JPH0611837A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To form good resist patterns for short wavelength light by incorporating a specified polysiloxane compd., nitro or alkoxybenzylester, or sulfonate compd. CONSTITUTION:This compsn. contains a polysiloxane compd. containing 1mol% siloxane unit in the cyclic heat-additive reaction product of a compd. expressed by formula I and a compd. expressed by formula II or the like. Also, the compsn. contains 2-nitrobenzylester or sulfonate compd., or 2- or 3-alkoxybenzyl ester or sulfonate compd. In formula I, R<1>-R<5> may be same or different hydrogen atoms, alkyl groups, substd. alkyl groups, etc., and X<1>-X<3> are hydroxy groups or groups which can be hydrolyzed. In formula II, R<7>-R<9> are hydrogen atoms, alkyl groups, substd. alkyl groups, etc., P<1> is a single bond, alkylene group, substd. alkylene group, etc., Q is an acid group having <=12pKa.

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 Conventionally, as a pattern forming method for manufacturing electronic parts such as semiconductor elements, magnetic bubble memories, integrated circuits, etc., a method utilizing a photoresist sensitive to ultraviolet rays or visible rays has been widely put to practical use. Has been done. There are two types of photoresist, a negative type, in which the exposed portion is insoluble in the developing solution by light irradiation, and a positive type, which is solubilized in the opposite. However, the negative type has better sensitivity than the positive type and is necessary for wet etching. Because of its excellent adhesion to substrates and chemical resistance, photoresists have been the mainstream until recently. However, as the density and integration of semiconductor devices increase, the line width and spacing of patterns become extremely small.
Since the use of dry etching for substrate etching, photoresists are required to have high resolution and high dry etching resistance, and positive photoresists are now predominant. It was In particular, among positive photoresists, they are excellent in sensitivity, resolution, and dry etching resistance, and therefore, for example, by JC Strieter, Kodak Microelectronics Seminar Proceedings, No. 116.
Page (1976) (JCStrieter. Kodak Microelecron
Alkali-developable positive photoresists based on alkali-soluble novolac resins, such as ics Seminar Proceeings, 116 (1976)), have become the mainstream of the current process.

However, in recent years, with the increasing functionality and sophistication of electronic equipment, there is a strong demand for miniaturization of patterns in order to achieve higher density and higher integration.

On the other hand, in recent years, the wavelength of the exposure light source has been shortened,
That is, g-line (436 nm) to i-line (365 nm),
Although deep-UV light (200 to 300 nm) is being studied, the orthoquinonediazide compound, which is a photosensitive material of a conventional positive photoresist, has a large absorption in the deep-UV region, and the light in this region is large. Since the bleaching property is small, there is a problem that the shape of the resist pattern is deteriorated when Deep-UV light is used as a light source.

On the other hand, several proposals have been made regarding a photosensitive composition which positively acts without using an orthoquinonediazite compound. As one of them, for example, Japanese Patent Publication No. 56-2696, U.S. Pat. No. 4,551,141.
No. 6, J. Vac. Sci. Technol., 19 volumes. Page 1338 (1
981), J. Electrochem. Soc., 129 volumes. 2552
Page (1982), ibid. 130. Pp. 1433 (1983)
Compounds having a 2-nitrobenzyl ester or 2,6-dinitrobenzyl ester group described in, for example, JP-A-60-243653, Macromolecule.
s. Volume 21. 2001 (1988), SPIE. 92
Volume 0. Examples thereof include compounds having a 2-nitrobenzyl sulfonate or 2,6-dinitrobenzyl sulfonate group described on page 67 (1988) and the like.

Furthermore, as a method for obtaining a positive pattern by causing a de-CO ₂ reaction by exposure to reduce the dissolution inhibiting ability of an exposed portion in an alkali developing solution,
Examples include systems using various substituted benzyl ester compounds described in JP-A-1-140144, but these compounds have problems in dry etching resistance and oxygen plasma resistance described later.

