JP2736939B2 - Method for synthesizing functional group-containing polysiloxane - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention makes it possible to form fine resist patterns and the like when manufacturing lithographic printing plates, proofs for multicolor printing, drawings for overhead projectors, and integrated circuits of semiconductor devices. The present invention relates to a method for synthesizing a polysiloxane compound used for an optical functional material such as a photosensitive composition and various other recording elements.

[0002]

2. Description of the Related Art A photosensitive composition comprising an o-naphthoquinonediazide compound and a novolak-type phenol resin has been used as a very excellent photosensitive composition for producing a lithographic printing plate.

However, due to the properties of the novolak type phenol resin used as the main component, the adhesion to the substrate is poor, the film is brittle, the coating properties are poor, the abrasion resistance is poor, and the resistance to lithographic printing plates is poor. There are problems such as insufficient printing power.

On the other hand, as a pattern forming method for manufacturing electronic components such as a semiconductor element, a magnetic bubble memory, and an integrated circuit, a method utilizing a photoresist which is sensitive to ultraviolet light or visible light has been widely used. Have been. There are two types of photoresist: a negative type, in which the irradiated part is insoluble in the developer by light irradiation, and a positive type, in which the exposed part is solubilized.The negative type has higher sensitivity than the positive type and is necessary for wet etching. Until recently, photoresists occupied the mainstream because of their excellent adhesion to substrates and chemical resistance. However, with the increase in density and integration of semiconductor devices, the line width and spacing of patterns have become extremely small, and dry etching has been adopted for substrate etching. Will require high resolution and high drain etch resistance,
At present, positive photoresists occupy the majority. In particular, among positive photoresists, sensitivity,
Because of excellent resolution and dry etching resistance, for example, JC Strieta, Kodak Microelectronics Seminar Proceedings, p. 116 (1976) (JC Strieter. Kodak Micr)
oelectronics SeminarProceedings, 116 (1976)
Alkali-developing positive photoresists based on alkali-soluble novolak resins are the mainstream of the current process.

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

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

[0007] It has been found that many of these problems are eliminated by using a multilayer resist system. For the multilayer resist system, see Solid State Technology, 74 (1981) [Solid State Technolo
gy, 74 (1981)], but many other studies on this system have been published. Generally, a multilayer resist method includes a three-layer resist method and a two-layer resist method.
There is a layer resist method. In the three-layer resist method, an organic flattening film is applied on a stepped substrate, an inorganic intermediate layer and a resist are stacked thereon, and the resist is patterned. Then, the inorganic intermediate layer is dry-etched using the resist as a mask. This is a method of patterning an organic planarization film by O ₂ RIE (reactive ion etching) using the inorganic intermediate layer as a mask. Basically, this method has been studied from an early stage because a conventional technique can be used, but the process is very complicated. Another problem is that cracks and pinholes are liable to occur in the intermediate layer because the three layers having different physical properties overlap with the organic film, the inorganic film, and the organic film. In contrast to this three-layer resist method, in the two-layer resist method, a resist having both properties of the resist and the inorganic intermediate layer in the three-layer resist method, that is, a resist having oxygen plasma resistance is used. Since the generation of pinholes is suppressed, and the number of layers is reduced from three to two, the process is simplified. However, in the three-layer resist method, a conventional resist can be used as the upper resist,
The two-layer resist method has a problem that a new resist having oxygen plasma resistance has to be developed.

[0008] From the above background, it has excellent oxygen plasma resistance which can be used as an upper layer resist such as a two-layer resist method.
There has been a demand for the development of a high-sensitivity, high-resolution positive photoresist, in particular, an alkali developing type resist that can be used without changing the current process.

On the other hand, a photosensitive composition obtained by combining a conventional orthoquinonediazide photosensitive material with a polysiloxane having alkali solubility or a silicone polymer such as polysilmethylene is disclosed in, for example, JP-A-61-144639 and JP-A-61-16439. -256347, 62-159141, 6
2-191849, 62-220949, 62
-229136, 63-90534, 63-9
1654 and U.S. Pat. No. 4,722,881 and a photosensitive composition obtained by combining an effective amount of an onium salt with a polysiloxane / carbonate block copolymer described in JP-A-62-136638. Has been presented.

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

[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 has solved the above-mentioned problems. That is, an object of the present invention is to provide a method for synthesizing a polysiloxane compound which is easy to synthesize and can introduce various functional groups.

[0012]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, have found that the above object can be achieved by the following synthesis method.

