JPH07234504A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE:To provide a photosensitive resin composition having high sensitivity, high resolution and good aging stability and being manufactured easily, by forming it while containing a high molecular compound having a component unit expressed by a specified formula and a sensitizer having a cation group inside a molecule. CONSTITUTION:A photosensitive resin composition is formed by containing a high molecular compound having a component unit expressed by the following formula and a sensitizer having a cation group in a molecule. In the formula, X indicates cationic species and (n) indicates 0, 1 or 2. The cation group of the sensitizer having a cation group in a molecule is a quaternary ammonia group. Though (n) in the formula is 0, 1 or 2, they may be used separated or mixed to be used. A reaction mixture of aldehyde and acetol dehyde in which n=0 may be used as it is. Especially, in the case of using reaction mixture of aldehyde and acetol dehyde in which n=0, the manufacture can be facilitated.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition, and more particularly to a water-soluble photosensitive resin composition having high sensitivity, good stability over time, and easy production.

[0002]

2. Description of the Related Art Conventionally, water-soluble photosensitive resin compositions for screen printing plates, for forming a black matrix of a color Braun tube or for forming a phosphor pattern, or for forming a color filter of a CCD or an LCD include, for example, gelatin,
A natural protein such as casein and glue to which a dichromate is added, or a combination of a water-soluble polymer such as polyvinyl acetate saponified with a diazonium salt has been used. Has drawbacks such as needing consideration for pollution and poor stability over time.

A photosensitive resin composition prepared by blending a water-soluble bisazide compound with a water-soluble polymer such as polyvinylpyrrolidone is also used, but it has a drawback of low sensitivity.

For this reason, development of a highly sensitive photosensitive resin has been underway, and for example, JP-A-4-26849, JP-A-2-204750, JP-A-2-173007, JP-A-2-92905, JP-A-1-302348, JP-A-5-197141 and JP-A-5-11442 disclose an azido polymer having an azide group in its side chain as a highly sensitive photosensitive resin.

[0005]

Although these azido polymers have high sensitivity, they still have problems such as complicated production and poor stability over time. Further, as a water-soluble photosensitive resin having high sensitivity and good stability over time, it is disclosed in Japanese Examined Patent Publication No.
A styrylpyridinium group pendant polyvinyl alcohol (abbreviated as SbQ-PVA) disclosed in JP-5761-A is known, but this photosensitive resin has poor water resistance and swells during development, so that sufficient resolution can be obtained. It has the drawback of not having it.

The present invention is intended to solve the above-mentioned conventional problems, and an object thereof is to provide a water-soluble photosensitive resin having high sensitivity, high resolution, good stability over time, and easy production. It is to provide a resin composition.

[0007]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that a polymer compound having a constitutional unit represented by the following general formula (I) and a cation in the molecule It was found that a photosensitive resin composition containing a sensitizer having a group can achieve the object, and based on this, the present invention has been completed. The structure of the present invention based on such findings is characterized by containing a polymer compound having a structural unit represented by the following general formula (I) and a sensitizer having a cationic group in the molecule.

[Chemical 2]

Further, in the above-mentioned photosensitive resin composition, n in the general formula (I) is 0.

Further, in the above-mentioned photosensitive resin composition, the cation group of the sensitizer having a cation group in the molecule is a quaternary ammonium group.

The present invention will be described in detail below.

The polymer compound having the structural unit represented by the general formula (I) used in the composition of the present invention is
Saponified poly (vinyl acetate) or water-soluble copolymer of vinyl alcohol and other vinyl compound, aldehyde represented by the following (II), or

[Chemical 3] It can be easily obtained by reacting an acetal represented by the following general formula (III) under an acid catalyst.

[Chemical 4]

The saponified polyvinyl acetate used in the above reaction is, for example, an average degree of polymerization of 200 to 5,000.
Those having a saponification degree of 0 to 60 to 100% are preferably used. Here, the average degree of polymerization is set to 200 to 5,000, because when the degree of polymerization is less than 200, sufficient sensitivity cannot be obtained, and when it is more than 5,000, the solution of the photosensitive composition is Viscosity increases, and coating properties deteriorate
If the composition solution is used at a low concentration in order to avoid this, it becomes difficult to obtain a desired coating film thickness, and both are not preferable. Further, the saponification degree is 60 to 100.
The definition of "%" is because when the saponification degree is lower than 60%, sufficient water solubility and water developability cannot be obtained. As the saponified polyvinyl acetate, for example, modified polyvinyl acetate saponified by hydrophilic group modification, lipophilic group modification, anion modification, cation modification, or reactive group modification such as acetoacetyl group can be used.

