JPH067261B2 - Photosolubilizing composition - Google Patents

Description

The present invention relates to a novel photo-soluble polymer having a silyl ester group capable of being decomposed by an acid and a group capable of generating an acid upon irradiation with an actinic ray in the same molecule. The present invention relates to a novel photosolubilizing composition suitable for producing a lithographic printing plate, a proof for multicolor printing, a drawing for an overhead projector, an IC circuit, and a photomask, which uses a compound.

“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.
No. 2,767,092, No. 2,772,97
No. 2, No. 2,859,112, No. 2,907,6
No. 65, No. 3,046, 110, No. 3, 046.
No. 111, No. 3,046,115, No. 3,04
No. 6,118, No. 3,046,119, No. 3,0.
No. 46,120, No. 3,046,121, No. 3,
046,122, 3,046,123, 3,061,430, 3,102,809, 3,106,465, 3,635,709,
It is described in a large number of publications including the respective specifications of the above-mentioned No. 3,647,443.

These orthoquinonediazide compounds utilize the fact that they are decomposed by irradiation with actinic rays to generate a 5-membered ring carboxylic acid and become alkali-soluble, but they all have the drawback of insufficient photosensitivity. Have. This is because, in the case of the orthoquinonediazide compound, the quantum yield 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 it was very difficult to increase the photosensitivity while maintaining the development acceptability during development. . For example, as an example of such an attempt, Japanese Examined Patent Publication No. 48-12242 and Japanese Unexamined Patent Publication No.
2-40125, U.S. Pat. No. 4,307,173, and the like can be mentioned as the contents described in the specification.

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. Separately, a photosensitive system that is activated by a contact action is used separately, and as a method for 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) or 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 compound (JP-A-55-126236), and a polymer having an orthoester group in the main chain (JP-A-56-156).
17345) and a combination with a silyl ester compound (JP-A-60-10247). Since they have a quantum yield of more than 1 in principle, they may show high photosensitivity, but in the case of acetal or O, N-acetal compound, and in the case of a polymer having an acetal or ketal group in the main chain, Since the second reaction due to the acid generated by photolysis is slow, it does not exhibit sufficient photosensitivity for actual use. Further, in the case of an orthoester or amide acetal compound, in the case of an enol ether compound, and in the case of an N-acyliminocarbonic acid compound, high photosensitivity is certainly shown, but the stability with time is poor and it cannot be stored for a long time. . 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. The silyl ester compound has higher sensitivity than other compounds and polymers and is excellent in development acceptability, but the sensitivity and development acceptability are not sufficient for practical use.

"Problems to be Solved by the Invention" An object of the present invention is to provide a novel photosolubilizing composition using a novel photosoluble polymer compound and solving the above problems. That is, it is to provide a novel photosolubilizing composition having high photosensitivity and having a wide development latitude during development.

Another object of the present invention is to provide a novel photosolubilizing composition which has excellent stability over time and can be stored for a long period of time.

Still another object of the present invention is to provide a novel photosolubilizing composition using a novel photosoluble polymer compound which can be produced easily and can be easily obtained.

"Means for Solving Problems" The present inventor has found a novel photo-soluble polymer compound as a result of intensive studies to achieve the above object. The inventors have found that the above object can be achieved by using the polymer compound and reached the present invention.

That is, the present invention has a structural unit derived from a monomer having a polymerizable ethylenically unsaturated bond and a silyl ester group, and further has a polymerizable ethylenically unsaturated bond and a group capable of generating an acid upon irradiation with actinic rays. The present invention provides a photosolubilizing composition containing a structural unit derived from a monomer and containing a compound whose solubility in a developing solution is increased by irradiation with actinic rays.

Preferably, the photosoluble polymer compound is a compound containing at least one structural unit derived from each of the monomers represented by the following general formulas (I) and (II).

In the formula, R ₁ represents a hydrogen atom, a halogen, or an alkyl group which may have a substituent. Preferably a hydrogen atom,
Or, it represents an alkyl group which may have a substituent, more preferably a hydrogen atom or a methyl group. R _{2, R 3,} R ₄ may also be different from be the same, respectively a hydrogen atom, alkyl optionally having a substituent, aryl, or aralkyl, or -OR _5. It is preferably an alkyl, aryl, or aralkyl group which may have a substituent. R ₅ represents an alkyl, aryl, or aralkyl group which may have a substituent. Preferably, an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 15 carbon atoms is shown. A is a single _bond, -O-R 6 _-CO-,
Or -CO- is shown. R ₆ represents a divalent aliphatic or aromatic hydrocarbon which may have a substituent. R ₇ is a hydrogen atom,
The alkyl, aryl, or aralkyl which may have a substituent, or -CO-R < ₈ > is shown. Preferably hydrogen atom, alkyl having 1 to 4 carbon atoms, or -CO-R
₈ is shown. R ₈ is an alkyl optionally having a substituent,
It represents an aryl or aralkyl group. It is preferably an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms. Z represents a group capable of generating an acid upon irradiation with actinic rays. Preferred is a group containing an S-triazine unit substituted with a trihalomethyl group or an oxadiazole unit substituted with a trihalomethyl group.

