JPH075684A - Alkali-developing photosensitive composition - Google Patents

Abstract

PURPOSE:To provide such a photosensitive compsn. that can be developed with a water-base alkali soln. containing no org. solvent and has excellent development stability and sensitivity by incorporating an alkali-soluble copolymer containing specified monomers, photocation producing agent, and vinylether compd. CONSTITUTION:This compsn. contains a monomer expressed by formula I, etc., monomer expressed by formula II, photocation producing agent, and vinylether compd. Thereby, a photocation polymerizing photosensitive compsn. is obtd. Since photosetting of this compsn. is not prevented by oxygen, a treatment to form an overcoat layer is not required. After exposure for an image, the compsn. can be developed with a water-base alkali developer and has excellent development stability and higher sensitivity. When this negative-type photosensitive compsn. is used for a printing plate, a water-base alkali developer for a positive-type planographic printing plate can be used for development.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a photocurable photosensitive composition which is suitable for use in the production of lithographic printing plates, IC circuits or photomasks and which can be developed with an aqueous alkali and has excellent development stability. It is about.

[0002]

2. Description of the Related Art As one of photocurable photosensitive compositions, one utilizing photoradical polymerization is known. However, since such a composition suffers from polymerization inhibition of oxygen, it has hitherto been
It was necessary to provide, for example, an overcoat layer when producing the photosensitive layer.

Recently, many photosensitive compositions utilizing photo-cationic polymerization have been developed which do not require an overcoat layer or the like. These photosensitive compositions are roughly classified into those in which a cationically polymerizable monomer or oligomer is blended in a binder polymer, and those in which the main chain of the polymer itself has a cationically polymerizable photosensitive group. It contains a polymerization initiator (also referred to as a photocation generator or a photoacid generator).

The above-mentioned photo-cationic polymerization initiator is described, for example, in US Pat. No. 4,081,276.
An aromatic diazonium salt, a triallyl sulfonium salt, a thiopyrylium salt, a sulfoxonium salt or the like which generates a Lewis acid or a protonic acid can be used.

Epoxy polymers have been mainly used as the binder polymer or the photocationically polymerizable polymer in the photosensitive composition. Representative of epoxy polymers include epoxidized novolac polymers and polyepoxides consisting of epichlorohydrin and polynuclear dihydroxyphenols such as bisphenol A.

However, since the above-mentioned binder polymer and photocationically polymerizable polymer are insoluble in an aqueous alkaline solution, the unexposed area must be removed by development mainly with an organic solvent. However, organic solvents are generally toxic and odorous and have a high risk of fire. Therefore, in recent years, a developing method using a developer containing no organic solvent has been desired.

Although the present inventor previously provided a photocationically polymerizable photosensitive composition which can be developed with an aqueous alkaline solution containing substantially no organic solvent, it had some drawbacks in development stability.

[0008]

Therefore, the object of the present invention is to be developed by an aqueous alkaline solution containing substantially no organic solvent, and to be excellent in development stability.
It is intended to provide a cationic photopolymerizable photosensitive composition having improved sensitivity.

[0009]

The present invention comprises (a) a monomer represented by the following formula (I) and / or (II):
An alkali-developable photosensitive composition containing an alkali-soluble copolymer containing a monomer represented by the following formula (111), (b) a photocation generator, and (c) a vinyl ether compound. Is.

[Chemical 4]

[Chemical 5]

[Chemical 6]

In the present specification, "excellent in development stability" means that there is little swelling or separation of the image in the developer,
It is that there is no loss of images even after long-term development (the development latitude is wide), and it is said that the development stability is excellent when these are combined.

Examples of the monomer represented by the above formula (I) include N- (4-hydroxyphenyl) maleimide and the like, and examples of the monomer represented by the above formula (II) include N- (4- Examples thereof include hydroxyphenyl) methacrylamide and N- (4-hydroxyphenyl) acrylamide.

Further, examples of the monomer represented by the above formula (111) include glycidyl methacrylate, 4-vinylphenyl glycidyl ether, and epithiopropyl methacrylate.

