JPS63125510A - Novel photosensitive composition - Google Patents

Abstract

PURPOSE:To obtain a photosensitive composition of a high photosensitivity, by mixing a specified polymer with an oxime compound and a sensitizer. CONSTITUTION:A compound of formula I [wherein Z1 is -COOH, -COCl, -NCO, -NH2 or -OH, R* is a group having a C-C double bond, X is a (2+n)-valent carbocyclic or heterocyclic group, and n is 1 or 2] is polycondensed or addition- polymerized with a compound of formula II [wherein Z2 is -COCl, -COOH, -NCO or -NH2; and Y is a (2+m)-valent carbocyclic or heterocyclic group, W is a group which is reactive with the carbonyl group of -COOR* to form a ring and m is 0-2] to obtain a polymer (A) having repeating units of formula III (wherein Z is a group of any one of formulas IV-VI and -COOR* is ortho or peri to Z). Component a is mixed with 0.1-20wt% oxime compound (B) of formula VII (wherein R1 is a 1-6C alkyl, a 1-6C alkoxy or a 6-10C aromatic hydrocarbon group, R2 is R1 or a 6-10C aryloxy) and 0.01-20wt% sensitizer (C) of an absorption peak wavelength of 250-500nm (e.g., Michler's ketone).

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a novel photosensitive composition, and more specifically, to a photosensitive composition that can be converted into a heat-resistant polymer compound by heat treatment. be.

Conventionally, heat-resistant polymer compounds represented by Boliimige,
Taking advantage of its heat resistance and electrical properties, it is used as a structural member in fields such as electricity, automobiles, aircraft, space, and nuclear power.
Widely used for printed circuit board materials, heat-resistant insulation materials, etc.

On the other hand, photosensitive polymer compounds are widely used in applications such as paints and printing plates, and in recent years, their lithography properties have been used to create resists for producing printed circuits, resists for etching metal plates, and resists for producing semiconductor elements. It is well known that remarkable progress has been made in microfabrication materials such as

In recent years, polymer materials that have these two useful functions of heat resistance and photosensitivity have been actively developed, especially for use in electronic and optical materials. Applications are being considered, such as surface protection films for junction coats, insulating films for semiconductor devices such as interlayer insulating films for multilayer wiring, alignment films for liquid crystal display devices, and insulating films for thin film magnetic spatula r [e.g. , "Functional Materials", July issue, pages 9-19, ? (19
1983) and [Photographic Science and Engineering
5science and Engineering)
J No. 303-309 (1979)].

[Conventional technology]

Conventionally, as a heat-resistant photosensitive composition, for example, Boliimi r
A cross-linked structure is formed by adding a photosensitizer and a copolymerizable monomer to irimer, which is a precursor of polyamic acid with active functional groups such as double bonds introduced into the ester side chain. A moisturizing composition is known (Japanese Patent Publication No. 55-3020
7, Japanese Patent Publication No. 55-41422). This is a basic composition of a heat-resistant polymer material for lithography, typified by so-called photosensitive limide, but it had low photosensitivity and was insufficient for practical use. In addition, as a composition that improves these drawbacks, a methacrylate group or an acrylate group is used as the side chain active functional group, and p-acetamido-phenylsulfonate is used as a photoinitiator.
) has been proposed to which an azide compound such as (JP-A-55-155347) is added. however,
Although this composition has slightly improved photosensitivity, it is still not sufficient.

On the other hand, a photosensitive composition containing as a main component a mixture of polyamic acid and an amine compound having an active functional group such as a double bond has been proposed (Japanese Unexamined Patent Publication No. 168942/1989,
JP-A-54-145794, JP-A-59-160
140).

However, because the viscosity of this solution is extremely high, it is necessary to handle it with a solution of low concentration, and when using a spin coater, etc., which is commonly used for forming films on the surface of semiconductor elements, it is difficult to form thick films. It was difficult to form. or,
Since these are ionically bonded phosphors, there is a problem in that if they are left to stand after being applied and dried, they tend to crack due to moisture absorption.

The method of using the compositions disclosed in these prior art techniques is to apply the compositions as a solution onto a substrate, dry it, irradiate it with active light such as ultraviolet rays through a photomask, and then remove the unexposed areas with a suitable developing solvent. A heat-resistant film is formed by dissolving and removing the polyamide to form an image, followed by high-temperature treatment to close the imide ring, etc., and at the same time vaporize the poly(am)tetra-acid side chain, crosslinking chain, initiator, etc. A typical example of this is the process of instigation.