On the other hand, in the trend of high density and high integration, since the vertical dimension of the integrated circuit is not reduced so much as compared with the horizontal dimension reduction, the height with respect to the width of the resist pattern is reduced. There was no choice but to increase the ratio. Therefore, it is necessary to suppress the dimensional change of the resist pattern on the wafer having a complicated step structure.
As the pattern becomes finer, it becomes more difficult. Further, in various exposure methods, problems have arisen with the reduction of the minimum size. For example, in light exposure, the interference effect of reflected light due to the steps of the substrate has a great influence on dimensional accuracy, while in electron beam exposure, fine resist is generated due to the proximity effect caused by electron backscattering. It is no longer possible to increase the pattern height to width ratio.

It has been found that many of these problems are overcome by using a multilayer resist system. For multi-layer resist systems, see Solid State Technology, 74 (1981) [Solid State Technolo.
gy, 74 (1981)], but many other studies have been published on this system. Generally, the multi-layer resist method is divided into three-layer resist method and two
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 superposed on the stepped substrate, the resist is patterned, and then the inorganic intermediate layer is dry-etched using this as a mask. This is a method of patterning the organic planarizing film by O ₂ RIE (reactive ion etching) using the inorganic intermediate layer as a mask. Basically, since this method can use the conventional technique, the study was started early, but the process is very complicated. Another problem is that cracks and pinholes are likely to occur in the intermediate layer because the organic film, the inorganic film, and the organic film have different three-layer physical properties. In contrast to the three-layer resist method, the two-layer resist method uses a resist having both properties of the three-layer resist method and the inorganic intermediate layer, that is, a resist having oxygen plasma resistance, so that cracks and Generation of pinholes is suppressed, and since the number of layers is changed from three to two, the process is simplified. However, in the three-layer resist method, while a conventional resist can be used as the upper layer resist,
The two-layer resist method has a problem that a new resist having oxygen plasma resistance must 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.
It has been desired to develop a high-sensitivity, high-resolution positive photoresist, particularly an alkali developing type resist that can be used without changing the existing process.

On the other hand, a conventional orthoquinonediazide photosensitive material is combined with a polysiloxane having an alkali solubility or a silicon polymer such as polysilmethylene, for example, a photosensitive composition, for example, JP-A-61-144639 and 61-61. -256347, 62-159141, 6
No. 2-191849, No. 62-220949, No. 62
-229136, 63-90534, 63-9
1654, and the photosensitive composition described in U.S. Pat. No. 4,722,881 and further, a photosensitive composition obtained by combining an effective amount of an onium salt with a polysiloxane / carbonate block copolymer described in JP-A No. 62-136638. Has been presented. Further, a photosensitive composition in which an o-nitrobenzyl ester compound and the above-mentioned silicone polymer are combined is disclosed in Japanese Patent Laid-Open No.
No. 3-195650. Further, a silicon polymer having a nitrobenzyl phenyl ether group is described in JP-A-63-146038.

However, all of these silicone polymers have a phenolic OH group or a silanol group (≡Si--O).
H) Alkali-solubility is imparted by the generation of the group in the introduction or exposure process, both of which are extremely difficult to manufacture, and when the alkali-solubility is imparted by a silanol group, stability with time is not always good. , There was a problem.

[0012]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel positive type photosensitive composition which solves the above problems. That is, it is to provide a novel positive-type photosensitive composition capable of forming a good resist pattern with respect to light having a short wavelength, particularly light in the Deep-UV region.

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.

[0015]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventor has found that the above object can be achieved by using a novel positive photosensitive composition described below. It was That is, the present invention includes (a) the general formula (I),
The compound represented by (II), (III) or (IV) (hereinafter referred to as [A]) and the compound represented by the general formula (V), (VI), (VII) or (VIII) (hereinafter referred to as [[ B)), and a polysiloxane compound containing at least 1 mol% of siloxane units derived from the reaction product of cycloaddition reaction with
(B) A 2-nitrobenzyl ester or sulfonate compound, or a 2- or 3-alkoxybenzyl ester or sulfonate compound is provided.

