JP2684246B2 - Photosensitive composition - Google Patents

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 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 Orthoquinonediazide compounds are conventionally known as positive-acting photosensitive substances which are solubilized by actinic rays in applications such as lithographic printing plates, and have been widely used in lithographic printing plates. Was. Examples of such orthoquinonediazide compounds include, for example, U.S. Patent Nos. 2,766,118, 2,767,092, and 2,772,97.
No. 2, No. 2,859,112, No. 2,907,665, No. 3,04
No. 6,110, No. 3,046,111, No. 3,046,115, No.
3,046,118, 3,046,119, 3,046,120,
No. 3,046,121, No. 3,046,122, No. 3,046,123
No. 3, No. 3,061,430, No. 3,102,809, No. 3,106,
It is described in numerous publications, including the specifications of No. 465, No. 3,635,709, and No. 3,647,443.

[0003] These orthoquinonediazide compounds are:
Although the property of being alkali-soluble is obtained by decomposing upon irradiation with actinic rays to generate a 5-membered ring carboxylic acid, all of them have the drawback of insufficient photosensitivity. This is the case of orthoquinonediazide compounds,
This is essentially because the quantum yield does not exceed 1.

Various attempts have been made to increase the photosensitivity of a photosensitive composition containing an orthoquinonediazide compound, but it is very difficult to increase the photosensitivity while maintaining the development tolerance during development. Met. For example, an example of such an attempt is disclosed in Japanese Examined Patent Publication No. 48-12242.
No. 52-40125, U.S. Pat. No. 4,307,173.
No. and other publications and specifications.

Recently, regarding a photosensitive composition which positively acts without using an orthoquinonediazide compound,
Some suggestions have been made. One of them is, for example, a polymer compound having an orthonitrocarbinol ester group described in JP-B-56-2696. However, also in this case, the photosensitivity is not sufficient for the same reason as in the case of orthoquinonediazide. In addition, as a method of increasing photosensitivity by using a photosensitive system activated by a contact action, a second reaction is caused by an acid generated by photolysis to thereby solubilize an exposed area. The principle has been applied.

As such an example, for example, a combination of a compound capable of generating an acid by photolysis with an acetal or an O, N-acetal compound (JP-A-48-89003), or a combination of an orthoester or amide acetal compound. (JP-A-51-120714), combination with a polymer having an acetal or ketal group in the main chain (JP-A-53-133429), combination with an enol ether compound (JP-A-55-12995).
No.), in combination with an N-acyliminocarbonic acid compound (JP-A Sho
55-126236), a combination with a polymer having an orthoester group in the main chain (JP-A-56-17345), and a combination with a silyl ester compound (JP-A-60-10247).
No.) and a silyl ether compound (JP-A-60)
No. 37549, JP-A-60-12146) and the like. Since they have a quantum yield of more than 1 in principle, they exhibit high photosensitivity, but there are problems such as storage stability with time and sensitivity fluctuation with time from exposure to development. Further, a system which is stable at room temperature with time but decomposes by heating in the presence of an acid to solubilize with an alkali is disclosed in, for example, JP-A-59-45439 and 60-59.
No. 3625, No. 62-229242, No. 63-362
40, Polym. Eng. Sci., 23, 1012 (19
83), ACS. Sym. 242, pp. 11 (1984), Se.
miconductor World 1987, November issue, page 91, Ma
cromolecules, vol.21, p.1475 (1988), SPI
E, 920, p. 42 (1988), and the like, which generate an acid upon exposure, and a tertiary or secondary carbon (for example, t-butyl, 2-cyclohexenyl, etc.).
And a combination system with an ester or carbonate compound. These systems are certainly excellent in storage stability over time and sensitivity variation over time after exposure, but when used as a resist material for semiconductors, there is a problem that they do not have oxygen plasma resistance described later. was there.

On the other hand, as a pattern forming method for manufacturing an electronic component such as a semiconductor element, a magnetic bubble memory and an integrated circuit, conventionally, a method using a photoresist sensitive to ultraviolet rays or visible rays has been widely put into practical use. Has been done. There are two types of photoresist: a negative type, in which the irradiated part is insoluble in the developer by light irradiation, and a positive type, in which the exposed part is solubilized.The negative type has higher sensitivity than the positive type and is necessary for wet etching. Until recently, photoresists occupied the mainstream because of their excellent adhesion to substrates and chemical resistance. 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. Demanded high resolution and high dry etching resistance,
At present, positive photoresists occupy the majority. In particular, among positive photoresists, sensitivity,
Because of its excellent resolution and dry etching resistance, for example, JC Striator, Kodak Microelectronics Seminars, Proc. 1,
Page 16 (1976) (JC Strieter, Kodak Microel
ctronics Seminar Proceedings, 116 (1976))
Alkali-developable positive photoresists based on alkali-soluble novolac resins, such as those mentioned above, have become the mainstream of the current process.

However, in recent years, electronic devices have become multifunctional,
As the sophistication increases, there is a strong demand for finer patterns in order to achieve higher density and higher integration.

That is, since the vertical dimension of the integrated circuit is not so much reduced as compared with the lateral dimension reduction, the ratio of the height to the width of the resist pattern must be increased. For this reason, it has become more difficult to suppress the dimensional change of the resist pattern on a wafer having a complicated step structure as the pattern becomes finer. Further, in various exposure methods, a problem has arisen with the reduction of the minimum size. For example, in light exposure, the interference effect of reflected light due to the step of the substrate has a great effect on dimensional accuracy, whereas in electron beam exposure, the fine resist is exposed due to the proximity effect caused by backscattering of electrons. It is no longer possible to increase the height to width ratio of the pattern.

It has been found that many of these problems are overcome by using a multilayer resist system. For the multilayer resist system, see Solid State Technology, 74 (1981) [Solid State Technolo
gy, 74 (1981)], but many other studies on this system have been published. Generally, a multilayer resist method includes a three-layer resist method and a two-layer resist method.
There is a layer resist method. In the three-layer resist method, an organic flattening film is applied on a stepped substrate, an inorganic intermediate layer and a resist are stacked thereon, and the resist is patterned. Then, the inorganic intermediate layer is dry-etched using the resist as a mask. This is a method of patterning an organic planarization film by O ₂ RIE (reactive ion etching) using the inorganic intermediate layer as a mask. Basically, this method has been studied from an early stage because a conventional technique can be used, but the process is very complicated. Another problem is that cracks and pinholes are liable to occur in the intermediate layer because the three layers having different physical properties overlap with the organic film, the inorganic film, and the organic film. In contrast to this three-layer resist method, in the two-layer resist method, a resist having both properties of the resist and the inorganic intermediate layer in the three-layer resist method, that is, a resist having oxygen plasma resistance is used. Since the generation of pinholes is suppressed, and the number of layers is reduced from three to two, the process is simplified. However, in the three-layer resist method, a conventional resist can be used as the upper resist,
The two-layer resist method has a problem that a new resist having oxygen plasma resistance has to be developed.