[Problem that the invention seeks to solve]

By the way, it has been found that in the conventional prior art, as the film thickness of the so-called photosensitive polyimide is increased, the photosensitivity decreases extremely and the exposure time required for curing becomes longer. .

In addition, we have already discovered that photosensitivity can be improved by combining an oxime compound with a certain structure with a sensitizer as a photoinitiator (Japanese Patent Application Laid-Open No. 1983-1973-1).
118423), but it is necessary to further improve the sensitivity.

In view of these circumstances, the inventors of the present invention have developed a material with high photosensitivity.
We have conducted intensive research to provide a heat-resistant photosensitive composition that has high photosensitivity, especially when used in thick films.

[Means for solving problems]

As a result, a polymer with a specific structure as an essential component,
Oxime compound and absorption peak wavelength of 250 to 500
It was discovered that a composition containing a sensitizer in the range of nm is suitable for the purpose, and based on this finding, the present invention was completed.

That is, the present invention provides (a) general formula (1) [wherein X is a (2+n)-valent carbocyclic group or heterocyclic group, and Y is a (2+
m) a valent carbocyclic group or heterocyclic O00 R* is a group having a carbon-carbon double bond, W is a group capable of reacting with the carzenyl group of -COOR* to form a ring upon heat treatment; n is 1 or 2, m\'i0.1 or 2,
and 0OOR* and Z are in an ortho- or peri-position relationship with each other] (hereinafter referred to as 0) component), (b) general formula (2) [8ri in the formula is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms; R is an alkyl group having 1 to 6 carbon atoms; an alkoxy group, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms (hereinafter referred to as component (b)); and (c) absorption peak. The present invention provides a photosensitive composition containing as an essential component a sensitizer having a Ki wavelength of 250 to 500 nm (hereinafter referred to as "component").

In the composition of the present invention, the polymer used as component (a) has a repeating unit represented by the general formula (1) above, where X is a trivalent or tetravalent carbocyclic group or A heterocyclic group, such X includes, for example, a benzene ring, a fused polycyclic aromatic ring such as a naphthalene ring, an anthracene ring, a heterocyclic group such as pyridine or thiophene, and a general formula (Il) or OFs] and the like. Of these, carbon number 6
~14 aromatic hydrocarbon groups, Xl is +CH2 old (l is O or 1), -C-, -8-, -0-? A group represented by the general formula (e) which is F3 or -〇- is preferred (
3F3, and those represented by the formula % () are preferred.

Y in the general formula (1) is a divalent, trivalent, or tetravalent carbocyclic group or a heterocyclic group, and -C1 is, for example, a group having 10 to 18 carbon atoms derived from naphthalene, anthracene, etc. Divalent aromatic hydrocarbon ring, pyridine,
Heterocyclic groups and formulas derived from imidazole etc. [Yl in the formula is H, OH3, (OHs)zOH, 0OH
s, 0OOH.

A halogen atom or So, H, or Y is +0H2-)- (however, p is O or 1), -So-9OH.

-O-, -CII=OH-, -0-, -8-, -0-.

H3O 0H.

Y3 and Y4 are H+ OH1+ O! H5+ 00H3
+ halogen atom, 000H, 80, H or Not,
y and Y6 are H, ON, halogen atom, OHs *
0OH3, 5O3H or OH. Among these, divalent aromatic hydrocarbon rings having 10 to 14 carbon atoms, Y2 = +0) to 1 (however, p is ° or 4゛), -υ, -SO-, -0- or - S-,
A group represented by the formula (5) in which both Y3 and Y4 are hydrogen atoms is preferred, and a group represented by the formula is more preferred.

W in the general formula (1) can be converted to -0O by heat treatment.
A group that reacts with the carzenyl group of OR* to form a ring, and -O-NH is particularly preferred as such a group. Further, n is preferably 2.

Furthermore, R* in the general formula (1) is a group having a carbon-carbon double bond, and as such,
For example, -R”-OH=OHz
(Ib) [In the formula, R' is a hydrogen atom or a methyl group, R
“ is an alkylene group having 1 to 3 carbon atoms, n is 1 or 2]
Examples include.

As an example of (■1), As an example of (■2), As an example of (■3), As an example of (■4), ors) as an example: OH2OH=0Hz OHz　OH2-0H=OHz As an example of (L), OOH.

Examples of 10Hx OH2-NH-0-OH=0H2 (■A) include the following.

Among these, -OH, due to photosensitivity, storage stability, etc.
-OH, -0-0-OH=OH,.

〇1〇H* OHz 0H=OHt, Olh
OH2NH00H=OH2 etc. are preferred.

The oxime compound used as component (b) in the composition of the present invention is represented by the general formula (2).