[0016]

[Chemical 4] 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 group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, isopropyl group, isobutyl group, tert-butyl group, 2-ethylhexyl group, cyclohexyl group 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, such as a phenyl group, in the above alkyl group. Included are substituted aryloxy groups such as phenoxy group, nitro group, cyano group, and the like, specifically, monochloromethyl group, dichloromethyl group, trichloromethyl group, bromomethyl group, 2-chloroethyl group, 2-bromoethyl. 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 monocyclic or bicyclic, and examples thereof include a phenyl group, an α-naphthyl group and a β-naphthyl group. The substituted aryl group is an aryl group as described above,
For example, alkyl group having 1 to 6 carbon atoms such as methyl group and ethyl group, alkoxy group having 1 to 6 carbon atoms such as methoxy group and ethoxy group, halogen atom such as chlorine atom, nitro group and phenyl. Group, carboxy group,
Those substituted with a hydroxy group, an amide group, an imide group, a cyano group and the like are included, and specifically, 4-chlorophenyl group, 2-chlorophenyl group, 4-bromophenyl group, 4
-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,
4-bromo-2-naphthyl group, 5-hydroxy-2-naphthyl group and the like can be mentioned. 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, and examples of such an alkyl-aryl group include those shown above. Further, in the case of a siloxy group or a substituted siloxy group, as shown below, a structure in which these groups are bonded to a siloxy group or a substituted siloxy group of adjacent structural units, or a siloxy group in another molecule or It may have a two-dimensional or three-dimensional structure such as a structure bonded to a substituted siloxy group.

[0017]

[Chemical 5]

[0018]

[Chemical 6] 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 with each other to form a ring.

X ^{1 to} X ³ are hydroxy groups or hydrolyzable groups, preferably halogen atoms such as chlorine atom and bromine atom, and 1 to 10 carbon atoms such as methoxy group, ethoxy group and 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 include bromonaphthylene group and 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, N-sulfonylurethane group, N-sulfonylureido group or active methylene. A group having a group, and more specifically,

[0026]

[Chemical 7]

A specific example of Z will be shown below.

[0028]

[Chemical 8] The components of the photosensitive composition of the present invention will be described in detail below.

(Polysiloxane Compound) The polysiloxane compound of the present invention has a thermal addition reaction between [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.

[0030]

[Chemical 9]

[0031]

[Chemical 10]

[0032]

[Chemical 11]

[0033]

[Chemical 12] 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. Further, it is not necessary to add a metal catalyst at the time of manufacturing.

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 the alkali-soluble From the viewpoint of, 3 mol% or more is preferable, and 5 mol% or more is more preferable.

[0036]

[Chemical 13] 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 also be improved by allowing the following compounds (XXX) or (XXXI) to coexist alone or in combination during the heat addition of [A] and [B]. it can.

[0040]

[Chemical 14] 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, and 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 thereof include dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, toluene, ethyl acetate, methyl lactate, ethyl lactate, γ-butyrolactone, dioxane and tetrahydrofuran. These solvents may be used alone or in admixture 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.

[0046]

[Chemical 15]

[0047]

[Chemical 16]

[0048]

[Chemical 17]

[0049]

[Chemical 18]

[0050]

[Chemical 19]

[0051]

[Chemical 20]

[0052]

[Chemical 21]

[0053]

[Chemical formula 22]

[0054]

[Chemical formula 23]

[0055]

[Chemical formula 24]

[0056]

[Chemical 25]

[0057]

[Chemical formula 26]

[0058]

[Chemical 27]

[0059]

[Chemical 28]

[0060]

[Chemical 29]

[0061]

[Chemical 30]

[0062]

[Chemical 31]

[0063]

[Chemical 32]

[0064]

[Chemical 33]

[0065]

[Chemical 34]

[0066]

[Chemical 35]

[0067]

[Chemical 36]

[0068]

[Chemical 37]

[0069]

[Chemical 38]

[0070]

[Chemical Formula 39]

[0071]

[Chemical 40]

[0072]

[Chemical 41]

[0073]

[Chemical 42] (2-nitrobenzyl ester or sulfonated
Compound, or 2- or 3-alkoxybenzyl ester
Or sulfonate compound) used in the present invention 2
-The nitrobenzyl ester or sulfonate compound, or the 2- or 3-alkoxybenzyl ester or sulfonate compound is preferably a compound represented by the following general formula (XXXII) or (XXXIII), or a general formula (XXXIV) or (XXXV), (XXXVI) or (XXXVII)
A polymer compound having at least 1 mol% of a structural unit derived from the monomer represented by

[0074]

[Chemical 43]

[0075]

