JPH01204917A - Photosensitive composition excellent in storage stability - Google Patents

Abstract

PURPOSE:To improve the storage stability and heat resistance, by blending a polymer having specific repeating units with a C-nitroso compound. CONSTITUTION:0.001-5wt.% C-nitroso compound (B) (e.g., 5-nitroso-8- hydroxyquinoline) is incorporated into a polymer (A) having repeating units of formula I, wherein X is a (2+n)-valent carbocyclic or heterocyclic group; Y is a (2+m)-valent carbocyclic or heterocyclic group; Z is a group of formula II-IV; R* is alkoxy having a C-C double bond or a group containing a salt; W is a group which can react with the carbonyl of -COR* to form a ring by heat treatment; n is 1 or 2; m is 0-2; and -COR* and Z are ortho or peri to each other.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention provides a photosensitive composition with excellent storage stability, more specifically, a photosensitive composition with excellent storage stability that can be converted into a heat-resistant polymer by heat treatment. This invention relates to a photosensitive composition.

(Prior art and its problems) Polyimide is known as a typical heat-resistant polymer,
Due to its excellent insulation and mechanical properties, it has a wide variety of uses. In the semiconductor industry, in addition to being used as a film, it is also being applied to semiconductor devices.

Applications to semiconductor devices are often used as surface protection films and interlayer insulation films, and this is done by applying polyamic acid to semiconductor elements to form a coating film, and converting it into a polyimide film through heat treatment. It is formed. In addition, a photopolymerization initiator or the like is added to a mixture of polyamic acid and a photosensitive compound or a precursor polymer in which an active functional group such as a double bond is introduced into the side chain of a polyamic acid ester, and a crosslinked structure is formed by light irradiation. Heat-resistant photosensitive polymer compositions capable of obtaining relief patterns are known. These are called photosensitive polyimides, and are disclosed in Japanese Patent Publication No. 55-30207, Japanese Patent Publication No. 55-41422, and Japanese Patent Application Laid-open No. 54-14579.
It is disclosed in Publication No. 4. Photosensitive polyimide is used to provide a heat-resistant film by performing heat treatment after passing through steps such as coating, exposure, and development. These compositions are characterized by having active functional groups in the side chains of the polymer. Therefore, conventional U containing polyfunctional monomers as the main component
It has higher sensitivity than photosensitive compositions such as V-curing paints and dry film resists for making printed circuit boards, and even slight local crosslinking causes gelation of the entire composition. This problem of gelation becomes particularly noticeable when these compositions are stored in a solution state dissolved in a polar solvent. Since these photosensitive compositions are often stored and used in a solution state, improving the storage stability of the composition is an extremely important issue.

radical polymerization inhibitors used in conventional photosensitive compositions,
For example, hydroquinone, p-methoxyphenol, 4-1
-butylcatechol, 2,6-di, monozotyl-p-cresol, etc. tend to have an insufficient gelling prevention effect, and when added to a practically satisfactory level, the photosensitivity decreases. In addition, thermal polymerization inhibitors such as quinone and phenol are only effective in the presence of oxygen, so if they are stored in a sealed container, they will not be effective in preventing polymerization due to insufficient contact with air. There was also the problem.

(Means for Solving the Problems) In view of the above circumstances, the present inventors have conducted intensive studies to provide a heat-resistant photosensitive composition with excellent storage stability, and as a result, as an essential component, The present inventors have discovered that a composition containing a polymer having a specific structure and a C-nitrone compound is suitable for the purpose, and have completed the present invention based on this finding.

That is, the present invention provides (a)-Noshiro (I) [wherein X is (
2+n) valent carbocyclic or heterocyclic group, Y is (2+m
) valent carbocyclic group or heterocyclic group, W is an alkoxy group having a carbon-carbon double bond or a group containing a salt, W is a group in which -CO 8 and 2 are in an ortho- or peri-position relationship with each other by heat treatment. be. The present invention relates to a photosensitive composition having excellent storage stability, comprising a polymer having a repeating unit represented by the following formula, and (b) a C-nitroso compound.

