JPH067260B2 - Photosolubilizing composition - Google Patents

Description

The present invention relates to a photosolubilizing composition suitable for producing a lithographic printing plate, school printing for multicolor printing, drawings for overhead projectors, IC circuits, and photomasks. For more details (a)
A compound capable of generating an acid upon irradiation with actinic rays, (b) a compound having at least one silyl ether group capable of being decomposed by an acid in a molecule, and (c) methyl cellosolve: water = 9
The pH of a 5% solution of 0:10 wt% at 25 ° C is 3.
It relates to a photosolubilizing composition comprising an alkali-soluble resin of 5 to 9.0.

(Prior Art) As a photosensitive substance which is solubilized by actinic rays and acts so-called positively, an orthoquinonediazide compound has been conventionally known and has been widely used in planographic printing plates, photoresists and the like. Examples of such orthoquinonediazide compounds include, for example, US Pat. No. 2,766,118,
It is described in many publications, including the specifications of the above-mentioned No. 2,767,092.

These orthoquinonediazide compounds utilize the fact that they are decomposed by irradiation with an actinic ray to form a 5-membered carboxylic acid and become alkali-soluble, but they all have the drawback of insufficient photosensitivity. Have. This is because the quantum yield of the orthoquinonediazide compound does not essentially exceed 1.

Various methods have been tried until now for increasing the photosensitivity of a photosensitive composition containing an orthoquinonediazide compound, but all of them have only increased the sensitivity by about 2 to 3 times. For example, as an example of such an attempt,
The contents described in the specifications of JP-A-8-12242, JP-A-52-40125 and US Pat. No. 4,307,173 can be mentioned.

Also, recently, some proposals have been made regarding a photosensitive composition which positively acts without using an orthoquinonediazide compound. As one of them, for example, Japanese Patent Publication No. 56-
The polymer compounds having an orthonitrocarbinol ester group described in the specification of 2696 are mentioned. However, also in this case, the photosensitivity is not sufficient for the same reason as in the case of orthoquinonediazide. In addition to this, a photosensitive system activated by a catalytic action is used separately, and as a method of increasing the photosensitivity, a second reaction is caused by an acid generated by photolysis, thereby solubilizing an exposed area. The principle of is applied.

As such an example, for example, a combination of a compound that generates an acid by photolysis with an acetal or an O, N-acetal compound (JP-A-48-89003), a combination of an orthoester or an amide acetal compound (JP-A-489003). Sho 51
No. 120714), and a polymer having an acetal or ketal group in the main chain (JP-A-53-13342).
No. 9) in combination with an enol ether compound (Japanese Patent Application Laid-Open No. Sho 5
5-12995), N-acyliminocarbonate compounds (JP-A-55-126236), and polymers having an orthoester group in the main chain (JP-A-5-126236).
6-17345). In principle, the quantum yield exceeds 1, which may result in high photosensitivity. However, in the case of an acetal or N-acetal compound and a polymer having an acetal or ketal group in the main chain, photolysis Since the rate of the second reaction due to the acid generated in (2) is slow, it does not exhibit sufficient photosensitivity for actual use. Further, in the case of an ortho ester or amide acetal compound, in the case of an enol ether compound, and in the case of an N-acyl imino carbonic acid compound, it certainly shows high photosensitivity, but the stability over time is poor and it can be stored for a long time. Absent.
A polymer having an orthoester group in the main chain also has a high sensitivity but has a drawback that the development tolerance at the time of development is narrow.

(Object of the Invention) An object of the present invention is to provide a photosolubilizing composition which solves these problems, has excellent stability over time, and can be stored for a long period of time. That is, it is an object of the present invention to provide a photosolubilizing composition having high photosensitivity, broad development tolerance during development, excellent stability over time, and long-term storage.

Still another object of the present invention is to provide a photo-solubilized product which is easy to manufacture and can be easily obtained.

(Structure of the Invention) As a result of intensive studies to achieve the above object, the present inventors have found that the above object can be achieved by using the following photosolubilizing composition, and have reached the present invention.

That is, the present invention provides (a) 0.01 to 10% by weight of a compound capable of generating an acid upon irradiation with actinic rays, and (b) a compound 10 to 40 having at least one silyl ether group capable of being decomposed by an acid in a molecule. %, And (c) Methyl cellosolve: water = 90: 10% by weight of a 5% solution of 60% to 90% by weight of an alkali-soluble resin having a pH of 3.5 to 9.0 at 25 ° C.
And a highly sensitive photo-solubilizing composition which is excellent in stability over time and can be stored for a long period of time.

The silyl ether group-containing compound used in the present invention is a compound represented by the following general formula (I) and having at least one silyl ether group which can be decomposed by an acid.

