JPS61254605A - Photosensitive composition - Google Patents

Abstract

PURPOSE:A composition, consisting of a polymer having specific repeating units and N-nitrosodiarylamine compound, convertible into a heat-resistant high polymer by heat treatment, and having high photosensitivity and sufficient storage stability. CONSTITUTION:A photosensitive composition containing a polymer having repeating units expressed by the formula [X is (2 + n)-valent carbocyclic or heterocyclic group; Y is (2 + n)-valent carbocyclic or heterocyclic group; Z is -CONH-, -NHCONH- or -OCONH-; R and W are group having C=C; m and n are 0-2 but not 0 at the same time; COOR and Z and W are mutually in the o- or peri-position] and an N-nitrosodiarylamine compound, e.g. N-nitroso- diphenylamine. USE:Used as an insulation film for semiconductor elements, orientation film for liquid crystal display elements, etc.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to novel photosensitive compositions, and more particularly, to novel photosensitive compositions.

The present invention relates to a photosensitive composition that can be converted into a heat-resistant polymer compound by heat treatment.

In recent years, heat-resistant photosensitive polymer materials have been actively developed for use in electronic and optical materials.

For example, surface protection films such as Eva, junction coat film, back shielding film, buffer coat film, alpha ray shielding film, insulating film for semiconductor devices such as glabella insulating film for multilayer wiring, or alignment film for liquid crystal display devices, Applications such as insulating films for thin-film magnetic heads and insulating films for multilayer printed circuit boards are being considered.

[Problems to be solved by conventional technology and invention] Conventionally,
As the heat-resistant photosensitive polymer composition, for example, Boria 4
A mixture of a photoacid and a photosensitive compound or a polyamic acid ester with an active functional group such as a double bond introduced into the side chain.
A composition in which a crosslinked structure is formed by light irradiation is known, in which a photopolymerization initiator is added to
Publication No. 07, Publication No. 3j-≠/≠-2, Publication No. 3J-≠/≠-2, Publication No. 07, Publication No. 3J-≠/≠-2, Publication No. 3-2
Goo/Hiroshi! 7rihiro issue). These are called photosensitive polyimides, and after processes such as coating, exposure, and development, heat treatment is performed to provide a heat-resistant film. Because these compositions have active groups bonded to their polymer side chains, they are highly sensitive compared to conventional UV paints based on polyfunctional monomers and photosensitive compositions such as dry film resists for making printed circuit boards. Sensitivity results and even slight local crosslinking is accompanied by gelation of the entire composition. This problem of gelation becomes particularly noticeable when these compositions are stored in a state dissolved in a solvent, but as a commercial product form of these photosensitive compositions, a solution state is preferable. Therefore, improving storage stability is an extremely important issue. Radical polymerization inhibitors used in conventional photosensitive compositions, such as hydroquinone, p
-Benzoquinone, p-methoxy7, ? ,/-l, tert-butylcatechol, pyrogallol, phenothiazine, floranil, naphthylamine, β-naphthol, +
21 O-di-tertiaryptyl-paracresol, 2°
Trobenzene, para-toluidine, methylene blue, and the like have insufficient antigelation effects, and when added to a practically satisfactory level, photosensitivity decreases and there is a problem of shimmering. In addition, thermal polymerization inhibitors such as quinone and phenol are effective only in the presence of seismic elements, so they do not exhibit sufficient polymerization prevention effects, especially when they are stored in a sealed container, with insufficient contact with air. There was also the problem that it was not done.

[Means for solving problems]

In view of these circumstances, the inventors of the present invention have developed a material with high photosensitivity.
As a result of extensive research in order to provide a heat-resistant photosensitive composition that also has sufficient storage stability, we have developed a composition that contains a polymer having a specific structure and N-nitrosodiarylamine as essential components. discovered a scale suitable for the purpose, and based on this knowledge, completed the present invention.