- To describe the polymer represented by Noshiro (1) in more detail, X in the formula is a trivalent or tetravalent carbocyclic group or a heterocyclic group, and examples of the more specific X include, for example, a benzene ring or , fused polycyclic aromatic rings such as Natsutaleno ring and anthracene ring, heterocyclic groups such as pyridine and thiophene,
and -Noshiro (■1) OH3 X, is OH3 or OF3. ] Examples include groups represented by the following. Of these, carbon number 6
~14 aromatic hydrocarbon groups, Xt is 1,000) (2+tO
F.

or -C-, a group represented by -Noshiro (■1) is preferable F
3 and more preferably those represented by the formula (112) (IIs) (q is O or 1).

Y in the above - Noshiro (1) is a divalent, trivalent or tetravalent carbocyclic group or heterocyclic group, such as 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 a formula Y+ (I[4) (IIs) (I[a)
<117>OH,0H3 (■8) [Yl in the formula is H, CH3, (OH3)20H, 0OH
3,0OOH.

Halogen atom or 5o3H,y, is +0I-12ki(
However, p is 0 or 1), 802 +H3 0H1 CI (30) (3 halogen atom, 0OOH, 303H or No2, Y,
and Y6 is H, ON, halogen atom, OH3,0O
H3,80sH or OH. ] The following groups are listed. Among these, carbon number 1
0 to 14 divalent aromatic hydrocarbon ring, Y2 is 15o2
-, -o- or -S-, and a group represented by the formula (■5) in which both ¥3 and Y4 are hydrogen atoms is preferred, and a group represented by the formula is more preferred.

The W in -Noshiro (1) is converted into -con by heat treatment.
A group capable of reacting with the carzenyl group of * to form a ring, and -〇-NH2 is particularly suitable as such a group. Further, n is preferably 2.

Furthermore, R* in -Noshiro (1) above is an alkoxy group having a carbon-carbon double bond or a group containing a salt, such as -0-*Otsu0H=
Examples include OH, (IIIs) [wherein R' is a hydrogen atom or a methyl group, R'' is an alkylene group having 1 to 3 carbon atoms, and n is 1 or 2].

As an example of (■1), -0-OH2000H=OHz 0 0H.

0 0H2 (3Hz As an example of O-00H=OH2 (1■2), As an example of (■3), As an example of (■4), As an example of (■5), -0-0 )I2-CH=CH.

-0-OH2-OH, -0H=OH2 (■6) Examples are -0-0)1. Examples of -OH, -NH-0-OH=OH2 (capital) include HO0H3 0Hs 0 0Hs.

Among these, due to photosensitivity, storage stability, etc. 0 0Hs OH30 00H20H2000H=OH2.

0 0H20HI 0H=CH2.

-0-OH2-OHsu-NH-0-OH=OH2 and the like are preferred.

The polymer used in the present invention 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 (■) are -000H(Vl), -0001(V2),
-NOO(Vs).

-NHS (Vl), -OH (V5) are present, the corresponding general formula (■ is shown within 0). Also, as an example of Z2 in the general formula (to), -0001 (■
t), =OOOH(Vl2).

-NOO(Vs) and NH2(ML), and the abbreviations of the corresponding general formulas (to) are shown within 0. In addition, X
, 几, Y and W have the same meanings as above.

By polycondensation or polyaddition reaction between the compound represented by the above formula M and the compound represented by the general formula M, Zl and Z2
A bonding chain 2 is formed by the reaction.

Zl and 2 at this time! Table 1 summarizes the preferable combinations with the above, the type 1 of 2 produced, and the ring structure defects produced when the obtained polymer is heat-treated.

