JPH0683047A - Positive photosensitive composition - Google Patents

Abstract

(57) [Summary] [Structure] A positive photosensitive composition containing a diazonium salt represented by the following general formula (II) and an alkali-soluble polymer. [Chemical 1] In the formula, R ¹ represents an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group, and R ² represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group or a halogen atom. A represents an organic group, and X ¹⁻ represents a counter anion. n is an integer of 1 to 4, m is an integer of 1 to 3,
n + m = 4. Further, l is an integer of 2 to 10. [Effect] The development speed is high.

Description

Detailed Description of the Invention

[0001]

INDUSTRIAL APPLICABILITY The present invention is capable of forming a fine resist pattern when manufacturing a lithographic printing plate, a proof printing plate for multicolor printing, a drawing for an overhead projector, and an integrated circuit of a semiconductor device. It relates to a positive photosensitive composition.

[0002]

2. Description of the Related Art Conventionally, in applications such as lithographic printing plates, various proposals have been made as a so-called positive acting photosensitive composition which is solubilized by actinic rays.
A photosensitive composition in which a natural polymer such as egg white or glue or polyvinyl alcohol and dichromate are blended,
A photosensitive composition containing (b) orthoquinonediazide compound, a photosensitive composition containing (c) diazonium salt, etc. are known. However, the above-mentioned photosensitive composition has merits and demerits and is not sufficiently satisfactory. The photosensitive composition of the above (a) is inexpensive and therefore advantageous from the economical point of view, but has poor storage stability, and since dichromate is used as a raw material, there are problems in disposal and other handling. It was The orthoquinonediazide compound (b) above is excellent as a positive image-forming material, and has been widely used in planographic printing plates and the like.

Examples of such orthoquinonediazide compounds include, for example, US Pat. Nos. 2,766,118 and 2,767,09.
No. 2, No. 2,772,972, No. 2,859,112, No. 2,90
No. 7,665, No. 3,046,110, No. 3,046,111, No.
3,046,115, 3,046,118, 3,046,119,
No. 3,046,120, No. 3,046,121, No. 3,046,122
No. 3,046,123, No. 3,061,430, No. 3,102,
No. 809, No. 3,106,465, No. 3,635,709, No. 3,
It is described in numerous publications, including the specification No. 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 none of them show sufficient sensitivity. This is because it is difficult to achieve photochemical sensitization depending on the orthoquinonediazide compound, and the quantum yield thereof does not essentially exceed 1. In addition, since the photosensitive wavelength is fixed, the light source suitability is poor, it is difficult to give white light safety, and since absorption in the deep UV region is large, the aim is to improve the resolution of the photoresist by using low wavelength light. Not suitable for use.

In order to overcome these drawbacks, for example, Japanese Patent Publication No. 48-12242, Japanese Unexamined Patent Publication No. 52-40125,
The methods described in the respective publications and specifications such as US Pat. No. 4,307,173 have been tried, but all of them have been insufficient improvements. Examples of the positive composition containing the diazo compound (c) include, for example, US Pat. No. 3,219,44
No. 7, No. 3,211,553, Japanese Examined Patent Publication No. 39-7663, and Japanese Unexamined Patent Publication No. 52-2519 are listed, but they have low sensitivity and lack stability in image formation. It could not be put to practical use. In addition, recently, some proposals have been made for the purpose of developing new materials replacing these positive photosensitive compounds. One of them is, for example, a polymer compound having an orthonitrocarbinol ester group described in JP-B No. 56-2696. However, even in this case, sufficient sensitivity was not obtained.

On the other hand, as a pattern forming method for manufacturing an electronic component such as a semiconductor element, a magnetic bubble memory, an integrated circuit, a method of using a photoresist is generally used. The photoresist is classified into a negative type in which the irradiated portion is insoluble in the developing solution by light irradiation and a positive type in which the exposed area is solubilized. The negative type has better sensitivity than the positive type,
It has been the mainstream of photoresists until recently because of its excellent adhesion to substrates and chemical resistance required for wet etching. However, with the increase in the density and integration of semiconductor devices, the line width and spacing of patterns have become extremely small, and dry etching has been adopted for substrate etching. Now that high resolution and high dry etching resistance are desired, positive photoresists are now the mainstream. In particular, among positive photoresists, they are excellent in sensitivity, resolution, and dry etching resistance. For example, JC Strieter, Kodak Microelectronics Seminar Proceedings No. 11
Page 6 (1976) (JC Strieter, Kodak Microele
ctoronics Seminar Proceedings, 116 (1976))
Alkali-developing positive photoresists based on alkali-soluble novolac resins described in U.S. Pat.

