JPS63218728A - Amphoteric polymeric compound and production thereof - Google Patents

Abstract

PURPOSE:To provide the titled compound capable of film formation by the Langmuir-Blodgett procedure, constituted of such linear necurring units with each specific two organic groups linked alternately that specific hydrocarbon- contg. group is linked thereto through covalent bond. CONSTITUTION:A monomer containing at least divalent >=2C organic group R2 and a second monomer containing at least divalent >=2C organic group R2 are used in such a combination as of formula I, II, III or IV (A is acidic group; B is basic group), also being selected so that either or both of said monomers contain one or two replaceable 10-30C hydrocarbon-contg. group R3, followed by polycondensation of these monomers, thus obtaining the objective compound constituted of such linear recurring units with said organic groups R1 and R2 linked alternately through divalent group that the hydrocarbon-contg. group R3 is linked thereto through covalent bond. Said combination is e.g., one between a monomer of formula V and a second monomer of formula VI.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an amphoteric polymer compound, particularly an amphoteric polymer compound modified so that it can be formed into a film by the Langmuir-Prodgett method, and a method for producing the same. Already in the 1930s, Langmuir and Prodgett discovered that fatty acids with about 16 to 22 carbon atoms could form a monomolecular film on the surface of water and accumulate it on a substrate, but studies on its technical application remained unclear. It has only recently begun to be carried out.

For an overview of past research, see Solid State Physics 17 (12
) 45 (1982) Th1n 5olid Fi
lms 88 No. 1 (1980).

ibi+L 99 No. 1.2.3 (1983)
In5olable monolayer sat l
iquid-gas 1nterfaces (G,L
, Ga1ns, Inter-science Pu
blishers, New York+ 1966)
However, the conventional Langmiea-Prodget membrane (hereinafter referred to as "rLB membrane") made of straight-chain saturated fatty acids has shortcomings in heat resistance and mechanical strength, and cannot be used as is for practical applications. There is a problem.

Unsaturated fatty acids, such as ω-
Polymer films made of tricosenic acid, ω-pebutadenoic acid, α-octadecyl acrylic acid, unsaturated esters of fatty acids such as vinyl stearate, octadecyl acrylate, and diacetylene derivatives have been investigated, but they do not have sufficient heat resistance. It cannot be said that it is electrically superior.

Regarding polymers, polymers with hydrophilic groups such as polyacrylic acid, polyvinyl alcohol, ethyl acrylate, and polypeptide are known to have film-forming properties, but they are particularly modified as materials for Langmuir-Prodgett membranes. Polymers have not been studied so far, and there is no material that can be considered an excellent LB film material.

On the other hand, polyimide is used as a heat-resistant film, but depending on methods such as spin cording, the thickness is usually at least 1,000 Å or more, and it is extremely difficult to create a heat-resistant thin film with no pinholes of 1,000 Å or less.

The purpose of the present invention is to modify a polymer compound that is originally difficult to form into a film using the Langmier-Projet method, thereby making it possible to form a film using the Langmier-Projet method. An object of the present invention is to provide an amphoteric polymer compound, which is a material for a polymer LB film having a thickness that is generally difficult to form, and which has improved mechanical properties such as durability, chemical resistance, and adhesive strength, and a method for producing the same. .

According to the present invention, an at least divalent first organic group R1 having at least 2B carbon atoms and an at least divalent second organic group R1 having at least 2B carbon atoms can be solved by the present invention.
having a linear repeating unit in which the organic groups R2 are alternately connected by divalent bonding groups, and having a carbon number of 10 to 30 and may contain a substituent covalently bonded to the repeating unit.
The present invention is solved by providing an amphoteric polymer compound containing at least one hydrocarbon-containing group R3.

To explain in more detail, the polymer compound of the present invention has linear repeating units as a basic skeleton of -1÷-A-R.
1-AB -Rz-B-÷-1 (1)-1÷-A -R
1-B A -R2-B-÷--(2)-H-B-R
It is composed of 1-BA-R2-A-÷-1 (3).

wherein R1 is an at least divalent first organic group containing at least 2B carbon atoms, and R2 is at least 2B carbon atoms.
B is an at least divalent second organic group containing a carbon atom. More preferably, one or both of R1 and R2 is a group characterized by benzonoid unsaturation having at least 6 carbon atoms.

AB and BA in formulas (1) to (3) are O, N, S,
It is a divalent bonding group formed by a reaction between an acidic group A containing a heteroatom such as P or B and a basic group B. More specifically, -COOR, (R is an alkyl group or a hydrogen atom,
(Same below) -COX, (X is α or Br+ Same below) -NCO, -NC5, -CN, -CONHR
, -5OzNOR and other acidic groups A and -11HR, -O
A group formed by the reaction of basic group B such as R, -5R, -X, etc., etc.

The polymer compound of the present invention may have a substituent covalently bonded to the same repeating unit of the basic skeleton of (1) to (3) with a carbon number of 10 to 30. Preferably carbon number 16
It contains at least one, preferably two, of ~22 hydrocarbon-containing groups R3, and is modified so that it can be formed into a film by the Langmuir-Prodgett method.

There are three possible methods for achieving such modification.

(1) AB in the linear repeating unit of formulas (1) to (3)
, A method of substituting R3 to an atom included in the group of BA.

(n) A method of directly substituting R3 on R1, R2, and further, (III) Substituting R3 through a substituent of R1, Rz other than those used to create the linear repeating unit of Rt, Rz. It's a method.

Of course, (1) (II) (I[[) may be used together, and when R3 is two or more, they may be the same or different.

(1) (II) To specifically illustrate (III), (1) is a method in which R3 is substituted for the hydrogen atom on the nitrogen atom of AB or BA as shown in the above table.

The method [■] is a method in which R3 is directly substituted for R1 and R2, and these are some specific examples thereof.

A method that includes even more possibilities is the method of [I[r). This will be explained in detail.

Method (III) is a method in which one, R1, and R2 are small (one of which uses at least a trivalent organic group, and R1゜R
This is a method of substituting R3 through a substituent other than that used to create a repeating unit containing 2, and is of course not limited to this, but it is a method in which R1 has a valence equal to or greater than R2. To give an example of numbers up to 6, these are: MU Tachi 1 H 2 ball supervised ■ 32 ■ 42 ■ 52 ■ 62 ■ 33 ■ 43 ■ 53 ■ 63 ■ 44 [phase] 54 ■ 55 ■ 65 0 6G.

Although examples in which R1 and R2 have a valence of 5 or more are listed here, it is particularly preferable that R1 and R2 have a valence of up to 4.

Rt=3. Rz=bivalent R1 gourd4. Rz■2 R1 snow 3. R2 proverb 3 R1 dew 4. Rz=3 Rx=4. Possible specific examples for Rz 4 are listed below: R1 error 3.
When R2 is 2, R5-4, when Rz-2, R1-3* When R2 is 3, R1 is 4. In R2 proverb 3, when R1-4, R2=4, there is A/B that is not used to create, but (II
The method [] is a method of substituting R3 through this substituent.0 For example, if A in (4) to (75), -COOR3,
-CONHR3, -NHCOOR3, -NHCSOR3
etc., B can be replaced by -N)IR3, -0R3, -5R3, etc.

Next, R1 and R2 will be explained. R1, RZ are small (both containing 2B carbon atoms, preferably 5 to 20
is a group of at least 2 (il[i) containing 2 carbon atoms, which may be an aromatic group, an aliphatic group, or a cycloaliphatic group; These groups may be a combination of groups, and furthermore, these groups may be aliphatic, cycloaliphatic, or aromatic (these groups may be combined with each other) monovalent group having 1 to 30 carbon atoms. Group (
These 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 a monovalent group may be substituted with -Q +, -c
oo-・-Nl(Co-, -CO--S +, -cs
s,-,-NHC5-.

It may be a group substituted with a group bonded to -C3-, etc. to become an octoconductor, but if R1 and Rz are at least 6
A group characterized by a benzenoid structure G having the number of carbon atoms is preferred from the viewpoint of heat resistance, chemical resistance, mechanical properties, etc.).

The benzenoid unsaturation of the present invention is a carbocyclic compound (the following is a blank space). Preferred examples for describing R1 and Rz in more detail are as follows.

Here R4 is -o-, -co-, -s-.