Examples of vinyl monomers copolymerizable with vinyl alcohol include N-vinylpyrrolidone and acrylamide.

When reacting such saponified polyvinyl acetate with the compound of the general formula (II) or (III) in the presence of an acid catalyst, for example, formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, benzaldehyde, etc. The aldehydes or the acetals thereof can be simultaneously reacted.

The introduction ratio of the azide compound of the general formula (I) or (II) to the saponified polyvinyl acetate is preferably about 0.1 to 5.0 mol% per monomer unit. Here, the introduction rate is set to about 0.1 to 5.0 mol% per monomer unit, because when it is less than 0.1 mol%, a sufficient cured film cannot be obtained, and when it is more than 5.0 mol%, the azide is decomposed. This is because the generation of nitrogen gas increases and the adhesion of the photosensitive film to the substrate decreases.

N in the general formulas (II) and (III) is 0.
Although they may be 1 or 2, these may be used alone or as a mixture, or a reaction mixture of an aldehyde with n = 0 and acetaldehyde may be used as it is. In particular, n = 0
When the reaction mixture of the aldehyde and acetaldehyde is used, its production becomes easy. Further, n = 1 and 2 are preferable in that the photoreactivity is further improved because the absorption wavelength is longer than that of the n = 0 azide compound.

X in the general formula (I) represents a cation species, and examples thereof include Li, Na, K and ammonium.

The sensitizer used in the composition of the present invention is a sensitizer having at least one cation group such as ammonium group, phosphonium group, sulfonium group and oxonium group in the molecule. An ammonium group is preferable because it is easy. Specific preferred examples (S-1 to S-25) of such a sensitizer are shown below.

[0019]

[Chemical 5]

[0020]

[Chemical 6]

[0021]

[Chemical 7]

[0022]

[Chemical 8]

[0023]

[Chemical 9]

[0024]

[Chemical 10]

[0025]

[Chemical 11]

In the composition of the present invention, the compounding ratio of the sensitizer having a cationic group in the molecule to the structural unit represented by the general formula (I) is preferably about 10 to 90 mol%. If it is less than 10 mol%, some sensitizing effect can be obtained, but it is not preferable in that the photoreaction rate of the azide group is slow and the performance of the introduced azide group is not sufficiently exhibited. This is because if it exceeds the range, the water developability is lowered and the adhesiveness to the substrate is lowered, which is not preferable. Further, even if it is added in an amount of about 90 mol% or more, no further sensitizing effect can be obtained.

The composition of the present invention may be further blended with a polymer compound other than the above-mentioned polymer compounds, particularly a polymer compound containing azide group such as pyrrolidone or amide structure and a group susceptible to photoreaction. It can also increase sensitivity. Examples of this polymer compound include polyvinylpyrrolidone, a copolymer of diacetone acrylamide and acrylamide, and polyacrylamide.

Further, the composition of the present invention has the following properties:
Polymeric emulsions can be mixed to improve properties such as water resistance. Examples of such polymer emulsions include polyvinyl acetate emulsion, vinyl acetate-ethylene copolymer emulsion, vinyl acetate-acrylic acid ester copolymer emulsion, polystyrene emulsion, ethylene-butadiene copolymer emulsion, styrene-acryl. Examples thereof include acid ester copolymer emulsion, acetonitrile-butadiene copolymer emulsion, chloroprene polymer emulsion, polyvinyl chloride emulsion, silicone resin emulsion, polyurethane emulsion and the like.

In the composition of the present invention, if necessary,
Surfactants that improve coatability and developability, adhesion aids that improve adhesion, dyes and pigments that prevent halation, storage stabilizers, defoamers, and the like can be appropriately added.

The composition of the present invention comprises the above-mentioned polymer compound having an azido group in the side chain, a sensitizer having a cationic group in the molecule and, if necessary, various compounding agents in a solvent containing water as a main component. It can be prepared by dissolving or dispersing in.

As the solvent used at this time, water is generally used, and a solvent soluble in water at a ratio of 50% by weight or less, such as methyl alcohol, ethyl alcohol, isopropyl alcohol, acetone, tetrahydrofuran, Water-soluble agents such as dioxane, dimethylformamide and N-methylpyrrolidinone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and the like can be added.

