JPS6322831A - Ampholytic polyimide precursor and production thereof - Google Patents

Abstract

PURPOSE:To obtain the titled precursor having excellent heat-resistance, adhesivity and chemical resistance, formable to a film by Langmuir-Blodgett's technique and useful in electronic field, by reacting a tetracarboxylic acid dianhydride. CONSTITUTION:The objective precursor having the recurring unit of formula IV (one of R<3>-R<6> is not 1-11C group nor H) is produced by reacting a tetracarboxylic acid dianhydride of formula I (R<1> is tetravalent group having >=2C atoms) with compounds of formula R<3>OH and R<4>OH (R<3> and R<4> are 1-30C univalent aliphatic group, etc.), converting the resulting compound of formula II to an acid halide in an essentially anhydrous polar organic solvent at >=-10 deg.C and reacting the acid halide with a compound of formula III (R<2> is bivalent group having >=2C atoms; R<5> and R<6> are same as R<3> and R<4>) at >=-10 deg.C.

Description

[Detailed description of the invention] Industrial Joko Hada Rito Bean! The present invention relates to an amphoteric polyimide precursor, and more particularly to an amphoteric polyimide precursor modified so that it can be formed into a film by the Langmuir-Prodgett method (hereinafter referred to as the LB method), and a method for producing the same.

'no' , 'B<” '
-Already in the 1930s, number of carbon atoms is 16~
Langmuir and Prodgett discovered that about 22 fatty acids can form a monomolecular film on the water surface and accumulate it on the substrate, but studies have begun to consider the application of this cumulative film. This is a recent thing. However, Langmuir-Prodgett membranes (hereinafter referred to as LB membranes) of straight-chain saturated fatty acids have a problem in that they do not have sufficient heat resistance or mechanical strength for practical applications, and cannot be used as they are.

To improve these problems, membranes formed from unsaturated fatty acids such as ω-tricosenoic acid, ω-peptadenoic acid, or α-octadecyl acrylic acid, and unsaturated fatty acid esters such as vinyl stearate and octadecyl acrylate have been proposed. Polymerized membranes are being researched, but their heat resistance is not sufficient.

On the other hand, there is polyimide film as a heat-resistant film, but when using methods such as spin cord, the film thickness is at most 1000 m or more, and usually only 1 μm or more, and pinholes with a film thickness of less than 1000 m are obtained. It is extremely difficult to create a heat-resistant thin film without this.

The present invention was made in order to obtain an LB film with improved mechanical properties such as heat resistance and adhesive strength, and chemical resistance, and aims to obtain a material that can provide a heat-resistant ultra-thin film material. This is the purpose.

The present invention has been made based on the discovery that it is possible to introduce a substituent for imparting hydrophobicity to a polyamic acid unit. In the formula, R1 is a tetravalent group containing at least 2 carbon atoms, R2 is a divalent group containing at least 2 carbon atoms, R3, R4
, R5 and R6 are each a monovalent aliphatic group having 1 to 30 carbon atoms, a monovalent cycloaliphatic group, a monovalent group combining an aromatic group and an aliphatic group, and is a group substituted with a halogen atom, a nitro group, an amino group, a cyano group, a methoxy group, an acetoxy group, or a hydrogen atom, and R3
, one of R41, R5 and R6 has 1 to 11 carbon atoms
is not the above-mentioned group or hydrogen atom), and an amphoteric polyimide precursor having a repeating unit represented by the general formula (4
): (In the formula, R1 is the same as above) to the tetracarboxylic dianhydride, R30H and R40H (in the formula, R3,)
24 is the same as above) General formula (5) obtained by reacting
: (wherein R1, R3, and R4 are the same as above) is converted into an acid halide in a substantially anhydrous polar organic solvent at -10°C or higher, and combined with the general formula (6):% Formula %(6
) (wherein R2, R5, and R6 are the same as above) are reacted at 10°C or higher to produce an amphoteric polyimide precursor having a repeating unit represented by general formula (1). The method, furthermore, the tetracarboxylic acid dianhydride represented by the general formula (4) and the general formula (7);
A valent group, R7 or R8, has 12 to 30 carbon atoms.
a monovalent aliphatic group, a monovalent cycloaliphatic group, a monovalent group combining an aromatic group and an aliphatic group, or those groups are a halogen atom, a nitro group, an amino group, or a cyano group. , a group substituted with a methoxy group or an acetoxy group) at 50° C. or lower to form a compound represented by the general formula (3); (wherein R1, R2, R7, and R8 are the same as above) The present invention relates to a method for producing an amphoteric polyimide precursor having a repeating unit represented by:

