JPH07145371A - Liquid-crystal high-molecular photochromic material - Google Patents

Abstract

PURPOSE:To obtain the subject material which, when colored, is yellow to orange by copolymerizing a specific monomer having a chromene backbone with a specific monomer having a mesogenic group. CONSTITUTION:This photochromic material is produced by copolymerizing at least a monomer of formula I (wherein A<1> is H or methyl; and X is a group having a chromene backbone) and a monomer of formula II (wherein A<2> is H or methyl; and Y is a mesogenic group). The material can be formed on a part or the whole of a substrate by coating or printing. The durability of the material in repeated use is effectively improved by using it in the absence of oxygen and water. The durability is further improved by using a singlet oxygen quencher, a nitroxy radical compd., a hindered amine compd., an antioxidant, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid crystalline polymer photochromic material, and the liquid crystalline polymer photochromic material is particularly useful for printing, optical equipment, information recording materials,
It is preferably used as a display material, a light control material, clothing, a decorative material, and an optical element.

[0002]

2. Description of the Related Art Heretofore, some examples have been known as liquid crystal polymer photochromic materials. For example, Ange
wandte Chemie International
alEdition in English, Vol. 26 (No. 11), page 1178 (1987) and the same magazine 3.
Volume 0 (No. 1), page 76 (1991), shows an example of a liquid crystalline polymer photochromic material having a liquid crystal molecule and a photochromic molecule in the side chain of the polymer.

[0003]

However, the conventional liquid crystal polymer photochromic material has a problem that red
Only those exhibiting colors such as purple and blue were known.

It is an object of the present invention to provide a liquid crystalline polymer photochromic material which exhibits a yellow to orange color when colored.

[0005]

In order to solve the above problems, the liquid crystalline polymer photochromic material of the present invention is
It has the following configuration.

"At least the following formula (A)

[Chemical 5] [In the formula, A ¹ represents hydrogen or a methyl group.

X represents a substituent having a chromene skeleton. ] And the following formula (B)

[Chemical 6] [In the formula, A ² represents hydrogen or a methyl group.

Y represents a mesogenic group. ] A liquid crystalline polymer photochromic material obtained by copolymerizing a monomer represented by In the formula (A), A ¹ represents hydrogen or a methyl group.

X can be used without particular limitation as long as it is a substituent having a chromene skeleton, but is preferably of the following formula (C), (D) or (E).

[Chemical 7] [Wherein R ¹ , R ² , R ⁹ , R ¹⁰ , R ¹⁷ and R ¹⁸ are
It represents a substituent selected from hydrogen, an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 19 carbon atoms, and an amino group having 0 to 10 carbon atoms.

R ^{3 to} R ⁸ , R ^{11 to} R ¹⁶ and R ^{19 to} R ²²
Is hydrogen, hydroxyl group, alkoxy group having 1 to 20 carbon atoms, aralkoxy group having 7 to 15 carbon atoms, and 6 to 1 carbon atoms.
4 aryloxy group, C1-20 acyloxy group, C1-20 alkyl group, C7-15 aralkyl group, C6-14 aryl group, halo group, carboxyl group, C2 To C20 alkoxycarbonyl group, C8 to C20 aralkoxycarbonyl group, C7 to C20 aryloxycarbonyl group, C1 to C2
Represents a substituent selected from 0 carbamoyl group and Z, yet at least one of R ³ ~R ^8, R ¹¹
At least one of R ¹⁶ to R ¹⁶ and at least one of R ^{19 to} R ²² represents Z.

Z is the following formula

[Chemical 8] {N represents an integer of 1 to 10. } Represents a divalent substituent selected from.

R ^{23 to} R ^{28 each} independently represent a substituent selected from hydrogen, an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms and an aryl group having 6 to 19 carbon atoms. When not independent, at least one set of R ²³ and R ²⁴ , R ²⁵ and R ²⁶ , and R ²⁷ and R ²⁸ together represents a cyclic substituent having 5 to 20 carbon atoms. ] The substituent shown by these is used.

In the formula (C), (D) or (E), R ¹ ,
R ² , R ⁹ , R ¹⁰ , R ¹⁷ and R ¹⁸ are hydrogen and have 1 carbon atom
An alkyl group having 20 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms,
It represents a substituent selected from an aryl group having 6 to 19 carbon atoms and an amino group having 0 to 10 carbon atoms, and preferable specific examples thereof include a methyl group, an ethyl group, a propyl group, a hexyl group, an octadecyl group, and icosyl. Group, isopropyl group,
tert-butyl group, 2-ethylhexyl group, cyclohexyl group, norbornyl group, adamantyl group and other alkyl groups; benzyl group, phenethyl group, naphthylmethyl group and other aralkyl groups; phenyl group, naphthyl group and other aryl groups; amino group, Examples thereof include a piperidino group, a 1-pyrrolidyl group, a morpholino group, an amino group such as a dimethylamino group and a diethylamino group.

R ^{3 to} R ⁸ , R ^{11 to} R ¹⁶ and R ^{19 to} R ²⁶
Is hydrogen, hydroxyl group, alkoxy group having 1 to 20 carbon atoms, aralkoxy group having 7 to 15 carbon atoms, and 6 to 1 carbon atoms.
4 aryloxy group, C1-20 acyloxy group, C1-20 alkyl group, C7-15 aralkyl group, C6-14 aryl group, halo group, carboxyl group, C2 To C20 alkoxycarbonyl group, C8 to C20 aralkoxycarbonyl group, C7 to C20 aryloxycarbonyl group, C1 to C2
Represents a substituent selected from 0 carbamoyl group and Z, yet at least one of R ³ ~R ^8, R ¹¹
At least one of R ¹⁶ to R ¹⁶ and at least one of R ^{19 to} R ²² represents Z, and specific examples thereof include hydrogen; hydroxyl group; methoxy group, ethoxy group, propoxy group, Hexyloxy group, icosyloxy group,
Alkoxy groups such as isopropoxy group and tert-butoxy group; aralkoxy groups such as benzyloxy group, phenethyloxy group and naphthylmethyloxy group; aryloxy groups such as phenoxy group and 2-naphthyloxy group; formyloxy group, acetoxy group, propanoyloxy Group, valeryloxy group, hexanoyloxy group, lauroyloxy group,
Acyloxy groups such as palmitoyloxy group, stearoyloxy group, cyclohexanecarbonyloxy group, benzoyloxy group, nicotinoyloxy group, anisoyloxy group, veratroyloxy group and naphthoyloxy group;
Alkyl groups such as methyl group, ethyl group, propyl group, hexyl group, octyl group, octadecyl group, isopropyl group, tert-butyl group, 2-ethylhexyl group, cyclopentyl group, cyclohexyl group, norbornyl group, adamantyl group; benzyl group, Aralkyl groups such as phenethyl group and naphthylmethyl group; aryl groups such as phenyl group and naphthyl group; halo groups such as fluoro group, chloro group, bromo group, iodo group; carboxyl group; methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group Base,
Alkoxycarbonyl groups such as hexyloxycarbonyl group, isopropoxycarbonyl group and (2,2,6,6-tetramethyl-4-piperidyl) oxycarbonyl group; Aralkoxy groups such as benzyloxycarbonyl group and phenethyloxycarbonyl group Carbonyl group; aryloxycarbonyl group such as phenoxycarbonyl group and naphthyloxycarbonyl group; carbamoyl group, N-methylcarbamoyl group, N-ethylcarbamoyl group, N-propylcarbamoyl group, N-hexylcarbamoyl group, N-benzylcarbamoyl group , Carbamoyl groups such as N-phenylcarbamoyl group, and Z.
R ^{23 to} R ^{28 each} independently represent a substituent selected from hydrogen, an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms and an aryl group having 6 to 19 carbon atoms. Preferred specific examples are alkyl groups such as methyl group, ethyl group, propyl group, hexyl group, octadecyl group, icosyl group, isopropyl group, tert-butyl group, 2-ethylhexyl group, cyclohexyl group, norbornyl group and adamantyl group; Examples thereof include aralkyl groups such as benzyl group, phenethyl group and naphthylmethyl group; aryl groups such as phenyl group and naphthyl group.

R ^{23 to} R ²⁸ are R ²³ when they are not independent.
And at least one of R ²⁴ , R ²⁵ and R ²⁶ , and R ²⁷ and R ²⁸
The group together represents a cyclic substituent having 5 to 20 carbon atoms, and specific examples in this case include those shown below.

[0016]

[Chemical 9] In the formula (B), A ² represents hydrogen or a methyl group.

Y represents a mesogenic group, and the mesogenic group can be used without particular limitation as long as it is a substituent capable of imparting liquid crystallinity to the copolymer.

[Chemical 10] [Wherein W ¹ and W ² are respectively the following formulas:

[Chemical 11] Represents a substituent selected from

A ³ is an alkoxy group, an aralkoxy group,
Aryloxy group, halo group, cyano group, carboxyl group,
Alkoxycarbonyl group, aralkoxycarbonyl group,
It represents a substituent selected from an aryloxycarbonyl group and an alkyl group.

K represents an integer of 1 to 5. When k is 2 or more, each A ³ may be the same or different. ] It means the substituent shown by.

The liquid crystalline polymer photochromic material of the present invention may be in any of copolymerization forms such as random, block, graft and alternating.

The random copolymer can be obtained by polymerizing using a conventional radical polymerization method in the presence of each of the copolymerizable monomers and the polymerization initiator.

Besides, copolymers having various copolymerization forms can be obtained by using known polymerization methods such as ionic polymerization, photopolymerization, radiation polymerization and iniferter polymerization.

In the liquid crystalline polymer photochromic material of the present invention, the content of the monomer of the general formula (A) as a monomer unit is 0.1% by weight to 50% by weight, preferably 1% by weight to 20% by weight. Is. When the content of the monomer of the general formula (A) is less than 0.1% by weight, sufficient photochromic properties cannot be obtained, and when it is more than 50% by weight, liquid crystallinity is deteriorated, which is not preferable.

The liquid crystal polymer photochromic material of the present invention has a weight average molecular weight of 1,000 to 1,000.
The range of 50,000 is preferable, and the range of 5,000 to 100,000 is more preferable from the viewpoint of film-forming property as a polymer.

The liquid crystalline polymer photochromic material of the present invention may contain a monomer other than the monomer of the general formula (A) and the monomer of the general formula (B) as a copolymerization component. The monomer in that case may be a compound having a polymerizable substituent, and may be a compound having two or more polymerizable substituents in one molecule. Specific examples thereof include acrylic acid. Acrylic monomers such as acid, methacrylic acid, acrylic acid ester, methacrylic acid ester, acrylic acid amide, methacrylic acid amide, acrylonitrile, methacrylonitrile, ethylene glycol dimethacrylate; styrene, divinylbenzene,
Styrene-based monomers such as α-methylstyrene; vinyl acetate-based monomers; olefin-based monomers such as ethylene, propylene, butadiene, vinyl chloride, and vinylidene chloride; silane-based compounds having organic polymerizable functional groups; organic polymerizable functional groups Spirooxazine compounds having; spiropyran compounds having organic polymerizable functional groups; diarylethene compounds having organic polymerizable functional groups; fulgide compounds having organic polymerizable functional groups; chromene compounds having organic polymerizable functional groups, etc. Is mentioned.

The liquid crystalline polymer photochromic material of the present invention can be formed on a part or all of various substrates by applying a coating method or various printing methods. As the coating method, various methods such as a dip coating method, a spin coating method, a roll coating method, a bar coating method, a spraying method and a flow coating method can be adopted.

Further, the liquid crystal polymer photochromic material of the present invention can be used as a bulk molding or as a film.

From the viewpoint of improving the repeated durability of the liquid crystalline polymer photochromic material of the present invention, it is particularly effective to block oxygen and water during use. Further, known additives for the purpose of improving durability, for example, singlet oxygen quencher typified by nickel salt, nitroxy radical compound, antioxidant represented by hindered amine compound or polymer thereof, ultraviolet absorber, A triplet quencher or the like can be used.

Applications of the liquid crystalline polymer photochromic material of the present invention include inks, printed materials, sunglasses lenses, various goggles, protective eyeglass lenses, camera light control filters, helmet shields, information recording materials, displays,
Display materials that can be repeatedly erased, windshields, automobile windows such as sunroofs, curtains, window blinds, light control film, light control laminated glass, change in light intensity, refractive index, electrical resistance, light transmittance, Optical elements that convert to changes in absorbance, clothes, toys, cosmetics,
A suitable example is a writing instrument. In particular, the liquid crystalline polymer photochromic material of the present invention is preferably used as an information recording material which is rewritable and has excellent thermal stability of information.

[0030]

EXAMPLES The present invention will now be described with reference to examples, but the present invention is not limited thereto. Synthesis Example 1 [1] 1,5-diacetoxynaphthalene (20.0
g), aluminum chloride (30.0 g) and toluene (200 ml) were mixed and stirred under a nitrogen stream while stirring.
The mixture was heated under reflux for 30 minutes. After allowing to cool, water (400 ml)
After adding, toluene was distilled off using a rotary vacuum evaporator. The insoluble matter that had precipitated was collected by filtration and dried under reduced pressure. It was purified by a recrystallization method (ethyl acetate solvent) to obtain 1 ', 5'-dihydroxy-2'-acetonaphthone.

[2] 1 ', 5'-dihydroxy-2'
-Acetonaphthone (7.0 g), 2-adamantanone (5.0 g), and pyrrolidine (8 ml) were dissolved in toluene (150 ml), and the mixture was heated under reflux for 3 hours while removing water by the Dean-Stark method. After the reaction, toluene was distilled off using a rotary vacuum evaporator. Add acetone (about 200 ml),
Shake well. The remaining insoluble matter crystals were collected by filtration, washed twice with acetone, and then dried to obtain the following formula (1).

[Chemical 12] Was obtained.

[3] The compound of the formula (1) (1.0 g) was dissolved in 2-propanol (200 ml), sodium borohydride (1.0 g) was further added, and the mixture was heated under reflux for 6 hours. After allowing to cool, water (100 ml) was added, and the mixture was extracted with ethyl acetate. Anhydrous sodium sulfate was added to the extract for dehydration, and then sodium sulfate was removed by filtration. The solvent was distilled off from the filtrate using a rotary vacuum evaporator. Glacial acetic acid (100 ml) was added thereto, and the mixture was heated under reflux for 2.5 hours. After distilling off acetic acid using a rotary vacuum evaporator, the product was purified by silica gel column chromatography (developing solvent: chloroform) to obtain the following formula (2).

[Chemical 13] Was obtained.

[4] Compound of formula (2) (395 m
g), triethylamine (125 mg), methylene chloride (70 ml) and acetone (3 ml) were ice-cooled and stirred while a solution of methacryloyl chloride (139 mg) and methylene chloride (15 ml) was added for 10 minutes. It dripped over. After the completion of dropping, stirring was continued for 30 minutes under ice cooling, and further stirring was performed for 30 minutes at room temperature. After the solvent was distilled off using a rotary vacuum evaporator, the product was purified using silica gel column chromatography (developing solvent; ethyl acetate / hexane mixed solvent), and the following formula (3) was used.

[Chemical 14] Was obtained.

[5] Analysis Results The elemental analysis results of the compound of formula (3) are shown below.

Elemental analysis value: (as C ₂₆ H ₂₆ O ₃ ) Theoretical value: C (80.8), H (6.8) (%) Actual value: C (80.8), H (6. 8) (%) 1 H-NMR: (measuring instrument; Hitachi 90 MHz, measuring solvent; CDCl ₃ ) around 5.6 ppm to 8.4 ppm (9
H), around 1.4 ppm to 2.7 ppm (17H) Synthesis Example 2 [1] 3 ′, 6′-dimethyl-1 synthesized by the method described on page 3756 of J. Chem. Soc. (1962). ',
8'-dihydroxy-2'-acetonaphthone (7.0
g), 2-norbornanone (5.0 g) and pyrrolidine (8 ml) were dissolved in toluene (150 ml),
The mixture was heated under reflux for 3 hours while removing water by the Dean-Stark method. After the reaction, the solvent was distilled off using a rotary vacuum evaporator, followed by purification using silica gel column chromatography (developing solvent; ethyl acetate / hexane mixed solvent), and the following formula (4)

[Chemical 15] Was obtained.

[2] Compound of formula (4) (500 m
g), triethylamine (200 mg), methylene chloride (1000 ml) and acetone (5 ml) were ice-cooled and stirred while a solution of acryloyl chloride (200 mg) and methylene chloride (30 ml) was added for 20 minutes. It dripped over. After the completion of dropping, stirring was continued for 30 minutes under ice cooling, and further stirring was performed for 30 minutes at room temperature. The solvent was distilled off using a rotary vacuum evaporator, followed by purification using silica gel column chromatography (developing solvent; ethyl acetate / hexane mixed solvent), and the following formula (5)

[Chemical 16] Was obtained.

[3] Analysis Results The results of elemental analysis of the compound of formula (5) are shown below.

Elemental analysis value: (as C ₂₄ H ₂₄ O ₃ ) Theoretical value: C (80.0), H (6.7) (%) Actual value: C (80.0), H (6. 7) (%) 1 H-NMR: (measuring instrument; Hitachi 90 MHz, measuring solvent; CDCl ₃ ) around 5.6 ppm to 7.4 ppm (8H), 1.1 pp
Around m to 2.8 ppm (16H) Example 1 The following formula (6)

[Chemical 17] And a compound of formula (3) (0.1 g) obtained in Synthesis Example 1 with tetrahydrofuran (3
ml), and azobisisobutyronitrile (4 mg) was added as a polymerization initiator, followed by polymerization at reflux temperature for 24 hours in a nitrogen atmosphere. After completion of the polymerization, reprecipitation and purification were carried out three times using ethanol, and then dried to obtain a liquid crystal polymer photochromic material. The liquid crystalline polymer photochromic material exhibited an interference color peculiar to liquid crystals at a temperature of 70 ° C. when observed under a polarizing microscope.

Example 2 The following formula (7)

[Chemical 18] (1.0 g), a compound of formula (5) obtained in Synthesis Example 2 (0.05 g), tetrahydrofuran (3 ml) and azobisisobutyronitrile (2 m
g) was placed in a glass ampoule, oxygen was removed by freeze deaeration, and then the ampoule was sealed. Polymerization was carried out at 80 ° C. for 24 hours. The solution was taken out from the ampoule, reprecipitated and purified using ethanol three times, and then dried to obtain a liquid crystalline polymer photochromic material. The liquid crystalline polymer photochromic material exhibited an interference color peculiar to liquid crystals at a temperature of 70 ° C. when observed under a polarizing microscope.

Claims (3)

[Claims] 1. At least the following formula (A): [In the formula, A ¹ represents hydrogen or a methyl group. X represents a substituent having a chromene skeleton. ] And a monomer represented by the following formula (B): [In the formula, A ² represents hydrogen or a methyl group. Y represents a mesogen group. ] A liquid crystalline polymer photochromic material obtained by copolymerizing a monomer represented by 2. X is the following formula (C), (D) or (E): [Wherein R ¹ , R ² , R ⁹ , R ¹⁰ , R ¹⁷ and R ¹⁸ are
It represents a substituent selected from hydrogen, an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 19 carbon atoms, and an amino group having 0 to 10 carbon atoms. R ³
To R ^8, R ¹¹ to R ¹⁶ and R ¹⁹ to R ²² are hydrogen, hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, 7 carbon atoms
15 aralkoxy group, C 6-14 aryloxy group, C 1-20 acyloxy group, C 1-20
Alkyl group, C 7-15 aralkyl group, C 6-14 aryl group, halo group, carboxyl group, C 2-20 alkoxycarbonyl group, C 8-20
Represents an aralkoxycarbonyl group, an aryloxycarbonyl group having 7 to 20 carbon atoms, a carbamoyl group having 1 to 20 carbon atoms, and a substituent selected from Z, and R ^{3 to} R
^At least one of ⁸ , at least one of R ^{11 to} R ¹⁶ , and at least one of R ^{19 to} R ²² represents Z. Z is the following formula: {N represents an integer of 1 to 10. } Represents a divalent substituent selected from. R ^{23 to} R ²⁸ each independently represent a substituent selected from hydrogen, an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an aryl group having 6 to 19 carbon atoms, and are not independent. In the case of, R ²³ and R ²⁴ , R ²⁵ and R ²⁶ ,
And at least one set of R ²⁷ and R ²⁸ together represents a cyclic substituent having 5 to 20 carbon atoms. ] The liquid crystal polymer photochromic material according to claim 1, which is a substituent represented by the following formula. 3. An information recording material comprising the liquid crystalline polymer photochromic material according to claim 1 or 2.