JPH05178815A - Phenol derivative and recording material produced by using the same derivative - Google Patents

Abstract

PURPOSE:To provide the subject new phenol derivatives useful as an electron acceptor compound for a recording material excellent in the developed color density and stability of the image part and the non-image part. CONSTITUTION:Phenol derivatives of the formula (R1 is H, a halogen or an alkyl; Ar is phenyl; Y is an alkyl or an aralkyl respectively having a polymerizable group), e.g. 2-phenyl-4-p-vinylbenzylsulfonyl phenol. The compound of formula I can readily be obtained by oxidizing its corresponding sulfide derivative. This recording material is high in the developed color density and excellent in chemical resistance and stability with time.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel phenol derivative useful as an electron-accepting compound for a recording material and a recording material using the same, and is particularly excellent in color developability and further storage-stable in non-image areas and image areas. To a recording material having excellent properties.

[0002]

2. Description of the Related Art Recording materials using an electron-donating colorless dye and an electron-accepting compound are pressure-sensitive paper, thermal paper, photosensitive pressure-sensitive paper,
It is already well known as an electrically conductive recording paper and a thermal transfer paper. For example, British Patent 2140449 and US Patent 448.
No. 0052, No. 4436920, Japanese Patent Publication No. 60-239
92, JP-A Nos. 57-179836 and 60-123.
For details, see No. 556 and No. 60-123557.

As a recording material, in recent years, studies have been earnestly conducted to improve characteristics such as (1) color density and color sensitivity (2) storage stability of non-image area and image area. Conventional electron-accepting compounds for an electron-donating colorless dye include bisphenol A, p-hydroxybenzoic acid esters,
Various types such as bis- (4-hydroxyphenyl) sulfone are known, but all have color density, color sensitivity, storage stability of non-image area and image area (weather resistance, chemical resistance, plasticizer resistance). Etc. had some drawbacks. For example,
When bis- (3-phenyl-4-hydroxyphenyl) sulfone was used as a heat-sensitive recording material, there was a problem that the background part was fogged when writing with a marker or a highlighter pen.

[0004]

SUMMARY OF THE INVENTION The present invention provides an electron-accepting compound for a recording material having a good color density and good storage stability in the non-image area and the image area, and a recording material using the same. Is.

[0005]

The object of the present invention is to provide a recording material using an electron-donating colorless dye and an electron-accepting compound, which is represented by the following general formula (1). It has been solved by a recording material characterized by using a phenol derivative. General formula (1)

[0006]

[Chemical 3]

(In the formula, R ₁ represents a hydrogen atom, a halogen atom or an alkyl group, Ar represents a phenyl group, and Y represents an alkyl group or an aralkyl group having a polymerizable group.)

In the general formula (1), the group represented by R ₁ is preferably a hydrogen atom, a chlorine atom or an alkyl group having 1 to 4 carbon atoms.

Of the groups represented by Y, an alkyl group and an aralkyl group having a vinyl group, an acryloyloxy group, an acryloylamino group, a methacryloyloxy group, a methacryloylamino group and the like are preferable, and an aralkyl group having a vinyl group is particularly preferable. Acryloyloxyphenoxyalkyl group, methacryloyloxyphenoxyalkyl group,
An acryloyloxyalkyl group and a methacryloyloxyalkyl group are preferred.

Specific examples of the alkyl group and aralkyl group represented by Y include p-vinylbenzyl group, m-vinylbenzyl group, 2-acryloyloxyethyl group and 2-
Methacryloyloxyethyl group, 2-acryloyloxypropyl group, 2-methacryloyloxypropyl group,
3-acryloyloxypropyl group, 3-methacryloyloxypropyl group, 4-acryloyloxybutyl group, 4-methacryloyloxybutyl group, 5-acryloyloxypentyl group, 5-methacryloyloxypentyl group, 6-acryloyloxyhexyl group, 6 -Methacryloyloxyhexyl group, 8-acryloyloxyoctyl group, 8-methacryloyloxyoctyl group, 1
0-acryloyloxydecyl group, 14-methacryloyloxydecyl group, 12-acryloyloxidedecyl group, 12-methacryloyloxidedecyl group, 2- (m
-Acryloyloxyphenoxy) ethyl group, 2- (m
-Methacryloyloxyphenoxy) ethyl group, 2-
(M-methacryloylaminophenoxy) ethyl group, 2
-Methacryloylaminoethyl group, 4- (methacryloyloxymethyl) benzyl group, 2- (methacryloyloxyethoxy) ethyl group, 3- (methacryloyloxypropoxy) propyl group, 2,3-bis (methacryloyloxy) propyl group, etc. Can be mentioned.

