JPS606725A - Photosensitive polyamide soluble in organic solvent - Google Patents

Abstract

PURPOSE:The titled polymer excellent in heat resistance and electrical and mechanical properties, and capable of easily forming a relief pattern, comprising a polycondensate of an aromatic dicarboxylic acid component with a diamine component containing a photosensitive group-containing aromatic diamine compound. CONSTITUTION:The titled photosensitive polyamide comprising a (co)condensate of an aromatic dicarboxylic acid component (e.g., terephthaloyl dichloride) with a diamine component comprising 100-10mol% photosensitive group-containing aromatic diamine compound of formula I (wherein R1 is a resiude of a photosensitive group-containing aromatic diamine group), e.g., ethyl 3,5-diaminobenzoate, and 0-90mol% photosensitive group-free aromatic compound of formula II(wherein R2 is a residue of a photosensitive group-free aromatic group), e.g., p- phenylenediamine. This polyamide is excellent in heat resistance and electrical and mechanical properties, and suitable as a material for forming insulation films or passivation films on solid elements in the semiconductor industry or a layer insulation material for use in semiconductor integrated circuits or multi- layer printed circuit boards.

Description

Detailed Description of the Invention The present invention relates to a novel aromatic polyamide containing a photosensitive group in the main chain of the polymer, which has excellent solubility in organic solvents, and in particular has excellent heat resistance, electrical and mechanical properties. The present invention relates to an organic solvent-soluble photosensitive polyamide which is excellent and suitable as a material for forming insulating films and passivation films on solid-state devices in the semiconductor industry, and as a glabella insulating material for semiconductor integrated circuits, multilayer printed wiring boards, etc.

Materials for forming insulating films and passivation films on solid-state devices in the semiconductor industry, and insulating materials for semiconductor integrated circuits and multilayer printed wiring boards, are required to have high heat resistance and insulation properties, and are required to have high density. Due to the demand for high integration, photosensitive and heat-resistant materials are being used.

Conventionally, there have been many requests for photosensitive polyamides, but most of them are made by blending polyamides that do not contain photosensitive groups with photopolymerizable unsaturated compounds (monomers), and do not have sufficiently high photosensitivity. (Japanese Unexamined Patent Publication No. 48-8900
4, JP-A-49-74739, JP-A-56-93704, etc.). Polyamides containing photosensitive groups have also been proposed (Japanese Patent Application Laid-Open No. 50-860
(Refer to Publication No. 5 and Japanese Unexamined Patent Publication No. 122833/1983, etc.)
However, all of them are aliphatic polyamides and have insufficient heat resistance and photosensitivity.

Furthermore, various proposals have been made to form the above-mentioned pansivation film and the like using various polymers having high insulation properties and high heat resistance.

However, among these, those using heat-resistant polyimide generally have problems in solubility and photosensitivity in solvents, and heat-resistant polymers that are solvent-soluble and contain photosensitive groups are, for example, polyimide precursors. It is a modified form in which a photosensitive group is introduced into the carboxyl group of polyamic acid, which is a polyamic acid, or polyamide aminic acid, which is a polyamideimide precursor, by amidation, esterification, etc., and the storage stability of its solution is In addition, it is necessary to imidize or post-bake a precursor into which a photosensitive group has been introduced during or after photocuring to produce polyimide or polyamideimide, and there are various problems associated with this reaction.

In view of the current situation described above, the present inventors have conducted various studies with the aim of providing a photosensitive resin that can easily form relief patterns with excellent heat resistance, electrical properties, and mechanical properties. group dicarboxylic acid or its acid halide and a specific aromatic diamine compound containing a photosensitive group,
It has been found that an aromatic polyamide made of a polycondensate has excellent photosensitivity and is soluble in organic solvents, and can achieve the above object.

