JPH03139523A - Amphoteric polyamide and thin film comprising the same - Google Patents

Abstract

PURPOSE:To obtain an amphoteric polyamide which can give a thin film excellent in heat resistance, chemical resistance and mechanical properties and showing interesting electrical properties by the Langmuir-Blodgett method by selecting an amphoteric polyamide based on specified repeating units. CONSTITUTION:An amphoteric polyamide based on repeating units of formula I [wherein R<1> is a 2C or higher tetravalent group; R<2> ls a group of formula II or III; R<3> to R<6> are each a 1-30C (halogen-, nitro-, amino-, cyano-, methoxy- or acetoxy-substituted) (cyclo)aliphatic or aromatic monovalent group or H, and at least one of them is a 12-30C group.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to amphoteric polyamides and thin films formed therefrom. More specifically, the present invention relates to an amphoteric polyamide modified so that it can be formed by the Langmuir-Prodgett method (hereinafter referred to as the LB method), and a monomolecular film or a cumulative film formed using the same by the LB method.

[Problems to be solved by conventional technology/inventions] Already 1
In the 930s, fatty acids with about 16 to 22 carbon atoms were on the water surface.
Second, Langmuir and Prodgett discovered that it is possible to create a monomolecular film and accumulate it on a U-layer, but it is only recently that studies have begun to consider the application of this cumulative film. However, Langmuir-Prodgett membranes (hereinafter referred to as LB membranes) made of straight-chain saturated fatty acids have a problem in that they do not have sufficient heat resistance or mechanical strength for practical applications, and cannot be used as they are.

To improve these problems, products formed from unsaturated fatty acids such as ω-tricosenic acid, ω-hebutadecenoic acid or α-octadecyl acrylate, and unsaturated fatty acid esters such as vinyl stearate and octadecyl acrylate, etc. Research has been conducted on films made by polymerizing these films, but their heat resistance and other properties are not sufficient.

On the other hand, there is a polyimide film as a heat-resistant film, but when using methods such as spin-coding, the film thickness is at most 1000 Å or more, and usually only 100 Å or more can be obtained; It is extremely difficult to create a heat-resistant thin film without holes.

The present inventors have already filed an application for a material that can provide a heat-resistant ultra-thin film with improved mechanical properties such as heat resistance and adhesive strength, and chemical resistance (Japanese Patent Application Laid-Open No. 12-12931
Publication No. 7). However, most thin films made from this material are electrically insulating, and there is a problem in that it is difficult to apply them to purposes other than insulating films.

[Means for Solving the Problems] The present invention has been made based on the discovery that the above-mentioned problems can be solved by using a special diamine component in the polyamic acid unit. : is a group having 12 to 30 carbon atoms, preferably 14 to 22 carbon atoms. membrane or cumulative membrane).

[Example] The amphoteric polyamide of the present invention has the general formula (1): (wherein R
1 is a tetravalent group containing at least 2 carbon atoms, R
2 is R3R4R5 and R6 are aliphatic, cycloaliphatic or aromatic (these may be combined with each other) monovalent group having 1 to 30 carbon atoms (these groups are halogen atoms,
(optionally substituted with a nitro group, amino group, cyano group, methoxy group, acetoxy group) or a hydrogen atom,
It is an amphoteric polyamide mainly composed of a repeating unit represented by at least one of R3R4R5 and R6, and its number average molecular weight is usually 2.000 to 300,000, preferably to, 000 to 150,000. If the number average molecular weight is outside the range of 2,000 to 300,000, the strength of the obtained thin film will be too low, or the viscosity during film formation will become too high, making it difficult to successfully prepare the film. arise.

R1 in the general formula (1) is a tetravalent group containing at least 2 carbon atoms, preferably 5 to 20 carbon atoms, and may be an aromatic group, It may be an aliphatic group, a cycloaliphatic group, or a combination of these groups; (
These may be combined in the phase IL) with a carbon number of 1
-30 monovalent groups (these groups may be substituted with groups such as halogen atoms, nitro groups, amino groups, cyano groups, methoxy groups, acetoxy groups) or -0--
COO--NIICO-1-CO-1-9--C3S-
It may also be a group substituted with a group bonded to -NllC9-1-CS- or the like to become a derivative. However, when R1 is a group characterized by benzenoid unsaturation having at least 6 carbon atoms, it is preferable from the viewpoint of heat resistance, chemical resistance, mechanical properties, etc.

Specific examples of R1 as described above include those in the analogous repeating unit.

The term "benzenoid unsaturation" as used herein is a term used in contrast to a quinoid structure regarding the structure of a carbocyclic compound, and refers to a structure having the same shape as a carbocyclic ring contained in ordinary aromatic compounds.

