JPH11228528A - Production of quinonediazide-sulfonic acid ester - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject ester useful for, e.g. photosensitive compounds by using an esterification solvent having both ester and ether groups, controlling side reactions, giving a high conversion, allowing the product to be easily isolated, and low in toxicity. SOLUTION: This ester is obtained by reacting a polyhydroxy compound having a repeating structure unit shown by the formula [R is H or methyl; and (n) is 2 or 3] with 1,2-naphthoquinonediazide-5-sulfonyl chloride and/or 1,2-naphthoquinonediazide-4-sulfonyl chloride for the esterification in the presence of a basic compound (e.g. triethylamine), wherein a compound having both ester and ether groups (e.g. ethyl ethoxypropionate) is used as the esterification solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a quinonediazidesulfonic acid ester. INDUSTRIAL APPLICABILITY The present invention can be used, for example, as a method for producing various quinonediazidesulfonic acid esters which are used as a photosensitive compound used for forming a photosensitive material.

[0002]

2. Description of the Related Art Quinonediazidesulfonic acid esters are:
It is used as a photosensitive compound for photosensitive materials such as photosensitive lithographic printing plates (referred to as PS plates). As a method for producing such a quinonediazidesulfonic acid ester,
Conventionally, there have been various proposals. A polyhydroxy compound and 1,2-naphthoquinonediazide-5-sulfonyl chloride and / or 1,2-naphthoquinonediazide-4-
In a method for obtaining a quinonediazidesulfonic acid ester by subjecting a sulfonyl chloride to an esterification reaction in the presence of a basic compound, 1,4-dioxane is generally used as a reaction solvent conventionally used in the reaction. is there. However, due to its toxicity, 1,4-dioxane is required to be changed to use of other solvents.

Acetone and tetrahydrofuran (THF) have also been used as solvents other than 1,4-dioxane, but have disadvantages in the reaction such as insufficient reaction conversion and easy side reaction to proceed. is there. Furthermore, when the reaction solution is poured into water to precipitate a product, there are operational inconveniences, such as a particle size of the precipitate being too small, or agglomeration into a candy-like form, which hinders the filtration operation. .

[0004] Therefore, there is a need for the development of an improved method of producing quinonediazide sulfonic acid esters which has less toxicity problems and which has reduced problems in reaction and operation.

[0005]

SUMMARY OF THE INVENTION According to the present invention, when a quinonediazide sulfonic acid ester is obtained by an esterification reaction, the progress of side reactions is small, the reaction conversion is excellent, and the isolation of the product is easy. An object of the present invention is to provide a method for producing a quinonediazidesulfonic acid ester using a low-toxic reaction solvent.

[0006]

An object of the present invention is to provide a polyhydroxy compound having a repeating structural unit represented by the general formula (1) (described in detail below), 1,2-naphthoquinonediazide-5-sulfonyl chloride and / Or 1,2-
Naphthoquinonediazide-4-sulfonyl chloride;
A method for producing a quinonediazidesulfonic acid ester by an esterification reaction in the presence of a basic compound, wherein a compound having both an ester group and an ether group is used as a reaction solvent for the esterification reaction. This is achieved by a method for producing a quinonediazidesulfonic acid ester.

The general formula (1) is as follows. In the following general formula (1), R represents a hydrogen atom or a methyl group. n is 2 or 3.

[0008]

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In the present invention, the polyhydroxy compound having a repeating structural unit represented by the general formula (1) includes polyhydroxybenzenes selected from pyrogallol and resorcinol, and carbonyl selected from formaldehyde and acetone. Examples include a polymer compound obtained by polycondensation with a compound. Preferably, a polycondensate of pyrogallol and acetone is used.

The naphthoquinonediazide compound which undergoes an esterification reaction with the polyhydroxy compound is 1,2-naphthoquinonediazide-5-sulfonyl chloride or
2-naphthoquinonediazide-4-sulfonyl chloride, both of which may be used in the reaction.

As the basic compound to be present at the time of the esterification reaction, either an inorganic base or an organic base can be used. Of the inorganic bases, preferably used are
Potassium carbonate, sodium carbonate, potassium acetate, sodium acetate, potassium hydroxide and sodium hydroxide.
Of the organic bases, preferably used are triethylamine, pyridine and N, N-dialkylaniline.

In the present invention, a compound having both an ester group and an ether group is used as a reaction solvent for the esterification reaction. As examples of such compounds, ethyl ethoxy propionate, methyl ethoxy propionate, methyl methoxy propionate, ethyl methoxy propionate, and methoxy ethyl acetate are preferably used.

In the present invention, for example, a quinonediazidesulfonic acid ester can be produced under the following reaction conditions.

That is, a polyhydroxy compound having a repeating structural unit represented by the general formula (1), 1,2-naphthoquinonediazido-5- (and / or -4-) sulfonyl chloride, is contained in the above-mentioned reaction solvent. After dissolution, a basic compound is added.

The basic compound is preferably 0.8 to 1.5 equivalents, more preferably 1.0 to 1.5 equivalents to 1,2-naphthoquinonediazide-5- (and / or -4-) sulfonyl chloride. It is good to add in the range of 1.3 equivalents.

With regard to the addition of a basic compound, if this addition is carried out rapidly, a side reaction is likely to proceed. Therefore, if necessary, the basic compound is dissolved in an appropriate diluting solvent, and then added slowly. Is preferred. After the addition of the basic compound, it is preferable to secure a reaction time necessary for the reaction to proceed sufficiently. The reaction is preferably performed at a temperature in the range of 5 ° C to 60 ° C.

