U.S. patent application number 09/851008 was filed with the patent office on 2001-12-06 for method for producing 1,2-naphthoquinonediazide photosensitive agent.
Invention is credited to Hayakawa, Masamichi, Yamanaka, Tomotaka.
Application Number | 20010049433 09/851008 |
Document ID | / |
Family ID | 18643037 |
Filed Date | 2001-12-06 |
United States Patent
Application |
20010049433 |
Kind Code |
A1 |
Yamanaka, Tomotaka ; et
al. |
December 6, 2001 |
Method for producing 1,2-naphthoquinonediazide photosensitive
agent
Abstract
A method for producing a high-purity 1,2-naphthoquinonediazide
photosensitive agent containing a low level of impurities, by
condensing, in an organic solvent other than amide, polyhydric
phenolic compound and 1,2-naphthoquinonediazide-sulfonic acid
halide in the presence of organic amine; subsequently adding amide
solvent to the resultant reaction mixture; and separating the
resulting organic amine acid salt through filtration.
Inventors: |
Yamanaka, Tomotaka; (Chiba,
JP) ; Hayakawa, Masamichi; (Chiba, JP) |
Correspondence
Address: |
HUNTLEY & ASSOCIATES
1105 N. MARKET STREET
P. O. BOX 948
WILMINGTON
DE
19899-0948
US
|
Family ID: |
18643037 |
Appl. No.: |
09/851008 |
Filed: |
May 8, 2001 |
Current U.S.
Class: |
534/557 ;
430/193 |
Current CPC
Class: |
C07C 2602/10 20170501;
C07C 303/28 20130101; C07C 303/28 20130101; C07C 309/76
20130101 |
Class at
Publication: |
534/557 ;
430/193 |
International
Class: |
C07C 245/00; G03F
007/023 |
Foreign Application Data
Date |
Code |
Application Number |
May 8, 2000 |
JP |
2000-134836 |
Claims
We claim:
1. A method for producing 1,2-naphthoquinonediazide photosensitive
agent, comprising condensing, in organic solvent other than amide,
at least one polyhydric phenolic compound and at least one
1,2-naphthoquinonediazide-s- ulfonic acid halide in the presence of
organic amine; subsequently adding amide solvent to the resultant
reaction mixture; and filtering off the formed organic amine acid
salt.
2. A method for producing 1,2-naphthoquinonediazide photosensitive
agent, comprising condensing, in organic solvent other than amide,
at least one polyhydric phenolic compound and at least one
1,2-naphthoquinonediazide-s- ulfonic acid halide in the presence of
organic amine; subsequently adding amide solvent to the resultant
reaction mixture; further adding volatile acid so as to render the
resultant reaction mixture acidic; and filtering off the resulting
organic amine acid salt.
3. A method for producing 1,2-naphthoquinonediazide photosensitive
agent, comprising condensing, in organic solvent other than amide,
at least one polyhydric phenolic compound and at least one
1,2-naphthoquinonediazide-s- ulfonic acid halide in the presence of
organic amine; subsequently adding amide solvent to the resultant
reaction mixture; further adding volatile acid so as to render the
resultant reaction mixture acidic; filtering off the resulting
organic amine acid salt; pouring the resultant filtrate into pure
water or an aqueous solution of a volatile acid, to thereby form
precipitates; and collecting the precipitates through
filtration.
4. A method for producing a 1,2-naphthoquinonediazide
photosensitive agent according to claim 1, wherein the amide
solvent is at least one amide selected from N-methylpyrrolidone,
N,N-dimethylformamide, N,N-dimethylacetamide, and
N,N-dimethylimidazolidinone.
5. A method for producing a 1,2-naphthoquinonediazide
photosensitive agent according to claim 2, wherein the amide
solvent is at least one amide selected from N-methylpyrrolidone,
N,N-dimethylformamide, N,N-dimethylacetamide, and
N,N-dimethylimidazolidinone.
6. A method for producing a 1,2-naphthoquinonediazide
photosensitive agent according to claim 3, wherein the amide
solvent is at least one amide selected from N-methylpyrrolidone,
N,N-dimethylformamide, N,N-dimethylacetamide, and
N,N-dimethylimidazolidinone.