However, in recent years, electronic devices have become multifunctional,
With higher sensitivity, there is a strong demand for finer patterns to achieve higher density and higher integration. To meet these demands, a conventional orthoquinonediazide photosensitive composition is combined with an alkali-soluble polysiloxane or a silicone polymer such as polysilmethylene, for example, a photosensitive composition, for example, JP-A-61-256347 and 61-61. 14
4639, 62-159141, 62-191.
No. 849, No. 62-220949, No. 62-2291.
No. 36, No. 63-90534, No. 63-91654 and the like, and the photosensitive compositions described in JP-A-62-136.
No. 638 discloses a photosensitive composition in which a polysiloxane / carbonate block copolymer is combined with an effective amount of an onium salt. However, the production of these silicone polymers is extremely difficult due to the addition of an alkali-soluble function, and their stability with time is not sufficient. The present inventors have proposed a novel positive photosensitive composition, which solves the above problems, in Japanese Patent Application No.
No. 325859 proposes a combination of a specific diazonium salt and an alkali-soluble polymer. However, in recent years, a photosensitive composition having a faster developing speed has been desired in view of the demand for improvement of working efficiency.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel positive-working photosensitive composition in which the above problems have been solved, and a new positive-working photosensitive composition in which the development speed is further improved. Especially.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to achieve the above object, and as a result, by incorporating a diazonium salt having a specific structure in an alkali-soluble polymer such as cresol resin, It has been found that a positive image can be obtained at a high developing speed, that is, in a short time. That is, the present invention is a positive photosensitive composition comprising a diazonium salt represented by the following general formula (I) and an alkali-soluble polymer. In _{^{(Ar-N + ≡N) l}} X l- (I) formula, Ar represents an organic residue of an aromatic, X ^l-is a counter anion. l is an integer of 2 to 10. With this system, a clear positive image can be obtained in a short development time. Although the reason for this is not clear, in the unexposed area, the specific diazonium salt represented by the general formula (I) and the alkali-soluble polymer strongly interact with each other to lower the solubility of the photosensitive layer in an alkali developing solution. On the other hand, in the exposed area, the diazo compound represented by the general formula (I) having the above-mentioned dissolution inhibiting property is decomposed by irradiation with light, and a polyvalent acid is generated, so that the solubility in an alkali developing solution is increased. It is presumed that this is due to a large increase.

The positive photosensitive composition of the present invention will be described in detail below. As the specific diazonium salt in the present invention, those represented by the general formula (I) are preferable, and among them, those represented by the general formulas (II) to (V) are preferable. Further, more preferably, the counter anion X ^{1 −} is represented by the general formula (VI). Next, the diazonium salts represented by the general formulas (II) to (V) will be described in more detail.

[0010]

[Chemical 3] In the formula, R ¹ represents an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group, and R ² represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group or a halogen atom. A represents an organic group, and X ¹⁻ represents a counter anion. n is an integer of 1 to 4, m is an integer of 1 to 3,
n + m = 4. Further, l is an integer of 2 to 10.
Further, the diazonium salt represented by the general formula (II) is rapidly decomposed by light irradiation, the dissolution inhibiting effect is released, and a polyvalent acid is generated by the polyvalent counter anion, resulting in a clear positive An image is formed with a fast development time. Among them, a particularly effective diazonium salt is represented by the general formula (II
Examples thereof include diazonium salts represented by I), (IV) or (V), and more preferably the counter anion X.
^Examples thereof ^include those in which ^l- is represented by the general formula (VI).

