JPS61167945A - Photo-soluble composition - Google Patents

Abstract

PURPOSE:To provide high photosensitivity and to extend the development latitude by adding a compound which produces an acid on being irradiated with active light, a compound having a silyl ether group decomposable with a specified acid, and a compound which produces a radical forbidding species on being irradiated with active light. CONSTITUTION:The compound (a) which can produce an acid on being irradiated with the active light, the compound (b) having at least one silyl ether group decomposable with the acid represented by the formula in the molecule, and the compound (c) which produces a radical forbidding species on being irradiated with active light and can capture the radical species of the acid produced from the compound (a) or the precursor of the acid are added to an alkali-soluble resin to obtain a photosensitive resist forming composition. The molar ratio between the compounds (c) and (a) is 0.01:1-10:1. The amount of the alkali-soluble resin is about 40-90wt% of the amount of the composition. The aqueous soln. of an inorg. alkali such as sodium silicate or potassium silicate is suitable for use as a developer for the photo-soluble composition, and the concn. is regulated to 0.1-10wt%. Difference in gray scale level with the lapse of time is reduced, and the again stability of the sensitivity between exposing and developing stages is improved.

Description

DETAILED DESCRIPTION OF THE INVENTION "Industrial Application Field" The present invention relates to a photometric solubilizing composition suitable for the production of lithographic printing plates, multicolor printing proofs, drawings for overhead ZA dioctors, IC circuits, and photomasks. For more details, see (
a) A compound that can generate υ and acid when irradiated with active light; (b) A compound that has at least/one silyl ether group that can be decomposed by acid; and (C) A compound that generates a radical-inhibiting species when irradiated with active light. and (a) a compound capable of scavenging the 2 dihydric species of the acid or pre-acid precursor generated from (a).

``Prior Art'' Orthoquinone diazide compounds have been known as photosensitive substances that act on so-called positives and become more soluble in actinic rays, and in fact have been widely used in lithographic printing plates, photoresists, etc. Examples of orthoquinone diazide compounds include those described in US Patent No. J, 744. //r
No. λ.

7≦7,0 de No. 4, same No. ko, 77λ, ri 74, same No. ko, rz ri, //, No. 2, same No. 2, 907, jbu 2
No. J, Out, /10, J/ZJ.

44.111, same No. 3,04Ala, 111, same No. 3,04t6,111, same No. J, Out, //ri,
Same KJ, 044. /Co□No.J,Ollbu,741
No. J, 0444. /Ko λ No. J, 04A&
, No. 123, No. J, ot/, No. 4430, No. J,
No. 102,102, No. 3,101a.

4Lbu No. 1, same No. J, tJJ, No. 709, same No. 3゜44
It is described in numerous publications, including the specifications of '7, 44≠3.

These orthoquinonediazide compounds are decomposed by irradiation with actinic rays to produce I-membered ring carmenic acid,
Although they take advantage of their alkali solubility, they all have the drawback of insufficient photosensitivity. This is because, in the case of orthoquinonediazide compounds, the quantum yield essentially does not exceed lt-.

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 No. 441-122442 and Japanese Patent Publication No. 71-4AO/Co! No., U.S. Pat. No. 107.17
There are nine contents described in the specifications such as No. 3.

Also, recently, several proposals have been made regarding photosensitive compositions that act as positive chips without using orthoquinone diazide compounds. One example is Tokko Akira! ≦−
Examples include polymer compounds having orthonitrocarbinol ester it- described in the specification of No. t24. However, in this case too, the photosensitivity cannot be said to be sufficient for the same reason as in the case of orthoquinone diazide. Nine, apart from this, a photosensitive system activated by contact action is used,
As a method of increasing photosensitivity, an omniscient formation is applied in which a first reaction is caused by the acid produced by photolysis, thereby solubilizing the exposed area.

Examples of this include, for example, a combination of a compound that generates silicic acid by photolysis and an acetal or 0,N-acetal compound (JP-A-1-1-2003-003), or a combination of an orthoester or an amide acetal compound. Combination C Japanese Patent Publication No. 11
-/-〇7/≠), combination with a polymer having an acetal or ketal group in the main chain (JP-A No. 1!-IJJ#-
combination with enol ether compound (No. 4! Kaisho! J-71221), combination with N-acylimino carbonate compound (No. 4? Kaisho 1! -726234), and a combination with a polymer having an orthoester group in the main chain (4?
Kaisho J4-/7J Hiroj No.) can be mentioned. In principle, these have quantum yields exceeding ``/'', so they may exhibit high photosensitivity, but in the case of acetals or U,N-acetal compounds, and in the case of polymers with acetal or ketal groups in the main chain. , because the rate of the second reaction by the acid generated by photolysis is slow, it does not exhibit sufficient photosensitivity for practical use.In the case of te orthoester or amide acetal compounds and in the case of enol ether compounds, N- Although acylimino carbonate compounds certainly exhibit high photosensitivity, they are not stable over time and cannot be stored for long periods of time.Polymers with orthoester groups in the main chain also have high sensitivity, but It has the disadvantage that the development tolerance during development is narrow.

