JP3929367B2 - Photosensitive aromatic polyether polymer - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel aromatic polyether polymer containing a positive photosensitive substituent. More specifically, the present invention relates to a novel aromatic polyether polymer that not only exhibits high sensitivity and high resolution positive photosensitivity but also has heat resistance, high adhesion, mechanical properties, and low dielectric properties.
[0002]
[Prior art]
As a positive photosensitive resin having heat resistance, a resin composition obtained by adding a naphthoquinonediazide-based photosensitizer to polyamic acid or polybenzoxazole which is a precursor of polyimide has been known (for example, JP-A-5-11451). Gazette). However, these conventional photosensitive resin compositions have generally been recognized as having a low residual film ratio ([film thickness after development] / [film thickness before development] × 100%) in the unexposed area.
[0003]
In order to improve the residual film ratio, a method of increasing the amount of the photosensitive agent added has been studied. However, in this case, the film strength is lowered, so that it is not suitable for practical use. In addition, conventionally known polyamic acids and polybenzoxazoles require high-temperature heat treatment in order to heat and close the ring, but there is a problem in the dimensional stability of the remaining film portion due to heat shrinkage at this time. . There has been a demand for the development of a positive photosensitive resin capable of solving the above problems and forming a high-definition pattern.
[0004]
On the other hand, iminosulfonate compounds are listed as one of compounds exhibiting positive photosensitivity. Since the iminosulfonate skeleton is photocleavable by irradiation with ultraviolet light to generate sulfonic acid, attempts to apply the compounds as a partial structure of a photoacid generator or a photosensitive resin have already been studied. As a report example of the photosensitive resin, J. K. Polym. Sci. Polym. Chem. Ed. 27, 325-page (1989) and the like, but none of them is a non-heat-resistant resin such as polystyrene or polymethacrylate having a main chain skeleton, and could not meet application in fields requiring heat resistance. .
[0005]
[Problems to be solved by the invention]
It is an object of the present invention to provide a novel positive photosensitive polymer having high sensitivity and high resolution.
[0006]
[Means for Solving the Problems]
As a result of intensive studies, the present inventors have surprisingly found that the following compounds can solve the above problems, and have completed the present invention.
[0007]
That is, this invention relates to the aromatic polyether polymer which has a repeating unit represented by general formula (I), and the photosensitive film containing this.
[Chemical 3]
(In the formula, A represents a divalent alkylene group having 1 to 10 carbon atoms, —SO ₂ —, —SO—, —S—, —O—, —C (CF ₃ ) ₂ — or —CO—). m represents an integer of 0 or 1, and n represents an integer of 1 to 3. Each R independently represents a hydrogen atom, an organic substituent, or an organic substituent having an iminosulfonate structure represented by the following formula ( W ). And at least one is an organic substituent having an iminosulfonate structure represented by the following formula ( W ) .)
[0008]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
The aromatic polyether polymer of the present invention has a repeating unit represented by the formula (I).
[0009]
[Formula 4]
(In the formula, A represents a divalent alkylene group having 1 to 10 carbon atoms, —SO ₂ —, —SO—, —S—, —O—, —C (CF ₃ ) ₂ — or —CO—). m represents an integer of 0 or 1, and n represents an integer of 1 to 3. Each R independently represents a hydrogen atom, an organic substituent, or an organic substituent having an iminosulfonate structure represented by the following formula ( W ). And at least one is an organic substituent having an iminosulfonate structure represented by the following formula ( W ) .)
[0010]
In the formula (I) of the present invention, A is a divalent alkylene group having 1 to 10 carbon atoms, —SO ₂ —, —SO—, —S—, —O—, —C (CF ₃ ) — or —CO. If it is-, it will not specifically limit. The divalent alkylene group having 1 to 10 carbon atoms, and examples include a methylene group, an ethylene group, -C _{(CH 3) 2} - and the like.
[0011]
In the formula (I) of the present invention, m is not particularly limited as long as m is an integer of 0 or 1, and n is an integer of 1 to 3.
[0012]
In the formula (I) of the present invention, each R is independently a hydrogen atom, an organic substituent, or an organic substituent having an iminosulfonate structure represented by the following formula ( W ), wherein at least one of R is Any organic substituent having an iminosulfonate structure represented by the following formula ( W ) is not particularly limited. The iminosulfonate structure refers to a structure containing —SO ₂ —O—N.
[0013]
Preferred examples of the organic substituent include halogen atoms, halogenated hydrocarbon groups, aromatic groups, condensed polycyclic aromatic groups, alkoxy groups such as methoxy groups and ethoxy groups, phenoxy groups, nitro groups, amino groups, sulfones. Examples include, but are not limited to, protonic acid groups selected from acid groups, carbonyl groups, hydroxyl groups, phosphoric acid groups, and sulfonimide groups, and metal salts thereof.
[0014]
The organic substituent containing an iminosulfonate structure has the following formula (W)
[Chemical formula 5]
[0015]
It is represented by
[0016]
In the present invention, the logarithmic viscosity ηinh of the aromatic polyether polymer is not particularly limited, but a preferable logarithmic viscosity is 0.1 to 2.0 dl / g, and 0.2 to 1. 8 dl / g is more preferable, and 0.3 to 1.6 dl / g is more preferable.
[0017]
If the logarithmic viscosity of the aromatic polyether polymer is too low, in general, there may be a case where the remaining film ratio of the unexposed portion is lowered or the strength and toughness of the processed product is lowered, which is not preferable. If the logarithmic viscosity of the aromatic polyether polymer is too high, a fine pattern is produced during the development process when a film obtained from the aromatic polyether polymer obtained for the purpose of producing a circuit substrate is processed by photolithography. In some cases, such as inability to process, the reliability of the product is lowered, which is not preferable.
[0018]
The method for evaluating the logarithmic viscosity of the aromatic polyether polymer is not particularly limited. For example, after dissolving 0.50 g of the aromatic polyether polymer in 100 ml of N-methyl-2-pyrrolidone, It can be measured at 35 ° C.
[0019]
The aromatic polyether polymer used in the present invention contains various diols and dihalide compounds in addition to the repeating unit component having the structure represented by the general formula (I), and various physical properties such as heat resistance, hygroscopicity, For the purpose of controlling the thermal expansion coefficient, dielectric constant, refractive index, birefringence, etc., it may be copolymerized as necessary. However, the aromatic polyether type polymer having the structure represented by the general formula (I) It is a preferable embodiment that the coalescence is contained in the composition in an amount of 10 to 100% by weight.
[0020]
The aromatic polyether polymer used in the present invention may be produced by any method.
A preferred method for producing an aromatic polyether polymer used in the present invention is a method obtained by condensation polymerization of a diol represented by the formula (II) and a dihalide compound represented by the formula (III): IV) and the dihalide compound represented by the formula (V) are subjected to condensation polymerization, and then the sulfonic acid metal base contained is converted to a sulfonic acid chloride group by an acid chlorination reaction through an acid treatment. -A method obtained by reacting with a hydroxyimine compound, and an aromatic polyether polymer obtained by condensation polymerization of a diol represented by formula (VI) and a dihalide compound represented by formula (VII). And the like, and a method of obtaining a sulfonic acid chloride group by an acid chlorination reaction and reacting this with an N-hydroxyimine compound, but is not limited thereto. Not.
[0021]
[Chemical 6]
[0022]
(In the formula, A represents a divalent alkylene group having 1 to 10 carbon atoms, —SO ₂ —, —SO—, —S—, —O—, —C (CF ₃ ) ₂ — or —CO—). m represents an integer of 0 or 1, and n represents an integer of _{1 to} 3. R _{1 to} R ₁₆ each independently represents a hydrogen atom, an organic substituent, or an organic substituent having an iminosulfonate structure. , At least one of R _{1 to} R ₁₆ is an organic substituent having an iminosulfonate structure, R _{17 to} R ₃₂ each independently represents a hydrogen atom, an organic substituent, or a metal sulfonate group; At least one of R _{17 to} R ₃₂ is a sulfonic acid metal base, each of R _{33 to} R ₄₈ independently represents a hydrogen atom or an organic substituent, and at least one of R _{33 to} R ₄₈ is , A hydrogen atom.)
[0023]
The photosensitive film of the present invention is characterized by containing the above aromatic polyether polymer.
In the photosensitive film of the present invention, an aromatic polyether polymer is preferably used as a composition component, and any other component such as a sensitizer, a photopolymerization initiator, a leveling agent, a cup is used depending on the purpose. Although it may contain a ring agent, a monomer, an oligomer, a stabilizer, a wetting agent, a pigment, a dye, etc., the aromatic polyether polymer is preferably contained in the film in an amount of 10 to 100% by weight. .
[0024]
The photosensitive film of the present invention may be produced by any method. For example, for example, the aromatic polyether polymer is dissolved in an organic solvent, and this is dissolved on a supporting substrate. The method of apply | coating to and drying can be mentioned.
In producing the photosensitive film of the present invention, when the aromatic polyether polymer is applied on a support substrate, a method of applying the aromatic polyether polymer dissolved in an appropriate organic solvent is preferable. Is the method. The solvent used here is not limited, but for example,
[0025]
(A) a phenolic solvent,
Phenol, o-chlorophenol, m-chlorophenol, p-chlorophenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6 -Xylenol, 3,4-xylenol, 3,5-xylenol,
[0026]
(B) an aprotic amide solvent,
N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-methylcaprolactam, hexamethylphosphorotri Amide,
[0027]
(C) an ether solvent,
1,2-dimethoxyethane, bis (2-methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, tetrahydrofuran, bis [2- (2-methoxyethoxy) ethyl] ether, 1,4-dioxane ,
[0028]
(D) an amine solvent,
Pyridine, quinoline, isoquinoline, α-picoline, β-picoline, γ-picoline, isophorone, piperidine, 2,4-lutidine, 2,6-lutidine, trimethylamine, triethylamine, tripropylamine, tributylamine,
[0029]
(E) other solvent,
Dimethyl sulfoxide, dimethyl sulfone, diphenyl ether, sulfolane, diphenyl sulfone, tetramethyl urea, anisole, water, benzene, toluene, o-xylene, m-xylene, p-xylene, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p -Dichlorobenzene, bromobenzene, o-dibromobenzene, m-dibromobenzene, p-dibromobenzene, o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, o-bromotoluene, m-bromotoluene, p-bromo Toluene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentane, hexane, Heptane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride, fluorobenzene, methyl acetate, ethyl acetate, butyl acetate, methyl formate, ethyl formate and the like. These solvents may be used alone or in combination of two or more.
These solvents are preferably used in an amount of 100 to 10000 parts by weight, more preferably 200 to 5000 parts by weight, based on 100 parts by weight of the aromatic polyether polymer used.
[0030]
In producing the photosensitive film of the present invention, the method for applying the aromatic polyether polymer to the supporting substrate is not particularly limited. For example, application using a spin coater, application using a spray coater, bar coater Application, spraying, dipping, printing and the like using can be mentioned. The amount to be applied is not particularly limited, but for example, the final film thickness after curing is 0.5 μm to 500 μm, preferably 1 μm to 100 μm.
[0031]
In the step of drying after applying the aromatic polyether polymer on the support substrate, the drying time and drying temperature are not particularly limited, but generally 25 ° C. to 250 ° C., 10 minutes to 24 hours is sufficient. Drying may be performed in an air atmosphere, but may be performed in a nitrogen atmosphere or under reduced pressure.
[0032]
The photosensitive film obtained from the aromatic ether polymer of the present invention has a high residual film ratio in an unexposed portion after development. In addition, since a final heat treatment at a high temperature is unnecessary, a high-resolution relief pattern insulating film having excellent workability and dimensional stability can be obtained. Therefore, the photosensitive film is extremely useful for applications such as highly integrated semiconductor devices and highly integrated multilayer wiring boards as surface protective films and interlayer insulating films.
[0033]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not restrict | limited at all by this.
〔Evaluation methods〕
The test methods of the tests in the examples are as follows.
(A) Logarithmic viscosity of aromatic ether polymer 0.50 g of aromatic ether polymer was dissolved in 100 ml of N-methyl-2-pyrrolidone (hereinafter sometimes abbreviated as NMP), and then the viscosity at 35 ° C. Measured with a meter.
[0034]
Example 1
(Synthesis Example 1)
[Production of 5,5′-carbonylbis (sodium 2-fluorobenzenesulfonate)]
A reactor equipped with a thermometer, a reflux condenser, and a stirrer was charged with 4,4′-difluorobenzophenone (0.525 mol) and 210 ml of 50% fuming sulfuric acid, and then reacted at 100 ° C. for 12 hours. This was discharged into 1000 g of ice water and then neutralized with 210 g of NaOH. Next, 10 g of NaCl was added, dissolved by heating, allowed to cool, and left overnight. After the precipitated crystals were filtered, 400 ml of water and 400 ml of ethanol were added and dissolved by heating, followed by cooling and recrystallization. The precipitated crystals were filtered and dried at 100 ° C. for 6 hours to obtain white crystals of 5,5′-carbonylbis (sodium 2-fluorobenzenesulfonate). The yield was 155.2 g (0.368 mol, yield 70%).
[0035]
(Synthesis Example 2)
[Production of sodium sulfonate-containing polyether polymer]
In a five-necked reactor equipped with a nitrogen inlet tube, a thermometer, a reflux condenser, and a stirrer, 5,5′-carbonylbis (sodium 2-fluorobenzenesulfonate) synthesized in the above Synthesis Example 1, bisphenol- A, K ₂ CO ₃ was weighed. DMSO and toluene were added thereto, and the mixture was stirred under a nitrogen atmosphere and heated at 130 ° C. for 2 hours. Water generated during the reaction was removed out of the system by azeotropy with toluene. Toluene was distilled off, followed by reaction at 160 ° C. for 15 hours. The obtained viscous polymer solution was filtered, and then the polymer solution was discharged into strongly stirred toluene. As a result, a yellow powdery precipitate was obtained, which was separated by filtration.
The precipitate was further washed twice with acetone and filtered off. This yellow powder was dried at 50 ° C. for 4 hours, and then dried at 150 ° C. for 4 hours in a nitrogen stream to obtain a sodium sulfonate-containing polyether polymer powder.
[0036]
(Synthesis Example 3)
[Production of sulfonic acid group-containing polyether polymer]
The sodium sulfonate-containing polyether polymer synthesized in Synthesis Example 2 was weighed and ion-exchanged water was added thereto. While stirring under a nitrogen stream, 2N-sulfuric acid was gradually added dropwise. After stirring overnight at room temperature, the polymer solution was discharged into strongly stirred acetone to obtain a yellow powdery precipitate, which was filtered off.
The precipitate was further washed twice with acetone and filtered off. This yellow powder was dried at 50 ° C. for 4 hours, and then dried at 150 ° C. for 4 hours under a nitrogen stream to obtain a sulfonic acid group-containing polyether polymer powder.
[0037]
(Synthesis Example 4)
(Production of aromatic polyether polymer)
The sulfonic acid group-containing polyether polymer powder obtained above was transferred to a five-necked reactor equipped with a nitrogen inlet tube, a thermometer, a reflux condenser, and a stirring device, and thionyl chloride was added. The reaction was carried out for 3 hours under reflux conditions. After excess thionyl chloride was distilled off, N-hydroxysuccinimide and DMAc were added, and pyridine was added dropwise while stirring under a nitrogen atmosphere. After completion of dropping, the reaction was carried out at 50 ° C. for 10 hours. The obtained polymer solution was filtered and then discharged into methanol with vigorous stirring. As a result, a yellow powdery precipitate was obtained, which was separated by filtration. The precipitate was further washed twice with methanol and filtered off. This yellow powder was pre-dried at 50 ° C. for 4 hours, and then dried at 150 ° C. for 4 hours under a nitrogen stream to obtain a polymer powder represented by the formula (VIII).
[Chemical 7]
[0038]
Example 2
[Production of photosensitive film]
2 g of the aromatic polyether polymer obtained in Example 1 was dissolved in 8 g of NMP to obtain a 20 wt% polymer solution. This solution was applied to a 35 μm thick copper foil (Mitsui Metals SQ-VLP) mat surface by bar coating. At this time, the gap of the applicator used was set to 0.025 mm. This was dried at 80 ° C. for 20 minutes under a nitrogen stream to obtain a photosensitive film. The film thickness at this time was 5 μm.
[0039]
Example 3
[Manufacture of relief patterns]
The photosensitive film obtained in Example 2 was placed on a photomask and exposed with an ultraviolet irradiation device (HMW-532D manufactured by ORC). The exposed portion was dissolved and removed by immersing a 5 wt% TMHA aqueous solution as a developer, and then rinsed with ion-exchanged water. Subsequently, it was dried in an oven at 80 ° C. for 30 minutes. As a result, it was confirmed that a good pattern was formed.
[0040]
【The invention's effect】
According to the present invention, it has become possible to provide a novel positive photosensitive polymer having high sensitivity and high resolution.

Claims (2)

An aromatic polyether polymer having a repeating unit represented by formula (I).
(In the formula, A represents a divalent alkylene group having 1 to 10 carbon atoms, —SO ₂ —, —SO—, —S—, —O—, —C (CF ₃ ) ₂ — or —CO—). m represents an integer of 0 or 1, and n represents an integer of 1 to 3. Each R independently represents a hydrogen atom, an organic substituent, or an organic substituent having an iminosulfonate structure represented by the following formula ( W ). And at least one is an organic substituent having an iminosulfonate structure represented by the following formula ( W ) .)
A photosensitive film comprising the polymer according to claim 1 .