7. A method for producing a 1,2-naphthoquinonediazide
photosensitive agent according to claim 1, wherein the organic
solvent used in the condensation step is at least one selected from
acetone, 1,4-dioxane, 1,3-dioxolane, THF, .gamma.-butyrolactone,
and propylene carbonate.
8. A method for producing a 1,2-naphthoquinonediazide
photosensitive agent according to claim 2, wherein the organic
solvent used in the condensation step is at least one selected from
acetone, 1,4-dioxane, 1,3-dioxolane, THF, .gamma.-butyrolactone,
and propylene carbonate.
9. A method for producing a 1,2-naphthoquinonediazide
photosensitive agent according to claim 3, wherein the organic
solvent used in the condensation step is at least one selected from
acetone, 1,4-dioxane, 1,3-dioxolane, THF, .gamma.-butyrolactone,
and propylene carbonate.
10. A method for producing a 1,2-naphthoquinonediazide
photosensitive agent according to claim 4, wherein the organic
solvent used in the condensation step is at least one selected from
acetone, 1,4-dioxane, 1,3-dioxolane, THF, .gamma.-butyrolactone,
and propylene carbonate.
11. A method for producing a 1,2-naphthoquinonediazide
photosensitive agent according to claim 5, wherein the organic
solvent used in the condensation step is at least one selected from
acetone, 1,4-dioxane, 1,3-dioxolane, THF, .gamma.-butyrolactone,
and propylene carbonate.
12. A method for producing a 1,2-naphthoquinonediazide
photosensitive agent according to claim 6, wherein the organic
solvent used in the condensation step is at least one selected from
acetone, 1,4-dioxane, 1,3-dioxolane, THF, .gamma.-butyrolactone,
and propylene carbonate.
Description
BACKGROUND OF THE INVENTION
[0001] The present invention relates to a method for producing
1,2-naphthoquinonediazide photosensitive agent used in a
positive-type photoresist.
[0002] Positive-type photo resists containing an alkali-soluble
resin and a 1,2-naphthoquinonediazide photosensitive agent are
materials known to have excellent resolution, sensitivity, and
etching resistance, and are used for producing semiconductor
elements and liquid crystal elements. Generally, the photosensitive
agent used in such a positive-type photoresist can be obtained
through esterification between a polyhydric phenolic compound
having hydroxyl groups and a 1,2-naphthoquinonediazide-- sulfonic
acid halide. In recent years, miniaturization of semiconductor
elements has imposed a requirement for a strict control of the
level of impurities in photoresists. Accordingly, there is demand
for reducing the impurity level of the 1,2-naphthoquinonediazide
photosensitive agent used in the photoresists.
[0003] Japanese Patent Application Laid-Open (kokai) No. 8-328247
discloses one previous method for producing a
1,2-naphthoquinonediazide. There, polyhydric phenolic compound and
a 1,2-naphthoquinonediazide-sulfo- nic acid halide are subjected to
a condensation reaction in an organic solvent in the presence of an
organic amine; the resultant reaction mixture is neutralized; the
formed organic amine acid salt is filtered off; and the filtrate is
poured into an aqueous acidic solution. However, this method
results in the presence of organic amine, acid, or organic amine
acid salt which cannot be removed to a satisfactory degree of
purity.
[0004] A 1,2-naphthoquinonediazide photosensitive agent containing
a low level of impurities may be obtained if the aforementioned
condensation is performed in an amide solvent serving as a reaction
solvent, then neutralizing the resultant reaction mixture,
filtering off the formed organic amine acid salt, and pouring the
filtrate into an aqueous acidic solution. However, this method is
also deficient in that a 1,2-naphthoquinonediazide-sulfonic acid
halide is decomposed in amide solvent, and the resulting
1,2-naphthoquinonediazide-sulfonic acid remains as an impurity in
the resulting photosensitive agent product.
[0005] Accordingly, a continuing need exists for a process which
provides 1,2-naphthoquinonediazide photosensitive agent containing
very small amounts of impurities such as an organic amine, an acid,
or acid salts of the organic amine, and
1,2-naphthoquinonediazide-sulfonic acid.