Examples of the monomer represented by the general formula (I) that constitutes the photosoluble polymer compound of the present invention include the followings.

(I-1) (I-2) (I-3) (I-4) (I-5) (I-6) (I-7) (I-8) (I-9) (I-10) (I-11) (I-12) (I-13) (I-14) (I-15) (I-16) (I-17) (I-18) (I-19) (I-20) (I-21) (I-22) (I-23) In the specific examples, R represents a hydrogen atom or a methyl group. Examples of the monomer represented by the general formula (II) include those shown below.

(II-1) (II-2) (II-3) (II-4) (II-5) (II-6) (II-7) (II-8) (II-9) (II-10) (II-11) (II-12) (II-13) (II-14) In the specific examples, R represents a hydrogen atom or a methyl group.

The photo-soluble polymer compound used in the present invention can be used as, for example, a binary copolymer of the monomers represented by the general formulas (I) and (II) as a preferable example, but it can be used as another polymerizable ethylene compound. It may be used in the form of a terpolymer or more copolymer with a compound (one or more) having a polyunsaturated bond.

Suitable compounds having a polymerizable ethylenically unsaturated bond include those shown below. For example, a compound having one addition-polymerizable unsaturated bond selected from acrylic acid esters, acrylamides, methacrylic acid esters, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, crotonic acid esters, etc. Is. Specifically, for example, acrylic acid esters, such as alkyl (wherein the alkyl group preferably has 1 to 10 carbon atoms) acrylate (eg, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, Amyl acrylate, ethylhexyl acrylate, octyl acrylate, acrylic acid-
t-octyl, chloroethyl acrylate, 2-hydroxyethyl acrylate, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, glycidyl acrylate, benzyl acrylate, methoxybenzyl acrylate, Furfuryl acrylate, tetrahydrofurfuryl acrylate, etc.), aryl acrylate (eg, phenyl acrylate, etc.); Methacrylic acid esters, such as alkyl (wherein the alkyl group preferably has 1 to 10 carbon atoms) methacrylate (eg, methyl Methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, amyl methacrylate , Hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylol Propane monomethacrylate, pentaerythritol monomethacrylate, glycidyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, etc.),
Aryl methacrylate (eg, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, etc.); Acrylamides such as acrylamide, N
-Alkyl acrylamide, (as the alkyl group,
Those having 1 to 10 carbon atoms, for example, methyl group, ethyl group, propyl group, butyl group, t-butyl group, heptyl group, octyl group, cyclohexyl group, benzyl group, hydroxyethyl group, benzyl group and the like. ), N-arylacrylamide, (the aryl group includes, for example, phenyl group, tolyl group, nitrophenyl group, naphthyl group, cyanophenyl group, hydroxyphenyl group, etc.), N, N-dialkylacrylamide (the alkyl group). Examples of the group include those having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, a butyl group, an isobutyl group, an ethylhexyl group, a cyclohexyl group, and N, N-arylacrylamide (as the aryl group, For example, a phenyl group), N-methyl-N-phenylacrylamide, N-hydroxyethyl-N-methylacrylamide, N-2-acetamidoethyl-N-acetylacrylamide, etc .; Methacrylamides, such as methacrylamide, N. -Alkyl methacrylamide (the alkyl Examples of the group include those having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, a t-butyl group, an ethylhexyl group, a hydroxyethyl group, a cyclohexyl group, and N-arylmethacrylamide (as the aryl group). Is a phenyl group, a hydroxyphenyl group, etc.), N, N-dialkylmethacrylamide (the alkyl group includes an ethyl group, a propyl group, a butyl group, etc.) N, N-diarylmethacrylamide (the Examples of the aryl group include a phenyl group), N-hydroxyethyl-N-methylmethacrylamide, N-methyl-N-phenylmethacrylamide, N-ethyl-N.
-Phenylmethacrylamide etc .; allyl compounds such as allyl esters (eg allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc.) , Allyloxyethanol and the like; vinyl ethers such as alkyl vinyl ether, (eg hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether) , 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethyl Amino ethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether), vinyl aryl ether (e.g., vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl -2,
4-dichlorophenyl ether, vinyl naphthyl ether, vinyl anthranyl ether, etc.); vinyl esters such as vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl barrate, vinyl caproate, vinyl chloroacetate. , Vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxy acetate, vinyl phenyl acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinyl cyclohexyl carboxylate, vinyl benzoate,
Vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, etc .; Styrenes such as styrene, alkylstyrenes (eg methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, Hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxymethyl styrene, acetoxymethyl styrene, etc.), alkoxy styrene (eg methoxy styrene,
4-methoxy-3-methylstyrene, dimethoxystyrene, etc.), halogen styrene (for example, chlorostyrene,
Dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene,
Trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, etc.); crotonates such as alkyl crotonates (eg, butyl crotonate, hexyl crotonate, glycerin monochrome) Dialkyl itaconic acid (eg, dimethyl itaconic acid, diethyl itaconic acid, dibutyl itaconic acid, etc.); dialkyl maleic acid or fumaric acid (eg, dimethyl maleate, dibutyl fumarate, etc.); acrylic acid,
Methacrylic acid, acronitrile, methacrylonitrile, etc. are available. In addition, any addition-polymerizable unsaturated compound that is copolymerizable with the compounds represented by the general formulas (I) and (II) may be used.

