JPS6010247A - Photosolubilizable composition - Google Patents

Abstract

PURPOSE:To obtain a photosolubilizable compsn. wide in development latitude and high in sensitivity by introducing a specified ester group as an acid-decomposable ester group. CONSTITUTION:A photosolubilizable compsn. consists of (A) a conpd. capable of producing an acid on irradiation of actinic rays, such as orthoquinonediazidosulfonyl chloride, (B) a compd. having at least one acid-decompozable ester group represented by formula I and increased in solubility by the action of the acid in a developing soln., and when needed, (C) an alkali-soluble resin, such as novolak type phenol resin, and the compd. (B) is preferably represented by general formula II or III in which R1 is a m-valent aliphatic or aromatic hydrocarbon group; R2, R3 are each alkyl or alkoxy; R5, R6 are each a divalent aliphatic or aromatic hydrocarbon; R7 is alkyl, aryl, or aralkyl; m is 1-1,000; n is 1-500; and a1, a2, b1, b2 are each 0 or 1.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a presolubilized composition suitable for the production of lithographic printing plates, proofs for multicolor printing, drawings for overhead projectors, IC circuits, and photomasks.

More specifically, a novel pre-solubilized composition containing (a) a compound that can generate an acid upon irradiation with actinic rays, and [b) an irr compound having at least one ester group that can be decomposed by an acid. relating to things.

Orthoquinonediazide compounds are conventionally known as photosensitive substances that act on so-called positeps, which are solubilized by actinic rays, and have been widely used in lithographic printing plates, photoresists, and the like. Examples of such orthoquinonediazide compounds include those described in US Patent No. 2. 'ytt,ii
No. r, No. 2°7t7,0g J, No. 2,772. No. 7, No. 2. IJ'9, 112, same No. 2,90
No. 7,665, same No. J, 0111. ．． No. 110, No. 3,0≠1.111, No. 3,0≠t, No. 111, No. 3,044t, No. 111, No. 3,0176, // No. 3,0 Gu J, No. 720, No. 3, 0≠1, . 1
No. 21, No. 3.0116, No. 2.2, No. 3.0
Gut, No. 123, No. 3.061.4! J.

No. 3,102. ZA Qri No. J, to
& ettts No. 3,631,702, No. 3
゜6≠7. It is described in numerous publications, including the specifications of Hiroshi ≠ No. 3.

These orthoquinone diazide compounds decompose upon irradiation with actinic rays to produce a J-membered ring carboxylic acid and become alkali soluble, but all of them have the drawback 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 orthoquinonediazide compounds, but it has been extremely difficult to increase photosensitivity while maintaining development tolerance during development. . For example, examples of such attempts include Japanese Patent Publication Shogu No. 1-72λ4/-2, Japanese Patent Publication No. Shoj, Z-≠0l-2 Evening No., and U.S. Patent No. 307,1.
Examples include the contents described in specifications such as No. 73.

Furthermore, recently, several proposals have been made regarding M&photosensitive compositions that act positively without using an orthoquinone diazide compound. As one of them, for example, Tokko Sho tj
Examples include polymer compounds having an orthonitrocarbinol ester group described in Specification 8A of No.-2tPA. 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, as a method of increasing photosensitivity using a photosensitive system that is activated by contact action, a second reaction is caused by the acid generated by photolysis, thereby increasing the exposure area. The known principle of solubilization is applied.

Examples of this include, for example, compounds that generate acids upon photolysis and acetals or 0. Combination with N-acetal compound (Japanese Patent Application Publication No. 2003-120011/a'-ryo.

No. 3), combination with an orthoester or amide acetal compound (%Kaisho!/-lco07/≠No.).

Combination with a polymer having an acetal or ketal group in the main chain (JP-A-13-/J, No. 3-22), combination with an enol ether compound (JP-A-13-12 Tata J)
, combination with N-acylimino carbonated food (Unexamined Japanese Patent Publication No. 1989)
-/, 2 Otsu-3), and a combination with a polymer having an orthoester group in the main chain (% Kaishoj&-/7J≠j). Since these have a quantum yield exceeding 1 in their original form, they may exhibit high photosensitivity, but they are acetal or 0. In the case of N-acetal compounds and in the case of polymers having acetal or ketal groups in the main chain,
Because the speed of the second reaction by the acid generated by photolysis is slow,
Does not exhibit sufficient photosensitivity for practical use. In addition, orthoester or amide acetal compounds, enol ether compounds, and N-acylimino carbonate compounds certainly exhibit high photosensitivity, but their stability over time is poor and they cannot be stored for long periods of time. Can not. Polymers having orthoester groups in their main chains also have high sensitivity, but have the disadvantage of narrow development tolerance during development.