R5: Alkyl or aryl group H3 ■ C)+30 - (CH2)IOCH-CH3, -(CH2)3-C
-(CHz)z +.

-(CHz)3-0-(CH2)2-o-(CH2)3
−.

(Margin below) (Ra is the same as above) Among the above, more preferable examples of R1 and R2 are given. (R4 is the same as above).

R3 is a hydrocarbon-containing group having 10 to 30 carbon atoms, preferably 16 to 22 carbon atoms, and is a monovalent group selected from aliphatic, cycloaliphatic and aliphatic, aromatic and aliphatic bonds, and substituents thereof. Preferred specific examples of the groups include (CHs) (CHz)nt, CHz-CH(
CHz)n-zH3 where 7+mxn-5, n-10~30 preferably 16
~22, etc., and straight chain aliphatic hydrocarbon groups are particularly preferred examples.

The substituent for these is a halogen atom.

There are nitro groups, amino groups, cyan groups, methoxy groups, acetoxy groups, etc., but they are not essential, but fluorine atoms improve hydrophobicity more than hydrogen atoms, so it is preferable to use them in some cases.

That is, by containing fluorine, the length of the alkyl chain can be shortened (for example, C3F17 (CH2) 4
In -, 2 roux is sufficient, and it is possible to form a film with 10 carbon atoms.

Specific examples of polymer compounds applicable to the film forming method of the present invention include R1, R2, Ra, and A in formulas (1) to (75).

It becomes clear by substituting specific examples of B, AB, BA and specific examples of the method of substituting R3. Although (1) to (75) do not contain copolymers,
Of course, copolymers analogous to these and mixtures thereof are also included in the present invention.

Further, although it is not essential, the polymer compound of the present invention may be CI
)(n)(m) may be substituted with a hydrocarbon-containing group having 1 to 9 carbon atoms.

There is no particular limitation on the molecular weight of the polymer compound of the present invention. However, even if the molecular weight is low, it is possible to form a film using the film forming method of the present invention. On the other hand, if the molecular weight is too large, the viscosity will be too high and film formation will not be successful.

Therefore, it is desirable that the number average molecular weight is about 2.000 to 300.000, more preferably 10.000 to 300.000.
It is 150.000.

In terms of synthesis of monomers and polymers, preferred specific examples from cost considerations are as follows; of course, the present invention is not limited to these.

(157”) In the formula, - represents isomerism.

For example, if explained using the formula (83) below, and represents.

The present invention includes cases where (83-1) and (83-2) are present alone, and cases where (83-1) and (83-2) coexist.

Other examples include "Heat resistance of polymers" edited by Hakutabe Kobe.
(Baifukan, S45.3.5"), "Thermal decomposition and heat resistance of r-polymer" (Baifukan, S49.3.15), etc.

The present invention also provides a method for producing the amphoteric polymer compound. In this method, a monomer containing a first organic group R1 and a monomer containing a second organic group R2 are A-R1-A +
B -R2-BA-R1-B + B -R2-
BB -R4-B + B -R2-AA -Rs
' + B -Rz-BB -R1+
A -Rz-A 8 Ij ABAA
B115 AB A k3BB
AA A B A
B8 5 ABIj
I3A ABi2
(8) In any combination of (8) (in the formula, A represents an acidic group and B represents a basic group), and at least one of the 2M hexamers to be combined has one or 2B hydrocarbon-containing groups R3. The method consists of polycondensing a monomer containing a first organic group R1 and a monomer containing a second organic group Rz using a hexamer contained therein.

The manufacturing method for the above-mentioned specific examples (76) to (178) is as follows.

(86)' → (94)' (96) Evening → (97)'(98)'(99)'(100)'(101)' → (102)' → (103)' → (104)' → (105)' - (106)' = (107)' = (108') - (109)' - (110)' 111 (111)' (112) ri - (113)' 111 ( 114)' = (115)' - (116)' - (117)' - (118)' - (119)' 11 → (120)' - (121)j - (122)' - (123)' -(124) Two (125)'-(126)'-(127)' -(128) Fu (129) Two (130)'-m-(131)'(132)' One one → (133)' 11 → (134)'(135)' = (136)' - (137)' R = (13B) U = (139)' - (140)' 111 (141)' = (142)' = (143)' 111 (144)'-(145)' □ (146'')'-(147)'-(148)' 111 (149)'(150)' (151) Fu (152) '11 → (153)' 111 (154)'(155") 2 (156)'(157)' - (15B)' - (159)' 111 (160)' - (161)'(162)'-m-(163)'-(164)" 1-→ (165)'11->(166)'-(167)' = (16B)' = (169)' 1-1 (170 )' 111 (171) 2 - (172)' 111111 - Yu (173) Rah → (174)' 111111 Yu (175) Ra → (176) 5 11 → (17?)' 111 (178") As can be inferred from these specific examples, copolymers can be easily produced by the following method. 0 The present invention includes such copolymers. Of course, copolymers containing a trivalent or higher valent organic group having a small number of carbon atoms (both have two carbon atoms) in one or both of R1 and R2 can be easily prepared using the following method. Copolymers produced in this way are also included in the present invention.Such copolymers are expected to improve thermostability, and are desirable embodiments!3.
Numerous other copolymers are included in the present invention, and these can also be produced by the production methods described above.

In order to explain the method for producing thin films of these modified polymer compounds, R'a -CHs(CHz) in formula (91)
The case of ty- will be described. obtained by alcoholysis of pyromellitic dianhydride under substantially anhydrous conditions in an organic polar solvent at a temperature of -1
Acylation is carried out with thionyl chloride at a temperature of 0°C or higher, preferably from about 0 to 40°C, and this is reacted with diaminodiphenyl ether at a temperature of -10°C or higher, preferably from 0 to +10°C, but a post-reaction is not necessary to complete the reaction. You may carry out at 20 degreeC or more.

Acylation and amidation reactions are usually below 0℃ -10℃
However, in the present invention, substituents such as long-chain alkyl groups tend to freeze and solidify, so it is preferable to carry out the process at the above temperature.Of course, in the above cases, raw materials with different substituents may be used. Mix to make a copolymer, or 0 to 3
It may be mixed with a tetracarboxylic acid dianhydride or diamine having about 0% of no substituents or a substituent having 10 or less carbon atoms.

The amphoteric polyimide precursor produced as described above may be separated and purified to be used as a film-forming material, or in the case of manufactured concentric W, chloroform, benzene, etc. may be added to it and used directly as a film-forming solution.

A method for forming a film from the polymer compound of the present invention will be described.

There are a solvent casting method, a spin cord method, and a Langmuir-Prodgett method, and the Langmuir-Prodgett method is preferred as a method for obtaining an oriented thin film with a controlled thickness in units of several tens of layers and fewer pinholes.

In the case of the solvent casting method and the spin-coding method, the polymer compound of the present invention or a mixture thereof is dissolved in a solvent such as benzene, chloroform, ethyl ether, ethyl acetate, tetrahydrofuran, dimethylformamide, N,N-dimethylacetamide, etc., and the spin-coding method is performed. If the film is coated on a substrate using a method such as (1), it is not possible to orient the molecules, but if the film is thicker than about 10,000 mm, a high-quality film without pinholes can be obtained.

Next, a method for manufacturing the Langmuir-Prodgett film used in the present invention will be explained.

The Langmuir-Prodgett film is manufactured by spreading the film-forming material on the water surface, compressing the material spread on the water surface to a certain surface thickness to form a monomolecular film, and then passing the film across the substrate. In addition to the method of transferring the material by moving it up and down onto the substrate (vertical dipping method), methods such as the horizontal attachment method and the rotating cylinder method (New Experimental Science Academy, Vol. 18, Interfaces and Colloids, 498-508
), and any commonly used method can be used without particular limitation.

The Langmuir-Prodgett method is an excellent method for forming thin films of 200 Å or less, even 1000 Å or less, hundreds or even tens of oriented films, in which the thickness can be controlled on the order of tens of layers. Thin films on substrates also have this characteristic. However, films with a thickness of 10°000 A or more can also be formed by this method.

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,
In order to increase solubility, it is desirable to use an organic polar solvent in combination. Preferred organic polar solvents include N,X-dimethylformamide, N,N-dimethylacetamide, N,N-
Diethylformamide, N,N-diethylacetamide, N,N-dimethylmethoxyacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, pyridine,
These include dimethyl sulfone, hexamethylphosphoramide, tetramethylene sulfone, and dimethyltetramethylene sulfone.

