JPS60121446A - Photosolubilizable composition - Google Patents

Abstract

PURPOSE:To enhance photosensitivity and to widen development latitude by incorporating a compd. for generating an acid on irradiation of actinic rays, and a compd. having a silyl ether group decomposable with the acid and a hydrophilic group in the molecule. CONSTITUTION:An intended compsn. incorporates (a) a compd. capable of generating an acid on irradiation of actinic rays, such as o-quinonediazidesulfonyl chloride, (b) a compd, having at least one silyl ether group decomposable with the acid represented by formula I , and at least one hydrophilic group, such as a group represented by formula II, in the molecule, and said compd. (b) is such as a compd. represented by formula III in which R1 is an aliphatic or aromatic hydrocarbon group, and R4 is H, alkyl, alkenyl, aryl, or the like. The photosolubilizable compsn. contg. such compds. (a) and (b) can be used for a positive type photosensitive material, and since it has high sensitivity and wide development latitude, it is used for a lithographic plate, a print proofreading plate, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a lithographic printing plate, a proof sheet for multicolor printing, a drawing for an overhead projector, and an IC circuit.

The present invention relates to a pre-solubilized composition suitable for the production of photomasks. More specifically, it contains (a) a compound capable of generating an acid upon irradiation with actinic rays, and (b) a compound each having at least one silyl ether group and at least one hydrophilic group capable of being oxidised by an acid. The present invention relates to a novel previously dissolved composition.

(Prior Art) Orthoquinonediazide compounds are conventionally known as photosensitive substances that act on so-called bozitib, 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 US Pat. Nos. 2 and 7! , J, //
J' No., same No. ko.

7t7.0 Octopus, same No. 2, 772.272, same No., z, tsri, ii2 No., same No. 2. ri07. tit
No. 3.0111. ．． No. 110, No. 3.04'J
, /// issue, same number 3.0114. //j issue, same number 3
．． o4Lt, IIS' No. 3. oat, iii issue,
3,0 IIA, No. 120, 3. O1/-A, 1
No. 27, Reference No. 3.0, No. 722, Reference No. 3.0116
, No. 123, No. 3.0&/, No. 11.30, No. 3
, No. 102,109, No. 3,104゜+a, No. 3,131,702, No. 3゜617, No. ≠4A3, and many other publications. There is.

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 orthoquinonediazide compounds, the quantum yield essentially exceeds .

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, as an example of such an attempt, Tokusho μf-/2.2≠2car/2.
Examples include contents described in specifications such as U.S. Patent No. 0/2j, U.S. Pat.

Recently, research has also been conducted on photosensitive compositions that act on bozitib without using an orthoquinone diazide compound.

Several suggestions have been made. One such example is a polymer compound having an orthonitrocarbinol ester group, which is described in the specification of Japanese Patent Publication No. Sho, TJ-2426. 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, a photosensitive system that is activated by contact action is used.

As a method of increasing photosensitivity, a known principle is applied in which a second reaction is caused by an acid generated by photolysis, thereby solubilizing the exposed area.

Examples of this include 1, for example, a combination of a compound that generates an acid by photolysis and an acetal or O,N-acetal compound (JP-A-Sho≠r-r-003), or a combination with an orthoester or amide acetal compound. (Tokukai Shozi
-Ha207/'I-No.).

Combination with a polymer having an acetal or ketal group in the main chain (Japanese Unexamined Patent Application Publication No. 13/1973 Hiroko), combination with an enol ether compound (No. 4? JP-A No. 12-12 Tata!)
Combination with N-acyliminocarbonate compound (JP-A-Sho J-1
-/21,236), and a combination with a polymer having an orthoester group in the main chain (JP-A-31-173≠j
(No.). In principle, these have a quantum yield exceeding 1, so they may exhibit high photosensitivity, but acetal or 0. In the case of N-acetal compounds and polymers with acetal or ketal groups in the main chain, the rate of the second reaction by the acid generated by photolysis is slow, so they do not exhibit sufficient photosensitivity for actual use. . In addition, orthoester or amide acetal compounds, enol ether compounds, and N-acyliminocarbonate compounds certainly exhibit high photosensitivity, but are not stable over time.

Cannot be stored for long periods. Polymers having orthoester groups in their main chains also have high sensitivity, but have the disadvantage of narrow development tolerance during development.

