JPH0463870A - Black photosensitive polymer composition and photosetting thereof - Google Patents

Abstract

PURPOSE:To obtain a black photosensitive polymer composition which is improved in photosensitivity and capable of providing readily a precise black matrix improved in photosensitivity by incorporating a photosensitive polymer, a photoinitiator, carbon black and a pair of colored pigments differing in color. CONSTITUTION:A black photosensitive polymer composition is obtained by incorporating 100 parts by weight photosensitive polymer (e.g. 3,5-diaminobenzoic acid/ethyl methacrylate); 5-50 parts by weight photoinitiator (e.g. benzoin); and 2-180 parts by weight black pigment components comprising 5-60wt.% carbon black and 40-95wt.% pair of colored pigments (other than carbon black) differing in color (preferably azochelate-based or condensed azobased organic pigments). Containing carbon black and a pair of colored pigments other than carbon black as the black pigment components, this photosensitive polymer composition can provide, though it (a film formed therefrom) is black, a clear and precise black matrix improved in photosensitivity, electric characteristics and film strength readily with a high degree of reproducibility when subjected to pattern exposure for photosetting.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] This invention provides a black pigment component consisting of a photosensitive polymer, a photoinitiator, and a set of colored pigments of carbon black and different colors other than carbon black. It mainly relates to a black photosensitive polymer composition that contains a black photosensitive polymer that can particularly form a black matrix part in filters for fine color separation such as color imaging devices, color sensors, and liquid crystal displays. It is a composition.

[Description of prior art]

Traditionally, vapor-deposited metal films such as AI and Cr have been used as black matrices for liquid crystal displays, etc., but these problems include high manufacturing costs, a difference in level between the black matrix part and other parts of the filter, and problems with the vapor-deposited film. Due to the problem of pinholes, it is expected that a black matrix will be formed using an organic film. In particular, photocurability is required to form a black matrix with high precision and fineness, but at present, photosensitive resin compositions containing black pigments block light to a large extent by the black pigment. It is said that this results in a significant decrease in photosensitivity, making it impossible to form a practical black photocured layer, and as a result, no black photosensitive polymer composition that can be used for such purposes has yet been proposed.

[Problem to be solved]

An object of the present invention is to provide a black photosensitive polymer composition that has excellent photosensitivity and can easily produce a highly accurate black matrix, and to provide a black photosensitive polymer composition that can be easily manufactured using the black photosensitive polymer composition. An object of the present invention is to provide a photocuring method for forming a black photocuring layer with high precision.

Means for Solving Problem C] This invention provides a black photosensitive material mainly containing a photosensitive polymer, a photoinitiator, and a black pigment component consisting of carbon black and a set of colored pigments of different colors other than carbon black. The present invention relates to a polymer composition.

The photosensitive polymer used in the composition of this invention is
It may be a polymer that is polymerized or crosslinked by ultraviolet light, or a photosensitive polymer component that can be photocured by a combination of a photopolymerizable monomer and a polymer, and its chemical structure is not particularly limited.

Examples of photosensitive polymers include those based on polymer main chains such as acrylic resins, urethane resins, epoxy resins, polyimides, polyamides, and polycarbonates;
Examples include photosensitive polymers having a photosensitive group (photopolymerizable or photocrosslinkable carbon-carbon unsaturated group, etc.); It can also be used as a polymer.

Furthermore, when the black photosensitive polymer composition of the present invention is used for liquid crystal displays, heat resistance may be required depending on the manufacturing process, so the photosensitive polymer described above may be required to have heat resistance. For example, polyimide.

Photosensitive polymers such as polyamides are suitable, and photosensitive aromatic polyamides are particularly preferred.

The photosensitive aromatic polyamide is preferably a photosensitive aromatic polyamide or a photosensitive aliphatic polyamide obtained by polycondensation of an aromatic diamine or aliphatic diamine having a photosensitive group and an aromatic dicarboxylic acid. . (
JP-A-60-6725 and JP-A-61-732
(See Publication No. 8) Examples of the aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, 4,4'-dicarboxybiphenyl, 4,4'-dicarboxydiphenylmethane, 4,4'-dicarboxydiphenylmethane,
Mention may be made of aromatic dicarboxylic acids such as 4°-dicarboxydiphenyl ether, or acid halides thereof.

