JPH0161103B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a substance belonging to the novel o-naphthoquinonediazide compounds. “Light-Sensitive Systems” by J. Kosar
(John Wiley & Sons, New York.1965)
Pages 343 to 351 of U.S. Patent No. 3046110, U.S. Patent No. 3046111, U.S. Patent No. 3046123,
Many photosensitive naphthoquinonediazide compounds are also described in various specifications such as JP-B No. 3046124, JP-A No. 3106465, JP-B No. 3130047, and Japanese Patent Publication No. 46-21247. These photosensitive naphthoquinone diazide compounds are widely used as photoresists for lithographic printing plates, letterpress printing plates, IC circuits, photomasks, and printed wiring because of their extremely excellent performance. However, when the yellow photosensitive o-naphthoquinonediazide compound is exposed to light, it fades and becomes a colorless or pale yellow photodegradable component, but under the yellow safety light during exposure work, the exposed and unexposed areas are separated after exposure. cannot be identified. In order to ameliorate this drawback, several attempts have been made to form a visible image after exposure of a photosensitive composition. For example, U.S. Patent Nos. 2066913 and 2618555
The use of various reducible salts described in the specification of the No. 1979-1983-1 by mixing them with diazo compounds,
A method for obtaining a visible image from a photosensitive diazo compound and an acid-base indicator described in Japanese Patent Publication No. 2203, and an o-naphthoquinonediazide-4-sulfonic acid halide and a dye described in JP-A-50-36209. Examples include those containing organic compounds having salt-forming ability. However, even with these improvements, the contrast of the visible image obtained by exposure is often insufficient under yellow safety lights in actual work, and even when sufficient contrast is obtained, the contrast of the original resist In addition to the naphthoquinonediazide compound that has formation ability, it contains a compound for obtaining a visible image, such as a diazo compound, so the naphthoquinonediazide compound may cause a decrease in resist formation ability, such as a decrease in resist sensitivity, poor developability, etc. The current situation is that we have not reached a satisfactory state. The object of the present invention is to eliminate such conventional drawbacks, and to provide a novel o-naphthoquinone compound, which can be applied as a photosensitive compound in positive resists, and which, in combination with a color change agent, gives a visible image after exposure. Our goal is to provide the following. As a result of various studies, the present inventors have discovered novel o-naphthoquinone diazide compounds represented by the following general formulas () to () that are useful for achieving the above object. In the formula, R ₁ and R ₂ each represent hydrogen or a straight-chain alkyl group having 1 to 12 carbon atoms. In the formula, R ₃ represents hydrogen or a phenyl group. In the formula, Z is a tetramethylene group,
Represents [formula] or [formula]. In the formula, R ₄ represents hydrogen or a straight chain alkyl group having 1 to 6 carbon atoms. In the formula, X ₁ , X ₂ , X ₃ and X ₄ each represent a chlorine or bromine atom. The compounds represented by the general formulas () to () of the present invention are described by GF Jaubert, Berichteder
Deutschen Chemischen Gesellschaft, 28 , 360
~364 (1895), by DEAmes et al.
Journal of the Chemical Society, 3518-3521
(1955), MAStolberg et al.
Journal of the American Chemical Society,
79, 2615-2617 (1957), L. Bauer et al., Journal of Organic Chemistry, 24 , 1293
~1296 (1959) method or LM
Werbel et al., Journal of Medical Chemistry,
General formula () synthesized according to the method described in 10, 32-36 (1967), etc. (Here, A represents the compound of the general formula () or the dotted line part of [Formula] of ().) The compound represented by and 1,2-naphthoquinone-2
It can be synthesized by carrying out a dehydrochlorination condensation reaction with -diazide-4-sulfonic acid chloride in the presence of a dehydrochlorinating agent. This reaction proceeds in either an aqueous solvent or an organic solvent as long as it is in the coexistence of a dehydrochlorinating agent. When in an aqueous solvent, suitable dehydrochlorination agents include lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and the like. When carrying out the reaction in an organic solvent, organic solvents that do not have an OH group, such as diethyl ether, diisopropyl ether, acetone, dichloromethane, chloroform, carbon tetrachloride, tetrahydrofuran, dioxane, ethyl acetate, benzene, toluene, acetonitrile, etc. is suitable, and as the dehydrochlorination agent, pyridine,
Diethylamine, triethylamine, N,N-dimethylaniline, N,N-diethylaniline and the like are preferred. The reaction is performed using 1,2-naphthoquinone-2-diazide-4- with respect to 1 equivalent of the compound of general formula ().
