JPS62215264A - New photosensitive composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition having a high optical sensitivity in case of using it as a thick film by incorporating a specific polymer, a specific compd. and a sensitizer having an absorption peak in 250-500nm wavelength to the titled composition as essential components. CONSTITUTION:The titled composition contains the polymer having a repeating unit shown by formula I, the compd. shown by formula II or III, and the sensitizer having the absorption peak in 250-500nm wavelength. The sensitizer is for example, Michler's ketone and 4,4'-bis-(diethylamino)-benzophenone, etc. However, the sensitizer is not limited to the prescribed compds. The compounding ratio of the compd. shown by formula II or III is preferably 1-15wt% per the polymer shown by formula I. The compounding ratio of the sensitizer is preferably a range of 0.05-15wt% per the prescribed polymer. In formula II and III, R1 is hydrogen atom or 1-4C alkyl group, R2 and R3 are each 1-2C alkyl group, R4 and R5 are each 1-4C alkyl group etc., R6 is 6-16C arylene group, R7 is 1-4C alkyl group.

Description

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

Conventionally, heat-resistant polymer compounds represented by polyimide are
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 particularly utilized to create printed circuits, resists for etching metal plates, and semiconductor devices. It is well known that remarkable progress has been made in materials for microfabrication such as resists.

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, such as passivation films, α-ray shielding films, and junction films. Applications are being considered such as surface protection films such as coating films, 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 sheets [for example, "Functional Materials", July issue, pages 9-19 (2019)
And, [Photographic Science Anr + Engineer 3P (Photographic 5c
J. 303-309 (1979)].

[Conventional technology]

Conventionally, heat-resistant photosensitive compositions such as polyimirr
A cross-linked structure is formed by adding a photosensitizer and a copolymerizable monomer to a polymer in which active functional groups such as double bonds are introduced into the ester side chains of polyamic acid, which is a precursor of A moisturizing composition is known (Japanese Patent Publication No. 55-3020
7, Japanese Patent Publication No. 55-41422). This is a basic composition of heat-resistant polymer materials for lithography, typified by so-called photosensitive polyimides, 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 active functional group in the side chain, and a 7-)r compound such as p-acetami-P-phenylsulfonazir is used as a photoinitiator. An additional method has been proposed (Patent Publication No. 55-155347).

However, although this composition has slightly improved photosensitivity, it is still far from 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 of the ionic bond type, there is a problem in that if left after application and drying, siflux is likely to occur 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 produced by dissolving and removing polyamide to form an image, followed by high-temperature treatment to close the imir ring, etc., and at the same time vaporize the polyamide acid side chains, crosslinking chains, initiator, etc. A process of forming is used as a typical form.

[Problem that the invention seeks to solve]

By the way, in the conventional prior art, the so-called photosensitivity? It has been found that increasing the film thickness of Reimirr has the drawback that the photosensitivity is extremely reduced and the exposure time required for curing becomes longer.

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,
It has been discovered that a composition comprising a compound represented by the following general formula (2) or (3) and a sensitizer having an absorption peak wavelength of 250 to 500 nm is suitable for the purpose,
Based on this knowledge, we have completed the present invention.

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 or heterocyclic group
〇10-0-NH-1. ．． * is a group having a carbon-carbon double bond, W is a group that can react with the carzenyl group of h and -aooR* to form a ring by heat treatment, n is 1 or 2, m is 0,
1 or 2, and C0OR* and Z are in an ortho- or peri-position relationship with each other] A polymer having a repeating unit (hereinafter referred to as component (a)) (b) General formula (2) or a compound represented by (3), R [formula (2), (3), R1 is a hydrogen atom, carbon number 1
-4 alkyl group, C1-4 alkoxy group, C1-4 alkylthio group, P, 2. YL3 is an alkyl group having 1 to 2 carbon atoms, R4 and R5 are an alkyl group having 1 to 4 carbon atoms, or -together 10- or -NR7-
an alkylene group having 4 to 5 carbon atoms which may be interrupted by R6
is an arylene group having 6 to 16 carbon atoms, and R7 is an arylene group having 1 to 16 carbon atoms.
4 shows the alkyl group. ] and (c) provides a photosensitive composition comprising a sensitizer having an absorption peak wavelength of 250 to 500 nm.

In the composition of the present invention, the polymer used as component (a) has a repeating unit represented by the above general formula (1), where X is a trivalent or tetravalent carbocyclic group. or a heterocyclic group, and examples of the more rigid )OH3 1 is 0 or 1, X2 is OH3 or OF], and the like. Among these, carbon number 6-14
aromatic hydrocarbon group, Xl is +0Hr) rOF.