The amphoteric polyimide precursor of the present invention has a repeating unit represented by the general formula (1) and has a number average molecular weight of 2.000.
~300,000, preferably 10°000-150.
000. Number average molecular weight is 2.000-30
If it is out of the range of 0.000, there is a tendency that the strength of the film produced is too low or the viscosity is too high, making it difficult to produce the film.

R1 in the general formula (1) is a tetravalent group containing at least 2 carbon atoms, preferably 5 to 20 carbon atoms, and may be an aromatic group, or a cycloaliphatic group. It may be a group in which an aromatic group and an aliphatic group are bonded, and furthermore, these groups may be an aliphatic group having 1 to 30 carbon atoms or a cycloaliphatic group. Or a group in which an aromatic group and an aliphatic group are bonded together, or these groups are monovalent groups such as a halogen atom, a nitro group, an amino group, a cyano group, a methoxy group, or an acetoxy group; The group is -0+, -coo +, -NHCO-, -CO
+.

It may also be a group substituted with a group bonded to -5-, -CSS +, -NHC5-, -CS-, etc. to form a derivative. However, it is preferable from the viewpoint of stability, heat resistance, chemical resistance, mechanical properties, etc. that R1 is a group characterized by benzenoid unsaturation having at least 6 carbon atoms.

Specific examples of R1 as described above include, for example. Furthermore, the term "benzenoid unsaturation" as used herein is a term used in contrast to a quinoid structure regarding the structure of a carbocyclic compound, and refers to a structure having the same shape as a carbocyclic ring contained in ordinary aromatic compounds.

There are no particular limitations on the positions of the four bonds of R1, that is, the positions of the bonds in the repeating unit represented by general formula (1), but two of each of the four bonds are adjacent to each other constituting R1. In the case where the carbon atoms are present in two carbon atoms, it is preferable because it prevents the formation of a five-membered ring when polyimidizing a film formed using an amphoteric polyimide precursor.

Preferred specific examples of R1 as described above include examples. Again preferred.

R2 in the general formula (11) is a divalent group containing at least two carbon atoms, and may be an aromatic group, an aliphatic group, or a cycloaliphatic group. It may be a group in which an aromatic group and an aliphatic group are combined, and furthermore, these divalent groups may have a carbon number of 1 to 3.
0 aliphatic group, a cycloaliphatic group, or a group in which an aromatic group and an aliphatic group are bonded, and these groups are halogen atoms, nitro groups, amino groups, cyano groups, methoxy groups, acetoxy groups, etc. or these monovalent groups are -0-, -Coo-, -NIICO-, -Co-.

It may be a group substituted with a group bonded to -S-, -CSS-, -NHC3-, -CS-, etc. but,
When R2 is a group characterized by benzenoid unsaturation having at least 6 carbon atoms, it is preferable from the viewpoint of heat resistance, chemical resistance, mechanical properties, etc.

As a specific example of R2 as mentioned above, Here R9 is (,83 F3 -C-, -0-, -Co-, -3-, -5Oz-.

R11 and R11 are both alkyl or aryl groups having 1 to 30 carbon atoms 'C)+3 83 L; t! 2 H3 (C)+2)P-(p=2~10), -(
C)+2)4=C-(CHz)z″″″.

C8H6Ca　Hs n=2-15 etc.

As a preferable specific example of R2 as described above, for example, (in the formula, R9 is 1C1 (ffr (m = integer of 1 to 3)).

−S −, −5O2+, −NR”−.