It is preferable to use 1 to 1.5 equivalents of sulfonic acid chloride and 1 to 1.5 equivalents of dehydrochlorination agent, and the reaction temperature is -
10°C to 40°C is preferred. Specific examples of compounds of the present invention are as follows. [Table] [Table] [Table] The o-naphthoquinone diazide compound of the present invention is
Similar to known o-naphthoquinonediazide compounds, a rearrangement reaction occurs upon irradiation with light, resulting in a difference in solubility between exposed and unexposed areas. For this reason, the o-naphthoquinone diazide compound of the present invention can be incorporated as a photosensitive resist-forming compound into photosensitive compositions used for producing printing plates such as lithographic plates, letterpress plates, and intaglio plates, photoresists, and photographic elements. . In the o-naphthoquinonediazide compound of the present invention, in addition to the above-mentioned rearrangement reaction based on the o-naphthoquinonediazide group, cleavage occurs in bonds near the ester bond when irradiated with light. For this reason, the o-
Naphthoquinone diazide compounds can be used for lithographic printing plates,
It is particularly useful in providing photosensitive resist-forming compositions for the production of IC circuits and photomasks with the ability to provide a visible image upon exposure without development. Since such a photosensitive resist composition can obtain a visible image only by exposure under a yellow safety light in the exposure operation, it is difficult to avoid the possibility that the work is interrupted, e.g., in the process of exposing many printing plates as well. It becomes possible to know whether the plate given to the plate maker has been exposed or not. Similarly, when a large plate is exposed to light many times, as in the so-called reprint printing method used to make lithographic printing plates, the operator must immediately check which areas have been exposed. Can be done. EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the content of the present invention is not limited thereto. Example 1 N-(1,2-naphthoquinone-2-diazide-
Synthesis of 4-sulfonyloxy)succinimide (Exemplary Compound No. 1) 6.9 g of N-hydroxysuccinimide and 1,
Add 100 ml of tetrahydrofuran to 16.1 g of 2-naphthoquinone-2-diazido-4-sulfonyl chloride, and add 6.1 g of triethylamine to 16.1 g of 2-naphthoquinone-2-diazide-4-sulfonyl chloride while stirring.
A solution dissolved in 1 ml of tetrahydrofuran was added dropwise over 2 hours while cooling the reaction solution so that the temperature did not rise above 25°C. After reacting for an additional 2 hours at 15°C to 25°C, the reaction solution was poured into 400ml of water and the precipitate was collected. Recrystallized from a mixed solvent of acetonitrile and methyl cellosolve to obtain N-(1,2-naphthoquinone-
15.5 g of 2-diazido-4-sulfonyloxy)succinimide was obtained. The melting point of this compound was determined, elemental analysis was performed, and the mass spectrum was measured. Melting point 168-171℃ (decomposition) Elemental analysis Measured value H = 2.45%, C = 48.35%,
N=12.22% Calculated value H=2.62%, C=48.42%,
N=12.10% Ion acceleration voltage 6kV Ionization voltage 70eV Mass spectrum results Ionization current 200μA Sample heating temperature 190℃ Ion source temperature 190℃ m/e intensity m/e intensity 63 6.7 157 48.0 64 10.3 205 100.0 113 35.0 319 11.3 1 29 28.2 347 10.1 141 33.9 Example 2 N-(1,2-naphthoquinone-2-diazide-
Synthesis of 4-sulfonyloxy)-2,2-dimethylsuccinimide (Exemplary Compound No. 3) 50 g of 2,2-dimethylsuccinic acid and 70 ml of acetic anhydride
After reacting at 140℃ for 3 hours, acetic acid and acetic anhydride were removed under reduced pressure, and 2,