[Chemical 4]

In the formula, R ¹ is an alkyl group, a substituted alkyl group,
It represents an aryl group or a substituted aryl group, and R ² represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group or a halogen atom. X ^1- represents a counter anion. n is an integer of 1 to 4, m is an integer of 1 to 3, and n
+ M = 4. L is an integer of 2 to 10. R ³
Represents an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an arylcarbonyl group or a substituted arylcarbonyl group, and R ⁴ represents an alkyl group, a substituted alkyl group,
An aryl group or a substituted aryl group is shown. Also, R ³ and R
⁴ may be bonded to each other to form a heterocyclic group such as a morpholino group, a thiomorpholino group, a piperidino group and a pyrrolidino group. Y is an oxygen atom, a sulfur atom, -NH-, -C
H ₂ - or -C (CH _{3) 2} - shows a. Z ¹ is a hydrogen atom,
It represents an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an alkoxy group, a substituted alkoxy group, an alkylcarbonyl group, a substituted alkylcarbonyl group, an arylcarbonyl group, a substituted arylcarbonyl group, a cyano group, a nitro group or a halogen atom. k represents an integer of 1 to 5.
Z ² represents an alkylcarbonyl group, a substituted alkylcarbonyl group, an arylcarbonyl group or a substituted arylcarbonyl group. Further, particularly preferably, the counter anion X ^{1 −} is
This is the case where it is a monovalent sulfonate anion represented by the general formula (VI). W- (SO ₃ ^-) in _l (VI) formula, W is a l-valent aryl connecting group or an alkyl linking group, may be substituted, -NH-CO-,
It may contain a divalent linking group such as —O—, —S—, and —CO—O—. L is an integer of 2 to 10.

General formula (II), (III), (IV) or (V)
The alkyl group of R ¹ in is preferably one having 1 to 18 carbon atoms. It may be linear, branched or cyclic, for example, methyl group, ethyl group, propyl group,
Examples thereof include a butyl group, a pentyl group, a hexyl group and an octyl group. The substituted alkyl group of R ^{1 is} an alkyl group having 1 to 10 carbon atoms, a halogen atom such as chlorine atom, an alkoxy group having 1 to 5 carbon atoms such as methoxy group,
A group substituted with a phenoxy group, a benzylthio group or the like, and a substituted alkyl group having 1 to 18 carbon atoms is preferable. Specifically, 4-chlorobutyl group, 4-ethoxybutyl group, 2-butoxyethyl group, 4-phenoxybutyl group, 2-benzylthioethyl group and the like are included. The aryl group of R ¹ is preferably monocyclic or bicyclic, and examples thereof include a phenyl group, an α-naphthyl group and a β-group.
A naphthyl group and the like are included. The substituted aryl group of R ¹ is
Examples of the aryl group as described above include an alkyl group having 1 to 8 carbon atoms such as methyl group and ethyl group, an alkoxy group having 1 to 5 carbon atoms such as methoxy group and ethoxy group,
For example, those in which a halogen atom such as a chlorine atom is substituted are included. Specific examples include a methylphenyl group, a t-butylphenyl group, a methoxyphenyl group, a chlorophenyl group and a methoxynaphthyl group.

The alkyl group for R ² may be linear, branched or cyclic and preferably has 1 to 10 carbon atoms. Examples thereof include a methyl group, an ethyl group, a butyl group, a hexyl group, and an octyl group. The substituted alkyl group for R ^{2 is} a group in which the above alkyl group is substituted with a halogen atom such as a chlorine atom, or an alkoxy group having 1 to 5 carbon atoms such as a methoxy group. Specific examples include a 2-chloroethyl group and a 2-methoxyethyl group. The aryl group of R ² is preferably monocyclic or bicyclic and includes, for example, a phenyl group, an α-naphthyl group, a β-naphthyl group and the like. The substituted aryl group represented by R ² is the above-mentioned aryl group, for example, an alkyl group having 1 to 5 carbon atoms such as a methyl group or an ethyl group,
For example, an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group, and a group substituted with a halogen atom such as a chlorine atom are included. Specific examples thereof include a methylphenyl group, a dimethylphenyl group, a methoxyphenyl group, a chlorophenyl group and a methoxynaphthyl group. The alkoxy group of R ² may be linear, branched or cyclic,
It preferably has 1 to 18 carbon atoms. For example, methoxy group, ethoxy group, butoxy group and the like can be mentioned. The substituted alkoxy group for R ^{2 is} a group in which the above alkoxy group is substituted with a halogen atom, an alkoxy group having 1 to 5 carbon atoms, a phenoxy group, a benzylthio group or the like, and examples thereof include 4-chlorobutoxy group and 4-ethoxy. Butoxy group, 2-
Butoxyethoxy group, 4-phenoxybutoxy group, 2-
A benzylthioethoxy group and the like are included.

