JP2763301B2 - Photosensitive resin composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a photosensitive resin composition containing a photosensitive agent having good solubility in a solvent, particularly a polar solvent.

<Related Art> A photosensitive resin composition comprising a water-soluble aromatic azide compound having a sulfonic acid group and a water-soluble binder is used for printing such as offset printing, screen printing, and proofing.
It is widely used for electronic materials such as color filters, black matrices and printed circuits, or for immobilizing biocatalysts.

Examples of the conventionally used water-soluble aromatic azide compound having a sulfonic acid group include a sulfonic acid represented by the following formula, and an alkali or ammonium salt of the sulfonic acid.

However, in the formula, X is H, Na, K or NH ₄ .

<Problems to be Solved by the Invention> However, among the above-mentioned water-soluble azide compounds, those having a sulfonic acid are strongly acidic, and therefore, when used for a metal substrate or the like, the metal is corroded by the sulfonic acid or has corrosion resistance. Problems such as the necessity of a coating device of Therefore, its use range is limited. On the other hand, water-soluble azide compounds that have become alkali metal salts or ammonium salts include, for example, water, alcohol, cellosolve,
It has disadvantages such as poor solubility in polar solvents such as dimethylformamide, dioxane or a mixed solvent thereof, and poor compatibility with the binder polymer.
In addition, the alkali metal salt has a problem that the solubility varies depending on the pH of the solution to be dissolved or the solubility varies depending on the crystal form. Further, those containing an alkali metal salt cannot be used for electronic materials.

An object of the present invention is to provide a photosensitive resin composition containing a photosensitive agent that has solved such problems.

<Means for Solving the Problems> The inventors of the present invention have conducted intensive studies in order to achieve the above object, and as a result, the aromatic azide compound containing an organic amine salt of sulfonic acid contains no metal and no solvent. In particular, it was found that the compound was well dissolved in a polar solvent, the solubility was not changed by pH, and the compatibility with the binder polymer was good.

The photosensitive resin composition of the present invention based on such findings uses an aromatic azide compound having an organic amine salt structure of sulfonic acid as the photosensitive agent in a photosensitive resin composition comprising a photosensitive agent and a water-soluble binder. It is characterized by the following.

 Hereinafter, the present invention will be described in detail.

Examples of the organic amine salt of an aromatic azide compound containing a sulfonic acid group used as a photosensitizer of the photosensitive resin composition of the present invention include compounds represented by the following general formula.

In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , and R ₉ may be the same or different and include hydrogen, methyl, ethyl, propyl An alkyl group such as a butyl group, a butyl group, a pentyl group, a hexyl group or an amyl group, a substituted alkyl group such as a hydroxyethyl group or a hydroxypropyl group, an aralkyl group such as a benzyl group, and an aryl group such as a phenyl group; ₁ to
R ₄ or two of R _{5 to} R ₆ may together form an alkylene group. However, R _{1 to} R ₄ or R _{5 to} R ₈ are not simultaneously hydrogen.

These azide compounds can be easily produced by neutralizing the aqueous azidosulfonic acid solution with an organic amine or a quaternary ammonium hydroxide of an organic amine, and then salting out or concentrating the compound. Azidosulfonic acid can be easily produced by a known general synthesis method, but in order to particularly reduce the alkali metal content, a method of ion-exchanging the alkali metal salt with an acidic ion exchange resin is suitably used.

Examples of the organic amines include trimethylamine, diethylamine, triethylamine, tributylamine,
Aliphatic amines such as ethanolamine and triethanolamine, alicyclic amines such as pyrrolidine and piperidine,
Preferred are aromatic amines such as pyridine and aniline, and quaternary ammonium compounds such as tetramethylammonium hydroxide, tetrabutylammonium hydroxide, N, N-dimethylpiperidinium hydroxide and trimethylbenzylammonium hydroxide. Used.

The photosensitive resin composition of the present invention generally contains a water-soluble resin having a film-forming ability as a water-soluble binder. Known film-forming resins include, for example, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, polyvinyl methyl ether, polyvinyl acetal, polyvinyl acrylic acid, copolymers of vinyl alcohol and vinyl pyrrolidone, (meth) acrylate and (meth) acrylamide. Copolymers (JP-A-59-191033, JP-A-51-103502, JP-A-63-10152), copolymers of (meth) acrylamide and 2-cyanoethyl (meth) acrylate Polymer (JP-A-51-14)
No. 3318), a copolymer of acrylamide and diacetone acrylamide (JP-A-49-68801), a copolymer of vinyl alcohol and maleic acid (JP-A-48-97602), grafted polyvinyl alcohol, Acetoacetate ester group or allyl group-containing polyvinyl alcohol resin (JP-A-58-174942), copolymerized polyamide having a sulfonate salt group (JP-A-50-54405),
Methylcellulose, carboxymethylcellulose, hydroxymesylcellulose, hydroxypropylcellulose, sodium poly-L-glutamate (JP-A-48-90)
No. 727), gelatin, shellac, gum arabic,
Casein and the like can be mentioned.

In the photosensitive resin composition of the present invention, the mixing ratio of the water-soluble binder and the azide photosensitizer is 100
The photosensitive agent is used in an amount of 1 to 50 parts by weight, preferably 3 to 20 parts by weight, based on parts by weight.

The photosensitive resin composition of the present invention may contain a silicon compound for improving adhesion to a substrate, a surfactant for improving coating properties, and the like.

<Example> Next, the present invention will be described in more detail with reference to examples.

