JP3478104B2 - Method for producing photosensitive heat-resistant resin precursor composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to a semiconductor surface protective film.
Also useful for photosensitive heat-resistant resin precursor composition useful as
Photosensitivity that can be developed in a short time with an aqueous developer
The present invention relates to a heat-resistant resin precursor composition. [0002] 2. Description of the Related Art At present, polyphenolic hydroxyl group-containing poly
Amide resin, polyamic acid is a naphthoquinonediazide compound
Positive photosensitivity where the exposed part dissolves by mixing
It is receiving attention as a heat-resistant material. However, this
When synthesizing a compound such as
Dimethylacetamide, N-methyl-2-pyrrolidone
Bisaminophenol in any dipolar aprotic solvent
Compound and compound such as acid chloride and acid anhydride acid chloride
Desalting tertiary amines such as triethylamine and pyridine
The general synthesis method is to react in the presence of an acid agent.
is there. However, in such a synthesis method,
Synthesizes where the amide group and the phenolic hydroxyl group are in close proximity
The amine or the amine formed with the amine and hydrochloric acid.
Min hydrochloride forms strong hydrogen bond with amide bond or hydroxyl group
In order to form, the resulting material should be ionic, such as chlorine.
There is a drawback that impurities become high. Improve this point
Use of ion exchange resin as a dehydrochlorinating agent
(Japanese Unexamined Patent Publication No. 8-269198)
Information). However, when using such a method,
The target polymer is adsorbed on the ion exchange resin and the yield is
There was a problem of lowering. Also, such a problem
Dicarboxylic acid, a synthesis method without using chloride
Compound and diamine compound with dicyclohexylcarbodii
A method using a dehydrating condensing agent such as amide has been reported
(JP-A-60-22837). However,
Dicyclohexylcarbodiimide turns off on skin contact
Problems, such as the
Poor solubility of rohexyl urea compound, causing
There was a problem that it always remained. Eliminate this problem
For this reason, many other dehydration condensing agents have been reported.
("Biochemistry Experiment Course 1 Protein Chemistry IV", Japan
Edited by The Society of Chemistry, Tokyo Kagaku Doujin (1977)). But this
Such compounds have problems such as being expensive.
To avoid such problems, the polymer amide bond
To establish a dehydrochlorination process with low interaction with
The present invention has been accomplished for the purpose. [0003] The present invention addresses such problems.
And the resulting polymer has a low chlorine ion concentration.
And heat-resistant resin precursor composition with high reaction yield
It is an object of the present invention to provide a production method of [0004] According to the present invention, there is provided:General formula
Polymer having a structural unit represented by (1) and naphthoki
Photosensitive heat-resistant resin precursor containing non-diazide compound
A method for producing a composition, comprising:Structure represented by general formula (1)
In the process of synthesizing a polymer having structural units,
Reaction of carboxylic acid chloride with hydroxydiamino compound
To synthesize the acid anhydride represented by the general formula (2)
Has an epoxy compound and / or an unsaturated bond
Using the compound, dehydrochloride,Salt of the obtained polymer
Elemental ion concentration should be 5ppm or lessCharacterized byFeeling
LightThis is a method for producing a heat-resistant resin precursor composition. [0005] Embedded image (R1 and R3 are at least 2 and more than 20
A trivalent or tetravalent organic group having the following carbon atoms, R2
Has at least 2 and not more than 20 carbon atoms
R3 is a trivalent to hexavalent organic group, and has 2 to 30 carbon atoms.
The lower organic group, R5, R6 has 1 to 10 carbon atoms.
Containing one or more of organic groups and / or hydrogen
Stuff. m is an integer from 1 to 100000, and n is 1
Or 2, and p represents an integer of 1 to 4. ) [0007] Embedded image (R7 and R9 each have 2 to 20 carbon atoms.
R8 is a trivalent organic group having 2 to 20 carbon atoms.
To hexavalent organic group, and q represents an integer selected from 1 to 4.
You. ) [0009] BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, general formula (1)
The polymer represented is polyhydroxyamide-amide acid
The structure of the copolymer is shown, and phenolic water is generally used.
Tetracarboxylic dianhydride having an acid group and diamine compound
It is obtained by subjecting a product to a condensation reaction. In general formula (1)
And R1 is a trivalent or tetravalent having 2 to 20 carbon atoms.