Specific examples of the compound represented by the general formula (1) are shown below, but the present invention is not limited thereto.

1.2-phenyl-4-p-vinylbenzylsulfonylphenol 2.2-phenyl-4-m-vinylbenzylsulfonylphenol 3.2-phenyl-4- (2-methacryloyloxyethylsulfonyl) phenol 4.2-Phenyl-4- (3-methacryloyloxypropylsulfonyl) phenol 5.2-Phenyl-4- (4-methacryloyloxybutylsulfonyl) phenol 6.2-Phenyl-4- (6-methacryloyl) Loryloxyhexylsulfonyl) phenol 7.2-Phenyl-4- (8-methacryloyloxyoctylsulfonyl) phenol 8.2-Phenyl-4- (12-methacryloyloxidedecylsulfonyl) phenol 9.2-Phenyl -4- (2-acryloryloxyethylsulfonyl) fur Examples include enol 10.2-phenyl-4- (6-acrylolyloxyhexylsulfonyl) phenol and the like.

The phenol derivative represented by the general formula (1) according to the present invention can be easily obtained by oxidizing the corresponding sulfide derivative. As the oxidation method, the method described in Shin Jikken Kagaku Koza, Vol. 14, page 1760 (Maruzen, published), etc. is used.

As the electron-donating colorless dye used in the present invention, conventionally known triphenylmethanephthalide compounds, fluorane compounds, phenothiazine compounds, indolylphthalide compounds, leukoauramine compounds, rhodamine lactams. Various compounds are known, such as a compound based compound, a triphenylmethane compound, a triazene compound, a spiropyran compound, and a fluorene compound. Specific examples of phthalides are US Reissue Patent Specification No. 23
No. 024, U.S. Pat. Nos. 3,491,111 and 3,
No. 491112, No. 3491116 and No. 350.
No. 9174, specific examples of fluoranes are US Pat. Nos. 3624107, 3627787, and 364.
No. 1011, No. 3462828, No. 368139
No. 0, No. 3920510, No. 3959571,
Specific examples of spiro dipyrans are described in US Pat. No. 3971.
No. 808, pyridine compounds and pyrazine compounds are described in US Pat. Nos. 3,775,424 and 3,853,869;
No. 4264318 and specific examples of fluorene compounds are disclosed in JP-A-59-199757 and JP-A-63-41183.
No. etc.

The electron-accepting compound according to the present invention includes compounds such as conventionally known phenol derivatives, salicylic acid derivatives, metal salts of aromatic carboxylic acids, acid clay, bentonite, novolac resins, metal-treated novolac resins and metal complexes. Can be used together. Examples of these are Japanese Patent Publication No. 40-9309.
No. 45-14039, JP-A-562-14048.
No. 3, No. 48-51510, No. 57-210886
No. 58-87089, No. 59-11286, No. 60-76795, No. 61-95988 and the like. When used in combination with another electron-accepting compound,
The amount of the electron-accepting compound of the present invention used is preferably 50% by weight or more.

When the recording material of the present invention is used as a thermal paper, it is disclosed in JP-B-59-53193 and JP-A-59-1974.
No. 63 and JP-A No. 62-114989. Specifically, the electron-donating colorless dye and the electron-accepting compound are pulverized and dispersed in a dispersion medium to a particle size of 10 μm or less, preferably 3 μm or less. As the dispersion medium, a water-soluble polymer aqueous solution having a concentration of about 0.5 to 10% is generally used. Examples thereof include polyvinyl alcohol, hydroxyethyl cellulose, hydroxypropyl cellulose, epichlorohydrin modified polyamide, ethylene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, isobutylene-maleic anhydride silicic acid copolymer, polyacrylic acid, Examples thereof include polyacrylic acid amide, methylol-modified polyacrylamide, starch derivative, casein, gelatin and the like. Further, for the purpose of imparting water resistance to these binders, a water resistant agent may be added, or a hydrophobic polymer emulsion, specifically, a styrene-butadiene rubber latex or an acrylic resin emulsion may be added. The dispersion is performed using a ball mill, a sand mill, a horizontal sand mill, an attritor, a colloidal mill, or the like.