Table 1 Note: *1 Ring structure IM: Imide ring QD: Quinazolinedione ring OD Nioxazinedione ring In addition, in the combination of numbers 1 and 2 in Table 1,
When W is OONH2, a diisoindoroquinazolinedione ring is formed by the heat treatment, and this structure is preferred because it exhibits particularly high heat resistance. .

In addition, the polymer of formula (1) can be obtained by the following method.
5 can also be produced. In other words, −Noshiro% expression% (
7) (X in the formula has the same meaning as above) A compound represented by the above general formula (■3) or (■4)
The carxyl group of the product obtained by reacting with the compound represented by is converted into an epoxy compound represented by the general formula (R in the formula is a group having a carbon-carbon double bond) or, for example, the general formula 0H3-N -R (R in the formula has the same meaning as above) or a quaternary ammonium salt shown in the general formula (R in the formula has the same meaning as above) Then, the polymer is obtained.

Note that these reactions are described, for example, in JP-A-56-3252.
No. 4 and Japanese Patent Application Laid-open No. 194444/1983.

The compound represented by the above general formula (vl) can be obtained by, for example, ring-opening the acid anhydride represented by the general formula (6) with an alcohol represented by R*H (几* has the same meaning as above). can get. Examples of the acid anhydride (6) include pyromellitic anhydride, 3.3', 4.4'-benzophenonetetracal dianhydride, and 3.3', 4.4'-diphenyl ether. Tetracarzenic dianhydride, 3,3'
, 4.4'-diphenyltetracaldic acid dianhydride,
3.3',4.4'-diphenylsulfonetetracarboxylic dianhydride, 2.3,6.7-naphthalentitracarzenic anhydride, thiophene-2,3,4,5-tetracarboxylic anhydride , 2,2-bis(3,4-biscarzexyphenyl)propane anhydride, etc., and examples of the alcohol R*H include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl acrylate, -Hydroxyzorobyl acrylate, allyl alcohol, ethylene glycol monoallyl ether, and the like.

When reacting these acid anhydrides (6) with alcohol R*1, the reaction is accelerated by adding pyridine, dimethylaminopyridine, etc.

The combination of numbers 1 and 2 in Table 1 above is an 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'-diaminobiphenyl, 2,4-diaminotoluene, 4.4'
-diaminobenzophenone, 4°4/, t-aminodiphenylsulfone, phenylindane diamine, 4.4
'-Diaminodiphenylmethane, p-phenylenediamine, m-phenylenediamine, 1,5-diaminonaphthalene, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diamino biphenyl, 0-toluidine sulfone, 2,2-bis(4
-aminophenoxyphenyl)propane, bis(4-aminophenoxyphenyl)sulfone, bis(4-aminophenoxyphenyl)sulfide, 1,4-bis(4-
7minophenoxy)benzene, 1.3-bis(4-aminophenoxy)benzene, 3.4'-di-aminodiphenyl ether, 9.9-bis(4-aminophenyl)anthracene-(10), 9,9-bis (4-aminophenyl)fluorene, 3.3'-diaminodiphenylsulfone, 4.4'-J-(3-7mi/phenoxy)diphenylsulfone, 4.4'-diaminobenzanilide, 3.4'-diamino diphenyl ether, 4.4'-
[,a-)unilenebis(1-methylethylidene)],
4.4'-[1,4-phenylenebis(1-methylethylidene)], 4.4'-(m-)unilene diimprogylidene)bis(m-toluidine)% 4.4' (
(p-)unilene diisopropylidene)bis(m-)luidine), and the like.

In this combination, the reaction between the compound represented by the general formula (Vl) and the compound represented by the general formula (■4) is carried out using a calzediimide-type dehydration condensation agent, such as dicyclohexyl calzediimide. Can be done.

Further, the compound represented by the general formula (■2) can be obtained by reacting the half ester represented by the general formula (vl) with thionyl chloride, phosphorus pentachloride, etc., and can be obtained as is. It can react with the compound shown in (■4).