That is, the present invention relates to (a) at least one compound represented by the following general formula (I) or (II) and at least one compound represented by the following general formula (III), (IV) or (V) After cycloaddition of one kind by heating, hydrolysis and further condensation, or (b) after hydrolysis and further condensation of at least one compound represented by the general formula (I) or (II),
In this method, at least one compound represented by the general formula (III), (IV) or (V) is subjected to cycloaddition by heating to synthesize a functional group-containing polysiloxane.

The functional group is preferably an acid group having a pKa value of 12 or less, a group decomposable by the action of an acid, or a group which reacts or responds to irradiation with actinic rays or radiation.
In one embodiment of the present invention, during hydrolysis and further condensation,
At least one compound represented by the following general formulas (VI), (VII), (VIII), (IX) or (X) coexists and is co-condensed.
In another embodiment of the present invention, at the time of cycloaddition by heating, at least one olefin or acetylene compound having no -YA group in the above general formula is present,
They are introduced together into the polysiloxane structure.

[0015]

Embedded image In the formula, R ^{1 to} R ⁵ may be the same or different, and represent a hydrogen atom,
Represents an alkyl, aryl, or alkoxy group, preferably a hydrogen atom, a linear, branched or cyclic alkyl having 1 to 10 carbon atoms, a monocyclic or polycyclic aryl having 6 to 15 carbon atoms,
It is an alkoxy group having 1 to 8 carbon atoms.

R ^{6 to} R ⁹ may be the same or different and include a hydrogen atom, a halogen atom, cyano, carbonyl, alkyl, aryl, alkoxy group, —SO ₂ —R ¹² , —SO ₃ —
^{R 12, -CO-R 12,} -CO-NH-R 12, -COO-R 12 or -
Represents YA, and is preferably a hydrogen atom, a chlorine atom, cyano, a linear, branched or cyclic alkyl having 1 to 6 carbons, a monocyclic or polycyclic aryl having 6 to 10 carbons, or 1 carbon
6 alkoxy _{^{group, -SO 2 -R 12, -SO 3}} -R 12, -CO
^{-R 12, -CO-NH-R} 12, a -COO-R ¹² or -Y-A, more preferably a hydrogen _{^{atom, -SO 2 -R 12, -SO 3}} -
^{R 12, -CO-R 12,} -CO-NH-R 12, -COO-R 12 or -
YA. R ¹⁰ and R ^{11 each} represent a hydrogen atom, an alkyl or aryl group, preferably a hydrogen atom or a carbon atom having 1 to 4 carbon atoms.
Represents a straight or branched alkyl group. Further, two of R ^{6 to} R ⁸ and Y or R ^{10 to} R ¹¹ may combine to form a ring. Y represents a single bond, a divalent aromatic or aliphatic hydrocarbon group, preferably a single bond, a linear or branched alkylene having 1 to 4 carbon atoms, a monocyclic or polycyclic ring having 6 to 10 carbon atoms. Shows an arylene group. Further, Y may contain a group such as ketone, ether, ester, amide, urethane and ureide. R ¹² 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 carbons, alkoxy having 1 to 8 carbons, a halogen atom, carboxy,
Those substituted by a carboxy ester, cyano, dialkylamino or nitro group are also preferable.

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

[0018]

Embedded image As the group which can be decomposed by an acid, the following groups are preferred.

[0019]

Embedded image R ^{29 to} R ³¹ may be the same or different, and include alkyl,
An aryl, alkoxy or aryloxy group, R ³²
To R ³⁸ may be the same or different and represent a hydrogen atom, an alkyl or an aryl group.

The group which reacts upon irradiation with actinic rays or radiation includes active species (eg, carbene,
Nitrene, radical, cation, cation radical,
Or an anion radical), specifically, s-triazine or oxadiazole substituted with 1,2-quinonediazide, azide, trihalomethyl, o-nitrobenzyl ester, o- or m-alkoxybenzyl ester And the following groups.

[0021]

Embedded image Here, R ³⁹ represents an alkyl, alkenyl or aryl group, and R ⁴⁰ represents a hydrogen atom, halogen atom, alkyl, aryl, alkoxy, nitro, cyano or dialkylamino group. R ^{41 to} R ⁴³ may be the same or different,
It represents an alkyl or aryl group, and B represents a divalent alkylene or arylene group. n shows the integer of 0-4.

The group which responds to irradiation with actinic rays or radiation is specifically a group having a photochromic structure, such as azobenzene, spirobenzopyran,
Examples include groups having a structure such as a diarylethene derivative represented by naphthoxazine, indigo, and fulgide.

X ¹ , X ² and X ³ may be the same or different and each represents a halogen atom, hydroxy, carboxy, oxime, amide, ureido, amino, alkyl, aryl, aralkyl, alkoxy, aryloxy, -Y-
A represents the following or the following groups.