Examples of R11 and R11 include alkyl or aryl groups having 1 to 30 carbon atoms.

In general formula (1), R3, R4, R5 and R6 are all monovalent aliphatic groups having 1 to 30 carbon atoms, preferably 1 to 22 carbon atoms, monovalent cycloaliphatic groups, and aromatic groups. and an aliphatic group, a group in which these groups are substituted with a halogen atom, a nitro group, an amino group, a cyano group, a methoxy group, an acetoxy group, etc. to become a derivative of those groups, or It is a hydrogen atom. In addition, in general formula +1), R3, R4, R5 and R6 all impart hydrophobicity to the polyamic acid unit represented by general formula (8): (wherein R1 and R2 are the same as above) and are stable. It is a group introduced to obtain a condensed film, and one of R3, R4, R5, R6 is not the above-mentioned group having 1 to 11 carbon atoms, preferably 1 to 15 carbon atoms, or a hydrogen atom. A stable condensate film is formed on top, which is necessary in order to be deposited on the substrate by the LB method.

Specific examples of R3, R4, R5, and R6 other than hydrogen atoms include, for example, C)+3(CH2Miya Ryo, (CH3)2CH(CH
Examples include 2 pieces of 1 (n is 12 to 30, preferably 16 to 22). However, in order to achieve the purpose of the present invention, it is most desirable to use a straight chain alkyl group represented by "CH3(C)127Fi'Ti" in terms of performance and cost. atom,
Nitro groups, amino groups, cyano groups, methoxy groups, acetoxy groups, etc. are not essential. However, since fluorine atoms dramatically improve hydrophobicity compared to hydrogen atoms, it is preferable to use one containing fluorine atoms.

Specific examples of the repeating unit of the amphoteric polyimide precursor of the present invention in which three of R3, R4, R5, and R6 are hydrogen atoms include general formula (2): (wherein, R1, R2, R3, R4 is the same as above, but R3 or R4 is not a group having 1 to 11 carbon atoms or a hydrogen atom), or a repeating unit represented by general formula (3)
(In the formula, R1, R2, R5, and R6 are the same as above, but R5 or R6 is not a group having 1 to 11 carbon atoms or a hydrogen atom.) When the repeating unit of the amphoteric polyimide precursor of the present invention is represented by general formula (2) or general formula (3),
This is preferable because it is easy to manufacture and inexpensive.

Specific examples of the amphoteric polyimide precursor of the present invention having repeating units represented by general formulas (1) to (3) include (specific examples of R3 in the formula: C)13(CH2) 1l-1CH3 (CH2) 13
-1CH3(CH2) ts -1CH3(CH2)
17-1CH3(CH2) ts-1CH3(CH2)
Specific examples of R such as 21-1CF3(CH2) ts- include H, CH3゜CH3CH2, CH3(CH2
) 2 etc.) (Specific examples of R5 in the formula are: CH3(CH2) u-1CH3(CHz) 13-1
CH3(C412) 15-1CH3(CH2) 5r
-1CH3(CH2) ts-1CH3(CH2) 2
1-1CF3(CH2) xi-, etc., R7) Specific examples include HlC)13tC)13CH2,CH3(CH
2) z etc.) (Specific examples of R3 in the formula are: CH3(CHz) 1l-5CH3(CH2) 13-
1CH3(CH2) R5-1CHa(C1lz) I
T-1CH3(CH2) ts -1CH3(CI+2
) 21-1CF3(CH2) 15-), specific examples of R include H1CH3-1CH3(CH2) 2-
1CH3(C112) a -1CH3(CH2)5-
etc.), (Specific examples of R3 in the formula are: CH3(CH2) 1l-1CH3(CH2) 13-
1CH3(CH2) ts -1CH3(CH2) 1
7-1CH3(CH2) ts-1CH3(C)lz)
Specific examples of R include 'L CH3-, such as 21-1CF3(CH2) 15-.

Examples include those containing repeating units such as CHa(CH2) -, CH3(C)12) 2-, etc.).

In the formula, - represents isomerism. For example, If you explain it with and represents.