X^l-Represents a valent counter anion, for example,
When l = 2, phthalate anion and fumarate anio
Dicarboxylic acid anions such as benzene, naphthalene-1,5-di
Sulfonate anion, 9,10-diethoxyanthracene
Disulfonic acid anions such as anion-2,6-disulfonic acid anion
Nion, and when l = 3, naphthalene-1,
Trisulfonic acid anions such as 3,6-trisulfonic acid anion
Examples include, but are not limited to
Not something. R in the general formula (III)³ , R^Four The alkyl
Groups, substituted alkyl groups, aryl groups, substituted aryl groups are
Note R² Alkyl group, substituted alkyl group, aryl group,
The same range as the substituted aryl group can be used.
It Also, R³ Arylcarbonyl group, substituted aryl
The carbonyl group is the above aryl group or substituted aryl group
Those linked to a bonyl group can be used. Well
R³ , R^Four Are bonded to each other to form a morpholino group, thio
Heterocycles such as morpholino, piperidino, and pyrrolidino
A formula group may be formed. Z in general formula (IV)¹The alkyl
Group, substituted alkyl group, aryl group, substituted aryl group,
Rucoxy group and substituted alkoxy group are R² The same range as
Can be used. In addition, the general formula (IV),
Z of (V)¹, Z²Alkylcarbonyl group of
Killcarbonyl group, arylcarbonyl group, substituted aryl
The carbonyl group is an alkyl group, a substituted alkyl group,
Reel group, substituted aryl group linked to carbonyl group
Can be used. Furthermore, the substituents are modified
May be. Further, the diazo compounds represented by the general formulas (III) to (V)
Counter anion X in zonium salts ^l-Is represented by general formula (VI)
It is preferable that the carboxylic acid anion is
In the general formula (VI), the W-valent aryl linking group or ar
Kill linking groups include, for example:
However, the present invention is not limited to this.

[0015]

[Chemical 5]

[0016]

[Chemical 6]

[0017]

[Chemical 7] R ⁵ represents an alkyl group, and p is an integer of 2-5. The examples of the compound represented by formula (II) used in the present invention are listed below, but the scope of the present invention is not limited thereto.

[0018]

[Chemical 8]

[0019]

[Chemical 9]

The compound represented by the general formula (I) can be used alone, but may be used as a mixture of several kinds. The addition amount of the compound represented by formula (I), (II), (III), (IV) or (V) in the photosensitive composition is preferably 1 to the total solid content of the photosensitive composition. 50% by weight, more preferably 5 to 30% by weight.

The alkali-soluble polymer used in the present invention is preferably a phenolic hydroxy group, a carboxylic acid group, a sulfonic acid group, an imide group, a sulfonamide group, N
-A polymer having an acidic group having a pKa of 11 or less such as a sulfonylamide group, an N-sulfonylurethane group, and an active methylene group. Suitable alkali-soluble polymers include novolac type phenolic resins, specifically phenol-formaldehyde resin, o-cresol-formaldehyde resin, m-cresol-formaldehyde resin, p-
Examples include cresol-formaldehyde resin, xylenol-formaldehyde resin, and co-condensates thereof. Further, as described in JP-A-50-125806, together with the above-mentioned phenol resin, carbon number 3 to such as t-butylphenol-formaldehyde resin is contained.
A condensate of phenol or cresol substituted with an alkyl group of 8 and formaldehyde may be used in combination.
Further, a polymer having a phenolic hydroxy group-containing monomer such as N- (4-hydroxyphenyl) methacrylamide as a copolymerization component, p-hydroxystyrene, o-
Hydroxystyrene, m-isopropenylphenol,
Homo- or copolymerized polymers such as p-isopropenylphenol, and partially etherified or partially esterified polymers of these polymers can also be used.