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 substrate used in the present invention is limited depending on the application of the thin film of the present invention, but is not particularly fixed, and may be a general inorganic substrate such as glass, alumina, quartz, etc. In addition to metals, plastics, and group II materials such as Si, GaAs, and ZnS,
IV, I[-Vl group semiconductors, PbTiO3,
A material containing a ferroelectric material such as BaTiOs, LiNbO5, LiTaO5, or a magnetic thin film 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. Among the surface treatments, a method of treating with a silane cuffing agent, especially a silane cuffing agent having an amine group or an epoxy group, or an aluminum chelate compound and applying heat treatment improves the adhesion between the polymer thin film of the present invention and the substrate. Of course, the substrate may be treated with several layers of higher fatty acid metals as is done in the art.

A feature of the present invention is that it is possible to form a thin film of a high-molecular compound with good image quality on a substrate using the Langmuir-Prodgett method. As a result, it is possible to form a thin film with even higher heat resistance on the substrate.

Among the examples (76) to (17B), the following are examples that can be partially or completely closed to a 5- or 6-membered ring containing a heteroatom, and the structure after complete ring closure is as follows. become that way.

or (106)'″
or (152)"(155)" The method of ring closure is not particularly limited, but for example, in the case of imidization, which is a specific example of the above formula (91), 200°
By heating to temperatures around ~400°C (91)
Reaction of the macromolecular compound of formula occurs to achieve ring closure. At this time, the group introduced for hydrophobization is eliminated as alcohol, but this eliminated alcohol must be placed under a gas flow or under vacuum at a temperature of around 200° to 400°C. Since it can be dispersed by the heat treatment, a polyimide thin film with very good heat resistance can be rubbed.

Of course, a chemical curing agent such as acetic anhydride, pyridine, or isoquinoline, which is commonly used in imidization, or heat may be used in combination with the curing agent.

As described above, the thin film on the substrate made by accumulating the polymer compound of the present invention on the substrate by the Langmuir-Prodgett method and, if necessary, conducting the ring-closing reaction, has heat resistance,
It has good mechanical properties and chemical properties, has excellent electrical insulation, and is a very thin film of less than 1000 yen.
It has the characteristic that it can hold up to 00 people.

In particular, it can be used in various devices because it can achieve dielectric breakdown strength of I x 10' V/cm or more, among other good physical properties, even when the temperature is less than 1,000 degrees, several hundred degrees, or about 50 to 100 degrees. In particular, for thin films with a thickness of about 50 to several hundred particles, a unique film thickness effect, such as a tunnel effect, is expected, and many interesting applications using this effect are possible.

Next, we will discuss the uses of these thin films.

The thin film of the present invention has excellent heat resistance, chemical resistance, and mechanical properties, and can be used in a wide range of fields such as electronics, energy conversion, and material separation by taking advantage of the fact that it is a very thin film.

First, we will discuss electrical and electronic devices, which are devices in the electronics field that take advantage of conductivity, photoconductivity, optical properties, insulation, thermal properties, and chemical reactivity.

The first important electric/electronic device containing the thin film of the present invention is a device with a metal/insulating film/semiconductor structure (hereinafter referred to as MIS), which is the basic structure of planar electronic devices and integrated circuits.

1 to 7 are representative schematic diagrams. In FIG. 1, a thin film of the present invention is formed as an insulating film on a semiconductor substrate, and a metal electrode is provided thereon. ■Group semiconductors such as Si+Ge, ■-V group semiconductors such as GaAs and GaP, and CdT
e, CdS+ ZnS, Zn5e, CdHgTe
By using n-vx group semiconductors such as, for example, photoelectric conversion elements such as solar cells, light emitting elements such as LEDs, ELs, and photodiodes, light receiving elements, photodetecting elements, and various other devices such as gas sensors and temperature sensors. A transducer can be configured.

Of course, the semiconductor of the present invention may be selected from single crystal, polycrystal, or amorphous.

Figure 2 is similar to Figure 1, but with two (II)
Such electrodes are attached when manufacturing the above element.

With this configuration, CCD (Charg@-co
Charge-transfer devices such as (upled devices) have been created and are an interesting application.

Next, Fig. 3 shows that a semiconductor (often a semiconductor thin film) is formed on an insulating substrate having an electrode (which may be a transparent electrode, or of course may be patterned), and a semiconductor thin film is formed on it. It has a structure in which the thin film and electrode of the invention are provided.

FIG. 4 differs from FIG. 3 in that the thin film is provided between the insulating substrate side electrode and the semiconductor thin film.

Semiconductor thin films are manufactured using methods commonly used to fabricate semiconductor thin films, such as molecular beam epitaxy (MBE), metal organic chemical vapor deposition (MOCVD), atomic layer epitaxy (ALE), evaporation, sputtering, spray pyrolysis, and coating methods. Created and not limited.

As the semiconductor, those mentioned above in the explanation of FIG. 1.2 can be used in the same manner, and the devices produced are also the same.

In the structure shown in FIG. 4, a semiconductor thin film is formed on the thin film of the present invention, so it is not desirable if the heat during formation exceeds the heat resistance of the thin film, but amorphous silicon etc. can be sufficiently accumulated in the thin film after ring closure. As low-temperature formation technology for other semiconductors is progressing, many semiconductors will likely become usable in the future.

The most important device structure of the MIS structure device is the so-called field effect transistor (CFET) structure, which is typically driven by controlling the channel current with a gate electrode, as shown in FIG.

The difference is that FIG. 5 uses a semiconductor substrate, whereas FIG. 6 uses a semiconductor formed on an insulating substrate, in most cases a semiconductor thin film.

MISFET is one of the basic types of devices, and various devices can be made using it.

If made on a large-area substrate, thin-film transistors can be used to drive a liquid crystal display, and if the degree of integration is increased, an integrated circuit can be constructed.

Another interesting application is the structure shown in Figure 5.6 with the gate electrode removed and an ion-sensitive FET (I 5FET) by adding an insulating film or a film sensitive to ions, gases, or active substances in conjunction with it. and gas sensitive EET
(Chem FET), Immune FET (IMFET)
), an enzyme FET (ENFET) can be constructed.

The operating principle can be explained by the electric field effect caused by the interaction of ions or gaseous active substances with the surface of the gate insulating film, but when using the thin film of the present invention, conventional methods are used to further modify it with various finite substances. It has advantages over inorganic materials. In particular, in thick films with residual long-chain alkyl groups, the interaction between the alkyl group (hydrophobic) portion and the hydrophobic portion of the protein can be utilized.

FIG. 7 shows an example of an 15FET, which has a structure in which a semiconductor film is formed on a quartz substrate as shown in the figure, and an insulating film and an ion-sensitive film are provided thereon. The thin film of the present invention can be used as this insulating film.

In the present invention, it is preferable to use a compound semiconductor such as I[[-V, ff-VT group, etc., which is difficult to form a good insulating film by oxidation or other methods, as a semiconductor when configuring a device with an MIS structure. In an embodiment, CaAs
In this case, when forming an FET, what are the above problems?
Ietal-Semiconductor FET (M
Although it has been put into practical use in the form of ESFET, it is expected that performance will improve by adopting an MIS structure.

Constructing MIS integrated circuits using GaAs not only has the effect of lowering the driving voltage, but also enables the creation of high-speed integrated circuits (HEMTs) that utilize the large carrier mobility in GaAs semiconductors in a very simple manner. can be made.

The second important electric/electronic device containing the thin film of the present invention is a device with a metal/insulating film/metallic structure (hereinafter referred to as MIM).

8 to 10 are schematic diagrams. An insulating substrate or a semiconductor substrate is used, and a metal, an insulating film, and a metal are formed thereon in this order.

Figure 8 shows the structure of a capacitor, which can be used as a humidity sensor by tracking changes in capacitance due to humidity. This structure also allows one MIM structure transistor to be included.

A thermionic transistor can be constructed as shown in FIG.

By forming a capacitor on a semiconductor or semiconductor device as shown in FIG. 10, it can be used as a capacitor for a VLSI memory cell.

It is also possible to fabricate a type of device in which hot electrons are injected into a semiconductor using the fi formation shown in FIG. Furthermore, by using a electromotive conductor such as Nb instead of metal, it is also possible to make a JJ device.