For the methods of these reactions, see, for example, JP-A-61-7
It is described in detail in Japanese Patent Publication No. 2022, Japanese Patent Publication No. 55-41422, Japanese Patent Application Laid-Open No. 61-118423, etc.

In addition, as the photosensitive polyimide precursor in the present invention, JP-A-60-198537, JP-A-59-31
948, JP 57-179242, JP 55-41422, JP 60-228537
Publication No. 1987-49748, Japanese Patent Application Laid-open No. 1987-49748
145794, JP 59-212832, JP 53-127723, JP 56-24
Also included are photosensitive polyimide precursors described in JP-A No. 343, JP-A-55-45746, and the like.

In addition, as the photosensitive polyimide in the present invention, JP-A-59-108031, JP-A-59-14521,
Publication No. 6, JP-A-59-220730, JP-A-5
Also included are photosensitive polyimide F described in JP-A No. 9-231122, JP-A-59-219330, JP-A-59-231533, and the like.

Further, a mixture of polyimide or a polyimide precursor having no photosensitive group and a photosensitive monomer is also included in the present invention, provided that the composition as a whole is not photosensitive.

Examples of C-nitroso compounds which are polymerization inhibitors used as component (b) in the present invention include nitronbenzene, 2-nitrosotoluene, p-nitrosophenol, 4-nitrosoresorcinol-1-monomethyl ether, 2-nitroso- 5-dimethylaminophenol, p
-Nitroso-N.

N-dimethylamine, p-nitrone-N, N-diethylamine, 1-nitrone-2-naphthol, 2-nitrone-1-naphthol, 5-nitrone-8-hydroxyquinoline, 2-nitrone-1-naphthol-4 -sulfonic acid, 1-nitrone-2-naphthol-3,6-disulfonic acid sodium salt, 2-nitroso-5(N-ethyl-N-
Examples include sulfopropylamino)phenol.

Among these, 5-nitrone-8-hydroxyquinoline, 1-nitrone-2-naphthol, 2-nitroso-1-
Naphthol, 2-nitrone-5-(N-ethyl-N-sulfopropylamino)phenol are preferred.

These C-nitrone compounds may be used alone or in combination of two or more. The photosensitive composition of the present invention preferably contains these C-nitroso compounds in an amount of 0.001 to 5% by weight, preferably 0.01 to 1%, based on the polymer. A photoinitiator, an azide compound, and a diazo compound can be added as necessary.

Various azide compounds can be selected for use in the composition of the present invention. Specific preferred examples include 1.
4-benzenebisulfone azide, 4-sulfoneazidophenylmaleimide, 4,4'-diazidochalcone, 1,3-bis(4-azidobenzal-)acetone, 2,6-bis(4-azidobenzal-)cyclohexane, Examples include 2,6-bis(4-7cytohenzalu)4-methylcyclohexane.

Various diazo compounds can be selected for use in the composition of the present invention. As a specific preferable example, 4
-Diazo-N-ethyl-N-β-hydroxyethylaniline, 1,2-naphthoquinonediazide-4-sulfonic acid, p-benzoquinonediazide-p-diazophenylamine, and the like.

