JP3502136B2 - Reactive UV absorber and thermal recording material - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a reactive ultraviolet absorber and a heat-sensitive recording material, more specifically, a specific benzophenone-based reactive ultraviolet absorber, a polymeric material obtained by reacting and adding the ultraviolet absorber to a resin, and The present invention relates to a thermosensitive recording material having a protective layer formed of a molecular material.

[0002]

2. Description of the Related Art A color or color reaction between a colorless or light-colored basic dye and an organic or inorganic color developing agent is used, and both color forming materials are brought into contact with each other by heat to obtain a recorded image. The thermal recording material thus prepared is well known.
Since such a thermal recording material (thermosensitive recording material) is relatively inexpensive, the recording device is compact, and its maintenance is easy, it is used not only as a recording medium for facsimiles and various calculators but also in a wide range of fields. ing.

One of the fields of use thereof is, for example, POS.
Thermal recording labels for systems can be mentioned, but with the expansion of the systemization, tag paper used for a long period of time in addition to food labels that end their mission in a short period as in the past, and used for products for a long time, Alternatively, the use as handy terminal paper for collecting and delivering, which is often handled outdoors, is increasing. However, in such applications, it is often exposed to room light or sunlight for a long period of time, which causes the background portion of the thermal recording material to turn yellow, resulting in a marked loss of product image. Therefore, there is a strong demand for a thermosensitive recording medium that does not cause yellowing of the background portion even after being exposed to room light or sunlight for a long time.

Conventionally, there has been proposed a method of adding a finely pulverized ultraviolet absorber to a heat-sensitive recording layer or a protective layer for the purpose of preventing yellowing of the background portion of a heat-sensitive recording material due to light. However, finely pulverized UV absorbers do not provide sufficient effect because of poor UV absorption efficiency, and increase in the amount used causes background fog, or new defects such as decrease in recording density. However, as a result, it is the current situation that a sufficiently satisfactory light resistance is not obtained. Further, in the thermal recording material used as the tag paper or the handy terminal paper as described above, plasticizers, solvents,
Since the resistance of the recorded image to oils and fats and sebum is required, it is common to provide a protective layer on the recording layer. However, if the protective layer contains a finely pulverized ultraviolet absorber, However, the ultraviolet absorber elutes under the influence of the plasticizer and oils and fats to impair the function of the protective layer, and as a result, the storability of the recorded image decreases.

In addition to this, it is proposed in JP-A-5-155134 to add a microencapsulated ultraviolet absorber to the protective layer to obtain a heat-sensitive recording material having excellent storage stability and light resistance. . However, this method requires microencapsulation of the UV absorber, and although it is superior to the finely pulverized product, the dispersibility of the UV absorber is lower than that at the molecular level, and the UV absorption efficiency deteriorates. The amount has to be increased, and there has been a demand for an ultraviolet absorber that is more excellent in retention and dispersibility in the protective layer.

Therefore, an object of the present invention is to provide a UV absorber having excellent retention and dispersibility in a protective layer, and a heat-sensitive recording material coated with the UV absorber and having excellent storage stability such as light resistance. Especially.

[0007]

Means for Solving the Problems As a result of extensive studies, the present inventors have used a specific compound as a reactive ultraviolet absorber and a polymer material obtained by reacting addition of the compound with a resin as a protective layer. It was found that a heat-sensitive recording material that can achieve the above-mentioned object can be obtained, and the present invention has been completed.

That is, the present invention provides a benzophenone-based reactive ultraviolet absorber represented by the general formula (I) of the following [Chemical formula 2] (the same as the above-mentioned [Chemical formula 1]).

The present invention also provides a polymer material obtained by reacting and adding the above-mentioned reactive ultraviolet absorber to a resin.

The present invention also provides a heat-sensitive recording material using the above polymer material as a protective layer for the heat-sensitive recording layer.

[0011]

[Chemical 2]

The present invention will be described in detail below.

The reactive ultraviolet absorber of the present invention is characterized by being a benzophenone-based reactive ultraviolet absorber represented by the above general formula (I). Examples of the alkyl group represented by R ₂ and R _{3 in} the above general formula (I) include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl,
Examples include groups such as tert-butyl, isobutyl, amyl, tert-amyl, octyl and tert-octyl groups.