Specifically, JP-A-60-37549 and JP-A-60-121
No. 446, No. 61-141442 and No. 61-151.
It is a silyl ether compound described in each publication of No. 643.

Of these, the silyl ether compounds containing a hydrophilic group described in JP-A-60-12146 are particularly useful. Specific examples of the hydrophilic group include those shown below.

In the formula, l represents an integer of 1 to 4, m and n are integers of 1 or more, preferably 1 to 100, more preferably 1 to
Indicates an integer of 20. R represents an alkyl or a phenyl group which may have a substituent. Particularly preferred hydrophilic groups are Is.

Specific examples of the compound in (b) of the present invention include the following.

No. 1 No.2 No.3 In the specific examples, x and y represent molar ratios, where x = 0 to 95 mol% and y = 5 to 100 mol%. n represents an integer of 1 or more.

The amount of silyl ether group-containing compound added to the total composition is 1
It is 0 to 40% by weight. If it is less than 10% by weight, no image is formed. Further, if it is 40% by weight or more, it is not preferable because it is unstable over time. The more preferable addition amount is 15 to 30% by weight.

Many known compounds and mixtures as suitable compounds capable of generating an acid upon irradiation with actinic rays used in the present invention,
Such as diazonium, phosphonium, sulfonium, and iodonium of _{^{BF 4 -, PF 6 -,}} SbF 6 -, SiF 6 -, ClO 4 - , an organic halogen containing compound, o-quinonediazide sulfonyl chloride, and organometallic / organohalogen compounds Combinations are suitable. Of course, U.S. Pat. No. 3,77
No. 9,778 and West German Patent No. 2,610,842.
The compounds capable of generating an acid by photolysis as described in the respective specifications of the publication are also suitable as the composition of the present invention.

Among the compounds that generate an acid by the photolysis, trihalomethyl compounds such as halomethyl-s-triazine compounds and halomethyloxadiazole compounds are particularly preferable.

The amount of the compound capable of generating an acid upon irradiation with actinic rays in the total composition is 0.01 to 10% by weight. It is more preferably 0.1 to 2% by weight.

Suitable alkali-soluble resins used in the present invention include phenol formaldehyde resins, cresol formaldehyde resins, p-ter-butylphenol formaldehyde resins, phenol-modified xylene resins, phenol-modified xylene mesitylene resins and other novolak resins, pyrogallol-acetone condensates, Polyhydroxystyrene polymers and copolymers, polyhalogenated hydroxystyrene polymers and copolymers (meth) acrylic acid copolymers with other vinyl compounds (for example, methylmethacrylate),
Examples thereof include crotonic acid copolymers, maleic acid copolymers and partial esterified products thereof, and itaconic acid copolymers. The above commercially produced alkali-soluble resin contains free acid, so methyl cellosolve: water = 9
The pH of a 5% solution of 0:10 wt% at 25 ° C is
It shows a value lower than 3.5.

The silyl ether group-containing compound in (b) of the present invention,
Since it is decomposed by an acid, the alkali-soluble resin contains a liberated acid, and the pH of a 5% solution of its methyl cellosolve: water = 90: 10 wt% at 25 ° C. is lower than 3.5. The compound containing a silyl ether group in (b) of the present invention decomposes with time, and when it is made into a high-sensitivity photosolubilizing composition, it becomes impossible to store it for a long period of time.

The above-mentioned commercially produced alkali-soluble resin is dissolved in an organic solvent, and a large amount of water or a large amount of alkaline aqueous solution (p
H is gradually added to about 9) with stirring, and the obtained precipitated product is filtered, washed and dried to remove the liberated acid.
The pH of a 5% solution of the product obtained, 90% by weight of methyl cellosolve: water = 25 ° C., rises in comparison with that without the above treatment. Thus, the free acid contained in the commercially produced alkali-soluble resin was removed, and methylcellosolve: water = 90: 10% by weight of 5%
By increasing the pH of the solution at 25 ° C, it is possible to provide a highly sensitive photosolubilizing composition which is excellent in stability over time and can be stored for a long period of time. Preferred alkali-soluble resin methyl cellosolve: water = 90: 10% by weight
The pH range of the 5% solution at 25 ° C is 3.5-9.
It is 0. A more preferable range is 5.5 to 7.0.
These alkali-soluble resins may be used alone or in combination of two or more.

The amount of alkali-soluble resin added in the total composition is 60 to 90.
More preferably, it is 70 to 85% by weight.

