JP2562956B2 - Colored photosensitive polyamide composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a colored photosensitive polyamide composition in which an organic pigment is dispersed in a composition of a heat-resistant polyamide having a photosensitive group and a bisazide compound. The present invention is a photosensitive polyamide composition that can be used for producing a color image sensor, a color sensor, a color filter for fine color separation such as a color display, and the like.

[Description of Prior Art]

Conventionally, as a method of manufacturing a color filter, (a) a method of producing a dye-type organic dye filter using gelatin or the like on a transparent substrate such as glass and bonding the filter onto a solid-state image sensor with an adhesive, b) The most convenient means for producing a multicolor surface coloring material such as a color filter is a method by printing, and (c) JP-A-60-237403 discloses a heat-resistant film-forming material having photosensitivity. , A method for producing a color filter using a polyamide resin, and (d) JP-A-62-212603 disclose a method using a transparent photosensitive polyamide.

Conventionally known color filters using gelatin described above have poor heat resistance and have a problem of fading in the processing step.

Further, the printing method described above has difficulty in positioning during multi-color printing, has limited positional accuracy and dimensional accuracy, and cannot manufacture a highly accurate and fine color filter.

Further, in the method described in JP-A-60-237403, since the photosensitive polyamide resin is supplied as a polyimide precursor, in order to convert to a polyimide having good coating properties, 200 ~ 300 ℃ or Higher temperature treatment than that is required, which causes a problem that the organic pigment is deteriorated by heat.

Further, the method described in JP-A-62-212603, although the heat resistance of the photosensitive polyamide resin composition is good,
The sensitivity was not enough.

[Problems to be solved]

Therefore, an object of the present invention is to provide a colored photosensitive resin composition which is excellent in heat resistance and photosensitivity and which can easily produce a highly accurate color filter at a low temperature.

[Means for solving problems]

This invention is a heat-resistant polyamide having a photosensitive group,
The present invention relates to a colored photosensitive polyamide composition in which an organic pigment is dispersed in a composition with a bisazide compound.

The heat-resistant aromatic polyamide having a photosensitive group used in the present invention has the following general formula (I). (However, R ₁ and R ₂ each represent a residue of hydrogen or a reactive organic compound, Ar ₁ and Ar ₂ each represent an aromatic residue, and Ar ₂ represents an aromatic residue having a photosensitive group. Indicates a group.)
10 mol% or more, preferably 20 mol% or more, more preferably 40 mol% or more, and the following general formula (II) (However, R ₃ and R ₄ each represent a residue of hydrogen or a reactive organic compound, Ar ₃ and Ar ₄ each represent an aromatic residue.) Less than 90 mol%, Particularly preferably, the aromatic copolyamide having a proportion of less than 80 mol%, more preferably less than 60 mol%, or 10 parts by weight of a photosensitive aromatic polyamide consisting only of the constitutional unit represented by the general formula (I) is used. %, Particularly preferably 20% by weight or more, and an aromatic polyamide in which the aromatic polyamide consisting only of the structural unit represented by the general formula (II) is mixed in a proportion of less than 90% by weight, particularly preferably less than 80% by weight. Examples thereof include a mixture of polyamides.

In the general formulas (I) and (II), the aromatic residue represented by Ar ₁ and Ar ₃ is most preferably an aromatic residue of an aromatic dicarboxylic acid, and examples of the aromatic dicarboxylic acid include: Aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 4,4'-dicarboxybiphenyl, 4,4'-dicarboxydiphenylmethane, 4,4'-dicarboxydiphenyl ether, or acid halides thereof can be mentioned. .

Among these aromatic dicarboxylic acid components, acid halides of the above aromatic dicarboxylic acids, particularly aromatic dicarboxylic acid chlorides are preferable.

Further, in the general formula (I), the aromatic residue having a photosensitive group represented by Ar ₂ is a photosensitive unsaturated hydrocarbon group (eg, ethylene group, acetylene group, methacryloyl group, etc.) The aromatic residue of the aromatic diamine having a group is optimal, and as such an aromatic diamine,
For example, 3,5-diaminebenzoic acid ethyl methacrylate ester, 2,4-diaminobenzoic acid ethyl methacrylate ester, 3,5-diaminobenzoic acid diglycidyl methacrylate ester, 2,4-diaminobenzoic acid diglycidyl methacrylate ester, Benzoic acid esters such as 3,5-diaminobenzoic acid cinnamic acid ester and 2,4-diaminobenzoic acid cinnamic acid ester, benzyl methacrylate such as 3,5-diaminobenzyl methacrylate and 2,4-diaminobenzyl methacrylate , 4-methacrylamido-3,4'-diaminodiphenyl ether, 2-methacrylamido-3,4'-diaminodiphenyl ether, 4
-Cinnamamide-3,4'-diaminodiphenyl ether, 3,4'-dimethacrylamido-3 ', 4-diaminodiphenyl ether, 3,4'-dicinnamamide-3', 4
-Diaminodiphenyl ether, 4-methyl-2'-
(2-methacryloyloxyethoxycarbonyl) -3,
Diphenyl ethers such as 4'-diaminodiphenyl ether, 4,4'-diaminochalcone, 3,3'-diaminochalcone, 3,4'-diaminochalcone, 3 ', 4-diaminochalcone, 4'-methyl-3 ′, 4-Diaminochalcone, 4′-methoxy-3 ′, 4-diaminochalcone,
Examples thereof include chalcones such as 3'-methyl-3,5-diaminochalcone.

