JPH06184355A - Photochromic resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition of improved light resistance by mixing a transparent resin with a spironaphthoxazine compound of a specified formula and a specified hindered amine light stabilizer. CONSTITUTION:100 pts.wt. transparent resin such as a polymethyl methacrylate resin is mixed with 0.01-100 pts.wt. spironaphthoxazine compound of formula I [wherein R1 is H, halogen, cyano, 1-6C alkyl, (CH2)nCOOH, (CH2)nCN or (CH2)<n>COOR (wherein R is 1-6C alkyl; and (n) is 1-4); R2 is 1-6C alkyl, (CH2)nCOOH, (CH2)nCN or (CH2)nCOOR; and R3 and R4 are each 1-6C alkyl or piperidyl], 0.1-150wt.%, based on the former compound, hindered amine light stabilizer of formula II with rolls, and the obtained mixture is deaerated. The obtained transparent resin composition has photochromic performance and excellent light resistance.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is capable of changing from colorless to transparent or opaque colored form upon irradiation with light containing ultraviolet rays such as sunlight or light from a mercury lamp, and the change is reversible. Moreover, the present invention relates to a transparent resin composition having a photochromic performance that is extremely excellent in light resistance.

[0002]

2. Description of the Related Art Conventionally, organic photochromic substances,
For example, it is known to apply a composition obtained by dissolving a spironaphthoxazine-based compound in a transparent resin such as polymethylmethacrylate or polycarbonate as a photochromic transparent material to a sunscreen material or a decorative material. (For example, Japanese Patent Publication No. 45-28892)
(JP-A-55-36284)

[0003]

However, a conventional resin composition having a photochromic performance containing a spironaphthoxazine compound has a problem that it is deteriorated by irradiation with light for a long time, and improvement of light resistance is a major problem. It was.

[0004]

Under the circumstances described above, the present inventors have studied to develop a resin compound having photochromic performance with excellent light resistance, and as a result, used a specific light stabilizer in combination. As a result, they found that the light resistance was improved without impairing the photochromic performance and completed the present invention. That is, the present invention has the following general formula (I) in a transparent resin. [In the formula, R ₁ represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, — (CH ₂ ) n —COOH,
_{- (CH 2) n -CN,} - (CH 2) n -COOR (R
Represents an alkyl group having 1 to 6 carbon atoms, and n is an integer of 1 to 4). R ₂ is an alkyl group having 1 to 6 carbon atoms, — (C
_{H 2) n -COOH, - (} CH 2) n -CN, - (CH
₂ ) n-COOR (R is an alkyl group having 1 to 6 carbon atoms, n
Is an integer of 1 to 4). Indicates. R ₃ and R ₄
Represents an alkyl group having 1 to 6 carbon atoms or a piperidyl group, which may be the same or different. ] The present invention provides a resin composition comprising a spironaphthoxazine-based compound and a hindered amine-based light stabilizer. Hereinafter, the present invention will be described in detail. The following are typical examples of the spironaphthoxazine-based compound represented by the above general formula (I) used in the present invention. 1,3,3-Trimethylspiro [indolino-2,3 '
-Naphtho [2,1-b] (1,4) -oxazine] 1,3,3,5-tetramethylspiro [indolino-
2,3′-naphtho [2,1-b] (1,4) -oxazine] 1,3-dimethyl-3-piperidyl spiro [indolino-2,3′-naphtho [2,1-b] (1, 4) -Oxazine] 5-chloro-1,3,3-trimethylspiro [indolino-2,3'-naphtho [2,1-b] (1,4) -oxazine] 1-β-cyanoethyl-3,3 -Dimethylspiro [indolino-2,3'-naphtho [2,1-b] (1,4)-
Oxazine] 1-β-carboxylethyl-3,3,5-trimethylspiro [indolino-2,3'-naphtho [2,1-b]
(1,4) -Oxazine] Such a spironaphthoxazine-based compound may be used not only in one kind but also in a mixture of two or more kinds.

