JPH048783B2 - - Google Patents

Description

[Detailed description of the invention]

"Industrial Application Field" The present invention is applicable to lithographic printing plates, proof sheets for multicolor printing, drawings for overhead projectors, IC circuits,
The present invention relates to photo-solubilizing compositions suitable for producing photomasks. More specifically, it relates to a novel photo-solubilized composition containing (a) a compound capable of generating an acid upon irradiation with actinic rays, and (b) a compound having at least one silyl ether group capable of being decomposed by an acid. . ``Prior Art'' Orthoquinonediazide compounds have been known as photosensitive substances that act so-called positively and are solubilized by actinic rays, and have been widely used in lithographic printing plates, photoresists, and the like. Examples of such orthoquinone diazide compounds include, for example, U.S. Pat.
No. 2772972, No. 2859112, No. 2907665, No. 3046110, No. 3046111, No. 3046115,
Same No. 3046118, Same No. 3046119, Same No. 3046120,
Same No. 3046121, Same No. 3046122, Same No. 3046123,
Same No. 3061430, Same No. 3102809, Same No. 3106465,
It is described in numerous publications including the specifications of the same No. 3635709 and the same No. 3647443. These orthoquinonediazide compounds are decomposed by irradiation with actinic rays to produce a five-membered carboxylic acid, which makes them soluble in alkali, but all of them have the disadvantage of insufficient photosensitivity. have This is because, in the case of orthoquinone diazide compounds, the quantum yield essentially does not exceed 1. Various attempts have been made to increase the photosensitivity of photosensitive compositions containing orthoquinone diazide compounds, but it has been extremely difficult to increase photosensitivity while maintaining development tolerance during development. . For example, examples of such attempts include the contents described in Japanese Patent Publication No. 48-12242, Japanese Patent Application Laid-Open No. 52-40125, and US Pat. No. 4,307,173. Furthermore, recently, several proposals have been made regarding photosensitive compositions that act positively without using an orthoquinone diazide compound. One such example is a polymer compound having an orthonitrocarbinol ester group, which is described in the specification of Japanese Patent Publication No. 56-2696. However, in this case too, the photosensitivity cannot be said to be sufficient for the same reason as in the case of orthoquinone diazide. In addition, we also use a photosensitive system that is activated by contact action,
As a method of increasing photosensitivity, a known principle is applied in which a second reaction is caused by the acid generated by photolysis, thereby solubilizing the exposed area. Examples of this include, for example, a combination of a compound that generates an acid by photolysis and an acetal or O,N-acetal compound (Japanese Patent Application Laid-open No. 89003/1983);
Combination with orthoester or amide acetal compound (JP-A-51-120714), combination with polymer having acetal or ketal group in the main chain (JP-A-53-133429), combination with enol ether compound (JP-A-53-133429). JP-A No. 55-12995), combination with N-acylimino carbonic acid compound (JP-A No. 55-126236)
(No.), and a combination with a polymer having an orthoester group in the main chain (Japanese Patent Application Laid-open No. 17345/1983). In principle, these have quantum yields exceeding 1, so they may exhibit high photosensitivity, but in the case of acetals or O,N-acetal compounds,
In the case of polymers having an acetal or ketal group in the main chain, the rate of the second reaction by the acid generated by photolysis is slow, and therefore they do not exhibit sufficient photosensitivity for actual use. In addition, orthoester or amide acetal compounds, enol ether compounds, and even N-acylimino carbonate compounds do exhibit high photosensitivity, but they are not stable over time and cannot be stored for long periods of time. Polymers having orthoester groups in their main chains also have high sensitivity, but have the disadvantage of narrow development tolerance during development. "Problems to be Solved by the Invention" The purpose of this research is to provide a novel photo-solubilizable composition in which these problems are solved. That is, the object of the present invention is to provide a novel photo-solubilizing composition that has high photosensitivity and wide development latitude during development. Another purpose of this research is to provide a novel photo-solubilized composition that has excellent stability over time and can be stored for a long period of time. Yet another objective of this research is to provide a novel photo-solubilized composition that is simple to manufacture and easily obtainable. "Means for Solving the Problems" As a result of intensive studies to achieve the above object, the present inventor discovered that the above object could be achieved by using a novel photo-solubilizing composition, and has developed the present invention. Reached. That is, the present invention provides (a) a compound capable of generating an acid upon irradiation with actinic rays, and (b) a partial structure represented by the following general formula () and a partial structure represented by the following general formula (), respectively, at least The object of the present invention is to provide a photo-solubilizing composition containing a silyl ether compound, the solubility of which is increased by the action of an acid in a developer. The mole ratio of the partial structures represented by the general formulas () and () of the silyl ether compound of the present invention is preferably in the range of 99.9:0.1 to 10:90, more preferably 99:1 to 60:40. Further, the silyl ether compound can have a hydrophilic group and/or at least one of an ester group, an amide group, a urethane group, and a ureido group. The molecular weight of the syl ether compound of the present invention is 300 or more in number average molecular weight, more preferably 1000 to 1000.
