SU759559A1 - Photochrome composition - Google Patents

Description

The invention relates to photochromic materials based on polymeric binders from the class of comb-shaped polymers and photochromic spiropyran, 5 new indoline series. The proposed photochromic materials can be used in single-color and multi-color optical recording and information processing systems, in duplicating equipment, microfilming, etc.

Known photochromic composition, including (co) polyalkylacrylate - polylauryl methacrylates and photo. the chromic compound is 1 ', 3', 3 * -tri- ⁵ methyl-6-nitro-8-methoxyspiro (2H-1-benzopyran -2,2-indoline) (1].

This composition has quite 20 high lighting characteristics.

At the same time, materials based on homo- and copolymers of lauryl methacrylate are characterized by considerable tackiness and, therefore, for their practical use, an additional polymer coating must be applied to the surface of the photosensitive layer, which significantly reduces

2

complicates the process of obtaining such materials. Also _? These materials have a limited spectral range of photoinduced absorption with a maximum at 570 - 600 nm, which corresponds to the blue color of the compositions.

The low manufacturability and narrow range of photoinduced absorption of polylauryl methacrylates based compositions hinders their use in single-color and multi-color data recording and processing systems.

The purpose of the invention is to reduce the stickiness and the expansion of the photoinduced absorption.

This goal is achieved by the fact that a composition including (co) polyalkyl methacrylates and a photochromic compound, as (co) polyalkyl methacrylates, contains polyalkyl methacrylates with the number of carbon atoms in the alkyl residue ^— η * = “6, 8, 10, or copolymers of alkyl methacrylates with methyl methacrylate ( MMA), and as a photo759559

lame compounds - indolinospiropyran formula

2?

1 * -hexadecyl - 3 ⁽ , 3 ^/ -dimethyl-8-bromo-6-nitrospiro (2n-1-benzopyran-2,2'indoline) (spiropyran IV). Yield 35%. Mp. 70 - 72 ° C.

Calculated,%: C 66.75, H 7.75, 4.58, Br 13.06.

N0

Sam _g 0 ₅ Vg

ten

where is hydrogen, K is methyl or butiroyloxyethyl; K, - bromine, B - octyl or hexadecyl

with the following ratios of components, masses,%: ........ , ·

Polyalkyl methacrylates with the number of carbon atoms in the alkyl residue η "6,8,10 or their copolymers with methyl methacrylate 90 - 99,

Photochromic compound 1-10.

The above composition is distinguished by the fact that to obtain a pink photoinduced coloration of the com position as a polymer bond. it contains polyhexylmeta-. krilat (PMA-b), or copolymers geksilmetakrilatas MMA, and blue to obtain photoinduced color in kachestvepolimernogo binder it comprises homo- or copolymers of octyl _r - Or decyl methacrylate.

The above indolinospiropyrans 30 with the substituents K, are hydrogen, K methyl or isobutyryloxyethyl (spiropyrans I and II, respectively) and bromine, K is octyl or hexadecyl (spiropyrans III and IV) synthesized by condensation of the corresponding methylene bases and salicylic aldehydes.

Spiropnran HI and IV were synthesized for the first time by the following method. 40

A solution of 0.75 mmol of 1-alkyl-3,3-dimethyl-2 methylenindoline and 0.90 mmol of 3-bromo-5-nitrosalicylic aldehyde in 30 ml of ethanol is boiled for 5 hours and left overnight at 0-5 ° C. The precipitate formed is filtered and crystallized three times from ethanol.

1'-octyl-3 ^ 3'-dimethyl-8-brOm-6-nitrospiro (2H - benzopyran-2,2'-indoline (spiropyran 1II). Exit 47%. So pl. 131-132 ⁱⁿ C.

Calculated,%: C 62.53, H 6.26,

K 5.61, Br 15.99.

^With TH> ^N 5? * 2 ^About J & ^T '

Found,%: C 62.41, H 6.39,

N 5.83, Br 16.15.

15

20

25

35

45

Found,%: C 66.43, H 7.70,

N 4.69, Br 12.82.

Photo-induced by UV light color of indolinospiropyrans III and IV in solution in toluene is blue, and in ethanol it is cherry-red.