In the present invention, it is important to use a hindered amine light stabilizer as a light stabilizer for imparting light resistance. Examples of such hindered amine light stabilizers include 2-methyl-2- (2,2,6,6-tetramethyl-4
-Piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide (trade name Sumisorb TM-061, manufactured by Sumitomo Chemical Co., Ltd.) Bis (2,2,6,6- Tetramethyl-4-piperidyl) sebacate poly {[6- (1,1,3,3-tetramethylbutyl)
Imino-1,3,5-triazine-2,4-diyl]
[(2,2,6,6-tetramethyl-4-piperidyl)
Imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]} bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2- (3,5- Di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate 4-hydroxy-2,2,6,6-tetramethyl-1-
Polyester of piperidine ethanol and succinic acid Bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate Tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3 , 4-butanetetracarboxylate 1,1 ′-(1,2-ethanediyl) bis (3,3,3
5,5-Tetramethylpiperazinone) 1,2,2,6,6-pentamethyl-4-piperidyl /
Examples thereof include tridecyl (mixed) -1,2,3,4-butane tetracarboxylate, and the like.
Methyl-2- (2,2,6,6-tetramethyl-4-piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide (trade name Sumisorb TM-061, Sumitomo Chemical Co., Ltd.) is preferably used.

Further, the resin composition having photochromic performance of the present invention may be used in combination with an ultraviolet absorber for the purpose of further improving light resistance. As a UV absorber preferably used, for example, 2-hydroxy-4-benzyloxybenzophenone (trade name Sumisorb # 130,
Sumitomo Chemical Co., Ltd.) can be mentioned. The transparent resin targeted by the present invention has a visible light transmittance of 6 at 550 nm when containing a photochromic compound.
Those holding a value of 0% or more are preferably used. Examples of such transparent resin include various polyamide resins, polycarbonate resins, polyvinyl chloride resins, ethylene-vinyl alcohol copolymers, polystyrene resins,
Various acrylic resins represented by polymethylmethacrylate resins, acrylonitrile-styrene resins, polyethylene terephthalate resins, 4-methylpentene resins and the like can be mentioned. Also, for example, crystalline vinylidene fluoride resin, vinyl fluoride resin, polyethylene, polypropylene, ethylene-tetrafluoroethylene resin,
Propylline-tetrafluoroethylene resin, polyphenylene oxide resin, polyvinyl alcohol resin and the like can also be used. Among them, polymethyl methacrylate is particularly preferably used.

The blending ratio of the transparent resin and the spironaphthoxazine compound can be changed depending on the application, but normally, the spironaphthoxazine compound is the resin 100.
0.01 to 100 parts by weight, preferably 0.1 to 5 parts by weight
0 parts by weight are used. Hindered amine compounds are
It is used in the range of 0.1 to 150% by weight, preferably 3 to 50% by weight, based on the spironaphthoxazine-based photochromic compound.

The resin composition of the present invention can be prepared by the usual compounding method,
For example, a method in which a photochromic compound, a light stabilizer and a polymerization catalyst are dissolved in a partial polymer of a medium resin and then heated in a mold to polymerize and mold, a transparent resin, a mixture of the photochromic compound and the light stabilizer is rolled or a mixer. After being kneaded by a method such as kneading, press molding, medium resin, photochromic compound and light stabilizer are mixed and granulated, then sheeting molded by an extrusion molding machine, mixed granulation, injection molding by an injection molding machine It can be obtained by a method, or by dissolving or dispersing the medium resin, the photochromic compound and the light stabilizer using a suitable organic solvent, and then casting and forming into a sheet. INDUSTRIAL APPLICABILITY The resin composition of the present invention is not only used as a sunscreen material for windows of buildings, automobiles, trains, airplanes, instrument panels, showcases, spectacle lenses, etc., but also for display materials, photometers, optical filters. It can be widely used as a material for decoration.

[0009]

INDUSTRIAL APPLICABILITY The photochromic compound-containing resin composition of the present invention can increase the light resistance without causing the problems of the conventional photochromic composition, such as the reduction of the coloring sensitivity and the returning speed.

[0010]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited thereto.

