JPS60188405A - Polymer containing photoisomerizable atomic group, and its use - Google Patents

Abstract

PURPOSE:A polymer which can give an optical memory material having a good film-forming property, comprising a polymer of an olefinic double-bond-containing compound and side chains bonded thereto and comprising proton-transfer-type photoisomerizable atomic groups and bulky groups capable of sterically hindering the atomic groups. CONSTITUTION:The titled polymer composed of the main chain comprising a carbon-carbon chain of a polymer of an olefinic double bond-containing compound and side chains bonded to the main chain and comprising proton transfer-type photoisomerizable atomic groups and bulky groups capable of sterically hindering the atomic groups. Representative examples of these polymers include those having structural units of the formula (wherein R1 and R2 are each H or CH3, R0 is a bulky group of which the bulky alkyl or aromatic group is bonded to the main chain directly or through an amino group or a carboxyl group, P is an atomic group in which the proton transfer-type photoisomerizable molecule is bonded to the main chain directly or through a bivalent group, and X is a number except 0). By introducing the guest molecules as pendants to the polymer, it is possible to obtain an optical memory material in which the heightening of the concentration of guest molecules and the heightening of the temperature of memory hold can be attained and which has good film-forming property.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention is directed to the entire main chain of carbon-carbon bonds in a polymer obtained from a compound having an olefinic double bond, and a proton-transfer type light on the side thereof. The present invention relates to a polymer to which an isomerizable atomic group is bonded, and an optical storage material capable of wavelength multiplexing storage, which takes full advantage of the photoisomerization phenomenon caused by 7" roton transfer @ at low temperatures.

[Prior art]

Conventionally, optical storage materials using guest molecules that exhibit photoisomerization due to proton transfer include the guest molecules, such as metal-free porphyrin, metal-free chlorin, metal-free phthalocyanine, and quinizarin, in a liquid such as an alkane or an alkanol. , or polyvinylcarbazonope polymethyl methacrylate (hereinafter referred to as PMMA)
Systems dispersed in polymeric host materials such as polystyrene, polyvinyl alcohol, polyethylene glycol, and polycarbonate have been used. Therefore, in the case of guest molecules with poor solubility, they can be dispersed only at low concentrations, and when the storage density is increased, there is a drawback that sufficient absorption or emission information cannot be obtained. Furthermore, since the guest molecule and the host molecule only interact electronically and there is no steric regulation effect, there is a drawback that memory retention is extremely poor in the region where molecular rotation is large, such as at liquid helium temperatures of ~80°C. Ta. In addition, liquid host materials such as alkanes and alkanols must be used in their entirety, including optical cells, in the production of optical storage materials, which poses problems in handling, thinning, and the like.

[Purpose of the invention]

The present invention was made in order to solve the above-mentioned problems, and its purpose is to provide a novel polymer particularly suitable for optical storage materials having the above-mentioned guest molecules, and An object of the present invention is to provide an optical storage material that has a high concentration and a high memory retention temperature and has good film-forming ability.

[Structure of the invention]

To summarize the present invention, the first invention of the present invention relates to a novel polymer, in which proton transfer type photoisomerization is applied to the side chain of a polymer obtained from a compound having an olefinic double bond. It is characterized by a bond between an atomic group and a bulky group that sterically restricts it.

Further, the second invention of the present invention relates to an optical memory material, and is characterized in that the material contains all of the polymer of the first invention.

That is, in the polymer of the present invention, the main chain is a compound having an olefinic double bond association. ! It is a carbon-carbon bond as in the polymer obtained from I, and the above-mentioned guest molecule and a bulky group that sterically restricts the entire structure are bonded pendantly to the side chain of the carbon-carbon bond.

Therefore, representative examples of the polymers of the present invention include the following general formula (1): (wherein R1 and R3 are hydrogen or methyl groups, Ro is a bulky alkyl group or an aromatic group, directly bonded to the main chain or A bulky group bonded via an amide group or a carboxy group; ① is an atomic group to which a proton transfer type photoisomerizable molecule, i.e., a guest molecule, is bonded directly to the main chain or via a divalent group; , and X means all real numbers other than zero).

