JPS63113019A - Copolymer polyamic acid salt and production thereof - Google Patents

Abstract

PURPOSE:To obtain the titled copolymer providing langmuir Blodgett film having excellent heat resistance, electrical characteristics and chemical resistance, by reacting tetracarboxylic acid dianhydride with a specific diamine to give a polyamic acid and reacting the polyamic acid with a tertiary amine. CONSTITUTION:A tetracarboxylic acid dianhydride shown by formula I (R<1> is tetrafunctional group containing at least 2C) is reacted with a compound shown by formula II (R<2> is bifunctional group containing at least 2C; R<5> and R<6> are 1-30C monofunctional alicyclic, cycloaliphatic or aromatic) at -10-+50 deg.C to give a polyamic acid shown by formula III. Then the polyamic acid is reacted with a compound shown by formula IV (R<31>, R<32> and R<33> are as shown for R<5> and R<6>) and a compound shown by formula V (R<41>, R<42> and R<43> are as shown for R<5> and R<6>) to give the aimed polymer salt shown by formula VI.

Description

Detailed Description of the Invention The present invention is an amphoteric polyimide precursor, more specifically 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 its manufacturing method.

’ no ’・
In the 1930s, Langmuir and Prodgett discovered that fatty acids with about 16 to 22 carbon atoms could form a monomolecular film on the water surface and accumulate it on a substrate. Consideration has only recently begun. However, Langmuir-Prodgett membranes (hereinafter referred to as LB membranes) made 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.

In order to improve these problems, for example, monomers formed from unsaturated fatty acids such as ω-tricosenoic acid, ω-hebutadecenoic acid or α-octadecyl acrylic acid, or unsaturated fatty acid esters such as vinyl stearate and octadecyl acrylate, etc. Polymerized membranes are being researched, but their heat resistance is not sufficient.

On the other hand, there is a polyimide film as a heat-resistant film, but when using methods such as spin cord, a film thickness of at most 1000 Å or more, usually IP or more, can be obtained, and a film thickness of less than 1000 Å without pinholes can be obtained. Heat resistance N
Membranes are extremely difficult to make.

The present invention features LBlI!, which has improved mechanical properties such as heat resistance and adhesive strength, and chemical resistance. The purpose was to obtain a material that could provide a heat-resistant ultra-thin film material.

. 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. R1 is a tetravalent group containing at least 2 carbon atoms, R2 is a divalent group containing at least 2 carbon atoms, ♂, R''
, R", R'l, furnace, ♂3. R5 and R6 are both aliphatic, cycloaliphatic, or aromatic (these may be combined with each other) monovalent group having 1 to 30 carbon atoms. (These groups may be substituted with a halogen atom, nitro group, amino group, cyano group, methoxy group, acetoxy group) or a hydrogen atom, preferably -2R'',
A copolymerized polyamic acid salt having a repeating unit represented by R'l, R', R'3゜R5 and R6, at least one, preferably two of which are the above-mentioned groups having 12 to 30 carbon atoms. , and general formula (2): (wherein, R1 is the same as the definition of general formula (1) above), general formula (3): % formula % (31 (formula Among them, R2, R5 and R6 all represent the general formula (
A compound represented by (same as the group defined in 1))
General formula (4) obtained by reaction at 0 to 50°C, preferably 0 to 40°C: (wherein, R1, R2, RlI, and R6 are
) is the same as the definition of general formula (1) above). General formula (101) obtained by reacting
, R'', R'', R'o, and R6 are all defined as in the general formula (1) above, and are also selected. ) and a method for producing a copolymerized polyamic acid salt having a repeating unit represented by the general formula (2
) At least two types of tetracarboxylic dianhydrides represented by the formula (3) are added with a compound represented by the general formula (3) at -10"C or more and 50'C or less, preferably 0 to 50"C. General formula (5) obtained by reaction at 40'C
): (In the formula, R2, R5, R6 are the same as the definition of the above general formula +11, RA and R crystal are the same as the definition of R1 of the above general formula (11), x and y represent the ratio, and 0<x <l, Q<1, 0<
y<1, x+y=1) (wherein, R", FP, R", R'l, R',
General formula (102') obtained by reacting (R' is the same as the definition of general formula (1) above): % formula %) (in the formula, RJI, R1R2, R", R", R",
R41, R', R''.

R5, R', x and y all represent the above general formula +1
) and (same as the definitions in (5)), and a method for producing a copolymerized polyamic acid salt having repeating units represented by the general formula (2): (
3): At least two of the compounds represented by the formula % are heated at 10°C or higher, 5
General formula (6) obtained by reaction at 0°C or lower, preferably 0 to 40°C: Same as the definition of R2 in formula (1), x and y represent ratios, O<x<l, Q<y<1.
X + y = 1) to a polyamic acid having a repeating unit position represented by
General formula (103) obtained by reacting (all 3 are the same as above): (wherein, R1, RA, Ri, R''
, R", R", R'l, R', R'.