The content of the monomer represented by the formula (I) and / or (II) in the alkali-soluble copolymer (a) is preferably 10 to 80% by weight, more preferably 20 to 70% by weight. Is. If it is less than 10% by weight, the solubility in an aqueous alkaline solution is insufficient, and 8
If it is 0% by weight or more, the image after photocuring tends to swell with an alkaline solution, leading to deterioration in strength.

The content of the monomer represented by the above formula (111) in the copolymer (a) is preferably 20 to 90.
%, More preferably 30 to 80% by weight. 20
If it is less than 10% by weight, the photocurability is poor and the sensitivity is lowered.
On the other hand, if it is 90% by weight or more, alkali development cannot be performed.

Alkali-soluble copolymer (a) of the present invention
Includes a monomer represented by the above formula (I) and / or (II) and a monomer represented by the above formula (111),
Further, another addition-polymerizable unsaturated compound can be copolymerized.

As the other addition-polymerizable unsaturated compound, a general unsaturated compound can be optionally used. Examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-amyl, n-hexyl, 2-ethylhexyl, octyl, lauryl, dodecyl, cyclohexyl, tetrahydrofuryl, benzyl, stearyl, Dimethylaminoethyl, diethylaminoethyl, chloroethyl, aryl (eg phenyl,
(Trilyl, naphthyl, etc.), acrylic acid esters or methacrylic acid esters of glycidyls, acrylonitrile, methacrylonitriles, and the like.

Furthermore, acrylates or methacrylates having a hydroxyl group such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate and 2-hydroxy-3-phenoxypropyl acrylate can be mentioned.

The content of the alkali-soluble copolymer (a) is preferably 60 to 98.9 with respect to the total weight of the photosensitive layer.
%, And more preferably 70 to 94.5% by weight.

The component (b) of the present invention is a photocation generator. Examples thereof include aryldiazonium salts, diaryliodonium salts, triarylsulfonium salts, trihaloalkylaryl sulfone compounds, triarylselenonium salts, sulfonates, o-nitrobenzyl sulfonates, p-nitrobenzyl sulfonates, iron-arene compounds. And so on.

Examples of the above-mentioned aryldiazonium salts include 4-phenylaminobenzenediazonium and 4-phenylaminobenzenediazonium.
(4'-Methoxyphenylamino) benzenediazonium, 4-N, N-diethylaminobenzenediazonium, 4-morpholino-2,5-dibutoxybenzenediazonium, 4- (4'-methoxyphenylthio) -2,
5-diethoxy benzene diazonium, 4-Piroridino-3-methyl benzene diazonium PF ₆ ^-, As
^{_{F 6 -, BF 4 -,}} SbF 6 -, SbCl 6 -, FeC
l ₄ ^- salts and the like.

Examples of the diaryliodonium salt include diphenyliodonium PF ₆ ⁻ , AsF ₆ ⁻ ,
Examples thereof include BF ₄ ⁻ , SbF ₆ ⁻ salt, and diphenyliodonium salt of 9,10-dimethoxyanthracene-2-sulfonic acid. Examples of the above triarylsulfonium salt include triphenylsulfonium PF ₆ ⁻ ,
Examples include AsF ₆ ⁻ and BF ₄ ⁻ salt.

Examples of the above trihaloalkylaryl sulfone compound include α, α, α-tribromomethylphenyl sulfone, α, α, α-tribromomethyl (p
-Nitrophenyl) sulfone, α, α, α-trichloromethylphenyl sulfone, α, α, α-trichloromethyl (p-nitrophenyl) sulfone, α, α, α
-Tribromomethylnaphthyl sulfone and the like.

Examples of the above triarylselenonium salt include triphenylselenonium PF ₆ ⁻ and AsF _{6
^{-, BF 4 -, SbF 6}} - salt, and the like. Examples of the sulfonic acid ester include α-hydroxymethylbenzoin sulfonic acid ester, N-hydroxyimide sulfonate, and α-sulfonyloxyketone.