Represents a group. Preferred as such
Is pyromellitic acid residue, benzophenonetetracarboxylic
Acid residue, biphenyltetracarboxylic acid residue, diphenyl
Ether tetracarboxylic acid residue, diphenyl sulfone
Toracarboxylic acid residue, bis (phthalic acid) hexafluoro
Propane residue, trimellitic acid residue, trimesic acid residue
Group, naphthalene tricarboxylic acid residue, diphenyl ether
Rutricarboxylic acid residue, benzophenone tricarboxylic acid
Aromatic group such as residue, tricarboxyl propane residue
Group, tricarboxylbutane residue, butanetetracarbo
Acid residue, cyclopentanetetracarboxylic acid residue, etc.
Aliphatic groups can be mentioned. R1 is composed of one of these.
May be used, or two or more
good. In the general formula (1), R2 has 2 or more carbon atoms and 20 or more carbon atoms.
Less than 3 to 6 valent organic groups, preferred examples
As the diaminophenol residue, diaminodihydro
Xybenzene residue, diaminotrihydroxybenzene residue
Group, diaminotetrahydroxybenzene residue, bis (A
Minophenol) propane residue, bis (aminopheno)
Le) Hexafluoropropane residue, diaminohydroxy
Naphthalene, diaminohydroxyterphenyl residue, etc.
Can be preferably used. Ma
In addition, 1 to 40 mol% of R2 is a phenyl group having no hydroxyl group.
Range amine residue, diamino diphenyl ether residue,
Diaminodiphenylmethane residue, bis (aminophenoki
B) benzene residue, bis (aminophenoxyphenyl)
Sulfone residue, bis (aminophenoxyphenyl) pro
Aromatic compounds such as pan residues, ethylene diamine residue
Group, hexamethylenediamine residue, diaminocyclohexene
Sun residue, diaminodicyclohexylmethane residue, etc.
Aliphatic diamine residue, bis (aminopropyl) tetrame
Tyldisiloxane, bis (aminophenyl) tetramethyl
Modified by silicon-containing diamino compounds such as rudisiloxane
You can also. R2 may be composed of one kind
Alternatively, it may be composed of two or more types. R3 in the general formula (1) is the same as R1.
Can be used. R4 in the general formula (1) has 2 carbon atoms
From 30 to 30 divalent organic groups.
Min residue, diamino diphenyl ether residue, diamino
Diphenylmethane residue, diaminodiphenyl sulfone residue
Group, diaminobenzophenone residue, tetramethyldiamine
Nodiphenylmethane residue, diaminobiphenyl residue, bi
(Trifluoromethyl) diaminobiphenyl residue,
Tylphenylenediamine residue, bis (aminophenoki
B) benzene residue, bis (aminophenoxyphenyl)
Sulfone residue, bis (aminophenoxyphenyl) pro
A group containing a divalent aromatic such as a pan residue is preferred. Ma
In addition, ethylenediamine residue which is an aliphatic group, diaminobu
Tan residue, hexamethylene diamine residue, diamino cycle
Rohexane residue, diaminodicyclohexylmethane residue
Can be modified by 1 to 40 mol%. further
Bis (aminopropyl) tetramethyl which is a silicon-containing group
Rudisiloxane residue, bis (aminophenyl) tetrame
Modifies 1 to 40 mol% of tildisiloxane residue etc.
You can also. R4 may be composed of only one kind
Alternatively, two or more types may be used. Also charcoal
When the prime number is 30 or more, the obtained general formula (1)
The solubility of the limmer in alkaline aqueous solution may be reduced.
There is. For R5 and R6 in the general formula (1), hydrogen
Use atoms or organic groups with 1 to 10 carbon atoms.
Can be used. These include hydrogen sources
, Methyl, ethyl, propyl, butyl, eth
Preferred examples are xyethyl group, ethoxymethyl group and the like.
Can be mentioned. Also, the amount of hydrogen atoms and organic groups
Control the solubility in aqueous alkaline solutions
I can do it. Thus, R5 and R6 are composed of only one type.
Or a combination of two or more
good. In the present invention, a phenolic hydroxyl group is contained.
Tetracarboxylic dianhydride
Trica such as phenol and anhydrous trimellitate chloride
Acid anhydride of monoanhydride and monoacid chloride of rubonic acid and hydroxy
Selectively reacting with an amino group of a diamino compound
Can be obtained at Having this phenolic hydroxyl group
When synthesizing tetracarboxylic dianhydride, it is generally widely used.
The method used is the reaction between the corresponding acid chloride and the amino group.
To remove hydrochloric acid by-produced in the reaction, triethylamine or
Reaction using tertiary amine compound such as pyridine
Is the way. However, it has a phenolic hydroxyl group
Tetracarboxylic dianhydride itself is a tertiary amine compound
To obtain high-purity to adsorb and its hydrochloride
I can't do that. Also, ion exchange with tertiary amine
When a resin is used, high purity products can be obtained,
Since the compound generated in step is adsorbed on the ion exchange resin,
This is not preferable because the yield of the desired product is reduced. In the present invention, an epoxy compound is used as a dehydrochlorinating agent.
