JPH0273830A - Resin having reversible color changing property - Google Patents

Abstract

PURPOSE:To obtain the title resin consisting of a polymer containing a specific structural unit as a part of constituent, providing vivid color in coloring and having excellent repeated endurance and solvent resistance and useful as a photochromic material. CONSTITUTION:The aimed resin obtained by subjecting at least a part of amino group of a polymer containing a structural unit expressed by the formula (a, b, c and d exhibit bond hand and each bonded to H to carbon constructing an aliphatic group, alicyclic group or aromatic group and having at least one hand bonded to carbon; R is H or hydrocarbon; X and Y are halogen or hydro carbon; m and n are 0-4) in polymer as part of the structural unit to quartanarizing treatment.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to a reversible color-changing material, and more specifically, a reversible color-changing material whose hue changes due to external stimulation such as thermal energy, light energy, electrical energy, etc. It is related to.

<Prior art> Photochromic materials that color reversibly under the action of light, and electrochromic materials that plastically color under the action of electricity are used in various display elements and memory elements.

It is being studied in various ways as a light control material.

Viologen is a well-known compound that exhibits such photochromism and electromism. Viologens provide vivid colors, and the colors can be selected depending on the type of derivative, so attempts are being made to put them into practical use.

However, for example, an electrochromic display (ECD) using a solution of low-molecular-weight viologens has a short cycle life, insufficient memory life, and inadequate response speed, and has not yet reached the level of practical use. In addition, a method has been proposed in which low-molecular-weight viologens are dissolved or dispersed in a soluble resin or its solution, and this is used alone or coated on a substrate to express the functions of viologens in the resin matrix. However, in general, the redox reaction of odorogens is greatly affected by the polarity of the matrix resin used, making it difficult to fully demonstrate the inherent properties of viologens, and furthermore, the solvent resistance of the matrix resin is insufficient. There are problems such as:

Therefore, various methods of polymerizing these materials have been attempted, but even with these methods, the response speed is still limited.

It cannot be said that it has satisfactory performance over its lifetime. In this way, conventional photochromic and electrochromic materials do not have satisfactory performance in terms of fundamental issues such as thermal stability, temporal stability, responsiveness, and reversibility, and there is a need for improvement. Contains many problems.

<Purpose of the invention> We demonstrate responsiveness, thermal and stability over time.

Polymer photochromic with excellent durability and reversibility.

We conducted intensive research to provide electrochromic materials.

As a result, we have discovered that polymers containing specific structural units as part of their constituent components develop and discolor with good responsiveness, thermal stability over time, durability, and reversibility when irradiated with light or applied voltage. [We have arrived at the present invention.

<Structure of the Invention> In other words, the present invention provides the following structural unit (I) r where a, b
, c and d represent bonding hands and are the same) as part of its constituent components, and is a reversible color-changing material in which at least a portion of the amino groups in the polymer have been subjected to quaternization treatment.

The present invention will be explained in detail below.

In the above structural unit (I), a, b, c, and d represent bonds, which are the same or different, and are each bonded to a hydrogen atom or a carbon atom constituting an aliphatic group, an alicyclic group, or an aromatic group, and at least One is bonded to a carbon atom.

An aliphatic group to which a, b, c, and d may be bonded.

The alicyclic group and aromatic group are part of the components constituting the main chain or side chain of the polymer in the present invention, and include, for example, an arylene group, an alkylene group, a cycloalkylene group, and the like. Preferably it is an alkylene group having 1 to 10 carbon atoms.

R is a hydrogen atom or a hydrocarbon group. Here, the hydrocarbon group includes an alkyl group and an aralkyl group.

Examples include a cycloalkyl group and an aryl group.

R is preferably a hydrogen atom or an alkyl group, particularly preferably a hydrogen atom.

X and Y are the same or different and are a halogen atom or a hydrocarbon group. Here, halogen atoms are fluorine, chlorine,
Examples include bromine. Hydrocarbon groups include alkyl groups,
Examples include a cycloalkyl group and an aryl group. Among the hydrocarbon groups, preferred are lower alkyl groups such as methyl and ethyl.

m and n may be the same or different and are integers of 0 to 4. Preferably it is O or 1, particularly preferably O.

Polymers having such structural units include polyamide, polyurethane, polyurea, polyester, polyether, polysulfone, and polyimide.

It may have any structure such as epoxy, polyolefin, polyamine, and copolymers thereof.

Such polymers can be synthesized preferably by using a compound of structure (II) below as part of the polymer forming components.

Here, the polymer-forming functional group is an amino group.

