JP2723303B2 - Chromen composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a chromene composition having photochromic properties and a high fading rate.

(Problems to be Solved by the Prior Art and the Invention) Photochromism is a phenomenon that has attracted attention in recent years, and when a certain compound is irradiated with light containing ultraviolet light such as sunlight or light from a mercury lamp, it is quickly lost. It is a reversible effect that changes color and returns to the original color when the light is stopped and left in a dark place. A compound having this property is called a photochromic compound, and various compounds have been conventionally synthesized. However, no special common structure is recognized in the structure.

Chromene or a derivative thereof is known as a photochromic compound. Chromene or a derivative thereof rapidly changes from a colorless form to a colored form by ultraviolet irradiation (Japanese Patent Application Laid-Open No. 63-66178). However, since the colored form has high thermal stability, it does not easily return to a colorless form at room temperature even when ultraviolet irradiation is stopped. That is, there is a disadvantage that the fading speed is slow.

Therefore, in order to expand the use of chromene or a derivative thereof as a photochromic article, it was necessary to improve the fading speed.

(Means for Solving the Problems) The present inventors have conducted intensive studies in order to improve the fading speed of the above-mentioned chromene or its derivative, and as a result, the above-mentioned chromene or its derivative has nitrogen, sulfur, and phosphorus atoms. It has been found that the above-mentioned objects can be achieved by combining specific compounds containing the following, and the present invention has been completed.

That is, the present invention provides: (a) 100 parts by weight of chromene or a derivative thereof, and (b) sulfide, a tertiary amine, and the following formula [1] A chromene composition comprising at least one compound selected from the group consisting of phosphorus compounds represented by the formula:

Chromene, which is a component of the chromene composition of the present invention, has the following formula: It is a compound shown by these. Further, as the chromene derivative, the compound having the above chromene skeleton is employed without any limitation. In the present invention, chromene or a derivative thereof represented by the following formula [A] or [B] is preferably used because it has excellent photochromic properties.

In the above general formulas (A) and (B), Is a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted unsaturated heterocyclic group. Specific examples of the aromatic hydrocarbon group include a divalent group derived from one benzene ring such as a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring or a fused ring of 2 to 4 benzene rings. Further, a hydroxyl group, a nitro group, a cyano group, a fluoroalkyl group,
Substituted amino group, halogen atom, alkyl group, alkoxy group, -R ₈ -S-R ₉ , [However, R ₈ is an alkylene group or O-R _{11 n} (provided that R
₁₁ is an alkylene group, and n is a positive integer. R ₉ and R ₁₀ are the same or different alkyl groups, and X is —N, —P, It is. And a substituted aromatic hydrocarbon group in which one or two or more heterocyclic groups such as a phenyl group, a phenyl group, a furyl group and a pyrrolyl group are substituted.

Also, Examples of the above unsaturated heterocyclic group represented by are a 5- or 6-membered ring containing oxygen, sulfur and nitrogen atoms, or a heterocyclic group in which a benzene ring is condensed to these. In particular,
Nitrogen-containing heterocyclic rings such as pyridine ring, quinoline ring and pyrrole ring; oxygen-containing heterocyclic rings such as furan ring and benzofuran ring; divalent heterocyclic groups derived from sulfur-containing heterocyclic rings such as thiophene ring and benzothiophene ring Is mentioned. Further, these unsaturated heterocyclic groups, substituted unsaturated heterocyclic group substituted by the substituent described in the description of the aromatic hydrocarbon group described above,
It is adopted without any limitation in the present invention.

Further, in the general formulas [A] and [B], R ₄ , R ₅ , R ₆
And R ₇ are the same or different hydrogen atoms, alkyl groups, aralkyl groups, aryl groups, and substituted amino groups, respectively. The alkyl group is not particularly limited, but generally has 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms. The alkylene group in the aralkyl group is
In general, those having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms are suitable. More specific examples of these alkyl groups and aralkyl groups include methyl, ethyl, propyl, butyl, benzyl, phenylethyl, phenylpropyl, and phenylbutyl. As the aryl group, for example, a phenyl group, a tolyl group, a xylyl group,
A naphthyl group and the like are preferred.

