JPS63318549A - Heatresistant photosensitive polymer composition - Google Patents

Abstract

PURPOSE:To form a thick pattern by specifying the structure of a polymer which is the main component of the titled composition. CONSTITUTION:The titled composition is composed of 100pts.wt. the polymer having a repeating unit shown by formula I as a main component, a photopolymerization initiator, a photocrosslinking agent and 0.1-30pts.wt. sensitizer. In the formula, R<1> is a four valent org. group contg. at least >=4 carbon atoms., R<2> is 3 or 4 valent org. group contg. an aromatic ring, R<3> and R<4> are each <=10C an organic group, Y is a photosensitive group, X is an org. group of binding the group R<2> and the photosensitive group. Thus, the pattern formation of the titled composition enables, even in the case of processing said composition with a developer which has low liquid viscosity and contains a weak polar solvent having low dissolving power. And the definition of the titled composition is improved, even in case of forming the pattern having the thick thickness.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a heat-resistant photosensitive polymer composition used for semiconductor devices, multilayer wiring boards, microelectronic devices, etc. Regarding type photosensitive materials.

[Conventional technology]

Conventionally, as a heat-resistant anti-glare material that becomes a heat-resistant polymer, (a) in Japanese Patent Publication No. 59-52822, a wholly aromatic polyamic acid and carbon-carbon which can be trimerized or polymerized by actinic radiation are used.
Comprising a compound containing a carbon double bond and an amino group, and an aggravating agent added as necessary, (+1) JP-A-56-
No. 110728 discloses a photosensitive polymer in which a photosensitive group is introduced into the aromatic diamine component, which is a polyamic acid synthesized from an aromatic tetracarboxylic dianhydride and an aromatic diamine.

However, since the resolution of the above-mentioned materials C-a) and (III) decreases when formed into a thick film, the final cured film thickness may be approximately 2 to 5 μm for the glabella insulating film of a semiconductor device or the like. Can be applied to protective film, but 10-20
．． It could not be applied to applications such as alpha ray shielding films for memory devices and glabella insulating films for thin film multilayer substrates that require a film thickness of crm or more.

[Problem that the invention seeks to solve]

The reason why the resolution decreases when the material in (a) above is made into a thick film is because the photosensitive group is not directly bonded to the polymer main chain, so the curing of the exposed area is low, while the unexposed area is This is thought to be due to poor solubility. For this reason, if the development temperature is increased in an attempt to completely dissolve the unexposed portions, or if the development time is lengthened, even the exposed portions may be dissolved, and patterns with different diameters may have significantly different deviation widths from the mask dimensions.

In the case of the material (II), the curability of the exposed area is sufficient, but the solubility of the unexposed area is low, resulting in poor resolution of fine patterns.

The main cause of the decrease in resolution is thought to be factors related to the developer. That is, the developing solution for dissolving the unexposed portion of the material in (II) above is mainly composed of an aprotic polar solvent such as N-methyl-2-pyrrolidone or N,N-dithimelacetamide. I have to say,
Since all of these have relatively high liquid viscosity, dissolution and diffusion in unexposed areas is suppressed. Since the dissolving power is strong, there is a problem that the exposed area may also be dissolved if the material is not sufficiently pretreated.

For this reason, it is thought that the resolution deteriorates.

The purpose of the present invention is to develop a heat-resistant photosensitive material that can form patterns even when a weakly polar solvent with low liquid viscosity and low dissolving power is used as a developer, in order to improve the resolution when forming a thick film. An object of the present invention is to provide a polymer composition with a high molecular weight.

[Means for solving problems]

The present invention has been made based on the basic idea that the above object can be achieved by changing the structure of the main component polymer as follows. That is, the above ((),
The reason why the material C11) is only soluble in solvents whose main component is aprotic polar solvents such as N-methyl-2-pyrrolidone is because polyamic acid has highly polar carboxyl groups bonded to it. It is considered. Therefore, it is basically possible to convert this into a less polar carboxylic ester.

