JPH0519478A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To provide a photosensitive compsn. having high sensitivity and excellent resolving power. CONSTITUTION:This photosensitive compsn. is a positive type photosensitive compsn. contg. a compd. having 1,2-naphthoquinone-2-diazido-4- and/or -5-oxime sulfonate groups represented by the formula, wherein D is 1,2-naphthoquinone-2- diazido-4-yl or 1,2-naphthoquinone-2-diazido-5-yl, each of R<1> and R<2> is H, etc., R<3> may be alkyl group having substitute, R<4> and R<5> may be identical or not, each of A<1>-A<3> is a single bond, alkylene which may have a substituent or arylene and R<1> and R<2> or R<1>, R<2> and one or more among A<1>-A<3> may bond to each other to form a ring.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithographic printing plate, a proof printing plate for multicolor printing, a drawing for an overhead projector, and a positive resist capable of forming a fine resist pattern when manufacturing an integrated circuit of a semiconductor device. Type photosensitive composition.

[0002]

2. Description of the Related Art Orthoquinonediazide compounds have been known as photosensitive substances which are solubilized by actinic rays in applications such as lithographic printing plates and act positively, and have been widely used in lithographic printing plates. It was Examples of such orthoquinonediazide compounds include, for example, U.S. Patent Nos. 2766118, 2767092, 2772972 and 28.
59112, 2907665, 3046110, 3046111
No. 30, No. 3046115, No. 3046118, No. 3046119, No. 30
No. 46120, No. 3046121, No. 3046122, No. 3046123
No. 30, No. 3061430, No. 3102809, No. 3106465, No. 36
It is described in numerous publications, including the specifications of 35709 and 3647443.

These orthoquinonediazide compounds are
This method utilizes the fact that it is decomposed by irradiation with actinic rays to generate a 5-membered ring carboxylic acid and becomes alkali-soluble, but both of them have the drawback of insufficient photosensitivity.

Various attempts have been made to date for increasing the photosensitivity of a photosensitive composition containing an orthoquinonediazide compound, but it is very difficult to increase the photosensitivity while maintaining the development acceptability during development. Met. For example, as an example of such an attempt, Japanese Patent Publication No. 48-1224
No. 2, JP-A-52-40125, and US Pat. No. 4,307,17.
The contents described in the specification such as No. 3 can be mentioned.

Oxime sulfonate compounds which generate a sulfonic acid upon exposure as a new photosensitive material acting as a positive type are disclosed in JP-A-61-251652, JP-A-1-12848, JP-A-1-163736, and JP-A-2-154266. It is described in. Other compounds that generate an acid such as sulfonic acid, sulfinic acid and carboxylic acid are disclosed in JP-A-60-260947 and JP-A-2-
7048, 2-100053, 2-10005
No. 4 and No. 2-100055, all of which are longer-wave light sources such as g-line (43
6 nm) and i-line (365 nm) are not suitable, and there is a problem that sufficient sensitivity is not exhibited depending on the light source.

On the other hand, as the positive photoresist composition, a composition containing an alkali-soluble resin and a naphthoquinonediazide compound as a photosensitive material is generally used. For example, "Novolak-type phenol resin / naphthoquinonediazide-substituted compound" is disclosed in US Pat. No. 3,666,473.
No. 4,115,128 and U.S. Pat. No. 4,173,470 and the most typical composition of "novolak resin / trihydroxybenzophenone-1,2-naphthoquinonediazide sulfonate consisting of cresol-formaldehyde". An example is Thompson "Introduction Toe Microlithography" (LF Thompson
"Introduction to Microlithography") (ACS Publication, No. 219, p112-121).

The novolak resin as a binder can be dissolved in an alkaline aqueous solution without swelling, and when the generated image is used as an etching mask, it imparts a high resistance to plasma etching, so that it is used in the present application. Especially useful for. Further, the naphthoquinonediazide compound used for the photosensitive material acts as a dissolution inhibitor which lowers the alkali solubility of the novolak resin by itself, but when it is decomposed by irradiation with light, an alkali-soluble substance is produced and the alkali solubility of the novolak resin is rather increased. It is unique in that it acts to enhance it, and because of its large property change with respect to light, it is particularly useful as a photosensitive material for a positive photoresist.

From this point of view, a large number of positive photoresists containing a novolac resin and a naphthoquinonediazide type photosensitive material have been developed and put into practical use.
We have achieved sufficient results in line width processing down to about μm.