The weight ratio of the electron-donating colorless dye to the electron-accepting compound used is preferably 1:10 to 1: 1 and more preferably 1: 5 to 2: 3.
At that time, a thermofusible substance may be contained in the thermosensitive coloring layer in order to improve the thermal response. Typical examples of the heat-fusible substance include aromatic ethers, thioethers, esters and / or aliphatic amides or ureides.

Examples of these are disclosed in JP-A-58-57989,
58-87094, 61-58789, 62.
-109681, 62-2132674, 63-
No. 151478, No. 63-235961, and the like.

These are used alone or as finely dispersed at the same time as the electron-donating colorless dye or the electron-accepting compound. These are used in a weight ratio of 20% or more and 300% or less with respect to the electron-accepting compound, and particularly preferably 40% or more and 150% or less. If necessary, additives are added to the coating liquid thus obtained in order to meet various requirements. Examples of the additive include an inorganic pigment, in order to prevent the recording head from being soiled during recording.
An oil-absorbing substance such as polyurea filler, a fatty acid, a metal soap, etc. are added to enhance the releasability of the head. Therefore, in general, in addition to electron-donating colorless dyes and electron-donating compounds, heat-fusible substances, pigments, waxes, antistatic agents, ultraviolet absorbers, defoamers, conductive agents, fluorescent dyes, surfactants, etc. The heat-sensitive coating liquid is formed by mixing the additives.
The obtained heat-sensitive coating liquid is applied to high-quality paper, high-quality paper having an undercoat layer, synthetic paper, plastic film and the like. At this time, it is particularly preferable from the viewpoint of dot reproducibility to use a support having a smoothness of 500 seconds or more, particularly 800 seconds or more as defined by JIS-8119.

If desired, a protective layer may be provided on the surface of the heat sensitive recording. Two or more protective layers may be laminated if necessary. A coating liquid similar to the protective layer may be applied to the back surface for the purpose of correcting the curl balance of the support or improving the chemical resistance from the back surface. An adhesive may be applied to the back surface, and release paper may be further combined to form a label.

The coating amount of the electron-accepting compound according to the present invention is optional, but is preferably 0.1 to 2.0 g / m ² on the support, particularly 0.2 to 1.5 g / m ² .

When an undercoat layer is provided on a support, an undercoat layer containing a pigment as a main component is preferable. As the pigment, all general organic or inorganic pigments can be used, but in particular, the oil absorption degree specified by JIS-K5101 is 40 cc /
It is preferably 100 g or more, and specifically, calcium carbonate, barium sulfate, titanium oxide, talc, wax, kaolin, calcined kaolin, aluminum hydroxide, amorphous silica, urea formalin resin powder, polyethylene resin powder and the like. Can be mentioned. When these pigments are applied to a support, the amount of pigment is 2 g / m ² or more, preferably 4
g / m ² or more.

The binder used in the undercoat layer is
Examples thereof include water-soluble polymers and water-soluble binders, and the binders may be used alone or in combination of two or more. As the water-soluble polymer, methyl cellulose, carboxymethyl cellulose, hydroxytyl cellulose, starches, gelatin, gum arabic, casein, styrene-maleic anhydride copolymer hydrolyzate, ethylene-maleic anhydride copolymer hydrolyzate, Examples thereof include polyvinyl alcohol and polyacrylamide.

As the water-soluble binder, synthetic rubber latex or synthetic resin emulsion is generally used.
Examples thereof include styrene-butadiene rubber latex, acrylonitrile-butadiene rubber latex, methyl acrylate-butadiene rubber latex, and vinyl acetate emulsion. The amount of binder used is 3 for pigments.
-100% by weight, preferably 5-50% by weight. Wax, decoloring inhibitor, surfactant, etc. may be added to the undercoat layer.

The pigment used as an additive to be added to the heat-sensitive recording layer is kaolin, calcined kaolin, talc, wax, diatomaceous earth, calcium carbonate, aluminum hydroxide, magnesium hydroxide, zinc oxide, lithopone, amorphous. Silica, colloidal silica, calcined stone, silica, magnesium carbonate, titanium oxide, alumina, barium carbonate,
Examples thereof include barium sulfate, mica, microballoons, urea-formalin filler, polyester particles, and cellulose filler.