Therefore, as a result of intensive studies based on the above idea, the present inventors found that (a) General formula (1) (wherein R1 is 4 containing at least 4 or more carbon atoms)
a valent organic group, R2 is a trivalent or tetravalent organic group containing an aromatic ring, R' and R' are each an organic group having 10 or less carbon atoms, Y
is a photosensitive group, X represents an organic group connecting R2 and the photosensitive group, or 10- or -N-, and n is 1 or 2. Photopolymerization initiator, photocrosslinking agent aggravator 0.1-30
It has been found that a heat-resistant photosensitive polymer composition consisting of parts by weight of That is, these heat-resistant photosensitive polymer compositions include γ-butyrolactone, dimethoxyethane, etc.
Solvents that could not be used in the heat-resistant photosensitive materials described above can be used as the main component of the developer, and further,
It has been found that the resolution is also good when formed into a thick film.

The present invention will be explained in detail below.

R1 of the polymer represented by the repeating unit of general formula (1)
Examples of preferable examples include, but are not limited to, the following.

A more preferable example is etc.

Preferred examples of R2 include (where Z is 10-, -S-, -5Oz-5-CO-, -
CHz-1), etc., but are not limited thereto.

As a more preferable example, etc.

Preferred examples of R3 and R4 include, but are not limited to, alkyl groups having 5 or less carbon atoms, alkoxymethyl groups, alkoxyethyl groups, alkoxypropyl groups, alkylcarboxyethyl groups, phenylcarboxyethyl groups, etc. .

More preferable examples include methyl group, ethyl group, isopropyl group, butyl group, methoxyethyl group, ethoxyethyl group, acetoxyethyl group, phenylcarboxylethyl group, and the like.

R3 and R4 may be the same or different.

Examples include, but are not limited to, H 11 -C-N-, -R'-0- (where R5 represents lower alkylene), and the like.

etc.

A preferable example of the photosensitive group Y is -CH2CH20-C-CH=CH-CH=CHR"(
However, R6 is a group selected from hydrogen, a cyan group, and a lower alkyl group, R7 is a group selected from hydrogen, a lower alkyl group, and an alkoxy group, R11, R9, and RIO.

Examples include, but are not limited to, R11 and RI2 each representing a group selected from hydrogen, a lower alkyl group, a vinyl group, and a phenyl group.

A more preferable example is -CHzCHz-0-C-CH=CH-CH=CH-C
Examples include H3.

The polymer represented by the repeating unit of general formula (1) can be produced by addition polymerization reaction of tetracarboxylic acid dichloride diester and an aromatic diamine compound having a photosensitive group, or by dehydration condensation polymerization reaction of a tetracarboxylic acid diester and an aromatic diamine compound having a photosensitive group. Synthesized by reaction.

In order to achieve a practically usable photosensitivity in the heat-resistant photosensitive polymer composition of the present invention, it is essential to add a photopolymerization initiator and/or a photocrosslinking agent and/or a sensitizer. Examples of these preferred include mihiraketone, bis-
4,4'-diethylaminobenzophenone, benzophenone, benzoin ether, benzoin isopropyl ether, anthrone, 1,9-benzoanthrone, acridine, nitropyrene, 1,8-dinitropylene, 5-
Nitroacenaphthene, 2-nitrofluorene, pyrene-
1,6-quinone, 9-fluorene, 1,2-benzaanthraquinone, anthantrone, 2-chloro-1,2-
Benzanthraquinone, 2-bromobenzanthraquinone, 2-chloro-1,8-phthaloylnaphthalene, 3,
5-diethylthioxanthone, 3.5-dimethylthioxanthone, 3.5-diisopropylthioxanthone, benzyl, 2.6-di(4'-azidobenzal)cyclohexanone, 2.6-di(4'-azidobenzal)-4-
Methylcyclohexanone, 2,6-di(4'-azidobenzal)-4-carboxycyclohexanone, 2,6-
Di(4'-azidobenzal)-4-hydroxycyclohexanone, 2,6-di(4'-azidocinnamylidene)
Cyclohexanone, 2,6-di(4'-azidocinnamylidene)-4-methylcyclohexanone, 2,6-di(
4'-azidocinnamylidene)-4-carboxycyclohexanone, 2,6-di(4'-azidocinnamylidene)-4-hydroxycyclohexanone, 1-phenyl-
5-mercapto-IH-tetrazole, 1-phenyl-
5-melteix, 3-acetylphenanthrene, 1-
Indanone, 7-H-benz(de)anthracene-7
-one, 1-naphthaldehyde, thioxanthin-9
-one, 10-thioxanthenone, 3-acedolindole and the like, but are not limited to these.

