JPS6238453A - Photo-solubilizable composition - Google Patents

Abstract

PURPOSE:To provide high photosensitivity and superior aging stability and to enable preservation for a long period by using a compound which can produce an acid when irradiated with rays of active light and a compound having at least one specified silyl ester group unit decomposable with the acid and showing solubility which is increased in a developer by the action of the acid. CONSTITUTION:This photo-solubilizable composition contains a compound (a) which can produce an acid when irradiated with rays of active light and a compound (b) having at least one silyl ester group unit represented by the formula and decomposable with the acid. The solubility of the compound (b) in a developer is increased by the action of the acid. The preferred weight ratio of the compounds (a):(b) is 0.001:1-2:1. Though the composition may be composed of only the compounds (a), (b), the compounds are preferably mixed with an alkali-soluble resin. Novolak type phenol resin is suitable for use as the alkali-soluble resin.

Description

DETAILED DESCRIPTION OF THE INVENTION "Industrial Application Field" The present invention relates to a pre-solubilized composition suitable for the production of lithographic printing plates, multicolor printing proofs, drawings for overhead projectors, IC circuits, and photomasks. For more details, see (
The present invention relates to a novel pre-solubilized composition containing a) a compound capable of generating an acid upon irradiation with actinic light, and (b) a compound having at least/one silyl ester group capable of being decomposed by an acid.

"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. Examples of such orthoquinone diazide compounds include, for example, U.S.%W+m2.7 A &
, / / r No. -1747,092, No. 2,772.272, No. 2. Ifri, No. 772, No. 2. ri07. tt! No. J, 0 Hirot, IIO No.,
Same No. 3.0≠1. ///No. J, 0IA4. //!
No. 3.0≠t, IIR No. 3.0 Hiroshi 6. l/
ri issue, same issue 3.0≠t, iso issue, same issue 3. O Hirot, 1
No. 21, No. 3.0≠A, /, No. 22, No. 3.0≠4
, No. 723, 3.01, 1. ≠No. 30, same No. 3. i
o co, tori issue, same number j, l01a.

≠Otsu! No. 3. Otsu No. 31,702, Otsu No. 3゜j44
7. It is described in numerous publications, including the specifications of Kou No. 13.

These orthoquinonediazide compounds are decomposed by irradiation with actinic rays to produce a J-membered ring carbo/acid, which makes them alkali-soluble, but they all have the disadvantage of insufficient photosensitivity. has. This is because, in the case of orthoquinone diazide compounds, the quantum yield essentially does not exceed .

Various attempts have been made to increase the photosensitivity of photosensitive compositions containing orthoquinonediazide compounds, but it is extremely difficult to increase photosensitivity while maintaining development tolerance during printing. It was difficult. For example, as an example of such an attempt, Japanese Patent Publication No. 411-122172,
Tokukai Akira! --Hiro 0/2j, U.S. Patent No. ≠, 307. /
Examples include the contents described in specifications such as No. 73.

-! Recently, several proposals have been made regarding photosensitive compositions that act on bozitib without using an orthoquinone diazide compound. As one of them, for example, Tokko Sho J-
Examples include polymer compounds having orthonitrocarbinol esters described in the specification a of No. A-2AYt. 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 to increase photosensitivity by using a photosensitive system that is activated by contact action, a reaction of @λ is caused by the acid generated by photolysis, and the exposed area is solubilized by K. The principle of fairness is applied.

An example of this is, for example, a combination of a compound that generates an acid upon photolysis and an acetal or O,N-acetal compound (JP-A No.

No. 3), combination with orthoester or amide acecooled hardware (No. % Kaisho J-/-/207/≠), combination with polymer having an acetal or ketal group in the main chain (
JP-A-J3-/334122), combination with enol ether compound (JP-A-Sho!!-72 Tata!), combination with N-acyliminocarbonic acid compound (%KAI-Sho!!-7λ6)
23z), a combination with a polymer having an orthoester group in the main chain (JP-A-Sho, No. 7 JIAj), and a combination with a silyl ester compound (JP-A, 40-102-7)
(No.). In principle, these can exhibit high photosensitivity because their quantum yield exceeds Because the rate of the λ-th reaction caused by the acid generated by photolysis is slow, it does not exhibit sufficient photosensitivity for practical action. In addition, orthoester or amide acetal compounds, enol ether compounds, and even N-acylimino carbonate compounds do exhibit high photosensitivity, but they are not stable over time and cannot be stored for long periods of time. Polymers having orthoester groups in their main chains also have high sensitivity, but have the disadvantage of narrow development tolerance during development. In the case of the above-mentioned silyl ester compound, it is highly sensitive and has excellent stability over time compared to other compounds and polymers, but it cannot be said that the stability over time is sufficient for it to actually work.

