JPH01300247A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE:To improve the water resistance of the title composition, and to make possible the development due to water of the composition, without injuring the dyeing properties of the composition by composing the composition of a specified polymer, a bisazide compd. and a compd. having a sulfonic acid group, as constituting elements. CONSTITUTION:The compd. having the sulfonic acid group is added to a photosensitive resin composed of a cationic polymer having a tertiary amine or a quarternary ammonium base, and a photocrosslinking agent of the bisazide compd. And the compd. having the sulfonic acid group is composed of a sulfonated compd., having 6-50 C and is exemplified by for example, an anionic type surface active agent or an anionic dye, etc. The polymer is obtd. by copolymerizing a monomer of a polymer having the structure of the tertiary amine or the quarternary ammonium salt, and an another monomer. Thus, the sufficient water resistance of the resin composition is obtd., and the development of the composition due to the water makes possible maintaining the sufficient dyeing properties of the composition.

Description

Detailed Description of the Invention <Industrial Application Field> The present invention relates to a photosensitive resin composition for forming colored images, and is particularly suitable for forming color filters used for colorizing image pickup devices and display devices. The present invention relates to a photosensitive resin composition.

<Prior art> Many methods have been proposed for manufacturing color filters used to color image pickup devices and display devices, including printing methods, electrodeposition methods, vapor deposition methods, etc. Among them, a method called relief dyeing method is , is a method of repeating the process of dyeing and coloring a fine relief pattern formed with dyeable resin as many times as necessary, and as a method of manufacturing color filters, -
It's a target.

In this method, fine patterns can be easily formed by imparting photosensitivity to the dyeable resin itself, and since a dye is used for coloring, the colored pattern is transparent and shows a sharp spectral i3 pass rate curve. This is an extremely practical method that allows for a large degree of freedom in design since it allows selection from a large number of types.

As the dyeable photosensitive resin used in the relief dyeing method, aqueous solutions of natural proteins such as gelatin, casein, and fish glue that have been photosensitized with dichromate have been used.

However, since these photosensitive resins have low sensitivity, productivity cannot be improved, and a number of photosensitive resins have been proposed. Particularly, those in which a tertiary amine or a quaternary ammonium salt is introduced as a phosphor group exhibit good dyeing properties and have sufficiently satisfactory properties in terms of stability.

<Problem to be solved by the invention> Determined by thio. In other words, the greater the content of the ion groups, the greater the amount of anionic dye that can be bound, making it possible to obtain a filter with a high color density with a thin film thickness.

However, there is a contradiction in that introducing such a cajon group reduces the water resistance of the polymer.

That is, the cationic groups introduced into the polymer cause problems such as wrinkles or peeling of the pattern from the base material. Therefore, if sufficient dyeability is desired, water cannot be used as a developer, but an organic solvent must be used.

An object of the present invention is to provide a photosensitive resin composition that has sufficient dyeability, sufficient water resistance, and can be developed with water.

The problem was solved by adding a compound having a sulfonic acid group to a photosensitive resin made of a photocrosslinking material of polymer and a bisazide compound. Examples of the compound having a sulfonic acid group here include sulfonated compounds having 6 to 50 carbon atoms, such as anionic surfactants, sulfonated aromatic hydrocarbons, and anionic dyes.

The present invention will be explained in more detail below.

The polymer having a tertiary amine group or quaternary ammonium base in the present invention can be obtained by copolymerizing a polymerizable monomer having a tertiary amine or quaternary ammonium salt structure with another monomer. .

Typical polymerizable monomers having a tertiary amine structure are shown below.

ORs desired R2(2)C
H-C-C-0-CH, CH-CH, -N0
0HR.

IR2 (3) CH=C-C-NH-'CH,CH2CH,-N
0
Rs (In (1) to (3), Rt is H or C
A monomer having a quaternary ammonium base (H, Rt, Rs represents CH or CxHs) can be obtained by quaternizing the tertiary amine of the above monomer with a suitable alkylating agent. The most widely used such alkylating agents include methyl chloride and dimethyl sulfate.

10 for the copolymer in order to obtain good dyeability.
Components other than the quaternary ammonium salt are usually 10 to 60% by weight, taking into consideration the reactivity with the bisazide compound that is the photocrosslinking agent, dye diffusivity, water resistance, developability, etc. Determined by

Monomers having hydroxyl groups are particularly useful in terms of reactivity with the photocrosslinking material.

A typical example is (R1=l(or CHs) (6) fjl=c-C-0-CHxCHzCHtCH
xOH0(R=Hor CHs) and the like.

In addition, hydrophilic monomers may be introduced in order to improve the diffusivity and developability of the dye in the polymer. Typical examples of such monomers include / (7) CI(,=CH-C-N ^ \ Rz (R+ =Hor CH3, Rt =Hor C
H3) (8) CH,=CH 0-CC1-1°CH, -CH.

