JPS60252341A - Photosensitive resin compound - Google Patents

Abstract

PURPOSE:To obtain the titled compound having superior storage stability, easy adjustment to keep the balance between photosensitivityh and dyability, good dyability and high resolution by using a polymer comprised essentially of the specified structure unit and the compd. consisting of specified compd., a sensitizer and photoiniciator. CONSTITUTION:The photosensitive resin compsn. consists of a polymer consisting essentially of structural units each represented by formula (in which R<1> is H, CH3, or C2H5; X is -O- or -NH-; n is 1, 2, or 3; and R<2>, R<3> are each 1-4C alkyl), one of compds. of represented by formulae II and III (in which R<4>-R<7> are each same as R<1>, and m is same as n), a sensitizer, and a photoinitiator. The structural units of formula I has functions of enhancing dying performance and water solubility, and it is added, preferably, in an amt. of >=20wt% of the copolymer to be formed. The compds. of formulae II and III have functions of insolubilizing the polymer in solvents, and holding it on a base for forming a filter. Such a photosensitive resin compsn. has good storage stability, capability of optional control to keep a balance between photosensittivity and dyability, and good operation efficiency.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a photosensitive resin composition. For more details,
It consists of a compound that has a carboxyl group and an ethylenically unsaturated double bond that can be addition-polymerized by light irradiation in the same molecule, and a polymer that contains an amine group or a substituted amine group as an essential component, and is soluble in a weakly acidic aqueous solution. The present invention relates to a photosensitive resin composition.

The photosensitive resin composition of the present invention has good dyeability with acid dyes, and is therefore particularly suitable as a forming material for color separation filters used in color video cameras, etc. It can also be used in general photoresist applications such as plate-making materials.

[Conventional technology]

Conventionally, photosensitive compositions made of natural polymers such as gelatin and glue using hexavalent chromium compounds such as ammonium dichromate and potassium dichromate as photocrosslinking agents have been widely used as forming materials for color separation filters. There is.

Such a photosensitive composition is applied onto a substrate such as glass or a solid-state imaging device by a spin code method.

Next, a colorless transparent pattern is formed on the substrate by exposure to ultraviolet light through a striped or mosaic pattern and development. This colorless transparent pattern is dyed by immersing it in a dyeing solution containing a dye or the like. A desired color separation filter is generally manufactured by repeating the above steps.

Gelatin and glue have good dyeability with acid dyes and excellent resolution, and also have the advantage in process of being able to be developed with water without using organic solvents.

However, since gelatin, glue, etc. are natural polymers, it is difficult to obtain a product with a constant molecular weight distribution or a constant amino group concentration when dyeing with an acid dye. Furthermore, a so-called dark reaction, in which a curing reaction similar to the photoinsolubilization reaction occurs before and after exposure, is likely to occur, making it impossible to store the photosensitive solution for a long time, and it is necessary to expose and develop the photosensitive solution within a short period of time after applying it to the substrate. . It also has drawbacks such as the need to use hexavalent chromium compounds that are harmful to the human body.

To improve these drawbacks, for example, a photosensitive resin composition containing as a main component a copolymer of 4'-methacryloxychalcone and a tertiary amine having a copolymerizable unsaturated bond (Unexamined Japanese Patent Publication No. 1987-48758), a photosensitive resin composition containing as main components a ternary copolymer consisting of 2-hydroxyethyl methacrylate, 3-dimethylaminopropyl methacrylate, and acrylamide, and a diazo compound photocrosslinking agent (Japanese Patent Laid-Open No. 1983-1999) -199342) are known.

However, although the former method did not use hexavalent chromium and was able to suppress dark reactions, it was not possible to develop with an aqueous solvent, and an organic solvent had to be used for development, resulting in operational difficulties from an occupational health management perspective. Another drawback is that the balance between photosensitivity and dyeability of the resin composition is poor. Furthermore, the latter has the disadvantage that the dark reaction is not completely suppressed and the resin yellows after curing.

[Problem that the invention seeks to solve]

As mentioned above, the problems to be solved by the present invention are (7) good storage stability with suppressed dark reactions, (a) no use of hexavalent chromium, which is a harmful substance, and (d) photosensitivity. 2) It is a photosensitive resin composition that can be developed with an aqueous solvent without using an organic solvent, and (3) The dyeability of the cured resin with acid dyes and (power) color The object of the present invention is to provide a composition whose resolution in forming a decomposition filter is on the same level or higher than that from conventional photosensitive compositions containing gelatin and glue as main components.

[Means to solve problems]

In order to improve the various drawbacks of the conventional color separation filter forming materials as described above, the present inventors have investigated various combinations of compounds having a dyeing function and compounds having a photosensitive function, and as a result, the present invention has been developed. I was able to complete it.