R', R', x and y all represent the above general formula +
The present invention relates to a method for producing a copolymerized polyamic acid salt having a repeating unit represented by (same as the definitions in 11 and (6)).

〔Example〕

The copolymerized polyamic acid salt of the present invention has the general formula (1)
: The number average molecular weight having a repeating unit represented by is 2.0
00-300,000, preferably 10°000-15
It is of 0.000. Number average molecular weight is 2.000~
If the number deviates from the range of 300,000, the strength of the film produced will tend to be too low or the viscosity will be 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 (such as cycloaliphatic It may be a group group or an aliphatic group,
These groups may be a combination of these groups, and furthermore, these tetravalent groups may be aliphatic, cycloaliphatic, or aromatic (these may be combined with each other) having 1 to 1 carbon atoms. It may be a group substituted with 30 monovalent groups (these monovalent groups may be substituted with a halogen atom, a nitro group, an amino group, a cyano group, a methoxy group, an acetoxy group, etc.) , or these tetravalent groups are -0+,
-coo-, -NIICO-, -Co-.

-S -, -css +, -NHC3+, -c
It may be a group containing s-, -3Oz-, etc., but if R1 is a group characterized by benzenoid unsaturation having at least 6 carbon atoms, heat resistance, chemical resistance It is preferable in terms of properties, mechanical properties, etc.

Specific examples of R1 as described above include, for example.

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.

p-quinoid structure There are no particular limitations on the positions of the four bonds of penzenoid unsaturated R1, that is, the positions of the bonds in the repeating unit represented by general formula (1), but each of the four bonds It is preferable that each of these carbon atoms exist in two adjacent carbon atoms constituting R1, because it is easy to form a 5-membered ring when polyimidizing a film formed using an amphoteric polyimide precursor, and it is easy to imidize. .

Preferred specific examples of R1 as described above include, for example, Examples include. Also is also preferable.

R2 in general formula +1) is a divalent group containing at least two carbon atoms, and may be an aromatic group, an aliphatic group, or a cycloaliphatic group. Furthermore, these divalent groups may be aliphatic groups having 1 to 30 carbon atoms, cycloaliphatic groups, or aromatic groups (these groups may not be combined with each other). monovalent groups having 1 to 30 carbon atoms (which may be substituted with halogen atoms, nitro groups, amino groups, cyano groups, methoxy groups, acetoxy groups, etc.) ), or these divalent groups may be -o-, -coo-.

-NIICO-, -CO-, -5+, -css-,
-NHCS-.

It may also be a group containing -C8- or the like. However, R2
is a group characterized by benzenoid unsaturation having at least 6 carbon atoms, which is preferable from the viewpoint of heat resistance, chemical resistance, mechanical properties, etc.

As a specific example of R2 as mentioned above, R9 is − (CH2)Il+ −(m=an integer of 4 to 3), −C
−.

t13 F3 -C-; -0-, -Co-, -3-, -5O2+
.

F3 (R16 and R11 are both alkyl or aryl groups having 1 to 30 carbon atoms) CH3-based CH3CN2 CH3 CH30 -(C)12)3-0- (C)+2)2-0- (C
H2) 3-.

(n=2-15) Preferred specific examples of R2 as described above include, for example: (wherein R9 is the same as defined above), and the like.

PSR” in general formula (1), furnace, R11, bleaching, RI
2, R5 and R6 are all monovalent groups having 1 to 30 carbon atoms, preferably 1 to 22 carbon atoms, aliphatic, cycloaliphatic, aromatic (these may be combined with each other); The monovalent group is )) or a hydrogen atom (which may be substituted with a λ rogen atom, a nitro group, an amino group, a cyano group, a methoxy group, an acetoxy group, etc.).

The aforementioned Gotoki P, W, R33, R41, Ru, R
Specific examples of 43, R5 and R6 are H-, CH3 (CHz'Fr (n=1 to 30).

(CHs)zcH (CHz Takumi Takumi (n = 3-30)
.

(Cl13) 3C(C)lz rough τ, (n = 4~3
0).

CF3 (CHz%i; (n = 1-30)
.

In general formula (1), -, R", R", R'l
, R42, R43, 'R5 and R6 all impart hydrophobicity to the polyamic acid unit represented by the general formula (7): (wherein R'%R2 is the same as above) and form a stable condensed film. The obtained rutamenyl group is introduced, R'', R12,R
13, R”.

f, at least one, preferably two of R43, R5, R6 have 12 to 30 carbon atoms, preferably 16
~30 of the aforementioned groups are necessary for the formation of a stable condensed film on the water surface, which is deposited on the substrate by the LB method. Also, these two are door, P, review, R'l
, R', -, R", R",
For stability of the film on the water surface, it is desirable to select one from R'' and one from R'l, R', and R'3.

Two of the above-mentioned preferred -, FP, P, R4
Specific examples of 1° furnace, furnace, R5, R8 other than hydrogen atoms include CH3(CH2i″T′:X, (CH3)2CH
(CH2 charge).

(The above n values are all 12 to 30, preferably 16 to 2.
2) etc. However, in order to achieve the purpose of the present invention, it is most desirable in terms of performance and cost to use a straight chain alkyl group represented by C) 13 (CH2). , nitro group, amino group, cyano group, methoxy group, acetoxy group, etc. are not essential. However, fluorine atoms dramatically improve hydrophobicity compared to hydrogen atoms, so it is recommended to use those containing fluorine atoms. preferable.

A desirable embodiment of the copolymerized polyamic acid salt of the present invention is a salt having a repeating unit represented by the general formula (101''), and further a salt having a repeating unit represented by the general formula (102): It is a salt having a unit, and further a salt having a repeating unit represented by the general formula (103): % formula %).

A further desirable embodiment is general formula (101).

(102''), (103) where R5 and R6 are hydrogen atoms, and general formula (104),
(105).

% formula %): It is a salt having a repeating unit represented by: When the repeating unit of the copolymerized polyamic acid salt of the present invention has the general formula %, it is preferable from the viewpoints of easy production and low cost.

Specific examples of the amphoteric polyimide precursor of the present invention having repeating units represented by general formulas (104) to (106) include general formulas (107), (108), and (109).
): (In the formula + R"+ R"+ ?I, %, F
Specific examples include ■-1C113, C2)15-1C
+Hv-1CH3(CH2) n-1CH3(Clf
z) 13-1CH3(CH2) 15-1CI+3(
C112)! ? -1CH3(CH2) ts-1CH
3(C1lz) 2l-1CF3(CI+2) +s
-, etc. (108') Specific examples of r, FP, furnace + R41+ 4, - in the formula are 1t, C113, C2H5-, C3)1y
-, C1st 3 (CH2) 11 -, CH3 (C
Hz) low, CH3 (CI+2) 15-1CH3 (C
112) IT-1CI+3(CH2) 59-1CI
+3 (CH2) 2l-1CF3 (CI+2) 15-
etc., X+ 'l represents the ratio, 0<x<1.9<y<
1, x+y=1.

Specific examples of -, P, P, R11,y, RU in the formula include H-1CHs, C2H5-1C3HT-5
CHa(C1lz) u -1CH3(CH2) 13
-1CH3(CHz) 15-1CH3(CH2) 1
7-1CI3(CH2) ts-1Cf13(CHz)
2l-1CF3(CH2) 15-, etc., where x and y represent the ratio, and O<x<1. Q<y<1, x+y=1.

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

In the present invention, when (al, (b) is alone, (al,
This includes cases where (b) coexists.

The amphoteric polyimide precursor of the present invention as described above has -a readily soluble in an organic polar solvent such as N,N-dimethylacetamide, N,N-dimethylformamide, N,N-diethylformamide, hexamethylphosphoramide, It is soluble in mixed solvents such as the above organic polar solvents and ordinary organic solvents such as chloroform. It is sparingly soluble to insoluble in ordinary organic solvents such as benzene, ether, chloroform, acetone, and methanol. Infrared absorption spectroscopy reveals that amide and carboxy There are characteristic absorptions of rate and long chain alkyl groups. Imidization is completed by immersion in an imidization reagent such as acetic anhydride or pyridine.

After completion, the absorptions of amide, carboxylate, and long-chain alkyl groups disappear, and absorption of imide rings appears.

In the above description, the case where all the repeating units of the precursor of the present invention are repeating units represented by general formula (1) was explained, but if it is within 30% of the repeating units, -i Formula (8):%Formula%) (In the formula, R1 and R2 are the same as above, and R has 1 to 1 carbon atoms.
11 aliphatic, cycloaliphatic, aromatic to (these may be combined with each other) monovalent groups, (these groups are halogen atoms, nitro groups, amino groups, cyano groups, methoxy groups, may be substituted with an acetoxy group, etc.) or a hydrogen atom, and may contain a repeating unit represented by 4 (R's in 11 may be the same or different).

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

First, a method for producing a copolymerized polyamic acid salt represented by general formula (101) will be described.