Further, in the general formulas [A] and [B], R ₄ , R ₅ , R ₆
And the substituted amino group represented by R ₇ has the general formula Indicated by Groups represented here by R _12, R ₁₃ is, R ₁₂ and R ₁₃
Is either a hydrogen atom and the other is an alkyl group, or represents the same or different alkyl groups. The alkyl group is not particularly limited, but specifically, the same groups as those described above for the alkyl group can be employed. R ₁₄ is an alkylene group having 3 to 6 carbon atoms such as a tetramethylene group and a pentamethylene group; _{-CH 2 OCH 2 CH 2 -,} - CH 2 CH 2 OCH 2 CH 2 -, -CH 2 O (CH 2) 3 - oxyalkylene group having 3 to 6 carbon atoms such as; -CH ₂ SCH ₂ CH ₂ −, −CH ₂ S (CH ₂ ) ₃ −, −CH ₂ CH ₂ SC
H ₂ CH ₂ - thioalkylene group having 3 to 6 carbon atoms such as; An azoalkylene group having 3 to 6 carbon atoms, such as, for example, is suitably employed.

In the general formula (B), Is a norbornylidene group Substituted norbornylidene group, bicyclo [3.3.1] 9-nonylidene group Substituted bicyclo [3.3.1] 9-nonylidene group, adamantylidene group Or a substituted adamantylidene group. Specific examples of the substituent include, for example, a hydroxy group; a methylamino group,
A substituted amino group such as a diethylamino group; an alkoxy group having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group and a tert-butoxy group; an aralkoxy group having 7 to 15 carbon atoms such as a benzyloxy group; a phenoxy group and a 1-naphthoxy group Etc. with 6 or more carbon atoms
14 aryloxy groups; lower alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group and t-butyl group; halogen atoms such as fluorine, chlorine and oxine; cyano group; carboxyl group; An alkoxycarbonyl group having 2 to 10 carbon atoms; 1 carbon atom such as a trifluoromethyl group
Or 2 halogen-substituted alkyl groups; nitro groups; aryl groups such as phenyl group and tolyl group; aralkyl groups such as benzyl group, phenylethyl group and phenylpropyl group, and these substituents are monosubstituted. May be included as a multi-substituted compound having a plurality of substituents having two or more substituents, and the substituents in the multi-substituted product may be the same or different. There is no problem, and the position of the substituent can be changed according to the purpose or use.

Among the above-mentioned chromene or a derivative thereof, in the general formulas (A) and (B), Is preferably a condensed ring of two or more rings because of high color density. Among them, compounds in which a ring is condensed at the 7th and 8th positions of the chromene derivative are more preferable. In the formula [B], a compound obtained by condensing a ring at the 5,6-position of the chromene derivative is also preferably used.

The other component of the chromene composition of the present invention comprises a sulfide, a tertiary amine and a compound represented by the following formula [I]: And at least one compound selected from the group consisting of phosphorus compounds (hereinafter, also simply referred to as a fading accelerator). As the sulfide, the tertiary amine and the phosphorus compound represented by the above general formula [I], known compounds are employed without any limitation. For example, sulfides include dimethyl sulfide, diethyl sulfide, dipropyl sulfide, dibutyl sulfide, dipentyl sulfide, dicyclohexyl sulfide, methyl ethyl sulfide, methyl propyl sulfide, methyl cyclohexyl sulfide, methyl phenyl sulfide and the like. Further, as the tertiary amine, trimethylamine, triethylamine, tripropylamine, tributylamine,
Tripentylamine, methyldiethylamine, methyldipropylamine, methyldibutylamine, methyldicyclohexylamine, cyclohexyldimethylamine,
-Methylpiperidine, 1-methylpyrrolidine, pyridine and the like. Further, as the phosphorus compound represented by the general formula (I), (CH ₃ CH ₂ ) ₃ P, (CH ₃ CH ₂ CH ₂ ) ₃ P, (CH _3
3 CH ₂ CH ₂ CH ₂ ) ₃ P, (CH ₃ CH ₂ CH ₂ CH ₂ CH ₂ ) ₃ P, CH ₃ P (CH ₂ CH ₂ CH ₃ ) ₂ , CH ₃ P (CH ₂ CH ₂ CH ₂ CH _{3) 2, CH 3 CH 2} P (OCH 2 CH 3) 2, CH 3 CH 2 CH 2 P (OCH 2 CH 2 CH 3) 2, CH 3 CH 2 CH 2 CH 2 P (OCH 2 CH 2 CH 2 CH ₃ ) ₂ , CH ₃ P (OCH ₂ CH ₂ CH ₃ ) ₂ , CH ₃ P (OCH ₂ CH ₂ CH ₂ CH ₃ ) ₂ , CH ₃ CH ₂ P (OCH ₂ CH ₂ CH ₃ ) ₂ , (CH ₍₃ CH ₂ O) ₃ P, (CH ₃ CH ₂ CH ₂ ) ₃ P, (CH ₃ CH ₂ CH ₂ CH ₂ O) ₃ P, (CH ₃ CH ₂ CH ₂ CH ₂ CH ₂ O) ₃ P, CH ₃ OP (OCH ₂ CH ₂ CH ₃ ) ₂ , CH ₃ OP (OCH ₂ CH ₂ CH ₂ CH ₃ ) ₂ , CH ₃ CH ₂ OP (OCH ₂ CH ₂ CH ₃ ) _{2 and the} like.