That is, the present invention represents the general formula ([in formula 19, R1 is I], CH3 or C2, X represents 10-NH-, R represents an integer of 1 to 3, R2 or R3 represents an alkyl group having 1 to 4 carbon atoms.) In the general formula % formula % ([R1 formula and U) formula, R', R5, R6 and R7 represents H, CH, or C, H, and m is 1 to
Indicates an integer of 3. ) at least one of the compounds represented by
This is a photosensitive resin composition comprising a sensitizer, a photoinitiator, and a sensitizer.

The structural unit represented by formula (1) plays the role of increasing dyeability and water solubility. The polymer having the structural unit (1) as a main component may be a copolymer with other structural units. In any polymer, it is desirable that the proportion of the structural unit (1) in the polymer is 20% by weight or more in view of requirements based on dyeability and solubility in water.

Specific examples of monomers that can be polymerized or copolymerized to obtain a polymer containing the structural unit (1) include 2-
(dimethylamino)ethyl acrylate, 2-(dimethylamino)ethyl methacrylate, 2T(diethylamino)ethyl acrylate, 2-(diethylamino)ethyl methacrylate, 3-(dimethylamino)propyl acrylate), 3-(dimethylamino)propyl Examples include methacrylate, N-(3-dimethylaminepropyl)acrylamide, N-(3-dimethylaminopropyl)methacrylamide, and the like.

Other monomers copolymerizable with these monomers, such as acrylic acid, methacrylic acid, acrylic esters, meth! Of course, it is also possible to obtain a polymer having the structural unit (1) by copolymerizing acrylic acid esters, styrene, methyl vinyl ether, acrylonitrile, etc. within a range that does not impair dyeability and solubility in water.

The compound represented by formula (II) or formula (III) is
Hydroquinone, esters or N-substituted amides of acrylic acid or methacrylic acid containing a hydroxyl group,
It can be easily obtained by heating with an acid anhydride in the presence of a polymerization inhibitor such as paramethoxyphenol.

Preferred examples of esters of acrylic acid or meth-X acrylic acid containing a hydroxyl group include 2-hydroxyethyl acrylate, 2-hydroxyethyl meth-X acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl meth
-hydroxyethyl acrylate, 2-hydroxypropylmethacrylate, and the like.

N of acrylic acid or methacrylic acid having a hydroxyl group
Examples of -substituted amides include N-(hydroxymethyl)acrylamide, N-(hydroxymethyl)methacrylamide, and the like.

Specific examples of the acid anhydride include maleic anhydride, citraconic anhydride, etc. Maleic anhydride is particularly preferably used from the viewpoint of photosensitivity.

[■] Formula is a compound represented by [■] formula, the ethylenically unsaturated bond it contains is polymerized by light irradiation,
It plays the role of insolubilizing a polymer whose main component is the structural unit of formula (1) in a solvent and holding it on the filter forming substrate.

Formula [ll] and (II) in the photosensitive composition of the present invention
It is necessary that the compound represented by the formula I) be used in an amount of 10% by weight or more, preferably 20% by weight or more, of the polymer whose main component is the structural unit represented by the formula [1], and
I) and (Iff) so that the carboxylic acid provided by the compound represented by the formula (Iff) is not more than twice equivalent, preferably not more than twice the equivalent of the total amine provided by the polymer whose main component is the structural unit of formula 0. It is necessary to use it for

(II) and the compound represented by formula (II) [1]
If the amount is less than 10% by weight of the polymer whose main component is the structural unit of the formula, it is not preferable because it results in a decrease in resolution and insufficient strength of the formed film. If the carboxylic acid provided by the compounds of formulas (n) and (1) exceeds twice the equivalent of all the amines provided by the polymer having the structural unit of (1) as a main component, this is not preferred because the dyeability deteriorates.

As the photosensitizer in the present invention, 5-nitroacenaphthene, Michler's ketone, etc. are preferably used. The amount of these photosensitizers is preferably 1 to 10% by weight, based on the total weight of the polymer containing the structural unit of formula (I) as a main component and the compound of formula [■] and (TIT). It is used in an amount of 3 to 7% by weight.

If the proportion of the sensitizer exceeds 10% by weight, the strength of the formed film will decrease, which is not good.

As the photoinitiator, benzoin alkyl ethers such as benzoin ethyl ether, 2,2-jethoxyacetophenone, benzophenone, etc. are preferably used.