[Chemical 44] Here, R ¹⁵ represents a hydrogen atom, an alkyl group or an aryl group, preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ^{16 to} R ^{20, which} may be the same or different, each represent a hydrogen atom, a halogen atom, a nitro group, an alkoxy group, an aryloxy group, a cyano group or an alkyl group,
Preferably, a hydrogen atom, a chlorine atom, a nitro group, and a carbon number of 1 to
6 alkoxy groups, C 6-15 aryloxy groups, or C 1-4 straight-chain or branched alkyl groups, more preferably hydrogen atoms, nitro groups, or C 1-6 carbon atoms. Indicates an alkoxy group. However, R ¹⁶ ~
At least one of R ²⁰ is a nitro group, an alkoxy group or an aryloxy group, preferably at least one of R ^{16 to} R ²⁰ is a nitro group, and at least one of R ¹⁶ or R ¹⁷ is an alkoxy group or an aryloxy group. It is a base. Further, two of R ^{16 to} R ²⁰ may combine with each other to form a ring.

A represents an m-valent aliphatic or aromatic hydrocarbon group, preferably an aliphatic group having 1 to 30 carbon atoms, or a monocyclic or polycyclic aromatic group having 6 to 20 carbon atoms. Further, A may contain a group such as a ketone, ether, ester, amide, urethane, ureido, or halogen. m
Represents an integer of 1 or more, preferably an integer of 1-10.

R ²¹ represents a hydrogen atom, a halogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a methyl group, and B represents a single bond or a divalent group. Aliphatic or aromatic hydrocarbon group, preferably single bond, divalent carbon number 1
To 30 aliphatic groups, or divalent monocyclic or polycyclic aromatic groups having 6 to 20 carbon atoms, more preferably single bonds, 2
A valent aliphatic group having 1 to 10 carbon atoms or a divalent monocyclic or polycyclic aromatic group having 6 to 15 carbon atoms is shown.

Further, B may contain a ketone, ether, ester, amide, urethane or ureido group in the chain or at the terminal.

2-nitrobenzyl group, 2- or 3-
Specific examples of the alkoxybenzyl group include 2-nitrobenzyl, 2,6-dinitrobenzyl, 2-alkoxybenzyl, 3-alkoxybenzyl, 2,3-dialkoxybenzyl, 2,4-dialkoxybenzyl, and 2,5. −
Dialkoxybenzyl, 2,6-dialkoxybenzyl, 3,4-dialkoxybenzyl, 3,5-dialkoxybenzyl, 2,3,4-trialkoxybenzyl,
3,4,5-trialkoxybenzyl and the like can be mentioned.

The polymer compound having a structural unit derived from the monomers represented by the general formulas (XXXIV) to (XXXVII) includes a compound having one or more polymerizable ethylenically unsaturated bond with the above monomer. Copolymers with and are also included. In this case, the polymerization ratio of the monomers represented by the general formulas (XXXIV) to (XXXVII) varies depending on the type of the copolymerizable monomer used, but is at least 1 mol%, preferably 5 mol%.
It is at least mol%, more preferably at least 10 mol%.

Suitable compounds having a polymerizable ethylenically unsaturated bond include those shown below.

For example, acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, allyl compounds, vinyl ethers,
Compounds having one addition-polymerizable unsaturated bond selected from vinyl esters, fumaric acid esters, maleic acid esters, maleimides, N-substituted maleimides, styrenes, itaconic acid esters, crotonic acid esters, etc. Is.

The weight average molecular weight of the polymer compound having a structural unit derived from the monomers represented by formulas (XXXIV) to (XXXVII) is 1,000 or more, preferably 5,000 to 1,
It is, 000,000.

The content of the 2-nitrobenzyl ester or sulfonate compound or the 2- or 3-alkoxybenzyl ester or sulfonate compound of the present invention is appropriately 5 to 95% by weight based on the solid content of the whole composition, It is preferably 10 to 70% by weight, more preferably 20 to 50% by weight.

The 2-nitrobenzyl ester or sulfonate compound, or the 2- or 3-alkoxybenzyl ester or sulfonate compound of the present invention is
It is characterized by generating carboxylic acid or sulfonic acid by irradiation with actinic rays or radiation and increasing the solubility in an aqueous alkaline solution.

Specific examples of these compounds are shown below.