Among the above sulfides and tertiary amines, in view of the fading rate of chromene or a derivative thereof, a compound in which only a chain or cyclic alkyl group is bonded to a sulfur atom or a nitrogen atom is preferably used. Further, among these sulfides, tertiary amines and phosphorus compounds represented by the above general formula [I], compounds having an alkyl group or an alkoxy group having 1 to 6 carbon atoms are more preferable from the viewpoint of the fading speed.

The mixing ratio of the above-mentioned chromene or a derivative thereof and the fading accelerator is in the range of 10 to 10,000 parts by weight for the latter with respect to 100 parts by weight of the former. When the fading accelerator is less than 10 parts by weight, the effect of improving the fading speed is hardly recognized, and when it exceeds 10,000 parts by weight, it is difficult to mold the resin when the chromene composition is dispersed in the resin described below. Is not preferred. In particular, from the viewpoint of the photochromic properties of the obtained chromene composition, the amount of the fading accelerator is preferably in the range of 50 to 5,000 parts by weight.

The chromene composition of the present invention can exhibit the above-mentioned desired photochromic function well by being uniformly dispersed in various polymer matrices. As the synthetic resin constituting the polymer matrix used by dispersing the chromene composition in the present invention, any resin capable of uniformly dispersing chromene or a derivative thereof may be used. Methyl acrylate, polyethyl acrylate, polymethyl methacrylate, polyethyl methacrylate, polystyrene, polyacrylonitrile, polyvinyl alcohol, polyacrylamide, poly (2-hydroxyethyl methacrylate),
Polymers such as polydimethylsiloxane, polycarbonate, and poly (allyl diglycol carbonate), or monomers forming these polymers or polymers obtained by copolymerizing the monomers with other monomers are preferably used. The amount of the chromene composition of the present invention dispersed in such a resin is 0.001 to 10 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the resin.

The chromene composition of the present invention is particularly suitably used for a photochromic lens. The method for producing a photochromic lens is not particularly limited as long as uniform light control performance can be obtained, and specifically, a polymer film obtained by uniformly dispersing the above chromene or a derivative thereof and a fading accelerator. There is a method of sandwiching in the lens.
Alternatively, there is a method of dispersing the above chromene composition in silicone oil, impregnating the lens surface at, for example, 200 ° C. for 15 minutes, and further coating the surface with a curable substance to form a photochromic lens. There is also a method in which the above-mentioned polymer film is applied to the lens surface, and the surface is coated with a curable substance to form a photochromic lens.

(Effect) As described above, the chromene composition of the present invention
In particular, by uniformly dispersing in various resins, the color changes from colorless to colored or darkened by light including ultraviolet rays such as sunlight or light from a mercury lamp, and the change is reversible and excellent dimming properties are obtained. Have. Further, in the present invention, the combined use of chromene or a derivative thereof and a fading accelerator has succeeded in increasing the fading speed without lowering the coloring concentration.

Therefore, the chromene composition of the present invention can be used in a wide range of fields, for example, various recording storage materials, copying materials, photoreceptors for printing, recording materials for cathode ray tubes, recording materials for lasers, etc. Can be used as various recording materials. In addition, the chromene composition of the present invention can also be used as a material for photochromic lens materials, optical filter materials, display material light meter, decoration and the like.

(Examples) Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the examples, “parts” is “parts by weight”.

Production Example 1 1-hydroxy-2-acetonaphthone 10 g (0.054mo
l) with 6.6 g (0.06 mol) of norcamphor and 8 g of pyrrolidine
(0.113 mol) was dissolved in 300 cc of toluene to prepare a solution. The mixture was boiled for 10 hours and the water was separated. After the completion of the reaction, the toluene was removed under reduced pressure, and the remaining chromanone compound was crystallized with acetone. Next, this chromanone compound was dissolved in 200 cc of methanol, and sodium borohydride was gradually added to obtain a chromanol compound. By heating 7.47 g of this chromanol compound together with 4.5 g of anhydrous copper sulfate in a stream of carbon dioxide at 150 to 160 ° C. for 10 minutes, and purifying the brown viscous liquid by chromatography on silica gel, a chromene compound of the following formula was obtained. 6.3 g of the derivative were obtained.

