JPS62106983A - Photochromic polymer and method for producing the same - Google Patents

Abstract

PURPOSE:To obtain the titled polymer which is excellent in respective rates of fading and color development and durability and suitable for use in optical filters and display materials, by introducing a dithizone metal complex into a polymer of chloromethylstyrene or the like through the Friedel-Crafts alkylation reaction. CONSTITUTION:A predetermined amt. of chloromethylstyrene and, if necessary, a monomer copolymerizable therewith (e.g., methyl acrylate) are dissolved in a solvent such as benzene and then polymerized by an ampoule polymerization in the presence of 0.01-0.05wt% polymerization initiator at 50-70 deg.C for 40-80hr in a nitrogen-sealed tube, thereby obtaining a (co)polymer (A) contg. chloromethylstyrene. The component A is dissolved in a solvent such as chloroform to prepare a soln. A dithizone metal complex of formula I (wherein R is H or a nuclear substituent; and M is a metal having a valence number of n) is added to the soln. in an amt. corresponding to the amt. of chloromethylstyrene contained in the component A, followed by the Friedel- Crafts alkylation reaction, thereby obtaining the titled (co)polymer contg. 0.001-70wt% polymer unit of formula II.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a novel polymer having photochromic properties with excellent reversible speed and durability of fading and color development.

The silicin metal complex represented by (1 μ and M is an n-valent metal) has a cis-trans j? −
It exhibits photochromism due to 1'l 11- and tautomerism.

(In the formula, M is an n-valent metal) Such a dithizone metal complex has a degree of freedom for cis-trans isomerization and tautomerism of the photochromism mechanism as described above in an organic solvent such as benzene or chloroform. The reversible speed of color development and fading is fast, on the order of seconds. The reversible speed of color development and fading of this dithizone metal complex in non-polar solvents is by no means superior to other photochromic compounds such as spiropyran and viologen, and the durability of reversible changes to ultraviolet light is poor. . However, if the ultraviolet rays are blocked, it is far superior to the photochromic compounds spiropyran and viologen in terms of durability and reversible changes.

For example, a spiropyran type shows only about 20 reversible changes, but a dithizone metal type shows a reversible change of more than 10,000 times when used in combination with an ultraviolet absorber.

In this way, the dithizone metal complex in a nonpolar solvent is
It has important elements as a photochromic compound, and
It has attracted much attention, and attempts have been made to apply it in solid matrices such as polymers.

(Problem to be solved by the invention) However, since the dithizone metal complex exhibits photochromic performance due to cis-trant isomerization and tautomerism, simply dispersing it in a solid matrix such as a polymer matrix does not allow for this freedom. As a result, the reversible speed of color development and fading becomes extremely slow, and the sensitivity to light irradiation becomes dull.

In the polymer obtained by copolymerizing a polymerizable dithizone metal complex represented by (IH, M is an n-valent metal) and a copolymerizable unsaturated monomer, polyvalent dithizone metals other than monovalent The vinyl group introduced into the complex acts as a crosslinking agent, and the degree of freedom of the dithizone metal complex in the polymer matrix is not fully exhibited.

(Means for Solving the Problem) As a result of intensive research to improve the photochromic properties of the dithizone metal complex in the above-mentioned polymer matrix, the present inventors have discovered that the present inventors have developed a method for improving the photochromic properties of the dithizone metal complex in the polymer matrix. A polymer (hereinafter referred to as
If it is a photochromic polymer), the degree of freedom of the dithizone metal complex in the polymer matrix increases, and we have found a scale that is suitable for the purpose, and based on this knowledge, we have made the present invention. .

That is, the present invention is a photochromic polymer having a polymerized unit represented by the following general formula.

-CH-CH2- (wherein, R is a hydrogen atom or a nuclear substituent,
(M is an n-valent metal) In the above general formula, an n-valent metal can be used as M without particular limitation, but representative examples of metals exhibiting photochromicity II include those exhibiting photochromicity 0 macroscopic. t Common% (I
c7) Metals such as Pd, Ag, Hg+ ZrxC
d, Pb, Pt, Bi, etc., especially Hg+Pdp7, n,
Ag is preferably used. Furthermore, as the nuclear substituent R in the above general formula, hydrogen atom; halogen atom of chlorine atom, bromine atom, iodine atom: carbon atom number of methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group 1 ~5 alkoxy groups; alkyl groups having 1 to 10 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, etc.; Alternatively, a fluorinated alkyl group consisting of the above-mentioned alkyl group completely substituted is preferably used.

By changing the nuclear substituent R, it is possible to change the color tone of the photochromic polymer during color development and fading, that is, to shift the absorption wavelength. For example, when R is an electron-donating group such as an alkoxy group or a halogen atom other than fluorine, the absorption wavelength of this photochromic polymer can be shifted to a longer wavelength of 11!11. Furthermore, depending on the requirements, these substituents can be introduced in combination.

