JP2704319B2 - Photosensitive composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to lithographic printing, proof printing for multicolor printing, drawings for overhead projectors, and positive resists capable of forming fine resist patterns when manufacturing integrated circuits of semiconductor devices. A photosensitive composition.

[0002]

2. Description of the Related Art Orthoquinonediazide compounds are conventionally known as positive-acting photosensitive substances which are solubilized by actinic rays in applications such as lithographic printing plates, and have been widely used in lithographic printing plates. Was. Examples of such orthoquinonediazide compounds are described in, for example, U.S. Pat.Nos. 2,766,118, 2,677092, 2,277,972, and 28.
59112, 2907665, 3046110, 3046111
Nos. 3046115, 3046118, 3046119, 30
No. 46120, No. 3046121, No. 3046122, No. 3046123
Nos. 3061430, 3102809, 3106465, 36
It is described in numerous publications, including the specifications of 35709 and 3647443.

[0003] These orthoquinonediazide compounds are:
It utilizes the fact that it is decomposed by irradiation with actinic rays to produce a 5-membered carboxylic acid and becomes alkali-soluble, but all have the disadvantage of insufficient photosensitivity.

Various attempts have been made to increase the photosensitivity of a photosensitive composition containing an orthoquinonediazide compound, but it is very difficult to increase the photosensitivity while maintaining the development tolerance during development. Met. For example, as an example of such an attempt, Japanese Patent Publication No. 48-1224
No. 2, JP-A-52-40125, U.S. Pat.
The contents described in the specification such as No. 3 can be cited.

Oxime sulfonate compounds which generate a sulfonic acid upon exposure as a new photosensitive material acting positively are disclosed in JP-A-61-251652, JP-A-1-124848, JP-A-1-163736 and JP-A-2-154266. It is described in. Other compounds generating an acid such as sulfonic acid, sulfinic acid and carboxylic acid are disclosed in JP-A-60-260947 and JP-A-2-260947.
No. 7048, No. 2-100053, No. 2-10005
No. 4, No. 2-100055, etc., each of which is a longer-wavelength light source, for example, g-line (43
6 nm) and i-line (365 nm), and there is a problem that some light sources do not exhibit sufficient sensitivity.

On the other hand, as a positive photoresist composition, a composition containing an alkali-soluble resin and a naphthoquinonediazide compound as a photosensitive material is generally used. For example, US Pat. No. 3,666,473 as “Novolak-type phenolic resin / naphthoquinonediazide-substituted compound”
And U.S. Pat. Nos. 4,115,128 and 4,173,470, as well as the most typical compositions of "novolak resin composed of cresol-formaldehyde / trihydroxybenzophenone-1,2-naphthoquinonediazide sulfonate". An example is Thompson's "Introduction Too Microlithography" (LF Thompson
"Introduction to Microlithography") (ACS Publishing, No. 219, pp. 112-121).

[0007] The novolak resin as a binder can be dissolved in an aqueous alkali solution without swelling, and when used as a mask for etching, gives a particularly high resistance to plasma etching. Especially useful for: Also, the naphthoquinonediazide compound used in the photosensitive material itself acts as a dissolution inhibitor that reduces the alkali solubility of the novolak resin, but when decomposed by irradiation with light, generates an alkali-soluble substance, and rather increases the alkali solubility of the novolak resin. It is unique in that it acts to enhance it, and is particularly useful as a photosensitive material for a positive photoresist because of its large property change to light.

From this point of view, many positive photoresists containing a novolak resin and a naphthoquinonediazide-based photosensitive material have been developed and put into practical use.
Sufficient results have been achieved in line width processing down to about μm.

[0009] However, the degree of integration of integrated circuits is increasing more and more, and in the manufacture of semiconductor substrates such as VLSI, 1 μm is required.
Processing of an ultrafine pattern having a line width of m or less has been required. In such applications, particularly high resolution, a photoresist having high sensitivity from the viewpoint of high pattern shape reproduction accuracy that accurately captures the shape of the exposure mask and high productivity is required, and the conventional positive photoresist described above is required. In fact, it is not possible to respond.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel photosensitive composition which solves these problems. 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 The present inventors have made intensive studies to achieve the above object, and as a result, have 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 provides 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): , Is provided.

