JPS6238450A - Photo-solubilizable composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition having a high photosensitivity and a broad developing allowability in a development by incorporating a compd. having a partial structure capable of generating an acid by irradiation of an active ray and a partial structure shown by a specific constitutional formula and also having a property of increasing the solubility in a developer with an action of the acid to the titled composition. CONSTITUTION:The titled composition comprises the compd. having the partial structure capable of generating the acid by irradiating the active ray and the partial structure (a silylether group) shown by the formula and having the property of increasing the solubility in the developer with the action of the acid. The partial structure which enables to generate the acid by irradiating the active ray is preferably the structure having a s-triazine unit substd. with a trihalomethyl group or an oxadiazole unit substd. with a trihalomethyl group. The compounding ratio of the silylether bond of the silylether compd. and the partial structure capable of generating the acid by irradiating the active ray is preferably (1:5)-(1:0.001), more preferably (1:1)-(1:0.01) in a molar ratio.

Description

Detailed Description of the Invention "Industrial Application Field" The present invention provides at least one partial structure that can generate an acid upon irradiation with actinic rays and a silyl ether group that can be partially decomposed by an acid in the same molecule. The present invention relates to a photo-solubilizable composition suitable for producing lithographic printing plates, multicolor printing proofs, drawings for overhead projectors, IC circuits, and photomasks, which contain a novel original compound.

"Prior Art" Orthoquinone diazide compounds have been 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. Such orthoquinonediazide compounds include, for example, U.S. Pat. No. 2,7Aj, 111
No. 2゜747.0 Octopus No. -, 772, 27
No. 2, same No. 2. rj ri, No. 112, same no. λ, ri 07. t
At No. J, 0174. / No. 10, No. j, 01
A&, No. 111, No. J, No. 0176.111, No. J
, oat, iir No. j, O1t&, //ri No. 3,04A6,120, same No. 3. o44, /λ1 No. j, 04At, /22, No. J, 0444. /
No. 2J, No. J, oti, tt3゜, No. J, 102
, No. 10, No. j, 106゜4Abu No. 1, No. j, 4
No. 31,709, same No. 3゜6μ7. It is described in numerous publications, including the specifications of No. ≠4/-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 due to the fact that in the case of orthoquinonediazide compounds, the quantum yield essentially does not exceed □.

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. Ta. For example, an example of such an attempt is Tokko Sho≠! -/Kotou-go, Tokukai Akira! −
-φ012! No., U.S. Pat. No. 307. Examples include the contents described in specifications such as No. 73.

Recently, several proposals have been made regarding photosensitive compositions that act positively without using an orthoquinone diazide compound. As for seven of them, for example, Tokko Sho J-A
Examples include polymer compounds having an orthonitrocarbinol ester group described in the specification of No. 1-16. 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, the known principle of causing the first reaction with an acid generated by photolysis and thereby solubilizing the exposed area is applied.

An example of such a combination is, for example, a combination of a compound that generates an acid upon photolysis and an acetal or O,N-acetal compound (Japanese Patent Application Laid-Open No. 2002-120002).

No. 3), combination with orthoester or amide acetal compound (JP-A No. 1-/207/≠), combination with polymer having an acetal or ketal group in the main chain (JP-A-JJ-/JJ≠λ) ), combination with enol ether compound (JP-A Sho! Yo1/2 Tata! issue), combination with N-acylimino carbonate compound (JP-A Sho! J-/2T Co-3)
), a combination with a polymer having an orthoester group in the main chain (% 1977-/73≠!), and a combination with a silyl ether compound (JP-A-6O-37J4C)
etc. can be mentioned. In principle, these can exhibit high photosensitivity because their quantum yield exceeds Since the rate of the second reaction by the acid generated by photolysis is slow, it does not exhibit sufficient photosensitivity for actual use. Orthoester or amide acetal compounds, enol ether compounds, and N-7 siliimino carbonate compounds certainly exhibit high photosensitivity, but they are not stable over time and cannot be stored for long periods of time. Can not. The IJ polymer having an orthoester group in the main chain also has high sensitivity, but has the disadvantage of narrow development tolerance during development.

In the case of silyl ether compounds, they have higher sensitivity and superior stability over time than the above compounds, but the sensitivity and development tolerance during development are still insufficient for application to high-sensitivity printing plates, etc. .

"Problems to be Solved by the Invention" The purpose of this research is to provide a novel photo-solubilizable composition in which these problems are solved. That is, the object of the present invention is to provide a novel photo-solubilizing composition that has high photosensitivity and wide development latitude during development.