Hydrochloric acid is converted to a salt
Use chlorinated alcohol, dihydropyran instead of form
Can be removed in the form of chlorinated cyclic ether
You. Such chlorinated alcohols, chlorinated cyclic ethers
Has little interaction with amide groups and phenolic hydroxyl groups.
Most likely, tetraca with the desired phenolic hydroxyl group
It was found that rubonic acid dianhydride could be obtained with high yield and high purity.
come. Examples of such epoxy compounds include
Jil methyl ether, glycidyl phenyl ether,
Lysidyl allyl ether, glycidyl butyl ether,
Examples of propylene oxide, compounds having an unsaturated bond and
Sesame oil, castor oil and other unsaturated fatty acid
Oleic acid, unsaturated fatty acids such as linoleic acid,
Having an (exo) methylene group such as tyl-1-butene
Terminal-unsubstituted-disubstituted olefin, allyl methyl ether
And β-methallyl methyl ether, 3-methoxy-2-me
Tilpropene, methylenecyclohexane, methylenecycline
Compounds such as lopentane, limonene, dihydropyran,
Cyclic vinyl ethers such as methyldihydropyran
Which have other epoxy rings
Compounds with unsaturated bonds or compounds with unsaturated bonds
I can do it. Among these, particularly preferred compounds are
Sidyl methyl ether, glycidyl allyl ether,
Cyclic dihydropyran, methyldihydropyran, etc.
Saturated bond-containing ether compound, methylenecyclohexa
Unsaturated bonds such as ethylene, methylenecyclopentane and limonene.
Compounds having a bond can be mentioned. Such an epoxy compound has an unsaturated bond.
Add more than the equivalent of the compound you have to the hydrochloric acid generated.
Is preferred. If it is less than the equivalent, the generated hydrochloric acid is completely removed
Can not do it. More preferably, it is added at least 4 times mol.
It is to get. Generally removes hydrochloric acid
For the purpose, epoxy compounds and compounds with unsaturated bonds
Substances and dihydropyran compounds should be added as much as possible
Is desirable, but if it is added in a molar amount of 20 times or more, the epoxy compound
Compounds, compounds with unsaturated bonds and carboxylic acids, amines
Side reaction occurs, and the yield of the obtained target product decreases.
There is a risk that. From such a point, these epoxidation
The amount of the compound or compound having an unsaturated bond is
Not less than an equivalent amount and not more than 20 moles per mole of the compound.
And more preferably at least 4 moles and not more than 15 moles.
is there. The hydroxyl group-containing acid 2 represented by the general formula (2)
N-methylpyrrolidone, gamma
Polar solvents such as butyrolactone and dimethylacetamide
And ketones such as acetone and methyl ethyl ketone
System solvent, tetrahydrofuran, dioxane, propylene
Ethers such as glycol monomethyl ether acetate
Solvents, ester solvents such as ethyl acetate and butyl acetate
Medium, ethanol, isopropyl alcohol, etc.
-10 ° C to 100 ° C in a mixed solvent with
The polymer represented by the general formula (1) is reacted by
Can be obtained. Here, in the general formula (2), R7,
R9 had an acid anhydride group having 2 to 20 carbon atoms
It represents a trivalent or tetravalent organic group, and pyromellitic acid
Anhydride residue, benzophenonetetracarboxylic anhydride residue
Group, diphenyl ether tetracarboxylic anhydride residue,
Biphenyltetracarboxylic anhydride residue, diphenyls
Rufontetracarboxylic anhydride residue, butanetetracar
No boronic anhydride residue, cyclopentanetetracarboxylic acid
Hydrate residue, trimellitic anhydride residue, diphenyl ether
Tertricarboxylic anhydride group, diphenyl sulfone tri
Carboxylic acid residue, naphthalene tricarboxylic anhydride group
Are preferred groups, but other
Those having one acid anhydride group can also be used.
You. In particular, it is preferable to use a trivalent group. Also, R
7, R9 may be composed of only one kind or two or more kinds.
May be configured. R8 in the general formula (2) is the same as R8 in the general formula (1)
The same thing as 2 can be used. Further, a polymer represented by the general formula (1)
Is obtained by adding 2 equivalents of the corresponding monoanhydride monochloride and hydroxy
1 equivalent of diamino compound is added to epoxy compound or dihydropyra
Reaction in the presence of a diamine compound.