The purpose of this study is to provide a novel pre-solubilized composition in which these problems are solved. That is, the object is to provide a novel pre-solubilized composition that has high photosensitivity and wide development latitude during development.

Another purpose of this research is to provide a novel pre-solubilized composition that has excellent stability over time and can be stored for a long period of time.

Still another objective of this research is to provide a new pre-solubilized composition that is simple to manufacture and easily obtainable.

As a result of intensive studies aimed at achieving the above object, the present inventors discovered that the above object could be achieved by using a novel pre-solubilized composition, thereby achieving the present invention.

That is, the present invention provides a compound that has at least one ester group that can be decomposed by (at) irradiation with actinic light and (bl) acid, and whose solubility in a developer is reduced by the action of the acid. (The ester group in the present invention is one in which the hydrogen atom H of the carboxyl group -COOH is replaced with another organic residue, and (Does not contain ester groups.)
.

Here, the compound (b) is characterized in that the acid-decomposable ester group is represented by the following general formula (I).

-c-o-si-(I) ＼ More preferably, the compound having an acid-decomposable ester group represented by the general formula (I) is a compound represented by the following formula, where l may have a substituent. aliphatic or aromatic hydrocarbon.几2.几3゜it 4 may be the same or different, and each may have a water atom, an alkyl slet substituent, or an aralkyl, an alkyl, a halogen, 1 or -〇- 3. Showing C-R7. Preferably, charcoal number/~≠ alkyl, carbon number/-4 alkyl 1; star, chlor, or -0-C-1 (,7, more preferably charcoal≦ several l~ ≠ alkyl, carbon number/5-g1
, Rs, I(, a may be the same or different, and each represents a divalent aliphatic or aromatic hydrocarbon which may have a substituent. R7 is 1a
Alkyl which may have a base group.

Indicates an aryl or aralkyl group.

m, n are integers in IE, or m is /, 1000%
n is an integer of /-300 9, al, a2゜b 1
, b 2 respectively represent Q or l.

Specific examples of compounds having at least one ester group represented by general formula (I) include those shown below.

I 2 3 &4 li 5 &, 6 7 2I-15 heat 2H5 8 A9 1 0 511 C10゜ CH-C00St 00 (--CsH Engineering □ 11 CH3 Ya12 ．． 613 14 boiled 15 Ha Ha 1 6 Ya17 18 x / y = 0 / / 00 heta o7i.

At least 7 ester groups that can be oxidized by these acids
There are many known compounds and mixtures of compounds that generate and absorb acids upon irradiation with actinic rays, such as diazonium, phosphonium, sulfonium, and iodonium, such as BF4, PF'6-1
Salts such as 8bF6-1SiFs, Q+04-, organic halogenated compounds, orthoquinonedioxytosulfonyl chloride, and organometallic/organohalogenated combinations are suitable. Of course, U.S. Patent No. 3,772,77g and West German Patent No. 2. Compounds that generate acid through photolysis +C described in the specification of Otsuio, T4T2 are also suitable as the chemical composition of the present invention. Furthermore, when combined with an appropriate dye, there is a visible contrast between the unmelted area and the exposed material when cutting the tip of the butterfly! Compounds aimed at giving
Compounds described in Hokkaido 1 can also be used as 41 components in the present invention.

Among the compounds that generate acid through photolysis, orthoquinonedioxytosulfonyl chloride is preferred in terms of taste. This is because, during exposure, three acid groups (namely hydrochloric acid, sulfonic acid, and carboxylic acid) are formed, so that a relatively large proportion of the ester groups can be decomposed.

The ratio of the compound capable of generating an acid upon irradiation with actinic rays and the compound having at least/an ester group capable of being decomposed by the acid is 1 weight ratio: o, oi:i~, 2:
/, preferably o, i:/ to l:l.

