JP3105712B2 - Positive 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 a positive photosensitive composition, and more particularly to a planographic printing plate, a proof print for multicolor printing, a drawing for an overhead projector, and a fine resist pattern for an integrated circuit of a semiconductor device. The present invention relates to a positive-working photosensitive composition useful for forming the composition.

[0002]

2. Description of the Related Art Conventionally, in applications such as lithographic printing plates, various proposals have been made as so-called positive-acting photosensitive compositions which are solubilized by actinic rays. For example, (a) natural polymers such as egg white or glue; A photosensitive composition containing polyvinyl alcohol and a dichromate, a photosensitive composition containing (ii) an orthoquinonediazide compound,
(C) A photosensitive composition containing a diazonium salt is known. However, these photosensitive compositions have advantages and disadvantages and have not been sufficiently satisfactory. That is,
The photosensitive composition (a) is inexpensive and therefore advantageous from the economical point of view, but has poor storage stability and has problems in disposal and other handling due to the use of dichromate as a raw material. . The orthoquinonediazide compound (b) is excellent as a positive image forming material and has been widely used in lithographic printing plates.

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.
No. 3,046,115, No. 3,046,118, No. 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 specifications of 647,443. These orthoquinonediazide compounds are based on the fact that they are decomposed by irradiation with actinic rays to produce a 5-membered carboxylic acid and become alkali-soluble, but none of them show sufficient sensitivity. This is because it is difficult to achieve photochemical sensitization with some orthoquinonediazide compounds, and the quantum yield thereof does not essentially exceed 1. In addition, since the photosensitive wavelength is fixed, the suitability for the light source is poor, it is difficult to provide white light safety, and since the absorption in the deep UV region is large, the aim was to improve the resolution of the photoresist by using low wavelength light. Not suitable for use. In order to overcome these drawbacks, for example, JP-B-48-12242, JP-A-52-40125 and the like have tried various methods such as adding various compounds to the photosensitive composition. However, all of them have been insufficiently improved.

As the positive composition containing the diazonium salt (c), for example, US Pat. No. 3,219,44
No. 7, No. 3,211,553, JP-B-39-7663, JP-A-52-2519, and the like, but low sensitivity and low stability of image formation. Due to the lack, it could not be put to practical use. Recently, several proposals have been made for the purpose of developing new materials that can replace these positive photosensitive compounds. One example is a polymer compound having an orthonitrocarbinol ester group described in Japanese Patent Publication No. 56-2696. However, even in this case, sufficient sensitivity was not obtained.

On the other hand, as a pattern forming method for manufacturing electronic components such as a semiconductor element, a magnetic bubble memory, and an integrated circuit, a method using a photoresist is generally used. Photoresists are classified into a negative type in which a portion to be irradiated becomes insoluble in a developing solution by light irradiation, and a positive type in which a portion to be irradiated becomes solubilized by light irradiation. The negative type has higher sensitivity than the positive type,
Until recently, photoresists occupied the mainstream because of their excellent adhesion to substrates and chemical resistance required for wet etching. However, with the increase in 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. In recent years, high resolution and high dry etching resistance have been demanded, and at present, positive photoresists are mainly used. In particular, among the positive photoresists, because of their excellent sensitivity, resolution, and dry etching resistance, for example, JC Strieta, Kodak Microelectronics Seminar Proceedings, No. 11
6 (1976) (JC Strieter, Kodak Microel
ectoronics Seminar Proceedings, 116 (197
6)) and the like, an alkali-developable positive photoresist based on an alkali-soluble novolak resin is currently widely used.

However, in recent years, multifunctional electronic devices have been
With the increase in sensitivity, there is a strong demand for finer patterns to achieve higher density and higher integration. In response to these requirements, conventional orthoquinonediazide photosensitive compounds
A photosensitive composition combining a polysiloxane having alkali solubility or a silicone polymer such as polysilmethylene, for example, JP-A-61-256347 and JP-A-61-256347.
Nos. 144639, 62-159141, 62-1
91849, 62-220949, 62-22
No. 9136, No. 63-90534, No. 63-9165
No. 4, No. 4, No. 4 and the like.
Photosensitive compositions have been proposed which combine an effective amount of an onium salt with a carbonate block copolymer. However, these silicon polymers are extremely difficult to produce due to the addition of alkali-soluble functions and the stability with time is not sufficient. The inventors of the present invention have proposed a positive photosensitive composition which solves the above-mentioned problems of each of these compositions, and furthermore, discloses a novel positive photosensitive composition having a high developing speed as disclosed in Japanese Patent Application No. 3-25859. Proposed a combination of a specific diazonium salt and an alkali-soluble polymer. However, in recent years, there has been a demand for a photosensitive composition having a higher developing speed due to a demand for improvement in working efficiency in recent years.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel positive photosensitive composition having a further improved developing speed.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that a positive photosensitive composition containing an alkali-soluble polymer and an aromatic diazonium salt having a specific structure is provided. As a result, a clear positive image can be obtained at a high developing speed, that is, in a short time. That is, the present invention relates to a positive photosensitive composition containing a diazonium salt represented by the following general formula (I) and an alkali-soluble polymer.

[0009]

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(Wherein, Ar represents a divalent aromatic group which may have a substituent; Y ₁ represents a divalent linking group; X ₁ ⁻ represents an anion; n is 0 or 1; Hereinafter, the positive photosensitive composition of the present invention will be described in detail. First, the aromatic diazonium salt represented by the general formula (I) will be described. Ar represents a divalent aromatic group which may have a substituent. For example, a phenyl ring, a naphthyl ring, an anthranyl ring and the like can be mentioned. Y ₁ represents a divalent linking group. Y ₁ represents, for example, a divalent linking group formed by combining H, C, N, O, S, or P;
-, - S -, - NA -, - NACO -, - CO 2 -, -
_{CO -, - SO 3 -,} - PO 3 -, - (CH 2) n 1 -, phenylene, naphthylene, but more can be mentioned a combination thereof, but is not limited thereto. Here, A represents an alkyl group, an aryl group, or a hydrogen atom. N1 represents an integer of ₁ to 15. X ₁ ^- represents an anion, for example, a sulfonate anion, an oxygenate anion of phosphorus or a carboxylate anion.