SUMMARY OF THE INVENTION
[0006] The present invention is based on the discovery that a
high-purity 1,2-naphthoquinonediazide photosensitive agent
containing a low level of impurities can be obtained by condensing,
in an organic solvent other than amide, at least one polyhydric
phenolic compound and at least one
1,2-naphthoquinonediazide-sulfonic acid halide in the presence of
an organic amine; subsequently adding an amide solvent to the
resultant reaction mixture; and filtering off the formed organic
amine hydrohalide salt.
[0007] Accordingly, the present invention provides a method for
producing 1,2-naphthoquinonediazide photosensitive agent,
comprising condensing, in organic solvent other than amide, at
least one polyhydric phenolic compound and at least one
1,2-napthoquinonediazide-sulfonic acid halide in the presence of
organic amine; subsequently adding amide solvent to the resultant
reaction mixture; and filtering off the formed organic amine acid
salt.
[0008] In an alternative embodiment of the invention, there is
provided a method for producing 1,2-naphthoquinonediazide
photosensitive agent, comprising condensing, in organic solvent
other than amide, at least one polyhydric phenolic compound and at
least one 1,2-naphthoquinonediazide-s- ulfonic acid halide in the
presence of organic amine; subsequently adding amide solvent to the
resultant reaction mixture; further adding volatile acid so as to
render the resultant reaction mixture acidic; and filtering off the
formed organic amine acid salt.
[0009] In still another embodiment of the present invention, there
is provided a method for producing 1,2-naphthoquinonediazide
photosensitive agent, comprising condensing, in organic solvent
other than amide, at least one polyhydric phenolic compound and at
least one 1,2-naphthoquinonediazide-sulfonic acid halide in the
presence of organic amine; subsequently adding amide solvent to the
resultant reaction mixture; further adding volatile acid so as to
render the resultant reaction mixture acidic; filtering off the
formed organic amine acid salt; pouring the resultant filtrate into
pure water or an aqueous solution of a volatile acid, to thereby
form precipitates; and collecting the precipitates through
filtration.
DETAILED DESCRIPTION OF THE INVENTION
[0010] According to the present invention, a
1,2-naphthoquinonediazide photosensitive agent can be obtained by
condensing, in organic solvent other than amide, at least one
polyhydric phenolic compound and at least one
1,2-naphthoquinonediazide-sulfonic acid halide in the presence of
organic amine; subsequently adding amide solvent to the resultant
reaction mixture; and filtering off the formed organic amine acid
salt.
[0011] Representative polyhydric phenolic compounds which can be
used in the instant process include benzophenones such as
2,3,4-trihydroxybenzoph- enone, 2,3,4,4'-tetrahydroxybenzophenone,
2,2',4,4'-tetrahydroxybenzopheno- ne,
2,2',3,4,4'-pentahydroxybenzophenone, and
2,3,3',4,4'-pentahydroxybenz- ophenone; gallic acid alkyl esters;
bis((poly)hydroxyphenyl)alkanes such as
bis(4-hydroxy-2-methylphenyl)methane,
bis(2,6-dimethyl-4-hydroxyphenyl- )methane,
1,1-bis(4-hydroxyphenyl)cyclohexane, bis(2,4-dihydroxyphenyl)met-
hane, 2,2-bis(2,4-dihydroxyphenyl)propane,
bis(2,4-dimethyl-3-hydroxypheny- l)methane,
(4-hydroxyphenyl)(2,3,4-hydroxyphenyl)methane, and
2-(4-hydroxyphenyl)-2-(2,3,4-hydroxyphenyl)propane;
polyhydroxytriphenylalkanes disclosed, for example, in Japanese
Patent Application Laid-Open (kokai) Nos. 3-142468, 3-158856,
4-29242, and 4-282454; polyhydroxybenzopyrans disclosed in Japanese
Patent Application Laid-Open (kokai) No. 3-215863;
polyhydroxyindanes disclosed, for example, in Japanese Patent
Application Laid-Open (kokai) Nos. 3-215862 and 6-95374;
polyhydroxycoumarones disclosed in Japanese Patent Application
Laid-Open (kokai) Nos. 3-185447 and 7-56331; polyhydroxyphthalides
disclosed in Japanese Patent Application Laid-Open (kokai) No.