[0014]

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Wherein 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 represents a hydrogen atom, an optionally substituted alkyl, alkenyl, aryl, aralkyl, alkoxy,
Aryloxy, cyano, -CO-R ³ or -CO-NR ⁴ R ⁵
Represents each group.

Preferably, R ¹ and R ² represent an alkyl, aryl, alkenyl or alkoxy group which may have a substituent.

Specifically, the alkyl groups of R ¹ and R ² are
It is straight-chain, branched, or cyclic, and preferably has 1 to 18 carbon atoms and includes, for example, methyl, ethyl,
Each group includes butyl, hexyl, octyl, dodecyl, hexadecyl and the like. The aryl group of R ¹ and R ² is preferably a monocyclic or bicyclic aryl group, and includes, for example, a phenyl group and a naphthyl group. R ¹ , R
The alkenyl group ² is, for example, a vinyl group, and further includes those substituted with a vinyl group such as an alkyl group such as a methyl group, for example, an aryl group such as a phenyl group. 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.

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

Preferred substituents which may be bonded to these groups include groups such as alkyl, aryl, alkoxy, nitro, cyano, amide, ureido and urethane.
Or a halogen atom is mentioned.

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, There are 1 to 6 alkoxy groups.

R ⁴ and R ⁵ may be the same or different and each represents a hydrogen atom, an alkyl, an aryl or an aralkyl group, preferably a hydrogen atom or a C 1 -C 1
It is an aryl group having 6 alkyls and 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, preferably a single bond, alkylene having 1 to 30 carbon atoms or 6 carbon atoms. And represents an arylene group which may have up to 20 monocyclic or polycyclic substituents. Preferred substituents are alkyl, aryl, alkoxy, nitro,
Examples include a cyano, amide, ureido, urethane group or halogen atom. Further, A ¹ , A ² and A ³ may contain a divalent group such as ether, ester, amide, urethane and ureide. p, q, and r are each 0 or an integer of 1 or more, preferably 0 or an integer of 1 to 10, more preferably 0 or an integer of 1 to 5.

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

The compound of the formula (I) of the present invention has a wide range of light source suitability and high sensitivity by combining different kinds of photosensitive groups (ie, naphthoquinonediazide group and oxime sulfonate group). Things.

Hereinafter, the components of the present invention will be described in detail. [Compound represented by the formula (I) ] The compound represented by the general formula (I) is obtained by reacting a ketone compound with hydroxylamine to obtain a compound represented by the general formula (II)
And the sulfonyl chloride represented by the general formula (III) are condensed under basic conditions.

[0027]

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

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

[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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The content of the compound of the present invention represented by the general formula (I) is suitably from 1 to 70% by weight, preferably from 3 to 50% by weight, more preferably from 3 to 50% by weight, based on the solid content of the whole 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 may contain, if necessary, a compound of the present invention represented by the formula (I) and another 1,2-naphthoquinone-2- compound. A diazide-4- and / or 5-sulfonic acid ester compound may be added and used in combination. Such 1,2
The -naphthoquinone-2-diazide-4- and / or 5-sulfonic acid ester compound is generally a mono- or a 1,2-naphthoquinone-2-diazide compound having a halogenosulfonyl group such as sulfonyl chloride at the 4- or 5-position. It can be represented as a sulfonylate compound obtained by condensation with a polyhydroxyphenyl compound. Typical examples of such a mono- or polyhydroxyphenyl compound are benzophenone compounds 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 And 3,3 ', 4,4'-tetrahydroxybenzophenone, benzophenone having 5 or more hydroxy groups as shown in JP-A-62-150245, and derivatives thereof. Further, p-cresol, pt-butylphenol, resorcinol, pyrogallol, 2,2'-dihydroxybiphenyl, 2,2 ',
Hydroxy group-substituted biphenyl compounds 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. .