In the present invention, the aromatic diazonium salt represented by the above general formula (I) is combined with an alkali-soluble polymer compound. Examples of the alkali-soluble polymer compound used in the present invention include a phenolic hydroxy group, a carboxylic acid group, a sulfonic acid group, an imide group, a sulfonamide group, an N-sulfonylamido group, an N-sulfonylurethane group, and an active methylene group. And a polymer compound having an acidic group having a pKa of 11 or less. In this system, a clear positive image can be obtained with a short development time. The reason is not necessarily clear, but is presumed as follows. That is, in the unexposed area, the specific aromatic diazonium salt represented by the general formula (I) and the alkali-soluble polymer have a strong interaction, and the solubility of the photosensitive layer in the alkali developing solution is low. In this case, the light irradiation causes the diazonium salt represented by the general formula (I) to be decomposed, and the anion of the diazonium salt is changed to an organic acid. This may be because solubility in an alkali developing solution is greatly increased. As the diazonium salt in the present invention, those represented by the following general formula (II) are preferable.

[0012]

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In the general formula (II), R ₁ , R ₂ , R ₃
And R ₄ are a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an alkoxy group, a substituted alkoxy group,

[0014]

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Or -Y ₂ -R _8, which may be the same or different, and may combine with each other to form a ring; The alkyl group as R ₁ , R ₂ , R ₃ and R ₄ is
Any of linear, branched and cyclic ones having 1 to 18 carbon atoms may be used. Examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group and the like. The substituted alkyl group as R ₁ , R ₂ , R ₃ and R ₄ is preferably an alkyl group having 1 to 10 carbon atoms, for example, a halogen atom such as a chlorine atom, for example, an alkoxy group having 1 to 5 carbon atoms such as a methoxy group. It is a group substituted with a group, a phenoxy group, a benzylthio group or the like, and a group having 1 to 18 carbon atoms in the total substituted alkyl group is preferable. Specifically, a 4-chlorobutyl group, a 4-ethoxybutyl group, a 2-butoxyethyl group, a 4-phenoxybutyl group, a 2-benzylthioethyl group and the like are included. R
The aryl group as ₁ , R ₂ , R ₃ and R ₄ is preferably a monocyclic or bicyclic aryl group, for example, a phenyl group,
α-naphthyl group, β-naphthyl group and the like are included. R
Substituted aryl groups as ₁ , R ₂ , R ₃ and R ₄ include the above aryl groups, for example, an alkyl group having 1 to 8 carbon atoms such as a methyl group and an ethyl group, for example, a methoxy group, an ethoxy group and the like. And those substituted with a halogen atom such as a chlorine atom. Specific examples include a methylphenyl group, a t-butylphenyl group, a methoxyphenyl group, a chlorophenyl group, a methoxyphenyl group, and a methoxynaphthyl group. R
Examples of the alkoxy group or substituted alkoxy group as ₁ , R ₂ , R ₃ and R ₄ include those in which the above alkyl group or substituted alkyl group is linked to oxygen.

In the general formula (II), R ₅ and R ₆ are
An alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an arylcarbonyl group or a substituted arylcarbonyl group, which may be the same or different, and which are bonded to each other to form a piperidino group, a pyrrolidino group, a tetrahydroisoquinolino Group, a tetrahydroquinolino group, an indolino group, a morpholino group or a thiomorpholino group. The alkyl group, substituted alkyl group, aryl group and substituted aryl group as R ₅ , R ₆ and R ₈ are the same as those described above for R 5
The same alkyl group, substituted alkyl group, aryl group and substituted aryl group of ₁ , R ₂ , R ₃ and R ₄ can be used. As the arylcarbonyl group or substituted arylcarbonyl group as R ₅ and R ₆ , those in which the above aryl group or substituted aryl group is linked to a carbonyl group can be used. R ₅ and R ₆ are bonded to each other to form a morpholino group, a thiomorpholino group, a piperidino group,
A heterocyclic group such as a pyrrolidino group, a tetrahydroisoquinolino group, a tetrahydroquinolino group, or an indolino group may be formed.

R ₇ represents an alkylcarbonyl group, a substituted alkylcarbonyl group, an arylcarbonyl group or a substituted arylcarbonyl group. As the alkylcarbonyl group, substituted alkylcarbonyl group, arylcarbonyl group or substituted arylcarbonyl group as R ₇ , those in which the above alkyl group, substituted alkyl group, aryl group or substituted aryl group is linked to a carbonyl group can be used. .
R ₈ represents an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group. X ₂ ^- represents a sulfonate anion or a carboxylate anion. Y ₂ is H, C, N,
It represents a divalent linking group in which one or more of O, S or P can be combined, and those in the same range as Y ₁ can be used. Y ₁ and n have the same meaning as described above. The diazonium salt represented by the general formula (II) is rapidly decomposed by light irradiation, the dissolution inhibiting effect is released, and the diazonium salt is converted into an organic acid by itself, thereby forming a clear positive image with a short development time. . Particularly effective diazonium salts include:
For example, diazonium salts represented by the following general formulas (III), (IV) and (V) can be mentioned.

[0018]

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(Wherein Z ₁ , Z ₂ and Z ₃ represent 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, Represents an arylcarbonyl group, a substituted arylcarbonyl group, a cyano group, a nitro group or a halogen atom, and may be the same or different, and Y ₃ is a combination of at least one of H, C, N, O, S or P R ₁ represents a divalent linking group formed by
R ₅ , R ₆ , R ₇ , Y ₁ , X ₂ ^- and n have the same meaning as described above. )

The alkyl group, substituted alkyl group, aryl group, substituted aryl group, alkoxy group or substituted alkoxy group represented by Z ₁ , Z ₂ and Z _{3 in the} general formula (IV) is represented by R ₁ ,
Those having the same range as R ₂ , R ₃ or R ₄ can be used. The alkylcarbonyl group, substituted alkylcarbonyl group, arylcarbonyl group or substituted arylcarbonyl group represented by Z ₁ , Z ₂ and Z _{3 in} the general formula (IV) is the above-mentioned alkyl group, substituted alkyl group, aryl group or substituted aryl group Is linked to a carbonyl group. Further, the substituent may be modified. Y ₃
It may be used having the same range as Y _1. Examples of the aromatic diazonium salt represented by the general formula (I) are listed below, but the scope of the present invention is not limited thereto.

