrylic acid chloride, cinnamic acid chloride, acetic acid chloride, benzyl chloride, para-azide benzoyl chloride, etc. to the above-mentioned reaction solution containing the polyamide. , 0.1 to 50 hours at a temperature of -5 to 100°C,
It may also be a modified polyamide obtained by reacting and substituting the hydrogen atoms of the amide bonds of the polyamide with organic groups such as acetyl groups, methacroyl groups, cinnamoyl groups, and para-azidobenzoyl groups.

[0026] Furthermore, the acidic organic pigment used in the colored photosensitive composition of the present invention has good transparency, heat resistance,
Acidic organic pigments with excellent light resistance and solvent resistance are preferred;
Examples include phthalocyanine organic pigments such as phthalocyanine green, isoindolinone organic pigments such as isoindolinone yellow, and perylene organic pigments such as perylene red. The above organic pigment has a particle size of 1 μm from the viewpoint of light transmittance, uniformity of the film surface, etc.
It is preferable to use the following.

Examples of the photopolymerization initiator to be incorporated into the colored photosensitive composition of the present invention include bisazide compounds, Michler's ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, 2-t-butylanthraquinone, 1,2-
benzo-9,10-anthraquinone, benzyl, anisyl, 4,4-bis(diethylamino)benzophenone,
Examples include photopolymerization initiators such as acetophenone, benzophenone, 1,5-acenaphthene, thioxanthone or its derivatives, and anthranilic acid dimethylaminobenzoate.

The bisazide compounds used as photopolymerization initiators in the colored photosensitive composition include 4,
Preferred examples include 4'-diazidochalcone, 4,4'-diazidobenzalacetone, 2,6-di-(4'-azidobenzal)cyclohexanone, and 4,4'-diazidostilbene. Further, examples of the thioxanthone used as a photopolymerization initiator include 2,4-diethylthioxanthone and 2-chlorothioxanthone.

The amount of the photopolymerization initiator to be blended is 0 to 100 parts by weight of the photosensitive resin such as the photosensitive polyamide.
．． The amount is preferably 2 to 40 parts by weight, particularly 0.5 to 30 parts by weight. If the amount is too small, the sensitivity of the composition obtained will be low, and if it is too large, the heat resistance of the film formed from the composition will be reduced, which is not preferable.

The mixing ratio of the photosensitive resin such as the photosensitive aromatic polyamide and the acidic organic pigment is as follows:
It is preferable that the acidic organic pigment is present in a proportion of 5 to 200 parts by weight, particularly 10 to 100 parts by weight, based on 00 parts by weight.

In the colored photosensitive composition of the present invention, the blending ratio of the carboxylic acid compound is 0.1 to 15 parts by weight, particularly 0.2 to 10 parts by weight, based on 100 parts by weight of the photosensitive resin. is preferred. In addition, in this invention, the carboxylic acid compound has a high acidity (pKa>5), a molecular weight of 300 or less, and a solubility of 2% by weight or more in an organic polar solvent. This is preferable because the amount of carboxylic acid compound added can be reduced, and it can be substantially removed from the pattern after heat treatment by sublimation, evaporation, decomposition, etc.

[0032] In this invention, a particularly characteristic requirement is that the above-mentioned carboxylic acid compound and acidic organic pigment are used together. Even if the coating film of a colored photosensitive resin composition in which a carboxylic acid compound and an acidic organic pigment are used together is irradiated with a small amount of light [or the light reaches the bottom of the coating film (substrate side)] Even if the amount of light is low, fine colored patterns can be effectively formed.

In the colored photosensitive resin composition of the present invention, if the amount of the carboxylic acid compound is too small, the sensitivity of the composition regarding photocuring will not improve, which is undesirable. If the amount is too large, the dispersion stability in the composition decreases, residues tend to remain in unexposed areas, and developability may deteriorate, which is not preferable.