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 that solves these problems, that is, it has high photosensitivity and is easy to develop during development. It is an object of the present invention to provide novel photo-solubilizable compositions that are broadly tolerated.

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" The present inventor has made extensive studies and found that the above objects can be achieved by using a novel photo-solubilizable composition. reached.

That is, the present invention provides (Jl) a compound capable of generating an acid upon irradiation with actinic rays; and (C) a compound that generates radical-inhibiting species upon irradiation with actinic rays and is capable of capturing the radical species of nonacid or acid precursor generated from (a). It is something to do.

The compound having an acid-decomposable silyl ether group represented by the general formula (1) used in Φ) of the present invention can preferably be represented by a repeating unit of the following general formula ([).

In the formula, R1 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.

Specifically, the hydrophilic groups referred to in the present invention include those shown below.

1,000 C1-120) 12-U+.

((C1, -3-, u coating C)l, C)i, -〇÷. .

÷CHc)1. -0sC)i2C)l, -0s. .

In the formula, 1 represents an integer of I-, m and n are integers of 2 or more, preferably integers of λ to 100, more preferably 2 to 100.
Indicate the integer gold of 〇. a represents alkyl or a phenyl group which may contain a substituent.

Particularly preferred hydrophilic groups are 1,000 CH2C)i, -〇+.

It is.

R12 and FL3 may be the same or different, and each is a hydrogen atom, alkyl, alkenyl, aryl or aralkyl that may have a substituent, or -oa4r
show. Preferably, it represents alkyl having a carbon number of Aμ, or -0R1. R+4 represents an alkyl, aryl, or aralkyl group which may have a substituent, preferably an alkyl group having l- carbon atoms, or an aryl group having t or it carbon atoms. Moreover, the compound (b) used in the present invention is
It may contain two or more types of repeating units represented by general formula (I).

Specific examples of the compound in (b) of the present invention include those shown below.

(I-ko) (I-j) (I-≠) ＾ ＾
＾Character faction one-one revenge oath oath-no
~of
-Nono Police
νNノ
−ノ ＋／ −ノ
--Written to Party A
Town - no ~
,t%+/1
No -no
%+/In the specific examples, n represents an integer of 2 or more.

In addition, Xs Ys z indicates a molar ratio, and Compound Example I-
≠3〜μ! Then, x=IO~rz morch, y=3~fO morch, and z=10-1j morch. Also, compound example i-
j~/7, i-/PSl-2≠, ■-3! , and 1-J
In 5'-12, x; j ~ ri O morti, y = 10-9j
Indicates the mole officer.

The present invention (a) is used in combination with a compound having at least 7 silyl ether groups that can be decomposed by these acids.
Compounds that can generate acids upon irradiation with actinic rays include many known compounds and mixtures, such as diazonium, phosphonium, sulfonium, and iodonium B.
F -1PF, -1SbF -18iF 5-5c
Salts such as tO4-, organohalogen compounds, orthoquinonediazide sulfonyl chloride, and organometallic/organohalogen compound combinations are suitable. Of course, U.S. Patent No. J, 775', 771 and West German Patent No. λ
.

&10. Also suitable as the composition of the invention are compounds described in the specification of r≠2 and which generate acids by photolysis.

Further, in combination with suitable dyes, nine compounds, such as JP-A-Sho! -7774c2, same j7-/
Compounds described in the specification of No. 6J Co. 3 can also be used as the composition of the present invention.

Among the compounds that generate acid upon photolysis, orthoquinonediazide sulfonyl chloride, and $-triazine derivatives or oxadiazole derivatives substituted with halomethyl groups 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, so that a relatively large proportion of the silyl ether groups can be decomposed. It is from.

The weight 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 oxidised by an acid in (b) is o, ooi :i-, 2:/Ashi, preferably 0.0λ:/-0, If:/"T: used.

Further, in (C) of the present invention, a compound (so-called radio
cal 1 inhibitor precursor), for example, aromatic nitro compounds, thiuram disulfide compounds, disulfide compounds, sulfide compounds,
Examples include mercazoto compounds.

Specifically, the following compounds are included.