37 g of 2-dimethylsuccinic anhydride was obtained. 22g of 2,2-dimethylsuccinic anhydride and 30ml of water
was added, and 11 g of sodium carbonate and 14 g of hydroxylamine hydrochloride were added while cooling so that the reaction temperature did not exceed 20° C., and the mixture was reacted at room temperature for 1 hour. After reacting at 40 to 50°C for 1 hour, the mixture was cooled to 5°C, 5 ml of concentrated hydrochloric acid and 10 ml of methanol were added, and the resulting N-hydroxy-2,2-dimethylsuccinimide was collected. Add 100 ml of dioxane to 5.7 g of N-hydroxy-2,2-dimethylsuccinimide and 10.7 g of 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride, and cool the reaction solution while stirring so as not to exceed 25°C. while triethylamine 4.1
A solution prepared by dissolving G in 20 ml of dioxane was added dropwise over 2 hours. After reacting for an additional 2 hours at 15°C to 25°C, the reaction solution was poured into 300ml of water and the precipitate was collected. This was recrystallized from acetonitrile and N-
10 g of (1,2-naphthoquinone-2-diazido-4-sulfonyloxy)-2,2-dimethylsuccinimide was obtained. Melting point 157-159℃ (decomposition) Elemental analysis Actual value H = 3.39%, C = 51.05%,
N=11.27% Calculated value H=3.49%, C=51.20%,
N=11.19% Ion acceleration voltage 6kV Ionization voltage 70eV Mass spectrum results Ionization current 200μA Sample heating temperature 150℃ Ion source temperature 260℃ m/e intensity m/e intensity 56 82.8 205 100.0 64 44.8 347 10.1 113 34.5 375 16.8 141 37.9 157 65.5 Example 3 N-(1,2-naphthoquinone-2-diazide-
4-sulfonyloxy)-5-norbornene-
2,3-dicarboxylic acid imide (Exemplary compound No.
Synthesis of 6) Add 30 ml of water to 24.6 g of 5-norbornene-2,3-dicarboxylic anhydride, and add 10.6 g of sodium carbonate and 13.9 g of hydroxylamine hydrochloride while cooling so that the reaction temperature does not exceed 20°C. The reaction was allowed to proceed at room temperature for 1 hour. The reaction was further carried out at 60 to 70°C for 1 hour, and after cooling to room temperature, the produced N-hydroxy-5-norbornene-2,3-dicarboxylic acid imide was collected. N-hydroxy-5-norbornene-2,3-
Dicarboxylic acid imide 9.0g, 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride 13.4g
Add 100ml of tetrahydrofuran to g, and the reaction solution is
A solution of 5.1 g of triethylamine dissolved in 20 ml of tetrahydrofuran was added dropwise over a period of 2 hours while cooling the mixture to a temperature not exceeding 25°C. After continuing the reaction for another 2 hours at room temperature, the reaction solution was poured into 400 ml of water, and the precipitate formed was collected. Recrystallized from a mixed solvent of methyl cellosolve and acetonitrile to obtain N-(1,2-
12.0 g of naphthoquinone-2-diazido-4-sulfonyloxy)-5-norbornene-2,3-dicarboxylic acid imide was obtained. Melting point 160-162℃ (decomposition) Elemental analysis Measured value H = 3.02%, C = 55.23%,
N=10.32% Calculated value H=3.19%, C=55.47%,
N=10.32% Ion acceleration voltage 6kV Ionization voltage 70eV Mass spectrum results Ionization current 200μA Sample heating temperature 155-160℃ Ion source temperature 240℃ m/e Intensity m/e Intensity 64 44.0 163 30.6 66 100.0 205 82.0 113 10.8 383 5 .8 141 16.0 411 12.0 157 30.0 Example 4 N-(1,2-naphthoquinone-2-diazide-
4-sulfonyloxy)-3,6-oxo-
Synthesis of 1,2,3,6-tetrahydrophthalic acid imide (Exemplary Compound No. 7) N-hydroxy-3,6-oxo-1,2,
3,6-tetrahydrophthalic acid imide 7.3g, 1,
80 ml of tetrahydrofuran was added to 10.8 g of 2-naphthoquinone-2-diazido-4-sulfonyl chloride, and while cooling the reaction solution so as not to exceed 25°C, a solution of 4.1 g of triethylamine dissolved in 20 ml of tetrahydrofuran was stirred for 2 hours. It was dripped.