The group used in the formula is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 6 to 6 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms, preferably a methyl group, an ethyl group, a methoxy group, or an ethoxy group. group, phenyl group, tosyl group, mesityl group, etc. In the formula, R8 is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and 6 carbon atoms.
aromatic hydrocarbon group having 1 to 10 carbon atoms, or 6 to 1 carbon atoms
0 aryloxy group, preferably ethyl group, butyl group, methoxy group, ethoxy group, phenyl group, tosyl group, phenyloxy group, etc.

(b) Examples of ingredients are: 0　0　002H＠　H 0-0-00. H.

Examples include, but are not limited to, 0-0-00tHs - 00-002H5r. Note that these may be used alone or in combination.

The sensitizer used as component (c) in the composition of the present invention has an absorption peak wavelength of 250 to 500 nm. or an ethyl group, R13 is a hydrogen atom or a methyl group, R14 is an aromatic hydrocarbon having 6 to 10 carbon atoms, B15 is a methyl group, an ethyl group, or an aromatic hydrocarbon having 6 to 10 carbon atoms, R
lgl R1γ is a hydrogen atom, an aliphatic group, a substituted aliphatic group, or a group consisting of an aromatic hydrocarbon having 6 to 10 carbon atoms, R111*R1? At least one of these is a group other than a hydrogen atom, R18 is a hydrogen atom, a methyl group, an ethyl group, or a hydrogen group, and m and n are each 0.1 or 2.

Examples of sensitizers include Michler's ketone, 4°4'-bis-(diethylamino)-benzophenone, 2,5-bis-(4'--,'ethylaminobenzal)-cyclopentanone, 2,6- Bis-(4'-diethylaminobenzal)-cyclohexanone, 2,6-bis-(4'-
dimethylaminobenzal)-4-methyl-cyclohexanone, 2,6-bis(4'-diethylaminobenzal)
-4-methyl-cyclohexanone, 4,4'-bis-(
dimethylamino)-chalcone, 4,4'-his-(diethylamino)-chalcone, 4-dimethylaminocinnamylidene indanone, 4-dimethylaminobenzylidene indanone, 2-(4'-dimethylaminophenylvinylene)-pezothiazole , 2-(4'-dimethylaminophene, 7L vinylene)-isonaphthothiazole, 1.3
-bis(4/-dimethylaminobenzal)-acetone,
1゜3-bis-(4/,7ethylaminobenzal)
-Acetone, 3.3'-Calzenylrubis(7-dinithylaminocoumarin), 7-danitylamino-3-benzoylcoumarin, 7-danitylamino-4-methylcoumarin, N-phenyl-getanolamine, N-p-) Examples include, but are not limited to, diethylamine. Note that these may be used alone or in combination. Preferably, (■1) or ■$
A sensitizer having the structure shown in ) and a sensitizer having the structure (1) are used in combination.

A compound having a carbon-carbon double bond can be added to the composition of the present invention, if necessary.

This compound having a carbon-carbon double bond is a compound that facilitates the photopolymerization reaction when added,
Examples of such substances include 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, N-vinyl-2-pyrrolidine, carpitol acrylate, tetrahydrofurfuryl acrylate, yn2runyl acrylate, and 1°6-hexane. Diol diacrylate, neopentyl glycol diacrylate, ethylene glycol diacrylate, polyethylene glycol diacrylate, pentaerythritol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, tetramethylolmethanetetraacrylate, tetra Examples include ethylene glycol diacrylate, nonaethylene glycol diacrylate, methylene bisacrylamide Y, N-methylol acrylamide r, and those in which the above 7 acrylates or acrylyl amyl are replaced with methacrylate or methacrylamide. Preferred are compounds having two or more carbon-carbon double bonds.

Furthermore, by adding a mercaptan compound to the composition of the present invention, the photosensitivity can be further improved. Examples of mercaptan compounds include, for example, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 1-phenyl-5-mercapto-IH-tetrazole, 2-mercaptothiazole, 2-mercapto-4-
7-enylthiazole, 2-amino-5-mercapto-1
゜3.4-thiazole, 2-mercaptoimidazole,
2-mercapto-5-methyl-1,3,4-thiadiazole, 5-mercapto-1-methyl-IH-tetrazole, 2,4.6-drimercabuto 3-triazine, 2
-diptylamino-4,6-dimercapto$-triazine, 2,5-dimercapto-1,3,4-thia diazole, 5-mercapto-1°3, 4-thiacyazole, 1-ethyl-5-mercapto-1, 2,3,4-tetrazole, 2-mercapto-6-nitroti7zole, 2-mercaptobenzoxazole, 4-phenyl-
2-mercaptothiazole, mercaptopyridine, 2-
Examples include mercaptoquinoline, 1-methyl-2-mercaptoimidazole, 2-mercapto-β-naphthothiazole, and the like.