Example 1 46.75 g of sodium 4,4'-diazidostilbene-2,2'-disulfonate was dissolved in 1416 ml of water, and the solution was dissolved in 180 ml of a strongly acidic ion exchange resin PK-228 (manufactured by Mitsubishi Chemical Corporation). Pass the packed column at SV 1.5 hr ^-1 to give 4,4'-diazide-2,
A 2'-disulfonic acid aqueous solution was prepared. 15
% Tetramethylammonium hydroxide aqueous solution (hereinafter abbreviated as TMAH, manufactured by Toyo Gosei Co., Ltd.)
After adjusting the pH to 9, the mixture was concentrated to a total of 180 g. The precipitated pale yellow crystals were washed, washed with water and dried to obtain 54.42 g (recovery rate 96.2).
%) Of tetramethylammonium salt. Table 1 shows the solubility of this salt. Note that λ _max is 335 nm and ε _max is 41.
890, the Na content was 0.5 ppm or less.

Example 2 A triethylamine salt of 4,4'-diazidostilbene-2,2'-disulfonic acid was synthesized in the same manner as in Example 1 (recovery rate 96.6%). Table 1 shows the solubility of this salt. Note that λ _max is 335 nm, ε _max is 41.300, and the Na content is
It was 0.5 ppm or less.

For comparison, 4,4′-diazidostilbene-2,
2'-disulfonic acid Na, together K, and the solubility of NH ₄ salt are shown in Table 1. (Comparative Examples 1-3).

Example 3 13.0 g of sodium 2,6-Bis- (4'azidobenzal) -methyl-cyclohexanone-2,2'-disulfonate was added to water
Dissolve in 1500 ml, and transfer the solution to a strongly acidic ion exchange resin PK-
228 (Mitsubishi Kasei Co., Ltd.) SV3.0h in 150ml packed column
The solution was desalted by passing through r- ¹ to prepare a sulfonic acid aqueous solution. This aqueous solution was adjusted to pH 9 by adding a 15% aqueous solution of tetramethylammonium hydroxide (manufactured by Toyo Gosei Kogyo Co., Ltd.), and then concentrated to 50 g in total. The precipitated pale red crystals were filtered, washed with water and dried to obtain 14.98 g (recovery rate 90.5%) of a tetramethylammonium salt. Table 2 shows the solubility of this salt.
Shown in Note that λ _max was 383 nm, ε _max was 27.835, and the Na content was 0.5 ppm or less.

Example 4 A triethylamine salt of 2,6-Bis- (4'-azidobenzal) -methylcyclohexanone-2-2-2'-disulfonic acid was synthesized in the same manner as in Example 3 (recovery rate 9).
1.0%). Table 2 shows the solubility of this salt. Note that λ _max
Was 383 nm, ε _max was 28.741, and the Na content was 0.5 ppm or less.

For comparison, the solubility of the sodium salt of 2,6-Bis- (4'-azidobenzal) -methylcyclohexanone-2-2-2'-disulfonic acid is also shown in Table 2 (Comparative Example 4).

Examples 5 and 6 In substantially the same manner as in Example 1, the compounds shown in Table 3 were produced, and the solubility of each compound in 2.5% ethyl cellosolve and the solubility in water were measured. The result was obtained.

Table 3 shows that the compounds of Examples 5 and 6 exhibit better solubility than the compounds of Comparative Examples 5 to 7.

Example 7 4,4'-diazidostilbene-2,2'-disulfonate (hereinafter abbreviated as DAZST) (Examples 1 and 2 and Comparative Examples 1 and 2)
3) Polyvinylpyrrolidone K-60 (MW = 160,000) (Tokyo Kasei Kogyo) 4.5% aqueous solution, silane coupling agent SH-6040 (Toray Silicone Co., Ltd.), Emulgen 91
3 (manufactured by Kao Corporation), water and isopropyl alcohol were blended in the proportions shown in Table 4 to prepare photosensitive solutions (hereinafter referred to as photosensitive solutions A to D).

The photosensitive solutions A to D were coated on a glass plate by spin coating, and prebaked at 80 ° C for 20 minutes. Their film thickness was 0.8 μm. Then, each glass plate is 15m
Exposure was performed for 7 seconds using a W ultra-high pressure mercury lamp. The sensitivities of A to D were almost the same according to the step tablet method (using Kodak Step Tablet No. 2).

Then, after burning at 180 ° C in a clean oven,
The transmittance at each wavelength was measured. The results are shown in Table-5.

As shown in Table-5, the compound according to this example shows almost the same transparency as the sodium salt. Thus, the composition of the present invention is suitable, for example, as a light-sensitive material for a color filter that requires heat resistance, transparency, and low metal properties.

<Effect of the Invention> As described above, the photosensitive resin composition of the present invention
Since it has a high solubility in aqueous solvents and does not contain metals, it is suitably used for electronic materials such as color filters.

Claims (3)

(57) [Claims] 1. A photosensitive resin composition comprising a photosensitive agent and a water-soluble binder, wherein an aromatic azide compound having an organic amine salt structure of sulfonic acid is used as the photosensitive agent. Stuff. 2. The photosensitive resin composition according to claim 1, wherein the photosensitive agent is a compound represented by the following general formula. In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are hydrogen, an alkyl group,
Substituted alkyl group, aralkyl group, aryl group, or R ₁ to
R ₄ or two of R _{5 to} R ₈ represent an alkylene group formed together. However, R _{1 to} R ₄ or R _{5 to} R ₈ are not simultaneously hydrogen. 3. The photosensitive resin composition according to claim 1, wherein the photosensitive agent is a compound represented by the following general formula. In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ are hydrogen, an alkyl group, a substituted alkyl group, an aralkyl group, an aryl group, or
Two of R _{1 to} R ₄ or R _{5 to} R ₈ represent an alkylene group formed together. However, R _{1 to} R ₄ or R _{5 to} R ₈ are not simultaneously hydrogen.