After continuing the reaction for another 2 hours at room temperature, the reaction solution was diluted with water.
The resulting precipitate was collected. Recrystallized from a mixed solvent of ethanol and acetonitrile,
N-(1,2-naphthoquinone-2-diazide-4
-sulfonyloxy)-3,6-oxo-1,
2,3,6-tetrahydrophthalic acid imide 11.2g
I got it. Melting point 149-151℃ (decomposition) Elemental analysis Measured value H = 2.52%, C = 52.14%,
N=10.02% Calculated value H=2.68%, C=52.30%,
N=10.17% Ion acceleration voltage 6kV Ionization voltage 70eV Mass spectrum results Ionization current 200μA Sample heating temperature 150-160℃ Ion source temperature 200℃ m/e Intensity m/e Intensity 64 42.4 205 87.8 68 100.0 233 22.7 113 51.5 317 8 .0 129 28.7 345 18.2 141 40.9 385 2.1 157 54.6 413 1.4 Example 5 N-(1,2-naphthoquinone-2-diazide-
Synthesis of 4-sulfonyloxy)phthalimide (Exemplary Compound No. 10) 8.2 g of N-hydroxyphthalimide, 1,2-
100 ml of acetonitrile was added to 13.4 g of naphthoquinone-2-diazide-4-sulfonyl chloride, and a solution of 5.0 g of triethylamine dissolved in 20 ml of acetonitrile was added dropwise over 2 hours while cooling the reaction solution so as not to exceed 25°C. . After continuing the reaction for another 2 hours at room temperature, the reaction solution was poured into 500 ml of water and the resulting precipitate was collected. methyl cellosolve,
Recrystallized from acetonitrile mixed solvent, N-
11.5 g of (1,2-naphthoquinone-2-diazido-4-sulfonyloxy)phthalic acid imide was obtained. Melting point 159-161℃ (decomposition) Elemental analysis Actual value H = 2.09%, C = 54.51%,
N=10.60% Calculated value H=2.29%, C=54.69%,
N=10.63% Ion acceleration voltage 6kV Ionization voltage 70eV Mass spectrum results Ionization current 200μA Sample heating temperature 170℃ Ion source temperature 215℃ m/e intensity m/e intensity 104 59.0 157 45.2 113 30.5 205 100.0 129 24.1 367 7.9 141 31.6 395 3.0 147 59.0 Example 6 N-(1,2-naphthoquinone-2-diazide-
Synthesis of 4-sulfonyloxy)-4-methylphthalimide (Exemplary Compound No. 12) Dissolve 5.3 g of sodium carbonate in 100 ml of water and add 6.9 g of hydroxylamine hydrochloride while stirring at room temperature.
g was gradually added. Furthermore, 15.0 g of 4-methylphthalic anhydride was added and reacted at 80°C for 1 hour. After cooling to room temperature, 3 ml of concentrated hydrochloric acid was added dropwise.
The generated N-hydroxy-4-methylphthalimide was collected. N-Hydroxy-4-methylphthalimide 3.5
g, 1,2-naphthoquinone-2-diazide-4-
5.4g of sulfonyl chloride and 40ml of acetonitrile
Add 1.2 g of triethylamine to acetonitrile while cooling the reaction solution so that it does not rise above 25°C.
A solution dissolved in 10 ml was added dropwise over 2 hours. Furthermore, after continuing the reaction at room temperature for 2 hours, the reaction solution was diluted with water.
