JPH0852940A - Optical recording composition - Google Patents

Abstract

PURPOSE:To provide an optical recording compsn. using an org. photochromic compd. and having practicality such that the recording due to light irradiation is stably held, the erasure of recorded data is easy and the adjustment of erasing temp. is easy. CONSTITUTION:An optical recording compsn. contains 1 pts.wt. of an org. photochromic compd. (i) and 10 pts.wt. or more of a hindered amine compd. (ii) having a m.p. or softening point of 50 deg.C or higher and a mol.wt. of 1500-10000.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition which develops color upon irradiation with ultraviolet rays or the like and is erased by heating, and which can be repeatedly written and erased in a recording medium, and its decoloring temperature is controlled. The present invention relates to an optical recording composition that is easy to manufacture.

[0002]

2. Description of the Related Art When a certain compound is irradiated with light such as ultraviolet rays, the compound changes to a color different from the color it had been exhibiting up to that point. The phenomenon in which the color returns to the color of has been known as a photochromism phenomenon since ancient times. It is explained that this process of color restoration does not occur directly by stopping the irradiation of light, but occurs by the involvement of thermal energy due to temperature such as room temperature, but generally, the photochromism phenomenon is simply a colorless phenomenon. Alternatively, since it is often observed as a remarkable coloring phenomenon that occurs when light-colored compounds are irradiated with light, it is perceived as a reversible coloring and decoloring phenomenon of compounds by light at a temperature of about room temperature.

Compounds that cause such a phenomenon are generally called photochromic compounds, and there are inorganic compounds and organic compounds. In recent years, in the field of information recording, which has been attracting attention, active research and development activities have been conducted to use such photochromic compounds in optical recording elements. From the viewpoints of diversity of selection, compatibility with other substances, and the like, expectations are placed on organic photochromic compounds, that is, organic photochromic compounds.

However, as described above, the organic photochromic compound has a unique property that it discolors (colors) upon irradiation with light, but at a temperature around room temperature, the color is restored (erased) immediately after the stop of irradiation with light. When this is used as an optical recording element, the information once recorded can be stably retained without color recovery after the light irradiation is stopped, and on the other hand, when the information becomes unnecessary, the information can be easily stored. Erasability is required as an important property. Therefore, in order to use an organic photochromic compound as an optical recording element, it is necessary to develop a compound that does not recolor immediately after the light irradiation is stopped in a normal use environment, that is, at a temperature of about room temperature. There are various types.

For example, in Japanese Examined Patent Publication No. 4-40395 and Japanese Patent Application Laid-Open No. 63-250380, after introducing a polymerizable group into an organic photochromic compound and polymerizing the organic photochromic compound, after the light irradiation is stopped. Examples of preventing color reversion are disclosed in Japanese Examined Patent Publication No. 5-49718 and Japanese Patent Application Laid-Open No. 63-14786, which prevent color reversion after light irradiation is stopped by dimerizing an organic photochromic compound. Examples, and JP-A-5-271648 and the like, respectively, disclose examples of introducing a long-chain aliphatic group into an organic photochromic compound for the same purpose.
All of these chemically modify an organic photochromic compound with some kind of group, which complicates the synthetic route, increases the manufacturing cost, and may not show the photochromism phenomenon at all due to the influence of side reactions. At any rate, it is difficult to put it into practical use.

On the other hand, JP-B-45-28894, JP-B-2-45668 and the like disclose an example in which an organic photochromic compound is included in a certain polymer matrix for the same purpose as described above. 2-21258
No. 5, JP-A-2-308891 and the like disclose examples of chelating an organic photochromic compound for the same purpose, but these are different from those exemplified above, and an organic photochromic compound is chemically synthesized. Although it does not need to be modified, it requires careful selection of other substances to be used in combination, and in some cases, the organic photochromic compound may be dyed on other substances or immobilized on other substances, resulting in reversibility. The disadvantage is that the sex is lost.

As described above, although the organic photochromic compound has a great possibility that it can be used as an optical recording element, a compound having sufficient performance to meet the demand is still provided. It is not done yet.

[0008]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide stable recording by light irradiation in a composition using an organic photochromic compound. An object of the present invention is to provide an optical recording composition which can be retained, can easily erase recorded information by heating, and is easy to adjust the erase temperature and suitable for practical use.

[0009]

In order to solve the above problems, the present inventor has repeatedly studied the photochromism phenomenon of various compositions containing an organic photochromic compound, and as a result, a specific hindered amine-based compound was identified as an organic photochromic compound. In a composition in which a certain amount of the compound is allowed to coexist, under normal use conditions of about room temperature, a color reversion phenomenon does not occur even when the light irradiation is stopped after being discolored by light irradiation. It was found that the color can be easily recolored by heating, and the temperature at which the color reversion phenomenon occurs can be easily adjusted by adjusting the type and blending amount of the hindered amine compound, and research was repeated based on this. As a result, the present invention was finally completed.