"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-solubilized composition that has high photosensitivity, excellent stability over time, and can be stored for a long period of time.

Another purpose of this research is to provide a novel photo-solubilized composition that is simple and easy to obtain.

"Means for Solving the Problems" As a result of intensive studies to achieve the above object, the present inventor discovered that the above object could be achieved by using a novel photo-solubilizing composition, and has developed the present invention. Reached.

That is, the present invention has (a) a compound capable of generating an acid upon irradiation with actinic rays, and (b) at least seven silyl ester group units represented by the following general formula (I) that can be decomposed by an acid, compounds whose solubility in the developer is increased by the action of acids,
A pre-solubilized composition containing the following is provided.

In the formula, R1 represents a divalent aliphatic or aromatic hydrocarbon, and R4 represents a divalent aliphatic or aromatic hydrocarbon.

R2, R3, R≦, R6 may be the same or different, and each is a hydrogen atom, alkyl, alkenyl, aryl or aralkyl that may have a substituent, or -
Indicates 0R5.

Preferably, it represents an alkyl group or -0R5, more preferably an alkyl group having carbon number/~hiro. R5 represents an alkyl, aryl, or aralkyl group which may have a substituent. Preferably, it represents an alkyl group having 1 to 1 carbon atoms or an aryl group having 6 to 1j carbon atoms. Further, the compound (b) used in the present invention may contain two or more types of silyl ester group units represented by the general formula +I).

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

ya / l wash l λ ya 13 boiled / dashi H3C) (3 ya / j ya 76 A / 7 / 16ir In addition, n in the specific example represents an integer greater than or equal to ko. Also, x and y represent the molar ratio, In compound example A/6, X/y = 20
/ IO-10720 is shown. The molecular weight of the compound in Mataya 3~it is the weight average! OO or more, preferably 1000 to 100,000.

Compounds that can generate an acid upon irradiation with actinic rays in (a) of the present invention, which are used in combination with a compound having at least/one silyl ester group unit that can be decomposed by these acids, include many common compounds and mixtures; For example, diazonium, phosphonium, sulfonium, and hiodonium BF4-BF4-1PF6-1AsF6-1Sb
Salts such as F6-1SiF6-1c, organohalogen compounds, orthoquinonediazide sulfonyl chloride, and organometallic/organohalogen compound combinations are suitable. Of course, U.S. Patent No. 3,772,77 and West German Patent No. 2. tio, r≠λ light+! Compounds which generate acids upon photolysis as described in B4 are also suitable as compositions of the invention. Furthermore, during exposure in combination with a suitable dye,
Compounds intended to provide visible contrast between unexposed and exposed areas, such as those described in JP-A No. 3. t-777≠
Compounds described in the specification of No. 2, No. 17-/6323 can also act as the composition of the present invention.

Among the compounds that generate acid upon photolysis, s-)IJ azines substituted with trihalomethyl groups and oxadiazole compounds substituted with trihalomethyl groups are particularly preferred.

The ratio of the compound capable of generating an acid upon irradiation with actinic light in (a) of the present invention and the compound having at least one silyl ester group unit that can be decomposed by an acid in (b) K is preferably a weight ratio. 0.007:/~2:l
and preferably 0.02:/~0. lr: Operated in the range of /.

The photosolubilizing composition of the present invention can act only with a combination of a compound capable of generating an acid upon irradiation with actinic rays and a compound having at least/one silyl ester unit that can be decomposed by an acid. It is preferable to use it in combination with a soluble resin. Suitable alkali-soluble resins include novolac type phenolic resins, and specifically include phenol formaldehyde fat-resistant resins, 0-cresol formaldehyde resins, m-cresol formaldehyde resins, and the like. In addition, Tokukai Shoro-lλrrot
As stated in the above publication, when 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-mentioned unaphenol resin, , more preferred. The alkali-soluble resin is about ≠Q based on the total weight of the photosensitive resist-forming composition.
~ about 0 weight, more preferably zO ~ tON amount.

