JPS6162507A - Polymer - Google Patents

Abstract

PURPOSE:To provide a photochromic film-forming polymer capable of reversibly fading and developing the color at a high speed, and having high durability, by bonding a dithizone metal complex monomer with a polymerization unit consisting of a monofunctional unsaturated monomer copolymerizable with said dithizone metal complex. CONSTITUTION:The objective polymer composed of a polymerization unit of a dithizone metal complex of formula I (R is H, halogen other than F, 1-5C alkoxy, 1-10C alkyl or haloalkyl; M is metal such as Pd, Ag, Hg, Zn, Cd, Pb, Pt, Bi, etc.; n is atomic valence of M) or formula II and bonded with a polymerization unit derived from the monomer B copolymerizable with the dithizone metal complex, can be prepared by the copolymerization of (A) a dithizone metal complex having one or more ethylenic unsaturated bonds and (b) a monofunctional unsaturated monomer copolymerizable with the component A (e.g. ethyl acrylate).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides that a dithizone metal complex represented by the general formula (where M is n-valent gold) that exhibits excellent color fading and color development has cis-trans isomerism as shown in the following formula. It exhibits photochromism through conversion and tautomerism.

(In the formula, M is an n-valent metal) Such a dithizone metal complex has a degree of freedom for cis-trans membering 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 gold B4#1 substance in a nonpolar solvent is different from that of other 7
It cannot be said that it is superior to the otochroic compounds spiropyrans and viologens, and the durability of reversible changes against ultraviolet rays is poor. It is far superior in terms of durability and reversible change. 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. As described above, the dithizone metal complex has important elements as a 7-otochroic compound in a nonpolar solvent, and has attracted attention from an early stage, and attempts have been made to apply it in a solid matrix such as a polymer.

However, since the dithizone metal complex exhibits 7 otochroic properties due to cis-tran(M) conversion and tautomerism, this degree of freedom is lost when it is simply dispersed in a solid matrix such as a polymeric polymer (IJ), resulting in color development and The reversible speed of fading becomes extremely slow, and the sensitivity to light irradiation becomes dull.

As a result of extensive research in order to improve the 7 otochromic properties of the dithizone metal complex in the above-mentioned polymer matrix, the present inventor discovered an unsaturated monomer copolymerizable with the dithizone gold scrap complex having a vinyl group or a divinyl group. The inventors have discovered that a copolymer with dithizone metal complex increases the degree of freedom of the dithizone metal complex in the polymer matrix and is suitable for the purpose.Based on this knowledge, the present invention has been completed.

That is, the present invention provides a structure in which the heavy content unit of the dithizone metal complex represented by the following general formula (1) or (U) and the polymerized unit derived from the functional unsaturated monomer copolymerizable with the dithizone metal scrap complex are It is a polymer formed by bonding.

(However, in the above formulas [1) and (n), R is a hydrogen atom, a halodane cryocarbon excluding fluorine, an alkoxy group having a/~5 carbon atoms, an alkyl group or a haloalkyl group having a/~10 carbon atoms. where M is an n-valent metal. ) The polymerized units of the dithizone metal complex are generally preferably contained in a proportion of 0.00 to 70% by weight.

In addition, in the general formula represented by (1) or (II) above, M can be any n-valent metal without any particular limitation, but a typical one exhibiting 7-otochromatic performance is one that exhibits the photochromic performance described above. Known metals such as Pd% AgxHgb Z
n%Cd, Pb, Pt, Bi etc., especially Hg
.

Pd, Zn%Ag is preferably used. Furthermore, the general formula (R in 11 is a hydrogen atom: a chlorine atom,
Bromine atom, iodine atom halodane atom: methoxy group, etowoxy group, propoxy group, butoxy group, pentoxy group carbon atom number/~5 alkoxy group: methyl group, ethyl group,
Alkyl groups with a to 10 carbon atoms such as propyl, butyl, benzyl, hexyl, octyl, etc.: 7 or all of the hydrogen atoms are substituted with chlorine, bromine, iodine or fluorine atoms. The above-mentioned alkyl groups are preferably used.

The metal dithizone is generally a colored crystalline solid at room temperature and pressure, and some metal complexes exhibit photochromism even in their crystalline state. The bath liquid shown in ## shows photochromism when irradiated with visible light.In addition, by changing R in the general formula (1) in this way, the color tone of this photochromic compound during color development and fading can be changed, that is, the absorption The wavelength can be shifted.

