JPS59227972A - Photochromic photosensitive material - Google Patents

Abstract

PURPOSE:To provide a photosensitive material comprising a layer of a macromolecular compd. contg. a specified comonomer unit, which shows good color development even after a long period of storage and is least dependent upon temp. CONSTITUTION:The photochromic photosensitive material comprises a layer of a macromolecular compd. contg. a comonomer unit of the formula (where R1 is 1-10C alkyl; R2 is 1-5C alkoxyl, 1-5C alkyl, halogen or cyano; R3 is halogen, 1-5C alkyl, nitro or cyano; R4 is a 1-5C divalent hydrocarbon group and R5 is H or methyl). The comonomer unit is contained in the compd. in an amt. of 3- 50mol%. When the amt. is less than 3mol%, sufficient color development is unobtainable while when it exceeds 50mol%, the macromolecular compd. is difficult to obtain.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a 7-otochromink photosensitive material, and particularly relates to a photochromink photosensitive material that has a high color preservation rate even after long-term storage and has a small temperature dependence. .

A rewritable image display material or optical recording material using a dispersed photochromic material in which a spiropyran compound is dispersed and dissolved in a binder such as a polymer compound is known. However, the most serious problem with such dispersed materials is the stability of their recording state. That is, colored spiropyran compounds can be stored even if they are protected from light.
Even if the recording medium is left for a long time, a decoloring reaction occurs due to thermal action, resulting in a decrease in the contrast of the recorded state. Various methods have been proposed to improve the reliability of this recording state. As one of the methods, an attempt has been made to increase the stability of the coloring state by bonding a spiropyran compound to the main chain of a polymer compound through a side chain. For example, the N or 8' position of the 1st position (for example, J, Ve
r Dangerous place.

G, Smets; J, Polym, Sci
,: Polym, Uhem, Ed, , 1225
11 (1974)) or the following weight formula (11)
5 of the thiazoline spiropyrans with the basic skeleton shown in
position or 8' position (e.g., G, Smets, Pur
e Appl.

Ohem, 30.1 (1972)), there is a method of bonding to the main chain of a molecular compound through an ester bond or the like. However, most of the photochromic substances obtained by such a method discolor at room temperature faster than the dispersion type materials, and even the photochromic substances, which are more stable than the dispersion type materials at room temperature, lose their color by several tens of minutes. It has been shown that the color density decreases by half within a certain period of time, and it cannot be said that the storage stability is sufficient. The reason for this low stability of the coloring state is that when spiropyran is bonded to the polymer main chain at each of the above positions, the effect of steric hindrance that suppresses the intramolecular rotation that occurs during the decolorization reaction of spiropyran is small. This is thought to be due to the

In light of the above, the present inventors conducted extensive research and found that spiropyran itself has a highly stable coloring state using benzothiazoline spiropyran, and by bonding it to the polymer main chain at the 6' position, the coloring state can be preserved. Highly stable Photok J
A photosensitive dye was obtained.

That is, one aspect of the present invention relates to a photochromic photosensitive material comprising a monomer unit represented by the following general formula (Ill) and a layer of a polymer compound that is combined as a copolymer component.

+C-(3H2+ -0 ■(4 (wherein, R1 is an alkyl group having 1 to 10 carbon atoms, R2 is an alkoxy group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a cyan group, R3 represents hydrogen or a halogen atom, an alkyl group having 1 to 5 carbon atoms, a nitro group, or a cyano group; 4 represents a divalent hydrocarbon group having 1 to 5 carbon atoms; and R5 represents a hydrogen atom or a methyl group. In the photosensitive material of the present invention, the amount of the monomer unit represented by the general formula (II) enriched in the polymer compound as a copolymerization component ranges from 6 to 50 mol, preferably from 5 to 20 mol. can do.

If the amount is less than 6 mol %, the photochromic ability will not be sufficient, and if it exceeds 50 mol %, it will be difficult to obtain a high molecular compound.