From the above background, it has excellent oxygen plasma resistance and can be used as an upper layer resist such as a two-layer resist method.
There has been a demand for the development of a high-sensitivity, high-resolution positive photoresist, in particular, an alkali developing type resist that can be used without changing the current process.

On the other hand, a conventional orthoquinonediazide photosensitive material is combined with a polysiloxane having alkali solubility, or a silicon polymer such as polysilmethylene, to obtain a photosensitive composition, for example, JP-A-61-144639 and JP-A-6144639. -256347, 62-159141, 6
2-191849, 62-220949, 62
-229136, 63-90534, 63-9
1654 and the photosensitive composition described in US Pat. No. 4,722,881 are proposed.

However, all of these silicone polymers have a phenolic OH group or a silanol group (≡Si--O).
H) The alkali solubility is imparted by introduction. When the alkali solubility is imparted by introducing a phenolic OH group, the production becomes extremely difficult. When the alkali solubility is imparted by a silanol group, the stability over time is not necessarily good. There was a problem that it was not.

Further, as a system which does not use orthoquinonediazide, a photosensitive composition obtained by combining an effective amount of onium salt with a block copolymer of polysiloxane / carbonate described in JP-A-62-136638, and further JP-A-63-63. -14
The silicone polymers having a nitrobenzyl phenyl ether group described in No. 6038 can be mentioned, but these are also extremely difficult to manufacture, and the alkali solubility of the exposed area is not sufficient.

[0015]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel positive photosensitive composition which solves the above problems. That is, it is an object of the present invention to provide a novel positive photosensitive composition having high sensitivity and excellent stability over time.

Another object of the present invention is to provide a positive photosensitive composition by an alkali developing method, which is excellent in oxygen plasma resistance.

Still another object of the present invention is to provide a novel positive-working photosensitive composition which is easy to manufacture and can be easily obtained.

[0018]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventor has developed a novel siloxane polymer, a compound having a group decomposable by an acid, and an acid generated by exposure. The inventors have found that the above objects can be achieved by using a combination system of compounds, and have reached the present invention.

That is, the present invention comprises (a) general formulas (I) and (I
Compounds represented by I), (III) or (IV) (hereinafter [A]
) And general formula (V), (VI), (VII) or (VII
A polysiloxane compound containing at least 1 mol% of a siloxane unit derived from a cycloaddition reaction product with a compound represented by I) (hereinafter referred to as [B]), and (b) a group decomposable by an acid At least one of them, the solubility of which in an alkali developing solution increases by the action of an acid (excluding the case of a siloxane polymer), and (c) an acid generated by irradiation with actinic rays or radiation. A photosensitive composition containing a compound is provided.

[0020]

Embedded image In the formula, R ^{1 to} R ⁵ may be the same or different, a hydrogen atom,
An alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, a silyl group, a substituted silyl group, a siloxy group or a substituted siloxy group is shown. Specifically, the alkyl group is a straight chain, branched chain or cyclic group, preferably having about 1 to about 10 carbon atoms. More specifically, for example, methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, isopropyl, isobutyl, tert-butyl, 2-ethylhexyl, cyclohexyl and the like are included. . Further, the substituted alkyl group is, for example, a halogen atom such as a chlorine atom, an alkoxy group having 1 to 6 carbon atoms such as a methoxy group, an aryl group such as a phenyl group, for example, Substituted ones such as an aryloxy group such as a phenoxy group, a nitro group, and a cyano group are included, and specifically, a monochloromethyl group, a dichloromethyl group, a trichloromethyl group, a bromomethyl group, a 2-chloroethyl group, and a 2-bromoethyl group Group, 2-methoxyethyl group, 2-ethoxyethyl group, phenylmethyl group, naphthylmethyl group, phenoxymethyl group, 2-nitroethyl group, 2-cyanoethyl group and the like. The aryl group is preferably a monocyclic or bicyclic aryl group, and examples include a phenyl group, an α-naphthyl group, and a β-naphthyl group. A substituted aryl group is an aryl group as described above,
For example, an alkyl group having 1 to 6 carbon atoms such as a methyl group and an ethyl group, an alkoxy group having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group, a halogen atom such as a chlorine atom, a nitro group, and phenyl Group, carboxy group,
Examples include those substituted with a hydroxy group, an amide group, an imide group, a cyano group, and the like. Specifically, 4-chlorophenyl group, 2-chlorophenyl group, 4-bromophenyl group,
-Nitrophenyl group, 4-hydroxyphenyl group, 4-
Phenylphenyl group, 4-methylphenyl group, 2-methylphenyl group, 4-ethylphenyl group, 4-methoxyphenyl group, 2-methoxyphenyl group, 4-ethoxyphenyl group, 2-carboxyphenyl group, 4-cyanophenyl Group, 4-methyl-1-naphthyl group, 4-chloro-1-
Naphthyl group, 5-nitro-1-naphthyl group, 5-hydroxy-1-naphthyl group, 6-chloro-2-naphthyl group,
Examples thereof include a 4-bromo-2-naphthyl group and a 5-hydroxy-2-naphthyl group. Examples of the silyl group and the substituted silyl group include alkyl and aryl-substituted silyl groups such as a trialkylsilyl group and a triarylsilyl group. Examples of such an alkyl and aryl group include those described above. In the case of a siloxy group or a substituted siloxy group, as shown below, these groups are bonded to a siloxy group or a substituted siloxy group of an adjacent structural unit, or a siloxy group or a siloxy group in another molecule. It may have a two-dimensional or three-dimensional structure such as a structure bonded to a substituted siloxy group.