Preferred examples include hydroxyl groups, epoxy groups, and unsaturated groups.

A polymer containing a component represented by general formula (I) is -
It is synthesized, for example, as follows, using a compound represented by (n) as a part of the reaction components.

(a) Example of using an epoxy compound having the structure (n) (i) Reacting with a conventionally known curing agent (epoxy resin) (ii) Reacting with carboxylic acid (polyester) (b) - Reacting (II) Example of using an amine compound with the structure (1) Reacting with a conventionally known epoxy compound (epoxy resin) (11) Reacting with isocyanate (polyurea) (
iii) React with carboxylic acid (polyamide)
(iv) Reacting with maleimide (maleimide resin) (v) Reacting with cyclic imino ether (polyamine amide) (C) Example using a hydroxy compound with the structure (n) (+) Reacting with isocyanate (polyurethane) (11) React with carboxylic acid (polyester) (
Examples of using an unsaturated compound having a structure of d)-Silction<II) (i) Reaction using a radical catalyst (polyolefin). These may be used alone, or may be appropriately combined to form a copolymer or a mixture.

The epoxy compound used in (a) above includes bis[4
-N,N-di(2,3-epoxypropyl)aminophenylcomethane, bis[4-N,N-di(3,4-epoxybutyl)aminophenylcomethane, bis[4-N,N
-di(4,5-epoxypentyl)aminophenylcomethane, bis[4-N.

N-di(5,6-epoxyhexyl)aminophenylcomethane, bis[4-N-(2,3-epoxypropyl)
Aminophenylcomethane, bis[4-N(3,4-epoxybutyl)aminophenylcomethane, bis[4-N-
(4,5-Epoxypentyl)aminophenylcomethane, bis[4-N-(5,6epoxyhexyl)aminophenylcomethane.

1.1-bis[4-N, N-di(2,3-epoxypropyl)aminophenylconitane, 1,1-bis[4-N
, N-di(3,4-epoxybutyl)aminophenylconitane, 1,1-bis[4,-N,N-di(4,5-epoxypentyl)aminophenylcoethane, ■, 1-bis[4 -N,N-di(5,6-■boxyhexyl)aminophenylconitane, 1.1bis[4-N,N-di(2,
3-Epoxypropyl)aminophenyl]propane, 1
,1-bis[4N,N-di(3,4-epoxybutyl)
aminophenyl]propane, 1,1-bis[4-N,N
-di(4,5-epoxypentyl)aminophenylconitane, 1,1-bis[4,-N,N-di(5,6-epoxyhexyl)aminophenylcopropane, bis[4-
N-(2,3-epoxypropyl)-N-methylaminophenylcomethane, bis[1-N-(2,3-epoxypropyl)-N-ethylaminophenylcomethane, bis[1-N-(2 ,3-epoxypropyl iN-propylaminophenyl]methane, bis[4-N-(2,3-epoxypropyl)-N-butylaminophenylcomethane, bis[1-N-(2,3-epoxypropyl) -N-
Pentylaminophenyl comethane, Dos Ul-N (2,
3-epoxypropyl iN-benzylaminophenyl]
Methane, bis[4-N-(2,3-epoxypropyl-
Examples include N-phenylaminophenylcomethane, particularly bis[4-N,N di(2,3-epoxypropyl)aminophenylcomethane, bis[3-chloro-4-N
, N-di(2°3-epoxypropyl)aminophenylcomethane.

Examples include bis[2-methyl-1-N,N-di(2,3-epoxypropyl)aminophenylcomethane, among which bis[4-N,N-di(2,3-epoxypropyl) Propyl)aminophenylcomethane is preferred.

Specific examples of the amino compound used in (b) above include 4
, 4°-diaminodiphenylmethane, N,N'dimethyl-4,4'-diaminodiphenylmethane.

N,N'-diethyl-4,4°-diaminodiphenylmethane, N,N'-dipropyl-4,4°-diaminodiphenylmethane, N,N'-dibenzyl-4,4°diaminodiphenylmethane, 1,1-bis( 4-aminophenyl)ethane, 1,1-dos(4-Nmethylaminophenyl)ethane, 1.1-bis(4ethylaminophenyl)ethane, 1.1-bis(4-N-propylaminophenyl)ethane , 1.1-bis(4-N-benzylaminophenyl)ethane, 1.1-dos(4-aminophenyl)propane, 1,1-bis(4-aminophenyl)butane.