A variety of photoinitiators can be selected for use in the compositions of the present invention. Specific preferred examples include benzophenone, methyl 0-benzoylbenzoate, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(dimethylamine)benzophenone, 4,4'-dichlorobenzophenone, Hesiphenone derivatives such as 4-pensoyl-4'-methyldiphenylketone, dibenzylketone, and fluorenone; acetophenone derivatives such as 2,2'-jetoxyacetophenone, 2-hydroxy-2-methylzolobiophenone, and p-3-butyldichloroacetophenone; , 1-hydroxychlorohexyl phenyl ketone, thioxanthone, 2-methylthioxanthone, 2
-thioxanthone derivatives such as chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyl, benzyl, dimethyl ketal, benzyl-
Benzyl derivatives such as β-methoxyethyl acetal, benzoin, benzoin methyl ether, benzoin isobutyl ether, anthraquinone, 2
- Anthraquinone derivatives such as 1-butylanthraquinone, 2-amylanthraquinone, β-chloranthraquinone, anthrone, benzanthrone, dibenzosuberone,
Anthrone derivatives such as methylene anthrone, 1-phenyl-1,2-propanedione-2-(o-ethoxycarzenyl) oxime, 1-phenyl-1,2-propanedione-2-(0-benzoyloxime), α-benzoin Oximes such as oxime, naphthalenesulfonyl chloride, quinolinesulfonyl chloride, N-phenylthioacridone, 4,4'-azobisisobutyronitrile, diphenyl disulfide, benzthiazole disulfide, trinoenylphosphine, camphorquinone,
Examples include carbon tetrabromide, tribromophenyl sulfone, benzoyl peroxide, and combinations of photoreducing dyes such as eosin and methylene blue with reducing agents such as ascorbic acid and triethanolamine.

A suitable sensitizer can also be added to the photoinitiator. Examples of sensitizers include triethylamine jetanolaniline, Michler's ketone, isoamyl dimethylaminobenzoate, ethyl diethylaminobenzoate, and sensitizing dyes.

These photoactive substances can be used alone or in mixtures of several types. In the photosensitive composition, these initiators are added in an amount of 0.1 to 20% based on the polyimide or its precursor.

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-hydroxyethyl acrylate, N-vinyl-2-pyrrolidone, carpitol acrylate, tetrahydrofurfuryl acrylate, inzelnyl acrylate, 1,6-hexanediol di Acrylate, neopentyl glycol diacrylate, ethylene glycol diacrylate, polyethylene glycol diacrylate, pentaerythritol diacrylate, trimethylolpronozone diacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, tetramethylolmethanetetraacrylate, The above acrylates are changed to methacrylates, methylenebisacrylamide, N-methylolacrylamide, di(acrylaminomethyl)ether, the above acrylamides are changed to methacrylamide,
N-phenylmaleimide, diphenylmethane-4,
Examples include 4'-hismaleimide, trimethylolpronocentric triallyl ether, pentaerythritol triallyl ether, etc., and preferred among these are compounds having two or more carbon-carbon double bonds. The compound having a carbon-carbon double bond can be added to the polyimide or its precursor in an amount of 50% or less, if necessary.

In addition, when an allyl ether compound is used as the above-mentioned compound having a carbon-carbon double bond, and among polyamides synthesized from dicarzene acid having a sensitive group of a carbon-carbon double bond, a sensitive group may be used as the polyamide. When using an allyl group, it is preferable to use it in combination with an azide compound as a photoactive substance, or as a composition containing a photoinitiator and a polythiol compound.

These polythiol compounds are represented by the formula -Noshiro%%) (wherein and fL2 are organic groups that do not contain a "reactive" unsaturated carbon-carbon bond group, and n is an integer of 2 or more). . As used herein, the term "reactive carbon-carbon unsaturated bond group" means a group that forms a group under appropriate conditions.

Examples of polythiol compounds suitable for the present invention include thioglycolic acid (H8-OH,0OOH), α-mercaptopropionic acid (H8-OH(0H3) -000H) and β-mercaptopropionic acid (H8-OH,0H20
00H) with polyhydroxy compounds such as glycols, triols, tetraols, pentaols, hexaols, and the like. Specific examples of suitable polythiols include ethylene glycol ditheoglycolate, ethylene glycol di(3-mercaptopropionate), trimethylolpronocentrithioglycolate, trimethylolpronocentri(3-mercaptopropionate), Pentaerythritol tetrathioglycolate, Pentaerythritol tetra(3-mercaptopropionate),
Examples include, but are not limited to, trimethylolethane trithioglycolate, trimethylolethane tri(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), and the like.

These polythiol compounds are added in an amount of 0 to 30% to the polyimide or its precursor, if necessary.

Furthermore, photosensitivity can be further improved by adding a mercaptan compound to the composition of the present invention.

Examples of mercaptan compounds include 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 1-phenyl-5-mercapto-IH-tetrazole, 2-mercaptothiazoline, 2-mercapto-4-
Phenylthiazole, 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-) dimercapto-S -triazine, 2-dibutylamino-4,6-dimercapto-S-triazine, 2,5-dimercapto-1,3,4-thiadiazole, 5-mercapto-1゜3,4-thiadiazole, 1-ethyl-5- Mercapto-1,2,3,4-tetrazole, 2-mercapto-6-nitrothiazole,
2-mercaptobenzoxazole, 4-pheni, Q/
-2-mercaptothiazole, mercaptopyridine 2
-mercaptoquinoline, 1-methyl-2-mercaptoimidazole, 2-mercapto-β-7tothiazole, and the like.

Further, the C-nitroso compound which is the polymerization inhibitor of the present invention is disclosed in Japanese Patent Publication No. 43-26869 and Japanese Patent Publication No. 45-252.
The photosensitive dry film resist disclosed in Japanese Patent Publication No. 31, Japanese Patent Publication No. 19125-1912, Japanese Patent Publication No. 45-3
It is also used for the purpose of improving the storage stability of unsaturated polyester-based photosensitive resins disclosed in Japanese Patent Publication No. 915, Japanese Patent Publication No. 45-23165, Japanese Patent Publication No. 45-25224, and Japanese Patent Publication No. 45-25829. can.

The following describes how to use the composition of the present invention.

The composition of the present invention is applied onto a predetermined substrate after being dissolved in a solvent that can dissolve all the components in the composition.

At this time, in order to improve the adhesion with the substrate, for example, triethoxyvinylsilane, trimethoxyvinylsilane,
- Silanes such as glydoxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, 3-(2-amineethylaminopropyl)trimethoxysilane, 3-methacryloxyzorobyldimethoxymethylsilane It is desirable to add a coupling agent or pre-coat the substrate.

The solvent is preferably a polar solvent, such as one having a not too high boiling point, such as dimethylformamide, N-methylpyrrolidone, dimethylacetamide, 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.

The method of coating on the substrate includes a method of filtering the solution obtained as described above with a filter, and then coating it on the substrate with a spin coater, a no-no-coater, a blade coater, a screen printing method, etc. Various methods can be used, such as immersing the substrate in the solution and spraying the solution onto the substrate.

Various materials can be selected as the substrate, such as metal, glass, silicon semiconductor, metal oxide insulator, silicon nitride film, polyester film, and glass epoxy plate.

Next, the coating film obtained in this way is air-dried, heat-dried,
After drying using a combination of vacuum drying and other methods, exposure is performed. In this case, the active light used includes, for example, ultraviolet rays, X-rays, electron beams, etc. Among these, ultraviolet rays are preferable, and the light sources include, for example, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, and halogen lamps. , germicidal lamps, etc. Among these light sources, ultra-high pressure mercury lamps are preferred. Further, it is preferable that the exposure be performed under a nitrogen atmosphere. During this exposure, a known process such as using a photomask or a reduction projection device is used to perform exposure according to the required turns.

After exposing in this way, in order to remove the unexposed area,
Development is performed using a dipping method, a spray method, etc. The developing solution 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
, N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoric triamide, N-benzyl-2-pyrrolidone, γ-
Aprotic polar solvents such as butyrolactone may be used alone, or they may be combined with alcohols such as ethanol and isonoropanol as a second component.
Aliphatic hydrocarbons such as hexane and cyclohexane, 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 zoropionate, and ethers such as tetrahydrofuran and quasane. You may use a mixture of solvents such as. Furthermore, it is preferable to rinse with a solvent such as that shown as the second component immediately after development.

The images obtained in this way are usually heated at 200°C to 40°C.
The polyimide can be obtained by heating to 00°C to remove volatile components or by changing the chemical structure.

