JP2541038B2 - Chromic resin, chromic resin, chromic resin composition, production method thereof, and chromic resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a chromic resin, a chromic resin, a chromic resin composition, a process for producing them and a chromic resin composition.

[0002]

2. Description of the Related Art Photochromic materials whose hue is reversibly changed by light and thermochromic materials whose hue is reversibly changed by heat have been studied as various display elements, recording materials and light control materials.

Conventionally, as photochromic materials, low molecular weight compounds such as viologen, spiropyran and fulgide have been studied. In recent years, it has been proposed to solidify these low molecular weight photochromic compounds by dispersing them in a polymer matrix or by covalently bonding them to a part of the polymer. These are obtained by incorporating a known photochromic compound into a resin.

On the other hand, a resin having a chromic property in the resin skeleton itself has been found and studied. For example, JP-B-64-976 discloses color development by ultraviolet rays of polyimide containing aliphatic diamine and decoloration by heat. Further, a polymer containing a specific diaminodiphenylmethane derivative as at least one of its constituents and capable of color development by ultraviolet rays and decolorization by heat is disclosed in JP-A-2-673.
No. 90, Japanese Patent Application Laid-Open No. 2-73830, and the like.

The polymers capable of coloring and erasing described in the above publication have a low coloring density upon irradiation with light and have a small contrast between a portion not irradiated with light and a portion irradiated with light. Therefore, further improvement is desired for practical use. Be done.

[0006]

DISCLOSURE OF THE INVENTION The present invention is firstly a novel material which can be colored by irradiation of ultraviolet rays and decolored by heating, and has a different mechanism of coloring / decoloring from the one described in the above publication. Second chromic resin
To provide a material having a large contrast between the coloring portion and the erasing portion.

[0007]

In the chromic resin according to the present invention, two nitrogen atoms are directly bonded to one aromatic ring at the most distant diagonal positions of the aromatic ring, and at least the nitrogen atoms of the aromatic ring are bonded to each other. An alkylene group is bonded to a part of the alkylene group, and a structural unit in which the above two nitrogen atoms are tertiaryized is included.

The characteristic structure of this chromic resin is represented by the following chemical formula 2 [general formula (I)].

Embedded image (However, in the general formula (I), Ar represents an aromatic ring, two nitrogen atoms are bonded to the most distant position of this aromatic ring, and symbols 1 to 4 are for identifying carbon atoms. A substituent such as hydrogen or an alkyl group or a residue constituting a chromic resin is bonded to the carbon atoms of 1 to 4, and the residue is at least one carbon atom of the symbols 1 to 4. And at least one of the residues is bonded to any of the carbon atoms 1 to 4 through an alkylene group). The aromatic ring represented by Ar may be a condensed ring.

Examples of Ar in the general formula (I) are represented by the following chemical formula 3 [general formula (II)], the following chemical formula 4 [general formula (III)] or the following chemical formula 5 [general formula (IV)]. There is a group

Embedded image (In the general formula (II), R ¹ , R ² , R ³ and R ⁴ may be the same or different, and each of hydrogen, halogen such as fluorine and chlorine, alkyl group, alkoxy group, aryl group, sulfone group and carboxy group. , A hydroxyl group, a nitro group, a cyano group and the like).

Embedded image (In the general formula (III), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be the same or different and each is a hydrogen atom or a halogen such as fluorine or chlorine, an alkyl group, an alkoxy group, It represents a substituent such as an aryl group, a sulfone group, a carboxy group, a hydroxyl group, a nitro group, and a cyano group).

Embedded image (In the general formula (IV), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷
And R ⁸ may be the same or different and each represents a hydrogen atom or a substituent such as halogen such as fluorine and chlorine, an alkyl group, an alkoxy group, an aryl group, a sulfone group, a carboxy group, a hydroxyl group, a nitro group and a cyano group. ).

The chromic resin may contain a bonded halogen atom in its molecular structure. In this case, the resin is a chromic resin capable of coloring and decoloring described later. The amount of halogen atoms is determined by the formula (I)
0.01 for one nitrogen atom in the structure represented by
It is preferable that the number is one or more. If the amount of halogen atoms is too small, the function as a chromic resin is insufficient.

The chromic resin may be in the form of a composition having a cation radical stabilizer dispersed therein. In this case, the composition is a chromic resin composition capable of coloring and decoloring described later. The cation radical stabilizer is a system in which the resin having the structure represented by the general formula (I) is converted into a cation radical on the basis of the structure of the resin, and the emitted electron is captured to form an anion radical. Has the ability to stabilize
It is a substance that emits electrons when heated after being converted into anion radicals.

The chromic resin can be produced by a method characterized by reacting a diamine compound represented by the following chemical formula 6 [general formula (V)] with an epoxy resin. In this case, when a halogenated epoxy resin is used as the epoxy resin, a chromic resin capable of coloring and decoloring described later can be obtained.

[Chemical 6] [However, in the general formula (V), Q ¹ , Q ² , Q ³ and Q ⁴ are hydrogen or an alkyl group which may have a substituent, and these may be the same or different, and At least two of these are hydrogen, Ar is the same as in general formula (I), and two nitrogen atoms are bonded to the furthest positions of Ar].

In the above general formula (V), Ar is a group represented by the above general formula (II), the above general formula (III) or the above general formula (IV), and Q ¹ , Q ² , Q ³ or When Q ⁴ is an alkyl group, the alkyl group may be a methyl group, an ethyl group,
n-propyl group, i-propyl group, butyl group, lauryl group,
There are stearyl group, benzyl group and the like. Ar is appropriately introduced with a substituent in order to improve the solubility in a solvent, the compatibility with an epoxy resin, the control of a coloring wavelength, the stability of coloring, and the like.

Among the above diamine compounds, those having two amino groups include paraphenylenediamine, 2,5
-Dimethyl-1,4-phenylenediamine, 2-methyl-1,4-phenylenediamine, 2,6-dichloro-1,
4-phenylenediamine, 5-chloro-2-methyl-
1,4-phenylenediamine, 2,5-diaminobenzoic acid, 2,5-diaminoterephthalic acid, 2-nitro-1,4
-Phenylenediamine, 2-cyano-1,4-phenylenediamine, 2-methoxy-1,4-phenylenediamine, 2,5-diaminobenzenesulfonic acid, 2,5-diaminophenol, 2,3,5, 6-tetramethyl-1,4-
Phenylenediamine, 2,3,5,6-tetrachloro-1,
4-phenylenediamine, 2,6-diaminonaphthalene, 1-methyl-2,6-diaminonaphthalene, 3-chloro-2,6-diaminonaphthalene, 3-fluoro-2,
6-diaminonaphthalene, 1,4-dimethyl-2,6-diaminonaphthalene, 1,5-dimethyl-2,6-diaminonaphthalene, 1,4-dichloro-2,6-diaminonaphthalene, 1,5-dichloro- 2,6-diaminonaphthalene,
1,4-difluoro-2,6-diaminonaphthalene, 1,
5-difluoro-2,6-diaminonaphthalene, 3,5-dimethyl-2,6-diaminonaphthalene, 1,5-dinitro-2,6-diaminonaphthalene, 4,8-dihydroxy-
2,6-diaminonaphthalene, 2,6-diamino-1,3,
4,5,7,8-hexamethylnaphthalene, 2,6-diamino-1,3,4,5,7,8-hexachloronaphthalene, 2,
6-diamino-1,3,4,5,7,8-hexafluoronaphthalene, 2,6-diamino-1,3,4,5,7,8-hexacyanonaphthalene, 2,6-diaminoanthracene,
1-methyl-2,6-diaminoanthracene, 3-chloro-2,6-diaminoanthracene, 3-fluoro-2,
6-diaminoanthracene, 1,4-dimethyl-2,6-
Diaminoanthracene, 1,5-dimethyl-2,6-diaminoanthracene, 1,4-dichloro-2,6-diaminoanthracene, 1,5-dichloro-2,6-diaminoanthracene, 1,4-difluoro-2, 6-diaminoanthracene, 1,5-difluoro2,6-diaminoanthracene, 3,5-dimethyl-2,6-diaminoanthracene,
1,5-dinitro-2,6-diaminoanthracene, 4,
8-dihydroxy-2,6-diaminoanthracene, 2,6
-Diamino-1,3,4,5,7,8-hexamethylanthracene, 2,6-diamino-1,3,4,5,7,8-hexachloroanthracene, 2,6-diamino-1,3, 4,5
7,8-hexafluoroanthracene, 2,6-diamino-1,3,4,5,7,8-hexacyanoanthracene, 9,
10-diaminoanthracene and the like can be mentioned.