That is, the present invention provides 0) general formula (I) [wherein X is (
co+n)-valent carbocyclic or heterocyclic group, Y is (co+n)-valent carbocyclic or heterocyclic group;
m) A valent carbocyclic group or a group having a double bond, m and n are ofk-, and neither m nor n is 0, C
0OR and 2 and W and z are in an ortho position or an ot position relationship with each other. The present invention provides a photosensitive composition comprising a polymer having 11 repeating units represented by the following formula, and (b) an N-nitrosodiarylamine compound.

In the composition of the present invention, the polymer used as component (a) has a repeating unit represented by the general formula (11), in which X is a di- or tetravalent carbocyclic group or a heterocyclic group. For example, as a group, this solid X is,
311, a fused polycyclic aromatic ring such as a naphthalene ring, an anthracene ring, and a perylene ring, a heterocyclic group such as pyridine and thiophene, and general formulas (B1), (&), (B
3) λ2 1 is O or /, X2 is CH, or CF3]
Examples include groups represented by. Among these, carbon groups are preferred.

Y in the above general formula (RI) is a di- to tetravalent carbocyclic group or a heterocyclic group, and such Y is,
For example, fused polycyclic aromatic rings such as benzene rings, naphthalene rings, anthracene rings, perylene rings, heterocyclic groups such as pyridine and imidazole, and general formulas (H4), (Bs
), (H6)>Yt-sσ (H4) D-y+→3 (B, ), and the like.

Among these, aromatic hydrocarbons with a carbon number of 6 to 2 g A group represented by (H6) is preferred.

COOR in the general formula II) is a group having a carbon-carbon double bond, such as -C-0-Rt CH=CHz
(ff6) In the C formula, R1 is a hydrogen atom or a methyl group, R2 is an alkylene group having 1 to 2 carbon atoms, R1 is a hydrogen atom or an alkyl group having 1 to ≠ carbon atoms, and R4 is an alkyl group having 7 to 2 carbon atoms. group, R3 and R6 are each hydrogen atom, methyl group, phenyl group, halogen atom, n/f
k is 2, X is 1 or O, y is o-*riul'J (L
) As an example of (Hz”) As an example of (I3) As an example of (H4) As an example of (IIs) As an example, -C-0-CHr-CH=CHt - As an example of C-0-Ckk CH2CH=CH!1), as an example of (Wataru 7), as an example of (I@), etc.

Furthermore, it is represented by the general formula (wherein W is a group selected from the same range as C0OR, or structural formula α, ) or Is) [wherein R1, nt , Rs , Rs , and Rs are as defined in the previous section]. It is a defined thing.] etc.

As an example of (11), An example of (&) is As an example of (Is), As an example of (I4), An example of (&) is Examples include.

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

When a compound with this carbon-carbon double bond is added, K
Compounds that facilitate photopolymerization reactions, such as -monoethylhexyl acrylate, co-hydroxyethyl acrylate, N-vinyl-
2-pyrrolidone, carpitol acrylate, tetrahydrofurfuryl acrylate, inborural acrylate, 4t-hexanediol diacrylate, neopentyl glycol diacrylate, ethylene glycol diacrylate, polyethylene glycol diacrylate, pentaerythritol diacrylate, trimethylolpropane triacrylate , pentaerythritol triacrylate, dipentaerythritol hexaacrylate, tetramethylolmethanetetraacrylate, and those in which the above acrylates are changed to methacrylates. Among these, preferred are It is a compound that has a bond.

In the composition of the present invention, N-nitrosodiarylamine, which is a thermal polymerization inhibitor used as component (b), has the general formula [wherein R7, R- and R1° are hydrogen atoms and carbon numbers, respectively] or Alkyl group, phenyl group, cyclohexyl group, halogen atom, methoxy group, ethoxy group,
dimethylamino group, diethylamino group].