Other copolymerizable components of the polymer compound in the present invention include acrylic acid, methacrylic acid, acrylic ester, methacrylic ester, and styrene.

Monomers such as vinyl acetate and acrylonitrile can be mentioned. Furthermore, in addition to one unit of the monomer represented by the general formula (1), the polymer compound in the present invention contains two or more of the other copolymer components 7! - In this case, as the 14-fold copolymerization component, an acid component such as acrylic acid or methacrylic acid is preferably present in an amount of 5 or more moles based on the two or more copolymerization components.

The polymeric arsenic metals used in the present invention include methanol, ethanol, isopropyl alcohol, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, ethers such as ethyl ether, dioxane, and tetrahydrofuran, ethyl acetate, and n-butyl acetate. Esters such as a, further rc benzene, toluene, xylene, n-hexane, cyclohexane, acetonitrile,
Dissolves in various solvents such as dimethylformamide, dimethylsulfoxide, chloroform, and mixed solvents thereof. In order to use this polymer compound as a photochromic photosensitive material, this polymer compound is dissolved in the solvent,
It can be used by forming a film or by coating it on a support or by rolling it. As the support, polyethylene terephthalate,
Cellulose acetate, polycarbonate, regular paper,
There are baryta paper, glass, metal, etc.

The polymer compound in the present invention can be obtained by copolymerizing with the following general formula GV) polymerization component 11"""
C cut・R5 (m R+, R2 in the formula
b B5, R4 and R5 have the same meanings as above) The heptadmer represented by the general formula (1v) can be synthesized as follows.

Mass, aminothiophenol and chloroacetyl chloride according to the method of R. Guglielmetti et al.
elv.

Ohim, Acta, 55, 1782 (1972
2-chloromethyl-benzothiazoline (■) 7! : Synthesize and then follow the next Sugiem.

(1) 2-chloromethyl-benzothiazoline (■) is added to a solution of metallic sodium dissolved in PI OH (R and 4 have the same meanings as above).

(Vl) (ii), the obtained compound of formula (Vl) and compound R15
o-1ri=)TOHa (R+ Its, *'a E
(!: Same meaning) f) 1. Make a reaction.

(R2 has the same meaning as above) and the formula (Vil,
) is obtained.

O, R+40H (■) Taste) 7! : @ and reacted to obtain compound (IV)'.

OR4α( (Vlll) l(,5 This compound (IV)' is represented by the general formula (J),
This corresponds to the case where R3 is a hydrogen atom. For the compound of the general formula (■), in the above (11), a derivative of the following formula (■)' (wherein R3 has the same meaning 7i as before) is used in place of the compound of the formula (Vl). can be obtained by

The compounds of formulas (VI) and (■)' are new substances. Synthesis examples of these new substances are shown below.

(R12-H)-oxyethoxymethylbenzothiazole (in the above formula (Vl), R4 is -H2-ai-
i2-group): N 8 metallic sodium in 100 cc of ethylene glycol
．． Add 44.9 of 2-chloromethyl-benzothiazoline to the 00.9i dissolved solution. Temperature of reaction mixture %5
Raise it to 'oc, 2Ff? After reacting for 30 minutes, it is poured into water, extracted with chloroform, and then washed with water. Then, it is dried over anhydrous magnesium sulfate, the solvent is removed, and then purified by vacuum distillation. 25.6 g of 2-hydroxyethoxymethylbenzothiazole 7)E are obtained. Yield 51
%, boiling point 168-180C (2000m).

Compounds that are a nitro group and R4 or 10H20H2- group)
:2-hydroxyethoxymethylbenzothiazole (9
0,! i') Vc9 Sulfuric acid (92cc) f Ice-cooled L S7>S La Add, when the temperature drops to 2DC, concentrated sulfuric acid (
72cc) and fuming nitric acid (72cc),
Add so that the temperature does not exceed 3DC. After the addition is complete, the reaction mixture is poured into a large amount of water, and the resulting crystals are filtered. 2-Hydroxyethoxymethyl-5-nitrobenzothiazole67. ? get. Yield: 57%.