Of the above diamine compounds, those having a monoalkylamino group or a dialkylamino group are as follows:
N, N-dimethylparaphenylenediamine, N, N-diethylparaphenylenediamine, N, N-di-n-propylparaphenylenediamine, N, N-di-i-propylparaphenylenediamine, N, N-dibutylpara Phenylenediamine, N, N-dilaurylparaphenylenediamine, N, N-distearylparaphenylenediamine, N, N-dibenzylparaphenylenediamine, N,
N-dimethyl-2,6-naphthalenediamine, N, N-
Diethyl-2,6-naphthalenediamine, N, N-di-
n-propyl-2,6-naphthalenediamine, N, N-
Di-i-propyl-2,6-naphthalenediamine, N,
N-dibutyl-2,6-naphthalenediamine, N, N-
Dilauryl-2,6-naphthalenediamine, N, N-distearyl-2,6-naphthalenediamine, N, N-dibenzyl-2,6-naphthalenediamine, N, N-dimethyl-2,6-anthracenediamine, N , N-diethyl-2,6-anthracene diamine, N, N-di-n-
Propyl-2,6-anthracene diamine, N, N-di-i-propyl-2,6-anthracene diamine, N,
N-dibutyl-2,6-anthracene diamine, N, N
-Dilauryl-2,6-anthracene diamine, N, N
-Distearyl-2,6-anthracene diamine, N,
N-dibenzyl-2,6-anthracene diamine, N,
N'-dimethylparaphenylenediamine, N, N'-diethylparaphenylenediamine, N, N'-di-n-propylparaphenylenediamine, N, N'-di-i-propylparaphenylenediamine, N, N ' -Dibutylparaphenylenediamine, N, N'-dilaurylparaphenylenediamine, N, N'-distearylparaphenylenediamine, N, N'-dibenzylparaphenylenediamine, N, N'-dimethyl-2,6- Naphthalenediamine, N, N'-diethyl-2,6-naphthalenediamine, N, N'-di-n-propyl-2,6-naphthalenediamine, N, N'-di-i-propyl-2,6- Naphthalenediamine, N, N'-dibutyl-2,6-naphthalenediamine, N, N'-dilauryl-2,6-naphthalenediamine, N, '-Distearyl-2,6-naphthalenediamine, N, N'-dibenzyl-2,6-naphthalenediamine, N, N'-dimethyl-2,6-anthracenediamine, N, N'-diethyl-2,6 -Anthracene diamine, N, N'-di-n-propyl-2,6
-Anthracene diamine, N, N'-di-i-propyl-2,6-anthracene diamine, N, N'-dibutyl-2,6-anthracene diamine, N, N'-dilauryl-2,6-anthracene diamine, Examples thereof include N, N'-distearyl-2,6-anthracene diamine and N, N'-dibenzyl-2,6-anthracene diamine.

As the epoxy resin, a compound having two or more epoxy groups in the molecule is used. For example, polyglycidyl ether obtained by reacting a polyhydric phenol such as bisphenol A or a polyhydric alcohol such as 1,4-butanediol with epichlorohydrin, phthalic acid,
Polyglycidyl ester obtained by reacting a polybasic acid such as hexahydrophthalic acid with epichlorohydrin, amine, amide, or N- of a compound having a heterocyclic nitrogen base
There are glycidyl derivatives, alicyclic epoxy resins such as (3 ', 4'-epoxycyclohexylmethyl) -3,4-epoxycyclohexanecarboxylate, phenol novolac type epoxy resins, orthocresol type epoxy resins. Such epoxy resins commercially available include Epicoat 1001 (epoxy equivalent of 450 to 50) as bisphenol A type epoxy resin.
0), Epicoat 1004 (epoxy equivalent of 900 to 10)
00), Epicoat 1007 (epoxy equivalent of 1750-
2100), Epicoat 1009 (epoxy equivalent 240
0-3300) [Both products of Shell Chemical Company]
Etc. Further, these epoxy resins may be used alone or in combination of several kinds.

Part of the epoxy resin is
A compound having only one epoxy group in the molecule may be used as a diluent. Diluents include n-butyl glycidyl ether, t-butyl phenyl glycidyl ether, dibromophenyl glycidyl ether, etc. These are used to the extent that they do not significantly impair the product properties such as hardness of the diamine compound.

The above epoxy resin and diluent may be halogenated. As such,
Chemical formula 7 [general formula (VI)], chemical formula 8 [general formula (VII)], chemical formula 9
Some are represented by [general formula (VIII)].

[Chemical 7]

Embedded image

[Chemical 9] However, in the general formula (VI), the general formula (VII) and the general formula (VIII), X is halogen such as chlorine and bromine, and R is -CH.
_{2 -, - C (CH 3} ) 2 -, - C (CF 3) 2 -, - C (= O)
-, - CH (Ph) - , - C (CH 3) (Ph) - such as an alkylene group (wherein, Ph represents a phenyl group), n is 0 or an integer of 1 or more, m is 1 to 3 Indicates an integer.

The halogenated bisphenol A type epoxy resin which has been halogenated with the above-mentioned epoxy resin is Sumiepoxy ELB240 (epoxy equivalent of 240 to 250).
[Sumitomo Chemical Co., Ltd. as a phenol novolac type epoxy resin Epicoat 152 (epoxy equivalent 17
5), Epicoat 154 (epoxy equivalent 176-18)
1) [Idemomo Shell Chemical product name], DEN431
(Epoxy equivalent 172 to 179), DEN438 (epoxy equivalent 175 to 182) [Dow Chemical trade name], etc., and halogenated phenol novolac type epoxy resins such as BREN-S (Nippon Kayaku Co., Ltd. trade name). BR-250 which is halogenated with the above diluent and which is commercially available
(Nippon Kayaku Co., Ltd. product name) etc.

A cation radical stabilizer may be present in the reaction of the above-mentioned diamine compound and epoxy resin. In this case, the cation radical stabilizer is dispersed in the obtained polymer.

