JPH01238565A - High-molecular-weight thermotropic liquid crystal and amphiphatic resin material - Google Patents

Abstract

NEW MATERIAL:A compound of formula I [R is -(CH2)1-, formula II-formula V; 1, m, n are positive number]. USE:High polymeric thermotropic liquid crystals are obtained from dietanol- stearylamine and a variety of diisocyanates. The high polymeric thermotropic liquid crystal is controllable in its crystalline states by temperature without use of solvent and keeps liquid crystal states over a wide temperature range including room temperature, thus being applied to a variety of functional devices.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention is applicable to a wide temperature range including room temperature, which exhibits liquid crystallinity due to the thermal properties of a substance, such as an image display device,
The present invention relates to a polymeric thermotropic liquid crystal having various uses as an information writing device and other various uses, and an amphiphilic resin material constituting the substance.

(Prior art) In recent years, polymer compounds have been developed into lyotropic (solvated) liquid crystals, which exhibit liquid crystallinity when dissolved in a solvent, and thermotropic (thermotropic) liquid crystals, which exhibit liquid crystallinity as thermal properties. (type) liquid crystal is known. These polymer compounds exhibiting liquid crystallinity (
Resins) are expected to have a variety of uses because they can take a crystalline state with sufficient strength to withstand use and a liquid crystalline state with excellent processability, and research and development is progressing.

Among the above-mentioned compounds, the polymer thermotropic liquid crystal allows the crystal state to be controlled by temperature without using a solvent. Therefore, it can be expected to have various uses, not just as a molding material.

As such a polymeric thermotropic liquid crystal, for example, the literature = "Liquid crystal properties of polyurethane containing biphenyl units"
(Collection of Polymer Papers, Vol. 43. No. 5゜pp3
11-314i986) is known.

According to the above-mentioned literature, polyurethanes obtained from 4,4-di(2-hydroxyethyloxy)biphenyl and various diisocyanates have been observed to have the above-mentioned properties as a polymeric thermotropic liquid crystal. Various polymer thermotropic liquid crystals disclosed in this document are
The temperature at which the transition from the crystalline state to the liquid crystal state is observed (hereinafter referred to as T) is a predetermined value within the range of about 135 to +88 ('C), and the temperature at which the transition from the liquid crystal state to the isotropic liquid state is observed. The transition temperature (hereinafter referred to as T) is approximately 172 to 203 (
``C) is observed at a predetermined value within the range.

In addition, the temperature difference between T7 and the bottom (hereinafter referred to as T, -T, and l) that can maintain the liquid crystal state must be within the range of about 15 to 58 (deq) for each compound. (See the above-mentioned literature for details).

(Problem to be Solved by the Invention) However, in the conventional polymer thermotropic liquid crystal described above, T
,,l is about +35 ("C) or more, and the temperature range in which the liquid crystal state can be maintained is about 58 (deer) or less. Therefore, the above-mentioned T7 is the thermoforming temperature when used as a resin material. However, when used as a display bag M etc. by utilizing the function as a shutter element, for example, the T7 is higher than room temperature and the above temperature range T
There was a problem that ffi-T was narrow.

In view of the above-mentioned conventional problems, an object of the present invention is to provide a polymer thermotropic liquid crystal that maintains a liquid crystal state over a wide temperature range including room temperature and can be used in various functional devices, and an amphiphilic resin. The goal is to provide materials.

(Means for solving the problem) In order to achieve this object, according to the polymer thermotropic liquid crystal according to the first invention of this application, ...(I) is shown, and β, m, and n are ), which represents a positive integer.

Further, according to the polymer thermotropic liquid crystal according to the second invention of this application, the following general formula % formula % (11) is shown, where β, m, and n represent positive integers. ).

Further, the amphiphilic resin material, which is the third invention of this application, is characterized by being represented by the following general formula (where m in the formula represents a positive integer).