It is 100000. The silyl ether compound of the present invention comprises an alcohol represented by the following general formula () and a general formula ()
It can be produced by mixing the silicon compound represented by and the silicon compound represented by the general formula () and eliminating H-X. In this case, the molar ratio of the silicon compounds represented by general formulas () and () is preferably in the range of 99.9:0.1 to 10:90,
More preferably, the ratio is 99:1 to 60:40. HO−R ₄ OH () In the formula, R ₁ , R ₂ , and R ₃ may be the same or different, and each represents a hydrogen atom, an alkyl group, a substituted or unsubstituted aryl group, or an aralkyl group. Preferably it represents an alkyl group having 1 to 4 carbon atoms. R ₄ represents a substituted or unsubstituted divalent aliphatic or aromatic hydrocarbon. Further, if necessary, R ₄ may have a hydrophilic group and/or at least one of an ester group, an amide group, a urethane group, and a ureido group. X is a halogen atom, -OR ₅ -, -NCO, cyano group, -OCO
_-R5 , -O- _SO2 - _R5 , and _R5 represents a substituted or unsubstituted alkyl group, aryl group, or aralkyl group. Furthermore, several types of alcohols represented by the general formula () may be used in combination. Specifically, the hydrophilic groups mentioned above include those shown below. −(CH ₂ CH ₂ −O−) _o , [−(−CH ₂ ) _l O−] _n −(CH
₂ CH ₂
-O-) _o , [−(−CH ₂ −) _l O−] _o ,

[Formula] In the formula, l represents an integer of 1 to 4, m and n represent an integer of 1 or more, preferably an integer of 1 to 100, more preferably an integer of 1 to 20. R represents an alkyl group or a substituted or unsubstituted phenyl group. A particularly preferred hydrophilic group is -( _{CH2CH2 -} O-) _o . Next, the following compounds can be mentioned as specific examples of the silyl ether compound of the present invention, but the compounds are not limited to the following. There are many known compounds and mixtures of compounds that can generate an acid upon irradiation with actinic rays, which can be used in combination with a compound containing at least one silyl ether group that can be decomposed by an acid.
Diazonium, phosphonium, sulfonium, and iodonium BF ₄ ^- , PF ₆ ^- , BbF ₆ ^- , SiF ₆ ^2- ,
Salts such as ClO ₄ ^- , organohalogen compounds, orthoquinonediazide sulfonyl chloride, and organometallic/organohalogen compound combinations are suitable.
Of course, compounds which generate acids upon photolysis as described in US Pat. No. 3,779,778 and DE 2,610,842 are also suitable as compositions according to the invention. Further, compounds intended to provide a visible contrast between the unexposed area and the exposed material during exposure in combination with a suitable dye, such as JP-A-Sho.