For example, when R in general formula (1) is an electron-donating group such as an alkoxy group or a halogen atom other than fluorine,
The absorption wavelength of this photochrome compound can be shifted to the longer wavelength side. These dithizone metal complexes are generally colored crystalline solids at room temperature and pressure.
Some metal complexes exhibit photochromism even in their crystalline state, and they are also highly soluble in organic solvents; for example, bath solutions dissolved in benzene, chloroform, etc. exhibit photochromism when irradiated with visible light. In addition, as described above, there is a tendency that the reversible speed of color development 2 and fading is generally a little slow.

'Efc The other polymerized units of the polymer of the present invention are derived from the l-functional unsaturated monomer copolymerizable with the dithizone metal complex. The monomers used to provide the polymerized units are not particularly limited and can be used. However, the following monomers are generally preferred.

(a) A monomer having the general formula C)-IX=CY-COR"T.

(However, in the formula, X is a hydrogen atom or...logon atom, and Y
is a hydrogen atom, a halogen atom or a methyl group, and R1 is an alkyl group having 1 to 10 carbon atoms or a phenyl group. ) (J General formula CH=CH2ge (wherein, X is a hydrogen atom or a halogen atom, and R2
]・Rogon atom, hydroxyl group or nitrile group. ) (c) A monomer represented by the general formula R' Co-CH=CH2.

(However, R3 is an alkyl monomer having up to 10 carbon atoms.

(However, heel R4 is CH2 spanning ○cH2, X is a hydrogen atom or a halodan atom, and n is 0 or /) By changing R in the blank formula (1) below, the coloring of this 7 otochrome compound Also, the color tone during fading can be changed, that is, the absorption wavelength can be shifted. For example, the general formula (
When a in 1) is an electron-donating group such as an alkoxy group or a hematopoietic atom other than fluorine, the absorption wavelength of this photochrome ε compound can be shifted to the longer wavelength side. Furthermore, if necessary, the other aromatic ring having a vinyl group in formula (1) is substituted with 70fiff1%, and tL< is 0.002 to 50! Ili more preferably 0.005
~aofxf&% The ratio of the amount of metal complex added is 0.
If the amount is less than 11%, the coloring density and contrast will be poor, and if it exceeds 70% by weight, the brightness of the dithizone metal in the polymer matrix will decrease.
Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, phenyl methacrylate, stearyl methacrylate, styrene, vinylpyrrolidone, vinyl acetate, vinyl butyrate, vinyl alcohol, #
Vinyl monide, vinylidene chloride, acrylonitrile, vinyl chloroacetate, methyl chloroacrylic powder, butyl chloroacrylate.

′ Butyl chloroacrylate, chloroacrylic acid-a@
a-butyl, cyclohexyl lysyl acrylate, allyl alcohol, fJi-modified asialyl allyl carbonate, allyl cinnamate, phenol diethyl allyl carbonate.

Metabromobenzyl allyl carbonate, alenyl allyl carbonate, etc., especially methyl acrylate, ethyl acrylate, ethyl methacrylate, vinyl acetate, and vinyl butyrate, which have a glass temperature near room temperature and can yield soft copolymers. It is preferable to use .

As the polymerization initiator, for example, a non-oxidizing initiator such as azobisinbutyronitrile (AXBN) is preferably used.

Figure 1 shows a typical manufacturing method of the 7-atomic polymer of the present invention.

First, dithizone gold [1] having a vinyl group or divinyl group represented by the above general formula (1) is substituted with an alcohol such as methanol, ethanol, isopropyl alcohol,
Chthones such as a7tone, methyl ethyl ketone, and cyclohexanone; ethers such as ethyl ether, dioxane, and tetrahydrofuran; esters such as ethyl acetate and n-butyl acetate; and benzene, toluene, and xylene.

Dissolves in various solvents such as acetonitrile, dimethylformamide, dimethyl sulfoxide, cufloformnat, and mixed solvents thereof. Next -, 1 copolymerizable with the upper ε solvent
Unsaturated sensuality! - and add 0.01 to 0.05 y of M as a polymerization initiator to this rain picker.
rxtts added for 40-8 Q hr at 50-70°C
.

Ampoule polymerization is carried out in a N2 sealed tube, and the resulting photochromic polymer is washed with distilled water before use.

A photochromic film is obtained by dissolving the photochromic polymer thus obtained in the above-mentioned solvent and forming a film on a glass slide. This photochromic film is normally colored yellow or orange, but when it is irradiated with visible light, it immediately develops a strong color and changes to a blue or purple color. Also, if you go into a dark place after this coloring, 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 occurs on the order of seconds and is repeated over 10,000 times.