Tetracarboxylic dianhydride represented by the general formula (2) and the general formula (
3): having a repeating unit represented by the general formula (4) obtained by reacting a compound represented by the formula (3) at -10°C or more and 50°C or less, preferably 0 to 40°C to polyamic acid (in the formula, R'', R'', R'', da, - are all R5
and R6 are selected such that they are the same as the groups defined and have different structures. ) can be obtained by reacting.

Usually, the reaction between the tetracarboxylic dianhydride of general formula (2) and the compound of general formula (3) is carried out at -10°C to 50°C.

Preferably, it is carried out at about 0 to 40°C in a substantially anhydrous polar solvent.

The molecular weight of the polyamic acid obtained varies greatly depending on the reaction conditions employed, that is, the reaction temperature, the purity of the reaction reagent, the solvent, the degree of purification, the water content, the ratio of general formulas (2) and (3), and the order of addition.

When trying to obtain a high molecular weight product, using a high purity reagent solvent with low water content at low temperature, general formulas (2) and (3) can be obtained.
It is desirable to keep the ratio to 1 as much as possible.

Since the preferred embodiment of the present invention is not necessarily a highly viscous copolymerized polyamic acid salt, it can be synthesized very easily without strictly adjusting the conditions as described above. There is no particular limitation on the method of reacting the polyamic acid (4) obtained in this way, but as a developing solution for the LB method, a solution of polyamic acid (4) in an organic polar solvent and benzene or chloroform is added. It is obtained by mixing solutions dissolved in the same solvent.

Specific examples of the compound represented by general formula (2) include the following.

Specific examples of the compound represented by the general formula (3) include: CH3(CH2)11NH2, CH3(C1,)13N
H2, CH3(CH2)15NH2.

CH3(C112) 17N112, CHs(
CH2) 19NH2, CH3(CHz) 21NH2
.

C! +3(CF2) 23N)+2, CF3(
C112) 15N) 12.

11(CFri2(CH2) 15N)121 )+
(CF2)4(C)12)13NH2.

F(CF2)8(CH2)2NH2, F(CF2)El
(CH2)4NH2.

C113(CH2) llNll(CH3) ,
CHa(CHz) 13NH(CH3).

CH3(CH2) t5NII(CH3), CH
3(C)12) 17NH(C)13).

Ctla(CHz) tsNH(CH3), C
H3(C112) 21NH(CH3).

CH3(CH2) 23NH(CH3), CF
3(CH2) 15Nll(CH3) 1)1(CF
2) 4(CHz) 13NII(CH3).

F(CF2)8 (CI(z)zNH(CH3).

(C)13)3C(CH2) 14NH(CH3).

C)+3(CHz) uN (CH3)21 CH
3(CH2) ssN (CH3)2゜CH3(CH
2) 15N (CH3)2. CHs (CHz)
Sumire rN (CH3) 2°CH3 (CHz) 1sN
(CH3)2. CH3(CH2) 21N (
CH3)2゜CH3(CH2)23N (CH3)2
．． CF3(CH2)tsN (CH3)2゜H(CF
2)<(CHz) 13N (CH3)2°F(C
F2)8(CH2)2N (CH3)2゜(CHs)
3C(CHz) s+N (CH3)2° Further, the method for producing the copolymerized polyamic acid salt represented by the general formula (102) (103) is as follows.

That is, the salt of general formula (102) is composed of at least two kinds of tetracarboxylic dianhydrides represented by the general formula (2): and the salt represented by the general formula (3): % formula % (3) The above general formula (5) obtained by reacting a compound at -10°C to 50°C, preferably θ to 40°C
It is obtained by reacting a polyamic acid having a repeating unit represented by: (in the formula, P, R32, P, R11, FP, and R43 are all the same as defined above).

The salt of the general formula (103) is a tetracarboxylic dianhydride represented by the general formula (2): at least two of the compounds represented by the general formula (3) (31). -lO℃ or more 50
℃ or lower, preferably 0 to 40℃ to a polyamic acid having a repeating unit represented by the general formula (6): (wherein, ♂ F, IP, R41, p, 13 are all (same as the above definition).

The precursor of the present invention having a repeating unit represented by the general formula obtained in this way is not only easy to manufacture, but also has the characteristics of being able to be formed into a film by the LB method and giving a polyimide copolymer by heating. It is something that you have.

Next, a method for manufacturing the Langmier-Projet membrane used in the present invention will be explained.