Specifically, for example, N-nitrosodiphenylamine,
N-nitro 7- J+3'-silyl-diphenylamine, N-nitro 7-44.4! '-diisopropyl-diphenylamine, N-nitroso-J, J', j, j'-
Tetramethyl-diphenylamine, N-nitro:/-a
+aI-diphenyl-diphenylamine, N-nitronotei, 4t'-cyclorodiphenylamine, N-nitroso-2,2'-dimethoxy-diphenylamine, N-
Hiromu Nitrono, Hiro I-jetoxy-diphenylamine,
N-nitronoda, μ'-di-dimethylamino-diphenylamine, N-nitroso-+, +'-di-diethylamino-diphenylamine, N-nitroso-hiro-tert-butyl-diphenylamine, N-nitroso-μ-nonyl-diphenylamine, N-nitroso-μm cyclohexyl-diphenylamine, N-nitroso-≠-methoxydiphenylamine, N-nitroso-≠-ethoxydiphenylamine, N-nitrone-hiro-monoethoxycomethyl-diphenylamine, etc. N-nitroso-diphenylamine is preferred.

Furthermore, a photopolymerization initiator can be added to the composition of the present invention as required. The photopolymerization initiator is well known, and examples are shown below.

Benzophenone, acetophenone, acenaphthene-quinone, methyl ethyl ketone, parellophenone, hexaphenone, r-phenylbutyrophenone, p-morpholinopropiophenone, dipenzosperone, Hiro-morpholinobenzophenone, μ'-morpholinodeoxype/zoin,
p-diacetylbenzene, daraminobenzopheno/,
Hiro'-methoxyacetophenone, benzaldehyde, α
-tetralo/, teracetylphenanthrene, coacetylphenanthrene, IO-thioxanthenon, 3-acetylphenanthrene, 3-acetylindole, terfluorenone, l-indanone, ! .

3.2-) Liacetylbenzene, thioxanthine-terone, xanthine-terone, 7-H-benz [d.
] Anthracen-7-one, l-nataldehyde, fluorene-terone, l'-acetonaphthone, -'-acetonaphthone, co,3-butanedione, Michler's ketone, benzyl, aromatic oximes and l-phenyl-!
-mercapto/H-tetrazole and the like, but are not limited to these.

As photosensitive compositions, these initiators can be used at a concentration of 0.0% for the polymer. 20% of IN is added, preferably o, r to 100%. These initiators may be used alone or in mixtures of several types.

Further, the compound represented by the general formula 01) may include conventionally known free radical polymerization inhibitors such as hydroquinone, p-benzoquinone, p-methoxyphenol, p-ethoxyphenol, tert-butylcatechol, pyrogallol, phenothiazine, Floranil, naphthylamine, β-naphthol, 6-di-tert-butyl-valacresol, nitrobenzene, para-toluidine, methylene blue, and the like may be added to an extent that is not substantially detrimental to the inhibition of photopolymerization. The proportion of the compound represented by the general formula (W) in the photosensitive composition of the present invention is usually 0.000/wt%, particularly generally 0.00/wt%, based on the polymer. and 3% by weight.

In the composition of the present invention, the polymer used as component (a) is obtained from K by polycondensation or polyaddition of a compound represented by the general formula and a compound represented by the general formula. As an example of zl in the general formula M,
-coon (V,), -CDCI (VJ, -N
Co (VJ), -'NH* (VJ), OH (Vs
), -COORtt (vs) CRIsFi) f
# group, ethyl group, phenyl group], and the corresponding abbreviations of the general formula M are shown within 0. Also, general formula C
Examples of z2 in vOK are -COCI (%),
-〇〇OH (%), -NGO (Ml), → crystal (M, ), and the corresponding abbreviations of general formula (6) are shown within 0. , X%R, Y and W have the same meanings as above.

Through the polycondensation or polyaddition reaction between the compound represented by the general formula M and the compound represented by the general formula (2), -4 and - react to form a bond chain 2.

In this case, the preferable combination of 21 and tame, generation sui 2
A summary of the types is shown in Table 1.

Table 1 Further, ring structures formed by heat treatment are illustrated in Table 2 for the compounds represented by the general formula (1).

