JPH0518866B2 - - Google Patents

Description

[Detailed description of the invention]

FIELD OF APPLICATION OF THE INVENTION The present invention relates to a method of sensitizing photopolymer compositions by using polar polymers. [Prior Art] Conventionally, as a related compound of Mihiraketone, which is famous as a sensitizer, p-aminophenyl (αβ-unsaturated) ketone or bis(p-aminophenyl (αβ-unsaturated) aminophenyl αβ, βγ unsaturated)
known as ketones. Compared to Mihiraketone, these compounds have a light absorption range that extends into the visible range, so they can be effectively used to sensitize photosensitive polymer compositions based on polymers that have absorption ranges in the ultraviolet range. can. However, these compounds, especially when based on polar polymers, have insufficient compatibility with the polymer, which poses a practical problem. This point becomes particularly problematic when a photosensitive polymer composition or a photosensitive polymer using these is used as a photoresist. In other words, when these varnishes are applied to a substrate and dried to form a coating film, if they are poorly compatible with the base polymer, they may precipitate as microcrystals from the film or separate, causing defects. It happens. In addition, these compounds have insufficient solubility in polar solvents that dissolve polar polymers, and therefore some of them have the drawback of requiring heating of the liquid during varnish preparation. [Object of the Invention] The object of the present invention is to eliminate the above-mentioned drawbacks of the prior art, and to improve the composition of photosensitive polymers by using a sensitizer that has high solubility in polar solvents and good compatibility with polar polymers. The objective is to provide a method for effectively sensitizing objects. [Summary of the Invention] In order to achieve the above object, the present inventors have discovered that the above-mentioned sensitizer is located at a position remote from the chromophore that plays a main role in the sensitizing effect in its structure. By introducing a polar group that strongly interacts with polar solvents and polar polymers, the sensitizing effect can be improved.
It was thought that solubility and compatibility would improve. As a result of extensive studies and tests based on this idea, we have discovered a sensitizer for use in the method of the present invention. The feature of the method for sensitizing the photosensitive polymer composition of the present invention as described above is that in order to sensitize the photosensitive polymer composition, the following general formula [] is used as a sensitizer. (However, R ¹ is a lower alkyl group, R ² is -H, X is a carbon or nitrogen atom, and Y is - when X is a carbon atom.
When OH, X is a nitrogen atom, -H or -COOR ⁴
(where R ⁴ is a lower alkyl group, and n is 0 or 1). If such a photosensitizer according to the present invention is used, it can be dissolved without heating when preparing a photosensitive polymer composition or a photosensitive polymer varnish, and there are no defects when forming a film. It is possible to obtain a small amount of film and to obtain sufficient sensitization. The present invention will be explained in more detail below. Examples of photosensitive polymer compositions sensitized with the compound represented by the general formula [] used in the present invention include those consisting of a phenol novolak resin or polyvinylphenol resin and an aromatic azide compound, and those consisting of a polyamic acid and an aromatic azide compound. Those consisting of an amine compound with an aromatic azide group, those consisting of an amine compound with a polyamic acid and a double bond, those consisting of an amine compound with a polyamic acid, a bisazide compound, and a double bond, those with a double bond in the side chain Examples include, but are not limited to, those consisting of a polyamic acid and a bisazide compound. Regarding the specific structure of these, please refer to Special Publication No. 56-29261,
Japanese Patent Publication No. 54-145794, Special Publication No. 53-34902, Special Patent Application No. 1987-145794
-177200, patent application 1984-54408, patent application 1982-157516
etc. are disclosed in detail. Examples of the photosensitive polymer used in the present invention and sensitized by the compound represented by the general formula [] include polyamic acid or polyamide having a double bond or an aromatic azide group in the side chain. However, it is not limited to these. Regarding these specific structures, please refer to JP-A-49-115541 and JP-A-55.
−45748, etc., are disclosed in detail. Specific examples of the sensitizer represented by the general formula [] used in the present invention include: (However, R ⁵ is −OH, −CH ₂ OH, −COOK, −
A group selected from COONa, -COOH, _-OCH3 , -N( _CH3 ) ₂ , ^R7 is -COOH, _-COOCH3 , -
Groups selected from COOC ₂ H ₅ , -COCH ₃ , -H, -CH 3 , R ⁶ and ^{R 8} _represent -H, -CH ₃ or -C ₂ H ₅ ), etc. Not limited. The compound represented by the general formula [] used in the present invention is prepared by adding dialkylaminophenylbenzaldehyde or dialkylaminophenyl cinnamaldehyde and a ketone having a cyclo structure to an alkaline catalyst such as sodium hydroxide or potassium hydroxide in an alcohol solvent. It can be synthesized by a dehydration condensation reaction in the presence of The compound represented by the general formula [] used in the present invention is usually dissolved in a solvent together with a photosensitive polymer composition or a photosensitive polymer. In the case of a photosensitive polymer composition, the compounding ratio of the compound represented by the general formula [] used in the present invention is 100 parts by weight of the total of the polymer and the photosensitizing component; When expressed as parts by weight, it is preferable to mix in a proportion of 0.01 parts by weight or more and 50 parts by weight or less. When the amount is less than this range, a sufficient sensitizing effect cannot be obtained, and when it is more than this range, the film forming ability is adversely affected. [Examples of the Invention] Hereinafter, the present invention will be explained in more detail with reference to Examples, and the effects of the present invention will be illustrated with reference to Comparative Examples. Example 1 Paradimethylaminocinnamaldehyde ()
7.7 g (44 mmole) and 2.28 g (20 mmole) of 4-hydroxycyclohexanone () were dissolved in 25 ml of ethanol. For this solution, 2g
A 40% aqueous sodium hydroxide solution was added, and the mixture was allowed to react at room temperature for 2 days. The precipitated dark orange crystals were collected by suction filtration, washed with ethanol, and then recrystallized from 2-methoxyethanol to obtain 3.4 g (41% yield) of a product with a melting point of 232-235°C. This product was identified as 2,6-bis(p-dimethylaminocinnamylidene)-4-hydroxycyclohexanone () from the following analysis results. NMR is Hitachi R-24 type nuclear magnetic resonance device (60Mz)