The 7 advantages of the present invention having these characteristics can be used in a wide range of fields, for example, various recording and storage materials in place of silver salt photosensitive materials, copying materials, photoreceptors for printing, and recording materials for cathode ray tubes.

It can be used as various recording materials such as photosensitive materials for lasers and photosensitive materials for holography.

It is also possible to make a photochromic lens by sandwiching these 7 otochromic polymers into a film, for example in a plastic lens. In addition, using the 7-O odomic combination of the present invention, for example, optical filters,
It can also be used as a material for display materials, masking materials, photometers, decorations, etc. irt7;+・ The present invention will be described in more detail below with reference to Examples and Comparative Examples.

The method for measuring the 7 otochromic properties of the photochromic films used in Examples and Comparative Examples is as follows.

07 Method for measuring photochromic properties The film was irradiated with Toshiba's sunlight lamp DR-400/T' at a temperature of 25±1°C at a distance of 10 cm for 90 seconds to develop color, and the photochromic properties were measured. The photochromic properties were expressed as follows.

Maximum absorption wavelength (input wax): ■ Input m&X of this coloring film was determined using a spectrophotometer 22OA manufactured by Hitachi, Ltd.

ε (90 seconds); Absorbance corrected for the film thickness of this film under the above conditions for 90 seconds of light irradiation at the maximum absorption wavelength ε (0 seconds); At the maximum absorption wavelength during light irradiation,
Thickness-corrected absorbance half-wave period t2 of unirradiated film; After 90 seconds of light irradiation, the absorbance of this film is (ε(90). seconds).

7 otochromic characteristics were expressed at t+.

Example 1 1.0 (l and N, M-dimethylformamide (DM
? ) No from A in 4IILl, 02. Ampoule polymerization was carried out at 50°C for 72 hours in an M2 sealed tube using P as a polymerization initiator. The resulting dark red photochromic polymer was washed with distilled water. The yield was 99.8%. Therefore, the amount of dithizone mercury contained in the polymer matrix is 3.99 ■. Thereafter, this photochromic polymer was dissolved in chloroform 5d and (L2X
3.7cm) Return to slide Dallas, room temperature + 1 to
The cast film was dried for 2 hours in a vacuum at 100 mA, and the 7 otochromic properties of this film were measured.

The results are shown in Table 1.

Examples 2 to 4 Polymerization was carried out in the same manner as in Example 1 except that the amount of dithizone mercury having a vinyl group was changed to produce a photochromic film, and its photochromic properties were measured.

The results are shown in Table 1.

Examples 5 to 12 Polymerization was carried out in the same manner as in Example 1, except that another unsaturated polymer was used instead of ethyl acrylate, a photochromic film was prepared, and its photochromic properties were measured. The results are shown in Table 1.

Polyethyl acrylate 1. Ol and chlorophor Example 1
3 moles) to 1.3 moles of vinyl acetate. (1) was polymerized in the same manner as in Example 1 to produce a photochromic film, and its photochromic properties were measured. The results are shown in Table 2.

mol) with 10.9 styrene in the same manner as in the example.
A photochromic film was prepared and its photochromic properties were measured.

The results are shown in Table 2.

) Vinyl alcohol 1. ol tomi! Polymerize in the same manner as in Example 1 to make a photochromic film,
Its photochromic properties were measured. The results are shown in Table 2.

Example 16 Dithizone mercury with groups 0.82! i (comimole)
Vinylpyrrolidone 1.0! i was polymerized in the same manner as in Example 1 to produce a 7 Otochromic film, and its photochromic properties were measured. The results are shown in Table 2.

Practical M Example/7 Dithizone zinc having a vinyl group 7.0P<0
．． 001j mol) topenzolylcargenate/, O
P was polymerized in the same manner as in Example 1 to form a film, and its photochromic properties were measured. The results are shown in the second column.

Comparative Examples 7 to // Comparative experiments corresponding to Examples 73 to 17 were carried out in the same manner as for comparison fl/. The results are shown in Table 2VC
show.

Claims (1)

[Claims] (1) A polymer formed by bonding a polymerized unit of a dithizone metal complex represented by the following general formula (I) or (II) with a polymerized unit derived from a monofunctional unsaturated monomer copolymerizable with the dithizone metal complex. Combined. (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, in the above formulas (I) and (II), R is a hydrogen atom,
M is a halogen atom other than fluorine, an alkoxy group having 1 to 5 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or a haloalkyl group, and M is an n-valent metal. )(2) The polymer according to claim (1), which contains polymerized units of dithizone metal complex in a proportion of 0.001 to 70% by weight. 3) Metal (M) is Pd, Ag, Hg, Zn, Cd, Pb
, Pt and Bi.