5-27429; polyhydroxycoumarins disclosed in Japanese Patent
Application Laid-Open (kokai) No. 5-27428; and polynuclear phenols
disclosed, for example, in Japanese Patent Publication (kokoku) No.
4-502519 and Japanese Patent Application Laid-Open (kokai) Nos.
3-48249, 6-167805, 7-104465, 7-104467, 7-159989, 7-159990,
7-168355, 7-175213, 7-219920, 7-225476, 7-230166, 8-29978,
8-202031, 8-245461, and 8-320558. These polyhydric phenolic
compounds can be used in reaction singly or in combination of two
or more species.
[0012] Examples of 1,2-naphthoquinonediazide-sulfonic acid halides
which can be used in the instant process include
1,2-naphthoquinonediazide-4-su- lfonyl chloride,
1,2-naphthoquinonediazide-5-sulfonyl chloride, and
1,2-naphthoquinonediazide-6-sulfonyl chloride. These
1,2-naphthoquinonediazide-sulfonic acid halides can be used singly
or in combination of two or more.
[0013] Examples of organic amines which can be used in the instant
process include ethylamine, diethylamine, triethylamine,
diisopropylamine, tripropylamine, triisobutylamine,
triethanolamine, monomethyldicyclohexylamine, N-methylpiperidine,
N-methylmorpholine, N-methylpyrrolidine, 1,4-dimethylpiperazine,
pyridine, N,N-dimethylaniline, and N,N-dimethylaminopyridine. These
amines can be used singly or in combination of two or more.
[0014] The reaction solvent used in the present invention is an
organic solvent other than amide. Examples of preferred organic
solvents include acetone, 1,4-dioxane, 1,3-dioxolane,
tetrahydrofuran (THF), .gamma.-butyrolactone, and propylene
carbonate. These specific solvents are preferred. These solvents
can be used singly or in combination of two or more.
[0015] After condensation is completed, amide solvent is added.
Examples of preferred amide solvents which can be used include
N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide,
and N,N-dimethylimidazolidinone, and at least one species selected
therefrom is used. Especially preferred amide solvents which can be
used include N-methylpyrrolidone, N,N-dimethylformamide,
N,N-dimethylacetamide and N,N-dimethylimidazolidinone.
[0016] In a typical procedure, at least one polyhydric phenolic
compound and at least one 1,2-naphthoquinonediazide-sulfonic acid
halide are dissolved in solvent, and, to the resultant solution,
organic amine or a solution of organic amine in solvent is added,
to thereby effect a condensation reaction. Alternatively,
polyhydric phenolic compound and organic amine can be dissolved in
solvent, and, to the resultant solution,
1,2-naphthoquinonediazide-sulfonic acid halide or a solution of the
halide in a solvent is added. Subsequently, the resultant mixture
is allowed to react for about ten minutes to five hours with
stirring. Combining the two solutions for effecting condensation is
performed at the temperature range of about from -10.degree. C. to
40.degree. C., preferably at about 10-35.degree. C., and
condensation is carried out over a period of about from ten minutes
to three hours.
[0017] The 1,2-naphthoquinonediazide-sulfonic acid halide is added
in an amount of about 0.3-1.1 mol, preferably about 0.5-1.0 mol,
based on 1 equivalent, in terms of hydroxyl group, of the
polyhydric phenolic compound. When the amount is less than about
0.3 mol, the photoresist formed from an alkali-soluble resin
exhibits poor contrast, whereas when the amount is greater than
about 1.2 mol, unreacted 1,2-naphthoquinonediazide-sulfonic acid
halide is prone to remain. The organic amine is added typically in
an amount of about 1.0-1.5 mol, preferably about 1.05-1.2 mol based
on 1 mol of the 1,2-naphthoquinonediazide-sulfonic acid halide.
When the amount is less than about 1.0 mol,
1,2-naphthoquinonediazide-sulfonic acid halide is prone to remain,
whereas when the amount is in excess of about 1.5 mol, a
1,2-quinonediazide moiety is readily decomposed by an excessive
organic amine. The solvent is used in an amount equal to about 2-10
times, preferably about 3-5 times, the total weight of the
1,2-naphthoquinonediazide-sulfonic acid halide and the polyhydric
phenolic compound. When the amount is less than about 2 times the
total weight, dissolution of a reaction component might be
incomplete, and storage stability, good storage stability being one
object of the present invention, becomes poor. When the amount of
in excess of about 10 times the total weight, a large amount of
water is required to cause re-precipitation, which is economically
disadvantageous.