The reaction can also be carried out by reacting one equivalent of the product. This one anhydride
As the monoacid chloride, a compound represented by the general formula (13)
Are preferred, such as anhydrous trim
Lit acid chloride can be mentioned as a typical one
But the two carboxy groups of the tricarboxylic acid as follows:
The carboxylic acid group is converted to an acid anhydride, and the remaining carboxylic acid is converted to the acid chloride.
Any shape can be used. Ma
R39 represents a trivalent organic group having 2 to 30 carbon atoms.
Represent. Preferred as such groups are trimellites.
Tonic acid residue, trimesic acid residue, naphthalene tricarboxylic acid
Acid residue, diphenyl ether tricarboxylic acid residue, diph
Phenyl sulfone tricarboxylic acid residue, benzophenone
Aromatic groups such as carboxylic acid residues, butanetricarboxylic acid
Fats such as acid residues and cyclohexanetricarboxylic acid residues
Group groups can be mentioned as preferred examples. R39 is
It may be composed of one kind or composed of two or more kinds
May be. [0018] Embedded image The photosensitive heat-resistant resin precursor composition of the present invention is
The naphthoquinonediazide compound to be obtained
Toquinone diazide sulfonic acid phenyl ester compound
preferable. Such compounds include tetrahydroxy
Naphthoquinonediazidosulfonic acid of cibenzophenone
Stele, naphthoquinonediazidosul of bisphenol A
Naphthoquinone diazide sulfonate, gallic acid
Naphthoquinonediazidos of phonates and naphthols
Preferable use of compounds such as sulfonic acid esters
But there are other phenolic esters,
Or hydroxyphthalimide, hydroxybenzotria
Naphthoquinonediazidesulfonic acid ester such as sol
And oximes such as benzaldoxime
Non-diazide sulfonic acid ester etc. can be used
I can do it. Also, naphthoquinonediazidosulfonic acid includes
One with a sulfonyl group bonded at the 4-position and one with a sulfonyl at the 5-position
Groups are bonded, and in the present invention, either compound
Can also be used. The photosensitive heat-resistant resin precursor group as in the present invention
As the photopolymerization initiator used for the product, N-phenyl
Aromatic amines such as glycine and Michler's ketone
Aromatic ketones, 1-phenyl-1,2-propanedio
Oximes such as 2--2- (o-acetyl) oxime
To 100 parts by weight of the polymer represented by the general formula (12)
On the other hand, 0.5 to 10 parts by weight can be added.
In order to further promote the photoreaction,
Nomer compounds can be added. Such an action
Methyl acrylate, meta
Methyl acrylate, ethylene glycol dimethacrylate
G, ethylene glycol diacrylate, trimethylo
Lepropane triacrylate, trimethylolpropane
Examples thereof include trimethacrylate.
In the present invention, only one of these may be used.
Alternatively, a plurality of types may be used in combination. Further, 7-diethylaminobenzene is used as a sensitizer.
Aminocoumarins such as nzoyl coumarin, 5-nitro
Acenaphthene, Thioxanthone, Leuco Crystal Buy
OLET, 2- (p-dimethylaminostyryl) benzo
It is also possible to use styryls such as oxazole in combination.
Wear. Further, in order to improve the photosensitive performance, N
-Phenyldiethanolamine, dimethylaminobenzoate
Amines such as ethyl acrylate, mercaptobenzoic acid
Mercaptos such as sasol are represented by the general formula (12).
0.1 to 10 parts by weight per 100 parts by weight of polymer
It can also be added. As the solvent used in the present invention, N-meth
Tyl-2-pyrrolidone, gamma-butyrolactone, N, N
-Dimethylformamide, N, N-dimethylacetoa
Polar aprotic solvents such as amides and dimethyl sulfoxide
Medium, ethers such as tetrahydrofuran and dioxane
, Acetone, methyl ethyl ketone, diisobutyl keto
Ketones, ethyl acetate, propylene glycol
S, such as monomethyl ether acetate and ethyl lactate
Aromatic hydrocarbons such as ters, toluene and xylene
Any solvent can be used alone or mixed
You. Further, in order to increase the viscosity or
Silicon dioxide, titanium dioxide, etc.
Add any inorganic particles or polyimide powder
You can also. Further, a base substrate such as a silicon wafer
Silane coupling agent, titanium
Varnish of the obtained polymer solution
0.5 to 10% by weight, or
It can also be treated with such a chemical solution. varnish
When added to, methyl methacryloxy dimethoxy sila
Silicone, 3-aminopropyltrimethoxysilane, etc.