Examples of the above o-nitrobenzyl sulfonate include 2-nitrobenzyl tosylate, 2,4-dinitrobenzyl tosylate, and 2,6-dinitrobenzyl tosylate.

Examples of the above-mentioned p-nitrobenzyl sulfonate include p-nitrobenzyl-9,10-dimethoxyanthracene-2-sulfonate. Examples of the iron-arene compound include (η-benzene)
PF salt of (η-cyclopentaphenyl) iron (II), (η
-Naphthalene) (η-cyclopentaenyl) iron (II)
PF salt and the like.

The content of the photocation generator (b) is preferably 0.1 to 25% by weight, more preferably 0.5 to 20% by weight, based on the total weight of the photosensitive layer. 0.1
If the content is less than 5% by weight, the amount of cations generated is small, so that photocuring does not occur sufficiently. When it is 25% by weight or more, the sensitivity is not further improved, and it is unnecessarily too much, which is uneconomical.

The component (c) of the present invention is a vinyl ether compound. Examples thereof include alkyl vinyl ethers, aromatic vinyl ethers, divinyl ethers, trivinyl ethers, α-substituted vinyl ethers, β-
Examples thereof include substituted vinyl ethers.

Examples of the above-mentioned alkyl vinyl ethers are those whose alkyl portion is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-.
Butyl, t-butyl, isoamyl, n-hexyl, n-
Octyl, 2-ethylhexyl, n-decyl, cetyl,
Examples thereof include alkyl vinyl ether compounds such as octadecyl, 2-chloroethyl, 2,2,2-trifluoroethyl and the like.

As examples of the aromatic vinyl ethers, the aromatic group moiety is phenyl, o-cresyl or p.
-Cresyl, p-chlorophenyl, α-naphthyl, β-
Examples thereof include aromatic vinyl ether compounds such as naphthyl.

Examples of the above divinyl ethers include compounds represented by the following structural formulas. CH ₂ = CHOCH = CH ₂ , CH ₂ = CHOCH ₂ O
_{CH = CH 2, CH 2 =} CHO (CH 2 CH 2 O) n C
H = CH ₂ (n is 2 or 3), CH ₂ = CHOCH ₂
CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ OCH = C
H ₂ ,

[Chemical 7]

Examples of the above trivinyl ethers include:
The following compounds may be mentioned. _{CH 3 CH 2 -C (CH 2} OCH 2 CH 2 OCH = CH
₂ ) ₃

Examples of the above α-substituted vinyl ethers include α-methyl vinyl ethyl ether, α-ethyl vinyl ethyl ether, α-phenyl vinyl ethyl ether and the like.

Examples of the β-substituted vinyl ethers include β-methyl vinyl ethyl ether, β-methyl vinyl isopropyl ether, β-methyl vinyl n-butyl ether, β-methyl vinyl isobutyl ether, β-
Methyl vinyl t-butyl ether and the like can be mentioned.

The content of the vinyl ether compound (c) is preferably 1 to 30% by weight, more preferably 5 to 25% by weight, based on the total weight of the photosensitive layer. If it is less than 1% by weight, the effect of development stability does not increase, and 30% by weight
With the above, it becomes difficult to develop the aqueous alkali.

In the composition of the present invention, in addition to the alkali-soluble copolymer (a), the photocation generator (b), and the vinyl ether compound (c), shellac, phenol-formaldehyde resin, cresol-formaldehyde are further added. Resins, substituted phenol-formaldehyde resins, polyhydroxystyrene, halogenated polyhydroxystyrene, copolymers of hydroxystyrene and acrylic compounds, styrene-maleic anhydride copolymers, acrylic resins, modified acrylic copolymers, etc. It is also possible to contain an alkali-soluble polymer compound. The alkali-soluble polymer compound is used in an amount of 40% by weight or less of the total composition.

In addition to the above components, the photosensitive composition of the present invention may further contain additives such as dyes, pigments, plasticizers and surfactants.

Examples of dyes added for the purpose of coloring the photosensitive composition include crystal violet, malachide green, Victoria blue, methylene blue, ethyl violet, rhodamine B, and basic oil dyes which are derivatives thereof. it can.