That is, the present invention was made based on the above findings, and comprises an aromatic dicarboxylic acid component, 100 to 10 mol% of an aromatic diamine compound containing a photosensitive group represented by the following general formula (I), and the following general formula: Provided is an organic solvent-soluble photosensitive polyamide consisting of a polycondensate or copolycondensate with a diamine component consisting of O to 90 mol% of an aromatic diamine compound represented by (II) that does not contain a photosensitive group. It is.

112 N -R1-N +12 (I) (However, in the formula, R1 represents a residue of an aromatic group containing a photosensitive group.) Hz N -82-N 82 (II) (However, in the formula, R2 indicates a residue of an aromatic group that does not contain a photosensitive group.) The polyamide of the present invention is obtained by using an aromatic diamine compound containing a photosensitive group represented by the above general formula (I) as a diamine component. A large number of photosensitive groups are introduced into the polymer main chain during polycondensation with an acid component, and it has high photosensitivity and excellent light transmittance and photocrosslinking properties, so it can be used like conventional non-photosensitive polymers. Since it does not require a separate photoresist (photocurable material) for image formation and has excellent solubility in organic solvents, it is extremely suitable for forming relief patterns.

In addition, the polyamide of the present invention is a photosensitive polyamic acid (
Unlike polyimide precursors) and polyamide amic acids, which do not require an imidization process after image formation, this not only simplifies the process, but also eliminates distortion and stress due to thermal effects and shrinkage on the device. It has many excellent effects.

The photosensitive polyamide of the present invention will be described in detail below along with its manufacturing method.

A typical structure of the photosensitive polyamide of the present invention consisting of the above-mentioned polycondensate (copolycondensate) is a polycondensate (copolycondensate) of approximately equimolar amounts of an acid component and a diamine component; Among them, the ratio of the aromatic diamine compound containing a photosensitive group represented by the general formula (I) to the aromatic diamine compound not containing a photosensitive group represented by the general formula (n) is 100 to 10 mol of the former. % of the latter 0 to 90 mol%, preferably 100 to 60 mol% of the former to 0 to 40 mol% of the latter
It is.

The copolycondensation effect of the aromatic diamine compound represented by the general formula (II) is useful for improving the thermal properties of polyamide, but if the proportion in the total diamine component exceeds the above range, the concentration of photosensitive groups decreases. This is not appropriate because the photosensitivity decreases.

The photosensitive polyamide of the present invention is produced by the following method.

That is, the photosensitive polyamide of the present invention comprising the polycondensate or copolycondensate is composed of an aromatic dicarboxylic acid component and two aromatic diamine compounds represented by the general formulas (I) and (II). (When obtaining a polycondensate, only the aromatic diamine compound represented by the general formula (1) is used as the diamine component.)

Specifically, the aromatic dicarboxylic acid component used in the production of the photosensitive polyamide of the present invention includes terephthalic acid, isophthalic acid, 4,4′-dicarboxy-biphenyl, 4,4°-dicarboxy-diphenylmethane, 4
．． Aromatic dicarboxylic acids such as 4''-dicarboxy-diphenyl ether and their acid halides can be mentioned.

Among these aromatic dicarboxylic acid components, acid halides of the above-mentioned aromatic dicarboxylic acids, particularly acid chlorides, are preferred.