Also, Japanese Patent Application Laid-Open No. Sho 56-1045,
JP-A-56-1044, JP-B-43-28403
Condensates of polyhydric phenols with aldehydes and ketones disclosed in JP-A-59-84361 and JP-B-49-24361.
No. 239, aldehydes of catechol, resorcin, or hydroquinone with substituted phenols.
Co-condensates with ketones, condensates of substituted phenols and benzaldehydes described in JP-A-60-31138, and aldehydes and ketones of phenols with substituted phenols such as o-, m- or p-cresol The co-condensate, p-hydroxystyrene polymer and the like 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 the naphthoquinone-2-diazide-4- and / or 5-sulfonate compound is 10: 1 to 1: 1 by weight.
20, preferably 5: 1 to 1:10, more preferably 2: 1 to 1: 5.

[Alkali-Soluble Resin] The positive photosensitive composition of the present invention preferably contains an alkali-soluble resin in order to make the alkali solubility of the exposed area more efficient and to impart film properties 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-sulfonylamido group, an N-sulfonylurethane group, an active methylene group, or the like. It is a polymer having an acidic hydrogen atom having a pKa of 11 or less. Suitable alkali-soluble polymers include novolak-type phenol resins, specifically phenol-formaldehyde resins, o-cresol-formaldehyde resins,
There are m-cresome-formaldehyde resin, p-cresome-formaldehyde resin, xylenol-formaldehyde resin, and co-condensates thereof. Further, as described in JP-A-50-125806, together with the above-mentioned phenol resin, phenol or cresol substituted with an alkyl group having 3 to 8 carbon atoms such as t-butylphenol formaldehyde resin and formaldehyde are used. And a condensate thereof. Also N-
Polymers containing a phenolic hydroxy group-containing monomer such as (4-hydroxyphenyl) methacrylamide as a copolymer component, p-hydroxystyrene, o-hydroxystyrene, m-isopropenylphenol, p-isopropenylphenol or the like alone or Copolymerized polymers and also partially etherified and partially esterified polymers of these polymers can be used.

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

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

These alkali-soluble polymers can be used alone, but may be used as a mixture of several kinds.
A 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 in the range of 60 to 95% by weight.

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

Dyes can be used as colorants, but preferred 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 (or more, Orient Chemical Industries, Ltd.)
Manufactured), Crystal Violet (CI42555), Methyl Violet (CI42535), Rhodamine B
(CI45170B), malachite green (CI42
000), methylene blue (CI52015) and the like.

A printing agent for obtaining a visible image immediately after exposure can be added. As such a baking agent, a combination of a photosensitive compound that releases an acid upon exposure and an organic dye capable of forming a salt can be exemplified. Specifically, JP-A-50-36209, 5
Combinations of o-naphthoquinonediazide-4-sulfonic acid halogenide and salt-forming organic dyes described in JP-A-3-8128 and JP-A-53-36223 and JP-A-54-747.
Combinations of a trihalomethyl compound and a salt-forming organic dye described in No. 28 can be mentioned.

In the composition of the present invention, a cyclic acid anhydride, another filler or the like can be added in order to further increase the sensitivity. As the cyclic acid anhydride, U.S. Pat.
Phthalic anhydride, as described in JP, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6-oxy - [delta ⁴ - tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, maleic acid anhydride, chlorosulfonic maleic 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 of the whole composition, the sensitivity can be increased up to about three 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 the above-mentioned components and applied on a support. For resist materials such as semiconductors, they are used as dissolved in a solvent. As the solvent used herein, 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, dimethylsulfoxide, sulfolane, γ-butyrolactone, toluene, ethyl lactate and the like, and these solvents are used alone or as a mixture. The concentration (total solid content including additives) in the above components is 2
５０50% by weight. When used in the form of a coating, the coating amount varies depending on the application. For example, in the case of a photosensitive lithographic printing plate, the solid content is generally 0.5 to 3.0 g / m ^2.
Is preferred. The photosensitivity increases as the coating amount decreases, but the physical properties of the photosensitive film deteriorate.