OF3 Furthermore, the expression %formula%) Those shown are preferred.

Y in the general formula (1) is a divalent, trivalent, or tetravalent carbocyclic group or heterocyclic group, and examples of such a group include a group having 10 to 18 carbon atoms derived from naphthalene, anthracene, etc. A heterocyclic group derived from a divalent aromatic hydrocarbon ring, pyridine, imidazole, etc. and the formula ¥1 3Y4 [Yl in the formula is H, OH3, (OH3)20H,00H
3.C! OOH.

Halogen atom or 5O3H, Y2 is +CH food (however,
? I(.

p is 0 or 1), -80, -1-0-1OH3 Y3 and Y4 are H, OH3, 02H5, 00H3, halogen atom, 0OOH, 80, H or No, , y, and Y
6 is H, ON.

A halogen atom, a group represented by CH3, OCH3, 503H or OH, and the like. Among these, there are divalent aromatic hydrocarbon rings having 10 to 14 carbon atoms, and Y2 is -
A group represented by the formula (I5) in which so, -1-〇- or -S- and Y3 and Y4 are both hydrogen atoms is preferred, and a group represented by the formula is more preferred.

W in the general formula (1) is -00 by heat treatment.
It is a group that reacts with the carzenyl group of 0R* to form a ring, and -O-NH is particularly suitable 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, such as,
For example, -R"-OH= 0H2(Its) [In the formula, R' is a hydrogen atom or a methyl group, R" is a fullkylene group having 1 to 3 carbon atoms, and n is 1 or 2]. .

As an example of (■1), OH2000H=OH2 As an example of (■2), As an example of (R3), As an example of (R4), As an example of (R5), 0H20H=0H2 -OH2-OH2-CH=OHz As an example of (R6), OH20H2NHO0H=OHz As an example of (R7), Examples include.

The compound used as component (b) in the composition of the present invention is represented by the above general formula (2) or (3).

In the formula, R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkylthio group having 1 to 4 carbon atoms, preferably a hydrogen atom, a methyl group, or an ethyl group. , methoxy group, ethoxy group, methylthio group, etc. In the formula, R2+R3 is an alkyl group having 1 to 2 carbon atoms, a methyl group, or an ethyl group. In the formula R4y
R5 is an alkyl group having 1 to 4 carbon atoms, or an alkylene group having 4 to 5 carbon atoms which may be interrupted by 10- or -NR,7-, preferably a methyl group. ,
Ethyl group is eclipsed. R6 is an arylene group having 6 to 16 carbon atoms.

R7 is an alkyl group having 1 to 4 carbon atoms.

Examples of formula (2) include, and examples of formula (3) include, but are not limited to, 02H5.

In the composition of the present invention (→ the sensitizer used as a component is
The absorption peak wavelength is in the range of 250 to 500 nm, such as [where R1*'fL2 is a methyl group or an ethyl group, R
3 is a hydrogen atom or a methyl group, R4 is a carbon number of 6 to 10
'R is a methyl group, an ethyl group, or an aromatic hydrocarbon having 6 to 10 carbon atoms, R6* R7 is a hydrogen atom, an aliphatic group, a substituted aliphatic group, and 6 to 10 carbon atoms is a group consisting of an aromatic hydrocarbon, at least one of R11t and R7 is a hydrogen atom, R is a hydrogen atom, a methyl group, an ethyl group, a hydroxyl group, m and n are 0
．． 1 or 2].

Examples of sensitizers include Michler's ketone, 4,4'-his-(diethylamino)-benzophenone, 2,5-bis-(4'-diethylaminobenzal)-cyclopentanone, 2,6-bis-(4 '-diethylaminobenzal)-cyclohexanone, 2,6-bis-(4'-dimethylaminobenzal)-4-methyl-cyclohexanone,
2.6-bis-(4/,)ethylaminobenzal)
-4-methyl-cyclohexanone, 4,4'-bis-(
dimethylamino)-chalcone, 4,4'-his-(diethylamino)-chalcone, 4-dimethylaminocinnamylideneindanone, 4-dimethylaminobenzylideneindanone, 2-(4'-dimethylaminophenylvinylene)-benzo Thiazole, 2-(4'-dimethylaminophenylvinylene)-isonaphthothiazole, 1.3-
Bis-(4/,)methylaminobenzal)-acetone, 1,3-his-(4/,)ethylaminobenzal)-acetone, 3,3'-carcinyl-bis-(
7--,,ff ethylaminocoumarin), 7-j ethylamino-3-penzoylcoumarin, 7-danitylamino-4-methylcoumarin, N-phenyl-getanolamine, N-p-)lyludiethylamine, etc. However, it is not limited to these.