In addition, in the combination of numbers 1 and 7' in IIIC, C0OR is a group having a carbon-carbon double bond, w 1
In the case of Xco■2, an isoindoroquinazolinedione ring is formed by heat treatment, and those with this structure exhibit high heat resistance.In addition, the polymer of component (a) can be prepared using the following method to produce 4J!
Li can be built. That is, a compound represented by the general formula % formula % () [X in the formula has the same meaning as above] is converted into a compound represented by the general formula (■, ) or (■4)
The carboxyl group of the product obtained by reacting with the compound represented by is reacted with an epoxy compound represented by the general formula, or, for example, an amine compound represented by the general formula, or a quaternary ammonium salt represented by the general formula. The polymer is obtained by adding K. [R-, as, R4 in the formula have the same meanings as above] These reactions are known, for example, JP-A-56-32-mu I, JP-A-Shoj #-/4c. ! It is described in No. 7 Rihiro Publication.

In addition, the amino group of the product obtained by reacting the compound (■6) and (v6) represented by the general formula [Y in the formula has the same meaning as above] is converted into the amino group of the product obtained by the reaction of the general formula % [Formula %] R1 has the same meaning as above] or the polymer can be obtained by reacting with the general formula (■). Furthermore, the general formula (■4) and the general formula (v2)
, (Vs) or (v6), the polymer can be obtained.

The compound represented by the general formula (vl) can be obtained, for example, by ring-opening the acid anhydride represented by the general formula (Vy) with ROM (R has the same meaning as above). Examples of axillary acid anhydride (v7) include pyromellitic anhydride, J, J
',+,4! '-Benzophenonetetracarboxylic dianhydride, 3.3', lA, II-diphenyl ether tetracarboxylic dianhydride, 31"+4'?ψ-diphenyltetracarboxylic dianhydride, 3.3', lA-,' l-
Diphenylsulfone tetracarboxylic dianhydride, Co, J
, A, 7-su7talentetracarboxylic anhydride, thiophene-λ, 3゜hiro,! -tetracarboxylic anhydride, λ,
2-Upper 2-(J,tA-biscarboxyphenyl)propane anhydride, etc., and alcohol ROH includes,
Examples include allyl alcohol, crotyl alcohol, cheraniol, nerol, citronellol, perillyl alcohol, and hydroxymethylstyrene. When these kuma anhydrides (v7) are reacted with alcohol ROM, the paper-forming reaction is accelerated by adding pyridine, dimethylaminopyridine, etc.

The combinations of numbers / and /' in Table 7 are seven examples of preferred embodiments, and the diami/ represented by the general formula (■4) used in this combination is, for example, ≠14''-diaminodiphenyl ether , Hiro, μ
'-Diaminobiphenyl, λ, q'-diaminotoluene, ≠, 4t'-diaminobenzopheno/, ≠, ≠I-diaminodiphenylsulfone, phenylindane diamine, μ, μI-diaminodiphenylmethane, p-phenylenediamine, m- Hey, phenylenediamine! -diaminonaphthalene, 3,3'-dimethoxy-+, 4t'-diaminobiphenyl,! ,,3'-Dimethyl-Hiro, ≠I-diaminobiphenyl, o-toluidine sulfone, Co, Corbis(Hiro-aminophenoxyphenyl)propane, Bis(Hiro-aminophenoxyphenyl)sulfone, Bis(μ
m-aminophenoxyphenyl) sulfide, /+≠-bis(≠-aminophenoxy)benzene, l,3-bis(
Hong-ding minophenoxy)benzene, 3,4tl-diaminodiphenyl ether, terbis(hiro-aminophenyl)anthracene-(10), terbis(hiro-aminophenyl)fluorene, 3,3'-diaminodiphenylsulfone, 4t, I/l'-di(3-aminophenoxy)diphenylsulfone, Hiroshi, 1Lt1-diaminobenzanilide, 3. ≠-diaminodiphenyl ether, ≠l Hiro'-C/, J-phenylenebis(/-methylethylidene)], 4t, ≠I-[/, Hiro-phenylenebis(l-methylethylidene)), 4'+4"- m-
phenylene diisopropylidene) bis(m-toluidine), ≠,! '-(p-phenylene diisopropylidene)
Bis(m-toluidine) and the like can be mentioned.

