JPH02204091A - Recording material - Google Patents

Abstract

PURPOSE:To obtain a recording material having excellent coloring sensitivity, adaptability for high speed recording and high skin whiteness by employing at least one type of specific phenol compound as a developer. CONSTITUTION:In a recording material, leuco dye, developer and auxiliary component are bound and supported on a support. The developer includes, for example, phenol compound represented by a formula (I), and, as required, various types of electron acceptive compound such as phenol compound, thiophenol compound, thiourea derivative, organic acid and metal salt, etc. Thus, a recording material adapted for high speed recording with excellent coloring sensitivity is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a recording material, and particularly to a recording material with excellent color development.

[Conventional technology]

Heat between a colorless or light-colored leuco dye and a color developer,
Various recording materials have been proposed that utilize color reactions caused by pressure or the like.

One type of thermal recording material is that it does not require complicated processing such as development and fixing, can be recorded in a short time using relatively simple equipment, generates little noise, and is low in cost. Due to computer, facsimile,
It is useful as a variety of recording materials for ticket vending machines, labels, recorders, etc.

Color-forming dyes used in heat-sensitive recording materials include, for example, colorless or light-colored leuco dyes having a lactone, lactam, or spiropyran ring, and organic acids, phenolic substances, and the like have been conventionally used as color developers. Recording materials using this leuco dye and color developer are widely used because they have a high image area density and a high whiteness of the background.

On the other hand, as the demand for thermal recording methods has increased in recent years, the demand for faster recording has also increased.

For this reason, there is a strong desire to not only increase the speed of the recording apparatus itself, but also to develop an RR2 recording material that can accommodate this.

In addition, particularly in fields where the reliability of recorded images is important, it is required to provide images that are highly stable against plasticizers contained in oils and fats, plastics, and the like.

[Problem to be solved by the invention]

In order to cope with faster recording, as a high-sensitivity color developer,
For example, p-hydroxybenzoic acid esters have been proposed in JP-A-56-144193, and hydroxynaphthoic esters have been proposed in JP-A-59-22793. Furthermore, JP-A-59-165680 proposes the use of a thioester compound as a color developer, but recording materials using this compound have high fastness to oils and fats in the image area, but do not have high sensitivity. Furthermore, there have been various proposals for increasing sensitivity by adding various thermofusible substances. Benzyl biphenyl and the like have been proposed in publications and the like.

However, recording materials using these color developers or thermofusible substances have poor color development sensitivity, background whiteness, and storage stability (
However, it is still far from satisfactory in terms of image fading, white powder generation, etc.).

Conventionally, in order to improve the stability of recorded images, for example, a thermosensitive coloring layer containing a large amount of water-resistant and chemical-resistant resin, a thermosensitive coloring layer containing a resin that hardens with heat or light, or a resin protective layer on the surface. However, these methods have the problem of complicating the process, increasing costs, and lowering the thermal response. On the other hand, as a proposal to improve the stability of images by improving the color developer,
Methods using bisphenol S derivatives such as No. 8, No. 59-96991, and No. 60-13852, methods using trisphenols such as JP-A-58-160i91, and JP-A-57-6795. , 61-47
There are methods using carboxylic acid metal salts such as those disclosed in Publication No. 292, but all of them are sufficient in terms of background coloring, background discoloration, background coloring due to plasticizers, solvents, etc., and image stability against oils, plasticizers, etc. It is difficult to say that it is.

The present invention has an excellent color development layer degree and is suitable for high-speed recording.
Moreover, our first priority is to provide recording materials with high background whiteness.
A second object of the present invention is to provide a recording material which has excellent stability of colored images and excellent background stability.

[Means to solve the problem]

According to the present invention, in a recording material that utilizes a color-forming reaction between a colorless or light-colored leuco dye and a color developer that causes the leuco dye to develop a color upon contact, the color developer is expressed by the following linear formula (1). A recording material characterized in that it uses at least one kind of phenolic compound represented by (II) is provided.

(In the formula, R and R1 each represent an alkyl group, an alkoxy group, an acyl group, an oxycarbonyl group, or a halogen group, and ■ represents an aromatic ring, and Q represents θ to 3.
(2) represents an integer of 0 to 5 and n represents an integer of 0 to 1O, respectively; each represents an aromatic ring, and k is l-
2.Q is 0-3. (w and n each represent an integer of 0 to 5, and n represents an integer of 0 to 10, respectively.) The recording material of the present invention has the general formula ([)
By using the compound represented by the formula (■), it has excellent color development sensitivity and is suitable for high-speed recording, and by using the compound represented by the general formula (■), it has excellent one-image stability. .

Specific examples of the phenolic compounds represented by the general formulas (1) and (■) used in the present invention are shown below, but the present invention is not limited thereto.

CH, CI (.

The leuco dyes used in the present invention may be applied singly or in a mixture of two or more types. As such leuco dyes, those applied to this type of recording material may be arbitrarily applied. For example, triphenyl Methane type, fluorane type, phenothiazine type.

Leuco compounds of dyes such as auramine, spiropyran, and indolinophthalide are preferably used. Specific examples of such leuco dyes include those shown below.

3.3-bis(P-dimethylaminophenyl)-phthalide, 3.3-bis(ρ-dimethylaminophenyl)-6-dimethylaminophthalide (also known as crystal violet lactone), 3.3-bis(ρ- dimethylaminophenyl)-6-dibutylaminophenyl.

3.3-bis(p-dimethylaminophenyl)-6-chlorophthalide, 3.3-bis(p-dibutylaminophenyl)phthalide, 3-cyclohexylamino-6-chlorofluoran.

3-dimethylamino-5,7-dimethylfluorane.

3-(N-Methyl-N-isobutylamino)-6-methyl-7-anilinofluorane.

3-(N-ethyl-N-ynamylamino)-6-methyl-7-anilinofluorane.

3-diethylamino-7-chlorofluorane.

3-diethylamino-7-methylfluorane.

3-diethylamino-7,8-benzfluorane, 3-
Diethylamino-6-methyl-7-chlorofluoran.

3-(N-P-)-lylu-N-ethylamino)-6-methyl-7-anilinofluorane.

3-pyrrolidino-6-methyl-7-anilinofluorane.

2- (N-(3'-trifluoromethylphenyl)
amino)-6-dinithylaminofluorane, 2-(3
, 6-bis(diethylamino)-9-(o-chloroanilino)xantylbenzoic acid lactam).

3-diethylamino-6-methyl-7-chloromethylanilino)fluoran, 3-diethylamino-7-(o-chloromethylanilino)fluoran.

3-Dibutylamino-7-(o-chloroanilino)fluoran.

3-N-methyl-N-amylamino-6-methyl-7-
Anilinofluorane.

3-N-Methyl-N-cyclohexylamino-6-methyl-7-anilinofluorane.

3-diethylamino-6-methyl-7-anilinofluorane.

3-diethylamino-6-methyl-7-(2',4'-
dimethylanilino)fluoran, 3-(N,N-diethylamino)-5-methyl-7-(
N,N-dibenzylamino)fluorane.

Benzoylleucomethylene blue 6'-chloro-8'-methoxy-benzoindolino-pyrylosbilane, 6'-bromo-3'-methoxy-benzoindolino-pyrylosbilane.

3-(2'-hydroxy-4'-dimethylaminophenyl)-3-(2'-methoxy-5'-chlorophenyl) phthalide.

3-(2'-hydroxy-4'-dimethylaminophenyl)-3-(2'-methoxy-5'-nitrophenyl)phthalide, 3-(2'-hydroxyl4'-diethylaminophenyl)-3- (2'-Methoxy-5'-methylphenyl)phthalide.

3-(2'-methoxy-4'-dimethylaminophenyl)-3-(2'-hydroxy-4'-chloro-5'
-methylphenyl)phthalide.

3-morpholino-7-(N-propyl-trifluoromethylanilino)fluorane, 3-pyrrolidino-7-trifluoromethylanilinofluorane.

3-diethylamino-5-chloro-7-(N-benzyl-trifluoromethylanilino)fluorane, 3-pyrrolidino-7-(di-p-chlorophenyl)methylaminofluorane.

3-diethylamino-5-chloro-7-(α-phenylethylamino)fluoran, 3-(N-ethyl-P-toluidino)-7-(α-phenylethylamino)fluorane, 3-diethylamino-7-(o -Methoxycarbonylphenylamino)fluoran, 3-diethylamino-5-methyl-7-(α-)-dimethylethylamino)fluoran, 3-diethylamino-7-piperidinofluorane.

2-chloro-3-(N-methyltoluidino)-7-(p
-n-butylanilino)fluoran, 3- (N-methyl-N-isopropylamino)-6-
Methyl-7-anilinofluorane.

3-dibutylamino-6-methyl-7-anilinofluorane.

3.6-bis(dimethylamino)fluorene spiro(9
,3')-i1i'-dimethylaminophthalide.

3-(N-benzyl-N-cyclohexylamino)-5
, 6-penzo 7-α-naphthylamino-4'-bromofluorane, 3-diethylamino-6-chloro-7-anilinofluorane.

3-N-ethyl-N-(2-ethoxypropyl)amino-6-menal-7-anilinofluorane.

3-N-ethyl-N-tetrahydrofurfurylamino-
6-Methyl-7-7nylinofluorane.

3-diethylamino-6-methyl-7-mesitidino 4
', 5'-benzofluorane.

3-(P-dimethylaminophenyl)-3-(1,1-
Bis(p-dimethylaminophenyl)ethylene-2-yl)phthalide, 3-(P-dimethylaminophenyl)-3-(1,1-
Bis(P-dimethylaminophenyl)ethylene-2-yl)-6-dimethylaminophthalide, 3-(p-dimethylaminophenyl)-3-(1-p-
dimethylaminophenyl-1-phenylethylene-2-
il) phthalide.

3-(p-dimethylaminophenyl)-3-(1-p-
dimethylaminophenyl-1-p-chlorophenylethylene-2-yl)-6-dimethylaminophthalide, 3-
(4,'-dimethylamino-2'-methoxy)-3-(
t''~p-dimethylaminophenyl-1''-p-chlorophenyl-111,311-butadien-4''-yl)benzophthalide, 3-(4'-dimethylamino-
2'-benzyloxy)-3-(1''-p-dimethylaminophenyl-1''-phenyl-1''.

3″-butadien-4″-yl)benzophthalide, 3-
Dimethylamino-6-dimethylamino-fluorene-9
-Spiro-3'-(fi'-dimethylamino)phthalide.

3.3-bis(2-(ρ-・dimethylaminophenyl)
-2-(p-methoxyphenyl)r-tenyl)-4,5
,6,7-titrachlorophthalide, 3-bis(1,1-bis(4-pyrrolidinophenyl)ethylene-2-yl)-5,6-dichloro-4,7-dibromophthalide, bis(P -dimethylaminostyryl)-1-naphthalenesulfonylmethane, etc.

Further, in the present invention, a phenolic compound represented by the above-mentioned -line formula is used as the R coloring agent.

Furthermore, if necessary, various electron-accepting compounds such as phenolic compounds, thiophenolic compounds, 5-thiourea derivatives, organic acids and metal salts thereof, etc. can be used in combination, and specific examples thereof are as shown below. There are things that can be mentioned.

4.4'-Isopropylidene bisphenol.

4.4'-Isozolobylidene bis(0-methylphenol), 4.4'-Secondary-butylidene bisphenol, 4.4. ' --isopropylidene bis(2-tert-butylphenol), 4.4'-cyclohexylidene diphenol, 4.4'
-isopropylidene bis(2-chlorophenol).

2.2'-methylenebis(4-methyl-6-tert-butylphenol).

2.2'-Methylenebis(4-ethyl-6-t-butylphenol).

4.4'-butylidenebis(6-tert-butyl-2-methylphenol), 1.1.3-tris(2-methyl-4-hydroxy-
5-tert-butylphenyl)butane.

1.1.3-tris(2-methyl-4-hydroxy-5
-cyclohexylphenyl)butane, 4,4' -thiobis(6-tert-butyl-2-
methylphenol), 4.41-diphenolsulfone, 4-impropoxy-4'-hydroxydiphenylsulfone.

4-benzyloxy-4'-hydroxydiphenylsulfone.

4,4'-diphenol sulfoxide, isopropyl P-hydroxybenzoate, benzyl P-hydroxybenzoate, benzyl protocatechuate, stearyl gallate.

Lauryl gallate.

Octyl gallate.

■, 3-bis(4-hydroxyphenylthio)-propane.

1.3-bis(4-hydroxyphenylthio)-2-hydroxypropane, N,N'-diphenylthiourea, N,N'-di(strict-chlorophenylinthiourea, salicylanilide).

5-chloro-salicylanilide.

Bis-(4-hydroxyphenyl)acetic acid methyl ester.

Bis-(4-hydroxyphenyl)acetic acid benzyl ester, 1#3-bis(4-hydroxycumyl)benzene, 1.
4-bis(4-hydroxycumyl)benzene, 2.4'
-diphenolsulfone, 2,2'-diallyl-4,4'-diphenolsulfone, 3,4-dihydroxy-41-methyldiphenylsulfone, zinc 1-acetyloxy-2-naphthoate.

Zinc 2-acetyloxy-1-naphthoconic acid, zinc 2-7cetyloxy-3-naphthonic acid, α, α-bis(
4-hydroxyphenyl) to α-methyltoluene.

Antipyrine complex of zinc thiocyanate.

tetrabromobisphenol A, Tetrabromobisphenol S, etc.

For producing the recording material of the invention, a leuco dye is used.

The color developer and auxiliary components may be bonded and supported on the support. In this case, various commonly used binders can be used as appropriate, and specific examples thereof include the following: can be mentioned.

Polyvinyl alcohol, lol! Powder and its derivatives, cellulose derivatives such as methoxycellulose, hydroxyethylcellulose, carboxymethylcellulose, methylcellulose, ethylcellulose, sodium polyacrylate, polyvinylpyrrolidone, acrylamide/acrylic ester copolymer, acrylamide/acrylic ester/
In addition to water-soluble polymers such as methacrylic acid terpolymer, styrene/7leic anhydride copolymer alkali salt, isobutylene/maleic anhydride copolymer alkali salt, polyacrylamide, sodium alginate, gelatin, and casein, Polyvinyl acetate, polyurethane, polyacrylate, polymethacrylate.

Vinyl chloride/vinyl acetate copolymer, ethylene! Emulsions such as vinyl acetate copolymers, latexes such as styrene/butadiene copolymers, styrene/butadiene/acrylic copolymers, etc.

Furthermore, when obtaining a heat-sensitive recording material according to the present invention, various heat-fusible substances can be used as a heat sensitivity improver, if necessary, and specific examples thereof include the following compounds.

Fatty acids such as stearic acid and behenic acid, fatty acid amides such as stearic acid amide and balmitic acid amide, fatty acid metal salts such as zinc stearate, aluminum stearate, calcium stearate, zinc valmitate, and zinc behenate, p- benzylbiphenyl, terphenyl,
Triphenylmethane, benzyl p-benzyloxybenzoate, β-benzyloxynaphthalene, β-naphthoic acid phenyl ester, ■-hydroxy-2-naphthoic acid phenyl ester,! -Human ,1
, 2-bis(phenoxy)ethane, 1,2-bis(3-
Methylphenoxy)ethane, l,2-bis(4-methylphenoxy)ethane, 1,4-bis(phenoxy)butane, 1,4-bis(phenoxy)-2-butene, 1.2
-bis(4-methoxyphenylthio)ethane, dibenzoylmethane, 1,4-bis(phenylthio)butane. 1
．． 4-bis(phenylthio)-2-butene, 1,2-bis(4-methoxyphenylthio)ethane, 1,3-bis(2-vinyloxyethoxy)benzene, 1,4-bis(2-vinyloxyethoxy) ) Benzene, P-(2-vinyloxyethoxy)biphenyl, p-aryloxybiphenyl, p-propargyloxybiphenyl, dibenzoyloxymethane, 1,3-dibenzoyloxypropane, dibenzyl disulfide, 1,1-diphenyl Ethanol, 1,1-diphenylpropanol, p-(
benzyloxy)benzyl alcohol, l,3-diphenoxy-2-propatol, N-octadecylcarbamoyl-toxycarbonylbenzene, N-octadecylcarbamoylbenzene, etc.

In addition, when obtaining a heat-sensitive recording material according to the present invention, in addition to the leuco dye and the R coloring agent, auxiliary additive components commonly used in this type of heat-sensitive recording material, such as fillers and surfactants, may be used in combination, if necessary. can do. In this case, fillers include, for example, calcium carbonate, silica, zinc oxide, titanium oxide, aluminum hydroxide, zinc hydroxide, barium sulfate, clay, talc, and surface-treated inorganic fine powders such as calcium and silica. Other examples include organic fine powders such as urea-formalin resin, styrene/methacrylic acid copolymer, and polystyrene resin.

Further, regarding the layer structure, it may be a single layer or a multilayer, and an over layer, an under layer, and a back layer may be provided as necessary.

Note that the color developer in the present invention can also be used as a pressure-sensitive recording material, and the pressure-sensitive recording material using the color developer is
It can be easily created by a conventionally known method.