Furthermore, a functional dialkoxysilane compound can be added to the composition of the present invention, or a base material can be precoated therewith, if necessary. This dialkoxysilane compound is a compound that improves the adhesion of the interface between the heat-resistant polymer film of the composition of the present invention and the Si and inorganic insulating film of the base material, and examples thereof include, for example. , γ-aminopropylmethyldimethoxysilane, N-β(aminoethyl)r-aminopropyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercazotopropylmethyldimethoxy7rane, dimethoxy-3-mercaptopropyl Methylsilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinoprosilane, jetoxy-3-glycyloxyzorobylmethylsilane, N-(3-fethoxymethyl -7 rilprovir) Succinimi P and the like.

The method of use and effects of these dialkoxysilane compounds are described in detail in, for example, Japanese Patent Application No. 60-38242 ('7). An inhibitor can also be added. Examples of the polymerization inhibitor include high P quinone, N-nitron diphenylamine, p-tert-
Examples include, but are not limited to, butylcatechol, phenothiazine, N-phenylnaphthylamine, 2,6-di-tert-butyl-p-methylphenol, and the like.

There is no particular restriction on the content of the oxime compound in the component (i) in the present invention, but it is preferably 0.1 to 20% by weight, more preferably 1 to 15% by weight based on the polymer of component (i). It is desirable to contain it within a range. If the content is low, the photosensitivity will not be sufficient, and if the content is too high, the film properties after heat treatment will deteriorate.

In addition, the content of the sensitizer as component (c) in the present invention is in the range of o, oi to 20% by weight, preferably 0.05 to 15% by weight, based on the polymer of component (a). This is desirable. When the content is small, the photosensitivity is insufficient, and when the content is too large, the photosensitivity decreases.

The amount of the compound having a carbon-carbon double bond is (a)
The content is preferably 2.0% by weight or less based on the component polymer. The amount of the mercaptan compound added is preferably 10% by weight or less, more preferably 5ti% or less, based on the polymer of component (a).

Further, when the functional dialkoxysilane compound is added and used, the amount added is 0.05 to 10%, preferably 0.1 to 4%, based on the polymer of component (f). It is.

Further, the polymerization inhibitor has a content of 5% to the polymer of component (a)
It is used in an amount of not more than 0.5% by weight, preferably not more than 0.5% by weight.

The polymer used as component (a) in the composition of the present invention can be obtained, for example, by polycondensation or polyaddition of a compound represented by the general formula and a compound represented by the general formula. Examples of Zl in the general formula (5) include -000H (Illt), -Cool (Hrz)
, NOO (Iffs).

-NHz (III4), OH (IIg),
The abbreviations of the general formula (g) corresponding to each are shown within 0.

Also, as an example of z in the general formula (goods), -000
1(fVt), 0OOH(fVz), NO
There are O(F/3) and NHZ (IV4), and the corresponding general 2ω abbreviations are shown within 0. In addition, X
IR, Y and W have the same meanings as above.

Sea z1 and 2 are obtained by polycondensation or polyaddition reaction of the compound represented by the above general formula (to) and the compound represented by general 2ω.
2- to form a bond chain 2.

2. A preferable combination of and Zl to produce Z
Table 1 summarizes the types of and the ring structure groups formed when the obtained polymer is heat-treated.

Table 1 Note: *1 Ring structure engineering M: Imide ring QD: Quinazoline dione ring OD Nioxazinedione ring The polymer of component (a) can also be produced by the method shown below. That is, it is obtained by reacting a compound represented by the general formula % formula %) () [X in the formula has the same meaning as above] with a compound represented by the general formula (■3) or (■4). The carzexyl group of the product obtained by combining the carzexyl group with an epoxy compound represented by the general formula [R* in the formula has the same meaning as above], an amine compound represented by the general formula, or a 4-carbon compound represented by the general formula The polymer can be obtained by reacting with a grade ammonium salt.

Note that these reactions are described, for example, in JP-A-56-32524.
No. 60-194444.