Such dyes include Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.), Oil Blue # 603 (manufactured by Orient Chemical Co., Ltd.), and Permanent Blue # 47 (manufactured by Daido Chemical Co., Ltd.). ) Etc. are commercially available.

Examples of pigments include phthalocyanine blue, phthalocyanine green, dioxazine violet, quinacridone red, and indanthrene blue. As the commercially available product, Neo-Zabone Blue FLE (manufactured by Birdish Aniline Co., Ltd.),
Oil blue BOS (manufactured by Orient Chemical Industry Co., Ltd.),
There is Spyron Blue GNH (manufactured by Hodogaya Chemical Co., Ltd.).

The content of the above-mentioned dye is preferably about 0.1 to 5.0% by weight, more preferably 0.5 to 4.0% by weight, based on the total weight of the photosensitive layer.

The content of the above pigment is preferably about 1.0 to 5.0% by weight, more preferably 2.0 to 4.0% by weight, based on the total weight of the photosensitive layer.

A plasticizer or a surfactant may be added for the purpose of improving the coatability of the photosensitive composition or improving the adhesion of the photosensitive composition to a support.

Examples of the plasticizer include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, di-2-ethylhexyl phthalate,
Examples thereof include di-n-octyl phthalate, diisodecyl phthalate, butylbenzyl phthalate, diisononyl phthalate, ethylphthalylethyl glycol and dimethyl isophthalate.

The content of the above plasticizer is preferably about 0.5 to 3.0% by weight, more preferably 0.6 to 2.0% by weight, based on the total weight of the photosensitive layer.

Examples of the surfactant include sorbitan monooleate, sorbitan stearylate, sorbitan monostearate, sorbitan sequisoleate, sorbitan monolaurate, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether and the like. You can The content of the surfactant is
Preferably about 0.4 to 2.0, based on the total weight of the photosensitive layer.
%, More preferably 0.6 to 1.6% by weight.

The photosensitive composition of the present invention includes, for example, methanol, methylene chloride, ethyl acetate, tetrahydrofuran, N, N-dimethylformamide, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, Dissolved in a single solvent such as propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl ethyl ketone, acetone, methyl lactate or a mixed solvent of two or more kinds, and then applied to various coating machines (for example, whiler, roll coater,
It can be coated on a support using a bar coater, an extrusion type coater, etc. and dried.

When a photosensitive lithographic printing plate is produced using the photosensitive composition of the present invention, the support thereof is paper, plastic film, copper, zinc, aluminum,
A metal plate such as stainless steel or a composite material in which two or more of these are combined can be used.

Among these, aluminum plates that have been brush- or ball-polished, aluminum plates that have been brush-polished and then anodized, aluminum plates that have been electrolytically-polished and then anodized, or a combination thereof. Aluminum plates are preferred.

The aluminum plate which has been subjected to such pretreatment is further subjected to chemical conversion treatment with alkali silicate, zirconium fluoride, alkyl titanate, trihydroxybenzoic acid or the like, boehmite treatment or strontium acetate, zinc acetate, magnesium acetate, benzoic acid. Coating treatment with an aqueous solution of calcium acidate, polyvinylpyrrolidone,
A coating treatment with polyaminesulfonic acid, polyvinylphosphonic acid, polyacrylic acid, polymethacrylic acid, poly-2-hydroxyethyl acrylate or the like can be performed as a post-treatment.

The photosensitive composition of the present invention is coated on a support, exposed to actinic rays such as ultraviolet rays, and developed with an aqueous alkaline developer to obtain a negative relief image with respect to the original image. You can

Examples of the alkaline aqueous solution used as the developing solution at this time include (1) sodium hydroxide and potassium hydroxide: (2) weak acid metal salts; for example, silicic acid, metasilicic acid, orthosilicic acid, phosphoric acid, and pyrroline. Acid, metaphosphoric acid, hexametaphosphoric acid, carbonic acid, tartaric acid, sodium salts such as boric acid,
Metal salts such as lithium salts and potassium salts: (3) Ammonia and its derivatives; for example, alkylamines (for example, amine compounds such as monomethyl, dimethyl, trimethyl, monoethyl, diethyl, triethyl), alkanolamines (for example, monoethanolamine, etc.) Diethanolamine, triethanolamine, diisopropanolamine) or an aqueous solution of an alkaline compound such as tetramethylammonium hydroxide.