[0021]

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[0022]

Embedded image Of these, an alkyl group and a substituted alkyl group are preferable,
Each having 1 to 10 carbon atoms, an aryl group,
The substituted aryl groups each have 6 to 14 carbon atoms, and specific examples thereof include the same as the specific examples of R ^{1 to} R ⁵ .

R ¹⁰ represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group, preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a substituted alkyl group having 1 to 10 carbon atoms. , An aryl group having 6 to 14 carbon atoms and a substituted aryl group having 6 to 14 carbon atoms, and specific examples of the alkyl group, the substituted alkyl group, the aryl group, and the substituted aryl group are R ^{1 to} R ⁵ respectively. The same as the example is given.

R ⁷ and R ⁸ or R ⁷ and P ¹ may combine to form a ring.

X ^{1 to} X ³ are a hydroxy group or a hydrolyzable group, preferably a halogen atom such as a chlorine atom or a bromine atom, a C 1 to C 10 atom such as a methoxy group, an ethoxy group or a propoxy group. C6-10 aryloxy group such as alkoxy group, phenoxy group, etc., C1-10 acyloxy group such as acetoxy group, etc., C1 atom such as methylaldoxime, etc. To 6 oxime groups, as well as amide groups, ureido groups, amino groups and the like.

P ^{1 to} P ³ represent a single bond, an alkylene group, a substituted alkylene group, an arylene group or a substituted arylene group, and are --O--, --CO--, --COO--, --OCO--, --CONR.
^It may contain ¹⁰ −, —NR ¹⁰ CO—, —SO ₂ —, or —SO ₃ —.

Specifically, the alkylene group is a straight-chain, branched or cyclic alkylene group, more preferably a straight-chain one, preferably having 1 to 10 carbon atoms, for example, Included are methylene, ethylene, butylene, octylene and like groups. The substituted alkylene group is, for example, a halogen atom such as chlorine atom, an alkoxy group having 1 to 6 carbon atoms, or a carbon atom having 6 to 10 carbon atoms in addition to the above alkylene group.
And aryloxy groups are substituted. The arylene group is preferably monocyclic or bicyclic, and includes, for example, a phenylene group and a naphthylene group. Further, the substituted arylene group is a group in which the above arylene group has, for example, a methyl group, an ethyl group or the like having 1 to 1 carbon atoms.
It includes those substituted with 6 alkyl groups, for example, alkoxy groups having 1 to 6 carbon atoms such as methoxy group and ethoxy group, and halogen atoms such as chlorine atom. Specifically, chlorophenylene group, bromophenylene group, nitrophenylene group, phenylphenylene group, methylphenylene group, ethylphenylene group, methoxyphenylene group, ethoxyphenylene group, cyanophenylene group, methylnaphthylene group, chloronaphthylene group, Examples thereof include a bromonaphthylene group and a nitronaphthylene group.

Y represents a trivalent aromatic ring, preferably an aromatic ring having 6 to 14 carbon atoms.

Q represents an acid group having a pKa of 12 or less.

Specifically, carboxylic acid group, sulfonic acid group, phenolic hydroxyl group, imide group, N-hydroxyimide group, N-sulfonylamide group, sulfonamide group,
A group having an N-sulfonylurethane group, an N-sulfonylureido group, an active methylene group or the like, and more specifically

[0031]

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[0032]

Embedded image Hereinafter, the components of the photosensitive composition of the present invention will be described in detail.

(Polysiloxane Compound) The polysiloxane compound of the present invention is a thermal addition reaction of [A] and [B], that is,
Cyclic Product (IX) Obtained by Diels-Alder Reaction
The siloxane unit derived from (XXIV) is at least 1 mol%, preferably 3 mol% or more, more preferably 5 mol% or more.
It is a polysiloxane having a mol% or more.

[0034]

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[0035]

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[0036]

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[0037]

Embedded image As the method for producing the polysiloxane compound of the present invention, a method of hydrolyzing or alkoxylating a single or a plurality of [A] and then condensing it and thermally adding a single or a plurality of [B] to the obtained polysiloxane And (A) by heat-adding one or more [A] and one or more [B].
There is a method of synthesizing (XIV) to (XXIV), followed by hydrolysis or alkoxylation and then condensation, and any method is convenient. Also, there is no need to add a metal catalyst during production.

The polysiloxane of the present invention comprises (IX) to (X
The following (XXV) to (XXIX) may be used alone or in combination in (XIV) to condense and improve the performance.

In this case, at least 1 mol% of the siloxane units derived from the cycloaddition reaction products of [A] and [B] must be contained in the polysiloxane after cocondensation, but it is alkali-soluble. From the viewpoint of, 3 mol% or more is preferable, and 5 mol% or more is more preferable.

[0040]

Embedded image R ^{11 to} R ¹⁴ are a hydrogen atom, an alkyl group, a substituted alkyl group,
Examples of the aryl group and the substituted aryl group include the same examples as R ⁶ .

X ^{4 to} X ⁷ represent a hydroxyl group or a hydrolyzable group, and specific examples thereof are the same as those of X ^{1 to} X ³ .

P ⁴ is a single bond, an alkylene group, a substituted alkylene group, an arylene group or a substituted arylene group, and --O
-, -CO-, -COO-, -OCO-, -CONR ^{10
-, - NR 10 CO -,} - SO 2 - or -SO ₃ - may contain. Specifically, examples similar to P ^{1 to} P ³ can be given.

In addition, the performance of the polysiloxane compound of the present invention can be improved by allowing the following (XXX) or (XXXI) compounds to coexist alone or in plural during the heat addition of [A] and [B]. it can.

[0044]

Embedded image D ¹ and D ² may be the same or different and may be bonded to each other to form a ring, but each is a group having no pKa 12 or more acidic group, preferably a hydrogen atom, An alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an alkoxy group, a substituted alkoxy group, a silyl group, a substituted silyl group, a siloxy group, a substituted siloxy group, a cyano group, a nitro group, and more preferably a hydrogen atom or carbon. The number is 1
-10 alkyl group, C1-C10 substituted alkyl group, C6-C14 aryl group, C6-C14
Is a substituted aryl group of. In addition, these are -O-, -C
O -, - COO -, - OCO -, - CONR 10 -, - N
_{^{R 10 CO -, - SO 2}} - or -SO ₃ - may contain.