However, the degree of integration of integrated circuits is increasing more and more, and in the manufacture of semiconductor substrates such as VLSI, 1 μ
It has become necessary to process an ultrafine pattern having a line width of m or less. In such applications, a photoresist having a particularly high resolution, a high pattern shape reproducibility that accurately copies the shape of an exposure mask, and a high sensitivity from the viewpoint of high productivity is required, and the conventional positive photoresist described above is required. But the reality is that we can't handle it.

[0010]

The object of the present invention is to provide a novel photosensitive composition in which these problems are solved. That is, it is to provide a novel photosensitive composition having high sensitivity.

Still another object of the present invention is to provide a positive photosensitive composition having a high resolution and capable of processing an ultrafine pattern having a line width of 1 μm or less.

[0012]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventor found that the above object can be achieved by using a novel positive photosensitive composition. The invention has been reached.

That is, the present invention is a positive photosensitive composition containing a compound having a 1,2-naphthoquinone-2-diazide-4- and / or 5-oxime sulfonate group represented by the following general formula (I). , Are provided.

[0014]

[Chemical 2]

In the formula, D is 1,2-naphthoquinone-2-
Diazido-4-yl group or 1,2-naphthoquinone-2-
Represents a diazido-5-yl group,

R ¹ and R ² may be the same or different and each is a hydrogen atom or an optionally substituted alkyl, alkenyl, aryl, aralkyl, alkoxy,
Aryloxy, cyano, -CO-R ³ or -CO-NR ⁴ R ⁵
Each group of is shown.

Preferably R ¹ and R ² represent an optionally substituted alkyl, aryl, alkenyl or alkoxy group.

Specifically, the alkyl groups of R ¹ and R ² are
Straight-chain, branched or cyclic, preferably having 1 to 18 carbon atoms, such as methyl, ethyl,
Included are groups such as butyl, hexyl, octyl, dodecyl, hexadecyl and the like. The aryl group of R ¹ and R ² is preferably monocyclic or bicyclic and includes, for example, a phenyl group and a naphthyl group. Also R ¹ , R
The alkenyl group of ² is, for example, a vinyl group, and further includes a substituted vinyl group such as an alkyl group such as a methyl group, an aryl group such as a phenyl group, and specifically 1-methyl Vinyl group, 2-methylvinyl group, 1,2-dimethylvinyl group, 2-phenylvinyl group, 2- (p-methylphenyl) vinyl group, 2- (p-
A methoxyphenyl) vinyl group, a 2- (p-chlorophenyl) vinyl group, a 2- (o-chlorophenyl) vinyl group and the like can be mentioned.

The alkoxy group of R ¹ and R ² preferably has 1 to 6 carbon atoms, and specific examples thereof include a methoxy group, an ethoxy group and a butoxy group.

Preferred substituents which may be bonded to these groups are groups such as alkyl, aryl, alkoxy, nitro, cyano, amido, ureido and urethane,
Alternatively, a halogen atom can be used.

R ³ represents an optionally substituted alkyl, aryl, aralkyl, alkoxy, or aryloxy group, preferably alkyl having 1 to 10 carbons, aryl having 6 to 15 carbons, and carbon. It is an alkoxy group having a number of 1 to 6.

R ⁴ and R ⁵ may be the same or different and each represents a hydrogen atom, an alkyl, aryl or aralkyl group, preferably a hydrogen atom or a carbon number of 1 to 1.
It is an alkyl group having 6 alkyl groups and an aryl group having 6 to 10 carbon atoms.

A ¹ , A ² , and A ^{3 each} represent a single bond, an alkylene which may have a substituent, or an arylene group, and preferably a single bond, an alkylene having 1 to 30 carbon atoms, or an alkylene having 6 carbon atoms. ~ 20 represents an arylene group optionally having a monocyclic or polycyclic substituent. Preferred substituents are alkyl, aryl, alkoxy, nitro,
Examples thereof include cyano, amide, ureido, urethane group and halogen atom. Further, A ¹ , A ² and A ³ may contain a divalent group such as ether, ester, amide, urethane and ureido. p, q, and r are each an integer of 0 or 1 or more, preferably 0 or an integer of 1 to 10, more preferably 0 or an integer of 1 to 5.