Among these, more preferable examples include Michler's ketone, bis-4,4'-diethylaminobenzophenone, ■-phenyl-5-mercapto IH-tetrazole, benzyl, 2,4-diethylthioxanthone, 2.4
-diisopropylthioxanthone, 2,4-dimethylthioxanthone, and the like. These may be used alone or in combination.

A suitable blending ratio of the photopolymerization initiator, photocrosslinking agent and/or sensitizer used in the present invention is 0.1 to 100 parts by weight of the polymer represented by the repeating unit of the general formula (11).
The amount is preferably 30 parts by weight, more preferably 0.5 to 20 parts by weight. Deviation from this range will have an unfavorable effect on developability.

In the present invention, the sensitizing aid added as necessary is used as a polymerization accelerator when using a photopolymerization initiator. Preferred examples include 4-diethylaminoethylbenzoate, 4-diethylaminoisopropylbenzoate, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisopropylbenzoate,
-dimethylaminoisoamylbenzoate, ethylene glycol dithioglycolate, -ethylene glycol di(3-mercaptopropionate), trinotyolpropanethioglycolate, trimethylolpropane tri(3-mercaptopropiolate), pentaerythritol tetrathioglycolate rate, pentaerythritol tetra(3-mercaptopropionate), trimethylolethane trithioglycolate, trimethylolethane tri(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate),
Examples include dipentaerythritol hexa(3-mercaptopropionate), thioglycolic acid, α-mercaptopropionic acid, and the like. However, it is not limited to these.

Among these, more preferred examples include 4-dimethylaminoethyl benzoate, 4-dimethylaminoisoamyl benzoate, pentaerythritol tetrathioglycolate, pentaerythritol tetra (3-mercaptopropionate), and trimethylolpropanethioglycolate. etc. These may be used alone or in combination.

In the present invention, when a sensitizing agent is used, the blending ratio is preferably 0.1 to 30 parts by weight, more preferably 0.5 to 30 parts by weight, based on 100 parts by weight of the polymer represented by the repeating unit of the general formula (11). The range is 20 parts by weight.

If the amount is less than this range, the effect of promoting polymerization cannot be obtained, and if it is more than this range, adverse effects such as a decrease in developability will occur.

The heat-resistant photosensitive polymer composition according to the present invention is used in the form of a solution in which the above constituent components are dissolved in a suitable organic solvent. The solvent used in this case is preferably an aprotic polar solvent from the viewpoint of solubility, specifically N-methyl-2-
Pyrrolidone, N-acetyl-2-pyrrolidone, N-benzyl-2-pyrrolidone, N-benzyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphortriamide, N -acetyl-ε-caprolactam,
Suitable examples include dimethylimidazolidinone, 1,2-dimethoxyethane, 1-acetoxy-2-methoxyethane, γ-butyrolactone, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether.

These may be used alone or in a mixed system. Furthermore, in order to improve coating properties, aromatic solvents such as toluene, xylene, and methoxybenzene may be mixed in as long as they do not adversely affect the dissolution of the polymer.

In order to improve the adhesion between the coating film of the heat-resistant photosensitive polymer composition according to the present invention or the polyimide coating after heat curing and the supporting substrate, the supporting substrate can be appropriately treated with an adhesion auxiliary agent.

The heat-resistant photosensitive polymer composition of the present invention can be patterned using ordinary microfabrication techniques. The present composition can be applied to the support substrate by means such as spin coating using a spinner, dipping, and spray printing, which can be selected as appropriate. The coating film thickness can be adjusted by the coating means, the solid content concentration of the composition, etc.

A desired relief pattern is formed by irradiating the composition of the present invention, which has undergone a drying process and formed a coating film on a supporting substrate, with ultraviolet rays through a photomask, and then dissolving and removing the unexposed areas with a developer. obtain.

The main components of the developer are γ-butyrolactone, 1.2
Polar solvents such as -dimethoxyethane, 1'-acetoxy-2-methoxyethane, and diethylene glycol dimethyl ether can be used.

