JPH1135684A - Polyimide precursor and polyimide and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject precursor suitable for a photosensitive resin composition, etc., providing a polyimide, good in light transmissivity and having low thermal expansibility and a low permittivity by including a tetrafluorobiphenylene structure. SOLUTION: This precursor has a recurring unit of formula I (X is a tetravalent organic group; R<1> and R<2> are each OH or a univalent organic group). The objective precursor is preferably obtained by reacting a tetracarboxylic acid or its derivative with a diamine containing 2,2',6,6'-tetrafluoro-4,4'- diaminobiphenyl and, as necessary, an alcohol, an amine, etc. Oxydiphthalic acid, pyromellitic acid, etc., are prepared as the tetracarboxylic acid. N- Methyl-2-pyrrolidone, dimethyl sulfoxide, etc., are prepared as a solvent used in the reaction. The objective precursor preferably has 10,000-200,000 weight- average molecular weight. The imide cyclization is carried out by usually heating the precursor to provide a polyimide having a unit of formula II.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyimide precursor, polyimide useful as a material for semiconductor devices, optical waveguides, multilayer wiring boards, and the like, and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, in the semiconductor industry, an organic material having excellent heat resistance, such as a polyimide resin, has been used as an interlayer insulating material, which has conventionally been formed using an inorganic material, taking advantage of its characteristics. Have been. However, since the diameter of a silicon wafer serving as a substrate tends to increase year by year, there is a problem that a silicon wafer formed with a polyimide as a surface protective film is warped due to a difference in thermal expansion coefficient between the polyimide and the silicon wafer. ing. Therefore, a polyimide having low thermal expansion property is strongly demanded. Further, as photosensitive polyimide, thickening, g-ray exposure, i
High transparency that can respond to line exposure and the like is required. Further, as the operation speed of the element increases, a signal delay proportional to the square root of the dielectric constant becomes a problem. Therefore, a polyimide having a lower dielectric constant is strongly demanded. However, at present, a polyimide excellent in these properties in a good balance has not been obtained.

[0003]

SUMMARY OF THE INVENTION The invention according to claim 1 is a polyimide precursor suitable for a photosensitive resin composition or the like, which gives a polyimide having good light transmittance, low thermal expansion and a low dielectric constant. Is provided. The invention of claim 2 solves the problem of the invention of claim 1, and further provides a polyimide precursor which is excellent in heat resistance, low thermal expansion property, mechanical properties of a film, and the like. The invention according to claim 3 is
An object of the present invention is to provide a method for producing a polyimide, which has good light transmittance, low thermal expansion, and a polyimide having a low dielectric constant. The fourth aspect of the present invention is to provide a polyimide having good light transmittance, low thermal expansion and low dielectric constant.

[0004]

The present invention provides a compound represented by the general formula (I):

Embedded image Wherein X represents a tetravalent organic group, and R ¹ and R ² each independently represent OH or a monovalent organic group.

Further, the present invention relates to a compound represented by the formula (I) wherein the tetravalent organic group represented by X is

Embedded image The polyimide precursor is a group selected from the group consisting of:

[0006] The present invention also relates to a method for producing a polyimide, wherein the polyimide precursor is subjected to imide ring closure. Further, the present invention provides a compound represented by the general formula (II):

Embedded image (Wherein, X represents a tetravalent organic group).

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The polyimide precursor of the present invention has a repeating unit represented by the above general formula (I). X in the general formula (I) is a tetravalent organic group, and is preferably a residue of a tetracarboxylic acid or a derivative thereof capable of reacting with a diamine to form a polyimide precursor. As the tetravalent organic group, a tetravalent aromatic group, an aliphatic group, a group containing a siloxane bond, and the like are preferable, and a tetravalent aromatic group is more preferable. 4 to 30 in terms of the number of carbon atoms
Are preferable, those of 6 to 24 are more preferable, and
To 12 are more preferred. Note that a tetravalent aromatic group refers to a tetravalent aromatic group containing an aromatic ring (a benzene ring, a naphthalene ring, or the like).
It is a valence organic group, and it is preferable that all four binding sites are from an aromatic ring. These binding sites are divided into two sets of two, and it is preferable that the two binding sites in each set be located at the ortho position or the peri position existing at the adjacent carbon of the aromatic ring. The two sets may be from the same aromatic ring, or may be from separate aromatic rings linked through various bonds.