The electrical/electronic device including the third thin film is a device with an insulating film/metal structure (1M structure), and is schematically represented in FIG. The simplest method is obtained by forming the thin film of the present invention as an insulating film on a metal.

One application is liquid crystal alignment films, where patterned electrodes,
It is usually obtained by forming the thin film of the present invention on a transparent electrode such as ITO.

In the next application, by forming the thin film of the present invention on two independent layers of 'tyJ12.13, it can be used as a sensor for humidity, gas, etc.

Although the electrical/electronic devices containing the thin film of the present invention have been described above, other application examples can be found in the above-mentioned documents, especially P.
, S. Vincett, G.G. Roberts
Review of (Thin 5solid Filn+s u13
5-171 (1980).

For other semiconductor devices and compound semiconductor devices, please contact E, S, Yang+ Fundamentals.
of Sem1-conductor Device
s MaGraw-Hill, 1978+edited by Imai et al., Compound Semiconductor Devices [■] [■] Kogyo Kenkyukai (1
984) can be used as a reference.

Next, we will discuss devices other than electrical and electronic devices.

Recording methods are increasingly being adopted in which a thin film containing a dye or an inorganic thin film such as TeOx undergoes bit formation or phase change, and the change is optically read out at 0.1.

The thin film of the present invention causes a reaction with light, heat, especially laser light commonly used in optical recording, and the thickness of the thin film becomes thinner and bits are formed.This reaction also changes the refractive index of the thin film. It is suggested that optical recording using this is possible.

It is clear from the above explanation that the thin film of the present invention is reactive to heat. Taking advantage of this reactivity, we create thermally ring-closed parts and non-thermal ring-closed parts, and remove the non-thermal ring-closed parts with a solvent. It can be patterned by removing it. The remaining portion can be used as a resist film because it has excellent heat resistance, mechanical strength, and chemical resistance.

Furthermore, as in one embodiment of the present invention, it is possible to make the alkyl group reactive to light by using an alkyl moiety containing a double bond or a triple bond.

In addition, it can also be used as a cladding material for Unibu guides or as an optical circuit component.

An optical circuit can also be formed by patterning using the method described for resist. In the case of the thin film of the present invention, the refractive index can be adjusted by accurately controlling the thickness and changing the compound. This is an important requirement for optical circuit components.

The mixture of the present invention may be suitable as a protective coating material in all fields. By using it instead, it can exhibit various functionalities, and it can be used to create photoelectric conversion elements and biosensors.

It is also conceivable that this thin film could be used in the field of substance separation.

Recently, there have been many attempts to form thin films with fine pores on porous film substrates and use them for material separation.

A thin film having fine pores can be formed by producing the thin film of the present invention under conditions in which a known Langmuir film material is present, and then carrying out a ring-closing reaction.

For example, by forming a film of a compound having a polyimide precursor structure on a polyimide porous film in the presence of an excess of stearyl alcohol, and then imidizing it at 300 to 400°C, a polyimide N film with fine pores is formed into a polyimide porous film. Can be made on quality film.

Next, a method for producing an amphoteric polymer compound and a method for forming a film according to the present invention will be explained based on Examples.

Example 1 200 equipped with mechanical stirrer and cooling pipe
p-phenylenediamine (97
%, 15.6 g, 0.140 mol), stearyl bromide (15.5 g, 0.0466 mol) and sodium hydroxide (pulverized, 1.96 g.

0.0466 mol) and heated to 140 to 150° C. for about 3.5 hours while stirring under nitrogen gas flow.

Approximately 50 g of water was added to the reaction solution, and the mixture was cooled to room temperature to precipitate. Cut the black-purple solid into pieces and wash with water and ethanol in that order. Further washing with hot ethanol followed by methylene chloride yields the desired N,N'-distearyl-p
- 5.77 g (yield: 40%) of phenylenediamine was obtained as a pink powder. When this powder was recrystallized from chloroform, pink plate-like crystals were obtained. This structure is II-NM
It was determined by R (FIG. 14) and IR spectra (FIG. 15), melting point measurements, and elemental analysis.

(4): rll, p, 102-103℃Ana
1. Ca1cd for (a)bNz :own
d C,82,28:H,13,15,N,4.57C,8
1,93; H, 13,22: N, 4.63 eu 1'' 1.23 g (2 milliliters) of N, N'-distearyl-p-phenylenediamine was dried in 140- Melted in hexamethylphosphoramide at about 60°C, 0.406
A dry hexamethylphosphoramide solution of isophthalic acid chloride (g) was added dropwise, and the reaction mixture was further reacted for 2 hours. The reaction mixture was poured into redistilled water to separate the precipitate.

After washing with water and ethanol, polyamide was obtained as a gray-blue powder.

IH-NlIR, IR spectrum, thermal analysis (TG
A-DTA) was performed and the following results were obtained.

WangjiN? Figure 1 shows the proton NMR chart measured in IR Odoka CDae3.
It was like 6.

δ-1,25ppm 74H (ZXQsJ amount) δ=
The IR chart taken using the 6-8.25 ppm 8H (aromatic) unit and Hichika KBr disc method is shown in Figure 17, showing the characteristic properties of esters, amides I, I, alkyl groups, and ethers. I was able to absorb a lot.

Because of the presence of the alkyl chain on the nitrogen, no amide ■ absorption band was observed.

a' (TGA-DTA) Rigaku IRTG-DTA (H) type, full scale TGA10q, DTA100#V, temperature 1000℃, temperature increase 10℃/min, nitrogen flow (30mffi/lll)
Figure 18 shows the results measured in 1n).

TGA has an inflection point at 435,480,635,785°C, and there is a weight loss of 92.6% between 435° and 480°C, and it is thought that the polyamide has decomposed.
Corresponding to this, an endothermic peak also appears in TA.

Implementation (Da! 2) In order to evaluate the basic characteristics of polyamide as an LB film, a surface pressure-area (π-A) curve was drawn according to the conventional method, and then it was applied to an aluminum-deposited glass substrate by the vertical dipping method (LB method). Tried to accumulate.

The conditions are as follows.

Apparatus Joyce-Loeble) rough solvent
Chloroform concentration 0.795xlO-3mol/1Sub
phase Double distilled water (does not contain Cd4-) water temperature
18-19℃ The π-A curve of polyamide is shown in Figure 19.0 surface pressure is 45
The rise is gradual up to dyne/cm, which is considered to be in the liquid film region. At 45 dyne/cm or higher, the slope becomes steeper and it is considered to be a solid film, but at 64 dyne/cm, the area occupied by a unit molecule at 0 surface pressure (0 surface pressure) where the film collapses (limit area) is approximately It was 47.5 A”/unit.

This polyamide is spread on the water surface, and the surface pressure is approximately 2
Accumulation was attempted using the LB method on an aluminum vapor-deposited glass plate while maintaining the temperature at 9 dyne/am. A decrease in the film area was observed both when the substrate was raised and when it was lowered, and the cumulative ratio was 1, indicating that an ideal Y-type film was formed.

Example 3.4 1.23 g (2 mmol) of N,N'-distearyl-
0,j, which was dissolved in p-phenyl diamine in tetrahydrofuran/water and dissolved in benzene under good stirring at room temperature.
06 g of isophthalic acid chloride was added dropwise to synthesize polyamide by interfacial polycondensation method. Hydrogen chloride was trapped using sodium carbonate.

In addition, a polyamide with the following structure was synthesized using terephthalic acid chloride instead of isophthalic acid chloride.

1) (-NMR, IR spectrum, thermal analysis (TGA-
DTA), almost the same results as the polyamide of Example 1 were obtained.

Example 5.6 The basic properties of the polyamide synthesized in Example 3.4 as an LB film were the same as those of the polyamide in Example 1, and it was deposited in a Y-shape on an aluminum vapor-deposited substrate by a vertical dipping method.

Example 7 2.18 g (0.01 mol) of biromellitic dianhydride and 5.40 g (0.02 mol) of stearyl alcohol
mol) in a flask at about 100°C under a flow of dry nitrogen.
Allowed time to react.

The obtained reaction product was added to 40 cc of hexamethylene phosphamide.
2. Melt and cool to 0-5°C to produce thionyl chloride.
38 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 reaction for about 1 hour, the reaction solution was poured into 600 cc of ethanol to precipitate a reaction product. The precipitate was passed through the mouth and dried under vacuum at 40° C. to obtain about 6 g of a polymer compound having a repeating unit of formula (82).