Therefore, examples of the compound represented by the general formula (I) include compound Nos. 1-No. 6 and the like.

[0015]

[Chemical 3]

[0016]

[Chemical 4]

[0017]

[Chemical 5]

[0018]

[Chemical 6]

[0019]

[Chemical 7]

[0020]

[Chemical 8]

Next, specific synthesis examples of the compound (reactive ultraviolet absorber) represented by the above general formula (I) of the present invention and the polymer material of the present invention will be given. The present invention is as follows. It is not limited by the synthesis example.

Synthesis Example 1 Compound No. 3 "The following [Chemical formula 9] (the same as the above-mentioned [Chemical formula 5])
"Shown in".

[0023]

[Chemical 9]

2,4-dihydroxybenzophenone 1
0.7 g (0.05 mol), 12.8 g (0.065 mol) of bromoacetaldehyde diethyl acetal and 100 ml of diglyme were added to a mixed solution of potassium carbonate 7.6 g.
(0.055 mol) was added, and the mixture was reacted at 154 ° C. for 8 hours. After cooling the reaction solution, the precipitate was filtered off, the filtrate was dried under reduced pressure, the residue was dissolved in chloroform and washed thoroughly with water. Further, the organic layer was dried over magnesium sulfate, the solvent was distilled off, and the residue was treated with silica gel to obtain 6.4 g (yield 40%) of the desired product as a yellow liquid.

Synthesis Example 2 Compound No. 1. Synthesis of "shown in [Chemical Formula 10] (the same as the above-mentioned [Chemical Formula 3])".

[0026]

[Chemical 10]

3.2 g of the compound obtained in Synthesis Example 1 (0.
01 mol) and 5 ml of water, 20 ml of isopropanol,
0.2 g of concentrated hydrochloric acid was added, and the mixture was reacted under reflux for 3 hours. After cooling, the precipitate was collected by filtration and recrystallized from benzene to obtain 2.5 g of the desired product as a white powder (yield 98%, melting point 69.7 ° C.).

Synthesis Example 3 Compound No. Addition of 1 UV absorber to polyvinyl alcohol

0.1 g of the compound obtained in Synthesis Example 1 and a 10% aqueous solution of polyvinyl alcohol (Kuraray Poval 20
5) Add 10 g, isopropanol 10 ml, 1% sulfuric acid aqueous solution 1 ml and react under reflux for 11 hours, confirm disappearance of acetal in TLC (hexane / ethyl acetate = 2/1), and confirm that polyvinyl alcohol at the origin has ultraviolet absorption. It was confirmed. After cooling, KYOWARD 500,
0.4 g was added and stirred. After confirming pH = 7, insoluble matter was removed by filtration, and isopropanol was removed from the filtrate by reduced pressure. The residue was replenished with azeotropically distilled water. Further, 20 g of a 10% aqueous solution of polyvinyl alcohol was added to obtain a slightly cloudy polyvinyl alcohol solution. The ultraviolet absorption spectrum of this solution is 239.5 nm.
And two absorption maxima at 288 nm.

The H ¹ -NMR and IR spectra of the benzophenone compounds obtained in Synthesis Examples 1 and 2 are as follows.

H ¹ -NMR (*: reference peak of measured number of protons) Chemical shift (ppm) Attributable H number (measured value) H number (calculated value) Synthesis example 1 6.1 to 7.3 Aromatic ring 8. 2 8 4.5-4.7 Methine 1.1 1 3.4-3.9 Methylene ^* 6.0 6 0.9-1.1 Methyl 5.9 6 Synthesis Example 2 9.7 Aldehyde 0.9 1 6.3-7.5 Aromatic ring 8.2 8 3.9-4.0 Methylene ^* 2.0 2

[0032] IR spectrum Synthesis Example ^{1 1610cm -1 1100cm -1 690cm -1 (} Neat) Synthesis Example ^{2 1630cm -1 1100cm -1 680cm -1 (} KBr)

The reactive ultraviolet absorber of the present invention is added to a resin to be used as a heat-sensitive recording material, and is particularly useful in fields requiring high light resistance such as agricultural materials and automotive coatings. For example, it can be used by being added to films, fibers, tapes, sheets, various molding materials, paints, binders for lacquers, adhesives, putties, and base materials in photographic materials.