The compound represented by the general formula (■1) can be obtained, for example, by ring-opening the acid anhydride represented by the general formula (■6) with R*0H (R* has the same meaning as above). Examples of the acid anhydride (■6) include pyromellitic anhydride, 3°3', 4
, 4'-benzophenonetetracardanic dianhydride,
3.3',4.4'-diphenyl ethertetracardic dianhydride, 3.3',4.4'-diphenyltetracardic dianhydride, 3.3',4.4'-diphenyl sulfone Tetracardic dianhydride, 2,316.7-
7 talent tetracal? phosphoric acid anhydride, thiophene-2,
3,4,5-tetracarminic anhydride, 2,2-bis-
Examples of the alcohol I'L*OH include (3,4-bisproxyphenyl)propane anhydride, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl methacrylate, and 2-hydroxypropyl methacrylate. Examples include hydroxypropyl acrylate, allyl alcohol, and ethylene glycol monoallyl ether.

When these acid anhydrides (6) are reacted with alcohol-'OH, the reaction is accelerated by adding pyridine, dimedelaminopyridine, etc.

The combination of numbers 1 and 1' in Table 1 above is one example of a preferred embodiment, and the diamine represented by the general formula (4) used in this combination is, for example, 4,4'-diaminodiphenyl ether. , 4.4'
-diaminopiphenyl, 4,4'-diaminotoluene,
4.4'-diaminobenzophenone, 4゜4'--,'
aminodiphenyl sulfone, phenylindane diamine, 4,4'-diaminodiphenylmethane, p-phenylenediamine, m-phenylenecyamine, 1,5-diaminonaphthalene, 3,3'-dimethoxy-4,4'-diaminopiphenyl, 3.3'-dimethyl-4,4'-diaminopiphenyl, 0-toluydinesulfone, 2.2-
Bis(4-aminophenoxyphenyl)furopane, bis(4-aminophenoxyphenyl)sulfone, bis(4-aminophenoxyphenyl)furopane, bis(4-aminophenoxyphenyl)sulfone,
-aminephenoxyphenyl)sulfur, 1,4-bis(4-aminophenoxy)(nzene, 1,3-bis(
4-aminophenoxy)benzene, 3.4'-diaminodiphenyl ether, 9.9-bis(4-7minophenyl)anthracene-(10), 9.9-bis(4-aminophenyl)fluorene, 3.3'- Diaminodiphenylsulfone, 4,4'-di(3-aminophenoxy)
diphenyl sulfone, 4.4'-7aminopenzanyl, 3.4'-diaminodiphenyl ether, 4.4'
-[1,3-722lenepis (1-methylethythelene)
], 4.4'-[1,4-phenylenebis(1-methylethythene)1. 4.4'-(m-phenylenediisopropylidene)bis(m-)luidine), 4°4'
-(p-)unilene diisozolobylidene)bis(m-toluidine), and the like.

Among these combinations, the reaction between the compound represented by the general formula (IIIs) and the compound represented by the general formula (■4) is as follows:
This can be carried out using a calzediimide type dehydration condensation agent, for example dicyclohexyl calzediimide.

In addition, the compound represented by the general formula (■2) is represented by the general formula (
It can be obtained by reacting a half ester represented by Illt) with thionyl chloride, phosphorus pentachloride, etc.

For methods of these reactions, see, for example, JP-A-61-
It is described in detail in JP-A No. 702022, JP-A-61-118423, and the like.

The method for producing the oxime metal compound used as component (b) in the present invention begins with 1-mesityl-3-substituted 1,3-
A 1-mesityl-3-substituted-1,2,3-propanetrione-2-oxime compound is synthesized by nitrosating the active methylene group of a propanedione compound with nitrite or an alkyl nitrite ester. . These synthetic methods are organic.

Synthesis Collective Serium ll, 513~
It can be carried out in the same manner as the method described in p.sxe, id, Organic Synthesis Collective Ill, p. Furthermore, the oxime compound of the present invention can be produced by reacting the obtained oxime compound with an acid halide.

The composition of the present invention is used by dissolving it in a solvent that can dissolve all the components in the composition and coating it on a predetermined substrate. At this time, in order to improve the adhesion to the substrate, the dialkoxysilane compound may be pre-coated on the substrate.

The solvent is preferably a polar solvent, such as one having a not too high boiling point, such as dimethylformamide P1 N-methylpyrroli, dimethylacetamide P, diglyme, isobutyl acetate, or cyclopentanone. Furthermore, solvents such as alcohols, aromatic hydrocarbons, ethers, ketones, and esters can be added to the extent that the components are not precipitated.

As a method for coating the solution on the substrate, the solution obtained as described above is filtered, and then applied to the substrate using, for example, a spin coater, a nozzle coater, a blade coater, a curtain coater, a screen printing method, etc. A method of immersing the substrate in the solution, a method of spraying the solution onto the substrate, etc. can be used.

