JPH0545024B2 - - 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, (a) a compound that can generate an acid when irradiated with actinic rays; (b) a compound that has at least one silyl ether group that can be split by an acid; and (c) a compound that can generate an acid by irradiation with actinic rays. A novel photo-solubilizing composition containing a compound capable of generating species and scavenging the radical species of the acid or acid precursor generated from (a). "Prior Art" Orthoquinone diazide 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. Such orthoquinone diazide compounds include:
For example, US Pat.
Same No. 3046118, Same No. 3046119, Same No. 3046120,
Same No. 3046121, Same No. 3046122, Same No. 3046123,
Same No. 3061430, Same No. 310809, 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. Furthermore, compositions based on such acid-decomposable compounds have the disadvantage that the effective sensitivity gradually increases with the time elapsed between exposure and 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, it is an object of the present invention to provide a novel photo-solubilizable composition that has high photosensitivity and wide development latitude during development. Another objective of this work is to provide novel photosolubilizable compositions whose sensitivity does not depend on the elapsed time between exposure and development. 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 compound containing at least one silyl ether group in the molecule that can be split by an acid shown in the general color () below.
and (c) a compound capable of generating radical-inhibiting species upon irradiation with actinic light and capturing the radical species of the acid or acid precursor generated from (a). This is what we provide. The compound having a silyl ether group that can be decomposed by an acid represented by the general color () used in (b) of the present invention can preferably be represented by a repeating unit of the following general formula (). In the formula, R ₁ represents a divalent aliphatic or aromatic hydrocarbon. Preferably, it represents a divalent aliphatic or aromatic hydrocarbon having a hydrophilic group, urethane group, ureido group, amide group, or ester group. Note that the hydrophilic group referred to in the present invention specifically includes 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, and m and n represent an integer of 2 or more, preferably an integer of 2 to 100, and more preferably an integer of 2 to 20. R represents alkyl or a phenyl group which may have a substituent. A particularly preferred hydrophilic group is (--CH ₂ CH ₂ --O)-- _o . R ₂ and R ₃ may be the same or different, and each represents a hydrogen atom, alkyl, alkenyl, aryl or aralkyl which may have a substituent, or -OR ₄ . Preferably it represents alkyl having 1 to 4 carbon atoms or _-OR4 . R ₄ represents an alkyl, aryl, or aralkyl group which may have a substituent, preferably an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 15 carbon atoms. Moreover, the compound (b) used in the present invention has the general formula ()
It may contain two or more types of repeating units represented by. Specific examples of the compound in (b) of the present invention include:
Includes: (-1) (-2) (-3) (-Four) (-Five) (-6) (-7) (-8) (-9) (-Ten) (-11) (-12) (-13) (-14) (-15) (-16) (-17) (-18) (-19) (-20) (-twenty one) (-twenty two) (-twenty three) (-twenty four) (-twenty five) (-26) (-27) (-28) (-29) (-30) (-31) (-32) (-33) (-34) (-35) (-36) (-37) Note that n in the specific examples represents an integer of 2 or more. In addition, x, y, and z indicate the molar ratio, and Compound Example-43
~45, x = 10 to 85 mol%, y = 5 to 80 mol%,
z=10 to 85 mol%. Also, compound example-5~
17, -19, -24, -35, and -39 to 42, x = 5 to 90 mol% and y = 10 to 95 mol%. Compounds capable of generating an acid upon irradiation with actinic rays according to the present invention (a), which are used in combination with a compound having at least one silyl ether group that can be decomposed by these acids, include many known compounds and mixtures, such as: Diazonium, phosphonium, sulfonium, and iodonium BF ₄ ^- , PF ₆ ^- ,
Salts such as ZbF ₆ ^- , SiF ₆ ^- , ClO ₄ ^- , organohalogen compounds, orthoquinonediazide sulfonyl chloride, and organometallic/organohalogen compound combinations are suitable. Of course, the compounds which generate acid upon high decomposition as described in US Pat. No. 3,779,778 and DE 2,610,842 are also suitable as compositions according to the invention. Furthermore, a compound intended to provide a visible contrast between the unexposed area and the exposed object during exposure in combination with a suitable dye;