The amount of the reactive ultraviolet absorber added is not particularly limited, but is usually 0.05 to 5 parts by weight, preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the resin.

The resin to be reactively added to the reactive ultraviolet absorber may be any acetalizable resin having a hydroxy group, and specifically, polyvinyl alcohol, carboxy-modified polyvinyl alcohol, acetoacetyl group. Examples thereof include modified polyvinyl alcohol, silicon-modified polyvinyl alcohol, and polymer compositions containing these polyvinyl alcohols. As the application of the polymer material of the present invention in which the above-mentioned reactive ultraviolet absorber is added to these resins by reaction, other than the protective layer of the heat-sensitive recording material, paint,
Examples include cosmetics.

Next, as the normally colorless or light-colored color-forming compound used in the heat-sensitive recording material of the present invention, which uses a polymer material obtained by adding the above-mentioned reactive ultraviolet absorber to a resin as a protective layer, various dyes are available. There is no particular limitation as long as it is well known and is used for general thermal recording paper.

Specific examples of the above-mentioned dyes (color-forming substances) include (1) triarylmethane compounds;
3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide (crystal violet lactone), 3- (p-dimethylaminophenyl) -3- (2
-Phenyl-3-indolyl) phthalide, 3- (p-dimethylaminophenyl) -3- (1,2-dimethyl-3)
-Indolyl) phthalide, 3,3-bis (9-ethyl-)
3-carbazolyl) -5-dimethylaminophthalide,
3,3-bis (2-phenyl-3-indolyl) -5-
(2) Diphenylmethane compounds such as dimethylaminophthalide; for example, N-halophenylleuco such as 4,4-bis (dimethylamino) benzhydrin benzyl ether, N-2,4,5-trichlorophenylleucoauramine (3) xanthene compounds such as auramine;
For example, rhodamine-β-anilinolactam, 3- (N
-Methyl-N-cyclohexylamino) -6-methyl-
7-anilinofluorane, 3-diethylamino-7-octylaminofluorane, 3-diethylamino-7-
(2-chloroanilino) fluorane, 3-diethylamino-6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7- (2,4-dimethylanilino) fluorane, 3-diethylamino-7-di Benzylaminofluorane, 3-diethylamino-6-chloro-
7- (β-ethoxyethylamino) fluorane, 3-diethylamino-6-chloro-7- (γ-chloropropylamino) fluorane, 3- (N-ethyl-N-isoamylamino) -6-methyl-7-ani Reno Fluoran, 3
-(N-ethyl-N-ethoxyethylamino) -6-methyl-7-anilinofluorane, 3- (N-ethyl-N
-Tetrahydrofurfurylamino) -6-methyl-7-
Anilinofluorane, 3- (N-ethyl-N-tolylamino) -6-methyl-7-anilinofluorane, 3-dibutylamino-6-methyl-7-anilinofluorane,
3-dibutylamino-7- (2-chloroanilino) fluorane, 3-dipentylamino-6-methyl-7-anilinofluorane, 3-piperidino-6-methyl-7-anilinofluorane, 3- (4- (4-anilino) anilino) anilino-6-methyl-7-chlorofluorane, etc., (4) thiazine-based compounds; for example, benzoylleuco methylene blue, p-nitrobenzoylleucomethylene blue, etc., (5) spiro-based compounds; 3-methylspirodinaphthopyran, 3-ethylspirodinaphthopyran, 3-benzylspirodinaphthopyran, 3-methylnaphtho- (3-methoxybenzo) spiropyran, etc.,
In addition, 3,5 ′, 6-tris (dimethylamino) -spiro [9H-fluorene-9,1 ′ (3′H) -isobenzofuran] -3′-one, 1,1-bis [2- (4 −
Dimethylaminophenyl) -2- (4-methoxyphenyl) ethenyl] -4,5,6,7-tetrachloro (3
H) isobenzofuran-3-one, etc., and these dyes may be used alone or in combination of two or more.