(Objective of the Invention) The object 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-solubilized composition that has high photosensitivity and wide development latitude during two-stage 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-solubilizable composition that is simple to manufacture and easily obtainable.

(Structure of the Invention) As a result of intensive studies to achieve the above object, the present inventor found that the above object could be achieved by using a novel photo-solubilized composition, and thus arrived at the present invention.

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 represented by the general formula (I) in the molecule and capable of being oxidised by an acid.
The present invention provides a photo-solubilizable composition characterized in that it contains a compound having at least seven hydrophilic groups.

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

+CH2CH2-0+,.

-1-+CH2-+-l〇9keCH2CH2-0÷0l
- H R In the formula, l represents an integer of l-day, m and n are integers of 1 or more, preferably an integer of /-100, more preferably /, 2
Indicates an integer of 0. R represents an alkyl group or a phenyl group which may have a substituent.

A particularly preferred hydrophilic group is +CH2CH2-0÷0.

Preferably, as the compound (b) used in the present invention, a compound having a silyl ether group and a hydrophilic group that can be decomposed by an acid represented by the general formula (I) is the following general formula (I[) or (I It is characterized by being a compound represented by [).

In the formula, R0 represents an n□-valent aliphatic or aromatic hydrocarbon having a hydrophilic group and optionally having a substituent. R2,
R3 and R4 may be the same or different, and each is a hydrogen atom, alkyl, alkenyl, aryl or aralkyl that may have a substituent, halogen, or -0
Indicates R8.

Preferably, it represents alkyl having 7 to 1 carbon atoms, chloro, or -0R8, more preferably alkyl having 1 to V carbon atoms, or -0R8. R5 represents a divalent aliphatic or aromatic hydrocarbon which may have a substituent. R6 represents a divalent hydrophilic group, and R7 represents R5 or R6. R8 represents an alkyl, aryl, or aralkyl group which may have a substituent, preferably an alkyl group having /~ carbon atoms, or an aryl group having j−/j carbon atoms. Further, R5 and R8 may be combined to form a part of an aliphatic ring or an aromatic ring. n1tn21''3 and R4 are positive integers, preferably n□ is 1 to 1ooo.

n 2 , n 3 and R4 each represent an integer of /-300.

-l θ- So≠ N11.1 N[L6 336- -77- 2,2 3 ,24A -/I- 339- ! t CI■3 H3 CI(2-0-C4H9n N[LJ/ CH 3 In addition, X+Y and Z in the specific examples indicate the molar ratio, and Compound Example 1
For i/-2, x=θ~ri0 mol%, y=! ~ri5 mol%, z==j~L? jmol%. Also, compound example Na
3-N [L, 23 and Na, 2. At t, X=θ~ri5
Mol%, y=7~IOθmol% gold is shown. Compound example N[L
m and n in /~m2t represent integers of 7 or more.

It is used in combination with a compound having a silyl ether group and a hydrophilic group that can be decomposed by an acid.

There are many known compounds and mixtures of compounds capable of generating sialic acid upon irradiation with actinic rays, such as diazonium, phosphonium, sulfonium, and hyodonium BF-
, PF, SbF6.

Salts such as 6SiF6-, ClO4-, organohalogen compounds, orthoquinonediazide sulfonyl chloride, and organometallic/organohalogen compound combinations are suitable. Of course, U.S. Patent No. 3,772°771 and West German Patent No. Z.l. Compounds that generate acid upon photolysis as described in the specification of ♂tco are also suitable as compositions of the present invention.

Furthermore, compounds intended to provide a visible contrast between the unexposed area and the exposed material during exposure in combination with suitable dyes, such as those described in JP-A-J-J-777≠-, Ibid. ;7-
Compounds described in No. 11323 can also be used as compositions of the present invention.

Among the compounds that generate acid through photolysis, orthoquinonediazide sulfonyl chloride is particularly preferred. 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 silyl ether groups can be decomposed.

What is the ratio of the compound that can generate an acid upon irradiation with actinic rays and the compound that has a silyl ether group and a hydrophilic group that can be decomposed by the acid?

The weight ratio is O6θO7:lNλ:l, preferably 0
．． OJ! , :1,0. ♂: Used in l.