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

Further, as the aromatic diamine having the photosensitive group,
For example, 3,5-diaminobenzoic acid ethyl methacrylate, 2,4-diaminobenzoic acid ethyl methacrylate, 3,5-diaminobenzoic acid glycidyl methacrylate ester, 2,4-diaminobenzoic acid glycidyl methacrylate ester, 3. Benzoic acid esters such as 5-diaminobenzoic acid cinnamate ester and 2,4-diaminobenzoic acid cinnamate ester; hensyl methacrylates such as 3,5-diaminobenzyl methacrylate and 2,4-diaminobenzyl methacrylate; 4-Methacrylamide-3,4'-diaminodiphenyl ether, 2-methacrylamido-3,4'-diaminodiphenyl ether, 4-cinnamamide-3,4'-diaminodiphenyl ether, 3,4''-dimethacrylamide 3', Diphenyl ethers such as 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.

The photosensitive polymer used in the present invention is preferably uniformly dissolved in an organic solvent at a concentration of about 1 to 40% by weight.

The black pigment component used in this invention consists of carbon black and a set of colored pigments of different colors other than carbon black (particularly a set of colored pigments exhibiting black color).

In this invention, when the black pigment component is composed only of carbon black, if a sufficient amount is used to reduce the transmittance in the entire visible range and produce a black color, it is possible to reduce the transmittance in the entire visible range and produce a black color. The transmittance in the ultraviolet region is extremely low, making it extremely difficult to photocure photosensitive polymers, and increasing the amount of carbon black added to produce a sufficient black color will make the film less conductive. This is not suitable because it cannot be used as a black matrix for liquid crystal displays, etc.

In addition, if you try to produce a sufficient black color by composing the black pigment component only with a set of colored pigments of different colors other than carbon black without using carbon black, it is possible to The amount of addition of 20% is extremely large, and the strength of the photocured film and the adhesion to the substrate are extremely reduced.

In view of the above, in the present invention, carbon fluff and a set of colored pigments of different colors other than carbon black are combined as a black pigment component and used in combination with a photosensitive polymer, etc., to achieve a sufficient effect. It was possible to obtain a black photosensitive polymer composition that simultaneously has a high degree of blackness and photocurability, and is capable of forming a photocured layer with good film characteristics.

In this invention, in order to satisfy all of these characteristics at a high level, the mixing ratio of the photosensitive polymer and the black pigment component is 5 to 60 parts by weight of the carbon blank per 100 parts by weight of the photosensitive polymer. % by weight (relative to the total amount of black pigment components) and a set of colored pigments of different colors 40
2 to 180 parts by weight, especially 10 to 160 parts by weight of a black pigment component consisting of ~95% by weight (relative to the total amount of black pigment components)
Preferably, it is a proportion of parts by weight.

If the total amount of black pigment components is less than 2 parts by weight, sufficient black color cannot be obtained even if the film thickness is increased, and if it exceeds 180 parts by weight, the film strength may decrease or the adhesion to the substrate may deteriorate. This is not preferable because it lowers the temperature.

The carbon black used in this invention may be a general carbon blank such as acetylene black, channel black, or furnace black, but may be surface-treated to improve its dispersibility. Examples of surface-treated carbon black include Microlith manufactured by Ciba Geigy.

In addition, the organic pigments J of different colors used in combination with carbon black in the present invention preferably have relatively good transparency (and are excellent in heat resistance, light resistance, and solvent resistance). Particular preference is given to a set of organic pigments which exhibit a substantially black color.

The coloring pigments include azochelate, condensed azo, phthalocyanine, benzimidazolone, quinacridone, isoindolinone, pyranthrone, dibromuanthanthrone, indanthrone, anthrapyrimidine, and flavanthrone. perylene series, perinone series, quinophthalone series, thioindigo series, dioxazine series,
Examples include organic coloring pigments such as anthraquinones.