IR spectrum analysis, thermal IT analysis (TGA-DT
A) When the molecular weight was measured by GPC, the following results were obtained.

IR Spectrum The IR chart taken with the KBr disk method is shown in Figure 20, and characteristic absorptions of ester, amide I, ■, ■, alkyl chain, and ether were displayed.

(TGA-DTA) Rigaku Denki layer RTG-DTA, full scale (H) type
/L/TGA 10 w, DTA 100 # v,
Temperature: 1000°C, heating rate: 10°C/min, nitrogen flow (30°C)
Figure 21 shows the results measured in mffi/min).

TGA shows significant inflection points at 207°C and 262°C. Although there is no clear decomposition point, decomposition appears to progress at temperatures above 400°C.

On the other hand, Figure 22 shows the TGA-DTA curve when the temperature was raised to 300°C and kept at 300°C for 1 hour. This is almost the same as the weight loss (calculated value) of 43.1% when stearyl alcohol is removed from the polymer compound of Example, and it is considered that imidization is completed and polyamide-imide is produced.

This is also suggested by the IR spectrum of the product after this treatment (Figure 23).

By GPC The number average molecular weight calculated by comparing the GPC results measured with a mixed solvent of N,N-dimethylacetamide and chloroform with a standard sample of boristyrene is approximately 2.
It was 0.000.

Example 8 Formula (83) was synthesized in the same manner as in Example 7 using p-phenyl diamine instead of diaminodiphenyl ether.
A polymer compound with repeating units was obtained. The IR spectrum and thermal analysis results are as shown in Figure 24.25, and Example 7
showed similar characteristics.

Example 9 Chloroform/dimethylacetamide-57 distilled with 2.389 milliunits of each of the products of Examples 7 and 8.
A developing solution for LB film of 25 compositions was prepared by dissolving it in a mixed solution of 5 (volume ratio).

When the relationship between the surface pressure and the area per repeating unit was measured at 20° C. over double-distilled water, the results shown in FIGS. 26 and 27 were obtained. 75 people/unit+50 people/un each
The surface pressure rose rapidly from about 100 mt, and a good condensed film was formed. Also, the ultimate area is 60 A2/u for each
nit, 38 A2/unit, and the collapse pressure is also 4
It showed a very high value of 0 dyne/am or more for a polymer membrane.

Next, the surface pressure of the film on the water surface was maintained at 25 dyne/co+, and 25 and 247 ii of the films were accumulated on a glass substrate or a CaFZ plate, respectively, by the LB method at an accumulation rate of 10 w/min. It was also confirmed that the FT-IR from the film obtained on the CaFz plate was a Y-type film from the 0 area 1 hour curve that coincided with the IR of the compound obtained in Example 7.

It should be noted that when the film of Example 7 used in this example was formed, no peak was observed in analysis by X-ray diffraction because Cd'' etc. were not included and the film thickness was thin.

Example 10, 2.18 g (0.01 mol) of lomeliftic dianhydride, and 5.40 g (0.02 mol) of stearyl alcohol were mixed in a flask at about 100°C under a stream of dry nitrogen.
Allowed time to react.

The obtained reaction product was added to 40 cc of hexamethylene phosphamide.
2. Melt and cool to 0-5°C to produce thionyl chloride.
38 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.

Then dimethylacetamide 5 Q cc nit8! 2 g (0.01 mol) of soluted diaminodiphenyl ether
was added dropwise at 0 to 5°C, and after reacting for about 1 hour,
The reaction solution was poured into 600 cc of distilled water to precipitate the reaction product. The precipitate was passed through the mouth and dried under reduced pressure at about 40°C to obtain about 9 g of pale yellow powder.

The obtained powder was subjected to IR spectrum analysis and thermal analysis (T
CA-DTA), the molecular weight was measured by GPC.

IR spectrum analysis The IR spectrum measured by the KBr disk method was
The IR spectrum shown in the figure includes characteristic absorptions of ester, amide I absorption band, (2) absorption band, (2) absorption band, alkyl chain, and ether.

Thermal analysis (TGA-DTA) Full scale TGA 10 tg, DTA 100 /JV, RTG-DTA (H) type manufactured by Rigaku Denki,
Temperature 1000℃, temperature increase 10℃/min, nitrogen flow (
Figure 29 shows the results of the measurement at 30 mg/min).

TGA has inflection points at 271.318 and 396.592°C, and DTA has a characteristic peak around 657°C.

Figure 30 shows how the obtained precursor was heated at 10°C/10°C to 400°C.
The results are shown when the temperature was raised at 111n, kept at 400°C for 1 hour, returned to room temperature, and then raised to 1000°C at a rate of 10°C/win.

By keeping it at 400°C for 1 hour, the weight almost reaches a constant weight and the imidization reaction is completed. Even when this was returned to room temperature and heated again, the weight did not change until it exceeded 450°C, and it became clear that thermal decomposition started at 584°C, which is the same as the thermal decomposition temperature of polyimide film, and the imidization reaction was terminated. It can be seen that by doing so, a film having the same heat resistance as a polyimide film can be obtained.

Molecular weight measurement by GPC GPC measured with N,N-dimethylacetamide solvent
The number average molecular weight calculated by comparing the results with polystyrene standard samples was about 5o, ooo.

Example 11 A developing solution for LB membrane was prepared by dissolving 55.1 ml of the product of Example 10 in a mixture of distilled chloroform/dimethylacetamide-872 (volume ratio) to make a 25r1 solution.

Using the obtained developing solution, place the surface pressure π on double distilled water at 20°C.
When the relationship between this and the area per repeating unit (unit) was measured, the results shown in FIG. 31 were obtained. The surface pressure rose rapidly from around 75/unit, forming a good condensed film. The ultimate area is 60 A”/unit
The collapse pressure was also 55 dyne/ca, which is a very high value for a polymer membrane. Also, the surface pressure is 25 dyn.
Even when the membrane was held on the water surface at a constant temperature of e/am, no decrease in area was observed over 2 hours, indicating that the membrane was stable. Next, the surface pressure of the film on the water surface was kept at 25 dyne/mouth at 20° C., and the cumulative speed was 10 m/min, and 60 layers were accumulated on a glass substrate or a CaFz plate by method B.

When the film formed on the CaFt plate was analyzed by FT-IR, a spectrum as shown in Figure 32 was obtained, indicating that it was a cumulative film of the compound obtained in Example 10, and that it was a Y-type film from the area-hour curve. was confirmed. Although the aqueous layer used in this example does not contain Cd'' ions, etc., only one peak was observed at 20-4.65° in analysis by cumulative film 90FtOX ray diffraction.

This was a cumulative film of the compound obtained in Example 1, and it was confirmed from the area-hour curve that it was a Y-type film. Although the water layer used in this example does not contain Cd" ions, etc., only one peak was observed at 20-4° and 65° in the X-ray diffraction analysis of the 90 layers of the cumulative film. It was done.

Bragg diffraction conditions: nλ-2dsin θ, n=3.
+λ-1,5418 people, d (-N film thickness) is calculated to be 28.5 people, which is almost the same as the value when the long chain alkyl group stands vertically in the amphoteric polyimide precursor. Match.

Further, by heating the cumulative film at 400°C for 1 hour, α, β-unsaturated 5-membered ring imide is produced.
-1790011-”% 17 by ATR-IR analysis
It was confirmed by the peak of 10aa-1.

Furthermore, when the product of Example 10 was heated at 400°C for 1 hour, it was confirmed that the weight decreased by 58% (weight %, the same applies hereinafter) and that it was imidized by infrared absorption spectrum analysis. The decrease was in good agreement with the calculated value of 58.7% when stearyl alcohol disappears by imidization.

Comparative Example 1 A polyimide precursor was synthesized in the same manner as in Example 10 using n-decyl alcohol (n-CmfhOH) instead of stearyl alcohol.

This polyimide precursor was analyzed by IR spectrum analysis, thermal analysis,
As a result of molecular weight measurement by GPC, it was found that the polyimide precursor had the same characteristics as the polyimide precursor of Example 10, but the measurement results of the surface pressure area curve were as shown in FIG.
It showed only a liquid expanding phase and no condensed phase. Therefore, it has become clear that the length using an alkyl group having 10 carbon atoms is too short to obtain a safe condensed phase.