[0018] After condensation is complete, amide solvent is added. The
amide solvent is used in an amount by weight preferably about 0.2-2
times, more preferably about 0.25-1 times, the weight of the
solvent employed for condensation. When the amount is less than
about 0.2 times the weight, sufficient effects of the present
invention cannot be attained, whereas when the amount is about 2
times or more the weight, a large amount of water is required to
cause re-precipitation, which is economically disadvantageous.
[0019] After addition of the amide solvent to the reaction mixture
is complete, the resulting organic amine acid salt is separated off
through filtration. Preferably, the reaction mixture is rendered
acidic by adding a volatile acid prior to filtration and
subsequently separating off the formed organic amine acid salt
through filtration. Examples of volatile acid which can be so used
in acidification include hydrochloric acid, acetic acid, and formic
acid. The volatile acid is added in an amount, represented by the
ratio of (1,2-naphthoquinonediazide-sulfonic acid halide/mol+acid
to be added/mol) to (organic amine/mol), of about 1.0-1.5,
preferably about 1.02-1.15.
[0020] After removal of the organic amine acid salt through
filtration, the reaction mixture is poured into pure water or an
aqueous solution of a volatile acid, to thereby re-precipitate a
1,2-naphthoquinonediazide photosensitive agent. The re-precipitated
1,2-naphthoquinonediazide photosensitive agent is then filtered
off, washed with pure water or a diluted aqueous solution of acid,
and dried, to thereby yield the desired 1,2-naphthoquinonediazide
photosensitive agent. In a typical procedure, the reaction mixture
is poured into pure water, to thereby re-precipitate the
photosensitive agent, and the re-precipitated
1,2-naphthoquinonediazi- de photosensitive agent is separated
through filtration. However, pouring the reaction mixture into an
aqueous acidic solution is preferred so as to facilitate
filtration, since use of pure water might make filtration
difficult. Examples of preferred acids to render the reaction
mixture weakly acidic include volatile acids such as hydrochloric
acid, acetic acid, and formic acid. The diluted aqueous acidic
solution has an acid concentration of approximately 0.02-0.5 N. The
amount of pure water or the aqueous acidic solution used for
re-precipitation is about 2-10 times the weight of the organic
solvent used, preferably about 3-6 times. The re-precipitated
photosensitive agent is separated through filtration, washed with
pure water or a diluted aqueous acidic solution, and dried in
vacuum, to thereby remove the volatile acid.
[0021] The present invention is still more fully described in the
following examples, which are representative and should not be
construed as limiting the invention.
EXAMPLES
Example 1
Comparative Production Example 1
[0022] Into a three-neck flask, 2,3,4,4'-tetrahydroxybenzophenone
(31 g), 1,2-naphthoquinonediazide-5-sulfonyl chloride (85.5 g), and
tetrahydroifuran (570 g) were placed, and the resultant mixture was
dissolved, to thereby provide a homogeneous solution. Subsequently,
a mixture of triethylamine/tetrahydrofuran (35.4 g/35.4 g) was
added dropwise to the solution at 30-35.degree. C. over one hour.
Thirty minutes after completion of addition, 35% hydrochloric acid
(6.6 g) was added dropwise to the resultant mixture. The formed
triethylamine hydrochloride was separated off through filtration.
The resultant filtrate was poured into a 0. 1% aqueous hydrochloric
acid solution (3,000 ml) maintained at 30-35.degree. C. The formed
precipitates were collected through filtration, washed with water,
and dried at 45.degree. C., to thereby yield 100 g of a
2,3,4,4'-tetrahydroxybenzophenone
1,2-naphthoquinonediazide-5-sulfonate ester.