The present invention provides (a), (when bl is alone, (al,
(Including cases where bl coexists.

It will be described below that the amphoteric polyimide precursor having a repeating unit represented by the general formula +11 includes various copolymers.

In general formula T1), R1, R2, R3, R4, R5
, R6 is at least one of the previously listed R1. R2
, R3, R4°, R5, R8, various copolymers are provided.

For example, when two types are selected as R1, X and V represent the ratio, and O<x<1. Q<y<lx+y
=1. (The same applies hereafter) etc. The above example is just an example, and R3゜R4
, R5, and R6 have been described several times in the previous explanation.

The amphoteric polyimide precursor of the present invention as described above is generally easily soluble in organic polar solvents such as N,N-dimethylacetamide, N,N-dimethylformamide, N,N-diethylformamide, and hexamethylphosphoramide; Soluble in mixed solvents such as polar solvents and ordinary organic solvents such as chloroform, slightly soluble to insoluble in ordinary organic solvents such as benzene, ether, chloroform, acetone, methanol, etc. Infrared absorption spectrometry shows that amide, carboxylic acid ( In some cases there are characteristic absorptions of carboxylic acid esters) and long-chain alkyl groups. Thermal analysis results also have characteristics, with a rapid decrease in Chongjin starting at about 200°C and ending at about 400°C. After completion, amide,
The absorption of carboxylic acids (carboxylic acid esters in some cases) and long-chain alkyl groups disappears, and the absorption of imide rings appears.

In the above explanation, all the repeating units of the precursor of the present invention are repeating units represented by the general formula (11), but among the repeating units (in the formula, R1, R
2 is the same as above, R is a monovalent aliphatic group having 1 to 11 carbon atoms, a monovalent cycloaliphatic group, a monovalent group in which an aromatic group and an aliphatic group are bonded; is a group substituted with a halogen atom, a nitro group, an amino group, a cyano group, a methoxy group, an acetoxy group, etc., or a hydrogen atom, and four R
may be the same or different).

Next, a method for producing the precursor of the present invention will be explained.

The precursor of the present invention having a repeating unit represented by the general formula (1) is first prepared by adding I? General formula (5) obtained by reacting 30H and R40H (R3 and R4 are the same as above)
: (wherein R1, R3, R4 are the same as above) is prepared, and -1 is prepared in a substantially anhydrous polar organic solvent.
It is made into an acid halide using thionyl chloride, phosphorus pentachloride, benzenesulfonyl chloride, etc. at 0°C or higher, preferably about θ to 40°C, and then the general formula (6): % formula % (61 (in the formula, R2, R5, When reacting a compound represented by (R6 is the same as above), the temperature is -10°C or higher, preferably 0 to 10°C.
The reaction is carried out at +10℃, but in order to complete the reaction, 2
The reaction may be carried out at 0°C or higher.

Even if the compound represented by the general formula (6) is added to the acid halide of the general formula (5), or vice versa, the acid halide of the general formula (5) is added to the compound represented by the general formula (6). You may.

When synthesizing the precursors of the present invention, it may be necessary to use reaction temperatures other than those described above.

That is, when R5 or R6 is not the above-mentioned group having 1 to 11 carbon atoms or a hydrogen atom, in order to react the compound represented by general formula (6) in a homogeneous system,
A method is adopted in which an acid halide of general formula (5) is added to a solution at 60°C.

Specific examples of the compound represented by the general formula (4) include υ υ and the like.

Further, as specific examples of R30H and R40H, for example, CH30H, CH3CH20H, CH3(CH2)
20H.

CH3(CH2)30H, CH3(CH2)50H, C
H3(C112)70H.

CH3(CH2) 90H, CH3(CH2) llOH
,CH3(CH2)tsOH.

CH3(C1,) tsOH,C113(CH2)!
70H, CH3(CH2)tsOH.

CH3(CH2) 210H, CH3(CH2) 2:
IOH, CF3(CH2) tsOH.