Roughly speaking, according to the amphiphilic resin material which is the fourth invention of this application, it can be expressed by the following general formula % formula % () (However, m in the formula represents a positive integer) It is characterized by

(Function) According to the polymeric thermotropic liquid crystal according to the first and second inventions of this application, the polymeric thermotropic liquid crystal has a hydrophilic main chain derived from an amino group or an ammonium bromide group and a diisocyanate, and has a side chain. An alkyl group is attached to the above-mentioned amino group or ammonium bromide group, and it has an amphipathic polyurethane structure.

Therefore, it is possible to achieve the processability and strength of a resin, which is a polymer having amphiphilic properties, and the optical effects of a liquid crystal material.

In general, the amphiphilic resin materials according to the third and fourth inventions of this application are composed of a head hydrophilic group consisting of an amino group or an ammonium bromide group and a tail hydrophobic group consisting of an alkyl group. be done.

Therefore, the amphiphilic resin materials according to the third and fourth inventions of this application are combined with diisocyanate, and
It is considered that the substance constitutes the polymeric thermotropic liquid crystal according to the second invention and imparts amphiphilic properties to the substance.

(Example) Hereinafter, an example of the present invention will be described in detail. Also,
In the following description, in order to facilitate understanding of the present invention, a preferred synthesis method for obtaining the polymeric thermotropic liquid crystal according to this application will be described under specific numerical conditions. .

First, an example of a polymer thermotropic liquid crystal, which is the first invention of this application, will be described.

As can be understood from the above-described structure, the polymeric thermotropic liquid crystal according to the first invention is obtained by synthesizing the jetanolstearylamine according to the embodiment of the third invention of this application and various diincyanates. In the following explanation, the synthesis of jetanolstearylamine as an example of the third invention will be explained, and then the synthesis of a polymeric thermotropic liquid crystal having an amphiphilic polyurethane structure according to the first invention of this application will be explained. This will be explained in detail. In addition, the raw materials in the following explanation,
Although detailed explanations of the solvents and the like will be omitted, they are all readily available and have sufficient chemical purity for practical use.

・As an example of the amphipathic resin material of the third invention of this application, the coefficient m in the general formula (III) is 17.
The case will be explained using an example.

First, stearyl bromide 33.3 (9) (equivalent to 0.1 mole) and jetanolamine 42.0 (9) (0
, 4 moles equivalent), and add about 500 m of inpropatool (hereinafter referred to as IPA) as a solvent.
II). Thereafter, the solvent to which these mixtures were added was refluxed for about 3 hours to obtain a reaction mixture.

Next, the above-mentioned reaction mixture is concentrated under reduced pressure until the volume becomes about 1/3, and then cooled.

Next, a suitable amount of chloroform is added to the above-mentioned concentrated solution, and the mixture is washed several times with pure water.

Thereafter, the solution obtained by the washing (corresponding to the chloroform layer) is dehydrated by a conventionally known method, and concentrated in the same manner as described above to precipitate jetanolstearylamine. Furthermore, the above-mentioned jetanolstearylamine was recrystallized several times using ether and used as a sample.

The reaction related to the synthesis of such jetanolstearylamine is shown below as reaction formula (2).

The jetanolstearylamine obtained according to the above-mentioned reaction formula
NM day) method (using DMSO-d6).

First, according to the measurement results of the IR method, 3250 (
An absorption peak of cm-') was observed. Zarani, 'H
-NMR method measurement results are shown in Table 1 below with functional groups containing protons considered to be derived from each measurement value.

Table 1 Below, as an example of the first invention of this application, the above formula
The synthesis method using the jetanolstearylamine obtained in the above and various diisocyanates will be explained in detail.

In this example, the above-mentioned jetanolstearylamine and the respective diisocyanates described below were added in a 1:1 molar ratio to a suitable amount of dimethylformamide as a solvent, and the mixture was heated at a temperature of about 120°C for 5 hours. Compounds (1) to (2) according to Examples 1 to 5 were obtained by continuing the reaction.