Compounds described in the specifications of No. 55-77742 and No. 57-163234 can also be used as the composition of the present invention. Among the compounds that generate acid upon photolysis, orthoquinonediazide sulfonyl chloride, s-triazine derivatives substituted with halomethyl groups, and oxadiazole derivatives are particularly preferred. This is because, for example, in the case of orthoquinonediazide sulfonyl chloride, three acid groups (i.e., hydrochloric acid, sulfonic acid, and carboxylic acid) are formed during exposure.
This is because the silyl ether group can be decomposed at a relatively large rate. The ratio of the compound capable of generating an acid upon irradiation with actinic rays and the compound having at least one silyl ether group capable of being decomposed by the acid is 0.001:1 to 2:1 by weight, preferably
Used at a ratio of 0.02:1 to 0.8:1. The photo-soluble composition of the present invention can be used only in combination with a compound capable of generating an acid upon irradiation with actinic rays and a compound having at least one silyl ether group that can be decomposed by an acid.
It is preferable to use it in combination with an alkali-soluble resin. Suitable alkali-soluble resins include novolak type phenolic resins, and specifically include phenol formaldehyde resins, o-cresol formaldehyde resins, m-cresol formaldehyde resins, and the like. Furthermore, JP-A-50-125806
As described in the above publication, a phenol substituted with an alkyl group having 3 to 8 carbon atoms such as t-butylphenol formaldehyde resin or a condensation product of chrysol and formaldehyde is used in combination with the above phenol resin. Then, it is even more preferable. The alkali-soluble resin is contained in an amount of about 40 to about 90% by weight, more preferably 60 to 80% by weight, based on the total weight of the photosensitive resist-forming composition. The photo-soluble composition of the present invention may further contain dyes, pigments, plasticizers, and compounds (so-called sensitizers) that increase the acid generation efficiency of the acid-generating compound, if necessary. . Suitable dyes include oil-soluble dyes and basic dyes. Specifically, oil yellow #101, oil yellow #130, oil pink #312, oil green
BG, oil blue BOS, oil blue #603,
Oil Black BY, Oil Black BS, Oil Black T-505 (manufactured by Orient Chemical Industry Co., Ltd.) Crystal Violet (CI42555),
Methyl violet (CI42535), rhodamine B
(CI45170B), malachite green (CI42000),
Examples include methylene blue (CI52015). The photosoluble composition of the present invention is dissolved in a solvent that dissolves each of the above components and applied onto a support. The solvents used here include ethylene dichloride,
Examples include cyclohexane, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, toluene, and ethyl acetate, and these solvents may be used alone or in combination. and the concentration in the above ingredients (total solids including additives)
is 2 to 50% by weight. Among these, the preferred concentration (solid content) of the composition of the present invention is 0.1 to 25% by weight. Further, although the coating amount varies depending on the application, for example, for photosensitive planographic printing plates, it is generally preferable to have a solid content of 0.5 to 30 g/m ² . As the coating amount decreases, the photosensitivity increases, but the physical properties of the photosensitive film deteriorate. When producing a lithographic printing plate using the photosoluble composition of the present invention, the support may be a hydrophilized aluminum plate, such as a silicate-treated aluminum plate, an anodized aluminum plate, a grained aluminum plate, or a silicate electrode. In addition, zinc plates, stainless steel plates, chromed steel plates, hydrophilized plastic films and paper can be used. Supports suitable for producing printing proof plates, films for overhead projectors, and films for second originals include transparent films such as polyethylene terephthalate film and triacetate film, and the surface of these plastic films can be chemically or physically modified. I can give you something that has turned into matte. Supports suitable for producing photomask films include polyethylene terephthalate films deposited with aluminum, aluminum alloys, and chromium, and polyethylene terephthalate films provided with colored layers.