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 = 10/,
Oil Yellow $/J O, Oil Pink #3/λ,
Oil Green BG, Oil Blue BO8, Oil Blue #AO3, Oil Black BY, Oil Black BS
1 Oil Black 'l'-J-0! (The above are manufactured by Orient Chemical Industry Co., Ltd.) Crystal Violet (CI)
≠λj! , Methyl Violet (CI≠-I3), Rhodamine B (C Engineering IIt 170B), Malachite Green (CI412000), Methylene Blue (CIt20
1j) 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 that act here include ethylene dichloride, cyclohexanone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, -monomethoxyethyl acetate, toluene, and ethyl acetate, and these solvents may act alone or in combination. do.

And the concentration in the above ingredients (total solid content including additives) is:
λ~30 weight ratio. Among these, the preferred concentration (solid content) of the composition of the present invention is 0. /~2j! It's lt. The coating amount varies depending on the application, but for example, for photosensitive planographic printing plates, the solid content is generally 0. j~3.
077 m2 is preferred.

As the coating amount decreases, the photosensitivity improves, 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 hydrophilic aluminum plate, such as a silicate-treated aluminum plate, an anodized aluminum plate, a grained aluminum plate, There are aluminum plates with electrodeposited silicate, other zinc plates,
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 λ originals include transparent films such as polyethylene terephthalate films and triacetate films, and the surfaces of these plastic films are chemically or physically matted. 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@) can also work in the present invention. Such laser beams include helium neon lasers, argon lasers, chrysoton 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, aqueous ammonia, etc. are suitable; /~10 weight section,
Preferably, it is added so that the ratio by weight is o, r to J'.

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 Aj) Adipic acid/4t, iGri ((1), 100 mole)
, pyridine/7. Bis(chlorodimethylsilyl)ethaneco/,j? (0,100 mole) of toluene solution was added through the dropping funnel while stirring.
It was added over a period of minutes. After addition! o At 0C! Stirring was continued for an hour. The white salt produced (pyridine hydrochloride) is
Separated, the methyl ethyl ketone solution was washed 3 times with 100 g of an aqueous sodium bicarbonate solution, and then with 1 ooml of saturated saline. After drying this with anhydrous sodium sulfate, the solvent was distilled off under reduced pressure to obtain a pale brown viscous solid. Collection i2
3.0? . NMR reveals its structure as a compound example &! It was confirmed that Furthermore, when the molecular weight was measured by gel permeation chromatography (GPC, polystyrene standard), the weight average Mw was 2200.

Synthesis Example 2 (Synthesis of Compound Example A/3) Isophthalic acid i instead of adipic acid in Synthesis Example /
A, At(0,10omoLe) was applied, and the reaction and post-treatment were carried out in the same manner as in Synthesis Example. Light brown viscous solid, yield ii
, 2≠, If, what is the structure of the compound according to NMR?/3
It was confirmed that the molecule i! was confirmed by GPC. - Mw = 1100 after all measurements.

Example/Thickness 0.211. A 2S aluminum plate was degreased by immersing it in a 10% aqueous solution of tertiary sodium phosphate kept at 00C for 3 minutes, and then grained with a nylon film, etched with sodium aluminate for about 10 seconds, and then diluted with sodium hydrogen sulfate. Desmut treatment was performed using a 3% aqueous solution. This aluminum plate was anodized in 20% sulfuric acid at a current density of 2 A/dm 2 for 2 minutes to produce an aluminum plate.

Next, by changing the type of the compound (b) of the present invention in Photosensitivity 7 [A) below, three types of photosensitive solutions CA:]-/~(A)-3 were adjusted to y1, and this photosensitive solution was used as an anode. It was applied onto an oxidized aluminum plate and dried at 100C for 1 minute to produce photosensitive lithographic printing plates (A)-/ to [A)-J. The amount of coating at this time was 117 m 2 in dry weight.

Further, the compound (b) of the present invention used in the photosensitive solution [A)-/~[:A]=-j is shown in Table 1.

Photosensitive liquid [A] rCompound (b) of the present invention 0, Hiro O
? Next, as a comparative example, the following photosensitive liquids CB) and [C] were applied in the same manner as photosensitive liquid (A) to prepare photosensitive planographic printing plates [B] and [C].

Photosensitive liquid CB) Photosensitive liquid [C] 脣) Compound shown in JP-A-702≠7 that acted on photosensitive liquid (C).

Weight average molecular weight Mw = 2100 (GPC, polystyrene standard) Coating time after drying was /, 197 m2.