Daigo1 Property 1 In this Example 1, hexamethylene diisocyanate (NGO-(CH2)8-NCO) was used as diincyanate.
), and according to the synthesis method described above, a polyurethane compound shown as compound (2) on page 17 was obtained.

Hemostasis l In this Example 2, 4,4-dicyclohexylmethane diisocyanate (NGO-CsH+o-CH2-C6H+
.

-NGO) was used to obtain a polyurethane compound shown as compound (2) on page 17.

In this Example 3, ω, ω°
-Diisocyanate Using 1,3-dimethylcyclohexane (NCO-CH2-C8HI.-CH2-NGO) as the diisocyanate, a polyurethane compound shown as compound (2) on page 17 was obtained.

In this Example 4, 2,4-tri was used as the diisocyanate to obtain the polyurethane compound shown as Compound 1 on page 18 according to the synthesis method described above. According to the method, 4.4'-diphenylmethane diisocyanate (NGO-C8H4-CH2-C
8Hd-NGO) as the diisocyanate, the first
Polyurea e shown as compound ■ on page 8
OO Shit Details 5gu0
<0 40OR a <10 Furthermore, in order to confirm that these compounds (1) to (2) were polyurethane compounds, each of these compounds was identified by an IR method. That is, the urethane bond (-NH
-CO-0-), the above-mentioned compounds ■ to ■ can be identified by the presence or absence of the spectrum derived from the stretching of the amino group (-NH-) and the spectrum derived from the stretching of the carbonyl group (-GO-). I did it.

Sararyu Kinkoashi Eni 1 (i) Compound ■, Compound ■ and Compound ■-NH-335
0 (cm-') -GO-1690 (cnr') (2) Compound ■ and compound ■ -NH-3350 (cm -ri-GO-1710 (cm-')) Also, for each of these compounds ■ to ■, When the molecular weight of each compound was measured using a conventionally known method, it was approximately 2,000 to 50,000, with a maximum of 100.0.
The molecular weight was within the range of about 0.00. From this, the value of n indicating the degree of polymerization in the structural formula shown on pages 17 to 18 is 3 to
It can be understood that the number is about 110, and the maximum is about 220.

From these measurement results, it can be understood that the above-mentioned compounds (1) to (2) are amphiphilic polyurethane compounds of each of the above-mentioned diisocyanates and jetanolstearylamine.

・A 1 to 5 g, ・1 Next, the results of measuring T1 and Tl described above with respect to compounds ① to ② according to Examples of the first invention described above will be explained.

In this example, the conventionally well-known differential scanning calorimetry was used to measure the transition point, and the temperature was measured for each of Compounds (1) to (2). The results are shown in Table 2 on the next page.

Table 2 As can be understood from Table 2, the compounds 1 to 2 of Examples according to the first invention have a transition temperature T7 from a crystalline state to a liquid crystal state of 20°C (room temperature at the time of measurement) or lower, However, the difference between this Tffi and the temperature Ti at which the liquid crystal state transitions to isotropy is 280 (de9
) That's it.

In order to roughly confirm that each of these compounds 1 to 2 acts effectively as a liquid crystal substance, polarized light microscopy observations revealed that they exhibited a continuous light state in the temperature range of T and 11-Ti, and that A lamellar striped pattern indicating medium properties was observed, and a transparent state was observed at temperatures exceeding TI.

Next, the second invention of this application, the polymer thermotrobi
An embodiment of the liquid crystal display will be described in the same manner as the embodiment described above.

First, as an example of the amphiphilic resin material of the fourth invention of this application, a case where the coefficient m in the above-mentioned general formula (IV) is 17 will be explained.