There is no particular limitation on the position of the bonding hands, but if two of each of the four bonding hands are present on two adjacent carbon atoms constituting R1, it is possible to form the bond using an amphoteric polyamide. It is preferable because it is easy to form a 5-membered ring when polyimidizing a film or the like, and it is easy to imidize.

Preferred specific examples of R1 as described above include, for example, p-quinoid benzenoid unsaturated R1
This is a table of the four bonds, that is, the general formula (1).

Ann Trachino present in the group two connections Specifically showing the position of the hand etc.

If it is within the range of 10 to 20% of 2, the following 2
A repeating unit having a valence group in place of 2 may also be used.

For example, 2 is a divalent anthraquinone group (in the formula, 7 is +CH2) (6 and 9 in the above formula are both carbon numbers → CH2) -10 (CH2)4-CI-(CH2 )2-1 to 30 alkyl group or aryl group)) CH30 (C)12)η Cl1(CH3) -(CH2)3-CI(CH2)2(CH2)3-0-(CH2)2-O- (CH2)s C1(3 CH3 113 CH3 s R5 e R5, etc.).

In general formula (1), R3 R4R5R6 is an aliphatic, cycloaliphatic, or aromatic group having 1 to 30 carbon atoms, preferably 1 to 22 carbon atoms.
A valent 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. to form a derivative) or a hydrogen atom.

In addition, in general formula (1), R3R4R5 and R6 both give hydrophobicity to the polyamic acid unit represented by general formula (2): % formula % (wherein RI R2 is the same as above), resulting in stable condensation. It is a group introduced to obtain a film, and at least one, preferably two of R3R4R5R6 has 12 to 12 carbon atoms.
30, preferably 14 to 22 of the above groups,
This is necessary to form a stable condensed film on the water surface and accumulate it on the substrate by the LB method.

The specifics of R3R4R5R6 as mentioned above are all 12
-30, preferably 14-22). In order for the amphoteric polyamide of the present invention to be formed into a film by the LB method,
The above-mentioned group is most preferably a linear alkyl group formed by CII s (CH2Fukuka) in terms of performance and cost.
Although amino groups, cyano groups, methoxy groups, acetoxy groups, etc. are not essential, it is preferable to use those containing fluorine atoms, as the introduction of fluorine atoms dramatically improves hydrophobicity compared to hydrogen atoms. .

Specific examples of repeating units of the amphoteric polyamide of the present invention in which two of R3, R4, R5, and R6 are hydrogen atoms include general formula (3): (wherein, RI R2R3R4
is the same as above, except that R3 and R4 have 12 to 3 carbon atoms.
0 group) or the general formula (4
); if it is represented by general formula (4),
This is preferable because it is easy to manufacture and inexpensive.

Specific examples of the amphoteric polyamides of the present invention having repeating units represented by general formulas (1), (3), and (41) include, for example, The repeating unit of the amphoteric polyamide of the present invention is represented by the general formula (3) or (in the formula, R3 CH3 (CH2) n - Cl5 (CH2) 17- CF5 (CH2 ) +s - is CH3-1 CH3(CH2) s - Specific examples of R4 are 1, Cl13(CH2) +3-, CH3(CH2)
+s -1CH3(CH2) +9- ,C)13(C
H2) 2+ -, specific examples of R5R6 include CH3(CH2) 2-, CH3(CH2) 3-, etc.), and (specific examples of R3R4 in the formula include CH2(CH2)I+ -, CTo(C) I2)+3-
, CHx(C)12)+s -C1(3(C142)
+7-, C113(C)h)+s-, CH3(CH
2) Examples include those containing repeating units such as 2+ -CF3 (ClI2> +s-, etc.). - in the formula represents isomerism.

Isomerism is explained based on, for example, the general formula: The above formula represents the two formulas in one formula, and in such a case, - is used to represent isomerism.

In this specification, isomerism refers to either a case where a moiety represented by the (ω formula, mountain) formula is contained alone or a case where a moiety represented by the formula (a) or the formula (■) coexists. represent

The amphoteric polyamide having a repeating unit represented by the general formula (1) may be composed of a single repeating unit, or may be a copolymer composed of different repeating units.

In the general formula (1), various copolymers can be provided by using at least one of R1 to R6 as at least two groups selected from the above-mentioned specific examples of R1 and Re.

When two types are selected, the repeating unit of the amphoteric polyamide has the general formula;
<1, x+y=1).

It is expressed as Note that y in this case is in the range of about 0.1 to 0.2, as described above.

