JPH04363326A - Synthesis of functional group-containing polysiloxane - Google Patents

Abstract

PURPOSE:To easily synthesize the title polysiloxane by cyclic addition between a silyl group-substituted diene compound and olefin or acetylene compound(s) followed by hydrolysis and condensation. CONSTITUTION:Cyclic addition is made by heating (pref. to 70-160 deg.C) (A) a compound of formula I or II [R<1>-R<5> are each H, alkyl, aryl or alkoxy; X<1>-X<3> are each hydrolyzable group, alkyl, aryl, aralkyl, Y-A (Y is single bond or divalent aromatic or aliphatic hydrocarbon group; A is functional group), etc., where, at least two of them being hydrolyzable groups] and (B) at least one kind of compound of formula III-V [R<6>-R<9> are each H, halogen, CN, alkyl, aryl, -SO2R<12> (R<12> is alkyl or aryl), etc.; R<10> and R<11> are each H, alkyl or aryl], followed by hydrolysis and then condensation. The functional group A is pref. an acid group <=12 in pka value, group degradable by the action of an acid, or group reactive or responsive by the irradiation of active rays or radiation.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention can form fine resist patterns, etc. when manufacturing lithographic printing plates, proof sheets for multicolor printing, drawings for overhead projectors, and even integrated circuits of semiconductor devices. The present invention relates to a method for synthesizing polysiloxane compounds used in photosensitive compositions and other optical functional materials such as various recording elements.

0002

BACKGROUND OF THE INVENTION A photosensitive composition comprising an o-naphthoquinone diazide compound and a novolak type phenol resin has been used as an excellent photosensitive composition for producing lithographic printing plates.

However, due to the nature of the novolac type phenolic resin used as the main material, it has poor adhesion to the substrate, brittle film, poor coating properties, poor abrasion resistance, and has poor durability when used in lithographic printing plates. There are problems such as insufficient printing power.

On the other hand, as a pattern forming method for manufacturing electronic components such as semiconductor elements, magnetic bubble memories, and integrated circuits, methods using photoresists that are sensitive to ultraviolet rays or visible light have been widely used in practice. has been done. There are two types of photoresists: negative type, in which the irradiated area becomes insoluble in the developer when exposed to light, and positive type, in which the irradiated area becomes soluble in the developing solution.Negative type has better sensitivity than positive type, and is necessary for wet etching. Due to its excellent adhesion to substrates and chemical resistance, it has been the mainstream of photoresists until recently. However, with the increasing density and integration of semiconductor devices, the line width and spacing of patterns have become extremely small.
As dry etching has come to be used for substrate etching, photoresists are required to have high resolution and high dry etching resistance, and today, positive photoresists account for the majority of photoresists. Ta. In particular, it has excellent sensitivity, resolution, and dry etching resistance even among positive photoresists, so for example,
6 pages (1976) (JC Strieter. Ko
dakMicroelectronics Semin
Alkali-developable positive photoresists based on alkali-soluble novolak resins, such as those listed in arProceedings, 116 (1976), are the mainstream of current processes.

However, in recent years, electronic devices have become multi-functional,
As devices become more sophisticated, there is a strong demand for finer patterns in order to achieve higher density and higher integration.

That is, since the vertical dimension of an integrated circuit has not been reduced as much as the horizontal dimension has been reduced, the ratio of the height to the width of the resist pattern has been forced to increase. For this reason, it has become more difficult to suppress dimensional changes in a resist pattern on a wafer having a complicated step structure as patterns become finer. Furthermore, problems have also arisen in various exposure methods as the minimum dimension is reduced. For example, in light exposure, the interference effect of reflected light due to the step difference in the substrate has a large effect on dimensional accuracy, while in electron beam exposure, the proximity effect caused by back scattering of electrons causes fine resist It is no longer possible to increase the height to width ratio of a pattern.

It has been found that many of these problems can be overcome by using a multilayer resist system. For multilayer resist systems, see Solid State Technology, 74 (1981) [Solid Stat
e Technology, 74 (1981)], and many other studies regarding this system have also been published. Generally, multilayer resist methods include a three-layer resist method and a two-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 layered on top of it, the resist is patterned, and the inorganic intermediate layer is dry-etched using this as a mask. This is a method of patterning an organic planarization film by O2RIE (reactive ion etching) using an inorganic intermediate layer as a mask. This method has been studied from an early stage because it basically allows the use of conventional techniques, but the process is very complicated. Another problem is that cracks and pinholes are likely to occur in the intermediate layer due to the overlapping of three layers with different physical properties: an organic film, an inorganic film, and an organic film. In contrast to this three-layer resist method, the two-layer resist method uses a resist that has the properties of both the resist in the three-layer resist method and the inorganic intermediate layer, that is, a resist that is resistant to oxygen plasma, so it is free from cracks. The generation of pinholes is suppressed, and the process is simplified since there are two layers instead of three. However, in the three-layer resist method, a conventional resist can be used as the upper layer resist, whereas in the two-layer resist method,
The challenge was to develop a new resist that was resistant to oxygen plasma.

[0008] From the above background, a resist with excellent oxygen plasma resistance that can be used as an upper layer resist in a two-layer resist method, etc.
It has been desired to develop a positive photoresist with high sensitivity and high resolution, especially an alkaline development type resist that can be used without changing the current process.