Examples of the substrate include metal, glass, silicon semiconductor,
Heat-resistant materials such as compound semiconductors, metal oxide insulators, and silicon nitride are preferable, and if heat treatment is not performed, materials such as copper-clad glass epoxy laminates can be used.

Next, the coating film obtained in this way is air-dried, heat-dried,
After drying using a combination of vacuum drying and the like, exposure is usually performed through a photomask. At this time, the active light used includes, for example, ultraviolet rays, X-rays, electron beams, etc. Among these, ultraviolet rays are preferable, and the light source thereof is as follows:
Examples include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, and nitrogen lamps. Among these light sources, ultra-high pressure mercury lamps are preferred. Further, it is preferable that the exposure is performed under a nitrogen atmosphere.

After exposing in this way, in order to remove the unexposed area,
Development is performed using a dipping method or a spray method. The developer used for this removal is preferably one that can completely dissolve and remove the unexposed film within a suitable time, such as N-4
Tylpyrrolidone, N-acetyl-2-pyrrolidone, N,
N-dimethylformamide, N,N-dimethylacetamide r1 dimethylsulfoxy P1 hexamethylphosphoric triamide, N-benzyl-2-pyrrolid/,
An aprotic polar solvent such as γ-butyrolactone may be used alone, or as a second component,
For example, solvents such as alcohols such as ethanol, isopropanol, aromatic hydrocarbon compounds such as toluene and xylene, ketones such as methyl ethyl ketone and methyl isobutyl ketone, esters such as ethyl acetate and methyl propionate, and ethers such as tetrahydrofuran and dioxane. They may be used in combination. Furthermore, it is preferable to rinse with a solvent such as that shown as the second component immediately after development.

After drying, the image obtained in this way has an image density of 150 to 450
By heating in the temperature range of .degree. C., it is converted into a heat-resistant polymer compound having an imide ring, an isoine rquinazolinedione ring, an oxazinedione ring, a quinazolinedione ring, and the like.

〔Effect of the invention〕

The compositions of the present invention have many advantages over compositions disclosed in the prior art. The advantages of this include, first, that high photosensitivity was achieved;
The lithography properties, which are considered important as photoresist properties, have also been significantly improved. These results show that the composition of the present invention has ideal properties as a photoresist, such as exhibiting high resolution at low exposure doses. Further, the composition has the advantage that it has extremely excellent long-term storage stability and does not cause undesirable gelation, cracking, or formation of a surface film when the coating film dries.

When the composition of the present invention is used as an interlayer insulating film or a surface protective film for semiconductor devices, it reflects the above characteristics.

The process can be shortened, microfabrication is easy, and a very flat layer can be formed.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to these examples in any way. In addition, s? used in the example? Table 2 shows the names of the limer, oxime compound, sensitizer, compound (monomer) having a carbon-carbon double bond, mercaptan compound, functional dialkoxysilane compound, polymerization inhibitor, etc.

(3) The absorption peak wavelength of the sensitizer was measured using a Nonorian RY219 spectrophotometer (Varlan Q-RY219 Spectr
(photometer) using ethanol as a solvent.

(4) Nanatsumer (5) Mercaptan compound (6) Functional dialkoxysilane compound (7) Polymerization inhibitor Examples 1 to 20 Additives shown in Table 3 were added to 100 parts by weight of the polymer shown in Table 3. The mixture was dissolved in 120 parts by weight of N-methylpyrrolidone. This solution was dried on a Crycon wafer using a spin code (700 rpm x 75 ec) in air at 70° C. for 6 hours to obtain a uniform coating film.

Next, gray scale (1 (odakPh)
otographic 5tep Tablet, I
S, 2) through an ultra-high pressure mercury lamp (8 mW/Crn
”) for 5 minutes. The wafer was exposed for 30 minutes at 23°C.
After being left for a minute, it was developed using a spray developing machine with an isostatic mixture of γ-butyrolactone and xylene, rinsed with xylene, and dried.

The curing state and sensitivity of each gray scale step were calculated as the number of steps. (The higher the number of steps, the higher the sensitivity. When the number of steps increases by one step, it means that the exposure amount is lower by f orders.) The obtained results are shown in the same table.

Comparative Examples 1 to 5 Experiments were conducted on the compositions in Table 4 in the same manner as in Examples 1 to 20, and the results shown in the table were obtained.

Comparative Examples 6 to 11 Using other photopolymerization initiators in addition to the oxime compound of the present invention, the compositions shown in Table 5 were tested in the same manner as in Examples 1 to 20, and the results shown in the table were We obtained the following results.