Production Example 1
[0023] Into a three-neck flask, 2,3,4,4'-tetrahydroxybenzophenone
(31 g), 1,2-naphthoquinonediazide-5-sulfonyl chloride (85.5 g), and
tetrahydrofuran (450 g) were placed, and the resultant mixture was
dissolved, to thereby provide a homogeneous solution. Subsequently,
a mixture of triethylamine/tetrahydrofiran (35.4 g/35.4 g) was
added dropwise to the solution at 30-35.degree. C. over one hour.
Thirty minutes after completion of addition, N,N'-dimethylacetamide
(100 g) was added to the resultant mixture. Further, 30 minutes
after addition of the amide was complete, 35% hydrochloric acid
(6.6 g) was added dropwise to the resultant mixture. The formed
triethylamine hydrochloride was separated off through filtration.
The resultant filtrate was poured into a 0.1% aqueous hydrochloric
acid solution (2,800 ml) maintained at 20-25.degree. C. The formed
precipitates were collected through filtration, washed with water,
and dried at 45.degree. C., to thereby yield 100 g of a
2,3,4,4'-tetrahydroxybenzophenone
1,2-naphthoquinonediazide-5-sulfonate ester.
[0024] The chloride ion content of the photosensitive agent
obtained in Comparative Production Example 1 and that obtained in
Production Example 1 were measured. As shown in Table 1, the
chloride ion content of the photosensitive agent obtained in
Production Example 1 according to the present invention is
remarkably low.
1 TABLE 1 Chloride ion content Comparative Production Example 1 230
ppm Production Example 1 .ltoreq.10 ppm
Example 2
Comparative Production Example 2
[0025] Into a three-neck flask, 2,3,4,4'-tetrahydroxybenzophenone
(29 g), 1,2-naphthoquinonediazide-5-sulfonyl chloride (95 g), and
1,3-dioxolane (600 g) were placed, and the resultant mixture was
dissolved, to thereby prepare a homogeneous solution. Subsequently,
a mixture of triethylamine/dioxane (39.4 g/39.4 g) was added
dropwise to the solution at 30-35.degree. C. over one hour. Thirty
minutes after completion of addition, 35% hydrochloric acid (7.4 g)
was added dropwise to the resultant mixture. The formed
triethylamine hydrochloride was separated off through filtration.
The resultant filtrate was poured into a 0. 1% aqueous hydrochloric
acid solution (3,000 ml) maintained at 30-35.degree. C. The formed
precipitates were collected through filtration, washed with water,
and dried at 45.degree. C., to thereby yield 100 g of a
2,3,4,4'-tetrahydroxybenzophenone
1,2-naphthoquinonediazide-5-sulfonate ester.
Production Example 2
[0026] Into a three-neck flask, 2,3,4,4'-tetrahydroxybenzophenone
(29 g), 1,2-naphthoquinonediazide-5-sulfonyl chloride (95 g), and
1,3-dioxolane (400 g) were placed, and the resultant mixture was
dissolved, to thereby prepare a homogeneous solution. Subsequently,
a mixture of triethylamine/1,3-dioxolane (39.4 g/39.4 g) was added
dropwise to the solution at 30-35.degree. C. over one hour. Thirty
minutes after completion of addition, N-methylpyrrolidone (100 g)
was added to the resultant mixture. Further, 30 minutes after
addition of N-methylpyrrolidone, 35% hydrochloric acid (7.4 g) was
added dropwise to the mixture. The formed triethylamine
hydrochloride was separated off through filtration. The resultant
filtrate was poured into a 0.1% aqueous hydrochloric acid solution
(2,800 ml) maintained at 20-25.degree. C. The formed precipitates
were collected through filtration, washed with water, and dried at
45.degree. C., to thereby yield 100 g of a
2,3,4,4'-tetrahydroxybenzophenone
1,2-naphthoquinonediazide-5-sulfonate ester.
[0027] The chloride ion content of the photosensitive agent
obtained in Comparative Production Example 2 and that obtained in
Production Example 2 were measured. As shown in Table 2, the
chloride ion content of the photosensitive agent obtained in
Production Example 2 according to the present invention is
remarkably low.