In taking out the product after the reaction,
It is convenient and preferable to throw the reaction solution into water to which an acidic substance such as hydrochloric acid has been added, if necessary, to precipitate, collect by filtration and dry. When adding an acid to the water to which the reaction solution is poured, the acid to be added is in a range that maintains the acidity after the reaction solution is charged.
Preferably, the amount is small.

[0018]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will be described below. However, needless to say, the present invention is not limited by the embodiments described below.

EXAMPLE 1 400 ml of methoxyethyl acetate was placed in a 1000 ml three-necked flask equipped with a thermometer and a dropping funnel, and 16.62 g of a pyrogallol / acetone condensed resin having a weight average molecular weight of 2,500 was charged and stirred. Dissolved. After confirming dissolution, 1,2-naphthoquinonediazide-5
16.12 g of sulfonyl chloride was charged and dissolved by stirring. After dissolution, the reaction solution was heated to 40 ° C., and a solution of 7.29 g of triethylamine dissolved in 30 ml of methoxyethyl acetate was added dropwise to the reaction solution over 15 minutes. After the completion of the dropwise addition, the mixture was stirred for 45 minutes while maintaining the temperature of the reaction solution at 40 ° C., and the reaction was completed.

When the reaction solution at the end of the reaction was developed by TLC, the starting material, 1,2-naphthoquinonediazide-5, was obtained.
-No residual sulfonyl chloride was observed.

After the completion of the reaction, the reaction solution was slowly dropped into 1000 ml of water to which 1.6 ml of concentrated hydrochloric acid was added while stirring vigorously. As a result, a precipitate was obtained.
The precipitated resinous material had a large particle size, and could be easily filtered off with a 4A qualitative filter paper by suction filtration. The product is washed until the filtrate is neutral,
Dried for days. As a result, the photosensitive resin becomes 30.2
g was obtained.

The obtained photosensitive resin had a pale yellow color tone. 1.0 g of methyl cellosolve 100
When dissolved in milliliters and measured for absorption at 450 nm, the absorbance showed a low value of 0.15. As a result, it was found that there was almost no generation of a diazo coupling product as a by-product. The steps from the above reaction to the drying were all performed under illumination of a yellow fluorescent lamp in which the ultraviolet region was cut.

When triethylamine was used as in this example, the yield was higher than in the example using other basic compounds.

Example 2 In Example 1, 1,2-naphthoquinonediazide-5 was used.
1,2-Naphthoquinonediazide-4-sulfonyl chloride was used in place of -sulfonyl chloride, and the other conditions were the same. As a result, a similar photosensitive resin was obtained as in Example 1.

Example 3 In Example 1, 1,2-naphthoquinonediazide-5
In place of -sulfonyl chloride, an equivalent mixture of 1,2-naphthoquinonediazide-5-sulfonyl chloride and 1,2-naphthoquinonediazide-4-sulfonyl chloride was used, and the other steps were carried out in the same manner. As a result,
A similar photosensitive resin was obtained in the same manner as in Example 1.

In addition, when triethylamine is used as in each of these examples, compared with an example using another basic compound,
The yield was high.

Examples 4 to 7 In Example 1, instead of methoxyethyl acetate, solvents were ethyl ethoxypropionate (Example 4), methyl ethoxypropionate (Example 5),
Methyl methoxy propionate (Example 6) and ethyl methoxy propionate (Example 7) were used, respectively, and the other conditions were the same. As a result, a similar photosensitive resin was obtained as in Example 1.

In addition, when triethylamine is used as in each of these examples, compared with an example using another basic compound,
The yield was high.

Examples 8 to 15 In Example 1, potassium carbonate (Example 11), sodium carbonate (Example 12), potassium acetate (Example 13) and potassium carbonate (Example 11) instead of triethylamine were used as basic compounds.
Sodium acetate (Example 14), potassium hydroxide (Example 15), sodium hydroxide (Example 16), pyridine (Example 17), N, N-dialkylaniline (Example 18) in appropriate amounts It carried out similarly to use and others. As a result, a similar photosensitive resin was obtained as in Example 1.

Comparative Example 1 The procedure of Example 1 was repeated, except that the reaction solvent methoxyethyl acetate was replaced by tetrahydrofuran. All other operations were the same as in Example 1. As a result, the TLC development result of the reaction solution after the completion of the reaction showed
It was confirmed that 1,2-naphthoquinonediazide-5-sulfonyl chloride as a raw material remained. In addition, the particle size of the resin precipitated when the reaction solution was poured into an aqueous hydrochloric acid solution was small,
Eight times as long as in Example 1 was required for filtration by suction filtration. Further, the photosensitive resin after drying has a slightly reddish color tone, and has an absorbance of 0.48 in the absorbance measurement under the same conditions as in Example 1, indicating that the diazo-coupled product which is a side reaction product I was told that generation was taking place.

[0031]

As described above, the method for producing a quinonediazidesulfonic acid ester of the present invention provides a method for producing a quinonediazidesulfonic acid ester by an esterification reaction.
This is an advantageous method because the progress of side reactions is small, the reaction conversion is excellent, the product can be easily isolated, and a low-toxic reaction solvent can be used.

Claims (1)

[Claims] 1. A polyhydroxy compound having a repeating structural unit represented by the following general formula (1): 1,2-naphthoquinonediazide-5-sulfonyl chloride and / or 1,2-naphthoquinonediazide-4-sulfonyl chloride. And a method for producing a quinonediazidesulfonic acid ester by an esterification reaction in the presence of a basic compound, wherein a compound having both an ester group and an ether group is used as a reaction solvent for the esterification reaction. A method for producing a quinonediazidesulfonic acid ester, characterized by the following. General formula (1) R represents a hydrogen atom or a methyl group. n is 2 or 3.