These photoinitiators are used in an amount of (0.5 to 5% by weight, preferably 1 to 3% by weight, based on the total weight of the polymer mainly composed of structural units of formula 0 and the compounds of formulas (II) and (TII')). It is appropriate to use % by weight. If the photoinitiator exceeds 5% by weight, a dark reaction will occur during storage and the stability of the composition will decrease, so it is not preferable. If the addition ratio of the agent is smaller than the above-mentioned value, the irradiation time required for the photocuring reaction will be prolonged, resulting in performance disadvantages such as a decrease in resolution, which is not preferable.

In addition to the monomers that provide the structural unit of formula (1) and the comonomers that are copolymerizable with vinyl, acrylamide, methacrylamide, dimethylacrylamide,
Dimethylmethacrylamide etc. can be used as a comonomer to improve the dyeability, while 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxyethoxyethyl acrylate, hydroxyethoxyethyl methacrylate etc. can improve the affinity with the substrate. It can be used as a comonomer to These copolymerizable monomers are mainly used when producing a polymer having the structural unit of formula (1), but also (U)
The formula (III') is added at the same time as the compound of formula (III'),
It can also be used as a component of a photosensitive resin composition.

As a component of the composition of the present invention (H) or CIII)
Methylenebisacrylamide, methylenebismethacrylamide, etc. can be used as a substance having a photosensitive function similar to the compound of the formula. By using these compounds, the dyeability can be further improved.

One of the features of the present invention is that a monoester of an unsaturated dicarboxylic acid represented by formula (II) or formula (1) is used as a component having a photosensitive function. It is thought that the photocuring reaction is carried out rapidly because the polymerization reactivity of the two types of unsaturated bonds contained in these compounds are appropriately balanced. Furthermore, the composition has the advantage that the balance between photosensitivity and dyeability can be adjusted as desired, since the main components of the composition are separated into a component with a dyeing function and a component with a photosensitivity function. .

The solution of the composition of the present invention suppresses dark reactions and has extremely good storage stability. One of the reasons for this is thought to be that a coordination bond exists between the cassyl group of the unsaturated dicarboxylic acid monoester and the amine of the polymer to stabilize it.

〔Example〕

The structure of the present invention and the effects brought about by the present invention have been described, and the present invention will be explained in detail below using Examples. The present invention is not limited to these examples.

Example 1 A mixture having the following composition was placed in a flask equipped with a stirrer,
After passing nitrogen gas through for 1 hour, heating and stirring were continued at 70° C. for 4 hours to carry out a polymerization reaction.

After completion of the reaction, the reaction mixture was poured into a large amount of cyclohexane to precipitate the product.

Next, the cyclohexane containing the reaction solvent was removed by decantation, the reaction product was dried under reduced pressure, and the polymer 44
I got 1.

A photosensitive liquid having a composition using this copolymer was prepared. This photosensitive solution was applied onto a glass substrate using a spinner at 25°C, 1500 r, p, m.
The coating was applied using a hot air dryer at 80° C. for 30 minutes. The coating film on the glass substrate (B) was exposed to ultraviolet light at a surface illuminance of 0.
It was exposed for 1 minute at 38 mVI shoulder, then developed with a 0.01 thiacetic acid aqueous solution (25°C), and then heat-treated at 150°C for 30 minutes. The resin film on this glass substrate was dyed under the following conditions.

(1) Dyeing Bath dye Aminyl Red E-3BL x weight% (manufactured by Sumitomo Chemical) Solvent Acetic acid aqueous solution (pH 3) (2) Dyeing temperature 60°C (3) Dyeing time 7 minutes Film thickness after dyeing is 0.8 μm A clear red pattern was obtained on the glass plate. A film made from a gelatin-dichromate material was dyed under the same dyeing conditions, and the film thickness showing the same optical density was 1 μm. Further, the resolution obtained under the above conditions was 10 μm.

Example 2 A photosensitive solution having the following composition was prepared using the copolymer produced in Example 1, and was stored at room temperature for 40 days in a brown bottle covered with light-shielding paper.

Using this photosensitive solution, a colorless transparent pattern was obtained on a glass plate in the same manner as in the example except that development was carried out with o, o o ss acetic acid aqueous solution (25°C).

Next, this glass plate was dyed under the following conditions.

(1) Dye Bath dye Kayathion Turquoise P-A 1% by weight (manufactured by Nippon Kayaku) Solvent Distilled water (2) Dyeing temperature 55°C (3) Dyeing time The film thickness after dyeing for 10 minutes is 0.7μ. , a clear blue pattern was obtained. The resolution obtained under these conditions was 5 μm. A film was made from a gelatin-dichromate-based material, dyed under the same conditions, and the film thickness showing the same optical density was 0.8 μm.

Example 3 Using the shida copolymer produced in Example 1, a photosensitive liquid having the following composition was prepared.

This photosensitive solution was applied onto a glass plate in the same manner as in Example 1, dried, exposed to ultraviolet light for 3 minutes at a surface illuminance of o and 3s R/d, and developed with a 0.01% acetic acid aqueous solution (40°C). and dried at 140°C for 20 minutes. This glass plate was then dyed under the same conditions as in Example 1.

The film thickness after dyeing was 0.9 μm, and a clear red pattern was obtained. Also, the resolution obtained under these conditions is 15μ
It was m.

A film made from a gelatin-dichromate material was dyed under the same dyeing conditions, and the thickness of the film exhibiting the same optical density was found to be 1.3 μm.

Example 4 A mixture having the following composition was placed in a flask, nitrogen gas was passed through the flask for 1 hour, and then the flask was heated and stirred at 70° C. for 4 hours to carry out a polymerization reaction. This reaction solution was poured into a large amount of cyclohexane, and the precipitated polymer was separated by decantation and dried under reduced pressure to obtain 459 polymer.

Using this polymer, a photosensitive solution having the following composition was prepared. Using this photosensitive solution, all operations were carried out under the same conditions as in Example 1, except that development was performed in a 0.001% acetic acid aqueous solution (25°C). A colorless transparent pattern was obtained on the glass plate. This glass plate was then dyed under the same dyeing conditions as in Example 1, except that the dyeing time was 5 minutes.

A clear red pattern with a film thickness of 0.7 μm was obtained, and the resolution was 10 μm.

A membrane made from a gelatin-dichromic acid material was dyed under the same conditions, and the thickness of the membrane exhibiting the same optical density as the filter of this example was found to be 1.2 μm.

Example 5 Using the copolymer produced in Example 1, a photosensitive liquid having the following composition was prepared.

This photosensitive solution was placed on a glass plate at 25°C using a spinner.
Coated at 1500'r, p, m and dried at 80' with a hot air dryer.
It was dried at ℃ for 30 minutes. The coating film on the glass plate was exposed to ultraviolet light for 30 seconds at an upward illuminance of 0.38 mW.
Next, after developing with 0.01% acetic acid aqueous solution (25°C),
Heated at 150°C for 30 minutes. Next, the resin film on this glass plate was dyed under the following conditions.

(1) Dye Bath dye Kayathion Turquoise P-A (manufactured by Nippon Kayaku)
1 weight" Solvent Distilled water (2) Dyeing temperature 55℃ (3) Dyeing time 10 minutes After dyeing, the film thickness was 0.8 μm, a clear blue pattern was obtained on the glass plate, and the resolution was 3 μm. Ta.

Further, a film made of a gelatin-dichromate-based material was dyed under the same conditions, and the thickness of the film exhibiting the same optical density was determined to be 1.2 μm.

〔Effect of the invention〕

The main features of the photosensitive resin composition of the present invention as a material for forming color separation filters are as follows: ) Harmful to the human body 6
It does not contain chromium compounds and is a mixture of a compound with a photosensitive function and a polymer with a dyeing function, so it is possible to change the balance between photosensitivity and dyeability at will. , 2) It can be developed with a weakly acidic aqueous solution, so there is little danger in terms of occupational health.

(3) Good stainability with acid dyes, thin film thickness,
Furthermore, the required dyeing density can be obtained in a short time in a relatively low-temperature dye bath, and high resolution comparable to that of conventional photosensitive compositions containing gelatin and glue as main components can be obtained. It is summarized in All of these are required of a photosensitive resin composition as a color separation filter material, and the present invention aims to obtain a photosensitive resin composition having both of these characteristics. Patent attorney Yatabe Sasai and Katsuhiko Uenonaka, Agent of Co., Ltd.

Claims (1)

[Claims] (1) Represents the general formula ([in formula 11, R1] (, CH3 or C,)T, X represents -0- or -NH-, and L represents 1 to 3. It represents an integer, and R2 or R3 represents an alkyl group having 1 to 4 carbon atoms. ) and the general formula % formula % ([■] formula Oyo, formula (III) niote, R4, R5,
Rcl O and R7 represent H, CH3 or C, H,
m represents an integer of 1 to 3. ), a sensitizer, and a photoinitiator. (2. A photosensitive resin composition in which the structural unit represented by formula ('I) in claim (1) is at least one selected from or or or. In item (1) and item (2), the compound represented by formula [IT] is mono(2-acryloyloxyethyl) maleate or CH represented by 0 0 . CH2=C-C0-CH2CHtO-CCH=CHC0
A photosensitive resin composition which is mono(2-methacryloyloxyethyl) maleate represented by 0HII II 0 .