[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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Next, the method for synthesizing the aromatic diazonium salt represented by the general formula (I) will be described with reference to the case where n = 0 in the general formula (I) and n
Will be described separately for the case where is 1. When n = 0, ie,
When X ₁ ^- is directly bonded to Ar, the desired product can be obtained through an acid hydrolysis and diazotization reaction using an acedamide (a) having an anion X ₁ ^- as a starting material.
The synthesis route is shown below.

[0029]

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[0030] in the formula, Ar and X ₁ ^- are as defined in formula (I). When n is 1, for example, the following method (i) -a or (i) -b can be used. Both (i) -a and (i) -b are methods using a nitro compound (b-1) having a halogen group as a starting material. (i) -a (b-1) is reacted with an aromatic compound HQ-Ar ₁ -H having a nucleophilic reactive group (HQ), and sulfonation or chlorosulfonation, neutralization, reduction, and diazotization are further performed. The desired product is obtained by performing. The synthesis route in this case is shown in the following equation.

[0031]

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In the formula, Ar is as described above. Ar ₁ is synonymous with Ar. HQ represents HO, HS or HNR ^c , and R ^c represents an alkyl group or an aryl group. (i) nitro compound having -b halogen group (b-1) nucleophilic reactivity (HQ) and the anion X ₁ as a starting material ^- compound having two groups of the (b-x) is reacted, followed by , Reduction and diazotization to obtain the desired product. The synthetic route is shown in the formula.

[0033]

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In the formula, Ar, X ₁ ^- and HQ are as defined above. ^Ra represents an alkyl linking group or an aryl linking group. (ii) Nitro compound having a nucleophilic reactive group (HQ) (b-2)
Is used as a starting material to react with various acid anhydrides (bY), followed by reduction and diazotization to obtain the desired product.
The synthesis route in this case is shown in the following equation.

[0035]

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In the formula, Ar, X ₁ ^- and HQ are as defined above. R ^b has the same meaning as R ^a . The method (i) -a
Is described in Synthesis Example 1 described below, and the method (ii) is described in Synthesis Example 2 described below, but the synthesis method is not limited to these synthesis methods. The aromatic diazonium salt represented by the general formula (I) can be used alone, but may be used as a mixture of several kinds. The amount of the compound represented by the general formula (I) in the photosensitive composition is preferably 1 to 50 based on the total solid content of the photosensitive composition.
% By weight, more preferably 5 to 30% by weight.

The positive photosensitive composition of the present invention further comprises:
If necessary, another positive-working photosensitive compound may be added. Such a positive photosensitive composition is disclosed in JP-B-43-28403 and JP-A-64-7604.
7, JP-A-2-96661 and JP-A-4-226458.
O-naphthoquinonediazide compounds described in JP-A Nos. 3,188,210 and the like;
For example, a polymer compound having an orthonitrocarbinol ester group described in JP-A-2696 can be mentioned. Furthermore, a combination system of a compound that generates an acid by photolysis and a compound having a —CO—C group or a —CO—Si group dissociated by an acid can be added. Examples of such a system include a combination of a compound capable of generating an acid by photolysis with an acetal or an O, N-acetal compound (Japanese Patent Application Laid-Open No. 48-89003), a combination of an orthoester or an amide acetal compound (Japanese Patent Application Laid-Open (JP-A) No. 48-89003). Showa 51-120
714), a combination with a polymer having an acetal or ketal group in the main chain (JP-A-53-133429),
Combination with enol ether compound (JP-A-55-12
No. 995), a combination with an N-acylimino carbon compound (JP-A-55-126236), a combination with a polymer having an orthoester group in the main chain (JP-A-56-173).
No. 45), a combination with a silyl ester compound (JP-A-6
No. 0-10247) and a combination with a silyl ether compound (JP-A-60-37549, JP-A-60-1214).
No. 46).

As the alkali-soluble polymer compound suitable for the positive photosensitive composition of the present invention, a novolak obtained by subjecting 0.6 to 2.0 moles of an aldehyde to addition condensation with 1 mole of a phenol in the presence of an acidic catalyst is used. Type phenol resin and resol type phenol resin. Specifically, a phenol-formaldehyde resin, an o-cresol-formaldehyde resin, an m-cresol-formaldehyde resin, a p-cresol-formaldehyde resin, an m- / p-mixed cresol-formaldehyde resin,
Phenol-cresol (m-, p-, or m- / p-
Cresol formaldehyde resin such as mixed formaldehyde resin, phenol-modified xylene resin, xylenol-formaldehyde resin or a co-condensate thereof. In addition, p-
Formaldehyde condensation resins such as chlorophenol, ethylphenol, resorcinol, and naphthol are also included. Also, a polymer having a phenolic hydroxy group-containing monomer such as N- (4-hydroxyphenyl) methacrylamide as a copolymer component, p-hydroxystyrene, o-hydroxystyrene, m-isopropenylphenol, p-isopropenylphenol Homogenized or copolymerized polymers, and partially etherified or partially esterified polymers of these polymers can also be used.

Further, a polymer compound containing a carboxy group-containing monomer such as acrylic acid or methacrylic acid as a copolymer component, a carboxy group-containing polyvinyl acetal resin described in JP-A-61-267042, and JP-A-63-124.
The carboxyl group-containing polyurethane resin described in Japanese Patent No. 047 is also preferably used. Furthermore, 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-63-127239 can also be used. . These alkali-soluble polymer compounds have a weight average molecular weight of 500 to
Those having a number average molecular weight of 200 to 60,000 and a molecular weight of 200 to 60,000 are preferred. These alkali-soluble polymer compounds can be used alone, but may be used as a mixture of several kinds. The addition amount of the alkali-soluble polymer compound in the positive photosensitive composition of the present invention is generally in the range of 5 to 99% by weight, preferably 10 to 90% by weight, based on the total solid content of the photosensitive composition. Further, a polyvinyl butyral resin, a polyurethane resin, a polyamide resin, and an epoxy resin may be added to the photosensitive composition as needed.