That is, the present invention comprises i) 1 part by weight of an organic photochromic compound, and ii) 10 parts by weight or more of a hindered amine compound having a melting point or softening point of 50 ° C. or higher and a molecular weight in the range of 1,500 to 10,000. The present invention relates to an optical recording composition comprising:

In the present invention, it is necessary to use a combination of an organic photochromic compound and a specific hindered amine compound. It is generally known that a hindered amine compound acts as a light stabilizer when added in a small amount of about 0.1 times by weight or less with respect to a polymer material, and it is also extremely effective for an organic photochromic compound. It is known that the addition of a small amount has an effect of improving the light resistance of the organic photochromic compound. According to the research conducted by the present inventor, among hindered amine-based compounds, a special hindered amine-based compound that satisfies a specific condition that the molecular weight is large and the melting point or the softening point is high is used, and this is used as an organic photochromic compound. By using a large amount of 10 parts by weight or more with respect to 1 part by weight, completely different from the conventionally known action of the hindered amine-based compound, at a temperature of about room temperature, the color restoration after the light irradiation is stopped in the organic photochromic compound. It has been found that the phenomenon can be prevented, the color reversion reaction can be easily caused by heating, and the temperature at which the color reversion reaction occurs can be easily adjusted by adjusting the kind and blending amount of the hindered amine compound. It was By utilizing such properties, it is possible to use a composition in which an organic photochromic compound and a specific hindered amine compound are combined, as a recording medium that can stably record and retain information and that can easily erase and record. became. The action and effect of such a hindered amine-based compound found in the present invention was first clarified by the study of the present inventors, and has never been known in the past.

The optical recording composition of the present invention will be described in more detail below.

Examples of the organic photochromic compound used in the present invention include azobenzene compounds, thioindigo compounds, dithizone metal complex compounds, spirooxazine compounds, spiropyran compounds, pyran compounds, spirothiopyran compounds, fulgide compounds and dihydro. Conventionally known organic photochromic compounds such as pyrene compounds, triphenylmethane compounds and viologen compounds can be mentioned. In particular, it is preferable to use spirooxazine-based compounds, spiropyran-based compounds, pyran-based compounds and fulgide-based compounds, which are excellent in response speed upon light irradiation, color density and compatibility with the hindered amine-based compounds described below. Specific examples of these compounds will be given below, but the organic photochromic compound of the present invention is not limited to these.

The spirooxazine compounds include 1,
3,3-Trimethyl-spiro [indoline-2,3'-
(3H) naphtho (2,1-b) (1,4) oxazine], 5-chloro-1,3,3-trimethyl-spiro [indoline-2,3 ′-(3H) naphtho (2,1-)
b) (1,4) oxazine], 1,3,3,5-tetramethyl-spiro [indoline-2,3 ′-(3H) naphtho (2,1-b) (1,4) oxazine], 1 , 3, 3
-Trimethyl-9'-methoxy-spiro [indoline-
2,3 '-(3H) naphtho (2,1-b) (1,4) oxazine], 1,3,3,5-tetramethyl-9'-methoxy-spiro [indoline-2,3'-( 3H) naphtho (2,1-b) (1,4) oxazine], 1,3
3,5,6-Pentamethyl-9'-methoxy-spiro [indoline-2,3 '-(3H) naphtho (2,1-
b) (1,4) oxazine], 4-trifluoromethyl-1,3,3-trimethyl-5′-methoxy-spiro [indoline-2,3 ′-(3H) naphtho (2,1-
b) (1,4) oxazine], 6'-trifluoromethyl-1,3,3-trimethyl-5'-methoxy-spiro [indoline-2,3 '-(3H) naphtho (2,1-
b) (1,4) oxazine], 4-trifluoromethyl-1,3,3-trimethyl-9'-methoxy-spiro [indoline-2,3 '-(3H) naphtho (2,1-
b) (1,4) oxazine], 1,3,5,6-tetramethyl-3-ethyl-spiro [indoline-2,3'-
(3H) pyrido (3,2-f) (1,4) benzoxazine], 1,3,3,5,6-pentamethyl-spiro [indoline-2,3 ′-(3H) pyrido (3,2-
f) (1,4) benzoxazine], 1-methyl-3,
3-diphenyl-spiro [indoline-2,3 '-(3
H) pyrido (3,2-f) (1,4) benzoxazine], 1-benzyl-3,3-dimethyl-spiro [indoline-2,3 '-(3H) naphtho (2,1-b)]
(1,4) oxazine], 1- (4-methoxybenzyl) -3,3-dimethyl-spiro [indoline-2,
3 '-(3H) naphtho (2,1-b) (1,4) oxazine], 1- (3,5-dimethylbenzyl) -3,3-
Dimethyl-spiro [indoline-2,3 '-(3H) naphtho (2,1-b) (1,4) oxazine], 1- (4
-Chlorobenzyl) -3,3-dimethyl-spiro [indoline-2,3 '-(3H) naphtho (2,1-b)
(1,4) oxazine], 1- (2-fluorobenzyl) -3,3-dimethyl-spiro [indoline-2,
3 '-(3H) naphtho (2,1-b) (1,4) oxazine], 6'-piperidino-1,3,3-trimethyl-
Spiro [indoline-2,3 '-(3H) naphtho (2,
1-b) (1,4) oxazine], 6'-indolino-
1,3,3-trimethyl-spiro [indoline-2,
3 ′-(3H) naphtho (2,1-b) (1,4) oxazine], the following formula

[0015]

Embedded image

Examples thereof include compounds represented by:

The spiropyran compounds include 1-
(2,3,4,5-pentamethylbenzyl) -3,3-
Dimethyl-spiro [indoline-2,3 '-(3H) naphtho (2,1-b) pyran], 1- (2-methoxy-5)
Examples include -nitrobenzyl) -3,3-dimethyl-spiro [indoline-2,3 '-(3H) naphtho (2,1-b) pyran].

As the pyran compound, 3,3-di-p-methoxyphenyl-3H-naphtho (2,1-b) is used.
Pyran, 2,2-di-p-methoxyphenylphenanthra (2,1-b) pyran, 3,3-diphenyl-3H-
Naphtho (2,1-b) pyran, 2,2-diphenylphenanthra (2,1-b) pyran, spiro [3H-naphtho [2,1-b] pyran-3,9 ′-[9H] thio Xanthene], spiro [3H-naphtho [2,1-b] pyran-
3,9 '-[9H] xanthene], spiro [2H-naphtho [1,2-b] pyran-2,2'-tricyclo [3,3]
3,1,13,7] decane], 3,3-dimethyl-3H
-A naphtho (2,1-b) pyran etc. can be illustrated.