The photosensitive resin composition of the present invention obtained as described above is a metal plate such as aluminum or stainless steel, a screen mesh, paper, a glass plate, a semiconductor substrate, or any other base material depending on the application. On top, for example 0.5-10
It is applied so as to have a dry thickness of 00 μm, dried and used.

These coatings have ultraviolet rays, for example, a wavelength of 3
After irradiating the irradiated part with an actinic ray such as 0 to 500 nm to cure the irradiated part, the non-irradiated part is removed with water or the like to obtain a pattern image. It can be used as a fluorescent material pattern formation, a color filter for CCD and LCD, a color proof for printing, various etching resists and the like.

[0034]

EXAMPLES Next, the contents of the present invention will be described in more detail with reference to examples.

(Synthesis Example) Synthesis Example 1 <Polymer compound P-1 containing an azide group> 50 g of polyvinyl alcohol (GH-17: manufactured by Nippon Synthetic Chemical Industry) was dissolved in 200 ml of water. 17% of a 2.4% aqueous solution of p-azidobenzaldehyde-o-sulfonic acid was added.
0 g was added and reacted at 50 ° C. for 10 hours. After the reaction, the mixture was cooled and 19.5 g of a 5% aqueous solution of NaOH was added, and the mixture was neutralized to complete the acetalization to obtain an aqueous solution of the polymer compound P-1. The aqueous solution was reprecipitated with acetone, and the rate of introduction of sodium p-azidobenzaldehyde-o-sulfonate into polyvinyl alcohol was measured by UV absorption, and it was 1.6 mol%.

Synthesis Example 2 <Polymer compound P-2 containing an azide group> 50 g of polyvinyl alcohol (EG-30: manufactured by Nippon Synthetic Chemical Industry) was dissolved in 200 ml of water. 1.03 g of sodium p-azidobenzaldehyde-o-sulfonate and 2.4 of p-azidobenzaldehyde-o-sulfonic acid
% Aqueous solution (170 g) was added and reacted at 30 ° C. for 24 hours. After the reaction, the mixture was cooled and 19.5 g of a 5% NaOH aqueous solution was added, and the mixture was neutralized to complete acetalization to obtain an aqueous solution of polymer compound P-2. The aqueous solution was reprecipitated with acetone, and the rate of introduction of sodium p-azidobenzaldehyde-o-sulfonate into polyvinyl alcohol was measured by UV absorption, and it was 2.0 mol%.

Synthesis Example 3 <Polymer compound P-3 containing azido group> 10 g (0.046 mol) of sodium p-azidobenzaldehyde-o-sulfonate and acetaldehyde 10.
14 g (0.23 mol) was dissolved in 160 ml of water. After cooling this to 2 to 3 ° C., 9.2 g of a 10% sodium hydroxide aqueous solution was added, and the mixture was further treated at 2 to 3 ° C. for 4 hours and further 60
The reaction was carried out by stirring for 1 hour and a half at ° C. Salt was added to the obtained reaction mixture for salting out, followed by purification from isopropyl alcohol / water to obtain orange crystals. When the crystals were analyzed by high performance liquid chromatography, they were found to be sodium p-azidoaldehyde-o-sulfonate (general formula (II)
In, n = 0 and X = Na. ) 38.5%, p
-Azidocinnamaldehyde-sodium o-sulfonate (n = 1, X = Na in the general formula (II))
34.2%, and in the general formula (II), it was shown to be a mixture of 15.6% of aldode having n = 2 or more (X = Na). 50 g of polyvinyl alcohol (EG-30: manufactured by Nippon Synthetic Chemical Industry) was dissolved in 200 ml of water, and 4.3 g of the above orange crystals and 1.5 of phosphoric acid were dissolved in the solution.
g was added and reacted at 40 ° C. for 15 hours. The reaction mixture was treated with an ion exchange resin to remove the phosphoric acid catalyst to prepare an aqueous solution of polymer compound P-3 containing an azide group.

Synthesis Example 4 <Polymer compound P-4 containing azide group> Synthesis Example 2 except that EG-30 of Synthesis Example 2 was changed to acrylamide-modified polyvinyl alcohol (EP-240: manufactured by Denki Kagaku Kogyo). By operating in exactly the same manner, an aqueous solution of polymer compound P-4 containing an azide group was obtained.