The photo-solubilizing composition of the present invention can also be used as a photoresist by coating it on various supports other than those mentioned above, such as copper plates, copper-plated plates, and glass plates. Examples of active light sources used in the present invention include mercury lamps, metal halide lamps, xenon lamps, chemical lamps, and carbon arc lamps. Scanning exposure with a high-density energy beam (laser beam or electron beam) can also be used in the present invention. Such laser beams include helium neon lasers, argon lasers, krypton ion lasers, helium
Examples include cadmium lasers. Developers for the photosoluble composition of the present invention include sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, tribasic ammonium phosphate, Aqueous solutions of inorganic alkaline agents such as ammonium diphosphate, sodium metasilicate, sodium bicarbonate, aqueous ammonia, etc. are suitable, and their concentration is 0.1 to 10% by weight,
It is preferably added in an amount of 0.5 to 5% by weight. Moreover, a surfactant and an organic solvent such as alcohol can be added to the alkaline aqueous solution as required. "Examples" The present invention will be explained in more detail with reference to synthesis examples and examples, but the content of the present invention is not limited thereto. Synthesis Example 1 (Synthesis of Compound Example No. 1) Tetraethylene glycol 8.00g
(0.0412mole) and pyridine 7.90g (0.0999mole)
was dissolved in 100 ml of toluene, and while stirring, a solution of 3.56 g (0.0276 mole) of dimethyldichlorosilane in 5 ml of toluene was added using a dropping funnel at room temperature.
Added over 10 minutes. After the addition, stirring was continued for 3 hours at 50°C on an oil bath. This was returned to room temperature, and a solution of 1.77 g (0.0118 mole) of methyltrichlorosilane in toluene (5 ml) was added via a dropping funnel over 10 minutes. After the addition, stirring was continued for 3 hours at 50°C. Separate the generated white salt (pyridine hydrochloride) and add 100ml of 3% sodium bicarbonate aqueous solution.
Then, it was washed with 100 ml of saturated saline. After drying this with anhydrous sodium sulfate, the solvent was distilled off under reduced pressure to obtain a colorless transparent viscous liquid. Yield 9.59
g. The number average molecular weight was 4900 by gel permeation chromatography and polystyrene standard. Synthesis Example 2 (Synthesis of Compound Example No. 2) p-xylylene glycol 5.69g
(0.0412mole) and pyridine 7.90g (0.0999mole)
was dissolved in 100 ml of toluene, and while stirring, a toluene (5 ml) solution of 5.03 g (0.0389 mole) of dimethyldichlorosilane and 0.65 g (0.0043 mole) of methyltrichlorosilane was added at room temperature using a dropping funnel over 20 minutes. . After addition, on oil bath, 50℃
Stirring was continued for 5 hours. The white salt formed (pyridine hydrochloride) was separated and the solution was washed with 100 ml of 3% aqueous sodium bicarbonate solution and then with 100 ml of saturated brine. After drying this with anhydrous sodium sulfate, the solvent was distilled off under reduced pressure to obtain a colorless transparent viscous liquid. Yield 7.90g. The number average molecular weight was 3500 as measured by gel perfusion chromatography and polystyrene standard. Synthesis Example 3 (Synthesis of Compound Example No. 3) Tetraethylene glycol 31.6g (0.163mole)
and p-xylylene glycol 15.0g (0.109mole)
and 43.9g (0.555mole) of pyridine in toluene
A solution of 30.1 g (0.233 mole) of dimethyldichlorosilane in toluene (40 ml) was added to the solution over 30 minutes from a dropping funnel at room temperature while stirring. After the addition, stirring was continued for 2 hours at 70°C on an oil bath. This was returned to room temperature, and a solution of 3.87 g (0.0259 g mole) of methyltrichlorosilane in toluene (20 ml) was added from the dropping funnel over 10 minutes. After the addition, stirring was continued for 4 hours at 70°C. Separate the white salt (pyridine hydrochloride) produced, and add 200 ml of 3% sodium bicarbonate aqueous solution to the solution.