Further, a polymer having a carboxy group-containing monomer such as acrylic acid or methacrylic acid as a copolymerization component, a carboxy group-containing polyvinyl acetal resin described in JP-A-61-267042, and JP-A-63-124047.
The carboxyl group-containing polyurethane resin described in the publication is also preferably used. 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-63-127239 can also be used. . These alkali-soluble polymers can be used alone, but may be used as a mixture of several kinds. The amount of the alkali-soluble polymer added to the photosensitive composition is preferably in the range of 5 to 99% by weight, more preferably 10 to 90% by weight, based on the total solid content of the photosensitive composition.

Dyes, pigments, plasticizers, etc. can be further added to the positive photosensitive composition of the present invention, if necessary. Various known dyes can be used as the dye used as the colorant in the present invention, but an oil-soluble dye and a basic dye are preferably used. Specifically, for example, Oil Yellow # 101, Oil Yellow # 130, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Black BY, Oil Black BS,
Oil Black T-505 (all manufactured by Oriental Chemical Co., Ltd.), Crystal Violet (CI4255)
5), methyl violet (CI42535), rhodamine B (CI45170B), malachite green (C
I42000), methylene blue (CI52015) and the like.

These dyes are 0.01 to 10% by weight, preferably 0.1 to 3% by weight, based on the total solid content of the photosensitive composition.
Can be added to the photosensitive composition at a ratio of. Cyclic acid anhydrides, other fillers, etc. may be added to the composition of the present invention to further enhance the sensitivity. Examples of the cyclic acid anhydride include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6-endooxy-tetrahydrophthalic anhydride and tetrachlorophthalic anhydride as described in U.S. Pat. No. 4,115,128. , 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 preferably 1 to 15% by weight based on the total solid content of the photosensitive composition, the sensitivity can be increased up to about 3 times.

When the positive-type photosensitive composition of the present invention is used as a material for a lithographic printing plate, it is dissolved in a solvent capable of dissolving the above components and applied on a support. Further, for a resist material such as a semiconductor, 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, 1-methoxy- 2-propyl acetate, dimethoxyethane, methyl lactate, ethyl lactate, N, N-dimethylacetamide, N, N-dimethylformamide, tetramethylurea, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane, γ-butyl lactone, toluene, lactic acid There are ethyl and the like, and these solvents are used alone or as a mixture. The concentration of the above components (total solids including additives) in the solvent is preferably 2 to 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 as solid content.
/ M ^2, also 0.1 to 3.0 g / m ² is preferred as generally solids As for the photoresist. As the coating amount decreases, the photosensitivity increases, but the film characteristics of the photosensitive film deteriorate.

When a lithographic printing plate is produced using the positive photosensitive composition of the present invention, its support is, for example,
Paper, paper laminated with plastics (eg polyethylene, polypropylene, polystyrene, etc.), metal plates such as aluminum (including aluminum alloys), zinc, copper, etc., eg cellulose diacetate, cellulose triacetate, cellulose propionate , Plastic films such as cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, and the like, such as metal laminated or vapor-deposited paper, or plastic film. included. Among these supports, the aluminum plate is particularly preferable because it is dimensionally remarkably stable and inexpensive. Furthermore, Japanese Patent Publication 48-18
A composite sheet in which an aluminum sheet is bonded onto a polyethylene terephthalate film as described in Japanese Patent No. 327 is also preferable. Mechanical method such as wire brush graining on the surface of aluminum plate, brush graining by pouring a slurry of abrasive particles with a nylon brush, ball graining, graining by liquid honing, buff graining, HF and AlCl ₃ ,
After chemical graining using HCl as an etchant, electrolytic graining using nitric acid or hydrochloric acid as an electrolytic solution, or complex graining performed by combining these roughening methods, the surface is grained, and then acid or What is etched with an alkali, and then anodized in sulfuric acid, phosphoric acid, boric acid, chromic acid, sulphamic acid, or a mixed acid of these with a direct current or an alternating current power source to provide a strong passivation film on the aluminum surface. preferable.