First, 35.7 (9) (equivalent to 0.1 mol) of jetanolstearylamine obtained by the above reaction formula (1) and 9.5 (9) (equivalent to 0.1 mol) of methyl bromide were precisely weighed, Approximately 500 mβ of ethanol using these as a solvent
Add to. Thereafter, these mixed solutions are sealed in a pressure bottle and kept at a temperature of about 80''C for 24 hours to obtain a reaction mixture.

Next, the above-mentioned reaction mixture was cooled to about room temperature, and the resulting precipitate was collected by filtration, and the precipitate was recrystallized several times using ethanol to be used as a sample.

The reaction involved in the synthesis of such diethanol methyl stearyl ammonium bromide is shown below as reaction formula (2).

CH3(CH2)17 N(CHzCH20H)2+
cH3Br The jetanol methyl stearyl ammonium bromide obtained by the above reaction formula (2) and according to the example of the fourth invention was identified by the IR method and +H-NMR method (using DMSO-da) in the same manner as described above. .

First, according to the measurement results of the IR method, 3300 (
An absorption peak of cm-') was observed. Zarani, 'H-
The measurement results of the NMR method are shown in Table 3 below in the same manner as Table 1 described above.

Table 3 However, *1 indicates a triplet signal.

・Miya Thermotrobi・Under the synthetic fiber of 2 crystals, as an embodiment of the third invention of this application, the above formula ■
The synthesis method using the jetanol methyl stearyl ammonium bromide obtained in the above and various diisocyanates will be explained in detail.

In this example, the above-mentioned jetanol methyl stearyl ammonium bromide and the respective diisocyanates described below were added in a 1:1 molar ratio to a suitable amount of dimethylformamide as a solvent, and 5 By reacting over a period of time, compounds ① to [stock] according to Examples 6 to 10 were obtained.

In Example 6, hexamethylene diisocyanate (NGO-(CH2)8-NGO) was used as the diisocyanate.
), and according to the synthesis method described above, a polyurethane compound shown as Compound (1) on page 27 was obtained.

In this Example 7, 4,4-dicyclohexylmethane diisocyanate (NGO-CJ+o-CHz-CeH+) was used as the diisocyanate according to the synthesis method described above.

-NCO)! A polyurethane compound shown as compound (2) on page 27 was obtained.

In this Example 8, according to the synthesis method described above, ω, ω°
-diisocyanate 1,3-dimethylcyclohexane (NCO-C) + 2-CIIHI. -〇)b-NGO)
1 diisocyanate, compound ■ on page 27
A polyurethane compound shown as was obtained.

Husband Blood 1 In this Example 9, 2,4-tri-diisocyanate was used as a diisocyanate to obtain the polyurethane compound shown as compound (■) on page 28 according to the synthesis method described above.
Now, according to the synthesis method described above, 4.4"-diphenylmethane diisocyanate (NGO-CsH4-CH2-
C6Ha-NCO) @diisocyanate and■
O ■ t da 4 ta
tshi10 mouth
zu0 ■ ■ 8 s <0 Also, in order to confirm that these compounds ~ [phase] are polyurethane compounds, these compounds were treated with I in the same manner as above.
Identified by R method.

As a result, the measurement results were the same as the measurement data already explained. Therefore, the above-mentioned urethane bond (-NH
-CO-0-) formation was observed.

In addition, when molecular j18 was measured in the same manner as described above for each of these compounds ① to ②, the molecular weight of each compound was within the range of approximately 2,000 to 50,000, with a maximum of approximately 100,000. . From this, the 27th ~
28 The value of n, which indicates the degree of polymerization in the structural formula shown in True, is also 3 to 110.
It can be understood that the maximum value is about 220.

Therefore, from these measurement results, it can be understood that the above-mentioned compounds 1 to 0 are amphiphilic polyurethane compounds of each of the above-mentioned diincyanates and jetanol methyl stearylamine bromide.

・A 6~ No. 88, ・1 Next, the results of measuring the above-mentioned T and T1 with respect to the compounds ① to [strain] according to the example of the second invention described above will be explained.

As already explained, differential scanning calorimetry was carried out to measure the transition point, and the temperature was measured for each of compounds (1) to [phase]. The results are shown in Table 4.

Table 4 As can be understood from Table 4, compounds (1) to [phase] of Examples according to the second invention have a transition temperature T from a crystalline state to a liquid crystalline state at a room temperature of 20°C or less. can be,
And, this T□ and the temperature T at which the liquid crystal state transitions to isotropy
For example, in the case of a compound [phase], the difference from 1 is 280 (de
9) That's all.

Furthermore, in the same manner as described above, for the purpose of confirming that each of the compounds ■ to [phase] effectively acts as a liquid crystal substance,
When observed under a polarizing microscope, it was observed that in the temperature range of 1 to T, a continuous light state was observed, as well as a lamellar striped pattern indicating amphiphilic properties, and at temperatures above T1, a transparent state was observed. Admitted.

From the above explanation and various measurement results, it can be understood that compounds 1 to [phase] according to this example are amphiphilic bowurethane compounds and thermotropic liquid crystals.

Although the embodiments of the present invention have been described above, it is clear that the present invention is not limited only to the above-mentioned embodiments.

For example, in the above-mentioned embodiments, a specific diisocyanate was exemplified and explained in synthesizing a polymeric thermotropic liquid crystal. However, for example, instead of hexamethylene diisocyanate, benkumethylene diisocyanate, hexamethylene diisocyanate, etc., and instead of 4,4°-dicyclohexylmethane diisocyanate (such as
, 4°-dicyclohexylmethane diisocyanate or 3.4°-dicyclohexylmethane diisocyanate, ω,ω′-diincyanate 1, ω,ω′-diisocyanate 1 instead of 3-dimethylcyclohexane
．． 2-dimethylcyclohexane or ω,ω゛-diincyanato 1,4-dimethylcyclohexane, 2.4
- 2.5-tolylene diisocyanate, 2.6-tolylene diisocyanate, or other diisocyanate instead of tolylene diisocyanate, and the amphipathic resin material according to the third and fourth inventions of this application. Even with compounds obtained using

In addition, as an example of the third and fourth inventions 1 of this application, the case where the coefficient m is 17 in the above-mentioned general formulas (III) and (IV) has been illustrated, but the invention is not limited to this. However, depending on the design of the polymer thermotropic liquid crystal according to the first and second inventions, various values of m can be used.

It is clear that the materials, numerical conditions, and other specific conditions described above may be modified and modified as desired within the scope of the invention.

(Effects of the Invention) As is clear from the above explanation, according to the polymer thermotropic liquid crystals according to the first and second inventions of this application, by having the above-mentioned structure, processing as an amphiphilic resin is possible. It has properties such as strength and strength, and optical effects as a liquid crystal material at around room temperature. Therefore, the liquid crystal property can be utilized in a wide temperature range including room temperature, and it can be simply and easily processed into a film form by various processing techniques such as rolling or casting.

In addition, compared to conventional liquid crystal materials that require hermetic sealing, by processing them into the film form described above, they can be applied to optoelectronic devices such as display devices, recording devices, and polarizing elements. In addition, various developments can be expected, such as application to tree xm fibers such as lyotropic liquid crystals.

In general, according to the amphiphilic resin materials according to the third and fourth inventions of this application, for example, l! It can be used for various purposes.

Claims (4)

[Claims] (1) The following general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ... (I) (However, R in the formula ▲ 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,
There are tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and l, m, and n represent positive integers. ) A polymer thermotropic liquid crystal characterized by the following: (2) The following general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ... (II) (However, R in the formula ▲ 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,
There are tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and l, m, and n represent positive integers. ) A polymer thermotropic liquid crystal characterized by the following: (3) The following general formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・(III) (However, m in the formula represents a positive integer.) An amphipathic resin material characterized by: (4) The following general formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・(IV) (However, m in the formula represents a positive integer.) An amphipathic resin material characterized by: