JPH10168440A - Resin molding containing light-resistant photochromic material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To solve the problem that a resin molding containing a conventional photochromic material has poor light resistance, therefore loses its property of reversibly changing its color when exposed to ultraviolet rays for a long time and is not yet practicable. SOLUTION: The molding of this invention contains a resin and a light- resistant photochromic material being a photochromic compound represented by the formula (R2 is an alkylselenol) and contains 0.05-4wt.% light-resistant photochromic material. In the formula, R1 is hydrogen, an alkoxyl or a halogen; R3 and R4 are each an alkyl; R5 is piperidino, morpholino, N-methylpiperazino, N-phenylpiperazino, tetrahydroisoquinolino, indolino, thiomorpholino, homopiperidino, 1,2,3,4,4a,9a-hexahydrocarbazolino or an aziridino; R6 is hydrogen or alkoxyl; and X and Y are each -CH= or -N=.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin molding containing a light-fast photochromic material.

[0002]

2. Description of the Related Art Photochromic discoloration is caused by reversible physical phenomena, which change color when exposed to ultraviolet light and return to the original color when the ultraviolet light is shielded. Conventional photochromic materials include, for example, JP-A Nos. 7-48363, 7-26253, and 6
-161023, 6-289529 and 6-29
No. 3756, No. 6-263375, No. 6-26376
7, No. 6-256758, No. 6-240242,
5-271648 and 5-208980 4-7
Nos. 6087 and 2-221282.

In these publications, there is described a method for producing a resin molded product containing a photochromic material mixed into a resin by using an appropriate number of spirooxazine compounds by reacting an indoline derivative or a trimethylpiperidine compound with nitrosonaphthol or the like. I have.

[0004]

However, the above-mentioned conventional molding has a disadvantage that the property of reversibly discoloring is lost when the molding is left exposed to ultraviolet light for a long time.
It was still poorly practical.

[0005] The present invention has been made in view of the above-mentioned points, and solves the above-mentioned conventional disadvantages, and does not lose reversible discoloration even when exposed to ultraviolet light for a long time. It is an object of the present invention to provide a photochromic material-containing resin molded article having excellent light resistance that can withstand use.

[0006]

The present invention provides a photochromic compound represented by the following general formula (1):
_{2. A} resin molding containing a light-resistant photochromic material, comprising a light-resistant photochromic material, wherein ₂ is an alkyl selenol, and a resin, wherein the light-resistant photochromic material is contained at a ratio of 0.05 to 4% by weight. Make the object a summary.

Embedded image (However, R ₁ is any _one of a hydrogen atom, an alkoxy substituent and a halogen substituent, R ₃ and R ₄ are each an alkyl group, R ₅ is piperidine, morpholine, N-methylpiperazino, N-phenylpiperazino, tetrahydro Isoquinolino, indolino, thiomorpholino, homopiperidino,
1,2,3,4,4a, 9a-Hexahydrocarbazolino, any of aziridino substituents, R ₆ is a hydrogen atom or an alkoxy substituent, and each of X and Y is -CH = or-
N =. )

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described specifically. A feature of the present invention is that a photochromic material that is more stable to ultraviolet light (having a longer life) than the conventionally known photochromic material, that is, is superior in light resistance to ultraviolet light, is used. In the general formula (1), R ₂ is an alkyl selenol whose general formula is represented by C _n H _{2n + 1} Se. Here, n is an integer of 1 or more. In the present invention, the alkyl selenol is preferably methyl selenol.

Each of R ₁ , R ₅ and R ₆ is selected from the following (a) to (d). (A): a hydrogen atom or an amine functional group of -NR 'or -R "(provided that each of R' and R" is a hydrogen atom, or an alkyl, cycloalkyl or phenyl group or a substituted group thereof, or one Or an amine function that is a cycloheteroalkyl ring containing two or more heteroatoms).

(B): -R, -OR, -SR, -COR
Or a -COOR group (where R represents hydrogen, alkyl, aryl or heteroaryl).

(C): -X, -CH ₂ X, -CHX ₂ or -CX ₂ (where X represents halogen).

(D): -NO ₂ , -CN or -SCN.