Further, the solution of the colored photosensitive resin composition of the present invention can be prepared by various compounding procedures, and the method for preparing the solution is not particularly limited. It is preferable to prepare a solution uniformly dissolved in the organic polar solvent, add an acidic organic pigment and a carboxylic acid compound to the solution, and finally add a photopolymerization initiator.

Methods for adding and dispersing the acidic organic pigment into the solution of the photosensitive resin composition include ball milling,
A roll method, an ultrasonic method, etc. can be employed, and these methods can be used in combination. Note that the carboxylic acid compound may be added before or after the above-mentioned addition of the acidic organic pigment.

The solution of the colored photosensitive resin composition of the present invention has a concentration of about 3 to 40% by weight, particularly about 5 to 30% by weight, and has a rotational viscosity (at 25° C.) of the solution.
is preferably about 0.1 to 1000 poise, particularly about 0.2 to 500 poise.

[0037] If necessary, a dispersant such as a surfactant may be added to the solution of the colored photosensitive resin composition of the present invention in order to improve the dispersibility of the acidic organic pigment.
A bonding promoter such as a silane coupling agent may be added to enhance the adhesion of the colored photosensitive resin composition to the support (substrate).

[0038] Furthermore, the colored photosensitive resin composition of the present invention (
solution) contains hydroquinone, 2,6-t-butyl-
A thermal polymerization inhibitor such as 4-methylphenol (BHT), methyl ether hydroquinone, phenothiazine, and N-nitrosophenylhydroxylamine ammonium salt may be blended.

[0039] The colored photosensitive resin composition of the present invention can be obtained by, for example, applying a solution thereof onto a substrate at a temperature of 0 to 60°C and drying it to form a coating film (dry coating film) of the composition. , then
The coating film is irradiated with parallel light from an ultra-high pressure mercury lamp through a pattern mask to photocure the coating film in each pattern, and then immersed in a developer solution to remove the unexposed parts of the coating film. A colored pattern can be formed on the substrate by performing development to elute and remove the (uncured portion).

The solution of the colored photosensitive resin composition can be applied to the surface of the substrate by a spin coating method, a roll coating method, a dipping method, a spraying method, or the like. The coating film is preferably dried using a hot air dryer, a hot plate, or the like at 150° C. or lower, particularly 100° C. or lower, for about 1 to 60 minutes, especially about 2 to 30 minutes. The pressure may be reduced during this drying.

[0041] The thickness of the coating film (film after drying) made of the above-mentioned colored photosensitive resin composition is usually about 0.1 to 3.
The thickness is preferably about 0 μm. As mentioned above, when immersing a substrate with a photocured coating in a developer,
Ultrasonic waves may also be applied.

Examples of the above developer include N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, hexamethylenephosphoramide, diglyme, triglyme,
A developer consisting of "organic polar solvent (a) capable of dissolving photosensitive resin" such as cyclohexanone and γ-butyllactone, or these organic polar solvents and methanol, ethanol, ethyl cellosolve, butyl cellosolve, and ethyl carbitol. It is preferable to use a developer mixed with "an organic solvent (b) having an alcoholic hydroxyl group" such as butyl carbitol.

In the above mixed developer, the organic polar solvent (a) is blended in a proportion of 10 to 50% by weight, and the organic solvent (b) having an alcoholic hydroxyl group is blended in a proportion of 50 to 90% by weight. It is preferable that it contains. In the mixed developer, if the blending ratio of the organic polar solvent (a) is too low, the unexposed parts of the coating film of the colored photosensitive resin composition will not be sufficiently dissolved and a colored pattern cannot be reliably formed. This is not desirable.

After the above-mentioned development, the formed colored pattern (
(image) is rinsed with a solvent having a hydroxyl group such as 1,1,1-trichloroethane, ethanol, isopropyl alcohol, ethyl carbitol, water, etc., and then heated to about 150° C. or lower, especially at 100° C., using a hot air dryer, hot plate, etc. It is preferable to perform a heat treatment (post-baking) at a temperature of 1 to 60 minutes, particularly 2 to 30 minutes, at a temperature of 0.degree. C. or lower.