Further, in the general formula (II), the aromatic residue represented by Ar ₄ is an aromatic residue of an aromatic diamine having no photosensitive group, and examples of the aromatic diamine include: (i) ) 3,5-diaminobenzoic acid, paraphenylenediamine, metaphenylenediamine, aromatic diamine having one benzene ring such as 2,4-diaminotoluene, (ii) 4,4'-diaminodiphenyl ether, 4,4 ′ -Diaminodiphenylmethane, o-tolidine, o-toluidine sulfone, 4,4′-diaminobenzophenone, 4′-
An aromatic diamine having two benzene rings such as 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-
Aromatic diamines having three or more benzene rings such as diaminobenzophenone) -naphthalene can be given.

In addition, the residues R ₁ , R ₂ , R ₃ and R ₄ of the reactive organic compound in the above general formulas (I) and (II) have reactivity with the hydrogen atom of the amide bond of the polyamide. An organic compound (reactive organic compound) is an organic group formed as a result of substitution reaction with a hydrogen atom of an amide bond of the polyamide, and examples of the group include an acetyl group, a metacroyl group, a cinnamoyl group, and a paraazide. A benzoyl group etc. can be mentioned.

Examples of the reactive organic compound having a residue of these organic groups include methacrylic acid chloride, cinnamic acid chloride, acetic acid chloride, benzyl chloride, and paraazido benzoyl chloride.

The aromatic polyamide used in the present invention comprises, for example, an acid component composed of the aromatic dicarboxylic acids described above, an aromatic diamine having a photosensitive group described above, and an aromatic diamine having no photosensitive group described above. Aromatic diamine component, approximately, using equimolar, in an organic solvent, 100 ℃ or less, particularly preferably at a reaction temperature of 80 ℃ or less, 0.1 ~ 50
It is produced by carrying out the polymerization reaction for a period of time, particularly 1 to 20 hours.

Further, in the above aromatic polyamide, those having R ₁ , R ₂ , R ₃ or R ₄ which are the residues of the reactive organic compound,
In the above synthetic reaction liquid containing the “aromatic polyamide in which R ₁ , R ₂ , R ₃ and R ₄ are hydrogen atoms” produced as described above, the reactive organic compound is added, 5-100
It is produced by reacting at a reaction temperature of 0.1 to 50 hours, particularly 0.5 to 30 hours.

In the aromatic polyamide, the compound represented by the general formula (II)
The presence of the structural unit represented by is effective in improving the thermal properties of the polyamide, but if it is too much, the concentration of the photosensitive group in the polymer chain becomes low and the photosensitivity decreases. It is preferable to adjust within the range as appropriate.

The aromatic polyamide has a concentration of aromatic polyamide of 0.5 g / 100 ml; a solution having N-methyl-2-pyrrolidone is prepared, and the logarithmic viscosity measured at a temperature of 30 ° C. is 0.1 to
It is preferably 3.5, particularly about 0.2 to 2.5.

The aromatic polyamide used in the present invention can be used in organic solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, hexamethylenephosphoramide and diglyme. It is soluble, and it is preferable to use it by uniformly dissolving it in the organic solvent at a concentration of about 1 to 40% by weight.

The organic pigment used in the present invention preferably has good transparency, and is also excellent in heat resistance, light resistance and solvent resistance, and examples thereof include azo chelate type, condensed azo type, phthalocyanine type and benzo. Imidazolone, quinacridone, isoindolinone, pyranthrone, dibromanthanslone, indanthrone, anthrapyrimidine, flavanthrone, perylene, perinone, quinophthalone, thioindigo, dioxazine, anthraquinone Examples thereof include organic pigments such as pigments, and one or more of these can be appropriately selected and used.

The organic pigment preferably has a particle size of 1 μm or less from the viewpoints of light transmittance, film surface uniformity, and the like.

Further, as the bisazide compound used in the present invention, 4,4'-diazidochalcone, 4,4'-diazidobenzalacetone, 2,6-di- (4'-azidobenzal) cyclohexanone, 4,4'- Examples thereof include diazidostilbene.