In addition, examples of the aromatic diamine compound represented by the general formula (■), which is one of the diamine components, include aromatic diaminobenzoic acid ethyl acrylate having a photosensitive hydrocarbon unsaturated group, 3,5- Diaminobenzoic acid ethyl methacrylate, 2,4-diaminobenzoic acid ethyl methacrylate, 3,5-diaminobenzoic acid glycidyl acrylate, 2,4-diaminobenzoic acid glycidyl acrylate, 3,5-diaminobenzoic acid glycidyl Methacrylate ester, 2,4-diaminobenzoic acid glycidyl methacrylate ester, 3
, 5-diaminobenzoic acid cinnamic ester, benzoic acid esters such as 2,4-diaminobenzoic acid cinnamic ester, benzyl acrylates such as 3,5-diaminobenzyl acrylate, 3,5-diaminobenzyl methacrylate, 4- Acrylamide-3,4''-diaminodiphenyl ether, 2-acrylamide-3°4°-diaminodiphenyl ether, 4-cinnamamide-3,4
"-diaminodiphenyl ether, 3.4°-diacrylamide-3", 4-diaminodiphenyl ether,
3.4°-dicinnamamide-3”, 4-diaminodiphenyl ether, 4-methyl-2′-carboxyethyl methacrylate-3,4°-diaminodiphenyl ether [carboxyethyl methacrylate is C
H2= C(CH3) COOC+(2CH200C)
, 4-methyl-2'-carboxyethyl acrylate-3,4°-diaminodiphenyl ether [carboxyethyl acrylate is CI (2=CHCOO
Schiff, z-nyl ethers such as CH2C1 (200C-) and 4,4'-diaminochalcone, 3.3°-diaminochalcone, 3,4'-diaminochalcone, 3',4
-diaminochalcone, 4'-methyl-3', 4-diaminochalcone, 4'-methoxy-3', 4-diaminochalcone, 3'-methyl-3,5-diaminochalcone, and other chalcones. .

In addition, the above general formula <U) which is another diamine component
Specifically, the aromatic diamine compound represented by
．． 4-Diaminotoluene, 4,4′-diaminodiphenyl ether, 4,4°-diaminodiphenylmethane, 0
) luidine, 1,4-bis(4-aminophenoxy)benzene, 2,2-bis(4-aminophenoxyphenyl)propane, 0-toluidine sulfone, and the like.

The aromatic diamine compound represented by the general formula (I) is
If necessary, two or more types may be used in combination, and the aromatic diamine compound represented by the above general formula (old) used in combination with this may also be
Two or more types can be used in combination if necessary.

The photosensitive polyamide of the present invention is polyamide 0°5g/N.
- Methyl-2-pyrrolid 7100 ml (7) Logarithmic viscosity measured at 30 mm as a 4 degree solution 0.1 to 1.
5, particularly preferably within the range of 0.2 to 1.0.

To explain in more detail the production of the photosensitive polyamide of the present invention, the aromatic dicarboxylic acid component and the general formulas (1) and (II) used in synthesizing the polycondensate (copolycondensate)
The usage ratio of the diamine component consisting of two types of aromatic diamine compounds represented by the above formula (1) is approximately equimolar;
The usage ratio with the aromatic diamine compound represented by n) is
As mentioned above, the former is 100 to 10 mol% and the latter is 0 to 9 mol%.
It is 0 mol%. In these synthetic reactions, it is preferable to carry out the polymerization reaction at a relatively low temperature.

That is, it is preferable to carry out the polymerization reaction in an organic solvent at a reaction temperature of 100° C. or lower, preferably 80° C. or lower for 0.1 to 48 hours, and as a result, the copolycondensate is synthesized and the polyamide of the present invention is obtained. .

As the organic solvent in the above polymerization reaction, for example, N, N
-dimethylsulfoxide, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N-methyl-2-pyrrolidone, hexamethyleneposboamide, etc. are used.

Further, in the aromatic diamine compound represented by the general formula ('I) used for producing the polyamide of the present invention,
Diaminodiphenyl ethers, diaminobenzoic acid esters, and diaminohensyl acrylate-1-s are new compounds, and there are no restrictions on their synthesis methods, but preferred synthesis methods include the following. I can do it.

(1) Synthesis method of diaminodiphenyl ethers (Mono- or di)amino-dinitrophenyl ether obtained by hydrolyzing (mono- or di)acetylamide-dinitrophenyl ether is reacted with acrylic acid chloride, etc., and then the reaction is carried out. One example is a method of synthesizing a target aromatic diamine compound by reducing a compound.

