JPS6372375A - Amphoteric high-molecular compound and its preparation - Google Patents

Abstract

PURPOSE:To form an ultrathin LB film excellent in physical properties, by using an amphoteric high-molecular compound obtained by bonding a specific hydrocarbon-containing group to a repeating unit consisting of the first and second org. groups through a covalent bond. CONSTITUTION:An amphoteric high-molecular compound has a fundamental skeletal composed of repeating units, for example, represented by formulae I, II (wherein R1 is the first tetravalent org. group having at least two carbon atoms, R2 is the second divalent org. group having at least two carbon atoms, A is an acidic group containing a heteroatom such as O, N or S, B is a basic group containing a heteroatom such as O, N or S and AB and BA are a divalent bonding group formed by the reaction of A and B). By interoducing a 10-30C hydrocarbon-containing group R3 into said repeating units by at least one covalent bond, said compound can be modified so as to be capable of being formed into a film by an LB method.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field The present invention relates to an amphoteric polymer compound, particularly an amphoteric polymer compound modified to form an M 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 water surface and accumulate it on a substrate, but there were no technical applications. It is only recently that studies have begun to be conducted.

For an overview of past research, see Solid State Physics 17 (12
) 45 (1982) Th1n 5olid Fi
lms 68 No. 1 (1980).

1bid, 99 No. 1.2.3 (1983)
In5olable monolayer sat l
iquid-gas 1nterfaces (G,L
, Ga1ns, Inter-science Pu
blishers+ New You+ 1966)
However, the conventional Langmuir-Prodgett membrane (hereinafter referred to as rLB membrane 2) of straight-chain saturated fatty acids
has drawbacks in heat resistance and mechanical strength, and cannot be used as is for practical applications.

Unsaturated fatty acids, such as ω-
Polymer films made of tricosenic acid, ω-hebutadenoic 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. This is not possible, and 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 Langminia-Prodgett membranes. Polymers have not been considered so far, and excellent L
There is nothing that can be called a B film material.

On the other hand, polyimide is used as a heat-resistant film, but depending on methods such as spin cording, it is usually 1p or more and at most 100oA or more, and it is very difficult to create a heat-resistant thin film without pinholes of 10008 or less.

III. Fortune telling.

The purpose of the present invention is to make it possible to form films using the Langmuir-Prodgett method by modifying polymer compounds that are originally difficult to form into films using the Langmuir-Prodgett method. Polymer LBIj with improved mechanical properties and a thickness that is generally difficult to form! An object of the present invention is to provide an amphoteric polymer compound that is a material for the production of an amphoteric polymer compound, and a method for producing the same.

. According to the present invention, the above-mentioned problem can be solved by combining a tetravalent first organic group R1 having at least 2 (!I carbon atoms) and a divalent second organic group R1 having at least 2 carbon atoms. The organic group R2 is 2
A hydrocarbon-containing group R having from 10 to 30 carbon atoms, which may contain a substituent group, and which has linear repeating units alternately connected by valent bonding groups and is covalently bonded to the repeating units.
The present invention is solved by providing an amphoteric polymer compound containing at least one of 3.

Specifically, the amphoteric polymer compound of the present invention has the following formulas (1) to
The repeating unit of (9) is used as the basic skeleton.

Here, A is an acidic group containing a heteroatom such as O, N, S, P, or B, preferably -COOR (R is an alkyl group or a water atom, the same applies hereinafter), -COX
(X is chlorine or bromine, the same applies below), -NCO,
-NCS, -CN.

-CONHR, -502NHR, etc.

B is a basic group containing a heteroatom such as o, N, S, P, B, preferably -NHR,,,OR,, -
SR, -X, etc.

In formulas (1) to (9), AB and BA are divalent bonding groups formed by the reaction of A and B, and examples thereof include: and the like.

The amphoteric polymer compound of the present invention has repeating units (1) to (9) having 10 to 30 carbon atoms. At least one, preferably two, preferably 16 to 22 hydrocarbon-containing groups R3 are introduced by covalent bonding and modified to allow film formation by the Langmuir-Prodgett method.

Methods for introducing the hydrophobic group R3 do not exclude the method of directly substituting R3 to R1 and R2, but A, B, AB,
It is desirable from the viewpoint of synthesis, cost, etc. that at least one, preferably two, of BAs be replaced by R3. When two or more R3s are introduced into the same repeating unit, R3s with mutually different structures may be selected from the range of R3s previously carried.

More specifically, the method of increasing the substituent of R3 and the sequence of position I are listed as follows: A: -COOR3, -CONHR3, -NHCO
OR3, -3O2NHR3B: -NHR
*+ -OR3, -SR3゜, etc., and A and B are obtained by the method selected from these.

At least one, preferably two of AH, BA are substituted by R3.

Next, R1 and Rz will be explained.

R1 in general formulas (1) to (9) is a tetravalent group containing at least 2 carbon atoms, preferably 5 to 20 carbon atoms, and may be an aromatic group. , may be a cycloaliphatic group, or may be a group in which an aromatic group and an aliphatic group are bonded, and furthermore, these groups may be an aliphatic group having 1 to 3 carbon atoms, a cyclic An aliphatic group or a group in which an aromatic group and an aliphatic group are bonded, and these groups are monovalent groups such as a halogen atom, a nido tetragroup, an amino group, a cyano group, a methoxy group, an acetoxy group, Alternatively, the monovalent group is -0+, -coo +, -NHCO-
.

-CO-, -S +, -css +, -NHCS-
, -CS-, etc. may be a group substituted with a group bonded to -CS-, etc. to become a derivative.However, when R1 is a group characterized by a benzenoid structure having at least 6 carbon atoms, Preferable from the viewpoint of heat resistance, chemical resistance, mechanical properties, etc.

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

The term "benzenoid structure" as used herein is a term used in contrast to kihad 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 The four bonds of benzenoid structure R1, that is, the positions of the bonds in the repeating unit represented by general formulas (11 to (9)) are not particularly limited, but each of the four bonds When two atoms each exist on two adjacent carbon atoms constituting R1, it is preferable that a film formed using an amphoteric polymer compound is further reacted to form a 5- or 6-membered ring. .

Preferred specific examples of R1 as described above include, for example, lJ3
Examples include CF3. Again preferred.

R2 in general formulas (1) to (9) is a divalent group containing at least two carbon atoms, and may be an aromatic group or an aliphatic group ( It may be a cycloaliphatic group, or it may be a group in which an aromatic group and an aliphatic group are bonded, and furthermore, these divalent groups may be an aliphatic group having 1 to 30 carbon atoms. , a group in which a cycloaliphatic group or an aromatic group and an aliphatic group are bonded, and these groups are monovalent groups such as a halogen atom, a nitro group, an amino group, a cyano group, a methoxy group, and an acetoxy group. , or one of these
The valence group is 10-, -Coo-, -N)ICO-, -CO
It may be a group monosubstituted with a group bonded to -, -S-, -CSS-, -NHCS-, -CS-, or the like. However, R
When 2 is a group characterized by a benzenoid structure having at least 6 carbon atoms, it is preferable from the viewpoint of heat resistance, chemical resistance, mechanical properties, etc.

Preferred specific examples of R2 as described above include: where R4 is H3 Fa R5 and Rs are each an alkyl or aryl group having 1 to 3 carbon atoms CH3 CH3 (CH2)P (+) -2 to 10), -
(CHz)4-C-(CH2)2-.

CH30-(CH2)IOC)l-CH3,-(CH2)3-C
-(CH2)2-.

-(CH2)3-0- (CHz)2-0- (CH2
)3-.

CH3CH3 l CH3CH3CH3 (n-2 to 15) As a preferable specific example of R2 as described above, example (1 m
m integer from 1 to 3), -0-+ -5-1-5O2-
・-NR5-1 (hereinafter referred to as blank space) (all alkyl groups or allyl groups having 1 to 30 carbon atoms), and the like.

To explain R3, it has 10 to 30 carbon atoms. Preferably, 16 to 22 monovalent aliphatic groups, monovalent cycloaliphatic groups, monovalent groups in which an aromatic group and an aliphatic group are bonded, and these groups are halogen atoms, nitro groups, amino group, cyano group,
It is a group substituted with a methoxy group, an acetoxy group, etc.

R3 is a group introduced to impart hydrophobicity to the repeating unit -1 to obtain a stable condensed film, and forms a stable condensed film on the water surface of the amphoteric polymer compound of the present invention, which is LB; required to be deposited on the substrate.

Specific examples of R3 include, for example, CH3(CH2〒-1, (CR3)2 CH(CH2i
FV-3+ (n is 10-30, preferably 16-30)
22 integers), and CHz = C) I
CCHz'jT7z +CH3(CHz)rc a C
-CI' C (CHZ destination = (here 7+, 1-n-5)
There are groups such as Among them, the linear alkyl group represented by CR3 (CHz7FV-1) is the most desirable in terms of performance and cost. Although not essential, it is preferable to use a fluorine atom in some cases because it improves hydrophobicity compared to a hydrogen atom. Substituted groups are not excluded from the present invention.

There is no particular limitation on the molecular weight of the polymer compound of the present invention. Even if the molecular weight is low, it is possible to form a film by the film forming method of the present invention. However, in order to obtain good image sharpness, mechanical strength, and chemical resistance, it is desirable that the molecular weight is large. However, it is undesirable for the molecular weight to be too large, as the viscosity increases and film formation becomes difficult when the molecular weight becomes too large. Therefore, the weight average molecular weight is 2000-30
Something of the order of oooo is desirable.

For specific examples of the amphoteric polymer compound of the present invention (1
) to (9), the R1. Rz, R
Specific examples of z, specific examples of divalent bonding groups of AB and BA (a)
.

(Specific examples of the method and position of introducing bl and one substituent of R3 (This will become clear by substituting C+, but from the viewpoint of cost considerations in synthesizing the seven polymers and polymers, we will give a specific example) (11R31(71(If shown from formula 91, it will be as follows, fil (The example of formula 91 is a particularly desirable example.

(Type 11 (3) Formula In the formula, - represents isomerism. For example, the formula αω If you explain it with represents.

The present invention includes a case where (10-1) (10-2) is alone and a case where (10-1) (LO-2) coexists.

Other examples include Kobe Hakuta's research on thermoplasticity of polymers (Baifukan S45.3.5), thermal decomposition and heat resistance of polymers (Baifukan S49.3.15), etc. can.

The present invention also provides a method for producing the amphoteric polymer compound. In this method, a monomer containing a first organic group Rz and a monomer containing a second organic group R2 are either B B B B (wherein A represents an acidic group and B represents a basic group). In the combination, at least one of the two hepatomers to be combined uses a monomer containing one or two hydrocarbon-containing groups R3, and the first monomer containing the organic group R1 and the second monomer are used. It consists of tributary condensation of monomers containing an organic group R2.

An example of the WE method for the above specific columns (10) to (24) is as follows.

In order to explain in more detail the method for producing the amphoteric polymer compound of the present invention, the formula (1o) TE R3w CHa (CHz)
The case of rr will be described. obtained by alcoholysis of pyromellitic dianhydride under substantially anhydrous conditions in an organic polar solvent at a temperature of -1
M is produced by acylating with thionyl chloride at a temperature of 0°C or higher, preferably about 0 to 40°C, and reacting this with diaminodiphenyl ether at a temperature of -10°C or higher, preferably 0 to +10°C. Acylation and amidation reactions are usually carried out at a temperature of -10°C or higher, preferably around 0 to 40°C, since substituents such as long-chain alkyl groups in the -1 compound tend to freeze and solidify. It is desirable that the Of course, in the above cases, it is possible to mix raw materials with different substituents to make a copolymer, or to make a copolymer with no substituents in the range of 0 to 30%, or with a carbon number of 1.
It may be mixed with a tetracarboxylic dianhydride or diamine having one substituent of 0 or less.

The amphoteric polymer compound produced as described above may be separated and purified to be used as Langmier-Prodget membrane material, or after production, chloroform, benzene, etc. may be added to it to be used directly as a Langmire-Prodget sample developing solution.

Next, a Langminia O-Blodget membrane using the amphoteric polymer compound of the present invention as a material will be explained.

The Langminia O-Blodget film M method involves spreading a film-forming substance on the water surface, compressing the spread substance on the water surface with a constant surface pressure to form an acute molecular film, and then spreading the film on a substrate. In addition to methods such as the horizontal adhesion method and the one-turn cylinder method (New Experimental Chemistry Course, Volume 18, Interfaces and Colloids, 498-508), methods that are commonly used are particularly important. It can be used without limitation.

The Langmuir-Prodgett method is an excellent method for forming oriented thin films of hundreds or even tens of layers with a thickness of 2000 Å or less, or even 1000 Å or less, by a method in which the thickness can be controlled in units of tens of layers, and the present invention A thin film on a substrate has this characteristic, but a film of IP or thicker thickness can also be made into a M film using this method.In general, benzene and chloroform, which are insoluble in water and evaporate into the gas phase, are used as solvents. However, in the case of the polymer compound of the present invention, it is desirable to use an organic polar solvent in combination to raise the dissolved carbon.
Preferred organic polar solvents include N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylformamide, N,N-diethylacetamide, N,N
-dimethylmethoxyacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, pyridine, dimethylsulfone, hexamethylphosphoramide, tetramethylenesulfone, dimethyltetramethylenesulfone, and the like.

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 polymer thin film of the present invention, but there are no other major limitations, such as glass, alumina,
In addition to common inorganic substrates such as quartz, metals, plastics, Si, and GaAs.

Group II semiconductors such as ZnS, II[-V, II-Vl group semiconductors, PbTi3. BaTi3. LiNba
, ferroelectric materials such as LiTa3 can also be used as the substrate.

Of course, a fully refractive thin film on a substrate such as that described above may be patterned as appropriate for the application, and Si.

A substrate made of a semiconductor such as GaAs or ZnS or a ferroelectric material may be processed in advance to form an element.

Furthermore, it goes without saying that these substrates may be used after being subjected to a commonly used surface treatment.

In the case of the polyimide precursor of the present invention, glass, quartz,
Surfaces such as Si and 5iOz tend to have strong adhesive strength, and silane cuffing agents, especially silane cuffing agents with amino groups, epoxy groups, and alkoxy groups (such as UCC's A-1100 and A-187) treatment or treatment with a chelate containing aluminum metal to form a layer of aluminum oxide improves film forming properties and adhesive strength.
This is a preferred embodiment of the invention. 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 a thin film of a polymer compound with good heat resistance can be formed on a substrate by the Langmuir-Prodgett method, but it is also possible to partially or completely ring-close this thin film. This method has the characteristic that a thin film with improved heat resistance can be formed on a substrate.

Among examples of formulas (10) to (24), the structures after ring closure of those which can be partially or completely closed are described below.

(Left below) The ring closing method is not particularly fixed, but for example, in the case of imidization, which is an example of the α0 formula, 300 to 4
．． By heating to a temperature around 00°C, a reaction of the polymer □ ÷ 2R30H of the formula Δ001 occurs and ring closure is achieved. At this time, the group introduced for hydrophobization is eliminated as alcohol, but this eliminated alcohol is placed at a temperature of around 300 to 400°C, and if necessary, placed under a gas flow or under vacuum ( Since the polyamide-imide film can be dispersed by this process, a polyamide-imide thin film with very good heat resistance can be obtained.

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.

Optical recording films, resist films, insulating films, thin films for capacitors, liquid crystal alignment films,
I can be used as a polarizing film, a sensor film, etc., especially as an insulating film.
MIS combined with various semiconductors and metals as an insulating layer for C and LSI.

It can be used as an insulating layer in electrical and electronic devices having a structure such as MIM, and can constitute field effect transistors, photoelectric conversion devices, light emitting devices, light receiving devices, photodetecting devices, thermionic transistors, etc. In particular, the thin film of the present invention is effective for MIS and MIM devices that utilize the tunnel effect, and
It can also be used as an insulating film for J. Other applications include craft materials for Unibu guides and optical circuit components.

It would be suitable as a protective coating material in all fields, and the polymer of the present invention can be used as a substitute for fatty acids in the mixed film and laminated film method of functional LB materials and fatty acids, which are generally used in the field of LBFJ. By using it, various functionalities can be expressed, and there are many possible uses for it. For example, photoelectric conversion elements and biosensors can be created by creating films containing dyes, enzymes, etc.

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

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

Example 1 2.18 g (0.01 mol) of pyromellitic dianhydride and 5.40 g (0.02 mol) of stearyl alcohol
were reacted in a flask at about 100° C. for 3 hours under dry nitrogen flow.

The obtained reaction product was added to 40 cc of hexamethylene phosphamide.
Thionyl chloride was dissolved in 2. and cooled to 0-5°C.
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.