On the other hand, photosensitive compositions in which a conventional orthoquinonediazide photosensitive material is combined with a silicone polymer such as polysiloxane or polysylmethylene that has been imparted with alkali solubility, such as JP-A-61-144639 and JP-A-61-144639; -256347, 62-159141, 6
No. 2-191849, No. 62-220949, No. 62
-229136, 63-90534, 63-9
No. 1654, as well as the photosensitive compositions described in U.S. Pat. It is presented.

However, all of these silicone polymers have phenolic OH groups or silanol groups (≡Si
If alkali solubility is imparted by introducing a phenolic OH group, production becomes extremely difficult, and if alkali solubility is imparted by a silanol group, stability over time is not necessarily guaranteed. There was a problem that it was not good.

[0011]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for synthesizing a polysiloxane compound used in a novel photosensitive composition, which solves the above-mentioned problems. That is, it is an object of the present invention to provide a method for synthesizing a polysiloxane compound that is easy to synthesize and allows the introduction of various functional groups.

0012

[Means for Solving the Problems] As a result of intensive studies to achieve the above object, the present inventors have found that the above object can be achieved by the synthesis method described below.

That is, the present invention provides (a) at least one compound represented by the following general formula (I) or (II) and at least one compound represented by the general formula (III), (IV), or (V). After cycloadding one type by heating, hydrolysis and further condensation, or (b) general formula (I)
Or, after hydrolyzing and further condensing at least one compound represented by (II), the general formula (III), (I
This is a method for synthesizing a polysiloxane containing a functional group by subjecting at least one compound represented by V) or (V) to cycloaddition by heating.

The functional group is preferably an acid group having a pKa value of 12 or less, a group that can be decomposed by the action of an acid, or a group that reacts or responds to irradiation with actinic light or radiation. In one embodiment of the present invention, during hydrolysis and further condensation,
The following general formulas (VI), (VII), (VIII), (
At least one compound represented by IX) or (X) is allowed to coexist and co-condensed. Further, in another embodiment of the present invention, when carrying out cycloaddition by heating, at least one olefin or acetylene compound not having a -YA group in the above general formula is allowed to coexist,
Co-introduced into the structure of polysiloxane.

[0015]

embedded image In the formula, R1 to R5 may be the same or different and represent a hydrogen atom, an alkyl, an aryl, or an alkoxy group, preferably a hydrogen atom, a linear or branched group having 1 to 10 carbon atoms. or a cyclic alkyl, a monocyclic or polycyclic aryl having 6 to 15 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms.

R6 to R9 may be the same or different, and are hydrogen atoms, halogen atoms, cyano, carbonyl,
Alkyl, aryl, alkoxy group, -SO2-R12
, -SO3-R12, -CO-R12, -CO-
NH-R12, -COO-R12 or -Y-A,
Preferably hydrogen atom, chlorine atom, cyano, carbon number 1-6
linear, branched or cyclic alkyl, monocyclic or polycyclic aryl having 6 to 10 carbon atoms, or alkoxy group having 1 to 6 carbon atoms, -SO2-R12, -SO3-R12, -C
O-R12, -CO-NH-R12, -COO-R1
2 or -Y-A, more preferably a hydrogen atom, -
SO2-R12 , -SO3-R12 , -CO-R1
2, -CO-NH-R12, -COO-R12 or -
It is Y-A. R10 and R11 represent a hydrogen atom, an alkyl group, or an aryl group, preferably a hydrogen atom or a carbon number of 1
~4 straight-chain or branched alkyl groups. Also R6 ~
Two of R8 and Y or R10 to R11 may be combined to form a ring. Y represents a single bond, a divalent aromatic or aliphatic hydrocarbon group, preferably a single bond and a carbon number of 1 to 4
straight-chain or branched alkylene, monocyclic or polycyclic arylene group having 6 to 10 carbon atoms. Furthermore, Y may contain groups such as ketone, ether, ester, amide, urethane, and ureido. R12 represents an alkyl or aryl group, preferably a straight chain, branched or cyclic alkyl group having 1 to 10 carbon atoms, or a monocyclic or polycyclic aryl group having 6 to 15 carbon atoms. Further, on the aryl group, alkyl having 1 to 6 carbon atoms, alkoxy having 1 to 8 carbon atoms, halogen atom, carboxy,
Those substituted with carboxyester, cyano, dialkylamino or nitro groups are also preferred.

A is a functional group, preferably an acid group having a pKa value of 12 or less, a group that can be decomposed by the action of an acid, or a group that reacts or responds to irradiation with actinic rays or radiation. Specifically, acid groups with a pKa value of 12 or less include:
Carboxylic acid group, sulfonic acid group, phenolic hydroxyl group, imide group, N-hydroxyimide group, N-sulfonylamide group, sulfonamide group, N-sulfonylurethane group,
It is a group having an N-sulfonylureido group or an active methylene group, and more specifically, the following are mentioned.

[0018]

embedded image Preferred examples of the group decomposable by acid include the following.

[0019]

embedded image R29 to R31 may be the same or different and represent an alkyl, aryl, alkoxy or aryloxy group,
R32 to R38 may be the same or different and represent a hydrogen atom, an alkyl group, or an aryl group.