Further, R ¹ and R ² , R ¹ , R ² and A ¹ , A
^One or more of ² , A ³ or A ¹ , A ² , A ³ may combine to form a ring.

The compound of formula (I) of the present invention has a wide range of suitability for a light source and high sensitivity by combining different photosensitive groups (namely, naphthoquinone diazide group and oxime sulfonate group). It is a thing.

The components of the present invention will be described in detail below. [Compound Represented by Formula (I) ] The compound represented by the general formula (I) is a compound represented by the general formula (II) obtained by reacting a ketone compound with hydroxylamine.
The compound can be synthesized by condensing the oxime compound of 1 with the sulfonyl chloride represented by the general formula (III) under basic conditions.

[0027]

[Chemical 3]

D-SO ₂ -Cl (III) (wherein D, R ¹ , R ² , A ¹ , A ² , A ³ , p, q and r
Has the same meaning as that represented by the general formula (I). )

Specific compounds represented by the general formula (I) used in the present invention are exemplified below.

[0030]

[Chemical 4]

[0031]

[Chemical 5]

[0032]

[Chemical 6]

[0033]

[Chemical 7]

[0034]

[Chemical 8]

[0035]

[Chemical 9]

[0036]

[Chemical 10]

[0037]

[Chemical 11]

[0038]

[Chemical formula 12]

[0039]

[Chemical 13]

[0040]

[Chemical 14]

[0041]

[Chemical 15]

[0042]

[Chemical 16]

[0043]

[Chemical 17]

[0044]

[Chemical 18]

[0045]

[Chemical 19]

[0046]

[Chemical 20]

The content of the compound of the present invention represented by the general formula (I) is appropriately 1 to 70% by weight, preferably 3 to 50% by weight, and more preferably the total solid content of the composition. It is in the range of 5 to 40% by weight.

[1,2-naphthoquinone-2-diazide-
4- and / or 5-Sulfonic Acid Ester Compound] The positive photosensitive composition of the present invention contains, if necessary, the compound of the present invention represented by the general formula (I) and other 1,2-naphthoquinone-2- You may add and use a diazide-4- and / or 5-sulfonic acid ester compound together. Such 1,2
The -naphthoquinone-2-diazide-4- and / or 5-sulfonic acid ester compound is generally a 1,2-naphthoquinone-2-diazide compound having a halogenosulfonyl group such as sulfonyl chloride at the 4-position or 5-position as a mono- or mono- or It can be represented as a sulfonyl ester compound obtained by condensation with a polyhydroxyphenyl compound. A typical example of such a mono- or polyhydroxyphenyl compound is a benzophenone compound having a hydroxy group. For example, 4-hydroxybenzophenone, 2,4-dihydroxybenzophenone,
2,2'-dihydroxybenzophenone, 4,4'-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,4,4 ' -Trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,3,4,2'-tetrahydroxybenzophenone In addition to 3,3 ', 4,4'-tetrahydroxybenzophenone, benzophenone having 5 or more hydroxy groups as shown in JP-A-62-150245, and derivatives thereof are included. Furthermore, p-cresol, p-t-butylphenol, resorcin, pyrogallol, 2,2'-dihydroxybiphenyl, 2,2 ',
A hydroxy group-substituted biphenyl compound such as 4,4′-tetrahydroxybiphenyl can also be mentioned.

Still further, relatively high molecular weight compounds such as phenol-formaldehyde resins or o-, m-, or p-cresol-formaldehyde resins described in US Pat. No. 3,046,120 can be used in the present invention. ..

Similarly, Japanese Patent Laid-Open No. 56-1045,
JP-A-56-1044, JP-B-43-28403
Condensates of polyhydric phenols and aldehydes and ketones disclosed in JP-B No. 49-24361, JP-A-59-84238, and JP-A-59-84.
Aldehydes of catechol, resorcin, or hydroquinone and substituted phenols disclosed in Japanese Patent No. 239
Co-condensates with ketones, condensates of substituted phenols with benzaldehyde described in JP-A-60-31138, and aldehyde ketones with phenols and substituted phenols such as o-, m-, or p-cresol. The co-condensate, p-hydroxystyrene polymer, etc. according to the present invention are also effectively used in the present invention.