(9) CHyo = CHOmi CC
H.

O□ CR+ \R8 (R+ =Hor CH3, Rz =Hor
CHs)0[D CH,=CH C-〇□ CHz CH.

Hardware is used.

Representative examples are listed below.

θD 5OsH5OsH Ori　　　　　　　S　O,H3O,H θ one 〇 -2 to 20% by weight relative to - is suitable.

It has been found that water resistance can be improved by adding a compound having a sulfonic acid group to a photosensitive resin in which a polymer and a photocrosslinking material are dissolved in an appropriate solvent.

In other words, as mentioned above, troubles during water development occur due to the positive charge of the polymer, but it is also due to the increase in anion concentration near the polymer due to the addition of a compound having a sulfonic acid group, or the formation of ion complexes. It is thought that this formation suppresses swelling due to water.

Therefore, the base material of the compound having a sulfonic acid group needs to have a certain degree of molecular weight and hydrophobicity, and in the case of aliphatic sulfonic acids, sulfonated compounds with about 6 to 40 carbon atoms are preferably used. can.

Many such compounds can be found among those known as anionic surfactants.

That is, as aliphatic sulfonic acids, (a) higher alcohol sulfate salt ROS Os Na (b) liquid fatty oil sulfate salt R (S Os Na ) COOR' (C) aliphatic amine and aliphatic amide. Sulfate RCON HR'
CHz CHt OS Os Na (cl) Sulfonic acid salt of diacid fatty acid ester ROCOCH.

ROCOCHS Os N a (e) Fatty acid amide sulfonates RCON R' CH! CH! Further, examples of aromatic sulfonic acid type surfactants include ff) alkylaryl sulfonates and the like.

However, the aromatic sulfonic acid is not limited to the above-mentioned surfactants, but any aromatic sulfonic acid can be used as long as it is compatible with the photosensitive liquid.

Examples include sulfonated aromatic hydrocarbons such as benzene, toluene, naphthalene, anthracene, stilbene, and pyrene.

Additionally, sulfonated derivatives of aromatic hydrocarbons are also useful. A large number of such compounds are known as anionic dyes, and for example, azo-based, stilbene-based, anthraquinone-based, triphenylmethane-based, and phthalocyanine-based dyes can be used.

Such compounds are effective when added in very small amounts, but adding too much is not only meaningless, but also increases the hydrophobicity and molecular weight of the polymer, making it completely insoluble in water and making patterning impossible. Therefore, it is necessary to avoid introducing sulfonic acid groups, which are equivalent to cationic groups, and the appropriate amount of addition is about 2 to 50% by weight based on the polymer. We will describe how to obtain images.

A cationic polymer, a bisazide compound, and a compound having a sulfonic acid group are dissolved in a suitable solvent, applied to a substrate on which a colored image is to be formed, and then dried to remove the solvent. Next, the area where a pattern is to be formed is irradiated with ultraviolet light and developed with water, whereby the light-exposed area is dissolved and removed, forming a relief pattern of the cationic polymer. By immersing the base material on which this relief pattern is formed in a solution of a dye having an anionic group, the cationic group of the polymer and the anionic group of the dye bond to form a colored pattern.

Note that when an anionic dye is used as the compound having a sulfonic acid group, it is also possible to obtain a colored image without performing a dyeing step after development by using a dye having a desired color tone in advance.

Here, a feature of the present invention that should be noted in particular is that by adding a sulfonic acid group or a compound having a sulfonic acid group, resistance to water is greatly improved, but no decrease in dyeability is observed. . This means that
It can be interpreted that this is because a compound having a sulfonic acid group bonded to a cationic group undergoes ion exchange with the dye anion during dyeing.

What should be noted in this regard is the case where the photocrosslinking material itself has a sulfonic acid group, such as the compound 011 or Q21.

According to experiments conducted by the present inventors, when the photocrosslinking material itself has a sulfonic acid group, water resistance clearly improved by increasing the amount of the crosslinking material, but dyeability decreased accordingly.

This is thought to be because in the case of a crosslinking material, exchange with the dye anion is difficult to occur because it is fixed in the polymer. Therefore, when using a compound having a sulfonic acid group as a photocrosslinking agent, excessive addition should be avoided, but since the additive of the present invention is not involved in the photocuring reaction,
A photosensitive resin composition that has both water resistance and dyeability can be obtained.

<Example 1> A cationic polymer having a tertiary amine group was synthesized as follows.