A printing-out agent for obtaining a visible image immediately after exposure or a dye or pigment as an image coloring agent can be added to the positive photosensitive composition of the present invention. Representative examples of the printing-out agent include a combination of a compound that releases an acid upon exposure (photoacid releasing agent) and an organic dye that can form a salt. Specifically, JP-A-50-3620
Nos. 9 and 53-8128.
A combination of a naphthoquinonediazide-4-sulfonic acid halogenide and a salt-forming organic dye;
Nos. 54-74728, 60-3626, 6
1-1143748, 61-151644 and 6
Examples thereof include a combination of a trihalomethyl compound and a salt-forming organic dye described in each publication of JP-A-3-58440. Such trihalomethyl compounds include oxazole-based compounds and triazine-based compounds, both of which have excellent temporal stability and give clear print-out images.

As the colorant for the image, other dyes can be used in addition to the above-mentioned salt-forming organic dyes. Suitable dyes, including salt-forming organic dyes, include oil-soluble dyes and basic dyes. Specifically, Oil Yellow # 101, Oil Yellow # 103, Oil Pink # 312, Oil Green BG, Oil Blue BOS,
Oil Blue # 603, Oil Black BY, Oil Black BS, Oil Black T-505 (all manufactured by Orient Chemical Industry Co., Ltd.), Victoria Pure Blue, Crystal Violet (CI42555), Methyl Violet (CI42535), Ethyl Violet, Rhodamine B (CI145170B), malachite green (CI42000), methylene blue (CI5201)
5) and the like. Also, Japanese Unexamined Patent Publication No. Sho 62-2
The dyes described in JP 93247 A are particularly preferred. Further, as described in U.S. Pat. No. 4,123,279, a condensate of phenol having an alkyl group having 3 to 8 carbon atoms as a substituent and formaldehyde, such as t-butylphenol formaldehyde resin and octylphenol formaldehyde resin, is used. When used in combination, the oil sensitivity of the image can be improved. Cyclic acid anhydrides, phenols, and organic acids can be added to the positive photosensitive composition of the present invention in order to increase sensitivity.

As the cyclic acid anhydride, US Pat. No. 4,115,12
No. 8, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6-
Endoxy-tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, α-phenylmaleic anhydride, succinic anhydride, pyromellitic anhydride and the like can be used. Examples of phenols include bisphenol A, p-nitrophenol, p-ethoxyphenol, 2,4,4'-trihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 4-hydroxybenzophenone, 4,4 ', 4 ″ −
Trihydroxy-triphenylmethane, 4,4 ',
3 ", 4" -tetrahydroxy-3,5,3 ', 5'-
Tetramethyltriphenylmethane and the like can be mentioned. Further, examples of the organic acids include sulfonic acids, sulfinic acids, alkyl sulfates, phosphonic acids, phosphoric esters, and carboxylic acids described in JP-A-60-88942 and JP-A-2-96755. Is mentioned. The proportion of the above-mentioned cyclic acid anhydrides, phenols and organic acids in the photosensitive composition is preferably 0.05 to 15% by weight, more preferably 0.1 to 5% by weight.

The positive photosensitive composition of the present invention contains a non-photosensitive composition such as that described in JP-A-62-251740 in order to increase the stability of processing under development conditions (so-called development latitude). An ionic surfactant, and an amphoteric surfactant as described in JP-A-59-121044 and JP-A-4-13149 can be added. Specific examples of nonionic surfactants include
Sorbitan tristearate, sorbitan monopalmitate, sorbitan triolate, stearic acid monoglyceride, polyoxyethylene sorbitan monooleate,
And polyoxyethylene nonyl phenyl ether. Specific examples of the amphoteric surfactant include alkyldi (aminoethyl) glycine, alkylpolyaminoethylglycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine and N
-Tetradecyl-N, N-betaine type (for example, trade name Amogen K, manufactured by Daiichi Kogyo Co., Ltd.) and alkylimidazoline type (for example, trade name Levon 15, Sanyo Chemical Co., Ltd.)
Manufactured).

The proportion of the nonionic surfactant and amphoteric surfactant in the photosensitive composition is preferably 0.05 to 15% by weight, more preferably 0.1 to 5% by weight.
In the positive photosensitive composition of the present invention, a surfactant for improving coating surface quality, for example, JP-A-62-17095
No. 0 can be added. The preferable addition amount is 0.001 to 1.0% by weight of the total photosensitive composition, and more preferably 0.001 to 1.0% by weight.
005 to 0.5% by weight. Further, a plasticizer for imparting flexibility and abrasion resistance to the coating film can be added.
Further, in the positive photosensitive composition of the present invention, in order to extend the stability over time, for example, phosphoric acid, phosphorous acid, citric acid, oxalic acid, dipicolinic acid, benzenesulfonic acid, alkylbenzenesulfonic acid, naphthalene sulfone It is preferable to add an acid such as an acid, dialkylnaphthalenesulfonic acid, sulfosalicylic acid, 4-methoxy-2-hydroxybenzophenone-5-sulfonic acid, and tartaric acid.

The positive photosensitive composition of the present invention is dissolved in a solvent capable of dissolving each of the above components, and applied on a support.
As the solvent used herein, for example, 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, dimethylsulfoxide, sulfolane, γ-butyllactone, toluene, 4-ethoxy-2-butanone, 4
Keto ethers such as -methoxy-4-methyl-2-pentanone; ethers such as dioxane and ethylene glycol dimethyl ether; 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 in the form of a coating, the amount of coating varies depending on the application. For example, a photosensitive lithographic printing plate generally has a solid content of 0.5 to 3.0 g / m ² , and a photoresist generally has a solid content of 0.5 to 3.0 g / m ² . Preferably, the solid content is 0.1 to 3.0 g / m ² . As the coating amount decreases, the photosensitivity increases, but the film characteristics of the photosensitive layer deteriorate. On the surface of the photosensitive layer provided as described above, a mat layer may be provided in order to shorten the time for evacuation during the close contact exposure using a vacuum printing frame and to prevent printing blur. More specifically,
No. 0-125805, Japanese Patent Publication No. 57-6582, 61
A method of providing a mat layer as described in each of JP-A-28986 and a method of thermally fusing a solid powder as described in JP-B-62-62337.