For example, compounds described in the specifications of JP-A-55-77742 and JP-A-57-163234 can also be used as the composition of the present invention. Among the compounds that generate acid upon high decomposition, orthoquinonediazide sulfonyl chloride, and s-triazine derivatives or oxadiazole derivatives substituted with halomethyl groups are particularly preferred.
For example, in the case of orthoquinonediazidolsulfonyl chloride, three acid groups (i.e., hydrochloric acid, sulfonic acid, and carboxylic acid) are formed upon 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 in (a) of the present invention and the compound having at least one silyl ether group capable of being decomposed by an acid in (b) is 0.001:1 to 2 by weight. :1, preferably 0.02:1 to 0.8:1. In addition, examples of compounds (so-called radical inhibitor precursors) that generate radical inhibiting species by irradiation with actinic rays in (c) of the present invention and can capture the radical species of the acid or acid precursor generated from (a) include, for example. Examples include aromatic nitro compounds, thiuram disulfide compounds, disulfide compounds, sulfide compounds, and mercapto compounds. Specifically, the following compounds are included. (C-1) (C-2) (C-3) (C-4) (C-5) (C-6) (C-7) (C-8) (C-9) (C-10) (C-11) (C-12) (C-13) (C-14) (C-15) (C-16) (C-17) (C-18) (C-19) (C-20) (C-21) (C-22) (C-23) (C-24) (C-25) (C-26) (C-27) (C-28) (C-29) (C-30) (C-31) (C-32) (C-33) The molar ratio of the compound of the present invention (c) to the compound capable of generating an acid upon irradiation with actinic rays in the present invention (a) is 0.01:1 to 10:1, preferably 0.1:1 to 10:1. Used in a 1:1 ratio. The photo-solubilized composition of the present invention comprises the above (a), (b), and
Although the compound (c) can be used alone in combination, 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-1987-
As described in Publication No. 125806, in addition to the above-mentioned phenol resin, a phenol substituted with an alkyl group having 3 to 8 carbon atoms such as t-butylphenol formaldehyde resin or a condensation product of cresol and formaldehyde is used. It is more preferable to use them together. The alkali-soluble resin is about 40 to about 90% based on the total weight of the photosensitive resist forming composition.
It is contained in an amount of 60 to 80% by weight, preferably 60 to 80% by weight. 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 cyclohexanone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, toluene, and ethyl acetate.
These solvents may be used alone or in combination.
The concentration of the above components (total solid content 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. Also, the amount of application varies depending on the application, but
For example, for photosensitive planographic printing plates, the solid content is generally preferably 0.5 to 3.0 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, chrome-treated copper 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. Examples of such laser beams include helium/neon lasers, argon lasers, crypto ion lasers, helium/cadmium lasers, and the like. 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, ammonium diphosphate,
Aqueous solutions of inorganic alkaline agents such as sodium metasilicate, sodium bicarbonate, aqueous ammonia, etc. are suitable and are added at a concentration of 0.1 to 10% by weight, preferably 0.5 to 5% by weight. Moreover, a surfactant or an organic solvent such as alcohol can be added to the alkaline aqueous solution as necessary. "Examples" The present invention will be explained in more detail by Examples below, but the content of the present invention is not limited thereto. Example 1 A 0.24 mm thick 2S aluminum plate 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 sulfate. This aluminum plate was heated at a current density of 20% sulfuric acid.
An aluminum plate was prepared by performing anodic oxidation at 2 A/dm ² for 2 minutes. Next, eight types of photosensitive liquids [A]-1 to [A]-8 were prepared by changing the type of compound (c) of the present invention in the following photosensitive liquid [A].
This photosensitive solution was applied on an anodized aluminum plate, dried at 100℃ for 2 minutes,
Photosensitive lithographic printing plates [A]-1 to [A]-8, respectively.
was created. Also, the compound of the present invention in photosensitive liquid [A]
As (b), compound example (-12) (n=4, x/
y=40/60, molecular weight is GPC (Gel Permeation
Chromatography) Polystyrene standard was 3500. ) was used. The total coating amount at this time was 1.5 g/m ² in terms of dry weight. Table 1 shows the compound (c) of the present invention used in photosensitive solutions [A]-1 to [A]-8 and the amount thereof added. Photosensitive liquid [A]

[Table] Next, as a comparative example, the following photosensitive liquid [B] and a photosensitive liquid [C] which does not contain the compound (c) of the present invention in the photosensitive liquid [A] were coated in the same manner, and a photosensitive planographic printing plate [ B] and [C] were produced. Photosensitive liquid [B]

[Table] The coating weight after drying was 1.5 g/m ² in both cases.
Photosensitive lithographic printing [A]-1 to [A]-8, [B], and [C] A gray scale with a density difference of 0.15 was brought into close contact with the photosensitive layers, and a 30 ampere carbon arc lamp was used.
Exposure was performed from a distance of 70 cm. DP-
4 (product name: manufactured by Fuji Photo Film Co., Ltd.) in an 8-fold diluted aqueous solution at 25°C for 60 seconds to develop the density difference.
The exposure time that would make the fifth step completely clear with a gray scale of 0.15 was determined. Furthermore, in order to show excellent sensitivity stability over time between exposure and development, photosensitive lithographic printing plates [A]-1 to [A]
-8, [B], and [C] were exposed for 20 seconds by the above method and then allowed to stand for 30 seconds and 60 minutes. Thereafter, development was carried out in the same manner, and the difference in level difference at which a completely clear gray scale with a density difference of 0.15 was obtained after 30 seconds and 60 minutes was determined, and the results were as shown in Table 1.

[Table] As can be seen from Table 1, the photosensitive lithographic printing plates [A]-1 to [A]-8 using the compounds of the present invention were more effective than [B] using the naphthoquinone diazide compound.
Both have short exposure times and high sensitivity. Furthermore, compared to [C] which does not contain the compound (c) of the present invention, the difference in the number of gray scale steps over time is smaller,
Excellent sensitivity stability over time between exposure and development. Example 2 Photosensitive liquids [A]-9 to [A]- in which the type of compound (b) of the present invention was changed in the photosensitive liquid [A] of Example 1
Photosensitive lithographic printing plates [A]-9 to [A]-12 were prepared in the same manner as in Example 1 using No. 12. Similarly, photosensitive lithographic printing plates [C] were prepared using photosensitive solutions [C]-9 to [C]-12 which do not contain the compound (c) of the present invention among photosensitive solutions [A]-9 to [A]-12. -9 to [C]-12 were produced. As the compound (c) of the present invention in photosensitive solutions [A]-9 to [A]-12, 0.020 g of Compound Example (C-17) was used. All coating amounts are dry weight
It was 1.5g/ ^m2 . Also, photosensitive liquid [A]-9~
The compound (b) of the present invention used in [A]-12 is shown in Table 2. The photosensitive lithographic printing plates [A]-9 to [A]-12 and [C]-9 to [C]-12 were exposed and developed by the method shown in Example 1, and after 30 seconds of exposure and 60
Table 2 shows the difference in level that becomes completely clear in a gray scale with a density difference of 0.15 over a period of minutes.

【table】

[Table] Compound (-6) of the present invention in Table 2,
(-9), x/y=50/50 (molar ratio), n=4
I used the one from In addition, the molecular weight of the compound (b) of the present invention in Table 2 is (-6) and (-9).
1600~ with VPO (Vapour Pressure Osmometer)
2100, (-25), and (-38) were 2500 to 5000 according to the GPC polystyrene standard. As can be seen from Table 2, the photosensitive lithographic printing plates [A]-9 to [A]-12 using the compounds of the present invention do not contain the corresponding compounds of the present invention (C-17) [C] -9 to [C]-12, the difference in the number of gray scale steps over time is small, and the sensitivity stability over time between exposure and development is excellent.

Claims (1)

[Scope of Claims] 1 (a) A compound capable of generating an acid upon irradiation with actinic rays; (b) having at least one silyl ether group in the molecule that can be decomposed by an acid represented by the following general formula () A photo-solubilizing composition comprising a compound, and (c) a compound that generates radical-inhibiting species upon irradiation with actinic light and can capture the radical species of the acid or acid precursor generated from (a).