Further, as the fulgide compound, 2,5
-Dimethylfuryl-trimethylfulgide, 2-methyl-
5-chloro-trimethylfulgide, 2,5-dimethyl-
4-nitrofuryl-trimethyl fulgide etc. can be illustrated.

In the present invention, these organic photochromic compounds may be used alone or in combination of two or more.

Next, the hindered amine compound used in the present invention will be described. Generally, the compounds generally called hindered amine compounds are structurally a series of compounds having a sterically hindered amine group represented by a hindered piperidine skeleton. In the present invention, among such hindered amine compounds, in particular, they have a melting point or softening point of 50 ° C. or higher and a molecular weight of 1500.
It is necessary to use compounds in the range of 10,000. In the present invention, various hindered amine compounds can be mixed and used, and in such a mixture, the average molecular weight is 1500 to 1000.
It may be in the range of 0, and some compounds having a molecular weight below this range may be included.

The hindered amine compound used in the present invention satisfies both conditions that the melting point or softening point is 50 ° C. or higher and the molecular weight is 1500 or higher at the same time. It is possible to maintain the color development state of the organic photochromic compound after the light irradiation is stopped. If either one of the melting point or the softening point and the molecular weight falls below the above range, the organic photochromic compound easily recolors after the light irradiation is stopped at a temperature of about room temperature, and thus cannot be used as a recording material. . When the molecular weight of the hindered amine compound exceeds 10,000, the erasing temperature becomes extremely high when erasing the record by heating after the light irradiation is stopped, which is not preferable in actual use.

There is no particular upper limit to the melting point or softening point of the hindered amine compound, but it is preferably 20.
It is preferable to use one having a temperature of about 0 ° C. or lower. This is because if a material having a too high melting point or softening point is used, the temperature required for decolorization becomes a high temperature, which not only leads to energy loss but also may adversely affect the support carrying the composition. It is because it is done.

Specific examples of the hindered amine compound suitable for use in the present invention include the following formula (I)

[0025]

Embedded image

(In the formula, n represents an integer of 6 or more; hereinafter, this compound is referred to as HA-1);
Formula (II) below

[0027]

[Chemical 3]

(In the formula, n represents an integer of 2 or more, and A is

[0029]

[Chemical 4]

And B. T. C. Is

[0031]

[Chemical 5]

Represents In the following, this compound is
Called A-2. ), The following formula (III)

[0033]

[Chemical 6]

(In the formula, n represents an integer of 2 or more, and A represents

[0035]

[Chemical 7]

And B. T. C. Is the same as above. Hereinafter this compound is referred to as HA-3. ), A compound of the following formula (IV)

[0037]

Embedded image

(In the formula, x, y and z are each an integer of 1 or more, and x + y + z = n is an integer of 5 or more,
R is

[0039]

[Chemical 9]

Represents In the following, this compound is
Call it -4. ), The following formula (V)

[0041]

[Chemical 10]

(In the formula, n represents an integer of 3 or more, R represents H or CH ₃ , and this compound is hereinafter referred to as HA-5.) A compound of the following formula (VI):

[0043]

[Chemical 11]

(In the formula, n represents an integer of 3 or more and R represents H or CH _{3. In the} following, this compound is represented by H.
Called A-6. ), The following formula (VII)

[0045]

[Chemical 12]

(Wherein n represents an integer of 3 or more, R represents H or CH ₃ , and this compound is hereinafter referred to as HA-7), a compound of the following formula (VIII)

[0047]

[Chemical 13]

(In the formula, n represents an integer of 5 or more, m represents an integer of 2 to 10, R represents H or CH ₃ , and X represents O or N. In the following, this compound is referred to as HA-8. However, the hindered amine compounds that can be used in the present invention are not limited to these. In addition, in the compounds represented by the above formulas, a mixture of compounds having different values of n or m can be used. In this case, if the average molecular weight is 1500 or more, n or m defined in the above formulas can be used. A compound below the value of may be partially contained, and the average value of n or m may not be an integer.

In the present invention, the organic photochromic compound as described above is used in combination with a specific hindered amine compound, so that a normally colorless or light-colored composition is irradiated with light such as ultraviolet rays. A unique color-developing state based on the photochromic compound is maintained, and this color-developing state is kept extremely stable even at a temperature around room temperature even after the light irradiation is stopped. Therefore, the retention of the recorded information is guaranteed.

On the other hand, the recorded information can be erased by heating the composition, and by applying heat energy by heating, the organic photochromic compound restores its color and the recorded information can be erased. In other words, this phenomenon is
It means that the recorded information is stably held until the thermal energy is applied.

The heating temperature for erasing recorded information varies depending on the composition of the composition used, but by appropriately selecting the kind and addition amount of the hindered amine compound,
The temperature can be freely set within the range of 40 ° C to 200 ° C. Specifically, the erasing temperature tends to increase as the melting point or softening point of the hindered amine compound increases, and the erasing temperature also tends to increase when the molecular weight increases. By properly selecting the amount, the information erasing temperature of the composition of the present invention can be appropriately set to a desired temperature according to the use environment and the like. Usually, when the composition of the present invention is used at a temperature of about room temperature, the erasing temperature may be about 40 ° C. or higher, preferably about 50 ° C. or higher. Thus, the composition of the present invention is extremely practical in that the heating temperature for erasing recorded information can be set relatively arbitrarily.