[ Production of a lithographic printing plate] When a lithographic printing plate is produced using the positive photosensitive composition of the present invention, examples of the support include paper and plastics (polyethylene, polypropylene, polystyrene, etc.). , Laminated paper, metal plates such as aluminum (including aluminum alloy), zinc, copper, etc., cellulose acetate, cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, Plastic films, such as polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.
Metal laminates or vapor-deposited paper or plastic films as described above are included. Of these supports, the aluminum plate is extremely dimensionally stable,
Moreover, it is particularly preferable because it is inexpensive. In addition,
A composite sheet in which an aluminum sheet is bonded on a polyethylene terephthalate film as described in US Pat. Mechanical method such as wire brush graining, brush graining, ball graining, solution honing, buff graining, etc., HF, AlCl
Chemical graining with ₃ or HCl as an etchant,
The surface is grained by electrolytic graining using nitric acid or hydrochloric acid as an electrolytic solution, or composite graining performed by combining these surface roughening methods, and then, if necessary, is etched with an acid or alkali, followed by sulfuric acid. It is preferable to use a phosphoric acid, an oxalic acid, a boric acid, a chromic acid, a sulfamic acid, or a mixed acid thereof, which is subjected to anodic oxidation with a DC or AC power supply to provide a strong passive film on the aluminum surface. The aluminum surface is hydrophilized by such a passivation film itself. However, if necessary, silicate treatment (sodium silicate, potassium silicate) described in U.S. Pat. No. 2946638, potassium fluorozirconate treatment described in U.S. Pat. No. 3,2012,47, phosphomolybdate treatment, alkyl titanate treatment described in British Patent No. 1108559, German Patent No. 109143
No.3 polyacrylic acid treatment, German patent No.
No. 1134093, British Patent No. 1230447, polyvinylphosphonic acid treatment, JP-B-44-6409, phosphonic acid treatment, U.S. Pat. 58-1689
No. 3, No. 58-18291, an undercoating treatment with a complex of a water-soluble organic polymer and a divalent metal ion,
It is particularly preferable that a hydrophilic treatment is carried out with an undercoat of a water-soluble polymer having a sulfonic acid group described in JP-A-59-101651. Other hydrophilic treatment methods include silicate electrodeposition described in US Pat. No. 3,866,662.

It is also preferable to perform graining treatment, anodic oxidation and sealing treatment. Such a 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.

[Active Light or Radiation] Examples of the light source of the active light used for exposure of the photosensitive composition of the present invention include a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, and a carbon arc lamp.
Examples of the radiation include an electron beam, an X-ray, an ion beam, and far ultraviolet rays. Preferably, g-line, i-line, 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 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, tertiary sodium phosphate,
Aqueous solutions of inorganic alkali agents such as sodium diphosphate, ammonium tertiary phosphate, ammonium diphosphate, sodium metasilicate, sodium bicarbonate, aqueous ammonia and organic alkali agents such as tetraalkylammonium OH salts are suitable. And their concentration is 0.1 to 10% by weight, preferably 0.5% by weight.

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

[0067]

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

Synthesis Example 1 (Material of compound (Example I-21))
Ii) 120 g (1.00 mol) of acetylbenzene was dissolved in 800 ml of ethanol, and hydroxylamine hydrochloride 8 was added thereto.
A solution of 3.5 g (1.20 mol) in 200 ml of water was added with stirring. Subsequently, a solution of 60 g (1.50 mol) of sodium hydroxide in 80 ml of water was added dropwise, and the mixture was refluxed 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.
NMR and elemental analysis confirmed that the crystals were acetonephenone oxime.

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

Thereafter, 20 ml of distilled water was added, and the pH of the reaction solution was adjusted to 5 to 6 with triethylamine. Water the reaction solution
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 a yellow powder.
I got According to NMR, the powder was identified as Compound Example (I-21)
It confirmed that it was a structure of.