Also in this case, at least 1 mol% or more of siloxane units derived from the thermal addition reaction products of [A] and [B] are contained in the polysiloxane compound, preferably 3
It is at least mol%, more preferably at least 5 mol%.

The weight average molecular weight of the polysiloxane compound of the present invention is preferably 500 or more, more preferably 1,
000 to 500,000.

A solvent may be used when synthesizing the polysiloxane compound of the present invention. Examples of the solvent include cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-
Examples include dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, toluene, ethyl acetate, methyl lactate, ethyl lactate, γ-butyrolactone, dioxane, tetrahydrofuran and the like. These solvents are used alone or in combination of two or more.

The polysiloxane compound of the present invention may be used alone or in combination. The content of these polysiloxane compounds contained in the photosensitive composition is about 5 to 95.
%, Preferably 20 to 80% by weight.

Typical examples of the polysiloxane compound of the present invention are shown below.

[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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[0072]

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[0073]

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[0074]

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[0075]

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[0076]

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[0077]

Embedded image (Compound decomposable by acid) The component (b) of the present invention is
It is a compound having at least one group capable of being decomposed by an acid and having a solubility in an alkali developing solution increased by the action of the acid.

In a preferred embodiment of the present invention, the component (b) of the present invention capable of being decomposed by an acid is represented by the following general formula (X
A polymer having structural units of XXII) to (XXXVI),
Alternatively, it is a compound represented by the general formula (XXXVII) or (XXXVIII).

[0079]

Embedded image In the formula, R ¹⁵ represents a hydrogen atom or an alkyl group, preferably R ¹⁵ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom or a methyl group.

B is --CR ¹⁶ R ¹⁷ R ¹⁸ , --SiR ¹⁶ R ¹⁷ R ¹⁸ or-
CR ¹⁹ R ²⁰ —O—R ²¹ group, A is B or —CO—O—B
Represents a group.

E represents a single bond or a divalent aromatic group, preferably a single bond or a group having 6 to 15 carbon atoms, or an arylene group having 6 to 15 carbon atoms. Include phenylene and naphthylene groups. R ¹⁶ ,
R ¹⁷ , R ¹⁸ , R ¹⁹ and R ^{20, which} may be the same or different, each represent a hydrogen atom, alkyl, cycloalkyl,
It represents an alkenyl or aryl group, and the alkyl group is a straight chain, branched chain or cyclic group, preferably having 1 to 8 carbon atoms. Specifically, for example, methyl group, ethyl group, propyl group, butyl group, octyl group,
An isopropyl group, an isobutyl group, a 2-ethylhexyl group and the like are included. Further, a halogen atom as described above, for example, an alkoxy group having 1 to 6 carbon atoms such as a methoxy group, an aryl group such as a phenyl group, a substituted one such as a phenoxy group, and the like are specifically included. Are monochloromethyl group, dichloromethyl group, trichloromethyl group, bromomethyl group, 2-chloroethyl group, 2-bromoethyl group, 2-methoxyethyl group, phenoxymethyl group and the like.

The cycloalkyl group preferably has 3 to 8 carbon atoms, specifically, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group,
Examples thereof include a cyclopentenyl group and a cyclohexenyl group.

The alkenyl group is, for example, a vinyl group, and the substituted alkenyl group includes a vinyl group substituted with an alkyl group such as a methyl group, an aryl group such as a phenyl group, and the like. 1-methyl vinyl group, 2-methyl vinyl group, 1,2-dimethyl vinyl group,
2-phenylvinyl group, 2- (p-methylphenyl) vinyl group, 2- (p-methoxyphenyl) vinyl group, 2-
(P-chlorophenyl) vinyl group, 2- (o-chlorophenyl) vinyl group and the like.

The aryl group 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. Further, the above aryl group includes, for example, an alkyl group having 1 to 6 carbon atoms such as methyl group and ethyl group, an alkoxy group having 1 to 6 carbon atoms such as methoxy group and ethoxy group, such as chlorine atom. Such as those substituted with halogen atoms, nitro groups, phenyl groups, cyano groups, and the like, specifically, 4-chlorophenyl group, 2-chlorophenyl group, 4-bromophenyl group, 4-nitrophenyl group, 4- Phenylphenyl group, 4-methylphenyl group, 2-methylphenyl group, 4
-Ethylphenyl group, 4-methoxyphenyl group, 2-methoxyphenyl group, 4-ethoxyphenyl group, 4-cyanophenyl group, 4-methyl-1-naphthyl group, 4-chloro-1-naphthyl group, 5-nitro -1-naphthyl group, 5
A -nitro-1-naphthyl group, a 6-chloro-2-naphthyl group, a 4-bromo-2-naphthyl group and the like can be mentioned.

R ²¹ represents an alkyl or aryl group,
Preferably, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 15 carbon atoms is shown. More preferably, alkyl having 1 to 8 carbon atoms, or 6 carbon atoms
10 to 10 aryl groups are shown. Further, these groups include those having a halogen atom, an alkoxy group, a nitro group or a cyano group substituted. However, at least two of R ^{16 to} R ¹⁸ are groups other than hydrogen atoms, and two groups of R ^{16 to} R ¹⁸ and R ^{19 to} R ²¹ may combine to form a ring. Good.

F represents a p-valent aliphatic or aromatic hydrocarbon group, preferably having 1 carbon atom which may have a substituent.
~ 30 p-valent aliphatic groups, or a p-valent aromatic group having 6 to 24 carbon atoms which may have a substituent. m is 1
Indicates an integer of 5. p represents an integer of 1 or more, preferably an integer of 1 to 10.

Specific examples of the compound having at least one group capable of being decomposed by an acid used in the present invention include:
Polymers represented by poly (Pt-butylcarbonyloxystyrene) described in JP-A-59-45439, JP-A-62-229242, and SPIE, 631, vol.
Polymers represented by poly [N- (t-butoxycarbonyl) maleimide-CO-styrene described in page 8 (1986), JP-A-63-36240, and ACS Symp.,
346, 200 (1987), poly [N-
(Pt-butoxycarbonyloxyphenyl) maleimide-CO-styrene], a polymer represented by SPIE,
771, p. 24 (1987), represented by poly (t-butyl P-vinylbenzoate).
Macromolecules, 21: 14755 (1988)
Poly (t-butyl methacrylate) described, poly (2
-Cyclohexenyl methacrylate), poly (2-cyclopropyl-propyl methacrylate), poly (2-phenyl-propyl methacrylate), and the like, JP-A-60-52845, and SPIE, 926.
Vol., Page 162 (1988), typified by poly (P-trimethylsiloxystyrene).
Polymers typified by poly (Pt-butoxystyrene) described in 3-250642, Polymer Bull., 20 volumes,
Polymer represented by poly (P-2-cyclohexenyloxystyrene) described on page 427 (1988), ACS
Polym. Mater. Sci. Tech., 61 , 417 (1988)
The polymer represented by poly (P-2-pyranyloxystyrene) described in (Year), the polymer represented by poly (silyl methacrylate) described in JP-A-62-40450, and the like.