In the composition of the present invention, the compounding ratio of the organic photochromic compound and the hindered amine compound is 10 parts by weight or more, preferably 15 parts by weight or more with respect to 1 part by weight of the former. The blending amount of such hindered amine compounds is extremely large compared to the blending amount when used as a light stabilizer of a conventional polymer material, and by such a blending amount, the action and effect of the present invention are exhibited for the first time. It When the content of the hindered amine compound is less than 10 parts by weight, the organic photochromic compound cannot be stably dissolved or dispersed in the hindered amine compound, and the organic photochromic compound is precipitated or poorly dissolved to achieve a desired effect. It is not preferable because it is difficult to be done. The upper limit of the blending ratio of the hindered amine-based compound is not particularly limited, but if it exceeds 100 parts by weight with respect to 1 part by weight of the organic photochromic compound, the color density at the time of light irradiation is lowered, and the recording portion and the non-recording portion are Since the contrast may become unclear, it is preferably less than about 100 parts by weight.

The optical recording composition of the present invention is applied to various base materials (supports) as it is or after being diluted with a suitable carrier solvent. The application method is not particularly limited, and the usual printing method, coating method, spray method,
A dipping method, a vapor deposition method, a kneading method and the like can be mentioned.

As the carrier solvent, an organic solvent having a relatively low boiling point is preferably used, and use of an organic solvent remaining in the system after application should be avoided to such an extent that it adversely affects the action and effect of the composition. is there. As the carrier solvent preferably usable in the present invention, toluene, xylene,
Acetone, MEK, ethyl acetate, chloroform, diethyl ether, methanol, ethanol, cyclohexane, liquid paraffin and the like can be mentioned, and the amount used is not particularly limited and may be appropriately determined depending on the application method, etc. It is necessary to keep the residual amount of the compound within the range that does not adversely affect the action and effect of the composition.

When a printing method, a coating method, a spray method or the like is adopted as the above-mentioned application method, the composition of the present invention and the carrier solvent added as the case requires may be included in the paint or printing ink used. In addition to the binder as the adhesive component, various additives contained in the paint or ink of the usual formulation can be blended as desired.

Examples of such additives include a surfactant, a drying modifier, a viscosity modifier, an antifoaming agent, an antistatic agent,
UV absorbers, antioxidants, light stabilizers, antioxidants, lubricants, flame retardants, general dyes, fluorescent dyes, phosphorescent pigments, thermochromic materials, pearl pigments, glass beads, metal powder,
An extender pigment, a fluorescent whitening agent, a preservative, an antibacterial agent, a deodorant, an insect repellent, a repellent, a fragrance, a foaming agent and the like can be appropriately added depending on the application. The blending amount of these additives is not particularly limited, and is usually 0.0 with respect to 1 part by weight of the total amount of the organic photochromic compound and the hindered amine compound.
It is possible to select from a wide range of about 01 to 100 parts by weight, and the desired performance of the additive is exhibited in a range that does not adversely affect the action and effect of the composition of the present invention depending on the type of the additive used. It may be determined as appropriate.

In addition to the above-mentioned general additives, organic acids such as fatty acids such as citric acid, lauric acid and stearic acid; aromatic acids such as benzoic acid and phthalic acid; phenol, bisphenol A and gallic acid. Acids, salicylic acids, and phenols such as various hindered phenols are added to the composition of the present invention in a small amount, which is effective for finely adjusting the erasing temperature and finely adjusting the response speed to light energy. . For example, if such an additive is used in an amount of about 0.1 to 10 times by weight that of the organic photochromic compound, the erasing temperature tends to increase by several degrees Celsius, and the stability of recording retention is further improved.

The base material to which the composition of the present invention is applied is not particularly limited, and materials such as papers, fibers, leathers, synthetic resins, wood, glass, ceramics and metals can be widely used. It can be applied to various things, and also in terms of shape, it can be applied to various things such as film-like, sheet-like and plate-like ones to various three-dimensional molded articles.

The composition of the present invention usually has a thickness of 0.
It is preferable to form it on the substrate as a film having a thickness of about 1 to 500 μm, and depending on the type of ink or paint used,
A medium for recording information can be obtained by natural drying or heat drying, or by curing means using various electromagnetic waves.

Further, the optical recording composition of the present invention is not only used for forming a film on a substrate as described above, but also is usually added to a raw material for producing the substrate during the production process of the substrate itself. It can also be contained in the base material by adding it in the same manner as the agent and manufacturing the base material using the same. As such an example, an optical recording or photochromic article obtained by molding a resin composition containing the optical recording composition of the present invention can be mentioned. Such an article discolors (colors) by irradiation with light, as in the case of forming a film from the composition of the present invention,
After the light irradiation is stopped, the effect of recoloring (decoloring) by heating is exhibited. In such a case, the addition amount of the composition of the present invention may be appropriately determined depending on the type of the base material to be used so as to obtain a desired color density.

Although the recording composition of the present invention described above can be used as it is, it can be used as a microencapsulated product by utilizing a known microencapsulation technique if desired. If this method is adopted, for example, including a strongly acidic substance or a strongly alkaline substance, it is possible to prevent adverse effects on the composition even when other reactive substances must be used together.
Further, there are various advantages such that the composition ratio of the composition can be always kept constant. Therefore, the optical recording composition as a microencapsulated product is an example of a preferred embodiment of the present invention. Various known methods can be adopted as the microencapsulation method, for example, the interfacial polymerization method and the in-situ (in-
Situ) polymerization method, coacervation method, in-liquid curing coating method, spray drying method, suspension polymerization method, NAD method and the like can be mentioned, but the invention is not limited thereto and one or more kinds thereof can be used. The method can be freely selected, and a microcapsule having a single-layer or multi-layer structure can be obtained.