Rubenzene (a compound in which R3 is a chlorine atom and R4 is 10H2-0f (2-group) in the above formula (■)'): 2
-Hydroxyethoxymethyl-5-nitrobenzothiazole (,150I) was dissolved in ethanol (150 cc), tin (30,9) and concentrated hydrochloric acid (300 cc) were added, and the reaction was carried out at 300 ml for 6 hours. Neutralize with NaOH,
Extract with benzene to extract 2-hydroxyethoxymethyl-
Obtain 5-aminobenzothiazole 25, p (yield: 9
Section 4).

Concentrated hydrochloric acid (40 cc) was added to this 2-hydroxyethoxymethyl-5-aminobenzothiazole (2!M), and while cooling with ice, NaNO2 (a, 3 g) y-,
In addition, when the crystals dissolve, 0uO12 ('7e, &j
iii 679, Na069.71. P, NaH8
A concentrated hydrochloric acid solution containing 790 g of O5 and Na0f (synthesized from 5, 20, and !9) was added, and the mixture was reacted at 30 °C for 1.5 hours and at 600 °C for 60 minutes, and then extracted with chloroform to obtain 2-
Hydroxyethoxymethyl-5-chlorobenzothiazole is obtained.

The polymer compound of the present invention can be obtained by copolymerizing the hexamer of the general formula (1) with the other copolymer component by a conventional method. For example, if the other copolymer component is methacrylic In the case of acid (MAA) and/or methyl methacrylate (MMA), the copolymerization reaction can be carried out in a solvent such as dimethylformamide (DMF) in the presence of an initiator such as azobisisobutytetranitrile (ABIN).

The photosensitive material of the present invention is colorless or lightly colored in a normal state, but when irradiated with ultraviolet light, it becomes strongly colored, and the stability of this colored state is excellent, and the temperature dependence of this stability is small. The photosensitive material of the present invention having these characteristics 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 cathode thin tubes, laser Photosensitive materials for use, holography
It can be used as a variety of recording materials, such as photosensitive materials for commercial use and photosensitive materials for phototypesetting. Also, optical filters, display materials, masking materials, and light meters.

It can also be used as a material for decoration.

Note that the hue or tone of color development can be varied depending on the monomer unit of the general formula (III) and the type of coheavy metal component.

Next, the implementation of the present invention will be described in more detail.Example 2-hydroxyethoxymethylbenzothiazole (15,92,
u methyl p-toluenesulfonate (17, UO
,y) After sealing the tube, it was kept at 1υoC and reacted for 60 minutes, washed with acetone, recrystallized with an ethanol/acetone mixed solvent, and converted to %2-hydroxyethoxymethylbenzothiazole tosylate (m2o, 2oy). Obtained.

Yield: 67 Jl; melting point 1 iocO (At) of penzothiazole tosylate (12,0[,1,17) and 6-medoxy-5-nitroterityl aldehyde (6,20 Jl and piperidine (2,7[,1, P) is added to ethanol and refluxed for 60 minutes to obtain a precipitate.After cooling, it is recrystallized with a mixed solvent of ethanol/chloroform and 98C
g 6'-hydroxyethoxy-87-medoxy6-
Methyl-6'-nitrospiro (2f(-1-benzobilane-2,2'-benzothiazoline) (obtained BJ) spirobenzobilane benzothiazoline (6
, 60, 9) was dissolved in anhydrous benzene, triethylamine (2, 23!tri+ was added, and acrylic acid chloride (2, 23!) was dissolved in anhydrous benzene.
00, P) was added dropwise over 60 minutes. After the completion of this 1° reaction, the reaction mixture was stirred for 60 minutes, washed thoroughly with water, dried over anhydrous magnesium sulfate, and after removing soot, was recrystallized with a benzene/ether mixed medium. TABN
Identified M7.11.9.

Yield: 95%; melting point: 152U.

The results of the spectra of T A and E N M and their assignments were as follows.

'H-NMR δ3.04(3H,8): N-methyl group; δ3.76(
3H,S): Q-methyl group; δ6.70-7.45 (
5H, m) Niacrylic group; δ7.58-8,50 (
4H, m): Hydrogen at positions 4, 5.6 and 7; δ8.56 (d, J=2.5Hz IH):
Hydrogen at 7'position; δ6.8J1H,S): Hydrogen at 4/position;
δ8.64 (in, d, J=2.5Hz): Hydrogen at 5'position; (δ is TMS standard, S is singlet, d is doublet and m
indicates multiplet] IR: 1730, 1520, 1340 cm-1
UV, :λ engineering 341' m (e 284 υ 0) Synthesis of polymer compound (1) TAENM-MMA copolymer: T, IM (1
,00,9), MMA(7,[]0.9) and DMF(
-6CJcc) and stirred for 60 minutes at an external bath temperature of 60C while pulling the desired gas.
40 ip)> was added and reacted for 8.5 hours. After the reaction is complete, the reaction mixture is poured into methanol containing a small amount of 7-hydroquinone to precipitate the product. After filtering this precipitate, it was dissolved in acetone and poured into methanol to precipitate it. After repeating this reprecipitation operation six times, vacuum drying was performed at 80C for one day and night to obtain a copolymer of 3.811 (sample P-(2-MMA)). Yield: 48 mol; TAENM content: 2,4 mol.

In the same manner, two types of copolymer samples (P-(1-MMA)) and (P-(io-MMA)) with different T A E N M Shu Yujing were obtained.

(2) TAENM-MAA copolymer: TABNM (600m9),! rMAA (4,
29) MP (15cc) Ic was dissolved and reacted for 8 hours under the same conditions as in (1). The reaction mixture is then poured into ether containing a small amount of hydroquinone to precipitate the product. This precipitate was dissolved in methanol and poured into ether for precipitation. After repeating this reprecipitation operation twice, vacuum drying was performed for 2 days, and 3.
73. A copolymer of li+ was obtained (sample symbol P −(2−
MAA)). Yield near 8 cm; TAENM content = 1 factor above content.

Similarly, a copolymer with a TAENM content of 10.6 moles (sample symbol P-(10-MAA)) was obtained.

+3) TAENM-MMA-MAA copolymer = MA
A (1g), MMA (1,9) and TAENM (1,
3,9) Dissolve DMF in the same manner as in (1) above, react at 70C for 8 hours, and then filter the precipitated product into ether containing a small amount of hydroquinone in the reaction solution. Thereafter, it was dissolved in a methanol-acetone mixed solvent and poured into ether to precipitate it.

After repeating this reprecipitation operation 7i twice, vacuum drying was carried out for one day and night to obtain a copolymer of 2.29 (sample symbol P-
12-(MMA-MAA)). Yield: 67%; TAB
NM content: 12.0 molti; MMA content = 46.2
Molar fissure; ff1vi A A content: 41.2 moles.

Similarly, two types of copolymer samples with different compositions (P-(5-MMA-MAA)) and (P-(15,
-MMA-MAA)) was obtained.

The compositions and yields of the above copolymer samples are summarized in Table 1.

(The following is a blank space, continued on the next page.) 1) Calculated from the value of the molecular extinction coefficient of λmax (303 μm) in DMF.

2) NMR shows δ12.0 (TM8 standard) around 10
0 obtained from the integral value of the spectrum caused by OOH groups 5) 10O around δ4.0 (TMS standard) by NMR
It was determined from the integral value of the spectrum of OOH3.