'd (CF2)2(CH2) +50)1. H(
CF2)4(C)12) 1308°F(CF2)8
(CH2)20H,F(CF2)II (CHz)+0
11゜Tetracarboxylic dianhydride represented by general formula (4) and l? There are no particular limitations on the reaction conditions for producing the compound represented by the general formula (5) from 30H and R40H; for example, it can be obtained by continuing stirring for several hours at about 100°C under a nitrogen stream. , in a solvent such as hexamethylphosphoramide, and continued stirring at room temperature for about 4 days may be employed.

The reaction time is shortened by heating at about 100° C. for 3 hours with stirring under a nitrogen stream, followed by dissolving into hexamethylphosphoramide and subsequent acid halide formation. That is, it is preferable from the viewpoint of improving productivity.

Specific examples of polar solvents used in the acid halide conversion include hexamethylphosphoramide, N,N-dimethylacetamide, N,N-dimethylformamide, etc. In other words, thionyl chloride, phosphorus pentachloride, benzenesulfonyl chloride, etc. used in the acid halide reaction are not decomposed, and the acid halide reaction is carried out in a nearly quantitative manner.

If the temperature during acid halide conversion is less than -10°C, the reaction becomes heterogeneous due to freezing and solidification due to the influence of long-chain alkyl groups, which is undesirable. It has become clear that it can be used without any particular limitations up to the temperature. Usually O~4
The temperature is preferably about 0°C.

The acid halide produced in this way has the general formula (
The compound represented by 6) is reacted to produce the precursor of the present invention.

The acid halide used in this case is preferably used as it is after being produced in terms of workability and the like.

Furthermore, when reacting a nucleic acid halide with a compound represented by general formula (6), R3.
Since both reactants and products tend to freeze and solidify due to R4, Rj R6, etc., N, N
A solvent such as -dimethylacetamide or N,N-dimethylformamide is generally used, and the reaction temperature is -10°C to +20°C.

If the salinity of the reaction is less than 110°C, which is preferably 0 to +10°C, the reaction becomes heterogeneous due to freezing and solidification, and the temperature is +2
If the temperature exceeds 0°C, undesirable reactions are likely to occur, and both are unfavorable. However, it has become clear that in order to complete the reaction and conduct the reaction in a homogeneous manner until completion, it is preferable to continue the reaction at a temperature of 20° C. or higher after addition.

Specific examples of the compound represented by the general formula (6) include:
For example, (as a specific example of R5 or R6 in the formula, CH3-
9CH3C)12 + CR3(C)12)2-
9CR3(CR2)3 +CH3(CH2)5-,
CH3(CH2) u −, CH3(CH2) +3
-+CHs (CHz) ts -, CH3 (CH2)
17−, CH3(CH2) 1s −+CH3(C
)12) 21-, C)13(C)+2) n-,
CF3(C)12) 15-.

H(CF2)z (C)(2) 15 −,
H(CF2)4 (CH2) +3-1F(CF2)
II (CH2)2-, F(CF2)II (C
H2) 4-, etc.).

The reaction ratio between the acid halide and the compound represented by general formula (6) may be appropriately selected in order to obtain a desired molecular weight of the precursor of the present invention, but it is usually When producing acids, stoichiometrically purified monomers and purified solvents are used to obtain high molecular weight products.

However, it has been found that when accumulated on a substrate like the precursor of the present invention, sufficient properties can be exhibited even if the precursor does not necessarily have a high molecular weight, and the molar ratio may deviate from stoichiometry. It has become clear that there is no problem with a value of about 110.8 to 1/1.2.

R3 or R of R3011 and R40H reacted with the tetracarboxylic diacid anhydride represented by the general formula (4)
When 4 is not a group having 1 to 11 carbon atoms or a hydrogen atom, R5 and R6 of the compound represented by general formula (6)
may all be hydrogen atoms (in this case, the precursor of the present invention having a repeating unit represented by the general formula (2) is obtained.

When both R5 and R6 of the compound represented by the general formula (6) are hydrogen atoms, the reactivity is good and the raw material cost is low, which is preferable. In addition, the resulting precursor is thermally stable because the carboxylic acid is an ester, and the isolation and drying operation prevents the reaction from proceeding, so it can be separated as a solid powder, and this makes it easy to purify. Become what you have.