Further, the compound represented by the general formula (Ms) is, for example, J, J', ≠, μ'-tetraaminobiphenyl, 3.
! '.

IIL, p'-tetraamino diphenyl ether, 3,
3-≠.

≠I-tetraaminodiphenylketone, 3,3-≠, Hiro'-tetraaminodiphenylsul7one, 3.3', u
, μ′-tetraaminodiphenylmethane, /, J, ≠,
Examples include j-tetraaminobenzene.

In the reaction between the compound represented by the general formula (V) and the compound represented by the general formula (6) in this combination, examples of solvents such as dimethylformamide, hexamethylphosphoric triamide, N-methylpyrrolidone, It is preferable to use an aprotic polar solvent such as , N-dimethylacetamide.

Furthermore, by changing the molar ratio of compound (2) to compound (2), the molecular weight of the resulting polymer can be adjusted. Furthermore, when the reaction is carried out under conditions where one component is in excess, it is preferable to add a capping agent for the remaining terminal groups. As this sealant, when compound M is in excess, alcohols such as methanol, ethanol, ROM (R has the same meaning as above), and amines such as butylamine and aniline are suitable. On the other hand, when compound (9) is in excess, acid chlorides such as acetyl chloride and propion chloride are suitable. In addition, when adding amines such as pyridine and triethylamine as a dehydrochlorination agent, for example, tetrahydrofuran, γ-butyrolactone,
Dimethyl sulfoxide and the like can also be used. In addition, in the case of Table 1, number l, 1 patent application 3737
It is also possible to use the condensing agents disclosed in the publication.

For isolating the produced polymer from the reaction mixture, it is preferable to use a method in which the reaction mixture is added little by little to a large amount of water. The solid thus obtained is purified by further pulverizing it finely and washing it, or by repeatedly dissolving it in an organic solvent such as the one used in the reaction, adding it to water, and reprecipitating it.

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, divinylsilane, tri(methoxyethoxy)vinylsilane,
r-glycidoxypropyltrimethoxysilane, N-β
It is preferable to add a silane coupling agent such as (aminoethyl>r-anob a-pyltrimethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldimethoxysilane) or to pre-coat the substrate.

The solvent is preferably a polar solvent, such as dimethylformamide, N-methylpyrrolidone, or dimethylacetamide, whose boiling point is not too high. 1 more
Solvents such as alcohols, aromatic hydrocarbons, ethers, esters, and ketones can also be added to the extent that the components do not precipitate.

Kl on the base! The method of applying the solution as described above is to pass the solution obtained as described above through a filter, and then apply it to the substrate using an evaporator, spin coater, bar coater, blade coater, screen printing method, etc.; A method of immersing the substrate in a solution, a method of spraying the solution onto the substrate, etc. can be used.

Examples of the substrate include metal, glass, and silicon.

Heat-resistant materials such as semiconductors, metal oxide insulators, and silicon nitride are preferable, and if heat treatment 17 is not performed, materials such as copper-clad glass epoxy laminates may be used.

Next, the nine coating films obtained in this way were air-dried, heated and 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, and electron beams, and among these, ultraviolet rays are preferable, and examples of the light source include 1 low-pressure mercury lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, Examples include halogen lamps and germicidal lamps. Among these light sources, ultra-high pressure mercury lamps are preferred. Furthermore, it is preferable that the exposure be performed in a nitrogen atmosphere.

After exposing in this way, in order to remove the unexposed area,
Genwei is performed using methods such as dipping and spraying. The developing solution used for this removal is preferably one that can completely dissolve and remove the unexposed film within an appropriate heating time, such as N-
Methylpyrrolidone, N-a7thyl-copyrrolidone, N
, N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoric triamide, N-benzyl-2-pyrrolidone, γ-
Non-polar polar solvents such as butyrolactone may be used alone, or they may be combined with alcohols such as ethanol and isopropanol as a second component.
A mixture of solvents such as 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 may be used. Further, it is preferable to rinse with a solvent such as the one shown as the second component immediately after the application.

The image obtained in this way is /10~41- after drying.
By heating in a temperature range of 10° C., it is converted into a heat-resistant polymer compound having an imide ring, an isoindoroquinazolinedione ring, an oxadione ring, a quinazoline dione ring, an imidazole ring, an imidazopyrrolone ring, etc.

〔Effect of the invention〕

The heat-resistant photosensitive composition of the present invention has many advantages over conventional compositions. The advantages include that the composition containing N-nitrosodiarylamine has significantly improved storage stability; This means that there is no possibility of lowering the value. For example, conventional heat-resistant photosensitive compositions have problems with storage stability, making long-term storage difficult. On the other hand, the heat-resistant 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 3 to 40 degrees Fahrenheit compared to conventional quinone and phenol thermal polymerization inhibitors. It has a stability of /month before gelling. Furthermore, in the composition of the present invention, the irradiation time required for photocuring is no different from that in the case where N-2) logarylamine is not added.

In particular, compositions containing polymers in which active functional groups such as double bonds are introduced into polyamide side chains via covalent bonds can be formed into thick films by spin coating, since they can be prepared in highly concentrated solutions. However, at high concentrations, it rapidly gels during storage and becomes different.
The effects of the present invention are particularly exhibited in this case.

〔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.

Reference Example 1 Pyromellitic dianhydride in a 31-paraple flask≠
49, J-hydroxyethyl methacrylate) j/,
1wt, γ-butyrolactone 711Q- and pyridine IO! - was added and stirred at room temperature for 2Q hours.

Thionyl chloride TOG was added dropwise to this solution over 7 hours under ice cooling, and then stirred at room temperature for 2 hours. Add to this solution Hiromu'-diaminodiphenyl ether 31. lr
A mixture of 9 and γ-butyrolactone 310 was added and stirred for 2 hours. Further, 1 wt of ethanol jY was added and stirred for 10 hours. Next, γ-butyrolactone 100- was added and slowly poured into 101 water, and a thread-like solid was precipitated. Wash thoroughly by changing the water several times, and then
After thorough washing with ethanol and water, vacuum drying was performed. This product is designated as p-/.

Reference Examples 2 to 3 Products were obtained by performing synthesis in the same manner as in Reference Example 1 except for the following matters. Pyromellitic dianhydride 44
7. (1) Benzophenone tetracarboxylic dianhydride was used instead of Ap (P-J), (
11 CP-3 using benzophenonetetracarboxylic dianhydride 3λ, richness, pyromellitic dianhydride, 2 /, I Q >> Reference example ≠ Acrylic acid l! Dimethylacetamide solution 7j containing
dlllc, dimethylacetamide solution in which 22 g of dicyclohexylcarbodiimide was dissolved under ice-cooling and stirring.jOw
After adding d dropwise, the mixture was allowed to react at room temperature for 7 nights. The generated dicyclohexyl flare was passed through, and the resulting p solution was added to a dimethylacetamide solution containing 109 f of diaminobenzidine (10 o), and reacted at room temperature for 7 hours. To this reaction solution, triethylane/A, jsdi-
After the addition, 10 dl of a dimethylacetamide solution in which iso7taloyl chloride/29 was dissolved was slowly added dropwise. After reacting at room temperature for 1 hour, ethanol λ- was added to this and reacting at room temperature for 30 minutes. The reaction mixture obtained in this way was mixed with 2. The resulting product was t-filtered and vacuum dried. This product is designated as P-group.