Examples of the guest molecules in the polymer of the present invention include the known ones mentioned above.

Therefore, the polymer of the present invention can be produced, for example, by the Tani method described below.

(11) A method of completely copolymerizing a guest molecule and an olefinic double bond with a sulmonomer (A) and a monomer (B) having a bulky group and an olefinic double bond, (2) a reactive functional group and A monomer (0) containing an olefinic double bond, a monomer (i, f3 in which the guest molecules are all pendant by copolymerizing Bl and t, and then reacted with the reactive functional group), and a monomer (OJ and the monomer (A)
There is a method in which a bulky fund is introduced by reacting with the reactive functional group and then reacting with the reactive functional group.

Examples of monomers (A) include olefins, dienes, (meth)acrylic acid esters or N-substituted amides of guest molecules, to which the guest molecules are bonded directly or via alkylene groups or amine groups. Nanatsuma (B
) Examples include higher olefins, dienes, (meth)
Examples include higher alkyl esters or N-substituted amides of acrylic acid, and styrenes. And, seven months
Examples of (0) include vinyl halides, (meth)acrylic acid, lower alkyl esters thereof, and acid halides. The copolymerization or substitution reaction may be carried out by a conventional method.

The preferred range of the molecular weight of the polymer of the present invention is 1
000 to several 100,000.

As mentioned above, the polymer of the present invention is useful as the optical storage material of the second aspect of the present invention.

In that case, the polymer preferably has the ability to form a thin film.

Historically, in addition to the above uses, the polymer of the present invention is also useful as a metal ion trapping material.

Next, since the optical storage material of the present invention has the above-described structure, the guest molecules can be made to be highly specific and sterically restricted.

In addition, it prevents the S/N ratio from decreasing due to high-density recording, and has high memory retention at sat or lower temperatures.
It is easy to increase the holding temperature. Furthermore, by using all polymers that have the ability to form thin films, it is effective to achieve thin films of materials necessary for high-density recording.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples.
The invention is not limited to these examples.

Note that FIG. 1 shows Example (a) of the present invention and Comparative Example (1)).
It is a graph showing the relationship between temperature (X) (horizontal axis) and hole depth (%).

Example 1 Benzaldehyde 25j', p-2) Robenzaldehyde 11.95f dissolved in total propionic acid, virol 21
．． Collect all the crystals precipitated by reacting with 119, and add 500ml of concentrated hydrochloric acid.
After dissolution in the JK bath, 40% of S O4.2 Hz O was added, and the mixture was allowed to react for about 25 minutes for complete reduction, and by column separation, metal-free tetraphenylporphyrin (hereinafter referred to as
The monoamino compound 2.1r of the monoamino compound (abbreviated as TPP) was obtained. This monoamino compound was mixed with the total equivalent of triethylamine in methylene chloride, all of the methacrylic acid chloride was added dropwise, and after the reaction, the meso-mono-(p- (methacrylamidophenyl)-triphenylporphyrin (hereinafter MATP)
(abbreviated as P) 1.5 f was obtained. Obtained MATP
P 5.6 mW and t-butylmethacrylamide were dissolved in tetrahydrofuran (hereinafter abbreviated as THE') and polymerized at 60°C for 12 hours to form MATPP and t-butylmethacrylamide.
A copolymer i2f of butyl methacrylamide was obtained. The copolymerization ratio is 5X10-4:1. In addition, its molecular weight is
Approximately 12,000.

This copolymer was dissolved in THF K, produced into a film with a thickness of 0.1 wa by a casting method, cooled by 4.2 KK in a cryostat, and holes were generated in the absorption spectrum using a dye laser.