The aluminum surface is hydrophilized by such a passive film itself, but if necessary, the silicate treatment described in US Pat. No. 2,714,066 and US Pat. No. 3,181,461 ( Sodium silicate, potassium silicate), potassium fluorozirconate treatment described in US Pat. No. 2,946,638, US Pat.
Phosphomolybdate treatment described in 3,201,247, Alkyl titanate treatment described in British Patent 1,108,559, Polyacrylic acid treatment described in German Patent 1,091,443, Germany Patent No.
Polyvinylphosphonic acid treatment described in 1,134,093 and British Patent 1,230,447, Japanese Examined Patent Publication No. 44
No. 6409, phosphonic acid treatment, US Pat. No. 3,307,951, phytic acid treatment, JP-A-58-16893 and JP-A-58-16.
Undercoating treatment with a complex of a water-soluble organic polymer compound and a divalent metal ion described in JP-A No. 291, and a water-soluble polymer having a sulfonic acid group described in JP-A-59-101651. Those subjected to a hydrophilic treatment by a combined undercoat are particularly preferable. Other hydrophilic treatment methods include silicate electrodeposition described in US Pat. No. 3,658,662.

Further, it is 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. When the positive photosensitive composition of the present invention is used as a photoresist, a substrate made of various materials such as a copper plate, a copper plated plate, a silicon plate, a stainless plate, or a glass plate can be used as a support. The positive photosensitive composition of the present invention is coated on the above support by a known coating technique. Examples of the above coating technique include a spin coating method, a wire bar coating method, a dip coating method, an air knife coating method, a roll coating method, a blade coating method, a curtain coating method and a spray coating method.

The positive type photosensitive composition layer coated as described above is dried at 40 to 150 ° C. for 30 seconds to 10 minutes using a hot air dryer, an infrared dryer or the like. The photosensitive lithographic printing plate, photoresist and the like containing the positive photosensitive composition of the present invention are usually subjected to image exposure and development steps. Examples of the light source of actinic rays used for image exposure include a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, and a carbon arc lamp. The radiation includes electron beams, X-rays, ion beams, far ultraviolet rays and the like. Light sources for photoresist include g-line, i-line, De
Ep-UV light is preferably used. Scanning exposure with a high-density energy beam (laser beam or electron beam) can also be used in the present invention. Examples of such a laser beam include a helium / neon laser, an argon laser, a krypton ion laser, a helium / cadmium laser, and a KrF excimer laser.

As a developer used for developing the positive photosensitive composition of the present invention, sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium triphosphate, and dibasic sodium phosphate are used. Aqueous solutions of inorganic alkaline agents such as ammonium triphosphate, dibasic ammonium phosphate, sodium metasilicate, sodium bicarbonate, aqueous ammonia and organic alkaline agents such as tetraalkylammonium hydride are suitable, The concentration of 0.1 to 10% by weight, preferably
It is added so as to be 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.

Synthetic Polyvalent Sulfonic Acid Used in the Present Invention As the aromatic polyvalent sulfonic acid, a commercially available product which can be easily obtained as a Na salt may be used, or "New Experimental Chemistry Course". (Maruzen), P.1773-1784, vol 14
It can also be synthesized by utilizing a sulfonation reaction using sulfur trioxide, chlorosulfonic acid or sulfuric acid as described in (III). It can also be synthesized from an alkyl halide by using sodium sulfite. Furthermore, by utilizing amidation, esterification, etc., two or more sulfonic acids can be linked and synthesized. For example, in this case, use of o-sulfobenzoic anhydride and the like can be mentioned.