The molecular weight of the photo-soluble polymer compound used in the present invention is
The weight average is 1000 or more, preferably 5,000 to
It is 1,000,000.

In the photosoluble polymer compound of the present invention, the ratio of the structural unit derived from the monomer having a silyl ester group and the structural unit derived from the monomer having a group capable of generating an acid upon irradiation with actinic rays is preferably The molar ratio is 1: 0.0001 to 1:10, more preferably 1: 0.005 to 1: 0.5.

When the photo-soluble polymer compound of the present invention is used in a lithographic printing plate, an IC circuit or the like, the polymer compound can be used alone, or may be used as a mixture with another alkali-soluble resin. Suitable alkali-soluble resins include novolac type phenol resins, specifically, phenol-formaldehyde resin, o-cresol-formaldehyde resin, m-cresol-formaldehyde resin, p-cresol-formaldehyde resin, and co-condensates thereof. and so on. Further, carboxyl group-containing polyacrylate, polymethacrylate, polyester, polyurethane, polyamide and the like are included. The alkali-soluble resin is preferably contained in an amount of about 10 to 90% by weight, more preferably about 40 to 80% by weight, based on the total weight of the photosolubilizing composition.

If necessary, the photo-soluble composition of the present invention further comprises a dye,
A pigment, a plasticizer, a compound that increases the acid generation efficiency of the acid-generating group (a so-called sensitizer), and the like can be included. Suitable dyes include oil-soluble dyes and basic dyes. Specifically, Oil Yellow # 101, Oil Yellow # 130, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 60.
3, Oil Black BY, Oil Black BS, Oil Black T-505 (above, manufactured by Orient Chemical Industry Co., Ltd.) Crystal Violet (CI42555), Methyl Violet (CI42535), Rhodamine B
(CI45170B) Malachite Green (CI420
00), methylene blue (CI52015) and the like.

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. Examples of the solvent used here include ethylene dichloride, cyclohexanone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, toluene, ethyl acetate, etc., and these solvents are used alone or as a mixture. To do.
And the concentration in the above components (total solid content including additives) is
It is 2 to 50% by weight. Among these, the preferred concentration (solid content) of the composition of the present invention is 0.1 to 25% by weight. Further, the coating amount varies depending on the use, but in the case of a photosensitive lithographic printing plate, for example, the solid content is generally 0.5 to 3.
0 g / m ² is preferred. 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 net 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. Such laser beams include helium / neon laser, argon laser, krypton ion laser, helium /
A cadmium laser etc. are mentioned.

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.

[Examples] 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 (Example Compound (I-8) (R = CH 3), (II-
2) (R = CH ₃ ) and Synthesis of Copolymer of Benzyl Methacrylate) Compound Example (I-8) (R = CH ₃ ) 33.5 g (0.1
_{52mole), (II-2)} (R = CH 3) 3.8g
(0.01 mole) and 6.7 g (0.038 mole) of benzyl methacrylate were dissolved in 120 m of 2-methoxyethanol and heated to 70 ° C under a nitrogen stream, and then α, α'-azobisisobutyronitrile 0 0.25g
Was added and the polymerization reaction was carried out for 8 hours.