When a lithographic printing plate is produced using the positive photosensitive composition of the present invention, the support may be, for example,
Paper, paper laminated with plastics (eg, polyethylene, polypropylene, polystyrene, etc.), eg, 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, metal-laminated or evaporated paper, or plastic film included. Among these supports, the aluminum plate is particularly preferable because it is extremely dimensionally stable and inexpensive. Furthermore, Japanese Patent Publication No. 48-18
A composite sheet in which an aluminum sheet is bonded on a polyethylene terephthalate film as described in JP-A-327-327 is also preferable. The aluminum plate is selected from a pure aluminum plate, an alloy plate containing aluminum as a main component and containing a trace amount of a different element, or a plastic film on which aluminum is laminated or vapor-deposited. The foreign elements contained in the aluminum alloy include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth,
Nickel, titanium and the like. The content of the foreign element in the alloy is 10% by weight or less. Aluminum suitable for the present invention is pure aluminum. However, completely pure aluminum is difficult to produce due to refining technology, and therefore may contain a slightly different element. As described above, the composition of the aluminum plate is not specified, and those of conventionally known and used materials, for example, JIS A1050, JIS A1100
, JIS A 3103, JIS A 3005, etc. can be used as appropriate. The thickness of the aluminum plate is about 0.1
It is about mm to 0.6 mm.

As a method for treating the surface of the aluminum plate,
Mechanical method such as brush graining, ball graining, liquid honing, buff graining, etc., and HF or AlCl ₃ to roughen the surface of aluminum plate by pouring slurry of abrasive particles by wire brush graining Chemical graining using HCl as an etchant, electrolytic graining using nitric acid or hydrochloric acid as an electrolytic solution, composite graining performed by combining these surface roughening methods, and electrochemical graining methods include hydrochloric acid. Alternatively, there is a method in which alternating current or direct current is performed in a nitric acid electrolyte. Further, as disclosed in JP-A-54-63902, a method in which both are combined can also be used. After graining the surface in this manner, if necessary, perform an etching treatment with an acid or an alkali, and then apply an anode in a sulfuric acid, phosphoric acid, boric acid, chromic acid, sulfamic acid or a mixed acid thereof with a DC or AC power supply. It is preferable to perform oxidation and provide a strong passivation film on the aluminum surface.

The aluminum surface is hydrophilized by such a passivation film itself. Further, if necessary, US Pat.
No. 714,066 and U.S. Pat. No. 3,181,461, silicate treatment (sodium silicate, potassium silicate), U.S. Pat. No. 2,946,638, potassium fluoride zirconate treatment, U.S. Pat. 3,201,
No. 247, phosphomolybdate treatment, British Patent 1,108,559, alkyl titanate treatment, German Patent 1,091,443, polyacrylic acid treatment, Germany Patent No. 1,13
No. 4,093, British Patent No. 1,230,447, JP-B-44-6.
No. 409, phosphinic acid treatment described in U.S. Pat. No. 3,307,951, JP-A-58-16893 and JP-A-58-1629.
Japanese Unexamined Patent Publication No. Sho.
Those which have been subjected to a hydrophilization treatment with an undercoat of a water-soluble polymer having a sulfonic acid group described in JP-A-9-101651 are particularly preferable. As another hydrophilic treatment method, silicate electrodeposition described in US Pat. No. 3,658,662 can be exemplified.

It is preferable that the aluminum surface is subjected to graining treatment and anodic oxidation treatment, and then subjected to 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. A hydrophilic undercoat layer may be further provided on the aluminum plate that has been subjected to the above treatment, if necessary, and the positive photosensitive composition of the present invention can be applied thereon. Preferred compounds used for the hydrophilic undercoat layer include compounds having an amino group and a carboxyl group or a sulfo group disclosed in JP-A-60-149949, and disclosed in JP-A-60-232998. Compounds having an amino group and a hydroxyl group, phosphates disclosed in JP-A-62-19494, JP-A-59-1016
Japanese Patent Application Laid-Open No. H4-51, containing a polymer having a sulfo group-containing monomer as a repeating unit disclosed in JP-A-51
Compounds described in JP-A-282637 are exemplified.

On the back surface of the aluminum support, in order to suppress the elution of the anodic oxide film of aluminum during development, and to prevent the photosensitive layer from being damaged when a large number of photosensitive lithographic printing plates (PS plates) are stacked. To prevent this, a back coat layer made of a polymer compound may be provided. As a material of the back coat layer, a polymer compound insoluble in an alkaline developer as described in JP-A-5-2271 is used. In particular, as a main component of the back coat layer, a saturated copolymerized polyester resin having a glass transition point of 20 ° C. or higher,
At least one resin selected from the group consisting of a phenoxy resin, a polyvinyl acetal resin and a vinylidene chloride copolymer resin is used.

When the positive photosensitive composition of the present invention is used as a photoresist, substrates of various materials such as a copper plate or a copper-plated plate, a silicon plate, a stainless plate, and a glass plate may be used as a support. it can. The positive photosensitive composition of the present invention is coated on the above-mentioned support by a known coating technique. Examples of the 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 layer of the positive photosensitive composition applied as described above has 4
It is dried at 0 to 150 ° C. for 10 seconds to 10 minutes using a hot air dryer, an infrared dryer, or the like. The PS plate, the photoresist, and the like including the photosensitive layer formed from the positive photosensitive composition of the present invention are usually subjected to image exposure and development processing. As the light source of the actinic ray used for image exposure, for example, a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp,
There are carbon arc lamps and the like. Examples of the radiation include an electron beam, an X-ray, an ion beam, and far ultraviolet rays. As a light source for the photoresist, g-line, i-line, and Deep-UV light are preferably used. Scanning exposure using a high-density energy beam (laser beam or electron beam) can also be used in the present invention. Such laser beams include helium-neon laser, argon laser,
Krypton ion laser, helium, cadmium laser, KrF excimer laser, and the like can be given.