[0087]

[Chemical formula 45]

[0088]

[Chemical formula 46]

[0089]

[Chemical 47]

[0090]

[Chemical 48]

[0091]

[Chemical 49]

[0092]

[Chemical 50]

[0093]

[Chemical 51]

[0094]

[Chemical 52]

[0095]

[Chemical 53]

[0096]

[Chemical 54]

[0097]

[Chemical 55]

[0098]

[Chemical 56]

[0099]

[Chemical 57]

[0100]

[Chemical 58]

[0101]

[Chemical 59] In addition, Japanese Patent Publication No. 56-2696 and U.S. Pat.
No. 1416, J. Vac. Sci. Technol., Volume 19, 1338.
Page (1981), J. Electrochem., Soc., 129, 2
552 (1982), 130, 1433 (19).
83), JP-A-60-243653, Macromolecule
s, vol. 21, p. 2001 (1988), SPIE, 92.
0, page 67 (1988), and JP-A-1-14014.
The compounds described in No. 4 and the like can also be used in the present invention.

(Alkali-Soluble Polymer) In the positive photosensitive composition of the present invention, an alkali-soluble polymer may be further added to the above polysiloxane compound and quinonediazide compound.

Such an alkali-soluble polymer is preferably a pKall such as phenolic hydroxyl group, carboxylic acid group, sulfonic acid group, imide group, sulfonamide group, N-sulfonylamide group, N-sulfonylurethane group and active methylene group. It is a polymer having the following acidic hydrogen atoms.
Suitable alkali-soluble polymers include novolac type phenol resins, specifically phenol formaldehyde resin, o-cresol-formaldehyde resin, m-
Examples include cresol-formaldehyde resin, p-cresol-formaldehyde resin, xylenol-formaldehyde resin, and co-condensates of these. Furthermore, JP-A-5
No. 0-125806, and 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. Further, polymers containing a phenolic hydroxy group-containing monomer such as N- (4-hydroxyphenyl) methacrylamide as a copolymerization component, p-hydroxystyrene, o-hydroxystyrene, m-isopropenylphenol, p-isopropenylphenol, etc. Homogeneous or copolymerized polymers of, and polymers obtained by partially etherifying or partially esterifying these polymers can also be used.

Further, a polymer having a carboxyl group-containing monomer such as acrylic acid or methacrylic acid as a copolymerization component,
A carboxyl group-containing polyvinyl acetal resin described in JP-A-61-267042, JP-A-63-1240.
The carboxyl group-containing polyurethane resin described in Japanese Patent No. 47 is also preferably used.

Further, a polymer containing N- (4-sulfamoylphenyl) methacrylamide, N-phenylsulfonylmethacrylamide, 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. The preferable addition amount in the photosensitive composition is in the range of 1 to 90% by weight, and more preferably 5 to 80% by weight based on the total solid content of the photosensitive composition.

(Other Preferred Components) In the composition of the present invention, a sensitizer for increasing the efficiency of photodegradability of the compound of the present invention having a 2-nitrobenzyl or 2- or 3-alkoxybenzyl group. A cyclic acid anhydride for increasing sensitivity, a printout agent for obtaining a visible image immediately after exposure, a dye as an image colorant, and other fillers can be added. As the cyclic acid anhydride, U.S. Pat.
Phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, as described in 128,
There are 3,6-endooxy-Δ ⁴ -tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, α-phenylmaleic anhydride, succinic anhydride, pyromellitic acid and the like. By containing these cyclic acid anhydrides in an amount of 1 to 15% by weight based on the solid content in the entire composition, the sensitivity can be increased up to about 3 times. As a printout agent for obtaining a visible image immediately after exposure, a combination of a photosensitive compound which releases an acid upon exposure and an organic dye capable of forming a salt can be mentioned as a representative example. Specifically, combinations of o-naphthoquinonediazide-4-sulfonic acid halides and salt-forming organic dyes described in JP-A-50-36209 and JP-A-53-8128, and JP-A-53- No. 36223, 5-74
No. 728, No. 60-3626, No. 61-143748.
And the salt-forming organic dyes described in JP-A Nos. 61-151644 and 63-58440. In addition to the salt-forming organic dyes described above, other dyes can be used as the image colorant. Suitable dyes including salt-forming organic 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.), Victoria Pure Blue, Crystal Violet (CI4
2555), methyl violet (CI42535),
Rhodamine B (CI145170B), Malachite Green (CI42000), Methylene Blue (CI520
15) etc. can be mentioned. In addition, JP-A-62-1
The dyes described in Japanese Patent No. 293247 are particularly preferable.