Then, it was washed with 200 ml of saturated saline. After drying this with anhydrous sodium sulfate, the solvent was distilled off under reduced pressure to obtain a colorless transparent viscous liquid. Yield 55.6
g. The number average molecular weight was 3000 using gel permeation chromatography and polystyrene standards. Synthesis Example 4 (Synthesis of Compound Example No. 11) Hexane-1,6-diol 10.7g
(0.0906mole) and pyridine 15.8g (0.0997mole)
Dissolve in 100ml of toluene and add to this while stirring,
A solution of 10.4 g (0.0659 mole) of diethyldichlorosilane and 2.47 g (0.0165 mole) of methyltrichlorosilane in toluene (5 ml) was added via a dropping funnel at room temperature over 20 minutes. After addition, on oil bath, 70℃
Stirring was continued for 5 hours. The white salt formed (pyridine hydrochloride) was separated and the liquid was washed with 100 ml of 3% sodium bicarbonate solution and then with 100 ml of saturated saline. After drying this with anhydrous sodium sulfate, the solvent was distilled off under reduced pressure to obtain a colorless transparent viscous liquid. Yield: 15.0g. The number average molecular weight was 3600 by gel permeation chromatography and polystyrene standard. Example 1 A 2S aluminum plate with a thickness of 0.24 mm was degreased by immersing it in a 10% aqueous solution of tertiary sodium phosphate kept at 80°C for 3 minutes, grained with a nylon brush, and then etched with sodium aluminate for about 10 seconds. Then, desmut treatment was performed with a 3% aqueous solution of sodium hydrogen sulfate. This aluminum plate was anodized in 20% sulfuric acid at a current density of 2 A/dm ² for 2 minutes to produce an aluminum plate. Next, three types of photosensitive liquids [A]-1 to [A]-3 were prepared by changing the type of the compound of the present invention in photosensitive liquid [A] below, and this photosensitive liquid was coated on an anodized aluminum plate. and dried at 100° C. for 2 minutes to prepare photosensitive lithographic printing plates [A]-1 to [A]-3. All coating amounts at this time are dry weight.
It was 1.5g/ ^m2 . The compounds of the present invention used in photosensitive solutions [A]-1 to [A]-3 are shown in Table 1. Photosensitive liquid [A] Compound of the present invention 0.31g Cresol-formaldehyde novolac resin
1.0g 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride 0.05g Oil Blue #603 (manufactured by Orient Chemical Industry Co., Ltd.)
0.01g Ethylene dichloride 10g Methyl cellosolve 10g Next, as a comparative example, the following photosensitive solution [B] was applied in the same manner as photosensitive solution [A], and a photosensitive lithographic printing plate [B] was prepared.
was created. Photosensitive liquid [B] Condensation product of phenol formaldehyde novolac resin and 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride 0.45g Cresol-formaldehyde novolac resin
1.0g 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride 0.02g Oil Blue #603 (manufactured by Orient Chemical Industry Co., Ltd.)
0.01 g Ethylene dichloride 10 g Methyl cellosolve 10 g The coating weight after drying was 1.5 g/m ² . A gray scale with a density difference of 0.15 was closely adhered to the photosensitive layers of photosensitive planographic printing plates [A]-1 to [A]-3 and [B], and exposure was performed from a distance of 70 cm using a 30 ampere carbon arc lamp. . Photosensitive lithographic printing plates [A]-1 to [A]-3 and [B] exposed to show the excellent photosensitivity of the present invention
DP-3B (product name: manufactured by Fuji Photo Film Co., Ltd.)
The film was immersed and developed in a 12-fold diluted aqueous solution at 25°C for 60 seconds, and the exposure time at which the fifth stage was completely clear on a gray scale with a density difference of 0.15 was determined, and the results were as shown in Table 1.

[Table] As can be seen from Table 1, all of the photosensitive lithographic printing plates [A]-1 to [A]-3 using the compound of the present invention had a shorter exposure time and higher sensitivity than [B]. In addition, compounds No. 1, 2 of the present invention in Table 1,
The number average molecular weight of 10 is 3000 using gel permeation chromatography and polystyrene standard.
