JP3047580B2 - Negative photosensitive diazo resin and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aromatic diazo resin. More specifically, the present invention relates to a negative photosensitive diazo resin that exhibits good solubility even in non-cellosolve solvents.

[0002]

2. Description of the Related Art Aromatic diazo resins are applied to papers, films, metal plates and the like, and are widely used in copying papers, non-silver film, photosensitive printing plates, photoresists and the like.
In any of these, a diazo resin is dissolved in a solvent together with a binder polymer, a dye, a stabilizer and the like to form a photosensitive liquid, which is then applied to a medium according to the use, and then image formation is performed by exposure and development. Among them, diazo resins having an inorganic anion such as hexafluorophosphoric acid or tetrafluoroboric acid as anions of the photosensitive diazo resin are P
When combined with a dye whose color tone changes with H, it exhibits a vivid color tone change before and after exposure, thereby improving the workability of the photosensitive material and is particularly widely used. A diazo resin can be obtained by condensing a diazonium compound and a carbonyl compound in a known manner, for example, in concentrated sulfuric acid. No. 498) and the condensation temperature may be 70 ° C. or higher, but an advantageous temperature range is + 10 ° C. to + 50 ° C. (JP-B-49-480).
No. 01 gazette) and various other condensation methods are known, but the condensation is usually carried out on the plus side of Celsius even when the temperature is low. On the other hand, the most widely used solvent for photosensitive solutions containing photosensitive diazo resin is a cellosolve-based organic solvent. Conversion is required. Non-cellosolve solvents that are currently considered to be the most safe for the human body include propylene glycol alkyl ether and alkyl lactate.

[0003]

However, since the photosensitive diazo resin has a diazonium group having a high polarity, none of the non-cellosolve solvents has sufficient solubility in the photosensitive diazo resin, and particularly, the diazonium group Is insufficient when the anion is an inorganic anion, and at present it is difficult to find a satisfactory alternative solvent.
Therefore, development of a diazo resin having sufficient solubility in non-cellosolve solvents has been expected.

[0004]

The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems and obtain an excellent diazo resin. The inventors have found that the content of an element affects the solubility in a non-cellosolve solvent, and a method for producing a diazo resin capable of suppressing the content of the specific element to a low level. That is, an object of the present invention is to provide a photosensitive diazo resin having sufficient solubility even in a non-cellosolve solvent. Another object of the present invention is to provide a method for producing a photosensitive diazo resin having excellent solubility in a non-cellosolve solvent. It is a further object of the present invention to provide a safe and effective coating method when a diazo resin having sufficient solubility is used as a photoreceptor. Thus, an object of the present invention is to provide a negative photosensitive diazo resin condensed in a sulfuric acid catalyst, containing an aromatic diazonium compound in a structural unit, wherein the anion is an inorganic anion soluble in an organic solvent,
This is easily achieved by a negative photosensitive diazo resin characterized in that the amount of S element contained in the resin is 0.5% by weight or less. Hereinafter, the present invention will be described in detail.

[0005] The photosensitive diazo resin of the present invention is obtained by reacting a diazonium compound with an active carbonyl compound in a sulfuric acid catalyst. The aromatic diazonium compound used in the present invention is not limited, but specific examples thereof are described in JP-A-1-102456 and JP-A-1-10
No. 2457

TABLE 1 4-diazonium salt diphenylamine, 4-diazonium salt-4'-methoxydiphenylamine, 4-
Diazonium salt-4′-methyldiphenylamine, 4-
Diazonium salt-4'-chlorodiphenylamine, 3-
Diazonium salt-4,4'-dimethyldiphenylamine, 4-diazonium salt-2-carboxydiphenylamine, 1-diazonium salt-2-phenoxy-5-chlorobenzene, 1-diazonium salt-4-N, N'-dimethylaminobenzene, 1-diazonium salt-4-morpholinobenzene and the like.

[0006] The active carbonyl compound used in the present invention is not limited, but specific examples include formaldehyde, acetaldehyde, butyraldehyde and the like. An aromatic unit having a diazonium group is obtained by mixing aromatic compounds such as phenol 4-methoxybenzoic acid 4-hydroxybenzoic acid 1,4-dimethylol-benzene 4-hydroxycinnamic acid 2-phenoxy-ethanol which does not have a diazonium group. And a co-condensed diazo resin having an aromatic unit having no diazonium group.