Various sensitizers may be used in combination for increasing the color developing sensitivity of the heat-sensitive recording material of the present invention. For example, zinc acetate, zinc octylate, zinc laurate, zinc stearate, zinc oleate. , Zinc behenate, zinc benzoate, zinc salt of salicylate dodecyl ester, calcium stearate, magnesium stearate, metal stearates such as aluminum stearate, stearic acid amide, methylol stearate, stearoyl urea, acetanilide, acetotoluidide, acetoacetic acid Amide compounds such as anilide, benzoic acid stearylamide, ethylenebisstearic acid amide, hexamethylenebisoctylic acid amide, 1,2-bis (3,4-dimethylphenyl) ethane, m-terphenyl, 1,2-diphenoxy Ethane, , 2-bis (3-methylphenoxy) ethane, p-benzylbiphenyl, p-benzyloxybiphenyl, diphenyl carbonate, bis (4-methylphenyl) carbonate, dibenzyl oxalate, bis (4-methylbenzyl) oxalate, 1-hydroxy-2-naphthalenecarboxylic acid phenyl, 1-hydroxy-2-naphthalenecarboxylic acid benzyl, 3-hydroxy-2-naphthalenecarboxylic acid phenyl, 3-hydroxy-2-naphthalenecarboxylic acid anilide, methylenedibenzoate, 1, 4-bis (2-vinyloxyethoxy) benzene, 2-benzyloxynaphthalene, 4-benzyloxybenzoate benzyl, dimethylphthalate, dibenzyl terephthalate, dibenzoylmethane, 4-methylphenoxy-p-biphenyl, etc. Rukoto can, these sensitizers are usually 0.1 to 10 parts by weight per color forming substance 1 part by weight is used.

If desired, a color developer can be used in the heat-sensitive recording material of the present invention. As the developer used, any of the commonly used developers can be used.

Examples of the developer include p-octylphenol, p-tertiary butylphenol, p-phenylphenol, p-hydroxyacetophenone, α-naphthol, β-naphthol, p-tertiary octylcatechol, 2,2. '-Dihydroxybiphenyl, bisphenol-A, 1,1-bis (p-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) heptane, 2,2-bis- (3-methyl-4-hydroxyphenyl) ) Propane, 2,2-bis (3,5-dimethyl-4)
-Hydroxyphenyl) propane, 2,2-bis (4-
Hydroxy-3,5-dichlorophenyl) propane, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy-3-allylphenyl) sulfone, bis (3,3
4-dihydroxyphenyl) sulfone, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (4
-Hydroxyphenyl) ether, bis [2- (4-hydroxyphenylthio) ethoxy] methane, 4- (4-
Isopropoxybenzenesulfonyl) phenol, 4-
Examples include phenols such as hydroxyphthalic acid dimethyl ester, bis (4-hydroxyphenyl) acetic acid butyl ester, benzyl p-hydroxybenzoate, and 3,5-di-tert-butylsalicylic acid, or organic carboxylic acids. When the agent is used, it is usually used in an amount of 0.1 to 10 parts by weight based on 1 part by weight of the color forming substance.

Examples of storage stabilizers that can be used in the heat-sensitive recording material of the present invention include 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3-tris (2-methyl-4-hydroxy-5-cyclohexylphenyl) butane, 4,
4'-butylidene bis (2-tert-butyl-5-methylphenol), 4,4'-thiobis (2-tert-butyl-5)
-Methylphenol), 2,2'-thiobis (6-tert-butyl-4-methylphenol), 2,2'-methylenebis (6-tert-butyl-4-methylphenol), and other hindered phenol compounds, 4 -Benzyloxy-4 '
-(2-Methylglycidyloxy) diphenyl sulfone, sodium-2,2'-methylenebis (4,6-di-tert-butylphenyl) phosphate, etc. may be mentioned. 0.1 to 10 parts by weight are used per part.

In the heat-sensitive recording material of the present invention, additives such as other general-purpose antioxidants and light stabilizers can be used in combination depending on the application.