[Effects of the Invention The recording material according to claim (1), which uses the phenolic compound represented by the general formula (f) as a color developer, has excellent color density and sensitivity, and has a high degree of background color development. It is something. Furthermore, the recording material according to claim (2), which uses the phenolic compound represented by the general formula (II), has excellent image stability.

〔Example〕

Next, the present invention will be explained in more detail with reference to examples. Note that all parts and percentages shown below are based on weight.

Examples 1 to 3 and Comparative Example 1 The following mixtures were each ground in a magnetic ball mill for two days to prepare [Liquid A], [Liquid B], and [Liquid C].

[Liquid A]

3-(N-methyl-N-cyclohexyl)amino 2
0 parts - 10% aqueous solution of 6-methyl-7-anilite fluorane polyvinyl alcohol 20 parts water
60 parts [Liquid B] Phenolic compound in Table 1 20 parts 1.0% aqueous solution of polyvinyl alcohol 20 parts water

60 parts [Liquid C] Calcium carbonate 20 parts 5% aqueous solution of methylcellulose 20 parts water
6
0 parts, then [Liquid A] 10 parts, [Liquid B] 30 parts, (Liquid C] 3
0 parts and 20 parts of isobutylene/maleic anhydride copolymer
% alkaline aqueous solution was mixed to prepare a heat-sensitive coloring layer forming liquid.

The amount of dye adhesion after drying was 0.5 oz. After coating and drying to provide a heat-sensitive coloring layer, the surface smoothness is 500 to 600.
A heat-sensitive recording material was prepared by calendering the surface of the layer to a temperature of seconds.

Regarding the heat-sensitive recording material obtained as described above.

The voltage is 13.3V using a thermal printing device manufactured by Matsushita Electronic Components.
The density was measured using a Macbeth densitometer RD-914. The results are shown in Table-1.

Table-1 Examples 4 to 6 and Comparative Examples 2 to 3 Same as Example 1 except that the phenolic compounds listed in Table 1-2 were used instead of the phenolic compounds in [Liquid B] in Example 1. A thermosensitive recording material was prepared in the same manner.

Next, the obtained heat-sensitive recording material was subjected to a temperature of 150° C. using a thermal gradient tester manufactured by Toyo Seiki Seisakusho.

Printing was performed under the conditions of a pressure of 2 kg/aJ and 1 second, and the image density was measured using a 7-cubes densitometer RD-+1114 (7 I/L/T: V-106). The hardener resistance and oil resistance were tested. These results are shown in Table-2.

(2) Resistance to softeners: A reagent di(2-ethylhexyl adipate) manufactured by Tokyo Kasei Kogyo Co., Ltd. was applied to the print area, and the density of the image area was measured after being left at room temperature for 1 hour.

■Oil resistance: Apply cottonseed oil to the printing surface at 40°C.
After storage for 24 hours under dry conditions, the density of the image area was measured.

The concentration measurements after each of the above storage tests were also carried out using a Maches Densitometer RD-914 (Near A/L/T: V-106).
Table 2 From the results shown in Table 1, it was found that the heat-sensitive recording material of claim (1) has extremely excellent high-speed recording properties.

Furthermore, from the results shown in Table 2, it can be seen that the heat-sensitive recording material of claim (2) is excellent in that the image area is less likely to fade due to plasticizer or oil.

Patent applicant Rico Co., Ltd.

Claims (1)

[Claims] (1) In a recording material that utilizes a color-forming reaction between a colorless or light-colored leuco dye and a color developer that causes the leuco dye to develop color upon contact, the color developer is expressed by the following general formula (I):
A recording material characterized by using at least one type of phenolic compound represented by ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the formula, R_1 and R_2 are an alkyl group, an alkoxy group, an acyl group, an oxycarbonyl group, or a halogen atom,
X is -S-, ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼ or a direct bond, and ■ is an aromatic ring. respectively, and n is 0 to 3, m is 0 to 5, and n is 0 to 1.
Each represents an integer of 0. )(2) In claim (1),
A recording material characterized in that at least one phenolic compound represented by the following general formula (II) is used as the color developer. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, R_1 and R_2 are an alkyl group, an alkoxy group, an acyl group, an oxycarbonyl group, or a halogen atom,
X is -O-, -S-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or a direct bond, and■ represents an aromatic ring, k represents an integer of 1 to 2, l represents an integer of 0 to 3, m represents an integer of 0 to 5, and n represents an integer of 0 to 10, respectively. )