This zottern is useful for many purposes such as insulating films, protective films, and resist materials.

(Effects of the Invention) The photosensitive composition of the present invention has many advantages over conventional compositions. The advantage is that compositions containing C-nitroso compounds have significantly improved storage stability. For example, conventional photosensitive compositions have problems with storage stability and are difficult to store for long periods of time. In contrast, the photosensitive composition of the present invention shows no change in performance even when left at room temperature for several months, and even in accelerated tests at 40°C, conventional quinone and phenol thermal polymerization inhibitors gel in one day. However, it has stability for more than 30 days. Also,
In the composition of the present invention, the irradiation time required for photocuring is the same as when no C-nitroso compound is added.

In particular, compositions containing active functional groups such as double bonds via covalent bonds in polyamic acid side chains have the characteristic of being able to form thick coatings by spin coating because they can be prepared as highly concentrated solutions. However, when the concentration becomes high, gelation tends to occur at an accelerated rate, and the effects of the present invention are particularly exhibited in this case.

(Examples) Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way.

Reference Example 1 A photosensitive polyimide precursor was synthesized using the raw materials shown in Table 2.

Table 2 * Weight average molecular weight determined by 20PO * 3 Pyromellitic anhydride * 4 3,3',4,4'-benzophenonetetracarboxylic dianhydride Examples 1 to 4 and Comparative Example 1 Polymer as P-11Of, tetraethylene glycol diacrylate as monomer 0.61, and 1,3-diphenyl-propa7 as sensitizer) IJon-
2-(o-ethoxycarzenyl)oxime 0.3f, 1
-Phenyl-5-mercapto IH-tetrazole 0.2
2, Jetanolaniline 0.2'/, 5-nitrone-8-hydroxyquinoline, 1-nitrone-2-naphthol, 2-nitrone-1-naphthol, as a polymerization 9 inhibitor;
0-01 ?2-nitrone-5-(N-ethyl-N-sulfopropylamino)phenol, respectively. Added (Examples 1 to 4) or not added (Comparative Example 1) was dissolved in N-methyl-2-pyrrolidone 15f to make a homogeneous solution,
Storage stability tests were conducted on each of these solutions at room temperature.

The test results are shown in Table 3.

Table 3 *5 Addition amount of polymerization inhibitor to polymer Examples 5 to 8 and Comparative Examples 2 to 5 Tetraethylene glycol diacrylate as monomer 0.6r, ta to P-110F as polymer
1,3-diphenyl-propanetrione-2 as g agent
-(o-ethoxycarbonyl)oxime 0,3? , 1-
Phenyl-5-mercapto LH-tetrazole 0.2?
, jetanol aniline 0.22, 5 as polymerization inhibitor
-Nitroso-8-hydroxyquinoline, 1-nitrone-
to 2-naphtho-, 2-=to01-1-1-phthol, 2
-2) -0.01 each of -0so5-(N-ethyl-N-sulfopropylamine)phenol? addition (Examples 5 to 8), or 4-1-butylcatechol (Comparative Example 2), hydroquinone (Comparative Example 3), 2,6-di-t
-butyl-p-cresol (Comparative Example 4), respectively.
The product with or without addition of 012 (Comparative Example 5) was dissolved in N-methyl-2-pyrrolidone 152 to form a homogeneous solution, and allowed to stand in a room at 40°C for an accelerated test. The test results are shown in Table 4.

Margin below

Claims (1)

[Claims] (a) General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) [In the formula, X is a (2+n)-valent carbocyclic group or heterocyclic group, and Y is (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 containing a carbon-carbon = alkoxy group with a double bond or a salt, and W is a group that reacts with the carbonyl group of -COR^* by heat treatment. n is 1 or 2, m is 0, 1 or 2, and -COR^* and Z are in an ortho-position or peri-position relationship with each other. ] A photosensitive composition with excellent storage stability comprising a polymer having a repeating unit represented by and (b) a C-nitroso compound