It was ~4900. Example 2 Four types of photosensitive liquids [C]-1 to [C]-4 were prepared by changing the type of compound that can generate an acid upon irradiation with actinic rays in the following photosensitive liquid [C]. In the same manner as above, photosensitive planographic printing plates [C]-1~
[C]-4 was produced. Photosensitive liquid [C] Compound No. 13 of the present invention 0.31g Cresol-formaldehyde novolak resin
1.0g Compounds that can generate acid upon irradiation with actinic rays
0.05 g Oil Blue (manufactured by Orient Chemical Industry Co., Ltd.) 0.01 g Ethylene dichloride 10 g Methyl cellosolve 10 g All coating amounts were 1.5 g/m ² in terms of dry weight.
Table 2 shows the compounds used in photosensitive solutions [C]-1 to [C]-4 that generate acids upon irradiation with actinic rays. A density difference was formed on the photosensitive layer of photosensitive lithographic printing plates [C]-1 to [C]-4 and [B] prepared in Example 1.
Exposure was performed from a distance of 70 cm using a 30 amp carbon arc lamp with a 0.15 gray scale in close contact. Exposed photosensitive lithographic printing plates [C]-1 to [C]
-4 and [B] with an 8-fold diluted aqueous solution of DP-3B (product name: Fuji Photo Film Co., Ltd.) at 25°C.
After second immersion development, the exposure time at which the fifth stage was completely clear in a gray scale with a density difference of 0.15 was determined, and the results were as shown in Table 2.

[Table] Compounds of the present invention used in photosensitive liquid [C]
The number average molecular weight of No. 13 was 4200 as measured by gel permeation chromatography and polystyrene standard. As can be seen from Table 2, all of the photosensitive lithographic printing plates [C]-1 to [C]-4 using the compounds of the present invention have a shorter exposure time and higher sensitivity than [B]. Example 3 Photosensitive planographic printing plates [A]- were prepared in the same manner as in Example 1 using the photosensitive solutions [A]-1 to [A]-3 of Example 1.
1[A]-3 was produced. The coating weight in all cases was 1.5 g/m ² by dry weight. Next, as a comparative example, the photosensitive solution [B] of Example 1 and the following photosensitive solution [D] were coated in the same manner as the photosensitive solution [A] to prepare photosensitive planographic printing plates [B] and [D]. Photosensitive liquid [D] Silyl ether compound represented by the following formula ()
0.31g Cresol formaldehyde novolak resin
1.0g 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride 0.05g Oil Blue #603 (manufactured by Orient Chemical Industry Co., Ltd.)
0.01g Ethylene dichloride 10g Methyl cellosolve 10g The number average molecular weight is 3000 as measured by gel permeation chromatography and polyethylene standard. The coating weight after drying was 1.5 g/m ² in each case. Photosensitive planographic printing plate [A] to check development tolerance
A gray scale with a density difference of 0.15 was closely adhered to the photosensitive layers of -1 to [A]-3, [B] and [D] and exposed for 30 seconds from a distance of 70 cm using a 30 ampere carbon arc lamp. Exposed photosensitive lithographic printing plate [A]
-1 to [A]-3, [B] and [D] were immersed and developed in the same developer as in Example 1 at 25°C for 60 seconds and 3 minutes. Table 3 shows the difference in the number of completely clear steps when developing for 60 seconds and 3 minutes on a gray scale with a density difference of 0.15.

[Table] As can be seen from Table 3, all of the photosensitive lithographic printing plates [A]-1 to [A]-3 using the compound of the present invention had a small change in the number of grayscale steps in the clear area, and had good development tolerance. was very good.

Claims (1)

[Claims] 1. (a) A compound capable of generating an acid upon irradiation with actinic rays, and (b) a partial structure represented by the following general formula () and a partial structure represented by the following general formula (), respectively. A photo-solubilizing composition containing at least one silyl ether compound, the solubility of which increases in a developer by the action of an acid.