When used in combination with the compound of the present invention represented by the general formula (I), the compound of the general formula (I) and the 1,2-
The ratio of naphthoquinone-2-diazide-4- and / or 5-sulfonic acid ester compound is 10: 1 to 1: 1 by weight.
It is 20, preferably 5: 1 to 1:10, and more preferably 2: 1 to 1: 5.

[Alkali-Soluble Resin] The positive-type photosensitive composition of the present invention is preferably an alkali-soluble resin in order to make the alkali solubility of the exposed area more efficient and to impart film-forming property and heat resistance. Add and use.

Such an alkali-soluble polymer is preferably a phenolic hydroxyl group, a carboxylic acid group, a sulfonic acid group, an imide group, a sulfonamide group, an N-sulfonylamide group, an N-sulfonylurethane group, an active methylene group, or the like. It is a polymer having acidic hydrogen atoms having a pKa of 11 or less. Suitable alkali-soluble polymers include novolac type phenolic resins, specifically phenol formaldehyde resin, o-cresol-formaldehyde resin,
Examples include m-cresome-formaldehyde resin, p-cresome-formaldehyde resin, xylenol-formaldehyde resin, and co-condensates of these. Further, as described in JP-A-50-125806, a phenol or cresol substituted with an alkyl group having 3 to 8 carbon atoms such as t-butylphenolformaldehyde resin and formaldehyde together with the above-mentioned phenol resin. You may use together with the condensate of. Also N-
Polymers containing a phenolic hydroxy group-containing monomer such as (4-hydroxyphenyl) methacrylamide as a copolymerization component, p-hydroxystyrene, o-hydroxystyrene, m-isopropenylphenol, p-isopropenylphenol, etc., alone or Copolymerized polymers, and polymers obtained by partially etherifying or partially esterifying these polymers can also be used.

Further, a polymer containing a carboxyl group-containing monomer such as acrylic acid or methacrylic acid as a copolymerization component,
Polymer obtained by hydrolyzing or half-esterifying a copolymer of maleic anhydride and styrene, a polyvinyl acetal resin containing a carboxyl group described in JP-A-61-267042, and a carboxyl group described in JP-A-63-124047. A containing polyurethane resin can also be used suitably.

Furthermore, N- (4-sulfamoylphenyl) methacrylamide, N-phenylsulfonylmethacrylamide, a polymer containing maleimide as a copolymerization component, and an active methylene group-containing polymer described in JP-A-63-127237. Can be used.

These alkali-soluble polymers can be used alone or as a mixture of several kinds.
The preferable addition amount in the photosensitive composition is 30 to 99% by weight, preferably 50 to 97% by weight based on the total solid content of the photosensitive composition.
%, More preferably 60 to 95% by weight.

[Other Preferred Components] The positive photosensitive composition of the present invention may further contain a dye, a pigment, a plasticizer, and a compound (so-called sensitizer) that increases photodegradation efficiency, if necessary. Can be made

Dyes can be used as colorants, but 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 # 603,
Oil Black BY, Oil Black BS, Oil Black T-505 (above, Orient Chemical Industry Co., Ltd.)
Made), crystal violet (CI42555), methyl violet (CI42535), rhodamine B
(CI45170B), Malachite Green (CI42
000), methylene blue (CI52015) and the like.

A printing agent may be added to obtain a visible image immediately after exposure. A typical example of such a printing agent is a combination of a photosensitive compound that releases an acid upon exposure and an organic dye that can form a salt. Specifically, JP-A-50-36209 and 5
3-8128, a combination of o-naphthoquinonediazide-4-sulfonic acid halogenide and a salt-forming organic dye, and JP-A Nos. 53-36223 and 54-747.
The combination of the trihalomethyl compound described in No. 28 and a salt-forming organic dye can be mentioned.

Cyclic acid anhydrides and other fillers may be added to the composition of the present invention in order to further enhance the sensitivity. Examples of cyclic acid anhydrides include U.S. Pat. No. 4,115,128.
, Phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6-endooxy-Δ ⁴ -tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride. , Α-phenyl maleic anhydride, succinic anhydride, pyromellitic acid and the like. By containing these cyclic acid anhydrides in an amount of 1 to 15% by weight based on the solid content in the entire composition, the sensitivity can be increased up to about 3 times.