Specifically, the light transmittance, low thermal expansion property,
In terms of mechanical properties, etc.

Embedded image Are preferred, and in terms of low thermal expansion

Embedded image Is more preferred.

The polyimide precursor of the present invention has the general formula (I)
The excellent properties of the present invention are exhibited by including the tetrafluorobiphenylene structure shown in (1).
This is preferably a residue of a diamine that can react with a tetracarboxylic acid to form a polyimide precursor. R ¹ and R ² in the general formula (I) are each independently OH or a monovalent organic group. Examples of the monovalent organic group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group,
Alkyl group such as -butyl group, aryl group such as phenyl group, aralkyl group such as benzyl group, vinyl group, hydrocarbon group such as alkenyl group such as allyl group, acryloyl group,
Methacryloyl group, methacryloyloxyalkyl group,
An acryloyloxyalkyl group, a vinyl ether group, a group having a polymerizable unsaturated double bond such as a cinnamyl group, a glycidyl group, a hydroxyphenyl group, etc. are -O- or-
A monovalent organic group having a total carbon number of 1 to 20 is preferable, and a carbon atom having 1 to 20 carbon atoms is preferable.
10 to 10 are more preferable.

In particular, a part or all of R ¹ and R ² are
When the photosensitive group is a photosensitive group such as a group having a polymerizable unsaturated double bond (for example, a group capable of leaving upon irradiation with light, a group capable of dimerization or copolymerization upon irradiation with light, etc.), the polyimide precursor itself Is preferred for use as a photosensitive material because it can impart photosensitivity to the polymer. Particularly, a group having a polymerizable unsaturated double bond is preferable because good photosensitivity can be easily provided. If the portion of R ¹ and R ² and the photosensitive group, 10 mol% or more with respect to the sum of R ¹ and R ² and R ⁷ which will be described later in the general formula (IV) and R ⁸ is a photosensitive group Is preferred.

Examples of the group having a polymerizable unsaturated double bond include, for example, the following general formula (III)

Embedded image (However, R ³ , R ⁴ and R ⁵ are each independently selected from hydrogen, an alkyl group, a phenyl group, a vinyl group and a propenyl group, and R ⁶ represents a divalent organic group.) The organic group to be used is preferable because it can impart high-sensitivity photosensitivity. The alkyl group preferably has 1 to 4 carbon atoms. The divalent organic group represented by R ⁶ is preferably an alkylene group having 1 to 4 carbon atoms such as a methylene group, an ethylene group, and a propylene group. In particular, a methacryloyloxyalkyl group and an acryloyloxyalkyl group (alkyl having 1 to 4 carbon atoms) are suitable for the present invention because they not only achieve high sensitivity but also are easy to synthesize.

The polyimide precursor used in the present invention may contain a repeating unit represented by the following general formula (IV) in addition to the repeating unit represented by the general formula (I).

Embedded image (In the formula, X ′ represents a tetravalent organic group, Y represents a divalent organic group, and R ⁷ and R ⁸ each independently represent OH or a monovalent organic group.)

In this case, the content of the repeating unit represented by the general formula (I) is preferably at least 10 mol%, more preferably at least 30 mol%, of all the repeating units from the viewpoints of transparency and mechanical strength. More preferably, it is even more preferably at least 50 mol%.

X 'in the general formula (IV) is represented by the general formula (I)
And the preferable ones are also the same. R ⁷ and R ⁸ are the same as R ⁷ in the general formula (I).
^{The same as 1} and R ² can be mentioned, and the preferable ones are also the same. Y is a divalent organic group other than the tetrafluorobiphenylene group represented by the general formula (I), and is a residue of a diamine compound capable of forming a polyimide precursor by reacting with a tetracarboxylic acid or a derivative thereof. It is preferably a group. Examples of the divalent organic group include an aromatic group, an aliphatic group, a group containing an alicyclic ring, and a group containing a siloxane bond. In the case of a group containing an aromatic group, an aliphatic group and an alicyclic ring, carbon is used. Those having 6 to 18 atoms are preferable, and aromatic groups having the above-mentioned number of carbon atoms are more preferable. Here, the aromatic group is a divalent organic group containing an aromatic ring (a benzene ring, a naphthalene ring, or the like), and it is preferable that the two bonding sites be directly from the aromatic ring. The two binding sites may be from the same aromatic ring or may be from different aromatic rings.

The polyimide precursor of the present invention can be obtained by various known production methods. Materials include tetracarboxylic acid or a derivative thereof, a diamine containing 2,2 ', 6,6'-tetrafluoro-4,4'-diaminobiphenyl, an alcohol as a raw material constituting a side chain, if necessary, An amine or the like is used. When R ¹ and R ² are OH in the general formula (I), they can be obtained by reacting a tetracarboxylic anhydride and a diamine in an organic solvent used as required. When R ¹ and R ² are monovalent organic groups, and in the case of via —O—, tetracarboxylic dianhydride and a hydroxy group-containing compound are mixed and reacted to form a half ester of tetracarboxylic acid. After the production, it can be synthesized by a method of acid chloride with thionyl chloride and then reacting with a diamine, or a method of reacting the tetracarboxylic acid half ester with a diamine using a carbodiimide as a condensing agent. When R ¹ and R ² are monovalent organic groups,
In the case where the reaction is carried out, the compound can be produced by reacting a tetracarboxylic anhydride and a diamine in an organic solvent used as required, and then reacting with an isocyanate compound.

Examples of the tetracarboxylic acid used as the material of the polyimide precursor include oxydiphthalic acid, pyromellitic acid, 3,3 ', 4,4'-benzophenonetetracarboxylic acid, 3,3', 4,4'- Biphenyltetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid,
1,4,5,8-naphthalenetetracarboxylic acid, 2,
3,5,6-pyridinetetracarboxylic acid, 3,4,9,
10-perylenetetracarboxylic acid, sulfonyldiphthalic acid, m-terphenyl-3,3 ', 4,4'-tetracarboxylic acid, p-terphenyl-3,3', 4,4'-tetracarboxylic acid, 1,1,1,3,3,3-hexafluoro-2,2-bis (2,3- or 3,4-dicarboxyphenyl) propane, 2,2-bis (2,3- or 3,4 -Dicarboxyphenyl) propane, 2,2-bis {4 '-(2,3- or 3,4-dicarboxyphenoxy) phenyl} propane, 1,1,1,3,3,3-
Hexafluoro-2,2-bis {4 '-(2,3- or 3,4-dicarboxyphenoxy) phenyl} propane, the following general formula (V)

Embedded image (Wherein R ⁹ and R ¹⁰ represent a monovalent hydrocarbon group, and may be the same or different, and s is an integer of 1 or more). Acids and the like are used, and these are used alone or in combination of two or more.

Among them, oxydiphthalic acid, pyromellitic acid, 3,3 ', 4,4'-benzophenonetetracarboxylic acid and 3,3', 4 are preferable because the light transmittance and the coefficient of thermal expansion are easily adjusted. 4,4'-biphenyltetracarboxylic acid is preferred, and oxydiphthalic acid, pyromellitic acid and 3,3 ', 4,4'-biphenyltetracarboxylic acid are more preferred. As derivatives of tetracarboxylic acid,
For example, dianhydrides of the above-mentioned various tetracarboxylic acids, chlorides of the tetracarboxylic acids and the like can be mentioned.

The diamine giving the general formula (IV) includes 4,4 '-(or 3,4'-, 3,3'-, 2,
4'- or 2,2'-) diaminodiphenyl ether, 4,4'- (or 3,4'-, 3,3'-, 2,
4'- or 2,2'-) diaminodiphenylmethane, 4,4'- (or 3,4'-, 3,3'-, 2,
4'- or 2,2 '-) diaminodiphenylsulfone, 4,4'- (or 3,4'-, 3,3'-, 2,
4'- or 2,2 '-) diaminodiphenyl sulfide, paraphenylenediamine, metaphenylenediamine, p-xylylenediamine, m-xylylenediamine, o-tolidine, o-tolidine sulfone, 4,4'-
Methylene-bis- (2,6-diethylaniline), 4,
4'-methylene-bis- (2,6-diisopropylaniline), 2,4-diaminomesitylene, 1,5-diaminonaphthalene, 4,4'-benzophenonediamine, bis- {4- (4'-aminophenoxy) Phenyl disulfone, 1,1,1,3,3,3-hexafluoro-2,
2-bis (4-aminophenyl) propane, 2,2-bis {4- (4'-aminophenoxy) phenyl} propane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetramethyl-4,
4'-diaminodiphenylmethane, bis {4- (3'-
Examples thereof include aminophenoxy) phenyl} sulfone and 2,2-bis (4-aminophenyl) propane, and these are used alone or in combination of two or more.

As fluorine-containing diamines other than 2,2 ', 6,6'-tetrafluoro-4,4'-diaminobiphenyl used in the general formula (I),
2,2'-difluoro-4,4'-diaminobiphenyl, 2,2'-di (trifluoromethyl) -4,4'-
Diaminobiphenyl, 2,2 ', 6,6'-tetra (trifluoromethyl) -4,4'-diaminobiphenyl and the like can also be used. In this case, the amount of the diamine containing a fluorine atom is preferably in the range of 10 to 100 mol% of the total amount of all diamines, more preferably 30 to 100 mol%, and more preferably 50 to 100 mol%. More preferred. If the amount is less than 10 mol%, the transmittance tends to decrease, and the mechanical and thermal properties of the polyimide film tend to decrease.

In addition, the above-mentioned diamines may have the following general formula (VI) in order to improve adhesion.

Embedded image (Wherein, R ¹¹ and R ¹² each represent a divalent hydrocarbon group, which may be the same or different, and R ¹³ and R ¹⁴ each represent a monovalent hydrocarbon group, each of which may be the same or different. Often, t is an integer of 1 or more.) It is also possible to use an aliphatic diamine such as diaminopolysiloxane. R ¹¹ and R ¹² represent a methylene group, an ethylene group,
R ¹³ and R ¹³ include alkylene groups such as propylene groups, arylene groups such as phenylene groups, and bonding groups thereof.
^Examples of ¹⁴ include an alkyl group such as a methyl group and an ethyl group, and an aryl group such as a phenyl group. R ¹¹ , R ¹² ,
The groups represented by R ¹³ and R ¹⁴ each have a total carbon number of 1 to
Ten are preferred. When used in combination, these are preferably used in an amount of 30 mol% or less, more preferably in an amount of 20 mol% or less, and still more preferably in an amount of 10 mol% or less, based on the total amount of the diamine compound. .

In order to improve heat resistance, 4,4'-diaminodiphenyl ether-3-sulfonamide,
4'-diaminodiphenylether-4-sulfonamide, 3,4'-diaminodiphenylether-3'-sulfonamide, 3,3'-diaminodiphenylether-4-sulfonamide, 4,4'-diaminodiphenylether-3-carboxamide, 3,4'-diaminodiphenyl ether-4-carboxamide, 3,4'-diaminodiphenyl ether-3'-carboxamide,
Diamine compounds having a sulfonamide group or a carboxamide group such as 3,3'-diaminodiphenyl ether-4-carboxamide can be used alone or in combination of two or more. When used in combination, these are preferably used in an amount of 30 mol% or less based on the total amount of the diamine compounds.
More preferably, it is used in a range of not more than 10 mol%.
More preferably, it is used in the range of mol% or less.

The organic solvent used for the reaction of the tetracarboxylic acid or its derivative and the diamine is preferably a polar solvent which completely dissolves the polyimide precursor to be produced. For example, N-methyl-2-pyrrolidone, N, N- Dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, tetramethylurea, hexamethylphosphoric triamide, and γ-butyrolactone are preferred.

In addition to the polar solvent, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons and the like can also be used. For example, acetone, diethyl ketone, methyl ethyl ketone, methyl Isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether,
Examples include tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene and the like. These organic solvents can be used alone or
Used in combination of more than one type.

In the reaction of the tetracarboxylic acid or its derivative and the diamine, although it depends on the type of reaction, it is preferable to mix both of them in an amount of 80 to 120 mol% with respect to one amount, and particularly to equimolar amounts. Is preferred. The amount of the solvent is preferably 2 to 10 times the weight of the total amount of the tetracarboxylic acid or its derivative and the diamine. The reaction temperature and time are preferably 10 to 50 hours at room temperature in the case of an acid anhydride and a diamine.