1.1-bis(4-N-methylaminophenyl)propane, 1,1-bis(4-N-ethylaminophenyl)propane, 1,1-bis(4-N-propylaminophenyl)propane, 1, 1-Dos(4-N-benzylaminophenyl)propane, bis(4-aminophenyl)-phenylmethane, bis(4-N-methylaminophenyl)-
phenylmethane.

Bis(4-N-ethylaminophenyl)-phenylmethane, bis(2-methyl-4-aminophenyl)methane, bis(3-methyl-4-aminophenyl)methane, bis(
2-ethyl-4-aminophenyl)methane, bis(3-
Ethyl-4-aminophenyl)methane, bis(2-chloro-4-aminophenyl)methane, bis(3-chloro-
Examples include 4-aminophenyl)methane, bis(2-bromo-4-aminophenyl)methane, bis(3-brom-4-aminophenyl)methane, and bis(4-N-(aminoethyl)aminophenyl)methane. However, 4,4'-diaminodiphenylmethane is particularly preferred.

The hydroxy compound used in (C) above includes bis[
Examples include 4-N-(hydroxyethyl)aminophenylcomethane, bis[4-N,N-bis(hydroxyethyl)aminophenylcomethane, and the like.

The unsaturated compound used in the above (d) is bis(4-
N-allylaminophenyl)methane, bis(4-N,N
-diallylaminophenyl)methane and the like.

Examples of the compound (reactant) to be reacted with the compound represented by -killing (II) above include the following.

The curing agent used in (a) to (i) above includes aromatic polyamine, aliphatic polyamine, and polyamideimide.

Conventionally known compounds such as polyphenols such as phenol novolak and polyhydroxystyrene, cyclic carboxylic acid anhydrides, and cationic catalysts such as BF3 are used.

(a)-(ii), (b)-(iL (C)-(
The carboxylic acid used in ii) is an aliphatic, alicyclic or aromatic polycarboxylic acid or an ester thereof. !
Examples include anhydrides, and aliphatic polycarboxylic acids or derivatives thereof are particularly preferred.

The epoxy compound used in the above (b)-(+1) may be any polyepoxy compound having two or more epoxy groups in the molecule, and specifically, the following compounds are exemplified.

1) Glycidyl ether compounds: 2.2-bis(4-hydroxyphenyl)propane (bisphenol A), 4,4"-dihydroxydiphenylmethane, 4.4'-dihydroxydiphenylsulfone, resorcinol, phenol novolak, cresol novolak, resorcinol Aromatic polyols such as novolak, naphthol novolac, dihydroxynaphthalene, dihydroxynaphthalene novolac, etc.: Aromatic hydroxy compounds such as phenol, dihydroxybenzene, naphthol, dihydroxynaphthalene, etc. and glyoxal, glutaraldehyde, p-hydroxybenzaldehyde, banzaldehyde, etc. Polyols obtained by dehydration reaction with aldehydes such as, for example, under an acidic catalyst, nibutanediol, polypropylene glycol,
Glycidyl ethers of polyols such as polyhydric alcohols such as polyethylene glycol, glycerol, etc. and precursor polymers thereof.

2) Glycidyl ester compounds: Glycidyl esters of dicarboxylic acids such as phthalic acid, isophthalic acid, tetrahydrophthalic acid, naphthalene dicarboxylic acid, etc., and precursor polymers thereof.

3) N-glycidyl compound A compound in which the active hydrogen bonded to the nitrogen atom of a nitrogen-containing compound such as nearaniline, isocyanuric acid, methylene dianiline, etc. is replaced with a glycidyl group.

4) Glycidyl ether ester compounds: glycidyl ether esters of hydroxycarboxylic acids such as p-hydroxybenzoic acid and hydroxynaphthoic acid.

5) Epoxy resins obtained from other alicyclic compounds such as dichloropentadiene, dicyclopentadiene, etc.

Triglycidyl compound of p-aminephenol.

Vinyl cyclohexene dioxide, etc.

Among these, 2,2-bis(4-hydroxyphenyl)
Diglycidyl ether of propane (bisphenol A), diglycidyl ether of 4,4'-dihydroxydiphenylmethane, polyglycidyl ether of phenol novolak, polyglycidyl ether of naphthotuborac, phenol and glydioxal, glutaraldehyde.

Polyglycidyl ether of polyol and diglycidyl ether of polypropylene glycol obtained by dehydrating benzaldehyde or p-hydroxybenzaldehyde over an acidic catalyst.