When a set of colored pigments of different colors is appropriately selected from two or more of the above-mentioned colored pigments and used together with carbon black in the composition of the present invention, the resulting black window photopolymer composition The film made of substances covers the entire visible range (approximately 450 to 6
less than 3% (especially 2.7% or less) for the maximum transmittance (in the range of 0.00 nm) and 0.1 to 2.5% (0.2 to 2.0%) for the average transmittance in the entire visible range For example, (a) a blue pigment and a violet pigment, (c) a red pigment and a blue pigment, (C) a yellow pigment and a blue pigment. pigment and purple pigment,
Suitable examples include combinations of (d) a green pigment, a blue pigment, and a violet pigment, and (e) a red pigment, a blue pigment, and a violet pigment.

From the viewpoint of light transmittance, film surface uniformity, etc., it is preferable to use the above-mentioned color pigments having a particle size of ltIm or less.

Furthermore, photoinitiators used in the compositions of the invention include, for example, Michler's ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, 2-tert-butylanthraquinone, 1,2-benzo-9, 10 anthraquinone, benzyl, anisyl, 4.4-bis(diethylamino)benzophenone, acetophenone, benzophenone, 1.5
- acenaphthene, thioxanthone or derivatives thereof (e.g. chlorothioxanthone, ethylthioxanthone),
Examples include dimethylaminoanthranilic acid alkyl ester, rose(dimethylamino)benzoic acid alkyl ester, and the like.

In this invention, in particular, since the black film has no choice but to lower the light transmittance in the ultraviolet region necessary for photocuring,
In order to improve photocurability, it is preferable to blend a bisazide compound with a high quantum yield.

Such bisazide compounds include 4,4'' diazidohensiphenone, 4,4''-diazido diphenylmethane, 4,4''-diazido chalcone, 4,4''-diazidobenzalacetone, 2.6 Preferred examples include -bis-(4-azidobenzal)-4-methylcyclohexanone and 4,4'' diazidostilbene.

Moreover, in the composition of this invention, hydroquinone,
2.6-tert-butyl-4-methylphenol (BIT)
, hydroquinone methyl ether, phenothiazine,
A small amount (5% by weight or less) of a thermal polymerization inhibitor such as N-nitrosophenylhydroxylamine ammonium salt may be blended.

The amount of the photoinitiator is 100% of the photosensitive polymer.
The amount is preferably 5 to 50 parts by weight, particularly 10 to 40 parts by weight.

Further, it is preferable to use a bisazide compound as a part of the photoinitiator, and the amount of the bisazide compound is 0 to 20 parts by weight, particularly 1 to 15 parts by weight, based on 100 parts by weight of the photosensitive polymer. It is preferable to set the amount to be a proportion.

If the amount of the photoinitiator is too small, the photosensitivity of the resulting black photosensitive polymer composition will be low, and if it is too large, the heat resistance of the film formed from the resulting composition will be reduced, so it is preferable. do not have.

The photocuring method of this invention uses a photosensitive polymer, a photoinitiator, carbon black, and a material other than carbon black.
A thin film layer of a black photosensitive polymer composition containing a black pigment component consisting of a set of colored pigments of different colors is formed on a support, and a black photocured coating layer is formed by irradiation with light. The black photosensitive polymer composition is photocured.

In the photocuring method of the present invention, a film of a black photosensitive polymer composition is prepared by dispersing a black pigment component in a photosensitive polymer solution. By coating the black photosensitive polymer composition on top and drying the coating film, a thin film made of the black photosensitive polymer composition can be formed.

Is the black pigment component mentioned above dispersed? "Black photosensitive polymer solution composition" has a rotational viscosity of 0.1 at 25°C.
It is preferably about 1000 poise, particularly about 0.2 to 500 poise.

If necessary, a dispersant such as a surfactant may be added to the black photosensitive polymer solution composition in which the black pigment component is dispersed, in order to improve the dispersibility of the color pigment, etc. Silane force 7 to improve adhesion to the support
Bonding promoters such as pulling agents may also be added.