Groups that react upon irradiation with actinic rays or radiation include active species (such as carbene,
nitrene, radical, cation, cation radical,
or anion radical), specifically 1,2-quinonediazide, azide, trihalomethyl-substituted s-triazine or oxadiazole, o-nitrobenzyl ester, o- or m-alkoxybenzyl ester , and the following groups.

[0021]

embedded image Here, R39 represents an alkyl, alkenyl or aryl group, and R40 represents a hydrogen atom, a halogen atom, an alkyl, aryl, alkoxy, nitro, cyano or dialkylamino group. R41 to R43 may be the same or different and represent an alkyl or aryl group, and B represents a divalent alkylene or arylene group. n represents an integer of 0 to 4.

[0022] Specifically, the group that responds to irradiation with actinic light or radiation is a group having a photochromic structure, such as azobenzene, spirobenzopyran,
Examples include groups having structures such as diarylethene derivatives represented by naphthoxazine, indigo, and fulgide.

X1, X2, and X3 may be the same or different, and are halogen atoms, hydroxy, carboxy, oxime, amide, ureido, amino, alkyl, aryl, aralkyl, alkoxy, aryloxy, -Y
-A or the following group.

[0024]

Preferably, a chlorine atom, a straight chain, branched or cyclic alkyl having 1 to 10 carbon atoms, a monocyclic or polycyclic aryl having 6 to 15 carbon atoms, an aralkyl having 7 to 15 carbon atoms, and a carbon Numbers 1-8
represents an alkoxy group having 6 to 10 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms. However, at least two of X1, X2, and X3 are halogen atoms, hydroxy, carboxy,
Indicates an oxime, amide, ureido, amino, alkoxy or aryloxy group.

[0025]

embedded image In the formula, R13 to R19, R21 to R23, and R25 to R26 may be the same or different, and represent a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an alkenyl group, Indicates a substituted alkenyl group, silyl group, substituted silyl group, siloxy group, or substituted siloxy group. Specifically, the alkyl group is linear, branched, or cyclic, and preferably has about 1 to about 10 carbon atoms. Specifically, for example, methyl group, ethyl group, propyl group, butyl group, hexyl group,
Included are octyl group, decyl group, isopropyl group, isobutyl group, tert-butyl group, 2-ethylhexyl group, cyclohexyl group, and the like. Substituted alkyl groups include the above-mentioned alkyl groups, for example, halogen atoms such as chlorine atoms, alkoxy groups having 1 to 6 carbon atoms such as methoxy groups, aryl groups such as phenyl groups, e.g. Substituted aryloxy groups such as phenoxy groups are included, specifically monochloromethyl group, dichloromethyl group, trichloromethyl group, bromomethyl group, 2-chloroethyl group, 2-bromoethyl group, 2-methoxyethyl group. group, 2-ethoxyethyl group, phenylmethyl group, naphthylmethyl group, phenoxymethyl group, and the like. Further, the aryl group is preferably a monocyclic or bicyclic group, such as a phenyl group, an α-naphthyl group, a β-naphthyl group, and the like. The 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 or an ethyl group, an alkoxy group having 1 to 6 carbon atoms such as a methoxy group or an ethoxy group, Examples include those substituted with a halogen atom such as a chlorine atom, a nitro group, a phenyl group, a carboxy group, a hydroxy group, an amide group, an imide group, a cyano group, and specifically, a 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-methoxy Phenyl 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-
Examples include bromo-2-naphthyl group and 5-hydroxy-2-naphthyl group. The alkenyl group is, for example, a vinyl group, and the substituted alkenyl group includes vinyl groups substituted with an alkyl group such as a methyl group, an aryl group such as a phenyl group, and specifically a 1-methyl group. Vinyl group, 2-methylvinyl group, 2-methylvinyl group, 1,2-dimethylvinyl 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. Examples of the silyl group and substituted silyl group include alkyl- and aryl-substituted silyl groups such as trialkylsilyl group and triarylsilyl group, and examples of such alkyl and aryl groups include those shown above. In addition, in the case of a siloxy group or a substituted siloxy group, as shown below, there is a structure in which these groups are bonded to a siloxy group or a substituted siloxy group in an adjacent structural unit, or a siloxy group or a substituted 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.

[0026]

embedded image R23, R27, and R30 may be the same or different and represent a single bond, divalent alkylene, substituted alkylene, arylene, or substituted arylene group. in particular,
The alkylene group is linear, branched, or cyclic, more preferably linear, and preferably has 1 to 10 carbon atoms, such as methylene, ethylene, butylene, octylene, etc. Each group is included. The substituted alkylene group is one in which the above alkylene group is substituted with, for example, a halogen atom such as a chlorine atom, an alkoxy group having 1 to 6 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or the like. The arylene group is preferably monocyclic or bicyclic, and includes, for example, a phenylene group, a naphthylene group, and the like. In addition, the substituted arylene group includes an arylene group as described above, an alkyl group having 1 to 6 carbon atoms such as a methyl group or an ethyl group, or an alkyl group having 1 to 6 carbon atoms such as a methoxy group or an ethoxy group. It includes groups substituted with, for example, halogen atoms such as chlorine atoms. 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.