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

Still another objective of this research is to provide a novel photosolubilized 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-soluble compound, and arrived at the present invention. .

That is, the present invention has at least one partial structure capable of generating an acid upon irradiation with actinic rays and at least one partial structure (silyl ether group) represented by the following general formula (I), A photosolubilizable composition containing a compound whose solubility is increased by the action of an acid.

Preferably, the partial structure that generates an acid upon irradiation with actinic light is characterized by having an 8-triazine unit substituted with a trihalomethyl group or an oxadiazole unit substituted with a trihalomethyl group.

Further, the partial structure represented by the general formula (I) is preferably a silyl ether group represented by the following general formula (I[), (■), or (Ill/).

In the formula, R1, R2, R3, R'2, and R6 may be the same or different, and each represents a hydrogen atom, alkyl, alkenyl, aryl or aralkyl that may have a substituent, -0R5, or active group. Shows a partial structure that generates acid upon irradiation with light. Preferably, it represents an alkyl group having a carbon number of 1 or 2, or -0R5. R4 represents a divalent aliphatic or aromatic hydrocarbon which may have a substituent. R5 represents an alkyl, aryl or aralkyl group which may have a substituent, or a partial structure which generates an acid upon irradiation with actinic rays. Preferably, it represents an alkyl group having from / to r carbon atoms, an aryl group having A-/j carbon atoms, or a partial structure that generates an acid upon irradiation with actinic rays.

Specific examples of the silyl ether compounds of the present invention include those shown below.

Sarazuma Kanoiso T -d Koko Q Ko'4'4 Ko) 10) Ko
Iso The weight average molecular weight of the silyl ether compound in the present invention is preferably 200 or more, and more preferably 200 or more.
o-λoooooo.

The ratio of the silyl ether bond of the silyl ether compound in the present invention to the partial structure capable of generating an acid upon irradiation with actinic rays is preferably a molar ratio of /:j to /:0,00/,
More preferably, the ratio is 1:1 to /:0.0/.

Although the silyl ether compound of the present invention can be used alone as a photo-soluble compound, it is preferable to use it in combination with an alkali-soluble resin. Suitable alkaline soluble resins include novolac type phenolic resins, and specifically include phenol formaldehyde m-fat, o-cresol formaldehyde resin, m-cresol formaldehyde resin, and the like. Furthermore, Tokukai Akira! 0-/2j1
As described in Publication F06, a phenol substituted with an alkyl group having 3 to r carbon atoms such as t-butylphenol formaldehyde resin or a condensate of cresol and formaldehyde is used in combination with the above phenol resin. Then, it is even more preferable. The alkali-soluble resin contains from about 4 LO to about 0 weight gold, more preferably to-to-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, a compound that increases the acid generation efficiency of the acid-generating compound (so-called sensitizer), etc. can be contained. Suitable dyes include oil-soluble dyes and basic dyes. Specifically, oil yellow $/0
/, oil yellow @/30. Oil pink #3 no 2,
Oil Green BG, Oil Blue BO8, Oil Blue #tOJ, Oil Black BY, Oil Black BS
, Oil Black '1'-rot (manufactured by Orient Chemical Industry Co., Ltd.) Crystal Violet ((I≠
λj! , methyl violet ((I4t2131),
Rhodamine B ((I4tj/70B), malachite green ((I≠2000), methylene blue ((Ij)
7) etc.

The photosoluble composition of the present invention is dissolved in a solvent that dissolves each of the above components and applied onto a support. Solvents used here include ethylene dichloride, cyclohexanone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glyfur monoethyl ether, 2-methoxyethyl acetate, toluene, and ethyl acetate, and these solvents may be used alone or in combination. and use it.

And the concentration in the above ingredients (total solid content including additives) is:
λ~! O is in charge of weight. Among these, the preferred concentration (solid content) of the composition of the present invention is 0. /- It is a double weight section. The coating amount varies depending on the application, but for example, for photosensitive planographic printing plates, the solid content is generally 0.7 to 0.
97m2 is preferred.

As the coating amount decreases, the photosensitivity increases, but the physical properties of the sensitive and photosensitive film decrease.

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 coated aluminum plate, as well as a zinc 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 also be used as a photoresist by coating it on various supports other than those mentioned above, such as copper plates, copper-plated plates, and glass plates.