In the present invention, in the general formula (1), R ₁ is preferably a 5-alkoxy substituent or a 5-halogen substituent, and more preferably a 5-methoxy or 5-chloro substituent. Also, R ₅ is preferably coordinated at the 6′-position.

R ₆ is preferably a 9'-alkoxy substituent, especially 9'-methoxy. In addition, the aspect in which R ₆ is coordinated to the position of X and X is CR ₆ is also included in the present invention. Further, as in the case of X, an embodiment in which R ₁ is coordinated to the position of Y and Y is C—R ₁ is also included in the present invention.

In the general formula (1), X is 7 ′,
It may be located at any of the 8 ', 9' and 10 'positions, but is preferably located at the 7' position. Y is 4,
It may be coordinated at any of positions 5, 6, and 7, but is preferably coordinated at position 7. The structural formula when X and Y take the above preferred coordination positions is shown below as formula (2).

[0015]

Embedded image

Particularly preferred in the present invention are compounds having a chemical structure represented by the following formulas (3) and (4).

[0017]

Embedded image

[0018]

Embedded image

The photochromic compound of the present invention represented by the general formula (1) can be produced by a general method based on the following reaction formula. That is, the following (5)
The halogen compound represented by the formula is reacted with sodium hydrogen selenide to obtain a compound represented by the following formula (6). In the following formula (6), the case where the functional group corresponding to R ₂ is methylselenol and Y is located at the 7-position is shown. R ₇ represents a hydrogen atom or an alkyl group.

[0020]

Embedded image

Next, an α-nitro-β-naphthol derivative represented by the following formula (7) is added to the compound represented by the formula (6):
The reaction is carried out based on the following reaction formula to obtain one embodiment of the photochromic compound of the present invention represented by the following formula (8). In addition, in Formulas (7) and (8), the case where X is located at the 7'-position is shown.

[0022]

Embedded image

The above chemical reactions are carried out together by refluxing in a solvent such as trichloroethylene or toluene. When using an indolenium salt, a base such as triethyleneamine must be present. The desired spironaphthoxazine selenol product is separated from the solvent and purified by conventional methods such as chromatographic separation and recrystallization.

The photochromic compound produced as described above has extremely excellent light resistance to ultraviolet rays as compared with conventionally known products.

The resin molded article containing a photochromic material of the present invention comprises a novel photochromic compound represented by the general formula (1) and a plastic (resin) material. 0.05 to 4% (weight ratio).

Suitable plastics materials include, for example, polymers of polyol (arly carbonate) monomers,
Polyacrylate, polymethyl acrylate pama poly (allyl acrylate), cellulose acetate,
Cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate,
Poly (vinyl alcohol), poly (vinyl acetate), polyurethane, polycarbonate, polyethylene, polypropylene, terephthalate, polystyrene,
Plastics (resins) such as poly (styrene / acrylonitrile) copolymer, poly (styrene / methyl methacrylate) copolymer, and polyvinyl butyrate can be mentioned.

The photochromic material of the general formula (1) can be incorporated into plastics by the usual methods known in the art, for example by the method described in EP 41407. Generally, this method heats or disperses or disperses in a plastic material. The novel photochromic material can be dispersed in the plastic material by absorption, i.e., the novel photochromic can be dispersed in the plastic material by diffusion by a suitable machine such as immersion, heat transfer or gas phase transfer. Furthermore, if the plastic material is formed from highly reactive polyfunctional monomers, the novel photochromic material can be incorporated by direct pouring into the plastic material. This direct casting process uses high reactive polyfunctional monomers and low catalyst concentrations to prevent the degradation of the new photochromic material, and the process uses high reactive polyfunctional monomers and the monomer. Of a polymerization catalyst in an amount of 0.01 to 1% (weight ratio) based on the volume of
Mix 5-4% of this new photochromic material,
The resulting polymerizable composition can be introduced into a mold and cured to produce a plastic molding.