In addition, the above-mentioned various additives may be added to the composition encapsulated in these microencapsulated materials within a range that does not inhibit the working effects of the composition of the present invention or exert any adverse effects. it can. When it is necessary to reduce the viscosity of the composition or prevent solidification, such as when the composition is microencapsulated in an aqueous medium, it can be diluted with the carrier solvent described above. Also in this case, it is preferable that the carrier solvent is volatilized out of the system during the microencapsulation process until a residual amount that does not adversely affect the action and effect of the composition in the actual use stage.

The particle size of the microcapsules is not particularly limited, but is usually about 0.1-100 μm, preferably 1-5.
It may be about 0 μm. The microencapsulated product thus obtained can be applied to the above-mentioned various substrates by the same method as in the case where the composition of the present invention is used as it is.

Writing of information on a recording medium formed from the composition of the present invention is generally performed by exposing a desired information recording portion to light rays such as ultraviolet rays, sunlight and various laser beams at a temperature in a normal environment such as room temperature. It can be performed by irradiating. Of course, in the case of using an optical recording composition in which the erasing temperature of recording is set to a relatively high temperature, even if it is kept at a heating temperature of room temperature or higher, if it is kept at a temperature not higher than the recording erasing temperature of the composition, Information can be recorded by irradiation of light rays. The recorded information can be easily erased by heating the recording medium to a temperature not lower than the recording / erasing temperature depending on the type of the optical recording composition used.

In the above description, the mode of information recording by light irradiation / recording erasing by heating is described for the sake of convenience. However, since the property of the composition of the present invention is utilized, the mode of information recording is described. Is not limited to this. For example, by irradiating the composition with light to bring it to the full color-developed state, and then partially heating it to the erasing temperature or higher to bring part of the composition into the decolorized state, which is the reverse of the above embodiment. The contrast between the color-developed portion and the color-erased portion allows a so-called negative recording. In this case, it is needless to say that the recording can be erased by light irradiation, and it is also possible to return to the information writing mode again by light irradiation after applying the heat energy so as to completely erase the color.

As described in detail above, the optical recording composition of the present invention can well control color development by light energy such as ultraviolet rays and decolorization by heat energy and can be used as various recording materials. Of course, by grasping the reversible color change as a kind of coloring means, it can be used for various industrial materials, daily sundries, ornaments, toys, learning materials, stationery, writing instruments, clothes, various indicators and the like. An example is given below. The expression "optical recording composition" in the following description naturally includes the microencapsulated product.

(1) In a liquid material in which the optical recording composition is dispersed,
Optically recordable textile products which are exhausted and colored by a yarn, a sliver, a raw cotton, a woven fabric, a knitted fabric, a nonwoven fabric, a web, and a sewn product obtained by sewing each of these.

(2) Obtained by padding a padding bath containing an optical recording composition and a thermoplastic resin with a thread, a sliver, a raw cotton, a woven fabric, a knitted fabric, a non-woven fabric, a web and a sewn product obtained by sewing each of these. Optical recordable textile products.

(3) Jumpers, coats, jackets, sweaters, blouses, and T printed with printing ink (water-based or vinyl chloride blastisol ink) containing the optical recording composition
Shirt, pants, skirt, dress, stockings, socks, gloves, hat, handkerchief, towel, tie,
Clothing such as ski wear, swimwear, sportswear, ribbon, muffler, neckerchief, slippers, sandals,
Footwear such as shoes and boots, curtains, carpets, cushions,
Interior items such as Noren, national flags, pennants, table cloths, mats, artificial flowers, coasters, bags, handbags, miscellaneous goods, as well as toys, stationery, sports equipment, etc.

(4) An ink containing the optical recording composition is printed on a substrate having a peeling property to form a pattern, letters, numbers, symbols or the like, or the entire surface is colored with the ink, and then an adhesive is applied. Printed or sprayed with a heat transfer sheet, and fibers, leather, plastic products (such as vinyl chloride products) obtained by heat transfer of this sheet, for example, clothing, interior products, footwear,
Miscellaneous goods, toys, stationery, sports equipment, etc.

(5) Mono- or multi-filaments whose surfaces are coated with a coating containing the optical recording composition, doll hair, wigs, animal hair, embroidery threads obtained from the mono- or multi-filaments, and knitted and woven fabrics of the filaments such as clothing, interior products, Footwear, miscellaneous goods, etc.

(6) A color masterbatch in which the optical recording composition is uniformly dispersed in plastic, a color masterbatch in which the optical recording composition is uniformly dispersed in wax and plastic, and the optical recording composition are salified. Conxol evenly dispersed in vinyl plastisol, and injection molding, vacuum molding, compression molding, foam molding, blow molding, extrusion molding by further adding molding plastic, vinyl chloride plastisol or shape memory resin to these , Dolls obtained by slush molding, calendar molding, etc., toys such as animals, fish, cars, balls, simulative foods, mama set, plastic cups, plastic bottles, straws, etc. for food, drinking water and cosmetics containers, Artificial flowers, brooches, ornaments such as pendants, packaging films, shrink films, sundries, stationery, etc. Filaments obtained by melt-spinning or extrusion-spinning the above masterbatch or concusol, doll hairs obtained from the filaments, wigs, animal hair, plush toys, carpets, curtains, clothing obtained from knitted and woven fabrics of the filaments, interior goods, footwear, sundries etc.