Although the precursor of the present invention is produced by the method described above, when R3 and R4 of the repeating unit represented by the general formula (il) are both hydrogen atoms, the precursor of the present invention can be produced without using the method described above. Directly reacting the tetracarboxylic acid dianhydride represented by the general formula (4) with a compound represented by the general formula (7); % formula %) (wherein R7 and R8 are the same as above) In this manner, a precursor of the present invention having a repeating unit represented by general formula (3) is obtained.

Of course, the compound represented by general formula (7) may be added to the tetracarboxylic acid dianhydride represented by general formula (4), or vice versa, the compound represented by general formula (7) may be added to Formula (4
) The precursor of the present invention can also be obtained by adding a tetracarboxylic diacid anhydride represented by:

Specific examples of the compound represented by the general formula (7) are:
For example, N)lR8 (Specific examples of R7 or R8 in the above formula include CH
3 (CHz) n-1- (n = 12 to 30), CF3
(CH2) 15-1H(CF2)2 (CH2) 1
5-1 H(CF2)4 (CH2) 13-1H(
CF2)8 (CH2)2-1H(CF2)8 (C
R2)4-, etc.).

The conditions for reacting the tetracarboxylic diacid anhydride represented by the general formula (4) with the compound represented by the general formula (7) are almost the same as those for producing ordinary polyamic acid. Often, for example, N,N-dimethylacetamide, N
, in a substantially anhydrous organic polar solvent such as N-dimethylformamide at a reaction temperature of 50°C or less, preferably at room temperature,
Tetracarboxylic diacid anhydride 1 represented by general formula (4)
The amount of the compound represented by general formula (7) per mole is 0.8 to
The reaction was carried out using 1.2 mol. In this case as well, the precursor of the present invention can exhibit sufficient properties even if it deviates from the stoichiometry.

The precursor of the present invention having a repeating unit represented by the general formula (3) obtained in this way is not only easy to manufacture, but also has the characteristics that it can be formed into a film by the LB method and forms polyimide by heating. It has the following.

Next, an LB film using the precursor of the present invention will be explained.

The method for manufacturing LB155 using the precursor of the present invention is to spread the precursor on the water surface, compress it with a constant surface pressure to form a monomolecular film, and transfer the film onto a substrate. In addition to certain LB methods, methods such as horizontal attachment method and rotating cylinder method (
New Experimental Chemistry Course Volume 13, Interfaces and Colloids, 498-5
(page 08), and any commonly used method can be used without particular limitation.

Generally, when a substance that forms an LB film is spread on the water surface, benzene is not dissolved in water and evaporates into the gas phase.
A solvent such as chloroform is used, but in the case of the precursor of the present invention, it is desirable to use an organic polar solvent in combination to increase solubility. Examples of such organic polar solvents include N,N-dimethylformamide, N,N-
Dimethylacetamide, N,N-diethylformamide, N,N-diethylacetamide, N,N-dimethylmethoxyacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, pyridine, dimethylsulfone, hexamethylphosphoramide, tetramethylenesulfone ,
Examples include dimethyltetramethylene sulfone.

When benzene, chloroform, etc. are used together with an organic polar solvent, it is thought that when developed on the water surface, the benzene, chloroform, etc. will evaporate into the gas phase, and the organic polar solvent will dissolve in a large amount of water.

There is no particular limitation on the concentration of the solution used when spreading the precursor of the present invention on the water surface, but usually about 2 to 5XIO-3M is used.

The substrate on which the LB film using the precursor of the present invention is formed is not particularly limited, and may be selected depending on the purpose of the formed LB film, but when the LB film is heated and used as a polyimide, It is necessary to have good heat resistance.

Specific examples of the above-mentioned substrates include inorganic substrates such as glass, alumina, and quartz, as well as metal and plastic substrates, as well as group Ⅰ, m-v group, such as Si, GaAs, and ZnS. Semiconductors such as II-Vl group, Pb
TiQs, BaTiO3, LiMbOa, LiTa0a
Examples include ferroelectric substrates and magnetic substrates such as . Of course, these substrates may be used after being subjected to a commonly used surface treatment.