However, depending on the purpose, more polar solvents (aprotic polar solvents such as highly soluble N-methyl-2-pyrrolidone, N,N-dimethylacetamide, dimethyl sulfoxide, dimethylimidazolidinone, etc.) or less polar It can also be used in a mixed system with aromatic solvents such as toluene and xylene, alcohol, which is a non-solvent for the polymer represented by the repeating unit of general formula (1), and water. It can also be developed using a mixed system of polar solvent, alcohol, and water.

The relief pattern formed by development is then washed with a rinse solution to remove the development solvent.

The rinsing liquid has good miscibility with the developing solution and has a general
A non-solvent for the polymer represented by the repeating unit is used.

Suitable examples include methanol, ethanol, isopropyl alcohol, benzene, toluene, xylene, water, and the like.

The leaf pattern polymer obtained by the above treatment is a polyimide precursor, and by treatment at a heating temperature selected from the range of 150° C. to 450° C., a heat-resistant polymer pattern can be obtained.

[For production]

As described above, according to the present invention, even if a weakly polar solvent with relatively low polarity and low dissolving power is used as a developer,
Sufficient solubility of the unexposed portions can be ensured, and dissolution and diffusion of the unexposed portions can also be made good, while dissolution of the exposed portions can be sufficiently suppressed. Therefore, even in the case of a thick film, excellent resolution can be obtained.

〔Example〕

The present invention will be explained in detail below.

Example 1 3.3'-di(chlorocarbonyl)-4,4'-di(methoxycarbonyl)biphenyl, 3.3'-di(methoxycarbonyl)-4,4'-di(chlorocarbonyl)biphenyl, 3 .4'-di(chlorocarbonyl)-4
, 3'-di(methoxycarbonyl)biphenyl, a mixture of three isomers Th7.9 g (0.02 mol) was dissolved in 50 g of anhydrous N,N-dimethylacetamide under a nitrogen stream, and 1.58 g of pyridine was dissolved. g (0.02 mol) was added to prepare an acid chloride solution.

To this solution, 5.28 g of 3,5-diamino (2'-methacryloyloxyethyl)benzoate (0,
A solution of 0.02 mol) dissolved in 28.4 g of anhydrous N,N-dimethylacetamide was added dropwise to the water bath with stirring. After the dropwise addition, the mixture was further reacted at room temperature for 3 hours (Formula 1). The reaction mixture was slowly poured into 700 mj2 of methanol with vigorous stirring.

As soon as the reaction mixture is mixed with methanol, the polymer (I a
) was precipitated.

0 0CHtCHiOCC=CHz OCI+.

The precipitated polymer was collected by suction filtration, and further 20 Off1
Washed with methanol 13 times. Furthermore, 8.3 g (yield 70%) of Polymer Ia was finally obtained by drying under reduced pressure.

2.5 g of Polymer Ia obtained above, 0.075 g of 2,4-diethylthioxanthone, and 0.15 g of 4-dimethylaminoethylbenzoate were mixed with 7.5 g of N
, dissolved in N-dimethylacetamide, then 1 μm
A photosensitive face was obtained by pressure filtration using a filter with holes.

The above film was spin-coated onto a silicon wafer using a spinner, and then dried at 85° C. for 30 minutes to obtain a coating film of 28 μm. This coating film was closely covered with a photomask having rectangular patterns with different diameters in steps of 10 μm, and irradiated with ultraviolet rays for 1 minute using a 500 W high-pressure mercury lamp. The intensity of ultraviolet rays at the light receiving surface was 51/d at a wavelength of 365 nm. After exposure, it was developed for 10 minutes at 25°C with a developer consisting of 7 volumes of T-butyrolactone and 3 volumes of N,N-dimethylacetamide.
Then, rinse with isopropyl alcohol to a minimum of 30μ
A relief pattern with m holes resolved was obtained. Next, this was heated at 200° C. for 30 minutes and at 350° C. for 30 minutes to obtain a heat-resistant polyimide pattern with a thickness of 16 μm. At this time, no pattern blurring was observed.