Thereafter, 2 g (0.01 mol) of diaminodiphenyl ether dissolved in 50 cc of dimethylacetamide was added to
The temperature was lowered at °C, and after the dropwise addition, the mixture was allowed to react for about 1 hour, and then the reaction solution was poured into 600 cc of purified distilled water to precipitate the reaction product. The precipitate was passed through the mouth and dried at 40°C to obtain about 9 g of pale yellow powder.

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

IR spectrum analysis The IR chart taken using the KBr disc method is shown in Figure 1, and characteristic absorptions of ester, amide I', n, III, alkyl chain, and ether were observed.

Thermal analysis (TGA-DTA) Rigaku Corporation RTG-DTA (H) type, full scale TGAIO ■, DTA 100μV, temperature 10OO℃, temperature increase 10℃/ff1in, nitrogen flow (30m /
Figure 2 shows the results measured in 1 lin.

192,271,318,396,592℃ for TGA
There is an inflection point at , and DTA has a characteristic peak around 657 degrees Celsius.

On the other hand, in Figure 3, the temperature is increased to 400°C at a rate of 10°C/min.
After keeping it for a while, return it to room temperature for 10 minutes at 10°C/min.
These are the results when the temperature was raised to 00°C.

By keeping it at 400°C for 1 hour, the weight almost reaches the mass of beans, and the polyimide conversion process is completed.Even if it is returned to room temperature and the temperature is raised, the weight does not change until it exceeds 450°C, and the weight of the polyimide film is Same as the thermal decomposition temperature shown 58
It became clear that thermal decomposition started at 4°C, and by terminating the polyimidation reaction, a film with heat resistance similar to that of a polyimide film was obtained.

Molecular weight measurement by GPC GPC measured with N,N-dimethylacetamide solvent
Therefore, the number average molecular weight is approximately 30.00 in terms of polystyrene.
It was 0.

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

When the relationship between surface pressure and area per repeating unit was determined on double-distilled water at 20° C., the results shown in FIG. 4 were obtained. The surface pressure rose rapidly from about 75 A2/unit, and a good condensed film was formed.

The ultimate area is 60p/unit and the collapse pressure is 55dy
ne/cf11, which is a very high value for a polymer membrane.

Further, even when the surface pressure was maintained at 25 dyne/cm and the membrane was held above the water surface, no decrease in area was observed over the two JP-A-2006-12002 patents, and the membrane remained stable.

Next, the surface pressure of the liquid on the water surface was maintained at 25 dyne/ci, and 6 t and 6 oi of the liquid were accumulated on a glass substrate or a CaFz plate, respectively, using the LB method at an accumulation rate of LOn/win. FT from the film obtained on the CaF z plate as shown in Figure 5.
-IR was obtained, and it was also confirmed from the 0-face precision one-time curve that coincided with the IR of the compound obtained in Example 1 that it was a Y-type film. Note that Cd was used during film formation in Example 1 used in this example.
4 was not included, but only one X-ray diffraction peak was found at 2θ-4.65° from the 91 layered film.

The resulting cumulative film had a thickness of about 1800 mm and had good insulation properties as determined by capacitance measurements.

Furthermore, by heating the cumulative film at 400°C for 1 hour, α, β-unsaturated 5-membered ring imide was produced.
This was confirmed by the peak at 1790,171Qcm-'' by IR analysis.

On the other hand, it has been confirmed by the IR spectrum that heating the product of Example 1 at 400° C. for 1 hour causes a 58% (wt%) reduction and imidization. The weight loss described above is in good agreement with the value of 58.7% when stearyl alcohol is calculated to disappear due to imidization.

Example 3 A polyimide precursor was synthesized in the same manner as in Example 1 using n-decyl alcohol (n-axis bou) instead of stearyl alcohol. This polyimide precursor showed the same characteristics as the polyimide of Example 1 in the molecular weight measurement by IR spectrum analysis, thermal analysis, and GPC, but the measurement result of the surface pressure area curve was as shown in Figure 6, and it was condensed only in the liquid expanding phase. No phase was shown. Therefore, it is clear that an alkyl group having 10 carbon atoms is too short to obtain a stable condensed phase.

Example 4 In the case of lauryl alcohol, myristyl alcohol, and cetyl alcohol having 12, 14, and 16 carbon atoms, the carbon number is 1.
2.14 showed intermediate behavior between 10 and 18, but it became stable when the aqueous phase was adjusted to about 5"C, and it became clear that 16 carbon atoms formed a stable condensed film similar to that of 18. Ta.