The compounds used to introduce the side chains R ¹ , R ² , R ⁷ and R ⁸ in the general formulas (I) and (IV) include methanol, ethanol, isopropanol, n-propanol and n-propanol. Alkyl alcohols such as butanol, aryl alcohols such as benzyl alcohol, alcohol compounds such as vinyl alcohol and allyl alcohol, hydroxymethyl acrylate, hydroxymethyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate. Compounds having a hydroxyl group and a polymerizable unsaturated double bond such as alkyl acrylate or methacrylate; amines such as monoalkylamine and dialkylamine; alkylmonoisomers Cyanates and the like can be mentioned, and these are used alone or in combination of two or more. When the side chain is introduced, the amount of the compound used therefor is not particularly limited and varies depending on the type of the reaction. However, when the side chain is introduced into all the repeating units, 2 to 1 mol of the tetracarboxylic acid is used. Mol or more, preferably 2 to 3 mol. As described above, the polyimide precursor of the present invention is obtained.

The obtained polyimide precursor preferably has a weight average molecular weight of 5,000 to 500,000, more preferably 10,000 to 200,000.
When the weight-average molecular weight is less than 5,000, there is a tendency that the film after imidization has a disadvantage in film characteristics such as brittleness and the like.
If it exceeds 000, the solution of the polyimide precursor becomes high in viscosity, so that workability tends to be poor. The weight average molecular weight can be determined by measuring by gel permeation chromatography (GPC) and converting from a standard polystyrene calibration curve.

The polyimide of the present invention can be synthesized by subjecting the above polyimide precursor to imide ring closure. This imide ring closure can be usually performed by heating. The heating conditions are not particularly limited, but the heating temperature is preferably from 80 to 450 ° C. If the temperature is lower than 80 ° C., the ring closure reaction tends to be slow, and if the temperature exceeds 450 ° C., the produced polyimide tends to deteriorate. The heating time is preferably set to 10 to 100 minutes. If the time is less than 10 minutes, the ring-closing reaction tends to be slow, and if it exceeds 100 minutes, the produced polyimide tends to deteriorate and the workability tends to decrease.

The polyimide precursor and polyimide of the present invention are suitable as materials for interlayer insulating films and surface protective films of electronic components such as semiconductor devices and high-density multilayer wiring boards. In these applications, by using a composition containing the polyimide precursor having a photosensitive group introduced therein and a photoinitiator or a composition of the polyimide precursor and a photosensitive compound, even a thick film, g-line, Even with exposure to i-line or the like, a favorable negative or positive pattern can be formed. Furthermore, since it has high light transmittance, it can be used for an optical waveguide.

[0029]

The present invention will be described below with reference to examples. Examples 1 to 3 In a 100 ml flask equipped with a stirrer and a thermometer, Table 1 was added.
2,2 ', 6,6'-tetrafluoro-4,
4'-Diaminobiphenyl (TFAP) and N-methyl-2-pyrrolidone were added and dissolved by stirring at room temperature. The acid component shown in Table 1 was added to this solution, and the mixture was stirred for 30 hours to obtain a viscous polyimide precursor. Was obtained. Further, this solution was heated at 70 ° C. for 5 hours, the viscosity was adjusted to 100 poise (solid content: 25% by weight), and the polyimide precursor solution (P
I-1 to PI-3). The weight average molecular weight is shown according to Table 1.

The viscosity was measured using an E-type viscometer (Toki Sangyo Co., Ltd.)
, EHD type) at a temperature of 25 ° C and a rotation speed of 2.
It was measured at 5 rpm. The weight average molecular weight was determined by gel permeation chromatography (GPC, apparatus manufactured by Hitachi, Ltd.) in terms of standard polystyrene. Moreover, the solution of the obtained polyimide precursor (PI-1 to PI-3)
The dried product was measured for an infrared absorption spectrum (manufactured by JEOL Ltd., JIR-100 type) by the KBr method. In each case, the C = of the amide group was found around 1600 cm ^-1.
O absorption and N-H absorption were confirmed at around 3300 cm ^-1 .