If necessary, an activator can be added to the above alkaline aqueous solution. As the activator, an anionic surfactant or an amphoteric surfactant can be used.

Examples of the anionic surfactant include sulfuric acid esters of alcohols having 8 to 22 carbon atoms (for example, polyoxyethylene alkyl sulfate soda salt), alkylaryl sulfonates (for example, sodium dodecylbenzene sulfonate, poly Oxyethylene dodecylphenyl sulfate soda salt, alkyl naphthalene sulfonic acid sodium salt, naphthalene sulfonic acid sodium salt, formalin condensate of sodium naphthalene sulfonic acid), sodium dialkyl sulfosuccinate, fatty acid amide sulfonate, alkyl phosphate ester, alkyl ether phosphate ester Etc. can be used.

As the amphoteric surfactant, for example, alkyl betaine type or alkyl imidazoline type surfactant can be used.

[0055]

The photosensitive composition of the present invention is a cationic photopolymerization type photosensitive composition, and therefore is not inhibited by oxygen during photocuring. Therefore, there is no need for a treatment such as providing an overcoat layer.

Further, after image exposure, it can be developed with an aqueous alkaline developing solution, which is more excellent in development stability than ever, and the sensitivity is also improved. When the photosensitive composition of the present invention is used as a printing plate, it can be developed also by using an aqueous alkaline developing solution known as a developing solution for a positive lithographic printing plate. Moreover, since the photosensitive composition of the present invention is a negative type, it is possible to obtain a positive plate and a negative plate with one kind of developing solution, and work efficiency, equipment cost, arrangement space, etc. are remarkably improved.

[0057]

EXAMPLES Synthesis of Copolymer First, copolymers (1) to (3) were synthesized as follows. Under a nitrogen stream of a copolymer, a mixture having the following composition was added to 150 g of tetrahydrofuran (THF) as a reaction solvent, and the mixture was heated to 65 ° C. and then 1,1′-azobis (cyclohexane-1- Add 0.3 g of carbonitrile to give 6
The mixture was stirred at 5 ° C for 5 hours. After completion of the reaction, T. H. F150
g was added and poured into water to precipitate the copolymer. The precipitate was vacuum dried (60 ° C.) to obtain a copolymer. Note N- (4-hydroxyphenyl) maleimide 40 g Glycidyl methacrylate 30 g Methyl methacrylate 30 g 20% by weight of T. H. Prepare the F solution,
As a result of measuring the viscosity, it was about 500 CPS (25 ° C.).

Copolymer A copolymer was synthesized in the same manner as the copolymer except that a composition having the following composition was used. Note N- (4-hydroxyphenyl) methacrylamide 40 g Glycidyl methacrylate 40 g Methyl methacrylate 20 g

Copolymer A copolymer was synthesized in the same manner as the copolymer except that the composition having the following composition was used. Note N- (4-hydroxyphenyl) maleimide 30 g 4-vinylphenyl glycidyl ether 50 g ethyl methacrylate 20 g

Copolymer A copolymer was synthesized in the same manner as the copolymer except that the composition having the following composition was used. Note N- (4-hydroxyphenyl) methacrylamide 40 g Epithiopropyl methacrylate 40 g Ethyl methacrylate 20 g

Copolymer A copolymer was synthesized in the same manner as the copolymer except that a composition having the following composition was used. Note N- (4-hydroxyphenyl) maleimide 15 g N- (4-hydroxyphenyl) methacrylamide 25 g Ethipiopropyl methacrylate 40 g Methyl methacrylate 20 g

Production of a photosensitive lithographic printing plate An aluminum plate (material 1050) having a thickness of 0.24 mm and a width of 1000 mm was alkali degreased, and then the surface was polished with a nylon brush while applying an aqueous suspension of permistone, and then thoroughly Washed with water.