In addition, polyphthalaldehyde described in ACS Symp., Vol. 242, page 11 (1984), JP-A-62-136638, J. Imaging Sci., Vol. 30, 59.
Page (1986), and Makromol. Chem., Rapid Com
The polycarbonate described in Mun, Vol. 7, p. 121 (1986) can also be used. Further, the above-mentioned JP-A-60-3
625, Polym. Eng. Sci., 23, 1012 (1
983) Semiconductor World, November 1987,
The compounds described on page 91, SPIE, vol. 920, page 42 (1988), and JP-A-2-6958 and JP-A-2-245756 can also be used in the present invention.

The weight average molecular weight of these polymers is preferably 500 or more, more preferably 1,000 to 500,
000.

The content of the component (b) in the photosensitive composition of the present invention is 5 to 95% by weight, preferably 20 to 70% by weight, more preferably 25 to 50% by weight in terms of solid content.
It is.

(The acid is emitted by irradiation with actinic rays or radiation.
As the compound capable of generating an acid upon irradiation with actinic rays or radiation, which is the component (c ) of the present invention, many known compounds and mixtures, for example, BF ₄ -of diazonium, phosphonium, sulfonium, and iodonium ,
Salts such as AsF ₆ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , SiF ₆ ⁻ , ClO ₄ ⁻ , organohalogen compounds, and organometallic / organohalogen compound combinations are suitable. Of course, U.S. Patent No. 3,779,77
No. 8, West German Patent No. 2,610,842 and European Patent No. 1
The compounds which generate an acid by photolysis as described in the specification of No. 26712 are also suitable as the composition of the present invention. Further, in combination with a suitable dye, upon exposure, a compound intended to give a visible contrast between the unexposed area and the exposed area,
For example, JP-A-55-77742 and JP-A-57-16323.
The compounds described in the publication No. 4 can also be used as the component (c) of the present invention.

Typical compounds among the compounds capable of generating an acid upon irradiation with actinic rays or radiation are described below.

(1) Oxadiazole derivative represented by the following general formula (XXXIX) or S-triazine derivative represented by the general formula (XXXX) substituted with a trihalomethyl group

[0094]

Embedded image In the formula, R ²² represents a substituted or unsubstituted aryl or alkenyl group, and R ²³ represents R ²² , —CG ₃ or a substituted or unsubstituted alkyl group. G represents a chlorine atom or a bromine atom.

Specific examples include the following.

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[0096]

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[0097]

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[0098]

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[0099]

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[0100]

Embedded image (2) Iodonium salt represented by the following general formula (XXXXI) or sulfonium salt represented by the general formula (XXXXII)

[0101]

Embedded image Here, Ar ¹ and Ar ² in the formula may be the same or different,
It represents a substituted or unsubstituted aromatic group. Preferred substituents are alkyl, haloalkyl, cycloalkyl, aryl, alkoxy, nitro, carbonyl, alkoxycarbonyl, hydroxy, mercapto group and halogen atom, more preferably alkyl having 1 to 8 carbon atoms and 1 carbon atom. ~ 8 alkoxy, nitro and chlorine atoms. R ²⁴ , R ²⁵ and R ²⁶ may be the same or different and each represents a substituted or unsubstituted alkyl group or aromatic group. Preferably, an aryl group having 6 to 14 carbon atoms, and 1 to 8 carbon atoms
Alkyl groups and substituted derivatives thereof. Preferred substituents are those having 1 to 8 carbon atoms for the aryl group.
Alkoxy, alkyl having 1 to 8 carbons, nitro,
A carbonyl group, a hydroxy group and a halogen atom, and an alkyl group is an alkoxy, carbonyl or alkoxycarbonyl group having 1 to 8 carbon atoms. Z ^1- is B
F ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , ClO ₄ ⁻ , and CF ₃ SO ₃ ⁻ are shown. Also, two of R ²⁴ , R ²⁵ , and R ²⁶ and Ar ¹ , Ar
Each ² may be bonded via a single bond or a substituent.

Examples of the compound represented by the general formula (XXXXI) include JP-A-50-158680, JP-A-51-110016, and JP-B-52-142.
The compounds described in Japanese Patent No. 77 are mentioned. Specifically, the following compounds are included.

[0103]

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[0104]

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[0105]

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[0106]

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[0107]

Embedded image Examples of the compound represented by the general formula (XXXXII) include JP-A-51-56885 and JP-B-52-142.
78, U.S. Pat. No. 4,442,197, West German Patent No. 2,90.
The compounds described in each specification of 4,626 may be mentioned. Specifically, the following compounds are included.

[0108]

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[0109]

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[0110]

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[0111]

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[0112]

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[0113]

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[0114]

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[0115]

Embedded image The above-mentioned compounds represented by the general formulas (XXXXI) and (XXXXII) are known, for example, JW Knapczk et al., J. Am.
Chem. Soc., 91, 145 (1969), A.
L. Maycock et al., J. Org. Chem., Vol. 35, page 2532 (1070), E. Goethals et al., Bull. Soc. Chem. B.
elg., 73, 546 (1964), HM Leic
Ester, J. Am. Chem. Soc., 51, 3587 (1929), JV Crivello et al., J. Polym. Sci. Po.
Lym. Chem. Ed., Vol. 18, p. 2677 (1980).
), U.S. Pat. Nos. 2,807,648 and 4,247,473, FM Beringer et al., J. Am. Chem. Soc., 75.
Volume, 2705 (1953), JP-A-53-101,
It can be manufactured by the procedure shown in Japanese Patent No.