In the photosensitive diazo resin of the present invention, the S component is incorporated into the resin during the condensation reaction in sulfuric acid. As a side reaction of the condensation reaction, the reaction between the solvent sulfuric acid and the diazonium compound occurs, and it is estimated that the S element is taken into the resin, but the S component taken in the condensation reaction undergoes subsequent ion exchange reactions many times. It is difficult to reduce even if repeated. When various methods for reducing the S component were examined, correlations with the temperature and the reaction time during the condensation were found. The temperature at the time of the condensation reaction needs to be 0 ° C. or lower. The reaction temperature is preferably from -20C to 0C, particularly preferably -1C.
0 ° C to 0 ° C is preferred.

The time required for dissolving the diazonium raw material in sulfuric acid and adding an active carbonyl compound such as formaldehyde to carry out condensation is not suitable for the condition of 2 hours or more as described in the known literature. It is desirable to shorten it within. By conducting the condensation reaction under such conditions, it is possible to obtain a photosensitive diazo resin having a low S component. The S component concentration is desirably 0.5% by weight or less, and more desirably 0.35% or less. The molar ratio of diazounium units to non-diazonium units is 4
A range of 0-90 to 60-10 is preferable, and a range of 50-80 to 50-20 is more preferable.

The weight average molecular weight of the diazo resin is in the range of 1,000 to 5,000, and more preferably 2,000 to 4,000.
Is desirable. If it is less than 2000, the sensitivity of the diazo resin may be insufficient, and if it is more than 4000, the developing speed may be slow. The diazo resin after the condensation reaction is
According to a conventional method, for example, an excess amount of alcohol is added to an aqueous solution to precipitate a diazo resin, which can be collected by filtration. After the completion of the condensation reaction, the anion component of the diazo resin can be freely changed by performing an anion exchange reaction by a method described in, for example, JP-A-3-87831. The anion component of the diazonium group of the diazo resin soluble in the organic solvent is not limited, but specific examples include hexafluorophosphoric acid, tetrafluoroboric acid, p-toluenesulfonic acid, and benzenesulfonic acid. Hexafluorophosphate or tetrafluoroborate anion, which has a clear color tone upon exposure, is particularly desirable.

[0010]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples unless it exceeds the gist thereof. Example 1 p-diazodiphenylamine sulfate 14.5 g (50 m
Mol) was dissolved in 40 g of concentrated sulfuric acid under ice-cooling.
(35 mmol) of paraformaldehyde was added over 1 hour so that the reaction temperature did not exceed -5 ° C. After stirring was continued for 2 hours under ice cooling, the mixture was added dropwise to 500 ml of ethanol, and the resulting precipitate was separated by filtration. After the precipitate was washed with ethanol, the precipitate was dissolved in 100 ml of water, and an aqueous solution in which 6.8 g of zinc chloride was dissolved was added. The resulting precipitate was separated by filtration, washed with ethanol, and dried at 25 ° C. for 3 hours. 15 g of a diazo resin zinc chloride double salt was obtained. 15 g of this double salt
After dissolving in 50 ml of water, an aqueous solution in which 8 g of ammonium hexafluorophosphate was dissolved was added, and the resulting precipitate was separated by filtration, washed with water and then with ethanol, and dried under reduced pressure overnight at 25 ° C. 12.5 g of diazo resin hexafluorophosphate (DR) was obtained. The weight average molecule of the obtained DR resin was 2,100, and the S concentration was 0.42% by weight.
When a 5% by weight methyl lactate solution was prepared, a clear solution was obtained within 5 minutes.

Comparative Example 1 In the same manner as in Example 1, except that the condensation reaction temperature was 11 ° C.
The weight average molecular weight and S concentration of the obtained DR resin were measured to be 2,000 and 0.91% by weight.
Although a 5% by weight methyl lactate solution was prepared, it did not completely dissolve even after 1 hour, resulting in an opaque solution.