Example 2 3.3'-dicarboxy-4,4'-(methoxycarbonyl)biphenyl, 3.3'-di(methoxycarbonyl)-4,4'-dicarboxybiphenyl, 3°4'-dicarboxy- 8.95 g (0,025
5.28 g (0.02 mol) of 3,5-diamino (2'-methacryloyloxyethyl)benzoate was added to 350 ml of anhydrous γ under a nitrogen stream.
-butyrolactone and added an additional 4.55 g of pyridine. To this solution, 10.3 g of dicyclohexylcarbodiimide (0,0
5 mol) was added. After the addition was completed, the reaction was allowed to proceed for another 2 hours, and then 10+n6 methanol was added. When the reaction mixture was slowly poured into vigorously stirring methanol, the polymer (I b) was precipitated (Formula 2). .

0 0CHzCHzOCC-CHz CH3 The precipitated polymer was collected by suction filtration, and further 200ml
Washed with methanol 3 times. It was further dried under reduced pressure to finally obtain 11 g (yield 77%) of polymer (1b).

2.5 g of polymer Ib obtained above, 0 Mihiraketone
．． 075 g, pentaerythritol thioglycole)
0.2 g was dissolved in 8 g of N,N-dimethylacetamide, and then a photosensitive face was obtained using a filter with 1 μm pores.

The above film was spin-coated onto a silicon wafer using a spinner, and then dried at 85° C. for 30 minutes to obtain a 31 μml coating film. This coating film was tightly covered with a photomask having rectangular patterns of different diameters with a pitch of 10 μm, and was irradiated with ultraviolet rays for 1 minute using a 500 W high-pressure mercury lamp. The intensity of ultraviolet rays at the light receiving surface was 5 mW/cj at 365 nm. It was developed with γ-butyrolactone at 25° C. for 10 minutes and then rinsed with methanol to obtain a relief pattern with a minimum 30 μm pore resolution.

Examples 3 to 26 With the compositions shown in Table 1, Examples 3 to 18 were operated in the same manner as in Example 1, and Examples 19 to 26 were operated in the same manner as in Example 2. The obtained results are shown in the same table.

Comparative Example 1 g of diaminodiphenyl ether was converted into N-methyl-2-
An amine solution was prepared by dissolving in 51.8 ml of pyrrolidone. 12 g of pyromellitic anhydride was added to the amine solution and reacted at 50° C. for 3 hours to obtain a polyamic acid solution.

1.15 mihiraketone to 50g of the above polyamic acid solution
A solution prepared by dissolving 10.2 g of diethylamino methacrylate in 10 g of dimethylacetamide were mixed, and the mixture was filtered under pressure using a filter with 1 μm pores.

The obtained solution was applied with a spinner and heated to 100°C.

After drying for 5 minutes, a coating film of 27 μm was obtained. Exposure was performed for 1 minute using the same exposure device and photomask as in Example 1, and 2 volumes of dimethylformamide and 2 volumes of methanol were used.
Although it was developed at 5° C. for 10 minutes, the unexposed areas were not completely dissolved and the pattern was not resolved. Therefore, the developing temperature was set to 35
℃, but in all cases no pattern could be obtained since the entire area, including the exposed area, was melted. Next, the exposure time was set to 5 minutes, and development was performed at 35° C. for 15 minutes. At this time, the minimum dimension of the resolved pattern was 150 μm. 200℃, 20
The thickness of the final film obtained by heating at 350° C. for 30 minutes was 8 μm.

〔Effect of the invention〕

As detailed above, according to the present invention, the development characteristics of the heat-resistant photosensitive polymer composition can be significantly improved, and thick film pattern formation has become possible. This has made it possible to use it as an α-ray blocking film for LSI memories and as an insulating film material for thin film multilayer substrates.

Patent applicant: Hitachi, Ltd. Hitachi Chemical Co., Ltd.

Claims (1)

[Claims] 1. (a) General formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(1) (However, in the formula, R^1 is a tetravalent compound containing at least 4 carbons. Organic group, R^2 is a trivalent or tetravalent organic group containing an aromatic ring, R^3 and R^4 are each an organic group with 10 or less carbon atoms, Y is a photosensitive group, and X is a photosensitive group with R^2. There are organic groups connecting groups or -O- or ▲mathematical formulas, chemical formulas, tables, etc.▼
100 parts by weight of a polymer whose main component is a repeating unit represented by (n is 1 or 2) and (b) 0 photopolymerization initiator, photocrosslinking agent and/or sensitizer.
．． A heat-resistant photosensitive polymer composition comprising 1 to 30 parts by weight. 2. The heat-resistant photosensitive polymer composition according to claim 1, further comprising 0.1 to 30 parts by weight of a sensitizing aid. 3. In the above general formula (1), R^1 has ▲mathematical formula, chemical formula, table, etc.▼, ▲mathematical formula, chemical formula,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲ mathematical formulas, chemical formulas,
The heat-resistant polymer composition according to claim 1, which has tables, etc. ▼ or ▲ has mathematical formulas, chemical formulas, tables, etc. ▼. 4. In the above general formula (1), R^2 has ▲mathematical formula, chemical formula, table, etc.▼, ▲mathematical formula, chemical formula,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, Z is -O-, -S-, -SO_2-, -CO-,
-CH_2-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
The heat-resistant photosensitive polymer composition according to claim 1, which represents a group selected from ▼. 5. In the above general formula (1), R^3 and R^4 are an alkyl group having 5 or less carbon atoms, an alkoxymethyl group,
The heat-resistant photosensitive polymer composition according to claim 1, which is an alkoxyethyl group, an alkoxypropyl group, an alkylcarboxyethyl group, or a phenylcarboxyethyl group. 6. In the general formula (1) above, the photosensitive group Y is: ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas There are , chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc.▼, or▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, R^6 is a group selected from hydrogen, cyano group, and lower alkyl group, and R^7 is hydrogen, lower alkyl group, and alkoxy group. A group selected from R^8, R^9, R^1^0
, R^1^1, and R^1^2 represent a group selected from hydrogen, a lower alkyl group, a vinyl group, and a phenyl group), the heat-resistant photosensitive polymer composition according to claim 1. thing. 7. The photopolymerization initiator, photocrosslinking agent and/or sensitizer include Mihiraketone, bis-4,4'-diethylaminobenzophenone, benzophenone, benzoin ether,
Benzoin isopropyl ether, anthrone, 1,9
-Benzanthrone, acridine, nitropyrene, 1,
8-dinitropyrene, 5-nitroacenaphthene, 2-nitrofluorene, pyrene-1,6-quinone, 9-fluorene, 1,2-benzoanthraquinone, andanthrone, 2-chloro-1,2-benzanthraquinone, 2 −
Bromobenzanthraquinone, 2-chloro-1,8-phthaloylnaphthalene, 3,5-diethylthioxanthone, 3,5-dimethylthioxanthone, 3,5-diisopropylthioxanthone, benzyl, 2,6-di(4'-
azidobenzal)cyclohexanone, 2,6-di(4'
-azidobenzal)-4-methylcyclohexanone, 2
, 6-di(4'-azidobenzal)-4-carboxycyclohexanone, 2,6-di(4'-azidobenzal)
-4-hydroxycyclohexanone, 2,6-di(4'
-azidocinnamylidene)cyclohexanone, 2,6-
Di(4'-azidocinnamylidene)-4-methylcyclohexanone, 2,6-di(4'-azidocinnamylidene)-4-carboxycyclohexanone, 2,6-di(4
'-azidocinnamylidene)-4-hydroxycyclohexanone, 1-phenyl-5-mercapto-1H-tetrazole, 1-phenyl-5-merticus, 3-acetylphenanthrene, 1-indanone, 7-H-benz[de ] The heat-resistant photosensitive polymer composition according to claim 1, which is anthracen-7-one, 1-naphthaldehyde, thioxanthene-9-one, 10-thioxalyanone and/or 3-acetylindole. 8. The above sensitizing aids include 4-diethylaminoethylbenzoate, 4-diethylaminoisopropylbenzoate, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisopropylbenzoate, 4-dimethylaminoisoamylbenzoate, ethylene glycoldithioglycolate, ethylene glycol Di(3-mercaptopropionate), trimethylolpropanetoglycolate, trimethylolpropane tri(3-mercaptopropionate), pentaerythritol tetrathioglycolate, pentaerythritol tetra(3-mercaptopropionate), trimethylolpropane Methylolethane trithioglycolate, trimethylolethane tri(3-mercaptopropionate, dipentaerythritol hexa(
3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), thioglycolic acid and/or α-mercaptopropionic acid according to claim 1. thing.