Examples of the metal soap include higher fatty acid polyvalent metal salts such as zinc stearate, aluminum stearate, calcium stearate and zinc oleate. Further, in the present invention, a wax having a melting point of 40 to 120 ° C. may be used in combination from the viewpoint of the head matching property with respect to the facsimile. As a wax,
Paraffin wax, polyethylene wax, carnauba wax, microcrystalline wax, candelia wax, montan wax, fatty acid amide wax having a melting point of 40 to 120 ° C. are preferable,
Paraffin wax, montan wax and methylol stearamide having a melting point of 50 to 100 ° C. are preferable. The amount of wax used is 5 to 200% by weight, preferably 20 to 150% by weight of the electron-donating colorless dye.

The hindered phenol compound is preferably a phenol derivative in which at least one of the 2-position and the 6-position is substituted with a branched alkyl group. UV absorbers include cinnamic acid derivatives, benzophenone derivatives,
Benzotriazole phenol derivatives such as butyl α-cyano-β-phenylcinnamate, o-benzotriazole phenol, o-benzotriazole-p-chlorophenol, o-benzotriazole-2,4-di-t-
Butylphenol, o-benzotriazolyl-2,4-
There are di-t-octylphenol and the like.

As the waterproofing agent, N-methylol urea,
Water-soluble initial condensates such as N-methylol melamine and urea-formalin, dialdehyde compounds such as glyoxal and glutaraldehyde, inorganic crosslinking agents such as boric acid and borax,
Examples include blending heat treatment of polyacrylic acid, methyl vinyl ether-maleic acid copolymer, isobutylene-maleic anhydride copolymer and the like. Materials used for the protective layer include polyvinyl alcohol, carboxy-modified polyvinyl alcohol, vinyl acetate-acrylamide copolymer,
Silicon modified polyvinyl alcohol, starch, modified starch, methyl cellulose, carboxymethyl cellulose, hydroxymethyl cellulose, gelatins, gum arabic, casein, styrene-maleic acid copolymer hydrolyzate, styrene-maleic acid copolymer half ester hydrolyzate,
Isobutylene-maleic anhydride copolymer hydrolyzate, polyacrylamide derivative, polyvinylpyrrolidone, water-soluble polymers such as sodium polystyrene sulfonate and sodium alginate, and styrene-butadiene rubber latex, acrylonitrile-butadiene rubber latex, methyl acrylate-butadiene Water-insoluble polymers such as rubber latex and vinyl acetate emulsion are used.

Further, for the purpose of improving the matching property with the thermal head, a pigment, metal soap, wax, water-proofing agent and the like may be added to the protective layer. Further, when the protective layer is coated on the thermosensitive coloring layer, a surfactant may be added to obtain a uniform protective layer. As the surfactant, a sulfosuccinic acid-based alkali metal salt or a fluorine-containing surfactant is used. Specifically, sodium salts such as di- (n-hexyl) sulfosuccinic acid and di- (2-ethylhexyl) sulfosuccinic acid, ammonium salts and the like are preferable, but anionic surfactants are effective.

When used for pressure-sensitive paper, US Pat.
No. 05470, No. 25054571, No. 250548
No. 9, No. 2548366, No. 2712507, No. 2
No. 730456, No. 2730457, No. 310340
It can take various forms as described in prior patents such as No. 4, No. 3418250 and No. 4010038. Most commonly it consists of at least a pair of sheets containing separately an electron donating colorless dye and an electron accepting compound.

Regarding the method of manufacturing capsules, US Pat.
No. 800457, No. 2800458, a method utilizing coacervation of hydrophilic colloid sol, British Patent Nos. 867797, 950443, and 9
89264, 1091076 and the like.

Generally, an electron-donating colorless dye is used alone or in a mixture, and a synthetic oil such as a solvent (alkylated naphthalene, alkylated diphenyl, alkylated diphenylmethane, alkylated terphenyl, chlorinated paraffin, etc .; cotton oil,
A color-developing sheet by dissolving it in vegetable oil such as castor oil; animal oil; mineral oil or a mixed oil thereof, including it in microcapsules, and coating it on paper, high-quality paper, plastic sheet, resin-coated paper, etc. To get

On the other hand, the electron-accepting compound is mixed with an additive as required and dispersed in a binder such as styrene-butadiene latex or polyvinyl alcohol to support the pigment, paper, plastic sheet, resin coated paper and the like. Apply to the body to form a developer sheet.

As the binder, it is preferable to use a carboxy-modified styrene-butadiene latex in combination with a water-soluble polymer from the viewpoint of light resistance and water resistance. Further, as the pigment, it is preferable to use calcium carbonate having an average particle size of 5.0 μm or less in an amount of 60% by weight or more based on all pigments in terms of color developing ability.