Examples 1 to 5 A 2S aluminum plate having a thickness of 0.24 mm was immersed in a 10% aqueous solution of sodium tertiary phosphate kept at 80 ° C. for 3 minutes to be degreased. Etching was performed with sodium for about 10 minutes, and desmutting was performed with a 3% aqueous solution of sodium hydrogen sulfate. This aluminum plate was placed in a 20% sulfuric acid solution at a current density of 2 A / dm ² .
Anodizing was performed for a minute to prepare an aluminum plate.

The type of the compound represented by formula (I) of the present invention used in the following photosensitive solution [A] was changed to 5
Various types of photosensitive solutions [A] -1 to [A] -5 were prepared, and this photosensitive solution was applied on an anodized aluminum plate.
It dried at 00 degreeC for 2 minutes, and produced each photosensitive lithographic printing plate [A] -1-[A] -5. 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 lithographic printing plates [A] -1 to [A] -5 and [B]
A gray scale having a density difference of 0.15 was adhered to 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] were immersed and developed in DP-8 (trade name: manufactured by Fuji Photo Film Co., Ltd.) in an 8-fold diluted aqueous solution at 25 ° C. for 60 seconds to completely dissolve and remove the fifth stage of the gray scale. Was measured and the results were as shown in Table 1.

Table 1 II Examples Photosensitivity Gray scale of the present invention used The fifth row is the number. Lithographic printing plate compound. Exposure time to dissolve and remove. Example 1 [A] -1 Compound Example (I-2) 30 seconds Example 2 [A] -2 Compound example (I-8) 35 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Example 3 [A] -3 Compound example (I-21) 35 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Example 4 [A] -4 Compound example (I-39) Example 5 [A] -5 Compound Example (I-50) 25 Comparative Example [B] Compound 55 of Comparative Example

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

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

Examples 6 to 9 By changing the type of the compound of the present invention in the following photosensitive solution [C],
Each type of photosensitive solution [C] -1 to [C] -4 was prepared, and 0.2 µ
Then, the mixture was filtered through a microfilter of m 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 on a silicon wafer having an oxide film of 2500 A using a spinner and dried in a convection oven under a nitrogen atmosphere at 90 ° C. for 2 minutes to obtain a resist film having a thickness of 1.0 μm. Was. Next, exposure was performed through a test chart mask using a reduction projection exposure apparatus manufactured by Nikon Corporation, developed with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide for 1 minute, and rinsed with ion-exchanged water to obtain a resist pattern. 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 amount for reproducing a 2.0 μm mask pattern, and was shown as a relative value to the sensitivity of the photosensitive solution [D] of the following comparative example. The resolving power was represented by the line width of the smallest resolved mask pattern at the exposure dose for reproducing a 2.0 μm mask pattern. Table 2 shows the results.

[0085]

Table 2 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Example Relative resolution of the present invention using a photosensitive solution No. 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 ━━━━━━━━━━━━━━━━━━ ━━━━━━━━━━━

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

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

[0089]

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

Continuation of front page (56) References JP-A-4-328552 (JP, A) JP-A-4-362647 (JP, A) JP-A-2-53056 (JP, A) JP-A-1-163736 (JP) JP-A-1-124848 (JP, A) JP-A-63-116148 (JP, A)

Claims (1)

(57) [Claims] 1. A 1,2-formula 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. Embedded image Wherein D is 1,2-naphthoquinone-2-diazide-4
-Yl group or 1,2-naphthoquinone-2-diazide-5
R ¹ and R ² may be the same or different, and each represents a hydrogen atom, an alkyl, alkenyl, aryl, aralkyl, alkoxy, aryloxy, cyano, which may have a substituent, -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, and R ⁴ and R ⁵ may be the same or different and each represents a hydrogen atom, an alkyl, an 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. Further, R ¹ and R ² , R ¹ , R ² and A ¹ , A ² , A
³ or ^one or more of A ¹ , A ² and A ³ may combine to form a ring.