Polymeric photochromic materials are prepared in the form of films by pouring a solution of a polymer and spiropyran in toluene onto a glass, polyethylene terephthalate or triacetate substrate using the specified ratio of polymer-pyropyrane components and polymer concentration · c. a solution of 6 wt.%.

’Pry'm * e'r'1. Cooking one. color photochromic material.

To a solution of 0.964 g of PMA-b in 11 ml of toluene, 0.036 g of indo-Linospiropyran II is added and the mixture is mixed to completely dissolve the indole-pyropyran. ...: ·.. · ···; · ..

Examples 2 - 11. Samples of materials based on indolinospiropirayov I, III, IV, as well as 1 ', 3'

350

55

-trimethyl-b-nitro-8-methoxy-spiro- (2H-1-benopyran-2,2'-indoline) (V) is prepared as in Example 1.

The copolymers of alkyl methacrylates (MA-η) with MMA, used to prepare photochromic films, are obtained by radical polymerization of the corresponding monomers.

Preparation of copolymer MA-8 with Ϊ01.

The copolymerization of MA-8 (3.5 ml,

18 mmol) with MMA (1 ML, 9.5 mmol) In the presence of 0.001 g of azobisisobutyronitrile in benzene (8 ml) is carried out in argon atmosphere at b ° s for 30 hours. The copolymer is planted with methanol. 75% yield. Characteristic viscosity (η) - 1.2 dl / g (25 ° C, chloroform). ..... ··· '

I The table shows the photochromic characteristics of the composite compositions, including some indolinospiropyrans and polymeric binders.

Example, one" Composition, mass, ratio,% Film thickness, MKM nm 5, „J / cm tag, min YAL * WITH . g> - ⁴ five 6 R eight

3.0

0.02

4.2

2.6

2.5

PMA-6 + 1I (99/1)

60

(550)

0.04

(550)

1.9

0.025 3.5

five

759559

6

Table continuation

four ² 1 but. four 1 l 6 7 eight 3 PMA-6 + 11 (90/10) 20 0.15 3.9 0.02 4.8 2.8 four PMA-8 + 11 (96.8 / 3.2) 40 (550) 0.08 2.4 0.02 2.5 18 five PMA-10 + 11 (97.2 / 2.8) 60 (600) 0.04 2.0 0.02 5.8 ' ^ 40 6 Copolymer MA-6 and MMA (75/25 mol.%) + 11 (97/3) 40 (600) 0.07 3.5 - 0.02 3.5 <0.2 7 Copolymer MA-8 and MMA (65/35 mol.%) + 11 (96/4) 60 (550) 0.05 3.6 0.02 3.5 <0.2 eight PMA-6 + 111 (97/3) 20 (600) 0.05 2.8 0.05 3.3 2.6 9 PMA-8 + 1I I (97/3) AO (555) 0.09 3.8 0.02 5.3 18 ten PMA-6 + U (97/3) 60 (595) 0.20 2.6 0.02 /*15 2.6 eleven ΠΜΑ-12 + ν (97/3) 60 (570) 0.08 2.8 0.02 12 > 50 1-1 · ιγ 7 (580)

Note. The photo stability of photochromic films is about 150 "staining-bleaching" cycles. The photochromic and technological characteristics of materials based on spiropyrans ί and IV are close to those of films with spiropyrans II and III, respectively.

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The data presented in the table indicate a rather high processability of films prepared on the basis of spiropyrans I -1V and the proposed polymer binders. .. The value characterizing the stickiness ^{40 * * 43 of the} proposed compositions is (and <4 G) g for homopolymers and (and <

0.5 g for all copolymers studied, and a known composition based on .θ

polylauryl methacrylate (PMA-12) and ³

spiropyran V (example 11) - u> 50 g. At the same time, the use of the proposed comb-shaped polymers does not change the basic photochemical parameters of the proposed ones. ” compositions and allows to obtain materials with similar lighting characteristics. The photosensitivity (5) of photochromic materials is 0.02-0.5 J / cm ² , the time £ 0 of storing information in projected light (¢ 1/2) is 2.5–5.8 min, photostability is about 150 cycles "staining - discoloration ", the initial optical density of the color (0 _o ) - 0 * 04 - 0.15, and the maximum attainable optical density (Omsk) - 1.9 - 3.9.

The photoinduced coloration of materials depending on the optical absorption maximum of the colored fort (> me "b is determined in comb-shaped polymers with an alkyl substituent length. In polymeric binders made of PMA-b 'or MA-6 copolymers with MMA, the color is pink (L * ax“ ⁵ ^ 0 nm ), and in the homo-or copolymers MA-8 and MA 10 - blue 600 'nm). The magnitude of the spectrum shift by the polymers hexyl methacrylate depends on the nature of the spiropyran. Thus, for the known spiropyran V, this value is only 10 nm (see table, example 10), while for the spiropyrans proposed by the authors, the shift reaches ~ 50 nm.

This property of comb-shaped polymers to change the color of the compositions, while maintaining their photochemical parameters almost constant, allows to obtain a two-color material.

759559

eight

terial using the same indoline spiropyran.

Example 12. Preparation of two-color photochromic material. A 9% solution of copolymer MA-8 and MMA (80-20 mol.%) In toluene, containing spiropyran II in an amount of 5 wt.% By weight of the main components, is applied to one of the sides of the glass plate. A photochromic film is prepared in the same way as in Example 1. After that, a film on the other side of the plate is prepared in the same way, starting from the 8% aqueous solution of copolymer MA-6 and MMA (75:

25 mol.%) In toluene and spiropyran II with a content of components 95:

5 wt.%. The film thickness is ~ 70 microns.

The resulting material can be used for recording and subsequent reading of two different images, which are produced simultaneously on both photosensitive sides of the plate. The color of the image from the side of the film from the copolymer MA-6 pink = 550 nm),

and from the side of the copolymer ΜΑ-8-blue (* max ^{= 6} θθ nm). This difference in color is sufficient for the visual separation of information while reading it at the same time.

Activating light, acting on one of the light-sensitive sides of the material, does not affect the opposite. '

The two-color photochromic material has high lighting characteristics: the photosensitivity is 0.02 J / cm ^g , the storage time of information in projected light is 3.5 minutes, the photostability is about 150 cycles of "staining discoloration".

Thus, the data presented for photochromic materials based on comb-shaped polymer binders indicate high processability of the compositions (no stickiness) without deterioration of their basic lighting characteristics, which is an important advantage of comb-shaped polymers.

A weak change in the photo-technical parameters of materials depending on the length of the alkyl substituent in _ comb-like polymers, but a strong hypochromic shift with n = 6,

is another very valuable advantage of comb-shaped polymer binders.

These properties of comb-shaped polymers make it possible to obtain new photochromic materials with high lighting characteristics that differ in photo-induced OKVNIIPI. Order 5979/10

Branch PPP ¹ 'Patent' *,

suitable for use in single-color and multi-color information recording and processing systems.

Claims (3)

Claim 1. A photochromic composition comprising (co) polyalkyl methacrylates and . “Photochromic compound, which is based on the fact that, in order to reduce the stickiness and expand the photo-induced absorption region of the composition, it contains (co) polyalkyl methacrylates as polyalkyl15 methacrylates with the number of carbon atoms in the alkyl residue η = 6.8,10 or copolymers of the indicated alkyl methacrylates with methyl methacrylate, and as a photochromic compound, in20 are the di-spiropyrans of the formula K is methyl or butyryloxyethyl, - bromine, K - octyl or hexadecyl, component with the following ratio tov, mass: Polyalkyl methacrylates with the number of carbon atoms in the alkyl residue, n = 6.8.10 40, or their copolymers with methyl methacrylate. Photochromic compound 45 2. Composition according to π. one, I drink tea with it. what 90-99 1-10 about tl and with a view to obtain a pink photo-induced color of the composition; as a polymeric binder, it contains polyhexyl methacrylate or copolymers of hexyl methacrylate with methyl methacrylate. 3. Composition pop. 1, that is, so that in order to obtain a blue photoinduced 55 color composition, as a polymer binder, it contains homo - or copolymers of octyl - or decylmethacrylate.