As a specific example of the method for forming the colored pattern, for example, a rectangular glass substrate (length of one side: about 10 to 15 cm) that has been thoroughly degreased with detergent and dried is used.
The thickness of the coating film after drying is 0.1~
The solution composition is applied (coated) by spin coating to form a coating film to a thickness of 100 μm, particularly 0.5 to 50 μm, and at a temperature of about 50 to 150°C, particularly 60 to 100°C, Drying is performed for 0.1 to 50 minutes, particularly 1 to 20 minutes, to substantially remove the solvent and form a dried coating.

Next, the coating film formed as described above was exposed to light using a high-pressure mercury lamp (5 mW/cm2) through a pattern having a stripe pattern of 4 to 100 μm to photocure it in a pattern. A coating film is formed, and finally, as described above, the substrate with the pattern-cured coating film is immersed in a developing solution and subjected to a development operation in which high-frequency ultrasonic waves are applied to remove the unexposed areas. can be substantially removed to obtain a substrate on which a colored pattern is formed by photocuring.

[0047]

[Examples] Below are examples of producing a photosensitive resin (photosensitive aromatic polyamide) having a carbon-carbon unsaturated bond, and examples of preparing a solution of the colored photosensitive resin composition of the present invention, and
The present invention will be explained in more detail by illustrating an example of a method for forming a colored pattern.

In each example, when forming a colored pattern on a substrate, the flatness of the "coating film of the colored photosensitive resin composition" formed on the substrate is determined by rotating the solution composition. After spin-coating onto a substrate with a coating machine and drying the coating film to form a dry coating film made of a colored photosensitive resin composition, the center of rotation of the coating film (film) and 5 points from the center are
The film thickness of the coating film was measured at every mm interval, and the flatness was indicated by the average value and standard deviation of the film thickness.

[0049] In each example, the smoothness of the coating film (film) made of the colored photosensitive resin composition was determined by measuring the surface condition of the coating film according to the surface roughness standard described in JIS B0601-1982. Measured based on the Rma
The smoothness was indicated by the x value.

Reference Example 1 [Production of photosensitive aromatic polyamide] After replacing the gas in the flask by passing dry air into a three-necked flask,
119.98 g of 3,5-diaminobenzoic acid ethyl methacrylate was added, and 720 ml of N-methyl-2-pyrrolidone (NMP) was added and dissolved therein. After cooling this solution, 91.16 g of terephthalic acid dichloride was added little by little while cooling to 0° C. and stirring. At this time, heat is generated and the temperature of the solution rises, but about 10
The temperature was maintained below ℃. This solution was further added to ice water for 2 hours.
The mixture was stirred for hours to carry out a polymerization reaction.

Next, after diluting the reaction solution by adding 500 ml of NMP, this solution was added to a mixture of 1 liter of NMP and 10 liters of water to precipitate aromatic polyamide, and the precipitate was filtered, collected, and dried. 167.8 g of aromatic polyamide white powder was obtained. Logarithmic viscosity (concentration; 0.5 g/1
00ml solvent, solvent; NMP, measurement temperature; 30°C) is 0
．． It was 88.

Example 1 [Preparation of solution of green photosensitive composition A] N-methyl-
Phthalocyanine Green (manufactured by Dainippon Ink Co., Ltd., Fas) was added to 64 g of 2-pyrrolidone (NMP) as a green pigment.
tgen green S0) 2.8g, Reference Example 1
7 g of the photosensitive aromatic polyamide powder obtained above and hydroquinone monomethyl ether (
MEHQ) 0.07g, 50W ultrasonic wave (27Hz)
This solution was then filtered under pressure using a 1 μm fluororesin filter (Teflon filter) to obtain an NMP solution in which the green pigment was uniformly dispersed.