The above examples are just a few examples. Also, R'R4R5R6
Numerous examples are also given for , but when it is described as a repeating unit, for example, the formula: % Formula %
- dissolved in an organic polar solvent such as dimethylacetamide, N,N-dimethylformamide, N,N-diethylformamide, hexamethylphosphoramide, etc., dissolved in a mixed solvent such as the above organic polar solvent and a normal organic solvent such as chloroform, Slightly soluble to insoluble in common organic solvents, such as benzene, ether, chloroform, acetone, methanol, etc., and infrared (IR) absorption spectroscopy reveals amide, carboxylic acid (carboxylic ester in some cases) and long-chain alkyl groups. A characteristic absorption of is observed. The amphoteric polyamide selected for its good heat resistance has characteristics in the results of thermal analysis, and its weight begins to rapidly decrease at about 200°C and ends at about 400°C. After the weight reduction is completed, I
In R absorption spectrum analysis, the absorptions of amide, carboxylic acid (carboxylic ester in some cases) and long-chain alkyl groups disappear, and the absorption of imide rings disappears.

In the above explanation, the case where the repeating units of the amphoteric polyamide of the present invention are all repeating units represented by general formula (1) except for partial substitution of R2 was explained,
If it is in the range of 30% or less of the repeating units, general formula (5): (these groups may be combined with each other), a group in which these groups are substituted with a halogen atom, a nitro group, an amino group, an ano group, a methoxy group, an acetoxy group, or a hydrogen atom; The R's may be the same or different)
It may also include the repeated il1 position expressed as a).

Next, the LII film using the amphoteric polyamide of the present invention will be explained.

The method for manufacturing the LB film using the amphoteric polyamide of the present invention is to spread the amphoteric polyamide on the water surface, compress it with a constant surface pressure to form a monomolecular film, and transfer the film onto the substrate 1.1. In addition to the vertical immersion method, there are other methods such as the horizontal layering method and the rotating cylinder method (New Experimental Chemistry Course, Volume 18, Interfaces and Colloids, pp. 498-508). 7J can be used without particular limitation.

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

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

There is no particular limitation on the concentration of the solution used when spreading the amphoteric polyamide of the present invention on the water surface, but it is usually 2 to 5×1
About 0-3M is used.

The substrate on which the LB film using the amphoteric polyamide of the present invention is formed is not particularly limited, and may be selected depending on the intended use of the formed LB film.

Specific examples of the above-mentioned substrates include inorganic substrates such as glass, alumina, and quartz, as well as metal and plastic substrates, and even 511G a A S % Z.
Conductors such as ■ group such as n S, m-v group, ■-■ group, PbT103, BaTl03, LINbO,, L
Ferroelectric substrates such as iTaO3 and magnetic substrates can be manufactured. These substrates are t
Of course, it may be used after surface treatment.

If the obtained films 1 and 13 are to be heated and used as polyimide, it is necessary to select a substrate with good heat resistance.

When the amphoteric polyamide of the present invention is used, a thin film with few defects and good heat resistance can be formed on a substrate by the LB method.

Furthermore, by partially or completely imidizing this thin film, a thin film with even better heat resistance can be obtained.

The amphoteric polyamide of the present invention is a conventional 1. Since the heat resistance and chemical resistance of the compound used in the B film have been improved, the amphoteric polyamide LD film of the present invention also has excellent heat resistance and chemical resistance.
It also has good mechanical properties and can be used as is for devices and other applications. Also, the 1.8 film is 10000Å
It is a very thin film of less than 5 to 100 O if desired.
It also applies to A.

Furthermore, repeating 11 constituting the amphoteric polyamide of the present invention
Since it contains an anthraquinone group having a large number of π electrons at the 1st position, it is expected to have various interesting physical properties such as semiconductivity and photoconductivity, and electronic devices using these properties can be fabricated. In addition, since a rigid structure has been introduced, it can be used as a highly oriented amphoteric polyamide thin film, and can be used as a liquid crystal alignment film or a polarizing film.

When the obtained amphoteric polyamide thin film of the present invention is further imidized and used, there are no particular limitations on the imidization method, but it is common to heat it at a temperature around 200 to 400°C, and to use a laser. This may be done using light or the like. Of course, acetic anhydride and pyridine used in the imidization of polyamic acid may be used, or they may be used in combination with a thermal reaction. For example, in the case of the repeating unit represented by general formula (3), the following reaction occurs, and the following reaction occurs as shown in general formula (4), resulting in a polyimide compound. Of course, in the case of the polyamic acid unit represented by general formula (5), H
Either 2O is generated and becomes a polyimide, or in this case, it cannot be used as a material for the LB film.