Example 2 11 g of p-diazodiphenylamine sulfate (37.5 m
Mol), 1.73 g of p-hydroxy-benzoic acid (12.
(5 mmol) was dissolved in 44 g of concentrated sulfuric acid under ice-cooling, and then 1.4 g.
g (45 mmol) of paraformaldehyde was added over 1 hour, and a condensation reaction was carried out at 0 ° C. or lower. After stirring for 2 hours under ice cooling, the mixture was added dropwise to 340 ml of ethanol to precipitate a polymer, which was separated by filtration. After washing the precipitate with ethanol, the precipitate was dissolved in 90 ml of water, an aqueous solution in which 6.6 g of zinc chloride was dissolved was added, and the resulting precipitate was separated by filtration.
Washed with ethanol. This precipitate was dissolved in 200 ml of water, and an aqueous solution in which 6.1 g of ammonium phosphofluoride was dissolved was added to carry out a salt exchange reaction. The precipitate was precipitated while adding acetone dropwise, followed by filtration and washing with water and ethanol. The mixture was dried overnight under reduced pressure at ℃ ° C. to obtain 9.8 g of a composite diazo resin (DHR) having 75 mol% and 25 mol% of diazo units and hydroxybenzoic acid units, respectively. The weight average molecular weight of the obtained DHR resin is 3000, and the S concentration is 0.3.
When a 5% by weight methyl lactate solution was prepared, a clear solution was obtained within 5 minutes.

Comparative Example 2 The same conditions as in Example 2 were used, except that the condensation reaction was carried out at 10 ° C.
An R resin was obtained. A 5% by weight solution of methyl lactate in DHR was prepared, but it did not completely dissolve even after 1 hour, resulting in an opaque solution.

Example 3 11 g of p-diazodiphenylamine sulfate (37.5 m
Mol), 1.73 g of p-hydroxy-benzoic acid (12.
(5 mmol) was dissolved in 44 g of concentrated sulfuric acid under ice-cooling, and then 1.4 g.
g (45 mmol) of paraformaldehyde was added over 25 minutes, and a condensation reaction was performed at 0 ° C. or lower. After continuing stirring under ice cooling for 2 hours, the mixture was added dropwise to 340 ml of ethanol to precipitate a polymer, which was separated by filtration. After washing the precipitate with ethanol, the precipitate was dissolved in 90 ml of water, an aqueous solution in which 6.6 g of zinc chloride was dissolved was added, and the resulting precipitate was separated by filtration.
Washed with ethanol. This precipitate was dissolved in 200 ml of water, and an aqueous solution in which 6.1 g of ammonium fluoride was dissolved was added to carry out a salt exchange reaction. The precipitate was precipitated while adding acetone dropwise, followed by filtration and washing with water and ethanol. The mixture was dried under reduced pressure overnight at 9.0 ° C. to obtain a composite diazo resin (DHR) 9.0.
g was obtained. The weight average molecular weight of the obtained DHR resin is 29.
The S and S concentrations were 0.28% by weight, and when a 5% by weight ethyl lactate solution was prepared, a clear solution was obtained within 3 minutes.

[0015]

The photosensitive diazo resin of the present invention can exhibit good solubility in non-cellosolve solvents such as ketones such as cyclohexanone and methyl ethyl ketone, and esters such as propylene glycol monomethyl ether, methyl lactate and ethyl lactate. .

Continuation of front page (56) References JP-A-63-144092 (JP, A) JP-A-64-294391 (JP, A) JP-A-64-90451 (JP, A) JP-A-54-98613 (JP) JP-A-2-66 (JP, A) JP-A-2-4258 (JP, A) JP-A-2-29650 (JP, A) JP-A-2-219060 (JP, A) (58) Field surveyed (Int.Cl. ⁷ , DB name) G03F 7/021 C08G 8/08

Claims (2)

(57) [Claims] 1. A negative photosensitive diazo resin condensed in a sulfuric acid catalyst containing an aromatic diazonium compound in a structural unit, wherein the anion is an inorganic anion soluble in an organic solvent,
A negative photosensitive diazo resin, wherein the amount of S element contained in the resin is 0.5% by weight or less. 2. A method for producing a negative photosensitive diazo resin, comprising subjecting an aromatic diazonium compound and a carbonyl compound to a condensation reaction in a sulfuric acid catalyst at 0 ° C. or lower, and exchanging an anionic component for an inorganic anion.