The developing solution used for developing the positive photosensitive composition of the present invention includes sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate and dibasic sodium phosphate. And inorganic alkali agents such as tribasic ammonium phosphate, dibasic ammonium phosphate, sodium metasilicate, sodium bicarbonate, sodium carbonate, aqueous ammonia and the like. Also, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, An aqueous solution of an organic alkali agent such as ethyleneimine, ethylenediamine, pyridine or tetraalkylammonium halide is suitable, and the concentration thereof is 0.1 to 10% by weight, preferably 0.5 to 5% by weight. Is added. Among these, a developer containing an alkali silicate such as potassium silicate, lithium silicate, sodium silicate or the like is preferable since stains during printing are less likely to occur, and the composition of the alkali silicate is preferably in a molar ratio of (SiO ₂ ).
/ (M) = 0.5~2.5 (here (SiO _2), (M), respectively indicate the molar concentration and the molar concentration of the total alkali metal SiO _2.) It is, and the SiO ₂ 0. A developer containing 8 to 8% by weight is preferably used. Also preferred are sodium carbonate, monoethanolamine and triethanolamine.

In the above developer, for example, water-soluble sulfites such as sodium sulfite, potassium sulfite and magnesium sulfite, resorcin, methylresorcin, hydroquinone, thiosalicylic acid and the like can be added. The content of these compounds in the developer is preferably 0.002 to 4% by weight, and more preferably 0.01 to 1% by weight. Also, in the above developer, JP-A-50-513 is disclosed.
No. 24, anionic surfactants as described in JP-A-59-84241, and amphoteric surfactants,
JP-A-59-75255, JP-A-60-111246
And at least one of the nonionic surfactants described in JP-A No. 60-213943 and the like.
By incorporating seeds or as disclosed in JP-A-55-9594.
No. 6, JP-A-56-142528, the incorporation of a polymer electrolyte enhances wettability to a photosensitive composition and enhances development stability (development latitude). And it is preferably used. The amount of the surfactant added is 0.001-2% by weight.
Is particularly preferable, and 0.003 to 0.5% by weight is particularly preferable.

Further, the developing solution may contain a small amount of an organic solvent such as an alcohol, a chelating agent described in JP-A-58-190952, and a metal such as described in JP-B-1-30139. An antifoaming agent such as a salt or an organic silane compound can be added. The PS plate using the positive photosensitive composition of the present invention is subjected to plate-making processing by the methods described in JP-A-54-8002, JP-A-55-115045, and JP-A-59-58431. Needless to say, this may be done. That is, after the development processing, it may be washed with water and then desensitized, or may be directly desensitized, or may be subjected to an acid-containing aqueous solution and then desensitized. Further, in the development process of this kind of PS plate, the alkaline aqueous solution is consumed depending on the processing amount to reduce the alkali concentration, or the alkaline developer decreases by the air due to long-time operation of the automatic developing solution, so that the processing capacity is reduced. However, at that time, the processing capacity may be restored by using a replenisher as described in JP-A-54-62004. In this case, it is preferable to replenish by the method described in U.S. Pat. No. 4,882,246. Further, the plate making process as described above is disclosed in
It is preferably carried out by an automatic developing machine as described in JP-A Nos. 7054 and 2-32357.

Further, the PS plate is image-exposed, developed, and
In the case where unnecessary image portions are erased after rinsing or rinsing, a so-called non-polluting erasing liquid (excluding hydrofluoric acid, which is a powerful chemical) as described in Japanese Patent Publication No. 13293/1990 is used. be able to. Furthermore, desensitized gums to be applied as required in the final step of the plate making process include JP-B-62-16834, JP-B-62-25118, and JP-B-62-25118.
3-52600, JP-A-62-7595 and JP-A-62-7595
Those described in JP-A-11693 and JP-A-62-83194 are preferable. Further, the photosensitive lithographic printing plate using the photosensitive composition of the present invention is suitable for a burning treatment when high printing durability is desired. When the photosensitive lithographic printing plate is image-exposed, developed, rinsed or rinsed, erased with a hydrofluoric acid-free erasing solution, washed with water, and then burned, before burning, Japanese Patent Publication No. 61-2518
No. 55-28062, JP-A-62-31859.
And JP-A-61-159655.

[0057]

The present invention will be further described below with reference to Synthesis Examples and Examples.
Will be described in detail.The aromatic diazonium salt (compound 4 and
Synthesis of 6) [Synthesis Example 1 (Synthesis of Compound 4)] 2,4-dichloronit
Robenzene (192 g) and pt-octylphenol
(206 g) of N, N-dimethylformamide (DMA
c) (200g) solution with K _TwoCO_Three(150 g) was added.
After heating and stirring at 150 ° C for 5 hours, water (500 g) was added.
And extracted with ethyl acetate (total of 2000 g)._Four
After drying with, the solvent was removed under reduced pressure. The obtained oily substance is CH
_TwoCl_Two(1000 g), and cooled to 0 ° C.
Losulfonic acid (130 g) was added dropwise over 30 minutes. Room
After returning to warm and stirring for 3 hours, the CH_TwoCl_TwoSolution with water
(1000 g) twice, and then NaOH water (NaOH 80 g / water)
(1000 g). MgSO_FourAfter drying with CH
_TwoCl_TwoWas removed under reduced pressure to give a yellow clay. This
This is reslurried in hexane / ethyl acetate = 2/1
And 2- (2-nitro-5-chlorophenoxy) -5-
White powder of sodium t-octylbenzenesulfonate
(388 g, yield 90%) was obtained.