The photo-soluble composition of the present invention can be used only in combination with a compound that can generate an acid upon irradiation with actinic rays and a compound that has a silyl ether group and a hydrophilic group that can be decomposed by an acid. It is preferable to use it in combination with a resin, an alkali-soluble resin, or an organic solvent-soluble resin. These resins are contained in an amount of about 30% to about 0% by weight, more preferably zo-, ro% by weight, based on the total weight of the photosensitive resist-forming composition.

The photosoluble composition of the present invention may further include a dye, if necessary.
A pigment, a plasticizer, and a compound (so-called sensitizer) that increases the acid generation efficiency of the acid-generating compound can be contained. Suitable dyes include oil-soluble dyes and basic dyes. Specifically, oil yellow +10/,
Oil Yellowna/301 Oil Pink+,? /, 2,
Oil Green, 2J- One BG, Oil Blue BO8, Oil Blue≠603
, Oil Black BY, Oil Black BS1 Oil Black T-30 Yu (manufactured by Orient Chemical Industry Co., Ltd.) Crystal Violet (C14'1tJ-j),
Methyl violet (CI Hiro-233, Rhodamine B
(CI Hiroj/70B), malachite green (CI4L)
2000), methylene-1-ru (CI!t20/j), and the like.

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, cyclohexanone, methyl ethyl ketone, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether, λ-
Examples include methoxyethyl acetate, toluene, and ethyl acetate, and these solvents can be used alone or in combination.

And the concentration in the above ingredients (total solid content including additives) is:
It is 2 to 50% by weight. Among these, composition (a) of the present invention
+ The preferred concentration (solid content) of (b) is θ, /~-,
24'-2.3-% by weight. Well, the coating amount varies depending on the application, but for example, for photosensitive planographic printing plates, the solid content is generally 0. j~3-0 g/m2 is preferred. As the coating amount decreases, the photosensitivity greatly 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. There is a plated aluminum plate, and other plated lead plate,
Stainless steel plates, chromium-treated 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 surfaces of these plastic films are matted chemically or physically. I can give you what I have transformed into. 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-soluble composition of the present invention can be used as a Ti 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, and helium neon lasers.
Examples include cadmium lasers.

Examples of developing solutions 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, dibasic diphosphate, Aqueous solutions of inorganic alkaline agents such as ammonium acid, sodium metasilicate, sodium bicarbonate, and aqueous ammonia are suitable, and their concentrations are o, i to 10% by weight,
It is preferably added in an amount of 0.1-1% by weight.

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

Hereinafter, 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 NaJ) i, r-octanediol 7°J, 2.9 (0,0j0
7 mole), tetraethylene glycolta.

7/, 9 (o, orooomole), pyridine/7゜tAfi (0, u, 20 mole), dichlorodimethylsilane lλ to a mixture of dehydrated and distilled toluene rO
, 2g (O,/00mole) tor x 720ml
Stir the solution and add to the dropping funnel under ice cooling for 30 minutes = 2
7--A'J was added. After the addition, stirring was continued for 5 hours at 0°C. The produced white salt (pyridine hydrochloride) t-F was separated, and the toluene solution was concentrated under reduced pressure.

Thereafter, it was dried for 70 hours under vacuum (about /mmH, !9) while heating to about tθ0C. Colorless transparent liquid, yield -
0.7μ. NMRK confirmed that the structure was compound example Na3. Furthermore, VPO (Vapour Pr
The number average molecular weight was measured using an essure osmometer (Essure Osmometer) and found that Mn=191rO.

In place of /,♂-octanediol in Synthesis Example 1, 1.72 g of i,io-decanediol (0,Oroom
ole), and the reaction and post-treatment were carried out in the same manner as in Synthesis Example 1. Colorless transparent liquid Yield j/, jfio NMR data, confirm that the structure is compound example Nα≠, V
When the number average molecular weight was measured by PO, Mn=/lj
It was O.

/, ♂-octanediol, 2 g- in Synthesis Example 1 l each instead of dichlorodimethylsilane.

10-decanediol 1.721!9 (0,0jt00
mole), dichlorodiethylsilane/j, rg(O,
10/mole), and the reaction and post-treatment were carried out in the same manner as in Synthesis Example 1 except that the reaction conditions were heating and refluxing for 3 hours. It was a colorless transparent viscous liquid, yield 2μ, /9° NMR confirmed that the structure was the same as the compound, and the number average molecular weight was measured by vPO and it was found that Mn=/≠IO.

l in place of /, t-octanediol, and tetraethylene glycol in Synthesis Example 1, respectively.

≠-Cyclohexanediol z, rig (,o,.

! OOmole), polyethylene glycol Luna 200 (
Manufactured by Kanto Kagaku ■, average molecular weight, zoo) 10fi (OoO
,,tOmole), and the reaction was carried out in the same manner as in Synthesis Example 1.
Post-processing was performed. Colorless transparent viscous liquid, yield 1, y9o
The structure was confirmed to be Compound Example N1110 by NMR, and the number average molecular weight was measured by vPO and found to be Mn''=/620.

Synthesis Example 5 (Compound Example N (Synthesis of L/j) 3.5 p-xylylene glycol was used in place of l,♂-octanediol and tetraethylene glycol in Synthesis Example 1, respectively.
3 μ (o, o g 00 mole), polyethylene glycol ≠ 300 (manufactured by Kanto Kagaku ■, average molecular weight 300) / l'
9 (0°0 & Omole), the reaction and post-treatment were carried out in the same manner as in Synthesis Example 1. Colorless transparent viscous liquid, yield λt
.

It was confirmed by f,9oNMR that the structure was Compound Example 1/j, and the number average molecular weight was measured by vPO and found to be Mn-1730.

In place of /, I-octanediol and dichlorodimethylsilane in Synthesis Example 1, 1 g (0,0100 mole) of p-xylylene glycol and 1 g (0,0100 mole) of methylphenyldichlorosilane were used.

Using 2/l (O, 100 mole), the reaction and post-treatment were carried out in the same manner as in Synthesis Example 1 except that the reaction conditions were heating and refluxing for 3 hours. Colorless transparent viscous liquid, yield 2t, structure confirmed to be Compound Example 1@/A by 29°NMR, v
When the number average molecular weight of PO was measured, it was Mn-/3!
It was O.

Synthesis Example 7 (Compound Example N (Synthesis of 1LJ4')-dihydroxyethylhydroquinone/di, 2g (OlloOmo
le), Virigi 7/7.4l-9 (0°, 2.20mo
dichlorodimethylsilane/-2.2 g (0.100 mol
The tor xyJOytl solution of e) was added in the same manner as in Synthesis Example 1, and then the reaction and post-treatment were carried out in the same manner. Slightly brownish white solid, yield: 1, the structure was confirmed to be compound example Nα24t by 79°NMR, and vPO
When the number average molecular weight was measured, it was found that Mn-, 20≠O
Met.

Example 1゜ 28 aluminum plate-2r with thickness 0, -24'7 nm.

Tertiary phosphoric acid maintained at 0C) was degreased by immersing it in a 10% aqueous solution of IJum for 3 minutes, sanded with a nylon brush, and then etched with sodium aluminate for about 70 seconds.
A friend who performs desmut treatment with a 3% aqueous solution of sodium hydrogen sulfate. This aluminum plate was anodized in -3/-20% sulfuric acid at a current density of 2 A/dm2 for 2 minutes to produce an aluminum plate.

Next, six types of photosensitive liquids [A]-/ to [A]-1 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. Apply to
The plates were dried at 1000C for 2 minutes to produce photosensitive planographic printing plates (A)-/ to [A)-1. The amount of coating at this time was /-3 g/m2 in terms of dry weight.

The compounds of the present invention used in photosensitive solutions [A]-/-[A)-1 are shown in Table 1.

Photosensitive liquid [A] 32- Next, as a comparative example, the following photosensitive liquid [B)' (i=photosensitive liquid [
A photosensitive planographic printing plate [B] was prepared by coating in the same manner as Al.

Photosensitive liquid [B] A density difference of 0.00000 on the photosensitive layer of the photosensitive lithographic printing plate [Al-/~[, l-1 and CB]. /j gray scale was placed in close contact with the sample, and exposure was performed from a distance of 700 In with a 30 ampere carbon arc lamp.

In order to show the excellent photosensitivity of the present invention, the photosensitive lithographic printing plates [A)-/~[A)-1 and [B] exposed to Dr-3B
<Product name: Fuji Photo Film ■) 10 times diluted aqueous solution was immersed and developed at 23°C for 60 seconds, and the density difference was 0.7.
In grayscale of j! The exposure times for completely clearing the rows were determined as shown in Table 1.

Table 1 Compounds of the present invention in Table 1 HrlLti-1i
o.

In /4Z, /j, 2/, X / y =j O/!
0 (molar ratio), """ was used. Also, the first
The molecular weights of the compounds of the present invention in the table were all Mn-1too, zloo in number average molecular weight.

35- Photosensitive lithographic printing plates using the compounds of the present invention as shown in Table 1 [A) -/~ [All Al-7 is [B]! llll Exposure time is short and sensitivity is high.

Example 2 Example 1. photosensitive solution [Al-/, [Al-,! , [Al
-≠, and changing the compound of the present invention*[A)-7~[A]
Example 1.-2 was used. Photosensitive lithographic printing plates [Al-i, [Al-2, [A)-Hiroshi, and [Al-7
~ [Al-ta was produced.

All coating amounts were dry weight/j9/m2.

Compounds Fi of the present invention used in photosensitive solutions [Al-7 to [Al-ta] are shown in Table λ.

In order to check development tolerance, photosensitive planographic printing plates [A]-/, [
A)-2, [A, 1-≠, [A,:l-7~[Al-ta] and [B] have a density difference of 0. /J gray scale is closely attached, and 70
Exposure was performed for 30 seconds from a distance of CIrL. Exposed photosensitive lithographic printing plates [A']-7, [A]-2, [A,)
-Hiro, [:Al-7~[A]-ta and CB] Example 1
．． The film was developed by immersion in the same developer as above at 2j0C for 60 seconds and 3 minutes.

Table 2 shows the differences in the number of stages that result in complete clearing in to second and 3 minute development with a density difference of o and a gray scale of IR.

In addition, the compound of the present invention in Table 2 has μ, lO1/! ,
/7.23.23, X/y = j O/!
0 (molar ratio), use one with n=+. Second
The molecular weights of the compounds of the present invention in the table were all number average molecular weights of Mn=/100-2/00.

As shown in Table 2, photosensitive lithographic printing plates using the compounds of the present invention [A]-/, [A)-2, [A]-g, and [A:]-7 to [A]- In all cases, the change in the number of gray scale steps in the clear part was small, and the development tolerance was excellent.

Example 1 Photosensitive solution [A)-4' according to the example and photosensitive solution [C″ below]
A photosensitive planographic printing plate [A
)-≠ and [C] were produced.

Photosensitive liquid [C] Silyl ether compound (1) Number average molecular weight Mn = /120 All coating amounts are dry weight /
, jg/rrL2.

Example 1. According to the method shown in , the concentration difference θ.

Determine the exposure time to completely clear the jth stage with a gray scale of /j, and then use the method shown in Example 2 to determine the density difference of 0. /j gray scale, 6-≠O- The differences in the number of completely clear stages in 0 second and 3 minute development were determined and are shown in Table 3.

-4/- -4j - In addition, in the compound NrLit of the present invention in Table 3,
/ y = j O/! θ (molar ratio), n = average x
, r were used. Mayu molecular weight is M with number average molecular t
n=irro-'ctotsu*.

As can be seen from Table 3, the compounds of the present invention that have a silyl ether group that can be decomposed by acid and a hydrophilic group in the same molecule have increased sensitivity and development tolerance compared to systems in which a hydrophilic compound is simply added. did.

Patent Applicant: Fuji Photo Film Co., Ltd. -≠ 3- Procedural Amendment: January 1, 1939, Commissioner of the Japan Patent Office 1, Indication of Case: Showa SR, Patent Application No. 230377, No. 2
, Title of the invention Previously dissolved composition 3, Relationship with the case of the person making the amendment Patent applicant name (520) Fuji Photo Film Co., Ltd. 4, Subject of the amendment Iran in the "Detailed Description of the Invention" in the specification 5. Contents of correction/) Correct the entire "jJ-/33μ2" on the 13th line of the Hiro page to "jJ-133μkota".

2) Page 2, line j [Rt 40-8 IRa) n IJ kr R2 summer R140-8i-R4) n 1 fermentation R3” correct it with 3) Replace page 7μ with Attachment-7.

μ) No. 20, page 20, replace with λ.

-i) No. λ page // line "lt3+23" "lA3.23≠" and correct it.

Claims (1)

[Scope of Claims] (a) A compound capable of generating an acid upon irradiation with actinic rays. and (b) a compound having at least 7 silyl ether groups that can be oxidised by an acid and having at least one hydrophilic group represented by the following general formula CI) in the molecule. Features of previously dissolved compositions. 7C-0-8i Ma (I)