Next, 0.42 g of glycolic acid as a carboxylic acid compound and 0.28 g of 4,4'-diaminochalcone as a photopolymerization initiator were added to the green pigment-dispersed NMP solution.
g, and 0.24 g of γ-glycidoxypropyltrimethoxysilane as an adhesion promoter, stirred thoroughly to make a uniform viscous liquid, and then heated with 30 W ultrasonic waves (10 Hz) in a water tank. Let it act for about 30 minutes, and then add 1
A solution of a green photosensitive aromatic polyamide composition (solution composition of green photosensitive composition A) in which a green pigment is uniformly dispersed is filtered under pressure using a μm fluororesin filter (Teflon filter). Prepared.

[Formation of a green pattern] A solution of the green photosensitive composition A in which the green pigment is uniformly dispersed is coated on a glass substrate so that the thickness of the dried coating film is 1.5 μm. A coating film is formed by spin coating on the substrate, and is dried at 80° C. for 10 minutes to substantially remove the solvent, thereby forming a film of green photosensitive composition A on the glass substrate ( A coating film) was formed.

Next, the film was exposed to 200 mj of light for 40 seconds using a light source of an ultra-high pressure mercury lamp through a striped pattern mask having an interval of 10 μm.
The coating film was photocured in a pattern.

Next, the substrate on which the pattern-exposed film of the green photosensitive composition A is formed is treated with a mixed solution of diglyme and ethyl cellosolve (the volume ratio of diglyme and ethyl cellosolve is 30:70). A blue patterned substrate was prepared by immersing it in a developer at room temperature and simultaneously applying a 15 W ultrasonic wave (27 KHz frequency) for 4 minutes to develop the substrate.

Finally, the substrate was rinsed with ethyl cellosolve, and then heat treated at 200° C. for 30 minutes to form a substrate with a clear green pattern consisting of a 10 μm green stripe pattern (green pattern). (with attached substrate) was manufactured.

The coating film (film) of green photosensitive composition A formed as described above had a flatness of 1.52±0.06.
.mu.m, and the smoothness was Rmax: 0.05 .mu.m. Further, in the development operation of the substrate on which the pattern-exposed film of the green photosensitive composition A is formed, a pattern appears after 60 seconds of development, and even after 4 minutes of development, pattern distortion, blistering, and deformation occur. was not recognized. [Properties of green pattern] The green patterned substrate obtained as described above was heated at 250° C. for 1 hour, but no discoloration or fading was observed.

Comparative Example 1 [Preparation of solution of green photosensitive composition B] Green photosensitive composition B containing no glycolic acid was prepared in the same manner as in Example 1 except that no glycolic acid was used.
A solution was prepared. [Formation of green pattern] A substrate with a green pattern was formed in the same manner as in Example 1, except that the green photosensitive composition B was used.

The coating film (film) of green photosensitive composition B formed as described above has a flatness of 1.50±0.05.
.mu.m, and the smoothness was Rmax: 0.05 .mu.m. In addition, in the development operation of the substrate on which the pattern-exposed film of green photosensitive composition B was formed, the pattern appeared after 40 seconds of development, and peeling was observed in the green pattern after 1.5 minutes of development. It was done.

Examples 2 to 3 [Preparation of solutions of green photosensitive compositions C and D] As the carboxylic acid compound, 0.14 g (Example 2) or 0.28 g (Example 4) of oxalic acid dihydrate was used. ), except that a solution of a green photosensitive aromatic polyamide composition in which a green pigment was uniformly dispersed (solution compositions of green photosensitive compositions C and D) was prepared in the same manner as in Example 1. Prepared. [Formation of green pattern] Green photosensitive composition C or D
Green patterned substrates were formed in the same manner as in Example 1, except that each solution was used.

The coating film (film) of the green photosensitive composition C formed as described above had a flatness of 1.51±0.04.
The coating film of green photosensitive composition D has a flatness of 1.48±0.04 μm and a smoothness of Rmax: 0.04 μm.
x: 0.05 μm.