Example 1 1 kg of a partial polymer of methyl methacrylate (polymerization rate: 2
5%), 1,3-dimethyl-3-piperidyl spiro [indolino-2,3'-naphtho [2,1-b] (1,
4) -Oxazine], and Sumisorb TM-061
0.4 g and 0.8 g of 2,2'-azobis (2,4-dimethylvaleronitrile) were mixed and dissolved, and then degassed. This mixture is poured into a mold made of a glass plate which is set in advance so that the thickness of the cast polymer plate is 3 mm.
A cast polymer plate was obtained by heating in warm water of ℃ for 2 hours and further in an oven of 110 ℃ for 2 hours. Example 2 A cast polymer plate was obtained in the same manner as in Example 1 except that 1 g of Smithsorb # 130 was further added. Comparative Example 1 A cast polymer plate was obtained in the same manner as in Example 1 except that Sumisorb TM-061 was not added. Comparative Example 2 In Example 1, as the light stabilizer, the following formula (III) A cast polymer plate was obtained in the same manner as in Example 1 except that 0.4 g of 2- (2'-hydroxy-5'-methylphenyl) benzotriazole was used. Example 3 10 kg of acrylic resin (trade name: Sumipex B M
H, Sumitomo Chemical Co., Ltd.), 1,3,3-trimethylspiro [indolino-2,3'-naphtho (2,1-b)
14 g of (1,4) -oxazine], 10 g of 1,3-dimethyl-3-piperidyl spiro [indolino-2,3′-naphtho (2,1-b) (1,4) -oxazine],
4 g of Sumisorb TM-061, and Sumisorb # 1
10g of 30 was mixed. This mixture was granulated by an extruder adjusted to 230 ° C., and further an injection molding machine adjusted to 220 ° C. was used to form an injection molded plate having a thickness of 3 mm. Comparative Example 3 Instead of using 4 g of Smithsorb TM-061 and 10 g of Smithsorb # 130 in Example 3, 2- (2'-
An injection-molded plate was obtained in the same manner as in Example 3 except that 2 g of hydroxy-5′-methylphenyl) benzotriazole and 5 g of Sumisorb # 130 were used. The following experiments were conducted on the cast polymer plate and the injection-molded plate obtained in the above Examples and Comparative Examples, and the results shown in Table 1 were obtained. Mercury lamp (100W) for cast polymer plate and injection molded plate
The sample was irradiated with light at a distance of 15 cm to evaluate the color development performance. In Table 1, the chromaticity refers to the degree of difference in chromaticity of the sample plate before and after light irradiation, and is a gray scale for contamination (JIS
L-0807) and is represented by 1 to 5 levels. 1 means the highest degree of color development. The cast polymer plate and the injection molded plate were put into a sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd.) to carry out a weather resistance accelerated test. The above experimental results show that the photochromic material of the present invention is
It shows that it has an excellent dimming effect, and that it is significantly superior in light resistance to conventional photochromic materials.

[0012]

Claims (3)

[Claims] 1. A resin composition having photochromic performance, characterized in that a transparent resin contains a spironaphthoxoxazine compound represented by the following general formula (I) and a hindered amine light stabilizer. [In the formula, R ₁ represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, — (CH ₂ ) n —COOH,
_{- (CH 2) n -CN,} - (CH 2) n -COOR (R
Represents an alkyl group having 1 to 6 carbon atoms, and n is an integer of 1 to 4). R ₂ is an alkyl group having 1 to 6 carbon atoms, — (C
_{H 2) n -COOH, - (} CH 2) n -CN, - (CH
₂ ) n-COOR (R is an alkyl group having 1 to 6 carbon atoms, n
Is an integer of 1 to 4). R ₃ and R ₄ represent the same or different alkyl groups having 1 to 6 carbon atoms or piperidyl groups. ] 2. A hindered amine compound represented by the following formula (II):
2-methyl-2- (2,2,6,6-tetramethyl-4-piperidyl) amino-N- (2,2,6, represented by
The resin composition according to claim 1, which is 6-tetramethyl-4-piperidyl) propionamide. 3. The resin composition according to claim 1, wherein the transparent resin is a polymethylmethacrylate resin.