Particularly preferable examples of the above additives include phenol-based, sulfur-based, phosphite-based antioxidants, hindered amine-based light stabilizers, and the like, and when they are used in a heat-sensitive recording material. Ordinary non-reactive UV absorbers may be used in combination in the heat-sensitive layer.

Examples of the above-mentioned phenolic antioxidants include 2,6-di-tert-butyl-p-cresol and 2,6-
Diphenyl-4-octadecyloxyphenol, stearyl (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, thiodiethylene glycol bis [(3,5-di-tert-butyl-
4-hydroxyphenyl) propionate], 1,6-
Hexamethylene bis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,6-hexamethylene bis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionamide], 4,4'-thiobis (6-tert-butyl-m-cresol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-sec. Tributylphenol), bis [3,3-bis (4-hydroxy-3-tert-butylphenyl) butyric acid]
Glycol ester, 4,4'-butylidene bis (6-
Tert-butyl-m-cresol), 2,2'-ethylidene bis (4,6-di-tert-butylphenol), 2,2'-
Ethylidene bis (4-tert-butyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-
Tert-butyl-4-methyl-6- (2-hydroxy-3-
Tert-Butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-)
Hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris (3,5-di-tert-butyl-4-)
Hidoxybenzyl) isocyanurate, 1,3,5-
Tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3,5-
Tris [(3,5-ditert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate,
Tetrakis [methylene-3- (3,5-di-tert-butyl-
4-hydroxyphenyl) propionate] methane, 2
-Tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, 3,9-bis [1,1-dimethyl-2-{(3-tertiary Butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, triethylene glycol bis [(3-tert-butyl-4-hydroxy) -5
Methylphenyl) propionate] and the like.

Examples of the sulfur antioxidant include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl and distearyl, and polyols such as pentaerythritol tetra (β-dodecylmercaptopropionate). Β-alkyl mercaptopropionic acid esters of

Examples of the phosphite antioxidant include trisnonylphenyl phosphite, tris (2,4-ditert-butylphenyl) phosphite, tris [2-tert-butyl-4- (3). -Tert-butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl] phosphite, tridecylphosphite, octyldiphenylphosphite, di (decyl) monophenylphosphite, di (tridecyl) pentaerythritoldi Phosphite, distearyl pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl) -4-Methylphenyl) pentaerythritol diphos Aito, bis (2,4,6-tri-tert-butylphenyl) pentaerythritol diphosphite, tetra (tridecyl) isopropylidenediphenol diphosphite, tetra (tridecyl) -4,
4'-n-butylidene bis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl)
-1,1,3-Tris (2-methyl-4-hydroxy-
5-tertiarybutylphenyl) butanetriphosphite, tetrakis (2,4-ditertiarybutylphenyl) biphenylene diphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, etc. Is mentioned.

Examples of the hindered amine light stabilizer include 2,2,6,6-tetramethyl-4-
Piperidyl benzoate, N- (2,2,6,6-tetramethyl-4-piperidyl) dodecyl succinimide,
1-[(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] -2,2,6,6-tetramethyl-4-piperidyl- (3,5-di-tert-butyl-4- Hydroxyphenyl) propionate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-
4-piperidyl) sebacate, bis (1, 2, 2, 6,
6-pentamethyl-4-piperidyl) -2-butyl-2
-(3,5-di-tert-butyl-4-hydroxybenzyl)
Malonate, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine, tetra (2,2,6,6-tetramethyl-4-piperidyl) butanetetracarboxylate, Tetra (1, 2,
2,6,6-Pentamethyl-4-piperidyl) butanetetracarboxylate, bis (2,2,6,6-tetramethyl-4-piperidyl) di (tridecyl) butanetetracarboxylate, bis (1,2,2) 2,6,6-Pentamethyl-4-piperidyl) -di (tridecyl) butanetetracarboxylate, 3,9-bis [1,1-dimethyl-2- {tris (2,2,6,6-tetramethyl- 4-piperidyloxycarbonyloxy) butylcarbonyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [1,
1-dimethyl-2- {tris (1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyloxy)
Butylcarbonyloxy} ethyl] -2,4,8,10
-Tetraoxaspiro [5.5] undecane, 1,5
8,12-Tetrakis [4,6-bis {N- (2,2,
6,6-Tetramethyl-4-piperidyl) butylamino} -1,3,5-triazin-2-yl] -1,5
8,12-Tetraazadodecane, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / dimethyl succinate condensate, 2-tertiary octylamino-4,6-dichloro -S-triazine / N, N '
-Bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine condensate, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine / Examples thereof include dibromoethane condensate.