Preparation of photochromic photosensitive material To evaluate photochromic properties, 1 part by weight of the copolymer sample was dissolved in 10 parts by weight of solvent, and this solution was coated on a quartz glass plate (vertical x horizontal x thickness = 60 mm) using a spinner coater.
x 5082 mm), and the rotational speed of the spinner coater was adjusted so that the film thickness when dried was about 1 μmVC. The solvent is acetone dichlorohexanone = 1
:1 mixed solvent was used.

However, in the case of a copolymer with a high 1MAA content, methanol or DMF was appropriately used as a solvent.

In this way, a sample of the photochromic photosensitive material of the present invention was obtained.

Regarding these samples, first, the storage stability in a dark place of 30 tll' in a color-developed state by ultraviolet light irradiation was measured as follows.

The conditions for ultraviolet light irradiation were as follows: A 500W ultra-high pressure mercury lamp (manufactured by Ushio Inc.) was used, and a glass filter (IRA-manufactured by Toshiba Corporation) was used.
258 and UV-D360), and selectively irradiated with an emission line around 660 nm. A Hitachi 620 model self-recording spectrophotometer was used to measure the absorbance of the colored sample.

The storage stability of the color development state was expressed by the following color retention rate.

Color retention rate 2A/A.

However, A = 590 of the colored sample at the early stage of storage
Absorbance A at nm - The absorbance U/Uo at 590 nm of the colored sample after storage for each time was determined with respect to the storage time, and the results are shown in Figure 6 and Figure 1. In FIG. 1, curve 1 shows the storage stability of the coloring state of each of samples Nos. 1, 2 and 6 of this example.
．． 2 and 6.

As a comparative example, a sample of a dispersed primary chromic material was prepared using the following formula % -6-methyl-6'-nitrospiro (2H-1-benzopyran-2,2'-benzothiazoline) (hereinafter TAE
The sample was prepared using a model compound (referred to as NM') and polymethyl methacrylate (PMMA) at the mixing ratio shown in Table 2. The sample preparation method was the same as described above.

(The following is a blank space, continued on the next page.) 2. The modeling compound TAENM' was synthesized as follows. That is, the above (B) spirobenzobilane benzothiazoline (1,00,9) + anhydrous benzene was dissolved, triethylamine (340 mg) was added, and imbutyryl chloride (300 mg) was dissolved in benzene (
10 CC) and added dropwise over 60 minutes.

After the dropwise addition was completed, the reaction mixture was stirred for 60 minutes, washed thoroughly with water, dried with anhydrous sulfuric acid mag and nesium, and after removing the solvent, recrystallized with a benzene-ether mixed medium to obtain TABNM' 1. .07 g was obtained. Yield: 9
1%; Melting point: 144-145C0 For each sample of the comparative example, the color development state by ultraviolet light irradiation was 60
The storage stability at 0 darkness was measured. The results are shown in Figure 6 and Figure 1. In FIG. 1, Comparative Example 71; 1'
, 2' and 6' samples are shown in curve 1.
', 2'5 and 6'.

(The following margins are continued on the next page.) Samples A1 to A3, which are photochromic photosensitive materials of the present invention, have a sample A6 of approximately Except for a storage period of less than 200 minutes, it was slightly lower than the corresponding A6' sample.
It can be seen that the color retention rate is high. It can be seen that the A6 sample also had a higher color retention rate than A3' after about 200 minutes, and the longer it was stored, the more advantageous it became.

In addition, the samples A4.6 and 7 containing the acid component (MAA) had a high color retention rate compared to any of the samples AI' to AI6' of comparative examples. -MA
Each sample of A)) and Ai, 7 (P-(10-MAA)) was compared to 1'' Ia 3' (10/P MM4
) It can be seen that the color preservation rate has improved by two orders of magnitude.

Next, for the samples A)6 and A4 of this example, in order to examine the color storage stability at high temperatures, the color storage rates at 30C, 150C, and 70C in the dark were measured in the same manner as described above. As a comparative example, a sample of front bending house 6' was used. These results are shown in Fig. 2 (30C dark place), Fig. 6 (50C dark place), and Fig. 4 (70C).
Sample No. 4b is shown by curves 6 and 4, respectively, and sample No. 6', which is a comparative example, is shown by curve 6'.

As is clear from the graphs in FIGS. 2 to 4, the storage stability of the coloring state of the A3 and A4 samples, which are the photochromic photosensitive materials of the present invention, is higher than that of the comparative example A3' sample at higher temperatures. is significantly better and smaller. The small temperature dependence of the storage stability of the color development state can be considered an excellent feature considering that in practical use, the apparatus may be exposed to temperatures of several tens of degrees.

In this way, the photochromic photosensitive material of the present invention is
Compared to the corresponding dispersed photochromic photosensitive materials,
It has a high color preservation rate during long-term storage, and the temperature dependence of the color preservation rate is small.

[Brief explanation of the drawing]

FIG. 1 shows clubs at 60C, FIG. 2 shows clubs at 50C, and FIG. 6 shows clubs showing the storage stability of the coloring state of the photochromic photosensitive materials of the present invention and comparative examples in the dark at 70C. Agent Masaru Ueya Yoshio Tsuneko Toshiki Sugiura Figure 2 06002. -1θθθ (Voluntary) Procedural Correction Shop/1982 Patent Application No. 10!1471 ”'°5°l!
II tv /,, h Phuotok Mink photosensitive material. (218) Sony Corporation 6 Number of inventions increased by amendment (1), "5 timorti" on page 6, line 14 of the specification was changed to "5
Morchi,” he corrected. Aki (3), page 11, line 10 “-cH2=CH2-”
is corrected to "-CH2-CH2-J." (4) "Benzene" in the first line of page 13 is corrected to "perduthiazole." (5), page 14, line 6 [Methyl methacrylate corrected]. ” he corrected. (8), "2-human" on page 15, line 20 is corrected to [6-methyl-2-human]. (9), rU/UOj on page 23, line 16 is rA/A
,,j. aO), ``Small.'' on page 29, line 10 is corrected to ``Iru.''. 1 or more 1 (order) Procedural amendment (method) % formula % 1゜Indication of case 1982 Patent Application No. 103471 2. Relationship with title of invention case Patent applicant 6 Number of inventions increased by amendment - or more 1 (Spontaneous) Procedural Amendment April 29, 1982' 1. Indication of the Case 1982 Patent Application No. 103471''2°! 1′″
″′＋″Relationship with 67 Otoku Mick Disgraceful Photosensitive Materials Incident
Patent applicant Tokyo Il'l: Akikawa Tokita product! For i'! 17Vl'
? , '(, > issue. (218) Sony Corporation r1' 6, Number of inventions increased by amendment 7, Wr + positive (D subject Brief explanation column of drawings in the specification (1), page 29 of the specification From line 19 to page 60, line 1, ``Figure 1 is a photochromic photosensitive material'' is corrected as follows.``Figure 1 and 2 are... Photochromic photosensitive materials of Examples and Comparative Examples of the present invention at 30°C in a dark place, Figure 3 in a 50°C dark place, and Figure 4 in a 70°C dark place, respectively.

Claims (1)

[Claims] A photochromic photosensitive material comprising a layer of a polymer compound containing one monomer unit represented by the following general formula as a copolymer component. 5 +O-OH2+ -0 4 (wherein, R1 is an alkyl group having 1 to 10 carbon atoms, R2 is an alkoxy group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a cyan group, R3 is hydrogen atom, halogen atom, alkyl group having 1 to 5 carbon atoms, nitro group or cyano group, R4 represents a divalent hydrocarbon group having 1 to 5 carbon atoms, and R5 represents a hydrogen atom or methyl group)