(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, it is used as it is dissolved in a solvent. As the solvent used here, ethylene dichloride, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, propanol, ethylene glycol monomethyl ether, 1
-Methoxy-2-propanol, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1
-Methoxy-2-propylacetate, dimethoxyethane, methyl lactate, ethyl lactate, N, N-dimethylacetamide, N, N-dimethylformamide, tetramethylurea, N-methylpyrrolidone, dimethylsulfoxide, sulfolane, γ-butyrolactone, toluene , Ethyl acetate, ethyl cellosolve acetate, etc., and these solvents may be used alone or as a mixture. The concentration in the above components (total solid content including additives) is 2 to 50% by weight. Further, when used by coating, the coating amount varies depending on the use, but in the case of a photosensitive lithographic printing plate, for example, solid content is generally preferably 0.5 to 3.0 g / m ² . Although the photosensitivity increases as the coating amount decreases, the physical properties of the photosensitive film deteriorate.

(Production of Planographic Printing Plate etc.) When a lithographic printing plate is produced 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, etc., 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 dimensionally remarkably stable and inexpensive. Further, a composite sheet in which an aluminum sheet is bonded onto a polyethylene terephthalate film as described in JP-B-48-18327 is preferable.
The surface of the aluminum plate is a wire brush graining, a mechanical method such as brush graining for roughening a nylon brush while pouring a slurry of abrasive particles, ball graining, grain graining by solution honing, buff graining, HF and AlCl ₃ , Graining the surface by chemical graining using HCl as an etchant, electrolytic graining using nitric acid or hydrochloric acid as an electrolytic solution, or complex graining performed by combining these roughening methods, and then acidifying as necessary. Alternatively, it is subjected to an etching treatment with an alkali, and subsequently anodized with sulfuric acid, phosphoric acid, oxalic acid, boric acid, chromic acid, sulfamic acid or a mixed acid thereof with a direct current or an alternating current power source to form a strong passivation film on the aluminum surface. Those are preferable. The aluminum surface is hydrophilized by such a passivation film itself, but if necessary, the silicate treatment (sodium silicate treatment) described in U.S. Pat. No. 2,714,066 and U.S. Pat. No. 3,181,461. , Potassium silicate), potassium fluoride zirconate treatment described in U.S. Pat. No. 2,946,638, phosphomolybdate treatment described in U.S. Pat. No. 3,201,247, British Patent No. 1,108,559. Alkyl titanate treatment described, 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 No. 8-18291, and a water-soluble agent having a sulfonic acid group described in JP-A-59-101651. Those which have been hydrophilized by a polymer undercoat are particularly preferable. Other hydrophilic treatment methods include silicate electrodeposition described in US Pat. No. 3,658,662.

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

(Actinic Rays or Radiation) Examples of the light source of actinic rays used for 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 radiation include electron beams, X-rays, ion beams, and deep ultraviolet rays. Preferably as a light source for photoresist, g
Lines, i-lines, Deep-UV light are used. Scanning exposure with a high-density energy beam (laser beam or electron beam) can also be used in the present invention. Examples of such a laser beam include a helium / neon laser, an argon laser, a krypton ion laser, a helium / cadmium laser, and a KrF excimer laser.

(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 dibasic phosphate are 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.

[0114]

The positive-type photosensitive composition of the present invention is Deep
It has excellent suitability for a light source in the UV range and oxygen plasma resistance, and is capable of alkali development. Further, it is easy to manufacture and can be easily obtained.

[0115]

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

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 was 1,200 as determined by gel permeation chromatography.

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.

The weight average molecular weight of this polysiloxane measured by gel permeation chromatography was 8,600.

Synthesis Example 3. (Polysiloxane of the present invention (Compound Example 25)) N- (p
-Hydroxyphenyl) maleimide (18.9 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 ethylene glycol monomethyl ether as a solvent to obtain 18 g of a brown target product. Obtained.

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 1700 as measured by gel permeation chromatography.