Other non-reactive UV absorbers that can be used in combination with the reactive UV absorber of the present invention include, for example,
2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-
2-hydroxybenzophenones such as octoxybenzophenone and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone); 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2-
(2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2
-(2-Hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-dicumylphenyl) benzotriazole, 2,2'-methylenebis (4 -Third octyl-6
2- (2-hydroxyphenyl) benzotriazoles such as -benzotriazolyl) phenol, polyethylene glycol ester of 2- (2-hydroxy-3-tert-butyl-5-carboxyphenyl) benzotriazole; phenyl salicylate, resorcinol Benzoates such as monobenzoate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate and hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate; 2-ethyl Substituted oxanilides such as -2'-ethoxyoxanilide and 2-ethoxy-4'-dodecyloxanilide; ethyl-α-cyano-
Examples include cyanoacrylates such as β, β-diphenyl acrylate and methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate.

The heat-sensitive recording material of the present invention can be used in various applications to which the heat-sensitive recording material is applied. For example, the heat-sensitive recording material is used as a recording medium for facsimiles, various calculators and the like, as well as tag paper and handy terminal paper. It can also be used when the heat-sensitive recording material is often handled outdoors for a long period of time.

[0050]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples. However, the invention is not limited by these examples.

Example 1 20 g of 3-dibutylamino-6-methyl-7-anilinofluorane and 10% aqueous polyvinyl alcohol solution 1
Dispersion A was obtained by thoroughly grinding 00 g.

20 g of bisphenol A and 100 g of a 10% aqueous solution of polyvinyl alcohol were thoroughly ground to obtain a dispersion B.

20 g of 1,2-bis (3,4-dimethylphenyl) ethane and 100 g of a 10% aqueous polyvinyl alcohol solution were thoroughly ground to obtain a dispersion C.

Dispersion D was obtained by thoroughly grinding 20 g of zinc stearate together with 100 g of a 10% aqueous solution of polyvinyl alcohol in a ball mill.

Dispersion E was obtained by thoroughly grinding 20 g of polyethylene wax together with 100 g of a 10% aqueous solution of polyvinyl alcohol in a ball mill.

The above dispersions A, B, C, D and E are 1:
2: 2: 0.3 were mixed in a weight ratio of 0.3, adding calcium carbonate 50g To this mixture 200 g, and the coating solution was thoroughly dispersed, based on the coating solution of 50g / m ² It was coated on paper with a thickness of 32 μm and dried to form a color-developing layer.

A 10% aqueous solution of polyvinyl alcohol or a partially modified product of polyvinyl alcohol to which the reactive ultraviolet absorber of the present invention shown in Table 1 below was added in the same manner as in Synthesis Example 3 was added to 50 g / m ² . Was coated on the color-developing layer to obtain a heat-sensitive recording material.

Using the obtained heat-sensitive recording material, a heat-sensitive printing device (TH-PMD: manufactured by Okura Electric Co., Ltd.) was used to print with a pulse width of 0.8 msec. The density of each part was measured by a Macbeth densitometer (RD-933 type manufactured by Macbeth Co.) (original).

Further, the change in density after stamping dioctyl phthalate on the printed portion of the color-developed heat-sensitive recording material was measured to evaluate the oil resistance. Further, in order to evaluate the light resistance, the color-developed heat-sensitive recording material was placed in a carbon arc fade meter, and the densities of a printed portion and a background portion after irradiation for 10 hours were measured.

The results are shown in Table 1 below.