(3) Disulfone derivative represented by the following general formula (XXXXIII) or imidosulfonate derivative represented by the following general formula (XXXXIV)

[0117]

Embedded image Here, in the formula, Ar ³ and Ar ⁴ may be the same or different and represent a substituted or unsubstituted aryl group. R ²⁷ represents a substituted or unsubstituted alkyl or aryl group. K represents a substituted or unsubstituted alkylene, alkenylene or arylene group.

Specific examples include the compounds shown below.

[0119]

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[0120]

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[0121]

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[0122]

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[0123]

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[0124]

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[0125]

Embedded image (4) Diazonium salt represented by the following general formula (XXXXV) Ar ⁵ —N ₂ ⁺ Z ^{2 —} (XXXXV) wherein Ar ⁵ represents a substituted or unsubstituted aromatic group. Z
² is an organic sulfonic acid anion, organic acid anion, organic carboxylic acid anion, or _{^{BF 4 -, PF 6 -,}} AsF 6 -,
SbF ₆ ^- and ClO ₄ ^- are shown.

Specific examples include the following.

[0127]

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[0128]

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[0129]

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[0130]

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[0131]

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[0132]

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[0133]

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[0134]

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[0135]

Embedded image The amount of the compound capable of generating an acid upon irradiation with actinic rays or radiation is 0.001 based on the total solid content of the composition.
The range of -40% by weight, preferably 0.1-20% by weight, more preferably 1-15% by weight is suitable.

(Alkali-Soluble Polymer) The positive-working photosensitive composition of the present invention can be essentially used only by the combination of the compounds of the components (a), (b) and (c) of the present invention.
Further, an alkali-soluble polymer may be added and used.

Such an alkali-soluble polymer is preferably a pKall such as a phenolic hydroxyl group, a carboxylic acid group, a sulfonic acid group, an imide group, a sulfonamide group, an N-sulfonylamide group, an N-sulfonylurethane group and an active methylene group. It is a polymer having the following acidic hydrogen atoms.
Suitable alkali-soluble polymers include novolak-type phenol resins, specifically, phenol-formaldehyde resin, o-cresol-formaldehyde resin, m-
There are cresol-formaldehyde resin, p-cresol-formaldehyde resin, xylenol-formaldehyde resin, and co-condensates thereof. Furthermore, JP-A-5
As described in JP-A 0-125806, a condensate of formaldehyde with phenol or cresol substituted with an alkyl group having 3 to 8 carbon atoms, such as t-butylphenol formaldehyde resin, together with the above-mentioned phenol resin. You may use together. 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, etc. Homogenized or copolymerized polymers, and furthermore, polymers obtained by partially etherifying or partially esterifying these polymers can be used.

Further, a polymer having a carboxyl group-containing monomer such as acrylic acid or methacrylic acid as a copolymerization component,
JP-A-61-224042 discloses a carboxyl group-containing polyvinyl acetal resin.
The carboxyl group-containing polyurethane resin described in JP-A-47-47 is also preferably used.

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

These alkali-soluble polymers can be used alone, but may be used as a mixture of several kinds. A preferable addition amount in the photosensitive composition is 10 to 90% by weight, more preferably 30 to 8% by weight based on the total solid content of the photosensitive composition.
The range is 0% by weight.

(Other Preferred Components) In the positive photosensitive composition of the present invention, a compound that increases the acid generation efficiency of a dye, a pigment, a plasticizer and a compound capable of generating the acid (so-called, if necessary). A sensitizer) and the like can be included.

Examples of such sensitizers are described in the specifications of US Pat. Nos. 4,250,053 and 4,442,197 for the acid generators represented by the general formulas (XXXXI) and (XXXXII). A compound can be mentioned. Specifically, anthracene, phenanthrene, perylene, pyrene, chrysene, 1,2-benzanthracene, coronene, 1,6-diphenyl-1,3,5-hexatriene, 1,1,4,4-tetraphenyl-1. , 3-butadiene, 2,3,4,5-tetraphenylbenzene, 2,
5-diphenylthiophene, thioxanthone, 2-chlorothioxanthone, phenothiazine, 1,3-diphenylpyrazoline, 1,3-diphenylisobenzofuran,
Xanthone, benzophenone, 4-hydroxybenzophenone, anthrone, ninhydrin, 9-fluorenone, 2,4,7-trinitrofluorenone, indanone, phenanthraquinone, tetralone, 7-methoxy-
4-methylcoumarin, 3-keto-bis (7-diethylaminocoumarin), Michler's ketone, ethyl Michler's ketone and the like are included. The ratio of these sensitizers to the compound capable of generating an acid upon irradiation with actinic rays or radiation is 0.01 / 1 to 20/1 in terms of molar ratio, preferably 0.1 / 1 to
A range of 5/1 is appropriate.

Dyes can be used as colorants, and suitable dyes include oil-soluble dyes and basic dyes. Specifically, Oil Yellow # 101, Oil Yellow # 130, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 603,
Oil Black BY, Oil Black BS, Oil Black T-505 (above, manufactured by Orient Chemical Industry Co., Ltd.) Crystal Violet (CI42555), Methyl Violet (CI42535), Rhodamine B (C
I145170B), Malachite Green (CI420
00), methylene blue (CI52015) and the like.

In the composition of the present invention, a cyclic acid anhydride, a printout agent for obtaining a visible image immediately after exposure, other fillers and the like can be added to further enhance the sensitivity. Cyclic acid anhydride include U.S. Pat phthalic anhydride as described in No. 4,115,128 specification, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6-oxy - [delta ⁴ - tetrahydrophthalic anhydride, tetrachlorophthalic Phthalic anhydride, maleic anhydride, chloromaleic anhydride, α-phenylmaleic anhydride, succinic anhydride,
Pyromellitic acid and the like. By containing these cyclic anhydrides in an amount of 1 to 15% by weight based on the solid content in the whole composition, the sensitivity can be increased up to about three times.
As a printing-out agent for obtaining a visible image immediately after exposure, a combination of a photosensitive compound that releases an acid upon exposure and an organic dye capable of forming a salt can be exemplified. Specifically, JP-A-50-36209 and JP-A-53-8
Combinations of o-naphthoquinonediazide-4-sulfonic acid halogenide and salt-forming organic dyes described in JP-A-128, JP-A-53-36223 and JP-A-54-7
There can be mentioned a combination of a trihalomethyl compound and a salt-forming organic dye described in JP-A-4728.