Synthesis Example 5 <Polymer compound P-5 containing azide group> 50 g of polyvinyl alcohol (GH-17: manufactured by Nippon Synthetic Chemical Industry) was dissolved in 200 ml of water. 170 g of a 2.4% aqueous solution of sodium p-azidobenzaldehyde-o-sulfonate and 3.6 g of crotonaldehyde were added,
The reaction was carried out at 30 ° C for 24 hours. After the reaction, the mixture was cooled and neutralized with 19.5 g of a 5% aqueous sodium hydroxide solution to obtain an aqueous solution of polymer compound P-5 containing an azide group.

[Examples 1 to 20] Next, the above Synthesis Examples 1 to 5
Examples 1 to 20 and Comparative Examples 1 to 3 were carried out using the polymer compound obtained in.

Sensitivity Polymer compound P containing azide group obtained in Synthesis Examples 1 to 5
A photosensitive composition was prepared by mixing 10 g of an aqueous solution of -1 to P-4, a sensitizer having a cationic group shown in the table and 7 g of water, dissolving and filtering. These compositions were applied onto a glass substrate by spin coating and dried at 70 ° C. for 20 minutes to form a photosensitive layer having a film thickness of 1.2 μm. Illuminance 5.
0 mW / cm ² (UV illuminance meter UV-M manufactured by Oak Manufacturing Co., Ltd.
Exposure was performed through a Fuji step guide under the light of an ultra-high pressure mercury lamp (measured using a UV35 sensor at 01). After exposure, the film was washed with water for 1 minute and developed, the cured film was dyed with 1% methylene blue, and the sensitivity was evaluated by the number of curing steps. The results are shown in "Table 1".

[0042]

[Table 1] As can be seen from the results of Table 1, Examples 1 to 21 of the present invention
It was found that all of the photosensitive compositions according to (1) had higher sensitivity than those of Comparative Examples 1 to 3 in which no sensitizer was added.

Resolution Composition of Example 1 and SbQ-PVA (SPP-H-1)
3: manufactured by Toyo Gosei Co., Ltd.) was coated on a glass substrate and dried in the same manner as described above to form a photosensitive layer having a thickness of 1.2 μm. A chrome mask having a pattern of 50 μm was brought into close contact with the photosensitive layer, exposed, and developed with water. When the obtained pattern in 50 μm was observed with a Nomarski differential interference microscope, wrinkles were observed on the pattern surface with SbQ-PVA, but the pattern surface was clean with the composition of Example 1. Further, exposure was performed with a gap of 0.15 mm provided between the photosensitive layer and the chrome mask, and the same observation was performed, but a clear pattern was obtained with the composition of Example 1, but SbQ
-Multiple fringes were observed with PVA.

Examples 21 to 32 Next, Examples 21 to 32 were carried out using the polymer compound obtained in Synthesis Example 1 above. Polymer compound P-1 containing an azide group obtained in Sensitivity Synthesis Example 1
A photosensitizing composition was prepared by mixing 10 g of the above aqueous solution with a sensitizer and 7 g of water shown in Table 2, dissolving and filtering, and the sensitivity was evaluated by operating in exactly the same manner as in the above-mentioned Examples. The results are shown in "Table 2".

[0045]

[Table 2]

From the results of Table 2, Example 21 of the present invention was obtained.
It was demonstrated that the photosensitive resin compositions according to Nos. 32 to 32 have higher sensitivity than those of Comparative Example 1 in which the sensitizer was not added.

[0047]

As described above, the photosensitive resin composition of the present invention has high sensitivity, high resolution, good stability over time, and is easy to produce. For example, a screen printing plate or a black matrix of a color cathode ray tube. It is suitable for use as a phosphor pattern formation, a color filter for CCD and LCD, a color proof for printing, various etching resists, and the like.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hideo Kikuchi 563 Yonegasaki-cho, Funabashi-shi, Chiba Toyo Gosei Kogyo Co., Ltd.

Claims (3)

[Claims] 1. A photosensitive composition comprising a polymer compound having a structural unit represented by the following general formula (I) and a sensitizer having a cationic group in the molecule. [Chemical 1] 2. The photosensitive resin composition according to claim 1, wherein n in the general formula (I) is 0. 3. The photosensitive resin composition according to claim 1, wherein the cation group of the sensitizer having a cationic group in the molecule is a quaternary ammonium group.