(2) Synthesis method of diaminobenzoic acid esters One example is a method of synthesizing the desired aromatic diamine compound by reacting dinitrobenzoic acid chloride with hydroxyethyl methacrylate, etc., and then reducing the reactant. .

(3) Synthesis method of diaminohensyl acrylates One example is a method of synthesizing the desired aromatic diamine compound by reacting dinitrohensyl alcohol with acrylic acid chloride, etc., and then reducing the reactant. .

When the photosensitive polyamide of the present invention is used as a material for forming a relief pattern, it is used as a solution dissolved in an organic solvent. This organic solvent includes N,
N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, hexamethyleneposboamide, etc. can be mentioned, and the preferred concentration of the photosensitive polyamide solution is 5 to 30.
%.

Furthermore, a sensitizer, a photopolymerization initiator, and a light-polymerizable compound having an ethylenically unsaturated group can be added to the photosensitive polyamide solution, if necessary.

Examples of the sensitizer and photopolymerization initiator include Michler's ketone, benzoin, benzoin methyl ether, hengeine ethyl ether, hengeine isopropyl ether,
2-t-butylanthraquinone, ■, 2-benzo 9,
Examples include 1o-anthraquinone, 4.4°-bis(diethylamino)benzophenone, acetophenone, hensifhenone, thioxane 1-one, and 1,5-acenaphthene, and the amount of addition thereof can be determined based on the photosensitive polyamide 1.
0.1 to 10 parts by weight per 00 parts by weight.

In addition, as the photopolymerizable compounds having ethylenically unsaturated groups, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, tolmethylolpropanetri(meth)acrylate, tetramedylolmethanetetra (meth)acrylate, N,N'-methylenebis(meth)acrylate,
Diethylaminoethyl (meth)acrylate, 1,3.
Examples include 5-triacryloylhexahydro-5-yl-lyazine and tris(hydroxyethyl acryloyl) isocyanurate.

According to the photosensitive polyamide of the present invention, a relief pattern can be formed in the following manner by adjusting the photosensitive polyamide 2'8 liquid as described above.

That is, first, the photosensitive polyamide solution described above is applied to a substrate and dried to remove the organic solvent.

Coating onto the substrate can be performed using, for example, a rotary coater. The coating film is dried at a temperature of 150°C or lower, preferably 100°C or lower. At this time, the pressure may or may not be reduced. After drying, a negative photomask chart is placed on the coated film, and active light such as ultraviolet rays, visible light, electron beams, and X-rays is irradiated. The unexposed areas are then washed away with a developer to obtain a polyamide relief pattern. Examples of the above developer include N,N-dimethylborumamide, N,N-dimethylacetamide, dimethylsulfoxy 1! , N-methyl-2-pyrrolidone, hexamethylenephosphoamide, diglyme, or a mixture of the solvent and methanol or ethanol can be used.

As described above, the photosensitive polyamide of the present invention has a photosensitive group (a group having a photopolymerizable unsaturated bond) in the main chain of the polymer, and the acid heptamer component is an aromatic dicarboxylic acid or an acid halogen thereof. A copolycondensate in which the diamine monomer component is an aromatic diamine compound represented by the above general formula (1) and an aromatic diamine compound represented by the above general formula (II) [or the above general formula (II)] If the aromatic diamine compound represented by When forming a relief pattern, the polyamide of the present invention has high photosensitivity and excellent light transmittance and photocrosslinkability, so it can be used for image formation like conventional non-photosensitive polyimides and polyamides. This method not only simplifies the process but also eliminates the need for a separate photocurable material, and does not require an imidization process after image formation unlike photosensitive polyamic acid (polyimide precursor) or polyamide amic acid. , there are many excellent effects such as no thermal influence on the element, no strain or stress due to shrinkage, etc. Furthermore, the relief pattern formed from the photosensitive polyamide of the present invention has excellent heat resistance, electrical and mechanical properties, and is not only effective as an insulating film or a pansivation film for solid-state devices in the semiconductor industry. It can be used as an insulating film or solder resist for multilayer wiring supplements for hybrid circuits and printed circuits.