Examples 21-22 Diaminodiphenyl ether 100 F (0.5 mol) was dissolved in N-methylpyrrolidone 8802, pyromellitic dianhydride 101 (0.5 mol) was added, and 50-6
By reacting at 0°C for 3 hours, a polymer solution of 28 poise at 25°C was obtained. (Put this polymer solution into P-6
To 100 parts by weight of this 2 Lima solution, add the additives shown in Table 6 in parts by weight and dissolve. This solution was coated on silicone Ueno (500 rpm
10 sec) It was dried at 1,70°C for 1 hour to obtain a uniform coating film. Further, on this coating film, the solution was applied with a spin cord and dried four times to obtain a coating film. Next, gray scale (Kodak Photography
It was exposed for 5 minutes to an ultra-high pressure mercury lamp (8 mW/crn') through a 5 step 'l'ablet A 2 ). This Ueno film was left at 23° C. for 30 minutes, developed with a mixed solution of N-methylpyrrolidone (2 parts) and methanol (1 part) using a spray developing machine, rinsed with methanol, and dried. Cure sensitivity is expressed as number of stages. The results obtained are shown in Table 6.

In the following, reference examples 1 to 6 are shown below, which show the manufacturing method of the oxime compounds used in the examples of the present invention.

Reference Example 1 Su(1) Production method of oxime 1 (2'+4', 6'-)limethylphenyl)-1,3-butanedione 20.4 y (0.1 mol) was mixed with 60 trtl of acetic acid and 5 ml of etal. Sodium nitrite 8.28 y (0.12 mol)/
An aqueous solution of water 161F is added dropwise over 30 minutes. After finishing dropping -
Stir overnight at room temperature.

Pass through the precipitated crystals and wash with water three times.

The obtained crystals are dried under vacuum. The yield was 13.5f (yield: 58%).

(2) Production method of oxime compound Oxime compound 11.65 F (0.05 mol) and meriethylamine 5.555 y (o, oss mol) were dissolved in 300 d of acetone, and at 5°C or less, benzoyl chloride 7
．． 73 F (0,055 mol) is added dropwise. After the dropwise addition, stirring was continued for 30 minutes at room temperature. When the reaction is completed, the precipitated triethylamine hydrochloride is separated and the liquid is evaporated to dryness under reduced pressure.

The obtained oxime compound is recrystallized from ethanol.

The yield was 14.5 y (yield: 86%).

Reference Example 2 (1) Method for producing oxime 2.4.6-) 46.8 t (0.2 mol) of ethyl methylbenzoylacetate was dissolved in 120 g of acetic acid and 10 g of ethanol, and the solution was dissolved in nitrous chloride under water cooling. Sodium nitrate/6
．． An aqueous solution of 56 f (0.24 mol)/water 322
Drop in 5 minutes. After the dropwise addition was completed, the mixture was stirred at room temperature overnight.

Pass through the precipitated crystals and wash with water three times.

The obtained crystals are dried under vacuum. The yield was 40f (yield near 6%).

(2) Production method of oxime compound Oxime compound 13.15 P (0.05 mol) and triethylamine 5.555 P (0,055 mol) were dissolved in acetone 300 a/m, and ethyl chloroxate 5. 97 f (0,055 mol) is added dropwise. After dropping, separate the precipitated triethylamine hydrochloride,
The oral fluid is evaporated to dryness under reduced pressure. The obtained oxime compound is washed with hexane and then recrystallized with ethanol. The yield was 12.9 tons (yield near 7%).

Reference example 3 (1) Method for producing oxime bodies The oxime compound can be produced in the same manner as in Reference Example 2.

(2) Production method of oxime compound H Oxime compound 13.15 f (0.05 mol) and triethylamine 5.555 ? (0,055 mol) was dissolved in 300 g of acetate and heated at 5° C. or below.7.
73 y (o, oss mole) is added dropwise. After the dropwise addition, stirring was continued for 30 minutes at room temperature.

After the reaction is completed, the precipitated triethylamine hydrochloride is separated, and the liquid is evaporated to dryness under reduced pressure. The obtained oxime compound is recrystallized from ethanol.

The yield was 14.86 F (yield: 81%).

Reference Example 4 (1) Production method of oxime H 1-(2,4,6-4-limethylphenyl)-3-phenyl-1,3-propanedione 53,2 (0.2 mol)
was dissolved in 120 grams of acetic acid and 60 grams of ethanol, and cooled with water.
Sodium nitrite 41 y (0.6 mol) / water 801
An aqueous solution of is added dropwise over 1 hour. After the addition was completed, the mixture was stirred at room temperature overnight. Pass through the precipitated crystals and wash with water three times. The obtained crystals are dried under vacuum. The yield is 41? (yield 69%).