The above-mentioned black photosensitive polymer solution composition in which the black pigment component is dispersed can be applied to the support by, for example, a spin coating method, a roll coating method, a dipping method, a spray method, a screen printing method, etc. It can be carried out. When using screen printing, etc., in order to ensure its suitability for printing,
A thixotropic agent such as Aerosil, an extender pigment, etc. may be added.

The coating film is dried at 150°C or less, especially 100°C or less, using a hot air dryer, hot plate, etc.
It is preferable to carry out the heating for 60 minutes, particularly for about 5 to 30 minutes.

During this drying, the pressure may be reduced.

Furthermore, the thickness of the film of the black photosensitive polymer composition is as follows:
Usually, it is preferably about 0.2 to 3.0 μm.

The black film described above covers the entire visible range (approximately 450 to 650 nm).
m range) for a maximum transmittance of less than 3% (especially 2.7
% or less), and the average transmittance of the entire visible range is 0
．． It is preferably 1 to 2.5% (especially about 0.2 to 2.0%), and more preferably 0.6% or more in the wavelength range of light used for photocuring (ultraviolet light; 400 nm), especially It is preferably about 0.6 to 2.0%, more preferably 0.7 to 1.8%.

Next, a mask having a predetermined shape such as a dot pattern or a stripe pattern is closely attached to the film of the photosensitive polymer composition formed as described above, and parallel light from, for example, an ultra-high pressure mercury lamp (250 W) is applied through the mask. After pattern exposure by irradiation, development is performed to form a pattern such as a black matrix.

Development of the pattern-exposed film is carried out by immersing the film in a suitable developer at a temperature of about 0-100"C to elute and remove the uncured parts of the film. .

As the developer, organic solvents that dissolve photosensitive polymers, and mixtures of these organic solvents with methanol and ethanol can be used.

Furthermore, during the development, the developer may be subjected to ultrasonic waves or may be sprayed.

After the above-mentioned development, the formed colored image is rinsed with 1,1.1 trichloroethane, isopropyl alcohol, etc., and then dried at about 100 to 200°C for 10 to 20 minutes using a hot air dryer, hot burner, etc. Preferably, the heat treatment is performed for 120 minutes.

〔Example〕

EXAMPLES Hereinafter, the black photosensitive polymer composition of the present invention and its curing method will be described in more detail with reference to Examples.

Example 1 [Polyamide '1] After replacing the gas in the flask by passing dry air into a three-north flask, 9.98 g of 3,5-diaminobenzoic acid ethyl methacrylate II was added, and N-
8.00 ml of methyl-2-pyrrolidone (NMP) was added and dissolved.

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 °C.

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

Next, 500 m/! of NMP was added to the reaction solution. After diluting by adding NMP11!, this solution was diluted with NMP11! , and 10ffi of water to precipitate a photosensitive aromatic polyamide. The precipitate was collected by filtration and dried to obtain 167.8 g of white aromatic polyamide powder.

Logarithmic viscosity (concentration; 0, 5
g/Loom! 2 solvent, solvent, NMP, measurement temperature: 30°C) was 0.88.

[Black polymer] After dissolving 6 g of the above aromatic polyamide and 0.6 g of hydroquinone in 50 g of triethylene glycol dimethyl ether, 6 g of carbon black, 3 g of phthalocyanine blue (blue pigment) and 3 g of dioxazine violet (purple pigment) were dissolved.
A black pigment component consisting of g is added, and after mixing and stirring, the black pigment component is dispersed using three rolls to obtain a black pigment dispersion paste.

Add N-methyl-2- to 35 g of this black pigment dispersion paste.
Pyrrolidone (NMP) 150g, aromatic polyamide 7g
, 0.6 g of hydroquinone was added, and after mixing and stirring, 50 W ultrasonic waves were applied in a water bath for about 1 hour to form an NMP solution (viscous) of photosensitive aromatic polyamide in which the black pigment component was further sufficiently dispersed. liquid) was obtained.

To the viscous liquid thus obtained, 1.5 g of 4,4゛-diazide chalcone was added and stirred to obtain 1 μm of fluorine 1.
A photosensitive aromatic polyamide solution (black photosensitive polymer solution composition) in which a black pigment component was uniformly dispersed was prepared by pressure filtration using a greasy filter (Teflon filter).