X is a hydrolyzable group, preferably a halogen atom such as a chlorine atom or a bromine atom, a methoxy group,
1 or more carbon atoms such as ethoxy group, propoxy group, etc.
10 alkoxy groups, aryloxy groups with 6 to 10 carbon atoms such as phenoxy groups, carboxyl groups with 1 to 10 carbon atoms such as acetoxy groups, carbon atoms such as methylaldoxime, etc. It includes 1 to 6 oxime groups, as well as amide groups, ureido groups, amino groups, and the like.

The polysiloxane polymer of the present invention comprises a silyl group-substituted diene compound represented by the general formula (I) or (II), an olefin represented by the general formula (III), (IV) or (V), or Cyclic thermal addition products with acetylene compounds, the so-called Diels-Alder reaction products (XI), (XII), (XIII), (XIV
), or (XVI).

[0029]

embedded image (However, R1 to R12, X1 to X3, Y, and A have the same meanings as above.)

The method for producing the polysiloxane compound of the present invention includes formula (I) or (II) compounds alone or in combination, hydrolyzed or alkoxylated, and then condensed to form the formula (III), ( IV) A method of thermally adding a compound of formula (I) or (II) to a compound of formula (III), (IV), or (V); Formula (XI), (XII), (XIII)
, (XIV), (XV) or (XVI), hydrolysis,
Alternatively, there is a method of alkoxylation followed by condensation.

[0031] Also, general formula (III), (IV), or (
After synthesizing a polysiloxane skeleton in the same manner as above using the olefin or atyselene compound before introduction of the functional group A in V), reacting the compound having the functional group A,
A functional group A structure may be introduced into the polysiloxane.

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-dimethylformamide, N,N-dimethylacetamide,
Dimethyl sulfoxide, toluene, ethyl acetate, methyl lactate, ethyl lactate, γ-butyrolactone, dioxane,
Examples include tetrahydrofuran. These solvents may be used alone or in combination of two or more.

[0033] The temperature during the cyclic heat addition is 40°C or higher, preferably 50 to 200°C, more preferably 7°C.
The temperature is 0 to 160°C. Furthermore, when adding cyclic heat,
Catalysts such as aluminum chloride, Lewis acids such as trifluoroborane, or Bronsted acids may be used to increase the efficiency of heat addition.

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

When the polysiloxane synthesized according to the present invention is used in a photosensitive composition for a lithographic printing plate or a semiconductor resist, if necessary, a 1,2-naphthoquinone-2-diazide compound, a diazonium salt compound, etc. , in combination with a positive or negative photosensitive compound such as an azide compound.

More preferably, the following additives are used in combination.

(Alkali-Soluble Polymer) The photosensitive composition of the present invention can essentially be used with only the siloxane polymer of the present invention, but an alkali-soluble polymer may be further added thereto.

Such alkali-soluble polymers preferably have pKall groups such as phenolic hydroxyl groups, carboxylic acid groups, sulfonic acid groups, imide groups, sulfonamide groups, N-sulfonylamide groups, N-sulfonylurethane groups, and active methylene groups. It is a polymer having the following acidic hydrogen atoms. Suitable alkali-soluble polymers include novolac-type phenolic resins, specifically phenol-formaldehyde resins, o-cresol-formaldehyde resins, m-
Examples include cresol-formaldehyde resin, p-cresol-formaldehyde resin, xylenol-formaldehyde resin, and cocondensates thereof. Furthermore, JP-A-5
As described in Publication No. 0-125806, in addition to the above-mentioned phenol resins, phenol substituted with an alkyl group having 3 to 8 carbon atoms such as t-butylphenol formaldehyde resin or a condensation product of cresol and formaldehyde can be used. may be used together. Also, polymers containing phenolic hydroxy group-containing monomers such as N-(4-hydroxyphenyl) methacrylamide as a copolymerization component, p-hydroxystyrene, o-hydroxystyrene, m-isopropenylphenol, p-isopropenylphenol, etc. Single or copolymerized polymers of these polymers, and partially etherified or partially esterified polymers of these polymers can also be used.

Furthermore, polymers containing carboxyl group-containing monomers such as acrylic acid and methacrylic acid as copolymerization components,
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.

Furthermore, polymers containing N-(4-sulfamoylphenyl)methacrylamide, N-phenylsulfonylmethacrylamide, and maleimide as copolymerization components, active methylene group-containing polymers described in JP-A-63-127237; can also be used.

[0041] These alkali-soluble polymers can be used alone, or as a mixture of several types. The amount added in the photosensitive composition is preferably 10 to 90% by weight, more preferably 30 to 8% by weight based on the total solid content of the photosensitive composition.
It is in the range of 0% by weight.

(Other preferred components) The photosensitive composition of the present invention may further contain dyes, pigments, plasticizers, compounds that generate acid upon irradiation with actinic rays or radiation, and photoreaction of functional groups. Compounds that increase efficiency (so-called sensitizers) can be included.