(7) A coating cloth coated with a coating material containing an optical recording composition and a cloth, an interior article, footwear, sundries, or paper or a plastic film obtained from the coating cloth, or coated with the coating material. ,
Alternatively, colored paper, artificial flowers, paper cups, business cards, books, picture books, wallpapers, calendars, wrapping paper and the like obtained by printing an ink containing the optical recording composition.

(8) Plastic, metal, glass or ceramic products coated with a coating containing the optical recording composition, for example,
Cars, miniature cars, animals, dolls, sets for moms, toys such as simulated foods, containers for food, beverages, cosmetics, shape memory metal or shape memory resin molded products, various prepaid cards, etc.

(9) Glass, ceramics, plastic or metal products on which the ink containing the optical recording composition is screened or gravure printed, such as glass cups, glass bottles, aluminum cans, glasses, jugs, mugs, hot water, plastic cups, plastic bottles, etc. For food, drinking water and cosmetics, brooches, patches, business cards, cards, pencil boxes, erasers, bags and other ornaments, sundries, toys,
Stationery, etc.

(10) Plastic, metal, glass or ceramic products printed with tampo ink containing the optical recording composition,
For example, toys such as dolls, animals and cars, containers for food, beverages and cosmetics, brooches, patches, business cards, ornaments such as cards, stationery, sundries, etc.

(11) Writing instruments such as ballpoint pens, magic pens and paints filled with ink for optical recording type writing instruments.

(12) Flour clay, plastic clay, slime resin (highly viscous fluid), shape memory resin, candle, crayon, etc. in which the optical recording composition is uniformly dispersed.

(13) A pattern, letters, numbers, symbols, etc. are formed on the surface of the substrate with the ink containing the optical recording composition, a transparent film is laminated on the surface via an adhesive, and an adhesive is provided on the back surface of the substrate. A tack sticker to which release paper is attached via, and clothing, sundries, toys, stationery, etc. to which this sticker is attached.

(14) An adhesive is printed on a substrate having releasability, a pattern, letters, numbers, symbols, etc. are formed on the substrate with an ink containing the optical recording composition, and a cover coat layer is further formed thereon. Water transfer sheet provided, and plastic, glass, ceramics or metal products obtained by water transfer of this sheet, such as glass cups, glass bottles, wine glasses, jugs, mugs, plastic cups, plastic bottles for food, drinking water or cosmetics Containers, other miscellaneous goods, toys, stationery, etc.

(15) A flocked fabric in which a coating material containing an optical recording composition is coated on a cloth, and short fibers are flocked on the cloth, a stuffed animal and a carpet obtained from the flocked cloth, and various clothing, interior goods, footwear, and sundries. etc.

(16) Short fibers planted on a substrate having releasability, an ink containing the optical recording composition printed on the surface thereof, and formed on the ink layer in the form of patterns, letters, numbers and symbols. A flocked transfer sheet having an ink layer made of the above adhesive, and fibers, leather, plastic products, etc. to which this sheet is transferred, such as clothing, footwear, interior goods, sundries, toys, stationery and the like.

(17) A high-pile knit in which a mono- or multi-filament thread dipped with a coating material containing an optical recording composition is wound around a net-like base material and the back side is backed with an adhesive, and a stuffed toy, a doll hair, a wig, Carpet, various clothing, interior goods, footwear, sundries, etc.

(18) A pattern layer is formed with an ink containing the optical recording composition on a part of one side of a substrate made of a transparent synthetic fiber yarn, and a paint containing a polyurethane resin is further applied to the substrate including the pattern layer. An optical recording print cloth having a porous film layer and excellent in moisture permeability, and clothing, interior goods, miscellaneous goods and the like using this cloth.

[0085]

The composition of the present invention comprises a conventional organic photochromic compound that records information by utilizing the coloring phenomenon caused by irradiation with light such as ultraviolet rays and erases information by controlling the color restoration phenomenon by heating. It is a completely new optical recording composition that utilizes a novel phenomenon that could not be obtained with the composition used, and it is of course possible to use it as various recording materials by utilizing such properties, and it also exhibits reversible color change. By being regarded as a kind of coloring means, it can be used for various purposes.

The composition of the present invention is a mixture of an organic photochromic compound and a specific hindered amine compound, and each component can be easily obtained without a complicated synthesis process. It is very practical in that the information erasing temperature can be easily set by adjusting the combination and the blending ratio.

[0087]

The present invention will be described in more detail with reference to specific examples, but the present invention is not limited to these examples.

In the following description, "part" means "part by weight".

Example 1 1 part of 1,3,3-trimethylspiro [indoline-2,3 '-(3H) naphtho (2,1-b) (1,4) oxazine] as an organic photochromic compound and a hindered amine system HA-2 as a compound [molecular weight about 190
0, melting point: about 70 ° C., trade name: ADEKA STAB LA-6
8, manufactured by Asahi Denka Kogyo Co., Ltd.] to prepare an optical recording composition of 25 parts. 20 parts of ethyl cellulose, aromatic naphtha (trade name: Solvesso 100, manufactured by Esso Standard Oil Co., Ltd.)
An ink vehicle consisting of 70 parts, 30 parts of xylene and 1 part of a silicone-based defoaming agent was uniformly dispersed and dissolved with 10 parts of the above optical recording composition to prepare an ink using an air knife coater.
White coated paper so as to 00g / m ² (about 200μm
(Thickness) and then naturally dried, and then dried in a dryer at 100 ° C. for 5 minutes to obtain an optical recording sheet.

When the recording sheet was irradiated with ultraviolet rays,
A blue-colored record was obtained, and this record could be stably held at room temperature for 10 days or longer.