After the reaction was completed, the reaction solution was poured into 3 liters of water while stirring,
The white precipitate formed was dried to obtain 40.2 g of a copolymer.

Example 1 A 0.24 mm-thick 2S aluminum plate was immersed in a 10% aqueous solution of sodium triphosphate maintained at 80 ° C for 3 minutes to degrease it, and was sanded with a nylon brush, followed by 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.

Next, three kinds of photosensitive liquids [A] -1 to [A] -3 were prepared by changing the kind of the compound of the present invention in the following photosensitive liquid [A], and the photosensitive liquids were placed on the anodized aluminum plate. Apply to
The photosensitive lithographic printing plates [A] -1 to [A] -3 were prepared by drying at 100 ° C for 2 minutes. The coating amount at this time was 1.5 g / m ² in terms of dry weight.

The compounds of the present invention used in Photosensitive solutions [A] -1 to [A] -3 are shown in Table 1.

Photosensitive solution [A] Next, as a comparative example, the following photosensitive solutions [B] and [C] were applied in the same manner as the photosensitive solution [A] to prepare a photosensitive lithographic printing plate [B].
And [C] were produced.

Photosensitive liquid [B] Photosensitive liquid [C] Weight average molecular weight w = 30,000 (GPC, polystyrene standard) The coating weight after drying was 1.5 g / m ² .
A gray scale having a density difference of 0.15 was adhered onto the photosensitive layers of the photosensitive lithographic printing plates [A] -1 to [A] -3, [B] and [C], and a 70 cm light was applied with a carbon amp lamp of 30 amperes. Exposure was performed from a distance.

The photosensitive lithographic printing plates [A] -1 to [A] -3, [B] and [C] which have been exposed to exhibit the excellent photosensitivity of the present invention are D
P-4 (trade name: manufactured by Fuji Photo Film Co., Ltd.) is immersed in an 8 times diluted aqueous solution at 25 ° C for 60 seconds for immersion development, and a gray scale with a density difference of 0.15 makes the fifth step completely clear. When the time was obtained, it was as shown in Table 1.

As can be seen from Table 1, each of the photosensitive lithographic printing plates [A] -1 to [A] -3 using the compound of the present invention has a shorter exposure time and a higher sensitivity than [B] and [C]. Further, as compared with [A] -1 and [C], the photosoluble polymer compound of the present invention having a silyl ester group and a group capable of generating an acid upon irradiation with an actinic ray in the same molecule is different from each other. It can be seen that the sensitivity is higher than that of [C] added to.

In addition, the molecular weight of the photo-soluble polymer compound of the present invention in Table 1 is 2 by weight average by gel permeation chromatography (polystyrene standard) measurement.
It was 50,000-40,000.

Example 2 In order to show the excellent development acceptability of the present invention, the photosensitive lithographic printing plates [A] -1 to [A] -3 prepared in Example 1 were used.
A gray scale having a density difference of 0.15 was brought into close contact with the photosensitive layers of [B] and [C], and exposed for 30 seconds from a distance of 70 cm with a carbon arc lamp of 30 amperes. Exposed photosensitive lithographic printing plates [A] -1 to [A] -3, [B],
And [C] with the same developer as in Example 1 at 60 ° C. at 25 ° C.
Develop for seconds and 3 minutes. The difference in the number of completely clear steps in the development for 60 seconds and 3 minutes was obtained on a gray scale with a density difference of 0.15, and the results are shown in Table 2.

As can be seen from Table 2, all of the photosensitive lithographic printing plates [A] -1 to [A] -3 using the compound of the present invention are different from [B] and [C] in the change in the number of gray scale steps in the clear part. Is small and development tolerance is large. Further, as compared with [A] -1 and [C], the photosoluble polymer compound of the present invention having a silyl ester group and a group capable of generating an acid upon irradiation with an actinic ray in the same molecule is different from each other. It can be seen that the development tolerance is higher than that of [C] added to.

Claims (1)

[Claims] 1. A structural unit derived from a monomer having a polymerizable ethylenically unsaturated bond and a silyl ester group, and further has a polymerizable ethylenically unsaturated bond and a group capable of generating an acid upon irradiation with actinic rays. A photosolubilizing composition containing a structural unit derived from a monomer and containing a compound whose solubility in a developing solution increases upon irradiation with actinic rays.