The amount of the bisazide compound is 0.2 to 15 parts by weight, particularly 0.5 to 10 parts by weight, relative to 100 parts by weight of the photosensitive polyamide.
It is preferable that the amount be a ratio of parts by weight. If the blending amount is too small, the sensitivity of the resulting composition will be low, and if it is too large, the heat resistance of the film formed by the composition will be unfavorable.

The mixing ratio of the aromatic polyamide and the organic pigment is 5 to 200 with respect to 100 parts by weight of the aromatic polyamide.
It is preferable that the ratio is parts by weight, particularly 10 to 100 parts by weight.

The aromatic polyamide solution composition in which the organic pigment is dispersed has a rotational viscosity (25 ° C.) of 0.1 to 1000.
Poise, especially about 0.2 to 500 poise is preferable.

If necessary, a dispersant such as a surfactant may be added to the organic pigment-dispersed polyamide solution to enhance the dispersibility of the organic pigment, and silane may be added to enhance the adhesion to the support. A binding promoter such as a coupling agent may be added.

The organic pigment-dispersed aromatic polyamide solution includes, for example, 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, acetophenone, benzophenone, 1,5-acenaphthene, thioxanthone or a derivative thereof (for example, chlorothioxanthone, methylthioxanthone), a photopolymerization initiator such as anthranilate dimethylaminobenzoate, and A sensitizer may be added, and hydroquinone, 2,6-t-butyl-4-methylphenol (BHT),
Methyl ether hydroquinone, phenothiazine, N-
A thermal polymerization inhibitor such as nitrosophenylhydroxylamine ammonium salt may be blended.

The above-mentioned organic pigment-dispersed aromatic polyamide solution can be applied to the support by a method such as a spin coating method, a roll coating method, a dipping method, or a spray method.

The coating film is dried by a hot air drier, a hot plate, etc., at 150 ° C or lower, particularly at 100 ° C or lower for 1 to 60 minutes,
It is particularly preferable to carry out for 10 to 30 minutes. During this drying, the pressure may be reduced.

The thickness of the photosensitive aromatic polyamide film is usually preferably about 0.2 to 3.0 μm.

Next, a mask having a predetermined shape such as a dot pattern or a stripe pattern is adhered to the photosensitive aromatic polyamide film formed as described above, and through the mask, for example, parallel rays of an ultra-high pressure mercury lamp (250 W) are applied. After irradiation and pattern exposure, development is performed to form a colored pattern.

Development of the pattern-exposed photosensitive polyamide film
It is carried out by leaching and removing the unphotocured portion of the film by immersing the film in a suitable developing solution at a temperature of about 0 to 100 ° C.

The developer, N, N- dimethylformamide,
N, N-dimethylacetamide, dimethyl sulfoxide,
Organic solvents such as N-methyl-2-pyrrolidone, hexamethylenephosphoramide, diglyme and cyclohexanone,
Alternatively, a mixed system of these organic solvents and methanol or ethanol can be used.

Further, ultrasonic waves may be applied to the developer during the above-mentioned development.

After the above-mentioned development, the formed colored image is rinsed with 1,1,1-trichloroethane, isopropyl alcohol, etc., and then heat-treated at about 150 to 200 ° C for 10 to 120 minutes with a hot air dryer, a hot plate, etc. Preferably.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to production examples of heat-resistant aromatic polyamides having a photosensitive group used in the present invention and examples of the composition of the present invention.

Production Example 1 After passing dry air through a three-necked flask to replace the gas in the flask, 119.98 g of 3,5-diaminobenzoic acid ethyl methacrylic acid ester was added, and N-methyl-2-pyrrolidone (NMP) was added thereto. 240 ml was added and dissolved.

After cooling this solution, it was cooled to 0 ° C. and 91.16 g of terephthaloyl dichloride was added little by little while stirring.

At this time, heat is generated and the temperature of the solution rises.
C. or less.

This solution was further stirred with water in ice for 2 hours to carry out a polymerization reaction.

Next, after adding 500 ml of NMP to the reaction solution to dilute it, this solution was added to a mixed solution of NMP1 and water 10 to precipitate an aromatic polyamide.

The precipitate was collected by filtration and dried to obtain 167.8 g of white aromatic polyamide powder.

Logarithmic viscosity of this aromatic polyamide powder (concentration; 0.5g / 10
0 ml solvent, solvent; NMP, measurement temperature; 30 ° C) was 0.88.

Example 1 Preparation of Organic Pigment Dispersed Aromatic Polyamide Solution Perylene red (4.25 g) was added as a red pigment to 86.0 g of N-methyl-2-pyrrolidone (NMP), and after mixing and stirring, ultrasonic waves of 50 W in a water tank for about 1 hour. The pigment was dispersed by acting, and this solution was filtered under pressure using a 1 μm fluororesin filter (Teflon filter) to obtain a pigment-dispersed NMP solution.

Next, 0.26 g of hydroquinone monomethyl ether as a thermal polymerization inhibitor and 8.5 g of the aromatic polyamide powder obtained in Production Example 1 above were added to the above-mentioned pigment-dispersed NMP solution, and the mixture was sufficiently stirred to form a uniform viscous liquid. Later, 30W in the water tank
Ultrasonic waves were applied for about 30 minutes.

To the viscous liquid obtained as described above, 0.34 g of 4,4′-diazidochalcone was added, stirred and filtered under pressure using a 1 μm fluororesin filter (Teflon filter) to give a red color. A pigment-dispersed aromatic polyamide solution (solution composition) was prepared.

Formation of Coloring Pattern The red pigment-dispersed aromatic polyamide solution is spin-coated on a glass substrate so that the dry film thickness is 1.5 μm,
The coating film is dried at 70 ° C. for 30 minutes to form a photosensitive aromatic polyamide film on a glass substrate, and the photosensitive aromatic polyamide film is applied to a super high pressure mercury lamp ( Contact exposure was performed at 5 mW / cm ² ) for 30 seconds.

Next, the pattern-exposed photosensitive aromatic polyamide film is developed with a diglyme solution for 1 minute, rinsed with isopropyl alcohol, and then heat-treated at 200 ° C. for 30 minutes to obtain a clear red pattern of a stripe of 10 μm. It was

Coloring pattern properties The red pattern on the substrate obtained as described above
After heating at 0 ° C. for 1 hour, no discoloration or fading was observed.

Example 2 A green pigment-dispersed aromatic polyamide solution (solution composition) was prepared in the same manner as in Example 1 except that phthalocyanine green was used as the green pigment instead of the perylene red that was the red pigment.

Using the green pigment dispersion aromatic polyamide solution,
Except that the exposure time of the supersonic pressure mercury lamp was changed to 40 seconds, a photosensitive aromatic polyamide film was formed on a glass substrate, exposed, and developed in the same manner as in Example 1. A clear green pattern of 10 μm stripe was obtained.

Apply 25 green patterns on the substrate obtained as described above.
After heating at 0 ° C. for 1 hour, no discoloration or fading was observed.

Example 3 Example 1 was repeated except that phthalocyanine blue was used as a blue pigment instead of perylene red which was a red pigment.
A green pigment-dispersed aromatic polyamide solution (solution composition) was prepared in the same manner as in.

In the same manner as in Example 1 except that the above green pigment-dispersed aromatic polyamide solution was used, a photosensitive aromatic polyamide film was formed on a glass substrate, exposed to light, and developed to obtain 10 μm. I got a clear blue pattern of the stripe.

Apply 25 blue patterns on the substrate obtained as described above.
After heating at 0 ° C. for 1 hour, no discoloration or fading was observed.

Example 4 Instead of 4,4'-diazidochalcone, 2,6-di-
A red pigment-dispersed aromatic polyamide solution (solution composition) was prepared in the same manner as in Example 1 except that 0.51 g of (4′-azidobenzal) -4-methylcyclohexanone was used.

In the same manner as in Example 1 except that the above red pigment-dispersed aromatic polyamide solution was used, a photosensitive aromatic polyamide film was formed on a glass substrate, exposed to light, and developed to obtain 10 μm. I got a clear red pattern of the stripe.

Apply 25 blue patterns on the substrate obtained as described above.
After heating at 0 ° C. for 1 hour, no discoloration or fading was observed.

Comparative Example 1 The same as Example 2 except that 4,4′-diazidochalcone was not used at all, and instead, 0.6 g of diethylthioxanthone, 0.4 g of benzyl, and 0.6 g of methyl dimethylaminoanthranilate were added. To prepare a green pigment-dispersed aromatic polyamide solution (solution composition).

Using the green pigment dispersion aromatic polyamide solution,
Except that the exposure time of the supersonic pressure mercury lamp was changed to 40 seconds, a photosensitive aromatic polyamide film was formed on a glass substrate, exposed, and developed in the same manner as in Example 1. Although a green pattern was formed, the pattern was partly deformed or partly peeled off, and the remaining pattern was changed to dark green, which was not a clear green pattern.

[Operation and effect of the present invention]

Since the colored photosensitive polyamide composition of the present invention contains, in particular, a photosensitive aromatic polyamide having high heat resistance and a bisazide compound, the heat resistance and the photosensitivity in the state where various organic pigments are contained are high. It is possible to easily and reproducibly manufacture a color filter which is excellent in sharpness and has high precision with relatively high temperature.

Claims (1)

(57) [Claims] 1. A colored photosensitive polyamide composition, wherein an organic pigment is dispersed in a composition of a heat-resistant polyamide having a photosensitive group and a bisazide compound.