In addition, in each development operation of the substrate on which each film of green photosensitive composition C or D was formed after pattern exposure, the pattern appeared after 1 minute of development, and the pattern appeared after 4 minutes of development. Even after development, no pattern distortion, peeling, or deformation was observed. [Properties of green pattern] Each green patterned substrate obtained in Examples 2 and 3 as described above was heated at 250°C.
Although it was heated for 1 hour, no discoloration or fading was observed.

Example 4 [Preparation of solution of green photosensitive composition E] A green color in which the green pigment is uniformly dispersed was prepared in the same manner as in Example 2, except that 0.28 g of lactic acid was used as the carboxylic acid compound. A solution of a photosensitive aromatic polyamide composition (solution composition of green photosensitive composition E) was prepared. [Formation of green pattern] A substrate with a green pattern was formed in the same manner as in Example 1, except that the solution of green photosensitive composition E was used.

The coating film (film) of green photosensitive composition E formed as described above had a flatness of 1.53±0.05.
μm, and the smoothness was Rmax: 0.04 μm. In addition, in the development operation of the substrate on which the pattern-exposed film of the green photosensitive composition E is formed, a pattern appears after 1 minute of development, and even after 4 minutes of development, the green pattern shows pattern skipping, peeling, and deformation. were not recognized at all. [Properties of green pattern] The green patterned substrate obtained in Example 4 as described above was heated at 250° C. for 1 hour, but no discoloration or fading was observed.

Example 5 [Preparation of solution of red photosensitive composition F] Example 1 except that 2.8 g of perylene red was used as the organic pigment and 0.28 g of glycolic acid was used as the carboxylic acid compound.
In the same manner as above, a solution of a red photosensitive aromatic polyamide composition in which a red pigment was uniformly dispersed (red photosensitive composition F) was prepared.
solution composition) was prepared. [Formation of green pattern] A red patterned substrate was formed in the same manner as in Example 1, except that the solution of red photosensitive composition F was used.

The coating film (film) of the red photosensitive composition F formed as described above had a flatness of 1.54±0.06.
μm, and the smoothness was Rmax: 0.12 μm. In addition, in the development operation of the substrate on which the pattern-exposed film of the red photosensitive composition F is formed, a pattern appears after 1 minute of development, and even after 4 minutes of development, the red pattern shows pattern skipping, peeling, and deformation. were not recognized at all. [Properties of red pattern] The red patterned substrate obtained in Example 5 as described above was heated at 250° C. for 1 hour, but no discoloration or fading was observed.

[0068]

[Operations and Effects of the Invention] The present invention generally relates to a colored photosensitive composition containing a photosensitive resin such as a photosensitive aromatic polyamide, a photopolymerization initiator, a carboxylic acid compound, and an acidic organic pigment. In order to promote the formation of a secondary structure of an acidic organic compound, the carboxylic acid compound forms a photocured pattern when the coating film (film) of the colored photosensitive composition of the present invention is exposed and developed. The developing solution does not swell or deform in the patterned areas, and the organic pigment does not flow out from the patterned areas.

The colored photosensitive composition of the present invention is obtained by forming a coating film (film) of the composition on a substrate, irradiating the coating film with light to photocure it in a pattern, and finally developing it. By performing a development operation that removes the unexposed parts (uncured parts) of the coating film with a liquid, color imaging elements, color sensors,
It can be used in a method for manufacturing colored pattern members such as color filters for fine color separation in color displays and the like.

Claims (3)

[Claims] 1. A colored photosensitive composition comprising a photosensitive resin having a carbon-carbon unsaturated bond, a photopolymerization initiator, a carboxylic acid compound, and an acidic organic pigment. 2. The method according to claim 1, wherein the photosensitive resin, a photopolymerization initiator, and a carboxylic acid compound are dissolved in an organic polar solvent capable of dissolving the photosensitive resin, and an acidic organic pigment is dispersed therein. colored photosensitive resin composition. 3. The colored photosensitive resin composition according to claim 1, wherein the photosensitive resin is a photosensitive aromatic polyamide having a large number of photosensitive groups containing carbon-carbon double bonds.