Examples 12 to 14 Polyimide precursors were synthesized in the same manner as in Example 10 using lauryl alcohol, myristyl alcohol, and cetyl alcohol each having 12.14.16 carbon atoms instead of stearyl alcohol (Examples 12 to 14, respectively). When alcohol with 12.14 carbon atoms was used, the behavior was intermediate between that with 10 and 18 carbon atoms, but when alcohol with 16 carbon atoms was used, the behavior was similar to that with 18 carbon atoms. It has been revealed that a stable condensation film can be formed in the same manner as in

Example 15, 10.91 g of lomeliftic acid dianhydride, and 27.05 g of stearyl alcohol were reacted at 120°C for 3 hours, and the product was recrystallized with 200-ethanol to give an M point of 133 to 13.
Distearyl pyromellitate at 7°C was obtained.

3.79 g of this distearyl pyromellitate was added to 6Q
cc of hexamethylene phosphamide, cooled to 5°C, added dropwise 1.19 g of thionyl chloride at about 5°C, held for about 1 hour after dropping to complete the reaction, and then dissolved in 30 cc of dimethylacetamide. 1 to 2 g of diaminodiphenyl ether dissolved in water was added dropwise at about 10°C, and about 2
After raising the reaction temperature to 0°C and reacting for 2°C, 400
The reaction product was precipitated by pouring into cc of ethanol.

The precipitate was filtered through the mouth and dried at 40°C to obtain about 3.4 g of pale yellow powder.

IR spectrum analysis, thermal analysis (TGA-DTA), GP
When the molecular weight was measured using C, the following results were obtained.

IR spectrum analysis The IR chart taken using the KBr disc method is shown in Figure 34, and characteristic absorptions of ester, amide I, n, III, alkyl chain, and ether were observed.

Thermal analysis (TQA-DTA) Rigaku Denki side RTG-DTA (H type full)
r-le TGA 10 m;t, DTA 1'OO,!
Figure 35 shows the results measured at a temperature of 1000°C, a temperature increase of 10°C/5h, and a nitrogen flow (30m/1in1).TGA contains 203,270,3
Although there is an inflection point at 54,403.580°C, there is no characteristic peak in DTA.

Molecular weight measurement by GPC Chloroform, N,N-dimethylacetamide (8
:2) The number average molecular weight measured using the mixed solvent was approximately 15,000 in terms of polystyrene.

Example 16 55.1 square centimeters of the product of Example 15 was dissolved in a mixture of distilled chloroform/dimethylacetamide-18/2 (volume ratio) to prepare a 25-volume developing solution for LB membrane.

Example 7 Chloroform distilled from 55.1 μ of the product of Example 1/
A developing solution for LB membrane of 25-2 was prepared by dissolving it in a mixed solution of dimethylacetamide-8/2 (volume ratio).

When we measured the relationship between the surface pressure and the area per repeating unit over double-distilled water at 20°C, we obtained the results shown in Figure 36.The surface pressure rises rapidly from about 60 A''/unit, indicating a good result. A condensed film was formed with an ultimate area of about 55 dyne/unit and a collapse pressure of 45 dyne/am.
Met. (Figure 36-A) Combine equal volumes of a solution of stearyl alcohol with the same molar concentration as the above solution:
When the surface pressure area curve was evaluated with the sum of the number of repeating units of the product of Example 1 and the number of stearyl alcohol molecules equal to Figure 3.6 = A, a result as shown in B was obtained. The addition of stearyl alcohol made the rise of the curve even steeper, and the collapse pressure was about 60 dyne/
cm, indicating that the film is stabilized.

The accumulation on the aluminum-deposited glass substrate and the glass substrate treated with the silane coupling agent A-1100 or A-187 was Y-type regardless of whether or not stearyl alcohol was added, and a good accumulated film was obtained. .

Furthermore, 1 of the product of Example 15 and stearyl alcohol
:1 (molar ratio) was accumulated on a germanium substrate and heated at 400°C under a nitrogen stream for 1 hour.
Disappearance of stearyl group and 1790 by ATR-IR method
．． The appearance of a 5-membered ring imide at 1710 am-1 was observed.

Example 1゛7 2.47 g of distearylpyromellita synthesized in the same manner as in Example 15 was added to dried hexamethylene phosphamide 12c.
thionyl chloride by cooling to 0-5°C in c
4 g was acylated.゛This acylated product was then mixed with 0.358 g of resorcinol and 0.26 g of caustic soda in advance.
It was added to the aqueous solution prepared from g at room temperature while drying. The generated precipitate was separated and purified by reprecipitation to obtain 0.92 g of white powder. IR spectrum analysis, thermal analysis, and molecular weight measurement by CPC gave the following results.

IR spectrum analysis An IR chart taken in the same manner as in Example 15 is shown in FIG. 37, and characteristic absorptions of ester and alkyl chains were observed.

The results measured in the same manner as in Thermal Analysis Example 15 are shown in FIG. TGA has an inflection point at 265, 355, 397°C, and rapid thermal decomposition begins above 265°C;
It is considered to be thermally stable up to about 0°C. On the other hand, for DTA, a sharp endothermic peak at 160''C and a broad exothermic peak that appears to be due to thermal decomposition were observed.

Molecular Weight Measurement by GPC The number average molecular weight measured in the same manner as in Example 15 was about 7,000 in terms of polystyrene.

Example 18 A developing solution for 10-LBFi was prepared by dissolving 17.3 .mu. of the product of Example 17 in a mixed solution of chloroform/dimethylacetamide-19=1 (volume ratio).

The relationship between the surface pressure and the area per repeating unit was measured on double distilled water at 22°C, and as shown in A in Figure 39, it was expansive and collapsed at about 30 dyne/cn.
When ne/C20 was accumulated at a cumulative speed of 10 m/min, it was accumulated only when the substrate was lifted.

Next, when the above solution and stearyl alcohol were mixed as in Example 16 and the surface pressure area curve was measured, the rise of the curve became steep as shown in B in FIG. Furthermore, it was confirmed from the area-hour curve that a Y-type film could be obtained on a glass substrate by mixing it with stearyl alcohol at a molar ratio of 181.

Example 19 In a 200 mi' four-loaf flask, trimellitic acid monostearyl ester (2.31 g, 5.00 mmol), HMPA (30 m) and thionyl chloride (1.
19 g, 10.0 mmol) and t of acid chloride solution.
2,5-diaminobenzamide (0,
756 g, 5.00 mmol).

Continue stirring for an additional hour or more, and gradually return to room temperature.

When the reddish-brown reaction solution is poured into 500i of ethanol while stirring with a mechanical stirrer, a white precipitate is formed. Separate this daily, wash it with water and ethanol in that order,
After drying under reduced pressure, polyamide was obtained as a pale yellow solid (2.30 g, yield 80%), the structure of which was determined by IH-NMR.
and IR spectrum.

Identified it more.

Polyamide was obtained as a body (2.30 g, yield 80
%), and the structure was identified from IH-NMR and IR spectra.

IH-NMRSI R spectrum analysis, thermogravimetric analysis (T
C, A-DTA), the molecular weight was measured by GPC and the following results were obtained.

IH-IJMR DMF-dy +CDCJ! The proton NMR spectra taken with the three solvents were assigned as follows.

60.7 ~1.7 (m, 35HC0zCH
zC1) H3ff) δ4.25 (
t, 2HC0zCHzCI? Hsr) δ7.90~
8.40 (m, 6H, Aromatic) CON
No H proton was observed.

131 The IR chart taken using the KBr disc method is shown in Figure 40, showing that ester, amide 1. Il, II[, characteristic absorptions of alkyl chains were observed.

Rigaku RTG-DTA (H) type, full scale TGA 10mg, DTA 100μv, temperature 1000℃
Temperature increase 10℃/min + nitrogen flow (302i/win
) The results measured in Figure 41 are ・TGA has 23
0,288,360. ．． There was an inflection point at 400°460.507°C, and a characteristic peak was seen around 525°C.

On the other hand, FIG. 42 shows the results when the temperature was raised to 450° C. at a rate of 10° C./min and maintained at 450° C. for 1 hour.

When heated at 450°C for 1 hour, the weight gradually decreases, but heat resistance of 400 to 450°C is expected.