C color burn] The black photosensitive polymer solution composition described above was spin-coated onto a glass substrate so that the dry film thickness was 1.0 μm, and the coated film was dried at 80°C for 10 minutes. A film of a black photosensitive polymer composition was formed on a glass substrate, and then a stripe-shaped mask with an interval of 10 μm was brought into close contact with the film, and an ultra-high pressure mercury lamp (5 mW/d) was applied through the mask. 3
A part of the film was photocured by pattern exposure for 0 seconds.

Next, the film that had been pattern-exposed and partially photocured was developed for 1 minute using a diglyme solution [uncured parts of the film (portions that were not exposed to light) were removed], and further,
After rinsing the developed film with isopropyl alcohol, it was heat-treated at 200°C for 30 minutes to obtain a clear black pattern with 10 μm stripes.

Examples 2 to 3 A black photosensitive material was prepared in the same manner as in Example 1, except that a black pigment component j consisting of "carbon black" and "V-group organic coloring pigment" in the amounts shown in Table 1 was used. Polymer solution composition J was prepared.

Except for using the black photosensitive polymer solution composition j described above, the same procedure as in Example 1 was carried out to form a partially photocured film through pattern exposure and evaluation. The results are shown in Table 1.

Example 4 "Black photosensitive" was prepared in the same manner as in Example 1, except that 50 parts of trimethylolpropane triacrylate was added to 100 parts of polymethyl methacrylate (Mw = 12000) as the photosensitive polymer component. Polymer solution composition j was prepared.

A partially photocured film was formed by pattern exposure by pattern exposure and evaluation was performed in the same manner as in Example 1, except that the above-mentioned "Black Photoreactive Polymer Solution Composition" was used. The results are shown in Table 1.

Comparative Example 1 Same as Example 1 except that the black pigment component was 50 parts by weight of carbon black. A black photosensitive polymer solution composition j was prepared.

Except for using the above-mentioned "black photosensitive polymer solution composition", the same procedure as in Example 1 was carried out to form a partially photocured film by pattern exposure and evaluation. The results are shown in Table 1.

Comparative Example 2 A black photosensitive polymer solution composition was prepared in the same manner as in Example 1, except that as a black pigment component, no carbon black was used at all, and the amount of R-group organic coloring pigment 1 shown in Table 1 was used. ``object'' was prepared.

Except for using the above-mentioned black photosensitive polymer solution composition j, the same procedure as in Example 1 was carried out to form a partially photocured film by pattern exposure and evaluation. The results are shown in Table 1.

In Comparative Example 2, there is a problem in that the film peels off from the support when photocuring the "r black photosensitive polymer solution composition" formed as described above and developing it with a developer.

[Actions and effects of the present invention]

The black photosensitive polymer composition of the present invention is composed of a combination of carbon black and a different set of colored pigments other than carbon black as the black pigment component, so the composition (film) is black. Nevertheless, it has excellent photosensitivity, sufficient electrical properties and film strength, and a clear and precise black matrix.
It can be easily formed with good reproducibility by photocuring through pattern exposure.

Claims (3)

[Claims] (1) A black photosensitive material characterized by containing a photosensitive polymer, a photoinitiator, and a black pigment component consisting of carbon black and a set of colored pigments of different colors other than carbon black. Polymer composition. (2) 100 parts by weight of photosensitive polymer and 5 to 5 parts by weight of photoinitiator
0 parts by weight, and 5 to 60% by weight of carbon black,
Black pigment components 2 to 18, other than carbon black, consisting of 40 to 95% by weight of a set of colored pigments of different colors
The black photosensitive polymer composition according to claim 1, containing 0 parts by weight. (3) A thin film layer of a black photosensitive polymer composition containing a photosensitive polymer, a photoinitiator, and a black pigment component consisting of carbon black and a set of colored pigments of different colors other than carbon black is deposited on a support. 1. A photocuring method for a black photosensitive polymer composition, which comprises forming a black photosensitive polymer composition and irradiating it with light to form a black photocurable coating layer.