(Solvent) The positive photosensitive composition of the present invention is
When it is used as a material for a lithographic printing plate, it is dissolved in a solvent that dissolves each of the above components and applied onto a support. For resist materials such as semiconductors, they are used as dissolved in a solvent. As the solvent used herein, ethylene dichloride, cyclohexanone, methyl ethyl ketone, methanol, ethanol, propanol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 2-ethoxyethyl Acetate, 1-methoxy-2-propyl acetate, dimethoxyethane, methyl lactate, ethyl lactate, N, N-dimethylacetamide, N, N-dimethylformamide, tetramethylurea, N-methylpyrrolidone, dimethylsulfoxide, sulfolane, γ- Butyrolactone, toluene,
There are ethyl acetate and the like, and these solvents are used alone or as a mixture. The concentration (total solid content including additives) in the above components is 2 to 50% by weight. Further, 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 as a solid content.
5 to 3.0 g / m ² is preferable. As the coating amount decreases, the photosensitivity increases, but the physical properties of the photosensitive film decrease.

(Manufacturing of planographic printing plate etc.) When a planographic printing plate is manufactured using the positive photosensitive composition of the present invention, the support thereof is, for example, paper, plastics (eg polyethylene, polypropylene, polystyrene). Etc.) laminated paper such as aluminum (including aluminum alloys), zinc, copper and other metal plates such as cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, nitric acid. Films of plastics such as cellulose, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal and the like, papers or plastic films laminated with the above metals, or vapor-deposited are included. Among these supports, the aluminum plate is particularly preferable because it is extremely dimensionally stable and inexpensive. Further, a composite sheet in which an aluminum sheet is bonded on a polyethylene terephthalate film as described in JP-B-48-18327 is preferred.
The surface of the aluminum plate is a wire brush graining, a mechanical method such as brush graining in which a slurry of abrasive particles is poured and roughening with a nylon brush, ball graining, graining by solution honing, buff graining, HF and AlCl. _3, HCl chemical graining to etchant, after the surface was grained by electrolytic graining and composite graining was conducted by combining these surface roughening method using nitric acid or hydrochloric acid and the electrolyte solution, if necessary Etched with acid or alkali, and subsequently anodize in sulfuric acid, phosphoric acid, oxalic acid, boric acid, chromic acid, sulfamic acid or mixed acid of these with direct current or AC power source to provide a strong passivation film on the aluminum surface. Those that are preferred are. The aluminum surface is hydrophilized by such a passivation film itself, but if necessary, it is further described in US Pat. No. 2,714,066 and US Pat. No. 3,181,461.
Silicate treatment (sodium silicate, potassium silicate) described in US Pat. No. 2,946,638, potassium fluorozirconate treatment described in US Pat. No. 2,946,638, US Pat. Phosphomolybdate Treatment, Alkyl Titanate Treatment Described in British Patent No. 1,108,559, German Patent No. 1,09
Polyacrylic acid treatment described in 1,433 specification,
German Patent No. 1,134,093 and British Patent No. 1,230,447
Treatment with polyvinyl phosphonic acid,
Phosphonic acid treatment described in JP-B-44-6409, phytic acid treatment described in US Pat. No. 3,307,951, JP-A-58-16893 and JP-A-5-16893.
Undercoating treatment with a complex of a water-soluble organic polymer and a divalent metal ion described in JP-A-8-18291, and water-soluble having a sulfonic acid group described in JP-A-59-101651. Those which have been hydrophilized by a polymer undercoat are particularly preferable. As another hydrophilic treatment method, silicate electrodeposition described in US Pat. No. 3,658,662 can also be mentioned.

It is also preferable that after the graining treatment and the anodic oxidation, the sealing treatment is performed. 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.

(Actinic Rays or Radiation) Examples of the light source of actinic rays used for exposing the photosensitive composition of the present invention include a mercury lamp, a metal halide lamp, a xenon lamp,
There are chemical lamps and carbon arc lamps. Examples of the radiation include an electron beam, an X-ray, an ion beam, and far ultraviolet rays. Preferably as a light source for photoresist, g
Lines, i-lines, Deep-UV light are used. Scanning exposure using 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, a KrF excimer laser, and the like.

(Developer) As a developer for the positive photosensitive composition of the present invention, sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium triphosphate, and diphosphoric acid can be used. Aqueous solutions of inorganic alkaline agents such as sodium, ammonium tertiary phosphate, dibasic ammonium phosphate, sodium metasilicate, sodium bicarbonate, aqueous ammonia, etc. and organic alkaline agents such as tetraalkylammonium OH salts are suitable. , Their concentration is 0.1 to 10% by weight, preferably 0.1.
It is added so as to be 5 to 5% by weight.

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

[0151]

The positive photosensitive composition of the present invention has high sensitivity, excellent stability over time and oxygen plasma resistance, and is capable of alkali development. The production is simple and easy to obtain.

[0152]

EXAMPLES The present invention will be described in more detail with reference to Synthesis Examples and Examples, which should not be construed as limiting the scope of the present invention.

Synthesis Example 1. (Polysiloxane of the present invention (Compound Example 50)) 7.3 g of maleimide and 13.1 g of 2-trimethoxysilyl-1,3-butadiene were dissolved in 500 ml of dioxane,
The reaction was carried out at 100 ° C for 1 hour. After adding 102 g of phenyltriethoxysilane to the reaction solution, 10 ml of distilled water and 0.2 ml of hydrochloric acid were added and the mixture was heated and concentrated for 30 minutes.

The concentrated solution was poured into 2000 ml of distilled water with stirring, and the precipitated solid was dried under reduced pressure to obtain 51 g of the desired polysiloxane.

The weight average molecular weight of this polysiloxane measured by gel permeation chromatography was 1200.

Synthesis Example 2. (Polysiloxane of the present invention (Compound Example 39)) Acetylenedicarboxylic acid 11.4 g, 2-trimethoxysilyl-
17.4 g of 1,3-butadiene and 122.6 g of tolyltrimethoxysilane were reacted in the same manner as in Synthesis Example 1 using dioxane as a solvent to obtain 43 g of the target polysiloxane. By gel permeation chromatography,
The weight average molecular weight of this polysiloxane was 8600.