[Solvent] When the positive photosensitive composition of the present invention is used as a material for lithographic printing, it is dissolved in a solvent that dissolves each of the above components and applied onto a support. For resist materials such as semiconductors, it is used as it is dissolved in a solvent. As the solvent used here, ethylene dichloride, cyclohexanone, methyl ethyl ketone, methanol, ethanol, propanol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 2-ethoxyethyl. Acetate, 1-methoxy-
2-propyl acetate, dimethoxyethane, methyl lactate, ethyl lactate, N, N-dimethylacetamide, N,
N-dimethylformamide, tetramethylurea, N-
There are methylpyrrolidone, dimethyl sulfoxide, sulfolane, γ-butyrolactone, toluene, ethyl lactate and the like, and these solvents may be used alone or in combination. And the concentration in the above components (total solid content including additives) is 2
~ 50% by weight. When used by coating, the coating amount varies depending on the application, but for example, in the case of a photosensitive lithographic printing plate, it is generally 0.5 to 3.0 g / m ² as a solid content.
Is preferred. As the coating amount decreases, the photosensitivity increases, but the physical properties of the photosensitive film deteriorate.

[ Manufacturing of planographic printing plate etc.] When a planographic printing plate is manufactured using the positive photosensitive composition of the present invention, the support thereof is, for example, paper, plastics (polyethylene, polypropylene, polystyrene, etc.). Laminated paper, metal plate such as aluminum (including aluminum alloy), zinc, copper, etc., cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, Films of plastics such as polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal etc.
Included are metal laminates or vapor deposited papers or plastic films as described above. Of these supports, the aluminum plate is dimensionally remarkably stable,
Moreover, it is particularly preferable because it is inexpensive. Furthermore, Japanese Patent Publication Sho 48
Also preferred are composite sheets in which an aluminum sheet is bonded onto a polyethylene terephthalate film as described in No. -18327. The surface of the aluminum plate is a wire brush graining, a mechanical method such as brush graining in which a nylon brush is roughened while pouring a slurry of abrasive particles, ball graining, graining by solution honing, buff graining, HF, AlCl.
Chemical graining with ₃ or HCl as etchant,
After graining the surface with electrolytic graining using nitric acid or hydrochloric acid as an electrolytic solution, or with composite graining performed by combining these roughening methods, the surface is grained with acid or alkali as necessary, and then sulfuric acid is added. It is preferable to use anodizing in phosphoric acid, oxalic acid, boric acid, chromic acid, sulfamic acid or a mixed acid thereof with a direct current or an alternating current power source to form a strong passive film on the aluminum surface. The aluminum surface is hydrophilized by such a passive film itself, but if necessary, silicate treatment (sodium silicate, potassium silicate) described in U.S. Pat. No. 2,714,066 and U.S. Pat. Treatment with potassium fluorozirconate as described in patent 2946638, treatment with phosphomolybdate as described in U.S. Pat. No. 3,201247, alkyl titanate treatment as described in British patent 1108559, German patent 109143.
Polyacrylic acid treatment described in No. 3, German patent No.
No. 1134093 and British Patent No. 1230447, polyvinylphosphonic acid treatment, Japanese Patent Publication No. 464009, phosphonic acid treatment, U.S. Pat. No. 3,307,951. 58-1689
No. 3, 58-18291, undercoat treatment with a complex of a water-soluble organic polymer and a divalent metal ion,
Particularly preferred are those obtained by subjecting a water-soluble polymer having a sulfonic acid group described in JP-A-59-101651 to undercoating for hydrophilic treatment to make it hydrophilic. Other hydrophilic treatment methods include silicate electrodeposition described in US Pat. No. 3658662.

It is also preferable that after the graining treatment and the anodic oxidation, the sealing treatment is performed. Such sealing treatment is performed by immersion in hot water and a hot aqueous solution containing an inorganic salt or an organic salt, a steam bath, or the like.

[Actinic Rays or Radiation] Examples of the light source of actinic rays used for exposure of the photosensitive composition of the present invention include mercury lamps, metal halide lamps, xenon lamps, chemical lamps and carbon arc lamps.
The radiation includes electron beams, X-rays, ion beams, far ultraviolet rays and the like. Preferably, g-rays, i-rays and Deep-UV light are used as the light source for the photoresist. High-density energy beam (laser beam or electron beam)
Scanning or pulse exposure with 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, a helium / cadmium laser, and a KrF excimer laser.