The use amount of the electron-donating colorless dye and the electron-accepting compound depends on the desired coating thickness, the form of the pressure-sensitive recording paper, the capsule manufacturing method, and other conditions, and may be appropriately selected according to the conditions. It is easy for a person skilled in the art to determine this usage amount.

[0036]

EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited thereto. In Examples, unless otherwise specified, weight% is expressed.

Example 1 10 g of 2-phenyl-4- (6-methacryloyloxyhexylthio) phenol, 8 g of 30% hydrogen peroxide and 15 ml of glacial acetic acid were weighed in an eggplant-shaped flask and stirred at 60 ° C. for 5 hours. I went. The reaction mixture was poured into water, extracted with ethyl acetate, and the ethyl acetate layer was concentrated under reduced pressure. Purified using silica gel column chromatography, 2-phenyl-4
9.2 g (-melting point 100 ° C) of-(6-methacryloyloxyhexylsulfonyl) phenol was obtained.

Example 2 10 g of 2-phenyl-4-vinylbenzylthiophenol, 8 g of 30% hydrogen peroxide solution and 15 ml of glacial acetic acid were weighed in an eggplant-shaped flask and stirred at 60 ° C. for 5 hours. The reaction mixture was poured into water, extracted with ethyl acetate, and the ethyl acetate layer was concentrated under reduced pressure. Purification using silica gel column chromatography gave 9.1 g of 2-phenyl-4-vinylbenzylsulfonylphenol (melting point: 76 ° C).

Example 3 2-anilino-3-methyl- which is an electron-donating colorless dye
6-dibutylaminofluorane, an electron-accepting compound 2-phenyl-4- (6-methacryloyloxyhexylsulfonyl) phenol, and a heat-fusible compound 2
-Benzyloxynaphthalene 20 g each 100 g 5
% Polyvinyl alcohol (Kuraray PVA105) aqueous solution and dispersed in a ball mill all day and night to give a volume average particle size of 3
was set to μ. On the other hand, calcined kaolin (Anisilex-9
3) 80 g of a 0.5% solution of sodium hexametaphosphate 1
It was dispersed with a homogenizer together with 60 g.

Each dispersion was dispersed as described above to obtain 5 g of an electron-donating colorless dye dispersion and 10 electron-accepting compound dispersions.
g, 10 g of the heat-fusible compound dispersion, and 22 g of the calcined kaolin dispersion, and then mixed with 4 g of zinc stearate emulsion and 5 g of an aqueous solution of 2% (2-ethylhexyl) sodium sulfosuccinate to obtain a coating liquid. I got it.
This coating liquid, dry coating amount neutral paper weighing 50 g / m ² was coated with a wire bar such that the 6 g / m ^2, to obtain a coated paper subjected to calendering treatment.

The coated paper obtained as described above was used as a thermal head (KLT-216-8MPD, manufactured by Kyocera Corp.).
1) and with a thermal printing experimental apparatus having a pressure roll of 100 kg / cm ² immediately before the head, a head voltage of 24
While using a pressure roll under the conditions of V and a pulse cycle of 10 ms, printing was performed with a pulse width of 1.0 and the print density was measured with a Macbeth reflection densitometer RD-918. The color density was 1.21. In addition, use a highlighter pen (Zebra highlighter 2, yellow) to draw lines in the image and non-image areas.
When the writing instrument resistance was examined, the image part did not fade and the non-image part did not fog.

Comparative Example-1 2-phenyl-4 which is the electron-accepting compound of Example-3
A coated paper was obtained in the same manner as in Example-3, except that bis- (3-phenyl-4-hydroxyphenyl) sulfone was used instead of-(6-methacryloyloxyhexylsulfonyl) phenol. When color was developed in the same manner as in Example-3, the color density was 1.28. When the image was written with a highlighter pen in the same manner as in Example 3, the image area was not decolored, but the white background was colored black and showed fogging.

Comparative Example-2 2-phenyl-4 which is the electron-accepting compound of Example-3
A coated paper was obtained in the same manner as in Example-3, except that 4-hydroxy-4'-isopropoxydiphenylsulfone was used instead of-(6-methacryloyloxyhexylsulfonyl) phenol. When color was developed in the same manner as in Example-5, the color density was 1.30. When the image was written with a highlighter pen in the same manner as in Example-5, the image area was erased, the white background area was also colored black, and fog was exhibited.