If necessary, the photosolubilizing composition of the present invention further comprises a dye (for example, an anthraquinone dye such as CI Solvent Orange 6, CI Solvent Red 143, CI Solvent Red 145, CI Solvent Blue 36, CI Solvent Blue 82, or monoazo dye). Metal complex salt dyes), pigments (eg CI Pigment Red 48, CI Pigment Blue 1)
5), fillers (eg silica powder, polyethylene powder, fluorinated polyethylene powder, calcium carbonate powder, barium sulfate powder, etc.) plasticizers, cyclic acid anhydrides (eg phthalic anhydride, tetrahydrophthalic anhydride, maleic anhydride) that enhance sensitivity. Acid, succinic anhydride, etc.) and a compound capable of increasing the acid generation efficiency of the compound capable of generating the acid (so-called sensitizer).

The photo-soluble composition of the present invention is dissolved in a solvent that dissolves each of the above components and applied onto a support. Here, as the solvent used, ethylene dichloride, cyclohexanone,
Methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-
There are methoxyethyl acetate, toluene, ethyl acetate and the like, and these solvents are used alone or as a mixture. And the concentration in the above components (total solid content including additives)
Is 2 to 50% by weight. Of these, the composition of the present invention
The preferred concentration (solid content) of (a) + (b) + (c) is 0.1-2.
It is 5% by weight. Also, although the coating amount varies depending on the application,
For example, in the case of a photosensitive lithographic printing plate, generally, the solid content is preferably 0.5 to 3.0 g / m ² . Although the photosensitivity increases as the coating amount decreases, the physical properties of the photosensitive film deteriorate.

In the case of producing a lithographic printing plate using the photo-soluble composition of the present invention, the support thereof may be a hydrophilized aluminum plate, for example, a silicate-treated aluminum plate, an anodized aluminum plate, a grained aluminum plate, or a silicate electrode. There is an aluminum plate worn, other zinc plate,
It is possible to use stainless steel plates, chrome-treated steel plates, hydrophilicized plastic films and papers.

Further, as a support suitable for manufacturing a proof plate for printing and a film for an overhead projector film 2nd original drawing, a transparent film such as polyethylene terephthalate film and triacetate film, and the surface of these plastic films are chemically or physically matted. I can give you what I did. Suitable supports for producing a photomask film include a polyethylene terephthalate film vapor-deposited with aluminum, an aluminum alloy or chromium, and a polyethylene terephthalate film provided with a coloring layer. Further, as the photoresist, various supports other than those described above, for example, a copper plate, a copper-plated plate, or a glass plate are coated with the photosolubilizing composition of the present invention and used.

Examples of the light source of actinic rays used in the present invention include a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, and a carbon arc lamp. Scanning exposure with a high-density energy beam (laser beam or electron beam) can also be used in the present invention. Examples of such a laser beam include a helium / neon laser, an argon laser, a krypton ion laser, and a helium / cadmium laser.

The developer for the photosoluble composition of the present invention includes sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium triphosphate, dibasic sodium phosphate, ammonium triphosphate, and Aqueous solutions of inorganic alkaline agents such as ammonium diphosphate, sodium metasilicate, sodium bicarbonate, aqueous ammonia, etc. are suitable and their concentration is 0.1-10% by weight,
Preferably, it is added in an amount of 0.5 to 5% by weight.

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

Hereinafter, the present invention will be described in more detail with reference to Synthesis Examples and Examples, but the content of the present invention is not limited thereto.

Synthesis Example 1 7.32 g (0.0501 mo) of 1,8-octanediol
le), tetraethylene glycol 9.71 g (0.05
00mole), 17.4 g (0.220mole) of pyridine,
To a mixture of 80 m of dehydrated and distilled toluene, a solution of 12.9 g (0.100 mole) of dichlorodimethylsilane in 20 m of toluene was added from a dropping funnel over 30 minutes while stirring and cooling with ice. After the addition, stirring was continued for 5 hours at 50 ° C. The white salt (hydrochloride of pyridine) thus formed was filtered off, and the toluene solution was concentrated under reduced pressure. Then, it was dried under vacuum (about 1 mmHg) while heating at about 80 ° C. for 10 hours. Colorless transparent liquid, yield 20.7 g. By NMR,
It was confirmed that the structure was Compound Example No. 1. Furthermore, VPO (Vapour Pressure Osmom)
eter) was measured number-average molecular weight _{by, n}
= 1980.

Synthetic Example 2 5.53 g (0.0400 mole) of p-xylylene glycol instead of 1,8-octanediol and tetraethylene glycol in Synthetic Example 1, polyethylene glycol # 300 (manufactured by Kanto Chemical Co., Inc., average molecular weight 300) ) 18 g (0.060 mole) was used and Synthesis Example 1
Reaction and post-treatment were performed in the same manner as in. Colorless transparent viscous liquid, yield 26.8 g. Its structure was determined to be Compound Example No. 2 by NMR.
Was confirmed, and the number average molecular weight was measured by VPO to find that _n 1 was 1,730.