The diazonium salt (compound used in the present invention
The synthetic method of Examples 3 and 5) or the method for synthesizing the diazonium salt in the present invention using the purchased polyvalent sulfonic acid or polyvalent sulfonic acid sodium salt is shown below. Synthesis Example 1 (Synthesis of Compound 3)] of 2,5-dibutoxy-4-morpholino benzene diazonium Cl ^- · 1/2 ZnCl
₂ salt (commercially available) (8.3 g) in water (1000 g),
1,5-Naphthalenedisulfonic acid Na salt (commercially available) (21.
When 9 g) is added and stirred, a precipitate is immediately formed. After suction filtration, air drying was performed to obtain Compound 3 (19.7 g, yield 82.5%). [Synthesis Example 2 (Synthesis of Compound 5)] 1,2,4-trichloro-5-nitrobenzene (22.6 g) in DMF (10
0 g) was added K ₂ CO ₃ (41.5g), added ^{p-t-butylphenol} (15.0 g). After heating and stirring at 150 ° C for 10 hours, p- ^t -butylthiophenol (16.6 g) was added, and the mixture was again heated and stirred at 150 ° C for 5 hours. When the reaction mixture was put into water (3000 g), crystals were precipitated,
Recrystallization from OH gave 2- (4- ^t- butylphenoxy) -4- (4- ^t -butylthiophenoxy) -5-chloronitrobenzene (32.9 g, 70.2%).
Next, after reducing the substituted nitrobenzene with Fe and NH ₄ Cl,
Diazotization with NaNO ₂ and ConcHCl and addition of (N- (2-sulfoethyl) -2-sulfobenzamide disodium salt) (13.0 g) that had been synthesized in advance cause precipitation. The compound 5 (3
2.2 g, total yield 52.0%) was obtained. Compound 1,
2 and 5 and 6 can be synthesized by the same method.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the contents of the present invention are not limited thereto. [Examples 1 to 6 and Comparative Examples 1 to 3] 1% sodium triphosphate obtained by keeping a 2S aluminum plate having a thickness of 0.24 mm at 80 ° C.
It was immersed in a 0% aqueous solution for 3 minutes to be degreased, grained with a nylon brush, etched with sodium aluminate for about 10 minutes, and desmutted with a 3% aqueous sodium hydrogen sulfate solution. This aluminum plate was anodized in 20% sulfuric acid at a current density of 2 A / dm ² for 2 minutes. Next, using the compounds shown in Table 1 below, 6 types of photosensitive solutions [A] -1 to [A] -6 were prepared according to the following formulations. Also, as comparative samples, three kinds of photosensitive solutions [P] -1 to [P] -3 using diazonium salts having a monovalent counter anion similarly shown in Table 1 were prepared.
Applying these photosensitive solutions on an anodized aluminum plate,
It was dried at 100 ° C. for 2 minutes to prepare each photosensitive lithographic printing plate. At this time, the coating amount is all 1.5 g in dry weight.
It was adjusted to be / m ² .

Photosensitive solution formulation [A] and [P] diazonium salt 3.0 × 10 ⁻⁴ mol cresol formaldehyde novolac resin 1.0 g Oil Blue # 603 (manufactured by Orient Industry Co., Ltd.) 0.01 g Methyl ethyl ketone 5 g Methyl cellosolve 15 g A gray scale having a density difference of 0.15 was brought into close contact with the photosensitive layer of the lithographic printing plate thus obtained, and exposed for 2 minutes from a distance of 50 cm with a high pressure mercury lamp of 2 KW. DP of exposed lithographic printing plate
-4 (trade name: manufactured by Fuji Photo Film Co., Ltd.) was developed with an 8-fold diluted aqueous solution at 25 ° C., and the time for obtaining a clear positive image, that is, the development time was examined. The results are shown in Table 1.

[0035]

[Table 1] Table 1 ─────────────────────────────────── Photosensitive solution Diazonium salt Graceke Development time ーNumber of steps (seconds) ─────────────────────────────────── Example 1 [A] -1 Compound 1 5 40 Example 2 [A] -2 Compound 2 6 35 Example 3 [A] -3 Compound 3 6 40 Example 4 [A] -4 Compound 4 7 40 Example 5 [A] -5 Compound 5 7 40 Example 6 [A] -6 Compound 6 5 30 Comparative Example 1 [P] -1 Compound 7 560 Comparative Example 2 [P] -2 Compound 8 6 60 Comparative Example 3 [P] -3 Compound 9 5 60 ─ ───────────────────────────────────

[0036]

[Chemical 10] From Table 1, the photosensitive layer containing the diazonium salt having a polyvalent counter anion of the present invention retains the same sensitivity as compared with the photosensitive layer containing a diazonium salt having a corresponding monovalent counter anion. It can be seen that the development time is shortened to 1 / 1.5 to 1 / 2.0 times as it is.

[Examples 7-9, Comparative Examples 4-6] Thickness 2 mm
The following photosensitive solutions [B] and [Q] were applied onto a silicon wafer of No. 1 by a spinner and dried on a hot plate at 90 ° C. for 2 minutes, and the film thickness when dried was adjusted to 1 μm. Photosensitive solution formulation [B] and [Q] diazonium salt 3.0 × 10 ^-4 mol cresol formaldehyde novolac resin 1.0 g perylene 0.003 g ethyl cellosolve acetate 7.5 g The resulting resist was irradiated with monochromatic light having a wavelength of 436 nm. Exposure using the reduction projection exposure device (stepper) used, development with a 2.4% aqueous solution of tetramethylammonium hydroxide, time to obtain a good pattern of lines and spaces of 0.8 μm in all samples, That is, the development time was examined. The results are shown in Table 2.