The thin film obtained by further imidizing the amphoteric polyamide thin film of the present invention has further excellent heat resistance, chemical resistance, and mechanical properties, and is a very thin film with a thickness of 10,000 or less, and if desired, a thickness of 5 to 1,000. It can be used for people, devices, etc.

Next, the amphoteric polyamide of the present invention and a thin film made of it will be explained based on Examples.

Example 1 Pyromellitic dianhydride 2.18 g (10 mmol)
and stearyl alcohol 5.40 g (20 mmol)
and 311 in a flask at about 100°C under dry nitrogen flow.
, ν, and re-purified with ethanol.

6 cc of thionyl chloride was added to 2.28 g (3 mmol) of the obtained half ester and acylated at about 70° C. for 1 hour. Thereafter, excess thionyl chloride was distilled off. The produced acid chloride was dissolved in 40 cc of hexamethylphosphoramide, and 0.71 g (3 mmol) of 2,6-diamithanthraquinone dissolved in 20 cc of dimethylacetamide was added dropwise at 0 to 5°C.
After being allowed to react for about 1 hour after dropping, it was further heated to room temperature and 40℃.
The reaction was continued for 1 hour at ℃. Pour the reaction solution into distilled water for 25 minutes.
Pour into 0ec to precipitate the reaction product, then filter it.
It was dried under reduced pressure at about 40°C to obtain about 2.0 g of pale yellow powder.

IR spectrum analysis and NMR of the obtained powder
Analysis was conducted and it was confirmed that it was the desired amphoteric polyamide. Further, as a result of molecular weight 4p1 determination by GPC, the molecular weight was approximately 30,000.

(IR spectrum analysis) Figure 1 shows the results measured by the KBr disk method.

The chart shows ester, amide I absorption band, ■ absorption band, ■
There is an absorption band, a characteristic absorption of alkyl chains.

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

Using the obtained developing solution, the relationship between the surface pressure π and the area per repeating unit (unit) was measured on FIT distilled water at 20°C, and the results shown in FIG. 2 were obtained. about 10
The surface pressure rose from 0 person 2/unil, and a good condensation film was formed. The limit area is 80 people/unit,
The collapse pressure was also 40 dyne/cm, which is a very low 1ω value for a polymer membrane. Also, the surface pressure is 25 dync/c
Even when the membrane was kept at a+ on the water surface, it was a stable membrane with no decrease in area observed over 2 hours.

Next, the surface pressure of the membrane at the water surface -1- was set to 25 dyne at 20°C.
/cIn and cumulative speed 1oads/win I, B
31 layers were deposited on a glass substrate with ITO using the method.

FT-11 film formed on glass substrate with ITO, E
? When analyzed by an analytical method, the spectrum was changed to have the same absorption peak as in FIG. 1, and it was confirmed that it was a cumulative film of the compound obtained in Example 1, and that it was a Y-type film from the area-time curve.

[Effect of the invention] When the amphoteric polyamide of the invention is used, the thickness can be reduced by the LB method.
Thin films of less than 10,000 Å and 5 to 1,000 Å can be formed, and the resulting LB films exhibit good heat resistance and interesting electrical properties, and are suitable for replacing amphoteric polyamide thin films with good chemical resistance and mechanical properties. It will be done. This thin film can be used as is, but it can be converted into a thin film with better heat resistance by heating.

[Brief explanation of the drawing]

Figure 1 shows 11 of the amphoteric polyamide produced in Example 1.
? A chart showing the spectrum analysis results, FIG. 2 shows the LB prepared using the amphoteric polyamide produced in Example 1.
It is a graph showing the results of measuring the relationship between the surface pressure π and the area per repeating unit at 20° C. by developing a membrane layer developing solution on double distilled water.

Claims (1)

[Claims] 1 General formula (1): ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (1) (In the formula, R^1 is a tetravalent group containing at least 2 carbon atoms, R^ 2 is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ R^3, R^4, R^5 and R^6 are aliphatic, cycloaliphatic or aromatic (these monovalent groups having 1 to 30 carbon atoms (which may be substituted with a halogen atom, a nitro group, an amino group, a cyano group, a methoxy group, or an acetoxy group) ) or a hydrogen atom, and at least one of R^3, R^4, R^5 and R^6 is a group having 12 to 30 carbon atoms). 2 A thin film made of amphoteric polyamide mainly composed of repeating units represented by the general formula (1) on a substrate by the Langmuir-Blodgett method. 3. The thin film according to claim 2, wherein the thin film is a monomolecular film. 4. The thin film according to claim 2, wherein the thin film is a cumulative film.