2 TABLE 2 Chloride ion content Comparative Production Example 2 270
ppm Production Example 2 15 ppm
Example 3
Comparative Production Example 3
[0028] Into a three-neck flask, 2,3,4-trihydroxybenzophenone (35
g), 1,2-naphthoquinonediazide-5-sulfonyl chloride (81.4 g), and
acetone (600 g) were placed, and the resultant mixture was
dissolved, to thereby prepare a homogeneous solution. Subsequently,
triethylamine (33.7 g) was added dropwise to the solution at
30-35.degree. C. over one hour. Thirty minutes after completion of
addition, 35% hydrochloric acid (6.3 g) was added dropwise to the
solution. The formed triethylamine hydrochloride was separated
through filtration. The resultant filtrate was poured into a 0.1%
aqueous hydrochloric acid solution (1,800 ml) maintained at
30-35.degree. C. The formed precipitates were collected through
filtration, washed with water, and dried at 45.degree. C., to
thereby yield 100 g of a 2,3,4-trihydroxybenzophenone
1,2-naphthoquinonediazide-5- -sulfonate ester.
Production Example 3
[0029] Into a three-neck flask, 2,3,4-trihydroxybenzophenone (35
g), 1,2-naphthoquinonediazide-5-sulfonyl chloride (81.4 g), and
acetone (400 g) were placed, and the resultant mixture was
dissolved, to thereby prepare a homogeneous solution. Subsequently,
triethylamine (33.7 g) was added dropwise to the solution at
30-35.degree. C. over one hour. Thirty minutes after completion of
addition, N,N-dimethylformamide (100 g) was added to the solution.
Further, 30 minutes after addition of N,N-dimethylformamide, 35%
hydrochloric acid (6.3 g) was added dropwise to the mixture. The
formed triethylamine hydrochloride was separated off through
filtration. The resultant filtrate was poured into a 0.1% aqueous
hydrochloric acid solution (1,700 ml) maintained at 20-25.degree.
C. The formed precipitates were collected through filtration,
washed with water, and dried at 45.degree. C., to thereby yield 100
g of a 2,3,4-trihydroxybenzophenone
1,2-naphthoquinonediazide-5-sulfonate ester.
[0030] The chloride ion content of the photosensitive agent
obtained in Comparative Production Example 3 and that obtained in
Production Example 3 were measured. As shown in Table 3, the
chloride ion content of the photosensitive agent obtained in
Production Example 3 according to the present invention is
remarkably low.
3 TABLE 3 Chloride ion content Comparative Production Example 3 130
ppm Production Example 3 10 ppm
Example 4
Comparative Production Example 4
[0031] Into a three-neck flask,
3,3'-bis(2-hydroxy-5-methylbenzyl)-2,2'-di-
hydroxy-5,5'-dimethyldiphenylmethane (47.0 g),
1,2-naphthoquinonediazide-5- -sulfonyl chloride (67.4 g), and
acetone (800 g) were placed, and the resultant mixture was
dissolved, to thereby prepare a homogeneous solution. Subsequently,
a mixture of triethylamine/acetone (27.9 g/27.9 g) was added
dropwise to the solution at 30-35.degree. C. over one hour. Thirty
minutes after completion of addition, 35% hydrochloric acid (5.2 g)
was added dropwise to the resultant mixture. The formed
triethylamine hydrochloride was separated through filtration. The
resultant filtrate was poured into a 0.1% aqueous hydrochloric acid
solution (2,700 ml) maintained at 20-25.degree. C. The formed
precipitates were collected through filtration, washed with water,
and dried at 45.degree. C., to thereby yield 100 g of a
3,3'-bis(2-hydroxy-5-methylbenzyl)-2,2'-dihydrox-
y-5,5'-dimethyldiphenylmethane
1,2-naphthoquinonediazide-5-sulfonate ester.
Production Example 4
[0032] Into a three-neck flask,
3,3'-bis(2-hydroxy-5-methylbenzyl)-2,2'-di-
hydroxy-5,5'-dimethyldiphenylmethane (47.0 g),
1,2-naphthoquinonediazide-5- -sulfonyl chloride (67.4 g), and
acetone (550 g) were placed, and the resultant mixture was
dissolved, to thereby prepare a homogeneous solution. Subsequently,
a mixture of triethylamine/acetone (27.9 g/27.9 g) was added
dropwise to the solution at 30-35.degree. C. over one hour. Thirty
minutes after completion of addition, N-methylpyrrolidone (150 g)
was added to the resultant mixture. Further, 30 minutes after
addition of N-methylpyrrolidone was complete, 35% hydrochloric acid
(5.2 g) was added dropwise to the resultant mixture. The formed
triethylamine hydrochloride was separated off through filtration,
and the resultant filtrate was poured into a 0.1% aqueous
hydrochloric acid solution (2,500 ml) maintained at 20-25.degree.