Further, this white powder (388 g) and p-butyl
Lomothiophenol (170g) and K_TwoCO_Three(130
g) into DMAc (200g), 10 hours at 150 ° C
The mixture was heated and stirred. After stirring, put into water (1000 g) and cool
After rejection, the mixture was filtered to obtain white crude crystals.
Dissolve the white crystals in isopropanol (1000 g).
Understand this, Fe (100g), NH_FourCl (20 g) and water
(100 g) and stirred at 90 ° C. for 5 hours.
Fe was removed by filtration. To the filtrate was added concentrated HCl (70
g) and add NaNO while cooling to 0 ° C._TwoWater (NaNO_Two69
g / water 1000 g), and after 30 minutes, yellow
A precipitate formed. This is filtered off to give the desired compound 4
(310 g, 60% overall yield). Compound 4 is
Had a gender value.Physical property values : D.p. (208.0 ° C.), λmax 360.6, εat
λmax 2.5 × 10^Four〔cm ^-1M^-1]

[Synthesis Example 2 (Synthesis of Compound 6)] A solution of 5-chloro-2-nitroaniline (173 g) and n-octyl bromide (200 g) in DMAc (200 g) was added to a solution of K ₂ CO 3.
₃ (150 g) was added. After heating and stirring at 150 ° C. for 6 hours, morpholine (100 g) was further added.
For 5 hours. When the reaction mixture was poured into water (1000 g), yellow crystals were obtained. This yellow crystal and o-
Sulfobenzoic anhydride (200 g) was added to MeCN (500 g).
And triethylamine (110 g) was added dropwise at room temperature. After stirring for 10 hours, the solvent was removed under reduced pressure to obtain an oily substance. Next, the oily substance was added to isopropanol (100
0 g), and Fe (100 g) and NH ₄ Cl (20 g).
g) and water (100 g) were added, the mixture was stirred at 90 ° C. for 5 hours, and Fe was removed by filtration through Celite. The filtrate is concentrated
HCl and (80 g) was added, while cooling to 0 ° C., the dropwise addition of NaNO ₂ water (NaNO ₂ 75 g / water 1000 g), After 15 min, by generating a yellow precipitate is filtered off, the compound is an object 6 (374 g, 75% overall yield). Compound 6 had the following physical data. Physical properties : dp (130 ° C), λmax 383.0, εatλ
max 3.0 × 10 ⁴ [cm ⁻¹ M ⁻¹ ] Other compounds can be synthesized by the same method.

Examples 1 to 8 and Comparative Examples 1 to 3 A JIS A 1050 aluminum plate having a thickness of 0.24 mm was placed on a surface of aluminum with a suspension of pumistone and water having an average particle size of about 21 μm. After the brush graining treatment with the rotating nylon brush shown in the figure, washing was performed well with water.
After being immersed in 10% sodium hydroxide at 50 ° C. for 10 seconds for etching, washed with running water and then neutralized with 20% nitric acid,
Washed with water. This was converted to 160 coulombs / cm 2 in a 1% aqueous nitric acid solution using a sinusoidal alternating current under a voltage of 12.7 V.
Electrolytic surface-roughening treatment was performed with an anode charge of dm ² . When the surface roughness was measured, it was 0.6 μ (Ra display).
Subsequently, it is immersed in a 30% sulfuric acid aqueous solution,
After desmutting for 20 minutes, the substrate was anodized in a 20% aqueous sulfuric acid solution at a current density of 2 A / dm ^{2 so} that the thickness of the oxide film was 2.7 g / m ² , thereby preparing a substrate. An undercoat liquid (A) having the following composition is applied to the surface of the substrate thus treated,
It was dried at 80 ° C. for 30 seconds. The coating amount after drying is 30 mg /
It was m ^2.

<Undercoat liquid A>-0.1 g of aminoethylphosphonic acid-0.15 g of phenylphosphonic acid-0.1 g of β-alanine-40 g of methanol-60 g of pure water Eight types as described in the following photosensitive solution formulation Of the present invention [A] -1 to [A] -8 and three kinds of comparative photosensitive solutions [P] -1 to [P] -3 using ordinary diazonium salts.

Photosensitive solution formulations [A] and [P]: 0.4 g of aromatic diazonium salt shown in Table 1 below 1.1 g of cresol-formaldehyde novolak resin (meta: para ratio = 6: 4, average) (Molecular weight: 1100, containing 0.5% of unreacted cresol) ・ Esterified product of 1,2-diazonaphthoquinone-5-sulfonyl chloride and 0.1 g pyrogallol-acetone resin ・ 0.05 g of tetrahydrophthalic anhydride ・ 4 -(P-N, N-di (ethoxycarbonyl) 0.02 g aminophenyl) -2,6-bis (trichloromethyl) -s-triazine phosphorous acid 0.01 g oil blue # 603 (Orient Industry Co., Ltd. ) Megafac F177 (a fluorinated surfactant manufactured by Dainippon Ink and Chemicals, Inc., 20% by weight methyl isobutyl ketone solution) 0.0 2 g. Methyl ethyl ketone 15 g. 1-methoxy-2-propanol 10 g. The diazonium salts used in the formulations [A] and [P] are shown in Table 1 below.

[0063]

[Table 1] Example 1 Photosensitive solution Diazonium Gray scale Development time段 1 [A] -1 Compound 1 7 20 2 [ A] -2 Compound 2 5303 [A] -3 Compound 3 6304 [A] -4 Compound 4 6255 [A] -5 Compound 5 7 206 [A] -6 Compound 6 7 20 7 [ A] -7 Compound 7 630 8 [A] -8 Compound 8 7 20 Comparative Example 1 [P] -1 Compound A 4602 [P] -2 Compound B 560 3 [P] -3 Compound C 550化合物 Compounds A to C used in comparative photosensitive solution [P] are as follows Is .

[0064]

Embedded image

These photosensitive solutions [A] -1 to 8 and [P]
-1 to 3 on anodized aluminum plate,
Dry at 0 ° C. for 2 minutes. At this time, the coating amount was 1.5 g / m ² in dry weight. Based on the method described in Example 1 of JP-B-61-28986, a copolymer of (methyl methacrylate / ethyl acrylate / sodium acrylate = 68/20/12) was formed on the photosensitive layer thus coated. A mat layer was provided by electrostatic spraying of the combined aqueous solution. A gray scale having a density difference of 0.15 was adhered on the photosensitive layer of the obtained PS plate, and 50 cm was applied with a 2 kW high-pressure mercury lamp.
Exposure was performed for 2 minutes from a distance of The exposed PS plate was developed with an undiluted developing solution having the following composition: an 8-fold diluted aqueous solution of DP at 25 ° C., and the time until a clear positive image was obtained (development time) was examined. Table 1 shows the results.