Comparative Example 1 Polyvinyl alcohol to which the ultraviolet absorber forming the protective layer of Example 1 was reacted was added to the following non-reactive [Chemical Formula 11].
A thermosensitive recording material was obtained in the same manner as in Example 1 except that 2% of Comparative Compound 1 was replaced with 10% aqueous solution of polyvinyl alcohol. The same measurement as in Example 1 was performed using the obtained thermal recording material. The results are shown in [Table 1] below.

[0062]

[Chemical 11]

[0063]

[Table 1]

Example 2 20 g of 3- (N-ethyl-N-isoamylamino) -6-methyl-7-anilinofluorane and 100 g of a 10% aqueous polyvinyl alcohol solution were thoroughly ground to obtain a dispersion A. .

15 g of 4-hydroxy-4'-isopropoxydiphenyl sulfone and 100% aqueous 10% polyvinyl alcohol solution were thoroughly ground to obtain a dispersion B.

Dispersion C was obtained by sufficiently grinding 20 g of 1,2-bis (3,4-dimethylphenyl) ethane and 100% aqueous 10% polyvinyl alcohol solution.

20 g of zinc stearate and 100 g of a 10% aqueous polyvinyl alcohol solution were thoroughly ground to obtain a dispersion D.

Dispersion E was obtained by thoroughly grinding 20 g of polyethylene wax with 100 g of a 10% aqueous solution of polyvinyl alcohol in a ball mill.

The above dispersions A, B, C, D and E were mixed with 1:
2: 2: 0.3 were mixed in a weight ratio of 0.3, adding calcium carbonate 50g To this mixture 200 g, and the coating solution was thoroughly dispersed, based on the coating solution of 50g / m ² It was coated on paper with a thickness of 32 μm and dried to form a color-developing layer.

Treatment amount of ultraviolet absorber of Synthesis Example 3 0.1 g
Was changed to the addition amount shown in [Table 2] below, and a 10% aqueous solution of polyvinyl alcohol, which had been added by reaction, was coated on the color forming layer so as to have a concentration of 50 g / m ² to obtain a heat-sensitive recording material. Using the resulting heat-sensitive recording material, the same measurement as in Example 1 was performed, and the results are shown in [Table 2] below.

Comparative Example 2 The polyvinyl alcohol to which the ultraviolet absorber forming the protective layer of Example 2 was added by reaction was treated with the non-reactive Comparative Compound 1 at the addition amount shown in Table 2 below. % Aqueous solution to obtain a thermosensitive recording material in the same manner as in Example 1. Using the resulting heat-sensitive recording material, the same measurement as in Example 1 was performed, and the results are shown in [Table 2] below.

[0072]

[Table 2]

From the results of the above-mentioned respective examples, when the specific benzophenone-based UV absorber of the present invention was used, the light resistance of the printed part was higher than that when the conventionally known non-reactive UV absorber was used. It is clear that the stability is remarkably improved, the soil on the background is small, and the stabilizing effect is remarkably large.

[0074]

INDUSTRIAL APPLICABILITY According to the present invention, a reactive ultraviolet absorber having excellent retention and dispersibility in a protective layer and a heat-sensitive recording material coated with the reactive ultraviolet absorber and having excellent storage stability such as light resistance. Can be provided.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shinya Mashita 5-2-13 Shirahata, Urawa-shi, Saitama Within Asahi Denka Kogyo Co., Ltd. (72) Keiji Oya 5-213 Shirahata, Urawa-shi, Saitama No. Asahi Denka Kogyo Co., Ltd. (56) Reference JP-A-3-31235 (JP, A) JP-B-55-12586 (JP, B1) (58) Fields investigated (Int.Cl. ⁷ , DB name) ) C09K 3/00 104 C08F 8/00-8/50 C08F 16/38 C08K 5/13-5/138

Claims (4)

(57) [Claims] 1. A benzophenone-based reactive ultraviolet absorber represented by the following general formula (I): [Chemical 1] 2. A polymer material obtained by reacting the reactive ultraviolet absorber according to claim 1 with a resin. 3. The polymer material according to claim 2, wherein the resin is polyvinyl alcohol or a polymer composition containing polyvinyl alcohol. 4. A heat-sensitive recording material using the polymer material according to claim 2 as a protective layer for the heat-sensitive recording layer.