The resulting precipitate was collected. Recrystallized from a mixed solvent of ethanol and acetonitrile,
N-(1,2-naphthoquinone-2-diazide-4
5.4 g of -sulfonyloxy)-4-methylphthalic acid imide was obtained. Melting point 160-161℃ (decomposition) Elemental analysis Measured value H = 2.52%, C = 55.84%,
N=10.37% Calculated value H=2.71%, C=55.75%,
N=10.26% Example 7 N-(1,2-naphthoquinone-2-diazide-
4-sulfonyloxy)cyclohexane-1,
Synthesis of 2-dicarboxylic acid imide (exemplified compound No. 5) N-hydroxy-1,2-dicarboxylic acid imide
2.0g, 1,2-naphthoquinone-2-diazide
20 ml of tetrahydrofuran was added to 3.2 g of 4-sulfonyl chloride, and a solution of 1.2 g of triethylamine dissolved in 10 ml of tetrahydrofuran was added dropwise over 2 hours while cooling the reaction solution so as not to exceed 25°C. After continuing the reaction for another 2 hours at room temperature, the reaction solution was poured into 200 ml of water, and the resulting precipitate was collected. Recrystallize from 100ml of acetonitrile, N
-(1,2-naphthoquinone-2-diazide-4-
3.2 g of sulfonyloxy)cyclohexane-1,2-dicarboxylic acid imide was obtained. Melting point 154-156℃ (decomposition) Elemental analysis Actual value H = 3.62%, C = 53.95%,
N=10.62% Calculated value H=3.77%, C=53.86%,
N=10.47% Example 8 N-(1,2-naphthoquinone-2-diazide-
Synthesis of 4-sulfonyloxy)-2-dodecylsuccinimide (Exemplary Compound No. 4) Dissolve 4.2 g of hydroxylamine hydrochloride in 50 ml of water and add 3.2 g of sodium carbonate while stirring at room temperature.
g was gradually added to form a homogeneous solution. Add 2-
13.4 g of dodecyl succinic anhydride was added and the reaction was continued at room temperature for 5 hours. 200 ml of water and 2 ml of concentrated hydrochloric acid were added, and the resulting N-hydroxy-2-dodecylsuccinimide was collected. N-hydroxy-2-dodecylsuccinimide
4.3g, 1,2-naphthoquinone-2-diazide
80 ml of tetrahydrofuran was added to 4.0 g of 4-sulfonyl chloride, and a solution of 1.5 g of triethylamine dissolved in 20 ml of tetrahydrofuran was added dropwise over 2 hours while cooling the reaction solution so as not to exceed 25°C. After continuing the reaction for another 2 hours at room temperature, the reaction solution was poured into 500 ml of water and the resulting precipitate was collected. Recrystallized from ethanol to form N-(1,2
4.0 g of -naphthoquinone-2-diazido-4-sulfonyloxy)-2-dodecylsuccinimide was obtained. Melting point 89-92℃ (decomposition) Elemental analysis Actual values H = 6.48%, C = 60.39%, N = 8.05% Calculated values H = 6.45%, C = 60.56%, N = 8.15% Example 9 The surface was grained Apply the following photosensitive liquid to an aluminum plate with a thickness of 0.15 mm using a Whaler, and heat it at 80℃ for 5 minutes.
After drying for a minute, a photosensitive printing plate was prepared. Cresol novolak resin 10.5g O-naphthoquinone diazide compound shown in Table 1 3.0g Crystal violet 0.1g Tetrahydrofuran 70ml Methyl cellosolve 15ml N,N-dimethylformamide 35ml These photosensitive printing plates were each printed using a jet printer (more than 2kW). High-pressure mercury lamp, manufactured by ORC Seisakusho)
The film was exposed to light for 15 counts, and the optical density of the exposed and unexposed areas of the photosensitive layer was measured using a reflection densitometer. Table 1 shows the optical densities of the exposed and unexposed areas and the difference (ΔD) between them. The larger ΔD, the clearer the image appears. [Table] [Table] As shown in Table 1, for the sulfonic acid esters or sulfonamides shown in (Comparative Example 2) to (Comparative Example 5), the difference in optical density (ΔD ) is small. On the other hand, 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride shown in Comparative Example 1 has a large value of ΔD, but has the drawback of lowering the optical density of unexposed areas. Compared to these, the o-naphthoquinone diazide compound of the present invention exhibited a sufficiently large ΔD value without reducing the optical density of the unexposed area, and the intended object of the present invention was achieved. Next, a step wedge (density step 0.15, number of density steps 0 to 15) was placed on the photosensitive printing plate prepared in this example, and after exposure for 15 counts using the jet printer described above, DP-3 (product name: : Fuji Photo Film Co., Ltd., positive PS plate developer) 15