By using the precursor of the present invention, a thin film with few defects and good heat resistance can be formed on a substrate by the LB method, and furthermore, by partially or completely imidizing this thin film, the heat resistance can be further improved. Excellent thin films can be obtained.

There is no particular limitation on the imidization method, but 300~
Heating is generally performed at a temperature of around 400° C., and laser light or the like may also be used.

For example, in the case of a repeating unit represented by general formula (2), the following reaction occurs, and in the case of a repeating unit represented by general formula (3), the following reaction occurs to form a polyimide. Of course, in the case of the polyamic acid unit represented by general formula (8), HzO
is produced and becomes a polyimide, but in this case, LB
It cannot be used as a material for membranes.

Since the precursor of the present invention has improved heat resistance and chemical resistance than ordinary LB films, the LBl! J can also be used as is for applications such as devices.

The polyimide thin film obtained as mentioned above has heat resistance,
Excellent chemical resistance, good mechanical properties, and 100%
It is a very thin film of 0.08 or less, and if desired, 10~
It could be up to 1,000 people. Therefore, it can be used in the electronics field not only as an insulating film for ICs and LSIs, but also as an insulating layer in various electrical and electronic devices with structures such as capacitors, MIS, and MIM. It can be used for a change element, a light receiving element, a light emitting element, a photodetecting element, a thermionic transistor, etc. J.J.
(Josephson Junction) can also be considered. In addition, it can be used as a cladding material for unibu guides, an optical circuit component, etc., and can also be suitably used as a coating material, including for protection. It can also be used in fields such as energy conversion and material separation.

Next, the precursor of the present invention and its manufacturing method will be explained based on Examples.

Example 1 2.18 g (0.01 mol) of pyromellitic dianhydride and 2.70 g (0.01 mol) of stearyl alcohol were reacted in a flask at about 100°C for 3 hours under dry nitrogen flow. I let it happen.

The obtained reaction product was added to 40 cc of hexamethylphosphoramide.
Thionyl chloride was dissolved in 1. and cooled to 0-5°C.
19 g was added dropwise at about 5°C, and after the dropwise addition, the temperature was maintained at about 5°C for 1 hour to complete the reaction.

After that, 2 g (0.01 mol) of diaminodiphenyl ether dissolved in 50 cc of dimethylacetamide was added to
The mixture was added dropwise at 5° C., and after reacting for about 1 hour, the reaction solution was poured into 600 cc of distilled water to precipitate a reaction product. The precipitate was filtered and dried under reduced pressure at about 40°C to obtain about 6 g of pale yellow powder.

The obtained powder was subjected to IR spectrum analysis and molecular weight measurement by GPC.

IR spectrum analysis The IR spectrum shows characteristic absorptions of esters, carboxylic acids, amide I absorption bands, ① absorption bands, ③ absorption bands, alkyl chains, and ethers.

Molecular weight determination by CPC GPC determined in N,N-dimethylacetamide solvent
The number average molecular weight calculated by comparing the results with polystyrene standard samples was about 3o, ooo.

Example 2 Chloroform/distilled product of Example 1 55.1
A developing solution for LB membrane was prepared by dissolving it in a mixed solution of dimethylacetamide = 8/2 (volume ratio) to make a 25-volume solution.

Using the obtained developing solution, the surface pressure was maintained at 25 dyne/cta at 20°C over double-distilled water at a cumulative speed of 10 m-
1 on an aluminum vapor-deposited glass substrate using the LB method at
Five layers were accumulated.

It was confirmed from the area-time curve that it was a Y-type film.