Note that these may be used alone or in combination.

Preferably, a sensitizer having the structure (1) to (4) and a sensitizer having the structure (2) 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,
These include 2-ethylhexyl acrylate, 2-hydroxyproxyethyl acrylate, N-vinyl-2-pyrrolidone, carpitol acrylate, tetrahydrofurfuryl acrylate, isodernyl acrylate, 1.6- Hexanediol diacrylate, neopentyl glycol diacrylate, ethylene glycol diacrylate, polyethylene glycol diacrylate, pentaerythritol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, tetramethylolmethanetetra Examples include acrylate, tethodiethylene glycol diacrylate, nonaethylene glycol cyacrylate, methylene bisacrylamide, N-methylolacrylamide r, and those in which the above acrylate or acrylamide r is replaced with methacrylate or methacrylamide P. Preferred among these 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 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 1-phenyl-5-mercapto-IH-tetrazole, 2-mercaptothiazoline, 2-mercapto-4-
7-enylthiazole, 2-amino-5-mercapto-1
, 3゜4-thiadiazole, 2-mercaptoimidazole, 2-mercapto-5-methyl-1,3,4-thiadiazole, 5-mercapto-1-methyl-IH-tetrazole, 2,4.6-drimercaptos -) Riazine, 2-dibutylamino-4,6-dimercapto-s
-) Leah, Jin, 2.5-u Mercapto-1゜3.4-
Thiadiazole, 5-mercapto-1,3゜4-thiadiazole, 1-ethyl-5-mercap)-1,2,3,
4-tetrazole, 2-mercapto-6-nitrothiazole, 2-mercaptobenzoxazole, 4-phenyl-2-mercaptothiazole, mercaptopyridine, 2-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 base material Sl and inorganic insulating film, and examples thereof include, for example. , γ-aminopropylmethyldimethoxysilane, N-β(aminoethyl)γ-aminopropyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, dimethoxy-3-mercaptopropylmethylsilane , 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinoprobylsilane, jetoxy-3-glycidoxypropylmethylsilane, N-(a-jetoxy Methylsilylprobyl) succinimide and the like.

The usage and effects of these dialkoxysilane compounds are described in detail in, for example, Japanese Patent Application No. 38242/1983. Furthermore, a polymerization inhibitor may be added to improve the storage stability of the solution of the composition of the present invention. Examples of the polymerization inhibitor include hydridetetraquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, and 2,6-tert-butyl-p-methylphenol. , but not limited to these.

In the present invention, the content ratio of the compound represented by the general formula (2) or (3) of the (→ component) is not particularly limited, but is preferably 0.1 to 20% by weight based on the polymer of the component (A). , more preferably in the range of 1 to 15% by weight.Also, the content ratio of the sensitizer as the component e in the present invention is 0.01% to the polymer of component (a). ~20% by weight, more preferably 0.05%
It is desirable to contain it in a range of 15% to 15%. The amount of the compound having a carbon-carbon double bond added is preferably 20% or less based on the polymer of component 0). The amount of the mercaptan compound added is preferably 10% by weight or less based on the polymer of component C), and more preferably,
It is 5% by weight or less. Further, when the functional qualkoxysilane compound is added and used, the amount added is 0.05 to 10% by weight, preferably 0.1 to 4% by weight, based on the polymer of component (A). be.

The polymerization inhibitor is used in an amount of 5% by weight or less, preferably 0.5% by weight or less, based on the polymer of component 0).

The polymer used as component 0 in the composition of the present invention is:
For example, it can be obtained 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 (to) are -000H (III), -0001 (L), -Neo
(IIIg), -NHz(L), -0H(first), and the abbreviations of the corresponding general formulas (to) are shown within 0. Also, as an example of Z2 in the general formula (goods), −
oocl (fl/l), -000H (IVz), -No
o(■x), -NHt(■4), and the corresponding abbreviations of general 2ω are shown within 0. Note that X, R, Y and W have the same meanings as above.

Sea Z
t and Z, - react to form a bond chain 2.

Table 1 summarizes the preferred combinations of 21 and z2, the types of 2 produced, and the ring structural groups produced when the obtained polymer is heat-treated.