Elemental analysis values of this compound were as follows: C86.93%, H6.89%, O6.
A 18%, a calculated value for C ₁₉ H ₁₈ O C87.02
%, H6.87% and O6.12%. When the proton nuclear magnetic resonance spectrum was measured, it was found that δ7.2
A peak of 6H based on a naphthalene ring proton at about 8.3 ppm, a peak of 2H based on an alkene proton near δ5.6 to 6.7 ppm, and a broad 10H peak based on a proton of a norbornylidene group near δ1.2 to 2.5 ppm showed that. Further measurement of ¹³ C-nuclear magnetic resonance spectrum revealed that
A peak based on the carbon of the norbornylidene group appears around 7 to 52 ppm, a peak based on the carbon of the naphthalene ring near δ 110 to 160 ppm, and a peak based on the carbon of the alkene around δ 80 to 110 ppm. From the above results, it was confirmed that the isolated product was the compound represented by the above structural formula (1).

Production Example 2 A solution prepared by dissolving 10 g (0.054 mol) of 1-acetyl-2-naphthol, 8.29 g (0.06 mol) of bicyclo [3.3.1] nonan-9-one, and 8.7 g (0.10 mol) of morpholine in 300 cc of toluene was prepared. Prepared. The mixture was boiled for 5 hours and the water was separated. After completion of the reaction, toluene was removed under reduced pressure, and the remaining chromanone compound was recrystallized from acetone. Next, this chromanone compound was dissolved in 200 cc of methanol, and lithium aluminum hydride was added to obtain a chromanol compound. The chroman compound 6.49 g was heated at 170 to 180 ° C. for 10 minutes together with anhydrous copper sulfate in a stream of carbon dioxide, and the brown viscous liquid was purified by chromatography on silica gel to obtain 5.8 g of a chromene derivative of the following formula. Was.

Elemental analysis of this compound gave C86.81%, H7.62%, O5.
A 57%, a calculated value for C ₂₁ H ₂₂ O C86.90
%, H7.59% and O5.52%. When the proton nuclear magnetic resonance spectrum was measured, it was found that δ7.2
A peak of 6H based on the proton of the naphthalene ring at ~ 8.3 ppm, a peak of 2H based on the proton of the alkene at about δ6.0 to 7.0 ppm, and a bicyclo at about δ1.2 to 2.5 ppm (3.3.1)
It showed a broad peak at 14H based on the proton of the 9-nonylidene group. Further, when the ¹³ C-nuclear magnetic resonance spectrum was measured, it was found that bicyclo [3.3.1] 9 was found around δ 27 to 55 ppm.
-Peak based on carbon of nonylidene group, δ 110 to 160 ppm
Near the peak based on the carbon of the naphthalene ring, δ80 ~ 110p
A peak based on the carbon of the alkene appears around pm. From the above results, it was confirmed that the isolated product was the compound represented by the above structural formula (2).

Production Example 3 3.06 g (0.01 mol) of a chromanone compound represented by the following formula Was dissolved in 50 cc of anhydrous ether, the solution was cooled to 0 ° C., and a freshly prepared Grignard reagent CH ₃ MgI (0.012 mol) was added dropwise to the solution in 50 cc of anhydrous ether over about 1 hour. After completion of the dropwise addition, the mixture was further stirred at room temperature for 2 hours, the ether solution was gently poured into cold water, the product was extracted with ether, the solution was dried over magnesium sulfate, and the ether was removed under reduced pressure. The compound was changed to a chromanol compound. Then, the chromanol compound was mixed with anhydrous copper sulfate in a stream of carbon dioxide at 200 ° C. for about 1 hour.
Heat for 0 min and purify the brown viscous liquid by chromatography on silica gel to give a chromene derivative of the formula
2.47 g were obtained.

Elemental analysis, proton nuclear magnetic resonance spectrum, and measurement of ¹³ C-nuclear magnetic resonance spectrum were performed in the same manner as in Production Example 1.
This compound was confirmed to be the compound represented by the above structural formula (3).

Production Example 4 1-acetyl-2-naphthol 10 g (0.054 mol), norcamphor 6.6 g (0.06 mol), and morpholine 8.7 g (0.10 m
ol) was dissolved in 300 cc of toluene, boiled for 15 hours, and water was separated. After the reaction, the toluene was removed under reduced pressure,
The remaining product was recrystallized from acetone to obtain 7.53 g of a compound represented by the following formula.

Next, 7.53 g of this compound was dissolved in 100 cc of methanol and reacted with methyl iodide to obtain 6.95 g of a chromanone compound represented by the following formula.

Next, the produced chromanone compound was changed to a chromanol compound in the same manner as in Production Example 3, and a dehydration reaction was performed. After separation and purification, 5.84 g of a chromene derivative represented by the following formula was obtained.

As in Production Example 1, elemental analysis, proton nuclear magnetic resonance spectrum and ¹³ C-nuclear magnetic resonance spectrum measurement confirmed that this compound was the compound represented by the above structural formula (4).

Production Example 5 5-n-octyloxy-1-hydroxy-2-acetonaphthone 10 g (0.0318 mol) and acetone 2.77 g (0.0477 m
ol) and 1.13 g (0.0159 mol) of pyrrolidine in 100 ml of toluene
Was prepared. The mixture was boiled for 10 hours and the water was separated. After completion of the reaction, toluene was removed under reduced pressure, the remaining chromanone compound was dissolved in 100 ml of methanol, and sodium borohydride was gradually added to obtain a chromanol compound. 6.0 g of this chromanol compound was mixed with 4.0 g of anhydrous copper sulfate in a stream of carbon dioxide at 150 to 160 ° C.
The mixture was heated for 10 minutes, and the brown viscous liquid was purified by chromatography on silica gel to obtain 3.8 g of a chromene derivative represented by the following formula.

As in Production Example 1, elemental analysis, proton nuclear magnetic resonance spectrum, and ¹³ C-nuclear magnetic resonance spectrum measurement confirmed that this compound was the compound represented by the above structural formula (5).

Production Examples 6 to 14 The chromene derivatives shown in Table 1 were synthesized in the same manner as in Production Examples 1 to 5.

The obtained product was subjected to structure analysis using the same means for structure confirmation as in Production Example 1, and as a result, was confirmed to be a compound represented by the structural formula shown in Table 1.

Example 1 100 parts of benzene, 10 parts of polymethyl methacrylate, the compound (1) obtained in Production Example 1, and (CH ₃ CH
₂ CH ₂ CH ₂ O) ₃ P was added and dissolved in 0.2 parts each, and a cast film was prepared on a slide glass (11.2 × 3.7 cm). The thickness was adjusted to be 0.1 mm. To this photochromic film, a mercury lamp SHL-100 manufactured by Toshiba Corporation was used.
Was irradiated at 25 ° C. ± 1 ° C. for 60 seconds at a distance of 10 cm, and the film was colored to measure photochromic properties. The photochromic properties were expressed as follows. Second result
It is shown in the table.

ε (60 seconds): Absorbance at the maximum absorption wavelength after 60 seconds of light irradiation of the film under the above conditions.

ε (0 seconds); absorbance of the unirradiated film at the maximum absorption wavelength upon light irradiation.

Half-life t ^1/2 ; time required for the absorbance of this film to fall to 1/2 of {ε (60 seconds) −ε (0 seconds)} after light irradiation for 60 seconds.

Examples 2 to 10 The same procedures were performed as in Example 1 except that the type of the fading accelerator used in Example 1 was changed. The results are shown in Table 2.

Comparative Example 1 The procedure of Example 1 was repeated except that no fading accelerator was used.

Examples 11 to 20 The same procedures were performed as in Example 1 except that the chromene derivative used in Example 1 was changed to the compound (2) obtained in Production Example 2. The results are shown in Table 3.

Comparative Example 2 The procedure of Example 11 was repeated except that no fading accelerator was used. The results are shown in Table 3.

Examples 21 to 28 All of the procedures were the same as in Examples 3 and 6, except that the amount of the fading accelerator was changed. The results are shown in Table 4.

Examples 29 to 40 All of the procedures were the same as in Example 1 except that the chromene derivative was changed to the compounds of Production Examples 3 to 14 and the type of the fading accelerator was changed. The results are shown in Table 5.

Claims (1)

(57) [Claims] (1) 100 parts by weight of chromene or a derivative thereof and (b) sulfide, a tertiary amine and a compound represented by the following formula: A chromene composition comprising at least one compound selected from the group consisting of phosphorus compounds represented by the formula: