JPS58212989A - Diazo heat-sensitive recording material - Google Patents

Abstract

PURPOSE:To obtain the titled recording material, whose practical density is sufficient and black coloring and shelf life are excellent, and wherein a heat- sensitive layer, whose main components are a diazo compound, a specified coupler, and a heat-fusible material, is provided on a support. CONSTITUTION:A coating liquid is prepared by mixing dispersions obtained by dispersing the following components and a binder: a diazo compound; a coupler wherein compounds shown by formulas I and II (wherein R1 and R2 are each an aromatic or alicylic group; X1 is H, halogen, acetyl, or the like; X2 and X3 are each H, halogen, alkyl, or the like; Y is cyano or acyl), e.g. Naphthol AS, are used in a ratio of 1/5-5/1; 0.1-10.0pts.wt. (per pt.wt. coupler) compound shown by formula III (wherein R3-R5 are each C1-12 aliyl, H, phenyl, or the like, provided that one or more of them are phenyl or cyclohexyl and both R4 and R5 are not H at the same time), e.g. N-methylacetanilide; 5-30pts.wt. (per pt.wt. diazo compound) heat-fusible material (e.g. stearamide). The coating liquid is applied on a support and dried to obtain an intended recording material.

Description

[Detailed description of the invention] The present invention relates to a diazo thermosensitive recording material.

A diazo thermal recording material is widely known in which a 1 m thermal layer containing a diazo compound, cassillary, a thermofusible substance, or a development accelerator as a main component is provided on a support such as paper or a plastic film.

Conventionally, diazo-based heat-sensitive recording materials (or heat-developable diazo copying materials) include: 1) R-CO having a melting point of 80 to 130 C as a thermofusible substance;
NH, (R is an alkyl group, allyl group) (
(See Japanese Patent Publication No. 44-15747) 2) It has been proposed to use the compound fatty acid gold salt S salt (see Japanese Patent Publication No. 45-8500) as a development accelerator.

However, all of the above have sufficient practical concentration (thermal sensitivity)
It was not possible to rU. Furthermore, it is difficult to obtain good black color development with one type of coupler, and the storage stability is also not satisfactory.

An object of the present invention is to overcome the above-mentioned drawbacks of the diazo heat-sensitive recording materials proposed so far, and to provide a heat-sensitive recording material with sufficient practical density, black color development, and good storage stability.

That is, the present invention relates to a diazo thermosensitive recording material in which a thermosensitive layer mainly composed of a diazo compound, a coupler, and a thermofusible substance is strung on a support, and the couplers include the following general formulas (1) and (I). ) is used in combination with A heavy (where R is an aromatic group or an alicyclic group, and X is an aromatic group or an alicyclic group.

are water volume, halogen, gamma cetyl group, sulfonic acid group, and alkoxyl group. ) (However, X and X are water volume, halogen, alkyl group,
It is an alkoxy group or an aryloxy group, R is an aromatic group or an alicyclic group, and Y is a cyano group or an acyl group.

) Furthermore, a compound represented by the following general formula (IID (however, R
,,It4. R, is an alkyl group where n = 1 to 12,
It is either hydrogen, phenyl group, or cyclohexyl group, and at least one of fill t R41R1 must be phenyl group or cyclohexyl group, and both R, , and R must not be hydrogen. . ) is characterized by chewing.

In the present invention, Cassirer of general formula (1) and general formula (I
A clear black color can be obtained by using t) Cassirer in combination, and they are used together so that l: 5 to 5jl. Thermal IJf melting v/J ratio is 5 to 30 lateral parts per 1 part of the diazo compound. The compound of the general formula (lit) may be regarded as one of the thermofusible substances, and may be used alone or together with the substance of Ujiyu.

The usage of the compound of general formula (lit) is cup, 7-1
0.1-10.0 parts by weight, preferably 0.5 parts by weight
~3.0 Jushabu is preferred.

The compound of general formula (2) is characterized in that it has a particularly high dissolving power for the coupler used in the present invention, compared to commonly used thermofusible substances and known development accelerators. At melting temperature, the dye-forming reaction is promoted by dissolving the coupler well, resulting in a high practical concentration.

When an alkyl group is included in any of R1#R4114H of the compound of general formula (2), the dissolving power of Cassirer decreases as the number of carbon atoms in the alkyl group increases. 1 to 6 is good.

Specific examples of general formula (I) include the following.

Specific examples of general formula (1) include the following O [Phase] CONii%N 11 COCH, (OcH.

(J Shi 2 Ko 1s Compounds of the general formula (1M) include, for example, the following compounds 0 () As a chemically compatible substance, the melting point or softening point is 50 to 25
A temperature range of 0C is adopted. Specific examples include the following.

Alcohol conductors such as 2-tribromoethanol, 2,2-dimethyltrimethylene glycol, 1,2-cyclohexanediol, acid i conductors such as malonic acid, glutaric acid, maleic acid, methylmaleic acid, beeswax, shellac wax, etc. of animal waxes, yuzu such as carna, etc.
J waxes, mineral waxes such as montan wax, petroleum waxes such as halafine wax, sulfur, microcrystalline wax, and other synthetic waxes such as polyhydric alcohol esters of higher fatty acids, higher amines, higher amides,
Ha'a Uj Condensate of acid and amine, condensate of aromatic and amine, synthetic paraffin, same grade lIt? fat-cutting money)/
J4, high monomer glycol, 3,4-functional, +5 dialkyl hexahydrophthalate obtained.

The thermofusible or thermosoftening substance used in the present invention preferably has a melting point or softening point in the range of 50 to 250C. If the melting point or softening point is less than 50C, the shelf life of the product tends to decrease, and if it exceeds 250C, the thermal response of the product to the thermal head becomes unsatisfactory. In addition, from the viewpoint of obtaining a product with high continuous photochromicity (high-speed dispersion property), these thermofusible or thermosoftening substances used in the present invention should be
It is preferably used in a mixture of 5 to 10 parts in total. If this number is less than the above range, the color development will be insufficient, and the resulting product will not be suitable for high-speed recording. For whales: q) It would be inappropriate as a record-taking fee. Book))@
In the case of +yj, it is recommended to use it for high-speed output recording such as facsimile, especially in cases of 5 quintillion bk or more.

On the other hand, if the amount of Mi and lIi is too large, blurring of the image may occur during color development by heating, which is not preferable. Therefore, in the case of the present invention, the amount of addition of the thermofusible substance is preferably kept within the above range.

In the present invention, in order to firmly support the 1% hot gray layer on the support, a heat-fusible or heat-softening adhesive is used as necessary, but such adhesives include: Examples include polyvinyl acetate, polyvinyl chloride, vinyl chloride/vinyl acetate copolymer, polyacrylic ester, y+5 listyrene, polycitadiene, polyacrylamide, styrene/butadiene/acrylic copolymer, and the like. These binders have a melting point or softening point of 50 to 250
It is preferable to use a binder in the range C0.In the present invention, thermofusible or thermosoftening binders such as those described in ft+1 are preferably used, but these binders do not necessarily need to be used alone. Not,
Other binders may be used in combination to more firmly bind each component in the layer to the support. Examples of such binders include the following.

? ribinyl alcohol, polyacrylamide, casein, gelatin, starch and its derivatives, polyvinylpyrrolidone, caly]? oxymethylcellulose, methylcellulose, ethylcellulose, polyester (1 out of 1
00,000 or more), polystyrene (MW: 100,000 or more), chlorinated rubber, styrene-1jle water maleic acid copolymer), iso(or diiso)butylene-maleic anhydride copolymer
Water-bathable, solvent-soluble, or aqueous dispersion type 4M such as urea-volumarin tree A1 phenolic resin, melamine resin, etc.
Fat.

Of course, these binders can also be used alone depending on the case.

Further, in the present invention, the heat-sensitive coloring layer may further contain acidic substances, basic substances, fillers, and other substances as auxiliary components, if necessary.

Hydrophilic substances Diacidic substances are added as necessary to prevent coupling reactions and maintain P stability, and include, for example, the following.

Tartaric acid, citric acid, boric acid, lactic acid, gluconic acid, sulfuric acid, etc.

Basic substance: A basic substance is added as necessary to cause a coupling reaction during heating, and for example, the following substances are added.

Caustic alkalis and alkali carbonates such as sodium hydroxide, calcium hydroxide, potassium carbonate, etc. Substances that generate basicity when heated include urea, thiourea, and the 5 most common substances thereof, alkali salts of trichloroacetic acid, ammonium chloride, ammonium sulfate, citric ammonium, etc. Benzoic acid is used to increase color density. 1-benzene sodium or guanisine My can be used.

Komato J. Sada: When heating with a thermal head or the like, fillers are added to improve the matching properties of the thermal head, and examples of such fillers include the following.

Organic and inorganic solid particles such as styrene resin imitation particles, urea-formalin condensate resin particles, aluminum hydroxide, magnesium hydroxide, calcium carbonate, titanium, talc, kaolin, silica, and alumina.

Other auxiliary ingredients include zinc chloride, citric soda, (Mtr+guanidine, calcium gluconate, sorbitol, Natsuri Rose, etc.) to suppress or assist color development, and saponin l (Doga Soda) as a solubilizer. used.

To obtain the heat-sensitive recording material according to the present invention, the above-mentioned forming components are dissolved or dispersed in a suitable solvent, a coating solution of 14 VA is applied, and this coating solution is applied onto a support. tl is applied and dried to form a product.

In this case, the solvent for dissolving all of the ingredients forming the compound is selected at discretion depending on the properties of the compound to be formed and the purpose of the preparation. Such solvents include water or an aqueous medium prepared by dissolving an organic solvent in water, benzene, toluene, xylene, n-hexane, n-hebutane, cyclohexane, kerosene, methylisozotyl t-ton, methyl cellosolve, Examples include nonpolar or polar organic solvents such as acetone, methyl ethyl ketone, dimethyl ether, and siloxane.

The heat-sensitive recording material of the present invention can be advantageously applied in the field of heat-sensitive recording, particularly as output recording paper for facsimile machines, electronic calculators, etc. that require high-speed recording. When a character or image is recorded on the surface, it is heated to form an image, and then exposed to light to remove unreacted dielectrics.
Fixation can be effected by decomposing the compound. Furthermore, the heat-sensitive recording material of the present invention can be applied to recording necessary information on securities, gift certificates, admission tickets, certificates, slips, etc., and for creating them, by taking advantage of its fixing properties.

Next, the present invention will be explained in more detail with reference to examples.

Example I A-stearin version amide 9
Heavy M part salt vinyl vinyl acetate combined IJχ
5 parts by weight Methyl cellosolve
ss path m part The above composition was dispersed in a gel mill [A
[Liquid] Completely prepared.

B liquid N-stearylbenzamide October i
, l, i-imidazole
5 layers & 1 layer 57 mice...≦ Methyl cellulose 5!
1XIAi part N-methylacetanilide
10fiid Tosui
6o Keihan: The above composition was dispersed in a sho-lumil, and [liquid B] was sub-dispersed. 50 gin? Dry type u2gΔ of calcium carbonate and PVA on high quality paper? It was undercoated so that it became t. 4. Spread [liquid A] on top of it so that the drying amount is 4-01/An', and leave [liquid B] on top of it to dry. o11Ar1'', and the Bekk flat f # degree was 80 seconds using a calender to obtain a one-sided thermal recording material. When printed with Rlfax 3300, the color was black.
00 and I+', and when measured at the Macbeth density d1, the print 161 degrees was 1.12 and the background density was 0.10.

Examples 2 to 5 Tests were conducted in the same manner as in Example 1 except that the CBB10N-methylacetanilide was replaced with the following compound, and the printing once and background density are shown below.

1: 1 tsubo density Background density Example 2 N-cyclohexylacetamide 1
．． 10 0.10 Example 3 0-Chloracetanilide 1.0? 0.10 Example 4 0-
Acedoanidishito 1.05 0.10
Example 5 N,N-diphenylacetamide
1.05 0.10 Comparative Example A recording material was prepared in the same manner as in Example 1 except that N-methylacetanilide was removed from [Liquid B]. The print density was 0.95 and the background density was 0.95. It was IO.

Claims (1)

[Scope of Claims] 1. A diazo-based 11-thermal recording material in which a heat-sensitive layer mainly composed of a diazo compound, a cassiller, and a thermofusible substance is provided on a support, and the coupler is represented by the following general formula (I).
) and (II) in combination, (However, It is an aromatic group or an alicyclic group, and X is hydrogen, halogen, acetyl group, sulfonic acid group, or alkoxyl group.) 8 (However, Xt and X are hydrogen, halogen, alkyl group,
It is an alkoxypa group or an -aryloxy group, R8 is an aromatic group or an alicyclic group, and Y is a cyano group or an acyl group. ) Furthermore, a compound represented by the following general formula (ID (however, R,
, R4, R, is any of an alkyl group, hydrogen, phenyl group, or cyclohexyl group where n = I N12, and "l
At least one of Ra1R4tRI needs to be a phenyl group or a cyclohexyl group, and
R4, I<, must not both be hydrogen. ) A diazo-based heat-sensitive recording material.