[0028]

The present invention will be described below in more detail with reference to specific examples. Production of Resin Fine Powder Using New Photochromic Dye Example 1 1) 10 kg of polyethylene pellets as a plastic (resin) material are put into a kneader heated to about 180 ° C. and melted. 2) 500 g of 100 g (1% based on resin) of a new photochromic material (the structure shown in the formula (3))
Make a liquid dispersed in ethylene glycol. 3) The liquid dispersed in the ethylene glycol is put into the above-mentioned plastic hot melt and kneaded for about 1 to 2 minutes. Here, the photochromic material is instantaneously dissolved or dispersed in the plastic hot melt. 4) The kneaded material is immediately extruded from the kneader nozzle (diameter 1 to 2 mm) to the outside, and at the same time, is inserted into water and cooled. The photochromic plastic kneaded material is a hard rod-shaped molded product having a diameter of 1 to 2 mm. 5) The hard rod-shaped molded product is cut into a length of 1 to 2 mm to form a pellet. In this way, a molded product in which the photochromic material is dissolved or dispersed in the plastic material is formed into a pellet. It has a high content of photochromic material. Hereinafter, this is called a master batch. 6) As in 1) above, 10 kg of a polyethylene resin as a plastic material is put into a kneader heated to about 180 ° C. and melted. 7) 500 g of the polyethylene resin master batch produced above is mixed into the molten resin of the above 6). 8) Since the whole is uniformly melted and kneaded in 1 to 2 minutes, it is immediately cooled by water simultaneously with extrusion into a molding machine. 9) After completely cooled, take out of the molding machine to complete a photochromic plastic molded product. Similarly, a conventional photochromic material (1,3-dihydro-
1,3,3-Trimethyl-6 '-(1-piperidinyl) -spiro [2H-indole-2,3- (3H) naphtho (2,1-b) [1,4] -oxazine) Plastic molded articles were produced in the same manner from the batch. A plastic molded article containing the photochromic material of the above formula (3) and a plastic molded article containing the conventional photochromic material were directly subjected to an exposure test with sunlight under the same conditions. The nature of the physical reversible phenomenon disappeared, and the discoloration disappeared in about 5 days.
In contrast, the molded article containing the photochromic material of the above formula (3) sustains the physical reversible phenomenon for about 30 days,
The nature of the discoloration was also confirmed for about 30 days.

Example 2 A plastic molded product was produced in the same manner as in Example 1 except that the plastic material and the polypropylene resin were used in Example 1. As in Example 1, a plastic molded article containing the novel photochromic material and a plastic molded article containing the conventional photochromic material were directly subjected to an exposure test with sunlight under the same conditions. The physical reversible phenomenon disappeared in about 7 days, and the discoloration disappeared in about 7 days. In contrast, the molded article containing the photochromic material represented by the above formula (3) maintained the physical reversible phenomenon for about 35 days, and the discoloration was confirmed for about 35 days.

Example 3 A plastic molded product was produced in the same manner as in Example 1 except that the plastic material and the polystyrene resin were used in Example 1. In the same manner as in Example 1, the plastic molded article containing the novel photochromic material shown in the above formula (3) and the plastic molded article containing the conventional photochromic material were directly exposed to sunlight under the same conditions. As a result of the exposure test, the properties of the conventional product disappeared in about 8 days, and the discoloration disappeared in about 8 days.
On the other hand, the molded article made of the novel photochromic material (material of the general formula (1)) sustained the physical reversible phenomenon for about 37 days, and the discoloration was confirmed for about 37 days.

Example 4 In Example 1, a plastic material and poly (styrene
Methyl methacrylate) copolymer resin,
A plastic molded article was manufactured in the same manner as in Example 1. In the same manner as in Example 1, the plastic molded article containing the novel photochromic material shown in the above formula (3) and the plastic molded article containing the conventional photochromic material were directly exposed to sunlight under the same conditions. As a result of the exposure test, the physical property of the conventional product disappeared in about 10 days, and the discoloration disappeared in about 10 days. In comparison, molded products containing a new photochromic material are about 4
The physical reversible phenomenon continued for 5 days, and the nature of the discoloration was confirmed for about 45 days.