Synthesis Example 3. (Polysiloxane of the present invention (Compound Example 25)) N-
(P-hydroxyphenyl) maleimide 18.9 g,
1-trimethoxysilyl-1,3-butadiene 17.
4 g was reacted in the same manner as in Synthesis Example 1 using 500 ml of ethylene glycol monomethyl ether as a solvent to obtain 18 g of a brown target product.

The weight average molecular weight of this polysiloxane was 3300 as measured by gel permeation chromatography.

Synthesis Example 4. (Polysiloxane of the present invention (Compound Example 27)) N- (p
-Sulfamoyl) maleimide 25.2 g and 2-trimethoxysilyl 1,3-butadiene 17.4 g were reacted in the same manner as in Synthesis Example 1 using 500 ml of N, N-dimethylacetamide as a solvent to obtain 36 g of a brown target product. Obtained.

The weight average molecular weight of this polysiloxane measured by gel permeation chromatography was 2,300.

Synthesis Example 5. (Polysiloxane of the present invention (Compound Example 44)) N- (p
-Toluenesulfonyl) acrylamide 22.5 g, 2-
Trimethoxysilyl-1,3-butadiene 17.4 g, 4
40 g of -chlorophenyltrimethoxysilane was reacted in the same manner as in Synthesis Example 1 with 500 ml of ethylene glycol monomethyl ether as a solvent to give the desired product 40.
g was obtained.

The weight average molecular weight of this polysiloxane measured by gel permeation chromatography was 4,700.

Synthesis Example 6. (Polysiloxane of the present invention (Compound Example 57)) Acetoacetoxyethyl acrylate (10.0 g), 1-trimethoxysilyl-1,3-butadiene (17.4 g) and N-phenylacrylamide (8.4 g) were added. The reaction was carried out in the same manner as in Synthesis Example 1 using dioxane as a solvent to obtain the desired polysiloxane 2
Obtained 5.1 g.

The weight average molecular weight of this polysiloxane was measured by gel permeation chromatography and found to be 1700.

Examples 1 to 6 A 2S aluminum plate having a thickness of 0.24 mm was immersed in a 10% aqueous solution of sodium tertiary phosphate kept at 80 ° C. for 3 minutes for degreasing, and was sanded with a nylon brush to give sodium aluminate. Etching was performed for about 10 minutes, and desmut treatment was performed with a 3% aqueous sodium hydrogen sulfate solution. This aluminum plate was anodized in a 20% sulfuric acid at a current density of 2 A / dm ² for 2 minutes to prepare an aluminum plate.

Next, by changing the kind of the polysiloxane compound of the present invention in the following photosensitive solution [A], six kinds of photosensitive solution [A]-
1 to [A] -6 were prepared, and this photosensitive solution was applied onto an anodized aluminum plate and dried at 100 ° C. for 2 minutes to prepare each photosensitive lithographic printing plate [A] -1 to [A] -1. A]-
No. 6 was created. The coating amount at this time is 1.5 on a dry weight basis
g / m ² .

Table 1 shows the polysiloxane compounds of the present invention used in the photosensitive solutions [A] -1 to [A] -6.

[0168]

Embedded image Next, as a comparative example, the following photosensitive solution [B] was applied in the same manner as the photosensitive solution [A] to prepare a photosensitive lithographic printing plate [B].

[0169] The coating weight after drying was 1.5 g / m ² . A gray scale with a density difference of 0.15 was adhered on the photosensitive layers of the photosensitive lithographic printing plates [A] -1 to [A] -6 and [B], and exposure was performed from a distance of 50 cm with a 2 kw high pressure mercury lamp. It was After exposure,
[A] -1 to [A] -6 were heated at 90 ° C for 1 minute. Then, the photosensitive lithographic printing plate [A] -1 to [A]-
6 and [B] were subjected to immersion development for 60 seconds at 25 ° C. in an 8 times diluted aqueous solution of DP-4 (trade name: manufactured by Fuji Photo Film Co., Ltd.) to obtain a gray scale (Fuji Photo Film Co. The exposure time required for the fifth step to be completely cleared was obtained as shown in Table 1.

[0170] As can be seen from Table 1, each of the photosensitive lithographic printing plates [A] -1 to [A] -6 using the siloxane polymer system of the present invention has a shorter exposure time and a higher sensitivity than [B].

Examples 7 to 12 On a silicon wafer, a novolac-based commercial resist HP is used.
R-204 (manufactured by Fuji Hunt Chemical Co., Ltd.) was applied with a spinner and dried at 220 ° C. for 1 hour to form a lower layer. The thickness of the lower layer was 2.0 μm.

In addition, six kinds of photosensitive solutions (C) -1 to (C) -1 to (C) in which the kind of the compound (c) of the present invention in the following photosensitive solution [C] is changed.
Apply [C] -6 with a spinner, and 9 on a hot plate.
It was dried at 0 ° C. for 2 minutes to form a coating film having a thickness of 0.5 μm.

[0173]

Embedded image The compounds (c) of the present invention used are shown in Table 2.

Next, exposure was carried out by a reduction projection exposure device (stepper) for monochromatic light having a wavelength of 365 nm, and post-heating was carried out at 90 ° C. for 1 minute. Then, a resist pattern was formed by developing with a 2.4% aqueous solution of tetramethylammonium hydroxide for 60 seconds. As a result, a good pattern with a line and space of 0.7 μm was obtained.

Next, using a parallel plate type reactive ion etching apparatus, etching was carried out for 20 minutes under the conditions of O ₂ gas pressure of 20 mmTorr and RF power of 200 mW / cm ² , and the upper resist pattern was completely HPR-204 of the lower layer.
And a resist pattern having a high aspect ratio consisting of two layers, upper and lower, was obtained.

That is, it was confirmed that this resist can be used as the upper layer resist of the two-layer resist method.

[0177]

Claims (1)

(57) [Claims] 1. A compound represented by the general formula (I), (II), (III) or (IV) and (a) a general formula (V), (VI) or (VII).
Alternatively, at least 1 mol% of a siloxane unit derived from the reaction product of the cycloaddition reaction with the compound represented by (VIII) is used.
A polysiloxane compound contained therein, and (b) a compound having at least one group capable of decomposing by an acid, the solubility of which in an alkali developing solution is increased by the action of an acid (provided that the compound is not a siloxane polymer),
And (c) a compound capable of generating an acid upon irradiation with actinic rays or radiation, a photosensitive composition. Embedded image Embedded image Embedded image