Diglycidyl ether of polyethylene glycol.

diglycidyl ether of butanediol, diglycidyl ether of glycerol, triglycidyl ether of glycerol, diglycidyl ether ester of p-hydroxybenzoic acid, diglycidyl ether ester of 2-hydroxy-6-naphthoic acid, triglycidyl ether of p-aminephenol Glycidyl compounds and vinylcyclohexene dioxide are preferred, especially diglycidyl ethers of bisphenols, polyglycidyl ethers of phenol novolacs, polyglycidyl ethers of α-naphthol novolacs, phenol with glyoxal, glutaraldehyde, benzaldehyde or p-hydroxybenzaldehyde. Diglycidyl ether of polyol, diglycidyl ether of polyethylene glycol, diglycidyl ether of butanediol, diglycidyl ether of glycerol, and triglycidyl ether of glycerol obtained by dehydration reaction over an acidic catalyst.

Triglycidyl compounds of p-aminephenol and vinylcyclohexene dioxide are preferred. These can be used alone or in combination of two or more.

As the isocyanate used in (b)-(ii) and (c)-(i), aromatic, aliphatic, and alicyclic compounds having at least two isocyanate groups in the molecule and modified products thereof are preferably used. Examples of aromatic polyisocyanates include 2,4-tolylene diinocyanate and 2,6-tolylene diinocyanate.

4.4°-diphenylmethane diisocyanate, polymethylene polyphenylisocyanate, xylylene diisocyanate, etc., and as the alicyclic polyisocyanate, for example, inphorone diisocyanate-1.

Methylene bis(cyclohexyl isocyanate) etc.
Examples of the aliphatic polyisocyanate include hexamethylene diisocyanate, and examples of modified products include dimers of the above polyisocyanates.

Examples include trimers, prepolymer-type modified products, carbodiimide-modified products, urea-modified products, and the like.

The maleimides used in (b)-(iv) are aliphatic, alicyclic and aromatic compounds having two maleimide structures in the molecule, specifically 4,4°-bismaleimide diphenylmethane, 3,3-bismaleimidodiphenylmethane, 4.4'-bismaleimidodiphenyl ether, 3.4°-bismaleimidodiphenyl ether, 4.4'-bismaleimidodiphenyl sulfone,
3,3°-Bismaleimidodiphenylsulfone, N,N
'-hexylylene bismaleimide, N,N'-neopentylene bismaleimide.

N, N'-dodecamethylene bismaleimide N.

Examples include N'-m-phenylene bismaleimide, N,N'-tolylene bismaleimide, N,N'-p-xylylene bismaleimide, N,N'-m-xylylene bismaleimide, and the like.

Examples of the cyclic iminoether used in (b)-M include polyoxazolines and polyoxazine compounds, specifically 2,2°-bis(2-oxazoline), 2
．． 2'-Ethylenebis(2-oxazoline).

2.2'-tetramethylenebis(2-oxazoline).

2.2'-hexamethylenebis(2-oxazoline).

2.2'-octamethylenebis(2-oxazoline).

2.2°-1,4-cyclohexylenebis(2-oxazoline), 2.2'-bis(4-methyl-2-oxazoline), 2.2'-bis(5-methyl-2-oxazoline), 2.2'-m-phenylenebis(2
-oxazoline), 2,2°-p-phenylenebis(2
-oxazoline), 2,2'-m-phenylenebis(4-methyl-2-oxazoline), 2,2°-m-phenylenebis(5-methyl-2-oxazoline), 2゜2゛-p-phenylene bis(4-methyl-2-oxazoline), 2.2” p-phenylenebis(5-methyl-2
-oxazoline), 1,3.5-tris(2oxazolinyl-2)benzene, 2,2°-bis(5,6-sihydro48-13-oxazine).

2,2-ethylenebis(5,6-cyhydro-4H-1°3-oxazine), 2,2°-tetramethylenebis(5
, 6-sihydro41-1-1,3-oxazine).

2.2-Hexamethylenebis(5,6-sihydro4H
-1,3-oxazine), 2,2°-octamethylenebis(5,6-cyhydro48-1,3-oxazine), 2,2'-1,4-cyclohexylenebis(5,
6-sihydro48-1,3-oxazine), 2.
2'-bis(4-methyl-5,6-sihydro4H-1
,3-oxazine), 2,2°-bis(5-methyl-5
,6-sihydro4H1,3-oxazine),2,2"
-bis(6-methyl-5,6-sihydro4H-1,3
-oxazine), 2,2°-m-phenylenebis(5,
6 dihydro 41-1-1,3-oxazine), 2.2
'-pphenylenebis(5,6-sihydro48-1.
3-oxazine), 2.2"-m-phenylenebis(4
-methyl-5,6-cyhydro48-1,3-oxazine), 2,2°-m-7enylenebis(5-methyl5.
6-dihydro-41-1-1,3-oxazine).

2.2'-m-phenylenebis(6-methyl-5,6-
Shihydro 4H-1,3-oxazine), 2,2°
-pphenylenedos(4-methyl-5,6-dihydro4
1,3-oxazine), 2,2'-p-ferenebis(5-methyl-5,6-cyhydro4H1,3-
oxazine), 2,2'-p-phenylenebis(6-methyl-5,6-cyhydro-4H-1,3-oxazine)
etc.

Among these, 2,2'-bis(2-oxazoline).

2.2°-tetramethylenebis(2-oxazoline).

2.2'-m-phenylenebis(2-oxazoline).

2.2'-p-phenylenebis(2-oxazoline).

2.2°-gos(5,6-sihydro-4H-1,3-oxazine), 2.2'-tetramethylenebis(5,
6-sihydro4H-1,3-oxazine), 2,2°
-mphenylenedos(5,6-sihydro4l-(-1
,3oxazine>,7-p-phenylenebis(5,6
dihydro 4H-L3-oxazine) is preferred.

In the present invention, a system in which a polymer is produced by an addition curing reaction, that is, (a)-(i), (ii), (b)-(
i), (ii).

(iv), M, (c)-(il, (cl)-(i
) systems are preferred, especially (a)-(i), (b)-(
Epoxy resins using t) and amine amide resins using (b) -M are preferred.

In addition, in the present invention, the structural unit (I) in the polymer
The proportion of structural units of (I> may be included at least in part, but preferably the structural units of (I> are 5% by weight or more, more preferably the structural units of (I> are 10% by weight or more, and the most Preferably, the structural unit (I>) is 30% by weight or more.

Therefore, for example, when synthesizing an epoxy resin containing the structural unit of the general formula (I>) by the method (a)-(i),
The epoxy compound of I) is reacted with a curing agent, or in some cases, a part of the epoxy compound of general formula (n) is replaced with another epoxy compound [(b)-(epoxy compound used in il)] Similar things are possible for other systems as well.

For example, when synthesizing an epoxy resin containing the structural unit of the general formula (I>) by the method (a)-(i), the general formula (II)
) and a curing agent, but in some cases, the epoxy compound used in (b) to (i) is used as the epoxy compound, and the curing agent contains a structural unit of general formula (I>). may also be used.

As a method for producing a polymer by reacting the above compound with a reactant, etc., which is a constituent component of another type of polymer, taking a preferable addition curing reaction type as an example, (A) a mixture of the above compound and a reactant is used. A method in which a homogeneous solution is prepared using no solvent or an organic solvent, the solution is coated or applied to various electrodes, sheets, films, molded products, etc., and the solution is heated and reacted.

(B) physically intimately mixing the compound and the reactant;
A method of filling the mixture into a mold of a desired shape and causing a heating reaction in the mold.

etc. can be given.

In this case, the proportions of the reaction components vary depending on the system, but are carried out at conventionally known proportions generally practiced for each system. A preferable ratio is, for example, a ratio in which the reaction components are close to equivalent amounts.

The reaction temperature varies depending on the type and proportion of each component, but is, for example, room temperature to 300°C, more preferably 50 to 250°C.
It is about ℃.

The reaction time is sufficient as long as the resin is sufficiently cured, and this time also depends on the type of raw materials used.

The usage ratio varies depending on the degree of repulsion, but preferably 1
The heating time is approximately 5 minutes to 3 hours, more preferably 3 minutes to 2 hours and 30 minutes, particularly preferably 5 minutes to 2 hours.

This reaction can be carried out at normal pressure to elevated pressure, but in order to prevent the influence of moisture in the atmosphere and oxidative deterioration of the resin, nitrogen,
It is more preferable to carry out under an inert gas atmosphere such as argon.

The reversible color-changing resin of the present invention can be obtained by subjecting at least a portion of the amino groups in the above polymer, for example, 1 equivalent % or more, to a quaternization treatment.

In the present invention, examples of methods for quaternizing at least some of the amino groups in the polymer include a method of treating with an acid, a method of treating with a salt, a method of treating with an alkyl halide, a method of treating with an acid ester, etc. However, this is not limited to this.

The acids used here include sulfuric acid, hydrochloric acid, and nitric acid.

Acetic acid, phosphorous acid, phosphoric acid, benzenesulfonic acid.

Examples include p-toluenesulfonic acid, methanesulfonic acid, and ethanesulfonic acid.