(2) Method for producing oxime compounds H O-000zHa Oxime 14.75 P (o, os mol) and triethylamine 5.555 P (0,055 mol) were dissolved in 77 tons, 300 mol, and the mixture was heated at 5°C or below. Ethyl chloroformate 5
．． 97 F (0,055 mol) is added dropwise. After completion of the dropwise addition, stirring was continued for 1 hour. After the reaction is completed, the precipitated triethylamine hydrochloride is separated, and the liquid is evaporated to dryness under reduced pressure.

The obtained oxime compound is washed with hexane and then recrystallized with ethanol. Yield: 15.4 F (Yield: 84%
)Met.

Reference example 5 (1) Method for producing oxime bodies The oxime compound can be produced in the same manner as in Reference Example 4.

(2) Production method of oxime compound H Oxime compound 14.75 P (0.05 mol) and triethylamine 5.555 y (o, oss mol) are dissolved in 300 g of acetone, and benzoyl chloride 7.
73y (0,055 mol) is added dropwise. After dropping, continue stirring at room temperature for 30 minutes. After the reaction is completed, the precipitated triethylamine hydrochloride is separated, and the liquid is evaporated to dryness under reduced pressure. The obtained oxime compound is recrystallized from ethanol. The yield is x7. sr (yield: 88%).

Reference Example 6 0 C02H5 (1) Method for producing oxime 1-(2,4,6-dolimethylphenyl)-a-(4-
methylphenyl)-1,3-furopanedione 282(
0.1 mol) was dissolved in 60 g of acetic acid and 30 g of ethanol, and under water cooling, an aqueous solution of 20.7 t (0.3 mol) of sodium nitrite/40 f of water was added dropwise over 45 minutes. After addition, stir overnight at room temperature. Vacuum dry the precipitated crystals. The yield was 202 (yield: 65%).

(2) Method for producing an oxime compound HO-○-02Hg 15.45 t (o, os mol) of oxime compound and 5.555 t (0,055 mol) of triethylamine were dissolved in 300 g of oxime compound, At below 5°C, propionylchloride rs,o9t (0,055 mol) is added dropwise.

After the dropwise addition, stirring was continued for 30 minutes at room temperature. After the reaction is completed, the precipitated triethylamine hydrochloride is separated, and the liquid is evaporated to dryness under reduced pressure. The obtained oxime compound is recrystallized with ethanol. The yield was 12f (yield: 66%).

Patent applicant Asahi Kasei Kogyo Co., Ltd. Procedural amendment (voluntary) February 15, 1988 Commissioner of the Patent Office Kuro 1) Yu Akira 1, Indication of the case 1986 Patent Application No. 271948 2, Title of the invention Novel Photosensitivity Sexual composition 3, relationship with the case of the person making the amendment Patent applicant Osaka, 1-2-6 Dojihama, Kita-ku, Osaka, Japan (003)
Makoto Seiko, President and Representative Director of Asahi Kasei Industries Co., Ltd. 4. Correction of ○ in the 1st line of page 15 of the specification in ``Detailed Description of the Invention J, 5, Contents of the Amendment (1), page 15 of the specification of the specification to be amended. do.

(2) Page 16 of the specification, line 2 do.

・ゞ・−■・'>, ([Ethyl group, or pa・'-i-:, on page 24 of the 31 specification, line 4.

``Hydrogen group'' is corrected to ``or ethyl group.''

\mini! (4) "2.0% by weight" on page 30 of the specification, line 2,
“Corrected to 20% J by weight.

that's all

Claims (1)

[Claims] (a) General formula (1) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (1) [In the formula, X is a (2+n)-valent carbocyclic group or a heterocyclic group, and Y is a (2+m)-valent carbocyclic or heterocyclic group, Z has ▲mathematical formula, chemical formula, table, etc.▼, ▲mathematical formula, chemical formula,
There are tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, R^* is a group with a carbon-carbon double bond, and W is a group that reacts with the carbonyl group of -COOR^* by heat treatment to form a ring. n is 1 or 2, m is 0, 1 or 2,
and COOR^* and Z are in an ortho- or peri-position relationship with each other] A polymer having a repeating unit represented by (b) General formula (2) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (2) [ R_1 in the formula is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 6 to 10 carbon atoms.
aromatic hydrocarbon group, R_2 is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms
An oxime compound represented by ] representing an aryloxy group,
and (iii) a photosensitive composition containing a sensitizer having an absorption peak wavelength of 250 to 500 nm.