Measured using Chemical shifts are expressed as δ values in ppm using tetramethylsilane as an internal standard. In addition, the signal pattern, coupling constant, integral ratio, and attribution are shown in order in parentheses. NMR
(CDCl ₃ ) δ3.0 (singlet, 6H, methyl proton of dimethylamino group), 2.9-3.5 (broad multiplet, 4H, methylene proton of cyclohexanone ring) 3.8-4.2 (broad multiplet,
1H, methine proton of cyclohexanone ring),
4.9 (broad singlet, 1H, hydroxy proton), 6.7 (doublet, J=9Hz, 4H, aromatic proton), 6.6-7.4 (multiplet, 6H, olefin proton), 7.3 (doublet, 4H, J=
9Hz, aromatic proton). IR was measured using a Hitachi 200-10 spectrophotometer using the KBr tablet method. IR (KBr) 3350 (O-H), 1580
(C=O), 1300 (C-N) cm ^<1> . The above reaction formula is shown as follows. Next, repeat unit: 2 g of polyamic acid represented by, 2-(N,N-dimethylamino)ethyl paraazidobenzoate 2.3
g, dissolved in N-methyl-2-pyrrolidone,
A total of 20 g of solution was prepared and designated as Solution A. For solution A, 0.5 g of 2,6-bis(p-dimethylaminocinnamylidene)-4-hydroxycyclohexanone synthesized as above as a sensitizer.
was added and stirred at room temperature for 30 minutes to obtain a homogeneous solution, which was then filtered under pressure using a 1 μm pore filter. The obtained solution was spin-coated onto a silicon wafer using a spinner, and then dried at 90°C for 30 minutes to form a 2μ
I got m. This coating was applied under conditions of 23℃ and 60% humidity.
Even after being left for 24 hours, the initial clean membrane state was maintained. Next, this coating film was closely covered with a striped mask and irradiated with ultraviolet light using a 500W high-pressure mercury lamp. The intensity of ultraviolet rays on the exposed surface was 25 mW/cm ² at 365 mm. After exposure N-methyl-2-pyrrolidone 4
Develop with a mixture of 1 volume of ethanol and 1 volume of ethanol, then wash with a rinse solution (ethanol) to create a relief.
I got the pattern. The remaining film thickness is plotted against the irradiation dose, and the coating film thickness is normalized by the film thickness after development, which is 0.5.
A sensitivity of 13 mJ/cm ² was obtained, with the irradiation amount giving . The sensitivity in this example without using a sensitizer is 18
mJ/cm ² , and a sensitivity improvement of 1.4 times was observed. In addition, the spectral sensitivity was separately measured using a spectral sensitometer using an X _e lamp as a light source. In the sensitivity shown in FIG. 2 of the system using this sensitizer, the sensitive region extended to longer wavelengths, and a clear sensitizing effect was observed. Example 2 Paradimethylaminobenzaldehyde ()
3.28 g (22 mmole) and 1.28 g (10 mmole) of 4-methylolcyclohexanone () were dissolved in ethanol. For this solution, 3g of 30%
An aqueous sodium hydroxide solution was added, and the mixture was allowed to react at room temperature for 2 days. The precipitated orange crystals were collected and washed with methanol, and then recrystallized from a mixture of methanol and water to obtain 1.83 g of a product with a melting point of 235-237°C (47% yield).
I got it. This product is determined from the following analysis and precipitation results.
2.6-bis(p-dimethylaminoaminobenzal)
It was identified as -4-methylolcyclohexanone (). NMR (DM50-ds) δ1.5-2.2 (broad multiplet, 1H, methylene proton of cyclohexanone ring), 3.0 (singlet, 6H, methyl proton of dimethylamino group), 2.6-3.3 (multiplet, 4H, cyclohexanone ring) methylene proton), 4.7 (broad singlet, 1H, hydroxy proton), 6.7 (double, J=9Hz,
4H, aromatic proton), 7.3 (doublet, J=9
Hz, 4H, aromatic proton), 7.7 (singlet,
2H, olefin proton). IR (KBr) 3450 (O-H), 1580 (C-O),
1300(C-N)cm ^-1 . The above reaction formula is shown as follows. To 20 g of the solution A prepared in Example 1, 2,6-bis(p-
When 0.7 g of dimethylaminobenzal)-4-methylolcyclohexanone was added and an experiment was conducted under the same filtration conditions, film formation conditions, and irradiation conditions as in Example 1,
The formed film maintained its initial clean state even after being left at 23°C and 60% humidity for 24 hours.
Increased sensitivity by 1.3 times. Example 3 1.54 g (10 mmole) of 4-piperidone monohydrate hydrochloride () was dissolved in 15 ml of ethanol, and then 1.0 mmol of 4-piperidone monohydrate was dissolved in 15 ml of ethanol.
A solution of g of sodium hydroxide dissolved in 2 ml of water was added, and the mixture was allowed to react at room temperature for 1 hour. The precipitated sodium chloride was separated by filtration, and 3.28 g (22 m
mole) and allowed to react at room temperature for 2 days. The precipitated orange crystals were collected by suction filtration, washed with methanol, and then recrystallized from 2-mexiethanol to give 2.1 g of a product with a melting point of 240-242°C (yield 58%).
I got it. From the following analysis results, this product is 3.
5-bis(p-dimethylaminobenzal)-4-
It was identified as piperidinone (). NMR (CDCl ₃ ) δ1.6 (singlet, 1H, amino proton), 3.0 (singlet, 6H, methyl proton of dimethylamino group), 4.1 (singlet,
4H, methylene proton of cyclohexane ring),
6.7 (doublet, J=9Hz, 4H, aromatic proton), 7.3 (doublet, J=9Hz, 4H, aromatic proton, 7.7 (singlet, 2H, olefin proton). IR (KBr) 1590 (C=O), 1320(C-N)cm
^-1 . The above reaction formula is shown as follows. To 20 g of the solution A prepared in Example 1, 3,5-bis(p-
Dimethylaminobenzal)-4-piperidinone 0.3
When an experiment was conducted under the same filtration conditions, film formation conditions, and irradiation conditions as in Example 1, the formed film was 23 g.
Even after being left for 24 hours at ℃ and 60% humidity, the initial clean film was maintained and the sensitivity was increased by 1.2 times. Example 4 Paradimethylbenzaldehyde () 3.28g
(22m mole) and N-ethoxycarbonyl-4-
10ml of piperidone () 1.71g (10m mole)
was dissolved in ethanol. For this solution, 1g
Add 20% aqueous sodium hydroxide solution and stir at room temperature for 5 minutes.
It was allowed to react for several days. The precipitated orange crystals were collected, washed with ethanol, and then recrystallized from 2-methoxyethanol to obtain 2.2 g (51% yield) of a product with a melting point of 250-252°C. This product was identified as 3,5-bis(p-dimethylaminobenzal)-N-ethoxycarbonyl-4-pyridinone () from the following analysis results. NMR (DMSO-ds) δ1.2 (triplet, J=
7Hz, 3H, methyl proton of ethyl group), 3.0 (singlet, 6H, methyl proton of dimethylamino group), 4.1 (quartet, J = 7Hz, 2H, methylene proton of ethyl group), 4.7 (singlet,
4H, methylene proton of cyclohexanone ring)
6.7 (doublet, J=9Hz, 4H, aromatic proton), 7.3 (doublet, J=9Hz, 4H, aromatic proton), 7.7 (singlet, 2H, olefin proton). IR (KBr) 1700 ( _−CO2Et )