Run coupling agent, titanium chelating agent, aluminum chelating
0.5 to 10% by weight of the polymer in the varnish
%Added. When processing substrates, the
Use coupling agents such as isopropanol, ethanol,
, Water, tetrahydrofuran, propylene glycol
Monomethyl ether acetate, propylene glycol
Monomethyl ether, ethyl lactate, diethyl adipate
Solution of 0.5 to 20% by weight in a solvent such as
Surface by pin coating, dipping, spray coating, steam treatment, etc.
Do the processing. In some cases, then 50 ° C to 300 ° C
By applying a temperature of up to ℃,
Use after the reaction with the agent has progressed. Next, the photosensitive heat-resistant precursor composition of the present invention
About the method of forming heat resistant resin pattern using
I will tell. Applying a photosensitive heat-resistant precursor composition on a substrate
I do. Substrates include silicon wafers, ceramics,
Gallium arsenide is used, but is not limited to these.
No. Spin coating using a spinner,
There are methods such as ray coating and roll coating. Ma
The coating thickness is determined by the coating method, the solid content concentration of the composition, and the viscosity.
Usually, the film thickness after drying is 0.1
To 150 μm. Next, the photosensitive heat-resistant precursor composition was applied.
The substrate is dried to obtain a photosensitive heat-resistant precursor composition film.
You. Use an oven, hot plate, infrared ray, etc. for drying.
For 1 minute to several hours in the range of 50 to 150 degrees
Is preferred. Next, the photosensitive heat-resistant precursor composition film
Actinic radiation through a mask with the desired pattern on top
Shoot and expose. Actinic rays used for exposure are ultraviolet
Line, visible light, electron beam, X-ray, etc.
Mercury lamp i-line (365 nm), h-line (405 nm), g
Preferably, a line (436 nm) is used. But
Et al., 450-550 nm visible light, 350 nm or less.
Ultraviolet rays, electron beams, X-rays and the like can also be used. Exposure to form a polyimide pattern
Later achieved by removing exposed areas using a developer
Is done. As a developer, tetramethylammonium
Aqueous solution, diethanolamine, diethylaminoethanol
, Sodium hydroxide, potassium hydroxide, sodium carbonate
, Potassium carbonate, triethylamine, diethylamido
, Methylamine, dimethylamine, dimethylamine acetate
Noethyl, dimethylaminoethanol, dimethylamino
Ethyl methacrylate, cyclohexylamine, ethyl
Alkaline such as diamine, hexamethylenediamine
An aqueous solution of a compound showing Also in some cases
Can be added to these aqueous alkali solutions by N-methyl-2-pyrrolidone.
Don, N, N-dimethylformamide, N, N-dimethyl
Luacetamide, dimethyl sulfoxide, γ-butyrol
Polar solvents such as octone, dimethylacrylamide, meta
Alcohols such as ethanol, ethanol, and isopropanol
, Ethyl lactate, propylene glycol monomethyl ester
Esters such as teracetate, cyclopentano
, Cyclohexanone, isobutyl ketone, methyl iso
Use ketones such as butyl ketone alone or several
A combination may be added. After development, remove with water.
Sense processing. Again, ethanol, isopropyl alcohol
Alcohols such as alcohol, ethyl lactate, propylene
Esters such as glycol monomethyl ether acetate
Water, acetic acid, carbon dioxide, oxalic acid, phosphoric acid, etc.
In addition, a rinsing process may be performed. After development, a temperature of 200 to 500 degrees is applied.
And convert it to a heat-resistant resin film. This heat treatment reduces the temperature
Select and raise the temperature stepwise, or select a certain temperature range and continuously
And for 5 minutes to 5 hours. As an example
Heat treatment at 130, 200 and 350 degrees for 30 minutes each
Manage. Or from room temperature to 400 degrees for 2 hours
For example, a method of linearly raising the temperature may be used. In the photosensitive heat-resistant precursor composition according to the present invention,
The heat-resistant resin film formed from the
Film, protective film for semiconductor devices, and multilayer wiring for high-density mounting.
Used for applications such as interlayer insulating films. [0033] DESCRIPTION OF THE PREFERRED EMBODIMENTS In order to explain the present invention in more detail,
An example will be described. How to measure properties Chlorine ion measurement 3 g of the sample was dispersed in 100 ml of water. This dispersion was added to 9
Extraction treatment was performed at 0 to 100 ° C. for 2 hours. This extract
Using an ion meter N-8M manufactured by Horiba, Ltd.
Using the chlorine ion electrode 8002
The ON concentration was measured. Chloride ion concentration exceeds 5ppm
Then, the obtained polymer can be used as a surface protection film for semiconductor devices.
When used for electrodes, chlorine ions cause corrosion on electrodes, etc.
Grows and is not preferred. Measurement of melting point Using a differential thermal analyzer DSC-50 manufactured by Shimadzu Corporation
Then, put about 50 mg of sample in an aluminum cell,
It was measured at a rate of 20 ° C./min from room temperature to 350 ° C.
The endothermic peak in the differential heat curve was defined as the melting point. Example 1 Dehydrochlorination agent using epoxy compound
Of acid anhydride (A) used as a catalyst In a 500 ml four-necked flask, stirrer, thermometer, nitrogen
Attach an inflow tube and attach 2,2'-bis (3-amino-4-
Hydroxyphenyl) hexafluoropropane (BAH
F) 18.3 g (0.05 mol) of glycidyl methyl ester
Mixing of 88 g (1.0 mol) of acetone and 50 ml of acetone
Dissolved in the liquid and cooled to -10 ° C. Trimellitic anhydride chloride (TMC) 2
3.1 g (0.11 mol) was dissolved in 50 ml of acetone.
To the above solution of BAHF, temperature
Was dropped so as not to exceed 0 ° C. After completion of the dropwise addition, stirring was continued at −10 ° C. for 2 hours.
The solution was then brought to room temperature. Add this solution to toluene
And the yellow precipitate was collected by filtration.
It was dried in a vacuum dryer at 50 ° C. for 20 hours. This yield is
31.4 g (yield: 88%), mp 281 ° C.
Was. The chlorine ion concentration is a good value of 1.5 ppm.
there were. Comparative Example 1 Triethylamine was used as a dehydrochlorinating agent.
Of acid anhydride (A) used as a catalyst In a 500 ml four-necked flask, stirrer, thermometer, nitrogen
Attach the inflow pipe, BAHF 18.3g (0.05M
Of triethylamine (TEA)
1 mol) and 100 ml of acetone.
Cooled to 10 ° C. 23.1 g (0.11 mol) of TMC
In 50 ml of acetone to make a solution.
Drop the solution so that the temperature does not exceed 0 ° C.
I dropped it. After completion of the dropwise addition, stirring was continued at −10 ° C. for 2 hours.
The solution was then brought back to room temperature. This solution was filtered to remove triethylamine.
Except for the hydrochloride, collect the filtrate with a rotary evaporator.
Concentrate the volume to 50 ml and add to 1500 ml of toluene
And the yellow precipitate is collected by filtration and dried in a vacuum dryer at 50 ° C.
Dry for 20 hours. This yield was 37.5 g (yield 10
5%), the melting point could not be detected in this range. Also salt
The element ion concentration is 100 ppm,
-There is a problem in using it as a raw material. Comparative Example 2 An ion exchange resin was used as a dehydrochlorinating agent.
Of acid anhydride (A) used In a 500 ml four-necked flask, stirrer, thermometer, nitrogen
Attach the inflow pipe, BAHF 18.3g (0.05M
E) and previously dried at 105 ° C for 4 hours.
Lugano's cation-type ion exchange resin "Amberlyst"
A-21 69.8 g (0.31-0.35 mol equivalent)
Dissolved in a mixture of 200 ml of acetone and -10 ° C
Cool. 23.1 g (0.11 mol) of TMC was
A solution dissolved in 50 ml of ton,
Add dropwise to the AHF solution so that the temperature does not exceed 0 ° C.
Was. After completion of the dropwise addition, stirring was continued at −10 ° C. for 2 hours.
The solution was returned to room temperature. This solution is filtered and ion
Except for the exchange resin, collect the filtrate with a rotary evaporator.
Concentrate the body to 50 ml and inject into 1500 ml of toluene.
, And the yellow precipitate was collected by filtration and dried at 50 ° C in a vacuum drier.
For 20 hours. The yield was 16.1 g.
(Yield: 45%). Melting point is 281 ° C
there were. The chlorine ion concentration was as good as 1 ppm.
However, the yield was higher than that of Example 1 using the epoxy compound.
It was low. Example 2 Cyclic unsaturated ether was dehydrochlorinated
Polyhydroxyamide-amic acid alternate copolymer used as
Polymerization of polymer (B) In a 500 ml four-necked flask, stirrer, thermometer, nitrogen
Attach the inflow pipe, BAHF 18.3g (0.05M
) Was converted to 84 g of 3,4-dihydro-2H-pyran (1.0 g).
Mol) and acetone (50 ml).
Cooled to ° C. 21.1 g (0.1 mol) of TMC
A solution dissolved in 50 ml of ton,
Add dropwise to the AHF solution so that the temperature does not exceed 0 ° C.