-Precedent! A dimethylacetamide solution/10- containing benzophenone tetracarboxylic anhydride/19 was added dropwise to 100 wt of a dimethylacetamide solution in which diaminobenzidine 109 was stirred and dissolved, and the mixture was reacted at room temperature for 7 hours. Next, triethylamine/3- was added to this reaction solution while stirring on ice, and then methacryloyl chloride ter was added dropwise. After reacting at room temperature for 1 hour, pyridine/3 dl, acetic anhydride/
r- was added and reacted at 40°C for 1 hour. The reaction mixture thus obtained was dropped into ion-exchanged water at a rate of 1/l with stirring, and the resulting product was temporarily dried under vacuum. This product is designated as P-1.

Examples/~7. Comparative Example 1 Michler's ketone was added as a sensitizer to p-/NP-j 109 as a polymer at a concentration of 0. Rich, camphorquinone 0.1-9, /-phenyl-! -Mercapto 1H-tetrazole O0λ, trimethylolpropane triacrylate as monomer t! and N-nitron diphenylamine and N-nitrone-4! as thermal polymerization inhibitors. ,
g'-diphenyl-diphenylamine, N-nitroso-
≠-tert-butyl-diphenylamine, respectively o
, i g added (Examples/~7) or without addition (Comparative example/) were dissolved in N-methylpyrrolidone/jd to make a homogeneous solution, and a storage stability test was conducted on each of these solutions at room temperature. . The test results are shown in Table 3.

Table 3 Example t, Comparative Example--t P-1 was used as the polymer at 109, Michler's ketone was used as the sensitizer at O, K, benzyl at 0. μri, l-7eniru! -mercapto-/H-tetrazole 0. Rich,
Trimethylolpropane triacrylate/, j9 as a monomer, N-nitron diphenylamine (Example t) or p-tert-butylcatechol (Comparative example, 2), hydroquinone (Comparative example 3) as a thermal polymerization inhibitor
, co, 6-di-tert-butyl-p-methylphenol (Comparative Example 4'), p-ethoxyphenol (Comparative Example j
) with Q, 0/9 added, respectively, or one without adding a polymerization inhibitor (Comparative Example 6) was dissolved in N-methylpyrrolidone/yo- to make a homogeneous solution of 4! An accelerated storage test was conducted by leaving the sample in a room at 0°C.

The test results are shown in Table μ.

10. Comparative Example 7~g 10 g of P-1 as a polymer, 0.6 g of Michler's ketone as a sensitizer, 0.0/g of N-nitrosodiphenylamine as a thermal polymerization inhibitor (example), o, i (implemented) Example IO), Hydroquino 10, oot9c Comparative Example 7), without addition (Comparative Example r') Dissolved in tN-methylpyrrolidone lj- and subjected to storage stability test and photocurability test at room temperature as a homogeneous solution. . In the photo-curing test, this solution was applied onto a silicon wafer to form a coating film with a thickness of about 10 microns.
ak Photo-graphic 5tep Thb
After exposure for 300 seconds with an ultra-high pressure mercury lamp (I mW/ad) using a 422/5 step), the film was developed with a mixed solution of equal amounts of γ-butyrolactone and xylene, and the cured state of the step was observed. The test results are shown in Table 5.

(Leaving space below) Table j Examples//R/J, Comparative Examples// N-nitron diphenylamine o, i was added as a thermal polymerization inhibitor to P-/~P-3109 as a polymer (Implementation) Examples 1/~13) or not added (Comparative Example~ll), N-methylpyrrolidone/! - A homogeneous solution was prepared in an indoor trap at 0°C, and an accelerated storage test was conducted. The test results are shown in Table 6.

(Margin below) Table z

Claims (1)

[Claims] (1) (A) General formula▲ Numerical formulas, chemical formulas, tables, etc.▼ [In the formula, X is a (2+n)-valent carbocyclic group or heterocyclic group, Y is a (2+m)-valent carbocyclic group or a heterocyclic group,
Z is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, R or / and W are groups having a carbon-carbon double bond, m and n are 0 to 2
Both m and n are never 0, and COOR and Z and W and Z are in the ortho or veri position with each other. ] A photosensitive composition comprising a polymer having a repeating unit represented by the following formula, and (b) an N-nitrosodiarylamine compound.