Then, a caustic soda solution of 20% at 70 ° C. is flowed over for 5 seconds to etch the surface with 3 g / m ² and then washed with running water to form hydrochloric acid (35 g / l) and aluminum ion (5 g / l). 30 at 25 ℃ in electrolyte
It was electropolished at a current density of A / dm ² for 30 seconds and washed with water.

Then, a caustic soda solution of 70% at 20 ° C. is poured to etch the surface, followed by washing with water, followed by anodizing treatment in a 10% sulfuric acid aqueous solution at 30 ° C. to oxidize 20 g / m ² . A film was formed.

After washing with water, it was immersed in an aqueous solution containing 5% of JIS No. 3 sodium silicate at 70 ° C. for 10 seconds, washed with water and dried.

The aluminum plate thus obtained was coated with each of the sensitizing solutions shown in Table 1 below so that the coating film weight after drying was 2.0 g / m ² to obtain a photosensitive lithographic printing plate. . The solvent at this time was methyl ethyl ketone:
70 g of tetrahydrofuran = 1: 1 was used, and 0.1 g of Victoria Pure-Blue BOH was used as a colorant.
In addition, it was mixed.

[0067]

[Table 1]

The following vinyl ether compounds in Table 1 were used. (1) CH ₂ = CHOCH ₂ CH ₂ OCH ₂ CH ₂ OC
H = CH ₂

[Chemical 8] _{(3) CH 3 CH 2 -C} (CH 2 OCH 2 CH 2 OCH
= CH ₂ ) ₃ (4) 2-chloroethyl vinyl ether

In the photosensitive lithographic printing plate thus obtained,
Negative film and Kodak step tablet N
o. 2 was vacuum-adhered and irradiated with ultraviolet rays at a distance of 1 m for 30 seconds using a 2 kW high pressure mercury lamp, and then standard development was performed using a developer having the following composition (developing solution temperature 25 ° C., developing time 30
Seconds), the number of solid steps of the step tablet (measurement of sensitivity), and long-term development (developer temperature 25 ° C.,
The stability of the image (developing latitude) when the developing time was 2 minutes) was examined. The results are shown in Table 2. Note Developer (composition similar to developer for positive PS plate) JIS No. 3 sodium silicate 25 g potassium hydroxide 15 g water 1 kg

[0070]

[Table 2]

The development latitude in Table 2 indicates the difference between the number of solid steps of the step tablet in standard development and the number of solid steps of the step tablet in long-time development (2 minutes). The smaller the number, the better the development latitude. In addition, in Comparative Examples 1 and 2, the solid portion of the image portion in the long-time development was swollen, and the image was easily scratched.

As is clear from the results shown in Table 2, Example 1
The photosensitive printing plates using the photosensitive compositions of Nos. 6 to 6 had extremely good sensitivity and development latitude (development stability).

[0073]

INDUSTRIAL APPLICABILITY The alkali-developable photosensitive composition of the present invention develops with an aqueous alkaline developer containing substantially no organic solvent capable of developing a positive PS plate even though it has a negative action. The advantage is that the developing method can eliminate the problem of odor and the risk of fire.

Further, in comparison with this type of photosensitive composition,
A photosensitive layer excellent in sensitivity and development stability can be obtained.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location G03F 7/30 7124-2H H01L 21/027

Claims (2)

[Claims] 1. (a) The following formula (I) and / or (I)
An alkali-developable type comprising a monomer represented by I), an alkali-soluble copolymer containing a monomer represented by the following formula (111), (b) a photocation generator, and (c) a vinyl ether compound. Photosensitive composition. [Chemical 1] [Chemical 2] [Chemical 3] 2. The alkali-developable photosensitive composition according to claim 1, wherein the vinyl ether compound (c) is mixed in an amount of 1 to 30% by weight based on the total weight of the photosensitive layer.