[0031]

[Table 1]

The polyimide precursor of each example was heated at 100 ° C.
For 30 minutes, at 200 ° C. for 30 minutes, and at 350 ° C. for 60 minutes to close the imide and obtain a polyimide. When the infrared absorption spectrum of a part of the obtained polyimide was measured by the KBr method, characteristic absorption of imide was confirmed at around 1780 cm ^-1 .

The light transmittance, the coefficient of thermal expansion after imidization, and the residual stress of each polyimide precursor obtained in each example were evaluated by the following methods. The evaluation results are shown in Table 2. The light transmittance was measured at 85 ° C. by spin coating the obtained resin solution of each polyimide precursor having a photosensitive group.
The coating film (10 μm) obtained by drying at 105 ° C. for 3 minutes and then at 105 ° C. was measured with a spectrophotometer. The coefficient of thermal expansion is as follows.
Thermophysical analyzer (TMA) under conditions of ° C / min and load of 10g
Was measured. Residual stress is obtained by forming a polyimide film on a 6-inch silicon wafer and using a Tencor Co. stress measuring device (F
LX-2320).

[0034]

[Table 2]

Comparative Examples 1 to 3 Polyimide precursors were produced in the same manner as in Example 1 except that the ingredients were changed to those shown in Table 3, and the same evaluation was conducted. Table 4 shows the results.

[0036]

[Table 3]

[0037]

[Table 4]

Application Example 10 g of each polyimide precursor (PAA-1 to PAA-6) solution obtained in each of the above Examples and Comparative Examples was
0.027 g of 2,6-bis (4'-azidobenzal) -4-carboxycyclohexanone (CA), 4,4'-
Bis (diethylamino) benzophenone (EAB)
027 g and 1-phenyl-2- (o-ethoxycarbonyl) oxyiminopropan-1-one (PDO).
054 g was added, and dimethylaminopropyl methacrylate (MDAP) equivalent to the carboxyl group of the polyimide precursor was further added, followed by stirring and mixing to obtain a uniform photosensitive resin composition solution. The obtained photosensitive resin composition solution,
The solution was filtered, and each of them was dropped and spin-coated on a silicon wafer. Then, using a hot plate, 10
After heating at 0 ° C. for 150 seconds to form a coating film of 23 μm, a pattern mask was applied, and an exposure amount of 200 was applied with an i-line stepper.
Exposure was performed at mJ / cm ² . This was further heated at 100 ° C. for 60 seconds, and N-methyl-2-pyrrolidone / water (75/25
(Weight ratio)), and paddle development was performed at 100 ° C. for 30 minutes, at 200 ° C. for 30 minutes, at 350 ° C.
It heated at 60 degreeC for 60 minutes, and obtained the relief pattern of the polyimide. The resolution of the pattern was evaluated as the minimum size of the developable through hole using the through hole test pattern. Table 5 shows the results.

[0039]

[Table 5]

The polyimide patterns obtained from the relief patterns of Examples 1 to 3 have a good trapezoidal pattern shape, reflecting that the pattern shape of the relief pattern is rectangular and the resolution is good. However, the polyimide patterns obtained from the relief patterns of Comparative Examples 1 to 3 had an undesired inverted trapezoidal pattern shape reflecting that the pattern shape of the relief pattern was inverted trapezoidal and the resolution was poor. Was.

[0041]

The polyimide precursor according to the first aspect is suitable for a photosensitive resin composition or the like which has good light transmittance, low thermal expansion and gives a polyimide having a low dielectric constant. The polyimide precursor according to claim 2 has excellent heat resistance, low thermal expansion property, mechanical properties of the film, etc. in addition to the effects of the invention according to claim 1. According to the method for producing a polyimide according to the third aspect, a polyimide having good light transmittance, low thermal expansion, and a low dielectric constant can be obtained. Claim 4
The polyimide described has good light transmittance, low thermal expansion, and low dielectric constant.

Claims (4)

[Claims] 1. A compound of the general formula (I) (Wherein X represents a tetravalent organic group, and R ¹ and R ² each independently represent OH or a monovalent organic group). 2. The tetravalent organic group represented by X in the general formula (I) is: The polyimide precursor according to claim 1, which is a group selected from the group consisting of: 3. A method for producing a polyimide, comprising imide-closing the polyimide precursor according to claim 1 or 2. 4. A compound of the general formula (II) (Wherein, X represents a tetravalent organic group).