[Formula], 1580 (C=O of cyclohexane ring), 1280 (C-N) cm
^-1 . The above reaction formula is shown as follows. 10 g of phenol novolac resin, 2-(N,N-dimethylamino)ethyl paraazidobenzoate 2
Dissolve g in 120 g of ethyl cellosolve acetate,
Solution B of the photosensitive polymer composition was prepared. In contrast, 0.2g of the sensitizer synthesized above
3,5-bis(p-dimethylaminobenzal)
-N-ethoxycarbonyl-4-piperidinone was added and dissolved at room temperature, and filtered under pressure using a 0.2 μm filter. The resulting solution was spin-coated onto a silicon wafer and then dried at 70°C for 20 minutes to form a 0.9μ
A coating film of m thickness was obtained. This coating was covered with a striped photomask and exposed to ultraviolet light using a 500W high-pressure mercury lamp. Developed using 0.1N aqueous sodium hydroxide solution, then washed with water to create a relief.
I got the pattern. The coating film formed here before exposure maintained its initial clean state even after being left at 23°C and 60% humidity for 24 hours, and the sensitivity was increased by 1.7 times. Example 5 To the solution B prepared in Example 4, 0.2 g of 2,6-bis(p-dimethylaminocinnamylidene)-4- synthesized in Example 1 was added as a sensitizer.
Hydroxycyclohexanone was added, dissolved at room temperature, and filtered under pressure using a 0.2 μm filter. The obtained solution was tested under the same film forming conditions and irradiation conditions as in Example 4. The coating film formed by Priebek is
Even after being left at 23°C and 60% humidity for 24 hours, the initial pure film state was maintained, and the sensitivity was increased by 1.5 times. Example 6 90 g (0.45 mol) of 4,4'-diaminodiphenyl ether, 12.2 g (0.05 mol) of 4,4'-diaminodiphenyl ether-3-carbonamide under a nitrogen stream
mol) in 1764 g of N-methyl-2-pyrrolidone to prepare an amine solution. Next, while keeping this solution at a temperature of about 15°C by ice-cooling, 54.5 g (0.25 mol) of pyromellitic dianhydride, 3.
80.5 g (0.25 mol) of 3',4,4'-benzophenonetetracarboxylic dianhydride was added. After addition, polyamic acid with a viscosity of 55 poise (30°C) is further reacted at about 15°C for 3 hours: (However, R ¹⁷ is