Further, the photosensitive polyamide of the present invention has excellent light transmittance and photocrosslinkability, and can form a thick film, so it can also be used for forming relief patterns for letterpress printing.

Below, examples of synthesis of aromatic diamine compounds used in the production of the photosensitive polyamide of the present invention, examples showing the production of the photosensitive polyamide of the present invention, and various physical property tests and tests showing the effects of the photosensitive polyamide of the present invention are shown. Here are the results.

Synthesis Example 1 Synthesis of 3.5-diaminobenzoic acid ethyl methacrylate 1st step Synthesis of 3.5-dinitrobenzoic acid ethyl methacrylate 29.6 g of 2-hydroxyethyl methacrylate and 18.1 g of pyridine were dissolved in THF (tetrahydrofuran). )
A solution prepared by dissolving 50 g of 3,5-dinitrobenzoic acid chloride in 150 ml of THF was added dropwise from a dropping funnel at 5 to 6° C. over a period of 1 hour.

After the dropwise addition, the mixture was further stirred at 10 to 15°C for 1 hour. after that,
The precipitated pyridine hydrochloride was filtered out using a Buchner funnel, the filtrate was concentrated, and then poured into water to precipitate a white-yellow precipitate.

After washing the obtained precipitate in several directions by decantation,
After drying in vacuo, 60 g of 3,5-dinitrobenzoic acid ethyl methacrylate was obtained.

Second step: Reduction of 3,5-dinitrobenzoic acid ethyl methacrylate A solution of 5 g of 3,5-dinitrobenzoic acid ethyl methacrylate obtained in the first step dissolved in 36 ml of acetic acid was added to 27 g of iron powder. was added in 2-4 ml portions to a solution of 15n+1 water/351 acetic acid with stirring so that the reaction temperature was maintained at 25°C±3°C. The addition was completed in about 20 minutes, and the mixture was stirred for an additional 10 minutes.

Then, using a Buchner funnel, add ice to the filtrate from which excess iron was separated and bring the temperature to about 0°C, and then purge with aqueous ammonia.
H was set to around 8, extracted using ethyl acetate, washed with water, dried, and ethyl acetate was removed to obtain 11.2 g of the crude target product (yield: 6).
7.5%). This crude target product was purified by column chromatography. That is, 200 g of Wako Gel (C-200) was packed into a 65 ml + φ column and separated using a 1:1 mixed solvent of ethyl acetate and benzene as a developing solvent to obtain 7.8 g of the target product.

Melting point: 88-89℃ Elemental analysis value (as C,, II,, N20) CH'
N Actual value (%) 59.36 6.08 10.49 Calculated value (%) 59.0B 6.10 10.60 In addition, the infrared absorption spectrum and H-NMR spectrum of the above target object were measured. I confirmed that it was a thing.

Synthesis Example 2 Synthesis of 3.5-diaminobenzyl acrylate First step Acryloylation of 3.5-dinitrobenzyl alcohol 40 g of 3.5-dinitrobenzyl alcohol was dissolved in THF4
Triethylamine 40.4
200 ml of THF containing 20 g of acrylic acid chloride was added to this solution at 3 to 4°C while stirring.
It was added dropwise over a period of minutes. After the dropwise addition was completed, the mixture was stirred for an additional hour. Thereafter, this solution was filtered using a Buchner funnel, and the filtrate was removed from the filtrate under reduced pressure using an evaporator.
2.5jl of concentrated liquid! The product was poured into water to precipitate the product, which was collected by filtration and dried to obtain 46 g of crude di-1-chloride.

The obtained crude dinitrated product was subjected to column chromatography (
The product was purified using a 651φ column, 300 g of Wakogel C-200, and a developing solvent of benzene/ethyl acetate = 1 νOI/1 vol) to obtain 42.8 g of 3.5-dinitropendyl acrylate (yield: 84%) as pale yellowish-white crystals.