[0024]

Embedded image Preferably, a chlorine atom, a linear, 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 1 to 8 carbon atoms
Represents an alkoxy group or an aryloxy group having 6 to 10 carbon atoms. However, at least 2 of X ¹ , X ² and X ³
One represents a halogen atom, a hydroxy, carboxy, oxime, amide, ureido, amino, alkoxy or aryloxy group.

[0025]

Embedded image In the formula, R ¹³ to R ¹⁹ , R ²¹ to R ²³ , and R ²⁵ to R ²⁶ 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, and an alkenyl. Group, substituted alkenyl group, silyl group, substituted silyl group, siloxy group, or substituted siloxy group. In particular,
The alkyl group is straight-chain, 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, octyl group, decyl group,
Isopropyl group, isobutyl group, tert-butyl group, 2-
Examples include an ethylhexyl group and a cyclohexyl group.
Further, the substituted alkyl group is, for example, a halogen atom such as a chlorine atom, an alkoxy group having 1 to 6 carbon atoms such as a methoxy group, an aryl group such as a phenyl group, for example, Substituted ones such as an aryloxy group such as a phenoxy group are included, and specifically, monochloromethyl group, dichloromethyl group, trichloromethyl group, bromomethyl group, 2-chloroethyl group, 2-bromoethyl group, 2-methoxyethyl Group, 2-
An ethoxyethyl group, a phenylmethyl group, a naphthylmethyl group, a phenoxymethyl group and the like can be mentioned. The aryl group is preferably a monocyclic or bicyclic aryl group, and examples include a phenyl group, an α-naphthyl group, and a β-naphthyl group. A substituted aryl group is an aryl group as described above,
For example, an alkyl group having 1 to 6 carbon atoms such as a methyl group and an ethyl group, an alkoxy group having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group, a halogen atom such as a chlorine atom, a nitro group, and phenyl Group, carboxy group,
Examples include those substituted with a hydroxy group, an amide group, an imide group, a cyano group, and the like. Specifically, 4-chlorophenyl group, 2-chlorophenyl group, 4-bromophenyl group,
-Nitrophenyl group, 4-hydroxyphenyl group, 4-
Phenylphenyl group, 4-methylphenyl group, 2-methylphenyl group, 4-ethylphenyl group, 4-methoxyphenyl group, 2-methoxyphenyl group, 4-ethoxyphenyl group, 2-carboxyphenyl group, 4-cyanophenyl Group, 4-methyl-1-naphthyl group, 4-chloro-1-
Naphthyl group, 5-nitro-1-naphthyl group, 5-hydroxy-1-naphthyl group, 6-chloro-2-naphthyl group,
Examples thereof include a 4-bromo-2-naphthyl group and a 5-hydroxy-2-naphthyl group. The alkenyl group is, for example, a vinyl group, and the substituted alkenyl group includes a vinyl group obtained by substituting an alkyl group such as a methyl group, for example, an aryl group such as a phenyl group.
-Methylvinyl 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 the substituted silyl group include alkyl and aryl-substituted silyl groups such as a trialkylsilyl group and a triarylsilyl group. Examples of such an alkyl and aryl group include those described above. In the case of a siloxy group or a substituted siloxy group, as shown below, these groups are bonded to a siloxy group or a substituted siloxy group of an adjacent structural unit, or a siloxy group or a siloxy group in another molecule. It may have a two-dimensional or three-dimensional structure such as a structure bonded to a substituted siloxy group.

[0026]

Embedded image R ²³ , R ²⁷ and R ³⁰ may be the same or different,
A single bond, a divalent alkylene, a substituted alkylene, an arylene, or a substituted arylene group is shown. Specifically, the alkylene group is linear, branched, or cyclic, more preferably linear, and preferably has 1 to 1 carbon atoms.
There are no groups, and each group includes, for example, methylene, ethylene, butylene, octylene and the like. The substituted alkylene group is obtained by substituting the alkylene group with 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. Arylene groups are preferably monocyclic and 2
It is a ring and includes, for example, a phenylene group and a naphthylene group. Further, the substituted arylene group may be an arylene group as described above, for example, an alkyl group having 1 to 6 carbon atoms such as a methyl group or an ethyl group, or an alkoxy group having 1 to 6 carbon atoms such as a methoxy group or an ethoxy group. It includes those substituted with a group, for example, a halogen atom such as a chlorine atom. Specifically, chlorophenylene group, bromophenylene group, nitrophenylene group, phenylphenylene group, methylphenylene group, ethylphenylene group, methoxyphenylene group, ethoxyphenylene group, cyanophenylene group, methylnaphthylene group, chloronaphthylene group, Examples thereof include a bromonaphthylene group and a nitronaphthylene group.