[0038]

[Table 2] Table 2 ──────────────────────────────── Photosensitive solution Diazonium salt Development time (sec) ─── ───────────────────────────── Example 7 [B] -1 Compound 1 40 Example 8 [B] -2 Compound 3 35 Example 9 [B] -3 Compound 6 30 Comparative Example 4 [Q] -1 Compound 7 60 Comparative Example 5 [Q] -2 Compound 8 55 Comparative Example 6 [Q] -3 Compound 9 55 ───── ─────────────────────────── From Table 2, the resist using the compound of the present invention has the same line & It can be seen that the development time for obtaining space is short.

[Example 10 and Comparative Example 7] The resists of Example 8 and Comparative Example 5 were irradiated with ultraviolet rays of 254 nm by a contact exposure method through a glass mask, and then developed in the same manner as in Example 8 and Comparative Example 5. Then, the development time for obtaining a good pattern with a line and space of 0.7 μm was examined. The results are shown in Table 3.

[Table 3] Table 3 ────────────────────────────── Used resist Development time (sec) ────── ──────────────────────── Example 10 Resist 35 of Example 8 Comparative Example 7 Resist 55 of Comparative Example 5 55 ───────── ────────────────────── From Table 3, it can be seen that the resist using the compound of the present invention has a shorter development time.

[0040]

The positive photosensitive composition of the present invention has an extremely high developing rate.

Claims (4)

[Claims] 1. A positive photosensitive composition containing a diazonium salt represented by the following general formula (I) and an alkali-soluble polymer. In _{^{(Ar-N + ≡N) l}} X l- (I) formula, Ar represents an organic residue of an aromatic, X ^l-is a counter anion. l is an integer of 2 to 10. 2. The diazonium salt represented by the general formula (I) is represented by the general formula (II).
The positive photosensitive composition described. [Chemical 1] In the formula, R ¹ represents an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group, and R ² represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group or a halogen atom. A represents an organic group, and X ¹⁻ represents a counter anion. n is an integer of 1 to 4, m is an integer of 1 to 3,
n + m = 4. Further, l is an integer of 2 to 10. 3. The positive photosensitive composition according to claim 2, wherein the diazonium salt represented by the general formula (II) is represented by the general formula (III), (IV) or (V). . [Chemical 2] In the formula, R ¹ represents an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group, and R ² represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group or a halogen atom. A represents an organic group, and X ¹⁻ represents a counter anion. n is an integer of 1 to 4, m is an integer of 1 to 3,
n + m = 4. L is an integer of 2 to 10. R
³ represents an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an arylcarbonyl group or a substituted arylcarbonyl group, R ⁴ represents an alkyl group, a substituted alkyl group,
An aryl group or a substituted aryl group is shown. Also, R ³ and R ⁴
May combine with each other to form a heterocyclic group. Y is an oxygen atom, a sulfur atom, -NH -, - CH ₂ - or -C (C
H ₃ ) ₂ −. Z ¹ is a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an alkoxy group, a substituted alkoxy group, an alkylcarbonyl group, a substituted alkylcarbonyl group, an arylcarbonyl group, a substituted arylcarbonyl group, a cyano group, a nitro group. Alternatively, it represents a halogen atom. k represents an integer of 1 to 5. Z ² represents an alkylcarbonyl group, a substituted alkylcarbonyl group, an arylcarbonyl group or a substituted arylcarbonyl group. 4. The counter anion X ^1- in the diazonium salt represented by the general formulas (III) to (V) is an l-valent sulfonate anion represented by the general formula (VI). 3) The positive photosensitive composition as described above. W- (SO ₃ ^-) in _l (VI) formula, W is a l-valent aryl connecting group or an alkyl linking group, may be substituted, -NH-CO-,
It may contain a divalent linking group such as -O-, -S- and -CO-O-. L is an integer of 2 to 10.