[Developer] As a developer for the positive photosensitive composition of the present invention,
Sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium triphosphate,
Aqueous solutions of inorganic alkaline agents such as sodium diphosphate, ammonium triphosphate, ammonium diphosphate, sodium metasilicate, sodium bicarbonate, aqueous ammonia, etc. and organic alkaline agents such as tetraalkylammonium OH salt are suitable. And their concentration is 0.1 to 10% by weight, preferably 0.5% by weight.

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

[0067]

EXAMPLES The present invention will be described in more detail with reference to synthetic examples and examples, but the present invention is not limited thereto.

Starting Material of Synthesis Example 1 (Compound (Example I-21))
Adult) acetyl benzene 120g (1.00 mol) was dissolved in ethanol 800 ml, hydroxylamine hydrochloride to 8
A solution of 3.5 g (1.20 mol) in 200 ml of water was added with stirring. Subsequently, a solution of sodium hydroxide (60 g, 1.50 mol) in water (80 ml) was added dropwise, and the mixture was heated under reflux for 3 hours. The reaction mixture was poured into about 1 kg of ice to precipitate a pale yellow solid. This solid was separated by filtration, washed with water, and recrystallized with ethanol to obtain 95 g of pale yellow crystals.
It was confirmed by NMR and elemental analysis that this crystal was acetone phenone oxime.

Synthesis Example 2 (Compound Example (I-21)
Adult) oxime compound was obtained in Synthesis Example 1 13.5 g (0.100 mol), 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride 26.9g of (0.100 mol) was dissolved in methyl ethyl ketone 200ml , With stirring, triethylamine 9.1 g (0.090 mol) / dimethylaminopyridine
A solution of 1.3 g (0.010 mol) of DMF in 40 ml was added through a dropping funnel. The addition took about 30 minutes. After addition
Stirring was continued at 30 ° C. for 5 hours.

Then, 20 ml of distilled water was added, and the pH of the reaction solution was adjusted to 5 to 6 with triethylamine. The reaction solution is water
It was poured into 2,000 ml and the precipitate was collected by filtration and purified by column chromatography (filler: silica gel, developing solution: hexane / ethyl acetate = 2/1) to give 16.8 g of yellow powder.
Got By NMR, this powder was identified as Compound Example (I-21).
It was confirmed that the structure was.

Examples 1 to 5 A 2S aluminum plate having a thickness of 0.24 mm was dipped in a 10% aqueous solution of sodium triphosphate kept at 80 ° C. for 3 minutes to degrease it, and was grained with a nylon brush, followed by aluminate. It was etched with sodium for about 10 minutes and desmutted with a 3% aqueous sodium hydrogen sulfate solution. This aluminum plate is 2% at a current density of 2 A / dm ² in 20% sulfuric acid.
Anodization was performed for a minute to prepare an aluminum plate.

By changing the kind of the compound represented by the general formula (I) of the present invention used in the following photosensitive solution [A], 5
One kind of photosensitive solution [A] -1 to [A] -5 was prepared, and this photosensitive solution was applied onto an anodized aluminum plate, and 1
The photosensitive lithographic printing plates [A] -1 to [A] -5 were prepared by drying at 00 ° C for 2 minutes. The coating amount at this time was 2.0 g / m ² in terms of dry weight.

[0073]

The compounds of the present invention used in the photosensitive solutions [A] -1 to [A] -5 are shown in Table 1.

Next, as a 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].

[0076]

The coating weight after drying was 2.0 g / m ² .
Photosensitive planographic printing plates [A] -1 to [A] -5, and [B]
A gray scale having a density difference of 0.15 was brought into close contact with the photosensitive layer of No. 1 and exposed with a 2 KW high pressure mercury lamp from a distance of 50 cm. Exposed photosensitive lithographic printing plate [A] -1 to [A] -5
And [B] are subjected to immersion development for 60 seconds at 25 ° C. for 60 seconds in an 8 times diluted aqueous solution of DP-4 (trade name: manufactured by Fuji Photo Film Co., Ltd.) to completely dissolve and remove the fifth grayscale step. Was measured, and the results are shown in Table 1.

Table-1 Examples Example Photosensitivity Gray scale of the present invention that was used in the following examples: Table 1 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ The fifth step is the number of the planographic printing plate Compound exposure time to dissolve and remove ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Example 1 [A] -1 Compound Example (I-2) 30 seconds ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Implementation Example 2 [A] -2 Compound Example (I-8) 35 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ 3 [A] -3 Compound Example (I-21) 35 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Example 4 [A] -4 Compound Example (I-39) 30 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━ ━━━━ Example 5 [A] -5 Compound Example (I-50) 25 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ ━━━ Comparative Example [B] Compound of Comparative Example 55 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━

The compounds of the present invention used in Examples 1 to 5 were all 1,2-naphthoquinone-2-diazide-
The 5-sulfonyl body was used.