Example 5 10.91 g of pyromellitic dianhydride and 27.05 g of stearyl alcohol were reacted at 120"C for 3 hours,
The product was recrystallized from 200% ethanol to a melting point of 133~
Distearyl pyromellitate at 137°C was obtained. This 2
．． 47 g dried hexamethylenephosphamide 12C
0.74 thionyl chloride by cooling to 0-5°C in C.
Acylation was carried out using 4 g. This acylated product was then treated with 0.358 g of resorcinol and 0.26 g of caustic soda.
It was added to the aqueous solution prepared from above at room temperature with stirring. The generated precipitate was separated and reprecipitated to obtain 0.92 g of white powder.

When IR spectrum analysis and thermogravimetric analysis were performed, the following results were obtained.

IR spectrum analysis An IR chart taken in the same manner as in Example 1 is shown in FIG. 7, and characteristic absorptions of ester and alkyl chains were observed.

The results measured in the same manner as in Thermal Analysis Example 1 are shown in FIG. TGA has inflection points at 265, 355, and 397°C, and rapid thermal decomposition begins above 265°C, but it is considered to be thermally stable up to about 200°C. On the other hand, DTA
A sharp endothermic peak and a broad exothermic peak that appeared to be due to thermal decomposition were observed at 160°C.

Example 6 17.3 ml of the product of Example 5 was dissolved in a mixture of chloroform/dimethylacetamide-19:1' (volume ratio) to prepare a 10d developing solution for LB membrane.

When the relationship between the surface pressure and the area per repeating unit was measured on double distilled water at 22°C, as shown in Figure 9, it was 4° expansive and collapsed at about 30 dyne/am. Surface pressure 20dy16
/ am and accumulated at a cumulative speed of 10 m/win, it was accumulated only when lifting the board.

Next, when the above solution and a chloroform solution of stearyl alcohol were mixed at a molar ratio of 1:1 and a surface pressure area curve was measured, the rise of the curve was steep as shown 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 1=1.

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. By converting the thickness into 100%, it has extremely good heat resistance, good chemical resistance, and good mechanical properties, and has a thickness that is generally difficult to produce.

000A or less, it is possible to obtain an ultra-thin film of 1 to 1000 A as desired.

[Brief Description of the Drawings] Figure 1 shows the infrared absorption spectrum of the polymer compound obtained in Example 1, and Figure 2 shows the results of thermogravimetric analysis. Figure 3 shows the weight change (TGA) and thermal change (DTA) when the temperature is raised from room temperature to 400"C, kept there for 1 hour, lowered to room temperature, and then further raised to 1000"C. Figure 4 is the relationship between the surface pressure and the area per repeating unit when the precursor obtained in Example 1 is spread on the water surface according to Example 2. Figure 5 shows the relationship between the surface pressure and the area per repeating unit when the precursor obtained in Example 1 is spread on a CaF2 plate using a Langmuir projector. FT-ATRIR of accumulated by law
This is the result. FIG. 6 is a surface pressure-area curve of the precursor obtained in Example 3. FIG. 7 shows the infrared spectrum of the polymer compound obtained in Example 5, and FIG. 8 shows the results of thermogravimetric analysis. FIG. 9 shows the relationship between the surface pressure and the area per repeating unit of the polymer compound obtained in Example 5.
Figure 0 is a surface pressure and area curve of a mixture of the polymer compound of Example 5 and stearyl alcohol at a molar ratio of 1:1. Figure 2 Time Figure 4 Figure 6 (A /unit,) Figure 6 flo a (A″2//unit)N9 Figure IY) it (A″2/unit,) Figure 10 non (A″2/ unit,)

Claims (7)

[Claims] (1) A tetravalent first organic group R_1 having at least 2 carbon atoms and 2 having at least 2 carbon atoms
10 carbon atoms, which have linear repeating units in which the valent second organic groups R_2 are alternately connected by divalent bonding groups, and which may contain a substituent covalently bonded to the repeating units. An amphoteric polymer compound containing at least one hydrocarbon-containing group R_3 of ~30. (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. , tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ Mathematical formulas, chemical formulas , tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. One side has 1 or 2 hydrocarbon-containing groups R_3
using a monomer containing the first organic group R_1
2. A method for producing an amphoteric polymer compound according to claim 1, which comprises polycondensing a monomer containing R_2 with a monomer containing the second organic group R_2.