X is a hydrolyzable group, preferably a halogen atom such as a chlorine atom or a bromine atom, a methoxy group,
1 to 1 carbon atoms such as ethoxy, propoxy, etc.
10 alkoxy groups, 6-10 carbon atoms such as phenoxy group, etc. 1-10 carbon atoms such as carboxyl group such as acetoxy group, acetoxy group, carbon atoms such as methylaldoxime, etc. It includes 1 to 6 oxime groups, and further includes an amide group, a ureide group, an amino group, 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) and an olefin represented by the general formula (III), (IV) or (V), or Cyclic thermal addition products with acetylene compounds, so-called Diels-Alder reaction products (XI), (XII),
It is a siloxane polymer having a structure derived from (XIII), (XIV), or (XVI).

[0029]

Embedded image (However, R ^{1 to} R ¹² , X ^{1 to} X ³ , Y, and A have the same meanings as described above.)

As a method for producing the polysiloxane compound of the present invention, the compound of the formula (I) or (II) may be used alone or in combination of several kinds, hydrolyzed or alkoxylated, and then condensed to obtain the compound of the formula (III), (III) A method of thermally adding a compound of the formula (IV) or (V), a compound of the formula (I) or (II) and a compound of the formula (II)
The compound of formula (I), (IV) or (V) is heat-added to give a compound of formula (X
A method of synthesizing a compound of (I), (XII), (XIII), (XIV), (XV) or (XVI), and then hydrolyzing or alkoxylating and then condensing the compound under conditions of a single type or a mixture of several types. There is.

Further, after using the olefin or acetylene compound before introduction of the functional group A of the general formula (III), (IV) or (V) to synthesize a polysiloxane skeleton in the same manner as described above, the functional group The compound having A may be reacted to introduce a functional group A structure into the polysiloxane.

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

The temperature at which the cyclic heat is added is 40 ° C. or higher, preferably 50 to 200 ° C., more preferably 7 ° C.
0-160 ° C. In addition, when adding a ring heat,
A catalyst, for example, a Lewis acid such as aluminum chloride or trifluoroborane, or a Bronsted acid may be used to increase the efficiency of heat addition.

The molecular weight of the polysiloxane compound synthesized according to the present invention is preferably 500 or more by weight average, more preferably 1,000 to 50,000.

When the polysiloxane synthesized according to the present invention is used for a lithographic printing plate or a photosensitive composition for a semiconductor resist, if necessary, for example, a 1,2-naphthoquinone-2-diazide compound, a diazonium salt compound And azide compounds and other positive or negative photosensitive compounds.

More preferably, the following additives are used in combination.

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

Such an alkali-soluble polymer is preferably a pKall such as a phenolic hydroxyl group, a carboxylic acid group, a sulfonic acid group, an imide group, a sulfonamide group, an N-sulfonylamido group, an N-sulfonylurethane group or an active methylene group. It is a polymer having the following acidic hydrogen atoms.
Suitable alkali-soluble polymers include novolak-type phenol resins, specifically, phenol-formaldehyde resin, o-cresol-formaldehyde resin, m-
There are cresol-formaldehyde resin, p-cresol-formaldehyde resin, xylenol-formaldehyde resin, and co-condensates thereof. Furthermore, Japanese Unexamined Patent Publication No.
No. 0-125806, together with the above-mentioned phenolic resin, together with a condensate of phenol or cresol substituted with an alkyl group having 3 to 8 carbon atoms such as t-butylphenol formaldehyde resin and formaldehyde. May be used in combination. Also, a polymer having a phenolic hydroxy group-containing monomer such as N- (4-hydroxyphenyl) methacrylamide as a copolymer component, p-hydroxystyrene, o-hydroxystyrene, m-isopropenylphenol, p-isopropenylphenol, etc. Homogenized or copolymerized polymers, and furthermore, polymers obtained by partially etherifying or partially esterifying these polymers can be used.

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

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

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

(Other Preferred Components) If necessary, the photosensitive composition of the present invention may further contain a dye, a pigment, a plasticizer, a compound capable of generating an acid upon irradiation with actinic rays or radiation, and a photoreaction of a functional group. A compound that increases the efficiency (a so-called sensitizer) or the like can be contained.