Was. After completion of the dropwise addition, stirring was continued at -10 ° C for 2 hours.
8.4,4'-diaminodiphenyl ether
01g (0.045 mol), 1,3-bis (3-amino
Propyl) tetramethyldisiloxane 1.24 g (0.
005 mol) to 100 g of N-methyl-2-pyrrolidone
The dissolved solution was added all at once. This solution at room temperature for 3 hours
The reaction was then carried out at 50 ° C. for 1 hour. The reaction solution was poured into 5 l of water, and
A precipitate of the xyamide-amic acid alternating copolymer was obtained. this
The precipitate is collected by filtration, washed with water, and dried in a vacuum at 50 ° C.
It was dried in a dryer for 20 hours. Chloride ion content is 1pp
m (yield: 90 g, 98%). Comparative Example 3 Triethylamine was used as a dehydrochlorinating agent.
Copolymerization of Polyhydroxyamide-Amidic Acid
Polymerization of body (B) In a 500 ml four-necked flask, stirrer, thermometer, nitrogen
Attach the inflow pipe, BAHF 18.3g (0.05M
) With 11.1 g (0.11 mol) of TEA and 9 parts of acetone
Dissolved in 0 ml of the mixture and cooled to -10 ° C. 21.1 g (0.1 mol) of TMC was
Make a solution dissolved in 50 ml of
The solution was added dropwise to the HF solution so that the temperature did not exceed 0 ° C.
After completion of the dropwise addition, stirring was continued at −10 ° C. for 2 hours.
9.01 g of 4'-diaminodiphenyl ether (0.0
45 mol), 1,3-bis (3-aminopropyl) tet
1.24 g (0.005 mol) of lamethyldisiloxane
Solution dissolved in 100 g of N-methyl-2-pyrrolidone
Was added all at once. The solution was reacted at room temperature for 3 hours.
The reaction was carried out at 50 ° C. for 1 hour. The reaction solution was poured into 5 l of water,
A precipitate of the xyamide-amic acid alternating copolymer was obtained. this
The precipitate is collected by filtration, washed with water, and dried in a vacuum at 50 ° C.
It was dried in a dryer for 20 hours. Chloride ion content is 50p
pm (yield 50 g). 110% for yield
It is clear that impurities are taken in, exceeding the theoretical value
You. Comparative Example 4 Use of pyridine as a dehydrochlorinating agent
Of the modified polyhydroxyamide (C) In a 500 ml four-necked flask, stirrer, thermometer, nitrogen
Attach the inflow pipe, 36.6 g (0.1 mol) of BAHF
With 10 g (0.13 mol) of pyridine and
Dissolve in 150 ml of amide mixture and cool to -10 ° C
did. 20.3 g of isophthalic dichloride (0.1 mol
Is dissolved in 100 ml of cyclohexanone.
And add it to the above BAHF solution at a temperature above 0 ° C.
It was dropped so that it could not be removed. After completion of the dropwise addition, stirring was continued at -10 ° C for 2 hours.
The solution is then allowed to warm to room temperature and
For 3 hours. The reaction solution was poured into 5 liters of water,
A precipitate of hydroxyamide was obtained. This precipitate is collected by filtration.
And further washed with water, and dried in a vacuum dryer at 50 ° C for 20 hours.
Let dry. The chloride ion content was 80 ppm
(Yield: 54 g). Also, the yield is 108%, exceeding the theoretical amount.
It can be seen that impurities were taken in. Comparative Example 5 Using pyridine as a dehydrochlorinating agent
Of Polyamide Ester (D) Stirrer, thermometer, drying in a 300 ml four-necked flask
Attach air inlet pipe, pyromellitic anhydride 10.9g
(0.05 mol) and 3,3 ', 4,4'-benzopheno
16.1 g of tetracarboxylic dianhydride (0.05 mole
G) butyralactone 100 ml and pyridine 1
Dissolved in 4.1 g (0.2 mol) and brought to 30 ° C.
Here, 26.2 g of 2-hydroxyethyl methacrylate
(0.2 mol) and reacted at 30 ° C. for 8 hours. This
Is poured into 1 liter of water, and the resulting precipitate is collected by filtration.
I did. The precipitate is further washed with water and dried at 50 ° C. in a vacuum drier.