Synthesis Example 7. 3,5-Dimethoxybenzylco
Synthesis of Lucol 7.6 g of lithium aluminum hydride (LiAlH ₄ ) was dispersed in 100 ml of dehydrated and dried THF. To this, 3,
200 ml of dehydrated THF containing 36.4 g of 5-dimethoxybenzoic acid
The solution of was added dropwise with stirring over 1 hour. Then, stirring was continued at room temperature for 1 hour. 20 ml of water was added dropwise, and the remaining Li
After treating AlH ₄ , the reaction mixture was poured into 1500 ml of water. Add 20 g of concentrated hydrochloric acid to acidify, and add ethyl acetate 7
Extracted twice with 00 ml. The extract was washed with water and dried over anhydrous magnesium sulfate. The dried ethyl acetate solution was concentrated and purified by column chromatography (filler: silica gel, developing solution; hexane / ethyl acetate = 2/1) to obtain 31 g of colorless needle crystals. It was confirmed by NMR that this crystal was 3,5-dimethoxybenzyl alcohol.

Synthesis Example 8. Synthesis of compound example (a-4) 3,5-dimethoxybenzyl alcohol 16.8 g (0.1
00 mol), 9.5 g of triethylamine (0.094 mol), 1.3 g of 4- (dimethylamino) pyridine (0.01
(1 mol) was dissolved in 120 ml of acetone, and a solution of 2-naphthyloyl chloride (20.0 g, 0.105 mol) in 50 ml of acetone was added dropwise at room temperature over 30 minutes. Then, stirring was continued for 1 hour. The salt produced was filtered off, concentrated and then purified by column chromatography (filler: silica gel, after development, hexane / ethyl acetate = 5/1) to obtain 21.5 g of colorless crystals.

According to NMR, this crystal was identified as compound example (a-
4) was confirmed.

Synthesis Example 9. Synthesis of compound example (a-13) 3-methoxybenzyl alcohol 13.8 g (0.100 mol), triethylamine 9.5 g (0.094 mol), 4-
1.3 g (0.011 mol) of (dimethylamino) pyridine was dissolved in 120 ml of acetone, and a solution of 10.6 g (0.052 mol) of 2-phthaloyl chloride in 50 ml of acetone was added dropwise at room temperature over 30 minutes. did. Then, stirring was continued for 1 hour. The salt produced was filtered off and concentrated, after which Synthesis Example 7 was used.
After purification in the same manner as in (1), 13.5 g of colorless crystals were obtained.

By NMR, this crystal was identified as compound example (a-
13) was confirmed.

Synthesis example 10. Synthesis of compound example (b-6) 2,6-dinitrobenzyl alcohol 19.8 g (0.10 g )
0 mol), triethylamine 9.5 g (0.094 mol),
1.3 g (0.011 mol) of 4- (dimethylamino) pyridine was dissolved in 120 ml of acetone, and 17.0 g (0.052) of 1,5-bis (chlorosulfonyl) naphthalene was dissolved in this solution.
50 ml of acetone solution of (mol) was added dropwise at room temperature over 30 minutes. Then, stirring was continued for 1 hour. The produced salt was filtered off, concentrated, and purified in the same manner as in Synthesis Example 7 to obtain 12.8 g of colorless crystals. It was confirmed by NMR that this crystal was the compound example (b-6).

Synthesis example 11. Synthesis of compound example (c-8) 3,5-dimethoxybenzyl alcohol 16.8 g (0.1
00 mol), 9.5 g of triethylamine (0.094 mol), 1.3 g of 4- (dimethylamino) pyridine (0.01
1 mol) was dissolved in 120 ml of acetone, and 11.0 g (0.105 mol) of acetone 5 was added to methacryloyl chloride.
The 0 ml solution was added dropwise at room temperature over 30 minutes. afterwards,
Stirring was continued for 1 hour. The generated salt is filtered off and concentrated, and then column chromatography (filler: silica gel,
Purification with a developing solution, hexane / ethyl acetate = 5/1) gave 17.5 g of an oily liquid.

According to NMR, this liquid was identified as compound example (c-
It was confirmed to be 3,5-dimethoxybenzyl methacrylate of 8).

Synthesis Example 12. Synthesis of compound example (c-4) 2-nitrobenzyl alcohol 153.2 g (1.0 mol), triethylamine 95.7 g (0.94 mol), 4-
12.9 g (0.11 mol) of (dimethylamino) pyridine was dissolved in 600 ml of acetone, and a solution of 95.0 g (1.05 mol) of acryloyl chloride in 150 ml of acetone was dissolved therein.
The mixture was added dropwise at 0 ° C over 1 hour while stirring. Then, stirring was continued for 1 hour. The generated salt was filtered off, concentrated and purified by column chromatography (filler: silica gel, eluent: hexane-ethyl acetate = 10-1). 141 g of an oily liquid was obtained.

By NMR, this liquid was confirmed to be compound example (c-
It was confirmed to be 2-nitrobenzyl acrylate of 4).

Synthesis Example 13. Synthesis of Compound Example (d-5) Instead of methacryloyl chloride of Synthesis Example 11, 4-
Using 21.3 g (0.105 mol) of chlorosulfonylstyrene, the reaction and post-treatment were carried out in the same manner as in Synthesis Example 11. 25.2 g of a viscous oil was obtained. From NMR, it was confirmed that this oil was 3,5-dimethoxybenzyl 4-styrenesulfonate of Compound Example (d-5).

Synthesis Example 14. 3,5-Dimethoxybenzylme
Synthesis of Tacrylate Polymer Dissolve 2,3.6 g of 3,5-dimethoxybenzyl methacrylate in 80 ml of 2-methoxyethanol, and under a nitrogen stream,
After heating to 65 ° C., 0.025 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was added. After continuing heating and stirring for 3 hours, 0.025 g of 2,2'-azobis (2,4-dimethylvaleronitrile) was added again, and the reaction was continued for another 4 hours.

The reaction solution was poured into 2 liters of water while stirring, and the precipitated white resin was collected by filtration and dried to obtain polymer 2
2 g was obtained. When the molecular weight was measured by gel permeation chromatography (GPC), the weight average (polystyrene standard) was 55,000.

Synthesis Example 15. 3,5-Dimethoxybenzyl-
Synthesis of 4-styrene sulfonate / styrene copolymer Instead of 3,5-dimethoxybenzyl methacrylate of Synthesis Example 14, 20.1 g (0.060 mol) of 3,5-dimethoxybenzyl 4-styrene sulfonate, and 4. Using 2 g (0.040 mol), the reaction and post-treatment were carried out in the same manner as in Synthesis Example 14. 23 g of white resin was obtained.
The weight average molecular weight (GPC, polystyrene standard) is 43.
It was 000.

Examples 1 to 6 Six kinds of photosensitive liquids [A] -1 to [A] -6 were prepared by changing the kind of the polysiloxane compound of the present invention in the following photosensitive liquid [A] on a silicon wafer. The photosensitive solution was applied with a spinner and dried on a hot plate at 90 ° C. for 2 minutes. The film thickness was 1.0 μm.

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

[0145] Next, a resist pattern was formed by performing pulse exposure with a 249 nm KrF excimer laser beam through a mask and then 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 0.5 μm was obtained.

[0146] Examples 7 to 12 Novolak-based commercial resist HP on a silicon wafer
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 film thickness of the lower layer was 2.0 μm.

Further, six kinds of photosensitive solutions [B] -1 to [B] -6 were prepared by changing the kind of the benzyl ester compound of the present invention in the following photosensitive solution [B], and the photosensitive solution was spinnered. And was dried on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 0.5 μm.

Table 2 shows the benzyl ester compounds of the present invention used in the photosensitive solutions [B] -1 to [B] -6.

[0149] Next, when exposure and development were carried out in the same manner as in Examples 1 to 6, a good pattern of 0.5 μm lines and spaces was obtained.

After that, oxygen gas plasma (2.0 × 10 ^-2)
As a result of oxygen plasma etching using Torr, RF 0.06 W / cm ² ), the lower layer resist not covered with the resist pattern completely disappeared. That is, it was confirmed that this resist can be used as the upper layer resist of the two-layer resist method.

[0151]

Claims (1)

[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 and (b) a 2-nitrobenzyl ester or sulfonate compound, or 2-
Alternatively, a photosensitive composition containing a 3-alkoxybenzyl ester or a sulfonate compound. [Chemical 1] [Chemical 2] [Chemical 3]