Examples of the salt include tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium verchlorate, tetramethylammonium chloride, lithium bromide, and lithium chloride.

Alkyl halides include methyl iodide, ethyl iodide, propyl iodide, butyl iodide, benzyl iodide,
Examples include benzyl bromide.

Examples of acid esters include methyl benzenesulfonate, ethyl benzenesulfonate, methyl p-toluenesulfonate, and ethyl p-toluenesulfonate.

Examples include dimethyl sulfate, trimethyl phosphate, and triphenyl phosphate.

As a method for quaternization treatment, (ao) after curing the polymer, use the above acids, salts, or alkyl halides.

Impregnation 1 reaction with acid ester etc. (bo) Boli 7- Before curing, acid together with the above compound 1 reactant.

Examples include a method in which salt, alkyl halide, acid ester, etc. are added in advance and then heated to effect curing and quaternization at the same time. It is also possible to use these methods in combination.

Specifically, the method of impregnation in the above method involves dissolving a quaternizing agent such as an acid, salt, alkyl halide, or acid ester in water or an organic solvent such as acetone or methanol, and adding the cured polymer thereto. An example of this method is to impregnate the quaternizing agent into the resin by immersing the resin in the resin, heating if necessary, and causing the quaternizing agent to react with the amine residue in the resin.

When used as an electrochromic material, it is desirable to use a salt as the quaternizing agent because the salt quaternizes the amine and also acts as an electrolyte.

The method for coloring and decolorizing the reversible color-changing material of the present invention is as follows:
Known methods conventionally used for photochromic materials and electrochromic materials can be applied as they are. For example, in the case of photochromic materials,
It can be rapidly colored blue or green by irradiation with ultraviolet rays, and can be decolored by irradiation with light at the wavelength absorbed by the coloring or by heating.

In the case of an electrochromic material, coloring and decoloring can be achieved by coating a transparent electrode with the material of the present invention in the form of a thin film and constructing a conventionally known ECD cell using the electrode. In this case, it is also preferable to include a so-called supporting electrolyte such as a quaternary ammonium salt in the reversibly color-changing material of the present invention, if necessary.

<Effects of the Invention> The reversibly color-changing material of the present invention has vivid colors when developed, and has excellent repeat durability and solvent resistance, and is extremely useful as a new photochromic material or electrochromic material.

Furthermore, the present invention is an oxidized electrode that develops a color when the electrode is brought to a positive potential, which is the opposite of the generally common reduced electrode.

<Examples> Hereinafter, the present invention will be described in detail with reference to Examples, but the Examples are for illustrative purposes and the present invention is not limited thereto. In the examples, "r parts" means "parts by weight."

Example 1 2.5 parts of 3.3'-diaminodiphenylsulfone, 4.6 parts of bis[4-N,N-di(2,3-epoxypropyl)aminophenyl]methane and 4 parts of ethyl p-toluenesulfonate were added. It was thoroughly dissolved in 50 parts of 1.1,2.2-tetrachloroethane and cast on glass.

The glass was heated at 180° C. for 30 minutes under a nitrogen atmosphere. The resulting resin was transparent.

When this transparent resin was irradiated with ultraviolet rays for about 1 minute using an IOWU V lamp (USHIO IJH102), it was colored transparently green. When this green transparent resin was heated at 240° C. for 2 minutes, it became colorless and transparent. It was possible to repeat the coloring and embellishment by the above-mentioned ultraviolet irradiation and heating.

Example 2 2.5 parts of 3.3°-diaminodiphenylsulfone, 4.6 parts of bis[1-N,N-di(2,3-epoxyprobyl)aminophenylcomethane, and 4 parts of ethyl p-toluenesulfonate and tetrabutylammonium barchlorate 3
1.1,2.2-tetrachloroethane was thoroughly dissolved in 50 parts of 1.1,2.2-tetrachloroethane, and cast onto a transparent electrode.

When this transparent electrode was heated at 180° C. for 1 hour in a nitrogen atmosphere, the coated resin was cured.

The resulting transparent electrode was used as a working electrode and the platinum electrode was used as a counter-photoelectrode.It was immersed in an electrolyte solution in which 3 parts of tetrabutylammonium barchlorate had been dissolved in 1000 parts of methanol, and when a voltage of 2.0V was applied using the working electrode as an anode, it became transparent. The working electrode immediately colored blue. Then, when the direction of voltage application was reversed, the color was quickly decolored.

By repeating the above coloring and decolorizing operations, the color of the electrode changed reversibly.