Photosensitive lithographic printing plate (A) -/~ (A: I-3, CBI, and a gray scale with a density difference of 0./! was brought into close contact with the photosensitive layer of [C], and 307 nm was printed using the carbon arc lamp of A. 70c
Exposure was performed from a distance of m.

Photosensitive lithographic printing plate [A]-/~(:A:)-J, [B] and (C) exposed to exhibit excellent round window optical properties of the present invention
io of Dr-4A (product name: Fuji Photo Film)
Immersion development was carried out for 10 seconds at 2!0C with a twice diluted aqueous solution,
Concentration difference 0. /j in gray scale! The exposure time for completely clearing the rows was determined and was as shown in Table 1.

Table 1 As can be seen from Table 1, all of the photosensitive lithographic printing plates [:A:]-/~[:A]-j using the compound of the present invention had a shorter exposure time than [B]. , high sensitivity. Also [C
] has the same level of sensitivity.

In addition, the molecular weights of the compounds of the present invention &Y, /2, /B in Table 1 are determined by GPC (polystyrene standard).
It was ooo-4Looo. Also, in the compound &/Otsu,
The molar ratio of x/y was 107ta0.

Example: In order to demonstrate the excellent stability over time of the present invention, the photosensitive lithographic printing plates (A)-/~[A)-J, C prepared in Example/
B) and [C] were left for 3 days at a temperature of 4tt'c and a humidity of 7j%. Under the above conditions, the density difference on the photosensitive lithographic printing plates (A)-/~CA)j, [B] and [C] J- before and after being left for 3 days is 0. 7 with a 30 ampere carbon arc lamp with a /J- gray scale in close contact.
Exposure was performed for 30 seconds from a distance of 0 cm. Exposed photosensitive lithographic printing plates [A]-/~[A)-j, [B] and [
C] was developed by the method shown in Example/, and the temperature was 4 Aj.
The difference in the number of completely clear gray scales of each photosensitive lithographic printing plate before and after being left for 3 days under the condition of 0C1 humidity of 7j% was determined, and the results are shown in Table 2.

As can be seen from Table 2, all of the photosensitive lithographic printing plates (, l-/~(A)-j) using the compound of the present invention have a smaller gray scale step difference than [C] and have poor stability over time. It is excellent. It also has the same degree of stability over time as [B].

Together with Example 1, it can be seen that the composition using the compound of the present invention has high sensitivity and excellent stability over time.

Patent applicant Fuji Photo Film Co., Ltd. Procedural amendment filed in February 1985 Mr. F. Commissioner of the Japan Patent Office
]1.Indication of the incident Showa to year patent application No. 1717/
J No. 2, Title of the invention Previously popularized composition 3, Relationship with the case of the person making the amendment Patent applicant contact information 10
6 East 5; 21-++26-30, Nishiazabu, S Miyako-ku,
/INyl ``, ,,,' 4 ?Ill Correct Subject Column 5 of ``Detailed Description of the Invention'' of the Specification, Contents of Amendment The description of ``Detailed Description of the Invention'' of the Description has been amended as follows. do.

l) Page j, line 0 After "stable" "sex" Insert.

j) On page 7, line 2, after ``The compound having a silyl ester group unit represented by the general formula (1) preferably has the following general formula (1) or (Il
This is a compound represented by l).

Insert.

3) After "-represents a group" in the first row of the page, [R6 is a hydrogen atom, has a substituent, or has a hydrogen atom, and has a number of carbon atoms/~3 carbon atoms (II) l 't3'R3R3' aN b represents 0 or /. n represents a positive integer, preferably an integer of /-100. ” is inserted.

≠) 20th page/≦th line "Post-processing has been completed." "I did some post-processing." and correct it.

Claims (1)

[Claims] (a) A compound capable of generating an acid upon irradiation with actinic rays;
and (b) has at least one acid-decomposable silyl ester group unit represented by the following general formula (I),
A photo-solubilizing composition comprising a compound whose solubility in a developer solution is increased by the action of an acid. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) In the formula, R_1 represents a mono- or divalent aliphatic or aromatic hydrocarbon, and R_4 represents a divalent aliphatic or aromatic hydrocarbon. R_2, R_3, R_2', and R_3' may be the same or different, and each represents a hydrogen atom, an alkyl, an alkenyl, an aryl or aralkyl which may have a substituent, or -OR_5. R_5 represents an alkyl, aryl, or aralkyl group that may have a substituent.