C. The formed precipitates were collected through filtration,
washed with water, and dried at 45.degree. C., to thereby yield 100
g of a 3,3'-bis(2-hydroxy-5-methylbenzyl)-2,2'-dihydrox-
y-5,5'-dimethyldiphenylmethane
1,2-naphthoquinonediazide-5-sulfonate ester.
[0033] The chloride ion content of the photosensitive agent
obtained in Comparative Production Example 4 and that obtained in
Production Example 4 were measured. As shown in Table 4, the
chloride ion content of the photosensitive agent obtained in
Production Example 4 according to the present invention is
remarkably low.
4 TABLE 4 Chloride ion content Comparative Production Example 4 185
ppm Production Example 4 20 ppm
Example 5
Comparative Production Example 5
[0034] Into a three-neck flask, 2,3,4-trihydroxybenzophenone (35
g), 1,2-naphthoquinonediazide-5-sulfonyl chloride (81.4 g), acetone
(400 g), and N-methylpyrrolidone (100 g) were placed, and the
resultant mixture was dissolved, to thereby prepare a homogeneous
solution. Subsequently, triethylamine (33.7 g) was added dropwise
to the solution at 30-35.degree. C. over one hour. Thirty minutes
after completion of addition, 35% hydrochloric acid (6.3 g) was
added dropwise to the resultant mixture. The formed triethylamine
hydrochloride was separated through filtration. The resultant
filtrate was poured into a 0.1% aqueous hydrochloric acid solution
(1,700 ml) maintained at 20-25.degree. C. The formed precipitates
were collected through filtration, washed with water, and dried at
45.degree. C., to thereby yield 100 g of a
2,3,4-trihydroxybenzophenone 1,2-naphthoquinonediazide-5-sulfonate
ester.
Production Example 5
[0035] Into a three-neck flask, 2,3,4-trihydroxybenzophenone (35
g), 1,2-naphthoquinonediazide-5-sulfonyl chloride (81.4 g), and
acetone (400 g) were placed, and the resultant mixture was
dissolved, to thereby prepare a homogeneous solution. Subsequently,
triethylamine (33.7 g) was added dropwise to the solution at
30-35.degree. C. over one hour. Thirty minutes after completion of
addition, N-methylpyrrolidone (100 g) was added to the resultant
mixture. Further, 30 minutes after addition of N-methylpyrrolidone
was complete, 35% hydrochloric acid (6.3 g) was added dropwise to
the resultant mixture. The formed triethylamine hydrochloride was
separated off through filtration. The resultant filtrate was poured
into a 0.1% aqueous hydrochloric acid solution (1,700 ml)
maintained at 20-25.degree. C. The formed precipitates were
collected through filtration, washed with water, and dried at
45.degree. C., to thereby yield 100 g of a
2,3,4-trihydroxybenzophenone 1,2-naphthoquinonediazide-5-
-sulfonate ester.
[0036] The sulfonate ion content of the photosensitive agent
obtained in Comparative Production Example 5 and that obtained in
Production Example 5 were measured. As shown in Table 5, the
sulfonate ion content of the photosensitive agent obtained in the
case in which the amide solvent was added after completion of
condensation is remarkably low.
5 TABLE 5 Sulfonate ion content Comparative Production Example 5
140 ppm Production Example 5 25 ppm
[0037] As described hereinabove, according to the present
invention, a high-purity 1,2-naphthoquinonediazide photosensitive
agent containing a low level of impurities can be produced by
effecting condensation, in an organic solvent other than amide,
between a polyhydric phenolic compound and a
1,2-naphthoquinonediazide-sulfonic acid halide in the presence of
an organic amine; subsequently adding an amide solvent to the
resultant reaction mixture; and separating off the formed organic
amine hydrohalide salt through filtration.
* * * * *