Example 5 A plastic molded article was produced in the same manner as in Example 1 except that the new photochromic material in Example 1 was replaced with the structure of the above formula (3) and the structure of the above formula (4). Was manufactured. In the same manner as in Example 1, a plastic molded product containing a novel photochromic material was added to a conventional photochromic material (1,3-dihydro-1,3,3).
3-trimethyl-6 '-(1-piperidinyl) -spiro [2H-indole-2,3- (3H) naphtho (2,
1-b) A plastic molded product containing [1,4] -oxazine) was directly exposed to sunlight under the same conditions, and as a result, the physical reversibility of the conventional product disappeared in about 6 days. Then, discoloration disappeared in about 6 days. In contrast, the molded article containing the novel photochromic material sustained the physical reversible phenomenon for about 35 days, and the discoloration was confirmed for about 35 days.

Example 6 A plastic molded product was produced in the same manner as in Example 5 except that the plastic material and polyethylene were replaced with polypropylene. Example 5
Similarly to the above, a plastic molded article containing the novel photochromic material represented by the above formula (4) and a conventional photochromic material (1,3-dihydro-1,3,3-trimethyl-6 '-(1-piperidiniyl) -Spiro [2H-
Indole-2,3- (3H) naphtho (2,1-b)
[1,4] -Oxazine) was directly exposed to sunlight under the same conditions as a plastic molded product,
In the conventional product, the property of the physical reversible phenomenon disappeared in about 8 days, and the discoloration disappeared in about 8 days. In contrast, the molded article containing the novel photochromic material sustained the physical reversible phenomenon for about 40 days, and the discoloration was confirmed for about 40 days.

Example 7 A plastic molded product was produced in the same manner as in Example 5 except that the plastic material and polyethylene were replaced with polystyrene. In the same manner as in Example 5, a plastic molded article containing the novel photochromic material represented by the formula (4) and a conventional photochromic material (1,3-dihydro-1,3,3-trimethyl-6'-) (1-piperidinyl) -spiro [2H-indole-2,3- (3H) naphtho (2,1-b)
[1,4] -Oxazine) was directly exposed to sunlight under the same conditions as a plastic molded product,
In the conventional product, the property of the physical reversible phenomenon disappeared in about 9 days, and the discoloration disappeared in about 9 days. In contrast, the molded article containing the novel photochromic material sustained the physical reversible phenomenon for about 45 days, and the discoloration was confirmed for about 45 days.

Example 8 A plastic molded product was produced in the same manner as in Example 5 except that the plastic material and polyethylene were replaced with poly (styrene / methyl methacrylate) copolymer resin. In the same manner as in Example 5, a plastic molded article containing the novel photochromic material represented by the formula (4) and a conventional photochromic material (1,3-dihydro-1,3,3-trimethyl-6'-)
(1-piperidinyl) -spiro [2H-indole-
A plastic molded product containing 2,3- (3H) naphtho (2,1-b) [1,4] -oxazine) was directly exposed to sunlight under the same conditions, and as a result, the conventional product was approximately The property of the physical reversible phenomenon disappeared in 9 days, and the discoloration disappeared in about 12 days. In contrast, the molded article containing the novel photochromic material sustained the physical reversible phenomenon for about 55 days, and the discoloration was confirmed for about 55 days.

[0036]

Since the photochromic material-containing resin molded product of the present invention is constituted as described above, it has excellent light resistance and does not lose its physical reversibility even when exposed to ultraviolet rays for a long period of time. There is an effect that long-term use under the above environment is possible.

Claims (1)

[Claims] 1. A photochromic compound represented by the following general formula (1), wherein R ₂ is a light-resistant photochromic material and a resin, wherein R ₂ is alkyl selenol;
0.05 to 4% by weight of the light-resistant photochromic material
A resin molded article containing a light-resistant photochromic material, characterized in that the resin molded article contains a photochromic material. Embedded image (However, R ₁ is any _one of a hydrogen atom, an alkoxy substituent and a halogen substituent, R ₃ and R ₄ are each an alkyl group, R ₅ is piperidine, morpholine, N-methylpiperazino, N-phenylpiperazino, tetrahydro Isoquinolino, indolino, thiomorpholino, homopiperidino,
1,2,3,4,4a, 9a-Hexahydrocarbazolino, any of aziridino substituents, R ₆ is a hydrogen atom or an alkoxy substituent, and each of X and Y is -CH = or-
N =. )