When the depth of the hole was observed using a spectroscopic system including a spectrometer with a focal length of 1 m while increasing the temperature of the cryostat, the temperature dependence shown in Fig. 1(a) was obtained. In FIG. 1, the horizontal axis is the temperature (K) of the medium, and the vertical axis is 4.
This is the ratio (%) of the hole depth at each temperature to the hole depth at 2x.

Comparative Example 1 TPP to PMMA (i-molar ratio 5 x 10-'
: 1O was mixed and dissolved with a THP solution and then cast to obtain a cod (2) film with a thickness of α1. After forming holes in this film in the same manner as in Example 1, the temperature dependence of the hole depth was examined and the results shown in FIG. 1(b) were obtained.

In Example 1, the guest molecule TPP is pendant and completely sterically restricted by the surrounding bulky t-butyl group, whereas TPP in Comparative Example 1 is free, so it is It was found that in a wide temperature range of ~160° C., the pendant polymer had a smaller rate of decrease in hole depth with increasing temperature and had better hole retention.

Example 2 1.04 f of methacrylic acid chloride and 170 f'ft' THIF of methacrylic acid hexyl ester After IC generalization, the mixture was polymerized at 60° C. for 12 hours to obtain a copolymer. The obtained copolymer and TPP synthesized in the same manner as in Example 1
by reacting with the monoamino form of ' in triethylamine,
rpp-6 pendant. The ratio of TPP to methacrylic groups is 1:10.

Its molecular weight is approximately 25,000.

After the high concentration TPP pendant polymer i THF Ic obtained in this manner was used, a sample with a film thickness of 10 μm was obtained by spin casting.

When all holes with a diameter of 10 μm were formed in this sample in the same manner as in Example 1, holes with an absorbance change of aoi were formed in the spectrum of absorbance α1, indicating that the film thickness was 10 μm.
A sufficient signal was obtained with the thin film of 0.0 m, and the effect of increasing the concentration was noticeable.

〔Effect of the invention〕

As explained above, as in the polymer of the present invention,
By making guest molecules pendant in the polymer, the optical storage material of the present invention achieves high concentration, steric regulation, and good film forming ability, and can be used as a photoisomerization medium at extremely low temperatures by high-density recording. / The big advantage is that it completely prevents the decline in the N ratio, has high memory retention at temperatures below SOX, makes it easier to raise the retention temperature, and also allows thinner media, which is necessary for high-density recording. has.

[Brief explanation of the drawing]

FIG. 1 is a graph showing the relationship between temperature and hole depth in Example (a) of the present invention and Comparative Example (b). No. / Drawing procedure amendment (voluntary amendment) June 28, 1980 Manabu Shiga, Commissioner of the Patent Office1, Indication of the case Patent Application No. 42858 of 19812 Title of the invention Polymer containing a photoisomerizable atomic group and its relationship to the case of the person making the fifth amendment of use Patent applicant address 1-1-6 Uchisaiwai-cho, Chiyoda-ku, Tokyo Name Name
(422) Hisashi Shindo, member of Nippon Telegraph and Telephone Public Corporation

Claims (1)

[Scope of Claims] t A proton-transfer type photoisomerizable atomic group and a bulky group that sterically regulates the group are bonded to the side chain of a polymer obtained from a compound having an olefinic double bond. A polymer characterized by: 2. The polymer has the following general formula: (2) is an atomic group to which a proton-transfer type photoisomerizable molecule is bonded directly to the main chain or via a divalent group, and (X) is a bulky group that is bonded through The polymer according to claim 1, which contains a structural unit represented by: & Includes a polymer in which a proton-transfer type photoisomerizable atomic group and a bulky group that sterically regulates it are bonded to the side chain of the polymer obtained from a compound with an olefinic double bond gold. An optical memory material characterized by: 4. The polymer has the following general formula I: (wherein and R3 are hydrogen or methyl groups, and Ro is a bulky alkyl group or an aromatic group directly bonded to the main chain or an amide group or a carboxy group). (2) is a bulky group that is bonded to the main chain; 4. The optical storage material according to claim 3, which contains all of the structural units represented by the following.