As the cation radical stabilizer,
Examples include alkyl halides, acids, salts and acid esters. Alkyl halides include methyl iodide, ethyl iodide,
Examples include propyl iodide, benzyl iodide, benzyl bromide, tosyl chloride. Acids include hydrochloric acid, sulfuric acid, nitric acid,
Inorganic acids such as phosphoric acid and phosphorous acid, acetic acid, benzene sulfonic acid, paratoluene sulfonic acid, methane sulfonic acid, ethane sulfonic acid, and other organic acids include tetrabuyl ammonium chloride, tetrabutyl ammonium bromide, tetramethyl. Examples include quaternary ammonium salts such as ammonium chloride and tetrabutylammonium perchlorate, and metal halides such as lithium chloride and lithium bromide. As the acid ester, methyl paratoluenesulfonate, ethyl paratoluenesulfonate,
Examples thereof include sulfonic acid esters such as ethyl benzene sulfonate and ethyl benzene sulfonate, sulfuric acid esters such as dimethyl sulfate, and phosphoric acid esters such as trimethyl phosphate and triphenyl phosphate.

The reaction of the above-mentioned diamine compound and epoxy resin can be carried out at room temperature, but it is from 100 ° C to 400 ° C
It is preferable to heat cure at a temperature within the range of. When a diamine compound having only two active hydrogens bonded to a nitrogen atom is reacted with an epoxy resin having only two epoxy groups, the polymer obtained is a chain, and such a chain polymer is acetone or methyl ethyl ketone. , Methyl isobutyl ketone, methylene chloride, chloroform, dimethylformamide, dimethylsulfoxide and the like can be dissolved. Except for such a combination, a cured product polymer is obtained by the above reaction.

The above-mentioned diamine compound and epoxy resin contain 0.01 to 10 active hydrogen bonded to the nitrogen atom of the diamine compound with respect to 1 equivalent of the epoxy group of the epoxy resin.
It is preferably used in an equivalent amount, particularly preferably 0.1 to 1 equivalent. The cation radical stabilizer is preferably used within a range of 0.01 to 100 equivalents, and particularly within a range of 0.1 to 1 equivalents, relative to 1 equivalent of the nitrogen atom directly bonded to the aromatic ring of the diamine compound. It is preferably used in.

A reaction (curing) accelerator may be present during the reaction of the diamine compound with the epoxy resin. As the reaction accelerator, imidazole, 2-methylimidazole, 2-ethylimidazole, 1,2-methylimidazole, 2-ethyl-4-methylimidazole,
Imidazoles such as 2-undecylimidazole and 2-phenylimidazole, amines such as N-aminoethylpiperazine, triphenylphosphine, tributylphosphine, methyldiphenylphosphine, butylphenylphosphine, dimethylphosphine, phenylphosphine and octylphosphine. Examples include organic phosphines and thiazoles.

The composition containing the above-mentioned diamine compound and epoxy resin and, if necessary, a reaction accelerator and a cation radical stabilizer is in liquid or solid form. Also, these compositions may be dissolved in a suitable solvent. The above composition can be molded into an appropriate shape by casting, melt molding, coating, etc. before the curing reaction, and the curing reaction can be performed after such molding or simultaneously with the molding. Alternatively, the above composition may be impregnated into a suitable liquid-absorbent material, for example, paper, cloth, glass cloth, or the like, for reaction.

Solvents for dissolving the above composition include dimethylformamide, dimethylsulfoxide, dimethylacetamide, methyl ethyl ketone, methyl isobutyl ketone, acetone, chloroform, dichloromethane, tetrachloroethane, methanol, ethanol, isopropanol and the like.

In the case of molding by coating in the above,
Polycarbonate, acrylic resin, resin such as polyimide, glass, ceramics, a suitable substrate made of a material such as metal, the spin coating method, bar coating method,
It can be carried out by forming a film by a knife coating method, a brush coating method, a casting method or the like.

By treating the reaction product of the above-mentioned diamine compound and epoxy resin with a cation radical stabilizer, a chromic resin composition in which the cation radical stabilizer is dispersed in the reaction product can be obtained. it can. As the treatment method, a liquid cation radical stabilizer or a method in which the cation radical stabilizer is dissolved in a solution prepared by dissolving it in a suitable solvent, a liquid cation radical stabilizer or a liquid cation radical stabilizer is suitable. There is a method of applying a solution prepared by dissolving it in another solvent to the above reaction product.
As the solution, a cation radical stabilizer is added to 0.0
What is dissolved in an organic solvent such as dimethylformamide, dimethylsulfoxide, dimethylacetamide, methylethylketone, methylisobutylketone, acetone, chloroform, dichloromethane, tetrachloroethane, methanol, ethanol, isopropanol so as to have a concentration of 1% by weight to saturation. is there.

The chromic resin of the present invention is characterized in that an epoxy resin having two diglycidylamino groups directly bonded to the aromatic ring at the most distant diagonal positions of the aromatic ring is reacted with a curing agent. It can also be manufactured by a method.

As the above-mentioned epoxy resin, chemical formula 10 [general formula (IX)]

[Chemical 10] However, there is one represented by the general formula (IX) wherein Ar is the same as the general formula (I). Specifically, N, N,
N ', N'-tetraglycidyl paraphenylenediamine, N, N, N', N'-tetraglycidyl-2,6-
Examples include naphthalenediamine, N, N, N ', N'-tetraglycidyl-2,6-anthracene diamine, and the like.

The epoxy resins represented by the general formula (IX) can be used in combination with the epoxy resins listed above to the extent that the object of the present invention is not impaired.

A compound having only one epoxy group in the molecule may be used as a diluent in the epoxy resin represented by the general formula (IX). As the diluent, there are those mentioned above. These are used to the extent that they do not significantly impair the curing characteristics such as hardness of the cured product.

As the curing agent, a dicarboxylic acid anhydride,
Examples include diamine compounds, phenol resins, polysulfide resins, and polyhydric phenols.

Examples of the dicarboxylic acid anhydride include phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, pyromellitic dianhydride, dodecylsuccinic anhydride and the like. . Etc. The curing reaction between the acid anhydride and the epoxy resin is preferably heat curing at a temperature in the range of 100 to 400 ° C.

As the diamine compound as the above curing agent, the above-mentioned diamine compounds can be used, as well as diethylenetriamine, triethylenetetramine,
Examples include diethylaminopropylamine, N-aminoethylpiperazine, metaxylenediamine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro (5,5) undecane. The curing reaction between these diamine compounds and the epoxy resin may be carried out at room temperature, but it is preferable to thermally cure at a temperature in the range of 100 ° C to 400 ° C.

As the above-mentioned phenol resin, novolac type or resol type phenol resin obtained by using phenol such as phenol, cresol and t-butylphenol can be used.

In the reaction of the epoxy resin represented by the general formula (IX) and the curing agent, the cation radical stabilizer can be present. In this case, the cation radical stabilizer is dispersed in the obtained cured polymer.

The epoxy resin and the curing agent represented by the general formula (IX) are preferably used so that the reactive group of the curing agent is 0.01 to 10 equivalents per 1 equivalent of the epoxy group of the epoxy resin. , 0.1 to 1 equivalent is particularly preferably used. The cation radical stabilizer is preferably used in the range of 0.01 to 100 equivalents, and particularly preferably in the range of 0.1 to 1 equivalents, relative to 1 equivalent of the diglycidylamino group of the epoxy resin. Is preferred.

When the epoxy resin represented by the general formula (IX) and the curing agent are reacted, the above-mentioned curing accelerator can be present. Examples of the curing accelerator include those exemplified above.

A chromic resin in which a cation radical stabilizer is dispersed in a cured product obtained by treating a cured product obtained from the epoxy resin represented by the general formula (IX) and a curing agent with the cation radical stabilizer. It can be a composition. The treatment method is the same as the treatment method of the cured product of the diamine compound and the epoxy resin described above.