The film was developed with a diluted solution for 60 seconds at 25°C, and the sensitivity was measured. Table 2 shows the number of steps and wedges corresponding to each image that appears. The higher the number of stages, the higher the sensitivity. [Table] [Table] As shown in Table 2, when the o-naphthoquinone diazide compound of (Comparative Example 4) is used, the sensitivity is high, but as shown in Table 1, the value of ΔD is small. When the o-naphthoquinonediazide compound of (Comparative Example 1) is used, the value of ΔD is large as shown in Table 1, but the sensitivity is low. The o-naphthoquinone compound of the present invention has a large ΔD value and sufficient sensitivity. Example 10 The following photosensitive solution was applied to an aluminum plate treated in the same manner as in Example 9 using a Whaler and dried at 100° C. for 2 minutes to prepare a photosensitive printing plate. Condensation product of 1,2-naphthoquinone-2-diazido-5-sulfonyl chloride and m-cresol formaldehyde novolak resin (condensation rate 33
(mol%) 0.60g o-naphthoquinone diazide compound shown in Table 3
0.14 g Cresol novolak resin 2.0 g Tetrahydrophthalic anhydride 0.15 g Crystal violet 0.02 g Ethylene dichloride 18 g Methyl cellosolve 12 g After each of these photosensitive printing plates was exposed to a 30 ampere carbon black lamp from a distance of 70 cm.
DP-3 (Product name: Fujifilm Corporation, positive type PS
The film was developed for 30 seconds at 25°C with a 6-fold dilution of a plate developer) and the sensitivity was measured. Sensitivity was evaluated using a step wedge (density step 0.15, number of density steps 0 to 15). The higher the number of stages, the higher the sensitivity. In addition, the optical density of the photosensitive layer in the exposed and unexposed areas of the exposed plate was measured using a Macbeth reflection densitometer. Further, the unexposed photosensitive printing plate was left in a natural state for 2 months, and after 2 months, it was exposed and the above measurements were repeated. The image obtained by exposure appears sharper as the difference (ΔD) between the density of the exposed area and that of the unexposed area is larger. [Table] As shown in Table 3, the value of ΔD is not large enough for 1,2-naphthoquinone-2-diazide-4-sulfonic acid-2,4-dinitrophenyl ester, and the optical This lowers the density and further reduces the resist sensitivity. However, the o-naphthoquinonediazide compound according to the present invention showed a large ΔD value, had excellent stability over time, and fully achieved the intended purpose without adversely affecting resist sensitivity. Example 11 Surface grained and then anodized, thickness 0.24mm
Apply the following photosensitive solution to an aluminum plate and heat it at 100℃.
and dried for 2 minutes. Naphthoquinone-(1,2)-diazide-(2)-5
- Esterification reaction product of sulfonyl chloride and cresol novolac resin 0.75g Cresol novolac resin 2.10g Tetrahydrophthalic anhydride 0.15g Exemplary compound No. 3 0.10g Crystal violet 0.01g Oil Blue #603 0.01g (Orient Chemical Industry) Co., Ltd.) Ethylene dichloride 18 g Methyl cellosolve acetate 12 g The coating weight after drying was 2.5 g/m ² . By imagewise exposing this photosensitive lithographic printing plate, it was possible to obtain a clear printed image without developing it. The exposed areas faded, while the unexposed areas maintained their original density, making it possible to recognize the details of the image even under safety lights.

Claims (1)

[Claims] 1 o- represented by the general formula () or ()
Naphthoquinone diazide compound. In the formula, R ₁ and R ₂ each represent hydrogen or a straight-chain alkyl group having 1 to 12 carbon atoms. In the formula, R ₃ represents hydrogen or a phenyl group. In the formula, Z is a tetramethylene group,
Represents [formula] or [formula]. In the formula, R ₄ represents hydrogen or a straight chain alkyl group having 1 to 6 carbon atoms. In the formula, X ₁ , X ₂ , X ₃ and X ₄ each represent a chlorine or bromine atom.