As can be seen from Table-1, the photosensitive lithographic printing plates [A] -1 to [A] -5 using the compound of the present invention have shorter exposure time and higher sensitivity than Comparative Example [B].

Examples 6 to 9 By changing the kind of the compound of the present invention in the following photosensitive solution [C], 4
0.2 kinds of photosensitive liquids [C] -1 to [C] -4 were prepared.
m through a microfilter to prepare a resist composition.

[0082]

The compounds of the present invention used in the photosensitive solutions [C] -1 to [C] -4 are shown in Table-2.

This resist composition was applied onto a 2500 A silicon wafer having an oxide film by using a spinner and dried at 90 ° C. for 2 minutes in a convection oven under a nitrogen atmosphere to obtain a resist film having a thickness of 1.0 μm. It was Next, exposure is performed through a test chart mask using a reduction projection exposure apparatus manufactured by Nikon Corporation, followed by development with a 2.38 wt% tetramethylammonium hydroxide aqueous solution for 1 minute, followed by rinsing with ion-exchanged water to obtain a resist pattern. It was The resist pattern thus obtained was observed with a scanning electron microscope to evaluate the resist pattern. The sensitivity was defined as the reciprocal of the exposure dose for reproducing a mask pattern of 2.0 μm, and shown as a relative value with the sensitivity of the photosensitive solution [D] of the following comparative example. The resolution is indicated by the line width of the minimum resolved mask pattern in the exposure amount that reproduces the mask pattern of 2.0 μm. The results are shown in Table-2.

[0085]

Table-2 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Example Relative resolution of the present invention using a photosensitizing solution Number Compound Sensitivity (Μm) ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Example 6 [C] -1 Compound example (I-7) 1.4 0.75 ━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Example 7 [C] -2 Compound Example (I-22) 1.3 0.70 ━━━━━━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Example 8 [C] -3 Compound Example (I-30) 1.4 0.70 ━━━━━━━━━━ ━━━━━━━━━━━━━━━━━━━━ Example 9 [C] -4 Compound Example (I-44) 1.2 0.70 ━━━━━━━━━━━━━━ ━━━━━━━━━━━━━━━━ Comparative Example [D] Compound of Comparative Example 1.0 0.80 ━━━━━━━━━━━━━━━━━━ ━━━━━━━━━━━

All the compounds of the present invention used in Examples 6 to 9 were 1,2-naphthoquinone-2-diazide-5-.
The sulfonyl form was used.

As can be seen from Table-2, the photosensitive solutions [C] -1 to [C] -4 using the compound of the present invention have higher relative sensitivity and excellent resolution as compared with Comparative Example [D].

[0089]

The photosensitive composition of the present invention has high sensitivity,
Excellent resolution.

Claims (1)

1. A 1,2-type compound represented by the following general formula (I):
A positive photosensitive composition containing a compound having a naphthoquinone-2-diazide-4- and / or 5-oxime sulfonate group. [Chemical 1] In the formula, D is 1,2-naphthoquinone-2-diazide-4
-Yl group or 1,2-naphthoquinone-2-diazide-5
Represents an yl group, R ¹ and R ² may be the same or different and each is a hydrogen atom, or an optionally substituted alkyl, alkenyl, aryl, aralkyl, alkoxy, aryloxy, cyano, −CO−R ³ or −CO−
Each group of NR ⁴ R ⁵ is shown. R ³ represents an alkyl, aryl, aralkyl, alkoxy or aryloxy group which may have a substituent, R ⁴ and R ⁵ may be the same or different, and each is a hydrogen atom, alkyl, aryl, Alternatively, it represents an aralkyl group. A ¹ , A ² , and A ^{3 each} represent a single bond, an alkylene which may have a substituent, or an arylene group, and p, q, and r each represent 0 or an integer of 1 or more. In addition, R ¹ and R ² , R ¹ , R ² and A ¹ , A ² , A
^One or more of ³ or A ¹ , A ² , and A ³ may be bonded to form a ring.