The composition containing the epoxy resin and the curing agent, and optionally a reaction (curing) accelerator and a cation radical stabilizer is in a liquid or solid form. It can be formed into a solution, molded, impregnated, or applied in the same manner as the composition containing the diamine compound and the epoxy resin described above.

The resin having the structure represented by the general formula (I) includes an ethyleneimine represented by the following chemical formula 11 [the general formula (X)] and a dithiol represented by the general formula 12 [the general formula (XI)]. It can also be produced by reacting with and then reacting with an alkyl halide. The reaction product is
3 has a repeating unit represented by the general formula (XII). In this reaction, it is preferable to use 0.01 to 10 mol% of dithiol for 1 mol of ethyleneimine, and it is preferable to use about 2 mol of the alkyl halide for 1 mol of used ethyleneimine. In this reaction, the cation radical stabilizer may be present in the same manner as described above, and the reaction product may be treated with the cation radical stabilizer in the same manner as described above.

[Chemical 11] However, in general formula (X), Ar has the same meaning as in general formula (I).

Embedded image However, in the general formula (XI), R is a methylene group, an ethylene group,
It is an alkylene group such as a propylene group or a butylene group, a cycloalkylene group such as a cyclohexylene group, or a divalent aromatic group such as a phenylene group.

[Chemical 13] However, in the general formula (XII), Ar is the same as in the general formula (X), R is the same as the general formula (XI), and R'is a methyl group, an ethyl group, a propyl group, a butyl group, a lauryl group, or a stearyl group. And a plurality of R's may be the same or different.

The chromic resin or chromic resin composition according to the present invention is characterized by having a structure represented by the general formula (I). When the chromic resin or chromic resin composition is irradiated with ultraviolet rays, , Or increases absorption in the near infrared region (colors). For example, when irradiated with a sufficient amount of ultraviolet rays, when Ar in the general formula (I) is a group represented by the general formula (II), it is colored green to deep blue-purple, and Ar in the general formula (I) is colored. Is the general formula (III) or the general formula (V
When it is a group represented by I), it is yellow to green and absorption in the near infrared region is increased.

At this time, in the structure represented by the general formula (I), the nitrogen atom in the structure is a cation radical like the structure represented by the following chemical formula 14 [general formula (XIII)].

Embedded image [However, in general formula (XIII), Ar, C ¹ , C ² , C ³ and C ⁴ are the same as in general formula (I)].

The anion radical which is a partner of the cation radical is a halogen atom in the chromic resin,
It is a cation radical stabilizer dispersed in the chromic resin. When heated in this colored state, the original state is restored and the color is erased. The chromophore at the time of coloring is represented by the general formula (X
It is a resonance structure of the following chemical formula 15 (general formula (XIV)) in III), and N-Ar-N in general formula (I) is a precursor structure of the chromophore.

Embedded image [However, in general formula (XIV), Ar is the same as general formula (I)].

The chromic resin in the present invention is usually colorless or light-colored.
When one electron is released from the tertiary nitrogen in (I), it becomes a cation radical as shown in the general formula (XIII), and absorbs in the visible region or infrared region. This change is not normally observed because the condition is unstable.
However, a substance that stabilizes the whole system by supplementing the electrons released from the chromophore precursor to this system (a halogen atom or cation radical stabilizer bound to the chromic resin)
By the presence of, the radicals in the chromophore can be stably present. Also, when electrons return from the stabilizing substance to tertiary nitrogen by heating, radicals disappear,
The chromophore becomes a colorless to light chromophore precursor.

For example, when ethyl paratoluene sulfonate is dispersed as a cation radical stabilizer in the chromic resin, it may be dispersed in the chromic resin as shown in the following chemical formula 16 (general formula (XV)) before irradiation with ultraviolet rays. Ethyl p-toluenesulfonate is dispersed, and when it is irradiated with ultraviolet rays, the nitrogen atom of the chromic resin and ethyl p-toluenesulfonate are colored as ion radicals, as shown in the following chemical formula 17 (general formula (XVI)), If heated after this,
The structure returns to the structure of [general formula (XV)] and is erased.

Embedded image [However, in the general formula (XV), Ar, C ¹ , C ² , C ³ and C ⁴
Is the same as in formula (I)].

[Chemical 17] [However, in the general formula (XVI), Ar, C ¹ , C ² , C ³ and C
⁴ is the same as general formula (I)].

As described above, the chromic resin or the chromic resin composition according to the present invention develops and disappears radicals due to the movement of electrons in the system, so that the structure in the resin is not destroyed. Therefore, it shows high stability. Further, since the coloring takes a photon mode by light irradiation and the decoloring takes a heat mode by heating, the stability of each state of coloring and decoloring is high. When a cation radical stabilizer having a boiling point or sublimation point higher than the decoloring temperature is used or when a halogen is bound to the chromic resin, the coloring and decoloring are stably repeated. When a cation radical stabilizer whose boiling point or sublimation point is lower than the decoloring temperature is used, color development and decolorization can be performed once. However, also in this case, coloring and decoloring are possible by treating the resin with a cation radical stabilizer.

The chromic resin or chromic resin composition according to the present invention is useful as a recording layer material of an optical recording medium and a display material of a display.

[0050]

EXAMPLES The present invention will be described below with reference to examples.

Example 1 Bisphenol A type epoxy resin [Epicoat 1001
(Yukaka Shell Epoxy Co., Ltd. product name), epoxy equivalent 45
0] 1.1 g, paraphenylenediamine 0.066 g
(0.61 mmol) and 0.122 g (0.061 mmol) of ethyl paratoluenesulfonate were dissolved in methyl isobutyl ketone to obtain a composition for chromic resin.
The resin content in the solution was 35% by weight. This solution vertically 2
6 mm, 26 mm wide, 100 mm on a 2 mm thick glass plate
Coating was carried out by a spin coater under the conditions of 0 rpm for 10 seconds and then 2000 rpm for 30 seconds. Then, heat curing was performed at 150 ° C. for 1 hour to obtain a film made of the chromic resin composition.

The film made of the chromic resin composition obtained above was slightly yellow. Hitachi Autograph Spectrophotometer U340
As a result of measuring a visible absorption spectrum with 0, there was no remarkable absorption at 500 to 700 nm. This visible absorption spectrum is shown as graph 1 in FIG. Further, the electron spin resonance (ESR) spectrum of this film was measured, and no absorption was observed, and no radical was detected. This film is exposed to ultraviolet rays of 1000 mJ / cm ² by a high pressure mercury lamp.
Upon irradiation, the film turned deep blue purple. As a result of measuring a visible absorption spectrum, remarkable absorption was observed at 500 to 700 nm. This visible absorption spectrum is shown as graph 2 in FIG. In addition, electron spin resonance (ES
R) spectrum is shown in FIG. The film was then heated on a hot plate heated to 200 ° C. with the glass plate down and the film turned a faint yellow color in 8 seconds (ie decolorized). The visible absorption spectrum of this film was similar to the spectrum before ultraviolet irradiation (graph 1 in FIG. 1). Again on this film 10
As a result of irradiation with ultraviolet rays of 00 mJ / cm ² , the film again turned deep blue-purple. The visible absorption spectrum of this film was similar in shape to the spectrum of the first dark blue-violet film (graph 2 in FIG. 1). Further, when heated in the same manner as described above, it became slightly yellow and the absorption at 500 to 700 nm disappeared. Such coloring and erasing were repeated 10 times, but the coloring and erasing were performed as described above, and no special abnormality such as sticky surface was observed. The film was left for several weeks in a dark blue-purple state, but no change in hue was observed.

Reference Example 1 1 mol of lithium perchlorate was dissolved in acetone with respect to 1 mol of N, N, N ', N'-tetramethylparaphenylenediamine, and left at room temperature for 1 day. Acetone slowly evaporated, with which the solution became bluish and finally purple crystals were obtained. When the obtained crystal was dissolved again in acetone, the color of the solution was blue purple. ES of this solution
The R spectrum was measured. The result is shown in FIG. The above crystal is known as the Ulsta salt and its structure is
It is known to be represented by the following chemical formula 18 [formula (XVII)].

Embedded image

When comparing the ESR spectrum of FIG. 2 in Example 1 with the ESR spectrum of FIG. 3 in Reference Example 1, it is clear that they show the same shape and the absorption position is also the same. From these results, it is presumed that the chromic resin composition of Example 1 irradiated with ultraviolet rays and the Ulster salt of Reference Example 1 have the same structure having radicals. Further, as described above, no radicals are present during decolorization of the chromic resin composition, the structure of the Wolster salt and the structure of the resin in the chromic resin composition (the amino group of the diamine and the epoxy group of the epoxy resin are (Formed by reaction), the coloring of the chromic resin composition is represented by the formula 19 (formula (XVIII)) as a chromophore.
On the basis of the resonance structure system represented by, when the chromic resin is decolored, the structure of Chemical formula 20 [Formula (XIX)] exists as a chromophore precursor.

[Chemical 19]

Embedded image

Example 2 Bisphenol A type epoxy resin [Epicoat 1001
(Yukaka Shell Epoxy Co., Ltd. product name), epoxy equivalent 45
0] 1.0 g and paraphenylenediamine 0.06 g
(0.56 mmol) was dissolved in methyl isobutyl ketone to obtain a chromic resin composition. The resin content in the solution was 35% by weight. This solution is 26 mm long and 26 m wide
m on a glass plate with a thickness of 2 mm at 1000 rpm for 10
Seconds, and then 2000 rpm for 30 seconds under the conditions of a spin coater. Then, heat curing was performed at 150 ° C. for 1 hour. Then, after dipping in a 10 wt% methyl isobutyl ketone solution of ethyl paratoluenesulfonate for 2 hours, the surface of the film was washed with methyl isobutyl ketone and dried to obtain a film made of a chromic resin composition.

The film made of the chromic resin composition obtained above was slightly yellow. Hitachi Autograph Spectrophotometer U340
As a result of measuring a visible absorption spectrum with 0, there was no remarkable absorption at 500 to 700 nm. This visible absorption spectrum is shown as graph 3 in FIG. When this film was irradiated with ultraviolet rays of 1000 mJ / cm ² with a high pressure mercury lamp, the film turned deep blue-purple. As a result of measuring a visible absorption spectrum, remarkable absorption was observed at 500 to 700 nm. This visible absorption spectrum is shown as graph 4 in FIG. The film was then heated with the glass plate down on a hot plate heated to 200 ° C. and the film turned a faint yellow color (ie, decolorized) in 10 seconds. The visible absorption spectrum of this film was similar to the spectrum before ultraviolet irradiation (graph 3 in FIG. 4). This film was again irradiated with 1000 mJ / cm ² of ultraviolet light, and as a result, the film turned dark blue-purple again. The visible absorption spectrum of this film was similar in shape to the spectrum of the first dark blue-violet film (graph 4 in FIG. 4). further,
When heated in the same way as above, it becomes slightly yellow and 500 to 700
The absorption at nm disappeared. Such coloring and erasing were repeated 10 times, but the coloring and erasing were performed as described above, and no special abnormality such as sticky surface was observed. The film was left for several weeks in a dark blue-purple state, but no change in hue was observed.

Example 3 Brominated phenol novolac type epoxy resin [BREN
-S (trade name of Nippon Kayaku Co., Ltd.), epoxy equivalent 28
4, bromine content 35% by weight] 1.08 g and paraphenylenediamine 0.18 g (1.64 mmol) were dissolved in methyl isobutyl ketone to obtain a chromic resin composition. The resin content in the solution was 50% by weight. This solution was placed on a glass plate having a length of 26 mm, a width of 26 mm and a thickness of 2 mm at 1000 rpm for 10 seconds, and then at 2000 rpm for 30 seconds.
It was applied by a spin coater under the condition of seconds. After this, 150
Heat curing was performed at 1 ° C. for 1 hour to obtain a film made of a chromic resin.

The film made of the chromic resin obtained above was slightly yellow. As a result of measuring a visible absorption spectrum by Hitachi Autograph U3400, 500 to 70
There was no significant absorption at 0 nm. This visible absorption spectrum is shown as graph 5 in FIG. When this film was irradiated with ultraviolet rays of 1000 mJ / cm ² with a high pressure mercury lamp, the film turned deep blue-purple. As a result of measuring a visible absorption spectrum, remarkable absorption was observed at 500 to 700 nm. This visible absorption spectrum is shown as graph 6 in FIG. The film was then heated on a hot plate heated to 200 ° C. with the glass plate down, and the film turned slightly yellow (ie, discolored) in 11 seconds. The visible absorption spectrum of this film was similar to the spectrum before ultraviolet irradiation (graph 5 in FIG. 5). This film was again irradiated with 1000 mJ / cm ² of ultraviolet light, and as a result, the film turned dark blue-purple again. The visible absorption spectrum of this film was similar in shape to the spectrum of the first dark blue-violet film (graph 6 in FIG. 5). Further, when heated in the same manner as described above, it became slightly yellow and the absorption at 500 to 700 nm disappeared. Such coloring and erasing were repeated 10 times, but the coloring and erasing were performed as described above, and no special abnormality such as sticky surface was observed. The film was left for several weeks in a dark blue-purple state, but no change in hue was observed.

Example 4 Bisphenol A type epoxy resin [Epicoat 1001
(Yukaka Shell Epoxy Co., Ltd. product name), epoxy equivalent 45
0] 0.43 g, 2,6 naphthalenediamine 37.3
mg (0.236 mmol) and 50.0 mg (0.25 mmol) ethyl paratoluenesulfonate were dissolved in methyl ethyl ketone to obtain a chromic resin composition.
The resin content in the solution was 40% by weight. This solution vertically 2
6 mm, 26 mm wide, 100 mm on a 2 mm thick glass plate
Coating was carried out by a spin coater under the conditions of 0 rpm for 10 seconds and then 2000 rpm for 40 seconds. Then, heat curing was performed at 150 ° C. for 1 hour to obtain a film made of the chromic resin composition.

The film made of the chromic resin composition obtained above was slightly yellow. Hitachi Autograph Spectrophotometer U340
As a result of measuring the visible near-infrared absorption spectrum with 0, 6
There was no significant absorption from 00 to 1000 nm. This visible / near-infrared absorption spectrum is shown as a graph 7 in FIG.
Ultraviolet rays of 500 mJ / cm ² are applied to this film by a high pressure mercury lamp.
Upon irradiation, the film turned slightly greenish.
As a result of measuring a visible near-infrared absorption spectrum, remarkable absorption was observed at 650 to 950 nm. This visible / near infrared absorption spectrum is shown as a graph 8 in FIG. Then 170
When the film was heated with the glass plate facing down on a hot plate heated to 0 ° C., the film became slightly yellow in about 15 seconds. The visible / near-infrared absorption spectrum of this film was similar to the spectrum before ultraviolet irradiation (graph 7 in FIG. 6). 50 again on this film
As a result of irradiation with 0 mJ / cm ² of ultraviolet light, the film again turned slightly greenish. The visible-near infrared absorption spectrum of this film was similar in shape to the spectrum of the first slightly greenish film (graph 8 in FIG. 6). Furthermore, when heated in the same manner as described above, it became slightly yellow and the absorption in the near infrared region (that is, 650 to 950 nm) disappeared. This kind of absorption change in the near infrared region (accompanied by a change in light yellow and light green) was repeated 10 times, but the absorption change in the near infrared region of the film was as described above, and the special change such as sticky surface was observed. The above was not observed. The film was allowed to stand for several weeks in the near infrared absorption state, but no change was observed in the near infrared absorption.

Example 5 Halogenated phenol novolac type epoxy resin [BR
EN-S (trade name of Nippon Kayaku Co., Ltd.), epoxy equivalent 2
84, bromine content 35% by weight] 0.35 g and 2,6 naphthalenediamine 48.0 mg (0.303 mmol) were dissolved in methyl ethyl ketone. The resin content in the solution was 38% by weight. This solution is 26 mm long and 26 mm wide.
mm at a thickness of 2 mm on a glass plate at 1000 rpm for 10
Seconds, and then 2000 rpm for 40 seconds under the conditions of a spin coater. Then, heat curing was performed at 150 ° C. for 1 hour to obtain a film made of a chromic resin.

The film made of the chromic resin obtained above was slightly yellow. The visible near-infrared absorption spectrum of this film is shown as graph 9 in FIG. 700 to 1000 nm
There was no noticeable absorption. When this film was irradiated with ultraviolet rays of 500 mJ / cm ² by a high pressure mercury lamp, the film was slightly changed to a greenish color. As a result of measuring a visible near-infrared absorption spectrum, remarkable absorption was observed at 650 to 950 nm. This visible near infrared absorption spectrum is shown as a graph 10 in FIG. The film was then heated on a hot plate heated to 170 ° C. with the glass plate facing down, and the film turned slightly yellow in about 15 seconds. The visible / near-infrared absorption spectrum of this film was similar to the spectrum before ultraviolet irradiation (graph 9 in FIG. 7). The film was again exposed to 500 mJ / cm ² of ultraviolet light, and as a result, the film again turned slightly greenish. The visible and near-infrared absorption spectrum of this film is that of the first slightly greenish colored film (graph 10 in Figure 7).
It had the same shape as. Furthermore, when heated in the same manner as above, it becomes slightly yellow and in the near infrared region (that is, 650 to 950n).
The absorption of m) disappeared. This kind of absorption change in the near infrared region (accompanied by a change in light yellow and light green) was repeated 10 times, but the absorption change in the near infrared region of the film was as described above, and the special change such as sticky surface was observed. The above was not observed. The film was allowed to stand for several weeks in the near infrared absorption state, but no change was observed in the near infrared absorption.

Example 6 Tetraglycidyl paraphenylenediamine (molecular weight 33
2, epoxy equivalent 83) 0.58 g, methyltetrahydrophthalic anhydride (HN220 manufactured by Hitachi Chemical Co., Ltd.)
0) 0.162 g (0.98 mmol) and ethyl paratoluenesulfonate 0.57 g (0.29 mmol) were dissolved in methyl ethyl ketone. The resin content in the solution is 43
% By weight. This solution is 26 mm long, 26 mm wide,
A glass plate having a thickness of 2 mm was coated by a spin coater under the conditions of 1000 rpm for 10 seconds and then 2000 rpm for 40 seconds. Then, heat curing was performed at 150 ° C. for 1 hour to obtain a film made of the chromic resin composition.

The film made of the photochromic resin composition obtained above was slightly yellow. The visible absorption spectrum of this film is shown as graph 11 in FIG. When this film was irradiated with ultraviolet rays of 500 mJ / cm ² by a high pressure mercury lamp, the film turned blue. As a result of measuring the visible absorption spectrum, the absorption increased to 500 to 700 nm. This visible absorption spectrum is shown as a graph 12 in FIG. Then 1
When the film was heated with the glass plate down on a hot plate heated to 70 ° C., the film turned slightly yellow in about 15 seconds. The visible absorption spectrum of this film was similar to the spectrum before ultraviolet irradiation (graph 11 in FIG. 8). 5 again on this film
As a result of irradiation with ultraviolet rays of 00 mJ / cm ² , the film turned blue again. The visible absorption spectrum of this film was similar in shape to the spectrum of the initial blue film (graph 12 in Figure 8). Further, when heated in the same manner as described above, it became slightly yellow and the absorption in the near infrared region (that is, 500 to 700 nm) was reduced. Such color development and decolorization were repeated 10 times, but the change in absorption in the visible region of the film was as described above, and no special phenomenon such as sticky surface was observed. The film was left in a colored state for several weeks, but no change in hue was observed.

Example 7 Bisphenol A type epoxy resin [Epicoat 1001
(Yukaka Shell Epoxy Co., Ltd. product name), epoxy equivalent 45
0] 0.43 g and 2,6-naphthalenediamine 37.
3 mg (0.236 mmol) was dissolved in methyl ethyl ketone to obtain a chromic resin composition. The resin content in the solution was 40% by weight. This solution is 26 mm in height and 2 in width
1 at 1000 rpm on a glass plate 6 mm thick and 2 mm thick
It was applied by a spin coater under the condition of 0 seconds and then 2000 rpm for 40 seconds. Then, heat curing was performed at 150 ° C. for 1 hour. 0.1 ml of ethyl bromide was applied to the obtained film and left at room temperature for 5 minutes to obtain a film made of the chromic resin composition.

The film made of the chromic resin composition obtained above was slightly yellow. Hitachi Autograph Spectrophotometer U340
As a result of measuring the visible near-infrared absorption spectrum with 0, 6
There was no significant absorption from 00 to 1000 nm. This visible near infrared absorption spectrum is shown as a graph 13 in FIG. Ultraviolet rays of 500 mJ / c are applied to this film by a high pressure mercury lamp.
Upon irradiation with m ² , the film turned slightly greenish. As a result of measuring the visible near infrared absorption spectrum, 650
Remarkable absorption was observed at ˜950 nm. This visible near infrared absorption spectrum is shown as a graph 14 in FIG. The film was then heated on a hot plate heated to 170 ° C. with the glass plate facing down, and the film turned slightly yellow in about 15 seconds.
The visible / near-infrared absorption spectrum of this film was similar to the spectrum before ultraviolet irradiation (graph 13 in FIG. 9). The film was again irradiated with ultraviolet rays of 500 mJ / cm ² , but recoloring did not occur. It is considered that ethyl bromide was volatilized by the above heating. Thereafter, ethyl bromide was applied to the film in the same manner as described above, dried at room temperature, and successively irradiated with ultraviolet rays and heated in the same manner as described above. As a result, color development and decolorization occurred.

Comparative Example 1 Bisphenol A type epoxy resin [Epicoat 1001
(Yukaka Shell Epoxy Co., Ltd. product name), epoxy equivalent 45
0] 1.0 g, 4,4'-diaminodiphenylmethane 0.1 g (0.51 mmol) and ethyl paratoluenesulfonate 0.1 g (0.50 mmol) were dissolved in methyl isobutyl ketone to prepare a composition for chromic resin. Got The resin content in the solution was 40% by weight. This solution was spin-coated on a glass plate in the same manner as in Example 1, and the temperature was 150 ° C.
Was heat-cured for 1 hour to obtain a film made of the chromic resin composition.

The film made of the obtained chromic resin composition was yellowish brown. The result of measuring the visible absorption spectrum by the Hitachi self-recording spectrophotometer U3400 is shown as a graph 15 in FIG. 1 ultraviolet ray is applied to this film by a high pressure mercury lamp.
Upon irradiation with 000 mJ / cm ² , the film turned light green. A visible absorption spectrum after ultraviolet irradiation is shown as a graph 16 in FIG. As is clear from the graph 16, the faint green color is caused by the mixed absorption of the yellowish brown color based on the absorption of 400 nm to 500 nm and the blue color based on the absorption of 600 nm. The membrane was then heated on a hot plate heated to 200 ° C. with the glass plate down and the membrane turned tan in 20 seconds. As is clear from the above results, the chromic resin composition of this comparative example had a small contrast during color development and during color erasing. When such coloring and decoloring were repeated 10 times, the brown color became dark when decoloring, and the hue after ultraviolet irradiation changed from the initial stage.

Comparative Example 2 Halogenated phenol novolac type epoxy resin [BR
EN-S (trade name of Nippon Kayaku Co., Ltd.), epoxy equivalent 2
84, bromine content 35% by weight] 1.5 g and 4,4'-
0.5 g (2.53 mmol) of diaminodiphenylmethane was dissolved in methyl ethyl ketone to obtain a chromic resin composition. The resin content in the solution was 50% by weight.
This solution was spin-coated on a glass plate in the same manner as in Example 1 and heat-cured at 150 ° C. for 1 hour to obtain a film made of a chromic resin.

The film made of the chromic resin obtained above was colorless. Graph 1 shows the result of measurement of visible absorption spectrum by Hitachi Autograph U3400
Shown as 7. Next, when the film was heated with the glass plate facing down on a hot plate heated to 200 ° C., the film disappeared in 1 minute 40 seconds. When such coloring and erasing were repeated 10 times, the color of the film became brown during erasing and became green after irradiation with ultraviolet rays, and the surface of the film became sticky and the molecular weight decreased. As is clear from the above results, such a decrease in molecular weight was not observed in the chromic resin or the chromic resin of the present invention.

Example 8 Bisphenol A type epoxy resin [Epicoat 1001
(Yukaka Shell Epoxy Co., Ltd. product name), epoxy equivalent 45
0] 0.55 g and 82.3 mg (0.61 mmol) of N, N-dimethylparaphenylenediamine were dissolved in 1.0 ml of methyl ethyl ketone and gradually heated to distill off methyl ethyl ketone, and finally at 150 ° C. Reacted for hours. The product was dissolved in 2.0 ml of methyl ethyl ketone and reprecipitated in 200 ml of hexane to obtain a polymer.
A solution was obtained by dissolving 0.1 g of this polymer in 0.5 ml of methyl ethyl ketone. This solution is 26 mm long and 26 m wide
m on a glass plate with a thickness of 2 mm at 1000 rpm for 10
Seconds, and then 2000 rpm for 40 seconds under the conditions of a spin coater. Then, it was left to stand at room temperature and dried to obtain a slightly yellow film. As a result of measuring UV-visible absorption spectrum with Hitachi Autograph U3400, 500 to 70
There was no significant absorption at 0 nm. The following tests were conducted using the above polymers and membranes.

(1) Test using ethyl paratoluenesulfonate (a) Treatment with ethyl paratoluenesulfonate and UV irradiation treatment This membrane was immersed in 10 ml of a methanol solution containing 0.5 g of ethyl paratoluenesulfonate and then allowed to stand at room temperature. Allowed to dry. Ultraviolet rays of 500 m are applied to this film by a high pressure mercury lamp.
Upon irradiation with J / cm ² , the film turned blue. As a result of measuring the UV-visible absorption spectrum, 500 to 700 n
A remarkable absorption was observed in m. This UV-visible absorption spectrum is shown in FIG. (b) Heat treatment Next, when the film was heated with the glass plate facing down on a hot plate heated to 150 ° C., the film became slightly yellow (that is, decolorized) in about 20 seconds. The UV-visible absorption spectrum of this film was similar to that before UV irradiation. (c) Repeatability test and stability test As a result of irradiating this film again with 500 mJ / cm ² of ultraviolet rays, the film turned blue again. The UV-visible absorption spectrum of this film had the same shape as the spectrum of the blue film (FIG. 12). Further, when heated in the same manner as described above, it became slightly yellow and the absorption at 500 to 700 nm disappeared. Such coloring and erasing were repeated 10 times, but the coloring and erasing were performed as described above, and no special abnormality such as sticky surface was observed. The film was left in a blue state for several weeks, but no change in hue was observed.

(2) Test using chloroform or methylene chloride (a) The film obtained above was immersed in chloroform or methylene chloride, and then dried at room temperature for 10 minutes. After that, ultraviolet irradiation treatment and heat treatment were performed in the same manner as in the test using ethyl paratoluenesulfonate. In both cases of using chloroform and methylene chloride, a blue color was developed by the ultraviolet irradiation treatment, and it was decolorized by the heat treatment to become a faint yellow color. When the initially blue film was left at room temperature, the blue color disappeared in about 1 day. The decolorized film did not develop color even when subjected to ultraviolet irradiation treatment. When the decolored film was treated with chloroform or methylene chloride in the same manner as above and subjected to ultraviolet irradiation treatment and heat treatment, color development and decolorization occurred in the same manner as above. (b) Reaction product of the bisphenol A type epoxy resin obtained above and N, N-dimethylparaphenylenediamine
(Polymer) is 1/1 of methyl ethyl ketone / chloroform
It was dissolved in the solution (volume ratio). UV light is added to this solution.
Upon irradiation with 0 mJ / cm ² , the solution was colored blue. This solution was placed on a glass plate having a length of 26 mm, a width of 26 mm, and a thickness of 2 mm at 1000 rpm for 10 seconds, and then 2000
It was applied by a spin coater under the condition of 40 seconds at rpm. Then, it was left at room temperature and dried to obtain a blue film. The UV-visible absorption spectrum of this film was similar to that shown in FIG. When this film was heat-treated in the same manner as the test using ethyl paratoluenesulfonate, the film was decolored and turned into a slightly yellow film. The blue colored film disappeared in about 1 day when left at room temperature. The decolorized film did not develop color even when subjected to ultraviolet irradiation treatment. When the above blue colored solution was poured into hexane, a blue polymer precipitated. When the blue polymer was collected by filtration and stored in a stoppered glass bottle, there was no change in hue even after 1 week.

(3) Test Using Iodine Solution For comparison, when the film obtained above was immersed in 20 ml of methanol in which 20 mg of iodine was dissolved, the film was colored blue.

Example 9 Bisphenol A type epoxy resin [Epicoat 1001
(Yukaka Shell Epoxy Co., Ltd. product name), epoxy equivalent 45
0] 0.31 g and 46.6 mg (0.34 mmol) of N, N'-dimethylparaphenylenediamine were dissolved in 1.0 ml of methyl ethyl ketone and gradually heated to distill off the methyl ethyl ketone, and finally at 150 ° C. The reaction was carried out for 1 hour. The product was dissolved in 2.0 ml of methyl ethyl ketone and reprecipitated in 200 ml of hexane to give 0.28 of polymer.
g was obtained. Using this polymer, a glass plate was coated according to Example 8 and dried to obtain a slightly yellow film. After that, a test using ethyl paratoluenesulfonate, a test using chloroform or methylene chloride, and a test using an iodine solution were performed according to Example 8 using the above product (polymer) and the membrane. It was the same result as.

Example 10 Bisphenol A type epoxy resin [Epicoat 828
(Yukaka Shell Epoxy Co., Ltd. product name), epoxy equivalent 17
0] 0.42 g and 73.5 mg (0.54 mmol) of N, N-dimethylparaphenylenediamine were dissolved in 1.0 ml of methyl ethyl ketone and gradually heated to distill off methyl ethyl ketone, and finally at 150 ° C. Reacted for hours. The product was dissolved in 2.0 ml of methyl ethyl ketone and reprecipitated in 200 ml of hexane to give a polymer of 0.39
g was obtained. Using this polymer, a glass plate was coated according to Example 8 and dried to obtain a slightly yellow film. After that, a test using ethyl paratoluenesulfonate, a test using chloroform or methylene chloride, and a test using an iodine solution were carried out in the same manner as in Example 8 using the polymer and the film, and the same results as in Example 8 were obtained. Met.

Example 11 Bisphenol A type epoxy resin [Epicoat 828
(Yukaka Shell Epoxy Co., Ltd. product name), epoxy equivalent 17
0] 0.12 g and 47.7 mg (0.35 mmol) of N, N-dimethylparaphenylenediamine were dissolved in 1.0 ml of methyl ethyl ketone and gradually heated to distill off the methyl ethyl ketone, and finally at 150 ° C. Reacted for hours. The product was dissolved in 2.0 ml of methyl ethyl ketone and reprecipitated in 200 ml of hexane to give 0.1 g of polymer.
I got Using this polymer, a glass plate was coated according to Example 8 and dried to obtain a slightly yellow film. After that, a test using ethyl paratoluenesulfonate, a test using chloroform or methylene chloride, and a test using an iodine solution were carried out in the same manner as in Example 8 using the polymer and the film, and the same results as in Example 8 were obtained. Met.

Example 12 Bisphenol A type epoxy resin [Epicoat 1001
(Yukaka Shell Epoxy Co., Ltd. product name), epoxy equivalent 17
0] 2.53 g and paraphenylenediamine 152.0
mg (1.41 mmol) of methyl ethyl ketone 5.0
It was dissolved in ml to obtain a solution. This solution was applied on a glass plate having a length of 26 mm, a width of 26 mm, and a thickness of 2 mm at 1000 rpm for 10 seconds and then at 2000 rpm for 40 seconds by a spin coater. Then, it was left to stand at room temperature for 20 minutes to be dried, and then reacted at 150 ° C. for 1 hour to obtain a slightly yellow film. After this, using the above polymer and membrane, Example 8
Test using ethyl paratoluenesulfonate according to
Test using chloroform or methylene chloride (however,
(Except the test using the methyl ethyl ketone / chloroform solution of (b)) and the test using the iodine solution, the same results as in Example 8 were obtained.

[0079]

The novel chromic resin according to claim 1 having chromic properties, the chromic resin according to claim 2, the chromic resin composition according to claim 3 or the chromic resin according to claim 4 are novel. ,
The contrast between color development and decolorization is large, and the chromic resin composition according to claim 5 is a raw material composition for producing the chromic resin according to claim 1 or the chromic resin according to claim 2, The resin composition for chromics according to claim 7 or 8 is a raw material composition for producing the chromic resin composition according to claim 3, and the chromic composition according to claim 1 by the method according to claim 9 or 10. The resin for use can be easily produced, and the method according to claim 11 is used.
The chromic resin in can be easily manufactured,
The chromic resin composition according to claim 3 can be easily produced by the method according to claim 12, claim 13 or claim 14.

[Brief description of drawings]

1 shows a visible absorption spectrum of the chromic resin obtained in Example 1. FIG.

FIG. 2 shows an electron resonance spectrum of the chromic resin obtained in Example 1 during coloring.

FIG. 3 shows an ESR spectrum of the Worcester salt obtained in Reference Example 1.

FIG. 4 shows a visible absorption spectrum of the chromic resin obtained in Example 2.

5 shows a visible absorption spectrum of the chromic resin obtained in Example 3. FIG.

FIG. 6 shows a visible near infrared absorption spectrum of the chromic resin obtained in Example 4.

FIG. 7 shows a visible near infrared absorption spectrum of the chromic resin obtained in Example 5.

8 shows a visible absorption spectrum of the chromic resin obtained in Example 6. FIG.

FIG. 9 shows a visible near-infrared absorption spectrum of the chromic resin obtained in Example 7.

10 shows a visible absorption spectrum of the chromic resin obtained in Comparative Example 1. FIG.

11 shows a visible absorption spectrum of the chromic resin obtained in Comparative Example 2. FIG.

FIG. 12 shows an ultraviolet-visible absorption spectrum in a colored state of the chromic resin obtained in Example 8.

[Explanation of symbols]

1,3,5,7,9,11,13,15,17 ... Visible and near-infrared absorption spectrum immediately after production, 2,4,6,8,10,12,14,16,18 ... Visible near infrared absorption spectrum.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Ritsuko Obata 48 Wadai, Tsukuba, Ibaraki Prefecture Hitachi Chemical Co., Ltd. Tsukuba Development Laboratory (56) Reference JP-A-2-67390 (JP, A)

Claims (10)

(57) [Claims] 1. Chemical formula 1 [general formula (V)] [However, in the general formula (V), Q ¹ , Q ² , Q ³ and Q ⁴ are hydrogen or an alkyl group which may have a substituent, and these may be the same or different, and at least two of these are hydrogen, Ar is base benzene ring, naphthoquinone
Indicates an aromatic ring selected from a tarene ring and an anthracene ring ,
Two nitrogen atoms are bonded to the most distant positions of Ar], and a resin composition for chromics containing a diamine compound represented by the above and an epoxy resin. 2. A chromic resin composition containing a diamine compound represented by the general formula (V) according to claim 1, an epoxy resin and a cation radical stabilizer. 3. A chromic resin composition comprising an epoxy resin in which two diglycidylamino groups are directly bonded to the aromatic ring at the most distant positions of the aromatic ring and a curing agent. 4. A chromic resin composition containing an epoxy resin in which two diglycidylamino groups are directly bonded to the aromatic ring at the most distant positions of the aromatic ring, a curing agent, and a cation radical stabilizer. . 5. A method for producing a chromic resin, which comprises reacting the diamine compound represented by the general formula (V) according to claim 1 with an epoxy resin. 6. A method for producing a chromic resin, which comprises reacting an epoxy resin in which two diglycidylamino groups are directly bonded to the aromatic ring at the most distant positions of the aromatic ring and a curing agent. 7. A method for producing a chromic resin, which comprises reacting the diamine compound represented by the general formula (V) according to claim 1 with a halogenated epoxy resin. 8. A method for producing a chromic resin composition, which comprises reacting the diamine compound represented by the general formula (V) according to claim 1 and an epoxy resin in the presence of a cation radical stabilizer. 9. A method for producing a chromic resin composition, which comprises reacting a diamine compound represented by the general formula (V) according to claim 1 with an epoxy resin and then treating with a cation radical stabilizer. . 10. An epoxy resin in which two diglycidylamino groups are directly bonded to the aromatic ring at the most distant positions of the aromatic ring and a curing agent are reacted in the presence of a cation radical stabilizer. A method for producing a chromic resin composition.