Example-4 1). [Preparation of Capsule Liquid] 2-anilino-3-methyl-6-diethylaminofluor
Run 14.0 g, Netakenate D110N (Takeda
Capsule wall agent manufactured by Co., Ltd.) 60 g and Sumisorb 200
(Sumitomo Chemical Co., Ltd. UV absorber) 2g 1-phenyl
55 g of 2-xylylethane and 55 of methylene chloride
g dissolved in a mixed solvent. This electron-donating colorless dye solution
100% of 8% polyvinyl alcohol aqueous solution and 40 g of water
And 2% sodium salt of dioctyl sulfosuccinate
Mix with 1.4 g of water and emulsify with a homogenizer
It was. Add 150 g of water and react at 40 ° C for 3 hours.
A capsule liquid having a capsule size of 0.7μ was obtained. 2). [Preparation of Electron-Accepting Compound Dispersion] 2- (o-chlorophenyl) 4-, 5-diphenylimi
Dazole dimer (photopolymerization initiator) 0.12 g, 7-die
Cylamino-4-methylcoumarin (spectral sensitizing dye) 0.
12 g, N-phenylglycine ethyl ester 0.1 g
And the electron-accepting compound of the present invention, 2-phenyl-4-vinyl
Lebenzylsulfonylphenol 8.0 g, 3,5-bi
1.0 g of zinc (α-methylbenzyl) salicylate
It was dissolved in 8.0 g of ethyl acidate. Add 7.5% poly to this solution.
Vinyl alcohol aqueous solution 9.6g and 2% nonylphenoki
0.8 g of sodium butyrate sulfonate aqueous solution and 2% dodeca
Add 0.8 g of sodium sulfonate aqueous solution and homogenize.
And emulsified to obtain an emulsified dispersion of an electron-accepting compound. 3). [Preparation of recording material] 4.0 g of electron-donating colorless dye capsule liquid and electron-accepting property
Compound dispersion 12g and 15% polyvinyl alcohol aqueous solution
A coating liquid was prepared by stirring and mixing 5.0 g. Thick this coating liquid
70μ transparent polyethylene terephthalate (PE
T) Film has a solid content of 15 g / m²Painted to be
Cloth was dried. In addition to the above-mentioned heat-sensitive layer, the following solid components
2.5 g / m protective layer having²Formed. Silicon-modified polyvinyl alcohol (PVAR-2105 manufactured by Kuraray Co., Ltd.) 2 parts by weight Colloidal silica (Snowtex 30 manufactured by Nissan Chemical Co., Ltd.) 3 parts by weight Paraffin wax emulsion (Cerosol 428 manufactured by Chukyo Yushi Co., Ltd.) 0.9 Parts by weight Zinc stearate emulsion (Hydrin Z-7 manufactured by Chukyo Yushi Co., Ltd.) 0.2 parts by weight 4). [Image recording and evaluation] The obtained recording material was applied to a thermal printing tester manufactured by Kyocera Corporation.
Used, 30 mJ / mm ²When printed with, a clear black color
An image was obtained. The obtained image is 1000 W high pressure mercury
After exposing with a lamp (Oak jet light),
The pull was printed again with the thermal printing tester, but the unprinted part was printed.
It didn't color. The obtained recording material is 40 ° C, 30RH
% Change the recording material after leaving it for 48 hours.
As a result of observation, it was confirmed that crystals did not precipitate in the recording layer and opaque.
How to get rid of.

Comparative Example-3 Instead of the electron-accepting compound used in Example-4, 3,
5-bis (α-, methylbenzyl) salicylic acid zinc salt
1.4 g, 4-hydroxybenzoic acid benzyl ester
3.4 g and 1,1-bis (4-hydroxyphenyl)
Ru) -2-Ethylhexane 3.2 g, other examples-
A recording material was prepared in exactly the same manner as in 4. Record obtained
Using a thermal printing tester manufactured by Kyocera Corp., the material is 30 m
J / mm ²When printed with, a black image was obtained,
Precipitation of some crystals was already observed. In addition, 4 recording materials
After leaving at 0 ° C and 30RH% for 48 hours,
Observation of changes in the recording material revealed that the recording layer was white.
It was opaque.