(C-t) (C-2) (c-3) (C-4A) (C-a) (C-7) (C-r) α α (C-2) (C-io) (C- //) (C-/, 2) (c-i3> (C-/Hiroshi) (c-it) (C-/j) (C-/7) (C-IP) (C-20) (C -ko/) (C-22) (C-koJ) (C-ko≠) (C-2ri (C-2≦) (C-27) (C-2g) (C-=ri) (C -30) (C-J/) (C-32) (C-JJ
) The ratio of the compound of the present invention (C) and the compound capable of generating an acid upon irradiation with actinic rays in the present invention (a) is:
The molar ratio is o, oi:i-, lo:i, preferably 0. Used in /:/~l:l.

The photo-soluble composition of the present invention can be used only in combination with the compounds (a), (b), and (C), but it is preferable to use them in combination with an alkali-soluble resin.

Suitable alkali-soluble resins include novolak-type phenolic resins, specifically phenol formaldehyde resin, o-pvy-formaldehyde resin, m-
Contains cresol formaldehyde resin, etc. Furthermore, as described in Japanese Unexamined Patent Publication No. 20-1λrrota, in addition to the above-mentioned phenol resins, phenol substituted with an alkyl group having 3 to r carbon atoms such as t-butylphenol formaldehyde resin can be used as cresol. When used in combination with a condensate with formaldehyde, the more preferred alkali-soluble resin contains about 4 Ao to about 0% by weight, based on the total ff1t of the photosensitive resist-forming composition;
Preferably to, r.

% by weight.

The photosoluble composition of the present invention may further include a dye, if necessary.
A pigment, a plasticizer, a compound that increases the acid generation efficiency of the acid-generating compound (optionally a sensitizer), etc. can be contained. Suitable dyes include oil-soluble dyes and basic dyes. Specifically, oil ye echo Hioi,
Oil Yellow 15/JO, Oil Pink #3 Noko, Oil Green BG, Oil Sol-BU8. Oil Blue #403, Oil Puttsuku BY, Oil Zo 2 Tsuk B8,
'0 on oil black T-! (The above are manufactured by Orient Chemical Industry Co., Ltd.) Crystal Violet (CI≠21!
! t), Methyl Iolette (CI≠2!3ri, RhodamiyB (CI#ztyoB), Malachite Green: /
(CI+1-2000n, methylene blue (CIjko0
1! ] and so on.

The photosoluble composition of the present invention is dissolved in a solvent that dissolves each of the above components and spread on a support. The solvents used here include ethylene dichloride, cyclohexanone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol sonoethyl ether, comethoxyethyl acetate, toluene, and ethyl acetate, and these solvents can be used alone or in combination. do.

And the concentration in the above ingredients (total solid content including additives) is:
λ˜10 wt. Among these, the preferred concentration (m type) of the composition of the present invention is 0. /-23 weight-. The coating amount varies depending on the application, but for example, for photosensitive lithographic printing plates, the solid content is generally 0.2 to 0.2 to 0.0
f/fn 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 electrode. attached aluminum plate, other zinc plates,
Stainless steel plates, Cucum treated copper plates, hydrophilic treated 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 surfaces of these plastic films are matted chemically or physically. Supports used in the production of photomask films include aluminum, aluminum alloys, chromium-deposited polyethylene terephthalate films, and polyethylene terephthalate films with colored layers.

The photo-soluble 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 with the present IjliK. Such a laser beam is a helium neon laser.
, argon laser, chrysoton ion laser, helium cadmium laser, etc.

Developers for the photosoluble composition of the present invention include sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, trisodium phosphate,
Suitable aqueous solutions of inorganic alkaline agents such as sodium diphosphate, ammonium triphosphate, ammonium diphosphate, sodium metasilicate, sodium bicarbonate, and ammonia are suitable, and their concentrations are 0. /~io weight, preferably 003 to 3 weight.

Moreover, a surfactant and 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 way of Examples below, but the content of the present invention is not limited thereto.

Example 1 A 0.14 cm thick aluminum plate was degreased by immersing it in a 10-aqueous solution of tertiary sodium phosphate kept at 10@C for 3 minutes, grained with a nylon bluff, and then soaked in sodium aluminate for about 10 seconds. It was etched and desmutted with a 3-dose aqueous solution of sodium hydrogen sulfate. An aluminum plate with λ0 current density in sulfuric acid - person/d m
” K died, anodized the aluminum plate for 1 minute, and then produced an aluminum plate.