DP: Water 80 g Triethanolamine 3 g Sodium t-butylnaphthalenesulfonate 8 g Benzyl alcohol 9 g From the results in Table 1, the photosensitive layer of the present invention using an aromatic diazonium salt having an anion in the molecule of the present invention. Has a sensitivity equal to or higher than that of a conventional photosensitive layer containing a diazonium salt and having no anion in the corresponding molecule, and the development time can be reduced to 1/20 to 1/30 times. all right. Separately, the PS plate is exposed to a positive film for 60 seconds using a 3KW metal halide lamp as a light source in a vacuum furnace, and then a developer DP-produced by Fuji Photo Film Co., Ltd.
4 (1: 8), Rinse solution FR-3 (1: 7), Fuji Photo Film Co., Ltd. automatic developing machine Stablon 900
Processed through D. A trace of film sticking was observed on the obtained plate, and an erasing solution RP-1 manufactured by Fuji Photo Film Co., Ltd. was applied to the portion with a brush for 30 seconds and then washed with water. Next, Burning Solution B made by Fuji Photo Film Co., Ltd.
After wiping the plate surface with C-3, the plate was subjected to a heat treatment at 260 ° C. for 7 minutes using a burning device BP-1300 manufactured by Fuji Photo Film Co., Ltd. After the plate cooled, the plate surface was treated with a solution obtained by diluting gum GU-7 manufactured by Fuji Photo Film Co., Ltd. with water twice. After leaving the planographic printing plate for one day, the printing press Heidelberg KO
When printing was performed on RD, good prints were obtained in all cases.

Examples 9 to 11 and Comparative Examples 4 to 6 The following photosensitive liquids [B] and [Q] were coated on a silicon wafer having a thickness of 2 mm with a spinner,
Dry for 2 minutes at ° C. The film thickness when dried was 1 μm. Photosensitive solution formulations [B] and [Q]: aromatic diazonium salts shown in Table 2 below 3.0 × 10 ⁻⁴ mol cresol formaldehyde novolak resin 1.0 g ethyl cellosolve acetate 7.5 g diazonium in photosensitive solution formulation The salts are shown in Table 2 below.

[0068]

[Table 2] Table 2 Example Photosensitive solution diazonium salt Development time (seconds) ━━━━━━━━━━━━━━━━━━━━━━━━━━━ 9 [B] -1 Compound 2 30 10 [B] -2 Compound 4 20 11 [B]- 3 Compound 7 25 Comparative Example 4 [Q] -1 Compound A 605 [Q] -2 Compound B 556 [Q] -3 Compound C 50}レ ジ ス ト The obtained resist is exposed using a reduction projection exposure apparatus (stepper) using monochromatic light having a wavelength of 436 nm, and a 2.4% aqueous solution of tetramethylammonium hydroxide is used. , And the time (development time) at which a good pattern of 0.8 μm line and space was obtained in all samples was examined. Table 2 shows the results. From the results in Table 2, it was confirmed that when the aromatic diazonium salt of the present invention was used, the development time for obtaining the same line and space was shorter in the resist than in the comparative example. Example 12 and Comparative Example 7 The resist of Example 10 and Comparative Example 5 was irradiated with ultraviolet light of 254 nm by a contact exposure method through a glass mask, and then developed in the same manner as in Example 10 and Comparative Example 5 to obtain a resist having a thickness of 0.7 μm.
The development time for obtaining a good pattern of m lines and spaces was investigated. Table 3 shows the results.

[0069]

[Table 3] Table 3 レ ジ ス ト Resist development time (seconds) ━━━━━━━━━━━ Example 12 Resist of Example 10 25 Comparative Example 7 Resist of Comparative Example 5 60か ら From the results in Table 3, when the aromatic diazonium salt of the formula (I) was used in the positive photosensitive composition of the present invention,
It was confirmed that the development time of the resist was shorter than that of the comparative example.

[0070]

According to the present invention, by using an aromatic diazonium salt represented by the general formula (I) in a positive photosensitive composition, a lithographic printing plate having a high sensitivity and a short development time can be prepared. A resist is obtained.

────────────────────────────────────────────────── (5) References JP-A-63-108334 (JP, A) JP-A-63-106743 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03F 7/016

Claims (3)

(57) [Claims] 1. A lithographic printing plate comprising an aromatic diazonium salt represented by the following general formula (I) and an alkali-soluble and water-insoluble polymer compound. Positive photosensitive composition. Embedded image (Wherein, Ar represents a divalent aromatic group which may have a substituent. Y ₁ represents a divalent linking group. X ₁ ⁻ represents an anion. N represents 0 or 1. ) 2. The positive photosensitive composition for a lithographic printing plate according to claim 1, wherein the aromatic diazonium salt is represented by the following general formula (II). Embedded image (Wherein, R ₁ , R ₂ , R ₃ , and R ₄ represent a hydrogen atom, a halogen atom,
An alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an alkoxy group, a substituted alkoxy group, Or -Y ₂ -R _8, which may be the same or different, and may combine with each other to form a ring. R ₅ and R ₆ represent an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an arylcarbonyl group or a substituted arylcarbonyl group, which may be the same or different, and are bonded to each other to form a piperidino group; A pyrrolidino group, a tetrahydroisoquinolino group, a tetrahydroquinolino group, an indolino group, a morpholino group or a thiomorpholino group may be formed.
R ₇ represents an alkylcarbonyl group, a substituted alkylcarbonyl group, an arylcarbonyl group or a substituted arylcarbonyl group. R ₈ represents an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group. X ₂ ^- represents a sulfonate anion or a carboxylate anion. Y ₂ is
Shows a divalent linkage in which one or more of H, C, N, O, S or P can be combined. Y ₁ and n have the same meaning as described above. ) 3. The method according to claim 1, wherein the aromatic diazonium salt is represented by the following general formula (III), (IV) or (V).
A positive photosensitive composition for a lithographic printing plate . Embedded image (Wherein, Z ₁ , Z ₂ and Z ₃ represent 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 or a halogen atom, which may be the same or different. Y ₃ is H,
2 formed by combining one or more of C, N, O, S or P
Shows a valent linking group. R ₁ , R ₅ , R ₆ , R ₇ , Y ₁ , X ₂
^- and n have the same meanings as above. )