Synthesis Example 3 Dihydroxyethylhydroquinone 19.9 g (0.1
00mole), 17.4 g (0.220mole) of pyridine,
A solution of 12.9 g (0.100 mole) of dichlorodimethylsilane in 20 m of toluene was added to a mixture of 80 m of dehydrated and distilled toluene in the same manner as in Synthesis Example 1, and thereafter, reaction and post-treatment were performed in the same manner. Slightly brownish white solid, yield 19.7 g. The structure is a compound example by NMR
It was confirmed to be No. 3, and the number average molecular weight was measured by VPO to find that _{n 2} = 2040.

Example 1 A 2S aluminum plate having a thickness of 0.24 mm was immersed in a 10% aqueous solution of sodium triphosphate maintained at 80 ° C for 3 minutes to be degreased, grained with a nylon brush, and then with sodium aluminate for about 10 seconds. It was etched and desmutted with a 3% aqueous solution of sodium hydrogen sulfate. The aluminum plate was anodized in 20% sulfuric acid at a current density of 2 A / dm ² for 2 minutes to prepare an aluminum plate.

To 100 g of methylene glycol, 50 g of a commercially produced cresol-formaldehyde novolak resin, which is an alkali-soluble resin, was gradually added and dissolved. Then, the obtained compound was gradually added to 1500 g of an aqueous KOH solution (pH = 9) while stirring, and the obtained precipitated product was filtered, washed, and dried to remove the liberated acid. The pH of a 5% solution of the resulting compound of methyl cellosolve: water = 90: 10% by weight at 25 ° C was 6.5.

Similarly, a commercially produced cresol-formaldehyde novolak resin, methylcellosolve: water = 90: 10 wt.
The pH at 5 ° C was 2.8.

The resulting photosensitive solution containing a cresol-formaldehyde novolak resin, which is an alkali-soluble resin from which the free acid of the present invention has been removed, is [A] -1, and a commercially produced cresol which has not been subjected to the above-mentioned treatment. A comparative example in which formaldehyde novolac resin was added [A]-
No. 2 at the same time, and this photosensitive solution was applied on an anodized aluminum plate and dried at 100 ° C. for 2 minutes to obtain each photosensitive lithographic printing plate [A] -1 to [A]-
2 was produced. The coating amount at this time was 2.
It was 0 g / m ² .

Photosensitive solution [A] Next, as another comparative example, the following photosensitive solution [B] was applied in the same manner as the photosensitive solution [A] to prepare a photosensitive lithographic printing plate [B].

Photosensitive liquid [B] The coating weight after drying was 2.0 g / m ² .

The obtained photosensitive lithographic printing plates [A] and [B] were heated at 40 ° C80.
% RH and 55 ° C. (about 15% RH) were left for 5 days.

A gray scale with a density difference of 0.15 was brought into close contact with the photosensitive layers of the photosensitive lithographic printing plates [A] -1 to [A] -2 and [B], and exposed from a distance of 70 cm with a high pressure mercury lamp of 10 amps. went.

The photosensitive lithographic printing plates [A] -1 to [A] -2 and [B] which were exposed to exhibit the excellent photosensitivity of the present invention were exposed to DP-3 after 30 seconds of exposure (trade name: Fuji Photo Film ( It was developed by immersion in a 10-fold diluted aqueous solution (produced by K.K. Co., Ltd.) for 60 seconds at 25 ° C., and the exposure time at which the fifth step was completely clear was obtained on a gray scale with a density difference of 0.15. Became.

As can be seen from Table 1, those using the alkali-soluble resin from which the free acid of the present invention has been removed are excellent in stability over time, can be stored for a long period of time, and are of the orthonaphthoquinonediazide type photosensitive material of [B]. It was more sensitive than the ones.

Example 2 Instead of the synthesis example 2 of the photosensitive solution [A] -1 of the example 1, the silyl ether resin of the synthesis example 1 and the synthesis example 3 was used.
Photosensitive lithographic printing plates [C] and [D] were prepared in the same manner as in. According to the method described in Example 1, the exposure time at which the fifth step was completely clear on a gray scale with a density difference of 0.15 was obtained. The photosensitive lithographic printing plate [C] showed all the results shown in Table 1. Under the conditions of about 4 seconds, photosensitive lithographic printing plate [D]
Was about 6 seconds.

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Claims (1)

[Claims] 1. (a) 0.01 to 10% by weight of a compound capable of generating an acid upon irradiation with actinic rays, and (b) a silyl ether capable of being decomposed by an acid represented by the following general formula (I) in the molecule. 10 to 40% by weight of a compound having at least one group, and (c) 5% of methylcellosolve: water = 90: 10% by weight.
A photosolubilizing composition comprising 60 to 90% by weight of an alkali-soluble resin having a pH of 3.5 to 9.0 at 25 ° C.