As described above, after ring-closing the amphoteric polymer compound of this example, an absorption similar to an imide bond was observed in the IR spectrum of the compound, and it was confirmed that the alkyl group had disappeared. The weight loss after heating at 450°C for 1 hour was 48.
At 4%, stearyl alcohol and water are eliminated to form a closed ring structure, which is in good agreement with the Mfa reduction i5' of 0.1%.

'-:IN by GPC The number average molecular weight was about 16,000 in terms of polystyrene, as determined by GPC using a mixed solvent of N,N-dimethylacetamide and chloroform.

The product of this example was dissolved in a mixture of distilled chloroform/dimethylacetamide-515 (volume ratio): c2
5r! A developing solution for Le's LB membrane was prepared.

When the relationship between surface pressure and area per repeating unit was measured on double-distilled water at 20°C, the results shown in Figure 43 were obtained*50. The surface pressure rose rapidly from about p/unit, and a good condensation film was formed.The collapse pressure was 30 d.
It was yne/cm. When equimolar amounts of stearyl alcohol were mixed, a very good surface pressure-area curve was obtained.

(FIG. 44) It was revealed that when the amphoteric polymer compound of this Example was mixed with an equimolar amount of stearyl alcohol and accumulated on an aluminum-deposited glass substrate, it was accumulated in a Y-shape.

Further, the obtained 61-layer cumulative film had a thickness of about 1800 Å and had good insulating properties from capacitance measurements.

Further, by heating the cumulative film at 450°C for 1 hour, FT-IR shows that bonds similar to imide bonds are generated.
This was confirmed by analysis of peaks at 1790 cm-'' and 1710 am'.

Example 20 10.91 g of pyromellitic dianhydride and 27.05 g of stearyl alcohol were reacted at 120°C for 3 hours, and the product was recrystallized with 200-ethanol to give a melting point of 133-13.
Lomellitic acid distearyl ester at 7°C was obtained.

Pyromellitic acid distearyl ester (3.80 g, 5.00 mmol), thionyl chloride (1.19 g, 10.Q mmol) at room temperature in a 2001ni four-bottle flask.
and HMPA (No. 50) in an acid chloride solution prepared from
2.5-Diaminohenzamide (0,765g, 5.
A dimethylacetamide (30d) solution of 00 mmol) was added dropwise, stirred for more than 1 hour, and gradually returned to room temperature.
When added to 0-ethanol, a pale yellow precipitate is formed. After washing it with water and ethanol in that order,
When dried under reduced pressure, the polyamide becomes a yellow solid (3°55
g, yield 81%) was obtained.

1M-NMR, IR spectrum analysis, thermal mass analysis (TG
A-GTA), the molecular weight was measured by PGC, and the following results were obtained.

H-NMR DMF-dr +Proton N taken with CDC1g solution
The MR spectrum was as shown in FIG.

The IR chart taken using the TR spectrum KBr disk method is shown in Figure 46, and characteristic absorptions of ester, amide I, n, m, and alkyl chains were observed.

-DTA (H) type full scale TGA 10nw, DTA 1"O'0 μV, temperature rise 10'C/win at 1000℃, nitrogen flow (3
Figure 47 shows the results measured in 0rtdl/min') - TGA has 238,292.3!55
There is an inflection point at , 400, 485, and 592 degrees Celsius, and no characteristic peaks are seen in DTA.

On the other hand, FIG. 48 shows the results when the temperature was raised to 500°C at a rate of 10°C/+nin and maintained at 500°C for 1 hour.

Even if heated for 1 hour in soo'c, there is almost no weight loss (thermally stable and heat resistance of 500°C or higher is expected).

The IR spectrum of the amphoteric polymer compound of this example after ring closure is as shown in FIG. 49, and although the transmittance is not good, absorption similar to imide bonds is observed. Also 5
The weight loss after heating at 00° C. for 12 hours was 64.7%, and stearyl alcohol and water were eliminated to form polyimide isoindoquinazolinedione. Theoretical weight loss 64.
It's 1% (it's consistent).

cpc: I According to GPC measured using a mixed solvent of N,N-dimethylacetamide and chloroform, the number average molecular weight was about 42.000 in terms of polystyrene.

The product 55.1 trg of this example was dissolved in a mixed solution of distilled chloroform/dimethylacetamide-872 (volume ratio) to prepare a 25r1 LB membrane developing solution.

When the relationship between surface pressure and area per repeating unit was measured at 20° C. over double-distilled water, the results shown in FIG. 50 were obtained. The surface pressure rose rapidly from about 90 mm/unit, and a good condensed film was formed.

The ultimate area is 75 A”/unit and the collapse pressure is 30 dy.
It was ne/mouth.

When equimolar amounts of stearyl alcohol were mixed, a very good surface pressure-area curve was obtained (FIG. 51).

It was found that when the amphoteric polymer compound of this example was mixed with equimolar stearyl alcohol and accumulated on an aluminum-deposited glass substrate, it was accumulated in a Y-shape.

Further, the obtained 61Jii cumulative film had a thickness of about 1800 Å and had good insulation properties as determined by capacitance measurement.

Furthermore, it was confirmed by the peaks of 1790aa-1 to 17103-1 by FT-IR analysis that bonds similar to imide bonds were generated by heating the cumulative film at 500° C. for 1 hour.

Example 21, 10.91 g of Lomeliftic dianhydride, and 27.05 g of stearyl alcohol were reacted at 120°C for 3 hours, and the product was recrystallized with 200-ethanol to give a melting point of 133-1.
Pyromellitic acid distearyl ester at 37°C was obtained.

Weighed pyromellitic acid distearyl ester (2.84 g, 3.74 mmol) into a 200 d four-bottle flask,
Hexamethylphosphoric triamide (HMPA, 30
Thionyl chloride (0.87 g,
After discharging 7.48 mmol) and continuing stirring for an additional hour, acid chloride in the form of a pale yellow paste was obtained. Add 30 to 40 d of methylene chloride (dried with calcium chloride) to this to make a homogeneous solution. Separately, put tetraaminobenzidine (0,800 g,
3°74 mmol) in dimethylacetamide (30d
), and the acid chloride solution is added dropwise over about 30 minutes at about 5° C. under nitrogen gas flow and stirring with a mechanical stirrer. After stirring for an additional 3 hours, the temperature was gradually returned to room temperature. After the reaction was complete, the reaction mixture was heated to 500 m
When added to ethanol with stirring using a mechanical stirrer, a pale yellow precipitate precipitates out. This was mixed with a Kiryama rotor, washed with water and ethanol, and then dried under reduced pressure to obtain 0.91 g of an amphoteric polymer compound (yield 26%).
Obtained.

IH-NMR, rR spectrum analysis, thermogravimetric fraction Fr (T
GA-GTA), the molecular weight was measured by GPC, and the following results were obtained.

IH-NMR The proton NMR spectrum taken with the DMF-dr + 'CDCl3 solution was assigned as follows.

δ1-20 (ffis 70HC02CH2C
I7 Lyri) 64.25 (t,
4HC0zCHzC1Hm>67.95~8.25
(m, 8H, Aromatic) CONH protons were not observed.

The IR chart taken with the IR spell KBr disc method is shown in Figure 52, and characteristic absorptions of ester, amide I, Il, III, and alkyl chain were observed.

a TGA-DTA) Rigaku Denki Rifu RTG-DTA (Hj type, full scale TGA 10mg, DTAloo, IJV, temperature 100
Temperature increase at 0℃ 10℃/1nin + nitrogen flow (30m12/
+jn) Figure 53 shows the measured results.

200,275,330,385゜605℃ for TGA
There was an inflection point in the area, and no characteristic peaks were observed in the DTA.

On the other hand, in FIG. 54, the temperature is increased to 400°C at a rate of 10°C/min,
These are the results when the temperature was kept at 450°C for 1 hour.

After heating at 400℃ for 1 hour, it reached almost constant weight.
Heat resistance of about 400 to 450°C is expected.

As described above, an absorption similar to an imide bond was observed in the IR spectrum of the amphoteric polymer compound of this example after ring closure, and it was confirmed that the alkyl group had disappeared. Also, the weight loss after heating at 400℃ for 1 hour was 65.0
%, which is almost in agreement with the theoretical weight loss of 61.7% when stearyl alcohol and water are eliminated to form a closed ring structure.