The method for manufacturing Langmuir-Prodgett membranes is to spread the membrane-forming substance on the water surface, compress the substance spread on the water surface with a constant surface pressure to form a monomolecular membrane, and then spread the membrane across the membrane. In addition to the method of moving the substrate up and down and transferring it onto the substrate (vertical immersion method), methods such as the horizontal attachment method and the single rotation cylinder method (New Experimental Chemistry Course).

Volume 18, Interfaces and Colloids, 49B-508), etc., and any commonly used methods can be used without particular limitation.

The Langmuir-Prodgett method is an excellent method for forming oriented thin films of 200 Å or less, or even 1000 Å or less, hundreds or tens of layers, by a method in which the thickness can be controlled in units of tens of layers, and the present invention Thin films on substrates also have this characteristic. However, membranes with a thickness of 10.000 mm or more can also be produced by this method. Furthermore, it has been found that the film forming performance is improved by mixing these polymer compounds with a known Langmuir-Prodgett membrane compound, which is a desirable embodiment of the present invention.

The known Langmuir-Prodgett membrane compound is a compound that is also described in the literature cited above and is known in the art. Particularly preferred are compounds of the following formula consisting of a hydrocarbon group having about 16 to 22 carbon atoms and a hydrophilic group.

CH3(CH2)n-12 CHz=C1l(C)12)n-2Z CH3(C112) pc = C-C= C(CH2
) m Z where n=16-22. r+m=n-5,
Z=O1l, NO3, Shrine HR', NR'R',
These include C0OH, C0NHz, C0OR' (Ro is a lower aliphatic hydrocarbon group), and the like.

! Ti! In order to improve J film properties, the method expressed by the formula CH3 (CHz) Rho 42 is superior in terms of cost, but
Those containing unsaturated bonds have the characteristic that they can be polymerized by irradiation with light or radiation.

There is no particular limitation on the mixing ratio of at least one compound selected from these and the polymer compound.

When components forming a film are spread on the water surface using the Langmuir-Prodgett method, benzene, chloroform, etc., which are not soluble in water and evaporate into the gas phase, are generally used as solvents, but the present invention In the case of polymer compounds,
It is desirable to use an organic polar solvent in combination to increase solubility. Preferred organic polar solvents include N,N-dimethylformamide, N,N-dimethylacetamide, N,N-
These include diethylformamide, N,N-diethylacetamide, N,N-dimethylmethoxyacetamide, dimethylsulfoxide, tomethyl-2-pyrrolidone, pyridine, dimethylsulfone, hexamethylphosphoramide, tetramethylenesulfone, dimethyltetramethylenesulfone, and the like.

Therefore, the polymer compound of the present invention and the known Langmuir
Also when developing the Projet film compound, it is desirable to use a mixed solvent of a solvent such as benzene or chloroform and an organic polar solvent.

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

The substrates used in the present invention are limited depending on the application of the thin film of the present invention, but are not limited to other substrates, such as general inorganic materials such as glass, alumina, quartz, etc. In addition to substrates, metals, plastics, Si+ GaAs, ZnS, etc.
, n-vt group semiconductors, PbTiOs, BaTiO
A ferroelectric material or a magnetic material such as S, LiNb0a, or LiTaO3 can also be used as the substrate.

Moreover, it is of course possible to use a material that has been subjected to a surface treatment that is commonly performed.

In surface treatment, silane coupling agents, especially silane coupling agents with amino groups or epoxy groups (UCC A
-1100, A-187, etc.) or treatment with an aluminum chelate compound and heat treatment to form an aluminum oxide layer improves the adhesion between the polymer thin film of the present invention and the substrate. This is preferable because it allows

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.

The imidization method is not particularly limited, but it is preferable to use a chemical curing agent used for curing polyamic acid, such as acetic anhydride or pyridine.

Of course, this method may be used in combination with heat or light.

For example, using general formula (1) A reaction occurs.

Of course, in the case of the polyamic acid unit represented by the general formula (4), H2O is also generated to form a polyimide, but in this case it cannot be used as a material for an LB film.

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 less than 00 Å, and if desired,
It can be as high as 1,000. 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, and is used in field effect transistors, photoelectric conversion, etc. It can be used for elements, light receiving elements, light emitting elements, photodetecting elements, thermionic transistors, etc. JJ(
Josephson Junction). 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 copolymerized polyamic acid salt of the present invention and its production method will be explained based on Examples.

Example 1 2.18 g (0.01 mol) of pyromellitic dianhydride was added to 50 cc of dry dimethylacetamide in a flask.
dimethylacetamide 39 at about 20°C under a stream of dry nitrogen.
2 g of diaminodiphenyl ether (0
, 01 mol) was added dropwise over about 10 minutes, and the reaction was continued for 2 hours after the addition. Dilute with dimethylacetamide and benzene (1:1) to make a 1X10-3M solution, and add N-n-hexadecyldimethylamine and N- in a molar ratio of 1=1.
The total amount of n-octadecyldimethylamine is 2X10-3
A solution of a copolymerized polyamic acid salt was prepared by mixing a solution of dimethylacetamide and benzene (1:1) prepared as M, and used as a developing solution for an LB film.

The surface pressure-area curve of the salt in this example is as follows:
When measured at .degree. C., the surface pressure increased when the area per repeating unit (Unit) was about 150 A2, and a condensed film was formed. The ultimate area was about 140. When this film on the water surface was accumulated on an aluminum vapor-deposited glass substrate using the LB method, a Z-type accumulation was obtained. FTI R-AT of cumulative film
Alkyl group of 3000 to 280 Qcm-1 by R analysis,
A characteristic absorption of salts between 1650 and 1600 cn+-1 was observed.

When this cumulative film is chemically cured with pyridine and acetic anhydride, the absorption of alkyl groups and salts disappears and the film becomes 1780°1720CID.
Absorption of imide bonds such as -' appeared, and it became clear that the imidization reaction occurred even in the accumulated film.

Example 2 1.09 g (0,005 mol) of pyromellitic dianhydride and 1.47 g (0,005 mol) of 3.4.3',4°-biphenyltetracarboxylic dianhydride were dried. 2 g (0.01 mol) of diaminodiphenyl ether dissolved in 30 cc of dimethylacetamide was added dropwise to 50 cc of dimethylacetamide in a flask at about 20° C. under dry nitrogen flow over about 10 minutes, and the reaction was allowed to proceed for 2 hours after the dropwise addition. Dilute with dimethylacetamide and benzene (1:1) to create a solution of 1X10-3M, and add dimethylacetamide and benzene (1:1) prepared so that N-n-octadecyldimethylamine is 2x10-3M. A solution of copolymerized polyamic acid salt was prepared by mixing the solutions of 1) and used as a developing solution for LB film.

The surface pressure-area curve of the salt in this example is as follows:
When the area per repeating unit (Unit) was about 160 A2, the surface pressure increased and a condensed film was formed. The ultimate area was about 150A2. When this film on the water surface was accumulated on an aluminum vapor-deposited glass substrate using the LB method, a Z-type accumulation was obtained. FTIR-ATR of cumulative film
Analyzed alkyl group from 3000 to 2800 cm-1, 16
A characteristic absorption of salts between 50 and 160 Q cm was observed.

When this cumulative film is chemically cured with pyridine and acetic anhydride, the absorption of alkyl groups and salts disappears and the film becomes 1780°1720cn+
Absorption of imide bonds such as -1 appeared, and it became clear that an imidization reaction occurred even in the accumulated film.

Example 3 2.18 g (0.01 mol) of pyromellitic dianhydride was added to 50 cc of dry dimethylacetamide in a flask at about 20°C under a stream of dry nitrogen to prepare diaminodiphenyl ethyl Ig.
(0,005 mol) and p-diaminobenzene 0.54
g (0,005 mol) was added dropwise over about 10 minutes, and the reaction was allowed to proceed for 2 hours after the dropwise addition. Dimethylacetamide and benzene (
1: diluted with 1) to create a 1X10-3M solution,
Add 2X10 N-n-octadecyldimethylamine to this.
A solution of a copolymerized polyamic acid salt was prepared by mixing a solution of dimethylacetamide and benzene (1:1) prepared to have a concentration of -3M, and used as a developing solution for an LB film.

The surface pressure-area curve of the salt in this example is as follows:
When the area per repeating unit (Unit) was about 140 A2, the surface pressure increased and a condensed film was formed. The ultimate area was about 130 people2. When this film on the water surface was accumulated on an aluminum vapor-deposited glass substrate using the LB method, a Z-type accumulation was obtained. FTI R-AT of cumulative film
Alkyl group from 3000 to 2800 cm-1 in R analysis, 1
A characteristic absorption of salt between 650 and 1609 cm was observed.

When this cumulative film is chemically cured with pyridine and acetic anhydride, the absorption of alkyl groups and salts disappears and the film becomes 1780°1720cm-
Absorption of imide bonds of the 1st order appeared, and it became clear that imidization reaction occurred even in the accumulated film.

By using the salt of the copolymerized polyamic acid of the present invention, a thin film can be formed by the LB method, and by imidizing the obtained LB film, it has extremely good heat resistance and electrical properties. , has good chemical resistance and mechanical properties, and has a thickness of 10,
000 Å or less, if necessary, an ultra-thin film of 10 to 1000 people can be obtained. Moreover, according to the copolymerization method of the present invention, polyimide thin films having a wide range of physical properties can be designed and easily obtained.

Claims (1)

[Claims] 1. General formula (1): ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (1) (In the formula, R^1 is a tetravalent group containing at least 2 carbon atoms, R ^2 is a divalent group containing at least 2 carbon atoms, R^3^1, R^3^2, R^3^3, R
^4^1, R^4^2, R^4^3, R^5 and R^
6 is aliphatic, cycloaliphatic, or aromatic (these may be combined with each other) and has 1 to 3 carbon atoms
0 monovalent group (these groups may be substituted with a halogen atom, nitro group, amino group, cyano group, methoxy group, acetoxy group) or a hydrogen atom, and R^3^
1, R^3^2, R^3^3, R^4^1, R^4^2
, R^4^3R^5 and R^6 are the aforementioned groups having 12 to 30 carbon atoms. ) R^1, R^2, R^3^1, R^3 in the repeating unit represented by
^2, R^3^3, R^4^1, R^4^2, R^4^
3. At least one of R^5 and R^6 is at least 2
A copolymerized polyamic acid salt consisting of seeds. 2. In the general formula (1), R^3^1, R^3^
2, R^3^3, R^4^1, R^4^2R^4^3,
R^5 and R^6 are both the above-mentioned monovalent group having 1 to 22 carbon atoms or a hydrogen atom, and R^3^1, R^
3^2, R^3^3, R^4^1, R^4^2, R^4
2. The salt according to claim 1, wherein at least one of ^3, R^5 and R^6 is a group having 16 to 30 carbon atoms. 3. In the general formula (1), one or both of R^1 and R^2 is a group characterized by benzenoid unsaturation having at least 6 carbon atoms, Claim 1 Salt as described in section. 4. In the above general formula (1), there are ▲ mathematical formulas, chemical formulas, tables, etc. bonded to R^1 ▼, ▲ mathematical formulas, chemical formulas,
There are tables, etc. ▼, -NR^5-CO- and -CO-
Two of each of the four groups NR^6-R^2- form a 5-membered ring with the adjacent 2
2. A salt according to claim 1, wherein the salt is bonded to 5 carbon atoms. 5. In the general formula (1) above, there are ▲mathematical formulas, chemical formulas, tables, etc.▼ and ▲mathematical formulas, chemical formulas,
The salt according to claim 1 is selected such that ▼ has a different structure. 6. General formula (102): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (102) (In the formula, R^1_a, R^1_b are tetravalent groups containing at least 2 carbon atoms, R^2 , R^3^1, R^
3^2, R^3^3, R^4^1, R^4^2, R^4
^3, R^5 and R^6 all represent the above general formula (1)
The salt according to claim 1, having a repeating unit represented by (same as the definition of). 7. General formula (103): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (103) (In the formula, R^2_a, R^2_b are divalent groups containing at least 2 carbon atoms, R^1 , R^3^1, R^
3^2, R^3^3, R^4^1, R^4^2, R^4
^3, R^5 and R^6 all represent the above general formula (1)
The salt according to claim 1, having a repeating unit represented by (same as the definition of). 8. In the general formula (1) (102) (103), R
Claims 1 and 5 in which ^5 and R^6 are hydrogen atoms
The salt according to item 7. 9. General formula (2): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (2) Tetra represented by (in the formula, R^1 is a tetravalent group containing at least 2 carbon atoms) General formula (3): R^5-NH-R^2-NH-R^6(3) (in the formula, R
^2 is a divalent group containing at least 2 carbon atoms,
R^5 and R^6 are both aliphatic, cycloaliphatic, or aromatic (these may be combined with each other) monovalent group having 1 to 30 carbon atoms, (these groups are halogen Atom, nitro group, amino group, cyano group, methoxy group,
General formula (4) obtained by reacting a compound represented by (optionally substituted with an acetoxy group) or hydrogen atom) at -10°C or higher and 50°C or lower: ▲ Numerical formula, chemical formula, table, etc. There are ▼ (4) (In the formula, R^1, R^2, R^5, and R^6 are the same as the above definitions) for polyamic acid that has a repeating unit represented by ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R^3^1, R^3^2, R^3^3, R^4
^1, R^4^2, and R^4^3 are all the same as R^5 and R^6, and ▲There are mathematical formulas, chemical formulas, tables, etc.▼ and ▲There are mathematical formulas, chemical formulas, tables, etc. The structures of ▼ are chosen differently. ) is obtained by reacting the general formula (101): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(101) (In the formula, R^1 is a tetravalent group containing at least 2 carbon atoms, R^ 2 is a divalent group containing at least 2 carbon atoms, R^3^1, R^3^2, R^3^3, R
^4^1, R^4^2, R^4^3, R^5 and R^
6 is aliphatic, cycloaliphatic, or aromatic (these may be combined with each other) and has 1 to 3 carbon atoms