Example-5 1). [Preparation of electron-donating colorless dye capsule solution] 3,3-bis (1-octyl-2-methylindole-
3-yl) phthalide (12.4 g) was dissolved in ethyl acetate (10.4 g), and dicyclohexylphthalate (12.4 g) and takenate were prepared.
27g of D-110N (manufactured by Takeda Pharmaceutical Co., Ltd.) and Millionate
3 g of MR200 (manufactured by Nippon Polyurethane Industry Co., Ltd.) was added. This solution is mixed with polyvinyl alcohol 4.6g and water 74
g, and then emulsified and dispersed at 20 ℃ to obtain an average particle size of 2.5.
A μm emulsion was obtained. 100 g of water was added to the obtained emulsion, and the mixture was heated to 60 ° C. with stirring, and after 2 hours, an electron-donating colorless dye capsule solution was obtained. 2). [Preparation of emulsion of photocurable composition] Accelerate polymerization with 0.12 g of 2-O-chlorophenyl-4,5-diphenylimidazole dimer and 0.12 g of 7-diethylamino-4-methylcoumarin. As an auxiliary agent, 0.06 g of N-phenylglycine ethyl ester was dissolved in 8 g of ethyl acetate to obtain the electron-accepting compound 2-phenyl-
4- (6-methacryloyloxyhexylsulfonyl)
4.0 g of phenol and 4.0 g of 2-phenyl-4-vinylbenzylsulfonylphenol were added. This solution was added to a mixed solution of 9.6 g of 7.5% PVA aqueous solution, 0.8 g of 2% sodium nonylphenoxybutanesulfonate aqueous solution and 0.8 g of 2% sodium dodecanesulfonate aqueous solution, and a homogenizer (Nippon Seiki Co., Ltd.). Emulsified at 10,000 rpm for 5 minutes to obtain an emulsion of the photocurable composition. 3). [Preparation of coating liquid for light- and heat-sensitive layer] 4 g of electron-donating colorless dye capsules, 12 g of photocurable composition emulsion and 12 g of 15% PVA aqueous solution were mixed to prepare coating liquid for light- and heat-sensitive layer. did. 4). [Preparation of coating liquid for protective layer] 4.5 g of 10% aqueous gelatin solution, 1.5 g of distilled water and 2% aqueous solution of sodium nonylphenoxybutane sulfonate 0.5 g and 1%
2,4-dichloro-6-hydroxy-s-triazine / sodium salt aqueous solution (1.5 g) and Cyloid 72 (FUJ
I-DEVISON CHEMICHAL LTD.
A coating solution for a protective layer was prepared by mixing an amount such that the coating amount was 50 mg / m ² and 1 g of Snowtex N. 5). [Preparation and evaluation of recording material] The coating liquid for the light- and heat-sensitive layer was coated on a 100 µ polyethylene terephthalate film with a coating bar so that the dry weight of the coating layer was 8 g / m ² , and 30 ° 1 in C
It was dried for 0 minutes. The protective layer coating solution was applied onto this layer using a coating bar so that the dry weight of the coated layer was 5 g / m ² , and dried at 30 ° C. for 10 minutes. The resulting light- and heat-sensitive recording material was exposed to ultraviolet light from a 1000 W high pressure mercury lamp (Oak Jet Light) for 60 seconds through a lith film on which an image was developed. Then 12
When heated for 5 seconds with a hot plate at 0 ° C., a clear magenta colored image was obtained. The image density was 1.75 and the non-image part density was 0.08. Further, in order to examine the storability of the obtained image, when it was left for 24 hours under the condition of 40 ° C. and 90 RH%, the color density of the image part did not change, and the non-image part had no crystal precipitation at all. Fog density is 0.08
was.

[0047]

From the results of "Examples", it can be seen that the recording material of the present invention is a recording material having a high color density and excellent chemical resistance and stability over time.

Claims (2)

[Claims] 1. A phenol derivative represented by the following general formula (1). General formula (1) (In the formula, R ₁ represents a hydrogen atom, a halogen atom or an alkyl group, Ar represents a phenyl group, and Y represents an alkyl group or an aralkyl group having a polymerizable group.) 2. A recording material using an electron-donating colorless dye and an electron-accepting compound, wherein the phenol derivative represented by the following general formula (1) is used as the electron-accepting compound. Recording material. General formula (1) (In the formula, R ₁ represents a hydrogen atom, a halogen atom or an alkyl group, Ar represents a phenyl group, and Y represents an alkyl group or an aralkyl group having a polymerizable group.)