Compounds that can generate acids upon irradiation with actinic rays or radiation include many known compounds and mixtures,
For example, JP-A-50-158680, JP-A No. 51-568
No. 85, No. 51-100716, Special Publication No. 52-142
No. 77, No. 52-14278, U.S. Patent No. 4,442
, 197 and West German Patent No. 2,904,626 of diazonium, phosphonium, sulfonium, and iodonium BF4-, AsF6-, PF6
-, SbF6-, SiF6-, ClO4-, salts, organohalogen compounds, and organometallic/organohalogen compound combinations are suitable. Of course, U.S. Patent No. 3,779,778 and West German Patent No. 2,610
, 842 and EP 126,712, which generate acids upon photolysis, are also suitable. Furthermore, compounds intended to provide a visual contrast between unexposed areas and exposed areas during exposure in combination with appropriate dyes, such as JP-A-55-77742 and JP-A-57-57-
Compounds described in Publication No. 163234 can also be used.

[0044]Also, 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 (manufactured by Orient Chemical Industry Co., Ltd.), Crystal Violet (CI42555), Methyl Violet (CI42535), Rhodamine B (C
I145170B), malachite green (CI420
00), methylene blue (CI52015), etc.

A cyclic acid anhydride, a printing-out agent for obtaining a visible image immediately after exposure, and other fillers may be added to the composition of the present invention in order to further increase the sensitivity. As a cyclic acid anhydride, U.S. Patent No. 4,115,128
Phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3
, 6-endoxy-Δ4-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 of the entire composition, the sensitivity can be increased up to about 3 times. Typical print-out agents for obtaining a visible image immediately after exposure include a combination of a photosensitive compound that releases an acid upon exposure and an organic dye that can form a salt. Specifically, JP-A-50-36209, JP-A-53-8
The combination of o-naphthoquinonediazide-4-sulfonic acid halide and salt-forming organic dye described in JP-A No. 128, JP-A-53-36223, JP-A-54-7
A combination of a trihalomethyl compound and a salt-forming organic dye described in Japanese Patent No. 4728 can be mentioned.

(Solvent) When the photosensitive composition of the present invention is used as a material for a lithographic printing plate, it is dissolved in a solvent that dissolves each of the above components and coated on a support. Furthermore, for resist materials such as semiconductors, it is used as it is dissolved in a solvent. The solvents used here include ethylene dichloride, cyclohexanone, methyl ethyl ketone, methanol, ethanol, propanol, ethylene glycol monomethyl ether,
-methoxy-2-propanol, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 2
-Ethoxyethyl 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, etc., and these solvents may be used alone or in combination. The concentration of 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 application, but for example, for photosensitive planographic printing plates, the solid content is generally preferably 0.5 to 3.0 g/m2. As the coating amount decreases, the photosensitivity increases, but
The physical properties of the photoresist film deteriorate.

(Production of lithographic printing plates, etc.) When producing lithographic printing plates using the photosensitive composition of the present invention, examples of the support include paper, plastics (eg, polyethylene, polypropylene, polystyrene, etc.). Paper laminated with metal plates such as aluminum (including aluminum alloys), zinc, copper, etc., such as cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, Examples include films of plastics such as polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc., and paper or plastic films laminated with or vapor-deposited with the metals mentioned above. Among these supports, aluminum plates are particularly preferred because they are extremely dimensionally stable and inexpensive. Furthermore, a composite sheet in which an aluminum sheet is bonded to a polyethylene terephthalate film as described in Japanese Patent Publication No. 48-18327 is preferred. The surface of the aluminum plate is processed by wire brush graining, brush graining, which roughens the surface with a nylon brush while pouring slurry of abrasive particles, ball graining,
Graining by solution honing, mechanical methods such as buff graining, chemical graining using HF, AlCl3, or HCl as an etchant, electrolytic graining using nitric acid or hydrochloric acid as an electrolyte, and a combination of these roughening methods. After the surface is grained by composite graining, it is etched with acid or alkali as necessary, and then subjected to direct current or alternating current in sulfuric acid, phosphoric acid, oxalic acid, boric acid, chromic acid, sulfamic acid, or a mixed acid thereof. Preferably, the aluminum is anodized using a power source to form a strong passive film on the aluminum surface. This passive film itself makes the aluminum surface hydrophilic, but
Furthermore, if necessary, silicate treatment (sodium silicate, potassium silicate) as described in U.S. Pat. No. 2,714,066 and U.S. Pat. No. 3,181,461, U.S. Pat. , 946,638, phosphomolybdate treatment as described in U.S. Pat. No. 3,201,247, and British Patent No. 1,108,55.
Alkyl titanate treatment described in No. 9 specification,
Polyacrylic acid treatment as described in German Patent No. 1,091,433, German Patent No. 1,134,0
Polyvinylphosphonic acid treatment described in No. 93 specification and British Patent No. 1,230,447, phosphonic acid treatment described in Japanese Patent Publication No. 44-6409, and U.S. Patent No. 3,307,951. The phytic acid treatment described in the specification of the No. 58-16893 and the complex of a water-soluble organic polymer and a divalent metal ion described in the respective publications of JP-A-58-16893 and JP-A-58-18291 Particularly preferred are those subjected to a hydrophilic treatment by undercoating a water-soluble polymer having a sulfonic acid group as described in JP-A-59-101651. Other hydrophilic treatment methods include silicate electrodeposition as described in US Pat. No. 3,658,662.

[0048] It is also preferable to carry out graining treatment, anodization, and then sealing treatment. Such a sealing treatment is performed by immersion in hot water and a hot aqueous solution containing an inorganic or organic salt, a steam bath, and the like.

(Active Ray or Radiation) Examples of the active light source used in the present invention include a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, and a carbon arc lamp. Examples of radiation include electron beams, X-rays, ion beams, and far ultraviolet rays. Preferably, g-line, i-line, or deep-UV light is used as a light source for photoresist. Scanning exposure with a high-density energy beam (laser beam or electron beam) can also be used in the present invention. Examples of such laser beams include helium-neon laser, argon laser, krypton ion laser, helium-cadmium laser, and KrF excimer laser.

(Developer) Examples of the developer for the photosensitive composition of the present invention include sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, Aqueous solutions of inorganic alkaline agents such as tertiary ammonium phosphate, diammonium phosphate, sodium metasilicate, sodium bicarbonate, aqueous ammonia, etc. and organic alkaline agents such as tetraalkylammonium OH salts are suitable; The concentration of is 0.1-1
It is added in an amount of 0% by weight, preferably 0.5 to 5% by weight.

[0051] Furthermore, a surfactant or an organic solvent such as alcohol can be added to the alkaline aqueous solution if necessary.

[0052]

EXAMPLES The present invention will be explained in more detail below using synthesis examples and examples, but the content of the present invention is not limited thereto.

Synthesis Example 1. Maleimide 7.3g, 2-trimethoxysilyl-1,3
-13.1 g of butadiene was dissolved in 500 ml of dioxane and reacted 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.
The mixture was heated and concentrated for 0 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 polysiloxane of the present invention.

The weight average molecular weight of this polysiloxane was determined to be 1200 by gel permeation chromatography.

Synthesis Example 2. 11.4 g of acetylene dicarboxylic acid, 17.4 g of 2-trimethoxysilyl-1,3-butadiene, and 122.6 g of tolyltrimethoxyxane were reacted in the same manner as in Synthesis Example 1 using dioxane as a solvent to obtain the polysiloxane of the present invention. 43g was obtained.

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

Synthesis Example 3. N-(p-hydroxyphenyl)maleimide 18.
9g, 2-trimethoxysilyl-1,3-butadiene 1
7.4 g of ethylene glycol monomethyl ether 50
A reaction was carried out in the same manner as in Synthesis Example 1 using 0 ml as a solvent to obtain 18 g of a brown target product.

The weight average molecular weight of this polysiloxane was determined to be 3,300 by gel permeation chromatography.

Synthesis Example 4. Synthesis of vinyl-1-naphthyldisulfone: Dissolve 189 g of sodium sulfite in 600 ml of water and
Heat to 70°C and add 1-naphthalenesulfonyl chloride 6.
After adding 8 g, the reaction was carried out at 50 to 60°C for 5 hours. After filtering off insoluble matter, the reaction solution was returned to room temperature and concentrated hydrochloric acid was added to make the reaction system acidic. The deposited precipitate was collected by filtration to obtain 55 g of 1-naphthalenesulfinic acid.

Add 15 ml of water to 9.6 g of 1-naphthalenesulfinic acid, and add 2 g of sodium hydroxide to this.
A solution prepared by dissolving this in 5 ml of water was added. A solution prepared by dissolving 6.3 g of vinyl sulfonyl chloride in 20 ml of acetonitrile was added to this solution while stirring at room temperature, and the mixture was further reacted with stirring at room temperature for 24 hours. Pour the reaction solution into 300 ml of water, collect the precipitate by filtration,
Recrystallization was performed from a mixed solvent of benzene and ethanol to obtain 3.5 g of vinyl-1-naphthyldisulfone.

Synthesis Example 5. 2-(trimethoxysilyl)-1,3-butadiene4.
4 g (0.025 mol) and 180 g (0.075 mol) of phenyltriethoxysilane were dissolved in 100 ml of dioxane, further dissolved in 10 ml of distilled water, and then 10 ml of distilled water and 0.1 g of concentrated hydrochloric acid were added. Stir for a minute. Thereafter, the solvent was distilled off under heating to concentrate. After 80 ml of dioxane was added to the concentrate to redissolve it, 7.1 g (0.025 mol) of vinyl-1-naphthyldisulfone was added, and the mixture was heated and stirred at 100° C. for 1 hour. The reaction solution was poured into 1 liter of water with stirring, and the precipitate was dried under vacuum. 17 g of brownish white resin was obtained. The structure was confirmed by NMR, and the molecular weight was measured by gel permeation chromatography (GPC), and the weight average (polystyrene standard) was 3,000.

Synthesis Example 6. N-Hydroxyphthalimide-vinylsulfonic acid ester 50 ml of acetone was added to 3.3 g of N-hydroxyphthalimide and 2.6 g of vinylsulfonyl chloride, and 2.0 g of triethylamine was added over 10 minutes while stirring at room temperature (approximately 20°C). It was added dropwise and further stirred at room temperature for 1 hour, then poured into 200 g of ice water, and the resulting precipitate was recrystallized from a benzene/ethanol mixed solvent to give N-
Hydroxyphthalimide-vinyl sulfonic acid ester 4
．． Obtained 0g.

Synthesis Example 7. 2-(trimethoxysilyl)-1,3-butadiene8.
7g (0.05 mol), N-hydroxyphthalimide
Vinyl sulfonic acid ester 12.7g (0.05mol)
was dissolved in 100 ml of dioxane, and the mixture was heated and stirred at 100°C for 1 hour. After cooling to room temperature, 9.9 g (0.05 mol) of trimethoxyphenylsilane was added. Furthermore, 10 ml of distilled water and 0.1 g of concentrated hydrochloric acid were added and stirred for 30 minutes. Then, heat the solvent dioxane,
Concentrated. The concentrate was poured into 1 liter of water with stirring, and the precipitated solid was dried under vacuum. 24 g of brownish white resin was obtained. The structure was confirmed by NMR, and the molecular weight was measured by gel permeation chromatography (GPC), and the weight average weight (polystyrene standard) was 3,500.

Synthesis Example 8. 2-(trimethoxysilyl)-1,3-butadiene8.
8g (0.05mol), phenyltriethoxysilane 1
Dissolve 2.0 g (0.05 mol) in 100 ml of dioxane, then add 10 ml of distilled water and concentrated hydrochloric acid.
．． 1 g was added and stirred for 30 minutes. Thereafter, the solvent dioxane and water were distilled off under heating to concentrate. After adding 80 ml of dioxane to the concentrate and redissolving it, 11.1 g of 3,5-dimethoxybenzyl acrylate was added.
(0.05 mol) was added, and the mixture was heated and stirred at 100°C for 1 hour. The reaction solution was poured into 1 liter of water with stirring, and the precipitate was dried under vacuum. 20.5 g of white resin was obtained. N
The structure was confirmed by MR, and the molecular weight was measured by gel permeation chromatography (GPC), and the weight average (polystyrene standard) was 3,600.

Synthesis Example 9. 2-(trimethoxysilyl)-1,3-butadiene 87
．． 1 g (0.50 mol) and 103.6 g (0.50 mol) of 2-nitrobenzyl acrylate were dissolved in 1 liter of dioxane, and the mixture was heated and stirred at 100° C. for 1 hour. After cooling to room temperature, 99.1 g of trimethoxyphenylsilane
(0.50 mol) was added. Furthermore, 70 ml of distilled water and 0.5 g of concentrated hydrochloric acid were added and stirred for 30 minutes. Thereafter, dioxane as a solvent was heated and concentrated. 1 part concentrate to water
0 liter with stirring, and the precipitated solid was dried under vacuum. 220 g of brownish-white resin were obtained. The structure was confirmed by NMR, and the molecular weight was measured by gel permeation chromatography (GPC).
The weight average (polystyrene standard) was 4,500.

Synthesis Example 10. 2-(trimethoxysilyl)-1,3-butadiene8.
1g (0.050 mol), N-(p-t-butoxycarbonyloxyphenyl)maleimide 14.5g (0.0
50 mol) in 100 ml of dioxane,
The mixture was heated and stirred at 100° C. for 1 hour. After cooling to room temperature,
9.1 g (0.050 mole) of trimethoxyphenylsilane was added. Additionally, 10 ml of distilled water and 0 concentrated hydrochloric acid.
．． 1 g was added and stirred for 30 minutes. Thereafter, dioxane as a solvent was heated and concentrated. The concentrate was poured into 1 liter of water with stirring, and the precipitated solid was dried under vacuum. 22.1 g of white resin was obtained. The structure was confirmed by NMR and gel permeation chromatography (GP).
When the molecular weight was measured using C), the weight average (polystyrene standard) was 4,000.

Synthesis Example 11. 2-(trimethoxysilyl)-1,3-butadiene8.
7 g (0.050 mol) and 9.5 g (0.050 mol) of N-(p-hydroxyphenyl)maleimide were dissolved in 100 ml of dioxane, and the mixture was heated and stirred at 100° C. for 1 hour. After cooling to room temperature, 9.9 g (0.050 mol) of trimethoxyphenylsilane was added. Furthermore, 10 ml of distilled water and 0.1 g of concentrated hydrochloric acid were added, and the mixture was stirred for 30 minutes. Thereafter, the solvent dioxane was concentrated by heating. 1 part concentrate to water
The precipitated solid was dried under vacuum. 22.4 g of white resin was obtained.

This resin was dissolved again in 100 ml of dioxane, 3.4 g (0.050 mol) of imidazole was added, and 5.5 g (0.05 mol) of trimethylchlorosilane was added.
0 mol) dioxane solution in 20 ml was added dropwise over 30 minutes. Thereafter, stirring was continued for 24 hours at room temperature. After filtering off the imidazole HCl salt, the reaction solution was diluted with 2 ml of water.
liter while stirring. As a result of drying the precipitated resin under vacuum, 24.5 g of white resin was obtained.

[0070] It was confirmed by NMR that a trimethylsilyl ether group had been introduced. In addition, when the molecular weight was measured by gel permeation chromatography (GPC), the weight average (polystyrene standard) was 5.30.
It was 0.

Synthesis Example 12. 2-(trimethoxysilyl)-1,3-butadiene8.
7 g (0.05 mol) and 8.2 g (0.05 mol) of N-(p-hydroxyphenyl)acrylamide were dissolved in 100 ml of dioxane, and the mixture was heated and stirred at 100° C. for 1 hour. After cooling to room temperature, 9.9 g (0.05 mol) of trimethoxyphenylsilane was added. Furthermore, 10 ml of distilled water and 0.1 g of concentrated hydrochloric acid were added and stirred for 30 minutes. Thereafter, dioxane as a solvent was heated and concentrated. The concentrate was poured into 1 liter of water with stirring, and the precipitated solid was dried under vacuum. Brownish white resin18.
2g was obtained.

This resin was redissolved in 100 ml of γ-butyrolactone, and 13.4 g (0.050 ml) of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride
mol) was added. Add 5.1 ml of triethylamine to this solution.
g (0.050 mol) was added dropwise over 20 minutes. Thereafter, 15 ml of water was added, and triethylamine was further added dropwise to adjust the pH of the reaction solution to about 6.5. The reaction mixture was poured into 3 liters of water with stirring. As a result of drying the precipitated resin under vacuum, a yellow resin 26.
5g was obtained. By NMR, 1,2-naphthoquinone-2
It was confirmed that the -diazide-5-sulfonic acid ester group was introduced. Further, when the molecular weight was measured by gel permeation chromatography (GPC), the weight average (polystyrene standard) was 4,800.

Reference Example 1 A 0.24 mm thick 2S aluminum plate was degreased by immersing it in a 10% aqueous solution of tertiary sodium phosphate kept at 80°C for 3 minutes, grained with a nylon brush, and then polished with sodium aluminate. After etching for 10 minutes, a desmut treatment was performed with a 3% aqueous solution of sodium hydrogen sulfate. This aluminum plate was anodized in 20% sulfuric acid at a current density of 2 A/dm 2 for 2 minutes to prepare an aluminum plate.

Next, the following photosensitive solution [A] was applied onto an anodized aluminum plate and dried at 100° C. for 2 minutes to prepare a photosensitive lithographic printing plate [A]. The coating amount at this time was 2.0 g/m2 in terms of dry weight.

Photosensitive liquid [A] A gray scale with a density difference of 0.15 was brought into close contact with the photosensitive layer of the photosensitive lithographic printing plate [A], and a 2 kW high-pressure mercury lamp was used to heat the photosensitive layer at 50° C.
Exposure was performed for 2 minutes from a distance of cm. When the exposed photosensitive lithographic printing plate [A] was immersed and developed in an 8-fold diluted aqueous solution of DP-4 (product name: Fuji Photo Film Co., Ltd.) at 25°C for 60 seconds, a clear blue positive image was obtained. It was done.

Reference Example 2 Novolac commercially available resist HP was applied on a silicon wafer.
R-204 (manufactured by Fuji Hunt Chemical Co., Ltd.) was applied using 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.

The following photosensitive solution [B] was applied thereon using a spinner and dried on a hot plate at 90° C. for 2 minutes to form a coating film with a thickness of 0.5 μm. Photosensitive liquid [B]

[0078] Next, it was exposed using a reduction projection exposure device (stepper) using monochromatic light with a wavelength of 436 nm, and exposed with a 2.4% aqueous solution of tetramethylammonium hydroxide.
A resist pattern was formed by developing for 0 seconds. As a result, a good pattern of lines and spaces of 0.8 μm was obtained.

After that, oxygen gas plasma (2.0×10
As a result of oxygen plasma etching using -2 Torr and RF of 0.06 W/cm2, the lower resist in the portions not covered by the resist pattern completely disappeared. That is, it was confirmed that this resist can be used as an upper layer resist in a two-layer resist method.

Claims (5)

[Claims] Claim 1: At least one compound represented by the following general formula (I) or (II) and general formula (III), (I
A method of synthesizing a polysiloxane containing a functional group by cycloadding at least one compound represented by V) or (V) by heating, followed by hydrolysis and further condensation. [Chemical formula 1] [Chemical formula 2] [Claim 2] General formula (I) according to Claim 1 or (
After hydrolyzing and further condensing at least one compound represented by II), at least one compound represented by general formula (III), (IV), or (V) is cycloadded by heating to obtain functionality. A method for synthesizing polysiloxanes containing groups. 3. An acid group in which the functional group has a pKa value of 12 or less,
The method according to claim 1 or 2, wherein the method is a group that can be decomposed by the action of an acid, or a group that reacts or responds to irradiation with actinic rays or radiation. 4. At the time of hydrolysis and further condensation, at least one compound represented by the following general formula (VI), (VII), (VIII), (IX) or (X) is co-present and co-condensation is carried out. Claim (1) or (2) characterized by
) method described. embedded image In the formula, R13 to R19, R21 to R23, and
R25 to R26 may be the same or different, and include a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an alkenyl group, a substituted alkenyl group, an aryl group, a substituted aryl group, a silyl group, and a substituted silyl group. group, siloxy group or substituted siloxy group. R20, R
24 and R27 may be the same or different, and represent a single bond, divalent alkylene, substituted alkylene, arylene,
or a substituted arylene group. X represents a hydrolyzable group. 5. A claim characterized in that during the cycloaddition by heating, at least one olefin or acetylene compound having no -YA group in the above general formula is present and introduced into the structure of the polysiloxane. The method described in item (1) or (2).