The present invention contains 0.001 to 70% by weight, preferably 0.00% by weight of the dithizone metal complex represented by the above general formula.
2-50% by weight, more preferably 0.005-:(0
It is recommended that the proportion be contained in the copolymer at a proportion of 0.001% by weight, which results in poor color density and contrast. The degree of freedom of the dithizone metal is reduced and the reversible speed of color development and fading tends to be slow.

The photochromic polymer of the present invention is generally produced by adding a dithizone metal to the side chain of the chloromethylstyrene polymer by adding a Friedel-Crafts alkylation reaction to a polymer of chloromethylstyrene or a copolymer with a copolymerizable monomer. It can be produced by introducing a complex.

Examples of monomers copolymerizable with the above-mentioned chloromethylstyrene include methyl acrylate, ethyl acrylate,
Butyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate.

Phenyl methacrylate, stearyl methacrylate.

Styrene, vinylpyrrolidone, vinyl acetate, vinyl acetate, vinyl alcohol, vinyl chloride, vinylidene chloride, acrylonitrile, vinyl chloroacetate.

Methyl chloroacrylate, propyl chloroacrylate,
Butyl chloroacrylate, chloroacrylic acid-5ee-
These include butyl, cyclohexyl chloroacrylate, allyl alcohol, allyl chloride, benzyl allyl carbonate, allyl cinnamate, phenoxyethyl allyl carbonate, metabromobenzyl allyl carbonate, and phenyl allyl carbonate, which have a glass temperature near room temperature and are soft. Methyl acrylate, ethyl acrylate, ethyl methacrylate, from which copolymers can be obtained
Preferably, vinyl acetate, vinyl butyrate, etc. are used.

Further, the polymerization initiator is not particularly limited and any known one can be used, but preferably a non-oxidizing initiator such as azobisisobutyronitrile (A'1BN) is used.

A typical method for producing the photochromic polymer of the present invention is shown. First, the copolymerizable monomer shown above and chloromethylstyrene are dissolved in a solvent such as benzene, and a polymerization initiator is generally added in an amount of 0.01 to 0.05 weight percent based on both monomers.
Adding N2 at a temperature of 50-70°C for 40-80 hours.
Polymerize the ampoule in a sealed tube. At this time, the amount of chloromethylstyrene added to the copolymerization monomer is such that the polymerized unit of the dithizone metal complex bonded to the chloromethylene side chain is 0.0
It is adjusted to have a heavy electric charge of 0.01 to 70%.

The copolymer containing chloromethylstyrene thus obtained was mixed with chloroform, 1,2-dichloroethane, benzene, toluene, and acetonitrile.

A dithizone metal complex represented by the following general formula is dissolved in a solvent such as dimethyl sulfoxide and added in an amount matching the abundance ratio of chloromethylstyrene in the copolymer.
Perform a craft reaction.

In the above general formula, R is a hydrogen atom or a nuclear substituent as described above, and M is also a zero-valent metal as described above.

The Friedel-Crafts reaction in the production method of the present invention includes, for example, aluminum chloride and antimony chloride.

The reaction is generally carried out at a temperature of 20 to 80° C. using a known catalyst such as iron chloride, tellurium chloride, tin chloride, titanium chloride, bismuth chloride, zinc chloride or the like in an equimolar amount to the dithizone metal complex. After cooling, the product is then purified of impurities, concentrated in an evaporator, dissolved in a small amount of chloroform if necessary, poured into a large amount of methanol with vigorous stirring, and purified by reprecipitation.

(Effects of the Invention) The photochromic polymer thus obtained can be provided in any shape depending on the use. for example,
The above photochromic polymer is dissolved in a solvent again,
A photochromic film can be created by forming a film on a glass slide.

This photochromic film is normally colored yellow or orange, but when irradiated with visible light, it immediately develops a strong color and changes to a blue or purple color. Furthermore, if left in a dark place after color development, it will immediately return to its original yellow or orange state, and if only ultraviolet rays can be blocked, this reversible change in color development and fading will occur on the order of seconds, and will be repeated over 10,000 times. . The photochromic polymer of the present invention having these properties can be used in a wide range of fields, such as various recording and storage materials in place of silver salt photosensitive materials, copying materials, photoreceptors for printing, recording materials for II8 pole ray tubes, and photosensitive materials for lasers. It can be used as a variety of recording materials such as photosensitive materials for holography. Further, these photochromic polymers can be made into a film, for example, sandwiched in a plastic lens to form a photochromic lens. In addition, the photochromic polymer of the present invention can be used, for example, in optical filters.