The compound capable of generating an acid upon irradiation with actinic rays or irradiation rays includes many known compounds and mixtures,
For example, JP-A-50-158680 and JP-A-51-568.
No. 85, No. 51-100716, Japanese Patent Publication No. 52-142
No. 77, 52-14278, U.S. Pat.No. 4,442,197
B, diazonium, phosphonium, sulfonium, and iodonium described in German Patent 2,904,626.
Salts such as F ₄ ⁻ , AsF ₆ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , SiF ₆ ⁻ , ClO ₄ ⁻ , organic halogen compounds, and organic metal / organo halogen compound combinations are suitable. Of course, U.S. Patent No.
The compounds which generate acids by photolysis described in 3,779,778, West German Patent 2,610,842 and EP 126712 are also suitable. Further, a compound intended to provide a visible contrast between an unexposed portion and an exposed portion when exposed in combination with an appropriate dye,
Compounds described in JP-A-77742 and JP-A-57-163234 can also be used.

A dye can be used as a coloring agent, 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 # 60
3. Oil black BY, oil black BS, oil black T-505 (all manufactured by Orient Chemical Co., Ltd.) crystal violet (CI42555), methyl violet (CI42535), rhodamine B
(CI145170B), malachite green (CI4
2000), methylene blue (CI52015) and the like.

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

(Solvent) When the photosensitive composition of the present invention is used as a material for a lithographic printing plate, it is dissolved in a solvent in which each of the above components is dissolved, and coated on a support. For resist materials such as semiconductors, they are used as dissolved in a solvent. As the solvent used here, ethylene dichloride, cyclohexanone, methyl ethyl ketone, methanol, ethanol, propanol, ethylene glycol monomethyl ether,
1-methoxy-2-propanol, ethylene glycol monoethyl ether, 2-methoxyethyl acetate,
2-ethoxyethyl acetate, 1-methoxy-2-propyl acetate, dimethoxyethane, methyl lactate, ethyl lactate, N, N-dimethylacetamide, N, N-dimethylformamide, tetramethylurea, N-methylpyrrolidone, dimethylsulfoxide, Sulfolane, γ-
There are butyrolactone, toluene, ethyl acetate and the like, and these solvents are used alone or in combination. The concentration (total solid content including additives) in the above components is 2 to 50.
% By weight. When used in the form of a coating, the coating amount varies depending on the application. For example, in the case of a photosensitive lithographic printing plate, the solid content is generally preferably 0.5 to 3.0 g / m ² . As the coating amount decreases, the photosensitivity increases, but the physical properties of the photosensitive film decrease.

(Production of a lithographic printing plate) When a lithographic printing plate is produced using the photosensitive composition of the present invention, the support may be, for example, paper, plastics (eg, polyethylene, polypropylene, polystyrene, etc.). , 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, cellulose nitrate, and the like. Plastic films such as polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.
Alternatively, vapor-deposited paper or plastic film is included. Among these supports, the aluminum plate is particularly preferable because it is extremely dimensionally stable and inexpensive. Further, a composite sheet in which an aluminum sheet is bonded on a polyethylene terephthalate film as described in JP-B-48-18327 is preferred. Mechanical methods such as wire brush graining, brush graining, ball graining, solution honing, buff graining, etc., and HF and AlCl ₃ , After graining the surface by chemical graining using HCl as an etchant, electrolytic graining using nitric acid or hydrochloric acid as an electrolytic solution, or composite graining performed by combining these surface roughening methods, if necessary Anodized with acid or alkali, then anodized with sulfuric acid, phosphoric acid, oxalic acid, boric acid, chromic acid, sulfamic acid or a mixed acid of these with a DC or AC power supply to provide a strong passivation film on the aluminum surface Are preferred. Although the aluminum surface is hydrophilized by such a passivation film itself, if necessary, the silicate treatment (sodium silicate) described in U.S. Pat. No. 2,714,066 and U.S. Pat. , Potassium silicate), US Patent No. 2,94
No. 6,638, potassium fluoride zirconate treatment; U.S. Pat.No. 3,201,247, phosphomolybdate treatment; British Patent 1,108,559
Alkyl titanate treatment described in US Pat. No. 3,091,433, polyacrylic acid treatment described in German Patent 1,091,433, German Patent 1,134,093 and British Patent 1,230,447. Polyvinylphosphonic acid treatment, phosphonic acid treatment described in JP-B-44-6409, phytic acid treatment described in U.S. Pat. No. 3,307,951, JP-A-58-16893.
Undercoating with a complex of a water-soluble organic polymer and a divalent metal ion described in JP-A-58-18291, and sulfonic acid described in JP-A-59-101651 Those which have been subjected to a hydrophilic treatment by undercoating of a water-soluble polymer having a group are particularly preferred. As another hydrophilic treatment method, silicate electrodeposition described in US Pat. No. 3,658,662 can also be mentioned.

Further, those subjected to graining treatment, anodic oxidation and sealing treatment are also preferable. Such a sealing treatment is performed by immersion in hot water and a hot aqueous solution containing an inorganic salt or an organic salt, a steam bath, or the like.

(Activating Ray or Radiation) Examples of the light source of the actinic ray 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 the radiation include an electron beam, an X-ray, an ion beam, and far ultraviolet rays.
Preferably, g-line, i
Line, Deep-UV light is used. Scanning exposure using a high-density energy beam (laser beam or electron beam) can also be used in the present invention. Examples of such a laser beam include a helium-neon laser, an argon laser, a krypton ion laser, a helium-cadmium laser, a KrF excimer laser, and the like.

(Developer) As a developer for the photosensitive composition of the present invention, sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, Aqueous solutions of inorganic alkali agents such as tribasic ammonium phosphate, dibasic ammonium phosphate, sodium metasilicate, sodium bicarbonate, aqueous ammonia and organic alkali agents such as tetraalkylammonium OH salts are suitable. Concentration of 0.1 to 10
%, Preferably 0.5 to 5% by weight.

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

[0052]

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

Synthesis Example 1. 7.3 g of maleimide, 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, distilled water 10
Milliliter and 0.2 ml of hydrochloric acid were added, and the mixture was heated and concentrated for 30 minutes.

The concentrate was poured into 2,000 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 Synthesis Example 1 using 11.4 g of acetylenedicarboxylic acid, 17.4 g of 2-trimethoxysilyl-1,3-butadiene and 122.6 g of tolyltrimethoxysilane using dioxane as a solvent.
The reaction is carried out in the same manner as in
g was obtained.

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

Synthesis Example 3 N- (p-hydroxyphenyl) maleimide 18.9
g, 2-trimethoxysilyl-1,3-butadiene 17.
4 g was reacted in the same manner as in Synthesis Example 1 using 500 ml of ethylene glycol monomethyl ether as a solvent to obtain 18 g of a brown target product.

The weight average molecular weight of this polysiloxane was determined to be 3300 by gel permeation chromatography.

Synthesis Example 4. Synthesis of vinyl-1-naphthyldisulfone: 189 g of sodium sulfite was dissolved in 600 ml of water to obtain
The mixture was heated to 70 ° C and 1-naphthalenesulfonyl chloride 6
After adding 8 g, the mixture was reacted at 50 to 60 ° C. for 5 hours. After filtering off insolubles, 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 and 1-
55 g of naphthalene sulfinic acid were obtained.

9.6 g of 1-naphthalenesulfinic acid was added to water 1
5 ml was added, and a solution prepared by dissolving 2 g of sodium hydroxide in 5 ml of water was added. A solution in which 6.3 g of vinylsulfonyl chloride was dissolved in 20 ml of acetonitrile was added to this solution while stirring at room temperature, and the mixture was further stirred and reacted at room temperature for 24 hours. The reaction solution was poured into 300 ml of water, the precipitate was collected by filtration, and recrystallized from a mixed solvent of benzene and ethanol to obtain vinyl-1.
3.5 g of naphthyldisulfone were obtained.

Synthesis Example 5. 2- (Trimethoxysilyl) -1,3-butadiene 4.4
g (0.025 mol), phenyltriethoxysilane 18
0 g (0.075 mol) was dissolved in 100 ml of dioxane, further dissolved in 10 ml of distilled water, 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 was evaporated by heating to concentrate. After 80 ml of dioxane was added to the concentrate and redissolved, 7.1 g of vinyl-1-naphthyldisulfone was added.
(0.025 mol), and the mixture was heated and stirred at 100 ° C. for 1 hour. The reaction solution was poured into 1 liter of water while stirring, and the precipitate was dried under vacuum. 17 g of a brownish white resin was obtained. The structure was confirmed by NMR, and the molecular weight was measured by gel permeation chromatography (GPC).
It was 0.

Synthesis Example 6. N-Hydroxyphthalimide-vinylsulfonate 50 ml of acetone was added to 3.3 g of N-hydroxyphthalimide and 2.6 g of vinylsulfonyl chloride.
While stirring at room temperature (about 20 ° C.), triethylamine 2.
0 g was added dropwise over 10 minutes, and the mixture was further stirred at room temperature for 1 hour, poured into 200 g of ice water, and the resulting precipitate was recrystallized from a benzene / ethanol mixed solvent to give N-hydroxyphthalimide-vinylsulfonic acid ester 4. 0.0 g was obtained.

Synthesis Example 7. 2- (Trimethoxysilyl) -1,3-butadiene 8.7
g (0.05 mol) and 12.7 g (0.05 mol) of N-hydroxyphthalimide-vinylsulfonic acid ester 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 were added. Further, 10 ml of distilled water and 0.1 g of concentrated hydrochloric acid were added and stirred for 30 minutes. Thereafter, the solvent dioxane was heated and concentrated. The concentrate was poured into 1 liter of water with stirring, and the precipitated solid was dried under vacuum. 24 g of a brownish white resin was obtained. The structure was confirmed by NMR, and the molecular weight was measured by gel permeation chromatography (GPC). The result was 3,500 in weight average (polystyrene standard).

Synthesis Example 8. 2- (Trimethoxysilyl) -1,3-butadiene 8.8
g (0.05 mol), phenyltriethoxysilane 12.0
g (0.05 mol) was dissolved in dioxane (100 ml), distilled water (10 ml) and concentrated hydrochloric acid (0.1 g) were added, and the mixture was stirred for 30 minutes. Thereafter, the solvent was concentrated by distilling off dioxane and water under heating. After adding 80 ml of dioxane to the concentrate and redissolving it, 3,5-
11.1 g (0.05 mol) of dimethoxybenzyl acrylate 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 while stirring, and the precipitate was dried under vacuum. 20.5 g of a white resin were obtained. The structure was confirmed by NMR, and the molecular weight was measured by gel permeation chromatography (GPC). The result was 3,600 in weight average (polystyrene standard).

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 heated and stirred at 100 ° C. for 1 hour. After cooling to room temperature, 99.1 g (0.50 mol) of trimethoxyphenylsilane were added. Furthermore, 70 ml of distilled water and concentrated hydrochloric acid
0.5 g was added and stirred for 30 minutes. Thereafter, the solvent dioxane was heated and concentrated. The concentrate was poured into 10 liters of water while stirring, and the precipitated solid was dried under vacuum.
220 g of a 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-butadiene 8.1
g (0.050 mol) and 14.5 g (0.050 mol) of N- (pt-butoxycarbonyloxyphenyl) maleimide were dissolved in 100 ml of dioxane.
The mixture was heated and stirred at ℃ for 1 hour. After cooling to room temperature, 9.1 g (0.050 mol) of trimethoxyphenylsilane were added. Further, 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 heated and concentrated. The concentrate was poured into 1 liter of water with stirring, and the precipitated solid was dried under vacuum. White resin 22.
1 g was obtained. The structure was confirmed by NMR, and the molecular weight was measured by gel permeation chromatography (GPC).
Was 4,000.

Synthesis Example 11. 2- (Trimethoxysilyl) -1,3-butadiene 8.7
g (0.050 mol), N- (p-hydroxyphenyl)
9.5 g (0.050 mol) of maleimide was added to dioxane 100
The mixture was dissolved in milliliters and heated and stirred at 100 ° C. for 1 hour. After cooling to room temperature, trimethoxyphenylsilane
9.9 g (0.050 mol) were added. Further, 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. Concentrate 1 water
The mixture was poured into a liter with stirring, and the precipitated solid was dried under vacuum. 22.4 g of a white resin were 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 (0.050 mol) of trimethylchlorosilane was added.
Was added dropwise over 30 minutes. Thereafter, stirring was continued at room temperature for 24 hours. After the imidazole HCl salt was filtered off, the reaction solution was poured into 2 liters of water while stirring. The precipitated resin was dried under vacuum to obtain 24.5 g of a white resin.

NMR confirmed that the trimethylsilyl ether group had been introduced. The molecular weight was measured by gel permeation chromatography (GPC) and found to be 5,300 in weight average (polystyrene standard).

Synthesis Example 12. 2- (Trimethoxysilyl) -1,3-butadiene 8.7
g (0.05 mol) and N- (p-hydroxyphenyl) acrylamide (8.2 g, 0.05 mol) in dioxane 100
The mixture was dissolved in milliliters and heated and stirred at 100 ° C. for 1 hour. After cooling to room temperature, trimethoxyphenylsilane
9.9 g (0.05 mol) were added. Further, 10 ml of distilled water and 0.1 g of concentrated hydrochloric acid were added and stirred for 30 minutes. Thereafter, the solvent dioxane was heated and concentrated. Concentrate 1 water
The mixture was poured into a liter with stirring, and the precipitated solid was dried under vacuum. 18.2 g of a brownish white resin were obtained.

This resin was redissolved in 100 ml of γ-butyrolactone, and 13.4 g (0.050 mol) of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride was added. 5.1 g of triethylamine was added to this solution.
(0.050 mol) was added dropwise over 20 minutes. Thereafter, 15 ml of water was added, and the pH of the reaction solution was adjusted to about 6.5 while dropping triethylamine. The reaction mixture was poured into 3 liters of water with stirring. The precipitated resin was dried under vacuum to obtain 26.5 g of a yellow resin. NMR confirmed that a 1,2-naphthoquinone-2-diazido-5-sulfonic acid ester group had been introduced. The molecular weight was measured by gel permeation chromatography (GPC) and found to be 4,800 in weight average (polystyrene standard).

REFERENCE EXAMPLE 1 A 2S aluminum plate having a thickness of 0.24 mm was immersed in a 10% aqueous solution of sodium tertiary phosphate kept at 80 ° C. for 3 minutes to degrease it, grained with a nylon brush, and then washed with sodium aluminate. Etching was performed for 10 minutes, and desmutting treatment was performed with a 3% aqueous solution of sodium hydrogen sulfate. This aluminum plate was anodized in a 20% sulfuric acid at a current density of 2 A / dm ² for 2 minutes to prepare an aluminum plate.

Next, the following photosensitive solution [A] was applied on 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 / m ² in terms of dry weight.

Photosensitive solution [A] A gray scale having a density difference of 0.15 was brought into close contact with the photosensitive layer of the photosensitive lithographic printing plate [A], and exposure was performed for 2 minutes from a distance of 50 cm with a 2 kw high-pressure mercury lamp. The exposed lithographic printing plate [A] was exposed to DP-4 (trade name: Fuji Photo Film Co., Ltd.)
Immersion development at 25 ° C. for 60 seconds with an 8-fold diluted aqueous solution of the above method, a clear blue positive image was obtained.

Reference Example 2 A novolak-based commercially available resist HP was placed 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 thickness of the lower layer was 2.0 μm.

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

Next, a resist pattern was formed by exposing with a reduction projection exposure apparatus (stepper) using monochromatic light having a wavelength of 436 nm and developing with a 2.4% aqueous solution of tetramethylammonium hydroxide for 60 seconds.
As a result, a good 0.8 μm line & space pattern was obtained.

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

Claims (4)

(57) [Claims] (1) at least one compound represented by the general formula (I) or (II);
At least one compound represented by formula (V) or (V) is subjected to cycloaddition by heating to give a compound represented by formula (XI) or (XI)
Forming a compound represented by I), (XIII), (XIV), (XV) or (XVI), followed by hydrolysis,
A method for synthesizing a polysiloxane containing an acid group having a pKa value of 12 or less, a group decomposable by the action of an acid, or a group that reacts or responds to irradiation with actinic rays or radiation (functional group) by further condensation. . In the formula, R ^{1 to} R ⁵ may be the same or different and each represent a hydrogen atom, an alkyl, an aryl, or an alkoxy group;
^{6 to} R ⁸ may be the same or different and include a hydrogen atom, a halogen atom, cyano, carbonyl, alkyl, aryl, alkoxy group, —SO ₂ —R ¹² , —SO ₃ —R
^{12, -CO-R 12, -CO} -NH-R 12, -CO
Represents OR ¹² , or -YA, wherein R ¹² is alkyl,
Or an aryl group. R ¹⁰ and R ¹¹ represent a hydrogen atom, an alkyl or an aryl group. Y represents a single bond, a divalent aromatic or aliphatic hydrocarbon group, and A represents a functional group. X ¹ , X ² and X ³ may be the same or different,
Hydrolyzable groups, alkyl, aryl, aralkyl,
-YA, However, at least two of X ¹ , X ² and X ³ represent a hydrolyzable group. Two of R ^{6 to} R ⁸ and Y, or R ^{10 to} R ¹¹ may combine to form a ring. 2. The method according to claim 1, wherein the compound represented by the general formula (I) or (I)
After hydrolyzing and further condensing at least one of the compounds represented by I), at least one of the compounds represented by the general formulas (III), (IV) and (V) is subjected to cycloaddition by heating. An acid group having a pKa value of 12 or less,
A method for synthesizing a polysiloxane containing a group that can be decomposed by the action of an acid or a group (functional group) that reacts or responds to irradiation with actinic rays or radiation. 3. When hydrolyzing and further condensing, at least one of compounds represented by the following general formulas (VI), (VII), (VIII), (IX) or (X) is allowed to coexist;
3. The method according to claim 1, wherein the co-condensation is carried out. In the formula, R ^{13 to} R ¹⁹ , R ^{21 to} R ²³ , and R ^{25 to} R
²⁶ may be the same or different, and may be a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group,
It represents an alkenyl group, a substituted alkenyl group, a silyl group, a substituted silyl group, a siloxy group or a substituted siloxy group. R
²⁰ , R ²⁴ and R ²⁷ may be the same or different and represent a single bond, a divalent alkylene, a substituted alkylene, an arylene, or a substituted arylene group. X represents a hydrolyzable group. 4. A cycloaddition by heating, wherein at least one of an olefin or an acetylene compound having no -YA group in the above general formula is coexisted and introduced together into a polysiloxane structure. Claim 1 or 2
The described method.