JPH0280490A - Highly heat-resistant photochromic material - Google Patents

Abstract

PURPOSE:To obtain the title material excellent in light fatigue resistance, high response, and color density by using a specified spiroindolinonaphthoxazine derivative. CONSTITUTION:This material comprises a spiroindolinonaphthoxazine derivative of formula I, wherein A is an arylenedicarbonyl group of, e.g., formula V or an arylene group of, e.g., formula VI; R is a group of any one of formulas II-IV; S1-4 and S'2 are groups known as the substituents of a photochromic spiroindolinonaphthoxazine compound and desirably selected from a halogen atom, a (halogenated) lower alkyl, a lower alkoxyl, a nitro and a cyano.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention provides a novel photochromic material useful as a photochromic material for optical equipment, a photochromic material for printing, a photochromic material for recording materials, a photochromic material for clothing, ornaments, etc. This invention relates to a highly heat-resistant photochromic material made of a compound. Specifically, the present invention relates to a spironaphthoxazine compound derivative useful as the material with improved heat resistance.

Typical literature on conventional photochromic compounds includes Wiley Interscience (New York), 197
There is a book entitled "Photochromism" published in 1999, and this specification describes this document as a known basic technology.

In particular, the literature on photochromic spironaphthoxazine compounds and various substituted derivatives thereof include Japanese Patent Publication No. 45-28892, Japanese Patent Publication No. 49-48631, Japanese Patent Application Publication No. 48-23787, Japanese Patent Application Publication No. 55-36284,
JP-A-61-53288, JP-A-61-138686
No. 61-263982, etc. are known.

Problems to be solved Conventional photochromic spironaphthoxazine compounds are practical photochromic materials, but
Further improvements are desired in some respects, such as light fatigue resistance, high responsiveness, heat resistance, color density, and especially heat resistance. The main object of the present invention is to provide a compound which has practically satisfactory properties other than the above-mentioned heat resistance, and which is particularly excellent in high-temperature heat resistance.

Means for Solving the Problems The present inventor has prepared two molecules of the spiroindolinonaphthoxazine compound described in the prior art section at the 9'-, 8'-, or 5'-position of the naphthoxalane ring. The above object has been achieved by a novel compound having a structure in which an ether bond is formed through an arylene group or an ester bond is formed through an arylene dicarbonyl group.

Therefore, according to the present invention, the following formula % [where A is an arylene group or an arylene carbonyl group: and s, s, s', s3 and S are hydrogen atoms or a monovalent substituent known as a substituent of a known 7-otoclomibuclic spironaphthoxazine compound, such as hydrogen, a halogen atom, a lower alkyl group (such as methyl), a lower alkoxy group, a nitro group, a cyano group, or a halogen lower alkyl groups (such as trifluoromethyl), etc. ] A photochromic material comprising a compound represented by the following is provided.

From the viewpoint of raw materials and synthesis, typical examples of the arylene carbonyl group mentioned above include the above A
Examples of the arylene group include the following.

The photochromic compound having the structure R-0-A-0-R of the present invention is, for example, the compounds R-OH rylene)- and -X
or X (arylene) - perform a de-HX reaction with the compound of X: or R or H
It can be produced by subjecting O-(arylene)-○H to a de-HX reaction. Here, X represents halogen, usually C
Q or Br. R and A are as defined above.

Specific example - 34.9 g of 1,3,3-)dimethyl-9゛-hydroxyspiroindolinonaphthoxazine (hereinafter abbreviated as 9゛HNO) and 10 g of terephthalic acid dichloride were mixed with 200 g of tetrahydrofuran (THF). - dissolved in
Triethylamine 8ai2 was added dropwise and reacted for 1.5 hours at room temperature with stirring. After the reaction, THF was distilled off and recrystallized and decolorized with benzene to obtain 40 grams of yellowish white crystals. The melting point was 266-267°C. The compound of the present invention had excellent high-temperature heat resistance as evidenced by its high melting point, and was also satisfactory in blue color density, light fatigue resistance, and response time. The obtained compound was identified by nuclear magnetic resonance (N!vlR) as follows: In the above formula, 81 is a methyl group, S, S, and S are hydrogen atoms, and A is a terephthalic group. It was done.

9'-, the raw material of Example 1, synthesized by a known method
The melting point of HNo was 214-215°C. Therefore,
It has been found that by bonding two molecules of a conventional spironaphthoxazine compound via an arylene compound, the melting point, which is a measure of heat resistance, increases by a large amount (for example, about 50° C.).

In addition, those skilled in the art can easily select the reaction solvent, reaction temperature and time, equipment, other conditions, etc. in the above synthesis step. As a purification method at each manufacturing step, recrystallization using a solvent, column chromatography using a silica column, treatment with activated carbon, etc. can be employed.

As known in the literature, the photochromic compound of the present invention is as follows:
Transparent resins, such as diethylene glycol bisallyl carbonate polymer, poly(meth)acrylate and its copolymers, cellulose resins, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyester resins, polycarbonate, polystyrene and its copolymers, It is preferably used in combination with epoxy resins, di(meth)acrylate polymers of (halogenated) bisphenol A and their copolymers, nylon resins, polyurethanes, and the like. The blended resins can be used as optical elements that change color due to light. Suitable examples of optical elements include sunglasses, skiing or swimming goggles, protective glasses lenses, curtains, clothes, toys, and the like. As a method for blending the photochromic compound of the present invention into resins, various methods such as dyeing, casting, and coating with a blended polymer solution can be applied. The blending amount is generally about 0.01 to 5% by weight.

Effects and Effects According to the present invention, two molecules of a photochromic spironaphthoxazine compound can be combined at 9° of the naphthoxazine ring.
Compounds are provided that are bonded via an arylene group or an arylene dicarbonyl group at the 8° or 5° position. Due to its structure, this new compound has significantly improved high-temperature heat resistance without impairing the photochromic properties of the compound as a raw material.

Patent applicant: Nagase Sangyo Co., Ltd. (1 other person)

Claims (2)

[Claims] (1) General formula R-O-A-O-R [where A is a group selected from the group consisting of arylene group and arylene dicarbonyl group; and R is ▲a mathematical formula, a chemical formula, a table, etc.▼ , ▲Mathematical formula, chemical formula,
There are tables, etc. ▼ and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ A group selected from the group consisting of the substituent S_1
, S_2, S'_2, S_3 and S_4 are known substituents of photochromic spiroindolinonaphthoxazine compounds. ] A highly heat-resistant photochromic material comprising a spiroindolinonaphthoxazine compound derivative represented by the following. (2) Substituents S_1, S_2, S'_2, S_3 and S_4 are hydrogen atoms, halogen atoms, lower alkyl groups,
The photochromic material according to item 1 above, each selected from the group consisting of a lower alkoxy group, a nitro group, a cyano group, and a halogenated lower alkyl group.