Example 3 Methylcyclohexane-1,2-dicarboxylic anhydride 3
．． 4 parts of bis[4-N,N-di(2,3-epoxypropyl)aminophenyl]methane and 2.5 parts of N as a catalyst.
, 0.1 part of N-dimethylbenzylamine in 1.1,2.
It was dissolved in 10 parts of 2-detrachloroethane. This solution was then cast onto glass and heated at 180° under a nitrogen atmosphere.
It was cured by heating at C for 1 hour. The resulting resin was transparent.

After immersing this resin in 9N sulfuric acid for 5 minutes, it was exposed to ultraviolet rays for 1
Using 00WU V lamp (Ushio Electric U former 02),
When irradiated for about 1 minute, it turned transparent green. When this green transparent resin was heated to 230'C for 2 minutes, it became transparent. It was possible to repeat the coloring and embellishment by the above-mentioned ultraviolet irradiation and heating.

Example 4 A resin cured in the same manner as in Example 3 was immersed in boiling iodoethane for 5 minutes. After that, ultraviolet rays were applied to this transparent resin using a 100 JJ V lamp (Ushio Electric U
When irradiated for about 1 minute using 02), it was colored transparent green. When this green transparent resin was heated to 220° C. for 1 minute, it became transparent.

Furthermore, coloring and embellishment could be repeated by the above-mentioned ultraviolet irradiation and heating.

Example 5 A 1.1,2,2-tetrachloroethane solution having the same composition as in Example 3 was cast onto a transparent electrode, and heated for 18 hours under a nitrogen atmosphere.
It was cured by heating at 0° C. for 40 minutes.

The obtained working electrode was immersed in an electrolyte solution prepared by dissolving 3 parts of tetrabutylammonium percrosite in 1000 parts of methanol, using the platinum electrode as the counter electrode, and the working electrode was used as the anode.2. When a voltage of OV was applied, the transparent working electrode immediately turned blue. Then, when the direction of voltage application was reversed, the color was quickly decolored. By repeating the above coloring and decolorizing operations, the color of the electrode changed reversibly.

Example 6 1.95 parts of an average molecular weight [400] phenol novolak and 2.5 parts of bis[4-N,N-di(2,3-epoxypropyl)aminophenyl]methane and 1 part of iodoethane, 2.4 parts as catalyst .6- 0.05 part of tris(dimethylaminomethyl)phenol was dissolved in 20 parts of tetrachloroethane. This solution was then cast onto glass,
It was cured by heating at 180° C. for 1 hour in a nitrogen atmosphere. The resulting resin was transparent.

When this transparent resin was irradiated with ultraviolet rays for about 1 minute using a 100WU V lamp (Ushio Electric Inc. 102), it was colored transparently green. When this green transparent resin was heated to 240° C. for 2 minutes, it became transparent.

Furthermore, coloring and embellishment could be repeated by the above-mentioned ultraviolet irradiation and heating.

Example 7 2.2 parts of 44°-diaminodiphenylmethane and 4.5 parts of a bisphenol A type epochine compound with an epoxy equivalent of 195(]/eq were thoroughly mixed, then cast on glass, and after purging with nitrogen, the mixture was heated at 200°C for 30 minutes. The resulting resin was pale yellow in color.

Separately, a solution was prepared by dissolving 5 parts of ethyl p-toluenesulfonate in 100 parts of acetone, and the obtained resin was placed in this solution and heated to impregnate the resin with ethyl p-toluenesulfonate. . When this pale yellow resin was irradiated with ultraviolet rays for 2 minutes from a distance of about 20 cm using a 10011U V lamp (Ushio Inc.-102), it was colored transparently green. When this green transparent resin was heated to 200° C. for 2 minutes, it became pale yellow and transparent. Furthermore, coloring and decoloring could be repeated by the above-mentioned ultraviolet irradiation and heating.

Example 8 1.0 part of 4.4'-diaminodiphenylmethane, 3.4 parts of bisphenol A type epoxy compound with epoxy equivalent of 195 MeQ, 1.0 part of tetrabutylammonium verchlorate and 1.1,2.2-tetrachloroethane It was dissolved in 40 parts. This solution was then cast onto a transparent electrode and cured by heating at 180° C. for 1 hour in a nitrogen atmosphere. Using the obtained working electrode and platinum electrode as counter electrodes, 30 parts of tetrabutylammonium barchlorate was added in advance to 100 parts of N dimethylacetamide.
2. Using the working electrode as an anode, the working electrode is immersed in an electrolyte solution dissolved in the liquid. When a voltage of OV was applied, the pale yellow working electrode immediately turned blue. Then, when the direction of voltage application was reversed, the color was quickly decolored. By repeating the above coloring and decoloring operations, the color of the electrode changed reversibly.