Second step 3. Reduction of 5-dinitrobenzyl acrylate 3,5-dinitrobenzyl acrylate 20 obtained in the first step
A solution of 140 g of vinegar M dissolved in 140 g of vinegar M was added to a solution of 140 g of iron powder suspended in 70 g of acetic acid/70 g of water while stirring.
The mixture was added little by little and reacted at 0 to 25°C.

After the reaction, the mixture was filtered to remove excess iron powder, and the filtrate was neutralized with aqueous ammonia and extracted with 2.34 g of ethyl acetate. After drying the extract over anhydrous sodium sulfate overnight, the ethyl acetate layer was added to a volume of 20 to 40 ml. iL'ta. The obtained concentrate was subjected to column chromatography (column 50 mmφ,
Silica gel Wakogel C-200 150g, developing solvent benzene/ethyl acetate = 3vol/2vol)
10.5 g of the target product as white crystals (yield 68
．． 9%) is E.

Elemental analysis value (as C,, II, □N2o2) HN Actual value (%) 62.24 6.46 14.58 Calculated value (%) 65.49 6.29 14.57 Also, regarding the above target substance, red The external absorption spectrum and H-NMR spectrum were measured, and it was confirmed that the product was the desired product.

Synthesis Example 3 n Synthesis of 4-acrylamido-3,4″-diaminodiphenyl ether First step Hydrolysis of 4-acetylamide-3,4″-dinitrodiphenyl ether Pa1 4-acetylamide-3,4″-dinitrodiphenyl ether 60 g (0.19 mol) was added with 300 ml of Claisen alkali (105 g of potassium hydroxide dissolved in 75 ml of water and then made up to 300 ml with methanol), melted, heated at 70°C for 10 minutes, and then 101
00O water was added to precipitate red-orange crystals.

The crystals were collected by filtration and dried under reduced pressure to give 4-amino-3,4゛-
Dinitro diphenyl ether 51.2g (yield 98%
) was obtained.

50 g (0.1.8 mol) of 4-amino-3,4''-dinitrodiphenyl ether obtained in the first step of acrylation of 4-amino-3,4''-dini-1-rodiphenyl ether
A solution of 66 g (0.72 mol) of acrylic acid chloride dissolved in 200 ml of THF was added dropwise at room temperature to a solution dissolved in a mixture of 800 ml of F and 86 g (1.08 ml) of pyridine, and the solution was dissolved in 1.5 hours. At that time, the temperature rose from 24°C to 35°C. After further reacting at 40-45°C for 1 hour, the temperature was returned to room temperature and the reaction solution was filtered. After concentrating the oak solution to about 50ml, ammonia water ( 5%
) 34 into ice water to precipitate crystals. Collect the crystals by filtration and dry under reduced pressure at room temperature.

The obtained crystals were separated by silica gel chromatography (Wako Gel C-200 200 g, developing solvent Hensen) to obtain 32.6 g (yield 55%) of 4-acrylamide-3,4''-dini]rodiphenyl ether as yellow crystals. Obtained.

Third step: Reduction of 4-acrylamide-3,4°-dinitrodiphenyl ether 16 g (0.05 mol) of 4-acrylamide-3°4°-dinitrodiphenyl ether obtained in the second step
A solution of 27g of iron powder dissolved in 60g of acetic acid and 15g of water
The mixture was added little by little to a solution made of 15 g of acetic acid and 15 g of acetic acid with stirring. At that time, there was an exotherm, and the mixture was cooled with water and reacted at around 50°C.

After the reaction, ammonia water (25%) was poured into 200 ml of ice water to make it alkaline, then 600 ml of water was added, extracted with ether-ethyl acetate (3:1), dried over anhydrous sodium sulfate, and the solvent was removed. , 8 g (yield 60%) of the target product was obtained.

Melting point 105-106℃ Elemental analysis value (as C+5Ht5N302) HN Actual value (%) 66.46 5.71 15.60 Calculated value (%") 66.90 5.61 15.60 Also, regarding the above target substance, red External absorption spectrum and H-N M
The R spectrum was measured and it was confirmed that it was the desired product.

Example 1 Polyamide of terephthalic acid dichloride and 3,5-diaminobenzoic acid ethyl methacrylate After purging the inside of the flask with dry nitrogen, 0.05 g of lithium chloride and 3,5-diaminobenzoic acid ethyl methacrylate were added to the flask. Add 0.5386 g of acid ester, and add 4.0 g of N-methyl-2-pyrrolidone (NMP).
ml was added and dissolved. After the solution was dissolved, 0.406 g of terephthalic acid dichloride was added while stirring at 0°C, and the mixture was reacted for 0.5 hours, and then at 50°C for 3 hours.

After the reaction, the reaction f6 solution to which 15 ml of NMP had been added was added to a mixed solution of 100 ml of methanol and 100 ml of water to precipitate polyamide. The precipitate was filtered and dried, and 0.78 g of white polyamide powder was added to it.

Examples 2-5 Terephthalic acid dichloride and 3,5 in Example 1
A polyamide was obtained in the same manner as in Example 1, except that -diaminobenzoic acid ethyl methacrylate ester was replaced with an acid component and a diamine component, which are not shown in Table 1 below.

Table 1 Physical property test Regarding the polyamides obtained in Examples 1 to 5 above, the following +11
The physical property tests (5) to (5) were conducted and the results shown in Table 2 below were obtained.

(Viscosity of IJ polyamide The logarithmic viscosity of a polyamide solution having a concentration of 0.5 g of polyamide/100 ml of NMP was measured at 30°C.

(2) Polyamide film forming property A polyamide film with a thickness of about 10μ was created on a glass plate, soaked in water, peeled off, and bent at 180 degrees. Items where the crank was formed during the coating were marked as ×.

(3) Solubility of polyamide in NMP The solubility (wt%) of polyamide in NMP was measured at the product temperature.

(4) Starting temperature of thermal decomposition The starting temperature of weight loss was measured using a differential ripening balance TG-DSC manufactured by Rigaku Denki A Rumor.

(5) Michler's ketone 6 in NMP 10% solution of photocurable polyamide
A solution containing PHR was applied onto a glass plate using a spin coating machine (2
000~5000rpm), and apply at a pressure of 1~5000rpm).
A thin film of several μm in thickness (see Table 2) was prepared by drying at 50° C. for 5 hours under reduced pressure of 2 mm and 11 g, and this N film was subjected to the photosensitivity and resolution tests described below.

■Photosensitivity The above thin film is photocured by irradiating it with an ultra-high pressure mercury lamp (jet light 2kW) at an illuminance of 7.2mW/cl (350mμ).
c) was measured.

■Resolving power As a test chart for the above thin film, Toppan Printing (11
℃M negative type test chart (Toppan test chart N
A relief pattern was formed using the minimum line 1jO, 98±0.25μ), and the quality of the pattern was determined.

Table 2

Claims (1)

[Claims] Aromatic diamine compounds 100 to 10 containing an aromatic dicarboxylic acid component and a photosensitive group represented by the following general formula (I)
An organic solvent-soluble photosensitive product consisting of a polycondensate or copolycondensate with a diamine component consisting of mol% and an aromatic diamine compound not containing a photosensitive group represented by the following general formula (II) from 0 to 90 mol%. polyamide. R2N-R1-N R2 (I) (However, in the formula, R1 represents a residue of an aromatic group containing a photosensitive group.) R2N -R2-N +12 (II) (However, in the formula, R2 is a photosensitive group. (Indicates the residue of an aromatic group that does not contain any groups.)