On the other hand, this recording could be immediately erased by warm air of 60 ° C. or higher, and such recording and erasing could be repeated many times.

Example 2 Instead of HA-2 used in Example 1, HA-3 [molecular weight: about 2000, melting point: about 80 ° C., trade name: ADEKA STAB L
A-63, manufactured by Asahi Denka Kogyo Co., Ltd.], and an optical recording sheet was obtained in the same manner as in Example 1 except for the above.

When the recording sheet was irradiated with ultraviolet rays,
A blue-colored record was obtained, and this record could be stably held at room temperature for 10 days or longer.

On the other hand, this recording could be immediately erased by warm air of 65 ° C. or higher, and such recording and erasing could be repeated many times.

Example 3 Instead of HA-2, HA-5 [molecular weight: about 2500, melting point: about 120 ° C., R = H, trade name: CHIMASSOR
B 944FL, manufactured by Ciba-Geigy] was used, and an optical recording sheet was obtained in the same manner as in Example 1 except for the above.

When the recording sheet was irradiated with ultraviolet rays,
A blue-colored record was obtained, and this record could be stably held at room temperature for 10 days or longer.

On the other hand, this recording could be immediately erased by hot air of 80 ° C. or higher, and such recording and erasing could be repeated many times.

Comparative Example 1 All the other examples except that bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate [melting point 84 ° C., molecular weight 481] was used in place of HA-2. An optical recording sheet was obtained in the same manner as in 1.

When the recording sheet was irradiated with ultraviolet rays,
Although a blue-colored recording was obtained, this recording disappeared immediately at room temperature after the light irradiation was stopped, and stable recording could not be left.

Examples 4 to 37 25 parts of a composition comprising an organic photochromic compound and a hindered amine compound shown in Table 1 as essential components, and further additives and a carrier solvent, if necessary, and an epoxy resin [trade name: Epicoat 828, made by Yuka Shell Epoxy Co., Ltd.]
Was added to 200 parts of a 10% aqueous gelatin solution of and was dispersed with stirring in the form of oil droplets having a diameter of 5 μm.

Next, 4 parts of a curing agent for an epoxy resin [trade name: Epicaur U, manufactured by Yuka Shell Epoxy Co., Ltd.] was added, the liquid temperature was raised to 90 ° C. under stirring, and the reaction was carried out at that temperature for 4 hours.

After cooling, the resulting microcapsules were washed with water, filtered, and air-dried to obtain microcapsulated optical recording compositions.

30 parts of the microencapsulated product, urethane resin emulsion [trade name: Iserax 40, manufactured by Hodogaya Chemical Co., Ltd.] 100 parts, melamine-based cross-linking agent [trade name: Sumitex Resin M-3, Sumitomo Chemical Co., Ltd. Made] 2
Part, acid catalyst [Product name: Sumitex Catalyzer Ac
x, manufactured by Sumitomo Chemical Co., Ltd.] 0.5 parts of a water-based ink was prepared, and a transparent polyester film (about 200 μm on average) was prepared.
An optical recording sheet was obtained by coating with a knife coater so as to have a thickness of 110 g / m ² and heat-drying.

When the recording sheet was irradiated with ultraviolet rays,
A record in which the color tone shown in Table 1 was vividly developed was obtained, and this record was very stable at room temperature.

On the other hand, this recording could be erased immediately by heating it to the erasing temperature shown in Table 1 or above, and such recording and erasing could be repeated many times.

[0106]

[Table 1]

[0107]

[Table 2]

[0108]

[Table 3]

The abbreviations in Table 1 mean the following compounds.