0 monovalent group (these groups may be substituted with a halogen atom, nitro group, amino group, cyano group, methoxy group, acetoxy group) or a hydrogen atom, and R^3^
1, R^3^2, R^3^3, R^4^1, R^4^2
, R^4^3, R^5 and R^6 are the above-mentioned groups having 12 to 30 carbon atoms, and ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼ and ▲ mathematical formulas, chemical formulas,
There are tables etc. ▼ are chosen to have different structures. ) A method for producing a copolymerized polyamic acid salt having a repeating unit represented by: 10. General formula (2): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(2) (In the formula, R^1 is a tetravalent group containing at least 2 carbon atoms) At least General formula (3): R^5-NH-R^2-NH-R^6 (3) (in the formula, R
^2 is a divalent group containing at least 2 carbon atoms,
R^5 and R^6 are both aliphatic, cycloaliphatic, or aromatic (these may be combined with each other) monovalent group having 1 to 30 carbon atoms, (these groups are halogen Atom, nitro group, amino group, cyano group, methoxy group,
General formula (5) obtained by reacting a compound represented by (optionally substituted with an acetoxy group) or a hydrogen atom at -10°C or higher and 50°C or lower: ▲ Numerical formula, chemical formula, table, etc. Yes▼(5) (In the formula, R^2, R^5, R^6 are the same as the above definitions, R
^1_a, R^1_b are the same as the definition of R^1, x and y represent the ratio, and for polyamic acid having repeating units expressed as 0<x<1, 0<y<1, x+y-1). ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R^3^1, R^3^2, R^3^3, R^4
The general formula (1
02): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (102) (In the formula, R^1_a and R^1_b are tetravalent groups containing at least two carbon atoms, and R^2 is a tetravalent group containing at least two carbon atoms. Divalent groups containing carbon atoms, R^3^1, R^3^2
, R^3^3, R^4^1, R^4^2, R^4^3,
R^5 and R^6 are both aliphatic, cycloaliphatic, or aromatic (these may be combined with each other) monovalent group having 1 to 30 carbon atoms, (these groups are halogen Atom, nitro group, amino group, cyano group, methoxy group,
(optionally substituted with an acetoxy group) or a hydrogen atom, R^3^1, R^3^2, R^3^3, R^4
At least one of ^1, R^4^2, R^4^3, R^5 and R^6 is the above-mentioned group having 12 to 30 carbon atoms. ) A method for producing a copolymerized polyamic acid salt having a repeating unit represented by: 11. General formula (2): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(2) (In the formula, R^1 is a tetravalent group containing at least 2 carbon atoms) Tetra General formula (3): R^5-NH-R^2-NH-R^6(3) (in the formula, R
^2 is a divalent group containing at least 2 carbon atoms,
R^5 and R^6 are both aliphatic, cycloaliphatic, or aromatic (these may be combined with each other) monovalent group having 1 to 30 carbon atoms, (these groups are halogen Atom, nitro group, amino group, cyano group, methoxy group,
(optionally substituted with an acetoxy group) or a hydrogen atom) at -10°C.
General formula (6) obtained by the above reaction at 50°C or lower:
▲There are mathematical formulas, chemical formulas, tables, etc.▼(6) (In the formula, R^1, R^5, R^6 are the same as the above definitions, R
^2_a, R^2_b are the same as the definition of R^2, x and y represent the ratio, and for polyamic acid having repeating units expressed as 0<x<1, 0<y<1, x+y=1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R^3^1, R^3^2, R^3^3, R^4
The general formula (1
03): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (103) (In the formula, R^1 is a tetravalent group containing at least two carbon atoms, R^2_a, R^2_b are at least two Divalent groups containing carbon atoms, R^3^1, R^3^2
, R^3^3, R^4^1, R^4^2, R^4^3,
R^5 and R^6 are both aliphatic, cycloaliphatic, or aromatic (these may be combined with each other) monovalent group having 1 to 30 carbon atoms, (these groups are halogen Atom, nitro group, amino group, cyano group, methoxy group,
(optionally substituted with an acetoxy group) or a hydrogen atom, R^3^1, R^3^2, R^3^3, R^4
At least one of ^1, R^4^2, R^4^3, R^5 and R^6 is the above-mentioned group having 12 to 30 carbon atoms). Method for producing polyamic acid salts. 12. The method according to claims 9 to 11, wherein R^5 and R^6 of the compound represented by the general formula (10), (102), or (103) are both hydrogen atoms.