Table 1 Notes *1 Ring structure IM: Imide ring QD: Quinazolinedione ring OD Nioxazinedione ring The polymer of component (a) can also be produced by the method shown below. That is, the compound represented by the general formula (% formula %) [X in the formula has the same meaning as above] is converted into the compound represented by the general formula (tVj) or (■4)
The carzexyl group of the product obtained by reacting with the compound represented by the formula is an epoxy compound represented by the general formula [R* in the formula has the same meaning as above], or an amine compound represented by the general formula, for example. Alternatively, the polymer can be obtained by reacting with a quaternary ammonium salt represented by the general formula.

Note that these reactions are described, for example, in JP-A-56-32524.
No. 60-19444, this issue.

The compound represented by the general formula (TITI) can be obtained, for example, by ring-opening with an acid anhydride R*OH (R* has the same meaning as above) represented by the general formula (6). Examples of the nucleic acid anhydride (■6) include pyromellitic anhydride, 3.3'.

4.4'-penzophenonetetracarzenic dianhydride,
3.3', 4.4'--j phenyl ethertetracardic dianhydride, 3.3', 4.4'-diphenyltetracardic dianhydride, 313', 4,4/-diphenyl Sulfone tetracarponic dianhydride, 2,3,6.7
-Natsuta lentithracaldic acid anhydride, thiophene-2
゜3.4.5-Tetracardic acid anhydride, 2,2-bis-(3,4-hiscarboxyphenyl)furopane anhydride, etc., and alcohol R*OH includes 2-hydroxyethyl methacrylate, 2-hydroxyethyl methacrylate, -hyroxyethyl acrylate, 2-hyroxyprogyl methacrylate,
Examples include 2-hydroxyzorobyl acrylate, allyl alcohol, and ethylene glycol monoallyl ether.

When these acid anhydrides (6) are reacted with alcohol R*OH, the reaction is accelerated by adding pyridine, dimethylaminopyridine, 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'-diamino diphenyl ether, 4.4'
-diaminobiphenyl, 2,4'-diaminotoluene,
4.4'-diaminobenzophenone, 4゜4'-diaminodiphenylsulfone, phenylindane diamine, 4
．． 4'-diaminodiphenylmethane, p-phenylenediamine, m-phenylenediamine, 1,5-diaminonaphthalene, 3.3'-dimethoxy414') yminobiphenyl, 3.3'--9methy/l/-4, 4'-
Diaminobiphenyl, 〇-Toluidine sulfone, 2,2
-Bis(4-aminophenoxyphenyl)propane, bis(4-aminophenoxyphenyl)sulfone, bis(
4-aminophenoxyphenyl)sulfur, 1. a-
Bis(4-aminophenoxy)benzene, 1,3-bis(4-7minophenoxy)benzene, 3.4' --7
Aminodiphenyl ether, 9,9-bis(4-aminophenyl)anthracene-(10), 9,9-bis(4
-7minophenyl)fluorene, 3.3'-diaminodiphenylsulfone, 4.4'-di(3-aminophenoxy)diphenylsulfone, 4.4'--, ffamino4densani+7)', 3.4'- J aminodiphenyl ether, 4,4'-[1,3-phenylene bis(1-
methylethylidene)], 4.4'-[1,4-7 22lenebis(1-methylethylidene)], 4,4'-
(m-phenylene diisopropylidene) bis(m-1-
luidine), 4°4'-(p--yenylenediisoprohyritene)bis(m-toluidine), and the like.

Of this combination, the reaction between the compound represented by the general formula (■1) and the compound represented by the general formula (■4) is carried out using a calzediimi P type dehydration condensation agent, for example, dicyclohexyl calzediimi P. be able to.

In addition, the compound represented by the general formula (■2) is represented by the general formula (
(2) It can be obtained by reacting the half ester shown in 1) with thionyl chloride, phosphorus pentachloride, etc.

For the methods of these reactions, see, for example, Japanese Patent Application No. 1983-
No. 193737, patent application No. 1983-9918, patent application No. 1983
-238545 etc. in detail.

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 dimethylformamyl N-methylpyrrolidone, dimethylacetamyl diglyme, isobutyl acetate, or cyclopentanone, which does not have an excessively high boiling point. Furthermore, solvents such as alcohols, aromatic hydrocarbons, ethers, ketones, and esters can be added to the extent that the components are not precipitated.

The method for coating the substrate on the substrate includes a method in which the solution obtained as described above is filtered and then coated on the substrate using, for example, a spin coater, a no-no-coater, a blade 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.

As the substrate, heat-resistant materials such as metallic glass, silicon semiconductors, metal oxide insulators, and silicon nitride are preferable, and when 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 halogen 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, a spray method, etc. The developer used for this removal is preferably one that can completely dissolve and remove the unexposed film within an appropriate time, such as N-methylpyrrolidone, N-acetyl-2-pyrrolidone, N-acetylpyrrolidone,
N-dimethylformamide FIXN, N-dimethylacetamide, dimethylsulfoxy P1 hexamethylphosphoric triamide, N-benzyl-2-pyrrolidone, γ-
Aprotic polar solvents such as butytetralactone may be used alone, or they may be combined with alcohols such as ethanol and isopropanol, aromatic hydrocarbon compounds such as toluene and xylene, and methyl ethyl ketone. , ketones such as methyl isobutyl ketone,
A mixture of solvents such as esters such as ethyl acetate and methyl propionate, and ethers such as tetrahydro7rane and dioxane may be used. Furthermore, immediately after development, the second
It is preferred to rinse with a solvent such as those indicated as components.

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

〔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. Furthermore, the composition has the advantage of long-term storage stability and no undesirable gelation or cracking during coating drying.

When the composition of the present invention is used as an interlayer insulating film or a surface protective film for semiconductor devices, the above-mentioned characteristics can greatly shorten the process and facilitate microfabrication. It exhibits characteristics such as being able to form a flat layer.

〔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, ? used in the example? Displays the names of reamers, compounds of general formula (2) or (3), sensitizers, compounds with carbon-carbon double bonds (monomers), mercaptan compounds, functional dialkoxysilane compounds, and polymerization inhibitors. Shown in 1.

Table 1 (1) Polymer (2) Compound (3) represented by general formula (2) or (3)
The sensitizer absorption peak wavelength was measured using a Varian 0ARY2195pectr spectrophotometer (Varian 0ARY2195pectr).
o Photometer) using ethanol as a solvent.

(4) Monomer (5) Mercaptan compound (6) Functional dialkoxysilane compound (7) Polymerization inhibitor Examples 1 to 15 For 100 parts by weight of the polymer shown in Table 2, add the additive by weight shown in the same table. part by weight and dissolved in 130 parts by weight of N-methylpyrrolidone. This solution was applied to a silicon wafer using a spin code (1300 rpm x 30 sec) L
, and dried in air at 70° C. for 1 hour to obtain a uniform coating film.

Next, under a nitrogen atmosphere, gray scale (KodakPho)
tographic 5tep Tablet A2)
The film was exposed to light for 5 minutes using an ultra-high pressure mercury lamp (8 mW/cm2). After this wafer was left at 23°C for 30 minutes, it was developed with a 2:3 (volume ratio) mixture of N-methylpyrrolidone and xylene at 23°C using a rocking immersion developer, 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; increasing the number of steps by one means that the exposure amount is lower by Vl-.) The obtained results are shown in the same table.

Comparative Examples 1 to 5 Experiments were conducted on the compositions in Table 3 in the same manner as in Examples 1 to 15, and the results shown in the table were obtained.

Comparative Examples 6 to 10 In place of the compound represented by general formula (2) or (3),
Experiments were conducted on the compositions in Table 4 in the same manner as in Examples 1 to 15 using other photopolymerization initiators, and the results shown in the table were obtained.

Margin below

Claims (1)

[Claims] 1 (a) General formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
...(1) [In the formula, X is a (2+n)-valent carbocyclic group or heterocyclic group, Y is a (2+m)-valent carbocyclic group or heterocyclic group, and Z is , tables, etc. ▼, ▲ mathematical formulas, chemical formulas,
There are tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, R^* is a group with a carbon-carbon double bond, W is -COOR by heat treatment
A group that can react with the carbonyl group of ^* 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], and (b) a compound represented by the general formula (2) or (3). Yes▼・・・・・・・・・・・・
(2) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
(3) [In the formula, R_1 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, and R_2 and R_3 are hydrogen atoms having 1 to 2 carbon atoms. The alkyl group, R_4, R_5 is an alkyl group having 1 to 4 carbon atoms, or together is an alkylene group having 4 to 5 carbon atoms which may be interrupted by -O- or -NR_7-, and R_6 is an alkyl group having 6 carbon atoms. ~16 arylene group, R_7 represents an alkyl group having 1 to 4 carbon atoms] and (iii) a sensitizer having an absorption peak wavelength of 250 to 500 nm.