For 20 hours. In a 300 ml four-necked flask, stirring wings,
Attach a thermometer and a dry air inlet pipe, and
It was dissolved in 100 ml of numabutyrolactone. Here
47.6 g (0.4 mol) of onyl chloride, hydroxy
Add 0.2 g of non-monomethyl ether and add
Allowed to react for hours. After the reaction is completed, the rotary evaporator
The remaining thionyl chloride was removed with a mouse. In a 1-liter four-necked flask, stirrer, temperature
4 and 4'-di
20.0 g (0.1 mol) of aminodiphenyl ether
31.6 g (0.4 mol) of pyridine and N-methyl
-2-Pyrrolidone was dissolved in 150 ml. This solution
After cooling to 5 ° C., the diester
Chloride gamma-butyrolactone solution was added to the reaction solution
The solution was dropped so that the temperature did not exceed 10 ° C. After dropping, 5
After the reaction at 2 ° C. for 2 hours, the reaction was carried out at 30 ° C. for 2 hours.
This solution is poured into 10 l of water and the polyamide acid ester is
A precipitate was obtained. This precipitate is dried in a vacuum dryer at 50 ° C. for 20 hours.
Let dry. The chlorine ion content of this polymer is 100
ppm (yield: 71 g, yield: 97%). Example 3 Positive photosensitive polyimide precursor
Synthesis of Stirrer, thermometer, nitrogen flow in a 500 ml four-necked flask
Attach the irrigation tube and place 4,4'-diaminodiphenyl
6.0 g (0.03 mol) of ether, bis (paraamino
Phenoxyphenyl) sulfone 13.0 g (0.03 m
), 1,3-bis (3-aminopropyl) tetramethyl
2.48 g (0.01 mol) of rudisiloxane
It was dissolved in 100 g of tyrolactone. Example 1 here
28.6 g (0.04 mol) of the acid anhydride synthesized in
3 ', 4,4'-biphenyltetracarboxylic dianhydride
5.9 g (0.02 mol) of gamma-butyrolactone 68
g, and stirred at 25 ° C. for 1 hour.
The reaction was performed for 2 hours. A naphthoquinonediazide compound was added to this solution.
(4NT-300 manufactured by Toyo Gosei Co., Ltd.)
20% by weight based on the rimer component)
Positive Photosensitive Polyimide Dissolved in Alkaline Aqueous Solution
A varnish of the precursor composition was obtained. Chloride ion content is 1p
pm or less. This varnish is applied to a 6-inch silicon wafer.
Coater developer SC manufactured by Nippon Screen Co., Ltd.
Spin coat using a W-636 spin coater,
Dry at 100 ° C for 3 minutes on SCW-636 hot plate
Coating was performed so that the thickness of the film afterwards became 7 μm. This is
After drying, the g-line stepper NSR- manufactured by Nikon Corporation
At the time of exposure through a predetermined reticle using 1505g6E
Exposure was performed at a focus of 0 μm for 800 milliseconds.
After exposure, 0.6% tetramethyl ammonium hydroxide
Development was carried out for 3 minutes with the aqueous sid solution. Then immerse in pure water for 20 seconds
After the pickling, nitrogen was blown to dry. After development, the pattern
As a result, the contact hole of 5 μm was resolved.
A good pattern could be obtained. [0056] According to the present invention, the chloride ion concentration can be reduced.
In addition to suppressing, the desired heat-resistant resin precursor and
And a polymer of the photosensitive heat-resistant resin precursor composition.
Can be.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08G 73/00-73/26

Claims (1)

(57) [Claim 1] having a structural unit represented by the general formula (1)
Photosensitivity containing polymer and naphthoquinonediazide compound
A method for producing a heat-resistant resin precursor composition , comprising reacting a tricarboxylic acid chloride with a hydroxydiamino compound in a process of synthesizing a polymer having a structural unit represented by the general formula (1), When synthesizing the acid anhydride represented by 2), dehydrochlorination was performed using an epoxy compound and / or a compound having an unsaturated bond to obtain
Method for producing a photosensitive heat-resistant resin precursor composition, wherein the this <br/> to less 5ppm of chlorine ion concentration of the polymer. Embedded image (R1 and R3 are a trivalent or tetravalent organic group having at least 2 or more and 20 or less carbon atoms, R2 is a trivalent to hexavalent organic group having at least 2 or more and 20 or less carbon atoms, R4 is an organic group having 2 to 30 carbon atoms, R5 and R6 are one or more of an organic group having 1 to 10 carbon atoms and / or hydrogen, and m is 1 An integer from 1 to 100, n represents 1 or 2, and p represents an integer from 1 to 4.) (R7 and R9 represent a trivalent organic group having 2 to 20 carbon atoms, R8 represents a tri- to hexavalent organic group having 2 to 20 carbon atoms, and q represents an integer selected from 1 to 4. .)