Example 9 2.0 parts of 4.4'-diaminodiphenylmethane and 3.6 parts of phenol novolac type epoxy compound of Ji180111/eQ (7, 3.0 parts of tetrabutylammonium barchlorate per epoxy) were added to 1.1,2.2- It was dissolved in 40 parts of tetrachloroethane.This solution was then cast onto a transparent electrode and cured by heating at 200'C for 45 minutes in a nitrogen atmosphere.The resulting working electrode and platinum electrode (counter electrode) was immersed in an electrolyte solution in which 3.0 parts of tetrabutylammonium verchlorate was dissolved in 100 parts of methanol, and then a voltage was applied in the same manner as in Example 2, and the working electrode was immediately colored blue. When the direction was reversed, the color was immediately decolored.By repeating the above coloring and decoloring operations, the color changed reversibly.

Example 10 21.0 parts of 4,4-diaminodiphenyl meta, 4,4-
Diaminodiphenylsulfone 0.8 part and epoxy equivalent 1
80MeQ 7 Enol Novolac Type Epoxy Compound 3.6L Tetrabutylammonium Bacrolate 3
．． 0 parts was dissolved in 50 parts of 1.1,2.2-tetrachloroethane. A working electrode was prepared by treating this solution in the same manner as in Example 3, and when a voltage was applied in the same manner as in Example 2, the working electrode was immediately colored blue. Furthermore, when the direction of voltage application was reversed, the color was quickly decolored. By repeating the above coloring and decoloring operations, the color changed reversibly.

Example 11 Bis(3-chloro-4-aminophenyl)methane 2.7
part and 4.3 parts of 2,2-metaphenylenebis(2-oxazoline), 2-paratoluenesulfonic acid 4, OPiS, and 4.0 parts of tetra-n-butylammonium barchlorate to 1.1,2,2-tetra It was dissolved in 50 parts of chloroethane. Next, this solution was reacted at 110° C. for 10 minutes under a nitrogen atmosphere, cooled, and cast onto a transparent electrode. When this transparent electrode was heated at 150° C. for 30 minutes, a transparent electrode with a resin film on the surface was obtained. Using the obtained working electrode and the platinum electrode as a counter electrode, 3.0 parts of tetrabutylammonium barchlorate was mixed in advance with 1 part of methanol.
When a voltage of 1.5 V was applied using the working electrode as an anode, the transparent working electrode immediately turned purple. Then, when the direction of voltage application was reversed, the color was quickly decolored. By repeating the above coloring and decoloring operations, the color of the electrode changed reversibly.

Example 12 Bis(2-methyl-4-aminophenyl)methane 2.3
parts, 4.3 parts of 2'-metaphenylenebis(2-oxazoson), 4.0 parts of para-toluenesulfonic acid, and 4.0 parts of tetra-n-butylammonium barchlorate in 1.1 and 2.2 parts. -Dissolved in 50 parts of tetrachloroethane. Next, this solution was reacted at 100° C. for 10 minutes under a nitrogen atmosphere, cooled, and cast onto a transparent electrode. When this transparent electrode was heated at 150° C. for 20 minutes, a transparent electrode with a thin resin film on the surface was obtained. Using the obtained working electrode and the platinum electrode as a counter electrode, 3.0 parts of tetrabutylammonium barchlorate was mixed in advance with 1 part of methanol.
When a voltage of 1.5 V was applied using the working electrode as an anode, the transparent working electrode was immediately colored blue. Then, when the direction of voltage application was reversed, the color was quickly decolored. By repeating the above coloring and decoloring operations, the color of the electrode changed reversibly.

Special permission Out wish Man Teijin Corporation 1゜ 2゜ 3゜ Procedural amendment July 21, 1986

Claims (1)

[Claims] (1) The following structural unit (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼...(I) [Here, a, b, c, and d represent bonds, the same or different, and each represents a hydrogen atom or an aliphatic group, alicyclic group,
It is bonded to a carbon atom constituting an aromatic group, and at least one is bonded to a carbon atom. R is a hydrogen atom or a hydrocarbon group. X and Y are the same or different and are a halogen atom or a hydrocarbon group. m and n are the same or different, and each is an integer of 0 to 4. ] A reversible color-changing material which is a polymer containing as a part of the constituent components, and at least a part of the amino groups in the polymer have been subjected to a quaternization treatment.