Examples of active light sources used in the present invention include mercury lamps, metal halide lamps, xenon lamps, chemical lamps, and carbon arc lamps. Scanning exposure with a high-density energy beam (laser beam or electron beam) can also be used in the present invention. Such laser beams include helium neon laser, argon laser, krypton ion laser, helium
Examples include cadmium lasers.

Developers for the photosoluble composition of the present invention include sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, trisodium phosphate,
Aqueous solutions of inorganic alkaline agents such as sodium diphosphate, triammonium phosphate, ammonium diphosphate, sodium metasilicate, sodium bicarbonate, aqueous ammonia, etc. are suitable, and their concentrations are 0.7 to 10. Weight factor, preferably 0.2~! It is added to the 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 below using synthesis examples and examples, but the content of the present invention is not limited thereto.

Synthesis Example/(Synthesis of Compound Example & 2) Compound (V)A shown below, //f (0,0200m
ot) and pyridimeta, 79 (0,/ko/mot) to methyl ethyl ketone! 04 and methyltrichlorosilane j, 2Pfi! (0,0220 mol) in methyl ethyl ketone (20 ml) at room temperature with stirring over a period of 7 hours using a dropping funnel. After the addition, stirring was continued for 2 hours on an oil bath at jo0c. Return this to room temperature, dimethyldichlorosilane λ,! r≠? (0
,0220mot), and after further stirring, add p-xylylene glycol t,j3? (0,04LoOmo
A methyl ethyl ketone (comi) solution of L) was added via the dropping funnel over a period of 30 minutes. 0°C after addition
Stirring was continued for 3 hours. The produced white salt (pyridine hydrochloride) was separated from the P solution, and the P solution was washed with a 3-superior sodium bicarbonate aqueous solution ROOMl and then with a saturated saline solution IOθ-.

After drying this with anhydrous sodium sulfate, the solvent was distilled off under reduced pressure to obtain a pale yellow viscous solid. Yield 10.2g! . Weight average molecular weight Mw=J
-600())' Rubermeation Chromatography (GPC), polystyrene standard).

Synthesis Example 2 (Compound Example/Synthesis of μ) Compound shown below (■)/Hiroshi, j? (0, OJOOm
ot) and m-xylylene glycol 2.679 (0,
0700mol) and pyridine/7. Hiro 2 (0, -22
0 moL) was dissolved in methyl ethyl ketone 200-, and while stirring, dimethyldichlorosilane/2.2f was added to it.
A 20 rttl solution of (O,/OOmot) in toluene was added from the dropping funnel at room temperature over io minutes. After the addition, stirring was continued for 3 hours in a jo'c on an oil bath. The generated white salt (pyridine hydrochloride) was separated from P, and the F solution was
It was washed with an aqueous solution of sodium bicarbonate, 110ml of aqueous sodium bicarbonate, and then 200ml of saturated saline. After drying this with anhydrous sodium sulfate, the solvent was distilled off under reduced pressure to obtain a colorless viscous liquid. Yield λt, oori. Weight average molecular weight mw=
trooo (GPC, polystyrene standard).

Compound (VI) Example 1 A λS aluminum plate with a thickness of 0.2≠n was degreased by immersing it in an IOS aqueous solution of tertiary sodium phosphate maintained at rooC for 3 minutes, grained with a nylon brush, and then treated with sodium aluminate. Etching was performed for about 70 seconds, and desmutting was performed using a trivalent aqueous solution of sodium hydrogen sulfate. This aluminum plate was anodized for λ minutes in 20% sulfuric acid at a current density of coA/dm2 to produce an aluminum plate.

Next, three types of photosensitive liquids CA)-/~CA)-J were prepared by changing the type of the compound of the present invention in photosensitive liquid (A) below, and this photosensitive liquid was placed on an anodized aluminum plate. Apply,
Each photosensitive lithographic printing plate (A) -/~ (A) -? was dried at 1oo0c for 2 minutes. was created. The amount of coating at this time was 397 m2 in dry weight.

Further, the compounds of the present invention used in the photosensitive solutions [:A)-/ to [A)-3 are shown in Table 1.

Photosensitive liquid [A] Compound of the present invention Q, ≠or cresol-formaldehyde novolak resin / Of oil blue #603 (manufactured by Orient Chemical Industry ■) 0,0/f ethylene dichloride 10? Methyl cellosolve ioyNext, as a comparative example, the following photosensitive solutions CB) and [C] were applied in the same manner as photosensitive solution [A] to prepare photosensitive planographic printing plates [B] and (C).

Photosensitive liquid CB) Condensation product of phenol-formaldehyde novolac resin and 2-naphthoquinone-2-diazide-y-sulfonyl chloride O1μ! 1 Cresol-formaldehyde novolac resin 7.0? /, 2-
Naphthoquinone-λ-Diazide-Hiro-sulfonyl chloride 0.029 Oil Blue #l, 03 (manufactured by Orient Chemical Industry ■) 0.0/l ethylene dichloride ioy methyl cellosolve 10f? Photosensitive liquid (C) Silyl ether compound represented by the following formula (■) 0.319 Cresol formaldehyde novolac resin /, 09λ-(≠
-methoxyphenyl) 1 μ, t-bistrichloromethyl-8-) riazine 0.01f Oil Blue #603 (manufactured by Orient Chemical Industry ■) 0.0/f ethylene dichloride IO? Methyl cell solve 10f? Weight average molecular weight pw=
rooo (GPC, polystyrene standard).

The coating weight after drying is 8 jr/m for both [B] and [C]
It was 2. Photosensitive lithographic printing plate CA)-/~(A)--
? , [B] and [C] have a density difference O0/! on the photosensitive layers. The gray scale of the image was brought into close contact with the image, and exposure was carried out from a distance of 7θ using a carbon arc lamp of 30 angstroms.

Photosensitive lithographic printing plates exposed to show the excellent photosensitivity of the present invention [person] -/~l: A) -J, [B] and (C"
7 of DP-JB (product name: Fuji Photo Film)
．． Immersion development was carried out with a 2-fold diluted aqueous solution at 2j'C for to seconds, and the density difference was 0. /J in grayscale! The exposure time for completely clearing the rows was determined and was found to be as shown in Table 7.

As shown in Table 1, all of the photosensitive lithographic printing plates (A)-/~(A]-j using the compound of the present invention are [B],
[C] Shorter exposure time and higher sensitivity.

In Table 1, the compounds of the present invention &2,! , /≠o molecules i were all 1300 to rooo using gel permeation chromatography polystyrene standards.

Example λ Using the photosensitive liquid [A:]-/-3 of Example 1, a photosensitive lithographic printing plate [A:]-/-3 was prepared in the same manner as in Example. All coated amounts were 127 m2/dry weight.

Next, as a comparative example, photosensitive liquid [B] and photosensitive liquid [C] of Example were coated in the same manner as photosensitive liquid [A] to prepare photosensitive planographic printing plates [B] and [C]. The coating weight after drying was /, jf/m2, respectively.

To check development tolerance, photosensitive planographic printing plate [A] -/~3
, [B] and EC) have a density difference O0/! on the photosensitive layer. The gray scale of 307 was brought into close contact with the image, and exposure was carried out for 30 seconds from a distance of 70 cm using the carbon arc lamp of 307. Exposed photosensitive lithographic printing plates (A)-/~3, CB) and [C]
was immersed in λr'C for 0 seconds and 3 minutes in the same developer as in Example. Table 2 shows the difference in the number of completely clear stages when developing for 60 seconds and 3 minutes using a gray scale with a density difference of o and IR.

As can be seen from Table 2, all of the photosensitive lithographic printing plates [:A)-/~3 using the compound of the present invention had small changes in the number of gray scale stages in the clear part and had greatly excellent development acceptability. It was something. That is, CAB-/~ using the compound of the present invention from CC''l using a compound having a silyl ether group and a compound that generates an acid upon light irradiation separately.
3 is better.

Patent Applicant: Fuji Photo Film Co., Ltd. 1, Indication of Case: 1935, Patent Application No. 17 Roto No. 20, Title of Invention: Previously Solubilized Composition 3, Relationship with the Amendment Person Case: Patent Applicant Contact Information: 10
6 No. 2-26-30 Nishi-Azabu, Minato-ku, Tokyo Target of amendment The description in the "Detailed Description of the Invention" section of the specification & Contents of the amendment Correct.

l) First page l! row "original compound" "Photosensitive compound" and correct it.

-) No. λ page 12th line “O0μoz "0.11" and correct it.

3) Page 23, line 1 f-0, JJfJ "o-aot" and correct it.

-'0 Take

Claims (1)

[Scope of Claims] It has at least one partial structure capable of generating an acid upon irradiation with actinic rays and at least one partial structure represented by the following general formula (I), and has a solubility in a developer that is equivalent to that of an acid. A photo-solubilizable composition containing an action-enhancing compound. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I)