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 M ester group that can be decomposed by dispersion. It is preferable to use it in combination with Suitable alkali-soluble resins include novolac type phenolic resins, and specifically include phenol formaldehyde resins, 0-cresol formaldehyde resins, Lm-cresol formaldehyde resins, and the like. Furthermore, as described in JP-A No. 30-/2jtrO4, in addition to the above-mentioned phenol 411JM, phenol substituted with an alkyl group having 3 to 3 g of carbon atoms such as t-i-thylphenol formaldehyde resin or It is more preferable to use a condensate of cresol and formaldehyde in combination. Alkali-soluble resin ('f,
, based on the total weight of the photosensitive resist-forming composition! 0 to about 0 to about rz-M fluoride, more preferably to-to weight percent.

The photo-soluble composition of the present invention may further contain a 1F-dye, an additive, a plasticizer, a compound that increases the acid generation efficiency of the acid-generating compound (so-called sensitizer), etc., as necessary. I can do it. Suitable dyes include oil-soluble dyes and basic dyes. Specifically, oil yellow @10
/, oil yellow @/30. Oil pink #3/2,
Oil Green BG, Oil Blue BO8, Oil Blue #t03, Oil Black BY, Oil Black BS
, Oil Black i'-jOj (manufactured by Orient Chemical Industry Co., Ltd.) Crystal Violet (ci<<-
2tt, methyl violet (CIp, 2s3t)
, *-Damine B (CI4Aj'/70B).

Malachite green (CI≠2000), methylene-1
Examples include h-(cxs2otz).

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 solvent used here is ethylene diflora 9ide.

Examples include dichlorohexanone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, +2-methoxy ether acetate, toluene, and ethyl acetate.

These solvents are used alone or in combination, and the concentration (total solid content including additives) in the above components is between 2 and 5.
It is 0% by weight. Among these, the composition (a) + (b) of the present invention
) is the preferred concentration (solid content) of o, i-2! He is in charge of weight. Also, the coating density varies depending on the application, but for example, when it comes to photosensitive planographic printing plates, the solid content is generally O.
0j~! , 09/m2 is preferred. 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 plate. There is a plated aluminum plate, and other plated lead plate,
Stainless steel plate, chromium-treated steel plate, hydrophilized plastic film or paper? can be raised.

Supports suitable for producing printing proof plates and films for overhead projectors (Figure 2) include transparent films such as polyethylene terephthalate film and triacetate film, and the surface of these plastic films can be chemically or physically treated. I can give you things that are 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. In addition, various supports other than those mentioned above can be used as photoresists, such as copper plates, copper plated plates,
The photosolubilizing composition of the present invention is used by coating it on a glass plate.

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 light beams with heavy density energy beams (laser beams or electron beams) can also be used in the present invention. Examples of such laser beams include helium/neon lasers, argon lasers, krypton ion lasers, helium/cadmium lasers, and the like.

The present liquid for the photosoluble composition of the present invention includes sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, trisodium phosphate,
Aqueous solutions of inorganic alkaline agents such as sodium 11um diphosphate, tertiary ammonium phosphate, ammonium diphosphate, sodium metasilicate, sodium bicarbonate, aqueous ammonia, etc. are suitable, and their concentrations range from 0.1 to 10% by weight, preferably 0. j~! It is added so that it becomes Yu Shigeharu.

Moreover, a surfactant and an organic solvent such as alcohol can be added to the alkaline aqueous solution as necessary.

Hereinafter, the present invention will be explained in more detail using Synthesis Examples and Examples 1 and 1, but the content of the present invention is not limited thereto.

Synthesis example 1. (Synthesis of compound lateral bending 1) While dissolving benzoin (g/2.29 g/00 mQ) in pyridine/00 mQ, hexamethyldisilazane 7,
♂2 was added through a dropping funnel at room temperature over 70 minutes. Subsequently, trimethylchlorosilane 2. 5 tP
It was added over a period of minutes. After the addition, stirring was continued for 5 hours and 1 hour at room temperature. The white salt produced (ammonium chloride salt and/or
After separating the pyridine solution (or pyridine hydrochloride), the pyridine solution was subjected to C condensation under reduced pressure. Vjgreux-Claisen (Vjgreux-Claisen)
Vacuum distillation was performed using a column.

Colorless transparent adult (b, p, Otsu00C10, JmmHP) yield it, ty. The structure was confirmed to be Compound 1 by NM analysis and elemental analysis.

Adipic acid l≠, 6 pyridine/20ml! Hexametheldine lazan is, ty
was added via a dropping funnel at room temperature over 20 minutes.

Subsequently, further trimethylchloro 7 runj, 2s' was added over a period of 70 minutes. After the addition, stirring was continued for 5 hours at room temperature. The white salt produced (ammonium chloride salt and/or
The pyridine solution was concentrated under reduced pressure. The resulting colorless transparent liquid (Vigreux-Claisen 7)
Vacuum distillation was performed using column f.

Colorless transparent liquid (b, p, J'J' 0C10, / 7
ITnnH5? ).

Yield, 21/-07ri. By NM and elemental analysis, it was confirmed that the structure was Compound Example A≠.

Synthesis example 3. (Synthesis of Compound Example A9) Benzoic acid, 2≠, ≠2 was dissolved in pyridine/jOmG', and dimethyldichlorosilane 12. 2 was added over 20 minutes using a dropping funnel. After addition, stirring was continued at room temperature for 3 hours. After separating the resulting white pyridine hydrochloride f:P, it was condensed into a pyridine solution under reduced pressure. The resulting colorless transparent liquid was vacuum-distilled using a Vigreux-Claisen column.

Colorless transparent liquid liquid (b, p, /JJ °C10, Ofm
mH9), yield/Li, 79°N Ml was also confirmed by elemental analysis to have the structure of compound fljl A9.

Synthesis example 4. (Synthesis of compound lateral bending 16) Fumaric acid 11. z2 was dissolved in pyridine/, fOrnQ, and dimethylcyclolonan/2. 2 was added via dropping funnel over 20 minutes. After the addition, stirring was continued for 3 hours at room temperature. After the generated white pyridine hydrochloride fund was poured into the solution, the pyridine solution was completely discharged under pressure. In order to separate the pyridine hydrochloride precipitated in the obtained reddish-brown liquid, 20 ml of methyl ethyl ketone was added and diluted, followed by filtration. Perform p-condensation again, under vacuum (approx./mmH5i'), ♂o 'c
It was dried for 10 hours without heating.

Reddish brown viscous liquid, yield/6. After confirming that the unit 4h structure is compound example A16 by P and NM, V
PO(Vapour Pressure(Jsmome)
The number average molecular weight was measured by ter) and found to be 10,110.

Example 1 A 29 aluminum plate with a thickness of 0.24 mm was immersed in an aqueous solution of 11 um of tertiary sulfuric acid /θ ice for 3 minutes at rooC to degrease it, and then grained with a nylon brush. Etching was performed with sodium hydroxide for about 10 seconds, and desmutting was performed with a 3% aqueous solution of sodium hydrogen oxide.

The current density of this aluminum plate was 2A/d in 20% M acid.
One minute in m2 [¥ii F,'! An aluminum plate was prepared by polar acid oxidation.

Next, a photosensitive solution (A)-/~[A)-arrow of -144 wA was prepared by changing the m class of the compound of the present invention, and this photosensitive solution was coated on an aluminum plate with anode jR, 1000
Each photosensitive lithographic printing plate [Al
-/~(A)-Arrows were produced.

All coating amounts at this time are dry weight / , j f/r
The compounds of the present invention used in the photosensitive solution CAB-/~[A)-g, which was n2, are shown in Table 1. ．． 3/fl Cresol formaldehyde tree 11 effect / 02 /, 2-naphthoquinone-λ-diazide-≠-sulfonyl chloride o, o ry Oil blue average 1,03 (Orient Chemical Industry G grade) 0.0/9 Ethylene dichloride 10fi' Methyl cellulose ioy Next, as a comparative example, photosensitive liquid CB) was coated in the same manner as photosensitive liquid CA) to prepare A&photosensitive lithographic printing plate CB).

Photosensitive liquid (13) Cresol-formaldehyde Resin and/5.2-naphthoquino.

Condensation product with 1-codiazido-5-sulfonyl chloride 11 O1≠j2 Cresol-formaltech resin 1.02 /, 2-naphthoquinone-2-diazide-≠-sulfonyl chloride 0.0 -29 Oil Blue@603 ( (manufactured by Orient Kagaku Kogyo CM) o, oiy ethylene dichloride 109 methyl cellosolve ioq The coating weight after drying was /, 397 m2.

A gray scale with a density difference of O and tS is brought into close contact with the photosensitive layer of the photosensitive lithographic printing plates (A) and CB].

Exposures were made with a 30 amp carbon arc lamp from a distance of 70 cIT+.

The photosensitive lithographic printing plates (A) -/~ [Al-Hiro and CB) exposed to show the excellent photosensitivity of the present invention are DP-, ?
Developed by immersion in a 72-fold diluted aqueous solution of B (product name: manufactured by Fuji Photo Film ■) at 25°C for 60 seconds, resulting in 0 basis difference.
．． In grayscale of II! The exposure times for completely clearing the rows were determined as shown in Table 1.

As shown in Table 1, photosensitive lithographic printing plates using the compounds of the present invention [Al-/~(A)-≠ are all ('B
) requires less exposure time and has higher sensitivity 〇Example 2゜In order to demonstrate the excellent development tolerance of the present invention, three types of photosensitive solutions (A)--t~ were prepared by changing the amount of the compound of the present invention. (Al-7
was prepared and applied on the anodized aluminum plate prepared in Example 1, and dried at 1000C for 2 minutes (R
& The composition of the photosensitive liquid is all the same as that of the photosensitive liquid [A] of Example 1 except for the type of compound of the present invention. Photosensitive liquid [A]
The compounds of the present invention used in -, -J- to (A)-7 are shown in Table 2. ).

The prepared "L-type lithographic printing plate Ck-]-j~[A]-
All coating amounts of No. 7 were /, j%'/m 2 on a dry weight basis.

11 & photolithographic printing plate CAl-≠ produced in Example 1,
CB] and newly prepared photosensitive lithographic printing plate [A]-t
A gray scale with an image intensity difference of 0./j was brought into close contact with ~(A]-7, and a 30 ampere carbon arc lamp was used for 30 seconds at a distance of 70 cm.The exposed photosensitive lithographic printing plate [ A) -j-~(A)-7 and [A]-μ,
[B] was heated to 2j0C using the same liquid as in Example 1.
Developed for 3 seconds and 3 times. Difference in degree of play 0. / Evening gray scale, the difference in completely clear step rcJ for to seconds and 3 minutes in the current 1 glow was as shown in Table 2.

7.9 2 As shown in Table 2, all of the photosensitive lithographic printing plates [A]-Hiroshi to [A)-7 using the compounds of the present invention are [B]
Clearer Some gray scale step changes are small,
The current helmet has great tolerance.

Patent Applicant: Fuji Photo Film Co., Ltd. Procedural Amendment Law 5yi4-Answer: Mr. Tsukiobi, Commissioner of the Patent Office 1, Indication of Case: Showa Yoza Year Patent Application No. TI7769 2,
Title of the invention Previously solubilized composition 3, Relationship to the case of the person making the amendment Appointment of patent applicant Location 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name (52)
0) Fuji Photo Film Co., Ltd. 4, Subject of the amendment Replace page 5 of the "Detailed Description of the Invention" of the "Detailed Description of the Invention" in the Specification A, Contents of the Amendment, page 7 with an attached sheet.

-) Page g, lt to line 17 ratsaz, blxbzJk ra,bJ and correct it.

3) Page 17, line j "Diclohexane" "Cyclohexane" and correct it.

4A) On page 26, line 16, in front of “From the 4th table, f) n = 104to.'' is inserted.

j) Before the line "As shown in Table 2" on page λ [The molecular weight of Compound A/1% 17 of the present invention in Table 2 is the number average molecular weight, Mrx=lo <t O~/
A friend of tiθ's. ” (To) Insert G10. Seizokunyo J rihoyou superku O θ field and 1st section # Dani) yo0=Q country0'7:J

Claims (1)

[Scope of Claims] (a) A compound capable of generating an acid upon irradiation with actinic rays;
and tb) a previously solubilized composition containing a compound represented by the following general formula (I), which has at least one acid-decomposable ester group and whose solubility in a developer increases by the action of an acid. thing. \