Claims (9)

[Claims] (1) General formula (1): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (1) (In the formula, R^1 is a tetravalent group containing at least 2 carbon atoms, R^2 is at least 2 R^3, R^4, R^5 and R^6 are all monovalent aliphatic groups having 1 to 30 carbon atoms, monovalent cycloaliphatic A monovalent group in which a group group or an aromatic group and an aliphatic group are bonded, a group in which these groups are substituted with a halogen atom, a nitro group, an amino group, a cyano group, a methoxy group, an acetoxy group, or hydrogen It is an atom, R^3, R^4, R
An amphoteric polyimide precursor having a repeating unit in which one of ^5 and R^6 is not the above group having 1 to 11 carbon atoms or a hydrogen atom. (2) R^3, R^4, R^5 and R^6 are all the above-mentioned monovalent groups having 1 to 22 carbon atoms or hydrogen atoms, and R^3, R^4, R^ The precursor according to claim 1, wherein one of 5 and R^6 is not a group having 1 to 15 carbon atoms or a hydrogen atom. (3) Claim 1 in which either one or both of R^1 and R^2 is a group characterized by benzenoid unsaturation having at least 6 carbon atoms.
Precursors described in Section. (4) R^3OCO-, R^4O bonded to R^1
CO-, -NR^5-CO- and -CO-NR^6-
Claim 1, wherein two of each of the four groups R^2 are bonded to two adjacent carbon atoms constituting R^1 so as to form a five-membered ring. precursor of. (5) The repeating unit represented by the general formula (1) is the general formula (2
): ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (2) (In the formula, R^1, R^2, R^3, R^4 are the same as above, but R^3 or R^4 is a carbon atom Claim 1 which is not a group of numbers 1 to 11 or a hydrogen atom)
Precursors described in Section. (6) The repeating unit represented by the general formula (1) is the general formula (3
): ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (3) (In the formula, R^1, R^2, R^5, R^6 are the same as above, but R^5 or R^6 is a carbon atom Claim 1 which is not a group of numbers 1 to 11 or a hydrogen atom)
Precursors described in Section. (7) General formula (4): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (4) Represented by (in the formula, R^1 is a tetravalent group containing at least 2 carbon atoms) R^3OH and R^4OH (in the formula, R^3 and R^4 are both monovalent aliphatic groups having 1 to 30 carbon atoms, monovalent cyclic aliphatic groups, group, a monovalent group combining an aromatic group and an aliphatic group, a group in which these groups are substituted with a halogen atom, a nitro group, an amino group, a cyano group, a methoxy group, an acetoxy group, or hydrogen General formula (5) obtained by reacting atoms): ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (5) (In the formula, R^1, R^3, R^4 are the same as above). The represented compound was prepared in a substantially anhydrous polar organic solvent at -10
℃ or higher to form an acid halide, and form this with the general formula (6): R^5
-NH-R^2-NH-R^6 (6) (wherein R^2 is a divalent group containing at least 2 carbon atoms, R^5
and R^6 are the same as the groups defined by R^3 and R^4) are reacted at -10°C or higher to form the general formula (1): ▲Mathematical formula, chemical formula, table, etc. Yes▼(1) (In the formula, R^1, R^2, R^3, R^4, R^5, R
^6 is the same as above, R^3, R^4, R^5, R
A method for producing an amphoteric polyimide precursor having a repeating unit in which one of ^6 is not a group having 1 to 11 carbon atoms or a hydrogen atom. (8) R^5 and R of the compound represented by general formula (6)
The method according to claim 7, wherein all ^6 are hydrogen atoms. (9) General formula (4): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (4) Represented by (in the formula, R^1 is a tetravalent group containing at least 2 carbon atoms) Tetracarboxylic dianhydride and general formula (7): R^7-NH-R^2-NH-R^8 (7) (wherein, R
^2 is a divalent group containing at least 2 carbon atoms,
R^7 or R^8 is a monovalent aliphatic group having 12 to 30 carbon atoms, a monovalent cycloaliphatic group, a monovalent group combining an aromatic group and an aliphatic group, or a group in which those groups are substituted with a halogen atom, a nitro group, an amino group, a cyano group, a methoxy group, or an acetoxy group) is reacted at 50° C. or lower to form the general formula (3): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(3) (In the formula, R^1, R^2, R^7, R^8 are the same as above) An amphoteric polyimide precursor having a repeating unit How to manufacture.