Next, two types of photosensitive solutions (A)-/-(A)-rt- were prepared by changing the type of the compound (C) of the present invention in the photosensitive solution (A) below, and this photosensitive solution was mixed with anodized aluminum. The compound of the present invention ( As b), compound example (1-/co) (n = x 4C1X / 'I 2
uO/40, molecular weight determined by GPC (Gel Per
Meation Chromatography) J with polystyrene standards,! It was TOO. ) was used. All coating amounts at this time are dry weight (t)
, zy/m De Atsutomo.

Further, Table 7 shows the compound (c) of the present invention used in the photosensitive solutions [human]-/-(A)-1 and the amounts added thereof.

Photosensitive liquid (A) Next, as comparative examples, the following photosensitive liquid CB) and photosensitive liquid (A
) does not contain the compound (C)' of the present invention (
C)? Coated in the same manner, photosensitive planographic printing plates CB), (C)
was created.

Photosensitive liquid CB) The coating weight after drying was 117 m in both cases.

Photosensitive lithographic printing plate (A)-/~(A)-'5(B),
There is a density difference of 0.0 on the photosensitive layer and [C]. /j gray scale and 70 amps with a 30 amp carbon arc lamp.
Exposure was performed from a distance of C111.

Photosensitive lithographic printing plates (A)-/~(A)-, r, CB), and (C) exposed to show the excellent photosensitivity of the present invention
=iDP-4c (product name: Fuji Photo Film ■g) 2
The diluted aqueous solution was immersed and developed for 40 seconds at λz'C, and the density difference was 0. We determined the exposure time for the first stage to be completely clear on a gray scale of /yo, and furthermore, in order to show excellent sensitivity stability over time between exposure and development, we used a photosensitive lithographic printing plate (A) -/~(A). )-r, CB
), and (C,It-# according to the above method) After exposure for 40 seconds, it was allowed to age for 30 seconds and 40 minutes. After that, development was performed in the same manner, and the density difference Q, /! at 30 seconds and 60 minutes. When the difference in the number of stages at which the gray scale becomes completely clear was determined, the results were as shown in Table 1. ~(:A)-4 all have shorter exposure times and higher sensitivity than CB) using a naphthoquinone diazide compound.

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 small, and the sensitivity stability over time between exposure and development is excellent.

Example 2 In the photosensitive solution (A) of Example/, the compound of the present invention (b
) Photosensitive lithographic printing plates (A)-ta to (A)-12f were prepared in the same manner as in Example 1 by changing the cover and using photosensitive solutions (A)-2 to (A)-/2. Similarly, photosensitive liquid (A)-2
Using the photosensitive solution (C)-5'-(C)-/co which does not contain the compound (C) of the present invention in ~(A, l-/-), the photosensitive lithographic printing plate (C)-2-(C )-/co was prepared.The photosensitive liquid (A)-(A)-/co was prepared using the compound of the present invention
As C), the compound cut (C-/7) is o, o,
2oy was used. All coating amounts are dry weight /, 197
It was m2. Also, photosensitive liquid (A)-2 ~ (A, l-/2
The compound (b) of the present invention used in Table 1 shows the compound (b) of the present invention.

Photosensitive lithographic printing plate (A)-ta~[A]-/λ and (C)
-f~(C)-/λ was exposed to light and developed according to the method shown in Example No. After exposure, the density difference was 0.30 seconds and 60 minutes. The difference in the number of stages that would be completely clear at the gray scale of /j was determined and was found to be as shown in Table 1.

Table 1 Previous Comparative Example (Compound (C) 1 of the present invention is not included).

The compounds (1-4) and (1-4) of the present invention in Table 1
/? ), x/y=j O/j O (molar ratio) and n=≠ were used. In addition, the molecular weights of the compound (b) of the present invention in Table 1 are (I-j), (I-15
In F), vPO (Vapour PressureO
smometer) at /10ONλ100. (1−λ
ri, (1-jr) H1GPC polystyrene/standard 2!
It was from 0O-jooo.

As shown in Table 1, the photosensitive lithographic printing plates (A)-F to (A)-/j used on the compounds of the present invention do not contain the corresponding compounds of the present invention (C-/7)i, respectively. Compared to (C)-/λ, 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.

Patent Applicant: Fuji Photo Film Co., Ltd. Procedural Amendment February 10, 1985 cormorant

Claims (1)

[Claims] (a) A compound capable of generating an acid upon irradiation with actinic rays;
(b) a compound having at least one silyl ether group in its molecule that can be decomposed by an acid represented by the following general formula (I), and (c) a compound that generates a radical inhibiting species by irradiation with actinic light, A photo-solubilizing composition comprising a compound capable of scavenging generated acid or acid precursor radical species. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I)