Display materials, masking materials, light meters.

It can also be used as a material for decoration.

(Examples) Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples. The products in Examples and Comparative Examples were confirmed by infrared absorption spectra, and the method for measuring the photochromic properties of photochromic films obtained from the product polymers was as follows.

-Measurement method of photochromic properties: The film was irradiated with Toshiba's sunlight lamp DR-400/1' at a temperature of 25±C at a distance of Pi 10 cm for 90 seconds to develop color, and the photochromic properties were measured. The photochromic properties were expressed as follows.

Maximum absorption wavelength (λIIIax); ■λIIIax of this coloring film was determined using a spectrophotometer 220A manufactured by Hitachi, Ltd.

ε (90 seconds): Absorbance corrected for film thickness during 90 seconds of light irradiation of this film under the above conditions at the maximum absorption wavelength.

ε (0 sec); thickness-corrected absorption i of unirradiated film at the maximum absorption wavelength during light irradiation! Aa The half-life is the time required for the absorbance of the film to decrease to 1/2 of [ε (90 seconds) - ε (0 seconds) after irradiation with light for 90 seconds.

Example 1 A copolymer (M
mofJ of MA/CMS, abundance ratio; 5B/1
) and a dithizone mercury complex represented by the following formula were dissolved in 50 mM of chloroform, and 50 mQ of 1,2-dichloroethane was added. Add l of zinc chloride to this.

Add Omg (0,0073 mmou) and heat at 80℃ for 2 hours.
It was refluxed for 4 hours. After cooling, impurities were removed, the mixture was filled with an evaporator, dissolved in a small amount of chloroform, poured into a large amount of methanol with stirring, and the resulting precipitate was further precipitated for purification. The product yield was 0.21 g.

The photochromic polymer thus obtained was dissolved in chloroform, formed into a film on a 1.2 x 3.7 cm slide glass, and dried at room temperature in a vacuum of 1 torr for 2 hours to prepare a cast film.

Table 1 shows the results of measuring the photochromic properties of this film.

Examples 2 to 4 Films were produced in the same manner as in Example 1 except that the abundance ratio of the MMA-CMS copolymer was changed, and their photochromic properties were measured. The results are shown in Table-1.

Comparative Examples 1 to 3 In Examples 1 to 4, the above dithizone mercury was simply dissolved in the MMA-CMS copolymer to produce a cast film, without combining CMS and dithizone mercury by Friedel-Crabt reaction. . Table 1 shows the results of measuring the odochromic properties of this film.

Examples 5 to 2 The same procedures as in Example 2 were carried out except that other unsaturated monomers were used in place of methyl methacrylate. The results are shown in Table 1.

Comparative Example/l~6 All the same procedures as in Comparative Example 1 were carried out except that the 11-thickness copolymer was used instead of the MMA-CMS copolymer. The results are shown in Table-1.

Example 13 The same procedure as in Example 1 was carried out except that dithizone silver 0.084 mmoQ shown below was used instead of dithizone mercury, and the photochromic properties of the photochromic film produced were measured. The results are shown in Table-2.

Example 14 The same procedure as in Example 13 was carried out except that dithizone palladium represented by the following formula was used instead of dithizone silver. The results are shown in Table-2.

Example 15 The same procedure as in Example 13 was carried out except that dithizone zinc represented by the following formula was used instead of dithizone silver. The results are shown in Table-2.

Example 16 The same procedure as in Example 13 was carried out except that dithizone mercury represented by the following formula was used instead of dithizone silver. The results are shown in Table-2.

Example 17 The same procedure as in Example 13 was carried out except that dithizone mercury represented by the following formula was used instead of dithizone silver. The results are shown in Table-2.

Example 18 The same procedure as in Example 13 was carried out except that dithizone mercury represented by the following formula % was used instead of dithizone silver. The results are shown in Table-2.

Comparative Examples 7 to 12 Comparative experiments corresponding to Examples 13 to 18 were conducted in the same manner as Comparative Example 1. The results are shown in Table-2.

Claims (1)

[Claims] 1) A photochromic polymer having a polymerized unit represented by the following general formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, in the formula, R is a hydrogen atom or a nuclear substituent,
(M is an n-valent metal) 2) The photochromic polymer according to claim 1, which contains polymerized units in a proportion of 0.001 to 70% by weight. 3) The photochromic polymer according to claim 1, wherein the metal is Pd, Ag, Hg, Zn, Cd, PbPt or Bi. 4) A dithizone metal complex is introduced into the side chain of a chloromethylstyrene polymer or a copolymer with a copolymerizable monomer by a Friedel-Crafts alkylation reaction. A method for producing a photochromic polymer represented by the following general formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, in the formula, R is a hydrogen atom or a nuclear substituent,
M is n-valent metal)