PH-1 ... 1,3,3-Trimethylspiro [indolino-2,3 '-(3H) naphtho (2,1-
b) (1,4) Oxazine] PH-2 ... 3,3-Dimethyl-3H-naphtho (2,1-
b) Pyran PH-3 ... 2,5-Dimethyl-4-nitrofuryl-trimethylfulgide PH-4 ... 6 '-(2,3-dihydro-1H-indol-1-yl) -1,3-dihydro- 1,3,3-Trimethyl-spiro [2H-indole-2,3 '-[3
H] naphtho (2,1-b) (1,4) oxazine] PH-5 ... 1,3-dihydro-1,3,3-trimethyl-6 ′-(1-piperidinyl) -spiro [2H-indole- 2,3 '-[3H] naphtho (2,1-b) (1,
4) Oxazine] PH-6 ... 3,3-Diphenyl-3H-naphtho (2,1
-B) Pyran PH-7 ... 5-Methoxy-1,3,3-trimethylspiro [indolino-2,3 '-(3H) naphtho (2,1-
b) (1,4) Oxazine] PH-8 ... 2,5-Dimethylfuryl-trimethylfulgide HA-1 (a) ... Represented by formula (I), melting point: about 60 ° C.,
Compound having a molecular weight of about 3000 HA-1 (b) ... Represented by formula (I), having a softening point of about 80-
Compound HA-1 (c) having a molecular weight of about 6000 at 90 ° C .... Represented by the formula (I) and having a softening point of about 110.
~ 120 ° C, compound with molecular weight of about 9000 HA-2 ... Represented by formula (II), softening point about 70-80
Compound HA-3 (a) having a molecular weight of about 1900 and a temperature of about 1900, represented by the formula (III) and having a softening point of about 80.
Compound having a molecular weight of about 2000 at ˜90 ° C. HA-3 (b) ... Represented by formula (III) and having a softening point of about 10
Compound HA-3 (c) having a molecular weight of about 4000 at 0 to 110 ° C .... Represented by the formula (III) and having a softening point of about 13
Compound HA-4 having a molecular weight of about 8,000 at 0 ° C., represented by the formula (IV), and having a softening point of about 85 to 90.
Compound HA-5 (a) having a molecular weight of about 2000 and represented by the formula (V), R = H, a softening point of about 70 to 90 ° C., a compound HA-5 (b) having a molecular weight of about 1800, the formula (V). ), R = H, softening point about 100 to 135 ° C., molecular weight about 2500 compound HA-5 (c) ... Represented by formula (V), R = H, softening point about 150 to 170 ° C. Compound HA-5 (d) having a molecular weight of about 4000, represented by formula (V), R = CH ₃ , a softening point of about 120 to 140 ° C., compound HA-6 (a) having a molecular weight of about 2700, formula (VI) ), R = H, a softening point of about 110 to 130 ° C., a molecular weight of about 3400 HA-6 (b) ... Represented by formula (VI), R = CH ₃ , a softening point of about 70 to 80 HA-6 (c), a compound having a molecular weight of about 3000, represented by the formula (VI), R = CH ₃ , and a softening point of about 100 to 120 ° C. , A compound having a molecular weight of about 5000 HA-6 (d) ... Represented by the formula (VI), R = CH ₃ , a softening point of about 120 to 135 ° C., a compound of a molecular weight of about 7,000 AD-1 ... Stearic acid AD-2 ... Bisphenol A AD-3 ... 4,4'-butylidene-bis- (3-methyl-6-tert-butylphenol) Example 38 Vinyl chloride resin [trade name: ZEON 121, manufactured by ZEON CORPORATION] 50 parts, dibutyl phthalate To 100 parts of vinyl chloride paste consisting of 40 parts, 8 parts of polyester plasticizer and 2 parts of dibutyltin laurate, 0.4 parts of the microencapsulated product obtained in Example 10 and the microcapsules obtained in Example 11 Compound (0.4 parts), microcapsule product (1.2 parts) obtained in Example 12, yellow organic pigment [trade name: PV Fast Yellow H10
G, manufactured by Hoechst] 0.05 parts, red organic pigment [trade name: Novaperm Red HF-3F, manufactured by Hoechst] 0.05 parts, titanium dioxide 3 parts and nonionic surfactant [trade name: Sorgen 30, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.]
1 part was added and stirred uniformly to prepare a vinyl chloride paste for slush molding.

This paste is poured into a slush molding die shaped like a doll, and heated at 180 ° C. for 2 minutes,
The paste gelled to a solid film with a thickness of about 1 mm from the mold surface. The liquid paste, which was separated by about 1 mm or more from the mold surface, was inverted and removed, and further heated at 200 ° C. for 2 minutes to obtain a complete gel product. After allowing to cool, the gelled product was taken out from the mold to obtain a slush molded doll.

This doll had a flesh color in a room where it was not exposed to the sun, but when exposed to the sun, it turned a wheat color and turned into a suntan doll. The wheat-colored doll was taken home and left to stand, but the doll remained wheat-colored and maintained a very stable coloration.

On the other hand, when the wheat doll was blown with hot air from a dryer, the doll returned to its original skin color. Such a discoloration phenomenon could be repeated any number of times.

Example 39 1 part of a compound represented by PH-5 in Table 1 as an organic photochromic compound, 20 parts of a compound represented by HA-6 (a) in Table 1 as a hindered amine compound, 10 parts of xylene, and 10 parts of toluene. , And polymethylenephenylisocyanate [trade name: Millionate MR, manufactured by Nippon Polyurethane Industry Co., Ltd.] 8 parts of a mixture are uniformly stirred, and an aqueous solution containing 2 parts of colloidal calcium phosphate 30
This mixture was added to 0 part and uniformly dispersed while adjusting the stirring speed so that the average particle size was 5 μm.

Then, 1.5 parts of xylylenediamine was added and stirring was continued for 3 hours to obtain a dispersion liquid of the microencapsulated product containing the optical recording composition.

Subsequently, 6 parts of melamine / formalin prepolymer was further added to this dispersion, and the liquid temperature was raised to 80 ° C. while continuing stirring. Thereafter, 10% acetic acid was added dropwise to adjust the pH of the system to 5, and the mixture was continuously stirred at this temperature for 2 hours, then allowed to cool, filtered, washed with water and dried to give a microcapsule having a multilayer structure of about 35 I got a part.

An ink consisting of 20 parts of the microencapsulated product, 20 parts of polyvinyl alcohol, 1 part of a silicone-based defoaming agent, and 200 parts of water was used in a roll coater to prepare 100 parts of ink.
White coated paper (approx. 200 μm thickness) to achieve g / m ^2.
It was coated on the above and naturally dried to obtain an optical recording paper.

This recording paper was irradiated with ultraviolet rays so that the entire surface was colored violet. The optical recording paper that developed color in this state was extremely stable at room temperature.

When the optical recording paper in this state was set in a thermal printer and printed by a thermal head, a negative recording was obtained, and this recording could be kept extremely stable at room temperature.

On the other hand, when ultraviolet rays were irradiated to erase this record, the entire surface was returned to the color-developed state, and such writing and erasing of the record could be repeated any number of times.

Needless to say, the recording paper of this example can be of a mode in which recording is performed by light as in Example 1, and it is extremely useful.

[0122]

Claims (2)

[Claims] 1. An organic photochromic compound 1 part by weight, and ii) a hindered amine compound having a melting point or softening point of 50 ° C. or higher and a molecular weight in the range of 1500 to 10,000 is contained by 10 parts by weight or more. An optical recording composition comprising: 2. An optical recording composition obtained by microencapsulating the composition according to claim 1.