[Formula] and

[Formula] is 1:1, R ¹⁸ is

[Formula] and

〔Effect of the invention〕

As detailed above, according to the present invention, it is possible to use a sensitizer that has good compatibility with a polar base polymer and is easily soluble in a polar solvent. On the other hand, it is possible to provide a sensitization method that causes fewer defects during film formation and facilitates the preparation of varnish.

[Brief explanation of drawings]

FIG. 1 is a graph showing the spectral sensitivity of an example of a photosensitive polymer composition without using a sensitizer according to the present invention. FIG. 2 is a graph showing the spectral sensitivity of an exemplary photosensitive polymer composition using the sensitizer according to the present invention, measured by the same method as in FIG. 1.

Claims (1)

[Scope of Claims] 1 As a sensitizer for a photosensitive polymer composition containing a polar polymer as a component, the following general formula [1] [However, R ¹ is a lower alkyl group, R ² is -H, X is a carbon or nitrogen atom, and Y is - when X is a carbon atom.
When OH, X is a nitrogen atom, -H or -COOR ⁴
(wherein R ⁴ is a lower alkyl group) and n is 0 or 1]. Method for sensitization of coalescent compositions. 2. The photosensitive polymer composition containing the above polar polymer as a component is a phenol novolac resin or a polyvinylphenol resin and an aromatic azide compound, a polyamic acid and an amine compound having a double bond, a polyamic acid and a bisazide compound and a double bond. an amine compound having a double bond in a side chain, a polyamic acid having a double bond in a side chain, or a bisazide compound. Sensation method. 3. The photosensitive polymer composition containing the polar polymer as a component is characterized in that the polymer is polyamic acid, polyamide, or polyvinyl alcohol having a double bond or an aromatic azide group in the side chain. A method for sensitizing a photosensitive polymer composition comprising the polar polymer according to item 1.