According to GPC measurement using a mixed solvent of N,N-dimethylacetamide and chloroform, the number average molecular weight was approximately 28,000 using a polystyrene substituted nose.

The product of this example was dissolved in a mixture of distilled chloroform/dimethylacetamide-8/2 (volume ratio).
A five-component developing solution for LB membrane was prepared.

When the relationship between the surface pressure and the area per repeating unit was measured on double-distilled water at 20°C, the results shown in Figure 55 were obtained.* From about 75 A2/unit, the surface pressure rises rapidly and a good result is obtained. A condensed film was formed.

The ultimate area is 63 i”/unit and the collapse pressure is 35 dy.
It was ne/mouth.

When equimolar amounts of stearyl alcohol were mixed, a very good surface pressure-area curve was obtained (FIG. 56).

It was found that when the amphoteric polymer compound of this example was mixed with equimolar stearyl alcohol and accumulated on an aluminum-deposited glass substrate, it was accumulated in a Y-shape.

The obtained 61rt1 cumulative film had a thickness of about 1,800 mm and had good insulation properties from capacitance measurements.

Furthermore, FT-IR shows that bonds similar to imide bonds are generated by heating the cumulative film at 400°C for 1 hour.
This was confirmed by analysis of peaks at 1790 lohe and 1710 cmt'.

main! According to the present invention, by modifying a polymer compound that is originally difficult to form into a film using the LB method, it becomes possible to form a thin film using the same method, and if necessary, partial or By completely cyclizing, it is generally possible to create i! which has extremely good heat resistance, chemical resistance, good mechanical properties, and few pinholes. I'! i.e. 10.000 Å
Below, if desired, an ultra-thin film of 10 to 1000 people can be obtained.

[Brief explanation of the drawing]

1 to 7 are schematic diagrams of typical MIS structure devices, FIGS. 8 to 10 are MTM structures, and FIGS. 11 to 13 are 1M structures. Figure 14.15 shows N, N'-distearyl-p, respectively.
- IH-NMR spectrum of phenylenediamine and I
This is the R spectrum. Figures 16 and 17 are the IH-NMR spectrum and IR spectrum of the polyamide synthesized in Example 1, respectively. Figure 18 shows thermal analysis of the polyamide synthesized in Example 1 (
FIG. 19 is a surface pressure-area curve of the polyamide of Example 1. Figures 20 and 24 are infrared absorption spectra synthesized in Example 7.8, and Figures 21 and 25 are the results of thermogravimetric analysis (TGA-DTA). Figure 22 shows that the temperature was raised at 10°C/win up to 300°C, and 30°C
The gravimetric analysis results were obtained when the sample was left at 0°C for 1 hour, and Figure 23 shows the infrared absorption spectrum after being treated at 300°C for 1 hour. 26 and 27 are surface pressure/area curves of the polymer compounds synthesized in Examples 7 and 8, respectively. Figure 28 is the IR spectrum of the precursor obtained in Example 10, Figure 29 is a graph showing the thermogravimetric analysis (TGA-DTA) results of the precursor obtained in Example 10, and Figure 30 is the example The precursor obtained in step 10 was heated from room temperature to 400°C, kept there for 1 hour, cooled to room temperature, and further heated to 400°C.
Thermogravimetric analysis (TGA-DTA) when the temperature is raised to 0℃
A graph showing the results, FIG. 31 is a graph showing the results of measuring the relationship between surface pressure and area per repeating unit when the precursor obtained in Example 10 was spread on the water surface according to Example 11, Figure 32 shows the spectrum showing the FT-IR measurement results of the film developed on the water surface and accumulated on the CaFz plate by the LB method, and Figure 33 shows the surface pressure and surface pressure of the precursor obtained in Comparative Example 1. It is a graph showing the results of measuring the relationship with the area per repeating unit. FIG. 34 shows the infrared absorption spectrum of the precursor obtained in Example 15, and FIG. 35 shows the results of thermal analysis. FIG. 36 is a surface pressure-area curve when the precursor obtained in Example 15 is mixed with stearyl alcohol at a molar ratio of 1:1. Figure 37 is the IR spectrum of the polymer compound obtained in Example 17, and Figure 38 is its thermal analysis (TGA-DTA).
Figure 39 shows the results of measuring the relationship between surface pressure and area per repeating unit when the polymer compound obtained in Example 17 was spread on the water surface according to Example 18. It is a graph. FIG. 40 shows the infrared absorption spectrum of the amphoteric polymer compound obtained in Example 19, and FIG. 41 shows the results of thermogravimetric analysis. Figure 42 shows the weight change (TGA) and thermal change (DTA) when the temperature was raised from room temperature to 450℃ and kept there for 1 hour.
). Figure 43 shows the relationship between the surface pressure and the area per repeating unit when the amphoteric polymer compound obtained in Example 19 is spread on the water surface, and Figure 44 shows the relationship between the area per repeating unit when the amphoteric polymer compound obtained in Example 19 is mixed with equimolar stearyl alcohol. is the surface pressure-area curve of . Figures 45 and 46 show the IH-NMR and infrared absorption spectra of the amphoteric polymer compound obtained in Example 20, and Figure 47 shows the results of thermogravimetric analysis. Figure 48 shows 500 degrees from room temperature.
Change in weight when heated to ℃ and kept there for 1 hour (T
GA), thermal change (DTA). Figure 49 shows the infrared absorption spectrum of the product ring-closed by heating at 500°C for 1 hour, and Figure 50 shows the surface pressure and per repeating unit when the amphoteric polymer compound obtained in Example 20 is spread on the water surface. Fig. 51 shows a surface pressure-area curve when equimolar amounts of stearyl alcohol are mixed. FIG. 52 shows the infrared absorption spectrum of the amphoteric polymer compound obtained in Example 21, and FIG. 53 shows the results of thermogravimetric analysis. Figure 54 shows the heavy N change (TGA) and thermal change (DTA) when the temperature was raised from room temperature to 400°C and kept there for 1 hour.
). Figure 55 shows the relationship between the surface pressure and the area per repeating unit when the amphoteric polymer compound obtained in Example 21 is spread on the water surface, and Figure 56 shows the relationship between the area per repeating unit when the amphoteric polymer compound obtained in Example 21 is mixed with equimolar stearyl alcohol. is the surface pressure-area curve of . Figure 1 Figure 2 Figure 7 Figure 9 Figure 10 Figure 11 Figure 29 Figure 81 L fi (A /unit) Area (A' unit) Figure 36 fo flu , (A'''/L+nit )Figure 55Figure 56

Claims (7)

[Claims] (1) At least 2 having at least 2B carbon atoms
A linear repeating unit in which a valent first organic group R_1 and at least a divalent second organic group R_2 having at least two carbon atoms are alternately connected by a divalent bonding group. , and a hydrocarbon-containing group R_ having 10 to 30 carbon atoms, which may contain a substituent and covalently bonded to the repeating unit.
An amphoteric polymer compound containing at least one of 3. (2) The amphoteric polymer compound according to item 1, which contains two hydrocarbon-containing groups R_3 per repeating unit. (3) The amphoteric polymer compound according to item 1 or 2, wherein the hydrocarbon-containing group R_3 contains 16 to 22 carbon atoms. (4) The amphoteric polymer compound according to item 1, item 2, or item 3, wherein one or both of the first and second organic groups R_1 and R_2 is a group having a benzenoid structure having at least 6 carbons. (5) The hydrocarbon-containing group R_3 is an aliphatic group, a group in which a cycloaliphatic and an aliphatic are bonded, a group in which an aromatic and an aliphatic are bonded,
or a substituent thereof, the amphoteric polymer compound according to any one of items 1 to 4. (6) Items 1 to 5, in which the repeating unit has a precursor structure that produces a 5-membered ring or a 6-membered ring containing a heteroatom.
The amphoteric polymer compound according to any one of paragraphs. (7) A monomer containing the first organic group R_1 and a monomer containing the second organic group R_2, (A-R_1-A)+(B-R_2-B) (A-R_1-B)+( B-R_2-B) (B-R_1-B)+(B-R_2-A) ▲There are mathematical formulas, chemical formulas, tables, etc.▼+(B-R_2-B
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using a monomer containing the first organic group R_1
2. The method for producing an amphoteric polymer compound according to claim 1, wherein a monomer containing R_2 and a monomer containing the second organic group R_2 are polycondensed.