In a 300d round bottom flask, 18 g dimethylaminopropyl methacrylamide, 15 g hydroxyethyl methacrylate, 27 g N,N''-dimethylacrylamide,
0.20 g of azobisisobutyronitrile and 140 g of methyl cellosolve were charged, mixed and dissolved while blowing nitrogen gas, heated to 70'C, and stirred for 5 hours to polymerize.

The polymerization solution was poured into a large amount of ethyl acetate to cause precipitation, and the precipitated resin was dried under reduced pressure. After drying, 10 g of resin was dissolved in 90 g of methyl cellosolve, and 4.4°-
0.5 g of sodium diazidostilbene-2,2" disulfonate was added and dissolved. (A) ~
(D) 15 g of a 10% aqueous solution of four types of sulfonic acid groups or compounds having sulfonic acid groups were added and mixed to obtain a photosensitive resin composition of the present invention.

(A) Dodecylbenzenesulfonic acid CB) Formaldehyde condensate of sodium naphthalene sulfonate (product name Demol N, manufactured by Kao ■) (C) Sodium 1,5-naphthalenedisulfonate (D) Anthraquinone acid dye (manufactured by Mitsubishi Kasei ■) Product name Old acid Light Blu
e2A) Next, these four resins were spin-coded onto a glass substrate and dried at 110"C for 30 minutes. The film thickness after drying was 0.80 to 0.85μ. A relief pattern of the cationic polymer was obtained by pattern exposure and development with water.For comparison, (A
When patterning was carried out without adding the compounds of ) to (D), a slight pattern remained, but most of it swelled and peeled off from the glass substrate. After baking the patterned glass substrate at 170°C for 1 hour, a 0.5% aqueous solution of acidic dye (Kayanoor Milling Red 3BW, manufactured by Nippon Kayaku ■) was added (pH adjusted to 3.5 with acetic acid).
After soaking at 60°C for 5 minutes in (adjusted to) water, a red colored pattern was obtained. The absorbance of this pattern at 53on- is 1.6 to 1.8 for both (A) to (D).
I was able to dye it to a sufficient concentration.

<Example 2> A polymer having a quaternary ammonium base was synthesized in the same manner as in Example 1. However, the monomer and the amount charged are
2-Hydroxy-3-methacroyloxypropyltrimethylammonium chloride 18g 1 ε-caprolactone adduct of hydroxylethyl methacrylate (Daicel Chemical Co., Ltd. Plaxel FM-1) 15g, N, N'
Dimethylacrylamide 27g1 azobisisobutyronitrile 0°12g1 methyl cellosolve 140g.

The obtained polymer was photosensitized in the same manner as in Example 1,
A photosensitive resin composition of the present invention was obtained by adding the compounds (A) to (D).

Spin-code the four types of resins described in Section 2 on a glass substrate, and
After drying at °C for 30 minutes, the film thickness was 0.65-0.7
It became 0μ. When these substrates were pattern-exposed in the same manner as in Example 1 and developed with water, good patterns without peeling or wrinkles could be formed.

Next, after beta-cubing at 170°C for 1 hour, 0.5% of direct dye (manufactured by Ciba Geigy, Lanazol Blue 8G) was added.
% aqueous solution at 60° C. for 5 minutes and then washed with water to obtain a blue colored pattern. The absorbance of this pattern at 630na+ is (A) ~ ([1) both 1.2 ~ 1.3
It showed good stainability.

In Examples 1 and 2, the samples using the compound (D) were already colored blue after development, and could be used as colored images as they were.

<Effects of the Invention> The photosensitive resin of the present invention can be dyed by adding a compound having a sulfonic acid group, such as a sulfonated compound having 6 to 40 carbon atoms, an anionic surfactant, or an anionic dye. Water resistance has been improved without sacrificing properties, and development with water has become possible, so there is no need to worry about contamination of the manufacturing environment with organic solvents, and it has also become possible to reduce manufacturing costs.

Furthermore, when an anionic dye is used as the compound having a sulfonic acid group, a colored image can be formed without going through a dyeing step, and the number of steps can be significantly reduced.

Special permission person Toppan Printing Co., Ltd. Representative: Kazuo Suzuki

Claims (5)

[Claims] (1) A photosensitive resin composition comprising as constituent elements a polymer having a tertiary amine group or a quaternary ammonium group, a bisazide compound, and a compound having a sulfonic acid group. (2) The compound having a sulfonic acid group has 6 to 40 carbon atoms.
The photosensitive resin composition according to claim 1, which is a sulfonated compound of the compound. (3) The photosensitive resin composition according to claim (1), wherein the compound having a sulfonic acid group is an anionic surfactant. (4) The photosensitive resin composition according to claim (1), wherein the compound having a sulfonic acid group is a sulfonated aromatic hydrocarbon. (5) The photosensitive resin compound according to claim (1), wherein the compound having a sulfonic acid group is an anionic dye.